MX2007010949A

MX2007010949A - Method for producing scratch-resistant cured materials.

Info

Publication number: MX2007010949A
Application number: MX2007010949A
Authority: MX
Inventors: Bernd Biallas; Martin Kamps; Ulf Schlotterbeck
Original assignee: Basf Coatings Ag
Priority date: 2005-05-27
Filing date: 2006-05-09
Publication date: 2007-11-07
Also published as: CA2606100A1; DE102005024362A1; JP2008545829A; WO2006125723A1; KR20080015417A; CN101184793A; EP1885773A1

Abstract

The invention relates to a method for producing cured material consisting of material mixtures that can be cured by actinic radiation, by irradiation with UV-radiation. The invention is characterised in that it uses UV-radiation of the following spectral distribution and dose: wavelength lambda = 400 to 320 nm; dose = 500 to 2,500 mJ/cm2; wavelength lambda = 320 to 290 nm; dose = 700 to 3,000 mJ/cm2; wavelength lambda = 290 to 180 nm; dose = 100 to 500 mJ/cm2.

Description

METHOD FOR PRQDUC8R CORRESPONDING MATERIALS RESHSTENT TO RALADURA Field of the Invention The present invention relates to a new process for producing cured materials. The present invention also relates to the use of the cured materials produced by means of the new process for the coating, adhesive bonding, sealing, wrapping and packing of bodies of means of transport, especially motor vehicle bodies and parts thereof, the interior and exterior of constructions and parts thereof, doors, windows, furniture, hollow glass articles, coils, cargo containers, packaging, small parts, optical elements, mechanical and electrical components, and components for household appliances.

Aníerioir Technique The cured materials are preferably thermoset materials. For the purposes of the present invention, the thermoset materials are substantial three-dimensional interlaced which in comparison with two thermoplastic materials are deformable only to a lesser degree or not at all to the heating.

A process for the production of materials removed from German patent application DE 102 02 565 A1 is known. In the known process the cured materials are produced from a composition, thermally curable and with actinic radiation, by heating and exposure to UV radiation, for which (1) a thermal composition is used which is curable and with actinic radiation which , after it has cured, it has a storage modulus E 'in the rubber elastic range of at least 107 5 Pa and a loss factor tand at 20 ° C of not more than 0.10, the storage modulus E' and the loss factor have been measured by means of mechanical thermoanalysis (DMTA) on free films with a thickness of 40 ± 10 μm, and (2) the exposure is carried out with UV radiation whose spectrum comprises, in addition to UV-A and UV-B, a UV-C fraction which in the wavelength range of 200 to 280 nm has from 2 to 80% of the relative spectral radiance of the spectrum of a medium pressure mercury vapor lamp within this range of longifud d e wave, the relative spectral radiance of the UV-C fraction in the wavelength range from 200 to 240 nm which is always less than the relative spectral radiance of the spectrum of a medium pressure mercury vapor lamp within this range of wavelength, and (3) the radiation dose is from 10 to 6000 mJ cm2. For the purposes of the present invention actinic radiation means electromagnetic radiation with the examples being radiation near infrared (NIR), visible light, UV radiation, rays or gamma radiation, preferably UV radiation and also corpuscular radiation, examples being electron beams, beta radiation, neutron beams, proton beams and alpha radiation, preferably electronic beams Means of acinic radiation, in particular UV radiation. It is known that the UV radiation spectrum is divided into three regions: UV-A: 320 to 400 NM UV-B: 320 to 290 nm UV-C: 290 A 100 NM In general, the UV spectrum of the UV radiation sources is available only below a wavelength of 180-200 nm, since the radiation of shorter wavelength is absorbed by the hollow quartz bodies of the radiation sources (cf Stephen Davidson, "Exploring the Science, Technology and Applications of U.V. and EB Curing ", Sita Technology Ltd., London, 1999, Chapter I," An Overvie, "pages 3 to 34). The yellowing of the resulting known cured materials is low. They are resistant to scratching, and after being scratched they exhibit less loss of gloss. At the same time, its hardness and chemical resistance are high. The demands of the market in continuous growth, however, require additional improvements in Da resistance to the scratching of cured materials, in particular its resistance to scratching. when they are exposed to automatic washing lines. It is also necessary to achieve additional improvements in the adhesion of the cured material to substrates, in particular those of metals, plastics and other cured materials. A particular need is to further improve the inter-coating adhesion between coatings of cured materials that differ in physical composition and / or functions, in particular in multi-coating paint systems.

Issue It is an object of the present invention to provide a new process for producing cured materials that no longer has the disadvantages of the prior art but instead, in a particularly simple and reliable way, obtain cured materials that meet the advantageous profile of previously established requirements and, in addition, exhibits improved resistance to scratching, in particular to exposure in washing lines, and also improved adhesion to substrates, in particular those of metals, plastics and other cured materials. The new process in particular must obtain cured materials that have improved undercoating adhesion between coatings of cured materials that differ in physical composition and / or function, particularly in multi-coating paint systems, and particularly to exposure to a steam jet .

Solution Accordingly, the new process has been found for the production of cured materials from compositions curable with actinic radiation ("compositions") by exposure to UV radiation, using UV radiation of the following spectral distribution and dose: - wavelength lambda = 400 to 320 nm; dose = 500 to 2500 mJ / cm2; - lambda wavelength = 320 to 290 nm; dose = 700 to 3000 mJ / cm2; - lambda wavelength = 290 to 180 nm; dose = 100 to 500 mJ / cm2; The new process for producing cured materials is referred to below as the "process of invention". The additional subject matter of the invention will arise from the description.

Advantages of the I nvention In light of the prior art it was unexpected and unexpected for the experienced worker that the object in which the present invention is based could be achieved by the process of the invention. In particular, it was surprising that the process of the invention, of a particularly simple and reliable way, using conventional UV radiation sources, using conventional electronic, optical and mechanical components, and using conventional irradiation units, obtained, in a particularly simple and reliable way, cured materials, especially ferro-hardened materials, which not only exhibited little yellowing, alpha hardness and alpha chemical resistance but also, additionally have improved resistance to scratching, in particular to exposure in washing lines, and also possess improved adhesion to substrates, in particular to those of metals and plastics and other cured materials. In particular, the process of the invention obtained cured materials exhibiting improved undercoating adhesion between coatings of cured materials that differ in physical composition and / or performance, in particular in multi-coating paint systems, and in particular exposure to a jet of water. steam. It was even more surprising that the process of the present invention could be carried out with UV-curable compositions that differ widely in their constitution. As a result, in an unexpectedly advantageous manner, it was possible to adapt the compositions optimally for a very wide variety of end uses, so that they could be used with advantage as coating materials, adhesives, sealants and starting materials for moils and films. In particular. It was surprising that the coating materials could be used with particular advantage as galvanic coating materials, gear, ampi-waste rock primers, smooth top coat, base coat and clear coat materials. A minor surprise was the extraordinarily wide use of cured materials or coatings, adhesives, coatings, seals, castings and films, preferably as coatings, especially galvanic coatings, surface coatings, primer coatings, rock residues, protective layers of plain color, base layers and transparent layers. They were especially suitable for the coating, adhesive bonding, sealing and packaging of bodies of means of transport, especially motor vehicle bodies, and parts thereof, the interior and exterior of buildings and parts thereof, doors, windows , furniture, hollow glassware, coils, cargo containers, packaging, small parts, such as nuts, bolts, wheel rims or bushing covers, optional components, mechanical components, electrical components, such as windings (coils, stators, rotors), and components for appliances, such as radiators, household appliances, refrigerator housings or washing machine housings.

Description desalis a dl @? A .Bw ©? P? E? ©? P? The process of the present invention serves to produce mate rial is cured, especially thermoset materials for curable compositions with aclinic radiation (referred to below for brevity as "compositions") by exposure to UV radiation. According to the invention, the UV radiation used is the following spectral distribution and dose: - long wavelength lambda = 400 to 320 nm; dose = 500 to 2500 and preferably up to 2000 mJ / cm2; - lambda wavelength = 320 to 290 nm; doses = 700 to 3000 and preferably 1000 to 2200 mJ / cm2; - lambda wavelength = 290 to 180 nm; doses = 1 00 to 500 and preferably 200 to 450 mJ / cm2; The power can vary widely. Preferably, the UV radiation used is of the following spectral distribution and dose: lambda wavelength = 400 to 320 nm; power = 1 00 to 600 and preferably 120 to 550 mW / cm2; - lambda wavelength = 320 to 290 nm; power = 1 00 to 600 and preferably 140 to 550 mW / cm2; - lambda wavelength = 290 to 180 n; power = 20 up 1 20 and preferably 30 to 100 mW / cm2; For irradiation in the context of the process of the invention, a wide variation in the distance of the UV radix source from the surface of the composition is possible. The distance is preferably from 20 to 250 mm and in particular from 40 to 1 00 mm.

For a given dose, the irradiation period is guided by the band speed or the rate of advance of the substrates in the irradiation unit and vice versa. As radiation sources for UV radiation for non-operational use it is possible to use any conventional UV lamps which emit the relevant spectrum. However, combinations of at least two UV lamps can also be used which, although they do not emit UV radiation for the inventive use, have spectra that are added to provide the UV radiation for inventive use. It is also possible to use UV lamps where the desired spectrum is fixed by means of filters and / or reflectors. Isthter lamps are also suitable. Examples of suitable intermittent lamps are the intermittent lamps of the company VISIT. As UV lamps it is preferred to use mercury vapor lamps, more preferably low, medium and alpha pressure mercury vapor lamps, especially medium pressure mercury vapor lamps. Particular preference is given to the use of unmodified mercury vapor lamps plus suitable filters and reflectors, or mercury vapor lamps that have been modified, in particular by doping. Examples of suitable modified mercury vapor lamps are lamps doped with gallium and / or doped with iron, especially mercury vapor lamps doped with iron, such as it is described, for example, in R. Stephen Davidson, "Exploring the Science, Technology and Applications of UV and EB Curing", Sita Technology Ltd. London, 1999, Chapter I, "An Overview", page 16, Figure 10, or in Dial-lng. Meter Claman, "eltosch System-Kompetenz, UV-Technik, Leiífaden für Anwender", page 2, October 1998. examples of unmodified mercury vapor lamps plus the appropriate filters and reflectors are Arccu re UV lamps. These lamps are constructed so that the curing compositions are not impacted by any UV radiation but only radiation reflected indirectly in two packaged lines. For both reflected packages it is possible to use different reflectors, which reflect the entire UV spectrum ("ampl io"), reflect the long-wave component of the UV spectrum more extensively on molded parts ("A + B"), or they reflect the wave component of the UV spectrum more extensively on the sample ("C"). The arrangement of the radiation sources can be adapted for the special circumstances of the compositions and / or the substrates to which they have been applied., and also the process parameters. In the case of a complex shape, as they are considered, for example, for automobile bodies, those regions not accessible to direct radiation (shaded regions), such as cavities, folds and other structural notches, can be cured using point sources, of small area or general, in conjunction with means of automatic movement for the irradiation of cavities or edges. In the context of the process of the invention it is preferred to effect irradiation under an oxygen depleted atmosphere. "Oxygen depleted" means that the oxygen content of the atmosphere on the surface of the compositions is lower than the oxygen content of the air (20.95% by volume). The maximum oxygen content of the oxygen-depleted atmosphere is preferably 18%, more preferably 16%, most preferably 14%, particularly preferably 10% and particularly 6.0% by volume. The atmosphere can in principle be free of oxygen; that is, it comprises an inert gas. However, the complete or substantial absence of oxygen can also be obtained by masking the surface of the composition with an oxygen impermeable film. However, the absence of the oxygen inhibiting effect can in such cases produce a pronounced acceleration in radiation curing, as a result of which inhomogeneities and stresses may arise in the coatings of the invention. Therefore it is not advantageous in all cases to reduce the oxygen condenide in the atmosphere to a volume percentage of zero. Preferably the minimum oxygen content is 0.1% and in particular 0.5% by volume. The oxygen-depleted atmosphere can be provided by a variety of ways. It is preferred to produce an appropriate gas mixture and make it available in pressurized Sata containers. More preferably, depletion is carried out by introducing at least one inert gas in the respective amounts required in the damping of air located on the surface of the layers to be cured. The oxygen content of the atmosphere located on the surface in question can be measured continuously through conventional methods and devices for determining elemental oxygen, and when appropriate it can be adjusted automatically to the desired level. A gas is represented by inert gas which, under the curing conditions used, is not separated by actinic radiation, does not inhibit curing or react with Das compositions. Preference is given to the use of nitrogen, carbon dioxide, helium, neon or argon, especially nitrogen and / or carbon dioxide. The compositions used for the process of the invention are curable with actinic radiation, especially UV radiation. This means that it can comprise or consist of constituents that can be activated with actinic radiation and thus undergo free radical or ionic polymerization, especially including free radical polymerization. This results in l-dimensional entanglement of the compositions to give the cured materials, in particular thermoset materials. The compositions can additionally be curable physical and / or therm i camenie. For the purposes of the present invention the term "physical cure" denotes the curing of the compositions, in particular in the form of a film of a coating material, by means of film formation as a result of the emission of solvenity from the compositions, with link inside. Coating that takes place by cycle formation of the polymer molecules of binders (in relation to the term cf. Ropp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Síufgarf, New York, 1998, "Binders", pages 73 and 74) . Or the film formation takes place through the coalescence of binder particles (see Ropp Lexikon Lacke und Druckfarben, Georg Thieme Veriag, Stutgart, New York, 1998, "Curado", pages 274 and 275). Normally interlacing agents are not necessary for this purpose. For the purposes of the present invention the term "thermal curing" denotes the curing initiated by heating a particular composition of a film of a coating material, in which a binder and a separate interlacing agent are normally used. . This is usually referred to by those with experience in the art as external entanglement. When the entanglement agents are already incorporated in the binders, the term "self-entanglement" is also used. According to the invention, external entanglement is advantageous and is therefore preferably used (cf. Ropp Lexikon Lacke u nd Druckfarben, Georg Thieme Verlag, Síuígart, New York, 1998, "Curing", pages 274 to 276, especially page 275, bottom).

Those skilled in the art also refer to curable compositions with actinic radiation and thermally as double curing compositions. In the process of the invention, it is preferred to use compositions which, after they have been cured, have a storage modulus E 'in the elastic rubber range of at least 10? 5, preferably of at least 107 6, more preferably of at least 108 * 0, and in particular of at least 108 * 3 Pa and a loss factor tand at 20 ° C of not more than 0.10, preferably not greater than 0.06, the storage modulus E 'and the loss factor that have been measured by means of dynamic mechanical dynamic analysis (DMTA) on free films having a thickness of 40 ± 10 μm. The recoverable energy component (elastic component) in the deformation of a viscoelastic material such as a polymer, for example, is determined by means of the parameter of the storage module E ', in which the component of energy consumed (dissipated) ) in this process is described by the parameter of the loss modulus E ", the modules E 'and E" depend on the speed of deformation and the temperature. The loss factor tand is defined as the ratio of the loss modulus E "to the storage module E '. Tand can be determined by dynamic mechanical thermoanalysis (DMTA) and is a measure of the relationship between the elastic and plastic properties of the film. DMTA is a widely known measurement method for determining the viscoelastic properties of coatings and is described, for example, in Wirayama, T., Dynamic Mechanics, Analysis of Polymeric Materials, Elsevier, Neww Cork 1978 and Loren W. H ill, Journal off coatings Technology, Vol. 64, No. 808, May 1992, pages 31 to 33. The conditions of the method that relate to the measurement of tan by means of DIMITA are described in detail by Th Frey, K.-H. Große Brinkhaus, and U. Róckrath in Cu re Moniíoring of Thermoset coatings, Progress in Organic coatries 27 (1996), 59-66, or in the application for German pafenie DE 44 09 715 A 1 or the German pa- llel DE 197 09467 C2. Preference is given to the use of the following conditions: mode of tension; Ampliíud: 0.2%; frequency: 1 Hz; temperature ramp: 1 ° C / min from the ambient temperature up to 200 ° C. The storage module E 'can be adjusted by the experienced worker through the selection of curable by particular actinic radiation and also, when appropriate, physically and / or chemically curable components, the functionality of the components and their proportion co o a fraction of the composition for the inventive use. The module E 'can be adjusted in a general way, by means of the curable components with the acynic radiation, by selecting the nature and the quantity of the components of preference so that for each gram of composition solids it is 0.5. to 6.0, preferably 1.0 to 4.0, and more preferably 2.0 to 3.0 meq of bonds that can be activated with acinic radiation. For the purposes of the present invention, "solids" represent the sum of those constituents of a composition that make up the cured material produced from said composition. For the purposes of the present invention, a bond that can be activated with actinic radiation is a bond that when reacted to actinic radiation becomes reactive and, together with other acylated bonds of its type, enters polymerization reactions and / or reactions of interlacing that proceed according to the free radical and / or ionic mechanisms. Examples of suitable bonds are simple carbon-hydrogen bonds or single or double bonds of carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon. Of these, the carbon-carbon double bonds are particularly preferred and, therefore, they are used with very particular preference according to the invention. For brevity purposes they are referred to below as "double bonds". Particularly preferred compounds containing double bonds are compounds containing acrylate groups. The compositions may contain acid groups. When the latter are used, they are present in an amount greater than 0.05, preferably more than 0.8, most preferably more than 0.15, and in particular of more than 0.2 meq / g solids, the amount of acid groups present will not exceed 15, preferably 10, more preferably 8, and in particular 5 meq / g solids. When acid groups are used, they are preferably selected from the group consisting of carboxyl groups, groups of phosphoric acid, sulphonic acid groups, acid phosphate ester groups, and acid sulfa acid ester groups, especially groups. carboxyl. The physical constitution of the compositions for use in the process of the invention is not critical; instead, all conventional compositions curable with acicular radiation, especially UV radiation and also, if desired, physically and / or thermally curable, can be used. Suitable components of said compositions, the suitable compositions themselves, and the processes for preparing them are known, for example from German patent application DE 102 02 565 A1, page 4, paragraph

[0029], to page 8, paragraph

[0079], or of German patent DE 197 09 467 C2. The process of the invention obtains particular advantages if it is carried out with compositions comprising at least one free radical or curable crosslinkable component which (i) contains one or more of oligourethane and / or one or more of polyurethane methacrylates and the which are (ii) an average of more than one olefinically double bond insoluble per molecule, (iii) a number average molecular weight of 1000 to 10,000 daltons, (iv) a double bond content of 1.0 to 5.0 double bonds per 1000 g of free radical crosslinkable component, (v) on average per molecule > 1 branch point. (vi) 5 to 50% by weight, based in each case on the weight of the component, of cyclic structural elements, and (vi i) at least one aliphatic structural element having at least 6 carbon atoms in the chain, The crosslinkable component of free radical containing carbamate and / or biuret and / or allophane and / or urea and / or amide groups. The free radical crosslinkable component preferably contains at least 50% by weight, more preferably at least 70% by weight, and most preferably contains at least 80% by weight, based in each case on the basis of solids content of the crosslinkable free radical component of one or more oligourethane mephacrylates and / or one or more polyurethane methacrylates. In particular, the crosslinkable free radical component is comprised of 100% of one or more oligourethane methacrylates and / or one or more polyurethane methacrylates. The free radical crosslinkable component also preferably contains not more than 50% by weight, more preferably not more than 30% by weight, and most preferably not more than 20% by weight, of additional monomers, although preferably oligomers and / or polymers, especially polyacrylate, methacrylates of epoxy, melacrylic methacryloyl functional copolymers, polyether methacrylates, unsaturated polyesters, amino methacrylates, melamine mefacrylates and / or silicone melacrylates, preferably polyester methacrylates and / or epoxy methacrylates and / or polyether methacrylates. Preference is given here to polymers which, in addition to those in double bonds, also contain hydroxyl, carboxyl, amino, and / or thiol groups. In the great majority of cases, the use of additional free-radical crosslinkable components is superfluous. The free radical crosslinkable component preferably contains less than 5% by weight, more preferably less than 1% by weight, based in each case on the weight of the free radical crosslinkable component, and in particular substantially does not contain free isocyanate groups available . Additionally, it is preferred that the free radical crosslinkable component comprises a mixture of different methacrylates of oligourelane and / or polyurethane, which may also have different double-bond contents, molecular weights, double bond equivalent weights, branch point contents and levels of cyclic and relatively long chain aliphatic structural elements, and different amounts of carbamate, biuret, allophane, amide and / or urea groups. The mixture can be obtained by mixing different oligoureic or polyurethane methacrylates or by preparing different products simultaneously during the preparation of an oligoureic or polyurethane methacrylate.

In order to obtain effective entanglement, the use of free radical crosslinkable components whose main functional groups are of alpha reactivity, more preferably free-radical crosslinkable components containing acrylic double bonds as functional groups, is preferred. The urethane methacrylates can be prepared in a manner that is known to the skilled worker, from a compound containing isocyanate groups and from at least one compound which contains groups that are reactive to the isocyanate groups, the preparation having place afterwards through mixing of the components of any order, when appropriate at an elevated temperature. It is preferred to add the compound that confers groups that are reactive to the isocyanate groups, preferably in two or more layers. In particular, urethane methacrylates are obtained by initially introducing the diisocyanate or polyisocyanate and subsequently adding at least one hydroxyalkyl methacrylate or hydroxyalkyl ester of other olefinically unsaturated acids, to give rise to the initial reaction of the groups. isocyanate. Subsequently, a chain exponent is added from the group of diols / polyols and / or diamines / polyamines and / or difioies / polyols and / or alkanolamines and in this way the remaining isocyanate groups are reacted with the exoensor of chain.

A further possibility is to prepare the urehane methacrylates by reacting a di- or polyisocyanate with a chain extender and subsequently reacting the remaining free isocyanate groups with at least one olefinically unsaturated hydroxyalkyl ester. It will be appreciated that all intermediate forms between these two techniques are also possible. For example, some of the isocyanate groups of a diisocyanate can be reacted first with a diol, subsequently an additional portion of the diisocyanate groups can be reacted with the hydroxyalkyl olefin ester unsaturated, or after the isocyanate groups can be reacted with a diamine. In general, the reaction is carried out at temperatures between 5 and 100 ° C, preferably between 2 and 9 ° C, and more preferably between 40 and 80 ° C, and especially between 60 and 80 ° C. It is preferred here to operate under anhydrous conditions. "Anh idro" means here that the water content of the reaction system is not more than 5% by weight, preferably not more than 3% by weight, and more preferably not more than 1% by weight. In particular, the water content is below the detection limit. In order to suppress the polymerization of the polymerizable double bonds, it is preferred to operate under a gas containing oxygen, more preferably air or air / nitrogen mixtures. As an oxygen-containing gas, it is possible to preferably use air or a mixture of oxygen or air and a gas which is inert under the conditions of use. As the gas is inerted, it can be made use of nylrogen, helium, argon, carbon monoxide, carbon dioxide, steam, lower hydrocarbons, or mixtures thereof. The oxygen content of the gas containing oxygen may be, for example, between 0.1% and 22% by volume, preferably from 0.5% to 20%, most preferably 1% up to 15%, most preferably 2% up to 10% and in particular from 4% to 10% by volume, it will be appreciated that, if desired, higher oxygen contents may also be used. The reaction can also be carried out in the presence of an inert solvenle, examples being acetone, isobutyl methyl cation, methylene ketone, toluene, xylene, butyl acrylate or ethoxyethyl acetyl. Through selection of the nature and quality of d i- and / or polyisocyanate, the chain exponent and the hydroxyalkyl ester employed, control is exercised over the additional variables of the urethane methacrylates, such as, for example, the double bond, double bond equivalent weight, number of branching points, number of cyclic structural elements, number of aliphatic structural elements that have at least 6 carbon atoms and amount of biuret, allophanate, carbamazo, urea and / or groups amide, and the like. Through the selection of the particular quantities of di- or polyisocyanate and the chain extender that are used and also to Through the functionality of the chain extender it is also possible, in addition, to prepare urethane methacrylates which, as well as the ethylenically unsaturated double bonds, also contain other functional groups, examples of which are two hydroxyl groups, carboxyl groups, amino groups and / or groups fiol or similar. Especially if the urethane methacrylate is to be used in aqueous compositions, some of the free isocyanal groups present in the reaction mixtures are also reacted with compounds containing an isocyanate reactive group, preferably selected from the group comprising primary and secondary hydroxyl, thiol and amino groups, in particular hydroxyl groups and also, at least one, especially an acid group, preferably selected from the group consisting of carboxyl groups, sulfuric acid groups, acid groups phosphoric, and phosphonic acid groups, especially carboxyl groups. Examples of suitable compounds of this class are hydroxyacetic acid, hydroxypropionic acid or gamma-hydroxybutyric acid, especially hydroxyacetic acid (glycolic acid). For the processes of the invention, the compositions may be present in any of a wide variety of physical states and 1-dimensional forms. For example, at room temperature the compositions can be solid or liquid or fluid. However, they can also be found in the solid state at room temperature and fluids at higher temperatures, preferably exhibiting n behavioral psychoplasm. In particular, they may be conventional compositions comprising organic solvents, aqueous compositions, substantially or completely solvent-free and water-free liquid compositions (100% systems), solvent-free or substantially solvent-free and water-free solid powders, or substantial powder suspensions. or completely solvenle-free (dust rails). The dual-curing compositions may additionally be one-component systems, wherein the binders and entangling agents are present one along the other, or two-component or multicomponent systems, wherein the binders and entangling agents are present. separated from each other until shortly before the application. In terms of the preparation method of the compositions for the inventive use, there are no peculiarities but rather the mixing and homogenization of the aforementioned constituents by means of conventional mixing techniques and apparatus such as agitation tanks. , stirring mills, exurors, mixers, Uliraturrax devices, in-line solvents, static mixers, micromixers, cogwheel dispersers, pressure release boquilizers and / or microfluidizers, preferably in the absence of acicular radiation. The selection of the method that is optimal for a given individual case is guided in particular by the physical state and the iridimensional form that the composition. When, for example, a thermoplastic composition is present in the form of a film or a laminate, extrusion through a slot mold is particularly suitable for producing the composition and forming it. For the purposes of the process of the invention, the compositions are used to produce cured materials, especially spanable materials, which serve a wide variety of end uses. The compositions are preferably starting materials for castings and films or are coating materials, adhesives and sealants. The cured materials with preferably molded parts, films, coatings, adhesive layers and sealants. The coating materials are used in particular as galvanic coating materials, fillers, antiresidue rock primers, solid color protective layer materials, water-based layer materials and / or translucent layer materials, especially transparent layer materials, to produce color and / or single-layer or multi-layer effect, electrically conductive, magnetic protection or fluorescent pinhole systems, in special multi-coating and / or pinura effect coloring systems. The coating systems of the coating can be produced using conventional wet-on-wet techniques and / or extrusion techniques and also conventional paint systems. movie . To produce the cured materials, in the process of the invention, the compositions for inventive use are applied to conventional temporary or permanent substrates. For the production of films and molded parts, the use of conventional temporary substrates, such as metal and plastic strips and sheets or hollow bodies of metal, glass, plastic, wood or ceramic, which can be easily removed without damaging the molded parts and films, is preferred. which are produced from the compositions. When the compositions are used to produce coatings, adhesives and seals, permanent substrates are used, such as bodies of means of transport, especially motor vehicle bodies, and parts thereof, the interior and the exterior of constructions and parts thereof, doors, windows, furniture, hollow glass articles, coils, containers, packaging, small parts, optical, mechanical and electrical components, and components for household appliances. The films and molded parts produced by means of the process of the invention can likewise serve as permanent substrates. In terms of the method, the application of the compositions for use in the process of the invention has no peculiarities but instead takes place through all conventional application methods suitable for the composition in issue, such as extrusion, galvanic coating, injection, spraying, including powder spraying, knife coating, coating, pouring, dipping, draining or rolling. Preference is given to the use of extrusion methods and spray application methods. During application it is advisable to operate in the absence of acicular radiation, in order to avoid premature entanglement of the compositions. In a preferred embodiment of the invention process the compositions are used in the form of films, in particular in the form of flat laminates, comprising at least one film of a composition and also, when appropriate, at least a support film, preferably a thermoplastic. In a particularly preferred embodiment of the process of the invention, the films or laminates are formed before being cured. The formation preferably takes place by thermoforming and / or by injection molding with thermoplastics or plastic reactive precursors (reaction injection molding) in conventional injection molding machines. This results in films or laminates formed, still curable, on plastic substrates formed in a corresponding manner. When the curable films or laminates comprise at least one thermoplastic support film, the films or laminates are preferably connected to the substrates or laminates. precursors thereof in such a way that the supporting films are confronting in distance from the UV radiation sources. Following its application the compositions are cured in the manner described at the beginning. The resulting cured materials, in particular the films, molded parts, coatings, adhesive layers and resultant seals, are remarkably suitable for the coating, adhesive bonding, sealing, wrapping and packaging of transporie means bodies, especially vehicle bodies of moior. and parts thereof, the interior and the exterior of constructions and parts thereof, doors, windows, furniture, hollow glass articles, coils, containers, packaging, small parts, such as nuts, bolts, wheel rims or lids bushing, optical components, mechanical components, electrical components, such as windings (coils, stators, rotors) and also components for household appliances, such as radiators, household appliances, refrigerator housings or housings for washing machines. The process of the invention allows particular advantages when it is used for the production of ransparent coatings. Upright coatings are usually the outermost coatings of multi-coating paint systems or films and / or laminates, which substantially determine the overall visual appearance and protection of the coatings. the substrates and / or the effect coatings of multi-coating paint systems or films and / or laminates of mechanical and chemical damage and starting from radiation damage. Consequently, the deficiencies in the hardness, scratch resistance, chemical resistance and yellowing resistance in the transparent coating are manifested to a particularly marked degree. However, the transparent coatings produced by the process of the invention exhibit only a low level of yellowing. They are highly resistant to scratching and, after being scratched, exhibit only very low levels of gloss loss. In particular the loss of brightness in the Amtec / Kistler car wash simulation test is very low. At the same time they have a high level of hardness and a particularly high chemical resistance. They exhibit a remarkable adhesion to substrate and adhesion between coatings, in particular in relation to exposure to steam jet.

Examples Example of preparation 11 The preparation of a free radical crosslinkable or ureirable urethane acrylate A urethane acrylate was prepared from the components of synthesis specified below, by approximate dispersion of hydrogenated bisphenol A in 2-hydroxyethyl acrylate at 60 ° C with stirring. To this suspension were added isocyanates, monomethyl hydroquinone ether, 1,6-di-tert-butyl para-creso and methyl ethyl ketone. After the addition of dibutyltin dilaurate there was an increase in the batch temperature. It was stirred at an internal temperature of 75 ° C for a number of hours until there was virtually no change in the NCO value of the reaction mixture. Any free isocyanate groups remaining even after the reaction were converted by the addition of a small amount of mei nol.

Compose of synthesis: 104. 214 g of hydrogenated bisphenol A (corresponding to 0.87 equivalent of hydroxyl groups); 147,422 g (corresponding to 0.77 equivalent of isocyanate groups) of Basonaf® Hl 100 of BASF AG = commercial isocyanurate of hexamethylene diisocyanate having an NCO content of 21.5% -22.5% (DIN EN ISO 11909); 147,422 g (corresponding to 0.77 equivalent of isocyanate groups) of Basonaí® HB 100 of BASF AG = commercial biuret of hexamethylene diisocyanate having an NCO content of 22% -23% (DIN EN ISO 11909); 124,994 g (corresponding to 0.51 equivalent of groups isocyanate) of Degussa's Vestanat® T1890 = commercial isocyanurate of isophorone diisocyanate having an NCO content of 11.7% -12.3% (DIN EN ISO 11909); 131,378 g of 2-hydroxyethyl acrylate (corresponding to 1.13 equivalents of hydroxyl groups); 0.328 g of monomelil hydroquinone ether (0.05% solids); 0.655 g of 1, 6-di-ter-bulyl-para-cresol (0.1% solids); methyl ethyl ketone (70% solids); 0.066 g of dibuylline dilaurate (0.01% solids); 4,500 g of methanol (corresponding to 0.14 equivalent of hydroxyl groups); The characteristics of the resulting urethane acrylate (free radical crosslinkable component) was as follows: on average 2.2 ethylene-unsaturated double bonds per molecule; a double bond content of 1.74 double bonds per 1000 g of urethane acrylate solids; on average 2.2 branch points per molecule; 25% by weight of cyclic structural elements, based on the solids content of the urethane acrylate.

Example 2 The preparation of a UV-curable transparent coating material A vessel with stirrer was initially charged with 100.0 parts by weight of the organic solution described above of the urease acrylate from Preparation Example 1. An admixture of 1.0 parts by weight of Tinuvin®292 (commercial HA LS light stabilizer from Ciba Specialty Chemicals based on a mixture of bis (1, 2, 2, 2) was added to the initial charge within 30 minutes. 6, 6-pentamethyl-4-piperidinyl) sebacate and methylated (1, 2, 2, 6,6-pentamethyl-4-piperidinyl) sebacaio), 2.0 paries by weight of Tinuvin®400 (commercial light stabilizer from Ciba specialiy Chemicals, based on a mixture of 2- (4 - ((2 -hydroxy-3-dodecyloxypropyl) oxy) -2-hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and 2- (4 - ((2-hydroxy-3 -Iridecyloxypropyl) oxy) -2-hydroxyphen-yl) 4,6-bis- (2,4-dimethylphenol) -1, 3,5-triazine), 0.8 parts by weight of Lucirin® TPO-L (commercial photoinitiator from BASF Aktiengesellschaft , based on 2, 4,6-trimethylbenzoyldiphenyl-phosphine oxide), 2.40 parts by weight of I rgacure® 184 (commercial photoinitiator of Ciba Specialty Chemicals, based on 1-hydroxycyclohexyl phenyl ketone) and 0.2 parts by weight of Byk ® 306 (Byk Chemie's trade additive, based on a polyether-modified polydimethylsiloxane) with continuous stirring at ambient temperature, and the resulting mixture was dissolved in 3- butoxy-2-propanol and adjusted with 3-butoxy-2-propanol to a solids content of 48%. It was then stirred at room temperature for 30 minutes.

Preparation example 3 The production of a coated thermoplastic support film The support film used was thermoplastic film of Luran® S 778 TE from BASF Akíiengesellschafftt with a thickness of 800 μm. The surface of the supporting film to be coated was subjected to a corona pre-treatment at 0.5 kilowatt. The film was coated on one side with a metallic aqueous base coating material (color: "metallic silver"). The base coat material was applied to the support film using a box-type coating rod with a width of 37 cm at a band speed of 0.5 m / min. The application was carried out with a moderate air flow of 0.2 m / s, at a temperature of 21 ± 1 ° C, and a constant relative humidity of 65 ± 5%. The thickness of the resulting wet base coating film (first basecoat film) was 100 μm. The first wet-based coating film was vaporized instantaneously under these conditions for 3 minutes and then dried to a volatile content residues of 4% by weight, based on the first base coat film. The first resulting conditioned base coat film, with a thickness of about 20 μm, was adjusted with cooling rollers at a surface temperature < 30 ° C. The same basecoating material was added to the first basecoat film conditioned and adjusted to temperature, under the following conditions, using a system for the application of pneumatic spraying. - discharge speed: 100 ml / min; - air pressures: atomizer air: 2.5 bar; horn air: 2.5 bar; - velocity of displacement of the nozzles: sufficiently high to result in an overlay of spray-jet of 60%; - distance nozzle / film: 30 cm. The application was carried out under a moderate air flow of 0.5 m / s (which impacts vertically on the film), at a constant temperature of 21 ± 1 ° C, and at a relative humidity of 65 ± 5%. The thickness of the wet base coating film resulting (second basecoat film) was 50 ± 2 μm. The second basecoat film was vaporized under these conditions for 3 minutes and then dried to a residual volatiles content of 4% by weight, based on the second basecoat film. The temperature The air was 90 ° C, the humidity was 10 g / min, and the air velocity was 10 m / s. The second conditioned base coating film resulting, with a thickness of about 10 μm, was adjusted with cooling rollers to a surface temperature of < 30 ° C. The UV-curable coating material of the preparation example 2 was applied to the second conditioned and temperature-adjusted basecoat film, using a 37 cm wide box covering bar. The application was carried out with a moderate air flow of 0.2 m / s, at a temperature of 21 ± 1 ° C and at a relative humidity of 65 ± 5%. The thickness of the ransparent film was 120 μm. It was vaporized under the conditions that were stable for d minutes and then dried to a residual volatile content of 2.5% by weight, based on the transparent coating film. The air temperature in the oven was 1 19 ° C for all the drying stages. The resulting dried coating, although not yet completely cured, with a coating thickness of 60 μm, was adjusted with cooling rollers to a surface temperature << 30 ° C and coated with the polypropylene proof film described in DE 103 35 620 A1, example 1 (commercial product G H-X 527 by Bischof + Klein, Lengerich). The resulting multilayered film was rolled up on a roll and stored in this way for later use.

Examples 1 to 3 The production of po m mp * © I p ades The molded plastic parts were produced in accordance with the following general instructions: The mulilac film of preparation example 3 was preformed. Subsequently, the transparlene coating, although not yet fully cured, was separated into strips from its pro-vacuum film and then completely entangled using UV radiation. The positive mold used was a cube. The resulting preformed part was inserted into a mold. The mold was closed and the cube was re-molded by injection with a liquid plastic material. The irradiation was carried out using a UV lamp of Arccure (non-doped mercury lubo). The construction of this lamp was that there was no direct UV radiation impact on the plastic molded parts; instead, only indirectly reflected radiation impact on molded parts, in two grouped lines. Different reflectors could be used for both reflected lines, which reflected the UV specimen ("wide"), which reflected the long-wave component of the UV speci fi cation more ex- tensively on the plastic molding pieces ("A + B") on the sample ("C"). In the case of examples 1 and 3 to 6 the selected reflector arrangement, visi- The direction of movement of the plastic molded parts through the UV exposure unit was as follows: 1. "width" and 2. "C". In the case of example 2 the selected reflector arrangement was as follows: 1. "A + B" and 2. "A + B". The plastic moles were irradiated in an atmosphere of carbon dioxide depleted in oxygen. The table provides a general overview of the shortest distances used between the source of UV radiation and the surface of the transparent coating film on plastic molded parts, the oxygen content of the atmosphere on the transparent coating film, the spectral distribution , with the appropriate dose and energy, and the resistance to scratching and adhesion of the transparenite coatings in the molded plastic parts.

Frame: C? Rad © aS® us® lió © ojias d @ r @ ©? To? Riii iD @ G * i) © üramisparente with UV radiation, and ?portable properties d® D®s transparent coatings Example Dist. * > Or, "'Dosage" Energy * Amtec 0) SJ " No. (m) (% par (mJfcm) (ní? Kan2) (residual (index; ral.) Bri or%) UV-A UV-B UV-C UV-A UV-B UV-C 1 40 0.5 782 cough 203 - - - 79.3 sat. 2 40 0.9 315 1240 251 474 CSJ 77 81 sat. 3 40 0.8 854 1194 235 470 474 78 87.7 sat. a) dissipation between the source of radiation and Da surface of transparent coating film; b) atmosphere oxygen content on the transparent coating film; c), d) measures using an EIT PoPuck®; e) waste gas after exposure in the simulation test Amule / Kisller air-washing machine with cleaning (rinsing with peiróleo); f) steam jet test; In the case of the car wash simulation test, a laboratory washing line from Amtec Kisler was used (see T. Klimmasch, T. Engebert, Technologieiage, Cologne, DFO, report volume 32, pages 59 to 66, 1997). The induced induction was determined by measuring the residual brightness of the sample after the simulation test and subsequent rinsing with a cleaning cloth soaked with petroleum ether. Residual brightness levels of more than 80% were achieved. For the steam jet test, according to the Daimler-Benz steam jet test instructions that are known in the art, a cross was marked on the blade within the transparenite coatings of each of the examples 1 to 6 The marked areas were subjected to a water jet spray (Walter model LTA2 instrument, pressure: 67 bar, water temperature: 60 ° C, nozzle tip diffusion / test sample: 10 cm, exposure time: 60 seconds; instrument fixation: F 1). The degree of separation in the form of scales and sub-film migration are determined visually. In all cases the result was saf. (satisfactory). The results in the table underline the fact that the transparent coatings in the plastic molded parts of examples 1 to 6 exhibited very good adhesion between Coating and resistance to scratching, especially under real conditions. In other respects the transparine coatings in the plastic molded parts of examples 1 to 6 were bright and had a very high gloss (20 °) according to DI N 67530. They were hard, flexible, resistant to chemical agents and free of yellow disruptive

Claims

CLAIMS 1. A process for producing cured materials from compositions curable with actinic radiation ("compositions") by exposure to UV radiation, which comprises using UV radiation of the following spectral distribution and dose: - lambda wavelength = 400 to 320 nm; dose = 500 to 2500 mJ / cm2; - lambda wavelength = 320 to 290 nm; dose = 700 to 3000 mJ / cm2; - lambda wavelength = 290 to 180 nm; dose = 100 to 500 mJ / cm2; 2. The process according to claim 1, characterized in that the UV radiation of the following spectral distribution and dose was used: lambda wavelength = 400 to 320 nm; dose = 750 to 2000 mJ / cm2; - lambda wavelength = 320 to 290 nm; dose = 1000 to 2200 mJ / cm2; - lambda wavelength = 290 to 180 nm; Dosage = 200 Hasía 450 mJ / cm2; 3. The process according to claim 1 or 2, characterized in that the UV radiation of the following spectral distribution and power was used: lambda wavelength = 400 to 320 n; power = 100 up to 600 mW / cm2: - lambda wavelength = 320 to 290 nm; power = 100 up to 600 mW / cm2; - Lambda wavelength = 290 to 180 nm; polenge = 20 to 120 mW / cm2; 4. The process according to claim 3, characterized in that the UV radiation of the following speci fi c distribution and po- lence was used: - lambda wavelength = 400 to 320 nm; power = 120 hasla 550 mW / cm2; - lambda wavelength = 320 to 290 nm; polenge = 140 hasla 550 mW / cm2; - Lambda wavelength = 290 to 180 nm; power = 30 up to 100 mW / cm2; 5. The process according to any of claims 1 to 4, characterized in that during the irradiation the dissipation between the source of UV radiation and the surface area of the composition is from 20 to 50 mm. 6. The process according to claim 5, characterized in that the distance is from 40 to 100 mm. 7. The process according to any of claims 1 to 6, characterized in that during the irradiation the oxygen content of Da atmosphere in the surface of the compositions is exhausted. 8 The process according to claim 7, characterized in that the oxygen content of the atmosphere is < 1 8% in volume. 9. The process according to any of claims 1 to 8, characterized in that the compositions are additionally curable physically or thermally. 10. The process according to any of claims 1 to 9, characterized in that the compositions are in the form of films or laminate components. eleven . The process according to any one of claims 1 to 10, characterized in that after the compositions have been cured they have a storage modulus E 'in the elastic rubber region of at least 107 5 Pa and a loss factor of at 20. ° C of not more than 0.10, the storage module E 'and the loss factor that have been measured by means of mechanical analysis (DWITA) on free films with a thickness of 40 + 10 μm 12. The process of compliance with any of claims 1 to 11, characterized in that the amount of bonds that can be activated with UV radiation in Das compositions is 0.5 to 6 meq / g solids. 13. The process according to claim 12, characterized in that the amount of bonds that can be activated with UV radiation is 1 to 4 meq / g solids. 14. The process according to claim 12 or 13, characterized in that the links that can be activated with UV radiation are carbon-carbon double bonds. The process according to any of claims 1 to 14, characterized in that the compositions comprise at least one free radical crosslinkable component which (i) contains one or more of oligourethane and / or one or more polyurethane methacrylates and which have (ii) an average of more than one olefinically unsaturated double bond per molecule, (iii) a number average molecular weight of 1000 to 10 000 daltons, (iv) a double bond content of 1.0 to 5.0 double bonds per 1000 g of free radical crosslinkable component, (v) on average per molecule > 1 branch point. (vi) 5 to 50% by weight, based in each case on the weight of the component, of cyclic structural elements, and (vii) at least one aliphatic structural element having at least 6 carbon atoms in the chain, interlazable component of free radical containing carbamate and / or biuret and / or allophane and / or urea and / or amide groups. 16. The process according to any of claims 1 to 15, characterized in that the compositions are coating materials, adhesives, sealants, and starting materials for moldings and films. 17. The process according to claim 16, characterized in that the cured materials are coatings, adhesive layers, seals, castings and films. The process according to claim 16, characterized in that the coating materials are galvanic coating materials, anti-rock debris primers or primers, smooth top coat materials, base coat materials or clear coat materials which serve to produce coatings. 19. The process according to claim 17 or 18, characterized in that the coatings are coating materials are galvanic coating materials, coatings of primer, primer coatings ampi-waste rock, smooth top coatings, base coatings or transparent layers. 20. The process according to claim 18 or 1 9, characterized in that the coatings are color systems of coating and / or effect paint or films and / or laminates. twenty-one . The process for producing cured materials according to any of claims 1 to 19, characterized in that the compositions are applied to permanent or temporary substrates and exposed to UV radiation. 22. The process according to claim 21, characterized in that the substrates are composed of metal, plastic, glass, wood, textiles, leather, natural rock, artificial rock, concrete, cement or assemblies of these materials. 23. The process according to claim 21 or 22, characterized in that the castings and films are removed from the temporary substrates. 24. The process according to any of claims 21 to 23, characterized in that the permanent substrates are bodies of means of transport and parts of the same, the interior and exterior of constructions and parts thereof, doors, windows, furniture. , hollow glassware, coils, containers, packaging, small parts, optical, mechanical and electrical components, and components for household appliances. RESUMEN OF THE I NVENC ION The invention relates to a method for producing cured material consisting of mixtures of material that can be cured by actinic radiation, by irradiation with UV radiation. The invention is characterized in that it uses UV radiation of the following spectral distribution and dose: lambda wavelength = 400 to 320 nm; dose = 500 to 2500 mJ / cm2; Lambda wavelength = 320 to 290 nm; dose = 700 to 3000 mJ / cm2; Lambda wavelength = 290 to 180 nm; dose = 100 to 500 mJ / cm2.