EP1263893A1

EP1263893A1 - Method for producing coatings, adhesive coatings and seals that can be cured using actinic radiation

Info

Publication number: EP1263893A1
Application number: EP01933689A
Authority: EP
Inventors: Ludger Dornieden; Jorge Prieto; Roland STEINRÜCKEN; Reinhard Wiesing
Original assignee: BASF Coatings GmbH
Current assignee: BASF Coatings GmbH
Priority date: 2000-03-15
Filing date: 2001-03-13
Publication date: 2002-12-11
Also published as: PL358210A1; WO2001068777A1; US20030129323A1; DE10012580A1; MXPA02008862A; CA2402920A1; BR0109183A; AU6011501A

Abstract

The invention relates to a method for producing coatings, adhesive coatings and/or seals from coating materials, adhesives and/or sealants that can be cured using actinic radiation, on or in primed and unprimed substrates. According to said method, the coating materials, adhesives and/or sealants are applied to and/or induced in the substrates and the resultant layers are subsequently cured using actinic radiation. Said method uses coating materials, adhesives and sealants which are devoid of photoinitiators and which contain or consist of the following as components that can be activated by actinic radiation: A) at least one (meth)acrylate copolymer which contains as the statistical mean per molecule at least one group (a) comprising at least one bond that can be activated by actinic radiation, whereby group (a) is linked to the basic structure of the (meth)acrylate copolymer (A) by reactions similar to those of polymers, or alternatively B) at least one compound which contains as the statistical mean per molecule at least one group (a) comprising at least one bond that can be activated by actinic radiation and C) at least one (meth)acrylate copolymer which is devoid of groups of type (a). Said coating materials, adhesives and sealants have a concentration of groups that can be activated by actinic radiation of between 70 and 400 mequ./100g solids.

Description

METHOD FOR PRODUCING ADHESIVE COATINGS AND GASKETS CURABLE WITH ACTINIC RADIATION

5 The present invention relates to a new method for producing coatings, adhesive layers and / or seals on and / or in primed and unprimed substrates from coating materials, adhesives and / or sealants curable with actinic radiation.

10 Here and below, actinic radiation means electromagnetic radiation such as near infrared, visible light, UV light or X-rays, but especially UV light, or corpuscular radiation such as electron beams.

15 coating materials that are curable with actinic radiation are known. For example, reference is made to the German patent DE 42 03 278 A1, in which (meth) acrylate copolymers with pendant functional groups, such as. B. epoxy groups or hydroxyl groups, with molecular weights in the range of Mn 1,000 to 10,000 with molecular weight distributions <4

20 are described. These (meth) acrylate copolymers are then reacted with acrylic acid or acrylic acid derivatives, such as acrylic acid chloride, to give the corresponding acrylated acrylates. These acrylated (meth) acrylate copolymers are used as binders in coating materials curable with actinic radiation (cf. also the European one

25 Patent EP 0 650 979 A I). Furthermore, coating materials based on (meth) acrylate copolymers with a low molecular weight (500-2,500) and a narrow distribution, which are obtained by anionic polymerization and functionalized by polymer-analogous reaction with double bonds (cf. US Pat. No. 4,064,161 A1), are known.

30 An essential part of the known coating materials curable with actinic radiation are the photoinitiators as described, for example, in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 444 to 446: "Photo initiators".

However, (meth) acrylate copolymers which are free from olefinically unsaturated bonds can also be used in coating materials curable with actinic radiation. These double bond-free (meth) acrylate copolymers are crosslinked via H transfer to photochemically excited, copolymeric photoinitiators of the Norrish type II (cf. German patent DE 44 13 436 A1). Likewise, double bond-free (meth) acrylate copolymers that

D ydrodicyclopentadienyl acrylate in copolymerized form, crosslinked via H-transfer to photochemically excited, copolymeric Norrish type II poto-initiators (cf. German Patent DE 196 00 147 A1).

With the aid of these known coating materials, in particular thermally sensitive substrates can be coated.

However, it is disadvantageous that the use of photoinitiators - including photoinitiators which are bound to the binders - leads in part to noise-intensive emissions of decay products and / or to the yellowing of the coatings.

German patent DE 693 04 472 T 2 discloses photomitator-free coating materials which are used to produce coatings on surfaces hardened with actinic radiation. For this purpose, a vinyl polymer with acetoacetyl-functional groups is reacted with ammonia or primary amines in order to obtain enamines which are stable to hydrolysis in aqueous dispersion at a pH of 9. As a result, the coating materials harden faster after their application to the surfaces reached. The comparatively high content of ammonia or primary arnines can cause an unpleasant smell when handling the coating materials and yellowing of the hardened coatings.

Coating materials curable thermally and with active radiation, which are also referred to as dual-cure coating materials, have advantages in curing the coatings on complexly shaped three-dimensional substrates, in which radiation curing in the shadow areas is sometimes not complete. On the one hand, the dual-cure coating materials can compensate for an incomplete thermal hold, which is carried out, for example, to protect thermally sensitive substrates, with UV curing or, for example, in the shade areas which is not completely complete with UV light with thermal hardening, so that overall a good result results in both cases.

Dual cure coating materials and processes for producing coatings from them are known from European patent EP-A-0 928 800. The known coating material necessarily contains a urethane (meth) acrylate which has (meth) acrylate groups and free isocyanate groups, a UV polymer initiator (photoinitiator) which initiates the radical polymerisation and an isocyanate-reactive compound. Possible isocyanate-reactive compounds are polyols such as polyesters from diols and triols and diacarboxylic acids, hindered amines from maleic esters and cycloaliphatic primary diamines, polyether polyols or hydroxyl-containing (meth) acrylate copolymers.

Another dual-cure coating material is known from US Pat. No. 4,342,793 A1. It contains a saturated polyol, in particular a hydroxy-functional (meth) acrylate copolymer, a reactive diluent for slurry curing and a polyisocyanate. Crosslinking with actinic radiation is initiated by photoinitiators. The known dual-cure coating materials therefore still have all of the disadvantages associated with the use of photoinitiators. In addition, they are not fully suitable for coating thermally sensitive substrates. Another disadvantage is that in the coating materials two different crosslinking mechanisms have to be fine-tuned to achieve good results. In addition, because of their high reactivity, the polyisocyanates must be kept separate from the other constituents and may only be added shortly before use. After this, the coating materials must be applied within a short time, since they are not stable in storage.

A common feature of all known coating materials curable with actinic radiation and dual cure coating materials is that they must be processed in the absence of daylight in order to prevent premature crosslinking with actinic radiation. However, this represents an additional logistical and equipment expenditure.

The problems described above also occur with adhesives and sealants containing photoinitiator which are cured with actinic radiation.

The object of the present invention is to provide a new process for the production of coatings, adhesive layers and / or seals on and / or in primed and unprimed substrates from coating materials, adhesives and / or sealants curable with actinic radiation, which has the disadvantages of the prior art no longer has, but that is carried out with coating materials, adhesives and / or sealants that can also be manufactured and processed in daylight, have a high storage stability, can be crosslinked below 50 ° C without the use of photoinitiators and coatings, adhesive layers and / or provide seals that are weather-resistant, essentially free from yellowing and free from odor-intensive fission products.

In addition, it was the object of the present invention to provide new coating materials, adhesives and sealants which can be used advantageously in the above-mentioned new process.

Accordingly, the new process for the production of coatings, adhesive layers and / or seals from coating materials, adhesives and / or sealants curable with actinic radiation on and primed and unprimed substrates by applying the coating materials, adhesives and / or sealants on and / or in the substrates and curing the resulting layers with actinic radiation using photomitiator-free coating materials, adhesives and sealants, which are components which can be activated with actinic radiation

A) at least one (meth) acrylate copolymer which contains, on statistical average, at least one group (a) with at least one bond which can be activated with actinic radiation, the group (a) using polymer-analogous reactions to the basic structure of the (meth) acrylate copolymer (A ) is bound,

or alternatively

B) at least one compound which contains on average at least one group (a) with at least one bond which can be activated with actinic radiation in the molecule, and

C) at least one (meth) acrylate copolymer which is free from such groups (a), contain or consist thereof and which have a content of groups of 70 to 400 meq. / 100 g of solids (A) or (B) + (C) which can be activated with active radiation.

The new process is referred to below as the “process according to the invention”.

In addition, the new photomitiator-free coating materials, adhesives and sealants with a content of groups activatable with actinic radiation of 70 to 400 meq. / 100 g solids were found, which act as components which can be activated with actinic radiation

A) at least one (meth) acrylate copolymer which contains, on statistical average, at least one group (a) with at least one bond which can be activated with actinic radiation in the molecule can be prepared by group (a) via polymer-analogous reactions to the basic structure of the (meth) acrylate copolymer (A) is bound,

or alternatively

C) at least one (meth) acrylate copolymer which is free from such groups (a),

contain or consist of.

Further objects according to the invention are evident from the description. In view of the prior art, it was surprising and unforeseeable for the person skilled in the art that photoinitiator-free coating materials, adhesives and sealants which contain the constituent (A) or the special combination of the constituents (B) and (C) or consist thereof without the Use of photoinitiators can be cured with actinic radiation, the curing taking place at comparatively low temperatures below 50 ° C.

The method according to the invention is used to produce coatings, adhesive layers and seals, preferably coatings, in particular single-layer and multi-layer clearcoats and color and / or effect coatings, on primed or unprimed substrates.

Suitable substrates are all surfaces to be painted, glued and / or sealed which are not damaged by hardening of the layers and masses thereon and or therein using actinic radiation; these are e.g. B. metals, plastics, wood, ceramics, stone, textiles, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as plaster and cement boards or roof tiles, as well as composites of these materials.

Accordingly, the method according to the invention is particularly suitable for the painting, bonding and / or sealing of motor vehicle bodies and parts of motor vehicle bodies, of furniture, buildings and industrial components, including coils, containers and electrical components. In the context of industrial use, it is suitable for painting, gluing and / or sealing, practically all parts for private or industrial use such as radiators, household appliances, small parts made of metal such as screws and nuts, hubcaps, rims, packaging or electrotechnical components such as motor windings or transformer windings. In the case of electrically conductive substrates, primers can be used which are produced in a customary and known manner from electrocoat materials (ETL). Both anodic (ATL) and cathodic (KTL) electrodeposition coatings, but especially KTL, come into consideration for this. In the case of metal, the substrate can also have been subjected to a surface treatment, for example galvanizing or phosphating or anodizing

In automotive OEM painting in particular, a filler or a stone chip protection primer is applied to the fully cured or only dried electrodeposition coating (ETL). This layer of paint is cured either on its own or together with the electrocoat layer below. The applied filler layer can also only be dried or partially cured, after which it is fully cured with the overlying lacquer layers and, if appropriate, with the electro-dipping lacquer layer underneath (extended wet-on-wet method). In the context of the present invention, the term primer also includes the combination of electro-dip coating and filler coating or stone chip protection primer.

With the inventive method primed or non-primed plastics such. B. ABS, AMMA, ASA, CA, GAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (short names according to DIN 7728T1) can be painted, glued and / or sealed. The plastics can of course also be polymer blends, modified plastics or fiber-reinforced plastics. The plastics typically used in vehicle construction, in particular motor vehicle construction, can also be used. In the case of non-functionalized and / or non-polar substrate surfaces, these plastics can be subjected to a pretreatment, such as with a plasma or with flame treatment, or provided with a hydro primer in a known manner before coating, bonding or sealing.

The method according to the invention is preferably used to produce coatings. The methods and devices used here, described in more detail below, can also be used for the production of adhesive layers and seals. The person skilled in the art can decide on the basis of his general specialist knowledge whether these methods and devices known per se are suitable for these purposes.

In a first advantageous variant of the process according to the invention, in the first process step the coating material described below, which is curable with actinic radiation and is to be used according to the invention, is applied to the primed or unprimed substrate, resulting in a layer of the coating material to be used according to the invention. This process variant is used in particular in the production of single-layer clear coats.

In a second advantageous variant of the method according to the invention, in the first method step the coating material to be used according to the invention is applied to at least one basecoat layer located on the substrate. The basecoat layer can also be a pigmented dual-cure coating material. The base lacquer layer is preferably merely dried or partially cured so that it can be cured together with the layer of the coating material to be used according to the invention (wet-on-wet method). In a third advantageous variant of the process according to the invention, the basecoat film is fully cured and then covered with the coating material to be used according to the invention.

The second and third variants of the method according to the invention are used above all for the production of multi-layer color and / or effect coatings.

The coating material to be used according to the invention can be applied by all customary application methods, such as e.g. Spraying, knife coating, brushing, pouring, dipping, watering, trickling or rolling. The substrate to be coated can rest as such, with the application device or system being moved. However, the substrate to be coated, in particular a coil, can also be moved, the application system being stationary relative to the substrate or being moved in a suitable manner.

Spray application methods are preferably used, such as, for example, compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as, for example, hot air - hot spraying. The application can be carried out at temperatures of max. 70 to 80.degree. C. are carried out so that suitable application viscosities are achieved without the change in or damage to the coating material to be used according to the invention and its overspray which may have to be reprocessed occurring under the briefly acting thermal load. For example, hot spraying can be designed in such a way that the coating material to be used according to the invention is heated only very briefly in or shortly before the spray nozzle.

The spray booth used for the application can be operated, for example, with a circulation that may be temperature-controlled, that with a suitable absorption medium for the overspray, e.g. B. the coating material to be used according to the invention itself is operated.

The coating material to be used according to the invention can be applied under visible light. In order to completely rule out a material change or damage to the coating material to be used according to the invention and the overspray, work can also be carried out under illumination with visible light of a wavelength of more than 550 μm or with exclusion of light, but this is not necessary in most cases.

In general, the coating materials to be used according to the invention are applied in a wet layer thickness such that, after they have hardened, coatings result in the layer thicknesses necessary and advantageous for their functions. In the case of a clear coat, they are 10 to 100, preferably 15 to 80, particularly preferably 20 to 75 and in particular 25 to 70 μm.

Of course, the application methods described above can also be used in the production of the remaining lacquer layers of a multi-layer lacquering within the scope of the method according to the invention.

In the context of the method according to the invention, the layer of the coating material to be used according to the invention is cured with actinic radiation after its application. The methods of curing with active radiation described below are preferably used here.

Within the scope of the method according to the invention, the hardening can take place immediately after the application of the layer of the material to be used according to the invention

Coating material done. If necessary, layers of paint that are not yet fully cured can also be cured. According to the invention, it is advantageous if the primer and / or basecoat has already been completely hardened.

Curing can take place after a certain rest period or flash-off time. It can have a duration of 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 45 min. The rest period is used, for example, for the course and degassing of the layers and for the evaporation of volatile constituents such as any solvents that may still be present.

When curing with actinic radiation, a dose of 2,000 to 3,000, preferably 2,100 to 2,950, particularly preferably 2,200 to 2,900, very particularly preferably 2,300 to 2,850 and in particular 2,400 to 2,800 mJ / cm ^{2 is} preferably used. If necessary, this hardening can be supplemented with actinic radiation from other radiation sources. In the case of electron fractions, work is preferably carried out under an inert gas atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the clear lacquer layer I. In the case of curing with UV radiation, it is also possible to work under inert gas in order to avoid the formation of ozone.

The usual and known radiation sources and optical auxiliary measures are used for curing with active radiation. Examples of suitable radiation sources are flash lamps from VISIT, high-pressure or low-pressure mercury vapor lamps, which may be doped with lead in order to open a radiation window up to 405 nm, or electron radiation sources. Their arrangement is known in principle and can be adapted to the conditions of the workpiece and the process parameters. In the case of workpieces of complex shape, such as those intended for automobile bodies, the areas not directly accessible to radiation (shadow areas) such as cavities, folds and other design-related undercuts can be combined with automatic, point, small area or all-round emitters Movement device for irradiating cavities or edges, (partially) cured.

The facilities and conditions of these hardening methods are described, for example, in R. Holmes, UN. and E.B. Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984.

The curing can take place in stages, i. H. by multiple exposure or exposure to actinic radiation. This can also take place alternately, i. that is, curing alternately with UV radiation and electron radiation.

Of course, the curing methods described above can also be used in the process of the invention in the production of multi-layer coatings for curing the other coating layers.

The single-layer or multilayer clearcoat or color and / or effect coating resulting from the process according to the invention can also be coated with a layer of an organically modified ceramic material, as is commercially available, for example, under the Ormocer® brand.

As already mentioned above, the devices and methods described can also be used for the production of adhesive layers and seals by the method according to the invention, provided that they are also suitable for this.

It is essential for the process according to the invention that photoimtiator-free coating materials, adhesives and sealing compounds are used. According to the first alternative of the process according to the invention, these photomitiator-free coating materials, adhesives and sealants contain at least one (meth) acrylate copolymer (A) which on average has at least one, preferably at least two and in particular at least three, group (s) (a) with at least one, contains in particular a bond that can be activated with actinic radiation in the molecule, or consist thereof.

The (meth) acrylate copolymers used according to the invention preferably contain essentially no monomers containing aceto groups, particularly preferably none at all.

In the context of the present invention, a bond which can be activated with actinic radiation is understood to mean a bond which becomes reactive when irradiated with actinic radiation and which undergoes polymerization reactions and / or crosslinking reactions with other activated bonds of its kind which take place according to radical and / or ionic mechanisms. Examples of suitable bonds are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds. Of these, the carbon-carbon double bonds are particularly advantageous and are therefore used with very particular preference in accordance with the invention. For the sake of brevity, they are referred to below as "double bonds".

Particularly suitable double bonds are, for example, in (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl groups (a); Contain dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups (a) or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups (a). Of these offer the acrylate groups (a) have very particular advantages, which is why they are used according to the invention with particular preference.

The groups (a) in the (meth) acrylate copolymers (A) are preferably bonded to the respective structural structures via urethane, urea, allophanate, ester, ether and / or amide groups, but in particular via ester groups. This is usually done by customary and known polymer-analogous reactions such as the reaction of pendant glycidyl groups with the olefinically unsaturated monomers (a4) described below which contain an acid group, or of pendant hydroxyl groups with the halides of these monomers (a4).

Examples of suitable monomers (a) for the preparation of the basic structure of the (meth) acrylate copolymers (A) are

Monomers (al):

(Meth) acrylic or alkyl cycloalkyl esters, which contain essentially no fractional groups, with up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl , Hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate; Cycloaliphatic (meth) acrylic acid esters, especially cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indene-methanol or tert.-

Butylcyclohexyl (meth) acrylate; (Meth) acrylic acid oxaalkyl esters or oxacycloalkyl esters such as ethyl triglycol (meth) acrylate and methoxyoligoglycol (meth) acrylate with a molecular weight Mn of preferably 550; or other ethoxylated and or propoxylated hydroxyl-free (meth) acrylic acid derivatives. These can be used in minor amounts of higher functional (meth) acrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1, 5-diol, hexane, 1,6-diol, octahydro 4,7-methano-1H-indene-dimethanol or cyclohexane-1,2-, 1,3- or -1,4-diol-di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or pentaerythritol di, tri or tefra (meth) acrylate; contain. In the context of the present invention, minor amounts of higher-functional monomers (a1) are to be understood as amounts which do not lead to crosslinking or gelling of the polyacrylate resins.

Monomers (a2):

Vinyl esters of monocarboxylic acids with 5 to 18 carbon atoms in the molecule which are branched in the alpha position and which contain essentially no functional groups. The branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be crack products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins. When such olefins are reacted with formic acid or with carbon monoxide and water, a mixture of carboxylic acids is formed in which the carboxyl groups are predominantly located on a quaternary carbon atom. Other olefinic starting materials are e.g. Propylene frimer, propylene teframer and diisobutylene. However, the vinyl esters can also be prepared from the acids in a manner known per se, e.g. by allowing the acid to react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used.

Monomers (a3):

Olefinically unsaturated monomers that are essentially non-functional

Groups contain like Olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and or or dicyclopentadiene;

vinyl aromatic hydrocarbons, such as styrene, alpha-alkylstyrenes, especially alpha-methylstyrene, arylstyrenes, in particular

Diphenylethylene, and / or vinyl toluene;

Nitriles such as acrylonitrile and / or methacrylonitrile;

Vinyl compounds such as vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene difluoride; N-vinylpyrrolidone; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether,

Isobutyl vinyl ether and or vinyl cyclohexyl ether; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl esters

Versatic® acids, which are sold under the brand name VeoVa® by Deutsche Shell Chemie (reference is also made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 598 and pages 605 and 606) and or the vinyl ester of 2-methyl-2-ethylheptanoic acid; and or

Polysiloxane macromonomers which have a number average molecular weight Mn from 1,000 to 40,000, preferably from 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated

Have double bonds per molecule as described in DE 38 07 571 A1 on pages 5 to 7, DE 37 06 095 A1 in columns 3 to 7, EP 0 358 153 B1 on pages 3 to 6, in US 4,754,014 A1 in columns 5 to 9, in DE 44 21 823 A1 or in international patent application WO 92/22615 on page 12, line 18, to page 18, line

10, or acryloxysilane-containing vinyl monomers, can be produced by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the reaction product with methacrylic acid and / or hydroxyalkyl esters of (meth) acrylic acid.

The monomers (a) described above are selected so that the resulting basic structures of the (meth) acrylate copolymers (A) are essentially determined in their property profile by the monomers (al).

The basic structures of the (meth) acrylate copolymers (A) furthermore contain functional groups which, as already mentioned above, serve to carry out groups (a). In addition, these functional groups can also be used to vary the property profile of the (meth) acrylate copolymers (A) to be used according to the invention.

The functional groups are expediently emitted into the basic structures of the (meth) acrylate copolymers (A) by the copolymerization of monomers (a) which contain corresponding functional groups. Examples of suitable monomers (a) of this type are:

Monomers (a4):

At least one acid group, preferably a carboxyl group, per molecule carrying ethylenically unsaturated monomers, particularly preferably acrylic acid and / or methacrylic acid. However, other ethylenically unsaturated carboxylic acids with up to 6 carbon atoms in the

Molecule can be used. Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid. Furthermore, ethylenically unsaturated sulfonic or phosphonic acids or their partial esters can be used. Furthermore come malemic acid mono (meth) acryloyloxyethyl ester, Succinic acid mono (meth) acryloyloxyethyl ester and phthalic acid mono (meth) acryloyloxyethyl ester into consideration.

Monomers containing hydroxyl groups, such as hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-ethylenically unsaturated carboxylic acid, which are derived from an alkylene glycol which is esterified with the acid, or can be obtained by reacting the acid with an alkylene oxide, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid or ethacrylic acid in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-

Hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, ethacrylate or crotonate; 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indenedimethanol- or methylpropanediol monoacrylate, monomethacrylate, monoethacrylate or monocrotonate; or reaction products from cyclic esters, e.g. epsilon-caprolactone and these hydroxyalkyl esters; or olefinically unsaturated alcohols such as alkyl alcohol or polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether. These higher-functional monomers are generally used only in minor amounts. In the context of the present invention, minor amounts of higher-functional monomers are understood to mean those amounts which do not lead to crosslinking or gelling of the polyacrylate resins.

Monomers containing epoxy groups, such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and or itaconic acid.

(Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl -, N, N-

Dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N-dipropyl, N-butyl, N, N-dibutyl, N-cyclohexyl and / or N, N-cyclohexyl-methyl- (meth) acrylic acid amide.

Reaction product of acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid branched in the alpha position with 5 to 18 carbon atoms per molecule. Implementation of the acrylic or

Methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary alpha carbon atom can be used before, during or after the

Polymerization reaction take place. The reaction product of acrylic and / or methacrylic acid with the glycidyl ester of Versatic® is preferred.

Acid used. This glycidyl ester is commercially available under the name Cardura® E10. In addition, varnish and varnish are used on Römpp

Printing colors, Georg Thieme Verlag, Stuttgart, New York, 1998, pages

605 and 606.

If used, especially monomers (a) containing glycidyl groups are used.

From a methodological point of view, the production of the basic structures of the (meth) acrylate copolymers (A) has no special features, but is carried out by the usual and known methods of radical polymerization in the presence of at least one polymerization initiator in bulk, in solution or in emulsion.

Examples of suitable polymerization initiators are free radical initiators such as dialkyl peroxides such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides such as cumene hydroperoxide or tert-butyl hydroperoxide; Peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethyl hexanoate or tert-butyl per-2-ethyl hexanoate; Azodinitriles such as azobisisobutyronitrile; CC-cleaving initiators such as benzpinacol silyl ether. The initiators are preferred in an amount of 0.1 to 25% by weight, especially preferably from 0.75 to 10% by weight, based on the total weight of the monomers (a). At least one conventional and known molecular weight regulator such as dodecyl mercaptan can also be used to regulate the molecular weight.

The polymerization is expediently carried out at a temperature of 50 to 200 ° C., preferably 70 to 180 ° C., if appropriate under pressure.

If used, the organic solvents (D) described below are preferably used as solvents, in particular mixtures of aromatic hydrocarbons or alcohols, esters, ethers, ether alcohols, ester ethers and / or ketones, or the reactive diluents (D) described below for thermal crosslinking. The solvents can serve as additive (D) in the coating materials, adhesives and sealing compounds to be used according to the invention.

Also in terms of equipment, the production of the large structures of the (meth) acrylate copolymers (A) has no special features in terms of method, but instead takes place with the aid of the methods of continuous or discontinuous copolymerization which are customary and known in the plastics field, under normal pressure or overpressure in stirred tanks, autoclaves, tubular reactors, loop reactors or Taylor reactors.

Examples of suitable copolymerization processes are described in the patents DE 197 09 465 A1, DE 197 09 476 C1, DE 28 48 906 A1, DE 195 24 182 A1, EP 0 554 783 A1, DE 198 28 742 A1, WO 95/27742 or WO 82/02387.

The introduction of groups (a) into the basic structures of the (meth) acrylate copolymers (A) also shows no methodological or apparatus

Special features, but takes place in conventional and known reactors such as Stirred tanks, autoclaves, tubular reactors, loop reactors or Taylor reactors or in extruders, as described, for example, in European patent application EP 0 650 979 A1.

Suitable (meth) acrylate copolymers (A) are commercially available and are sold, for example, by the Jäger company under the Jägalux® brand (for example Jägalux® 6154).

The content of the (meth) acrylate copolymers (A) in the coating materials, adhesives and sealants to be used according to the invention can vary very widely and is guided by the requirements of the individual case. For example, the content - always taking into account the limits according to the invention for the groups which can be activated with actinic radiation - can be almost 100% by weight or exactly 100% by weight. The (meth) acrylate copolymers (A) are preferably used in an amount of 5 to 80, preferably 10 to 75, particularly preferably 15 to 70, very particularly preferably 20 to 65 and in particular 25 to 60% by weight, based on the coating material, the adhesive or sealant used. In addition, the coating materials, adhesives and sealants to be used according to the invention may also contain the compounds (B), (meth) acrylate copolymers (C) and additives (D) described below in minor amounts. For the purposes of the invention, “minor amounts” mean amounts which advantageously vary but do not fundamentally determine the profile of properties of the coating materials, adhesives and sealants to be used according to the invention.

In a second alternative of the method according to the invention, photomitiator-free coating materials, adhesives and sealing compounds are used which B) at least one compound which contains on average at least one, preferably at least two and in particular at least three group (a) with at least one, in particular one, bond which can be activated with actinic radiation in the molecule, and

C) at least one (meth) acrylate copolymer which is free from such groups (a),

contain or consist of.

Examples of suitable groups (a) are those described above.

In compounds (B), groups (a) are preferably bonded to the basic structures via urethane, urea, allophanate, ester, ether and / or amide groups. Urethane groups are particularly preferred here. The following two linking structures I and II can be considered:

Basic structure-NH-C (0) -0-Gπιppe (a) (I) and

Basic structure-0- (0) C-NH group (a) (II).

Both linking structures I and II or only one of them can be present in compound (B). In general, icture I is advantageous because of the larger number of starting products available and their comparatively simpler manufacture and is therefore preferably used according to the invention.

The groups (a) are bound to the basic structures of the compounds (B) at the end and / or laterally. Which type of connection is chosen depends in particular on whether the functional groups in the basic structure are included to which the starting products of groups (a) are able to react, are terminal or lateral. Terminal groups (a) often have a higher reactivity than lateral groups (a) due to the lack of steric shielding and are therefore used with preference. On the other hand, the reactivity of the solid according to the invention can be specifically controlled via the ratio of terminal and lateral groups (a), which is a further particular advantage of the solid according to the invention.

The major structures of the compounds (B) are low molecular weight, oligomeric and / or polymeric. That is, the basic structures are low molecular weight compounds, oligomers or polymers. Or the compounds (B) have low molecular weight and oligomeric, low molecular weight and polymeric, oligomeric and polymeric or low molecular weight, oligomeric and polymeric basic structures, ie they are mixtures of low molecular weight compounds and oligomers, low molecular weight compounds and polymers, oligomers and polymers or low molecular weight compounds , Oligomers and polymers.

In the context of the present invention, oligomers are understood to mean resins which contain at least 2 to 15 monomer units in their molecule. In the context of the present invention, polymers are understood to be resins which contain at least 10 recurring monomer units in their molecule. In addition to these terms, reference is made to Rö pp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, »Oligomere«, page 425.

The low molecular weight, oligomeric or polymeric basic structures contain or consist of aromatic, cycloaliphatic and / or aliphatic structures or building blocks. They preferably contain or consist of cycloaliphatic and / or aliphatic structures, in particular cycloaliphatic and aliphatic structures. Examples of suitable aromatic structures are aromatic and heteroaromatic rings, especially benzene rings.

Examples of cycloaliphatic structures are cyclobutane, cyclopentane, cyclohexane, cycloheptane, norbonane, camphane, cyclooctane or tricyclodecane rings, in particular cyclohexane rings.

Examples of aliphatic Si structures are linear or branched alkyl chains with 2 to 20 carbon atoms or chains, as result from the (co) polymerization of olefinically unsaturated monomers.

The basic structures, in particular the oligomeric and / or polymeric basic structures, can also contain olefinically unsaturated double bonds.

The basic structures, in particular the oligomeric and or polymeric basic structures, are of linear, branched, hyperbranched or dendri er structure.

They can contain multi-bonded, in particular double-bonded, functional groups (b), by means of which the structures or building blocks described above are linked together to form the basic structures. These are generally selected so that they do not interfere with the reactions triggered by the actinic radiation or even completely prevent them. Examples of suitable functional groups are ether, thioether, carboxylic acid ester, thiocarboxylic acid ester, carbonate, tbiocarbonate, phosphoric acid ester, thiophosphoric acid ester, phosphonic acid ester, thiophosphonic acid ester, phosphite, thiophosphite, sulfonic acid ester, arnid, amine, Thioamide, phosphoric acid amide, TMophosphoric acid amide, phosphonic acid amide,

Thiophosphonic acid amide, sulfonic acid amide, I-mid, urethane, hydrazide, Urea, thiourea, carbonyl, thiocarbonyl, sulfone, sulfoxide or siloxane groups. Of these groups, the ether, carboxylic acid ester, carbonate, carboxamide, urea, urethane, frnid and carbonate groups, especially the carboxylic acid ester and urethane groups, are advantageous and are therefore used with preference.

Advantageous oligomeric and polymeric basic structures are thus derived from random, alternating and / or block-like linear, branched, hyperbranched, dendrimeric and / or comb-like (co) polymers (B) from ethylenically unsaturated monomers, polyaddition resins and / or polycondensation resins (B) , These terms are supplemented by Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition" and "Polyadditionharze (polyadducts)", as well as pages 463 and 464, "Polycondensates", "Polycondensation" and "Polycondensation Resins".

Examples of highly suitable (co) polymers (B) are (meth) acrylate copolymers and partially saponified polyvinyl esters. The (meth) acylate copolymers (A) described above are particularly suitable.

Examples of highly suitable polyaddition resins and or polycondensation resins (B) are polyesters, alkyds, polyurethanes, polyester-polyurethanes, polylactones, polycarbonates, polyethers, polyester-polyethers, epoxy resin-aniine adducts, polyureas, polyamides or polyimides. Of these, the polyesters, polyester-polyethers, polyurethanes and polyester-polyurethanes are particularly advantageous and are therefore used with very particular preference in accordance with the invention.

The polyaddition resins and / or polycondensation resins (B) are customary and known, commercially available products, for example from Bayer under the Roskydal® brand (for example Roskydal® UA LP V94 / 504-5), the Cray Valley company under the Sartomer® brand (for example Sartomer® 494 or 9003) or the BASF Aktiengesellschaft company under the Laromer® brand (for example Laromer® PO 84F or PO 83 F).

Examples of suitable low molecular weight compounds (B) are the reactive thinners, as are described, for example, in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 491: “Reaktiwerdünner”.

The content of the compounds (B) in the coating materials, adhesives and sealants to be used according to the invention can vary very widely, depending on the requirements of the individual case. They preferably contain the compounds (B) in an amount of 2.0 to 45, preferably 3.0 to 40, particularly preferably 4.0 to 35, very particularly based on the solids content of the coating material, the adhesive or the sealing compound preferably 5.0 to 30 and in particular 6.0 to 5% by weight.

In addition, the coating materials, adhesives and sealants to be used in this alternative of the process according to the invention contain at least one (meth) acrylate copolymer (C) which is free from groups (a) which can be activated with actinic radiation. The (meth) acylate copolymers (C) can contain functional groups. However, these only serve to vary the physico-chemical property profile of the (meth) acrylate copolymers (C) and are not essential for crosslinking with actinic radiation.

Examples of suitable (meth) acrylate copolymers (C) are the basic structures of the (meth) acrylate copolymers (A) described above. These are customary and known products which are commercially available and, for example, from Bayer AG under the Desmophen® A 450 brand, 365, 565, VP LS 2180, VP LS 2177 or LS 2009/1, from DSM under the brand Uracron® (e.g. Uracron® CY 467 E, 476 CY, CY 403 E, CY 455 XK1 or 458 XE), from the company Synthopol are sold under the Synthalat® brand (for example Synthalat® A 1613 or 1633).

The content of the (meth) acrylate copolymers (C) in the coating materials, adhesives and sealants to be used according to the invention can also vary very widely and depends on the requirements of the individual case. The (meth) acrylate copolymers (C) in the coating materials are preferably present in an amount of 65 to 98, preferably 60 to 97, particularly preferably 65 to 96, very particularly preferably 70 to 95 and in particular 75 to 94% by weight on the coating material, adhesive or sealant.

Regardless of which alternative of the method according to the invention is used and regardless of what the specific composition of the coating materials, adhesives and sealants to be used according to the invention is, these have, according to the invention, a group (a) content of 70 to 400, preferably 75 to 395 , preferably 80 to 390, particularly preferably 85 to 385 and in particular 90 to 380 meq. / 100 g solids (A) or (B) + (C).

The coating materials, adhesives and sealants to be used according to the invention contain at least one additive (D), selected from the group consisting of color and / or effect pigments, organic and inorganic, transparent or opaque fillers, nanoparticles, other of (A), ( B) and (C) various oligomeric and polymeric binders, thermally curable reactive thinners, low and high-boiling ("long") organic solvents, water, UV absorbers, light stabilizers, radical scavengers, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers and wetting agents Detergents, adhesion promoters, Announcements, film-forming aids, sag control agents (SCA), rheology-controlling additives (thickeners), flame retardants, siccatives, drying agents, skin-preventing agents, anti-corrosive agents, waxes and matting agents;

The type and amount of additives (D) depend on the intended use of the coatings, adhesive layers xmd seals produced using the method according to the invention.

If the coating material to be used according to the invention is used to produce solid-color top coats or basecoats, it contains coloring and / or effect pigments (D) and, if appropriate, opaque fillers. If the coating material to be used according to the invention is used for the production of clearcoats, these additives (D) are naturally not contained therein.

Examples of suitable effect pigments (D) are metal plate pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE 36 36 183 A1, and commercially available stainless steel bronzes and non-metallic effect pigments, such as pearlescent or interference pigments. In addition, reference is made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 176, "Effect Pigments" and pages 380 and 381 "Metal Oxide Mica Pigments" to "Metal Pigments".

Examples of suitable inorganic color pigments (D) are titanium dioxide, iron oxides, Sicofran yellow and carbon black. Examples of suitable organic coloring pigments (D) are thioindigo pigments indanthrene blue, cromophthal red, irgazine orange and heliogen green. In addition, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 180 and 181, "iron blue pigments" to "iron oxide black", pages 451 to 453 "pigments" to "pigment volume concentration", page 563 "thioindigo pigments" and See page 567 “Titanium dioxide pigments”. Examples of suitable organic and inorganic fillers (D) are chalk, calcium sulfates, barium sulfate, silicates such as talc or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour. In addition, reference is made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 250 ff., "Füllstoffe".

These pigments and fillers (D) can also be incorporated into the coating materials using pigment pastes. bearing the functional groups described above

(Meth) acrylate copolymers (C) come into consideration.

Examples of suitable binders (D) are other linear and / or branched and / or block-like, comb-like and / or randomly structured polyesters, alkyds, polyurethanes, acrylated polyurethanes, acrylated polyesters, polylactones, polycarbonates, curable thermally and / or with active radiation.

Polyethers, epoxy resin-amine adducts, partially saponified polyvinyl esters or

Polyureas or actinic radiation curable unsaturated polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and the corresponding methacrylates, which are used in minor amounts. In the context of the invention, “minor quantities” mean

Amounts that reflect the property profile of those to be used according to the invention

Coating materials, adhesives and sealants vary in an advantageous manner but do not determine them fundamentally.

Examples of suitable thermally curable reactive diluents (D) are positionally isomeric diethyloctanediols or hydroxyl group-containing hyperbranched compounds or dendrimers. Examples of suitable low-boiling organic solvents (D) and high-boiling organic solvents (D) (“long solvents”) are ketones such as methyl ethyl ketone or methyl isobutyl ketone, esters such as ethyl acetate or butyl acetate, ethers such as dibutyl ether or ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, Butylene glycol or

Dibutylene glycol dimethyl, diethyl or dibutyl ether, ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or

Methoxypropanol, ester ethers such as 3-methoxybutyl acetate, N-methylpyrrolidone or xylenes or mixtures of aromatic hydrocarbons such as Solvent Naphtha® or Solvesso®.

Examples of suitable light stabilizers (D) are HALS compounds, benzotriazoles or oxalanilides.

An example of a suitable deaerating agent (D) is diazadicycloundecane;

Examples of suitable emulsifiers (D) are nonionic emulsifiers, such as alkoxylated alkanols and polyols, phenols and alkylphenols, or anionic emulsifiers, such as alkali metal salts or ammonium salts of alkane carboxylic acids, alkane sulfonic acids, and sulfonic acids of alkoxylated alkanols and polyols, phenols and alkylphenols.

Examples of suitable wetting agents (D) are siloxanes, fluorine-containing compounds, carboxylic acid semiesters, phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes.

An example of a suitable adhesion promoter (D) is tricyclodecanedimethanol.

Examples of suitable film-forming auxiliaries (D) are cellulose derivatives, such as cellulose acetobutyrate (GAB). Examples of suitable transparent fillers (D) are those based on silicon dioxide, aluminum oxide or zirconium oxide; In addition, reference is made to the Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252.

Examples of suitable Sag control agents (D) are ureas, modified ureas and / or silicas, as described, for example, in references EP 0 192 304 A1, DE 23 59 923 A1, DE 18 05 693 A1, WO 94/22968, DE 27 51 761 C 1, WO 97/12945 or "färbe + lack", 11/1992, pages 829 ff.

Examples of suitable rheology control additives (D) are those known from the patent specifications WO 94/22968, EP 0 276 501 A1, EP 0 249 201 A1 or WO 97/12945; crosslinked polymeric microparticles, as disclosed, for example, in EP 0 008 127 A1; inorganic layered silicates such as aluminum-magnesium-silicates, sodium-magnesium and

Natrixxm magnesium fluorine lithium layered silicates of the montmorillonite type; Silicas such as aerosils; or synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl pyrrolidone, styrene-maleic anhydride or elhylene-maleic anhydride copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates;

An example of a suitable matting agent (D) is magnesium stearate.

Further examples of the additives (D) listed above and examples of suitable UV absorbers, radical scavengers, leveling agents,

Flame retardants, desiccants, drying agents, anti-caking agents, corrosion inhibitors and waxes (D) are described in detail in the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998. Furthermore, water can be used as additive (D), especially if coating materials are to be produced.

The additives (D) are used in customary and known, effective amounts.

The production of the coating materials, adhesives and sealants to be used according to the invention has no special features, but is carried out in a customary and known manner by mixing the above-described constituents in suitable mixing units, such as stirred kettles, dissolvers, agitator mills or extruders, in accordance with those used for the production of the respective inventive Processes suitable for coating materials, adhesives and sealants.

The coating materials, adhesives and sealing compounds to be used according to the invention can be in the form of almost or completely water and solvent-free liquids (100% systems) or powders, powders (powder slurries) dispersed in aqueous media, aqueous dispersions or solutions or dispersions or Solutions in organic solvents (conventional systems) are available.

The coatings produced with the aid of the method according to the invention, in particular the single-layer and multi-layer clearcoats and color and / or effect coatings, are of the highest optical quality in terms of color, effect, gloss and DOI (distinctiveness of the reflected image) smooth, sttnαktur-free, hard, flexible xmd scratch-resistant surface, are odor-free and weather, chemical and etch resistant, do not yellow and show no cracking and delamination of the layers. The adhesive layers produced by means of the method according to the invention have an extremely high adhesive strength even under extreme climatic conditions, which does not decrease even after long exposure to light xmd atmosphere.

The seals produced with the aid of the method according to the invention completely seal the substrates even in the presence of aggressive media.

The subsfrates coated, glued and / or sealed, primed or unprimed with the aid of the method according to the invention therefore have a particularly long service life and a particularly high utility value, which makes them technically and economically particularly attractive for manufacturers, users and end users.

Examples and comparative tests

Examples 1 to 4 and Comparative Experiment VI

The production of clearcoats in the procedure according to the invention (Examples 1 to 4) and in the procedure not according to the invention (comparative experiment VI)

For Examples 1 to 4 × md in Comparative Experiment VI, a mixture (A) of, based on the mixture, 50% by weight of a methacrylate copolymer of methyl methacrylate and ethyl acrylate which had been modified with glycidyl methacrylate and acrylic acid was 47% by weight of hexanediol -l, 6-diacrylate (B) and 3.0 wt .-% xylene (D) used.

The commonly used mixtures (D) of esters, ketones, ether alcohols and aromatic solvents were used as solvents (D). The clearcoats were prepared in a customary and known manner by mixing the constituents in a suitable mixing unit.

In Example 1, 56.4 parts by weight of solvent (D), 9.1 parts by weight of mixture (A), 27.7 parts by weight of a commercially available (meth) acrylate copolymer (C) (Uracron® CY 467 from DSM, 55% strength) in butyl acetate), 4.5 parts by weight of cellulose acetobutyrate, 1.8 parts by weight of a commercially available matting agent and 0.5 part by weight of a commercially available defoamer.

Example 1 was repeated for comparative experiment VI, except that an additional 5.0 parts by weight of a commercially available photoinitiator were added.

For Example 2, 36.4 parts by weight of the (meth) acrylate copolymer (C) used in Example 1, 9.0 parts by weight of the mixture (A) and 54.6 parts by weight of solvent (D) were mixed together.

For example 3, 47.7 parts by weight of a methacrylate copolymer (C) composed of methyl methacrylate, acrylic acid and acrylonitrile with an acid number of 40 to 50 mg KOH / g, 9.0 parts by weight of the mixture (A) and 43.3 parts by weight of solvent (D) were used together mixed.

For example 4, 47.7 parts by weight of a methacrylate copolymer (C) of butyl methacrylate and methyl methacrylate, 9.0 parts by weight of the mixture (A) and 43.3 parts by weight of solvent (D) were mixed together.

The clearcoats described above were using a 200 microns

Box squeegees applied to glass plates. After an evaporation time of 10 minutes, they were physically predried in a circulating air dryer at 50 ° C. for 30 minutes. The subsequent UV exposure was carried out with 2 CK lamps (80 W / cm) at a feed rate of 5.5 m / min. After a cooling time of 10 minutes, the pendulum damping according to the king of clearcoats (cf. Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 436: »Pendulum damping test«) was determined as a measure of its degree of crosslinking. For comparison, the pendulum damping of the dried clear lacquer layers before exposure was determined. The results can be found in Table 1.

Table 1: Pendulum damping test according to König

Example and pendulum damping (s)

Comparison test before exposure after exposure

1 25.6 104.4

VI 25.2 101.2

21.7 162.4

25.2 176.4

27.3 151.2

The results of the table show that no photoinitiators were required for crosslinking in the clearcoats to be used according to the invention. In addition, the results confirm the surprising finding that functionalization of the (meth) acrylate copolymers (A) or (C) was not necessary for the crosslinking. Example 5 and comparative experiment V2

The production of clearcoats in the procedure according to the invention (example 5) and in the procedure not according to the invention (comparative experiment V2)

For Example 5 and Comparative Experiment V2, a clearcoat comprising 61.1 parts by weight of a solvent mixture [mixture (D) from Examples 1 to 4] and 38.9 parts by weight of a commercially available (meth) acrylate copolymer (A) (Jägalux® UV 6154 from the company Hunter) used. For the comparative experiment V2, 0.5 parts by weight of a mixture of the commercially available Grenocure MBF and Irgacure 184 photo-initiators (weight ratio 6: 1) were added to this mixture.

The clearcoats were prepared as described in Examples 1 to 4 and Comparative Experiment VI.

In the case of Example 5, the König pendulum damping test gave a value of 92.4 s before exposure to UV light and a value of 165.2 s after exposure. The corresponding values of comparative test V2 were 92.4s and 168.7s. The clearcoat was thus fully crosslinked even without photoinitiators.

Examples 6 to 17 and comparative experiment V3 to V14

The production of clearcoats in the inventive (Examples 6 to 17) and in the non-inventive (comparative experiment V3 to V14) procedure

The clear lacquers given in Table 2 were used for Examples 6 to 17. For the comparative tests V3 to V14 they were still 0.5

Parts by weight of a mixture of the commercially available photoinitiators Grenocure MBF and Irgacure 184 (weight ratio 6: 1) added. Examples 6 to 17 and comparative tests V3 to V14 correspond as follows:

Example comparison test

6 V3

7 V4 8 V5

9 V6

10 V7

11 V8

12 V9 13 V10

14 vl l

15 V12

16 V13

17 V14

The clearcoats were produced as indicated in the examples and comparative experiments described above.

The content of double bonds and the results of the König pendulum damping test before and after UV exposure can be found in Table 3.

Table 2: Composition of the clearcoats to be used according to the invention (Examples 6 to 17)

Part by weight in example: 6 7 8 9 10 11 12 13 14 15 16 17

Solvent mixture ^a) 56.4 56.4 56.4 56.4 56.4 56.4 56.4 56.4 56.4 56.4

56.4 56.4

Uracron® CY 467 ^b) 27.7 27.7 27.7 27.7 27.7 27.7 27.7 27.7 27.7 27.7

27.7 27.7

Cellulose acetobutyrate 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5

4.5 4.5

Matting agent 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8

Mixture (A) ^c) 9.1

Laromer® PE55F ^d) - 9.1

Laromer® PO84F ^e) - - 9.1 - -

Laromer® 8986 ^e - 9.1 -

Sartomer® 494 ^s) - - 9.1

Roskydal® UA

V94 ^h) - - - 9.1 -

Parotal® ^i} - 9.1 Hexanediol diacrylate 9.1 -

Tripropylene glycol diacrylate 9.1 - - -

Trimethylolpropane triarylate 9.1 - -

Sartomer® 9003 ^j) 9.1 -

Laromer® DVE3 ^k) - - 9.1

a) cf. Example 5;

b) saturated (meth) acrylate copolymer from DSM;

c) cf. Examples 1 to 4;

d) acrylated polyester, 100%, from BASF Aktiengesellschaft;

e) acrylated polyether, amine-modified, from BASF Aktiengesellschaft;

f) acrylated epoxy resin, 100%, from BASF Aktiengesellschaft;

g) Oligoethertefraacrylat from Cray Valley;

h) aliphatic polyurethane acrylate, 80% in hexanediol diacrylate, from Bayer AG; i) unsaturated polyester based on maleic anhydride, 65% in styrene, from BASF Aktiengesellschaft;

j) neopentyl glycol propylene diacrylate, 100%, from Cray Valley;

k) divmyl ether derivative, 100%, from BASF Aktiengesellschaft;

Table 3: Pendulum damping test according to König

Example and double bonds pendulum damping (s)

Comparison test (mÄquJIOOg FK) ^a) before exposure after exposure

6 220 34.3 112

V3 220 32.3 113.4

7 100 28.7 53.9 V4 100 26.6 86.1

8 130 19.6 93.1

V5 130 19.6 93.1

9 160 21 53.9 V6 160 21 106.4

10 280 21 110.6 V7 280 221 114.1 11 100 30.8 107.1

V8 100 28.7 112

12,200 33.6 41.3

V9 200 32.2 52.5

13 320 9.8 131.6

V10 320 9.8 136.5

14 240 11.2 107.1

Vll 240 11.2 114.1

15 360 16.8 116.2

V12 360 15.4 107.8

16 220 18.2 104.3

V13 220 16.8 105

17 360 26.6 32.2

V14 360 26.6 39.9

a) FK = solid (B) + (C)

Examples 6 to 17 and comparative experiments V3 to VI 4 once again demonstrate that the photoinitiator-free clearcoats produced clearcoats in all cases with the aid of the process according to the invention, the crosslinking of which was at least as good as that of the clearcoats produced from the photoinitiator-containing clearcoats had been.

Claims

claims

Process for the production of coatings, adhesive layers and / or seals from coating materials, adhesives and / or sealants curable with actinic radiation on and in primed and unprimed substrates by applying the coating materials, adhesives and / or sealants on and / or in the substrates and hardness of the resulting layers with actinic radiation, characterized in that here photomitiator-free coating materials, adhesives and sealing compounds are used, the constituents which can be activated with actinic radiation

A) at least one (meth) acrylate copolymer which contains, on a statistical average, at least one group (a) with at least one bond which can be activated with actinic radiation, the group (a) via polymer-analogous reactions to the structure of the (meth) acrylate copolymer ( A) is bound,

or alternatively

B) at least one compound which contains on average at least one group (a) with at least one bond which can be activated with actinic radiation in the molecule, and C) at least one (meth) acrylate copolymer which is free from such groups (a),

contain or consist of them and have a content of groups which can be activated with actinic radiation of 70 to 400 meq. / 100 g solids.

2. The method according to claim 1, characterized in that UV radiation is used as actinic radiation.

3. The method according spoke 1 or 2, characterized in that as activatable with actinic bonds carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-Silicizmi-single bonds or double bonds can be used.

4. The method according to claim 3, characterized in that one uses carbon-carbon double bonds.

5. The method according to claim 4, characterized in that the groups (a) (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl - or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or

Butenyl ester groups can be used.

6. The method according to claim 5, characterized in that one uses acrylate groups.

7. The method according to any one of claims 1 to 6, characterized in that the basic fracture of the compound (B) is low molecular weight, oligomer and / or polymer.

8. The method according spoke 7, characterized in that the oligomeric and / or polymeric basic structure of the compound (B) contains olefinically unsaturated double bonds.

9. The method according spoke 7 or 8, characterized in that the oligomeric and / or polymeric basic structure of the compound (B) is different

₃ Derives statistical, alternating and / or block-like, linear, branched, hyperbranched, dendrimeric and / or comb-like polyaddition resins, polycondensation resins and / or (co) polymers from olefinically unsaturated monomers.

10. The method according spoke 9, characterized in that the (co) polymers (B) (meth) acrylate copolymers and / or partially saponified polyvinyl esters and the polyaddition resins (B) and / or polycondensation resins (B) polyesters, alkyds, polyurethanes, polyester polyurethane, polylactone, polycarbonate, polyether, polyether-polyester,

Epoxy resin-amine adducts, polyureas, polyamides or polyimides, in particular polyesters, polyester-polyethers, polyurethanes and polyester-polyurethanes.

11. The method according to claim 10, characterized in that the (meth) acrylate copolymers (B) are (meth) acrylate copolymers (A).

12. The method according to any one of claims 1 to 11, characterized in that the groups (a) in the (meth) acrylate copolymers (A) and / or in the compounds (B) via urethane, urea, allophanate, ester . Ether and or amide groups are bound to the respective Gn tract xren.

13. The method according spoke 17, characterized in that the groups (a) in the compounds (B) via urethane groups to the basic structures and in the (meth) acrylate copolymers (A) via ester groups to the respective grand structures.

14. The method according to any one of claims 1 to 13, characterized in that the coatings are single and multi-layer

Clear coatings and coloring and / or effect coatings.

15. The method according to any one of claims 1 to 8, characterized in that the substrates are motor vehicle bodies, parts of motor vehicle bodies, furniture, structures, windows, doors and industrial components, including containers, coils and electrotechnical components.

16. Photoinitiator-free coating materials, adhesives and sealants with a content of groups which can be activated with actinic radiation

70 to 400 meq. / 100g solids, the components that can be activated with actinic radiation

A) at least one (meth) acrylate copolymer which contains, on statistical average, at least one group (a) with at least one bond which can be activated with actinic radiation can be prepared in that the group (a) via polymer-analogous reactions to the basic fracture of (meth ) Acrylate copolymer (A) is bound,

or alternatively B) at least one compound which contains on average at least one group (a) with at least one bond which can be activated with actinic radiation in the molecule, and

C) at least one (meth) acrylate copolymer which is free from such groups (a),

contain or consist of.