EP1322718A1

EP1322718A1 - Method for producing a multicomponent system which can be thermally hardened and hardened by actinic radiation and the use thereof

Info

Publication number: EP1322718A1
Application number: EP01986708A
Authority: EP
Inventors: Egbert Nienhaus; Bernhard Lettmann
Original assignee: BASF Coatings GmbH
Current assignee: BASF Coatings GmbH
Priority date: 2000-10-02
Filing date: 2001-10-01
Publication date: 2003-07-02
Also published as: MXPA03001906A; US20040097611A1; US6903145B2; BR0114161A; DE10048849A1; AU2002220581A1; WO2002031071A1

Abstract

The invention relates to a method for the production of a multi-component system, which can be thermally hardened and hardened by actinic radiation (dual cure). The inventive system comprises (A) a component containing a component (A 1) with at least two isocyanate reactive functional groups per molecule, and (B) a component containing a polyisocyanate (B 1), which are mixed together. The component (A) and/or the component (B), are mixed shortly before mixing with an additional liquid component (C), containing (C 1) a component which can be hardened with actinic radiation, having at least two functional groups per molecule containing a bond which can be activated by actinic radiation, and/or (C 2) a component which can be hardened thermally and by actinic radiation, comprising at least one functional group per molecule containing at least one bond which can be activated by actinic radiation, and at least one isocyanate reactive functional group or at least one isocyanate group per molecule. The components (A/C) and (B), (A) and (B/C) or (A/C) and (B/C) are subsequently mixed and are homogenised.

Description

Process for producing a multicomponent system curable thermally and with actinic radiation and its use

The present invention relates to a new method for producing a multicomponent system curable thermally and with actinic radiation. In addition, the present invention relates to a new multi-component system curable thermally and with actinic radiation. In addition, the present invention relates to the use of the new multi-component system or the multi-component system produced by the new method as a coating material, adhesive or sealant. Furthermore, the present invention relates to the use of the coating materials for the automotive painting, car refinishing, the painting of furniture, doors, windows or structures in the interior and exterior as well as for industrial painting, including coil coating, container coating and the coating or impregnation of electrotechnical components.

Here and below, actinic radiation is understood to mean electromagnetic radiation such as near infrared (NIR), visible light, UV radiation or X-rays, in particular UV radiation, or corpuscular radiation such as electron beams.

The hardening process with heat and actinic radiation is also referred to as dual-cure for short.

A dual-cure multicomponent system is known, for example, from European patent application EP 0 928 800 A1. It contains a urethane (meth) acrylate with free isocyanate groups and (meth) acryloyl groups, a photoinitiator and an isocyanate-reactive compound, in particular a polyol or polyamine. This dual-cure coating material offers the possibility to vary the property profiles of coating material and coating and to adapt them specifically to different uses, but it is Flash-off time still too long and its initial hardness in the shadow zones of complex three-dimensional substrates, which cannot be achieved by the actinic radiation without major equipment expenditure, is too low.

In addition, such dual-cure multicomponent systems, in addition to numerous other non-polyisocyanate-based dual-cure multicomponent and single-component systems, are known from German patent application DE 198 18 735 A1. However, the advantages listed in the patent application, which are said to have all the systems described therein, are exhausted in general terms and are not substantiated by a specific example.

The processes for producing the known dual-cure multicomponent systems have the disadvantage that the composition of the dual-cure multicomponent systems has to be determined from the outset; Subsequent variations are hardly possible and can lead to a deterioration in the application properties profile, so that the dual-cure multicomponent systems in question are no longer suitable for demanding use such as automotive refinishing.

Overall, the known methods lack the necessary breadth of variation and flexibility. For example, in the case of car refinishing, the thermally curable multicomponent clearcoats already available in a workshop cannot be adjusted as dual-cure multicomponent clearcoats when a need arises suddenly by adding components curable with actinic radiation.

The object of the present invention is to provide a new process for the production

Finding dual-cure multicomponent systems, which, based on conventional multicomponent systems known per se, in a simple manner

Production of dual-cure multicomponent systems of the most varied Composition and the most varied content of bonds that can be activated with actinic radiation. The dual-cure multicomponent systems produced according to this procedure should also have an application-related property profile that is at least comparable, if not even better, to the application-related property profile of the dual-cure multicomponent systems produced in a customary and known manner. In particular, the coatings produced with this should have a high initial hardness even in the problematic shadow zones of complex three-dimensional substrates.

It is also an object of the present invention to find a new dual-cure multicomponent system which no longer has the disadvantages of the prior art, but which has a short flash-off time. In addition, the coatings produced with this should have a high initial hardness even in the problematic shadow zones of complex three-dimensional substrates.

In addition, the dual-cure multicomponent system produced by the new process and / or the new should be suitable both as a coating material and as an adhesive and sealant.

In addition, the new coating material produced according to the new process is said to be excellent for initial automotive painting, car refinishing, the painting of furniture, doors, windows or structures indoors and outdoors as well as for industrial painting, including coil coating, container coating and the like Coatings or impregnation of electrical components.

The coatings, adhesive layers and seals which are produced from the dual-cure multicomponent system produced by the new process and / or from the new dual-cure multicomponent system are intended to be one high scratch resistance, very good chemical, petrol, solvent and etch and weather resistance and show no cracks.

The adhesive layers and seals should have a permanent adhesive strength or a permanent sealability even under extreme and / or rapidly changing climatic conditions.

The coatings are also said to be outstandingly suitable as clearcoats in the context of multi-layer paint and / or effect coatings. The new clearcoats should have a high initial hardness even in the problematic shadow zones of complex three-dimensional substrates.

Accordingly, the new process for the production of a thermally and actinic radiation curable (dual cure) multicomponent system was found in which

(A) at least one component containing at least one constituent with on average at least two isoeyanate-reactive functional groups per molecule, and

(B) at least one component containing at least one polyisocyanate,

are mixed with one another, characterized in that component (A) and / or component (B) contains shortly before they are mixed with at least one further liquid component (C)

(C 1) at least one constituent curable with actinic radiation having, on average, at least two functional groups per molecule which contain at least one bond which can be activated with actinic radiation, and / or (C 2) at least one thermally and with actinic radiation curable component with on average at least one functional group per molecule which contains at least one bond which can be activated with actinic radiation, and with at least one isoeyanate-reactive functional group on average or with at least one statistical average an isocyanate group in the molecule

is or are mixed, after which components (A / C) and (B), (A) and (B / C) or (A / C) and (B / C) are mixed and homogenized.

In the following, the new process for producing a multi-component system that is curable thermally and with actinic radiation (dual cure) is referred to as the “process according to the invention”.

In addition, the new thenic and actinic radiation curable (dual cure) multicomponent system was found containing

(A) at least one component containing at least one thermally curable constituent (A 1) with on average at least two isoeyanate-reactive functional groups per molecule,

(B) at least one component containing at least one polyisocyanate (B 1), and

(C) at least one reactive diluent curable with actinic radiation with at least 5 bonds activatable with actinic radiation per molecule, the reactive diluent (C) not being introduced via a thixotropic agent. In the following, the new, new thermally and actinic radiation curable (dual cure) multicomponent system is referred to as "multicomponent system according to the invention".

Component (A) suitable for the process according to the invention or the multicomponent system according to the invention contains at least one constituent (A 1) with a statistical average of at least two, in particular at least three, isoeyanate-reactive functional groups per molecule.

Examples of suitable isoeyanate-reactive functional groups are thiol, primary or secondary amino, imino or hydroxyl groups, especially hydroxyl groups.

The component (A 1) can be low molecular weight, oligomeric or polymeric. It is preferably oligomeric or polymeric.

The basic structures of the low molecular weight components (A 1) are not critical, but can come from a wide variety of organic compound classes. Examples of suitable classes of compounds are optionally heteroatoms such as alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and / or arylcycloalkyl compounds, which optionally carry further substituents, such as oxygen, nitrogen, sulfur, silicon or phosphorus which, however, must not react with the bonds that can be activated with actinic radiation during the manufacture of the components, their storage and / or their use.

The basic structures of the oligomeric or polymeric constituents (A 1) are also not critical and can come from a wide variety of oligomer and polymer classes. Examples of suitable oligomer and polymer classes are random, alternating and / or block-like linear and / or branched and or comb-like (co) polymers of ethylenic unsaturated monomers, or polyaddition resins and / or

Polycondensation. 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". The statements made above apply mutatis mutandis with regard to possible substituents.

Examples of highly suitable (co) polymers (A 1) are poly (meth) acrylates and partially saponified polyvinyl esters.

Examples of highly suitable polyaddition resins and / or polycondensation resins (A 1) are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides or polyimides.

According to the invention, the (meth) acrylate copolymers, in particular those containing hydroxyl groups, have particular advantages and are used according to the invention particularly preferably as constituents (A 1).

The (meth) acrylate copolymers (A 1) are known polymers. Their production is not special in terms of process technology, but takes place with the aid of the methods known and known in the plastics field of continuous or discontinuous radical-initiated copolymerization in bulk, solution, emulsion, mini-emulsion or micro-emulsion under normal pressure or pressure in stirred tanks, autoclaves, tubular reactors, loop reactors or Taylor reactors at temperatures from 50 to 200 ° C.

Examples of suitable (meth) acrylate copolymers (A 1) and copolymerization processes are described in patent applications DE 197 09 465 A.

1, DE 197 09 476 A 1, DE 28 48 906 A 1, DE 195 24 182 A 1, DE 198 28 742 A 1, DE 196 28 143 A1, DE 196 28 142 A1, EP 0 554 783 A1, WO 95/27742, WO 82/02387 or WO 98/02466.

Their hydroxyl number is preferably 70 to 200, preferably 80 to 170, in particular 90 to or 150 mg KOH / g.

Components (A 1) are present in component (A) in widely varying amounts. The component preferably contains the constituents (A 1) in an amount of 40 to 95, preferably 45 to 95 and in particular 40 to 90% by weight, in each case based on component (A).

In addition, component (A) of the multicomponent system can also contain other customary and known additives in effective amounts. It is essential that the additives do not inhibit or completely prevent the dual-cure crosslinking reactions.

Examples of suitable additives are nanoparticles, thermally curable reactive thinners, low-boiling organic solvents and high-boiling organic solvents (“long solvents”), water, UV absorbers, light stabilizers, free radical scavengers, thennolabile free-radical initiators, photoinitiators and coinitiators, crosslinking agents such as those used in one-component systems are used, catalysts for technical crosslinking, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting and diperging agents, adhesion promoters, leveling agents, film-forming aids, sag control agents (SCA), rheology-controlling additives (thickeners), flame retardants, siccatives, drying agents,

Skin prevention agents, corrosion inhibitors, waxes, matting agents, precursors of organically modified ceramic materials or additional binders. Examples of suitable thermally curable reactive diluents are positionally isomeric diethyloctanediols or hydroxyl group-containing hyperbranched compounds or dendrimers, as are described, for example, in German patent applications DE 198 05 421 A1, DE 198 09 643 A1 or DE 198 40 405 5 A1.

Examples of suitable low-boiling organic solvents and high-boiling organic solvents (“long solvents”) are ketones such as methyl ethyl ketone, methyl isoamyl ketone or methyl isobutyl ketone, esters such as ethyl acetate,

10 butyl acetate, ethyl ethoxypropionate, methoxypropylacetate or butylglycol 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 or mixed or N-methylpyrrole or N or methylpyrrole or N-methylpyrrole or N-methylpyrrole or N-methylpyrrole or N-methylpyrrole or N-methylpyrrole or N-methylpyrrole Hydrocarbons such as Solventnaphtha®, petrol

15 135/180, Dipentene or Solvesso®.

Examples of suitable thermolabile free-radical initiators are organic peroxides, organic azo compounds or C-C-cleaving initiators such as dialkyl peroxides, peroxocarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers.

Examples of suitable catalysts for the crosslinking are dibutyltin dilaurate, dibutyltin dioleate, lithium decanoate, zinc octoate or bismuth salts such as bismuth lactate or dimethylol propionate. 5

Examples of suitable photoinitiators and coinitiators are described in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446.

Examples of suitable additional crosslinking agents, such as are used in one-component systems, are aminoplast resins, such as for example in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 29, »Aminoharze«, the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff, the book "Paints, Coatings and Solvents ", second completely revised edition, edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., The patents US 4,710,542 A1 or EP-B-0 245 700 A1 as well as in the article by B. Singh and co-workers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry", in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207, are described, compounds or resins containing carboxyl groups, as described, for example, in patent specification DE 196 52 813 A 1, epoxy group-containing compounds or resins, such as are described, for example, in the patents EP 0 299 420 A1, DE 22 14 650 B1, DE 27 49 576 B1, US 4,091,048 A or US 3,781,379 A, blocked polyisocyanates, as described, for example, in the patents US 4,444,954 A, DE 196 17 086 A1, DE 196 31 269 A1, EP 0 004 571 A1 or EP 0 582 051 A1, and / or tris (alkoxycarbonylamino) - triazines as described in US Pat. No. 4,939,213 A, US 5,084,541 A, US 5,288,865 A or EP 0 604 922 A1.

Examples of suitable deaerating agents are diazadicycloundecane or benzoin.

Examples of suitable emulsifiers are nonionic emulsifiers, such as alkoxylated alkanols, 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, polyols, phenols and alkylphenols.

Examples of suitable wetting agents are siloxanes, fluorine-containing compounds, carboxylic acid half-esters, phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes. An example of a suitable adhesion promoter is tricyclodecanedimethanol.

Examples of suitable film-forming aids are cellulose derivatives such as 5 cellulose acetobutyrate (CAB).

Examples of suitable transparent fillers are those based on silicon dioxide, aluminum oxide or zirconium oxide; In addition, reference is also made to the Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, 10 1998, pages 250 to 252.

Examples of suitable Sag control agents 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, 15 WO 97/12945 or "färbe + lack", 11/1992, pages 829 ff.

Examples of suitable rheology-controlling additives are those known from the patents WO 94/22968, EP 0 276 501 A1, EP 0 249 201 A1 or WO 97/12945; crosslinked polymeric microparticles, as described, for example, in

20 of EP 0 008 127 A1 are disclosed; inorganic layered silicates such as aluminum-magnesium silicates, sodium-magnesium and

Montmorillonite type sodium magnesium fluorine lithium layered silicates; Silicas such as aerosils; or synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide,

25 poly (meth) acrylic acid, polyvinylpyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates;

Magnesium stearate is an example of a suitable matting agent.

30 Examples of suitable precursors for organically modified ceramic materials are hydrolyzable organometallic compounds, in particular of silicon and aluminum.

Further examples of the additives listed above as well as examples of suitable UV absorbers, radical scavengers, leveling agents, flame retardants, siccatives, drying agents, skin inhibitors, corrosion inhibitors and waxes (B) are described in the textbook "Varnish Additives" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, described in detail.

The preparation of component (A) to be used according to the invention has no special features, but is carried out in a customary and known manner by mixing the constituents described above in suitable mixing units such as stirred kettles, dissolvers, stirrer mills or extruders.

Component (B) of the multicomponent system according to the invention contains at least one polyisocyanate (B 1).

The statistical average of the polyisocyanates (B 1) contains at least 2.0, preferably more than 2.0 and in particular more than 3.0 isocyanate groups per molecule. There is basically no upper limit to the number of isocyanate groups; According to the invention, however, it is advantageous if the number does not exceed 15, preferably 12, particularly preferably 10, very particularly preferably 8.0 and in particular 6.0.

Examples of suitable polyisocyanates (B 1) are polyurethane prepolymers containing isocyanate groups, which can be prepared by reacting polyols with an excess of diisocyanates and are preferably low-viscosity.

Examples of suitable diisocyanates are isophorone diisocyanate (= 5-isocyanato-l-isocyanatomethyl-l, 3,3-trimethyl-cyclohexane), 5-isocyanato-l- (2-isocyanatoeth- l-yl) -l, 3,3-trimethyl-cyclohexane, 5-isocyanato-l- (3-isocyanatoprop-l-yl) -l, 3,3-trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut- l-yl) -l, 3J-trimethyl-cyclohexane, l-isocyanato-2- (3-isocyanatoprop-l-yl) -cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-l-yl) cyclohexane, 1 - Isocyanato-2- (4-isocyanatobut-1-yl) cyclohexane, 1,2-diisocyanatocyclobutane, 1,3-diisocyanatocyclobutane, 1,2-diisocyanatocyclopentane, 1,3-diisocyanatocyclopentane, 1,2-

Diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-

Diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), ethyl ethylene diisocyanate, trimethyl hexane diisocyanate, heptamethylene diisocyanate or diisocyanates, derived from Dimer en derbenben derbe, by trade like from DDIENBENENEN under the trade, derived from DIMERENENEN10 the trade, derived from DIMERENENEN 10 the same as trade name, from DIMERBENENEN10, the trade name, derived from DIMERENBEN 10 the company, such as from DIMERBENENEN 10, the trade, derived from DIMERIKEN, the same as trade name, derived from DIMENFELEN10 10 and in the patent specifications WO 97/49745 and WO 97/49747, in particular 2-heptyl-3,4-bis (9-isocyanatononyl) -l-pentylcyclohexane, or 1,2-, 1, 4- or 1 , 3-bis (isocyanatomethyl) cyclohexane, 1,2-, 1,4- or 1,3-bis (2-isocyanatoeth-l-yl) cyclohexane, 1,3-bis (3-isocyanatoprop-l-yl) cyclohexane , 1,2-, 1,4- or 1,3-bis (4-isocyanatobut-l-yl) cyclohexane or liquid bis (4-isocyanatocyclohexyl) methane with a trans / trans content of up to 30% by weight, preferably 25% by weight and in particular 20% by weight, as described in patent applications DE 44 14 032 A1, GB 1220717 A1, DE 16 18 795 A1 or DE 17 93 785 A1 isophorone diisocyanate, 5-isocyanato-l- (2-isocyanatoeth-l-yl) -I, 3-trimethyl-cyclohexane, 5-isocyanato-l- (3-isocyanatoprop-l-yl) -l, 3, 3-trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1 -yl) - 1, 3, 3-trimethyl-cyclohexane, 1-isocyanato-2- (3 - isocyanatoprop-1 -yl) -cyclohexane, 1 - Isocyanato-2- (3-isocyanatoeth-l-yl) cyclohexane, l-isocyanato-2- (4-isocyanatobut-l-yl) cyclohexane or HDI, especially HDI.

It is also possible to have isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea carbodiimide and / or uretdione groups

Polyisocyanates (B 1) are used which are made in a customary and known manner the diisocyanates described above. Examples of suitable production processes and polyisocyanates are, for example, from the patents CA 2,163,591 A, US-A-4,419,513, US 4,454,317 A, EP 0 646 608 A, US 4,801, 675 A, EP 0 183 976 A1, DE 40 15 155 A1, EP 0 303 150 A 1, EP 0 496 208 A 1, EP 0 524 500 A 1, EP 0 566 037 A 1, US 5,258,482 A 1, US 5,290,902 A 1, EP 0 649 806 A 1, DE 42 29 183 A or EP 0 531 820 A1.

The content of component (B) in the polyisocyanates (B 1) can vary widely. It depends primarily on the viscosity that is necessary for mixing with the other components. The content is preferably 20 to 80, preferably 30 to 70 and in particular 35 to 65% by weight, based on component (B). Component (B) preferably also contains at least one of the organic solvents described above.

According to the invention, component (A) and / or component (B) are mixed with at least one further liquid component (C) shortly before they are mixed before application.

Component (C) contains at least one constituent (C 1) curable with actinic radiation with on average at least two functional groups per molecule which contain at least one bond which can be activated with actinic radiation.

Examples of suitable bonds which can be activated with actinic radiation 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 double bonds, in particular the carbon-carbon double bonds (“double bonds”), are preferably used. Suitable double bonds are, for example, in (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups. Of these, (meth) acrylate groups, in particular acrylate groups, are of particular advantage and are therefore used with very particular preference in accordance with the invention.

The component (C 1) can be low molecular weight, oligomeric or polymeric. It is preferably of low molecular weight.

The basic structures of the oligomeric or polymeric constituents (C 1) are not critical, but those described above for constituent (A 1) can be used.

The basic structures of the low molecular weight components (C 1) are also not critical, but can come from a wide variety of organic compound classes. Examples of suitable classes of compounds are optionally heteroatoms such as alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and / or arylcycloalkyl compounds, which optionally carry further substituents, such as oxygen, nitrogen, sulfur, silicon or phosphorus which, however, must not react with the bonds which can be activated with actinic radiation in the preparation of the components (C 1), their position and / or their use.

Examples of suitable constituents (C 1) are the reactive diluents curable with actinic radiation, as described, for example, in Römpp Lexikon Lacke and

Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the keyword, "reactive diluent", or in column 7, lines 1 to 26, DE 198 18 715 A 1 are described.

Particularly suitable constituents (C 1) are reactive diluents curable with actinic radiation with at least 5, in particular 5, of the groups described above which can be activated with actinic radiation, in particular acrylate groups. An example of such a reactive diluent (C 1) is pentaerythritol pentaacrylate. These reactive diluents (C 1), in particular pentaerythritol pentaacrylate (C 1), are not introduced via thixotropic agents.

The content of component (C 1) in component (C) can vary widely. It is preferably 30 to 90, preferably 40 to 80 and in particular 50 to 70% by weight, in each case based on component (C). Component (C) may also contain at least one further of the additives described above, provided that these do not react with component (C 1).

Component (C) containing component (C 1) described above is preferably mixed with component (A), after which the resulting component (A / C) with component (B) or component (B / C) is mixed and homogenized.

Instead of or in addition to the component (C 1) described above, component (C) contains at least one component (C 2).

The component (C 2) contains the statistical average

at least one, in particular at least two, of the functional groups described above which can be activated with actinic radiation and at least one, in particular at least two, of the isoeyanate-reactive functional groups described above or

at least one, in particular at least two, isocyanate groups

per molecule.

Examples of suitable basic structures for the constituents (C 2) which contain at least one, in particular at least two, of the isoeyanate-reactive functional groups described above are the low-molecular, oligomeric and polymeric basic structures described above. Of these, the polyurethanes (C 2) are of particular advantage and are therefore used with particular preference.

The production of polyurethanes (C 2) with terminal and / or lateral double bonds has no special features in terms of method, but is described in detail in patent applications and patents DE 196 45 761 A, WO 98/10028, EP 0 742 239 A1, EP 0 661 321 B1, EP 0 608 021 B1, EP 0 447 998 B1, or EP 0 462 287 B1. In addition, these components are commercially available products and are sold, for example, by the Rahn company under the brand Rahn® 99-664.

The content of component (C) in this component (C 2) can vary widely. It is preferably 30 to 90, preferably 40 to 80 and in particular 50 to 70% by weight, in each case based on component (C). In addition, the component C) in question may also contain at least one further of the additives described above, provided that these do not react with the component (C 2).

The component (C) containing the above-described component (C 2) is mixed with the component (A), after which the resulting component (A / C) is mixed with component (B) or component (B / C) and homogenized.

Instead of component (C 2) described above, component (C) may contain at least one component (C 2) with isocyanate groups.

As is known, these constituents (C 2) can be obtained by reacting the diisocyanates and polyisocyanates (B 1) described above with compounds which have at least one, in particular one, of the isoeyanate-reactive functional groups described above and at least one, in particular one, bond which can be activated with actinic radiation contain. Examples of suitable compounds of this type are

2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, bis (hydroxymethyl) cyclohexane, neopentyl glycol,

Diethylene glycol, dipropylene glycol, dibutylene glycol,

Triethylene glycol acrylate, methacrylate, ethacrylate, crotonate, cinnamate, vinyl ether, allyl ether, dicyclopentadienyl ether, norbornenyl ether, isoprenyl ether, isopropenyl ether or butenyl ether;

Trimethylolpropane, glycerol, trimethylol ethane, pentaerythritol tri or homopentaerythritol triacrylate, methacrylate, ethacrylate, crotonate, cinnamate, vinyl ether, allyl ether, dicyclopentadienyl ether, norbornenyl ether or isopropenyl ether, isopropenyl ether, or

Reaction products from cyclisGhen esters, e.g. epsilon-caprolactone, and the hydroxyl-containing monomers described above; or

2-aminoethyl (meth) acrylate and / or 3-aminopropyl (meth) acrylate. From a methodological point of view, the production of these constituents (C 2) has no special features, but takes place as described, for example, in European patent application EP 0 928 800 A1.

The content of component (C) in this component (C 2) can vary widely. It is preferably 60 to 95, preferably 70 to 95 and in particular 75 to 85% by weight, in each case based on component (C). In addition, the component (C) in question may contain at least one further of the additives described above, provided that these do not react with isocyanate groups (C 2).

Component (C), which contains the isocyanate-containing component (C 2), is mixed with component (B) and homogenized, after which the resulting component (B / C) with component (A) or component (A / C) is nibbled and homogenized.

From a methodological point of view, the mixing of components (A / C) and (B), (A) and (B / C) or (A / C) and (B / C) has no peculiarities, but is done with the help of the usual and known , Mixing devices and processes described above or by means of conventional two- or multi-component metering and mixing systems. Mixing is ideally carried out by hand, provided that the viscosity of the components permits this.

The volume ratio of components (A): (C) can vary very widely in the process according to the invention. If component (C) is added exclusively to component (B), this ratio can be mathematically infinite. Otherwise, it is preferably (A): (C) = 2: 1 to 1: 2, preferably 1.5: 1 to 1: 1, 5 and in particular 1.2: 1 to 1: 1, 2. Likewise, the volume ratio of components (B): (C) can vary very widely in the process according to the invention. If component (C) is added exclusively to component (A), this ratio can be mathematically infinite. Otherwise, it is preferably (B): (C) = 2: 1 to 1: 2, preferably 1.5: 1 to 1: 1.5 and in particular 1.2: 1 to 1: 1.2.

Furthermore, the volume ratio of components (A): (B / C), (A / C): (B) or (A / C): (B / C) can vary very widely in the process according to the invention. They are preferably 5: 1 to 1: 5, preferably 4: 1 to 1: 4 and in particular 3: 1 to 1: 3.

Which volume ratios are used depends primarily on the functionality and concentration of the reactive components of the components described above. The person skilled in the art can therefore easily determine the optimum volume ratio for each individual case on the basis of his specialist knowledge, if necessary with the aid of simple orienting tests.

It is a very special advantage of the method according to the invention that, based on a conventional thermally curable multicomponent system, dual-cure multicomponent systems can be produced in a simple manner in the event of a sudden need, which materials have a very different composition and functionality.

The dual-cure multicomponent systems produced with the aid of the process according to the invention, in particular the multicomponent system according to the invention, containing

at least one, in particular one, component (A) with at least one of the constituents (A 1) described above, at least one, in particular one, component (B) with at least one of the polyisocyanates (B 1) and

at least one, in particular one, component (C) with at least one of the reactive diluents (C 1) described above with at least 5 bonds per molecule which can be activated with actinic radiation, the reactive diluent (C 1) not being introduced via a thixotropic agent,

can therefore be used for a wide variety of purposes. They are preferably used as coating materials, adhesives and sealants.

The coating materials, adhesives and sealants are used to produce coatings, adhesive layers and seals on and / or in primed and unprimed substrates. In particular, the coating materials are used to produce clearcoats, in particular clearcoats in color and / or effect multi-layer coatings.

In terms of method, the application of the clear lacquers has no special features, but can be done using all common application methods, e.g. Spraying, knife coating, brushing, pouring, dipping, trickling or rolling. 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.

Surfaces are used as substrates which are caused by hardening of the coating materials, adhesives and / or sealing compounds located thereon

Use of heat and actinic radiation will not be harmed in consideration; 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 coating materials, adhesives and sealants are also for applications outside of automotive OEM painting and

Suitable for car refinishing. They are particularly suitable for painting, gluing and / or sealing furniture, windows, doors, structures indoors and outdoors and industrial painting, including coil coating, container coating and the impregnation or coating of electrical components. In the context of industrial painting, they are 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 electrical 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 electrocoating (KTL), but especially KTL, come into consideration for this.

The electrodeposition coating or the electrodeposition coating layer can be covered with a filler which is cured either on its own or together with the electrodeposition coating layer (wet-on-wet method). The overlay with a filler takes place in particular in areas that are exposed to strong mechanical stress, such as stone chips. Examples of suitable cathodic electrocoating materials and, if appropriate, wet-on-wet methods are described in Japanese Patent Application 1975-142501 (Japanese Patent Application Laid-Open JP 52-065534 A 2, Chemical Abstracts Unit No. 87: 137427) or in the patent documents and applications US 4,375,498 A, US 4,537,926 A, US 4,761, 212 A, EP 0 529 335 A 1, DE 41 25 459 A 1, EP 0 595 186 A 1, EP 0 074 634 A 1, EP 0 505 445 A 1, DE 42 35 778 A 1, EP 0 646 420 A 1, EP 0 639 660 A 1, EP 0 817 648 A 1, DE 195 12 017 C 1, EP 0 192 113 A 2, DE 41 26 476 A 1 or WO 98 / 07794.

Likewise, suitable fillers, in particular aqueous fillers, which are also referred to as stone chip protection primers or functional layers, are known from the patents and applications US 4,537,926 A, EP 0 529 335 AI, EP 0 595 186 A1, EP 0 639 660 A1, DE 44 38 504 A1, DE 43 37 961 A1, WO 89.710387, US 4,450,200 A, US 4,614,683 A or WO 490/26827.

Primed or unprimed plastic parts made of e.g. B. ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PC, PC / PBT, PC / PA, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (short names according to DEN 7728T1) can be painted, glued or sealed. In the case of non-functionalized and / or non-polar substrate surfaces, these can be subjected to a pretreatment in a known manner, such as with a plasma or with flaming, or provided with a suitable mixture before the coating.

To produce the clearcoats, the clearcoats are applied to the substrates described above, after which the resulting clearcoat layers are cured.

To produce the adhesive layers and seals, the adhesives and sealants are placed on and / or in the substrates described above applied. When bonding substrates, the surfaces to be bonded of two or more substrates are preferably coated with the adhesive according to the invention, after which the surfaces in question may be brought into contact under pressure and the resulting adhesive layers are cured.

As is known, the production of a color and / or effect multi-layer coating is carried out on a primed or unprimed substrate

(1) applying a basecoat to the substrate,

(2) drying and / or partial hardening or complete hardening of the basecoat film,

(3) application of a clearcoat to the dried and / or partially hardened basecoat or the hardened basecoat and

(4) curing the clearcoat together with the basecoat or separately curing the clearcoat.

Examples of suitable basecoats are from patent applications EP 0 089 497 A1, EP 0 256 540 A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 523 610 A1, EP 0 228 003 A 1, EP 0 397 806 A 1, EP 0 574 417 A 1, EP 0 531 510 A 1, EP 0 581 21 1 A 1, EP 0 708 788 A 1, EP 0 593 454 A 1, DE-A -43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP 0 590 484 A1, EP 0 234 362 A1, EP 0 234 361 A1, EP 0 543 817 A1, WO 95/14721, EP 0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 649 865 A1, EP 0 536 712 A1, EP 0 596 460 A1, EP 0 596 461 A 1, EP 0 584 818 A 1, EP 0 669 356 A 1, EP 0 634 431 A 1, EP 0 678 536 A 1, EP 0 354 261 A 1, EP 0 424 705 A 1, WO 97/49745, WO 97/49747, EP 0 401 565 A1 or EP 0 817 684, column 5, lines 31 to 45, are known. In general, the filler coat, top coat, basecoat and clear coat are applied in a wet coat thickness so that after curing, layers with the necessary and advantageous layer thicknesses for their functions result. In the case of the filler layer, this layer thickness is 10 to 150, preferably 15 to 120, particularly preferably 20 to 100 and in particular 25 to 90 μm, in the case of the topcoat it is 5 to 90, preferably 10 to 80, particularly preferably 15 to 60 and in particular 20 to 50 μm, in the case of the basecoat it is 5 to 50, preferably 6 to 40, particularly preferably 7 to 30 and in particular 8 to 25 μm, and in the case of the clearcoats it is 10 to 100, preferably 15 to 90, particularly preferably 20 to 80 and in particular 25 to 70 μm.

The curing takes place after a certain flash-off time. It is used, for example, to flow and degas the applied layers or to evaporate volatile components such as solvents or water. The flash-off time can be supported and / or shortened by using elevated temperatures up to 40 ° C or by blowing off the layers, provided that no damage or changes to the applied layers occur, such as premature complete crosslinking. The clearcoats according to the invention show an advantageously short flash-off time of <10, in particular <6 minutes. As a result, the process times are shortened overall.

The curing takes place with actinic radiation, in particular with UV radiation, and / or electron beams. If necessary, it can be carried out or supplemented with actinic radiation from other radiation sources. In the case of electron beams, 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 applied layers. Even in the case of curing with UV radiation, it is possible to work under inert gas in order to prevent the formation of ozone.

The usual and known radiation sources and optical auxiliary measures are used for curing with actinic radiation. Examples of more suitable

Radiation sources are high or low pressure mercury vapor lamps, which may be doped with lead to open a radiation window up to 405 n, or electron beam sources. Their arrangement is known in principle and can be adapted to the conditions of the workpiece and the process parameters. For complicated shaped workpieces like

Automobile bodies can be the areas not accessible to direct radiation

(Shadow areas) such as cavities, folds and other construction-related

Undercuts with point, small area or all-round emitters, combined with an automatic movement device for irradiating cavities or edges, are cured.

The facilities and conditions of these hardening methods are described, for example, in R. Holmes, UN. and E.B. Curing Fon ilations 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.

The thermal curing also has no special features in terms of method, but is carried out according to the customary and known methods, such as heating in a forced air oven or irradiation with IR lamps. As with curing with actinic radiation, the technical curing can also be carried out in stages. The technical curing advantageously takes place at room temperature or above room temperature, preferably at temperatures> 40 ° C, preferably> 50 for a period of 1 min to several days.

Technical curing and curing with actinic radiation can be used simultaneously or alternately. If the two curing methods are used alternately, thermal curing can be started, for example, and curing with actinic radiation can be ended. In other cases, it may prove advantageous to start with actinic radiation and end with it. The person skilled in the art can determine the hardening method which is most advantageous for the individual case on the basis of his general specialist knowledge, if necessary with the aid of simple preliminary tests.

The coating materials, adhesives and sealants produced using the process according to the invention and the coating materials, adhesives and sealants according to the invention based on the multicomponent system according to the invention have a high solids content with low viscosity and a long service life.

The flash-off time of the dual-cure multicomponent systems, in particular the clear lacquer, before curing is very short, so that the overall process times are reduced.

The coatings, adhesive layers and seals produced with the aid of the dual-cure multicomponent systems, in particular the clearcoats, also have a high initial hardness in the shadow areas of the substrates.

The resulting coatings, in particular the clearcoats and the color and / or effect multi-layer coatings containing them, have a high level of hardness, flexibility and chemical resistance excellent flow, no runners, very good interlayer adhesion, excellent overall optical impression (appearance), very good resistance to weathering, very high scratch and abrasion resistance and very good polishability

The adhesive layers are permanently adhesive, even under extreme and / or very strongly and rapidly changing climatic conditions.

In the long term, the seals completely seal against chemically aggressive substances.

Thus, the primed and unprimed substrates, which are coated with at least one of the coatings, bonded to at least one of the adhesive layers and / or sealed with at least one of the seals, have a particularly long service life in addition to the advantages listed above, which makes them particularly economical makes you valuable.

Examples

Production Example 1

The production of a thermally curable methacrylate copolymer

185.6 parts by weight of ethyl ethoxypropionate were placed in a steel reactor equipped with a stirrer, reflux condenser and two feed vessels and heated to 160 ° C. with stirring. A monomer mixture of 114.1 parts by weight of styrene, 136.9 parts by weight of methyl methacrylate, 79.3 parts by weight of butyl methacrylate, 109 parts by weight of n-butyl acrylate and 164.1 parts by weight of hydroxyethyl methacrylate was then metered in uniformly over a period of four hours. Starting at the same time and parallel to this, one Initiation of 35.8 parts by weight of ethyl ethoxypropionate and 36.2 parts by weight of di-tert-butyl peroxide are metered in uniformly. After one hour at 110 ° C with an initiator mixture of 5.7 parts by weight of butyl acetate and 0.5 parts by weight of tert-butyl peroxyethyl hexanoate. The resulting reaction mixture was then held at 110 ° C. for one hour. The solution was then adjusted to a solids content of 65% by weight at 80 ° C. with butyl acetate. The resulting solution had a viscosity of 15 dPas. The hydroxyl number of the methacrylate copolymer was 120 mg KOH / g.

Examples 1 to 4

The production of clear lacquers with the aid of the method according to the invention and their use for the production of color and effect multi-layer lacquers

The clearcoats 1 to 4 of Examples 1 to 4 were prepared by blending the components shown in Table 1.

For this purpose, in Example 1, components (A), (B) and (C / C 1) were mixed with one another in a volume ratio of 2: 1: 2, component (C / C 1) being added before the addition of (B) Component (A) was mixed.

In Example 2, components (A), (B) and (C / C 2) were mixed with one another in a volume ratio of 1: 1: 1, with component (C / C 2) being added before the addition of (B) Component (A) was mixed.

In Example 3, components (A), (B) and (C / C 2) were mixed together in a volume ratio of 4: 1: 1, component (C / C 2) being added before the addition of (A) Component (B) was missed. In Example 4, components (A), (B), (C / C 2 without isocyanate groups) and (C / C 2 with isocyanate groups) were mixed together in a volume ratio of 2: 2: 1: 1, component (C / C 2 without isocyanate groups) with component (A) and component (C / C 2 with isocyanate groups) with component (B) were mixed, after which the resulting components (A / C) and (B / C) were mixed together and were homogenized.

The clearcoats 1 to 4 of examples 1 to 4 were then diluted with 10%, based on the clearcoats, of a thinner (solvent mixture of xylene, solvent naphtha, gasoline 135/180, methoxypropyl acetate, butyl acetate, butylglycol acetate, ethylethoxypropionate and dipentene).

Table 1: The material composition of components (A), (B) and (C) of clearcoats 1 to 4

Part of Klarlacl -. - Example:

1 2 3 4

Component (A):

Methacrylate copolymer of preparation example 1 86 86 86 86 butyl acetate 4.5 4.5 4.5 4.5

Ethyl ethoxypropionate 4 4 4 4

Methyl isoamyl ketone 2 2 2 2

Byk® 325 ^a) 0.3 0.3 0.3 0.3

Byk® 358 ^a) 0.71 0.7 0.7 0.7 dibutyltin dilaurate

(10% in butyl acetate) 0.5 0.5 0.5 0.5 Tinuvin® 292 ^b) 1 1 1 1

Tinuvin® 400 ^b) 1 1 1 1

Component (B):

Desmodur® N 3600 ^c) 56 56 56 56

Methoxypropylacetate 22 22 22 22

Ethyl ethoxypropionate 22 22 22 22

Components (C):

Component (C 1):

Sartomer® 399 ^d) 60

Irgacure® 184 ^e) 0.7

Lucirin® TPO ^e) 0.3

Butyl acetate 16

Ethyl ethoxypropionate 16

Methyl isoamyl ketone 5

Byk® 325 0.3

Byk® 358 0.7

Tinuvin® 292 0.5

Tinuvin® 400 0.5

Component (C 2) without

Isocyanate groups:

Rahn® 99-664 ° - 60 60

Irgacure® 184 - 0.7 0.7

Lucirin® TPO - 0.3 0.3 Butyl acetate 16 16 ethyl ethoxypropionate 16 16 methyl isoamyl ketone 5 5 Byk® 325 0.3 0.3 Byk® 358 0.7 0.7 Tinuvin® 292 0.5 0.5 Tinuvin® 400 0.5 0.5

Component (C 2) with isocyanate groups:

Roskydal® 2337 ^s) 80 80 ethyl ethoxypropionate 20 20

a) commercial leveling agents;

b) commercial light stabilizers;

c) commercially available polyisocyanate based on hexamethylene diisocyanate from Bayer AG;

d) dipentaerythritol pentaacrylate from Cray Valley;

e) commercially available photoinitiators;

f) commercial urethane acrylate from Rahn; Hydroxyl number: 120 mg

KOH / g; Acrylate functionality: 3;

g) commercially available isocyanatoacrylate from Bayer AG; The clearcoats of Examples 1 to 4 were outstandingly suitable for the production of clearcoats, in particular in the context of coloring and effect-giving multicoat paint systems, despite a wide variety of material compositions.

For the production of the color and effect-giving multi-layer lacquers, ground steel sheets were first coated with a commercially available two-component polyurethane filler from BASF Coatings AG. The filler was applied in two spray passes, dried for 30 minutes at 60 ° C and then sanded. A commercially available waterborne basecoat from BASF Coatings AG was then applied in two spray passes and dried at 60 ° C. for 5 minutes. The clearcoats 1 to 4 were then applied in two spray passes with an intermediate flash-off time of 2.5 minutes.

The applied clear lacquer layers 1 to 4 were each briefly flashed off for 5 minutes, dried at 60 ° C. for 15 minutes and then cured with UV radiation at a dose of 1,500 mJ / cm ² . The resulting clearcoats 1 to 4 had a layer thickness of 50 to 60 μm. The multi-layer coatings of Examples 1 to 4 had an excellent appearance and interlayer adhesion.

In a second series of experiments, the curing behavior of clearcoats 1 to 4 in shadow zones of substrates was simulated by not curing the test panels described above with UN radiation. The resulting clearcoats were nevertheless not sticky, but had a good initial hardness.

Claims

1. A process for producing a multi-component system which is curable thermally and with actinic radiation (Dual Cure), in which

(A) at least one component containing at least one constituent (A I) with a statistical average of at least two isoeyanate-reactive functional groups per molecule, and

(B) at least one component containing at least one polyisocyanate (B 1),

are intermingled with one another, characterized in that component (A) and / or component (B) contains shortly before they are mixed with at least one further liquid component (C)

(C 1) at least one constituent curable with actinic radiation with, on average, at least two functional groups per molecule which contain at least one bond which can be activated with actinic radiation, and / or

(C 2) at least one component which is curable theoretically and with actinic radiation, with on average at least one functional group per molecule which contains at least one bond which can be activated with actinic radiation, and with at least one isoeyanate-reactive on average functional group or with a statistical average of at least one isocyanate group in the molecule

is or are vnπnischen, after which the components (A / C) and (B), (A) and (B / C) or (A / C) and (B / C) are mixed and homogenized.

2. The method according to Anspmch 1, characterized in that carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, as bonds which can be activated with actinic radiation,

Carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds can be used.

3. The method according to Anspmch 2, characterized in that carbon-carbon double bonds ("double bonds") are used.

4. The method according to Anspmch 3, characterized in that the double bonds as (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isoprenyl, Isopropenyl, allyl or

butenyl; Ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups are present.

5. The method according to any one of claims 1 to 5, characterized in that the isoeyanate-reactive functional groups are thiol, primary or secondary amino, imino or hydroxyl groups.

6. The method according to any one of claims 1 to 5, characterized in that the component (C 1) is one with actinic radiation curable reactive thinner with at least 5 bonds activatable with actinic radiation per molecule.

7. The method according to Anspmch 6, characterized in that the reactive diluent (C 1) of component (A) and / or component (B) is mixed.

8. The method according to any one of claims 1 to 7, characterized in that the component (C 2) is at least one urethane acrylate with a hydroxyl number of 50 to 200 mg KOH / g.

9. The method according to Anspmch 8, characterized in that the urethane acrylate (C 2) of component (A) is mixed.

10. The method according to any one of claims 1 to 7, characterized in that the component (C 2) is an isocyanatoacrylate.

1 1. The method according to any one of claims 1 to 10, characterized in that the isocyanatoacrylate (C 2) of component (B) is mixed.

12. Theπnitically and curable with actinic radiation (dual cure) multi-component system, containing

(A) at least one component containing at least one thermally curable constituent (A 1) with a statistical average of at least two isoeyanate-reactive functional groups per molecule,

(B) at least one component containing at least one

Polyisocyanate (B 1), and (C) at least one reactive diluent curable with actinic radiation with at least 5 bonds activatable with actinic radiation per molecule, the reactive diluent 5 (C) not being introduced via a thixotropic agent.

13. Multi-component system according to Anspmch 12, characterized in that dipentaerythritol pentaacrylate is used as the reactive diluent (C).

10

14. Multi-component system according to Anspmch 12 or 13, characterized in that hydroxyl groups are used as isocyanate-reactive functional groups.

15 15. Multi-component system according to one of claims 12 to 14, characterized in that at least one (meth) acrylate copolymer having a hydroxyl number of 50 to 200 mg KOH / g is used as component (A 1).

16. Multi-component system according to one of claims 12 to 15, characterized in that it additionally contains at least one component (C 2).

17. Use of the multi-component system according to one of claims 5 12 to 16 and / or of the one produced according to one of claims 1 to 1 1

Multi-component system as coating material, adhesive or sealant.

18. Use according to Anspmch 17, characterized in that the 0 coating material for automotive painting, the

Car refinishing, the painting of furniture, doors, windows or structures indoors and outdoors as well as for industrial painting, including coil coating, container coating and the coating or impregnation of electrical components.

19. Use according to Anspmch 18 and, characterized in that the coating material is used for the production of coloring and / or effect-giving multi-layer coatings by the wet-on-wet method.

Patent document Publlcation Patent family Publication cited in search report date member (s) date

US 4342793 03-08-1982 US 4128600 A 05-12-1978 CA 1122742 AI 27-04-1982 GB 1601401 A 28-10-1981

WO 9111479 08-08-1991 FR 2657613 AI 02-08-1991 EP 0466880 AI 22-01-1992 O 9111479 AI 08-08-1991 IE 910327 AI 14-08-1991 PT 96595 A 15-10-1991

EP 0928800 14-07-1999 DE 19800528 AI 15-07-1999 EP 0928800 AI 14-07-1999

JP 11263939 A 28-09-1999

WO 9955785 04-11-1999 DE 19818735 AI 28-10-1999

WO 9955785 AI 04-11-1999 EP 0991727 AI 12-04-2000 S 6332291 B1 25-12-2001

Form PCT ^. ISA ^. 2io tp3len- .amily ar-.ex. Uuty ¹ 992.