EP1320564A1

EP1320564A1 - Multicomponent system which can be hardened by means of heat and actinic radiation, and use of the same

Info

Publication number: EP1320564A1
Application number: EP01985715A
Authority: EP
Inventors: Egbert Nienhaus; Bernhard Lettmann
Original assignee: BASF Coatings GmbH
Current assignee: BASF Coatings GmbH
Priority date: 2000-09-29
Filing date: 2001-09-26
Publication date: 2003-06-25
Also published as: US20040039103A1; AU2002220568A1; US7037972B2; WO2002026853A1; DE10048275C1

Abstract

The invention relates to a multicomponent system which can be hardened by means of heat and actinic radiation (Dual Cure). The inventive system contains (A) at least one component comprising at least one constituent which has at least one isocyanate reactive functional group and at least one functional group having at least one bond which can be activated by actinic radiation, in addition to at least one vinylaromatic allylalcohol copolymer, and (B) at least one component containing at least one polyisocyanate. The invention also relates to the use of said system as coating material, adhesive and sealant.

Description

Thermally curable with actinic radiation

Multi-component system and its use

The present invention relates to a new multicomponent system curable thermally and with actinic radiation. The present invention also relates to the use of the new multicomponent system as a coating material, adhesive or sealant. Furthermore, the present invention relates to the use of the new coating materials for initial automotive painting, automotive refinishing, the painting of furniture, doors, windows or structures in the interior and exterior and for industrial painting, including coil coating, container coating and the coatings or impregnation electrotechnical components.

Here and below, actinic radiation means electromagnetic radiation such as near infrared (NIR), visible light, UN radiation or X-rays, in particular UV radiation, or corpuscular radiation such as electron radiation.

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. Although this dual-cure coating material offers the possibility of varying the property profiles of coating material and of coating and specifically adapting it to different uses, its flash-off time is still too long and its initial hardness in the shadow zones of complex three-dimensional substrates caused by the actmic radiation cannot be achieved without major expenditure on equipment, 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 A. 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 object of the present invention is 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 therewith are also intended to be complex in a high initial hardness even in the problematic shadow zones have shaped three-dimensional subtrates.

In addition, the new dual-cure multi-component system is said to be suitable both as a coating material and as an adhesive and sealant.

In addition, the new coating material is said to be excellently suited for the automotive painting, car refinishing, 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.

The coatings, adhesive layers and seals made from the new dual-cure multicomponent system are said to have high scratch resistance, very good chemical, petrol, solvent and etch and weather resistance and 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 multicomponent system curable with actinic radiation (dual cure) has been found to contain

(A) at least one component containing at least one constituent with at least one isocyanate-reactive functional group and at least one functional group with at least one bond which can be activated with actinic radiation, and at least one additive, and

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

wherein at least one vinyl aromatic-allyl alcohol copolymer is used as additive.

The new multicomponent system curable with actinic radiation is referred to below as the "multicomponent system according to the invention".

The essential component of the multicomponent system according to the invention is the vinylaromatic-allyl alcohol copolymer. Suitable vinyl aromatics are all substituted and unsubstituted aromatics containing vinyl groups. Examples of suitable vinyl aromatics are styrene, alpha-methylstyrene, vinyltoluene, p-tert-butylstyrene or p-methyl-alpha methylstyrene, but especially styrene.

The ratio of vinyl aromatics to allyl alcohol in the copolymers can vary widely. The allyl alcohol content, based on the total amount of the copolymer, is preferably 10 to 50, in particular 15 to 45,% by weight and the vinyl aromatic content, based on the total amount of the copolymer, is 50 to 90, in particular 55 to 85,% by weight .-%

The number average molecular weight of the copolymers can also vary. It is preferably 1,000 to 4,000, more preferably 1,200 to 3,800 and in particular 2,500 to 3,700 Daltons.

The mass average molecular weight is preferably 2,000 to 10,000, preferably 2,300 to 9,500 and in particular 2,400 to 9,300 Daltons.

The copolymer preferably has a hydroxyl number of 80 to 300, in particular 110 to 270 mg KOH / g.

The glass transition temperature of the copolymer is preferably 50 to 90, in particular 55 to 85 ° C.

The multicomponent system according to the invention preferably contains, based on its solid, the vinylaromatic-allyl alcohol copolymer in an amount of 1 to 30% by weight. In special cases, higher amounts of copolymer can also be used. The copolymer is preferably used in an amount of 2 to 27, in particular 3 to 25,% by weight, based in each case on the solid of the multicomponent system according to the invention. The vinyl aromatic-allyl alcohol copolymers to be used according to the invention are compounds known per se and are marketed, for example, under the name SAA-100, SAA-101 or SAA-103 by Lyondell Chem Nederland Ltd., Antwerp, the Netherlands.

As an isocyanate-reactive functional group-containing additive, the vinylaromatic-allyl alcohol copolymer is contained in component (A) of the multicomponent system according to the invention.

Component (A) contains at least one constituent with, on average, at least one, in particular two, isocyanate-reactive functional group (s) and at least one, in particular two, functional group (s) with, on average, at least one, in particular one, with actinic Radiation activatable bond per molecule.

Examples of suitable isocyanate-reactive functional groups are thiol, primary and secondary amino, primary imino or hydroxyl groups, of which the primary and secondary amino groups and the hydroxyl group are advantageous and the hydroxyl groups are particularly advantageous and are therefore used with particular preference in accordance with the invention.

The constituent preferably has a hydroxyl number of 50 to 200, preferably 80 to 170 and in particular 90 to 150 mg KOH / g.

Examples of suitable bonds that can be activated with actinic radiation are single-carbon bonds or hydrogen-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 can be low molecular weight, oligomeric or polymeric. It is preferably oligomeric or polymeric.

The double bonds can be present in the component as terminal and / or lateral double bonds.

The gnmststkruren of the low molecular weight components are not critical, but can come from the most diverse 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 principles of the oligomeric or polymeric constituents 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 ethylenically unsaturated 1

Monomers, or polyaddition resins and / or polycondensation resins. 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 are poly (meth) acrylates and partially saponified polyvinyl esters.

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

According to the invention, the polyurethanes have particular advantages and are therefore used with particular preference.

The production of polyurethanes 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 the constituent described in the multicomponent system according to the invention can vary widely. It is preferably 20 to 60, preferably 25 to 55, in particular 30 to 50% by weight, in each case based on the solid of the multicomponent system according to the invention. Component (A) of the multicomponent system according to the invention can also contain at least one purely thermally curable constituent with, on average, at least two isocyanate-reactive functional groups per molecule. Examples of suitable isocyanate-reactive functional groups are those described above. Hydroxyl groups are preferably used.

The purely mergable curable constituents are preferably oligomeric or polymeric resins, as are usually used in multi-component systems. Their hydroxyl number is preferably 70 to 200, preferably 80 to 170, in particular 90 to or 150 mg KOH / g.

The oligomers and polymers described above can be considered, except that they contain no functional groups with bonds that can be activated with actinic radiation. Here, (meth) acrylate copolymers have particular advantages and are therefore used with particular preference.

The (meth) acrylate copolymers are known polymers. Their production has no special procedural features, 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, miniemulsion or microemulsion under normal pressure or overpressure in stirred tanks, autoclaves, tubular reactors, loop reactors or Taylor reactors at temperatures from 50 to 200 ° C.

Examples of suitable (meth) acrylate copolymers and copolymerization processes are described in patent applications DE 19709465 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.

If used, the content of the (meth) acrylate copolymers in the multicomponent systems according to the invention can vary widely. It is preferably 1 to 30, preferably 3 to 20 and in particular 5 to 15% by weight, in each case based on the solid of the multicomponent system according to the invention.

In addition, component (A) of the multicomponent system according to the invention 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, reactive diluents curable thermally and / or with actinic radiation, low-boiling organic solvents and high-boiling organic solvents (“long solvents”), water, UV absorbers, light stabilizers, radical scavengers, thermolabile free-radical initiators, photoinitiators and coinitiators, Crosslinking agents as used in one-component systems, catalysts for mechanical 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 control additives (thickeners), Flame retardants, desiccants, drying agents, skin preventives, 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 hyperbranched hydroxyl groups

Compounds or dendrimers, such as those found in German Patent applications DE 198 05 421 A1, DE 198 09 643 A1 or DE 198 40 405 A1 are described.

Examples of suitable reactive diluents curable with actinic radiation are those described in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the keyword "reactive diluents".

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, butyl acetate, ethyl ethoxypropionate, methoxypropyl acetate or butyl glycol acetate, ethers such as dibutyl ether, ethylene glycol, diphenyl ether, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, or , Butylene glycol or dibutylene glycol dimethyl, diethyl or dibutyl ether, N-methylpyrrolidone or xylenes or mixtures of aromatic and / or aliphatic hydrocarbons such as solvent naphtha®, gasoline 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.

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 are found, 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 Solvente", 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 A1, compounds or resins containing epoxy groups, 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 weakly ionic 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 cellulose acetobutyrate (CAB).

Examples of suitable transparent fillers 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 are ureas, modified ureas and / or silicas, as described, for example, in references EP 0 192304 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-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 disclosed, for example, in EP 0 008 127 A1; inorganic layered silicates such as aluminum-magnesium-silicates, sodium-magnesium and sodium-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 ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates; Magnesium stearate is an example of a suitable matting agent.

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, flow control 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.

The statistical average of the polyisocyanates contains at least 2.0, preferably more than 2.0 and in particular more than 3.0 isocyanate groups per molecule. The

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 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-isocyanatomomyl-l, 3,3-trimethyl-cyclohexane), 5-isocyanato-l- (2-isocyanatoeth-1-y 1) - 1, 3, 3 -trimethyl -cyclohexane, 5-isocyanato-1 - (3-isocyanatatoprop-1-y 1) - 1,3,3-trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1-y) -l, 3,3 -trimethyl-cyclohexane, l-isocyanato-2- (3-isocyanatoprop-l-yl) -cyclohexane, l-isocyanato-2- (3-isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2- (4th -isocyanatobut- 1 -y 1) - 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 ^l -diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), ethyl ethylene diisocyanate, trimethyl hexane diisocyanate, trimethyl hexane diisocyanate, trimethyl hexane diamine diisocyanate, trimethyl hexane diamine diamineate, as sold under the trade name DDI 1410 by the Henkel company and described in the patents 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 of 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 122 0717 A 1, DE 16 18 795 A 1 or DE 17 93 785 A 1, preferably isophorone diisocyanate, 5-isocyanato-1 - (2-isocyanatoeth-1-yl) -l, 3, 3-trimethyl-cyclohexane, 5 -Isocyanato- 1 - (3 -isocy anatoprop- 1 -y 1) - 1, 3, 3 -trimethyl-cyclohexane, 5 -Isocy anato- (4-isocyanatobut-1 -yl) - 1, 3, 3-trimethyl- cyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) -cyclohexane, 1 -isocyanato-2- (3-isocyanatoeth-1 - yl) cyclohexane, l-isocyanato-2- (4-isocyanatobut-l- yl) -cyclohexane or HDI, especially HDI. It is also possible to use polyisocyanates containing isocyanurate, biuret, allophanate, imlnooxadiazinedione, urethane, urea carbodiimide and / or uretdione groups, which are prepared in a customary and known manner from 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 known.

The amount of polyisocyanates in the multicomponent systems according to the invention can vary widely and depends primarily on their functionality and on the functionality of the constituents with isocyanate-reactive groups contained in component (A). However, it can also depend on whether components with at least one isocyanate group and at least one functional group with at least one bond which can be activated with actinic radiation are still present in component (B). The polyisocyanates are preferably present in the multicomponent systems according to the invention in an amount of 10 to 70, preferably 15 to 65 and in particular 20 to 60% by weight, in each case based on the solids of the multicomponent system according to the invention.

Component (B) can also contain at least one constituent with at least one isocyanate group and at least one functional group with at least one bond which can be activated with actinic radiation. As is known, these constituents can be obtained by reacting the diisocyanates and polyisocyanates described above with compounds which have at least one, in particular one, of the isocyanate-reactive functional groups described above and at least one, in particular contain a binding which can be activated with actmic radiation. 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 di, glycerol di, trimethylol ethane di, pentaerythritol tri or homopentaerytlirit triacrylate, methacrylate, ethacrylate, crotonate, cinnamate, vinyl ether, allyl ether, dicyclopentadienyl ether, norbornenyl ether or isoprenyl ether; or

Reaction products from cyclic 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 components has no special features, but takes place as described, for example, in European patent application EP 0 928 800 A1.

If used, the content of the ingredient can be at least one

Isocyanate group and at least one functional group with at least one bond that can be activated by actinic radiation vary widely. The content is preferably 5 to 40, preferably 10 to 35, particularly 15 to 30% by weight, each based on the solid of the multicomponent system according to the invention.

The production of component (B) also has no special features in terms of method, but rather takes place by mixing its components. To set a low viscosity, component (B) can also be admixed with at least one of the organic solvents described above.

If the multicomponent system according to the invention contains only components (A) and (B), it is a two-component system. In the meantime, different constituents of the individual components (A) and / or (B) can be stored separately from them and only combined shortly before application to form the multicomponent system. In general, the two-component system is preferred because it requires less effort to manufacture.

The production of the multi-component systems according to the invention from the components described above does not offer any special features in terms of method, but rather is carried out using the customary and known mixing devices and methods described above or by means of customary two- or multi-component metering and mixing systems. The mixing should ideally be done by hand.

The multicomponent systems according to the invention can be used for a wide variety of purposes. They are preferably used as coating materials, adhesives and sealants.

The coating materials, adhesives and sealing compounds according to the invention are used to produce coatings, adhesive layers and seals on and / or in primed and unprimed substrates. In particular, the serve Coating materials according to the invention for the production of clearcoats, in particular clearcoats in color and / or effect multi-layer coatings.

In terms of method, the application of the clear lacquers according to the invention has no special features, but can be carried out by all customary application methods, such as 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.

Suitable substrates are surfaces which are not damaged by hardening of the coating materials, adhesives and / or sealing compounds located thereon using heat and 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 gypsum and cement boards or roof tiles, as well as connections of these materials.

Accordingly, the coating materials, adhesives and sealants according to the invention are also suitable for applications outside of automotive OEM painting and automotive 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). For this purpose, both anodic (ATL) and cathodic electrocoat materials (KTL), but especially KTL, come into consideration.

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-m-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 processes are described in Japanese Patent Application 1975-142501 (Japanese Patent Application Laid-Open JP 52-065534 A 2, Chemical Abstracts Section No. 87: 137427) or in the patents 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 A1, EP 0 639 660 A1, EP 0 817 648 A1, DE 195 12 017 C1, EP 0 192 113 A2, DE 41 26 476 A1 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 Pat. No. 4,537,926 A, EP 0 529 335 A 1, EP 0 595 186 A 1, EP 0 639 660 A 1, DE 44 38 504 A1, DE 43 37 961 A1, WO 89J10387, 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 DIN 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, such as with a plasma or with flame treatment, or provided with a primer in a known manner before the coating.

According to the invention, the clear lacquers according to the invention are applied to the substrates described above for producing the clear lacquers according to the invention, after which the resulting clear lacquer layers are cured.

According to the invention, for the production of the adhesive layers and seals according to the invention, the adhesives and sealants according to the invention are applied to and / or in the substrates described above. 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 clear coat together with the basecoat or 5 curing the clear coat separately.

Examples of suitable basecoats are from the patent applications EP 0 089497 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

10 510 A1, EP 0 581 211 A1, EP 0 708 788 A1, EP 0 593 454 A1, DE-A-43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP 0 590484 A1, EP 0234 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 1, EP 0 649 865 A1, EP 0 536 712 A1, EP 0 596 460 A1, EP 0 596461 A1, EP 0 584 818 A1, EP 0 669 356 A1, EP 0 634431 A1

15 1, EP 0 678 536 A1, EP 0 354 261 A1, EP 0 424 705 A1, WO 97/49745, WO 97/49747, EP 0 401 565 A1 or EP 0 817 684, column 5, lines 31 to 45, known.

Generally, the filler coat, top coat, basecoat

20 and clear coat applied in a wet film thickness that according to their

Curing layers with the necessary and advantageous for their functions

Layer thicknesses result. In the case of the filler layer, this layer thickness is included

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 μm,

25 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

Clear varnishes are 10 to 100, preferably 15 to 90, particularly preferably 20 to 80 and in particular 25 to 70 μm.

30 The curing can take 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 rest period can be supported and shortened by using elevated temperatures of up to 40 ° C and / 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.

According to the invention, 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 actmic sfrahhing 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.

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 actinic radiation. Examples of suitable radiation sources are 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 beam 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 automobile bodies, the areas (shadow areas) which are not accessible to direct radiation, such as cavities, folds and other design-related areas 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 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.

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, thermal curing can also be carried out in stages. The thermal curing is advantageously carried out at room temperature or above room temperature, preferably at temperatures> 40 ° C., preferably> 50, for a time from 1 minute to several days.

Thermal 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 and end herding with actinic radiation. 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 according to the invention have a high solids content with low viscosity and a long service life.

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

The coatings, adhesive layers and seals produced with the aid of the multicomponent systems according to the invention, in particular the clearcoats according to the invention, also have a high initial hardness in the shadow regions of the substrates. The resulting coatings according to the invention, in particular the clearcoats and the color and / or effect multi-layer coatings containing them, have high hardness, flexibility and chemical resistance, excellent flow, no runners, very good intermediate adhesion, excellent overall appearance (appearance), a very good weather resistance, a very high scratch and abrasion resistance as well as a very good polishability.

The adhesive layers according to the invention are permanently strong, even under extreme and / or very strongly and rapidly changing climatic conditions.

In the long term, the seals according to the invention completely seal off chemically aggressive substances.

Thus, the primed and unprimed substrates according to the invention, which are coated with at least one coating according to the invention, bonded with at least one adhesive layer according to the invention and / or with are sealed at least one seal according to the invention, in addition to the advantages listed above, a particularly long service life, which makes them economically particularly 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, backcooler and two feed vessels, and the mixture was heated to 160 ° C. with stirring. Thereafter, 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 metered in uniformly over a period of four hours. Starting simultaneously and at the same time, an initiator mixture of 35.8 parts by weight of ethyl ethoxypropionate and 36.2 parts by weight of di-tert-butyl peroxide was 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 and 2

The production of clear lacquers according to the invention and their use for the production of color and effect multi-layer lacquers The clearcoats 1 and 2 according to the invention of Examples 1 and 2 were prepared by mixing the constituents given in Table 1. For this purpose, components (A) and (B) were mixed together in a volume ratio of 2: 1 and then with 10%, based on the clearcoats, of a thinner (solvent mixture of xylene, solvent naphtha, gasoline 135/180, methoxypropyl acetate, butyl acetate, butyl glycol acetate),

Ethylethoxypropionat and Dipentene) diluted.

Table 1: The material composition of the clearcoats 1 and 2 according to the invention

Ingredient example 1 example 2

Component (A):

Methacrylate copolymer of preparation example 1 16.5 16.5

Urethane acrylate ^a) 40 40

SAA 103 ^b) 10.5 10.5

Butyl acetate 14 14

Ethyl ethoxypropionate 10 10

Methyl isoamyl ketone 4 4

Byk® 325 ^c) 0.3 0.3 Byk® 358 ^c) 0.7 0.7

Tinuvin® 292 ^d) 1 1

Tinuvin® 400 ^d) 1 1

Irgaciire® 184 ^e) 1.1 1.1

Lucirin® TPO ^e) 0.4 0.4

Dibutyltin dilaurate (10% in butyl acetate) 0.5 0.5

Component (B):

Desmodur® N 3600 *> 60 23

Roskydal® 2337 ^g) - 42

Methyl isoamyl ketone 20 20

a) commercially available Rahn® 99-664 urethane acrylate from Rahn;

b) commercially available styrene-allyl alcohol copolymer from Lyondell (hydroxyl number: 125 mg KOH / g; number average molecular weight: 3,200 Daltons; mass average molecular weight: 8,400 Daltons;

Glass transition temperature: 78 ° C);

c) commercial leveling agents;

d) commercial light stabilizers; e) commercially available photoinitiators;

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

g) commercially available isocyanatoacrylate from Bayer AG;

The clearcoats 1 and 2 according to the invention had a processing time of two hours.

For the production of the color and effect-giving multi-layer coatings, 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 waterborne basecoat was then applied in two spray passes and dried at 60 ° C. for 5 minutes. The clearcoats of Examples 1 and 2 were then applied in two spray passes with an intermediate flash-off time of 2.5 minutes.

The applied clearcoat layers 1 and 2 were flashed off for 5 minutes, dried at 60 ° C. for 8 minutes and then cured with UV radiation at a dose of 1,500 mJ / cm ² . The resulting clearcoats 1 and 2 had a layer thickness of 50 to 60 μm. The multicoat paint systems of Examples 1 and 2 according to the invention have an excellent appearance.

To determine the initial hardness, the pendulum hardness of the applied clearcoat layers was measured according to König (pendulum strokes). The results can be found in Table 2. They demonstrate the high initial hardness of clearcoat layers 1 and 2 or clearcoats 1 and 2. In a second series of tests, the curing behavior of clear coats 1 and 2 in shadow zones of. Simulated substrates in that the test panels described above were not cured with UV radiation. The resulting clearcoats 1 and 2 were nevertheless not sticky, but had a good initial hardness.

Table 2: Initial hardness of the clearcoat layers or clearcoats 1 and 2

Hardening conditions Pendulum strokes Example 1 Example 2

Test series 1:

UV radiation curing:

after 4 hours 85 68 after 7 days 155 150

Test series 2:

Hardening without UV radiation:

after 4 hours 25 19 after 7 days 79 72

Claims

Multicomponent system curable thermally and with actinic radiation and its use

1. Multi-component system curable thermally and with actinic radiation (dual cure), containing

(A) at least one component containing at least one component with at least one isocyanate-reactive functional

Group and at least one functional group with at least one bond which can be activated with actinic radiation and at least one additive, and

(B) at least one component containing at least one

polyisocyanate

characterized in that at least one vinylaromatic-allyl alcohol copolymer is used as additive.

2. Multi-component system according to claim 1, characterized in that styrene is used as the vinyl aromatic.

3. Multi-component system according to claim 1 or 2, characterized in that the vinyl aromatic-allyl alcohol copolymer, based on its total amount, contains 10 to 50 wt .-% allyl alcohol and 50 to 90 wt .-% vinyl aromatic.

4. Multi-component system according to one of claims 1 to 3, characterized in that the vinyl aromatic-allyl alcohol copolymer zaMean molecular weight of 1,000 to 4,000 Daltons and a mass average molecular weight of 2,000 to 10,000 Daltons.

5. Multi-component system according to one of claims 1 to 4, characterized in that the vinyl aromatic-allyl alcohol copolymer is a

Has hydroxyl number from 80 to 300 mg KOH / g.

6. Multi-component system according to one of claims 1 to 5, characterized in that the vinyl aromatic-allyl alcohol copolymer has a glass transition temperature of 50 to 90 ° C.

7. Multi-component system according to one of claims 1 to 6, characterized in that it contains, based on its solid, the vinyl aromatic-allyl alcohol copolymer in an amount of 1 to 30 wt .-%.

8. Multi-component system according to one of claims 1 to 7, characterized in that component (B) additionally contains at least one component with at least one isocyanate group and at least one functional group with at least one bond which can be activated with actinic sfrahhing.

9. Multi-component system according to one of claims 1 to 8, characterized in that as activatable with actinic bonds carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon Single bonds or double bonds can be used.

10. Multi-component system according to claim 9, characterized in that carbon-carbon double bonds ("double bonds") are used.

11. Multi-component system according to one of claims 1 to 10, 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 groups; Ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups are present.

12. Multi-component system according to one of claims 1 to 11, characterized in that the isocyanate-reactive functional groups are thiol, primary or secondary amino, imino or hydroxyl groups.

13. Multi-component system according to one of claims 1 to 12, characterized in that component (A) contains at least one purely thermally curable component with at least two isocyanine-reactive functional groups.

14. Use of the multi-component system according to one of claims 1 to 13 as a coating material, adhesive or sealant.

15. Use according to claim 16, characterized in that the 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.

6. Use of the multi-component system according to claim 15, characterized in that the coating material is used for the production of color and / or effect multi-layer coatings by the wet-on-wet method.