EP1355979A2

EP1355979A2 - Foam laminate, method for production and use thereof

Info

Publication number: EP1355979A2
Application number: EP01988036A
Authority: EP
Inventors: Maxime Allard; Giordano Staid
Original assignee: BASF Coatings GmbH
Current assignee: BASF Coatings GmbH
Priority date: 2000-12-18
Filing date: 2001-12-18
Publication date: 2003-10-29
Also published as: AU2002240845A1; WO2002050172A2; US20040096641A1; WO2002050172A3; DE10063158A1

Abstract

The invention relates to a foam laminate, comprising - a layer of foam enclosed by an outer skin, comprising or containing natural or synthetic rubber and at least one clear lacquer, hardened with actinic radiation and optionally, between the underside of the clear lacquer and the outer skin, a physically hardened base lacquer and/or on the side opposite the clear lacquer, or the clear lacquer and base lacquer, a physically-bonding adhesive layer, hardened with actinic radiation, comprising nanoparticles and a tackifier, or a layer of foam enclosed by an outer skin, at least one clear lacquer, hardened with actinic radiation, on the side opposite the clear lacquer, or the clear lacquer and base lacquer, a physically-bonding adhesive layer, hardened with actinic radiation, comprising nanoparticles and a tackifier and, optionally, between the underside of the clear lacquer and the outer skin, a physically hardened base lacquer, methods for production thereof and the use thereof for coating buildings, industrial plants or parts thereof in a decorative, signalling or thermal-, magnetic- or electrically-insulating manner.

Description

Foam laminate, process for its production and its use

The present invention relates to a new foam laminate. The present invention also relates to a new method for producing a foam laminate. Furthermore, the present invention relates to the use of the new foam laminate for decorative, signaling and / or thermally, magnetically and / or electrically insulating coating of objects, in particular buildings, industrial plants or parts thereof.

Foam laminates are used worldwide to insulate pipes or structures indoors and outdoors and to seal doors and windows. Foams made from styrene-butadiene rubber ("SBR") are preferably used. For this purpose, SBR is foamed using gases in the presence of flame retardants.

The resulting SBR foam, however, has a very sensitive outer skin, which has only a low abrasion and scratch resistance as well as a low weather resistance. Any scratch can do that

Destroy the outer skin, after which the foam laminates must be replaced with new ones. To prevent this, the

For outdoor use, foam laminates should be given a coating by hand or with a factory coating before use

Aluminum foil are glued. These measures significantly increase the cost of insulation. In addition, there is at least once a year

Inspection and, if necessary, an overhaul or repair or even replacement of the insulation is necessary. These disadvantages stand in the way of a wide use of the SBR foam laminates. In addition, the previously known SBR foam laminates are not suitable for decorative purposes.

A foam laminate is known from British patent application GB 2038241 A, which comprises a foam layer based on PVC, a coloring layer and at least one clearcoat hardened with actinic radiation. The foam laminate can contain a carrier or a substrate, such as a flexible film. Suitable flexible supports can be made from flexible polymers or from woven textiles and waterproof fabrics. Woven cellulose or woven asbestos that are waterproof impregnated are advantageous. However, these known foam laminates cannot be easily connected to objects, in particular buildings, industrial plants or parts thereof.

The object of the present invention is to provide new foam laminates which have the disadvantages of the prior art for longer, but which have an outer surface which is abrasion-resistant, scratch-resistant and weather-resistant, so that they are no longer provided with protective coatings by hand or with a factory setting Aluminum foil must be provided. In addition, the new foam laminates should have a considerably longer service life than the previously known ones, so that periodic inspections and, if necessary, repairs or replacement of the insulation can be omitted. Furthermore, the adhesive layers of the new foam laminates should be thermostable and should not lose their adhesive strength even after heating to 190 ° C for six hours.

Accordingly, the new foam laminate containing at least one layer of a sealed by an outer skin

Foam containing natural rubber or synthetic rubber or consists of this, and at least one clearcoat hardened with actinic radiation.

In addition, the new foam laminate, comprising at least one layer of a foam sealed by an outer skin, at least one clearcoat hardened with actinic radiation and on the side of the layer facing away from the clearcoat, a physically binding nanoparticle hardened with actinic radiation and containing at least one tackifier , found.

In the following, the new foam laminates are collectively referred to as "laminate according to the invention".

In addition, the new process for the production of a foam laminate has been found, in which at least one is applied to the outer skin of one side of a foam layer or to the outer foam layer, which contains or consists of natural rubber or synthetic rubber, or on a paint and / or effect coating thereon applied with actinic radiation curable clear coat and cured with actinic radiation.

Furthermore, the new process for producing a foam laminate was found, in which one

(1) at least one clear coat curable with actinic radiation is applied to the outer skin of one side of a foam layer or the outer foam layer or on a color and / or effect coating thereon and cured with actinic radiation and (II) an adhesive curable with actinic radiation is applied to the side of the foam layer (s) facing away from the clearcoat or the basecoat and the clearcoat and the resulting adhesive layer is cured with actinic radiation or, alternatively, the adhesive is applied to a temporary carrier, the resulting adhesive layer with actinic Radiation cures and connects the resulting physically setting, self-supporting adhesive film to said side of the foam layer (s) before or after removal from the temporary carrier.

The following are the new methods of making a

Foam laminate summarized as "inventive

Procedure ".

The laminates according to the invention can be of any three-dimensional shape. However, at least one of its surfaces or sides is preferably substantially or completely planar, so that they can be connected to the planar surfaces of other objects, for example for decorative, protective and / or thermally insulating purposes. The surface or side opposite this surface or side, however, can be contoured. For example, it can have decorative three-dimensional ornaments or structures that absorb sound, for example. The laminates according to the invention are particularly preferably generally or completely planar.

The laminate according to the invention contains at least one layer made of a foam sealed by an outer skin. In general, a foam layer is sufficient for the construction and use of the laminate according to the invention. Foams i. S. of DIN 7726: 1982-05 are materials with open and / or closed cells distributed over their entire mass and a bulk density that is lower than that of the framework substance. Preferably elastic and soft elastic foams i. S. of DIN 53580 (see also Römpp Lexikon Chemie, CD-ROM: Version 2.0, Georg Thieme Verlag, Stuttgart, New York, 1999, "Foams").

The foam contains or consists of at least one, in particular a synthetic or natural, occurring polymer. Examples of suitable polymers are natural rubber, 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, SBR, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM or UP (short names according to DIN 7728T1). Foams made of rubbers, preferably synthetic rubbers, in particular SBR, are preferably used.

The production of these foams has no special features, but is carried out in a customary and known manner by foaming the plastics with suitable inert gases such as water vapor, nitrogen, carbon dioxide, pentane or chlorinated and / or fluorinated hydrocarbons in open or closed vessels. The processes are carried out so that foams with a closed outer skin form.

The laminate according to the invention has at least one, in particular a clearcoat hardened with actinic radiation, on the surface or the side which later forms the outer surface or the outer side when used appropriately. Here and below, actinic radiation includes electromagnetic radiation such as near infrared (NIR), visible light, UV radiation and X-rays, especially UV radiation, as well

To understand corpuscular radiation like electron radiation. UV radiation is preferably used.

The clearcoat curable with actinic radiation for the production of the clearcoat can be an aqueous clearcoat, a conventional clearcoat, an essentially water- and solvent-free clearcoat (100% system), an essentially water- and solvent-free powder clearcoat or an essentially solvent-free one Be powder clearcoat slurry. A substantially water and solvent free 100% system is preferably used.

Examples of suitable clearcoats curable with actinic radiation can be found, for example, in the patent applications and the patent specification EP 0 540 884 A1, EP 0 568 967 A1, DE 199 20 801 A1 or US Pat. No. 4,675,234 A1.

A clear lacquer curable with actinic radiation is preferably used, which

at least one binder, containing, on average, at least one reactive functional group, containing a bond which can be activated with actinic radiation, in the molecule

( "Clear coat binder"),

at least one low molecular weight compound with at least one reactive functional group, containing a bond which can be activated with actinic radiation (“reactive thinner”), and at least one photoinitiator,

contains.

The statistical clearcoat binders contain on average at least one, in particular at least two, reactive functional group (s) containing a bond which can be activated with actinic radiation. In the following, the reactive functional groups are referred to as "radiation-curable groups".

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 carbon-carbon double bonds are particularly advantageous and are therefore used with very particular preference in accordance with the invention. For the sake of brevity, they are referred to below as "double bonds".

The double bonds are preferably in reactive functional groups such as (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups, but especially (meth) acrylate groups, especially acrylate groups.

If the clear coat binders contain more than one, in particular two, radiation-curable group (s), these can be the same or different be from each other. The radiation-curable groups are preferably the same.

The clear coat binders are oligomeric or polymeric compounds.

An oligomeric compound is understood to mean a compound which has an average of 2 to 15 monomer units. By contrast, a polymeric compound is understood to mean a compound which has on average at least 10 monomer units.

In contrast to this, a low-molecular compound is to be understood as a compound which is essentially derived only from a basic structure or a monomer unit. Compounds of this type are generally referred to by the experts as reactive thinners.

The polymers or oligomers used as clear lacquer binders usually have a number average molecular weight of 500 to 50,000, preferably 1,000 to 5,000. They preferably have a double bond equivalent weight of 400 to 2,000, particularly preferably 500 to 900. In addition, they preferably have a viscosity of 250 to 11,000 mPas at 23 ° C. They are preferably used in an amount of 5 to 90% by weight, particularly preferably 7 to 80% by weight and in particular 10 to 70% by weight, in each case based on the total amount of the clear lacquer.

Examples of suitable clear coat binders come from the oligomer and / or polymer classes of the (meth) acrylic functional groups

(Meth) acrylate copolymers, polyether acrylates, polyester acrylates, polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and phosphazene acrylates and the corresponding methacrylates. Clearcoat binders which are free from aromatic structural units are preferably used. Urethane (meth) acrylates, polyether (meth) acrylates, phosphazene (meth) acrylates and / or polyester (meth) acrylates are therefore preferred, particularly preferably urethane (meth) acrylates and polyether (meth) acrylates, in particular aliphatic urethane (meth) acrylates , used.

The urethane (meth) acrylates are obtained by reacting a di- or polyisocyanate with a chain extender from the group of the diols / polyols and / or diamines / polyamines and / or dithiols / polythiols and / or alkanolamines and subsequent reaction of the remaining free isocyanate groups with at least a hydroxyalkyl (meth) acrylate or hydroxyalkyl ester of other ethylenically unsaturated carboxylic acids.

The amounts of chain extender, di- or polyisocyanate and hydroxyalkyl ester are preferably chosen so that

1.) the equivalent ratio of the NCO groups to the reactive groups of the chain extender (hydroxyl, amino or

Mercaptyl groups) is between 3: 1 and 1: 2, preferably 2: 1, and

2.) the OH groups of the hydroxyalkyl esters of the ethylenically unsaturated carboxylic acids are present in a stoichiometric amount in relation to the free isocyanate groups of the prepolymer from isocyanate and chain extender.

It is also possible to prepare the urethane (meth) acrylates by first reacting some of the isocyanate groups of a di- or polyisocyanate with at least one hydroxyalkyl ester and the rest Isocyanate groups are then reacted with a chain extender. In this case, too, the amounts of chain extender, isocyanate and hydroxyalkyl ester are chosen so that the equivalent ratio of the NCO groups to the reactive groups of the chain extender is between 3: 1 and 1: 2, preferably 2: 1, and the equivalent ratio of the remaining NCO Groups to the OH groups of the hydroxyalkyl ester is 1: 1. Of course, all intermediate forms of these two processes are also possible. For example, part of the isocyanate groups of a diisocyanate can first be reacted with a diol, then another part of the isocyanate groups can be reacted with the hydroxyalkyl ester and then the remaining isocyanate groups can be reacted with a diamine.

These different methods of manufacturing the urethane (meth) acrylates are known (see e.g. EP 0204 161 A 1).

The urethane (meth) acrylates can be made more flexible, for example, by reacting corresponding isocyanate-functional prepolymers or oligomers with longer-chain, aliphatic diols and / or diamines, in particular aliphatic diols and / or diamines with at least 6 carbon atoms. This flexibilization reaction can be carried out before or after the addition of acrylic or methacrylic acid to the oligomers or prepolymers.

Examples of suitable urethane (meth) acrylates include the following commercially available polyfunctional aliphatic urethane acrylates:

- Crodamer® UVU 300 from Croda Resins Ltd., Kent,

Britain; Genomer® 4302, 4235, 4297 or 4316 from Rahn Chemie, Switzerland;

Ebecryl® 284, 270, 244, 230, 294, IRR351, 5129 or 1290 from UCB, Arzneimittelbos, Belgium; - Roskydal® LS 2989 or LS 2545 or V94-504 from Bayer

AG, Germany;

CN960, CN965, CN970 or CN980 from Cray Valley, France;

Viaktin® VTE 6160 from Vianova, Austria; or - Laromer® 8861 or PUA 8739 from BASF AG and modified test products.

Examples of suitable polyether (meth) acrylates are the products sold by Cognis under the brand Photomer® 6891 or RCC891.

An example of a suitable polyphosphazene (meth) acrylate is the phosphazene dimethacrylate from Idemitsu, Japan.

Examples of suitable reactive diluents are (meth) acrylic acid and its esters, maleic acid and its esters or half esters, vinyl acetate, vinyl ether, vinyl ureas and others. used. Examples include alkylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, vinyl (meth) acrylate, aliyl (meth) acrylate, = glycerol tri (meth) acrylate, trimethylolpropane tri ( meth) acrylate,

Trimethylolpropane di (meth) acrylate, styrene, vinyl toluene, divinyl benzene, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate,

Dipentaerythritol pentaacrylate, dipropylene glycol di (meth) acrylate,

Hexanediol di (meth) acrylate, ethoxyethoxyethyl acrylate, tridecyl acrylate, cyclohexyl acrylate, tert-butylcyclohexyl acrylate, N-vinylpyrrolidone, phenoxyethyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl (meth) acrylate, Butoxyethyl acrylate, isobomyl (meth) acrylate, dimethylacrylamide and dicyclopentyl acrylate, the long-chain linear diacrylates described in EP 0 250 631 A1 with a molecular weight of 400 to 4,000, preferably 600 to 2,500. For example, the two acrylate groups can be separated by a polyoxibutylene structure. It is also possible to use 1, 12-dodecyl diacrylate and the reaction product of 2 moles of acrylic acid with one mole of a dimer fatty alcohol, which generally has 36 carbon atoms. Further examples of suitable reactive thinners are known from Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Reaktiverdünner", page 491. Mixtures of the reactive thinners mentioned are also suitable.

Mono- and / or diacrylates, such as e.g. Isobornyl acrylate, hexanediol diacrylate, tridecyl acrylate, tert-butylcyclohexyl acrylate, tripropylene glycol diacrylate, Laromer® 8887 from BASF AG and Actilane® 411 from Akcros Chemicals Ltd., GB. Isobornyl acrylate, tridecyl acrylate, hexanediol diacrylate and tripropylene glycol diacrylate are particularly preferably used.

The reactive diluents are preferably used in an amount of 0.5 to 30% by weight, particularly preferably 1.0 to 25% by weight and in particular 1.5 to 20% by weight, in each case based on the total amount of the clearcoat material ,

The clearcoat also contains at least one photoinitiator.

Examples of suitable photoinitiators are those of the Norrish II type, the mechanism of action of which is based on an intramolecular variant of the hydrogen abstraction reactions, as they occur in diverse ways in photochemical reactions, or cationic photoinitiators, as expanded, for example, in Römpp Chemie Lexikon, 9th and revised edition, Georg Thieme Verlag Stuttgart, Vol. 4, 1991, or Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446, in particular benzophenones, benzoins or benzoin ethers or phosphine oxides. For example, the products commercially available under the names Irgacure® 184, Irgacure® 1800 and Irgacure® 500 from Ciba Geigy, Grenocure® MBF from Rahn and Lucirin® TPO from BASF AG can be used. The photoinitiators in the clear lacquer are preferably in an amount of 0.1 to 5, preferably 0.2 to 4.5, particularly preferably 0.3 to 4, very particularly preferably 0.4 to 3.5 and in particular 0.5 to 3 % By weight, based in each case on the total amount of the clearcoat.

The clearcoat can furthermore contain at least one transparent filler, preferably in an amount of 5 to 50, preferably 6 to 45 and in particular 8 to 40% by weight, based on the total amount of the clearcoat.

Examples of suitable transparent fillers are those based on silicon dioxide, aluminum oxide, in particular aluminum hydride (Al ₂ O ₃ xn H ₂ O) or zirconium oxide; In addition, reference is also made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252.

Some of the fillers can also be present as nanoparticles. Suitable nanoparticles are, in particular, those based on silicon dioxide with a particle size <50 nm, in particular 15 to 30 nm, which have no matting effect. Examples of suitable nanoparticles based on silicon dioxide are pyrogenic silicon dioxide, which as dispersions under the trade name Aerosil® VP8200, VP711 or R972 from Degussa or the trade names Gab O Sil® TS 610, CT 1110F or CT 1110G from CABOT, the trade name High Link® OG 103-31, OG 102-31 or OG 502-31 from Clariant Hoechst or the trade name Snowtex® MIBK or IPA from Nissan.

In general, these nanoparticles are sold in the form of dispersions in alcohols such as isopropanol, ketones such as methyl isobutyl ketone or in monomers curable with actinic radiation (reactive diluents). Examples of suitable monomers which are particularly suitable for the present use are alkoxylated pentaerythritol tetra- or triacrylate, ditrimethylolpropane tetra- or triacrylate, dineopentylglycol diacrylate, trimethylolpropane triacrylate,

Trishydroxyethyl isocyanurate triacrylate, dipentaerythritol penta- or hexaacrylate or hexanediol diacrylate. In general, these dispersions contain the nanoparticles in an amount of, based on the dispersions, 10 to 80% by weight, preferably 15 to 70% by weight, particularly preferably 20 to 60% by weight and in particular 25 to 55% by weight .-%. Dispersions in isopropanol are preferably used. An example of a dispersion of nanoparticles that is particularly suitable according to the invention is the dispersion, which is sold under the trade name High Link® OG 502-31 by Clariant Hoechst.

If the clear lacquer is used for the production of laminates according to the invention which are intended for use in the interior of buildings or industrial plants, it contains at least one flame retardant.

Examples of suitable flame retardants are halogenated, in particular chlorinated, olefinically unsaturated monomers, in particular acrylates or methacrylates, such as 3-chloro-2-hydroxypropyl methacrylate, which in the

Curing with actinic radiation in the three-dimensionally cross-linked matrix the clear coat. Further examples of suitable flame retardants are brominated aliphatic or aromatic compounds, in particular brominated aromatic compounds such as decabromodiphenyl ether or 1,2-bis (pentabromophenyl) ethane. These are compounds which are essentially insoluble in the clear lacquer. They are therefore incorporated into the clear lacquer as finely divided solid particles with a particle size of 1 to 30, preferably 2 to 20 and in particular 5 to 15 μm.

The flame retardants are preferably used in an amount of 5 to 75, preferably 6 to 70, particularly preferably 7 to 70, very particularly preferably 8 to 65 and in particular 10 to 60% by weight, in each case based on the total amount of the clear lacquer.

In addition, the clearcoat can contain at least one additive such as customary and known oligomeric or polymeric binders which do not contain a radiation-curable group, organic solvents, light stabilizers such as UV absorbers, sterically hindered amines (HALS), phenolic antioxidants or quenchers; thermolabile free radical initiators, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting and dispersing agents, adhesion promoters, leveling agents, film-forming aids, sag control agents, rheology-controlling additives (thickeners), siccatives, drying agents, skin-preventing agents and / or contain corrosion inhibitors. Examples of suitable additives are given in the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, or in “Paints, Coatings and Solvents”, Edit. Dieter Stoye and Werner Freitag, 2nd edition, Wiley-VCH, Weinheim, New York, 1998, described in detail. The production of the clear lacquer curable with actinic radiation has no special features in terms of method, but is carried out in a customary and known manner by mixing the above-described constituents in suitable mixing units such as stirred kettles, dissolvers or extruders. The process is preferably carried out with the exclusion of light of a wavelength λ <550 nm or with the complete exclusion of light in order to prevent premature crosslinking of the clearcoat.

The production of the clearcoat has no special features in terms of the method, but is carried out by applying the clearcoat to the surface or to the side of the foam layer which later forms the top of the foam layer (s) when the laminate of the invention is used. Or the clear lacquer is applied to the surface of a color and / or effect basecoat, which is located on this surface of the foam layer (s).

This can be done using all common application methods, e.g. Spraying, knife coating, brushing, pouring, dipping, watering, trickling or rolling. The molded part to be coated, in particular the plate, made of foam as such or as such, can rest, the application device or system being moved. However, the substrate to be coated can also be moved, the application system being at rest relative to the substrate or being moved in a suitable manner. It is preferable to work with the exclusion of light of a wavelength λ <550 nm or with the complete exclusion of light in order to prevent uncontrolled premature crosslinking of the clearcoat.

The thickness of the applied clear coat can vary widely.

It preferably has a layer thickness such that after curing the clearcoat has a dry layer thickness of 10 to 120, preferably 10 up to 110, particularly preferably 10 to 100, very particularly preferably 10 to 90 and in particular 10 to 80 g / m ² .

The clear lacquer layer can harden after a certain rest period. It can have a duration of 10 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 30 min. The idle time is used, for example, for the course and degassing of the clear coat or for the evaporation of volatile components such as solvents. The rest period can be supported and / or shortened by the use of elevated temperatures up to 80 ° C, provided that there is no damage or changes to the clear coat, such as uncontrolled premature crosslinking.

Hardening with actinic radiation also has no special features in terms of method, but instead takes place with the aid of electromagnetic radiation such as near infrared, visible light, UV radiation or X-rays, in particular UV radiation, and / or

Corpuscular radiation like electron radiation. UV radiation is preferably used.

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 are optionally doped with lead to open a beam window up to 405 nm, or electron beam sources. Further examples of suitable radiation sources are described in German patent application DE 198 18 735 A1, column 10, lines 31 to 61. Their arrangement is known in principle and can be adapted to the conditions of the substrate and the process parameters. In the case of intricately shaped foam layers, the areas (shadow areas) which are not directly accessible to radiation, such as cavities or other undercuts, can be cured using spot, small area or all-round emitters, combined with an automatic movement device for irradiating cavities or undercuts.

The facilities and conditions of these hardening methods are also 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 hardening can take place in stages, i. H. by multiple exposure or exposure to actinic radiation. This can also take place alternately, i. that is, for example, alternately curing with UV radiation and electron radiation.

A radiation dose of 1,000 to 3,000, preferably 1,200 to 2,900 and in particular 1,300 to 2,800 mJ / cm ^{2 is} preferably used. It is advisable to choose the radiation dose and the radiation duration so that the clear lacquer layer hardens completely, but that the foam layer is not damaged by the radiation. The specialist can set the parameters optimally in each individual case on the basis of his general specialist knowledge, if necessary with the aid of simple preliminary tests. It is a major advantage of this process that mechanically and / or thermally sensitive foam layers can also be provided with the clear coat. The resulting laminates according to the invention are distinguished by an abrasion-resistant, scratch-resistant and weather-stable outer surface, so that they cannot be easily damaged by mechanical or chemical action during transport, handling or their intended use. The laminates according to the invention therefore have a considerably longer service life and no longer have to be periodically inspected and, if necessary, replaced. In addition, the outer surface of the laminates according to the invention has a particularly good overall visual impression and is dirt-repellent.

In a preferred embodiment of the laminate according to the invention, at least one, in particular one, base coat is located between the underside of the clear coat described above and the outer skin of the outer foam layer.

The basecoat can be made from a wide variety of basecoats, such as conventional basecoats or waterborne basecoats. Waterborne basecoats are preferably used.

Waterborne basecoats are from the patent applications and patent specifications 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 0 581 211 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 A1, EP 0 584 818 A1, EP 0 669 356 A1, EP 0 634 431 A1, 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, DE 196 52 842 A1 or EP 0 817 684, column 5, lines 31 to 45, EP 0 787 195 A1, DE 40 05 961 A1, DE 41 10 5 520 A1, EP 0 752 455 B1, DE 198 55 455 B1, DE 199 488 121 A1, DE 198469 171 A1, EP 0 788 523 B1 or WO 95/12626.

As is known, they contain at least one water-dispersible or soluble polyurethane and / or 0 (meth) acrylate (co) polymer, in particular a (meth) acrylate polymer, as the basecoat binder. The (meth) acrylate copolymers are commercially available products and are sold, for example, under the Acronal® brand by BASF Aktiengesellschaft or the Neocryl® brand.

5 The basecoat binders are preferably used in the form of aqueous solutions or dispersions which preferably contain a solids content of 10 to 80, preferably 15 to 70 and in particular 20 to 60% by weight, based on the solution or the dispersion.

0 The basecoat binders are preferably physically curing. This means the hardening of a layer of a coating material by filming by release of solvent from the coating material, the linkage within the coating via loop formation of the polymer molecules of the binders (for the term cf.Römpp Lexikon 5 Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York , 1998, »Binder«, pages 73 and 74). Or the filming takes place via the coalescence of binder particles (cf. Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, »Hardening«, pages 274 and 275). No crosslinking agents are usually necessary for this. If necessary, the physical Hardening can be supported by atmospheric oxygen, heat or by exposure to actinic radiation.

The content of the waterborne basecoat in the basecoat binders described above can vary widely. It is preferably 5 to 70, preferably 6 to 65, particularly preferably 7 to 60, very particularly preferably 8 to 55 and in particular 9 to 50% by weight, in each case based on the solids of the water-based lacquer.

The basecoat also contains at least one organic and / or inorganic, color and / or effect pigment.

Examples of suitable effect pigments are metallic effect pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE 36 36 183 A1, and commercially available stainless steel bronzes as well as non-metallic effect pigments, such as pearlescent or interference pigments, platelet-shaped effect pigments based on iron oxide, which is a shade of pink to brownish red, liquid crystalline effect pigments or fluorescent pigments (daylight pigments) such as bis (azomethine) pigments. In addition, Römpp Lexikon Lacquers and Printing Inks, Georg Thieme Verlag, 1998, pages 176, "Effect Pigments" and pages 380 and 381 "Metal Oxide Mica Pigments" to "Metal Pigments", and the patent applications and patents DE 36 36 156 A1, DE 37 18 446 A1, DE 37 19 804 A1, DE 39 30 601 A1, EP 0 068 311 A1, EP 0 264 843 A1, EP 0 265 820 A1, EP 0 283 852 A1, EP 0 293 746 A 1, EP 0 417 567 A 1, US 4,828,826 A or US 5,244,649 A.

Metallic effect pigments are preferably used, in particular aluminum effect pigments (cf. Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 24 and 25, "Aluminum Pigments").

The aluminum effect pigments are leafing pigments (see Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 351, "Leafing-Pigments") or non-leafing pigments (see Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998 , Page 412, “Non-Leafing Pigments”). They are of a platelet-shaped, essentially round shape (silver dollar type) or of a platelet-shaped, essentially elongated shape.

Examples of suitable inorganic color pigments are white pigments such as titanium dioxide, zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron-manganese black or spinel black; Colored pigments such as chromium oxide, chromium oxide hydrate green, cobalt green or ultramarine green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red; = Cadmium sulfoselenide, molybdate red or ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases or chrome orange; or iron oxide yellow, nickel titanium yellow, chrome titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.

Examples of suitable organic coloring pigments are monoazo pigments, bisazo pigments, anthraquinone pigments, benzimidazole pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, iso pigment pigments, iso pigment pigments, iso pigment pigments, iso pigment pigments, iso pigment pigments, iso pigments

Thioindigo pigments, metal complex pigments, perinone pigments,

Perylene pigments, phthalocyanine pigments or aniline black. In addition, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 180 and 181, "Iron Blue Pigments" to "Iron Oxide Black", pages 451 to 453 "Pigments" to

»Pigment volume concentration«, page 563 »Thioindigo pigments«, page 567 »Titanium dioxide pigments«, pages 400 and 467, »Naturally occurring pigments«, page 459 »Polycyclic pigments«, page 52, »Azomethine pigments«, »Azo pigments« , and page 379, “Metal complex pigments”.

Examples of suitable electrically conductive pigments are titanium dioxide / tin oxide pigments.

Examples of suitable magnetic shielding pigments are magnetic pigments based on iron oxides or chromium dioxide.

Suitable soluble organic dyes are lightfast organic dyes with little or no tendency to migrate from the coating materials according to the invention and the coatings produced therefrom. The person skilled in the art can estimate the tendency to migrate on the basis of his general specialist knowledge and / or determine it with the aid of simple preliminary tests, for example in the context of sound tests.

The basecoat can also contain organic and inorganic fillers.

Examples of suitable organic and inorganic fillers are chalk, calcium sulfates, barium sulfate, silicates such as talc, mica or kaolin, silicas, oxides such as pyrogenic silicon dioxide, which can also serve as a rheology aid, or aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular from polylamide or polyacrylonitrile. In addition, reference is made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 250 ff., "Füllstoffe".

It can be advantageous to use mixtures of platelet-shaped inorganic fillers such as talc or mica and non-platelet-shaped inorganic fillers such as chalk, dolomite, calcium sulfate or barium sulfate, because this allows the viscosity and the flow behavior to be adjusted well.

The pigments, dyes and fillers described above can be in finely divided, non-opaque form.

The content of the basecoat of the pigments described above can vary very widely and depends primarily on the effects and / or the colors to be adjusted and on the hiding power of the pigments. They are preferably used in amounts such that a pigment / basecoat binder ratio of 1: 1 to 10: 1, preferably 1.2: 1 to 6: 1, particularly preferably 1.5: 1 to 5: 1, very particularly preferably 1: 8: 1 to 4: 1 and in particular 2.0: 1 to 3: 1 results.

The basecoat may also contain the additives described above for the clearcoats.

The production and application of the basecoat offers no special features in terms of method, but is carried out according to the methods described above for the clearcoats, although it is possible to work in daylight. The basecoat is preferably applied in a layer thickness such that, after physical curing, a basecoat with a dry layer thickness of 5 to 40, preferably 6 to 38, preferably 7 to 36, particularly preferably 8 to 34, very particularly preferably 9 to 30 and in particular 10 to 28 g / m ² results.

The embodiment of the laminate according to the invention described above is excellent for decorative and insulating purposes in

Suitable for indoor and outdoor use of buildings. Here, the

Basecoat the production of laminates according to the invention with a practically unlimited number of colors and / or optical

Effects, especially metallic and dichroic optical effects. The different colors and / or optical effects of the

Basecoat can also generally serve safety, in particular occupational safety, by using laminates according to the invention with warning and / or fluorescent colors at critical points in buildings or systems. However, the laminates according to the invention can also be used in addition to the thermal insulation for electrical and / or magnetic shielding.

On the side of the laminate according to the invention which is facing away from the clearcoat or the basecoat and clearcoat and is based on foam layers which contain or consist of natural rubber or synthetic rubber, d. H. the underside of the foam layer or the lowermost foam layer, there can be at least one, in particular a physically setting adhesive layer or adhesive film containing nanoparticles hardened with actinic radiation and at least one tackifier. The adhesive layer or adhesive film is mandatory if the foam layers do not contain or consist of natural rubber or synthetic rubber.

The adhesive layer or adhesive film is produced from adhesives containing curable with actinic radiation at least one tackifier,

at least one low molecular weight compound with at least one reactive functional group containing a bond which can be activated with actinic radiation, and

Nanoparticles.

The first essential component of the adhesive is at least one, in particular one, tackifier. Tackifiers are polymeric additives for adhesives that increase their tack, ie their inherent tack or self-adhesion, so that they stick firmly to surfaces after a short pressure (cf.Ullmann ^'s Encyclopedia of Industrial Chemistry, CD-ROM, Wiley VCH, Weinheim, 1997, "tackifier").

The tackifier can be at least one polymer which is inert or curable with actinic radiation, in particular with UV radiation, and which is soluble or dispersible in the low molecular weight compound.

Examples of suitable tackifiers are highly flexible resins selected from the group consisting of

- Homopolymers of alkyl (meth) acrylates, especially alkyl acrylates, such as poly (isobutyl acrylate) or poly (2-ethylhexyl acrylate), which are sold under the Acronal® brand by BASF Aktiengesellschaft, under the Elvacite® brand by Dupont the Neocryl® brand from Avecia and Plexigum® from Röhm; linear polyesters, as are usually used for coil coating and are sold, for example, under the Dynapol® brand by Dynamit Nobel or under the Skybond® brand by SK Chemicals, Japan;

5 linear difunctional oligomers curable with actinic radiation with a number average molecular weight of more than 2,000, in particular 3,000 to 4,000, based on polycarbonate diol or polyester diol, which are marketed under the name CN 0 970 by the company Craynor or the brand Ebecryl® by the company

UCB are distributed;

linear vinyl ether homopolymers and copolymers based on ethyl, propyl, isobutyl, butyl and / or 2-ethylhexyl vinyl ether, which 5 are sold under the Lutonal® brand by BASF Aktiengesellschaft; and

non-reactive urethane-urea oligomers which are prepared from bis (4,4-isocyanatophenyl) methane, N, N-dimethylethanolamine and diols such as propanediol, hexanediol or dimethylpentanediol and e.g. are sold by Swift Reichold under the Swift Range® brand or Mictchem Chemicals under the Surkopack® or Surkofilm® brands.

$ The nonlinear vinyl ether homo- and copolymers are particularly preferably used, very particularly preferably Lutonal® A50 and M40, in particular Lutonal® A50.

The tackifier content of the adhesive can vary widely. It is preferably 0 to 5 to 80, preferably 8 to 75, particularly preferably 10 to 70, very particularly preferably 12 to 65 and in particular 14 to 60% by weight, in each case based on the adhesive according to the invention.

The further essential component of the adhesive is at least one, in particular at least two, low molecular weight compound (s). They contain at least one of the radiation-curable groups described above, in particular acrylate groups.

Examples of suitable compounds of this type are the low molecular weight compounds described above for clearcoats.

Examples of particularly suitable compounds of this type are mono- or difunctional acrylates, preferably of long-chain, essentially linear, aliphatic diols, such as

2-ethylhexanediol, butanediol, decanediol, tridecanediol,

Dimethylhexanediol, trimethylhexanediol or dodecanediol,

the above-mentioned diols which are chain-extended by methoxy, ethoxy or propoxy groups, or

Polycaprolactone diols, poly (methylene oxides), poly (ethylene oxides) or poly (ethylene oxide-co-propylene oxides),

of which the monofunctional acrylates are used with particular preference.

It is also the most suitable

Compounds around the acrylates of long-chain, essentially linear, aliphatic alcohols such as butanol, hexanol, octanol, decyl alcohol, Lauryl alcohol or lauryl alcohol monoglycidyl ether, the acrylate of which is sold under the name CN152 by the Cray Valley company.

Furthermore, the particularly suitable compounds are the acrylates of cycloaliphatic alcohols, such as isobomyl alcohol, cyclohexanol, tert-butylcyclohexanol or dicyclopentadiene methanol, in particular isobomyl alcohol.

Of the particularly suitable compounds, the acrylates of long-chain, essentially linear, aliphatic alcohols and the acrylates of cycloaliphatic alcohols are used with particular preference. Of these, the acrylates of cycloaliphatic alcohols have the particular advantage that they solve the tackifiers, which have particularly good adhesion and particularly good wettability for rubbers, particularly well. They are therefore used with very particular preference.

In particular, mixtures are made from

(i) at least one, in particular one, monofunctional acrylate of a long-chain, substantially linear, aliphatic alcohol or a diol, in particular one monofunctional acrylate of a long-chain alcohol, and

(ii) at least one, especially one, acrylate of a cycloaliphatic alcohol

used.

In particular, a mixture of lauryl alcohol monoglycidyl ether acrylate and isobornyl acrylate is used. The mixing ratios can vary widely; Mixing ratios of 10: 1 to 1:10 are preferred, preferably 6: 1 to 1: 6, particularly preferably 1: 4 to 4: 1, very particularly preferably 2: 1 to 1: 2 and in particular 1.5: 1 to 1: 1.5.

The content of the low-molecular compounds described above can vary widely in the adhesive. It is preferably 10 to 90, preferably 12 to 80, particularly preferably 14 to 70, very particularly preferably 16 to 60 and in particular 18 to 50% by weight, in each case based on the adhesive according to the invention.

The third essential component of the adhesive according to the invention are nanoparticles. Examples of suitable nanoparticles are those described above for clearcoats.

The content of solid nanoparticles in the adhesive can vary widely. It is preferably 0.05 to 10, preferably 0.1 to 9, particularly preferably 0.2 to 8, very particularly preferably 0.3 to 7 and in particular 0.4 to 6% by weight, in each case based on the adhesive ,

The adhesive preferably also contains at least one photoinitiator, as described above for the clearcoats. If used, the photoinitiators in the adhesive are preferably in an amount of 0.1 to 5, preferably 0.2 to 4.5, particularly preferably 0.3 to 4, very particularly preferably 0.4 to 3.5 and in particular 0 , 5 to 3 wt .-%, each based on the adhesive.

In addition, the adhesive may also contain at least one of the additives described above for the clear lacquer.

The production, application and hardening of the adhesive does not offer any special features in terms of method, but rather the ones mentioned above Clearcoats and the clearcoats described methods and devices applied.

In a first preferred variant of the production of the adhesive layer, the adhesive is applied directly to the underside of the lowermost foam layer or the foam layer, after which the resulting adhesive layer is cured with actinic radiation.

In a second preferred variant of the production of the adhesive layer, the adhesive for producing an adhesive film is applied to at least one, in particular one, side of a preferably planar temporary carrier, as described above, and cured. The temporary carriers consist of materials which have little or no adhesion to the adhesive films thereon, so that they can be removed from the temporary carrier without damage. Examples of suitable materials are fluorinated plastics such as polytetrafluoroethylene or conventional and known non-stick layers made of silicones. The temporary carriers are preferably foils because the composite of adhesive foil and temporary carrier can be wound up in a simple manner and stored as a roll until use. When used appropriately, the adhesive films are laminated either under pressure onto the surface of the foam layers. Or the adhesive films are laminated onto the objects with which the laminates according to the invention are to be connected, after which they are attached to the. Surface of the foam layers are connected. The temporary carriers can be removed from the adhesive films before or after lamination.

A major advantage of the above-described production of adhesive layers on the surface of the foam layers is that the foam layers can be directly applied by the Adhesive layers or the lamination of the adhesive films are not damaged mechanically or thermally.

The adhesive films and adhesive layers adhere exceptionally firmly to the underside of the foam layer or the bottom foam layer and the objects with which they permanently bond the laminates according to the invention. They have very good chemical resistance and weather resistance, so that they can also be used for outdoor applications and / or in plants in which aggressive chemicals or solvents are handled. Last but not least, the adhesive layers and adhesive films are extremely thermostable and do not lose their adhesive strength even after heating to 190 ° C for six hours. They therefore also meet strict safety regulations, such as those that apply to the use of materials in the interior and exterior of buildings or industrial plants. Since the adhesive layers or adhesive films can be set physically, there is neither the risk of sticking to the packaging materials during transport, nor the risk of damage when the laminates according to the invention are connected, for example to the walls of buildings.

Examples

Production Example 1

The production of a clear lacquer to be used according to the invention

For the production of the clear lacquer to be used according to the invention

35 parts by weight of a commercially available urethane acrylate (CN965 from Cray Valley), 35 parts by weight of a commercial

Polyether acrylate (Photomer 6891 from Cognis), 5.0 parts by weight Tridecyl acrylate, 20 parts by weight of aluminum hydroxide, 2.8 parts by weight of a mixture of a commercial light stabilizer based on triazine (Cytec® 1164 from Cytec) and a commercial light stabilizer based on a hindered amine (HALS; Sandovur® 3058) in a weight ratio of 1 , 5: 1, 1, 5 ^' parts by weight of a commercially available photoinitiator (Lucirin® 8893 from BASF Aktiengesellschaft), 0.5 parts by weight of another commercial photoinitiator (Irgacure® from Ciba) and 0.2 parts by weight of a commercially available leveling agent.

Preparation example 2

The production of a waterborne basecoat to be used according to the invention

To produce the waterborne basecoat to be used according to the invention, 30 parts by weight of a commercially available dispersion of a methacrylate copolymer (Neocryl® A 1039; 40% in water), 0.2 part by weight of a commercially available wetting agent (Surfynol® 104 from Air Products), 0.3 part by weight commercial pyrogenic silicon dioxide (Aerosil® 200), 2.5 parts by weight of a conventional film-forming aid, 30 parts by weight of a 70% dispersion of titanium dioxide in water and 37 parts by weight of a 50% dispersion of iron oxide red in water mixed together.

Preparation example 3

The production of a clearcoat to be used according to the invention for the production of a flame-resistant clearcoat The clear lacquer to be used according to the invention was obtained by mixing 33.9 parts by weight of a commercially available polyether acrylate (Photomer 6891 from Cognis), 3.0 parts by weight of 3-chloro-2-hydroxypropyl methacrylate, 2 parts by weight of isobornyl acrylate, 25 parts by weight of aluminum hydroxide and 35 parts by weight

Decabromodiphenyl ether with a particle size of 10 μm, 1.0 part by weight of a commercially available photoinitiator (Lucirin® 8893 from BASF Aktiengesellschaft) and 0.1 part by weight of a commercially available film-forming aid.

Preparation example 4

The production of an adhesive to be used according to the invention

An adhesive to be used according to the invention was obtained by mixing 32 parts by weight of lauryl alcohol glycidyl ether acrylate, 32 parts by weight of isobornyl acrylate, 32 parts by weight of a commercially available vinyl ether polymer (Lutonal® A50 from BASF Aktiengesellschaft), 1.0 part by weight of a commercially available photoinitiator based on phosphine oxide, 0.2 part by weight commercial light stabilizer or antioxidant (Anox® IC 14 from Great Lakes) and 5.6 parts by weight of a 50% dispersion of nanoparticles in isopropanol (High Link® OG 502-31 from Clariant) and distilling off the isopropanol under vacuum. The adhesive was liquid and easy to apply.

example 1

The production of a laminate 1 according to the invention Sheets made of SBR foam, as are usually used for insulating buildings, were coated on one side with a layer of the clear lacquer from preparation example 1. The application was carried out by rolling. The layer thickness of the clear lacquer layer was adjusted so that after curing, clear lacquers resulted in a dry layer thickness of 30 to 50 g / m ² . Lead-doped mercury vapor lamps and radiation doses of 2,000 mJ / cm ^{2 were} used for the curing.

The laminates 1 of foam sheet and clear lacquer according to the invention could be packed without any problems and transported to their destination without causing damage to the surface. They could be easily connected to the outer walls of buildings using light pressure. An annual inspection of the laminates 1 according to the invention was no longer necessary because of their abrasion-resistant, scratch-resistant and weather-resistant surface.

Example 2

The production of a laminate 2 according to the invention for indoor use

Example 1 was repeated, only that instead of the clearcoat of preparation example 1, the clearcoat of preparation example 3 was used and the dry layer thickness of the clearcoat was 10 to 20 g / m ² . The resulting laminates 2 according to the invention were not only abrasion-resistant and scratch-resistant, but also flame-resistant, so that they were outstandingly suitable for indoor use in buildings or industrial plants. Example 3

The production of a laminate 3 according to the invention for indoor use

Example 2 was repeated, except that the water-based lacquer from preparation example 2 was applied in a dry layer thickness of 15 g / m ² by spraying before the clearcoat was applied. The clearcoat was then applied and cured as described. The resulting laminates 3 according to the invention were not only abrasion-resistant and scratch-resistant, but also flame-resistant and of a very good overall optical impression, so that they were outstandingly suitable for indoor use in buildings or industrial plants. Because of their intense color, they also had a high signal effect, which is why they could also be used as safety-related markings.

Example 4

The production of a laminate 4 according to the invention for outdoor use

Example 1 was repeated, except that before the laminates 1 according to the invention were used, a layer of the adhesive according to Preparation Example 4 was rolled on their side facing away from the clearcoat. The layer thickness of the adhesive layers was adjusted so that adhesive layers of a dry layer thickness of 60 to 65 g / m ² resulted after their hardening. Lead-doped mercury vapor lamps and radiation doses of 2,000 mJ / cm ^{2 were} used for the curing. The laminates 4 according to the invention could be packed without any problems and transported to the destination. They could easily be attached to walls using light pressure, after which they would stick very firmly in the long run. Even after the laminates had been heated to 190 ° C. for six hours, there was no decrease in the adhesive strength. Otherwise, the laminates 4 according to the invention had the same advantages as the laminates 1 according to the invention.

Example 5

The production of a laminate 5 according to the invention for outdoor use

Example 2 was repeated, except that before the laminates 2 according to the invention were used, a layer of the adhesive according to Preparation Example 4 was rolled on their side facing away from the clearcoat. The layer thickness of the adhesive layers was adjusted in such a way that adhesive layers of a dry layer thickness of 60 to 65 g / m ² resulted after their hardening. Lead-doped mercury vapor lamps and radiation doses of 2,000 mJ / cm ^{2 were} used for the curing.

The laminates 5 according to the invention could be packed without any problems and transported to their destination. They could easily be connected to walls using light pressure, after which they would stick very firmly in the long run. Even after the laminates had been heated to 190 ° C. for six hours, there was no decrease in the adhesive strength. Otherwise, the laminates 5 according to the invention had the same advantages as the laminates 2 according to the invention.

Example 6 The production of a laminate 6 according to the invention for outdoor use

Example 3 was repeated, except that before the laminates 3 according to the invention were used, a layer of the adhesive according to Preparation Example 4 was rolled on their side facing away from the clearcoat. The layer thickness of the adhesive layers was adjusted in such a way that adhesive layers of a dry layer thickness of 60 to 65 g / m ² resulted after their hardening. Lead-doped mercury vapor lamps and radiation doses of 2,000 mJ / cm ^{2 were} used for the curing.

The laminates 6 according to the invention could be packed without any problems and transported to their destination. They could easily be attached to walls using light pressure, after which they would stick very firmly in the long run. Even after the laminates had been heated to 190 ° C. for six hours, there was no decrease in the adhesive strength. Otherwise, the laminates 6 according to the invention had the same advantages as the laminates 3 according to the invention.

Example 7

The production of a laminate 7 according to the invention for the anise application

Example 4 was repeated, except that before the laminates 4 according to the invention were used, a layer of the adhesive according to Preparation Example 4 was rolled on their side facing away from the clearcoat. The layer thickness of the adhesive layers was adjusted so that after their hardening, adhesive layers one Dry layer thickness of 60 to 65 g / m ² resulted. Lead-doped mercury lamps under radiation doses of 2,000 mJ / cm ^{2 were} used for the curing.

The laminates 7 according to the invention could be packed without any problems and transported to their destination. They could easily be attached to walls using light pressure, after which they would stick very firmly in the long run. Even after the laminates had been heated to 190 ° C. for six hours, there was no decrease in the adhesive strength. Otherwise, the laminates 4 according to the invention had the same advantages as the laminates 4 according to the invention.

Claims

Foam laminate, process for its production and its use

1. Foam laminate containing at least one layer of a foam sealed by an outer skin, which contains or consists of natural rubber or synthetic rubber, and at least one clear coat hardened with actinic radiation.

2. Foam laminate according to claim 1, characterized in that the synthetic rubber is a styrene-butadiene rubber.

3. Foam laminate according to claim 1 or 2, characterized in that on the side of the foam layer facing away from the clear lacquer there is an adhesive layer hardened with actinic radiation, physically setting, containing nanoparticles and at least one tackifier.

4. Foam laminate containing at least one layer of a foam sealed by an outer skin, at least one clearcoat hardened with actinic radiation and, on the side of the layer facing away from the clearcoat, a physically setting, hardened with actinic radiation.

Nanoparticles and at least one tackifier-containing adhesive layer.

5. foam laminate according to claim 4, characterized in that the foam layer (s) is elastic or soft-elastic or are.

6. foam laminate according to one of claims 1 to 5, characterized in that at least its side facing away from the clearcoat is substantially or completely planar.

7. foam laminate according to one of claims 1 to 6, characterized in that it is planar overall.

8. foam laminate according to one of claims 1 to 7, characterized in that between the outer skin

Foam layer or outer foam layer and the underside of the clear coat is at least one color and / or effect base coat.

9. foam laminate according to one of claims -1. to 8, characterized in that at least one of the clearcoats contains at least one transparent filler.

10. Foam laminate according to one of claims 1 to 9, characterized in that the clear coat or, at least one of the

Clear coats and / or the base coat contains or contain at least one flame retardant.

11. A method for producing a foam laminate according to one of claims 1 to 3, characterized in that the

The outer skin of one side of the foam layer or of the outer foam layer, which contains or consists of natural rubber or synthetic rubber, or at least one clear coat curable with actinic radiation is applied to a color and / or effect coating thereon and cured with actinic radiation.

12. The method according to claim 11, characterized in that on the side of the foam coating (s) facing away from the clearcoat or the base coat and the clearcoat, an adhesive curable with actinic radiation is applied and the resulting adhesive layer is cured with actinic radiation or, alternatively, the adhesive onto one applied temporary carrier, the resulting adhesive layer cures with actinic radiation and connects the resulting physically setting, self-supporting adhesive film before or after removal of the temporary carrier with said side of the foam layer (s).

13. A method for producing a foam laminate according to one of claims 4 to 10, characterized in that

(I) at least applies a curable with actinic radiation clear coat on the outer skin of one side of the foam layer or the outer layer of foam or a color-imparting thereto located and / or effect ^"Painting and with actinic radiation, and

(II) an adhesive curable with actinic radiation is applied to the side of the foam layer (s) facing away from the clearcoat or the basecoat and the clearcoat and the resulting

The adhesive layer cures with actinic radiation or alternatively the adhesive is applied to a temporary carrier, the resulting adhesive layer cures with actinic radiation and the resulting physically setting, self-supporting adhesive film before or after Removing the temporary support connects to said side of the foam layer (s).

14. The method according to any one of claims 11 to 13, characterized in that the clear lacquer curable with actinic radiation

at least one binder containing, on average, at least one reactive functional group, containing a bond which can be activated with actinic radiation, in the molecule (“clear coat binder”),

at least one low molecular weight compound with at least one reactive functional group, containing a bond which can be activated with actinic radiation (“reactive thinner”), and

at least one photoinitiator

contains.

15. The method according to any one of claims 11 to 14, characterized in that the clear lacquer curable with actinic radiation contains at least one transparent filler and / or at least one flame retardant.

16. The method according to any one of claims 11 to 15, characterized in that the adhesive curable with actinic radiation

- at least one tackifier, at least one low molecular weight compound with at least one reactive functional group, containing a bond which can be activated with actinic radiation ("reactive diluent"), and

nanoparticles

contains.

17. The method according to claim 16, characterized in that the adhesive contains at least one photoinitiator.

18. The method according to any one of claims 14 to 17, characterized in that the coloring and / or effect-imparting basecoat by application of at least one physically curing, coloring and / or effect-imparting, aqueous basecoat comprising

at least one water-dispersible or soluble, physically curing binder ("basecoat binder") and

at least one coloring and / or effect pigment,

on the outer skin of the foam layer or the outer

Foam layer and physical hardening of the resulting basecoat layer (s) is produced.

19. The method according to any one of claims 14 to 18, characterized in that those which can be activated with actinic radiation

Bonds from the group consisting of carbon Hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon

Phosphorus or carbon-silicon single bonds or double bonds can be selected.

5

20. The method according to claim 19, characterized in that carbon-carbon double bonds ("double bonds") are used.

10. The method according to claim 20, characterized in that the double bonds as (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, ethenylarylene,

Dicyclopentadienyl, norbomenyl, isoprenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Ethenylarylen-,

15 dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or ethenylarylene, dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or

Butenyl ester groups are present.

22. Use of the foam laminate according to one of claims 1 to 10 or of the foam laminate produced by the method according to one of claims 11 to 21 for decorative, signaling and / or thermally, magnetically and / or electrically insulating coating of objects.

25

23. Use according to claim 22, characterized in that the objects are buildings, industrial plants or parts thereof.