DE102011079299A1 - Composite material useful as a layer of sheet-like component, which is useful e.g. in house construction, comprises metallic fibrous non-woven fabric or metal grid, polymer matrix and microcapsules with capsule core and capsule wall - Google Patents

Abstract

Composite material comprises a metallic fibrous non-woven fabric and/or a metal grid, a polymer matrix and microcapsules with a capsule core made of latent heat storage material and a capsule wall comprising a polymer, distributed in the polymer matrix. The composite material is obtainable by contacting the metallic fibrous non-woven fabric and/or the metal grid and an organic reactive binding agent comprising the microcapsules, and hardening the binding agent. Independent claims are also included for: (1) producing the composite material, comprising contacting the metallic fibrous non-woven fabric and/or the metal grid and the organic reactive binding agent comprising the microcapsules and hardening the binding agent by crosslinking reaction or by polymerization; (2) a sheet-like component obtainable by applying a polyurethane compact layer (i) and a polyurethane hard foam layer (ii) on a metal covering layer (iii) and applying a second metal covering layer and optionally an additional polyurethane compact layer between the adjacent layers (iii) and (ii); and (3) producing the sheet-like component, comprising applying a layer (B) made of the composite material and the polyurethane hard foam layer (ii) on the metal covering layer (iii) and applying the second metal covering layer and optionally a further layer made of the composite material, between the adjacent layers (iii) and (B).

Description

The present application relates to a composite material comprising a metallic nonwoven fabric and / or metal mesh and a polymer matrix and distributed therein microcapsules with a capsule core of latent heat storage material and a polymer as a capsule wall, a process for its preparation and its use as a heat-retaining building material in housing, industrial construction, cold storage , in sectional doors, in office containers or in caravans and shipbuilding.

Composite materials are often used in construction applications because they allow a variety of material properties to be combined and modified. Thus, for example, composite elements of two metallic cover layers and a rigid polyurethane foam layer, so-called sandwich elements, both used as components in housing as well as industrial construction for hall roofs and facades, as construction elements in cold storage, in sectional doors, in office containers or caravans and shipbuilding. Due to their very good insulation properties, they are widely used there. Their low mass, however, causes the buildings can hardly buffer temperature peaks. Due to internal and external temperature loads, such buildings heat up very quickly inside. This negative characteristic is summarized under the term "barrack climate".

Building materials and latent heat storage materials - also referred to as phase change materials (PCM for short) - have been investigated in recent years as new material combinations. Their mode of operation is based on the transformation enthalpy (melting enthalpy) occurring during the solid / liquid phase transition, which means an energy absorption or energy release to the environment at constant temperature. They can thus be used for temperature maintenance in a defined temperature range. Since the latent heat storage materials are also liquid depending on the temperature, they can not be processed directly with building materials, because emissions to the room air or the separation of the building material would be to be feared.

The EP-A-1 703 033 teaches components for interior fitting with two metal cover layers, wherein the intermediate layer contains a latent heat storage material. According to one embodiment, the heat-storing material is applied discontinuously and filled the gap with a thermally conductive material. The heat-storing material is macroscopically surrounded by a shell.

The WO 2006/021306 teaches a composite material with a metal topcoat, a gypsum board, and a rigid polyurethane foam layer connecting these two panels. The gypsum board contains microcapsules with a capsule core of latent heat storage material. However, gypsum board components have a span limited to 2 to 3 meters, which limits their capabilities.

The PCT / EP 2009/066386 teaches a sheet-like composite element comprising two metallic cover layers, a rigid polyurethane foam layer, and a polyurethane compact layer containing microcapsules having a capsule core of latent heat storage material. These components are self-supporting and can also be used in spanning constructions.

All of these documents have in common that measured by the total amount of latent heat storage material introduced an unsatisfactory efficiency is achieved. This can be determined by measuring the heat absorption over time.

The US 5,224,356 teaches the use of microencapsulated latent heat storage materials in an epoxy resin matrix for cooling electrical components. According to one embodiment, the addition of encapsulated copper powder is advantageous.

The object of the present invention was to provide a composite material which has improved heat storage with a view to faster heat removal. Furthermore, it should also have a better efficiency.

This object is achieved by a composite material comprising a metallic nonwoven fabric and / or metal mesh and a polymer matrix and distributed therein microcapsules having a capsule core of latent heat storage material and a polymer as a capsule wall, wherein the composite material is obtainable by contacting the metallic nonwoven fabric and / or metal mesh and a organic reactive binder containing the microcapsules and subsequent curing of the binder.

The composite material has substantially no voids, but is filled by the polymer matrix. For the purposes of the present invention, this means that up to 20% by volume, preferably up to 15% by volume, in particular not more than 5% by volume, of the composite body contains air or another inert gas such as nitrogen.

Non-woven fabrics are familiar to the expert. In the context of this document, this is intended to mean, for example, nonwovens, scrims, knitted fabrics, woven or knitted fabrics or combinations thereof. A nonwoven is usually understood to mean a nonwoven and nonwoven fabric which may contain fibers or ribbons. Under a clutch is usually understood loosely superimposed or nested fibers that may be straight or textured. Knitted fabrics are textile structures that are created by forming intertwined meshes that hold each other. Fabrics are textile structures made of perpendicular crossing yarns or ribbons. According to the invention is advantageous as fiber webs z. B. steel wool loose density used. The fiber webs which can be used according to the invention are preferably sheet-like structures of any desired thickness, more preferably the thickness of the sheet-like structures is 1 to 30 mm, in particular 1 to 20 mm or 1 to 10 mm.

The fiber webs that can be used according to the invention may consist of tapes or of fibers, the latter being preferably used. Suitable bands are for example tapes, in particular those made of metal fibers. As fibers staple fibers or filaments (filaments) can be used.

Under metal grate the expert usually understands expanded metal, also referred to as expanded metal. Expanded metal is a metal material with openings. They result from staggered cuts without loss of material and stretching at the same time. Usual mesh lengths are in the range of 1 mm to 300 mm. Suitable mesh shapes are, for example, diamond meshes, longstitch meshes, hexagonal meshes, circular meshes or square meshes.

Preferred metals for the nonwoven fabrics and metal mesh are steel, stainless steel, copper, aluminum, silver and / or gold.

The polymer matrix containing the microcapsules is formed by curing the organic reactive binder. This curing of the binder is usually done by a crosslinking reaction or polymerization. The polymer matrix is preferably a polyurethane, polyepoxide, polyester, cast polyamide, silicone, rubber or polysulfide. By reactive binders is meant binder systems which cure by mixing at least two mutually reactive components after the reaction has been initiated by a starting mechanism. This can be z. B. by increasing the temperature, UV irradiation, pH change or the like.

Preferred polymer matrices are compact polyurethanes, ie unfoamed polyurethanes. This is to be understood as meaning a polyurethane having a density of 400 to 1200, preferably 500 to 1100, particularly preferably 800 to 1000 kg / m ³ .

Its preparation is usually carried out by reacting organic di- and / or polyisocyanates a) with compounds having at least two isocyanate-reactive hydrogen atoms b), preferably polyols. If it is the not yet cross-linked mixture of components, is referred to below by a reactive polyurethane compact system.

The reaction ratio is preferably selected such that in the reaction mixture the ratio of the number of isocyanate groups to the number of isocyanate-reactive hydrogen atoms is 0.8 to 1.8 to 1, preferably 1 to 1.6 to 1.

Suitable organic di- and polyisocyanates a) are aliphatic, cycloaliphatic and preferably aromatic polyfunctional isocyanates. Specific examples include 2,4- and 2,6-toluene diisocyanate (TDI) and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate (MDI) and the corresponding mixtures of isomers, mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanates, polyphenyl-polymethylene-polyisocyanates, mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethane-diisocyanates and polyphenyl-polymethylene polyisocyanates (crude MDI) and mixtures of crude MDI and tolylene diisocyanates. The organic di- and polyisocyanates can be used individually or in the form of mixtures.

Frequently, so-called modified polyfunctional isocyanates, ie products obtained by chemical reaction of organic di- and / or polyisocyanates are used. Examples include uretdione, carbamate, carbodiimide, allophanate, isocyanurate and / or urethane groups-containing di- and / or polyisocyanates. The modified organic di- and polyisocyanates may optionally together or with unmodified organic di- and polyisocyanates such as 2,4'-, 4,4'-diphenylmethane diisocyanate, crude MDI, 2,4- and / or 2,6-toluylene Diisocyanate are mixed.

In addition, it is also possible to use reaction products of polyfunctional isocyanates with polyhydric polyols, so-called prepolymers, and mixtures thereof with other diisocyanates and polyisocyanates.

Has proven particularly useful as organic polyisocyanate crude MDI having an NCO content of 29 to 33 wt .-% and a viscosity at 25 ° C in the range of 100 to 2000 mPa · s, in particular in the range 100 to 800 mPa · s.

Suitable compounds having at least two isocyanate-reactive hydrogen atoms b) are generally those which carry at least two reactive groups selected from OH, SH, NH, NH ₂ groups and CH-acidic groups in the molecule, in particular polyetherpolyols and polyester polyols.

The polyester polyols are usually obtained by condensation of polyfunctional alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, butanediol, trimethylolpropane, glycerol, pentaerythritol, with polyfunctional carboxylic acids having 2 to 12 carbon atoms, for example succinic acid, Glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid and preferably phthalic acid, isophthalic acid, terephthalic acid, the isomers of naphthalenedicarboxylic acids or the anhydrides of the acids.

As further starting materials in the preparation of the polyester polyols and hydrophobic substances can be used. The hydrophobic substances are water-insoluble substances which contain a non-polar organic radical and have at least one reactive group selected from hydroxyl, carboxyl, carboxylic acid ester radical or mixtures thereof. The equivalent weight of the hydrophobic materials is preferably between 130 and 1000 g / mol. For example, fatty acids such as stearic acid, oleic acid, palmitic acid, lauric acid or linoleic acid, as well as fats and oils such as castor oil, corn oil, sunflower oil, soybean oil, coconut oil, olive oil or tall oil can be used. If polyester polyols contain hydrophobic substances, the proportion of hydrophobic substances in the total monomer content of the polyester polyol is preferably 1-30 mol%, particularly preferably 4-15 mol%.

The polyester polyols used usually have a functionality of 1.5-4 and an OH number of 50-400, preferably 150-300 mg KOH / g.

The polyether polyols are prepared by known processes, for example by anionic polymerization of alkylene oxides with the addition of at least one starter molecule in the presence of catalysts, for example alkali metal hydroxides.

The alkylene oxides used are usually ethylene oxide and / or propylene oxide, preferably pure 1,2-propylene oxide.

As starting molecules in particular compounds having at least 2, preferably 2 to 4 hydroxyl groups or having at least two primary amino groups in the molecule are used.

As starting molecules having at least 2, preferably 2 to 8 hydroxyl groups in the molecule are preferably propylene glycol, dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol, sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resoles such as oligomeric condensation products of phenol and formaldehyde and Mannich Condensates of phenols, formaldehyde and dialkanolamines and melamine used.

As starting molecules having at least two primary amino groups in the molecule are preferably aromatic di- and / or polyamines, for example phenylenediamines, 2,3-, 2,4-, 3,4- and 2,6-toluenediamine and 4,4'-, 2 , 4'- and 2,2'-diamino-diphenylmethane and aliphatic di- and polyamines, such as ethylenediamine used.

The polyether polyols have a functionality of 2 to 4, preferably 2 to 3, and hydroxyl numbers of preferably 30 mg KOH / g to 800 mg KOH / g and in particular 150 mg KOH / g to 570 mg KOH / g.

The compounds having at least two isocyanate-reactive hydrogen atoms b) also include the optionally used chain extenders and crosslinkers. To modify the mechanical properties, the addition of difunctional chain extenders, trifunctional and higher functional crosslinking agents or optionally also mixtures thereof may prove to be advantageous. As chain extenders and / or crosslinking agents it is preferred to use alkanolamines, diols and / or triols, in particular diols and / or triols having molecular weights of less than 400, preferably 60 to 300.

Chain extenders, crosslinking agents or mixtures thereof are expediently used in an amount of from 1 to 30% by weight, preferably from 2 to 10% by weight, based on component b), preferably the polyol component.

Further information on the polyether polyols and polyester polyols used and their preparation can be found, for example, in Kunststoffhandbuch, Volume 7 "Polyurethane", edited by Günter Oertel, Carl-Hanser-Verlag Munich, 3rd edition, 1993 ,

The preparation of the compact polyurethane is usually carried out in the presence of catalysts and, if necessary, further auxiliaries and / or additives, which are generally known in polyurethane chemistry and in the DE-A-101 24 333 described, to which express reference is made. Suitable auxiliaries and / or additives are the substances known per se for this purpose, for example surface-active substances, fillers, pigments, dyes, flameproofing agents, hydrolysis protection agents, antistatic agents, fungistatic and bacteriostatic agents. Further details about the starting materials, catalysts and auxiliaries and / or additives used for carrying out the process according to the invention can be found, for example, in US Pat Kunststoffhandbuch, volume 7, "Polyurethane" Carl-Hanser-Verlag Munich, 1st edition, 1966, 2nd edition, 1983 and 3rd edition, 1993 ,

As catalysts, it is possible to use all compounds which accelerate the isocyanate-water reaction or the isocyanate-polyol reaction. These include amine-based catalysts and catalysts based on organic metal compounds.

As catalysts based on organic metal compounds, for example, organic tin compounds, such as tin (II) salts of organic carboxylic acids, such as tin (II) acetate, tin (II) octoate, tin (II) ethyl hexoate and tin (II) laurate and the dialkyltin (IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, and also bismuth carboxylates, such as bismuth (III) neodecanoate, bismuth-2 ethylhexanoate and bismuth octanoate or alkali metal salts of carboxylic acids such as potassium acetate or potassium formate.

The catalyst used is preferably a mixture containing at least one tertiary amine. These tertiary amines are usually compounds which may also carry isocyanate-reactive groups, such as OH, NH or NH ₂ groups. Some of the most commonly used catalysts are bis (2-dimethylaminoethyl) ether, N, N, N, N-pentamethyldiethylenetriamine, N, N, N-triethylaminoethoxyethanol, dimethylcyclohexylamine, dimethylbenzylamine, triethylamine, triethylenediamine, pentamethyldipropylenetriamine, dimethylethanolamine , N-methylimidazole, N-ethylimidazole, tetramethylhexamethylenediamine, tris (dimethylaminopropyl) hexahydrotriazine, dimethylaminopropylamine, N-ethylmorpholine, diazabicycloundecene and diazabicyclononene.

Suitable flame retardants are, for example, brominated ethers (Ixol B 251), brominated alcohols, such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol. Preference is given to using bromine-free flame retardants, such as chlorinated phosphates, such as. Tris (2-chloroethyl) phosphate, tris (2-chloroisopropyl) phosphate (TCPP), tris (1,3-dichloroisopropyl) phosphate, tris (2,3-dibromopropyl) phosphate and tetrakis (2-chloroethyl ) -ethylenediphosphate, or mixtures thereof.

Besides the abovementioned halogen-substituted phosphates, it is also possible to use inorganic flameproofing agents such as red phosphorus, red phosphorus-containing finishes, expandable graphite, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate or cyanuric acid derivatives such as melanin, or mixtures of at least two flame retardants such as ammonium polyphosphates and melanin and optionally starch.

Diethyl ethane phosphonate (DEEP), triethyl phosphate (TEP), dimethyl propyl phosphonate (DMPP), diphenyl cresyl phosphate (DPK) and others can be used as other liquid halogen-free flame retardants.

The flame retardants are used in the context of the present invention preferably in an amount of 0 to 25% based on the total weight of the components of the polyurethane compact system.

The diisocyanates and polyisocyanates and the compounds containing isocyanate-reactive hydrogen atoms are reacted with one another in amounts such that the isocyanate index is in a range between 90 and 700, preferably in the range from 100 to 140.

The compact polyurethane is produced without added blowing agents. However, the polyols used may still contain residual water, which acts as a blowing agent. Preference is given to using polyols whose proportion of residual water is <1% by weight, preferably <0.5% by weight, in particular <0.2% by weight. The proportion of water can be reduced by "drying" the polyols by water-absorbing additives such as molecular sieve (physically active additives) or oxazolidines (chemically active additives).

According to a further embodiment, an anti-foaming agent or water-absorbing additives is additionally added to the reactive polyurethane compact system.

microcapsules

The microcapsules according to the invention contained in the reactive binder comprise a capsule core of latent heat storage material and a capsule wall of polymer. The capsule core consists predominantly, to more than 95 wt .-%, of latent heat storage material. The capsule core can be both solid and liquid, depending on the temperature.

Due to the manufacturing process, a protective colloid is generally incorporated into the capsule wall and is thus likewise part of the capsule wall. In general, the surface of the polymer in particular has the protective colloid. Thus, up to 10% by weight, based on the total weight of the microcapsules, may be protective colloid.

The average particle size of the capsules (Z means by means of light scattering) is 0.5 to 50 μm, preferably 0.5 to 30 μm. The weight ratio of capsule core to capsule wall is generally from 50:50 to 95: 5. Preferred is a core / wall ratio of 70:30 to 93: 7.

By definition, latent heat storage materials are substances which have a phase transition in the temperature range in which heat transfer is to be carried out, and are therefore often referred to in the literature as PCM (Phase Change Material). Preferably, it is an organic lipophilic substance having its solid / liquid phase transition in the temperature range of -20 to 120 ° C.

Examples include:
Aliphatic hydrocarbon compounds such as saturated or unsaturated C ₁₀ -C ₄₀ hydrocarbons which are branched or preferably linear, aromatic hydrocarbon compounds, saturated or unsaturated C ₆ -C ₃₀ fatty acids, fatty alcohols and the so-called oxo alcohols, which are obtained by hydroformylation of α-olefins and further reactions, ethers of fatty alcohols, C ₆ -C ₃₀ fatty amines, esters such as C ₁ -C ₁₀ alkyl esters of fatty acids such as propyl palmitate, methyl stearate or methyl palmitate and preferably their eutectic mixtures or methyl cinnamate, natural and synthetic waxes and halogenated hydrocarbons such she in the WO 2009/077525 are listed, the disclosure of which is expressly incorporated by reference.

Furthermore, mixtures of these substances are suitable, as long as it does not come to a melting point lowering outside the desired range, or the heat of fusion of the mixture is too low for a meaningful application.

Advantageously, for example, the use of pure n-alkanes, n-alkanes with a purity of greater than 80% or of alkane mixtures, as obtained as a technical distillate and are commercially available as such.

Furthermore, it may be advantageous to add soluble compounds to the lipophilic substances so as to prevent the crystallization delay which sometimes occurs with the non-polar substances. Advantageously, one uses, as in the US Pat. No. 5,456,852 described, compounds having a 20 to 120 K higher melting point than the actual core substance. Suitable compounds are the fatty acids mentioned above as lipophilic substances, fatty alcohols, fatty amides and aliphatic hydrocarbon compounds. They are added in amounts of from 0.1 to 10% by weight, based on the capsule core.

The latent heat storage materials are - depending on the temperature range in which the heat storage is desired - selected. For example, used for heat storage in building materials in a moderate climate preferred latent heat storage materials, the solid / liquid phase transition in the temperature range of 0 to 60 ° C. For indoor applications, for example, one chooses single substances or mixtures with transformation temperatures of 15 to 30 ° C.

Preferred latent heat storage materials are aliphatic hydrocarbons, particularly preferably those listed above by way of example. In particular, aliphatic hydrocarbons having 14 to 20 carbon atoms and mixtures thereof are preferred.

In principle, the materials known for the microcapsules for copying papers can be used as the polymer for the capsule wall. So it is possible, for example, the latent heat storage materials according to in the GB-A 870476 . US 2,800,457 . US 3,041,289 to encapsulate in gelatin with other polymers.

Preferred wall materials, since they are very resistant to aging, are thermosetting polymers. Under thermosetting wall materials are to be understood that do not soften due to the high degree of crosslinking, but decompose at high temperatures. Suitable thermosetting wall materials are, for example, highly crosslinked formaldehyde resins, highly crosslinked polyureas and highly crosslinked polyurethanes, as well as highly crosslinked methacrylic acid ester polymers and uncrosslinked methacrylic acid ester polymers.

• – Triazinen wie Melamin
• – Carbamiden wie Harnstoff
• – Phenolen wie Phenol, m-Kresol und Resorcin
• – Amino- und Amidoverbindungen wie Anilin, p-Toluolsulfonamid, Ethylenharnstoff und Guanidin,

oder ihren Mischungen.Formaldehyde resins are understood as meaning reaction products of formaldehyde with

• - Triazines such as melamine
• - Carbamides such as urea
• Phenols such as phenol, m-cresol and resorcinol
• Amino and amido compounds such as aniline, p-toluenesulfonamide, ethyleneurea and guanidine,

or their mixtures.

As the capsule wall material preferred formaldehyde resins are urea-formaldehyde resins, urea-resorcinol-formaldehyde resins, urea-melamine resins and melamine-formaldehyde resins. Also preferred are the C ₁ -C ₄ alkyl, in particular methyl ether of these formaldehyde resins and the mixtures with these formaldehyde resins. In particular, melamine-formaldehyde resins and / or their methyl ethers are preferred.

In the methods known from copying papers, the resins are used as prepolymers. The prepolymer is still soluble in the aqueous phase and migrates in the course of the polycondensation at the interface and surrounds the oil droplets. Methods for microencapsulation with formaldehyde resins are well known and are described, for example, in US Pat EP-A-562,344 and EP-A-974 394 described.

Capsule walls of polyureas and polyurethanes are also known from the copying papers. The capsule walls are formed by reaction of NH ₂ groups or OH-containing reactants with di- and / or polyisocyanates. Suitable isocyanates are, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate and 2,4- and 2,6-toluene diisocyanate. Also mentioned are polyisocyanates such as biuret derivatives, polyuretonimines and isocyanurates. Suitable reactants are: hydrazine, guanidine and its salts, hydroxylamine, di- and polyamines and amino alcohols. Such interfacial polyaddition processes are known, for example, from US 4,021,595 . EP-A 0 392 876 and EP-A 0 535 384 known.

Preference is given to microcapsules whose capsule wall is an uncrosslinked or crosslinked polymer based on acrylic and / or methacrylic acid esters, acrylic acid, methacrylic acid and / or maleic acid.

The polymers of the capsule wall generally contain at least 30 wt .-%, preferably at least 40 wt .-%, in a particularly preferred form at least 50 wt .-%, in particular at least 60 wt .-%, most preferably at least 70 wt. -% and up to 100 wt .-%, preferably at most 90 wt .-%, in particular at most 85 wt .-% and most preferably at most 80 wt .-% of at least one monomer from the group comprising C ₁ -C ₂₄ alkyl esters of acrylic and / or methacrylic acid, acrylic acid, methacrylic acid and maleic acid (monomers I), copolymerized, based on the total weight of the monomers.

Furthermore, the polymers of the capsule wall preferably contain at least 10% by weight, preferably at least 15% by weight, preferably at least 20% by weight and generally at most 70% by weight, preferably at most 60% by weight and in particular more preferably Form at most 50 wt .-% of one or more bi- or polyfunctional monomers which are insoluble or sparingly soluble in water (monomers II) polymerized, based on the total weight of the monomers.

In addition, the polymers may contain up to 40% by weight, preferably up to 30% by weight, in particular up to 20% by weight, of other monomers III in copolymerized form. Preferably, the capsule wall is composed only of monomers of groups I and II.

Preferably, the polymer of the capsule wall of the microcapsules by free radical polymerization of From 30 to 100% by weight one or more monomers (monomers I) from the group comprising C ₁ -C ₂₄ -alkyl esters of acrylic and / or methacrylic acid, acrylic acid, methacrylic acid and maleic acid, 0 to 70% by weight one or more bi- or polyfunctional monomers (monomers II) which is insoluble or sparingly soluble in water and 0 to 40% by weight one or more other monomers (monomers 111), in each case based on the total weight of the monomers.

Suitable monomers I are C ₁ -C ₂₄ -alkyl esters of acrylic and / or methacrylic acid and the unsaturated C ₃ - and C ₄ -carboxylic acids, such as acrylic acid, methacrylic acid and maleic acid. Suitable monomers I are isopropyl, isobutyl, sec-butyl and tert-butyl acrylate and the corresponding methacrylates, and particularly preferably methyl, ethyl, n-propyl and n-butyl acrylate and the corresponding methacrylates , Generally, the methacrylates and methacrylic acid are preferred.

Suitable monomers II are bi- or polyfunctional monomers which are insoluble or sparingly soluble in water but have good to limited solubility in the lipophilic substance. Low solubility is to be understood as meaning a solubility of less than 60 g / l at 20 ° C. By bi- or polyfunctional monomers is meant compounds having at least two non-conjugated ethylenic double bonds. In particular, divinyl and polyvinyl monomers come into consideration. They cause a crosslinking of the capsule wall during the polymerization. One or more divinyl monomers and one or more polyvinyl monomers and divinyl monomers may be copolymerized in admixture with polyvinyl monomers.

Suitable divinyl monomers are divinylbenzene and divinylcyclohexane. Preferred divinyl monomers are the diesters of diols with acrylic acid or methacrylic acid, furthermore the diallyl and divinyl ethers of these diols. Examples which may be mentioned are ethanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, methallyl methacrylamide, allyl acrylate and allyl methacrylate. Particularly preferred are propanediol, butanediol, pentanediol and hexanediol diacrylate and the corresponding methacrylates.

Preferred polyvinyl monomers are the polyesters of polyols with acrylic acid and / or methacrylic acid, furthermore the polyallyl and polyvinyl ethers of these polyols, trivinylbenzene and trivinylcyclohexane. Particularly preferred are trimethylolpropane triacrylate and methacrylate, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, pentaerythritol triacrylate and pentaerythritol tetraacrylate and their technical mixtures.

Preference is given to the combinations of divinyl and polyvinyl monomers, such as butanediol diacrylate and pentaerythritol tetraacrylate, hexanediol diacrylate and pentaerythritol tetraacrylate, butanediol diacrylate and trimethylolpropane triacrylate, and also hexanediol diacrylate and trimethylolpropane triacrylate.

Suitable monomers III are other monomers which are different from the monomers I and II, such as vinyl acetate, vinyl propionate, vinylpyridine and styrene or α-methylstyrene. Particularly preferred are itaconic acid, vinylphosphonic acid, maleic anhydride, 2-hydroxyethyl acrylate and methacrylate, acrylamido-2-methylpropanesulfonic acid, methacrylonitrile, acrylonitrile, methacrylamide, N-vinylpyrrolidone, N-methylolacrylamide, N-methylolmethacrylamide, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.

The production process of the microcapsules is a so-called in situ polymerization. The principle of microcapsule formation is based on the preparation of a stable oil-in-water emulsion from the monomers, a radical initiator, the protective colloid and the lipophilic substance to be encapsulated. Subsequently, the polymerization of the monomers is started by heating and optionally controlled by further increase in temperature, wherein the resulting polymers form the capsule wall, which encloses the lipophilic substance. This general principle is used for example in the DE-A-10 139 171 whose contents are expressly referred to.

The starting emulsion is stabilized using a protective colloid. Suitable organic or inorganic protective colloids and their amounts are in the WO 2008/071649 whose disclosure is expressly referred to.

Furthermore, it is possible for costabilization to add surfactants, preferably nonionic surfactants. Suitable surfactants can be found in the "Handbook of Industrial Surfactants", the contents of which are expressly incorporated by reference. The surfactants can be used in an amount of 0.01 to 10 wt .-% based on the water phase of the emulsion.

The preparation of the preferred polymethacrylate-based microcapsules and the auxiliaries suitable therefor, such as free-radical initiators, optionally regulators, are known and are described, for example, in US Pat EP-A-1 029 018 . DE 10 163 162 and WO 2008/071649 described, the disclosure of which is expressly incorporated by reference. Thus, in particular the peroxo and azo compounds mentioned herein as radical initiators for the free-radical polymerization reaction, advantageously in amounts of 0.2 to 5 wt .-%, based on the weight of the monomers used.

The microcapsules are distributed in the polymer matrix. The distribution may be irregular, but is preferably homogeneous. A homogeneous distribution is ideally achieved by uniformly dispersing the microcapsules in the organic reactive binder.

Optionally, the dispersion can be assisted by a dispersant as an excipient, which is given for example with the microcapsules to a single component of the reactive system, for example, to the polyol component in the case of a polyurethane. Dispersants which may be mentioned are, for example, commercially available dispersants, such as the BYK-W additive series from BYK-Chemie GmbH. Thus, the flowability of the component containing the memory material and the composite material can be improved.

The amount of microcapsules can be chosen freely and is determined by the desired amount of microcapsules in the composite material. Typically, this is determined by the desired maximum processing viscosity of the starting components for the composite.

Usually 15 to 50 parts by weight of microcapsules are used per 100 parts by weight of polymer matrix.

The composite material contains, based on the total amount of metallic fiber fleece and / or metal mesh, polymer matrix and microcapsules 5 to 50 vol.% preferably 10 to 20 vol .-%, metallic non-woven fabric and / or metal mesh and 50 to 95 vol.% preferably 80 to 90% by volume, polymer matrix containing the microcapsules.

The preparation of the composite material by contacting the reactive binder and the metal fleece and / or metal mesh can be done in many ways.

Thus, according to a variant of the method, the metallic fiber fleece and / or metal lattice can be initially introduced and the reactive binder containing the microcapsules can be incorporated, for example, by casting, spraying, suction, knife coating, pinching or shaking. The two components of the However, reactive binder systems can also be brought into contact first on the metallic nonwoven fabric and / or metal mesh, for example by means of 2-component spray application plus solids metering or premixing in one component of the reactive binder system. In the following, by applying the reactive binder containing the microcapsules, both the addition of the reactive binder system containing the microcapsules and the addition of combinations of individual components and microcapsules in any order of addition should be understood.

Application of the composite material

The composite material is suitable for the production of films, sheets, shaped articles, coatings and fillings.

Coatings are obtained by applying to a substrate, the metallic fleece and the reactive binder containing the microcapsules. After curing of the binder, the composite material depending on the substrate can be removed as a foil or lift off as a plate.

Preferably, the composite material is used as a layer of a sheet-like component.

Flat element

In the context of this application, the term sheet-like component is to be understood to mean a structure whose thickness is small compared to both its length and its width. Its thickness is preferably ≦ 1/5 of its length as well as its width.

The sheet-like components may have a topology, which is generated for example by shaping process.

• 1. metallische Deckschicht (A),
• 2. Schicht aus erfindungsgemäßem Verbundmaterial (B),
• 3. Polyurethanhartschaumschicht (C) und
• 4. eine metallische Deckschicht (A').

According to a preferred embodiment, the sheet-like component has two metallic cover layers, a layer of the composite material according to the invention and a rigid polyurethane foam layer. The polymer matrix of the composite material is preferably a compact polyurethane. Seen from the interior of the room, the following sequence of layers results:

• 1. metallic cover layer (A),
• 2nd layer of composite material (B) according to the invention,
• 3. Polyurethane hard foam layer (C) and
• 4. a metallic cover layer (A ').

• 1. metallische Deckschicht (A),
• 2. Schicht aus erfindungsgemäßem Verbundmaterial (B),
• 3. Polyurethanhartschaumschicht (C)
• 4. Schicht aus erfindungsgemäßem Verbundmaterial (B) und
• 5. eine metallische Deckschicht (A).

According to a further embodiment, the sheet-like component has a second layer of composite material according to the invention. Seen from the interior of the room, the following sequence of layers results:

• 1. metallic cover layer (A),
• 2nd layer of composite material (B) according to the invention,
• 3. Polyurethane hard foam layer (C)
• 4th layer of inventive composite material (B) and
• 5. a metallic cover layer (A).

In sandwich panels of the construction A-B-C-A ', the metallic cover layer A' is usually outdoors. Furthermore, indoor applications are conceivable as ceiling panels, wall panels and room-in-room systems. For applications such as room-in-room systems or internal partitions, sheet-like construction elements having the structure A-B-C-B-A are preferred.

The metallic cover layer

The two metallic cover layers can be different. One then distinguishes the boundary to the interior of the room (A) and the outer covering layer (A '). The two layers do not have to agree either in their form or in their material. On the other hand, surface-shaped components with the construction A-B-C-B-A preferably have the same metallic cover layers.

As cover layers flexible or rigid, preferably rigid cover layers can be used. The cover layer does not necessarily have to be profiled, but can also be used in a smooth form or as a stamped, contoured or shaped sheet metal (eg pan optics).

The metallic cover layer may be present in the metallic state or in the coated state. Preferred metals are aluminum, steel, galvanized or aluminized steel, copper, zinc, other metal strips or metal sheets. Preference should be given to aluminum foils, aluminum, copper or steel sheets, particularly preferably steel sheets.

The metallic cover layers can be pretreated, for example by corona, arc, plasma or other conventional methods. The metallic cover layer, preferably the outer metallic cover layer (A '), can be modified with the usual materials used for such components in order to increase the weather resistance.

Frequently, the metallic cover layers are also provided with organic coatings as in the PCT / EP 2009/066386 to which disclosures are expressly incorporated by reference.

The layer of composite material according to the invention

This layer is preferably a composite material according to the invention with a compact polyurethane as the polymeric matrix. As a polyurethane, the above-described compact, so not foamed, polyurethane is suitable.

The polyurethane foam layer

The rigid foams used for composite elements made of rigid polyurethane foam have long been known and widely described in the literature. If a reactive foam system is mentioned below, this is understood to mean the mixture of the starting components.

By rigid polyurethane foam is meant a polymer layer having an average density of from 20 to 150, preferably from 25 to 100, particularly preferably from 30 to 70, kg / m ³ .

In the context of the invention is preferably a foam according to polyurethane rigid foam DIN 7726 understood, ie the foam has a compressive stress at 10% compression or compressive strength after DIN 53 421 / DIN EN ISO 604 of greater than or equal to 80 kPa, preferably greater than or equal to 150 kPa. Furthermore, the rigid polyurethane foam has after DIN ISO 4590 over a closed cell size of greater than 85%, preferably greater than 90%.

For the purposes of the present invention, the isocyanate index is understood as meaning the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups multiplied by 100. Isocyanate-reactive groups are understood to mean all isocyanate-reactive groups, including chemical blowing agents, contained in the reaction mixture, but not the isocyanate group itself. The isocyanates and the compounds containing isocyanate-reactive hydrogen atoms are reacted with each other in such amounts that the isocyanate index is in a range from 100 to 700, preferably from 115 to 180. In a further preferred embodiment, an isocyanate index of from 180 to 700, in particular from 200 to 500, is used. This is referred to as so-called polyisocyanurate-modified polyurethane foams or Polyisocyanuratschäumen.

They are usually prepared by reacting organic di- and / or polyisocyanates a) with compounds having at least two isocyanate-reactive hydrogen atoms b), preferably polyols.

Suitable organic diisocyanates and polyisocyanates a) are the abovementioned, preferably aromatic polyfunctional isocyanates and also the modified polyfunctional isocyanates. In addition, it is also possible to use reaction products of polyfunctional isocyanates with polyhydric polyols, so-called prepolymers, and mixtures thereof with other diisocyanates and polyisocyanates.

Has proven particularly useful as organic polyisocyanate crude MDI having an NCO content of 29 to 33 wt .-% and a viscosity at 25 ° C in the range of 100 to 2000 mPa · s, in particular in the range of 100 to 800 mPa · s ,

Suitable compounds having at least two isocyanate-reactive hydrogen atoms b) are generally those which contain at least two reactive groups selected from OH, SH, NH, NH ₂ - Wear groups and CH-acidic groups in the molecule, in particular polyether polyols and / or the abovementioned polyester polyols having OH numbers in the range of 50 to 800 mg KOH / g used.

The polyester polyols used usually have a functionality of 1.5-4 and an OH number of 50-400, preferably 150-300 mg KOH / g.

The polyether polyols are prepared by known processes, for example by anionic polymerization of alkylene oxides in the presence of catalysts, for example alkali metal hydroxides.

The alkylene oxides used are usually ethylene oxide and / or propylene oxide, preferably pure 1,2-propylene oxide.

In particular, compounds having at least 2, preferably 3 to 8 hydroxyl groups or having at least two primary amino groups in the molecule are used as starting molecules.

As starting molecules having at least 2, preferably 2 to 8 hydroxyl groups in the molecule are preferably trimethylolpropane, glycerol, pentaerythritol, sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resoles such as oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols , Formaldehyde and dialkanolamines and melamine used.

As starting molecules having at least two primary amino groups in the molecule are preferably aromatic di- and / or polyamines, for example phenylenediamines, 2,3-, 2,4-, 3,4- and 2,6-toluenediamine and 4,4'-, 2 , 4'- and 2,2'-diamino-diphenylmethane and aliphatic di- and polyamines, such as ethylenediamine used.

The polyether polyols have a functionality of preferably 2 to 8 and hydroxyl numbers of preferably 50 mg KOH / g to 800 mg KOH / g and in particular 150 mg KOH / g to 570 mg KOH / g.

The compounds having at least two isocyanate-reactive hydrogen atoms b) also include those optionally used with chain extenders and crosslinkers. To modify the mechanical properties, the addition of difunctional chain extenders, trifunctional and higher functional crosslinking agents or optionally also mixtures thereof may prove to be advantageous. As chain extenders and / or crosslinking agents it is preferred to use alkanolamines, diols and / or triols, in particular diols and / or triols having molecular weights of less than 400, preferably 60 to 300.

Chain extenders, crosslinkers or mixtures thereof are suitably used in an amount of 1 to 20 wt .-%, preferably 2 to 5 wt .-%, based on the polyol component b).

Further information on the polyether polyols and polyester polyols used and their preparation can be found, for example, in Kunststoffhandbuch, Volume 7 "Polyurethane", edited by Günter Oertel, Carl-Hanser-Verlag Munich, 3rd edition, 1993 ,

The rigid polyurethane foams are usually prepared in the presence of blowing agents, the abovementioned catalysts and cell stabilizers and, if necessary, further auxiliaries and / or additives which are generally known in polyurethane chemistry and in which DE-A-101 24 333 described, to which express reference is made. Suitable auxiliaries and / or additives are the substances known per se for this purpose, for example surface-active substances, foam stabilizers, cell regulators, fillers, pigments, dyes, flame retardants, graphites, hydrolysis protection agents, antistatic agents, fungistatic and bacteriostatic agents. Further details about the starting materials, blowing agents, catalysts and auxiliaries and / or additives used for carrying out the process according to the invention can be found, for example, in US Pat Kunststoffhandbuch, volume 7, "Polyurethane" Carl-Hanser-Verlag Munich, 1st edition, 1966, 2nd edition, 1983 and 3rd edition, 1993 ,

The blowing agents used may be the chemical and / or physical blowing agents customary for polyurethane chemistry. Chemical blowing agents are compounds which form gaseous products by reaction with isocyanate, such as, for example, water or formic acid. Physical blowing agents are compounds which are dissolved in the starting materials of polyurethane production or emulsified and evaporate under the conditions of polyurethane formation. These are, for example, hydrocarbons such as pentane, cyclopentane, isopentane and mixtures of the isomers, halogenated hydrocarbons, and other compounds such as perfluorinated alkanes such as perfluorohexane, chlorofluorocarbons, and ethers, esters, ketones and / or acetals.

The propellant component is usually used in an amount of 1 to 30 wt .-%, preferably 2 to 20 wt .-%, and particularly preferably 3 to 12 wt .-%, based on the total weight of the polyol component b), and depends according to the desired target density of rigid polyurethane foam.

Furthermore, the flame retardants customary for polyurethane chemistry can be used.

For the rigid polyurethane foams, catalysts and catalyst mixtures are usually additionally used which catalyze the trimerization reaction of the NCO groups with one another. Examples include metal salts, especially ammonium, alkali or alkaline earth metal salts of carboxylic acids called. Preferably, the salts of linear or branched, substituted or unsubstituted, saturated or unsaturated carboxylic acids having 1 to 20 carbon atoms, such as formic acid, acetic acid, octanoic acid, tartaric acid, citric acid, oleic acid, stearic acid or ricinoleic acid or substituted or unsubstituted, aromatic carboxylic acids 6 to 20 carbons, such as benzoic acid or salicylic acid. Especially preferred are potassium formate, potassium acetate, potassium octoate (potassium 2-ethylhexanoate), ammonium formate, ammonium acetate and ammonium octoate, especially potassium formate and potassium acetate.

The rigid polyurethane foams can be prepared batchwise or continuously by means of known mixing devices. The polyol component can be previously metered with separate pumps catalysts and / or propellant. In general, all reaction components are mixed simultaneously, usually in a mixing head. The starting components are usually mixed at a temperature of 15 to 35 ° C, preferably from 20 to 30 ° C.

The component

The production of the component is usually layer by layer, analogous to their construction.

The microcapsules are applied by means of the reactive polyurethane compact system on the metallic cover layer. This application can take place in an isolated process step or directly in the production of the sheet-like component. The metallic non-woven fabric and / or metal mesh can already be present on the metallic cover layer or embedded in the freshly applied polyurethane compact layer.

According to the invention, microcapsules are dispersed in one or more of the starting components of the reactive polyurethane compact system. In this case, the microcapsules can be suspended directly before mixing the starting components and the application to a cover layer or stored in stock suspended in one or more starting components.

According to a preferred embodiment, the microcapsules are dispersed in the compound with at least two isocyanate-reactive hydrogen atoms b), preferably the polyol component. Preferably, the polyol component (without microcapsule additive) has a viscosity of 100-2000 mPa.s, preferably 150-800 mPa.s at 25 ° C.

Preferably, 20 to 6000 g, preferably 500 to 4000 g, in particular 800 to 3000 g microcapsules per m ² sheet-like component applied.

The layer of the composite material according to the invention preferably having a compact polyurethane matrix generally has a thickness of 0.1 to 4 cm, preferably 0.25 to 3.5 cm, particularly preferably 0.5 to 3 cm, in particular 1 to 2 cm.

The device can be produced both batchwise and continuously. The reaction mixture can also be poured into closed support tools (eg press molds) with high-pressure or low-pressure metering machines. By means of this technology, for example, discontinuous composite elements according to the invention are produced.

According to a preferred embodiment, the components are produced discontinuously, for example in a press mold.

According to a further preferred embodiment, the components are produced continuously z. B. in a double belt system. In this case, the upper and the lower metal cover layer are abgecoilt from a roll and optionally profiled, heated and pretreated, z. B. corona treated to improve the foamability of the outer layers. Thereafter, the different reaction mixtures, each mixed, for example, in a high-pressure mixing head, successively applied to the lower cover layer and cured between the upper and lower cover layer in the so-called double band. After leaving the double belt, the endless strand is cut to the desired dimensions.

The present invention also relates to a method for the production of sheet-like structural elements comprising the application of a layer of the composite material (B) according to the invention and a rigid polyurethane foam layer (C) to a metal top layer (A) and finally to the application of a second metal top layer (A ') and optionally one additional composite material layer (B) between the adjacent layers (A) and (C).

Furthermore, it is possible to use a conventional adhesion promoter to achieve better adhesion between the layers (A) and (C), ie in the case of the layer structure (A) - (B) - (C) - (A). Such adhesion promoters chemically correspond to the compact polyurethane system, with the difference that they contain no microcapsules.

According to a preferred variant, the microcapsule-containing reactive compact polyurethane system and the metallic nonwoven fabric is applied to a lower metal topcoat, cures there, then the order of the reactive polyurethane foam system, which then foams and cures, optionally followed by another layer of metallic nonwoven and the microcapsule-containing reactive compact polyurethane system applied and finally the upper Metalldeckschichteckschicht is applied.

According to a likewise preferred production variant, the reactive polyurethane rigid foam system is applied to the metal top layer, foams there and cures, followed by the application of metallic nonwoven and the reactive compact polyurethane system containing the microcapsules, and finally the top cover layer is applied.

In a particular embodiment of the method according to the invention, the time interval between application of the reactive foam system to the compact polyurethane system and the application of the reactive compact polyurethane system to the rigid foam system is chosen so that the compact polyurethane system or the rigid foam system is not fully cured to the To improve adhesion between both systems.

The manufacturing process described above is a preferred embodiment of the manufacturing process. Other preparation methods known in the art and known to those skilled in the art may be used as well.

In this way, the components according to the invention, so-called sandwich elements, can also be produced with different metal cover layers. They then have one or two thermally storable, near-surface layers directly behind the metal cover layer (s) with improved thermal connection to the metal cover layer.

The thickness of the components of the invention is usually between 20 and 300 mm, the usual density range of the rigid polyurethane foam for producing these moldings is 20 to 150 kg / m ³ , preferably 25 to 100 kg / m ³ ( Kunststoffhandbuch, 3rd edition, page 150 ).

The components according to the invention enable the avoidance of barrack climate. The buildings manufactured with them show not only good thermal insulation, but also a significant improvement in the temperature profile and thus in energy consumption. The composite materials are preferably used as a component of building components in residential construction, industrial construction, cold store construction, in sectional doors, in office containers or in caravans or shipbuilding.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 1703033 A [0004]
• WO 2006/021306 [0005]
• EP 2009/066386 [0006, 0098]
• US 5224356 [0008]
• DE 10124333 A [0037, 0118]
• WO 2009/077525 [0052]
• US Pat. No. 5,452,852 A [0055]
• GB 870476 [0058]
• US 2800457 [0058]
• US 3041289 [0058]
• EP 562344A [0062]
• EP 974394 A [0062]
• US 4021595 [0063]
• EP 0392876A [0063]
• EP 0535384A [0063]
• DE 10139171 A [0075]
• WO 2008/071649 [0076, 0078]
• EP 1029018 A [0078]
• DE 10163162 [0078]

Cited non-patent literature

• Kunststoffhandbuch, volume 7 "Polyurethane", edited by Günter Oertel, Carl-Hanser-Verlag Munich, 3rd edition, 1993 [0036]
• Kunststoffhandbuch, volume 7, "Polyurethane" Carl-Hanser-Verlag Munich, 1st edition, 1966, 2nd edition, 1983 and 3rd edition, 1993 [0037]
• DIN 7726 [0102]
• DIN 53 421 [0102]
• DIN EN ISO 604 [0102]
• DIN ISO 4590 [0102]
• Kunststoffhandbuch, Volume 7 "Polyurethane", edited by Günter Oertel, Carl-Hanser-Verlag Munich, 3rd edition, 1993 [0117]
• Kunststoffhandbuch, volume 7, "Polyurethane" Carl-Hanser-Verlag Munich, 1st edition, 1966, 2nd edition, 1983 and 3rd edition, 1993 [0118]
• Kunststoffhandbuch, 3rd edition, page 150 [0140]

Claims (12)

A composite material comprising a metallic non-woven fabric and / or metal mesh and a polymer matrix and distributed therein microcapsules having a capsule core of latent heat storage material and a polymer as a capsule wall, wherein the composite material is obtainable by contacting the metallic nonwoven and / or metal mesh and an organic reactive binder containing the microcapsules and subsequent curing of the binder. Composite material according to claim 1, characterized in that the metal of the metallic nonwoven fabric and / or metal mesh is selected from steel, stainless steel, copper, aluminum, silver and gold. Composite material according to claim 1 or 2, characterized in that the polymer matrix is selected from polyurethane, polyepoxide, silicone, polyester, rubber, cast polyamide, and polysulfide. Composite material according to one of claims 1 to 3, characterized in that the polymer matrix is a compact polyurethane. Composite material according to one of claims 1 to 4, characterized in that the latent heat storage material is an organic lipophilic substance having a solid / liquid phase transition in the temperature range from -20 to 120 ° C. Composite material according to one of claims 1 to 5, characterized in that the capsule wall of the microcapsules by radical polymerization of 30 to 100 % By weight of one or more monomers (monomers I) from the group comprising C ₁ -C ₂₄ -alkyl esters of acrylic and / or methacrylic acid, acrylic acid, methacrylic acid and maleic acid, 0 to 70 Wt .-% of one or more bi- or polyfunctional monomers (monomers II), which is insoluble or sparingly soluble in water, and 0 to 40 % By weight of one or more other monomers (monomers III), each based on the total weight of the monomers is obtained. Composite material according to one of claims 1 to 6, characterized in that it is based on the total amount of metallic non-woven fabric and / or metal mesh, polymer matrix and microcapsules 5 to 50 Vol .-% metallic nonwoven fabric and / or metal mesh and 50 to 95 Vol .-% polymer matrix containing the microcapsules contains. A process for the production of composite material according to claims 1 to 7, characterized in that one brings a metallic fiber structure and / or metal mesh and an organic reactive binder containing the microcapsules in contact and then curing the binder by a crosslinking reaction or polymerization. Use of the composite material as at least one layer of a sheet-like component. A sheet-like component obtainable by applying a polyurethane compact layer (B) and a rigid polyurethane foam layer (C) to a metal cover layer and finally applying a second metal cover layer and optionally an additional polyurethane compact layer between the adjacent layers (A) and (C). A method for producing a sheet-like component comprising applying a layer (B) of composite material according to one of claims 1 to 7 and a polyurethane foam layer (C) on a metal topcoat and finally applying a second metal topcoat and optionally another layer of the composite material according to one of the claims 1 to 7 between the adjacent layers (A) and (C). Use of the composite material-containing component according to claim 11 in residential construction, industrial construction, cold store construction, in sectional doors, in office containers, in caravans and shipbuilding.