Laminated composite material with chrome-plated metal decorative layer

ES 2 249 339 T3

DESCRIPTION

Laminated composite materials with a decorative layer made of chromed metal.

The present invention relates to a layered composite material containing a support made of a thermoplastic polymer, an intermediate layer arranged thereon, and a decorative layer applied to the intermediate layer, the decorative layer being constituted by a chromed metal. The present invention also relates to a process for obtaining this laminated composite material, as well as to its use as a reflective or insulating part of a domestic appliance, a piece of furniture or a molded part in the electronics, construction or automobile industry. , or in the health sector.

The layered composite materials known to date, which are used especially in the furniture or household appliance industry, consist essentially of a backing layer of wood or wood fibers, or insulated papers pressed with the addition of resin, on which is They apply decorative layers, as well as other thermoset layers, the so-called overlay layers, under the action of heat and pressure. The decorative layers used in this case often have betas made of wood, metal or marble. The decorative layers are used in many cases together with the thermoset layers applied thereon as so-called laminates.

Such laminated composite materials have the drawback of showing a certain sensitivity to moisture penetrating the central layer from the edges, since both wood, as well as wood fibers or insulated papers, tend to swell under the influence of moisture. . Furthermore, such laminated composites can be deformed only at relatively high expense.

For many industrial applications, for example in the automotive or electronics industry, surface materials are required as materials that exhibit high pressure resistance on the one hand and relatively high thermal stability on the other, and must also be capable of provide decorative conditioning.

In the production of furniture, surface materials have been used for a long time, providing a decorative laminated composite material with several layers, among others a support layer, a decorative layer, and a thermoset layer that rests on it, with the help of other composite layers, for example paper or adhesive foils. However, such a layered composite material is very expensive to obtain, since it frequently has a high formaldehyde fraction, and exhibits an unfavorable swelling behavior.

Furthermore, the layered composites described to date have the drawback that the applied layers are relatively thin, are frequently sensitive to mechanical stress, and do not have a reinforcing action on other components, if they are bonded therewith.

From DE-A 1 97 22 339 a laminated composite material is known which contains a polypropylene backing layer, a decorative layer arranged thereon, and a thermoset layer applied on the decorative layer. DE-A 19858173 also describes a layered composite material made up of a support layer of different thermoplastic polymers, such as, for example, made up of certain styrene copolymers, or polyoxymethylene, or polybutylene terephthalate, as well as a decorative layer applied on it, and a thermoset layer resting on it. Such laminated composite materials consisting of a support layer of thermoplastic polymers differ from conventional laminated composites with support layers of wood, wood fibers or paper, among other things, by their high stability to temperature and humidity, greater mechanical resistance , and easier workability. Due to a certain rigidity and brittleness of the isolated polymeric layers, also the layered composite materials known from DE-A 19 722 339 and DE-A 19 858 173 still show certain drawbacks in processing and shaping, especially in shaping. three-dimensional to give construction parts for the automotive, domestic or electronic sector. Furthermore, in such layered composites it is observed that their subsequent processing, for example by enamelling or by the application of other functional elements, causes difficulties in part.

Furthermore, for some industrial applications, for example in domestic appliances or in molded parts in the electronics, construction or automotive industries, it is important that such laminated composite materials have an insulating or reflective action against thermal or light radiation. , are suitable for mechanical and thermal loading, have good aging stability and adherence to other materials, are also easily recyclable, and make it possible to easily integrate functional elements.

EP-A 108 710 describes metal-polyolefin laminates with extraordinary properties, showing in particular an optimal bond strength between metal and polyolefin as a quality criterion. To this end, between the polyolefin and the metal an intermediate layer must be provided consisting of a copolymer of propylene and an alpha, beta-unsaturated carboxylic acid, or a copolymer of propylene-ethylene and an elastomer.

DE-A 42 18 369 describes metal-synthetic material composites based on polypropylene copolymers, which can be obtained without the appearance of white breakage. These joints should have low transparency and low gas permeability. To this end, according to the teaching of DE-A, a propylene copolymer is extruded through a wide slot nozzle, and then rolled onto a metal sheet. For the improvement of adhesion

In ES 2 249 339 T3, the plastic sheet is anchored onto the metal sheet with a solvent-containing or aqueous glue, or an adhering agent is coextruded.

GB-A 2 008 492 describes a metal olefin resin compound with improved adhesion and corrosion stability, in which a special bonding agent (first layer) is employed, which is called a modified olefin resin. Modification in the sense of GB-A is achieved by incorporation by polymerization of ethylenically unsaturated monomers with polar groups.

To all known solutions for improving the adhesion between metal and synthetic material, it is common that additional adhesion agents or adhesives with a different chemical composition than the synthetic material must be used, which limits the use of such composite elements as molded parts for special purposes. of use, in which the purity of the chemical composition constitutes a profile of special requirements.

Accordingly, the present invention was based on the task of remedying the drawbacks described, and making available an improved laminated composite material, which was, among other things, mechanically and thermally stable, and age-stable, which could be bonded easily with other functional elements, and will also have an insulating or reflective action against thermal or light radiation.

Accordingly, an improved laminated composite material was developed, containing a thermoplastic polypropylene backing with a melting rate (MFR) in the range of 0.2 to 100 g / 10 min, at 230 ° C, and a weight of 2 , 16 kg, an intermediate layer constituted by a thermoplastic polypropylene fleece, a decorative layer applied on the intermediate layer constituted by a chromed metal and a thermoset layer applied on the decorative layer.

Furthermore, the laminated composite material according to the invention can also contain on both layers of the thermoplastic polymer carrier an intermediate layer, a decorative layer arranged thereon, as well as, if appropriate, even a thermoset layer applied to the decorative layer, by means of which produces a sandwich structure with the support in the middle.

The support material may contain 1 to 60, preferably 5 to 50, particularly preferably 10 to 40% by weight, based on the total weight of the support, of reinforcing fillers, such as barium sulfate. , magnesium hydroxide, talc with a mean grain size in the range 0.1 to 10 pm, measured according to DIN 66 115, wood, flax, chalk, glass fibers, coated glass fibers, long or short glass fibers , glass balls or mixtures thereof. Furthermore, the usual additives, such as light, UV and heat stabilizers, pigments, soot, slip agents, flame retardants, propellants and the like, can still be added to the support material in the usual and necessary amounts.

Polyolefins, such as polypropylene, are in particular also used as carrier materials. Under the name polypropylene, in this case both homopolymers and copolymers of propylene are to be understood. Propylene copolymers contain monomers that can be copolymerized with propylene in minor amounts, for example C2-C8-alkenes, such as, inter alia, ethylene, 1-butene, 1-pentene or 1-hexene. Two or more different comonomers can also be used.

Particularly suitable carrier materials are, inter alia, propylene homopolymers or propylene copolymers with up to 50% by weight of other 1-alkenes incorporated by polymerization with up to 8 carbon atoms. In this case, the propylene copolymers are statistical copolymers or block or impact copolymers. As long as propylene copolymers have a statistical structure, they generally contain up to 15% by weight, preferably up to 6% by weight, of other 1-alkenes with up to 8 carbon atoms, especially ethylene, 1-butene, or a mixture of ethylene and 1-butene.

Propylene block or impact copolymers are polymers in which, in the first stage, a propylene homopolymer or a propylene statistical copolymer with up to 15% by weight, preferably up to 6% by weight, is added by polymerization, of other 1-alkenes with up to 8 carbon atoms, and then, in the second stage, a propylene-ethylene copolymer with ethylene contents of 15 to 80% by weight, the propylene-ethylene copolymer may additionally contain other C4-8-alkenes. As a general rule, such an amount of propylene-ethylene copolymer is added by polymerization that the copolymer generated in the second stage has a fraction of 3 to 60% by weight in the final product.

The polymerization to obtain polypropylene can be carried out by means of a Ziegler-Natta catalyst system. In this case, in particular, catalyst systems are used which, in addition to a solid component containing titanium a), also have cocatalysts in the form of organic aluminum compounds b) and electron donor compounds c).

However, catalyst systems based on metallocene compounds or based on polymerization-active metal complexes can also be used.

The usual Ziegler-Natta catalyst systems contain in particular a solid component containing titanium, inter alia trivalent or tetravalent titanium halides or alcohols, in addition to a magnesium compound

ES 2 249 339 T3 halogenated, inorganic oxides, such as silica gel as a support, as well as electron donor compounds. As such, in particular derivatives of carboxylic acids, as well as ketones, ethers, alcohols or organosilicon compounds come into consideration.

The solid component containing titanium can be obtained by methods known per se. Examples for this purpose are described, inter alia, in EP-A 45 975, EP-A 45 977, EP-A 86 473, EP-A 171 200, GB-A 2 111 066, US- A 4 857 613, and US-A 5 288 824. The method known from DE-A 195 29 240 is preferably applied.

Suitable aluminum compounds b) are, in addition to trialkylaluminum, also those compounds in which an alkyl group is substituted by an alkoxy group or by a halogen atom, for example by chlorine or bromine. The alkyl groups can be the same or different from each other. Linear or branched alkyl groups come into consideration. Trialkylaluminum compounds, the alkyl groups of which each have 1 to 8 carbon atoms, are preferably used, for example trimethylaluminum, triethylaluminum, triiso-butylaluminum, trioctylaluminum or methyldiethylaluminum, or mixtures thereof.

As a general rule, in addition to the aluminum compound b), electron donor compounds c), such as mono- or polyfunctional carboxylic acids, carboxylic acid anhydrides or carboxylates, as well as ketones, ethers, alcohols, lactones, as well as ketones, ethers, alcohols, lactones, are used as additional cocatalyst. organic phosphorus and silicon compounds, the electron donating compounds c) being able to be the same or different from the electron donating compounds used to obtain the solid component containing titanium a).

Instead of the Ziegler-Natta catalyst systems, it is also possible to use metallocene compounds or polymerization-active metal complexes to produce polypropylene.

In this case, metallocenes should be understood as complex compounds of metals of secondary groups of the Periodic System with organic ligands, which provide effective catalyst systems together with compounds that form metallocene ions. For a use to obtain polypropylene, the metallocene complexes are generally supported in the catalyst system. Organic oxides are frequently used as supports, but organic supports in the form of polymers, for example polyolefins, can also be used. The inorganic oxides described above, which are also used to prepare the solid component containing titanium a), are preferred.

The metallocenes used usually contain titanium, zirconium or hafnium as the central atom, with zirconium being preferred. In general, the central atom is linked to at least one generally substituted cyclopentadienyl group, as well as to other substituents, through a π bond. The other substituents can be halogen, hydrogen or organic residues, with fluorine, chlorine, bromine or iodine being preferred, or an alkyl group with 1 to 10 carbon atoms.

The cyclopentadienyl group can also be a component of a corresponding heteroaromatic system.

Preferred metallocenes contain central atoms that are attached via two identical or different π bonds to two substituted cyclopentadienyl groups, those in which the substituents of the cyclopentadienyl group are attached to both cyclopentadienyl groups being especially preferred. Especially preferred are complexes whose substituted or unsubstituted cyclopentadienyl groups are additionally substituted by cyclic groups on two adjacent carbon atoms, the cyclic groups can also be integrated in a heteroaromatic system.

Preferred metallocenes are also those that contain only one substituted or unsubstituted cyclopentadienyl group, but which is substituted with at least one moiety that is also attached to the central atom.

Suitable metallocene compounds are, for example, ethylenebis (indenyl) -zirconium dichloride, ethylenebis (tetrahydroindenyl) -zirconium dichloride, diphenylmethylene-9-fluorenylcyclopentadienylzirconium dichloride, dimethylsilandiylbisyl (3-5- tertiary chloride) methylcyclopentadienyl) -zirconium, dimethylsilandiyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-methylphenyl) -indenyl) -zirconium dichloride, Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-ethyl-4 (4'-tert-butylphenyl) -indenyl) -zirconium dichloride, ethanediyl (2-ethyl-4-azapentalene) (2-ethyl-4) dichloride (4'-tert-butylphenyl) -indenyl) -zirconium, dimethylsilandiylbis (2-methyl-4-azapentalene) -zirconium dichloride,

ES 2 249 339 T3 dimethylsilandiylbis (2-methyl-4-thiapentalene) -zirconium dichloride, dimethylsilandiylbis (2-methylindenyl) -zirconium dichloride, dimethylsilandiylbis (2-methylbenzoindenyl) -zirconium dichloride, dimethylsilandiyl (2-methylsilandiylbis (2-methylindenyl) -zirconium dichloride 4-phenylindenyl) zirconium, dimethylsilandiylbis (2-methyl-4-naphthylindenyl) zirconium dichloride, dimethylsilandiylbis (2-methyl-4-isopropylindenyl) zirconium dichloride, or dimethylsilandiylbis (2-methyl-4,6-diisopropyl) zirconium dichloride , as well as the corresponding dimethyl zirconium compounds.

The metallocene compounds are known or can be obtained by methods known per se. For the catalysis it is also possible to use mixtures of such metallocene compounds, in addition to the metallocene complexes described in EP-A 416 815.

Metallocene catalyst systems also contain compounds that form metallocene ions. Neutral, strong Lewis acids, ionic compounds with Lewis acid cations or ionic compounds with Br & ouml; nsted acids as cations are suitable. Examples for this purpose are tris (pentafluorophenyl) borane, tetrakis (pentafluorophenyl) borate or salts of N, N-dimethylanilinium. Cyclic or open-chain alumoxane compounds are equally suitable as metallocene ion-forming compounds. These are usually obtained by reacting trialkylaluminum with water, and are generally present as mixtures of molecules in chains of different lengths, both linear and cyclic.

In addition, metallocene catalyst systems can contain organometallic compounds of metals from main group I, II or III of the Periodic System, such as n-butyl-lithium, n-butyl-n-octyl-magnesium or tri-iso-butyl-aluminum, triethylaluminum or trimethylaluminum.

The production of polypropylenes used for the support layer is carried out by polymerization in at least one, frequently also in two or more reaction zones connected in series (reactor cascade), in the gas phase, in a suspension or in one phase. liquid (bulk loading phase). The usual reactors used for the polymerization of C2-C8-alkenes can be used. Suitable reactors are, inter alia, continuously driven stirred kettles, distillation columns with loop circulation, or fluidized bed reactors. In this case, the size of the reactors is not essential. This is adjusted to the discharge that will be achieved in the isolated reaction zone or zones.

Fluidized bed reactors and horizontally or vertically stirred powder bed reactors are used in particular as reactors. In this case, the reaction bed is generally constituted by the polymer of 1-alkenes with 2 to 8 carbon atoms, which is polymerized in the respective reactor. The polymerization to obtain polypropylenes used as support layers is carried out under normal reaction conditions at temperatures of 40 to 120 ° C, especially 50 to 100 ° C, and pressures of 10 to 100 bar, especially 20 to 50 Pub.

The polypropylenes used as support generally have a melting rate (MFR), according to ISO 1133, of 0.1 to 200 g / 10 min, especially 0.2 to 100 g / 10 min, at 230 ° C, and under a weight 2.16 kg.

Furthermore, the laminated composite material according to the invention still contains an intermediate layer, which is applied to the support. Preferably, the intermediate layer is made of the same thermoplastic synthetic material as the support, whereby the adhesion between the support and the intermediate layer is particularly improved. The intermediate layer is in particular present as a thin fleece with a thickness of 0.001 to 1.0 mm, especially 0.005 to 0.3 mm. Suitable materials for the interlayer are the same thermoplastic plastics that are already described for the support, that is to say especially polypropylene.

Furthermore, the layered composite material according to the invention has a chromed metal as a decorative layer. The chromed metal is present on the intermediate layer and has a layer thickness of 0.1 to 0.5 mm, especially 0.1 to 2.0 mm, and particularly preferably 0.1 to 1.0 mm. In this case, both a layer of chromium and a layer of another metal, such as, for example, refined steel, iron, copper, nickel, tin or zinc, or corresponding alloys of these metals, or corresponding alloys of these metals, can be used as chromium metal. then coat with an additional coat of chrome. Furthermore, it is possible to use as the chromium metal a layer consisting of a suitable thermoplastic polymer, which is coated with an additional layer of chromium. Conveniently suitable thermoplastic polymers for this purpose are, inter alia, polyolefins, such as polypropylene or polyethylene, polyamides, polycarbonates, as well as styrene copolymers, for example SAN or AbS.

Due to the structure of the decorative layer made of chromed metal, it has both reflective and insulating properties. In order to achieve good radiation reflection, the decorative layer had to have as smooth a surface as possible. So that the layered composites according to the invention

ES 2 249 339 T3 have good insulating properties, it is advisable to select the thickness of the decorative layer as high as possible, and still apply a thermoset layer that is as thick as possible (overlay). In this case, the overlay, which is generally made of a duroplastic resin, acts as a good insulator. Furthermore, by means of the laminar structure, the thermoplastic support is both thermally and mechanically shielded, which has the consequence that the layered composites do not tend to soften even at higher temperatures.

Furthermore, the laminated composite materials according to the invention may still contain a thermoset layer, which is applied over the decorative layer.

The thermoset layer arranged on the decorative layer (overlay) is preferably made of a synthetic duroplastic material, for example a paper impregnated with acrylic resin, phenolic resin, melamine resin or urea resin, which is cross-linked by the action of pressure or heat during the obtaining of the layered composite material. The weight of the thermoset layer (overlay) is usually in the range of 10 to 300 g per m², especially in the range of 15 to 150 g per m², and particularly preferably in the range from 20 to 70 g per m².

The thermoset layer (overlay) can also optionally be arranged on one side, or else on both sides, on the intermediate layer, together with the decorative layer as a finished laminate. Such finished laminates are known as such, and available, inter alia, from Melaplast in Schweinfurt, Germany.

The total thickness of the laminated composite material according to the invention is in the range of 0.5 mm to 100 mm, preferably in the range of 1.0 mm to 20 mm, especially in the range of 1.0 to 10 mm, suppressing in the support at least 80%, preferably at least 90% of total thickness.

The preparation of the layered composite materials according to the invention can be carried out according to a process in which the materials for the intermediate layer, the decorative layer and, if necessary, the thermoset layer are respectively arranged in the form of thin flat products, and subsequently they bond with the support material at temperatures of 150 to 300 ° C, especially 160 to 280 ° C. In this case, the intermediate layer, the decorative layer and the thermoset layer (overlay) can preferably also be used together in the form of a finished laminate, which is also in the form of a flat product.

Furthermore, it is possible to first bond the intermediate layer, the decorative layer and, if necessary, the thermoset layer together by immersion in a bath of glue, or by using thin adhesive strips in a press, preferably in a double press. band, and then apply this joint on the support. In this case, it can also be recommended to shape the joint of the intermediate layer, the decorative layer, and, if necessary, thermoset layer, in a two-dimensional way, first by means of a deep drawing process, or by direct forming, for example in a forming tool. injection molding, and then join it with the thermoplastic polypropylene, which will form the support, by injection, extrusion or heat pressing. Since, according to the invention, the support and the intermediate layer are made of thermoplastic synthetic materials that are identical in each case, a very high adhesion is observed between the two layers.

The process for obtaining the layered composite material according to the invention can also be modified so that the layered composite material conforms three-dimensionally after prior heat treatment at temperatures of 150 to 300 ° C, especially 150 to 250 ° C, and of particularly preferably 160 to 200 ° C. In this way, it is possible to obtain, inter alia, shaped bodies for the electronics, construction or automotive industries.

The laminated composite material according to the invention is also obtainable in such a way that the bonding of the intermediate layer, the decorative layer, if necessary the thermoset layer, and the support is carried out by means of processing procedures customary in the plastics industry. . The usual production processes in this case are, among others, injection molding, extrusion or heat pressing of isolated layers.

In the case of injection molding, the isolated layers, i.e. the carrier, the intermediate layer, the decorative layer, and if necessary the thermoset layer (the last layers also together as a finished laminate) are formed directly through a deep drawing procedure, and then they are subsequently injected into each other in an injection molding tool, or they are formed together and injected directly into the injection molding tool only. This can be done both on one side and on both sides, the intermediate layer, the decorative layer, and optionally the thermoset layer being arranged on both sides of the carrier in the latter case. This injection molding process is usually carried out at temperatures of 150 to 300 ° C, especially 180 to 280 ° C, preferably 190 to 270 ° C, and pressures of 50 to 100 N / cm², especially 60 to 80 N / cm². By means of the temperatures and pressures present in the injection molding tool, not only a very good bonding of the thermoplastic interlayer with the thermoplastic support is achieved, but also an additional hardening of the laminated composite material according to the invention. This is very flexible compared to the layered composites known to date, and can be conveniently shaped in subsequent processing steps.

In the case of extrusion process, the intermediate layer, the decorative layer, and if necessary the thermoen6 layer

ES 2 249 339 T3 of the laminated composite material according to the invention are fed on one side or both sides through crimping or stamping cylinders to the thermoplastic synthetic material of the support (the so-called coating), and are thus joined together. In this case, temperatures of 150 to 300 ° C, and in particular 160 to 250 ° C, preferably 170 to 220 ° C, and pressures of 40 to 200 N / cm are usually set.², especially 50 to 100 N / cm². In this way a very good adhesion of both flat products to each other is achieved. The layered composite material obtained also exhibits good surface properties.

A variant of the extrusion process is the so-called profile extrusion process, in which the isolated layers of the laminated composite material according to the invention, especially the intermediate layer, are shaped by means of a calibration, so that this can be fed directly to the actual profile below, that is to say the support made of thermoplastic synthetic material.

Furthermore, the layered composite material according to the invention is also obtainable by heat pressing the isolated layers, being able to preform them by means of a prior deep drawing process, or directly in the press. In this case, a granulate of thermoplastic synthetic material is added directly onto a laminated compound made up of the intermediate layer, the decorative layer, and, if necessary, the thermoset layer, and these are pressed together at temperatures of 150 to 300 ° C, and especially 160 to 250 ° C, preferably 170 to 230 ° C, pressures of 50 to 120 N / cm², especially 80 to 100 N / cm²as well as pressing times of 0.5 to 10 minutes, especially 1 to 5 minutes, and particularly preferably 1 to 3 minutes.

The laminated composites according to the invention are distinguished, inter alia, by good mechanical properties due to the adhesion between the isolated layers. These are conveniently conformable in two or three dimensions, they also have high resistance to high temperatures or chemicals, and are stable to aging. The layered composite materials according to the invention can be easily bonded with other functional elements, and also have good insulating and reflective properties against light or thermal radiation. A special advantage of these materials is also that they are resistant to breakage due to their laminar structure, which gives them special advantages compared to conventional reflectors, such as mirrors.

The layered composite materials according to the invention are suitable, inter alia, as reflective or insulating parts in household appliances, furniture parts, or in the electronics, construction or automobile industry, or in the healthcare sector.

The process for obtaining layered composite materials, also according to the invention, can be carried out easily, and is particularly distinguished by the fact that it employs the usual production and assembly process.

In the following examples and embodiments, the invention will be explained in even more detail. Within the scope of the examples, the following controls were carried out on test bodies:

- the gloss was determined visually.

- The stress due to collisions was determined by a drop test from 1.75 m in height.

- The flexural modulus E was measured at + 23 ° C, + 60 ° C and + 90 ° C according to ISO 178.

- The impact toughness was determined according to Charpy at + 23 ° C and at -20 ° C according to ISO 179 / leU.

- Dimensional thermal stability (HDT / A) was measured according to ISO 75/1 + 2.

Example 1 and comparative example A

A laminated composite material according to the invention (Example 1) was compared with a conventional mirror (Comparative Example A) with respect to its reflective properties.

The layered composite material consisted of a layer of a propylene homopolymer as a support, with a melting rate (MFR), according to ISO 1133, of 15 g / 10 min., At 230 ° C and 2.16 kg an intermediate layer made of a synthetic material fleece of the same propylene homopolymer, a decorative layer made of chrome-plated refined steel with a layer thickness of 0.2 mm, and an overlay of melamine resin with a layer thickness of 0.1 mm. The laminated composite material had a total thickness of 1.4 mm, with 90% of the total thickness being suppressed in the support.

The laminated composite material according to the invention and the conventional mirror were compared with respect to their gloss, their degree of reflection and their breaking behavior. The results of the measurements are represented in the following table I.

ES 2 249 339 T3

TABLE I

<td>Property</td><td>Example 1</td><td>Comparative Example A</td>

<td>Brightness</td><td>well</td><td>very good</td>

<td>Degree of reflection</td><td>very good</td><td>very good</td>

<td>Shock stress</td><td>no identifiable deterioration</td><td>destroyed</td>

The results in Table I show, inter alia, that the laminated composite material according to the invention is distinguished by good breaking behavior with still high gloss.

Example 2 and comparative example B

A laminated composite material according to the invention (example 2) was compared with a conventional polypropylene test body (comparative example B) with respect to its mechanical and thermal stability.

The laminated composite material of Example 2 consisted of the same support material, the same intermediate layer, the same decorative layer, and the same overlay as in Example 1, the decorative layer now having a layer thickness of 0.2 mm , and the superimposed layer a layer thickness of 0.1 mm. The laminated composite material had a total thickness of 1.4 mm, with 90% of the total thickness being suppressed in the support.

The shaped article of Comparative Example B consisted of a propylene homopolymer with a melting rate (MFR), according to ISO 1133, of 15 g / 10 min, at 230 ° C and 2.16 kg.

The laminated composite material according to the invention and the test body of Comparative Example B had the same dimensions. Both were compared with respect to their flexural modulus E, their impact toughness, according to Charpy, and their thermal dimensional stability (HDT / A). The results of the measurements are represented in the following table II.

TABLE II

<td>Property</td><td>Example 2</td><td>Comparative Example B</td>

<td>Bending modulus E (N / mm²] at + 23 ° C</td><td> 8.921</td><td> 2.000</td>

<td>at + 60 ° C</td><td> 7.224</td><td> 1.000</td>

<td>at + 90 ° C</td><td> 6.293</td><td> 800</td>

<td>Impact toughness according to Charpy [kJ / m²] at + 23 ° C</td><td> 25,6</td><td> 60</td>

<td>at -20 ° C</td><td> 18,9</td><td> 16</td>

<td>Dimensional thermal stability [° C] (HDT / A)</td><td> 160</td><td> 58</td>

From the results of Table II it can be seen that the laminated composite material according to the invention is distinguished, among other things, by a high flexural modulus E, a high Charpy impact toughness, as well as good values ​​with regard to thermal dimensional stability. (HDT / A).

Some exemplary embodiments of the laminated composites according to the invention are schematically represented in the following drawings (Figures 1 to 5), and explained in more detail below.

Show

FIG. 1 a layered composite toaster casing according to the invention. Figure 2 shows the "opaque" housing of an electric toothbrush.

ES 2 249 339 T3

Figure 3 shows the structure of a "break-proof" mirror.

Figure 4 the structure of a housing / reflector for high-altitude lamps / sun.

Figure 5 shows the structure of an electromagnetically shielded housing.

Description figure 1

On the lateral surfaces of the toaster casing support (1) made of a propylene homopolymer with a melting speed (MFR) according to ISO 1133 of 15 g / min. at 230 ° C and 2.16 kg, on the inside there is a laminate (2) made up of an intermediate layer of a fleece, which is made up of a polypropylene obtained with metallocene catalysts, and a chromed metal as a decorative layer, which serves as an insulating layer, and which separates from the toaster casing support (1) the heat emitted by the actual toaster device (4). For deformation reasons, a corresponding additional laminate (3), which is made up of the same components as laminate (2), is also applied on the side opposite it. In this way it is possible to reduce the gap between the toaster device (4) and the toaster housing support (1), allowing new toaster designs.

Description figure 2

The housing (1) of an electric toothbrush made of a propylene homopolymer with a melting speed (MFR), according to ISO 1133, of 50 g / min. at 230 ° C and 2.16 kg, it contains a perforation for a light diode (3). In order that the light diode is not visible through the entire housing, a laminate layer (2) is placed around the recess in the housing, which makes the housing (1) opaque around the light diode. In this case, the laminate layer is made up of an intermediate layer made from a fleece, which is made up of a polypropylene obtained with metallocene catalysts, and a decorative layer of chromed metal. The casing (1) constitutes the support of the laminate (2) in this case. The size and thickness of the laminate are selected corresponding to the light output of the light-emitting diodes.

Description figure 3

The mirror support (1) consists of a propylene copolymer with 20% by weight of ethylene incorporated by polymerization and a melting index of 15 g / 10 min. according to ISO 1133, at 230 ° C and 2.16 kg. On the support (1), through a film joint (5) a cover (4) is formed which, to protect the laminate with the reflective metal surface (2) from damage, can be closed through it. To prevent inadvertent closing of the cover (4), it is fixed to the support (1) by means of a spring hook (6). On the back of the support, a crossing train (3) of the same dimensions is applied, made up of the same laminate as the laminate with the reflective metal surface (2). In this case, the laminate layer is constituted by an intermediate layer from a fleece, which is constituted by a polypropylene obtained with metallocene catalysts, and a decorative layer of chromed metal and a melamine resin as an overlay.

Description figure 4

The lamp housing forms the support made of a propylene homopolymer reinforced with 20% by weight of talc, with a melting index of 15 g / 10 min. according to ISO 1133, at 230 ° C and 2.16 kg, on which the reflective metal surface laminate (2, 3) is located, in this case the front surfaces with separate laminate pieces (3) being indicated. In this case, the same laminate as described in figure 3 is used. In the housing (1), between both reflective laminate surfaces (2, 3) the lamp (4) is arranged so that its light can be reflected by the laminate surfaces (2) and (3). In the support (1) are also formed fixing devices (5) for mounting the lamp (4).

Description figure 5

The support (1) of the insulating laminate layers (2, 3) consists of a propylene homopolymer obtained with the aid of metallocene catalysts, with a melting rate (MFR), according to ISO 1133, of 50 g / min. at 230 ° C and 2.16 kg. In this case, the same laminate as described in figure 3 is used. The support (1) forms both the bottom of the casing, as well as the cover of the casing, both parts being joined together through a film hinge. (4). For the purpose of optimized shielding action, the insulated laminates for the bottom surface (2) and the side surfaces (3) are overlappingly molded in the angular areas.