WO2006005316A1

WO2006005316A1 - Composite material and method for the production thereof

Info

Publication number: WO2006005316A1
Application number: PCT/DE2005/001195
Authority: WO
Inventors: Volkmar Reinhardt Andre; Klaus Holtmann
Original assignee: Dekodur Gmbh & Co. Kg; Schollglas Holding Und Geschäftsführungs-Gmbh
Priority date: 2004-07-08
Filing date: 2005-07-07
Publication date: 2006-01-19
Also published as: EP1793992A1; DE202004020487U1; DE102004033301A1; DE112005002166A5

Abstract

A composite material obtainable by permanently joining a laminated material, based on an HPL or CPL laminate, to a panel of mineral glass on one or two sides by means of a polymer adhesive.

Description

Composite material and process for its production

description

The invention relates to a composite material made of a laminate material and a glass material.

Resin-bonded laminates, so-called H PL materials (HPL - high pressure laminates) or CPL materials (CPL - continuously pressed laminates) have long been known as robust and durable materials in sheet form. They are found as engineering materials e.g. in the electrical industry as a support for printed circuits ausge¬ expanded use. Laminated plates with a decoratively shaped surface are used as plastic surfaces in the broadest sense, e.g. in the household sector, in public places, e.g. used for the design of wall surfaces in railway and tram vehicles, as partitions in public sanitary areas, for table surfaces in canteens, for floors and on many other occasions. There is hardly any area of daily life that you do not encounter. In recent times, the imitation of metallic surfaces has become very popular.

HPL have many advantages as decorative materials over other materials, e.g. Wood, especially real wood veneer, metal, extruded plastic plates or glass. Depending on the chosen comparative material, for example, aging resistance, moisture and chemical resistance, relatively high fracture safety, favorable weight (for example in the case of plates whose surface is covered with metal foil compared to metal plates with corresponding rigidity) are to be emphasized. Other favorable properties are low thermal expansion, i. high dimensional stability, very low electrical conductivity combined with high electrical voltage breakdown resistance, i. favorable insulation effect, versatile appearance of the surface (eg gloss or matt effects, with almost arbitrarily variable relief structure, metallic effects - eg high glossy or brushed, just to name a few possibilities) as well as the body structure (transparent or opaque) and the Material thickness, which can be adjusted according to the intended use einge¬. For example, HPL can be made intrinsically stable or as a coating for a load bearing other material. Also noteworthy is the easy machinability (sawing, drilling, punching, edge grinding, sticking to other materials such as chipboard, in some cases thermal Imachverformung).

Disadvantages of HPL boards are, for example, low modulus of elasticity, often too low a resistance to mechanical stress, ie scratch sensitivity, which can be reduced, for example, by incorporation of mineral aggregates into the surface, the surface hardness of other materials, such as mineral glasses, ceramics or hardened metal surfaces but generally not achieved. Decorative coating materials are compared to mineral materials, ie mineral glass or glass-like materials in the broadest sense, eg ceramics. Typical advantages of mineral materials compared to coating materials are, for example, the possibility of giving the surface a better gloss, the better scratch and corrosion resistance, with certain glasses (ESG, single-layer safety glass) thermal shock resistance, high modulus of elasticity. Mineral glasses can be produced in a variety of settings - fully transparent, translucent or opaque - the surfaces can already be structured during production, eg embossed or can be machined later, eg by grinding, etching, sandblasting, enamelling, semi-transparent or opaque screen printing , With mineral glasses, the risk of breakage can be significantly reduced, especially by the thermal or chemical prestressing of the glass surface, and the residual capacity of glass elements can be increased.

As a disadvantage of mineral glasses compared to coating materials remains in the

Generally higher risk of breakage, which places higher demands on processing as a whole, as well as higher brittleness. In the case of mineral glasses, the risk of breakage can be reduced, in addition to the chemical composition and, to a certain extent, by thermal pre-treatment, by covering the discs with a layer of elastic organic polymer ("plastic") or more

Disks by means of a polymeric adhesive made of an elastic organic polyme ren (usually about polyvinyl butyral or a casting resin) are connected. An elastic layer of the non-mineral material is arranged between at least two mineral glass panes (so-called laminated glass). A so-called safety glass is obtained, from which special embodiments may possibly be produced to a higher degree of bulletproof security. It is possible to apply the glue e.g. but i.d.R. not the decorative effect, but other objectives are pursued, e.g. the light and / or heat absorption.

The variability of the decorative design of glasses leaves nothing to be desired. For example, to make opaque glass opaque, apart from the possibility of storing insoluble pigments in the glass (so-called opal glass), it is only possible to enamel the glass; In this case, a uniform layer of an inorganic enamel is applied to the glass on one or both sides by means of a rubber roller, which is then baked at about 600 ⁰ C. Disadvantage of this coating method is the fact that only homogeneous, possibly colored surfaces without pattern or structuring can be produced. As structuring option, instead of float glass, ornamental glass can also be used, which is then enameled on the non-ornamented glass surface.

With the current glass technology, an opaque glass element that has different colors and structures, each with the appearance of a decorative laminate, can not be achieved. The production of metallic effects on glass is essentially limited to the production of mirror glass, while the variety of effects achievable by coating HPL plates with correspondingly structured metal foils can not be achieved. Now it is generally known to connect at least two glass sheets by means of an adhesive film together (so-called VSG process). This is not limited to ebenflächi¬ ge discs, but can also be applied to curved discs. It is possible to process colored or structured films additionally with a metal sheet. The film or adhesive layer is then located between the glass and the metal. However, it is often disadvantageous that suitable sheets can usually only be processed in relatively large thicknesses. The required thickness of such a metal sheet (> 0.6 mm) can lead to warping of the disk if the thermal expansion of metal and glass is different. As the metal stainless steel is therefore advantageous, the coefficient of thermal expansion is similar to that of soda-lime glasses. Such sheets are very expensive. The color designability of the metals, however, is essentially limited to aluminum, the chemically or electrically protective oxidized surface can be colored. When using stronger aluminum sheets, the large difference in thermal expansion compared to soda-lime glass leads to severe distortions of glass-metal composite elements. The number of possible embossed designs is limited by the production process.

Another possibility for structuring or coloring glass is the screen printing process. Also in this decorative method is a spatial design i. S. the application of a relief structure only on the base glass (ornamental glass) possible. When screen printing on glass, a color sample is applied. There are screen printing processes that rely on the use of inorganic inks containing as pigment a glass frit that can be baked at about 600 ⁰ C. Thus, both different colors, as well as different patterns on the disc can be displayed. The disadvantage is that inorganic screen printing is not completely opaque. If this is desired, usually a second screen printing layer must be applied (black or dark gray), thus always resulting in two different views of the glass plate. Another possibility of surface coating of glass results from the organic screen printing; thereby thermally or in the ultraviolet light curing paints are applied. However, the disadvantage of such coatings is the low mechanical resistance and the lack of resistance to ultraviolet radiation. An orientation of such organic layers to the inside of a laminated safety glass is only conditionally possible, since the adhesion of the security film to the coated surface is dependent on the adhesion of the screen print to the glass surface. The advantage of organic screen printing is the availability of high-gloss metallic and transparent colored coatings. By means of screen printing, however, no high-gloss metallic surfaces can be produced. Nor are special surface effects (brushed, ground, embossed) to be achieved with this method.

It would be desirable to combine as many favorable properties of mineral materials as possible with those of resin-bonded HPL-type coating materials. This was, as I said, previously tried mainly by the incorporation of finely divided minerals in their surface. However, it is not possible in this way to obtain panel materials that are transparent or at least transparent translucent. Composite materials of coating materials with mineral glass in plate form have not been previously known.

It is an object of the invention to provide a panel material having the decorative design possibilities of an HPL or CPL type laminate having a higher gloss level than that of a typical HPL or CPL type laminate.

It is a further object of the invention to provide a material, in particular a decorative panel material, which is resistant to weathering and thus can be used outdoors.

It is a further object of the invention to provide a decorative panel material whose surface has the physical properties of a mineral glass, in particular its low surface roughness (high smoothness) and its high gloss.

It has now been found that it is possible to combine the properties, in particular the surface properties of glass materials, with the decorative possibilities resulting from the use of HPL or CPL-type coating materials, by virtue of the fact that the surface of an HPL or CPL Laminate plate by means of a polymeric adhesive on one or both sides with a mineral glass or ceramic plate is permanently bonded, so that a composite material with the basic layer structure glass // polymer adhesive // HPL / CPL laminate results. If required, this material structure can be expanded to include a reverse side applied by means of another layer of a polymeric adhesive, i. glued-on further layer of glass, so that a composite material with the basic structure glass // polymer adhesive // HPL plate // polymer adhesive // glass has (Fig. 1). It is surprising that the typical physical constants of two materials that are as different as HPL / CPL laminates on the one hand and mineral glasses on the other can be combined in the composite materials according to the invention. This relates in particular to the thermal expansion, which was expected to be contrary to the intention of the invention to create a special material which is also suitable for outdoor applications.

Whenever glass materials or mineral glass are mentioned below, the entire diversity of mineral materials in sheet form is meant, irrespective of whether they are plane-surface or arbitrarily curved sheet-like materials.

Subject of the invention is a plate-shaped composite material, as obtained by bonding a HPL or CPL-type laminate on one or both sides by means of a polymeric adhesive with a glass or ceramic plate permanently. Permanent connection means a connection in the manner of a bond, which in Generally only under mechanical destruction (breakage) of the material structure can be solved again.

The subject matter of the invention is a composite material having the features specified in claim 1, in particular in claim 2, wherein the layer structure claimed according to the invention relates to all sheet-like materials, irrespective of whether they have a planar or curved, homogeneous or discontinuous surface.

A particular embodiment of the invention consists in that the HPL or CPL laminates embedded between two glass layers are wholly or partly provided with recesses (holes), such that transparent regions are present in the composite material, which provide a view through the laminate Allow material. Such structures are particularly advantageously made of two outer glass sheets and a perforated inner laminate. The breakthroughs in the laminate, after their preparation, e.g. produced by punching or even before production, i. the pressing process, by placing stamped papers on an underlying continuous layer can be achieved. The laminate can be connected to the entire surface of the glass, wherein the size of the laminate is about the glass size or smaller than the glass element. Each element may also have apertures that pass through both the glass and the laminate. The design possibilities are so far no limits.

It is an advantage of the invention that the decorative panel material according to the invention has a surface with the physical properties of a mineral glass, in particular its low surface roughness (high smoothness) and its high gloss. The term of gloss and its determination is defined in DIN 55945, the content of which is considered part of the present description. It should be noted that the term "gloss" as used herein refers only to surface smoothness and has nothing to do with reflection, i. the reflection. The glasses used in the invention have a low

Reflection, which typically does not exceed about 10% of the incident light, and has the consequence that the decor of the composite material according to the invention remains readily apparent in almost plastic clarity even when viewed from the side, up to a viewing angle of, for example 45 ° ,

The materials required for constructing the composite material according to the invention and their processing will be described in detail below.

To produce a decorative laminate (laminate plate) of HPL type can be based on the known technology of such HPL coating materials. As a rule, a construction of different materials takes place, which depends on the intended use and the intended structure. For opaque, ie generally opaque, self-supporting plates are usually first a few layers of synthetic resin soaked inexpensive material webs ("carrier") of cellulosic material (eg fabric or other matted or woven cellulosic material, but usually paper, generally speaking a fibrous material) onto a stable metal plate placed, which serves as a transport pad, that can be brought later in a plate press. Instead of paper webs also inorganic materials such as glass or mineral fiber webs or synthetic fiber materials can be used. If the process described above is carried out continuously (ie, unseparated roll material is used instead of individual webs), the individual layers can also be obtained in the form of endless plates by means of suitable belt presses, which have heatable tables, which are only cut after curing or uncut as rolled goods to be marketed. These materials are referred to as CPL (continuously pressed laminates) laminate panels. When it comes to the use of H PL materials, this also means the equivalent CPL materials.

As a synthetic resin for the base body usually a thermosetting phenol-formaldehyde (pre) condensate ("phenolic") is used for economic reasons, but are technically other thermosetting curable formaldehyde (pre) condensates such as melamine or urea resins or thermosetting (ie, "crosslinkable" condensable to a three-dimensional network) other resins such as epoxy resins or polyurethanes suitable. For the composite material according to the invention, the phenolic resin-bonded base body is not always required, i. preferably omitted, because even by the bond with the glass material in general a sufficient rigidity is achieved. Of course, it is also possible to use HPL / CPL coating materials which have all the constituent layers of an ordinary HPL coating material. If the laminate plate to be used is to remain translucent, the use of the strongly colored phenolic resins is dispensed with in a manner known per se and corresponding material webs are also used, that is to say preferably pure cellulose-free papers.

According to the invention, it is essential to form a coating material which has the features of the decorative layer of an HPL coating material. For this purpose, one or more layers of paper, which are to form a decorative layer, usually a cellulose paper, which is impregnated with a light-colored binder, for example a thermosetting curable formaldehyde, are applied to the metal plate, optionally over the already mentioned material for a base body. Condensate of urea and / or melamine ("urea or melamine resin"). The decorative layer can be mono- or multi-layered, ie consist of one or more paper layers which are either only pigmented or additionally printed and, optionally together with the resin-impregnated base, cured in the heatable press, ie under pressure and heat. Over the decorative layer, a further layer can be arranged, a so-called overlay. Melamine-resin-bonded pure cellulose papers without pigmentation are generally used for this purpose. For the purposes of the invention, an overlay is not generally required, but it can be preferably dispensed with, since it does not depend on the resistance of the surface to external influences - eg water - here. In this way, a particularly clear reproduction of the decoration of great spatial effect can be achieved. Since the strength properties of the composite panel according to the invention are largely determined by the glass body, moreover, the proportion of melamine in the binder of the Decorative layer be low or missing, ie it can be a particularly inexpensive urea resin used.

Special HPL materials are e.g. obtained by the fact that the decorative surface instead of printed paper of natural materials such as real wood veneer, natural or technical fibers or tissues. It can be used all materials that were previously common in the production of HPL-materials or future.

The pressing process for forming a laminate plate is done in a conventional

Platen press. The pressing pressure can for example be between 10 and 200 bar, which also depends on the performance of the press and is not specific to the invention. The pressing temperature is generally between 100 and 200 ⁰ C. For economic or technischen reasons, it may be appropriate during the curing remove the temperature-temperature and / or pressure or to increase. Because of the different reactivity of the commercially available resins, a general time requirement for the curing can not be specified; the best hardening time is to be determined by a preliminary test.

If one uses only the relief formation (surface modeling) serving structural encoder, such as a metal foil without adhesive layer, which does not adhere to the layer structure of the invention (a so-called. Allowance), this is removed after demolding again.

The decorative layer thus generally consists of at least one layer of a substrate impregnated with light-colored resin, the binders used being, above all, thermosetting melamine resins, or else formaldehyde condensates prepared with the concomitant use of melamine, because of the desired durability. The above-indicated distinction between condensates and precondensates refers to the fact that the formaldehyde resins used for impregnation are already produced by a condensation process, but which is incomplete, so that only during the pressing irreversibly a chemically crosslinked three-dimensional network, ie a so-called thermoset arises. The precondensation usually takes place with the discharge of water and has nothing to do with the production of the considered layer materials. The fundamentals of the formation of formaldehyde condensates have already been extensively described in the older technical literature and therefore need no further explanation by the person skilled in the art.

When a composite material according to the invention is to be obtained which has a mineral glass surface on both sides, this is often done with the intention of achieving a decorative effect on both sides. In this case, one will choose the HPL middle layer such that it has a decorative surface on both sides. The layer can be transparent or opaque. If it does not depend on a particularly high material thickness or opacity, the use of the (phenolic resin-bonded) carrier layer can be dispensed with, so that the structure of an HPL material which can be used according to the invention in the simplest case is based on the composite of at least one layer a resin-impregnated fiber material and restricting at least one decorative layer (decorative layer). In the simplest case, a resin-impregnated, colored, eg printed, layer of a fiber material can be used as the decorative layer.

Decorative coating materials are now known which overlie the layer e.g. a metal foil (or more metal foils one above the other), which may be considered as a decorative layer in a broader sense. The metal foil (s) may be partially perforated so that they reveal the respective underlying decorative layer and / or the carrier layer. The imagination has virtually no limits in all these arrangements, depending on which effects one seeks. For example, For example, a laminate can be made which is outwardly similar to a solid metal plate and yet has all the advantages commonly known only from plastics on the one hand and mineral glass materials on the other hand. A special technique of surface treatment of plastic surfaces consists in vapor deposition with metal, and depending on the nature of the substrate also hochglän¬ zende surface are possible. Such vaporized layers are particularly durable to preserve with the inventive method, since the intrinsically sensitive metal layer (thickness of fractions of a thousandth of a millimeter (microns) up to a few hundredths of a millimeter) is then protected from damage.

Above all, by means of the layer structure according to the invention, the disadvantage of most metals is overcome that they do not permanently withstand atmospheric influences, which restricts their use outdoors for decorative purposes, as far as it is not pure construction materials. Specifically, as a long-term durable surface, e.g. for façade cladding, only stainless steel, possibly titanium and, with certain restrictions, certain types of surface-finished aluminum, but which must be high-purity aluminum, or certain alloys which are chemically or electrolytically oxidizable. Although there are also relatively resistant materials among the light metal alloys. However, these can not be produced with all surface structures, e.g. Especially high-gloss materials are not easily available in weatherproof design. Although it is known that coating material plates which are provided with a metal surface can be coated with a protective layer (for example coating, in the case of aluminum and also electrolytic or chemical oxidation).

For the permanent bonding of a metal foil to a synthetic resin surface, the foil is usually pretreated with a commercially available primer, for example a suitable intermediate layer in film form, which optionally represents a separate layer in an analysis of the layer structure of the composite material according to the invention. Suitable metal foils are films or thin sheets of virtually all suitable for decorative purposes metals, such as those of copper, aluminum, iron, titanium or their alloys, such as brass or stainless steel. They can be metallic bright or, depending on the decor designer's intention, also dull, electroplated with other metals, or otherwise superficially modified. Depending on the type of metal used, it may be advantageous to provide the metal foil with a protective layer. In the case of aluminum, the protective layer may, for example, be the oxide layer obtainable by anodic oxidation or a phosphate Be layer. It may be convenient to use surface-treated metal foils which in addition may in turn have a decorative pattern (eg be printed) or have a mechanically or chemically processed surface, eg ground, brushed or etched. The metal layer can be broken so that the purposefully decorative background remains partially visible. In this case, the entire surface of the laminate plate, ie both the metal parts and the plastic parts, can subsequently be coated with a protective layer or protective layer.

As a mineral glass material are suitable for the purpose of the invention, for. Flat glass panes of 1 mm - 20 mm thickness. Suitable are all technically conventional Flachglassorten, e.g. Lime-soda glass or borosilicate glass, available either in the form of cast glass, float glass or drawn glass. The glass can be colorless, colored in the mass or provided with a whole or partial coating on one or both surfaces. The type of coating can be a thick-film layer (applied, for example, by means of screen printing, enamelling, dipping, spraying) or a thin-film layer which, for B. is applied pyrolytically or by magnetron on the glass. The surface properties of the glasses used are generally given by the manufacturing method, i. the glass panes can be smooth (float glass, drawn glass) or structured (cast glass, ornamental glass), or else consist of smooth-surfaced glass, which can be retrofitted for example. B. by etching, sandblasting, grinding or laser machining was structured. The residual roughness of smooth flat glasses is generally below the wavelength of the light, ie at 300-400 nm or less. In general, the proportion of reflected light at normal incidence is less than 10%; typical reflectance values of a float glass are about 8% or less; this proportion can be achieved by surface treatment of the glass, e.g. by evaporation with antireflection agents in the usual way, even to surfaces that are no longer perceived even when viewing and only convey the impression of the underlying plastic surface. The measurement of the reflection takes place in a known manner, e.g. according to the EN 13300.

The glass panes can be used without strengthening measures, as well as after thermal or chemical prestressing.

For special purposes, it is also possible to use glasses which are already composed of several layers, such as e.g. Safety discs or bullet-proof discs.

It has surprisingly been found that in general no special consideration has to be given to the different coefficients of thermal expansion of HPL plates and glass plates, so that to this extent there are no restrictions with regard to the types of glass to be selected. In particular, in cases where both the show side and the back of the composite material are formed by a glass plate, a non-surface treated (thermally or chemically tempered) wafer may be used on the back side.

However, it should be taken into account that different coefficients of thermal expansion and possibly material thickness of the glasses lead to different thermal stresses lead to avoid deformation of the material during increased heating / cooling. In many cases, however, front and back of a composite panel according to the invention are used equally as a show side, for example in partitions of the material according to the invention. In that case you will be using identical glasses on both sides anyway.

As a polymeric adhesive for bonding HPL laminate and glass body are all materials with which glasses can be interconnected. Advantageously, laminate and glass are bonded by means of a commercially available fusible adhesive of PVB (polyvinyl butyral). The connection is made so that the

Decor side, optionally also the back of the laminate covered with a PVB film and heated with the then placed glass and pressed under high pressure with the glass. Commercially available PVB films have a standard thickness of 0.38 mm, i. When using thicker intermediate layers (for example due to the surface structure of the layer material), it is necessary to use several films one above the other and in each case achieve a multiple of this material thickness. Alternatively, it is also possible to use one- or two-component casting resins which cure by autokinesis, thermally or by high-energy radiation.

When it comes to high thermal shock resistance, the use of single-layer safety glass (ESG) is recommended, especially since, in construction, in many cases, this will be mandatory anyway. These are glasses in which by thermal or chemical treatment in the surface, a compressive stress is generated, which is neutralized in the center of the glass by a tensile stress zone.

The advantages of composite materials according to the invention will become apparent to the person skilled in the art directly from the above. Of particular note, however, is the particular advantage of the optical system according to the invention that in this way very thin metal foils can be processed in conjunction with glass and a material of high rigidity is obtained.

The composite material obtainable according to the invention consists (represented in order from one surface to the other and preferably in the form of a plate) according to the appended drawing (FIG. 1)

a) a first layer of a mineral glass Gl;

b) a first adhesive layer Kl;

c) if necessary, at least one first layer of a cellulosic resin-bound top layer (overlay) oil;

d) if necessary, at least one first metal foil Ml, which is optionally provided to the underlying decorative layer Dl or the top layer Ol out with a bonding agent Hl; e) if necessary, at least one resin-bound, serving as decor carrier paper layer Dl;

f) if necessary, a single or multi-layer, impregnated with resin fiber web P as a carrier layer, leveling layer or to adjust the material thickness;

g) if necessary, at least one second, resin-bound, serving as a second De¬ korträger paper layer D2;

h) if necessary, at least one second metal foil M2, which is optionally provided with a bonding agent H to the paper layer D2 and the cover layer 02;

i) if necessary, at least one second layer of a cellulosic resin-bound top layer (overlay) 02;

j) optionally a second adhesive layer K2;

k) if necessary, a - possibly second - layer of a mineral glass G2;

with the proviso that either at least one of the optional layers d) and e) or at least one of the layers d) and / or e) and a layer f) is present and further that the layers c) to i) together comprise an HPL or form CPL laminate.

If a mineral glass layer G2 is present, an adhesive layer K2 is also present; Otherwise, the layers of a) and k), b) and j), c) and i), d) and h) as well as e) and g) are obviously identical with respect to the type of material. These pairs of materials may be the same or different both in terms of construction and in terms of the aesthetic effect. It is understood that instead of a single metal foil Ml, M2, it is also possible to use a plurality of metal foils one above the other, e.g. a metal foil is ornamentally broken to release a partial view of the underlying second slide.

An HPL or CPL laminate with the minimum prerequisites according to the invention is obtainable from the fibrous web P used as a decor carrier paper layer D, if necessary the cover layer (overlay) O and, if necessary, the metal foil M obtainable in that these layers prior to bonding with the Mineral glass layer in a conventional manner in a separate operation under pressure and heat bonded together ("laminated").

It should be noted that the term "as needed" in the above description of the invention is used in place of the term most commonly used in the patent literature "optionally" to show that it is an optional feature within the scope of the invention, while the term "if appropriate" is used, if the referred feature depends on the presence of an optional feature. Thus, if a layer Ml, M2, ie a metal foil is present, an adhesive (bonding agent) Kl, K2 present, but not if the characteristic "metal foil M" is not occupied.

The structure according to the invention can easily be determined in accordance with the accompanying figures by cutting the respective composite material perpendicular to the surface, possibly looping it on and subjecting the subjectively recognizable layer structure to a corresponding enlargement, e.g. viewed with a magnifying glass. If necessary, the usual analytical methods for the identification of materials, such as X-ray fluorescence analysis, staining methods and / or chemical analysis, also serve to identify the layers.

The upper decorative layer, i. in the usual expert language use the decorative layer, it can be said as a metal foil or a decorative paper or both constructed of paper decorative elements and elements that are characterized by a, possibly also broken or non-contiguous metallic surface. In this embodiment of the composite according to the invention, e.g. a decorative laminate plate used, the recessed surface forms a continuous surface, while the raised decorative elements have no connection with each other. An example is, for example, a sublime dot pattern. At the perforated points of the die pressed during the pressing process, the still flowable material of the resin composition, the decorative layer to the allowance, so before the usual press plate. For a metallic surface of compliant metal, e.g. made of aluminum, which makes a particularly appealing impression, have e.g. after removal from a high-gloss press plate, the protruding elements have a high gloss, while the lower-lying elements have retained the original structure, for example a brushed surface.

In this case, especially in the case of a decorative plastic layer, the decorative elements at the perforated points assume the surface character of the allowance, thus appearing e.g. high gloss, while the recessed areas e.g. can appear dull. Of course you can also use a high-gloss sheet for the die.

A particularly advantageous embodiment of the invention results when a laminate with a very thin fiber core (<0.2 mm) is produced, which is coated on both sides with an optical layer (metal foil). This laminate behaves visually like a metal plate, but produces much less distortions in the glass composite, as a pure metal plate. In addition, this special laminate is easier to handle than ordinary laminates, z. B. to punch. As a result, it is possible to achieve partially transparent laminates, which are subsequently enclosed between two glass panes. The products thus obtained have hitherto been virtually inaccessible.

However, it is also possible to use laminate panels in which the perforated areas of the metal surface are not completely filled up by the resin composition, but the surface has a relief structure. If this is the case, the material thickness of the adhesive Kl or K2 should be chosen so large connect the laminate plate with the mineral glass plate no voids, but the adhesive fills the predetermined bumps.

The proportion of area and the shape of the metal foil in relation to the rest of the decorative (i.e., plastic) surface are not important here, i. the area ratio and the shape are determined solely by aesthetic, not by technical reasons and can therefore assume any values; e.g. For example, a metal foil M may be employed which, preferably in the form of a decorative pattern, covers between 10 and 99 percent of the total surface area of the material and leaves from 1 to 90 percent of the underlying decorative plastic surface.

When a metal foil is used as the uppermost layer, i.d.R. uses a material which is provided on one side with a primer H or more often with a glue coat which also cures when hot. According to a proposal in US Pat. No. 3,475,240, instead of a decorative layer of resin-impregnated paper, a metal foil etched back with a suitable adhesive can be pressed directly onto a base body of phenol resin-impregnated paper layers and thus serves as the only decorative layer. The metal foil can thus be applied directly above the base body; There is no need to use decorative paper. In some cases, it is expedient to apply a so-called compensating paper between the main body, optionally the decorative foil and the metal foil, which covers minor imperfections of the (usually particularly inexpensive) base body material.

In order to obtain surfaces in which the raised elements are contiguous while the recessed ones are singulated, it must be possible to place on a thin support, e.g. an overlay paper, the corresponding patterns are glued in the form of metallic elements. Conversely, surfaces in which the raised elements are interrelated while the recessed ones are singulated can be obtained by using metal foils having a punched-out pattern.

The heat / pressure treatment during the application of the compensating paper and / or the decorative paper can already be stopped as soon as a partial hardening has taken place, i. that an incompletely cured leveling or decorative layer is already sufficient for carrying out the invention, since during application of the metal foil and its

Bonding with the substrate in any case, a further heating takes place, which optionally has a hardening of an incompletely cured resin in the leveling layer result. The same applies to the compound of laminate and mineral glass, which takes place under short-term heating.

For bonding the metal foil to the plastic surface, different means may be used; For example, hot melt adhesives (thermoplastically processible adhesives based on, for example, vinyl polymers) or thermosettingly curable (heat-reactive) adhesives can be used which have a sufficient affinity for the metal surface. Thermosetting phenolic resins based on cresol-formaldehyde condensates, for example, which have been applied to one side of the metal foil in the form of (generally solvent-containing) coatings, are suitable. After removal of the solvent, these lacquered metal foils can readily be used according to the invention. Other heat-curable adhesives are, for example, precursors which harden by the action of heat and give polyurethanes or epoxy resins after curing. It seems to be important that they are products which do not split off any water during curing (crosslinking), since this would possibly impair the success desired according to the invention. From the literature suitable means are known for the permanent bonding of metals, which are suitable for carrying out the invention.

In summary, the following advantages are achieved, inter alia, with the composite material according to the invention:

It can be used all surface and plastic design options for the surface, which are possible with the production of HPL board materials, such as applying an unlimited number of decorative patterns; Applying a plurality of decorative layers one above the other with respective recesses through which the underlying layers remain visible; Embossing, painting, brushing.

The laminates give the glass / laminate composite a high residual capacity because they are not brittle.

The glass gives the composite mechanical rigidity. The rigidity results from the modulus of elasticity of the glass and the moment of resistance.

The glass makes the underlying material appear plastic and high gloss and creates a depth effect.

The glass protects the softer laminate from mechanical damage.

Claims

claims

1. Composite consisting of

a) a first layer of mineral or transparent ceramic

Material Eq.

b) a first adhesive layer Kl;

c) a multilayer laminate of the type obtained under pressure and heat

HPL or CPL type;

d) optionally a second adhesive layer K2;

e) if necessary, a further layer of a mineral glass or durchsich¬ term ceramic material G2.

2. A composite material according to claim 1, consisting, in order from one surface to the other and preferably in plate form according to the appended drawing (Figure 1)

a) a first layer of a mineral glass Gl;

b) a first adhesive layer Kl;

d) if necessary, at least one first metal foil Ml, which is optionally provided to the underlying decorative layer Dl or the top layer Ol out with a bonding agent Hl;

e) if necessary, at least one resin-bound, serving as decor carrier paper layer Dl;

f) if necessary, a single or multi-layer, resin-impregnated fiber web P as a carrier layer, leveling layer or to adjust the material thickness;

g) if necessary, at least one second, resin-bound paper layer D2 serving as second decor carrier;

i) if necessary, at least one second layer of a cellulosic resin-bound top layer (overlay) 02; j) optionally a second adhesive layer K2;

k) if necessary, a - possibly second - layer of a mineral glass G2;

3. A composite material according to claim 1, characterized in that the Papier¬ layers Dl and D2 and the outer layers of oil and 02 are impregnated with a urea or melamine-formaldehyde condensate.

4. A composite material according to claim 1, characterized in that a Metallfo¬ lie Ml or M2 used with a thickness of 0.01 to 1 mm or one of the layers Dl and / or D2 or Ol and / or 02 with a vapor-deposited Metall¬ layer is provided.

5. Composite material according to claim 1, characterized in that the mineral glass layers Gl or G2 have a thickness of 1 to 19 mm.

6. Composite material according to claim 1, characterized in that the adhesive layers Kl or K2 consist of polyvinyl butyral or a casting resin.

7. A composite material according to claim 2, characterized in that a Metallfo¬ lie Ml or M2 has been used, which covers, preferably in the form of a dekorati¬ ven pattern, between 10 and 99 percent of the total surface of the Werk¬ material and 1 to 90 Percent of the underlying decorative plastic surface leaves free.

8. Composite material according to one of claims 1 to 7, characterized in that the mineral glass at the time of processing has a surface roughness of not more than or a gloss level of at least.

9. Composite material according to one of claims 1 to 7, characterized in that the mineral glass has a refractive index n _D ²⁰ of at least 1.45.

10. A method for producing a composite material according to any one of claims 1 to 6, characterized in that the Aus¬ selected according to claim 1 aus¬ layers c) to i) prior to bonding with the mineral glass layer in a separate operation in per se known Way under pressure and heat are joined together.

drawing