DE202005020653U1 - Stone glass element comprises thin stone plate and support plate comprising windowpane, which is connected by means of opaque casting resin layer with the plate, where a substance deactivates the developed radical structures - Google Patents

Abstract

Stone glass element (I) comprises at least a thin stone plate (1) and widely associated support plate (2) comprising at least one windowpane, which is connected by means of a transparent or opaque casting resin layer (3) with the stone plate, where at least a substance (a), which is homogeneously distributed in a solid phase of the resin layer and deactivates the developed radical structures by chemical oxidation.

Description

The The invention relates to a stone-glass element with at least one thin stone slab and a large-scale connected Support plate comprising at least one glass sheet, which by means of a transparent or opaque casting resin layer with the stone plate connected is.

Such a stone-glass element is from the EP 799949 known.

One Composite of at least one plate made of natural stone is flat with connected to at least one other plate made of glass. As composite materials be a series of plastics, such as acrylates, silicones, polyurethanes etc. called. In order to ensure a durability of the alliance suitable for everyday use over a To achieve a long period of time, will be a series of adhesion agents described, which ensure the bond between glass and natural stone and to prevent delamination. In many cases have these combinations are proven and re the risk of delamination proved useless.

It However, it has been shown that in such natural stone elements clear discoloration, embrittlement or bubbles in the composite layer. This occurs in particular then often if, as a glass plate, not soda lime with a normal, but with a reduced iron content or borosilicate glass use place. This damage one finds also with commercial ones Float glass, but only under intense, prolonged UV irradiation. By the UV irradiation are in the Gießharzschicht as well as in the Steinplatte generates radical structures, which by their high reactivity the above mentioned damages cause.

These damage occur even if the for the production of the composite used plastic only small or no inherent absorption of ultraviolet radiation, so that a direct dependence of UV irradiation and frequency of damage is not obvious and the damage is also due to absorption of Energy caused by the stone material of the stone plate can.

task The present invention is therefore a stone-glass element to propose avoiding the damage described above become.

These Task is inventively characterized solved, in a solid phase of the casting resin layer at least one Substance homogeneously distributed exists by chemical oxidation deactivated radical structures deactivated. By intercepting free radicals in the cast resin layer Due to the substance prevents the radical structures due to their high reactivity with the cast resin layer react and thus discoloration or other impairments the casting resin layer cause.

A Further development of this embodiment provides that the substance that deactivates the radical structures, so selected is that in one, while the production of the stone-glass element temporarily existing, liquid phase the casting resin layer solved and in one, after curing the casting resin layer existing, dispersed solid phase dispersed. By loosening the Radical structures deactivating substance in the liquid phase the casting resin layer a homogeneous distribution of this substance is achieved after curing the casting resin layer preserved.

There the radical structure deactivating substance by the reaction With the free radicals gradually consumed, the concentration needs this substance, to provide a long-lasting protection, relative high chosen become. Preferably, the radical structures deactivating substance in the cast resin layer with a proportion by weight of not more than 2%, preferably 0.5% to 1 available.

at an advantageous embodiment of the stone-glass element are several different radical structures deactivating substances present in the casting resin layer. Consequently can react to different radical structure breaking up and these are disabled.

The casting resin contains preferably amines as a radical structure deactivating substance. Amines do not react to colored Products, so that the full transparency of the casting resin layer is maintained.

As well is it useful when the casting resin layer Phenols and / or tocopherols deactivating as radical structures Contains substance. These substances are relatively inexpensive and change their chemical and physical Properties, such as Young's modulus, after the reaction not with the radicals.

Further inexpensive substances that deactivate as radical structures Substance in the casting resin layer can be included are phosphates. They too are changing their chemical and physical properties during the reaction hardly with the radicals, but only react at higher temperatures.

Preferably is the flagstone of the stone-glass element of the invention Natural stone made. Such stone-glass elements have a high aesthetics on.

at a cheaper one embodiment the flagstone is made of artificial stone. Here comes also the opposite Natural stone slabs lower weight, as well as the almost arbitrarily selectable design positive to the validity.

A particularly preferred embodiment of the stone-glass element according to the invention provides that the cast resin layer based on polyester resin, polyacrylate, polymethacrylate, polyurethane, Epoxy or silicone is formed. Such casting resins are insensitive to the Absorption of moisture. This manifests itself both in a high durability the bonding under the influence of water as well as in a small Tendency to cloudiness when taking in water.

It is advantageous if in the cast resin layer an adhesion promoter based on one or more silanes and / or titanates and / or Aluminates is present. This allows the quality of the bond of the stone with the glass.

at a preferred embodiment of the stone-glass element according to the invention is at least one in a solid phase of the cast resin layer further substance homogeneously distributed, which radiation in the Wavelength range absorbed by ultraviolet (UV) light. By the absorption of UV radiation in the cast resin layer is an impact of UV radiation and thus the absorption the UV radiation in the stone surface and the resulting damage avoided. The resulting from absorption of UV radiation discoloration and embrittlement the stone surface can thus be counteracted.

Preferably The UV absorbing substance is selected so that she in one, while the production of the stone-glass element temporarily existing, liquid phase the casting resin layer solved and in one, after curing the casting resin layer existing, dispersed solid phase dispersed. In this way becomes a homogeneous distribution of the UV light-absorbing substance and thus a uniform absorption the incident UV radiation over the entire area the casting resin layer realized.

A preferred embodiment Provides that the UV light absorbing substance for light in the wavelength range between 280 nm and 360 nm is impermeable. In this case will exclusively the range of UV-B radiation, which is mainly for the damage described above the stone surface is responsible, hidden by the Gießharzschicht. Visible light, on the other hand, can pass unhindered through the casting resin layer penetrate, so no disturbing Color shimmer arises. About that It is due to the permeability of the cast resin layer for UV-A radiation possible, the cast resin layer by means of UV light to harden in the range between 360nm and 380nm.

In a preferred embodiment of the stone-glass element according to the invention is the ultraviolet absorbing substance in the cast resin layer with a proportion by weight of not more than 0.1%, preferably between 0.005% to 0.05% present. This concentration of UV light absorbing Substance is sufficient to contain the essential components of UV radiation filter out the solar spectrum and thus the Gießharzschicht and the stone surface to protect.

It may be advantageous if in the Gießharzschicht several different UV light absorbing substances are present. That way can be a big one Absorption spectrum covered, or the chemical properties the casting resin layer adapted, e.g. the sensitivity to acids or alkalis.

at an advantageous embodiment of the stone-glass element according to the invention contains the cast resin layer Benzophenones or derivatives of benzo phenone absorbing as UV light Substance. In particular in combination with a casting resin layer From acrylates this results in comparison to free-radical polymerization particularly stable layer.

It is likewise advantageous if the cast resin layer contains benzotriazoles and / or benzotriazines and / or derivatives thereof as UV-absorbing substance. The thermal stability of the casting resin layer is thereby increased significantly.

alternative or in addition this may be the casting resin layer cinnamic or derivatives of cinnamic acid esters As a UV light-absorbing substance, which is advantageous is, than that these are particularly low-priced substances is.

A another embodiment of the stone-glass element according to the invention provides that at least on the casting resin layer facing surface of the Steinplatte a barrier layer is applied, which is a diffusion of substances of the stone slab in the casting resin layer respectively of substances of the cast resin layer blocked in the stone plate. In this way it can be prevented that in the cast resin layer, for example ions in the stone plate, or vice versa in the stone plate located ions penetrate into the casting resin layer and change their color there by reaction with other substances and thus undesirable appear.

Around to prevent the diffusion of several different substances which can not all be blocked by a substance sees a development of this embodiment ago that the barrier layer several chemically different substances contains which avoid diffusion.

A similar Effect can be achieved if multiple barrier layers with different Substances are provided which a diffusion of substances of Stone slab in the cast resin layer or of substances of the casting resin layer in the stone slab blocked.

In an advantageous embodiment of the stone-glass element according to the invention, the barrier layer contains a copolymer of styrene with acrylates or methacrylates. As a result, in a wide temperature range, a very good resistance to H ₂ O diffusion in liquid or gaseous form is achieved.

It has come in handy proven when the barrier layer is a copolymer of polypropylene and / or polyethylene with acrylates or methacrylates. This is in polar solvents, such as water, alcohol, etc., insoluble and therefore has excellent durability and high resistance across from polar molecules on.

Regarding The diffusion of non-polar substances, it is advantageous if in the barrier layer acrylates or methacrylates as co- and / or Graft polymers are present. This is especially relevant if the stone-glass element or parts thereof nonpolar solvents, such as gasoline or hydrocarbons are exposed.

A further preferred embodiment provides that the barrier layer vinyl acetate, vinyl alcohol, in particular Ethylene vinyl acetate (meth) acrylic acid copolymers contains. This will give good adhesion to stone and a good chemical resistance guaranteed

This is also the case when the barrier layer contains epoxy resin. In contrast however, epoxy resin is very hard to the above mentioned substances and brittle.

A particularly preferred embodiment of the stone-glass element according to the invention provides that the barrier layer has a thickness between 1 μm and 100 μm, preferably about 5 to 50 μm, so that a sufficient protection of the stone-glass element realized can be.

Further Advantages of the invention will become apparent from the description and the Drawing. Likewise, the above and the further listed features individually or can be used for several in any combination. The shown and described embodiments are not as final enumeration but have rather exemplary character for the description of the Invention.

It demonstrate:

1a an exploded view of a schematic structure of a stone-glass element according to the invention, and

1b a sectional view of the stone-glass element 1a ,

1a and 1b show the schematic structure of a stone-glass element according to the invention, in which a thin stone slab 1 with a support plate 2 by means of a casting resin layer 3 is connected over a large area.

To reduce the radical structures in the casting resin layer 3 are the cast resin layer 3 added one or more substances that deactivate radical structures (antioxidants). As a result, the life of the composite is increased, since an unwanted reaction of free radicals with other substances of the casting resin layer or with substances of the stone surface is prevented, so that the resulting undesirable discoloration and structural changes of the stone-glass element are avoided.

there it has been proven that for different casting resins also various radical structure deactivating substances individually or in combination are particularly effective. Type and amount of radical structures hang deactivating substances but not only from the nature of the casting resin, but also from the used Stone off.

mit R1 = Wasserstoff, Methyl oder tert.- Butyl,
R2 = Wasserstoff, Methyl oder tert. – Butyl,
R3 = Wasserstoff, Methyl, Ethyl, und
R4 = gesättigte oder ungesättigte Seitenkette.Substances which deactivate free-radical structures include antioxidants from the substance classes of tocopherols, phenols and amines and phosphates:
The claimed tocopherols show the structural feature of a substituted phenol having the general structure (1):

with R1 = hydrogen, methyl or tert-butyl,
R2 = hydrogen, methyl or tert. - butyl,
R3 = hydrogen, methyl, ethyl, and
R4 = saturated or unsaturated side chain.

mit R = gesättigte oder ungesättigte aliphatische oder aromatische Gruppe, unter Einschluss von Heteroatomen im Kohlenstoffgerüst oder alsSubstituent,
R1 = Wasserstoff, Methyl oder tert.- Butyl, und
R2 = Wasserstoff, Methyl oder tert. – Butyl.The claimed phenols are structurally similar to the tocopherols. The mechanism of stabilization is also very similar to that of tocopherols. The phenols have the general structure (2):

with R = saturated or unsaturated aliphatic or aromatic group, including heteroatoms in the carbon skeleton or as a substituent,
R1 = hydrogen, methyl or tert-butyl, and
R2 = hydrogen, methyl or tert. - butyl.

mit R = gesättigte oder ungesättigte aliphtische oder araromatische Gruppe, unter Einschluss von Heteroatomen im Kohlenstoffgerüst oder als Substituent,
R1 = Wasserstoff, Methyl oder tert.- Butyl
R2 = Wasserstoff, Methyl oder tert.- Butyl,
R3 = Wasserstoff, Methyl oder tert.- Butyl,
R4 = Wasserstoff, Methyl oder tert.- Butyl, und
R5 = Wasserstoff, Alkyl, Alkanol.The claimed class of amines preferably includes the sterically hindered amines having the general structure (3):

with R = saturated or unsaturated aliphatic or aromatic group, including heteroatoms in the carbon skeleton or as a substituent,
R1 = hydrogen, methyl or tert-butyl
R2 = hydrogen, methyl or tert-butyl,
R 3 = hydrogen, methyl or tert-butyl,
R4 = hydrogen, methyl or tert-butyl, and
R5 = hydrogen, alkyl, alkanol.

mit R1 = aliphatische oder aromatische Struktur,
R2 = aliphatische oder aromatische Struktur,
R3 = aliphatische oder aromatische Struktur, und
R4 = aliphatische oder aromatische Struktur.According to the application, phosphates are phosphorous acid esters having the structural features of the general structures (4):

with R1 = aliphatic or aromatic structure,
R2 = aliphatic or aromatic structure,
R3 = aliphatic or aromatic structure, and
R4 = aliphatic or aromatic structure.

Below are some examples where the cast resin layer 3 contains a monomer mixture, which was divided in half and mixed in one half of a radical structure deactivating substance. Both blends were placed in a composite consisting of four millimeter thick, low-iron glass and a ten millimeter thick marble plate and cured by irradiation with 340-390 nm light. As a reference pattern, a composite of two glass plates of thickness four millimeters were each made. Parts of these plates were irradiated by means of an irradiation device in accordance with DIN EN 12543/4 with UV light.

Example 1:

One Acrylate of 35 parts of an aliphatic polyurethane acrylate and 65 parts of a monomeric acrylate was mixed with 0.02 parts of an alpha-hydroxy ketone (1-hydroxy-cyclohexyl phenyl ketone, CAS 947-19-3). To one half of the monomer mixture was 1 part of an oligomeric sterically hindered amine (CAS 152261-33-1) the general structure (3) mixed. After expiration of the above Irradiation showed the reference pattern of glass as well as the stabilized Composite of glass and marble no visible discoloration on. The pattern of glass and marble with the unstabilized showed clearly visible; brown and yellow discoloration.

Example 2:

Instead of of the amine of Example 1 was a phenolic antioxidant of general structure (2) (CAS 1709-70-2). The results corresponded to those of Example 1.

Example 3:

In a further embodiment of the stone-glass element of the invention, a casting resin layer of acrylate and the monomer mixture listed in Example 1 was also used, but 2 parts of a stabilizer (D, L - alpha tocopherol, CAS 10191-41-0) of the general Structure (1) too set. The stabilized resins had a slight yellow color before curing which changed only slightly over the course of aging. The unstabilized samples showed a strong shade of brown after aging.

Example 4:

at this embodiment were the cast resin layer from the first example 2 parts of a stabilizer (CAS 101-02-0) the general structure (4) added. While the samples with bilateral Glass cover showed only slight discoloration in the margins after aging The stabilized glass / marble sample showed no discoloration. The unstabilized sample had a clear color over the whole area.

Examples 5 - 8

Instead of a cast resin layer with acrylate it is also possible a radiation-curing Epoxide from 55 parts of a cycloaliphatic epoxide (Uvacure 1530 the company UCB) and 20 parts of a polyether polyol (CAS 25190-06-1) with a portion of an iodonium hexafluoroantimonate complex (CAS 121239 - 75 - 6) use. The epoxide was divided in half in the present example. To one half was deactivating one of the radical structures listed in Examples 1 to 4 Substances mixed.

Also Here, a significant increase in the discoloration of the unstabilized samples compared to the stabilized samples or the reference patterns that showed only a slight change.

Examples 9 - 12

alternative there is the possibility a cast resin layer with polyurethane of 35 parts of an aliphatic isocyanate and 65 parts of a polyether polyol, which with 0.02 parts of an organotin Catalyst is offset to use. The monomer mix became here too half divided. In one half, analogous to Example 1, 1 part of an oligomeric, sterically hindered Amines (CAS 152261-33-1) of the general structure (3) added. Likewise, embodiments have been of the stone-glass element according to the invention in each case one of the examples 2 to 4 listed Radical structure deactivating substances of the casting resin layer made of polyurethane. The sample structure otherwise corresponded each from Example 1. After testing in an irradiation device according to DIN EN 12543/4, the stabilized sample showed no Change, while the unstabilized samples had a clearly visible discoloration.

Example 13

at a further embodiment of the stone-glass element according to the invention were used as a cast resin layer 100 parts of an unsaturated Polyester resin (e.g., Viapal UP 576G from Solutia with two parts of a organic peroxide and part of an accelerator (V, Co) mixed and tested as in Example 1. The results corresponded those of Example 1.

Example 14

As well were in the stabilized masses of an embodiment of the stone-glass element, in the 100 parts of a silicone resin (for example Elastosil LR 3076 from Wacker Chemistry) mixed with the specified amount of hardener and as in Example 1 was further processed, after extended test time of> 5000 h significant advantages over the unstabilized samples were observed.

Examples 15-18

Of Further, samples were prepared as in Examples 1 to 4, However, the oven was aged at 130 ° C over a period of 4 weeks. The stabilized masses showed only slight discoloration, while the unstabilized masses showed marked discoloration.

In summary let yourself find that stone-glass elements according to the present invention particularly durable and resistant to various weather conditions are, for example, a use as facade elements for buildings without an optical or structural impairment of the same over a huge Period possible is

Claims (28)

Stone-glass element with at least one thin stone slab ( 1 ) and a large area connected support plate ( 2 ), which comprises at least one glass pane, which by means of a transparent or opaque casting resin layer ( 3 ) is connected to the stone slab, characterized in that in a solid phase of the casting resin layer ( 3 ) at least one substance is homogeneously distributed, which deactivates the radical structures formed by chemical oxidation. Stone-glass element according to claim 1, characterized in that the radical structure deactivating substance is selected so that they in a, temporarily during the production of the stone-glass element, the liquid phase of the casting resin layer ( 3 ) and in one, after curing of the casting resin layer ( 3 ), dispersed solid phase is dispersed. Stone-glass element according to one of the preceding claims, characterized in that the substance which deactivates the radical structures, in the casting resin layer ( 3 ) is present at a weight proportion of at most 2%, preferably 0.5% to 1%. Stone-glass element according to one of the preceding claims, characterized in that several different radical structures deactivating substances in the casting resin layer ( 3 ) available. Stone-glass element according to one of the preceding claims, characterized in that the casting resin layer ( 3 ) Contains amines as a radical structure deactivating substance. Stone-glass element according to one of the preceding claims, characterized in that the casting resin layer ( 3 ) Phenols and / or tocopherols as radical structure deactivating substance contains. Stone-glass element according to one of the preceding claims, characterized in that the casting resin layer ( 3 ) Contains phosphates as a radical structure deactivating substance. Stone-glass element according to one of claims 1 to 7, characterized in that the stone slab ( 1 ) is made of natural stone. Stone-glass element according to one of claims 1 to 7, characterized in that the stone slab ( 1 ) is made of artificial stone. Stone-glass element according to one of the preceding claims, characterized in that the casting resin layer ( 3 ) is formed on the basis of polyester resin, polyacrylate, polymethacrylate, polyurethane, epoxy or silicone. Stone-glass element according to one of the preceding claims, characterized in that in the casting resin layer ( 3 ) an adhesion promoter based on one or more silanes and / or titanates and / or aluminates is present. Stone-glass element according to one of the preceding claims, characterized in that in a solid phase of the casting resin layer ( 3 ), a further substance is distributed homogeneously, which absorbs radiation in the wavelength range of ultraviolet (UV) light. Stone-glass element according to claim 12, characterized in that the UV-absorbing substance is selected so that it is present in a, during the production of the stone-glass element temporarily present, the liquid phase of the casting resin layer ( 3 ) and in one, after curing of the casting resin layer ( 3 ), dispersed solid phase is dispersed. Stone-glass element according to one of claims 12 or 13, characterized in that the UV-absorbing substance for light in the wavelength range between 280 nm and 360 nm is impermeable. Stone-glass element according to one of claims 12 to 14, characterized in that the UV light-absorbing substance in the casting resin layer ( 3 ) is present at a weight fraction of not more than 0.1%, preferably between 0.005% to 0.05%. Stone-glass element according to one of claims 12 to 15, characterized in that in the casting resin layer ( 3 ) Several different UV light absorbing substances are present. Stone-glass element according to one of claims 12 to 16, characterized in that the casting resin layer ( 3 ) Benzophenones or derivatives of benzophenone as ultraviolet light absorbing substance. Stone-glass element according to one of claims 12 to 17, characterized in that the casting resin layer ( 3 ) Contains benzotriazoles and / or benzotriazines and / or derivatives thereof as UV light-absorbing substance. Stone-glass element according to one of claims 12 to 18, characterized in that the casting resin layer ( 3 ) Cinnamic acid ester or derivatives of cinnamic acid ester as ultraviolet light absorbing substance. Stone-glass element according to one of the preceding claims, characterized in that at least on the casting resin layer ( 3 ) facing surface of the stone slab a barrier layer is applied, which is a diffusion of materials of the stone slab ( 1 ) in the casting resin layer ( 3 ) or of materials of the casting resin layer ( 3 ) in the stone slab ( 1 ) blocked. Stone-glass element according to claim 20, characterized that the barrier layer several chemically different substances contains. Stone-glass element according to one of claims 20 or 21, characterized in that a plurality of barrier layers are provided with different substances, which is a diffusion of materials of the flagstone ( 1 ) in the casting resin layer ( 3 ) or of materials of the casting resin layer ( 3 ) in the stone slab ( 1 ) blocked. Stone-glass element according to one of claims 20 to 22, characterized in that the barrier layer is a copolymer of the styrene with acrylates or methacrylates. Stone-glass element according to one of claims 20 to 23, characterized in that the barrier layer is a copolymer of polypropylene and / or polyethylene with acrylates or methacrylates contains. Stone-glass element according to one of claims 20 to 24, characterized in that in the barrier layer acrylates or Methacrylates are present as co- and / or graft polymers. Stone-glass element according to one of claims 20 to 25, characterized in that the barrier layer is vinyl acetate, vinyl alcohol, in particular ethylene vinyl acetate (meth) acrylic acid copolymers. Stone-glass element according to one of claims 20 to 26, characterized in that the barrier layer contains epoxy resin. Stone-glass element according to one of claims 20 to 27, characterized in that the barrier layer has a thickness between 1 μm and 100μm, preferably about 5 to 50 microns having.