DK177104B1 - Glass-based wall covering - Google Patents

Abstract

The present invention relates to a glass-based wall covering, in particular in the form of tiles, adapted to cover the sidewalls of a dwelling, such as the walls, floors or ceilings, comprising a glass base which is coated on the surface to be coated with a lacquer layer having a low permeability to water so that the lining can be applied to the sidewalls using traditional mortar adhesives or cement adhesives.

Description

in DK 177104 B1

The present invention relates to a glass-based wall covering, in particular in the form of tiles, adapted to cover the sidewalls of a dwelling, such as the walls, floors or ceilings.

More specifically, the invention relates to a cladding which can be attached to the sidewalls by techniques customary for the application of traditional ceramic tiles.

Glass-based wall coverings, in the form of panels 10 or tiles, are especially appreciated for their aesthetic qualities and their light maintenance. The total absence of porosity of the glass provides a very simple cleaning, while transmis s in the viscous sheaths and the light reflectivity of the glass give much appreciated optical effects, e.g. a depth effect when decorations are placed on the back of the panels.

However, the commercial development has slowed down, and this for a number of years, due to the fact that the glass linings cannot be attached to the sidewalls by traditional adhesives used by the specialists for fixing ceramic tiles, such as cement adhesives, which are also called "mortar glue". The latter are mixtures of cement and sand to which water is added, namely so-called mixture to form a dough which is applied to the sidewalls to be coated and which cures due to the hydration reactions of the cement. Thus, the cement is incompatible with existing glass types such as glass of silico-sodium calcium composition, as their basic nature 30 induces corrosion reactions of the glass, preventing any adhesion of the glass to the cement, which severely degrades the aesthetics of the glass panel.

Various alternative fasteners for the glass linings are thus used. They may be mechanical but necessitate the execution of costly metal pieces (screws, rivets, bolts). Multi-component mechanical joints also present a disadvantage in that the internal stress concentrations and an uneven distribution of stiffness impede a good mechanical resistance of the unit. In addition, they are visible, which can be bothersome from an aesthetic point of view.

The glass covers may also be secured by means of adhesives, e.g. based on synthetic resin. Due to the high cost of the adhesives used, these are rarely used over the entire surface to be glued, resulting in a poor distribution of shear forces and thus a poorer quality bonding. One can expect a rapid aging reaction, which decreases their adhesive properties.

Solutions allowing cement adhesives have recently been proposed, but they are not without disadvantages.

Thus, U.S. Patent No. 6,015,622 discloses the use of a particular method of application which comprises, in particular, mixing mortar in an aqueous solution in a polyacrylic acid derivative. DE-A-100 34 981 relates to a glass tile coated with a cement of special composition, which is provided by means of an aqueous solution of a styrene-butadiene type resin. EP Patent Application 30 No. 722 027 also discloses the use of a specific mortar comprising 50% of an auxiliary consisting of an aqueous solution diluted with a synthetic resin. In these three cases, the use of a special composition mortar is unavoidable and the use of today's mortars for setting up ceramic tiles is not satisfactory.

Evidently, the smooth surface of the glass is also an obstacle to a good attachment of the glass tile to the brick walls. In 1925, FR Patent No. 599,239 disclosed the coating of tiles by a dough layer or varnish layer derived from synthetic resins, to which are attached glass fragments or fragments of metal, sand, gravel, marble or any other inert material. This method necessitates the use of broken fragments generated by a costly process.

Also known in the art are wall coverings of glass on which a lacquer layer of decorative function is applied to the contact surface with the wall to be clad. However, this type of varnish is also incompatible with the cement adhesives, and such products should be applied to the walls by other means, e.g. using 20 adhesive resin types.

DE 19813711 A1 discloses a glass-based wall covering comprising a glass base which is coated on its back with a lacquer layer, the lacquer layer comprising a synthetic resin binder. DE 25 19813711 A1, however, does not disclose the permeability of the paint to water.

The present invention aims to overcome the above disadvantages of proposing a glass-based wall covering, in particular in the form of tiles, adapted to cover the sidewalls of a dwelling and capable of applying the sidewalls by conventional techniques used for placement. of ceramic tiles, in particular using traditional 4 DK 177104 B1 mortar adhesives.

The inventors have thus discovered that the most important physicochemical property of the mixture is the water permeability varnish. When this size is not adjusted (in the case of an excess of the mortar glue used), the water in the mixture, which is made basic by the hydration reaction of the cement, makes it transverse to the lacquer layer and chemically reacts with the glass surface, thus making any 10 adhesion (especially the glass-lacquer adhesion) is impossible and makes the appearance of the glass lining worse.

Thus, the coating of the invention comprises in its broadest sense a glass substrate coated on its application side with a lacquer layer, characterized in that said lacquer has such water permeability that the cladding can be applied to the sidewalls by means of traditional mortar or cement adhesives, the lacquer has a water permeability at 25 ° of less than 10 "6, especially less than 10" 8, or even less than 10 "13 cm3. cm. cm" 2. s "1. Pa" 1.

The maximum value for the permeability of the lacquer may, in order to provide a durable bonding, depend on the type of mortar adhesive used. The coating varnish of the invention has a water permeability at 25 °, expressed in cm 3. cm. cm -2. S'1. Preferably less than 10 "6 in particular less than 5-10" 7 and especially less than 10 "7. To ensure perfect adhesion and mechanical durability, especially against long shear forces, it is preferred that the 30 lacquer has a water permeability at 25 ° of less than 10 "8, especially 10" 9, and even 10'10 cm3. cm. cm "2. s "1. Pa" 1. The coatings according to the invention, which in particular cases are arranged to be placed in places where the environment is humid (eg in bathrooms), is particularly preferred if the water permeability of the lacquer covering the lining of the invention is less than 10'11, in particular 10 "12, 5 and even 10" 13 cm3. cm. cm "2. s "1. Pa" 1.

Water permeability is defined as the product between the amount of water vapor diffusing across the material (in cm3) and the thickness of the material (in cm) relative to the exposed surface of the product (in cm2) and the exposure time (in seconds) and the difference in pressure (in Pascal) between the two material surfaces. It can be measured, e.g. by measuring the mass of a lacquer film after exposure to a climate room where the amount of moisture is controlled.

This size, in the case of a polymer, depends initially on the chemical nature of the polymer, then on the morphology, e.g. depends on the degree of cross-linking (for example, on the degree of cross-linking agent and / or cross-linking temperature) the degree of crystallisation, and on any orientation of the molecules. Furthermore, in this case, this size is dependent on the nature and amount of mineral fillers.

Thus, the lacquer of the coating of the invention preferably comprises a synthetic resin binder, preferably in liquid form prior to application and adapted for oven drying. It has been observed that the varnishes comprising binders which are dry at high temperatures (above 50 ° C, especially above 100 ° C) generally exhibit a lower permeability to dry binders under ambient air temperature, probably due to crosslinking reactions, e.g. . by polycondensation, which is more complete and gives rise to three-dimensional higher density grids.

The binder is preferably polyurethane resin, provided by cross-linking, of an isocyanate or polyisocyanate, of hydroxyl-substituted resins, in particular polyester resin or polyether resin or preferably acrylic resin (or polyacrylates) which has an enhanced resistance to high resistance. In this case, the hydroxyl-substituted acrylic resin is preferably the result of a polymerization of an acrylic styrene, while the isocyanate (or polyisocyanate) contains no aromatic group. In particular, this particular combination makes it possible to achieve lower permeability, good mechanical properties (e.g., resistance to radiation over 15) and an increased resistance to ultraviolet radiation.

The binder in the coating varnish of the invention may also contain or be based on alkyd resin provided by chemical reaction 20 between at least one polyol, at least one polyacid and at least one fatty acid or oil. These alkyds preferably have a low oil content, i.e. a weight amount of oil or fatty acid in the resin which is preferably lower than or equal to 40%. The polyols can e.g. be composed of glycerol or pentaerithritol. The polyacids may be based on phthalate anhydrides. The oils may be drying (such as linseed oil, tree oil or china oil), semi-drying (such as soybean oil, root oil, safflower oil or dehydrated castor oil), or non-drying (such as coconut oil or castor oil). To improve their water resistance properties, the alkydb can also be modified by monomers such as styrene, vinyltoluene or acrylates or by phenolic resin or epoxy resin. Aminoplastic alkyd resins which crosslink under the action of heat are binders which are particularly advantageous for the lacquer for the coating of the invention. Preferably, the crosslinking aminoplast is a ureaformol resin or melamine-formol resin, which provides good water resistance, especially when used in a 20 to 30% by weight ratio of the dry alkyd binder.

The lacquer may also comprise a binder based on a thermosetting acrylic resin, for example produced by crosslinking an acrylic resin carboxyl substituted with an epoxy resin, form-phenol or melamine formol, of an acrylic resin with carboxamide function with an epoxy or alkyd binder, or acrylic resin with epoxy function by acids or polyamines.

The coating of the invention is preferably provided with an adhesive or adhesive promoting layer (herein called "adhesion primer") positioned between the glass and the lacquer and the task of which is to improve the adhesion between the glass and the lacquer. This layer is preferably silane based, which avoids the risk of the glue dropping due to moisture.

25 Adhesive promoters with the glass, such as silanes, can also be dissolved in the lacquer.

The lacquer preferably comprises pigments, mineral and / or organic, preferably mineral, to provide the desired aesthetic properties.

The pigments are preferably of the kind resistant to ultraviolet radiation and moisture.

Among the pigments used within the scope of the invention, e.g. titanium oxides or zirconium oxides, optionally doped with transition elements, or of mixed zirconia (ZrSiO 4). The pigments are preferably free of heavy metals such as cadmium and lead.

Preferably, the lacquer may contain mineral fillers adapted to optimize its physicochemical parameters, e.g. its viscosity. The total content of mineral substances (pigments and fillers) in the varnish is preferably, expressed in weight percentages, between 40 and 70%, especially between 50 and 60%.

The coating varnish of the invention may be applied by any process known to those skilled in the art, such as blur application, aerial spraying, screen printing or roll-coating. The screen printing method has the advantage that only a portion of the substrate can be coated. The roll coating method consists of passing the substrate to be coated between two rollers, one of which (usually the upper roller) is coated with varnish. For cost reasons, the method used is preferably the veil application, where a lacquer stream is formed along a line substantially perpendicular to the direction of delivery of the glass substrate, which allows the entire surface of the substrates to be lined. The flow rate of the varnish and the feed rate of the substrate are controlled to achieve the desired deposition thickness, preferably 100-200 microns in the moist state. The substrate coated with lacquer then undergoes a heat treatment, which allows the lacquer to harden, ie. more accurately, the solvent is allowed to evaporate and the polymerization reactions and / or curing reactions of the resins used as a binder are allowed to proceed. The temperature used is preferably between 50 and 250 ° C, in particular between 100 and 200 ° C, to give the lacquer a degree of cross-linking adapted to reduce its water permeability. The thickness of the lacquer layer after curing is preferably between 20 and 100 microns, especially between 40 and 70 microns to achieve the desired opaque state.

The glass substrate used can be of any type of flat glass (possibly curved by the curvature processes known to those skilled in the art when it comes to coating curved surfaces). There may be 10 monolithic glass, ie. made of a single layer of glass, it may be made by the "float" method, which makes it possible to provide a layer which is completely flat and smooth, or by drawing or laminating. In the latter case, and when the laminating rolls have protruding shapes, the glass layer may be embossed and have motifs (for example, as disclosed in EP Patent No. 493,202) on at least one of its surfaces, preferably the substrate surface of the lacquer ( or the back).

20 The glass can be clear or have different colors, such as blue, bronze, green, gray or even pink. The light transmittance of the glass can be selected between 10 and 92% for a thickness of 4 mm. A particularly preferred embodiment of the case where the lacquer is white or ivory colored consists in the use of an extra clear glass layer, ie. whose iron oxide content is less than 250 ppm, preferably less than or equal to 200 ppm, in particular 150 ppm, and whose light transmittance under illuminant 30 D65 is greater than 89%, especially 90% for a thickness of 4 mm. It has been found that the optical properties of such a glass make it possible to achieve excellent conditions for the white or ivory color in the lacquer, while the green residual color in existing clear glass whose iron oxide content is in the order of 1000 ppm. is particularly evident.

The thickness of the glass substrate is preferably between 5 and 2 mm, preferably between 4 and 10 mm, especially between 5 and 9 mm.

This glass layer may be frosted on at least one of its sides (preferably the front) by various frosting processes, e.g. matting 10 by hydrogen fluoride or by sandblasting. This matting can be done all over the surface or in special zones, thus forming slightly submerged designs. This latter embodiment may be effected by protecting the zones which do not need to be engraved with a coating resistant to acids which is subsequently removed. The matted appearance can also be achieved by applying an organic or mineral enamel.

A reflective layer, preferably a silver layer 20 provided by traditional silver methods known to those skilled in the art, may also be interposed between the glass substrate (optionally provided with a silane type adhesive) and the latter thus fulfills the function of the silver varnish as a corrosion protection. .

A decoration in one or more colors provided by screen printing or ink jet is preferably inserted between the glass support (optionally provided with silane type adhesive) and the lacquer 30 and / or the front. One can, for example. combine the application of decorations on the front and back.

A particularly interesting embodiment relates to a wall covering according to the invention, which is thus coated with a lacquer on the back side, the back side being subsequently formed with incisions by mechanical means (in particular by milling by means of more or less complex milling profiles) for that e.g.

5 form lines with a width of 1-30 mm and a depth of 0.5-3 mm, whereby all the varnish is thus removed. A decorative layer, preferably a silver layer provided by traditional silver plating methods, can subsequently be applied to the backing. In the case where the incisions are made along straight and evenly spaced lines and at right angles to each other, it is also possible to obtain a unique glass panel which gives the wall a visual impression of a plurality of tiles separated by joints, while the advantages of a smooth front face is maintained, which avoids the problem of grouting the joints and greatly facilitates cleaning. In addition, this embodiment of the invention makes it possible to reduce the set-up time of the glass tiles by reducing the number of grouting steps.

The glass substrate may also be coated with functional layers, such as stacking of anti-reflective layers, functional self-cleaning layers (e.g. containing titanium oxide, preferably crystallized in anesthetic and / or rutile form, which also provides anti-fouling, antibacterial properties , anti-fog and anti-condensation), or even hydrophobic layers. The layers which provide anti-scratching properties, especially in the form of an enamel, are particularly appreciated in the case of floor coverings. Anti-abrasive or anti-scratch layers may also coat the substrate of the invention.

For security or to provide special functionalities, the glass substrate may preferably be a layered glass consisting of a composition of several glass, in particular two layers of glass separated by a plastic layer such as polyvinyl butyral (PVB). Electrically conductive layers and thus resistance heating layers may be integrated into one of the layer surfaces, e.g. makes it possible to achieve heated floors and / or walls. The plastic layer may also comprise liquid crystals capable of orienting under the action of an electric field, allowing passage in a transparent or opaque state to a transparent state, e.g. can reveal a special decoration on the back.

The glass layer may also be an illuminated pane, e.g. a double pane filled with a gas, in particular an inert gas such as xenon or neon capable of producing luminescent discharges, such as e.g. is disclosed in WO 2004/015739 which, by this reference, forms part of this specification, or a layered or multilayer pane containing electroluminescent diodes electrically supplied by thin conductive films or by 20 silk-screen bands or wires, e.g. on silver paste base.

When the glass lining is in the form of tiles, the tiles are preferably rectangular, the lateral lengths of which are multiples of 15 cm, taking into account a given size of joint (eg 3 mm). Thus, tiles of 15x15 cm2, 15x30 cm2, 15x45 cm2, 30x45 cm2, 30x300 cm2, 45x45 cm2 can be formed, etc. The fact that a given joint size is taken into account for each of these dimensions makes it possible to combine, on a 30 and the same wall, tiles of different sizes while maintaining the alignment of the joints, which is especially appreciated from an aesthetic point of view.

An advantage of glass tiles over traditional ceramic tiles is the modularity of the possible sizes and the possibility of easily obtaining large-size panels. The provision of the final size is simply achieved by cutting 5 large layers of glass, the surface of which can exceed 10 m2, since the dimensions of the ceramic tiles cannot be changed by anything other than making molds of different sizes. In addition, it is extremely difficult to provide large ceramic pieces, e.g. with a surface 10 exceeding 1 m2.

The shape of the edges of the tiles of the invention has been especially optimized to improve the application of joints and to avoid visible joint defects. The inventors have observed that some forms of 15 edges, particularly of the "rounded joint" type, made application of joints covering the entire tile edge difficult, with the transparency of the glass, among other things, made any defects in the joint visible through the edge. Thus, the tiles of the invention have 20 preferably beveled edges, optionally sanded and / or polished, and are characterized in that the beveled width is larger on the front. The backing is preferably much less affected by the molding, so that the lacquer layer covers almost the entire surface of the tile.

In particular, the width affected by the molding is preferably less than or equal to 0.5 mm, especially less than or equal to 0.3 mm. Generally, the lacquered surface is over the face after molding.

The cutting of the glass tiles according to the invention 30 is particularly simple and does not require special tools other than the tool used in cutting ceramic tiles, especially glazed stone tiles, or in cutting marble or granite. Also, the molding of the edges after cutting can be carried out by means of a grindstone according to the methods well known to those skilled in the art of laying ceramic tiles.

Listing some additional technical advantages over ceramic tiles: - the precision of the cutting is generally increased, thereby achieving a better adaptation to narrow tolerances, - the possibility of applying the varnish to sheets of 10 large dimensions before the cutting of the tiles. allows for improved reproducibility of the decorations, in particular of the color; - better flatness, which also allows reducing the overconsumption of mortar glue needed to compensate for any excess space between the cladding and the wall.

The present invention will be better understood by reading the following detailed description of examples of non-limiting embodiments shown in the accompanying figures:

FIG. 1 and 4 show perspective views of different embodiments of clothing according to the invention; 2, 3 and 5 show side views of various embodiments of clothing according to the invention,

FIG. 6-10 show various types of motifs which can be carried out by acid etching on the front of the garment according to the invention.

FIG. 1 is a perspective view of a square cross-sectional tile. The tile comprises a clear, monolithic glass layer 1 with a thickness of 6 mm, the back of which is lined with a lacquer layer 2 with a thickness of 50 microns and applied by the blasting application method. The obverse has motifs 3 which are acid etched in the form of evenly spaced parallelepipedic rectangles in the two perpendicular directions of the tile.

The lacquer 2, after drying, comprises the following components: - a polyurethane resin binder provided by cross-linking a non-aromatic isocyanate, of hydroxyl-substituted 10 acrylic resins resulting from polymerization of an acrylic styrene, - mineral substances (pigments and fillers) by weight .

This varnish is provided by veil application, followed by a drying of 5 minutes. The drying temperature is an important parameter to obtain a water permeability (water permeability) that is sufficiently low. Under these particular conditions and for a drying temperature below 180 ° C, the permeability 20 is too high, and after bonding on a wall using mortar glue, defects will appear after a period of time of several days, during the drying of the mortar. In this case, the water in the mixture of mortar glue passes through the lacquer layer, which gives a double effect, namely that the glue releases between the glass layer and the lacquer layer and chemically attacks the glass surface. In contrast, for a drying temperature above 180 ° C, a stronger cross-linking of the binder in the lacquer will result in a lower permeability to water, leaving no defect after mortar adhesive bonding.

FIG. 2 shows a side view of a tile. The edges of the monolithic glass layer 1 are shaped such that they exhibit beveled edges 4 by obliquely cutting edges 5 and 6, this step being carried out such that the lacquered surface 2 is lower than the surface 5 of the front.

FIG. 3 also shows a side view of a tile. In this embodiment, the back of the garment is covered with a silver layer 7 by a silver plating process. The lacquer layer 2 is positioned to cover this silver layer 7.

FIG. Figure 4 shows a perspective view of a tile formed of a layered pane of two glass layers having a thickness of 4 mm connected to a layer 13 of polyvinyl butyral having a thickness of 0.76 mm.

15 The front is acid-etched and has motifs 10 in the form of small waves. One of the glass layers is cut away in the drawing to show the presence of electroluminescent diodes 11 (LED) on the surface of polyvinyl butyral 13.

FIG. 5 shows a side view of a wall covering according to the invention, showing a cut 12 with a thickness of 3 mm and a depth of 0.5 mm made by milling after painting. A silver layer 7 is applied and covers the lacquer layer 2 and the incised portion 12. A second lacquer layer 2 (of a different composition) is subsequently applied to the entire silver-coated surface. From the front, the silver-plated layer 7 is only visible on the incision 12.

FIG. 6-10 illustrate various motifs which may be technically accomplished by acid etching treatments of the front of the wall coverings of the invention. The dark areas represent the etched zones which thus appear hollow or sunken in relation to the clear areas which appear in relief.

The present invention has been described above by way of example. It will be appreciated that those skilled in the art are able to provide 5 different variants of the invention, without departing from the scope of the patent as defined by the claims.

Claims (19)

A glass-based wall covering, in particular in the form of tiles, adapted to cover the sidewalls of a dwelling, such as the walls, floors or ceilings, comprising a glass base (1) which is coated on its application side with a lacquer layer (2), wherein said lacquer (2) has such water permeability that said coating can | the sidewalls are applied by means of traditional mortar or cement adhesives, wherein the lacquer (2) exhibits a water-permeable similarity at 25 ° C of less than 10'6, especially less than 10 ~ 8, or even less than 10 "13 cm3. cm. '2. s'1. Pa'1. Wall covering according to any one of the preceding claims, characterized in that the lacquer (2) as a binder comprises a synthetic resin. Wall covering according to any one of the preceding claims, characterized in that the binder is polyurethane resin-based, in particular produced by the cross-linking of an acrylic resin hydroxyl substituted with an isocyanate or a polyisocyanate. Wall covering according to claim 2, characterized in that the binder is alkyd resin-based. Wall covering according to any one of the preceding claims, characterized in that there is an adhesive promoting agent in the form of a layer inserted between the lacquer layer (2) and the glass substrate (1), or dispersed in the lacquer (2). Wall covering according to claim 5, characterized in that the adhesive promoting agent is silane based. Wall covering according to any one of the preceding claims, characterized in that a reflective layer, in particular of mirror coating for mirrors, and / or a decoration provided by screen printing or ink jet is inserted between the lacquer layer (2) and the glass base (1). , optionally coated with a layer which promotes adhesion. Wall covering according to any one of the preceding claims, characterized in that the lacquer layer (2) comprises pigments which are resistant to ultraviolet radiation. 10 Wall covering according to any one of the preceding claims, characterized in that the lacquer layer (2) comprises a mineral filling with a content, by weight, of between 40 and 70%. Wall covering according to any one of the preceding claims, characterized in that the glass substrate (1) is a layer of monolithic glass. Wall covering according to any one of claims 1-9, characterized in that the glass base (1) is a multilayer pane comprising a plurality of glass layers. 20 Wall covering according to any one of the preceding claims, characterized in that the glass substrate (1) has at least one of its surfaces motifs (3; 10. in relief provided by lamination and / or frosting by acid and / or sandblasting and / or etching. Wall covering according to any one of the preceding claims, characterized in that the entire front of the glass substrate (1) is matted by hydrogen fluoride or by sandblasting. i 30 Wall covering according to any one of the preceding! the requirements characterized in that the glass substrate (1) on at least one of its surfaces, preferably the front, has at least one functional layer which gives DK 177104 B1 j 20 j optical properties (stacking of anti-reflective layers) and / or non-slip properties and / or surface properties (especially anti-erosion, antibacterial, self-cleaning, hydrophobic, anti-fog, anti-scratch, anti-scrape properties). Wall covering according to claim 1, characterized in that the glass base (1) is a double pane filled with a gas which, under an electric field, produces luminous discharges. 10 Wall covering according to claim 11, characterized in that the glass substrate (1) is a layered or multilayer pane containing electroluminescent diodes (il). ! A wall covering according to any one of the preceding claims, characterized in that the lacquered surface is over the front after machining. Wall covering according to any one of the preceding claims, characterized in that a part of the back side is formed with incisions (12) by mechanical means and subsequently covered with a decorative layer, preferably a silver layer (7) provided by traditional silver plating methods. Wall covering according to claim 18, characterized in that the incisions (12) are made in the form 25 of lines having a width of 1-30 mm and a depth of 0.5-3 mm, at regular intervals and in two mutually perpendicular directions.