Patent ID: 12187654

DETAILED DESCRIPTION

A multilayer film1,1′ to be used according to the invention has a carrier ply10,10′ and a transfer ply13,13′, which contains at least one decorative element, arranged on the carrier ply10,10′, wherein the transfer ply13,13′ has at least one anionically functionalized primer layer15on the side facing away from the carrier ply10,10′.

Preferably, the carrier ply10,10′ comprises at least one carrier layer11made of preferably a polyester, for example a polylactide (PLA) or polyethylene terephthalate (PET), a polyolefin, for example polypropylene (PP) or polyethylene (PE), or a combination thereof, in particular made of PET.

Optionally, the carrier ply10,10′ has at least one detachment layer on the rear side, which comprises or consists of at least one wax, preferably montan ester wax, at least one silicone, at least one polyurethane or a combination thereof, on the side facing away from the transfer ply13,13′.

Preferably, an arrangement of at least one detachment layer on the rear side of the carrier ply10,10′ prevents the layers from adhering during the production of a multilayer film1,1′ to be used according to the invention.

Further preferably, the at least one carrier layer11of the carrier ply10,10′ has a layer thickness between 4 μm and 100 μm, preferably between 10 μm and 50 μm.

Optionally, the carrier ply10,10′ can furthermore comprise at least one detachment layer12, which is arranged on the side of the carrier ply10,10′ facing the transfer ply13,13″.

Preferably, the at least one detachment layer12can comprise at least one wax, preferably montan ester wax, at least one silicone, at least one polyurethane or a combination thereof.

Further preferably, the at least one decorative element influences the surface texture, the color of the surface, the mechanical properties and/or the chemical properties of the decorated mineral composite body2, wherein the at least one decorative element is preferably formed as a motif, as a decoration, for example individual image decoration or endless decoration, as a pattern, or a combination thereof.

In a preferred embodiment, at least one functional layer14is arranged between the at least one anionically functionalized primer layer15and the carrier ply10,10′, wherein the at least one decorative element is preferably arranged in the at least one functional layer14.

Preferably, the at least one functional layer14arranged between the at least one anionically functionalized primer layer15and the carrier ply10,10′ comprises or consists of at least one metal and/or semi-metal, alloys thereof or mixture thereof, preferably aluminum, iron, chromium, indium, copper, tin, zinc, silicon, alloys thereof or mixtures thereof, at least one polymer, preferably selected from cellulose-based polymers, chlorinated polyolefins, chlorinated rubbers, colophony resins, epoxy resins, EVA copolymers, formaldehyde resins, hydrocarbon resins, ketone/aldehyde resins, maleinate resins, melamine resins, phenolic resins, acrylates, polyacrylates, polyacrylate dispersions, polyester dispersions, polyurethane dispersions, polyether dispersions, polyamide resins, polyester resins, polyisocyanates, polyolefin resins, polystyrene resins, polyurethane resins, polyvinyl acetals, polyvinyl acetates, polyvinyl alcohols, polyvinyl butyrals, polyvinyl chlorides, polyvinyl propionates, polyvinylpyrrolidones, polyvinylidene chlorides, polyvinylidene fluorides, shellacs, silicone resins, styrene acrylate dispersions, sulfonamide resins, urea resins, acrylonitrile-1,3-butadiene-styrene (ABS) resins and mixtures thereof.

The at least one functional layer14arranged between the at least one anionically functionalized primer layer15and the carrier ply10,10′ can preferably furthermore comprise at least one additive which is preferably selected from the group which consists of hydrophobing agents, flow additives, defoamers, colorants, preferably selected from dyes, organic pigments, inorganic pigments and mixtures thereof, fillers, rheology additives, plasticizers, stabilizers, light stabilizers, antioxidants, flame retardants, reinforcing substances and mixtures thereof.

The at least one functional layer14arranged between the at least one anionically functionalized primer layer15and the carrier ply10,10′ is further preferably selected from the group which consists of transparent and/or colored varnish layers, in particular comprising one or more dyes and/or pigments, replication layers with a molded optically active surface structure, reflective layers, in particular opaque reflective layers, transparent reflective layers, metallic reflective layers or dielectric reflective layers, optically variable layers, optically active layers, interference multilayer systems, volume hologram layers, liquid crystal layers, in particular cholesteric liquid crystal layers, electrically conductive layers, antenna layers, electrode layers, magnetic layers, magnetic storage layers, barrier layers and combinations thereof.

Preferably, a protective ply18can be arranged on the side of the at least one anionically functionalized primer layer15facing away from the carrier ply10,10′. The protective ply18preferably prevents damage and/or contamination of the primer layer15, for example during the transport of a transfer film1to be used according to the invention, and can be peeled off the primer layer15before use of the transfer film1, preferably, in alternative I), before the at least one anionically functionalized primer layer15is brought into contact, at least partially, with the flowable or plastically deformable, mineral construction material mixture, and/or,

in alternative II), before the at least one multilayer film1,1′ is arranged, in and/or after step c), with the at least one anionically functionalized primer layer15at least partially on the dimensionally stable, mineral green body3a.

Preferably, the protective ply18comprises at least one carrier layer19amade of preferably a polyester, a polyolefin, a polyurethane or a combination thereof, in particular made of PET.

In an alternative embodiment, the protective ply18can be an in particular self-supporting varnish layer. The varnish layer is for example made of polyurethane with a thickness between 10 μm and 250 μm and can be peeled off the primer layer15before use of the transfer film1.

In an alternative embodiment, the protective ply18can be an in particular non-self-supporting varnish layer. The varnish layer has binding agents for example based on polyester and/or on maleinate resins and/or on polycarbonates and has a thickness between 0.1 μm and 5 μm, preferably 0.5 μm and 2 μm, and can remain on the primer layer15during the use of the transfer film1and in particular at least partially dissolves when the primer layer15is brought into contact with the still flowable construction material mixture.

Further preferably, the at least one carrier layer10aof the protective ply18has a layer thickness between 4 μm and 100 μm, preferably between 10 μm and 50 μm.

Optionally, the protective ply18can furthermore comprise at least one detachment layer19b,which is arranged on the side of the protective ply18facing the primer layer15.

Preferably, the at least one detachment layer19bcan comprise at least one wax, preferably montan ester wax, at least one silicone, at least one polyurethane or a combination thereof.

The method according to the invention for producing a decorated mineral composite body2using at least one multilayer film1,1′ comprises the following steps:a) providing at least one forming element30, preferably formwork, with at least one outer surface and at least one inner surface31,b) applying a flowable or plastically deformable, mineral construction material mixture, which comprises water and at least one mineral binding agent, to the at least one inner surface31of the forming element30, preferably formwork,c) at least partially solidifying the mineral construction material mixture to obtain a dimensionally stable, mineral green body3a,andd) at least partially hardening the mineral construction material mixture to obtain a mineral composite body2,

wherein the multilayer film1,1′ has a carrier ply10,10′ and a transfer ply13,13′, which contains at least one decorative element, arranged on the carrier ply10,10′,wherein the transfer ply13,13′ has at least one anionically functionalized primer layer15on the side facing away from the carrier ply10,10′, andwherein I), before step b), the at least one multilayer film1,1′ is arranged with the side of the carrier ply10,10′ facing away from the at least one anionically functionalized primer layer15on the at least one inner surface31of the provided forming element30, preferably formwork, with the result that the at least one anionically functionalized primer layer15of the multilayer film1,1′ preferably points away from the at least one inner surface31of the forming element30, preferably formwork, and wherein, in step b), the at least one anionically functionalized primer layer15is brought into contact, at least partially, with the flowable or plastically deformable, mineral construction material mixture, wherein, in step c), a decorated, dimensionally stable, mineral green body3is obtained,and/orwherein II), in and/or after step c), the at least one multilayer film1,1′ is arranged with the at least one anionically functionalized primer layer15on the dimensionally stable, mineral green body3a,wherein a decorated, dimensionally stable, mineral green body3is obtained, andwherein, in alternatives I) and II), a decorated mineral composite body2is obtained after step d).

The at least one forming element30used in the method according to the invention comprises at least one outer surface and at least one inner surface30, wherein the at least one inner surface31of the forming element30can preferably have a two-dimensional or three-dimensional geometric shape. The inner surface31of the forming element30can alternatively or additionally also have a structuring in the form of a macroscopic and/or microscopic structure.

Preferably, the at least one multilayer film1,1′ to be used according to the invention can be at least partially decorated using at least one decorative roller or can contain at least one decorative pattern.

In the method according to the invention, a protective ply18optionally arranged on the side of the at least one anionically functionalized primer layer15facing away from the carrier ply10,10′ is at least partially, preferably completely, removed, in alternative I), preferably before the at least one anionically functionalized primer layer15is brought into contact, at least partially, with the flowable or plastically deformable mineral construction material mixture, and/or, in alternative II), preferably before the at least one anionically functionalized primer layer15is arranged on the dimensionally stable, mineral green body3a.

A decorated, dimensionally stable, mineral green body3preferably comprises an at least partially solidified mineral construction material mixture and at least one transfer ply13,13′, which contains at least one decorative element, at least partially arranged on at least one surface of the green body3, wherein the side of the transfer ply13,13′ facing the green body3is formed by at least one anionically functionalized primer layer15, which is joined to the green body3in at least a positive-locking manner. Optionally, at least one carrier ply10,10′ is furthermore arranged on the at least one transfer ply13,13′ on the side of the transfer ply13,13′ facing away from the green body3.

A decorated mineral composite body2according to the invention comprises a mineral substrate S and at least one transfer ply13,13′, which contains at least one decorative element, at least partially arranged on at least one surface of the substrate S, wherein the side of the transfer ply13,13″ facing the substrate S is formed by at least one anionically functionalized primer layer15, which is joined to the substrate S in at least a positive-locking manner.

Preferably, the mineral substrate S of the decorated mineral composite body2according to the invention comprises or consists of at least one at least partially hardened mineral construction material which is selected from the group which consists of concrete, mortar, sand-lime brick, ceramic and combinations thereof.

Further preferably, at least one carrier ply10,10′ is arranged on the at least one transfer ply13,13′, wherein the at least one transfer ply13,13″ and the at least one carrier ply10,10′ form a multilayer film1,1′, which is preferably formed as a laminating film.

A multilayer film1,1′, which is preferably formed as a laminating film, can preferably be designed to be smaller than the at least one surface of the substrate S on which the transfer ply13,13′, which contains at least one decorative element, is at least partially arranged, preferably bonded.

Alternatively, a multilayer film1,1′, which is preferably formed as a laminating film, can be designed to be the same size as the at least one surface of the substrate S on which the transfer ply13,13′, which contains at least one decorative element, is at least partially arranged, preferably bonded.

Alternatively, a multilayer film1,1′, which is preferably formed as a laminating film, can be designed to be larger than the at least one surface of the substrate S on which the transfer ply13,13′, which contains at least one decorative element, is at least partially arranged, preferably bonded, wherein the multilayer film1,1′ further preferably forms an overhang at least at one edge of the decorated mineral composite body2.

Preferably, the overhang of the multilayer film1,1′ can, after arranging the multilayer film1,1′ on at least partial areas of the at least one surface of the decorated object, make it possible to join two or more composite bodies2decorated according to the invention through a joining manufacturing process, for example by crimping, folding and/or bending.

Preferably, the transfer ply13,13′ and/or the transfer ply10,10′ can be modified after application to the decorated mineral composite body2, for example by at least partial application, preferably overprinting and/or dousing and/or flooding, of at least one further layer, for example protective layer and/or varnish layer, by printing and/or casting methods known to a person skilled in the art.

A multilayer film1,1′ to be used according to the invention is preferably produced by sequential, preferably full-surface or partial, application of the individual layers of the transfer ply13,13′ to the transfer ply10,10′ by methods known in the state of the art, for example by printing methods such as gravure printing and/or screen printing and/or digital printing and/or flexographic printing and/or inkjet printing and/or offset printing, and/or by casting methods such as slot casting.

The layers produced with these methods are for example protective layers, barrier layers, decorative layers, adhesion-promoter layers, adhesive layers, detachment layers, color layers, which can be present in each case over the whole surface and/or partially.

Furthermore, the preferably full-surface or partial application of vapor-deposited and/or printed-on metal layers and/or metal oxide layers as decorative element or decorative layer is possible. Vapor-deposited metal and/or metal oxide layers can, for example, be applied by methods known in the state of the art, for example physical vapor deposition (PVD) or chemical vapor deposition (CVD).

The layers produced with these methods are for example reflective layers, conductive layers, barrier layers, decorative layers, which can be present in each case over the whole surface and/or partially.

Further preferably, after molding an optically active surface structure into a replication layer, at least one decorative layer is vapor-deposited, preferably in each case in areas or over the whole surface, on the replication layer.

The application over the whole surface followed by a removal of the at least one decorative layer in areas by means of known methods such as washing methods or lift-off varnishes or etching methods or mask exposure methods with the aid of a photoresist layer is also possible.

Preferably, the at least one anionically functionalized primer layer15of the transfer ply13,13′ is first arranged on or applied to the transfer ply10,10′, which can comprise at least one carrier layer made of a polyester, a polyolefin or a combination thereof, in particular made of PET, by at least one of the above-named printing and/or casting methods, wherein the at least one anionically functionalized primer layer15is further preferably applied with an application weight from a range of from 0.5 g/m2to 500 g/m2, preferably from 1 g/m2to 50 g/m2, preferably from 5 g/m2to 25 g/m2, preferably from 9 g/m2to 15 g/m2, in each case relative to the total weight of all constituents of the anionically functionalized primer layer15.

Further preferably, the at least one anionically functionalized primer layer 15 is produced using an aqueous polymer dispersion, which a pH of 6.5 or more, preferably 7.1 or more, preferably of 7.5 or more, preferably of 8.0 or more, further preferably of 8.5 or more, further preferably of 9.0 or more, further preferably of 9.5 or more, in each case measured at a temperature of 25° C. and a pressure of 1013 mbar, on.

Example 1

A PET carrier (thickness of the PET carrier of from 5 μm to 150 μm, preferably from 7 μm to 100 μm) as carrier ply, coated with an at least 50 nm thick layer of a montan ester wax, was coated with an aqueous primer coat made of Neocryl A-45 (DSM Coating Resins B.V.) in a mixture of water and isopropanol, solids approx. 15%, typically with an application weight of 10 g/m2.

The coating was dried to constant weight in a standard atmosphere (air temperature of 23° C. and a relative atmospheric humidity of 50%) according to DIN EN ISO 291:2008-08 (“Plastics—Standard atmospheres for conditioning and testing (ISO 291:2008”)—German version EN ISO 291:2008, issue date: 2008 August) and formed a closed transfer ply of the transfer film.

In each case 50 g EB screed concrete from quick-mix Gruppe GmbH & Co. KG (Osnabrück, DE) was prepared with 6.5 g water. The transfer film was arranged with the transfer ply on a panel made of ABS material with a thickness of 1 mm and the prepared screed concrete was applied in each case to the transfer film on the side of the primer coat.

After the screed concrete had cured completely at room temperature, a mineral composite body formed which had been coated on one side with the transfer film used in each case. A very good adhesive tape strength was achieved after approx. 5 days' curing time.

The PET carrier was then detached from the concrete, wherein the transfer ply remained adhering to the concrete and formed a smooth coating on the composite body.

FIG.8depicts a produced composite body, wherein the upper side of the composite body has been formed by the transfer ply adhering to the concrete.

The adhesion of the transfer ply to the concrete was tested by means of a cross-cut according to DIN EN ISO 2409: 2013-06.

In each case 6 cuts were made vertically and 6 cuts were made horizontally (at an angle of 90° to the vertical cuts) in the coating as far as the substrate with the aid of a blade and preferably with the aid of a template. The width of the cut was dependent on the layer thickness of the coating. In the case of coatings with a layer thickness of less than 60 μm the distance between the cuts is preferably approximately 1 mm.

A clear adhesive tape or an adhesive crepe tape with an adhesiveness of from 6 N/25 mm to 10 N/25 mm was stuck to the resulting square of cuts (measurement area). This was peeled off in a time of from 0.5 to 1 second at an angle of 60°.

The evaluation was effected in accordance with DIN EN ISO 2409: 2013-06 by visual assessment of the measurement area and classification into cross-cut characteristic values of from 0 (very good adhesion) to 5 (very poor adhesion), abbreviated to GT 0 to GT 5, or in accordance with ASTM D 3359-09, test method B.

The criteria for a classification of the corresponding characteristic values are summarized inFIG.12.

If the after a curing time of 28 days, cross-cut characteristic values between 5B and 4B were measured on the produced composite bodies.

For the assessment of the adhesion of the multilayer film and/or of the transfer ply of the multilayer film, a so-called adhesive tape test was also carried out. A self-adhesive adhesive strip (brand Tesa, type 4657) in particular with a length of 45 mm and a width of 25 mm was stuck in the middle to a solidified construction material mixture coated with the multilayer film and/or the transfer ply of the multilayer film free from wrinkles and bubbles and pressed on manually.

The solidified and coated construction material mixture was clamped in a Z005 material testing machines from ZwickRoell GmbH & Co. KG (Ulm, DE). At a peel angle of 90° , the adhesive strip was peeled off at a speed of 500 mm/min and in the process the force which was necessary in order to detach the adhesive strip from the multilayer film and/or the transfer ply of the multilayer film was measured.

The tests surprisingly showed that the multilayer film and/or the transfer ply of the multilayer film remained substantially completely on the solidified construction material mixture and only the adhesive strip was peeled off again. The force measured in the process was between 400 cN and 1000 cN.

The adhesiveness between the multilayer film and/or the transfer ply of the multilayer film and the solidified construction material mixture should accordingly be higher than this measured adhesiveness as, after the adhesive strip had been detached from the multilayer film and/or the transfer ply under this measured adhesiveness, still no defects occurred on the multilayer film and/or the transfer ply of the multilayer film.

Furthermore, SEM micrographs of parts of the composite bodies were produced, and are represented inFIG.9andFIG.10.

For the SEM micrographs, in each case an approx. 10×10×5 mm (10×10 mm base area, thickness 5 mm) test piece was broken off the coated composite body to be examined and coated with gold by sputtering.

In the SEM micrographs, in each case the break-off edges of the test piece were examined.

The SEM micrographs were in each case recorded with the following parameters: 8 kV voltage, 20 mm distance between the test pieces, spot size 39, observation angle 80°.

As can easily be seen inFIG.9andFIG.10, the polymer layer of the transfer ply had a strong adhesion to the concrete. At some tearing edges/breaking edges a thin layer of concrete clearly remained adhering to the polymer. It was furthermore evident that the concrete was mechanically “anchored” in the polymer layer. It was evident in particular that the polymer layer formed a closed and smooth surface which seals the concrete.

Comparison Example 2

In order to test what influence the transfer ply has on the stability and adhesiveness of the transfer ply, 50 g EB screed concrete was prepared with water as described above and the moist mixture was put on a panel made of ABS material with a thickness of 1 mm as substrate. The surface of the mixture lying opposite the ABS panel was smoothed out and coated with an aqueous primer coat made of Neocryl A-45 in a mixture of water and isopropanol, solids approx. 15%, by means of brushing.

In order to obtain a coating that is as complete as possible, a much higher application weight was necessary.

After the coated concrete mixture had dried out, as specified above in Example 1, the test piece obtained was examined visually.

In spite of the higher application weight of the coating, a closed film did not form on the coated surface after the concrete had dried out, as can be seen inFIG.11.

LIST OF REFERENCE NUMBERS

1,1′ multilayer film2decorated mineral composite body3decorated, dimensionally stable, mineral green body3adimensionally stable, mineral green body10,10′ carrier ply11carrier layer12detachment layer13,13′ transfer ply14functional layer15anionically functionalized primer layer18protective ply19acarrier layer19bdetachment layer30forming element31inner surfaceS mineral substrate