# Patent

## Title
Sealing device with improved adhesion

## Abstract

The present invention relates to a sealing device (1) comprising a barrier layer (2) and an adhesive layer (3), and which is suitable for sealing bases in the building sector. The adhesive layer comprises a polymer P2, the polymer P2 being polyethylene (PE), polypropylene (PP) or a copolymer of ethylene and propylene, and a polyolefin-based polymer P3, the polymer P3 having at least one functional group which is selected from the group consisting of carboxylic acids, OH-groups, anhydrides, acetates and glycidyl methacrylate, and azo-dicarbonamide A. The invention further relates to a method for sealing the said bases. The method according to the invention allows structures of civil engineering to be sealed rapidly and efficiently and ensures good adhesion of the sealing device on the base.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a national stage application of International Application Ser. No. PCT/EP2013/059413, filed on May 6, 2013, which in turn claims the benefit of EP 12183601.9, filed on Sep. 7, 2012, and CH 00641/12, filed on May 7, 2012, and all of which are hereby incorporated by reference in their entirety, for any and all purposes.
TECHNICAL FIELD
The invention relates to the field of sealing substrates and bases, in particular in the construction field.
STATE OF THE ART
Substrates and bases that must be waterproofed, in particular concrete structures, can be found in large numbers in structural and civil engineering. Such substrates and bases are typically sealed by way of bitumen sheets or mechanically attached plastic membranes. However, due to their thermoplastic behavior, bitumen sheets are susceptible to temperature fluctuations. Elastic plastic membranes, in contrast, exhibit elastic behavior that is constant over a wide temperature range and thus fulfill their function as a seal even under extreme temperature conditions. The combination of a plastic membrane with bitumen is not used due to numerous disadvantages. One problem, among other things, is that a good adhesive bond between the plastic membrane in combination with bitumen and a substrate or a base must be present, which naturally encompasses adhesion of all intermediate layers. The adhesion and compatibility between the plastic sheet and bitumen in particular poses a problem that is very difficult to solve as a result of the materials that are involved.
This system moreover has the major disadvantage that high heat output is required to fully melt the bitumen, which typically necessitates the use of an open flame. This is not only expensive, but the high heat output of such an open flame, which is difficult to control, can result in smoldering. Additionally, this system requires the plastic membrane, if a plastic membrane is used, to be applied directly after the bitumen has been melted, which makes positioning of the plastic membrane in advance impossible. Moreover, it is not possible to step on the base after the bitumen has been melted and before the sealing material is applied.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an illustration a sealing device 1 having a sealing layer bonded directly to an adhesive layer, according to one embodiment.
FIG. 2 is an illustration of a sealing layer having a foamed portion on the side facing the adhesive layer, according to one embodiment.
FIG. 3 is an illustration of a sealing layer having an adhesive layer on both sides, according to one embodiment.
FIG. 4 is an illustration of a sealing device having an incorporated carrier layer and a topcoat, according to one embodiment.
FIG. 5 is a cross-sectional view of through a substrate a sealing device is partially applied, according to one embodiment.
FIG. 6 is an illustration of a shaped body having a substrate to which is bonded to a sealing layer via an adhesive layer, according to one embodiment.
FIG. 7 is an illustration of a shaped body having a substrate to which is bonded to a sealing layer having a foamed portion via an adhesive layer, according to one embodiment.
FIG. 8 is an illustration of a shaped body having a substrate, which is bonded to a sealing layer by way of a first adhesive layer, and the sealing layer has a foamed portion, according to one embodiment.
FIG. 9 is an illustration of a shaped body having a substrate, which is bonded to a sealing layer by way of a first adhesive layer, where the sealing layer has a foamed portion, and the substrate is bonded directly to the sealing layer, according to one embodiment.
FIG. 10 is an illustration of a shaped body having a first and second substrate that are bonded to a sealing layer by way of an adhesive layer, where the sealing layer has a foamed portion, according to one embodiment.
FIG. 11 is an illustration of a shaped body having a first and second substrate that are bonded to a sealing layer by way of an adhesive layer, where the sealing layer has a foamed portion, according to one embodiment.
FIG. 12 is a graph of the 90° peel test of adhesive layers of polymer P3 in the amounts shown in % by weight, according to the examples.
FIG. 13 is a graph of the 90° peel test of adhesive layers of polymer P3 in the amounts shown in % by weight, according to the examples.
FIG. 14 is a graph of the 90° peel test of adhesive layers of 10% by weight of the polymers P3, 85% by weight P2-2, and 5% by weight azodicarbonamide (Azo), or 5% by weight of the chemical expanding agent 4,4′-oxybis(benzenesulfonyl hydrazide) (OBSH), or 5% by weight of the radical starter dicumyl peroxide (DP), according to the examples.
FIG. 15 is a graph of the 90° peel test of adhesive layers of the polymer P2-2 and the amounts of the polymer P3-5 or the amount of azodicarbonamide (Azo), according to the examples.
FIG. 16 is a graph as in FIG. 15 shown as a ratio of the percent by weight of Azo P3-5, according to the examples.
FIG. 17 is a graph as in FIG. 15 shown as weight ratios of 0.25 to 0.33, 0.5, and 1 of azocarbonamide:polymer P3-5, according to the examples.
FIG. 18 is a graph of the 90° peel test of adhesive layers of the polymer P2-2 and the amounts of the polymer P3-5 or the amount of azodicarbonamide (Azo) on concrete test specimens, according to the examples.
FIG. 19 is a graph of the 90° peel test of adhesive layers of P2-2, 10% by weight polymer P3-5 and epoxy resin GT 7004 (no azodicarbonamide), according to the examples.
FIG. 20 is a graph of the 90° peel test of adhesive layers of P2-2, 10% by weight polymer P3-5, 5% by weight azodicarbonamide (Azo) and epoxy resin GT 7004 shown, according to the examples.
FIG. 21 is a graph of the 90° peel test of adhesive layers of P2-2, 10% by weight polymer P3-5, 5% by weight azodicarbonamide (Azo) and epoxy resin GT 7004, on concrete test specimens treated in advance with an epoxy resin primer, according to the examples.



DESCRIPTION OF THE INVENTION
It is therefore the object of the present invention to provide a sealing device which does not have the disadvantages of the state of the art, and which in particular can be created and applied easily and efficiently and results in a good adhesive bond between the sealing device and the substrate or base. Moreover, a high level of waterproofing is to be ensured.
Surprisingly, it was found that this object can be achieved by a sealing device. Such a sealing device allows a substrate or a base, and more particularly a concrete structure, to be sealed quickly and cost-effectively.
It was further shown that the preferred embodiments can be used to easily avoid an essential problem of the related art, namely that of applying the adhesive promoter, this being the bitumen, in a uniform and controlled manner, and that thus quality assurance in the creation of a seal can be considerably increased.
Another major advantage here is that the necessary adhesive promoter can be distributed and fixed in a controlled manner on the sealing layer in an industrial process, and that this sealing layer can be used at the construction site ready-made with the adhesive promoter, namely an adhesive layer. In particular, it is advantageous that the use of mastic asphalt can be dispensed with.
Moreover, such sealing devices can also be applied to a base without open flame, which is in particular a safety advantage.
Another major advantage is the option of movably disposing the sealing device prior to the application to the base, due to the features of the adhesive layer. When provided in a suitable location, the sealing device can be firmly bonded to the base thereafter by heating the adhesive layer.
Further aspects of the invention are the subject matter of further independent claims. Particularly preferred embodiments of the invention are the subject matter of the dependent claims.
WAYS TO IMPLEMENT THE INVENTION
In a first aspect, the present invention relates to a sealing device 1, comprising

    
    
        a sealing layer 2, comprising a thermoplastic polymer P1,
        and an adhesive layer 3, comprising
        
            a polymer P2, wherein the polymer P2 is polyethylene (PE), polypropylene (PP) or a copolymer of ethylene and propylene, and
            a polyolefin-based polymer P3, wherein the polymer P3 includes at least one functional group, which is selected from the group consisting of carboxylic acids, OH groups, anhydrides, acetates and glycidyl methacrylate, and
            azodicarbonamide A.
        
        
    
    


The sealing layer 2 is preferably bonded directly to the adhesive layer 3. The expression “bonded directly” shall be understood to mean that no further layer or substance is present between two materials, and that the two materials are directly bonded to each other or adhere to each other. The two materials can be present mixed with each other at the transition between the two materials. The adhesive layer 3 can be bonded to the sealing layer 2 across the entire surface or discontinuously, in particular across the entire surface.
FIG. 1 shows the composition of such a sealing device 1 comprising a sealing layer 2 and an adhesive layer 3, where the sealing layer 2 is bonded directly to the adhesive layer 3.
If the sealing layer 2 is bonded directly to the adhesive layer 3, this is advantageous insomuch as the sealing layer and the adhesive layer can thus be coextruded, for example, and moreover a good bond of the two layers is ensured.
If the sealing layer 2 is bonded directly to the adhesive layer 3, it is particularly advantageous if the sealing layer and the adhesive layer include polymers that are compatible with, and more particularly can be homogeneously mixed with, the polymers of the other layer.
For example, it is in particular advantageous if the thermoplastic polymer P1 of the sealing layer 2 is polyethylene (PE), polypropylene (PP) or a copolymer of ethylene and propylene.
If the sealing layer 2 includes polymers P1 mentioned above as being preferred, this is preferably polyethylene (PE), if the polymer P2 of the adhesive layer 3 is polyethylene (PE). Similarly, if the polymer P2 of the adhesive layer 3 is polypropylene (PP), the sealing layer 2 preferably includes polymers P1 that are polypropylene (PP).
It is further preferred if the sealing layer 2 comprises more than 40% by weight of the polymers P1 listed above as preferred polymers P1, based on the total weight of the sealing layer 2.
The sealing layer 2 particularly preferably comprises 70 to 100% by weight, in particular 90 to 100% by weight, and in particular 95 to 100% by weight of polymers P1 selected from the list consisting of polyethylene (PE), polypropylene (PP) and copolymers of ethylene and propylene, based on the total weight of the polymers present in the sealing layer 2.
To be as suitable as possible as the sealing layer 2, it should be as waterproof as possible and not decompose or be mechanically damaged even under the prolonged influence of water or moisture.
The sealing layer 2 comprises a thermoplastic polymer P1. The thermoplastic polymer P1 is preferably thermoplastic polyolefins and/or polyvinyl chloride (PVC).
The thermoplastic polymer P1 particularly preferably is a polymer selected from the group consisting of high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS), polyvinyl chloride (PVC), polyamide (PA), ethylene vinyl acetate (EVA), chlorosulfonated polyethylene, and polyolefin-based thermoplastic elastomers (TPO).
Most preferably the thermoplastic polymer P1 involves polymers selected from the list consisting of polyethylene (PE), polypropylene (PP) and copolymers of ethylene and propylene.
In particular sheets as they are already used in the prior art for sealing purposes in structural and civil engineering are suited as the sealing layer. So as to be damaged or modified as little as possible by heating when the sealing device is applied to a base, it is particularly advantageous if the sealing layer are produced from a material having a softening point of greater than 70° C., and preferably between 80° C. and 110° C. The sealing layer should advantageously have at least a low degree of elasticity, for example so as to be able to accommodate differences in expansion between the sealing device and the substrate or base caused by temperatures, or stress caused by cracks in the base, without the sealing layer becoming damaged or tearing and impairing the sealing function of the sealing layer.
The sealing layer preferably has a thickness of 0.1 to 10 mm, and more particularly of 1 to 5 mm.
The sealing layer 2 preferably includes a foamed portion 2a on the side facing the adhesive layer 3. This is shown in FIG. 2, for example. This is advantageous inasmuch as lower heat input is required to heat the adhesive layer. Moreover, it is also possible to use heat sources for heating, the heat input of which is not as easy to control.
It is further advantageous if the thickness of the foamed portion of the sealing layer 2a is 20 to 80%, and more particularly 45 to 65% of the entire thickness of the adhesive layer 2.
The density of the foamed portion of the sealing layer 2a is preferably 200 to 700 kg/m3, and more particularly 300 to 500 kg/m3.
The adhesive layer 3 comprises a polymer P2, wherein the polymer P2 is polyethylene (PE), polypropylene (PP) or a copolymer of ethylene and propylene.
The adhesive layer 3 comprises a polyolefin-based polymer P3, wherein the polymer P3 includes at least one functional group, which is selected from the group consisting of carboxylic acids, OH groups, anhydrides, acetates and glycidyl methacrylate.
The polymer P3 is preferably a polymer selected from the group consisting of:

    
    
        maleic anhydride-functionalized polyethylene, and more particularly maleic anhydride-functionalized LDPE or maleic anhydride-functionalized HDPE (PE-MAH);
        maleic anhydride-functionalized polypropylene (PP-MAH);
        maleic anhydride-functionalized copolymer of ethylene and propylene;
        ethylene vinyl acetate copolymer functionalized with maleic anhydride (EVA-MAH);
        ethylene vinyl alcohol (EVOH) copolymers;
        ethylene vinyl acetate (EVA) copolymers;
        ethylene butyl acrylate (EBA) copolymers;
        ethylene methyl acrylate (EMA) copolymers;
        glycidyl methacrylate-functionalized polyethylene (PE-GMA), and
        ethylene-butyl acrylate-maleic anhydride copolymers (PE-BA-MAH);
        ethylene acrylic acid copolymers (EAA).
    
    


The polymer P3 is particularly preferably a polymer selected from the group consisting of:

    
    
        maleic anhydride-functionalized polyethylene, and more particularly maleic anhydride-functionalized LDPE or maleic anhydride-functionalized HDPE (PE-MAH);
        maleic anhydride-functionalized polypropylene (PP-MAH);
        maleic anhydride-functionalized copolymer of ethylene and propylene (PE/PP-MAH);
        ethylene vinyl acetate copolymer functionalized with maleic anhydride (EVA-MAH);
        ethylene vinyl acetate (EVA) copolymers;
        glycidyl methacrylate-functionalized polyethylene (PE-GMA), and
        ethylene acrylic acid copolymers (EAA).
    
    


Most preferably, the polymer P3 is

    
    
        maleic anhydride-functionalized polyethylene,
        maleic anhydride-functionalized polypropylene, or
        a maleic anhydride-functionalized copolymer of ethylene and propylene.
    
    


The content of the polymer P3,
in particular if the polymer P3 is

    
    
        maleic anhydride-functionalized polyethylene,
        maleic anhydride-functionalized polypropylene, or
        a maleic anhydride-functionalized copolymer of ethylene and propylene,
    
    


is preferably 1 to 18% by weight, in particular 2.5 to 15% by weight, preferably 5 to 12% by weight, and most preferably 8 to 12% by weight, based on the total weight of the sum of (polymer P2+polymer P3+azodicarbonamide A). This is beneficial for good adhesion to concrete, among other things.
The ratio (azodicarbonamide A):(polymer P3)=0.1 to 1.2, in particular 0.3 to 0.8, and preferably 0.4 to 0.6,
in particular if the polymer P3 is

    
    
        maleic anhydride-functionalized polyethylene,
        maleic anhydride-functionalized polypropylene, or
        a maleic anhydride-functionalized copolymer of ethylene and propylene.
        This is beneficial for good adhesion to concrete, among other things.
    
    


Moreover, it is advantageous if the content of polymer P3 is 5 to 12% by weight, and in particular 8 to 12% by weight, based on the total weight of the sum of (polymer P2+polymer P3+azodicarbonamide A),
and the content of azodicarbonamide A is 3 to 7% by weight, and in particular 4 to 6% by weight, based on the total weight of the sum of (polymer P2+polymer P3+azodicarbonamide A).
This is advantageous in particular if the polymer P3 is

    
    
        maleic anhydride-functionalized polyethylene,
        maleic anhydride-functionalized polypropylene, or
        a maleic anhydride-functionalized copolymer of ethylene and propylene.
    
    


This is beneficial for good adhesion to concrete, among other things.
Moreover, it can be advantageous if the content of polymer P3 is 2.5 to 15% by weight, and in particular 8 to 12% by weight, based on the total weight of the sum of (polymer P2+polymer P3+azodicarbonamide A),
and the content of azodicarbonamide A is 0.5 to 5% by weight, and in particular 1 to 3% by weight, based on the total weight of the sum of (polymer P2+polymer P3+azodicarbonamide A).
Surprisingly, it was found that this results in particularly good adhesion to concrete surfaces which were pretreated with an epoxy resin-based primer.
This applies in particular if the polymer P3 is

    
    
        maleic anhydride-functionalized polyethylene,
        maleic anhydride-functionalized polypropylene, or
        a maleic anhydride-functionalized copolymer of ethylene and propylene.
    
    


Such epoxy resin-based primers have a free-flowing consistency at room temperature and are typically applied to the base by way of brushing, spraying or pouring. It should be noted that the term “free-flowing” here shall be understood to include not only liquid, but also honey-like to pasty materials having higher viscosities, the shape of which conforms under the influence of the gravitational force of the earth.
These are in particular two-component epoxy resin compositions, and more particularly such in which the one (this being the first) component includes an epoxy resin, and more particularly an epoxy resin based on bisphenol A diglycidyl ether, and the other one (this being the second) component includes a curing agent, and more particularly polyamine or polymercaptane. Moreover, the epoxy resin compositions are advantageously low-viscosity compositions, and more particularly have a viscosity of less than 10,000 mPas, and preferably between 10 and 1,000 mPas. Low-viscosity, two-component epoxy resin compositions as they are sold under the trade names Sikaprimer®, Sikafloor®, Sikagard® or Sika Ergodur® by Sika Deutschland GmbH, or Sika Schweiz AG, are considered particularly preferred two-component epoxy resin compositions.
It is further advantageous if the adhesive layer 3 includes <1% by weight, in particular 0 to 0.5% by weight, preferably 0 to 0.1% by weight, and most preferably no epoxy resin at all, based on the total weight of the adhesive layer. The term “epoxy resin” in the present document shall be understood to mean both solid epoxy resins and liquid epoxy resins.
This is beneficial, among other things, for improved adhesion, in particular to concrete, and in particular to concrete treated in advance with an epoxy resin primer.
It is particularly advantageous if the polymer P2 and the polymer P3 are compatible with each other, and more particularly if they can be homogeneously mixed with each other.
If the polymer P2 is polyethylene (PE), it is advantageous if the polymer P3 is a polyethylene-based polymer P3, wherein the polymer P3 comprises at least one functional group selected from the group consisting of carboxylic acids, OH groups, anhydrides, acetates, and glycidyl methacrylates. In this case, the polymer P3 is particularly preferably maleic anhydride-functionalized polyethylene, and more particularly maleic anhydride-functionalized LDPE or maleic anhydride-functionalized HDPE (PE-MAH).
If the polymer P2 is polypropylene (PP), it is advantageous if the polymer P3 is a polypropylene-based polymer P3, wherein the polymer P3 comprises at least one functional group selected from the group consisting of carboxylic acids, OH groups, anhydrides, acetates, and glycidyl methacrylates. In this case, the polymer P3 is particularly preferably maleic anhydride-functionalized polypropylene (PP-MAH).
If the polymer P2 is a copolymer of ethylene and propylene, it is advantageous if the polymer P3 is an ethylene-propylene copolymer-based polymer P3, wherein the polymer P3 comprises at least one functional group selected from the group consisting of carboxylic acids, OH groups, anhydrides, acetates, and glycidyl methacrylates. In this case, the polymer P3 is particularly preferably a maleic anhydride-functionalized copolymer of ethylene and propylene (PE/PP-MAH).
The adhesive layer 3 comprises azodicarbonamide A.
So as to lower the activation temperature of azodicarbonamide (also referred to as azobisformamide or diazenedicarboxylic acid diamide), for example, it can be advantageous to add a catalyst, such as zinc oxide or urea, to the azodicarbonamide, typically in an amount of 10 to 50% by weight, based on the total weight of the azodicarbonamide A.
The adhesive layer 3 is preferably tack-free at 23° C. The term “tack-free” in connection with the adhesive layer 3 in the entire present document shall be understood to mean surface stickiness within the meaning of instant adhesion or tack, which is so low at 23° C. that, upon pressing a thumb with a pressure force of approximately 5 kg for 1 second against the surface of the adhesive layer, the thumb does not stick to the surface of the adhesive layer, or the adhesive layer cannot be lifted. In this way, the sealing device can be stored, transported and processed more easily.
Particularly preferred are adhesive layers 3 comprising 70 to 98% by weight, and more particularly 80 to 90% by weight, polymer P2, 1 to 20% by weight, and more particularly 5 to 15% by weight, polymer P3, this
preferably being

    
    
        maleic anhydride-functionalized polyethylene,
        maleic anhydride-functionalized polypropylene, or
        a maleic anhydride-functionalized copolymer of ethylene and propylene,
        1 to 10% by weight, and more particularly 3 to 7% by weight, azodicarbonamide A.
    
    


The above-mentioned components P2, P3 and A preferably account for more than 50% by weight, in particular more than 70% by weight, in particular more than 80% by weight, preferably more than 90%, and most preferably more than 98% by weight of the adhesive layer 3.
It is further advantageous if the adhesive layer 3 has a thickness of 0.05 to 0.5 mm, 0.1 to 0.3 mm.
The sealing layer 2 can preferably comprise an adhesive layer 3 on both sides; this is shown in FIG. 3, for example. The sealing layer can comprise one or two foamed portions, as is apparent as 2a and 2b in FIG. 3, or not.
It can further be advantageous if the sealing layer 2 comprises a carrier layer 9. The carrier layer 9 contributes to the dimensional stability of the sealing layer. This is preferably a fiber material or a mesh, in particular a fiber material. The term “fiber material” in the entire present document shall be understood to mean a material composed of fibers. The fibers comprise or consist of organic or synthetic material. These are in particular cellulose fibers, cotton fibers, protein fibers, synthetic fibers or organic fibers, for example glass fibers. Preferably fibers made of polyester, or made of a homopolymer or copolymer of ethylene and/or propylene, or made of viscose, shall be primarily mentioned as synthetic fibers. The fibers can be short fibers or long fibers, spun, woven or unwoven fibers or filaments. The fibers can moreover be aligned or drawn fibers. Moreover, it can be advantageous to use different fibers, both in terms of geometry and composition, together.
The body composed of fibers can be produced using a wide variety of methods known to a person skilled in the art. In particular bodies that are a woven fabric, laid scrim or knitted fabric are used. A felt or nonwoven fabric is particularly preferred as the fiber material.
The carrier layer is preferably incorporated into the sealing layer; moreover, it is advantageous if the carrier layer 9 comprises intermediate spaces, which are at least partially interspersed with the material of the sealing layer 2. This is beneficial for a good bond between the sealing layer and the carrier layer.
It can moreover be advantageous if the sealing layer 2 comprises a topcoat 10, which is preferably applied to the side facing away from the adhesive layer 3. If the topcoat includes UV stabilizers, the topcoat can protect the sealing device from aging by sunlight, for example. If the topcoat includes color pigments, damage to the side of the sealing device which faces away from the adhesive layer, for example caused by the transport or by the installation, can be discovered by the absence of the topcoat at the damaged location.
A sealing device, the sealing layer of which comprises an incorporated carrier layer 9 and a topcoat 10, is shown in FIG. 4, for example.
It is further advantageous if the sealing device 1 is a flexible membrane, and more particularly a flexible sheet. This can be easily rolled up and thus easily stored and/or transported. The sealing device is thus easy to take to the construction site and can be unrolled there and cut to the required dimensions. This is a very cost- and time-efficient work step.
A further aspect of the present invention relates to a method for sealing a substrate S14, comprising the following steps:

    
    
        i) applying a sealing device 1, as it is described above, to a substrate S14, wherein the adhesive layer 3 faces the substrate S14; and
        ii) heating the adhesive layer 3 of the sealing device 1, preferably to a temperature of 80 to 600° C.
    
    


The substrate S14 is preferably a structural or civil engineering structure, which is to be sealed against moisture and water. Moreover, it can be the soil, a building, insulating material, or formwork. The substrate S14 can be horizontal, or not.
The material of the substrate S1 is in particular wood, metal, a metal alloy, a mineral binding agent such as concrete or gypsum, plastic material or thermal insulation material, such as foamed polyurethane, mineral wool or cellular glass (Foamglas). It is particularly preferred if the material is wood, metal, a metal alloy or concrete, in particular concrete. The material is most preferably concrete, in particular concrete.
The sealing device 1 can be applied to a substrate S14 in step i), for example, by unrolling the sealing device or installing the sealing device across the entire surface. If the adhesive layer 3 is an adhesive layer that is tack-free at 23° C., the sealing device can be conveniently (re)positioned on the substrate S1 until the heating process in step ii).
Heating can take place in any arbitrary manner. Heating can be achieved by external or by internal heat sources, such as an exothermic chemical reaction. The heating in step ii) is preferably carried out by way of hot air, flame application, ultrasound, induction welding or an electric resistance heating element.
The adhesive layer 3 can be heated directly, for example by heating the surface of the adhesive layer, in particular by way of hot air or flame application. Direct heating is also possible by way of an electric resistance heating element, for example an electric resistance heating element disposed in the adhesive layer, such as a metal mesh.
In addition or as an alternative, the adhesive layer 3 can also be heated indirectly, for example by heating the substrate S1, in particular by way of hot air or flame application. However, this requires a substrate S1 that withstands such heat input without damage. Such heat input, however, typically necessitates higher heat input.
If the heating is carried out by way of flame application, it is advantageous if the surface of the adhesive layer 3 is heated for 0.1 to 30 seconds, in particular for 5 to 20 seconds, and preferably for 10 to 15 seconds, to a temperature of 400° C. to 600° C., in particular to 450° C. to 550° C., and in particular to 480° C. to 520° C.
The heating in step ii) can be carried out chronologically before and/or during and/or after step i). If the heating in step ii) is carried out chronologically before step i), this typically take place shortly, in particular within 30 seconds, and more particularly within 10 seconds, before the application in step i).
FIG. 5 shows a schematic cross-section through a substrate S14 to which the sealing device 1 is partially applied. Shown is the situation during or after the heating in step ii). On the one hand, indirect heating by way of a heat source 6 is shown, wherein the heating is carried out by heating the substrate S1, typically by way of hot air or flame application. The arrows are intended to indicate the direction of the heat that is given off, proceeding from the heat source. On the other hand, FIG. 5 also shows direct heating by way of a heat source, which is typically carried out by way of hot air or flame application. In the situation shown in FIG. 5, the step i) of applying the sealing device 1 and step ii) of heating the adhesive layer 3 essentially take place simultaneously. After heating 3a, the adhesive layer is firmly bonded to the substrate S1. Due to the roll shape of the sealing device, the sealing device can be unrolled after being initially positioned on the substrate S1 and steps i) and ii) can be carried out.
A further aspect of the present invention relates to a method for sealing a substrate S1′ 4, comprising the following steps:

    
    
        i′) applying a sealing device 1, which comprises an adhesive layer 3 on both sides, as it is described above, to a substrate S1′ 4;
        ii′) heating the adhesive layer 3 of the sealing device 1 which faces the substrate S1′ 4, preferably to a temperature of 80 to 600° C.;
        iii′) heating the adhesive layer 3 of the sealing device 1 which faces away from the substrate S1′ 4, preferably to a temperature of 80 to 600° C.; and
        iv′) applying a substrate S2′ 5 to the adhesive layer 3 of the sealing device 1 which faces away from the substrate S1′ 4 .
    
    


The substrate S1′ 4 preferably involves substrates as they were described above as the suitable and preferred substrate S1. The method is in particular suitable for sealing a substrate S1′ and additionally bonding it to a substrate S2′ 5.
The substrate S2′ 5 is preferably composed of a material as the materials that were described above as being suitable and preferred for the substrate S1.
Advantageous application and heating were described above.
A further aspect of the present invention relates to a method for sealing a substrate S1′′ 4, comprising the following steps:

    
    
        i′′) applying a sealing device 1, as it is described above, to a substrate S1′′ 4, wherein the adhesive layer 3 faces the substrate S1′′ 4;
        ii′′) heating the adhesive layer 3 of the sealing device 1, preferably to a temperature of 80 to 600° C.; and
        iii′′) applying a substrate S2′′ 5 to the sealing layer 2 of the sealing device 1.
    
    


The substrate S1′′ 4 preferably involves substrates as they were described above as the suitable and preferred substrate S1. The method is in particular suitable for sealing a substrate S1′ and additionally bonding it with a substrate S2′′ 5, wherein the S2′′ is able to form a firm bond with the sealing layer without the use of an adhesive promoter or an adhesive, in particular if the substrate S2′′ 5 has a temperature of 80 to 600° C. when it is applied to the sealing layer.
It is therefore advantageous if the substrate S2′′ 5 has a temperature of 80 to 600° C. when it is applied.
The substrate S2′′ 5 is preferably asphalt. The application of a substrate S2′′ preferably involves liquid asphalt having a temperature of 80 to 600° C.
Advantageous application and heating with respect to step i′′) and step ii′′) were described above.
A further aspect of the present invention relates to a method for sealing a substrate S1′′′ 4 and a substrate S2′′′ 5, comprising the following steps:

    
    
        i′′′) applying a sealing device 1, as it is described above, to a substrate S1′′′ 4 and to a substrate S2′′′ 5, wherein the adhesive layer 3 faces the substrate S1′′′ 4 and the substrate S2′′′ 5; and
        ii′′′) heating the adhesive layer 3 of the sealing device 1, preferably to a temperature of 80 to 600° C.
    
    


The substrate S1′′′ 4 and the substrate S2′′′ 5 are preferably structural or civil engineering structures, the contact surface of which, or optionally the intermediate space of which between the two substrates, is to be sealed. The substrate S1′′′ can be concrete, for example, and the substrate can be a pipe introduced into the substrate S2′′′.
The sealing device 1 here fulfills the function of sealing

    
    
        penetrating elements, such as rebars, cables and the like;
        transitions between different shaped parts, such as between concrete and steel components; and
        expansion and construction joints, both in the case of site-mixed concrete and in the case of construction by means of prefabricated units.
    
    


Moreover, the substrate S1′′′ and S2′′′ can be mutually facing shaped concrete bodies. The sealing device 1 here fulfills the function of a waterstop. The sealing device 1 can also have a shape and features as they are known for waterstops to a person skilled in the art.
The material of the substrate S1′′′ is in particular a mineral binding agent such as concrete or gypsum, and most preferably the material is concrete, in particular concrete. The material of the substrate S2′′′ is preferably metal or a metal alloy, or the material of the substrate S2′′′ is a mineral binding agent such as concrete or gypsum, in particular concrete.
Advantageous application and heating with respect to step i′′′) and step ii′′′) were described above.
A further aspect of the present invention relates to the use of the sealing device 1 described in detail above for sealing bases.
The sealing device is typically used as a prefabricated membrane. In this case, the sealing device is preferably produced in the form of sheeting by way of an industrial process and is preferably used in the form of a sealing device unwound from a roll at the construction site. However, the sealing device can also be used in the form of strips having a width of typically 1 to 20 cm, for example so as to seal connecting points between two roofing membranes. Moreover, the sealing device can also be present and used in the form of planar bodies for repairing damaged locations in seals, for example roofing membranes.
A preferred use of the sealing device 1 is thus a use for sealing structural and civil engineering projects, in particular of roofs and floors, against moisture.
A further aspect of the present invention relates to a method for producing a sealing device 1, as it was described above in detail, wherein the sealing layer 2 and/or the adhesive layer 3 are produced by way of calendering and/or extrusion and/or co-extrusion and/or lamination.
The sealing layer 2 is preferably bonded to the adhesive layer 3 by way of calendering and/or co-extrusion. The sealing device 1 can moreover be produced as endless material and rolled to form rolls, for example.
It can further be advantageous if portions of the sealing layer 2 are foamed during production, wherein the above-described foamed portions of the sealing layer 2a are obtained. This is typically achieved by way of physical and/or chemical expanding agents, which are optionally present in the sealing layer 2.
In a further aspect, the present invention relates to a shaped body, wherein the shaped body is firmly bonded to the adhesive layer 3 of the sealing device 1 by prior heating of the adhesive layer 3. The shaped body is typically a structural or civil engineering structure. The term “shaped body” denotes an object having a three-dimensional expansion.
For example, FIG. 6 shows a shaped body composed of a substrate S1, which is bonded to the sealing layer 2 by way of the adhesive layer 3a. The shaped body is preferably a prefabricated unit, which is industrially produced. Industrial production allows more controlled heat input into the adhesive layer than is possible at a construction site, for example. It can therefore be advantageous to dispense with a foamed portion 2a of the sealing layer. Such shaped bodies can be sealed prefabricated elements for tunnels, water pipes, sewers, flooring and the like, for example.
For example, FIG. 7 shows a shaped body composed of a substrate S1 4, which is bonded to the sealing layer 2 by way of the adhesive layer 3a. The sealing layer comprises a foamed portion 2a. Such shaped bodies can be sealed roofs and floors, for example, in particular such made of concrete.
For example, FIG. 8 shows a shaped body composed of a substrate S1 4, which is bonded to the sealing layer 2 by way of a first adhesive layer 3a. The sealing layer comprises a foamed portion 2a. A substrate S2 5 is bonded to a second foamed portion 2b of the sealing layer 2 by way of a further adhesive layer 3a. 
For example, FIG. 9 shows a shaped body composed of a substrate S1 4, which is bonded to the sealing layer 2 by way of a first adhesive layer 3a. The sealing layer comprises a foamed portion 2a. A substrate S2 5 is bonded directly to the sealing layer 2. Such shaped bodies can be a roadway structure, for example, in which the concrete substructure (substrate S1) is sealed with the aid of the sealing device and to which the asphalt (substrate S2) is applied.
For example, FIG. 10 shows a shaped body composed of a substrate S1 4 and a substrate S2 5, which are bonded to the sealing layer 2 by way of the adhesive layer 3a. The sealing layer comprises a foamed portion 2a. Such shaped bodies can be sealed floors, for example, in particular such made of concrete. The sealing device is a waterstop, for example.
For example, FIG. 11 shows a shaped body composed of a substrate S1 4 and a substrate S2 5, which are bonded to the sealing layer 2 by way of the adhesive layer 3a. The sealing layer comprises a foamed portion 2a. Such shaped bodies can be sealed penetrating elements or transitions between different substrates, for example. S1 is a floor, for example, in particular one made of concrete, and substrate S2 is a pipe made of metal or a metal alloy, penetrating the floor.
LIST OF REFERENCE NUMERALS


    1 sealing device
    2 sealing layer
    2a foamed portion of the sealing layer
    2b foamed portion of the sealing layer
    3 adhesive layer
    3a adhesive layer after heating
    4 substrate S1
    5 substrate S2
    6 heat source, or direction of the heat that is given off, proceeding from the heat source
    9 carrier layer
    10 topcoat


EXAMPLES
Experiments with Concrete Specimen
Production of Adhesive Layers:
Blends made of the polymer P2, the polymer P3 and optionally azodicarbonamide were extruded on a co-rotating twin-screw extruder made by OMC (temperature 110° C., rotational screw speed 200 revolutions/minute).
Production of the Test Specimen:
Test membranes were produced by first enclosing a reinforcing glass nonwoven having a thickness of 0.2 mm with two layers made of the above-described adhesive layer, each having a thickness of 0.8 mm, by way of compression molding at 110° C. for 1 minute.
If the adhesive layers that were used did not include any azodicarbonamide, the test membrane was heated to a temperature of 200° C. by placing it onto a polytetrafluoroethylene panel having such a temperature. Once this temperature was reached, a concrete test specimen (12×70 mm, height 25 mm; Rocholl, cut according to ISO 13640, method 1) was placed on the heated test membrane, additionally weighted with a weight of an additional 150 g and left in place for 2 minutes. The test specimen thus obtained was then removed from the polytetrafluoroethylene panel and allowed to cool to room temperature.
If the adhesive layers that were used included azodicarbonamide, the test membrane was placed onto a polytetrafluoroethylene panel and heated for one minute with an industrial hot blow dryer from a distance of 10 cm. Thereafter, a concrete test specimen (12×70 mm, height 25 mm; Rocholl, cut according to ISO 13640, method 1) was placed on the activated test membrane, additionally weighted with a weight of an additional 150 g and left in place for 2 minutes. The test specimen thus obtained was then removed from the polytetrafluoroethylene panel and allowed to cool to room temperature.
Application of the Primer:
In the examples of FIG. 18 and of FIG. 21, one side of the concrete test specimen (12×70 mm, height 25 mm; Rocholl, cut according to ISO 13640, method 1) was treated in advance with an epoxy resin primer (Sika Primer 210 in the examples of FIG. 18; Sikagard 186 in the examples of FIG. 21; both from Sika Schweiz AG) in accordance with the manufacturer's instructions. The treated side was then placed on the heated test membrane.
Measurement of the Test Specimen:
90° peel tests (at 23° C. and 50% humidity) were carried out on the test specimen that were obtained, using a tensile testing machine (Zwick), at a constant cross beam speed of 100 mm/min.














P2
P2-1
PE-PP copolymer, Vistamaxx 3980, ExxonMobil



P2-2
PE polymer, LDPE, LD251, ExxonMobil


P3
P3-1
PE-GMA copolymer, Lotader AX 8840, Arkema



P3-2
PE-GMA copolymer, PE-GMA copolymer 6, BASF



P3-3
PE-MAH copolymer (HDPE), Fusabond MB 265D, DuPont



P3-4
PE-MAH copolymer (LDPE), Fusabond EC 603D, DuPont



P3-5
LDPE-MAH, Bynel 42E703, DuPont



P3-6
PE-MAH copolymer, Licocene PE MA 4351, Clariant



P3-7
EVOH copolymer, EVAL G 176B, Kuraray



P3-8
Ethylene-acrylic acid copolymer, Primacor 3440, DOW



P3-9
Ethylene-acrylic acid ester-MAH copolymer, Lotader 3210,




Arkema



P3-10
EVA copolymer (28% by weight vinyl acetate), Elvax 260,




DuPont


A
Azo
Azodicarbonamide, Unicell DL75N, Dongjin Semichem




Co.



OBSH
4,4′-oxybis(benzenesulfonyl hydrazide) (OBSH), Luvopor




OB, Lehmann + Voss



DP
Radical donor, dicumyl peroxide



Prim
Epoxy resin primer, Sika Primer 210, Sika Schweiz AG



Epoxy
Bisphenol A-based solid epoxy resin, GT 7004, Huntsman









The term “MFI” in the present document shall be understood to mean the melt flow index, measured at 190° C./2.16 kg according to the ASTM D1238 standard for ethylene-based polymers, and at 230° C./2.16 kg according to the ISO 1133 standard for propylene-based polymers, indicated in g/10 min.
FIG. 12 shows 90° peel tests of adhesive layers composed of the polymer P3 in the amounts shown in FIG. 12 in % by weight; the polymer P2-1 accounts for the remainder of the composition.
FIG. 13 shows 90° peel tests of adhesive layers composed of the polymer P3 in the amounts shown in FIG. 13 in % by weight; the polymer P2-2 accounts for the remainder of the composition.
FIG. 14 shows 90° peel tests of adhesive layers composed of 10% by weight of the polymers P3 indicated in FIG. 14, 85% by weight P2-2, and 5% by weight azodicarbonamide (Azo), or 5% by weight of the chemical expanding agent 4,4′-oxybis(benzenesulfonyl hydrazide) (OBSH), or 5% by weight of the radical starter dicumyl peroxide (DP).
In the measuring series marked “without addition”, adhesive layers composed of 10.5% by weight of the polymers P3 indicated in FIG. 14 and 89.5% by weight P2-2 were used.
FIG. 15 shows 90° peel tests of adhesive layers composed of the polymer P2-2 and the amounts of the polymer P3-5 or the amount of azodicarbonamide (Azo) shown in FIG. 15.
The results of FIG. 15 are shown in FIG. 16 as the ratio of the percent by weight of (Azo:P3-5).
The results of FIG. 16 are also shown in FIG. 17. Shown are the weight ratios 0.25 to 0.33, 0.5 and 1 of (azodicarbonamide:polymer P3-5).
FIG. 18 shows 90° peel tests of adhesive layers composed of the polymer P2-2 and the amounts of the polymer P3-5 or the amount of azodicarbonamide (Azo) shown in FIG. 18. Concrete test specimen were used in the peel tests of FIG. 18, which were treated in advance with an epoxy resin primer as described above. Untreated concrete test specimen were used in the peel tests of FIGS. 12 to 17 and 19 to 20.
FIG. 19 shows 90° peel tests of adhesive layers composed of P2-2, 10% by weight polymer P3-5 and the amount of epoxy resin GT 7004 shown in FIG. 19 (no azodicarbonamide).
FIG. 20 shows 90° peel tests of adhesive layers composed of P2-2, 10% by weight polymer P3-5, 5% by weight azodicarbonamide (Azo) and the amount of epoxy resin GT 7004 shown in FIG. 20.
FIG. 21 shows 90° peel tests of adhesive layers composed of P2-2, 10% by weight polymer P3-5, 5% by weight azodicarbonamide (Azo) and the amount of epoxy resin GT 7004 shown in FIG. 21. Concrete test specimen were used in the peel tests of FIG. 21, which were treated in advance with an epoxy resin primer as described above.
Experiment for Heat Input into an Adhesive Layer:
The above-described adhesive layers were produced in two different thicknesses, a thickness of 2 mm on the other hand and a thickness of 0.3 mm on the other hand. Those mentioned first were placed directly onto a base (concrete); on those mentioned second, the adhesive layer was bonded with a foam layer measuring 1.7 mm thick and having a density of approximately 0.5 g/cm3 by way of a hot press before they were placed (with the foam layer facing the base) onto the base (concrete). Thereafter, the surface of the adhesive layers facing away from the base was heated by way of an IR heater (KRELUS, output P=4.3 kW, radiator field 24 cm×56 cm) at a distance of 8 cm. The adhesive layers comprising a foam layer behind the adhesive layer were activated twice as quickly. Moreover, a change in color was discernible in all activated adhesive layers as compared to the non-activated state.

## Claims

1. A sealing device, comprising:
a sealing layer, comprising: a thermoplastic polymer; and
an adhesive layer, comprising:
a first polymer that is a polyethylene, a polypropylene or a copolymer of ethylene and propylene;
a second polymer that is a polyolefin-based polymer comprising at least one functional group selected from the group consisting of a carboxylic acid, a OH group, an anhydride, an acetate, and a glycidyl methacrylate; and
azodicarbonamide A;
wherein: the adhesive layer includes from 0 to 0.5 wt % of an epoxy resin.

2. The sealing device of claim 1, wherein the second polymer is selected from the group consisting of:
a maleic anhydride-functionalized polyethylene;
a maleic anhydride-functionalized polypropylene;
a maleic anhydride-functionalized copolymer of ethylene and propylene;
an ethylene vinyl acetate copolymer functionalized with maleic anhydride;
an ethylene vinyl acetate copolymer;
a glycidyl methacrylate-functionalized polyethylene; and
an ethylene acrylic acid copolymer.

3. The sealing device of claim 1, wherein the second polymer is:
a maleic anhydride-functionalized polyethylene;
a maleic anhydride-functionalized polypropylene, or
a maleic anhydride-functionalized copolymer of ethylene and propylene.

4. The sealing device of claim 1, wherein a content of the second polymer in the adhesive layer is from 1 wt % to 18 wt %.

5. The sealing device of claim 1, wherein a content of the second polymer in the adhesive layer is from 2.5 wt % to 15 wt %.

6. The sealing device of claim 1, wherein a content of the second polymer in the adhesive layer is from 5 wt % to 12 wt %.

7. The sealing device of claim 1, wherein a ratio of azodicarbonamide A to the second polymer is from 0.1 to 1.2.

8. The sealing device of claim 6, wherein a content of azodicarbonamide A in the adhesive layer is from 3 to 7% by weight.

9. The sealing device of claim 1, wherein the second polymer is a maleic anhydride-functionalized polyethylene that is a maleic anhydride-functionalized low density polyethylene, or a maleic anhydride-functionalized high density polyethylene.

10. The sealing device of claim 5, wherein a content of azodicarbonamide A in the adhesive layer is from 0.5 wt % to 5 wt %.

11. The sealing device of claim 1, wherein the adhesive layer is free of an epoxy functionality.

12. The sealing device of claim 1, wherein the adhesive layer is tack-free at 23° C.

13. A method for sealing a substrate, the method comprising:
applying the sealing device of claim 1 to a substrate, wherein the adhesive layer of the sealing device faces the substrate; and
heating the adhesive layer.

14. The method of claim 13 further comprising applying a second substrate to the sealing layer of the sealing device.

15. The method according to claim 14, wherein the second substrate is asphalt.

16. A shaped body comprising the sealing device of claim 1,
wherein the shaped body is firmly bonded to the adhesive layer of the sealing device.

17. A sealing base comprising the sealing device of claim 1.