Intermediate layer for improved recycling of multi-layer composite materials

Abstract

The invention relates to the use of a polyvinylacetate intermediate layer for producing a multi-layer composite material and to the the multi-layer material containing such an intermediate layer for the purpose of improving separation of two contiguous layers in recycling processes.

Description

[0001] INTERLAYER FOR IMPROVED RECYCLING

[0002] OF MULTI-LAYER COMPOSITE MATERIALS

[0003] The invention relates to the use of a polyvinyl acetate intermediate layer for the production of a multilayer composite material and the multilayer material containing such an intermediate layer for improved separation of two adjacent layers.

[0004] To combine the positive properties of different materials, multilayer composite materials are used in various applications today. This is the case, for example, with plastic food packaging. Here, the necessary barriers against water / water vapor, gases, and flavorings are usually only achieved through the simultaneous use of different materials. The individual layers are sometimes held together only by adhesion-promoting layers or adhesives.

[0005] Recycling, as an essential component of the circular economy, helps close or slow down material cycles, thereby reducing the use of natural resources and emissions. In addition to saving packaging, a frequent goal of manufacturers, consumers, and increasingly legislators is to improve the recyclability of composite materials in general and, in particular, composite materials. To achieve this, it is important that the materials can be processed into secondary raw materials as completely as possible. The materials produced in this way are referred to as recyclates or regenerates. Furthermore, their quality and purity should be particularly high to ensure that these secondary raw materials can be used in a variety of ways. The purity of the recyclates from multi-layer composite materials can be improved by enabling the most complete separation of different layers or by simplifying the process to make them economical.In addition to protection against moisture, water, and grease, oxygen transmission resistance (OTR) is a key parameter for packaging structures used for food applications and is often difficult to achieve, especially when switching to mono-material systems. One solution is thin layers of barrier coatings. They can meet the high OTR requirements and also meet durability requirements. However, these coatings are often disruptive in the recycling process because they cannot be completely removed from the carrier material.

[0006] The object of the invention is to provide an intermediate layer for the production of a multilayer composite material which improves at least one of the disadvantages of previous multilayer packaging and at the same time retains the advantageous properties.

[0007] At least one of these aspects of the problem is solved by the use of an intermediate layer for the production of a multilayer composite material, wherein the intermediate layer contains at least 98 wt.% polyvinyl alcohol and is soluble in water at a maximum temperature of 40°C. Also disclosed is the use of an intermediate layer for the production of a multilayer composite material, wherein the intermediate layer contains at least 98 wt.% polyvinyl alcohol with a degree of hydrolysis of 80-98%. This allows layers or their materials, which previously could only be separated with difficulty or not completely, to be completely detached from one another.

[0008] The PVOH intermediate layer can have different functions. The PVOH intermediate layer can completely dissolve during a cold washing process in the recycling process, leaving two completely separate layers that were previously adjacent to the PVOH intermediate layer for the further process. These layers can then be recovered as pure recyclate. In this context, pure means that there are no contaminations from residues of the other layer and the intermediate layer. The PVOH intermediate layer can also serve as a gas barrier. In one embodiment, however, the PVOH intermediate layer is shaped in such a way, e.g., so thin that it cannot perform any significant gas barrier function. The additional oxygen barrier achieved by the PVOH intermediate layer can exceed 20 cm, even at low relative humidity (60%) and 20°C. 3 m 2 Day ' atm or preferably more than 50 cm 3 m 2Day ' atm or further preferably more than 100 cm 3 m 2 Day ' atm. The oxygen or general gas barrier function can then be taken over by another layer, if this function is needed.

[0009] Polyvinyl alcohol (PVOH) is a widely used polymer. It can be made from biogenic (renewable) raw materials and is biodegradable in an aqueous environment. PVOH is characterized by high tear strength and elasticity. These properties depend on the air humidity, as PVOH absorbs water. As a thermoplastic, some PVOH types can generally be processed using conventional plastics processing methods, while the water-soluble types can be processed as a solution in water. With a suitable raw material selection, including additives (especially the addition of plasticizers), it is suitable for film extrusion, thermoforming, injection molding, and blow molding. It is preferred if a solution of at least 4% in water can be produced with the PVOH of the present invention at 20°C.

[0010] The intermediate layers of the present invention contain at least 98% by weight polyvinyl alcohol. Additives such as plasticizers that promote processing or layer formation can be mixed with the PVOH. It is preferred if these additives are biodegradable. One possible additive is small amounts of water or salts. However, it can also be pure PVOH. The PVOH intermediate layer can also comprise or consist of a mixture of various PVOH polymers with different properties. The PVOH intermediate layer can contain hydrophobically modified polyvinyl alcohols (e.g., ethylene-vinyl alcohol copolymer), provided the water solubility described here is still present. The PVOH intermediate layer can also contain carboxylate-modified PVOHs. It has proven disadvantageous if the intermediate layer contains cellulose fibers. One embodiment therefore relates to PVOH intermediate layers that are free of cellulose.It can also be advantageous if the PVOH interlayers do not contain any metal particles or metal salts. One embodiment therefore relates to PVOH interlayers that are free of metals. Another embodiment relates to PVOH interlayers that are free of cellulose and metals.

[0011] It has been shown that water solubility, especially at low temperatures, depends, among other things, on the degree of hydrolysis and the degree of polymerization. For the application described here, a degree of hydrolysis of approximately 88% and a low degree of polymerization are particularly suitable.

[0012] The degree of polymerization indicates the number of basic building blocks per polymer molecule. For PVOH, the exact number can only be given as an average value over a sample under consideration (average degree of polymerization (DP)) and can range between 500 and 3000. A range of 550 to 1500, 600 to 1400, and more preferably 630 to 1000 is preferred.

[0013] The PVOH of the present invention may be a PVOH having a degree of hydrolysis of 60 to 98 mol%, and preferably of 75 to 95 mol%, more preferably of 80 to 90 mol%, and even more preferably of 85-90 mol%.

[0014] For the preferred polyvinyl alcohols, the degree of hydrolysis is 85-90 mol%, even better 87-89 mol%, and preferably 88 mol%. Furthermore, the degree of polymerization for these polymers is preferably between 600 and 1400.

[0015] In addition, polymers, and especially PVOH, are often described by the viscosity of a defined solution at a specific temperature, as this behavior is also strongly influenced by the degree of polymerization. For the present application as an intermediate layer, PVOHs are particularly well suited, with a viscosity of between 4 and 28 mPa s in a 4% water solution at 20°C. However, a viscosity of between 4.5 and 20 mPa s, or between 5 and 10 mPa s, is preferred. A Brookfield viscometer is used for viscosity measurement according to ISO 1652 (LV measuring body). A falling ball viscometer is also possible.

[0016] The PVOH used can have a molecular weight or a molecular weight distribution (M w) of 13,000 to 130,000, preferably of 15,000 to 80,000, and more preferably of 18,000 to 50,000. The PVOH can also be selected so that it forms a 4% solution in water at temperatures below 40°C, preferably below 35°C, and more preferably below 20°C within 45 minutes (better 30 minutes).

[0017] The PVOH intermediate layer of the present invention is soluble in water at a maximum temperature of 40°C. In one embodiment, the PVOH intermediate layer can dissolve completely in water. This enables the easy and complete detachment of the two layers adjacent to the PVOH intermediate layer. It is preferred that the PVOH intermediate layer dissolves completely and residue-free in water. The dissolution of the PVOH intermediate layer can preferably occur at a maximum temperature of 40°C, preferably below 35°C or below 20°C, and in less than one hour (preferably less than 30 minutes) and at atmospheric pressure. The duration of these dissolution processes can be between 5 and 60 minutes, preferably between 10 and 45 minutes, and more preferably between 15 and 30 minutes. In the recycling process, the dissolution of the PVOH intermediate layer can thus be integrated into existing cold washing steps. These can be preceded by a comminution step.

[0018] In dissolved form, PVOH can be directly processed into new products, such as films, recovered for reuse, or completely degraded into water (H2O) and carbon dioxide (CO2) by the action of microorganisms and bacteria. Unlike non-degradable polymers, whether fossil-based or bio-based, water-soluble PVOH granules and products, once dissolved, do not produce microplastics. Because the PVOH dissolves in a washing process in the recycling plant, the resulting layers and their materials (granules) are not contaminated.

[0019] When manufacturing a multilayer composite material, the PVOH interlayer can be created using various methods. For example, an aqueous solution of PVOH can be applied directly to one of the adjacent layers (e.g., paper or polymer). Subsequent drying then leads to film or layer formation. When an aqueous PVOH solution is used to form the layer, the still-moist layer can also be used as an adhesive for the other adjacent layer, e.g., in a laminating plant where both adjacent (neighboring) layers are pressed together using rollers after the aqueous PVOH interlayer has been applied. The thickness of the PVOH interlayer is 0.5 to 10 pm, preferably 1 pm to 8 pm, and more preferably 2 to 5 pm.

[0020] The PVOH interlayer can also be produced by coextrusion with one or both of the other layers. The PVOH interlayer requires no additional adhesion promoters and adheres directly to the adjacent layers described herein.

[0021] A second aspect of the present invention also relates to multilayer composite materials comprising a PVOH interlayer as defined herein.

[0022] PVOH is considered harmless to health. No health risks are expected when ingested or absorbed through the skin. It is also resistant to oils, fats, and organic solvents. PVOH interlayers are therefore also suitable for composite materials used in the production of food packaging, particularly a coffee bag for a beverage preparation system.

[0023] Polyethylene (PE) coated paper has become a popular choice for food packaging and labels. PE coating makes paper grease- and water-resistant, making it ideal for packaging many food products. Packaging for liquid food products, in particular, is therefore often made of PE-coated paper. Recycling of previously available PE-coated paper or cardboard requires a process in which the paper fibers are separated from the polymer coating using water and chemicals. This process is expensive and offers limited recycling options compared to other paper products. In other processes, some of the fibers in the paper layer cannot be recovered, or residues of the polymer on the fibers cause optical impurities to lower the recyclability rating.

[0024] It has been shown that the PVOH interlayers adhere well to both the paper and PE layers and can bond them together. At the same time, however, a simple waxing step in the recycling process—especially after shredding the packaging—can cause the two layers to separate.

[0025] There are a multitude of other paper products that must be provided with a liquid-tight or gas-tight coating. One aspect of the present invention therefore also relates to multilayer composite materials that have a paper layer or paper base layer with a liquid-tight or gas-tight coating, wherein a PVOH intermediate layer is present between the paper layer and the liquid-tight or gas-tight coating. In general, this aspect of the present invention therefore also relates to multilayer composite materials that have a paper layer or paper base layer with a polymeric coating that imparts a further property to the paper, wherein a PVOH intermediate layer is present between the paper layer and the polymeric coating. A water vapor barrier for paper packaging can also be achieved using lacquers made from ethyl acrylates.

[0026] One embodiment of the invention therefore relates to the use of the PVOH intermediate layer between a paper layer and a further layer which can consist of one or more polymers. The polymers of the further layer can be PE or copolymers of acrylic acid esters with ethylene (ethylene acrylic acid copolymer; EAA), in particular copolymers of ethyl acrylates with ethylene (EEA). Barrier lacquers based on EAA in particular have a very good water vapor barrier, but also the disadvantage that they cause considerable interference in paper recycling. It is therefore advantageous if the EAA lacquer can be completely separated from the paper in a very early washing step so that no residues remain in the waste paper. This can be achieved by applying a PVOH intermediate layer between the paper and the EAA lacquer.

[0027] In general, the second aspect of the invention relates to a multilayer composite material with a PVOH intermediate layer containing at least 98 wt.% polyvinyl alcohol and soluble in water at a maximum temperature of 40°C. The multilayer composite material can comprise a paper layer, a PVOH intermediate layer, and at least one further layer made of a polymer. If more than one further layer is present, it is preferred if these additional layers are also separated by a PVOH intermediate layer. The multilayer composite material can comprise a paper layer, a PVOH intermediate layer, and exactly one further layer made of a polymer. The further layer can comprise or consist of the following polymers: PE, polypropylene (PP), EEA, or polyester. It preferably consists of at least 98 wt.% of the pure polymer, such as PE, PP, EEA, or polyester.

[0028] The PVOH intermediate layer can in principle be applied using various known processes, e.g., as a varnish, printing varnish, or lamination. It can also be applied using all common coating methods. It is preferred if the intermediate layer is applied to the paper layer as an aqueous solution. This solution can be highly viscous. The PVOH intermediate layer can be 0.5 to 10 μm thick, preferably 1 to 5 μm thick, and more preferably 1.5 to 2.5 μm thick. The intermediate layer can possibly replace an adhesive that would otherwise be necessary for the second layer and can itself serve as an adhesive for the further layer on the paper.

[0029] The additional polymeric layer, e.g., made of PE, can have a thickness of 1 to 100 μm, preferably 5 to 50 μm, more preferably 10 to 35 μm. The composite materials with paper described herein are proven to be recyclable; the cellulose fibers can be fully recovered. By completely dissolving or detaching the PVOH intermediate layer, the polymer of the additional layer, such as PE or EAA, can also be recovered with a very high purity of at least 95 wt.%, or even at least 98 wt.%, preferably at least 99 wt.%.

[0030] Papers coated with PE or EAA offer a certain degree of protection against moisture, water, and grease. However, they lack sufficient barrier properties against oxygen and other gases. This makes them unsuitable for packaging applications that require high oxygen barrier properties. In addition to the paper, the PVOH interlayer, and the first additional (polymeric) layer, an additional oxygen barrier layer may be present. The PVOH interlayer is positioned between the paper and the first additional layer. The oxygen barrier can be integrated into this additional layer (a mixture of different polymers or as an additive) but can also form an additional, outer layer. PVOH may be present in the additional oxygen barrier layer.

[0031] If packaged products require low oxygen permeability, alternative packaging materials that offer strong oxygen barrier properties can be used. Such alternative packaging consists, for example, of composite materials made of different polyolefins, such as a PE and a PP layer.

[0032] Currently, these are usually not separated in the recycling process, but rather recovered as mixed recyclate, which is considered inferior because it can only be used to a limited extent for the manufacture of new products.

[0033] A further aspect (third aspect) of the application therefore relates to a multilayer composite material comprising a polyolefin layer consisting of a first polyolefin and at least one further polyolefin layer consisting of a second polyolefin, between which a PVOH layer is applied.

[0034] The first polyolefin can be PE and the second polyolefin can be PP. One embodiment of the application therefore relates to a multilayer composite material consisting of a first layer consisting of PE and a second layer consisting of PP, between which a PVOH intermediate layer is applied. Other possible polyolefins can also be polymethylpentene (PMP), polyisobutylene (PIB), and polybutylene (PB, polybutene-1). The PVOH intermediate layer is always located (directly) between layers of different polyolefins. The polyolefin layers can contain a small amount (no more than 5 wt.%, preferably no more than 2 wt.%, and more preferably no more than 1 wt.%) of additives that do not influence, or at least do not interfere with, their recyclability and reusability.

[0035] The density of PE is between 0.92 and 0.97 g / cm3, and that of PP is between 0.9 and 0.91 g / cm3. These values ​​are quite close to each other. To facilitate the separation of the first and second polyolefins, one of the two layers or both polyolefin layers can contain an additive that changes the density of the layer or the material of which the layer is made. It is preferred if the multilayer composite material of this third aspect does not contain any paper or cellulose layers.

[0036] In addition to the PVOH interlayer and the two layers separated by this interlayer, further layers can be added to all multilayer composite materials described herein. These can be made of the same materials or other components. In general, additional PVOH interlayers can contribute to the separability of other components from further layers of the composite materials according to the invention. The statements made herein regarding the use of the PVOH interlayer also apply in principle to the multilayer composite materials described herein, and vice versa.

Claims

PATENT CLAIMS 1. The use of an intermediate layer for producing a multilayer composite material, wherein the intermediate layer contains at least 98 wt.% polyvinyl alcohol and wherein the polyvinyl alcohol has a degree of hydrolysis of 80-98 mol.%.

2. The use according to claim 2, wherein the intermediate layer is soluble in water at a maximum temperature of 40°C and atmospheric pressure.

3. The use according to claim 2, wherein the intermediate layer is located between a paper layer and another layer.

4. The use according to claim 3, wherein the further layer consists of a polymer or polymer mixture.

5. The use according to claim 2, wherein the intermediate layer is located between a first polyolefin layer comprising PE and a second polyolefin layer comprising PP.

6. The use according to any one of the preceding claims, wherein the intermediate layer has been applied as an aqueous solution to another layer.

7. The use according to any one of the preceding claims, wherein the intermediate layer is 1 to 5 pm thick.

8. Multilayer composite material with a PVOH intermediate layer, wherein the intermediate layer contains at least 98 wt.% polyvinyl alcohol and wherein the polyvinyl alcohol has a degree of hydrolysis of 80-98 mol-%.

9. Multilayer composite material according to claim 8, wherein the intermediate layer is soluble in water at a temperature of not more than 40°C and atmospheric pressure.

10. Multilayer composite material according to claim 9 or 10, consisting of a paper layer, the PVOH intermediate layer and at least one further layer of a polymer or polymer mixture.

11. Multilayer composite material according to claim 10, wherein the further layer consists of PE or a copolymer of ethylene and ethyl acrylate.

12. Multilayer composite material according to claim 9 or 10, comprising a polyolefin layer made of a first polyolefin, the PVOH intermediate layer and at least one further polyolefin layer made of a second polyolefin.

13. Multilayer composite material according to claim 12, wherein the first polyolefin is a PE.

14. Multilayer composite material according to claim 13, wherein the second polyolefin is a PP.

15. A multilayer composite material according to claim 12, wherein the first or second polyolefin comprises an additive that modifies the density of the layer.