EP3350251A1 - Method for producing a lignocellulose plastic composite material - Google Patents

Abstract

The invention relates to a method for producing a lignocellulose plastic composite material. The problem addressed by the invention is that of providing an improved, with respect to the prior art, in particular simpler and more cost-effective option for producing lignocellulose plastic composite materials. In order to solve the problem, the invention provides a method for producing a lignocellulose plastic composite material, wherein a. thermoplastic particles and a mixture of water and lignocellulose-containing particles and thermoplastic particles are supplied to a refiner, and b. the lignocellulose-containing particles are reduced to fibres in the refiner, and wherein the thermoplastic particles are supplied to the refiner in a melted or fused state, or are melted or fused in the refiner, so that the melted or fused thermoplastic particles and the lignocellulose-containing particles that are reduced to fibres form material composite particles in the refiner.

Description

 METHOD FOR PRODUCING A LIGNOCELLULOSE PLASTIC COMPOSITE MATERIAL

The invention relates to a method for producing a lignocellulosic plastic composite material and a lignocellulose plastic composite material produced or producible thereby.

Lignocellulose-containing raw materials, such as e.g. Wood, bamboo or various natural fibers are increasingly being used as reinforcing or filling components in composite materials. This happens both due to a scarcity of raw materials as well as for reasons of

Sustainability. In addition, special material properties such as increased rigidity and heat resistance are achieved. So-called "wood-plastic-composites" (WPC) or natural-fiber-reinforced composites (NFK) are mainly used in the construction industry (eg terraced construction) or the automotive industry (eg interior door cladding) .WPC and NFK already had a market share of 15% in 2012 ( 352000 t) of the composite materials produced in Europe, however, there will be another sharp increase in the

Production volume expected. In certain applications, such as

In some cases, the construction sector or the automotive industry is even expected to double production (Carus and Eder 2014, Wood-Plastic Composites (WPC) and Natural Fiber Composites (NFC): European and Global Markets 2012 and Future Trends). The reason for these forecasts is an increasing demand for materials based on renewable energy

Raw materials are produced.

For the production of lignocellulosic plastic composite or composite materials, abbreviated to LKC, (compounds), it is known that preferably extruders, in particular co-rotating twin-screw extruder, but also internal mixers or slotted kneaders are used. For this purpose, the individual components (lignocellulose, plastic and optionally additives) have to be dried in several process steps prior to extrusion and worked up in a dosing manner. After a mostly energy-intensive treatment (milling), the materials are fed by appropriate devices the screw channel of the extruder, melted in the screw channel and mixed and discharged at the end of the process through a nozzle, cooled and crushed into granules. In the production of LKC with an extruder or internal mixer, were in

various publications Refiner fibers (PvMP = thermomechanical pulp, CTMP = chemothermo mechanical pulp) are used as reinforcing element in a thermoplastic matrix (Lerche, Henrik, Benthien, Jan T, Schwarz, Katrin U, Ohlmeyer, Martin , 2013, Effects of Defibration Conditions on Mechanical and Physical Properties of Wood Fiber / High-Density Polyethylene Composites. In: Journal of Wood

Chemistry and Technology 34 (2), 98-110; Peltola, H .; Laatikainen, E .; Jetsu, P., 2011, Effects of physical treatment of wood fibers on fiber morphology and biocomposite properties. In: Plastics, Rubber and Composites 40 (2), 86-92).

The results of the published studies show that the use of Refiner fibers significantly improves the strength of the composite material. The reason for this is besides a good length-to-diameter ratio (L / D ratio) of the fibers a large fiber surface. An increased fiber surface increases the contact area with a molten polymer and thus improves the strength properties of the polymer

Composite material. So far, however, such compounds with refractory fibers could only be produced in small amounts by combining several process steps. A direct compounding of fibers was previously not possible. The reasons are the following:

Bulk weight: Reflow fibers and fibers in general have a very low

Bulk density. The reason for this is that the fibers keep each other at a distance and so much air is contained in between. The air causes problems in subsequent processes as it must be removed from the material during processing. This means that processes are slower (less throughput) and larger technical

 Require effort, e.g. more and larger vents. One approach to solving this problem is the pelleting of the fibers. The fibers are pressed through a die and compacted so that a free-flowing material is formed. The production of pellets is associated not only with additional costs and a further process step but also with a fiber shortening which takes place by pressing through the die. Such

Fiber shortening has a negative effect on the strength properties of the composite

(Bengtsson, Magnus, Le Baillif, Marie, Oksman, Kristiina, 2007, Extrusion and mechanical Properties of highly filled cellulose fiber-polypropylene composites. In: Composites Part A: Applied Science and Manufacturing 38 (8), 1922-1931). In addition, arise

Agglomerates that can no longer be adequately dispersed (mixed) with the polymer. An industrial production in which pelletized fibers are used is not known.

- Moisture: In general, lignocellulose-containing material must be dried technically prior to thermoplastic processing, because excessively high humidities on the one hand lead to processes that are difficult to control (sudden loss of water vapor) and, on the other hand, the water that is contained must be evaporated with great energy expenditure. Due to their hygroscopic properties, the lignocelluloses absorb moisture from the environment, so that even after drying, moisture is returned to the composite. This means that even after drying water is absorbed by the material, which must be re-evaporated during the processing process. - Dosing capability: Due to the low bulk density, the fibers keep each other at a distance and interlock with each other whereby a dosage is prevented in a continuous processing process. Material drying reduces the flexibility of the refractory fibers, i. they become stiffer and tend to snag each other. If this happens, the material intake increases

Bridging that prevents independent forwarding.

Agglomeration: Due to the drying process, finely divided, e.g. milled or fibrous lignocellulose agglomerates. These agglomerates have such a high internal strength that they are not restored by the following

Compounding processes can be resolved. As a result, agglomerates are formed in the compound and in the final product, negatively affecting the appearance and also the technical properties of the compound.

Object of the present invention is to provide an improved over the prior art, in particular easier and more cost-effective way to produce lignocellulose plastic composite materials. To achieve the object, the present invention provides a method for producing a lignocellulosic plastic composite, wherein

a. Thermoplastic particles and a mixture of water and lignocellulose-containing particles are fed to a refiner, and

b. the lignocellulosic particles in the refiner become fiberized,

and wherein the thermoplastic particles are supplied to the refiner up or melted up or melted up in the refmer, so that the up or melted

Thermoplastic particles and the fibrillated lignocellulosic particles in the refmer

Form composite material particles.

In the method according to the invention are lignocellulose-containing raw materials in the form of, for example, fibers, chips, chips or flour and flowable thermoplastic

Plastics fed to a refiner. In the refmer, the thermoplastic particles in the melted or fused state with fibrillated lignocellulosic particles to a

Composite mixed. Thermoplastics and lignocellulose-containing material are mixed in one process in such a way that a composite product (compound) is produced for preferably direct further processing in subsequent thermoplastic processes. The present invention thus makes possible for the first time a wet compounding of thermoplastics and lignocellulose-containing material.

With the method according to the invention, a multiple drying can be avoided and a compounding of thermoplastic and lignocellulose without additional fiber destruction can be achieved. The compound thus prepared can be mixed with conventional

Shaping process such as e.g. thermoplastic technology (extrusion, injection molding, compression molding). In addition, larger throughputs (production quantities) can be realized with the method according to the invention than with a traditional compounding process.

A "composite material", also referred to as "composite material" or "compound", is understood as meaning a material made of two or more materials connected by means of a fabric or form fit or a combination thereof, whereby the composite material has other, usually better, material properties than its individual components. Under a "lignocellulosic Plastic composite 'is here a composite of one or more

Plastics, in particular a thermoplastic, and a lignocellulose-containing material understood. The term "lignocellulose-containing material", if appropriate synonymous as

"Lignocellulosic material" herein is preferably understood to mean a material composed of cellulose, hemicellulose and lignin in different proportions, but the term includes not only a material consisting predominantly or wholly of lignocellulose, but rather also lignin-free hemicellulose / Cellulose fibers if the lignin has been wholly or partly depleted by appropriate chemical pulping (CTMP, pulp or semi-pulp) The term also includes materials which, in addition to lignocellulose, hemicellulose and / or cellulose, also contain other constituents.

The term "lignocellulose-containing particles" refers to particles of lignocellulose-containing material Examples of lignocellulose-containing particles are wood shavings, woodchips, wood fibers and wood flour.

By a "mixture of water and lignocellulosic particles" is meant a mixture of lignocellulosic particles and added water, in particular a mixture of lignocellulosic particles, for example wood particles, and water, the

Water content above the fiber saturation of the lignocellulosic particles, e.g. the wood particles, lies. The term also includes mixtures which contain other constituents in addition to water and lignocellulose-containing particles. In particular, however, the term refers to mixtures containing only water and lignocellulosic particles. Under an "aqueous suspension of lignocellulose-containing particles and thermoplastic particles" is a suspension of lignocellulose-containing particles suspended in water and

Understood thermoplastic particles. The suspension may also contain, for example, additives, for example lubricants, adhesion promoters or the like. A "refiner" is understood to mean a grinding or comminution device which is usually used in the pulp and / or wood-based material industry and which serves for grinding or defibrating lignocellulosic material for the production of fibrous materials. The lignocellulose is added to the refiner usually in the form of wood chips, sawdust or fiber. As a rule, refiner have a static grinding element (stator) and a rotating grinding element (rotor). A "disk refiner" is understood as meaning a refiner with opposing grinding disks, between which a grinding gap is formed, in which the grinding stock is ground, whereby usually a grinding disk (rotor) rotates in relation to a second fixed grinding disk (stator) Refiner with more than two grinding discs, eg double disc refiner with double grinding set and two

Grinding gaps. The grinding discs are regularly crushed, e.g.

different distributed over the radius segments (bars) provided. The material to be ground is conveyed, for example, by a plug screw into the center of the grinding discs, and then finally to be conveyed by the rotor and the resulting centrifugal forces to the outside of the housing. Depending on the grinding disc distance and the

Grinding wheel sets result in compression and friction forces that cause the material to be ground (Gharehkhani, Samira, Sadeghinezhad, Emad, Kazi, Salim Newaz;

Yarmand, Hooman; Badaryudin, Ahmad; Safaei, Mohammad Reza; Zubir, Mohd Nashrul Mohd, 2015, Basic effects of pulp refining on fiber properties - a review, In: Carbohydr Polym 115, 785-803) and have a material effect on the material properties. Of the

Material discharge takes place through radially or tangentially arranged openings on the refiner housing. In the industrial process, the material is often continuously fed to and removed from the refiner.

By "thermoplastic" is meant a thermoplastic polymer or a mixture of thermoplastic polymers Thermoplastics are plastics that can be reversibly deformed in a specific temperature range (thermo-plastic) Examples of thermoplastics are polyethylene (PE), polypropylene (PP ), Acrylonitrile-butadiene-styrene (ABS), polyamide (PA), polylactate (PLA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polystyrene (PS), polyetheretherketone (PEEK), thermoplastic starch (TPS ) or polyvinyl chloride (PVC). The term "melted on" with respect to thermoplastic particles means that it at least partially heats at its surface above its glass transition temperature were so that the particles are at least viscous in at least a portion of its surface.

The quantitative ratio between thermoplastic and lignocellulosic material is variable. The lignocellulose content preferably ranges between 10 and 90% by weight, more preferably between 20 and 80% by weight, particularly preferably between 30 and 70% by weight, based on the weight of the compound.

The thermoplastic particles can either be melted up or melted in the refiner, for example, by shearing forces arising therefrom and / or heating of the rhombus, or fed to the refiner already in the up or melted state. In a preferred embodiment of the method according to the invention, the

Thermoplastic particles at least predominantly up in the refiner or melted. The refiner can for this purpose have corresponding heaters or be heated by appropriate heaters. For example, an electrical heating of a Mahlgarnitur, for example, one or both grinding discs in the case of a Scheibenrefmers be made. Alternatively or additionally, the refiner can be heated by superheated steam. The thermoplastic particles, which may have already been melted or fused on, and the mixture of water and lignocellulose-containing particles may be fed to the refiner separately or together. For example, those, possibly already up or

melted thermoplastic particles are added separately before refining a mixture of water and lignocellulose-containing particles and fed to the refiner together with the mixture of the water and the lignocellulose-containing particles. The, optionally already auf- or molten thermoplastic particles and the

Mixture of water and lignocellulosic particles can also be fed to the refiner separately and brought together in the refiner. However, it is preferred to co-feed the thermoplastic particles and the mixture of water and lignocellulose-containing particles to the refiner. If appropriate, the thermoplastic particles may be melted or melted by suitable means before being added to the mixture of water and lignocellulose-containing particles, preferably just before the refiner. In one embodiment of the process according to the invention, an aqueous suspension of lignocellulose-containing particles and thermoplastic particles is fed to the refiner, the thermoplastic particles in the refiner are melted up or fibrillated and the lignocellulose-containing particles are fiberized so that the molten thermoplastic particles and the fibrillated lignocellulose-containing particles in the composite particle refiner particles form.

Preferably, the temperature in the refiner is at or above the glass transition temperature of the thermoplastic particles. Unless a mixture of different thermoplastics with

different glass transition temperatures is used in the thermoplastic particles, it is preferred that the temperature in the refiner is at or above the glass transition temperature of the thermoplastic having the highest glass transition temperature. This is particularly preferred in embodiments of the method according to the invention, in which the

Thermoplastic particles are first melted or melted in the refiner. But this is also advantageous in embodiments in which the thermoplastic particles are supplied to the refiner already up or melted, for example, a cooling of the

To prevent thermoplastic particles below the glass transition temperature in the refiner.

In a preferred embodiment of the method according to the invention, the heat energy required for melting or melting the thermoplastic particles is at least partially generated by shearing energy in the refiner. In the preferred case of using a

Scheibenrefmers example, such a shear energy can be generated on the choice of Mahlscheibenabstands, the Mahlscheibengarnitur, the rotational speed of the grinding disc (s) and the supply (type, pressure and speed of the material to be crushed) that the thermoplastic material is on or melted and when passing radially along the grinding set of the stator and rotor with the fibrillated lignocellulose-containing material connects. The required heat energy can optionally be applied exclusively by the resulting shear energy. However, as indicated above, the required thermal energy may also be provided in addition or exclusively by heating the grinding set of the rhombus, e.g. by electrical

Heating or superheated steam. In a particularly preferred embodiment of the method according to the invention, the refiner is a disk refiner with grinding disks, the supply of the thermoplastic particles and the mixture of water and lignocellulose-containing particles takes place centrally via a grinding disk and the material composite particles are discharged radially or tangentially with respect to the grinding disks. In this way, plastic and lignocellulosic material are placed centrally in the grinding gap between the grinding discs, the coumpounding (crushing, mixing and possibly melting) is continued radially or tangentially from the inside out to the edge of the grinding discs, and the resulting composite material is on delivered to the outer edges of the grinding discs, where it can be collected and optionally further treated, for example, can be separated from the suspension liquid.

Preferably, the resulting composite material particles are at least largely separated from excess liquid. Preferably, the lignocellulose-containing particles are wood chips,

 Wood chippings, wood fibers or wood flour, or lignin-free cellulose fibers (CTMP) or pulps. The method is not limited to certain types of wood and wood species. The thermoplastics may be, for example, polyethylene (PE), polypropylene (PP), acrylonitrile-butadiene-styrene (ABS), polyamide (PA), polylactate (PLA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET ), Polystyrene (PS),

Polyetheretherketone (PEEK), thermoplastic starch (TPS) or polyvinyl chloride (PVC), or a mixture thereof. Additives such as lubricants, adhesion promoters, etc. can be added to the thermoplastics.

The invention also relates to a lignocellulosic Kunststo ff composite material, which is produced by a method according to the invention or can be produced. The invention is described below purely by way of illustration with reference to FIG

attached figures and embodiments explained in more detail. Figure 1. Schematic representation of a preferred embodiment of an apparatus for performing the method according to the invention.

Figure 2. Schematic representation of another preferred embodiment of a

Apparatus for carrying out the method according to the invention.

1 schematically shows the construction of a test refmer used in embodiment 1 (see below). The refiner 1 is a disc refiner with two grinding discs 2, 3, which form a grinding gap 5, in a housing 4. The first grinding disc (stator grinding disc) 2 is fixed, the second grinding disc (rotor grinding disc) 3 rotates about the axis 10, as indicated by the arrow. In the hollow axis 11 of the stator grinding disc 2, a screw conveyor 6 is arranged through which material to be ground can be introduced centrally into the grinding gap 5. The material to be ground can be fed via a hopper 7 on the screw conveyor 6. The housing 4 has on its upper side via a line 8, can be passed through the superheated steam into the interior of the housing 4. At the bottom of the housing 4, an outlet 9 is provided, can be removed from the housing 4 via the finished product.

Figure 2 shows schematically the structure of a rhombus, as it was used in Embodiment 2. The refiner 1 differs essentially in that instead of a funnel 7, a boiler 12 was used.

Exemplary Embodiment 1. For the experiments described below, a low-density polyethylene (LDPE) and spruce sawdust were used for the wet compounding according to the invention. In this case, a mixing ratio of 60% spruce chips and 40% LDPE (mass fractions) was used. Before defibering in the refiner, the sawdust was pre-cooked in a so-called paddle reactor at 170 ° C for 6 minutes. In the process, about 10 L of water was added to the 5 kg chips. By such a hydrothermal pretreatment, the middle lamella of the wood fibers is softened, whereby the modulus of elasticity decreases and the defibration in the refiner is facilitated. In the industrial manufacturing process, such as in MDF production, is the precooking of the wood chips and the subsequent defibration carried out in a continuous process. These are from the cooker to the refiner a closed pressure system at temperatures of 170 ° C to 200 ° C at 6 to 12 bar. By contrast, the experimental refiner used here was an open system in which temperatures around 100 ° C can be achieved. Immediately after the precooking of the chips, the weighed polymer was mixed by hand in granular form the softened chips and fed to the refiner without further treatment (screening, squeezing or the like). For reflow or melting of the polymer in the refiner 1, the refiner 1 was charged with steam (T approximately 100 ° C.) via the line 8 and preheated (see FIG. Due to the open system, the pre-heating of the Reimers 1 by steam only up to a temperature of about 100 ° C was possible. Further energy input, which causes the polymer to melt or melt, was introduced into the system by shearing energy generated by defibration of the shavings and polymer granules. During defibering, the refiner 1 was continuously steamed.

For defibering and wet compounding, the grinding disc spacing and thus the thickness of the grinding gap 5 was set to 0.1 mm. After switching on the rhombus 1 and the auger unit, the material was fed through the hopper 7 to the grinding unit, shredded and discharged by centrifugal forces at the lower end of the housing 4 Refmergehäuses 4 via the outlet. The residence time of the material in the Refmer 1 was from the

Enter material into the funnel up to the material outlet 9 by 10 seconds. The experimental parameters for the experiment described above are listed in Table 1.

Table 1 Experimental example for embodiment 1

Attempt paramters

Material spruce chips u. LDPE

 Mixing ratio (mass fraction) 60% spruce shavings

40% LDPE Refiner Sprout- Waldron 12 ", 3000 min-1

 Grinding disc distance 0.1 mm

 Grinding disc designation: Andritz R243

Throughput approx. 8 kg

 Hydrothermal pretreatment paddle reactor autumn engineering,

 Type: 1203027

 T = 170 ° C

 T = 6 min.

 Preheating Refiner using steam steam generator: Type CD9ST Dino, Bremen

 4 bar (max 8 bar)

 Steam outlet: approx. 100 ° C

The produced wet compound was heavily fiberized compared to the starting material. The polymer was heavily comminuted compared to the starting material and not visible to the naked eye. Signs of molten polymer were visually recognizable. Subsequent separation of wood and thermoplastic (e.g., by slurrying) was no longer possible.

Embodiment 2.

For the experimental procedure described below, polypropylene (PP) and high-density polyethylene together with spruce / fir wood chips were used according to the invention

compounded. The input material moisture of the chips was 13%. The individual test parameters as well as the material compositions and specification are listed in Table 2. For the test, a pressure refiner 1 of the type: Sprout-Waldron 12 "with an upstream cooker 12 (volume 55 1) was used (see Figure 2)., Through a pressure refiner 1, as used in the experimental procedure described is It is possible to model industry-related conditions over a longer compared to Embodiment 1 period.

The material was previously mixed by hand with the addition of water and then added to the digester 12. Prior to defibering, the materials were added for up to 10 minutes Heated to 125 ° C and 145 ° C. The disc distance of the rhombus was set to 0.1 mm. After heating, the material mixture was transported by steam pressure (manually controllable), starting from the digester, as well as a screw conveyor between the refracting discs, there frayed and discharged by centrifugal force tangentially through a valve opening (10 mm).

Immediately behind the passage valve, there is a sudden evaporation of the water in the material, which leads to a drying of the material. The

Material moisture immediately after material outlet was 35-40%. The material is

apparently, in comparison to the starting material (chips, granules), heavily shredded. The fiber geometry is comparable to that of MDF fibers. The thermoplastic is apparently shredded and inseparably bonded to the wood fiber.

Table 2 Experimental Example for Embodiment 1. Fi = Spruce, Ta = Fir, Specific. = Specification, PP = polypropylene, HDPE = high density polyethylene. "Fraction" indicates the particle size ranges.

Trial material specific. Ratio heating up no dry t u T

 (kg) (%) (min.u ° C)

Fi / Ta wood chips Fraction: 7.70 70 10 min Type: Rettenmaier FS 14 2.5-4.0 mm at 125 ° C

HDPE Density: 0.954 g / cm ³ 3.3 3.3 30 Sabic TC 3054 Melting temperature: 132 ° C

 MFI: 30 g / 10 min.

Fi / Ta wood chips fraction: 5.5 50 10 min. Type: Rettenmaier FS 14 2.5-4.0 mm at 125 ° C

HDPE Density: 0.954 g / cm ³ 50 Sabic TC 3054 Melt Temp .: 132 ° C

 MFI: 30 g / 10 min.

Fi / Ta wood chips fraction: 70 10 min. Type: Rettenmaier FS 14 2.5-4.0 mm at 145 ° C PP density: 0.905 g / cm ³

Sabic, PP 575p Melted: 160 ° C

 MFI: 10.5 g / 10 min.

Fi / Ta wood chips fraction: Type: Rettenmaier FS 14 2,5-4,0 mm

PP density: 0.905 g / cm ³

Sabic, PP 575p Melting temperature: 160 ° C

 MFI: 10.5 g / 10 min.

Claims

1. A process for producing a lignocellulosic plastic composite, wherein a. Thermoplastic particles and a mixture of water and lignocellulose-containing particles are fed to a refiner, and  b. the lignocellulose-containing particles are defibered in the refiner,  and wherein the thermoplastic particles are fed to the refiner or melted up or melted in the refiner, so that the molten thermoplastic particles and the fibrillated lignocellulose-containing particles form composite particles in the refiner. 2. The method of claim 1, wherein the thermoplastic particles and the mixture of water and lignocellulose-containing particles to the refiner separately or together, preferably together, fed. 3. The method of claim 2, wherein the thermoplastic particles in the refiner up or  be melted. 4. The method of claim 3, wherein an aqueous suspension of lignocellulosic particles and thermoplastic particles is supplied to the refiner, and in the refiner, the thermoplastic particles or melted on and the lignocellulosic particles are fiberized, so that the up or melted thermoplastic particles and the fibrillated lignocellulose-containing particles form composite particles in the refiner. 5. The method according to any one of the preceding claims, wherein the temperature in the refiner is at or above the glass transition temperature of the thermoplastic particles. 6. The method according to any one of the preceding claims, wherein the up or Melting of the thermoplastic particles required thermal energy is generated at least partially by shear energy in the refiner. 7. The method according to any one of the preceding claims, wherein the refiner is a disc refiner with grinding discs. 8. The method of claim 7, wherein the supply of the thermoplastic particles and the mixture of water and lignocellulose-containing particles centrally via a grinding disk and the discharge of the composite material particles takes place radially or tangentially with respect to the grinding disks. 9. The method according to any one of the preceding claims, wherein it is in the  lignocellulose-containing particles around wood particles, preferably wood chips,  Wood chippings, wood fibers or wood flour, or lignin-free cellulose fibers (CTMP) or pulps. 10. The method according to any one of the preceding claims, wherein it is in the  Thermoplastic particles around particles of polyethylene (PE), polypropylene (PP), acrylonitrile-butadiene-styrene (ABS), polyamide (PA), polylactate (PLA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polystyrene ( PS)  Polyetheretherketone (PEEK), thermoplastic starch (TPS) or polyvinylchloride (PVC) or a mixture thereof. 11. Lignocellulose plastic composite material, manufactured or producible by a  Method according to one of claims 1 to 10.