EP3242910A1

EP3242910A1 - Biological composite material

Info

Publication number: EP3242910A1
Application number: EP16701421.6A
Authority: EP
Inventors: Hans-Peter Meyerhoff
Original assignee: Individual
Current assignee: Individual
Priority date: 2015-01-11
Filing date: 2016-01-11
Publication date: 2017-11-15
Also published as: WO2016110600A1; US20180094123A1

Abstract

The invention relates to a plastics compound with a biological content. In said compound, at least (a) at least one bio-mineral filler and (b) at least one polymer are processed to form a compound. A renewable bio-mineral filler with a high content of silicon dioxide is used in this process.

Description

Biological composite material

description

Field of the invention

The invention relates to plastics with biological Füllstof ^¬ fen.

Biomaterials are plastics which are fully ^¬ or based on relevant proportions on renewable raw materials. In view of rising oil costs, the use of biomaterials is interesting not only for sustainability reasons but also for economic reasons.

More recently, there are many examples of biomaterials, mostly oil-based plastics with a certain proportion of biologically produced fillers and / or fibers.

A relatively new area is the replacement of plastics by plastics from renewable raw materials or waste products, such. As polypropylene or polyethylene from sugar cane, fats or oils. Very often, biological fillers based on wood are used.

A common problem of such biomaterials is the often inadequate thermostability.

In addition, the introduction of a mostly hydrophilic material in a hydrophobic environment, such as plastics, causes the biomaterials tend to absorb water. This is usually accompanied by a change in volume, eg. B. by 1 to 6%. This makes these materials unsuitable for outdoor applications or humid environments.

The hydrophobic environment is also problematic in biological fillers with high inorganic content, especially if a highly filled plastic is to be produced.

Also, the UV resistance of such materials is a problem.

There is therefore a need for biomaterials, which overcome the disadvantages of the known bio-materials and in particular have a low uptake of water and swelling, and to the extent mög ^¬ Lich a high impact resistance and good chemical resistance.

Also, previous fillers are often obtained from non-renewable ^¬ sources or come from fossil sources such as talc and chalk called as an example.

task The object of the invention is to provide a plastic composition with a biological filler, which avoids the disadvantages of the prior art. The plastics produced can also be highly filled plastics.

solution

This object is achieved by the inventions having the features of the independent claims. Advantageous developments of the inventions are characterized in the subclaims. Of the

The wording of all claims is hereby incorporated by reference into the content of this description. The inventions also include all meaningful and in particular all-mentioned combination Nati ^¬ ones of independent and / or dependent claims.

The object is achieved by a plastic compound with a biological component, wherein the plastic compound at least (a) min ^¬ least a biomineral filler, and (b) at least one polymer.

The biological filler can come from many different sources worldwide. Biomineralische fillers are bi ^¬ ologische fillers with a high proportion of inorganic Be ^¬ constituents, in particular from renewable raw materials. Particularly preferred are organic fillers having a Aschegeh ^¬ ago from about 5 percent by weight, preferably of more than 10 mass pro ^¬ percent (ash content 815 ° C according to DIN 51719). All information from Nor ^¬ men in the measurement of properties, eg. B. DIN 51719, refer to the latest version of the respective standard at the time of registration.

Particularly preferred are vegetable sources with a high proportion of silicon dioxide, more preferably with one share of at least 3 wt .-%, preferably at least 5 wt .-% (based on the biological filler measured by dispersive x-ray fluorescence analysis), preferably at least 10 wt .-%, particularly before Trains t ^¬ about 15 wt .-% or about 25 wt .-%. Preference is therefore given to sources with a content of 5 to 98 wt .-%, preferably 10 to 98 wt .-%, particularly preferably 15 to 98 wt .-% or 20 to 98 wt. -%.

A high proportion of silicon dioxide and a concomitant lower proportion of bioorganic materials ensure that the water absorption of the compositions according to the invention is low. Preference is given to a water absorption of <0.3% by mass, preferably ^ 0.2 (measured according to ISO 62). It may be necessary to dry the biomineral filler before use.

It is preferably a biological filler or biomineral filler which is obtained from an infinitely growing raw material.

The biological filler is preferably obtained from Reishül ^¬ sen, rice husks, sisal, hemp, cotton, pine, kenaf, bamboo, flax, pine wood and / or sugar cane.

The biomineral filler is preferably the ash obtained from rice hulls, rice husks, sisal, hemp, cotton, pine, kenaf, bamboo, flax, pine and / or sugar cane, more preferably ash from rice hulls and / or rice peas, most preferably the ash from rice hulls (RHA). Rice hull ash has the particular advantage that it is available as a waste product in rice production in large quantities. In addition, the structure of the rice causes the ashes to be very fine-grained. It can also be obtained in different quality levels.

A content of silicon dioxide in the filler of at least 20% by weight, preferably at least 40% by weight, particularly preferably at least 60% by weight, is preferred. Further preferably a proportion of 40 to 98 wt .-% (determined with X-ray fluorescence spectroscopy), preferably from 60 wt .-% to 98 wt .-%, special ^¬ DERS preferably from 80 wt .-% to 98 wt %. The proportion may also be in the range from 75% by weight to 98% by weight, preferably in the range from 85% by weight to 98% by weight.

Particularly preferred is a filler biomineralisches containing S1O ₂ of at least 80 wt .-%, preferably Minim ^¬ least 90 wt .-%. The content can be from 80% by weight to 99% by weight, preferably from 80% by weight to 98% by weight. Particularly preferred at 90 wt .-% to 99 wt .-%.

Depending in particular on the carbon content of the filling material can ^¬ a color of black, anthracite, light gray to dark gray or white ^¬ have.

Preferably, more than 50% by weight of the silica is amorphous silica, in particular more than 80% by weight, or more than 90% by weight. In a preferred embodiment of the invention, the proportion of carbon is in the biomineral filler at from 0 to 10 wt .-%, preferably 0 to 6 wt .-%, particularly before Trains t ^¬ at 0 to 3 wt .-%. Especially rice hull ash has a high proportion of amor ^¬ PHEM silica. Depending on the preparation, the proportion of crystalline SiO ₂ , in particular of cristobalite, can be minimized, in particular to below 20% by weight, preferably below 10% by weight, very particularly preferably below 5% by weight.

Many of the aforementioned components are by-produced or by-product. They are therefore often economically available in infinite quantities.

Also, by using the rice hulls, there is no competition with food production. At the same time the pro ^¬ domestic product in large quantities is available worldwide. The ash is mainly used as an additive for concretes or steel.

Also, the heat generated during the production can be used to generate energy.

The biological filling material still comprises up to 30% by weight. ~ 6 other ingredients, preferably up to 20 wt .-%. Preference is given to further oxides of Fe, Al, Zr, Na, K, Mg, Mn, Ca, each with an ^¬ share of 0 to 10 wt .-%, preferably 0 to 5 wt .-%, particularly preferably with proportions of 0 to 3% by weight. In one embodiment of the invention, the others include

Ingredients an oxide selected from the group of Fe, Al, Zr, Na, K, Mg, Mn, Ca in each case amounts of 0.1 to 10 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably with proportions of 0.1 to 3 wt .-%. Preferably, the oxide is selected from the group of Fe and Al. This does not rule out that other oxides occur in similar or lower proportions, the data always being 100% complementary with the content of the other constituents. In one embodiment of the invention, the biological filling material comprises at least the following components:

It is clearly a biomineral filler. In addition, further constituents, such as 0 to 10% by weight of carbon, preferably 0 to 5% by weight, particularly preferably 0 to 1% by weight, may always also be present. Furthermore, impurities and small amounts of moisture may still be present.

In a further embodiment of the invention, the biological filling material comprises at least the following constituents:

Weight%

Si0 ₂ 80-99

Fe ₂ 0 ₃ 0.1-1.5

CaO 0.1-1

MgO 0.1-2

K ₂ 0 0,1-5

Na ₂ 0 0,1-5

Zr0 ₂ 0-5 In addition, further constituents, such as 0 to 10 wt.% Carbon, preferably 0 to 5 wt.%, Particularly preferably 0 to 1 wt.%, Very particularly preferably 0.1 to 1 wt. be included. Furthermore, impurities may still be present and in small quantities moisture.

The proportion of VOCs (volatile organic compounds) is preferably less than 1% by weight (105 ° C., 20 hours, weight 8 g). Preferably, the filler material to a temperature biomineralische ^¬ turstabilität of at least 1000 ° C.

Fillers with a high content of so S1O ₂ have not only a ge ^¬ rings water absorption capacity, they also allow for higher temperatures during processing. Therefore, such fillers can be incorporated into many thermoplastics. Thus, processing temperatures of over 150 ° C or over 450 ° C, especially well over 450 ° C, possible. This allows ^¬ example, the incorporation into polyamides such as polyamide-6, 6th

In a non-preferred embodiment, the biomineralische filler has a mean particle size of up to 500 ym on, preferably between 5 and 400 ym ym (measured with light scattering ^¬). This specification refers to the particle size in the finished composition.

In a preferred embodiment, at least 90% of the particles of the filler when added to the composition have a particle size of less than 400 ym (90% value measured with laser diffraction), particularly preferably additionally with a 50% value of less than 300 ym. In a further embodiment, the biological filler has a 95% value of less than 600 ym, preferably zusätz ^¬ Lich a 50% value of less than 300 ym. In a further embodiment, all particles measured in the filler by laser diffraction are smaller than 1.5 mm, preferably additionally with a 90% value of less than 400 μm and a 50% value of less than 300 μm. The biomineral filler preferably has a specific gravity of between 0.08 and 3.2 g / cm ³ , preferably between 1.5 and 2.5 g / cm ³ .

Preferably, the biological filling material has a density of up to 2.5 g / cm ³ , preferably up to 2.4 g / cm ³ , preferably up to 2.3 g / cm ³ . A density of at least 1.8 g / cm ³ is preferred. The density is therefore preferably in a range from 1.8 g / cm ³ to 2.5 g / cm ³ , in particular from 1.8 g / cm ³ to 2.3 g / cm ³ , very particularly from 1.8 to 2 , 2 g / cm ³ . Preferred is a density of 2.0 to 2.4 g / cm ³ . The density refers to the density of the material (specific gravity) not the bulk density.

The particles of the biological filler are preferably slightly porous. It preferably has a specific surface area of 15 to 30 m ² / g (BET measurement with nitrogen).

In particular, rice hull ash has a low specific gravity of up to 2.3 g / cm ³ , in particular from 1.8 to 2.2 g / cm ³ . The density can be influenced accordingly by the manufacturing process. Together with the high content of silicon dioxide, it is possible to produce similar highly filled composites, which in comparison to conventional fossil filling materials such as talc or chalk, mica, wollastonite, etc., have a lower density.

In one embodiment of the invention, the biological filling material is present as a powder. Preferred with a bulk density of 200 to 800 kg / m ³ .

It may be advantageous for the filler to have a certain size distribution. This can be done by sieving

and / or grinding operations can be achieved.

Depending on the application, it may be advantageous to use biomineral filler with a certain size distribution. Thus, for example, on the filler in an upstream step, all particles having a size of more than 100 μm, preferably more than 80 μm, in particular more than 60 μm, can be removed by a sieving step. This sieved biomineral filler is particularly well suited. Preferably, suspensions of the biological filler in water have a pH of 4-7 in another embodiment of 6-8 (each measured as 5 wt% at room temperature).

In a preferred embodiment, at least 50% of the particles of the filler are spherical in number, preferably at least 60%, in particular at least 80% (determined by microscopy). This means that these particles can be ^¬ be written near ^¬ approximated by a sphere or an ellipsoid of revolution, wherein the aspect ratio of the axes is not greater than 3: 1, more preferably not greater than 1.5: 1.

The proportion of the biomineral filler is preferably at least 15% by weight, based on the compound, particularly preferably Trains t is at least 20 wt .-% preferably, more preferably from 15 wt% to 90 wt .-%, in particular 15 wt .-% to 80 wt .-%, Sonders be ^¬ a proportion of 10 parts by weight % to 40% by weight. The biomineral filler also increases the content of renewable raw materials in the composite material. As a result, the most oil-based plastics can be saved.

Mixtures of several biological fillers can also be used. For example, ash-based fillers can be combined with other biological fillers. Preference is given to at least one biological filler, a filler based on ash. The at least one further filler is preferably selected from rice husks, rice husks, wood, Si sal, hemp, cotton, pine, kenaf, bamboo, flax, Pi ^¬ nienholz and / or sugar cane. For example, ash from rice hulls or rice husks can be combined with other biological fillers. The additional biological filler may also comprise fibers, for example wood fibers, sisal fibers, hemp fibers, jute fibers, cotton fibers.

In a preferred embodiment of the invention, the biological filler comprises at least 30 wt .-% organic filler ^¬ materials on the basis of the ash, preferably at least 50 wt .-%, more preferably at least 60 wt.%, Based on all used biological fillers.

The at least one polymer is preferably a thermoplastic or crosslinkable polymer, thermoset or a thermoplastic elastomer.

Under thermoplastic polymer or thermoplastic elastomer (b) are any thermoplastically deformable poly- understood that may be new or recyclate / regrind from old thermoplastic polymers. Preference is given to thermoplastics having a viscosity corresponding to a melt index (MFI, 230 ° C./2.16 kg) of polypropylene (PP) of at least 20 g / 10 min. Preference is given to those whose viscosity corresponds to an MFI of PP of from 20 to 300 g / 10 min, more preferably from 50 g / 10 min to 200 g / 10 min corresponds.

For example, polyolefins such as polyethylene, polypropylene, polybutylene, polyisobutylene and poly-4-methyl-1-pentene, polyolefin copolymers such as Luflexen® (Basel), Nordel® (Dow) and Engage® (DuPont) can be used. Cycloolefincopolyme ^¬ re as Topas® (Celanese), polytetrafluoroethylene (PTFE), ethylene len / tetrafluoroethylene copolymers (ETFE), Polyvinylidendifluo- chloride (PVDF), polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl lyvinylalkohole, polyvinyl esters such as polyvinyl acetate, Vinyl ester copolymers, such as ethylene / vinyl acetate copolymers (EVA), polyvinylalkanals, such as polyvinyl acetal and polyvinyl butyral, (PVB), polyvinyl ketals, polyamides, such as Polyamed-6, polyamide-12, polyamide-6, 6, PA 6.66 triple 6 , or mixtures of PA 66 recyclate with PA 6 or other proportions of PA, polyamide-6, 10, polyimides, polystyrenes, polycarbonate, polycarbonate copolymers and physical blends of polycarbonates with acrylic-butadiene-styrene copolymers, acrylonitrile -styrene acrylics terpolymers, polymethyl methacrylates, polybutyl acrylates, polybutyl methacrylates, polybutylene terephthalates and polyethylene terephthalates, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN), copolymers, transesterification products and physical blends of the above mentioned polyalkylene terephthalates, poly (meth) acrylates, polyacrylamides, polyacrylonitrile, poly (meth) acrylate / polyvinylidene difluoride blends, polyurethanes,

Polystyrene, styrene copolymers, such as styrene / butadiene copolymers, Styrene / acrylonitrile copolymers (SAN), acrylic ester-styrene-acrylonitrile (ASA), alpha-methyl-styrene-acrylonitrile copolymer (AMSAN), styrene-butadiene-styrene (SBS), styrene / ethyl methacrylate copolymers, styrene / butadiene / ethyl acrylate Copolymers, styrene / acrylonitrile / methacrylate copolymers, acrylonitrile / butadiene / styrene copolymers (ABS) and methacrylate / butadiene / styrene copolymers (MBS), polyethers such as polyphenylene oxide, polyether ketones, vinyl ester copolymers, Polysulfone ne, such as. Polyethylene terephthalate or polybutylene terephthalate, polyethersulfone, polyetherimide, polyphenylene oxide,

Polyphenylene sulfide, polyglycols such as polyoxymethylene (POM), polyaryls such as polyhenylene, polyarylenevinylenes, silicones, low-density polyethylene (LDPE), high density polyethylene (HDPE), ionomers, thermoplastic and thermosetting polyurethanes and mixtures thereof.

The polyamides can Triple 6.66 and PA 66 PA 6 with proportions, mixtures and ent ^¬ speaking copolymers are used, for example polyamide-6, polyamide-66.

The at least one thermoplastic may also be part of a blend, for example in blends of styrene polymers such as SAN with polymethacrylonitrile (PMI) or chlorinated polyethylene, or polyvinyl chloride with methyl acrylate-butadiene-styrene copolymer (MBS), ASA and / or ABS. It is important that the resulting mixture is still a thermoplastic.

Preferably at least one thermoplastic is a polyolefin, special ^¬ DERS preferably polypropylene (PP) or polyethylene (PE) and de- ren copolymers or copolymers such as EPDM

(Ethylene-propylene-diene) modified PP, ethylene-vinyl acetate copolymer (EVA), rubber mixtures or in the reactor PP- EPDM manufactured types, eg cascade principle each stage brings eg + 5% EPDM.

It can also be used a thermoset. These are forthcoming Trains t polymers comprising the aforementioned polymers, wel ^¬ che are additionally crosslinked with each other. This can be done by appropriate choice of monomers and / or addition of at least ei ^¬ nes crosslinker. Examples are thermoset ^¬ resins such as diallyl phthalate resins (PDAP), epoxy resins (EP), amino noplaste (eg. As urea resins, melamine resins, Dicyandiamidhar- ze), phenolic resins (eg., Phenol resins, for example phenol-formaldehyde resin), furfuryl alcohol formaldehyde resins (FF), Unge ^¬ saturated polyester resins (UP), polyurethane resins (PU), Reakti ^¬ onsspritzgegossene polyurethane resins (RIM-PU), furan resins, vinyl nylesterharze (VE VU), polyester-melamine Resins, blends of diallyl phthalate (PDAP) or diallyl isophthalate (PDAIP) resins, silicone resins.

Also possible are plastics based on polylactate.

The polymers used must be processable at the temperatures used. It may be crystalline or amorphous polyolefin.

In a preferred development of the invention, at least 50% by weight, 60% by weight, 70% by weight, 90% by weight, preferably 100% by weight of the polymer and / or elastomer used is at least one polyolefin.

In a further embodiment of the invention, the polyolefin is at least partly also made from renewable sources. len, z. As sugarcane, fats or oils, won. Together with the biological filler, a composite material can thus be obtained which has been produced at more than 30% by weight, preferably more than 50% by weight, particularly preferably more than 65% by weight, from renewable sources. Such sources are, for example, plants, such as sugar cane, but it can also be fats or oils, which are also produced as waste products.

In one embodiment of the invention, the thermoplastic (b) has an average molecular weight M _w in the range of 10,000 to 200,000 (measured by ultracentrifuge), preferably from 100,000 to 200,000.

In this case, polyethylene and polypropylene also include copolymers of ethylene or propylene with one or more α-olefins or styrene. Thus, in the context of the present invention, polyethylene copolymers comprised, the (wt least 50th ~ 6) in addition to ethylene as the principal monomer one or copolymerized more comonomers, preferably selected from styrene, vinyl acetate or α-olefins such as Example ^¬, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, n-aC ₂₂ H ₄₄ , n-aC ₂₄ H ₄₈ and NaC ₂ oH ₄ o. In the Rah ^¬ men of the present invention are polypropylene also includes copolymers containing, as the main monomer in addition to propylene (at least 50 wt .-%) containing one or more comonomers einpolymeri ^¬ Siert, preferably selected from styrene, ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, n-α-C22H ₄₄ , n-α-C24H ₄₈ and Na-C2oH ₄ o. The compound preferably comprises at least 5% by weight. the compo ^¬ component (a), preferably from 5 wt .-% to 80 wt .-%. The glass transition temperature (T _G , determinable as inflection point in the DSC diagram) for the at least one thermoplastic is preferably below 150 ° C., preferably between 60 ° C. and 120 ° C.

During compounding, at least one compatibilizing additive (c) may also be processed.

Such compatibilizers or coupler (coupling agents) are preferably compounds based on maleic anhydride ^¬, maleated polyethylene or maleated Polyp- ropylene, or copolymers acid from ethylene or propylene and acrylic, methacrylic acid, or trimellitic acid. The content of ^such couplers is preferably between 0 and 8% by weight.

As a compatibilizer also saturated or unsaturated organosilanes can be used. Functional organosiloxanes can increase the compatibility. Functional organosiloxanes, eg. For example, organylorganyloxysilanes are in this context those silanes which carry at least one organic radical bound to the silicon atom via a carbon atom, which in turn may contain a functional group. The easier dispersion is likely to be due to be ^¬ worked through the silane waterproofing the surface of the biological filling material. Preference is therefore given to silanes which carry at least one hydrolyzable radical and at least one nonhydrolyzable radical.

If silanes are used having at least one crosslinkable group, these groups may contain silanes with at least one ungesät ^¬ saturated carbon bond, for example vinyl, Ac triacrylate or methacrylate groups. There may also be epoxide groups. It may be necessary to additionally add crosslinkers if substances with crosslinkable groups are added. In addition, it may be necessary to add at least one solvent. The solvent may also be water, for example to hydrolyze added silanes.

In one embodiment of the present invention, the composition further comprises at least one additive (d). Examples of additives are stabilizers, in particular light and UV stabilizers, for example sterically hindered amines (HALS), 2, 2, 6, 6-tetramethylmorpholine-N-oxides or 2, 2, 6, 6-tetramethylpiperidine-N-oxides ( TEMPO) and other N-oxide derivatives such as NOR.

Further examples of suitable additives are UV absorbers such as benzophenone or benzotriazoles. Further examples of suitable additives are pigments, which can also cause a stabilization against UV light, such as titanium dioxide (for. Example, as a white pigment), or suitable substitute of white pigments, carbon black, iron oxide, other Me ^¬-metal oxides and organic pigments, for example azo and phthalocyanine pigments.

Further examples of suitable additives are biocides, in particular fungicides. Further examples of suitable additives are Säurefän ^¬ ger, for example, alkaline earth metal hydroxides or alkaline earth metal oxides or fatty acid salts of metals, in particular metal stearates, be ^¬ Sonders preferably zinc stearate and calcium stearate, and further Chalk and hydrotalcite. In this case, some fatty acid salts of metals, especially zinc stearate and calcium stearate, also act as a lubricant in the processing. Further examples of additives are antioxidants z. Based on phenols, such as alkylated phenols, bisphenols, bicyclic phenols or antioxidants based on benzofuranones, organic sulfides and / or diphenylamines. Further examples of suitable additives are Weichma ^¬ cher, z. As esters of dicarboxylic acids such as phthalates, organic phosphates, polyesters and polyglycol derivatives.

Further examples of suitable additives are impact modifiers (for example polyamides, polybutylene terephthalates

(PBT)) and flame retardants. Examples of flame retardants, in particular polycarbonate-based compositions are Ha ^¬ homologous compounds, containing in particular based on chlorine and bromine, and phosphorus compounds. The compositions preferably contain phosphorus-containing flame retardants from the groups of the mono- and oligomeric phosphoric and phosphonic acid esters, phosphonatoamines and phosphazenes, it also being possible to use mixtures of a plurality of components selected from one or more of these groups as flame retardants. Other phosphorus compounds not specifically mentioned herein may be used alone or in any combination with others

Flame retardants are used. Other flame retardants may include organic halogen compounds such as Decabrombisphe- vinyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine minformaldehyd resins, inorganic hydroxide compounds, such as Mg, Al hydroxide, inorganic compounds such as antimony oxides, Ba ^¬ riummetaborat, hydroxoantimonate, zirconia , Zirconium hydroxide, Molybdenum oxide, ammonium, zinc borate, ammonium borate, Bari ^¬ ummetaborat, talc, silicate, silicon oxide and tin oxide, and Si be loxanverbindungen. The flame retardants are often used in combination with so-called anti-drip agents, which reduce the tendency of the material for burning dripping in case of fire. By way of example, compounds of the substance classes of the fluorinated polyolefins, the silicones and aramid fibers may be mentioned here. These can also be used in the compositions according to the invention. Fluorinated polyolefins are preferably used as antiperspirants.

Further examples of additives are inorganic fillers which are present in particles and / or layer form, such as

Talc, chalk, kaolin, mica, wollastonite, kaolin, Kieselsäu ^¬ reindeer, magnesium carbonate, magnesium hydroxide, calcium carbonate, feldspar, barium sulfate, ferrite, iron oxide, metallic powder, oxides, chromates, glass beads, hollow glass beads, pigments, silica, hollow globular silicate fillers and / or phyllosilicates. These preferably have a particle size between 2 and 500 ym (measured with light scattering).

The composition may also contain additional crosslinkers, which can lead to crosslinking of the thermoplastic or thermoset, for example by irradiation or heating.

If the molding produced from the composition to be foamed, chemical or physical blowing agent may be introduced in liquid or solid form in the Zusammenset ^¬ pollution, acid or sodium bicarbonate, for example, with Citronensäu- thermolabile carbamates. This en ^¬ dotherme foaming agents are preferably used. Another way, too to reach a foaming, is ren the use of Mikrosphä- which are filled for example with gases or vaporizable liquid ^¬ speeds. Suitable fillers are, in particular, alkanes, such as butane, pentane or hexane, but also their halogenated derivatives, such as, for example, dichloromethane or perfluoropentane.

Alternatively, foaming may also be achieved by adjustment of appropriate process parameters (extrusion temperature, full profile cooling rate) if the composition contains substances that become gaseous under the process conditions (e.g., water, hydrocarbons, etc.). Preferably, these are closed pores.

Mixtures of aggregates can also be used.

In particular, short glass fibers, carbon ^¬ fibers (carbon fibers, graphite fibers), boron fibers, aramid as further reinforcing materials as additives were in ^¬ way of example glass fibers, (p- or m-aramid fibers (eg Kevlar ® or Nomex ®, DuPont) or mixtures thereof), and basalt fibers called, wherein said reinforcing fibers can be used as long fibers or filaments with the usual ratios (length to diameter), also in the form of a mixture of different fibers. It is also possible to add thermoplastic fibers, for example of PP, PA, PET, PP silicon fibers, etc., or vegetable fibers, natural fibers or fibers of natural polymers. Examples are jute, cotton, sisal and hemp fibers.

In one embodiment of the invention, the compound produced comprises long glass fibers having a length of at least 0.5 mm and a diameter of 3 to 25 μm. In a further embodiment of the invention, the compound produced does not comprise long glass fibers with a length of at least 0.5 mm and a diameter of 3 to 25 μm. Upon addition of an aggregate of a particular filling material ^¬ is noted, however, that the viscosity of Com pounds ^¬ after processing is not does not fall below a value corresponding to a MFI of PP of less than 10 g / 10 min. The additives are preferably present in a content of 0 to 30 wt .-%, preferably, a content of 0 to 20 wt .-%.

The compounds of the invention can be used for the production of moldings of any kind. These can be produced by injection molding, extrusion and blow molding. Another form of processing is the production of moldings by deep drawing from previously prepared plates or films. Another object of the present invention is a master terbatch comprising at least the components (a) and (b), with the difference that the masterbatch in particular has high levels of biomineralisches filler. Thus, in the masterbatch a proportion of biological filler of at least 30 wt .-%, preferably 30 to 90% wt .-%, preferably at least 50 wt .-%, in particular 50 wt .-% to 90 wt .-%. As further constituents can 5 to 30 wt .-% component (b) and 0 to 6 wt .-% additives, preferably 0.5 wt .-% to 6 wt .-%, its hold ^¬ ent. All with the proviso that the proportions of the ingredients add up to 100% by weight. The masterbatch is preferably prepared by the process according to the invention. It is also possible to produce cable compounds, in particular based on PVC. Due to the inorganic biological content, the proportion of non-biological additives for insulation and / or flame retardance can be reduced.

The object is also achieved by a method for producing a plastic with organic fraction, wherein Minim ^¬ least (a) min ^¬ least one polymer are processed into a compound at least one biomineralischer filler, and (b). The preferred embodiments correspond to those of the above-described plastic compound.

Individual method steps are closer beschrie ^¬ ben. The steps do not necessarily have to be performed in the order given, and the steps to be described

Method may also include other, not mentioned steps.

In a preferred embodiment of the invention, the compounding takes place in a mixing apparatus with high shear forces. Particularly preferably, the mixing apparatus corresponds to an internal mixer ^¬ or a one- or multi-part / -well kneader. Particularly preferred mixing apparatuses are kneterartige Re ^¬ actuators, one or more parts kneader, single- or multi-screw kneaders, mixers or mills. Very particular preference is single or multi-shaft kneaders.

It has been found that with conventional single- or multi-shaft extruders, no adequate mixing of the components is achieved.

In a preferred embodiment, the mixing apparatus is a screw kneader, such as a single-screw kneader (eg Ko-kneader, single-screw extruder with mixing and shearing parts), two-shaft Kneader (eg twin-screw extruder type ZSK or ZE, Kombiplast extruder, twin-screw kneading mixer MPC, two-stage mixer FCM, kneading screw extruder KEX, heavy-roller extruder). Also suitable are kneaders with or without a punch, trough kneaders and banbury mixers. Preference is given kneaders with a rotational and a translational (forward / backward) movement.

In a most preferred embodiment of the invention, the mixing apparatus corresponds to a co-kneader, e.g. from Buss Compounding Systems AG (Pratteln, Switzerland).

The kneading time is usually 0.5 to 24 hours.

The temperatures in the mixing apparatus are generally from 20 ° C to 350 ° C, depending on the polymer used, preferably at 20 ° C to 230 ° C.

The temperature may change in the course of the mixing application, for example by one or more differently tempered zones.

In a preferred embodiment of the invention, the compound is obtained in the form of granules. This can be obtained by cutting the extrudate accordingly. As a result, for example, cylindrical granules can be obtained with a maximum extension of up to 20 mm, for example 1 mm to 5 mm. It can also discs or balls are obtained. The manufacturing process may have other common

Connect steps to auszusortie ^¬ granules wrong size, or even drying steps. It has surprisingly been found that a satisfactory compounding was possible by using high shear mixing devices such as co-kneaders. The invention also relates to the use of the invention ^shown SEN biomineral filler material according to the embodiments described above, particularly with a silica content of at least 60 wt .-%, preferably Minim ^¬ least 80 wt .-%, particularly preferably rice hull ash, especially prefers white rice hull ash, as filler in

Composite plastics, in particular according to the inventive composition or the masterbatch.

Examples of the composite material according to the invention manufacturing asked shaped articles are films (as an anti-blocking agent), Professional ^¬ le, housing parts of all kinds, for example for the automobile interior such as instrument panels, household appliances, such as juice presses, coffee machines and mixers; for office machines such as monitors, printers, copiers; for panels, pipes, electrical installation ducts, windows, doors and profiles for the construction sector, interior work and exterior applications, such as building interior or exterior parts; in the field of electrical engineering as for switches and plugs.

Examples of building interior parts are railings, for example for stairs in the interior, and panels. Examples of Gebudeau ^¬ ßenteile are roofs, facades, roof structures, window frames, porches, railings for external stairs, decking and cladding, for example, for buildings or parts of buildings. Examples of profile parts are technical profiles, connecting hinges, moldings for interior applications such as moldings with complex geometries, multifunction profiles or packaging parts and decorative parts, furniture profiles and soil ^¬ profile. Furthermore, composite materials according to the invention for Packaging suitable, for example, for boxes and boxes. Another object of the present invention is the use of composite materials according to the invention as or for the production of furniture, such as tables, chairs, especially garden furniture and benches such as park ^¬ benches, for the production of profile parts and for the production of hollow bodies such as hollow sections for decking or window sills. Inventive moldings show excellent Witterungsbestän ^¬ speed, still excellent grip and very good mechanical properties and low water absorption, resulting in good weather dependence. Measurement results of the filler and the moldings produced are shown in the figures.

Fig. 1 Grain size distribution of filler I (ACS 851);

Fig. 2 Grain size distribution of filler II (ACS 901);

Fig. 3 Grain size distribution of filler III (ACS 931);

Fig. 4 Grain size distribution of filler IVa (ACS 952);

Fig. 5 tensile tests according to DIN EN ISO 527-2 at 1.8 N / mm ² ;

Fig. 6 tensile tests according to DIN EN ISO 527-2 at 8 N / mm ² ;

Fig. 7 tensile tests according to DIN EN ISO 527-2 at 8 N / mm ² ;

Fig. 8 tensile tests according to DIN EN ISO 527-2 at 20 N / mm ² ;

Examples:

Experiments were carried out with pure and mixed samples of rice hull ash with different content of silicon dioxide ^¬ . The particle size distributions of the individual samples I to V are listed in Tables 5 and 6. Grain size distributions of the samples are shown in FIGS. 1 (I), 2 (II), 3 (III) and 4 (IVa) shown. The figures show the quantity in ym (set (Microns) against the transmitted portion Passing as

Bars) and the percentage of measured values (% Channel; line). The values were determined by means of laser diffraction. The filler IV was added as IVb and IVc in addition to another device

(ANALYSETTE 22 NanoTec plus, laser diffraction). The filler V was measured twice with the aforementioned device. The values in the table indicate the sizes below which X% of the measured particles fall, e.g. B. 90% 45.56 ym means that for 90% of the measured particles a size of less than 45.56 ym was determined.

The exact size distributions are given in Tables 7, 8 and 9.

Fillers according to the invention were incorporated into different Ge ^¬ weight shares in polypropylene. The properties of the samples are shown in Tables 1 and 2. Thereby be distinguished ^¬ A sample in which constituents> 60 ym were removed by a sieving method, while B shows the characteristics of samples with unscreened filler. Comparative samples containing 20% by weight of talc as filler show a higher density of 1.11 g / cm ³ . Comparative samples containing 30% by weight of talc as filler show a higher density of 1.15 g / cm ³ . Comparative samples with 40% by weight talc as filler show a higher density of 1.26 g / cm ³ .

The experiments with the fillers I to V in mixtures gave similar results.

The properties of polyamide 6, 6 (PA 66) samples are shown in Tables 3 and 4. A denotes samples in which constituents> 60 μm are produced by a sieving process. while B show the properties of unsupported filler samples. Comparative samples containing 30% by weight tungstonite as filler show a density of 1.36 g / cm ³ and with 40% by weight wollastonite a density of 1.48 g / cm ³ . The excavation leads to a significant improvement in the properties.

The bending test was carried out according to DIN EN ISO 178 (ISO standard rods (80x10x4 in mm); Sample preparation: storage for 16 to 24 hours at 23 ° C in a closed vessel for temperature control, tester: Instron 4466, test speed: 2 mm / min; ^¬ width: 64mm, test temperature: 23 ° C, number of samples: 2 - 3).

The impact strength according to Charpy was measured according to DIN EN ISO 179/1 (test equipment: pendulum impact tester with replaceable pendulums (Zwick)) specimens: ISO standard rods (80x10x5mm ³ ); sample preparation: storage for 16 to 24 hours at 23 ° C in closed vessel for tempering; tester: pendulum impact tester 5J; test conditions: leu; specimen type 1; e ^¬ for schmalseiti ger shock; Prüftemeratur: -30 ° C; number of samples: 5).

Tensile tests according to DIN EN ISO 527-2 were carried out with tension rods according to DIN EN ISO 527-2 as test specimen. The test specimens were 16 stored up to 24 hours at 23 ° C in a closed vessel for controlling the temperature (tester: Instron Universal 5900R; Test speed: 1 mm / min and 5 mm / min; Prüftempe ^¬ temperature: 80 ° C; number of samples: 4).

FIGS. 5 to 8 show tensile tests according to DIN EN ISO 527-2 for various samples. Here, TD20 stands for PP with 20% by weight of talc. For the other samples is z. B. PP 60-40-1 for a content of PP 60% and filler 40% (in each case% by weight). Therefore, specimens were tested with 20 to 60 wt .-% filler. All show no disadvantages compared to talc. FIGS. 7 and 8 show test specimens with a test body with 20% by weight filler and 20% by weight long glass fiber in PP in comparison with test specimens with PA6 with 30% by weight long glass fiber and PP with 40% by weight. -% long glass fiber.

Matrix proportion tensile modulus tensile modulus tensile strength ^¬ tensile strength ^¬

Filler A Bility A B

[Wt. -%] [GPa] [GPa] [MPa] [MPa]

F PP-20 20 20,7 19, 3 26 25

F PP-30 30 23,7 22, 3 25 25

F PP-40 40 29, 6 28.5 24 23

F PP-50 50 36, 2 35, 4 24 23

F PP-60 60 48.4 47.7 24 22

Table 1

Table 2

Filler A Bility A B

[Wt. -%] [GPa] [GPa] [MPa] [MPa]

F PA 66 20 4,4 4,2 36 34 - 20

F PA 66 30 5.1 4.5 35 34 - 30

F PA 66 40 5, 8 5,2 37 36 - 40

F PA 66 50 7,1 6, 5 40 38 - 50

F PA 66 65 10.1 9.2 43 41 - 65

PA 66 - 1.4 - 35 -

PA GF 30 GF 5, 6 - 130 -

Table 3

Table 4 sample

I: ACS 851 (85 wt% Si0 ₂ ) 90% 387.7 ym

95% 502.1 ym

50% 217.8 ym

MV 244.3; MN 75.51, MA 177.5;

SD 102.1

II: ACS 901 (90% by weight of Si0 ₂ ) 90% 226.8 ym

95% 269.6 yards

50% 125.0 ym

MV 133.0 MN 19.8, MA 84.05; SD

69, 69

III: ACS 931 (93% by weight Si0 ₂ ) 90% 372.3 ym

95% 480.5 ym

50% 196.9 ym

MV 220.2 MN 34.92, MA 130.2;

SD 114, 6

IVa: ACS 952 (95 wt% Si0 ₂ ) 90% 45.29 ym

95% 56, 37 ym

50% 19.89 ym

MV 23:39; MN 2.097; MA 10.52;

SD 15, 94

Table 5 sample

IVb: ACS 952 (95 wt% Si0 ₂ ) 90% 45.56 ym

50% 18.11 ym 10% 2.86 ym

IVc: ACS 952 (95 wt% Si0 ₂ ) 90% 45.24 ym

50% 18.25 ym 10% 2.82 ym

Va: ACS 951 (95% by weight Si0 ₂ ) 90% 36, 87 ym

50% 17.42 ym 10% 2.38 ym

Vb: ACS 951 (95 wt% Si0 ₂ ) 90% 36.71 ym

50% 16.99 ym 10% 2.22 ym

Table 6

Table 7 Size [ym] I II III IVa

% Pass% Pass% Pass% Pass

1408 100.0 100.0 100.0 100.0

1184 99, 75 100.0 99, 77 100.0

995, 6 99.48 100.0 99, 53 100.0

837, 2 98, 79 100.0 98, 90 100.0

704.0 97, 84 100.0 98, 05 100.0

592, 0 96, 64 100.0 96, 98 100.0

497, 8 94, 9 100.0 95, 42 100.0

418, 6 92, 01 99, 51 92, 86 100.0

352, 0 86.59 98, 56 88.21 100.0

296, 0 76, 88 96, 68 80.19 100.0

248, 9 62, 51 93, 06 68, 49 100.0

209, 3 46, 34 86, 60 54, 79 100.0

176, 0 32, 12 76, 44 41.78 100.0

148.0 21.74 63, 24 31.58 100.0

124, 5 14,74 49,70 24,41 99, 90

104.7 10.01 38, 12 19, 43 99.48

88.00 6, 73 29, 32 15.71 98, 88

74.00 4.44 22, 65 12, 62 97, 95

62, 23 2,88 17,34 9, 88 96, 38

52, 33 1.83 13, 01 7.44 93, 66

44.00 1, 12 9.59 5, 37 89, 11

37, 00 0, 61 7.04 3.73 82.24

31, 11 0, 22 5,20 2,49 73,38

26,16 0,00 3,86 1, 57 63, 90

22, 00 0.00 2.85 0.89 54, 79

18.50 0.00 2.06 0.38 46.80

15.56 0.00 1.42 0.00 39, 92

Table 8 Size [ym] I II III IVa

% Pass% Pass% Pass% Pass

13, 08 0.00 0, 90 0.00 33, 90

11.00 0.00 0.47 0.00 28, 54

9, 25 0.00 0.11 0.00 23.74

7.78 0.00 0.00 0.00 19.48

6, 54 0.00 0.00 0.00 15.77

5.50 0.00 0.00 0.00 12, 59

4, 62 0.00 0.00 0.00 9, 91

3.89 0.00 0.00 0.00 7, 67

3.27 0.00 0.00 0.00 5, 81

2,750 0.00 0.00 0.00 4.28

2,312 0,00 0,00 0,00 3, 04

1, 945 0.00 0.00 0.00 2.07

1, 635 0.00 0.00 0.00 1, 32

1, 375 0.00 0.00 0.00 0.75

1.156 0.00 0.00 0.00 0.32

0, 972 0.00 0.00 0.00 0.00

Table 9

Claims

claims

1. plastic compound with organic fraction comprising min ^¬ least (a) at least one biomineral filler, and (b) at least one polymer.

2. Composition according to claim 1, characterized in that the biomineralic filler material is obtained from a renewable raw material.

3. Plastic compound according to one of claims 1 or 2, characterized in that the biomineral filler ei ^¬ nen content of silicon dioxide of at least 20 wt .-% comprises.

4. plastic compound according to one of claims 1 to 3, characterized in that the biomineral filler comprises ash from rice hulls and / or rice husks.

5. Plastic compound according to one of claims 1 to 4, characterized in that the at least one polymer is a thermoplastic or crosslinkable polymer, thermoset or a thermoplastic elastomer.

6. Plastic compound according to one of claims 1 to 5, characterized in that the proportion of the biomineral filler is 15 to 90 wt .-%.

7. Plastic compound according to one of claims 1 to 6, characterized in that at least 90% of the particles of the filler have a particle size of less than 400 ym (measured by laser diffraction).

8. plastic compound according to one of claims 1 to 7, characterized in that it

in addition to (a) and (b) still (c) at least one compatibilizing requirement additive comprises.

9. Plastic compound according to one of claims 1 to 8, characterized in that the compound is in the form of a Granu ^¬ lats.

10. A method for producing a plastic compounds with organic fraction according to any one of claims 1 to 9 wherein at least (a) at least one biomineralischer filler, and (b) at least one polymer processed into a compound ^¬ the.

11. The method according to claim 10, characterized in that the compounding takes place in a mixing apparatus with high shear forces.

12. Shaped body produced using a compound according to any one of claims 1 to 9.

13. Masterbatch comprising a compound according to any one of claims 1 to 9, characterized in that it has a content of at least 20% wt .-% of biological filler.