RU2783077C1 - Electroconductive molding masses - Google Patents

Abstract

FIELD: material processing.

SUBSTANCE: invention relates to molding mass for the production of single-layer or multilayer hollow profiles. Mass contains at least 50% by weight of a semi-crystal polyamide component and contains a filler, which impacts on electroconductivity of molding mass. At the same time, mass is characterized by that molding mass is not characterized by a temperature of crystallite melting (Tm) of less than 50°C, where the polyamide component contains components A and B: A is homopolymer PA of PA X.Y or PA Z type, where X is a diamine residue (DA), Y is a dicarboxylic residue (DC), and Z is an alpha-, omega-amino acid residue; B is copolymer PA of PA X‘Y‘ type, where X‘ is a diamine residue (DA‘), and Y‘ is a dicarboxylic residue (DC‘); where some of diamine residues (DA‘) are substituted with polyester having at least two amino ends or at least two hydroxy ends; where the fraction of polyester in the sum of components A and B is from 0.5% to 15% by weight, and where the fraction of the filler is from 2.5% to 6% by weight per the total weight of the polyamide component and the filler; where no more than 10 mol.% of diamine residues (DA‘) can be substituted with polyester having only one amino end or only one hydroxy end; where copolymer PA of the component B is characterized by a polyester content from 8% to 18% by weight per the total weight of copolymer PA. The invention also relates to the use of molding mass for the production of hollow profiles, single-layer hollow profiles, multilayer hollow profiles, as well as a method for the production of mass.

EFFECT: proposed invention provides electroconductive molding masses, which do not require any plasticizers with low molecular weight or other extracted substances for improvement of mechanical properties and increase in aging resistance.

14 cl, 6 tbl, 5 ex

Description

The present invention is directed to semi-crystalline polyamide components as constituents of molding compositions in which the polyamide component does not have a crystallite melting point (T _m ) of less than 50°C.

Flexible tubes are well known and are used to convey liquid or gaseous media in motor vehicles. Previously, this problem has been satisfactorily solved with single-layer tubes made from polyamide or other thermoplastic molding compounds. In the case of these single-layer tubes, it has been found that the mechanical properties that are retained after installation, such as high elongation at break and high impact resistance, even over the entire life of an automobile vehicle, do not change very significantly under the influence of cold or heat or by contact with media, so that this leads to a malfunction of the pipeline.

Stricter environmental standards have led to the abandonment of further development and use of single-layer tubes as fuel lines and single-layer fuel tanks. In both cases, the automotive industry needs not only proper fuel resistance, but also improved barrier action to fuel components to reduce their emissions. This has led to the development of multilayer hollow bodies that use a barrier layer material. Multilayer composite materials of this type, which contain not only a barrier layer, but also additional layers based on aliphatic polyamides, are known, for example, from EP 1216826 A2.

Due to their good mechanical properties, their low water absorption capacity and their insensitivity to environmental influences, polyamides are a useful material for both the inner layer and the outer layer. Adhesion between adjacent layers is essential and can be provided by an intermediate adhesion promoter layer. There has also been a trend in the automotive industry over a period of time towards higher temperatures in the engine compartment and hence the need for stable hollow bodies used at these temperatures. Technical solutions providing for an adhesion-enhancing layer based on, for example, polyolefins are unsuitable due to their low deformation heat resistance. EP 1216826A2 solved this problem by using an adhesion promoter layer containing a polyamide selected from PA6, PA66 and PA6/66, optionally a polyamine-polyamide copolymer, and a polyamide selected from PA11, PA12, PA612, PA1012 and PA1212.

A common trend of "reducing the weight and size parameters of the engine", i.e. reducing the size of components while maintaining the same performance in order to reduce the energy consumption of motor vehicle engines, for example, is not only the cause of the increase in temperature that occurs in the engine compartment, but also the reduction in the size of the injection valves. These valves are injectors that inject fuel into the intake system or combustion chamber of an internal combustion engine. The presence of polar constituents in various fuels requires that the multilayer tube used be resistant to the extraction of the constituents from the materials used. US Pat. No. 6,467,508 describes the precipitation of such extracts in fuel and the possible blockage of injection valves as a problem. This problem was solved by using a "low precipitation polyamide" in the inner layer. "Low precipitation polyamide" is a purified polyamide that is obtained by complex and expensive extraction with methanol. By means of this method, constituents causing problems, such as oligomers, are removed.

With the progressive downsizing of injection nozzles, the automotive industry also requires not only a reduction in the amount of extracts that are deposited in the fuel, but also a reduction in the amount of extracts that are dissolved in the fuel. This demand has increased due to the advent of hybrid vehicles, since the internal combustion engines in these vehicles are used for a short period of time. Thus, soluble extracts in the fuel can also lead to clogging of injection nozzles due to drying out. The extracts are not only the oligomers described in US Pat. No. 6,467,508, but also additives such as plasticizers and stabilizers for the molding compositions used.

Both DE 37 24 997 C2 and DE 2 716 004 C3 and EP 0 566 755 B1 use polyether blockamides with laurolactam as monomer for the polyamide block. Suitable modified nylon-12 blends are also mentioned in Polyamid-Kunststoffhandbuch [Plastics Handbook - Polyamide], 3/4, 1998, Carl Hanser Verlag, page 872, paragraph 8.3.3. These mixtures show partial compatibility based on the co-crystallization of nylon-12 blocks with homopolyamide.

EP 1884356 discloses blends of polyamide/polyamide elastomers (TPE-A); the list of possible additives also mentions the addition of electrically conductive additives. The disclosed blends contain both large amounts of polyesteramides and large amounts of polyolefin-based impact modifiers.

The preparation of polyesteramides is described, for example, in EP0459862B1 and CH642982. Polyetheramides in this case are based on polyamide sequences having carboxyl groups at both ends of the chain, with polyoxyalkylene sequences having amino groups at both ends of the chain.

WO 2017/121961 A1 and WO 2017/121962 A1 claim multilayer tubes in which the inner layers contain at least three different polyamides with different chain lengths. These layers may also include polyether blockamides; they can also be electrically conductive.

Typical thermoplastic materials have surface resistivity in the range of 10 ¹⁶ to 10 ¹⁴ ohms (Ω) and therefore can generate voltages up to 15,000 volts. Effective antistatic agents can reduce the specific surface resistance of plastics to 10 ¹⁰ -10 ⁹ ohms. On the contrary, a much higher level of electrostatic dissipation must be achieved if the plastics are to be used in the electronic components of large devices, for example in the transformer or electrical switchgear sector, or in the many applications in the automotive and aircraft industries. In this case, it is necessary to use electrically conductive molding compositions, which must have a specific surface resistance of less than 10 ⁹ ohms. It is extremely important that in such applications of plastics, not only the surface resistance but also the volume resistance of plastic parts having a thickness of up to several millimeters must be in the same range, and in the case of parts that are produced by injection molding, effects often occur. anisotropy, which is usually difficult to prevent.

Thus, for the manufacture of electrically conductive plastic parts, it is possible to use only plastics that are already conductive, such as, in particular, polyanilines, or to make the aforementioned plastics, which can be characterized as electrical insulators, conductive through the use of carbon black, especially conductive types of carbon black. carbon black, carbon fibers, graphite, graphene and/or carbon nanotubes (CNT).

Carbon nanotubes, along with graphite, diamond, amorphous carbon and fullerenes, are another polymorph of the element carbon. The carbon atoms in this case are arranged in the form of hexagons. The structure corresponds to a rolled monatomic or polyatomic layer of graphite to form a hollow cylinder, typically a few nanometers in diameter and up to several millimeters long. The main distinction is made between multi-walled and single-walled carbon nanotubes, which are usually also abbreviated as MWNT and SWNT in the literature. Due to van der Waals forces, carbon nanotubes have a strong tendency to bundle up, and therefore it is important to decoupling/dispersing without significant contraction due to strong shear forces during the extrusion process. Typical commercial products are available from various manufacturers, of which the following are mentioned as examples: Bayer, Cyclics (formerly Electrovac), Nanocyl and Arkema and their Baytubes® C150P (trademark of Bayer AG, Germany), Baytubes C 150 HP, Baytubes C 70P, Electrovac HTF 110 FF, Nanocyl® NC 7000 (trademark Nanocyl SA, Belgium) and Graphistrength grade C100. Other manufacturers supply CMT as masterbatches, such as Hyperion and C-Polymers.

Accordingly, the problem addressed by the present invention is to provide electrically conductive molding compositions that do not require any low molecular weight plasticizers or other extractables to improve mechanical properties and improve aging resistance.

This problem is solved by using semi-crystalline polyamide components as constituents of molding compositions in which the polyamide component does not have a crystallite melting point (T _m ) of less than 50° C., as detailed below and in the claims.

The present invention provides a molding composition containing at least 50% by weight, preferably 60% by weight, more preferably 70% by weight, particularly preferably 80% by weight and most preferably at least 90% by weight of a semi-crystalline polyamide component and containing a filler that affects the electrical conductivity of the molding material, characterized in that the molding material is not characterized by a crystallite melting point of less than 50°C,

where the polyamide component contains components A and B:

A is a PA homopolymer of type PA X.Y or PA Z, where X is a diamine residue (DA), Y is a dicarboxylic residue (DC), and Z is an alpha, omega amino acid residue;

B PA copolymer type PA X'.Y', where X' is a diamine residue (DA') and Y' is a dicarboxylic residue (DC');

where some of the diamine residues (DA') are replaced by a polyester having at least two amino ends or at least two hydroxy ends;

where the proportion of polyester in the sum of components A and B is from 0.5% to 15% by weight,

and where the proportion of the filler is from 2.5% to 6% by weight, based on the total weight of the polyamide component and the filler,

where not more than 10 mol% of the PA homopolymer can be formed from other amide-forming units;

where not more than 10 mol% of diamine residues (DA') can be replaced by a polyester having only one amino-terminus or only one hydroxy-terminus.

The present invention also presents the use of the molding composition of the present invention for the production of hollow profiles.

The present invention also provides single-layer or multi-layer hollow profiles having at least one layer consisting of the molding composition of the present invention.

The molding masses and molded bodies of the present invention (such as hollow profiles) which include the molding masses of the present invention and the use of the present invention are described by way of example below, without any intention of limiting the present invention to these illustrative embodiments. When ranges, general formulas or classes of compounds are set forth below, it is assumed that they contain not only the corresponding ranges or groups of compounds mentioned explicitly, but also all subranges and subgroups of compounds that can be obtained by isolating individual values (ranges) or connections. If documents are cited in the context of this description, it is assumed that their entire contents are part of the disclosure of the present invention. Where percentages are given hereinafter, unless otherwise indicated, they are percentages by weight. In the case of compositions, these figures, expressed as a percentage, are based on the entire composition, unless otherwise indicated. Where averages are given throughout this document, unless otherwise noted, they are weight averages (weight averages). If measured values are given later in this document, unless otherwise indicated, such measured values were determined at a pressure of 101325 Pa and at a temperature of 25°C.

The scope of protection includes prepared and packaged forms of the products of the present invention that are common in the trade, both as such and in any reduced size forms, to the extent that they are not defined in the claims.

The various polyester units are in a statistical distribution. Statistical distributions are block construction with any required number of blocks and with any required sequence, or they are subject to a randomized distribution; they can also have an alternating design or form a gradient along the polymer chain; more specifically, they may also form any mixed form in which groups with different distributions may optionally follow each other. Particular embodiments may lead to limitations in statistical distributions as a result of this embodiment. The statistical distribution did not change for all areas not affected by the restriction.

One of the advantages of the molding compositions of the present invention is that a single-layer or multilayer hollow body having an inner layer consisting of the molding composition of the present invention is characterized by high resistance to washout. This is shown by testing fuel for testing in accordance with ASTM D471-15 "Reference fuel I" in relation to the tube, as described in the examples. A feature of the test fuel is that it contains 15% methanol by volume. Other methods for determining washout resistance may be known in the art; the method preferred in accordance with the present invention is described in detail in the examples. In this case, both soluble and insoluble components can be extracted. Preferably, less than 6 g per square meter of internal area of the test sample of soluble components are recovered from the test sample, preferably less than 5.5 g/m ² .

Another advantage of the molding compositions of the present invention is that the degree of crystallinity of a polyamide component consisting of components A, B and C is lower than the degree of crystallinity of a mixture comprising the same components A and C in the same amounts.

The multilayer hollow bodies of the present invention, which have an inner layer obtained from the molding composition of the present invention and have a barrier layer, have the advantage of low fuel permeability. This is shown by testing fuel for testing in accordance with ASTM D471 - 15 "Reference fuel I" in relation to the tube, as described in the examples. A feature of the test fuel is that it contains 15% methanol by volume. Other methods for determining washout resistance may be known in the art; the method preferred in accordance with the present invention is described in detail in the examples.

When stored at 60°C during a one-day test, diffusion from the test sample is observed not more than 6 g/m ² , preferably less than 5.5 g/m ² , more preferably less than 5.0 g/m ² and particularly preferably less than 4.5 g/m ² .

Amide-forming units are alpha-, omega-amino acid residues or a combination of diamine residues with dicarboxylic residues. Preferred alpha, omega amino acid residues are the free amino acids or their lactams, more preferably epsilon-caprolactam, 11-aminoundecanoic acid, 12-aminolauric acid or the corresponding laurolactam.

Diamine residues are residues containing a hydrocarbon bearing an amino group at each end, where the amino group can form the end of the polymer, but usually through its valency contributes to the formation of the chain.

Preferred hydrocarbons are aliphatic, more preferably having 2 to 18 carbon atoms, particularly preferably 3 to 14 carbon atoms, most preferably 4 to 12 carbon atoms. If the hydrocarbons have more than 3 carbon atoms, then they are linear, branched or cyclic, preferably linear, more preferably linear with 6 carbon atoms.

Particularly preferred diamine residues are ethylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,10-diaminodecane, 1,12-diaminododecane; most preferably 1,6-diaminohexane.

Dicarboxylic residues (DC) are residues having a hydrocarbon bearing a carboxyl group at each end, where the carboxyl group may form the end of the polymer, but usually participates as a carbonyl group through its valency in chain formation.

Preferred hydrocarbons are aliphatic, more preferably having 3 to 18 carbon atoms, particularly preferably 6 to 14 carbon atoms, most preferably 8 to 12 carbon atoms. The hydrocarbons are also preferably linear, branched or cyclic, more preferably linear.

Preferred dicarboxylic acid residues are those of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, most preferably dodecanedioic acid.

The PA homopolymer includes polyamides (PA) for component A; preferred polyamides are PA 6, PA 11, PA 12, PA 4.6, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 9.10, PA 9.12, PA 10.10, PA 10.12, PA 12.12; more preferably PA 6.6, PA 6.10, PA 6.12, PA 10.10; particularly preferably PA 6.10, PA 6.12, PA 10.10 and most preferably PA 6.12.

The PA copolymer component B is preferably characterized by a polyester content of 8% to 30% by weight, more preferably 9% to 25% by weight, particularly preferably 10% to 20% by weight, most preferably 12% to 18% by weight in calculated on the total weight of the PA copolymer.

The polyester preferably has 3 to 50 repeat units; more preferably 4 to 40, particularly preferably 5 to 30, most preferably 6 to 20, where the repeating units are linked by oxygen atoms.

The polyester preferably does not contain nitrogen atoms, which do not contain hydrogen atoms, and, in addition, it also preferably does not contain amino groups of the formula -NH-,=NH in the polymer chain.

More preferably, the polyester contains exclusively alkyleneoxy units; preferably, if there are alkyleneoxy units containing from 3 to 18 carbon atoms, the polymer has a regular molecular structure, i.e. is isotactic, syndiotactic, heterotactic, hemiisotactic, atactic.

Particularly preferred polyesters consist of ethyleneoxy, propyleneoxy and butyleneoxy units or mixtures thereof, the mixtures being random. Particularly preferred polyesters consist of ethyleneoxy and propyleneoxy units, or consist of n-butyleneoxy units, or consist of propyleneoxy units.

The polyester preferably has a number average molecular weight M _n of at most 5000 g/mol, particularly preferably at most 2000 g/mol and most preferably at most 1000 g/mol, where the lower limit is at least 200 g/mol, preferably 300 g/mol , more preferably 400 g/mol.

The polyester preferably does not contain more than two amino ends or two hydroxy ends, and more preferably contains strictly two amino ends or two hydroxy ends.

The polyamide component of the molding compositions of the present invention is preferably characterized by a polyester content of from 1% to 12% by weight, preferably from 1.5% to 9% by weight, particularly preferably from 2.0% to 8% by weight, most preferably from 2. 5% to 7% by weight based on the total weight of components A and B.

The chain lengths of the PA copolymer and the PA homopolymer of the polyamide component preferably differ from each other by no more than 10% on average with respect to the number of carbon atoms in the amide-forming units, where the difference is expressed in terms of higher chain lengths. In the case of using a PA copolymer PA 10.12 and a PA homopolymer, for example PA 10.10, the average PA 10.12 is 11 and thus the difference is 9.1%.

The molding compositions of the present invention have a proportion of conductive filler (component C) of 2.5% to 6% by weight, based on the combined weight of the polyamide component and the conductive filler, i. e. the sum of components A, B and C. The lower limit of 2.5% by weight in this case has the advantage that the conductivity values are high enough and the resistance values are low enough to be used in electronic components of large equipment, and also in the automotive and aircraft industries. Filler concentrations above 6% by weight furthermore result in low notch impact resistance which results in material embrittlement at excessively high filler concentrations.

Preferred electrical conductivity fillers do not form aggregates; thus, they are subject to dispersion when shear forces are applied.

Further, preferably, the molding composition of the present invention has a degree of crystallinity that is lower than the degree of crystallinity of a mixture comprising the same components A and C (electrical conductivity filler) in equal amounts, where any other constituents of the casting composition are likewise the same in nature. and quantity.

The degree of crystallinity is determined by methods known in the prior art; the degree of crystallinity is preferably calculated by equation (1)

(E1)

(E1)

The parameters T _m , T _g and ΔH _m within the present invention are determined by DSC, preferably in accordance with EN ISO 11354-1:2016D, more preferably in accordance with the description in the examples.

The ΔH _m ⁰ values for calculating the degree of crystallinity X _C are taken from tabular references, e.g. van Krevelen “Properties of Polymers”, 4th edition, 2009. The following values are preferably assumed:

Polyamide _∆Hm0 ^_ _{Tg Tm} PA 6 230 40 260 PA 11 226 46 220 PA 12 210 37 179 PA 6.6 300 fifty 280 PA 6.10 260 fifty 233 PA 6.12 215 54 215 PA 10.9 250 214 PA 10.10 200 60 216

The molding compositions of the present invention preferably do not include any addition of ionic liquids to increase electrical conductivity, as described, for example, in EP2635638A1 (US20130299750A1). Also preferably, the molding compositions of the present invention do not contain any metals in elemental form.

Preferably, the molding compositions of the present invention do not contain plasticizers, preferably low molecular weight plasticizers. Plasticizers in this context are given in DIN EN ISO 1043-3:2017 and are also, for example, esters of p-hydroxybenzoic acid having from 2 to 20 carbon atoms in the alcohol component, or arylsulfonic acid amides having from 2 to 12 carbon atoms in the amine component, preferably benzenesulfonic acid amides; ethyl p-hydroxybenzoate, octyl p-hydroxybenzoate, isohexadecyl p-hydroxybenzoate, N-n-octyltoluenesulfonamide, N-n-butylbenzenesulfonamide or N-2-ethylhexylbenzenesulfonamide.

The molding compositions of the present invention are produced from the individual constituents, preferably by melt mixing in a mixing plant, i.e. using shear forces.

Thus, the present invention also provides a method for producing the molding composition of the present invention, in which the individual constituents are mixed by melt mixing.

The individual components of the composition of the present invention in this case can be added simultaneously or sequentially. Even though, in preferred embodiments, the filler may first be dispersed in component A or B (especially component B) in the context of obtaining a masterbatch, and in this case the resulting masterbatch is subsequently diluted with the corresponding component B or A, absent in the masterbatch, a special preference is given to a method for producing the molding composition of the present invention, in which the individual components A and B and the filler are mixed simultaneously by melt mixing. Any additional constituents of the molding composition of the present invention may be added simultaneously as constituents A and B and filler, or subsequently.

Preferred carbon nanotubes are typically in the form of tubes formed from layers of graphite. Graphite plates are arranged concentrically around the axis of the cylinder. Carbon nanotubes are also called carbon nanofibrils. In them, the length to diameter ratio is at least 5, preferably at least 100, more preferably at least 1000. The diameter of the nanofibrils is usually in the range of 0.003 to 0.5 µm, preferably in the range of 0.005 to 0.08 µm, more preferably in the range of 0.006 to 0.05 μm. The length of the carbon nanofibrils is usually 0.5 to 1000 µm, preferably 0.8 to 100 µm, more preferably 1 to 10 µm. Carbon nanofibrils have a hollow cylindrical core. This cavity usually has a diameter of 0.001 to 0.1 µm, preferably 0.008 to 0.015 µm. In a typical embodiment of carbon nanotubes, the wall of fibrils around the cavity consists, for example, of 8 graphite plates. Carbon nanofibrils in this case can take the form of agglomerates up to 1000 μm in diameter, consisting of many nanofibrils. The agglomerates may be in the form of bird's nests, combed filaments, or open mesh structures. Carbon nanotubes are synthesized, for example, in a reactor containing carbonaceous gas and a metal catalyst, as described, for example, in US5643502A.

In addition to multi-walled carbon nanotubes (MWCNTs), it is also possible to use single-walled carbon nanotubes (SWCNTs) in the present invention. SWCNTs are typically around a few nanometers in diameter, but reach a considerable length relative to their cross section, typically around a few micrometers. The SWCNT structure is formed from plates of monatomic graphite (graphene), which can be represented as rolled into a single cylinder. SWCNTs can be excellent electrical conductors. The achievable current density of 10 ⁹ A/cm ² is approximately 1000 times higher than in the case of metal wires made of copper or silver. The preparation of SWCNT is described, for example, in US 5424054.

Preference is also given to a molding composition containing at least 70% by weight, particularly preferably 80% by weight and most preferably at least 90% by weight of a semi-crystalline polyamide component and containing a filler which affects the electrical conductivity of the investment, characterized in that the investment the mass is not characterized by a crystallite melting point of less than 50°C,

where the polyamide component contains components A and B:

A is a PA homopolymer of type PA X.Y or PA Z, where X is a diamine residue (DA), Y is a dicarboxylic residue (DC), and Z is an alpha, omega amino acid residue;

B PA copolymer type PA X'.Y', where X' is a diamine residue (DA') and Y' is a dicarboxylic residue (DC');

where some of the diamine residues (DA') are replaced by a polyester having two amino ends or two hydroxy ends;

where the proportion of polyester in the sum of components A and B is from 0.5% to 15% by weight,

and where the proportion of the filler is from 2.5% to 6% by weight, based on the total weight of the polyamide component and the filler,

where no more than 10 mol. % homopolymer PA may be formed from other amide-forming units;

where the PA copolymer component B is characterized by a polyester content of from 8% to 30% by weight, based on the total weight of the PA copolymer.

Preference is also given to a molding composition containing at least 70% by weight, particularly preferably 80% by weight and most preferably at least 90% by weight of a semi-crystalline polyamide component and containing a filler which affects the electrical conductivity of the investment, characterized in that the investment the mass is not characterized by a crystallite melting point of less than 50°C,

where the polyamide component contains components A and B:

A is a PA homopolymer of type PA X.Y or PA Z, where X is a diamine residue (DA), Y is a dicarboxylic acid residue (DC), and Z is an alpha, omega amino acid residue;

B PA copolymer type PA X'.Y', where X' is a diamine residue (DA') and Y' is a dicarboxylic residue (DC');

where some of the diamine residues (DA') are replaced by a polyester having two amino ends or two hydroxy ends;

where the proportion of polyester in the sum of components A and B is from 0.5% to 15% by weight,

and where the proportion of the filler is from 2.5% to 6% by weight, based on the total weight of the polyamide component and the filler,

where not more than 10 mol% of the PA homopolymer can be formed from other amide-forming units;

where the polyester has a number average molecular weight M _n not more than 5000 g/mol;

where the chain lengths of the PA copolymer and the PA homopolymer of the polyamide component differ from each other by no more than 10% on average with respect to the number of carbon atoms in the amide-forming units, where the difference is in terms of higher chain lengths.

Preference is also given to a molding composition containing at least 70% by weight, particularly preferably 80% by weight and most preferably at least 90% by weight of a semi-crystalline polyamide component and containing a filler which affects the electrical conductivity of the investment, characterized in that the investment the mass is not characterized by a crystallite melting point of less than 50°C,

where the polyamide component contains components A and B:

A PA homopolymer is selected from PA 6, PA 11, PA 12, PA 4.6, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 9.10, PA 9.12, PA 10.10, PA 10.12, PA 12.12;

B PA copolymer type PA X'.Y', where X' is a diamine residue (DA') and Y' is a dicarboxylic residue (DC');

where some of the diamine residues (DA') are replaced by a polyester having two amino ends or two hydroxy ends;

where the proportion of polyester in the sum of components A and B is from 0.5% to 15% by weight,

and where the proportion of the filler is from 2.5% to 6% by weight, based on the total weight of the polyamide component and the filler;

where not more than 10 mol% of the PA homopolymer can be formed from other amide-forming units;

where the molding composition has a degree of crystallinity that is lower than the degree of crystallinity of a mixture comprising the same components A and an electrical conductivity filler in equal amounts, where any other constituents of the composition are likewise the same in identity and quantity.

The molding compositions of the present invention preferably contain additional additives.

Preferred additives are oxidation stabilizers, UV stabilizer, hydrolysis stabilizers, impact modifiers, pigments, colorants and/or processing aids.

In a preferred embodiment, the molding compositions contain an effective amount of an oxidation stabilizer, and more preferably an effective amount of an oxidation stabilizer in combination with an effective amount of a copper-containing stabilizer. Examples of suitable oxidation stabilizers include aromatic amines, hindered phenols, phosphites, phosphonites, thiosynergists, hydroxylamines, benzofuranone derivatives, acryloyl-modified phenols, and the like. A significant number of such oxidation stabilizers are commercially available, for example, under the trade names Naugard 445, Irganox 1010, Irganox 1098, Irgafos 168, P-EPQ or Lowinox DSTDP. Typically, molding compositions contain from about 0.01% to about 2% by weight and preferably from about 0.1% to about 1.5% by weight of an oxidation stabilizer.

In addition, the molding compositions can also additionally contain a UV stabilizer or a light stabilizer of the HALS type. Suitable UV stabilizers are preferably organic UV absorbers, for example benzophenone derivatives, benzotriazole derivatives, oxalanilides or phenyltriazines. HALS type light stabilizers are derivatives of tetramethylpiperidine; they are inhibitors that act as radical scavengers. UV stabilizers and light stabilizers can advantageously be used in combination. A significant number of types of both stabilizers are commercially available; regarding dosing, the manufacturer's instructions can be followed.

The molding composition may additionally contain a hydrolysis stabilizer, for example a monomeric, oligomeric or polymeric carbodiimide, or bis-oxazoline.

The molding compositions may additionally contain impact modifiers. Impact modifying rubbers for polyamide molding compositions are known from the prior art. They contain functional groups derived from unsaturated reactive compounds that are either part of the polymer backbone or grafted onto the backbone of the polymer. The most commonly used is EPM or EPDM rubber which has been free radical grafted with maleic anhydride. Rubbers of this type can also be used in conjunction with a non-functionalized polyolefin, such as isotactic polypropylene, as described in EP0683210A2 (US5874176A).

Examples of suitable pigments and/or dyes include iron oxide, zinc sulfide, ultramarine, nigrosine, pearlescent pigments.

Examples of suitable processing aids include paraffins, fatty alcohols, fatty acid amides, stearates such as calcium stearate, paraffin waxes, montanates or polysiloxanes.

The multilayer hollow profiles of the present invention have at least one layer obtained from the molding composition of the present invention, which is in direct contact with the liquid. This is preferably the innermost layer of the hollow body.

The liquid is predominantly a mixture of chemicals containing hydrocarbons and at least one alcohol; the liquid is more preferably a fuel suitable as a power fuel for internal combustion engines; the fuel is most preferably an automotive fuel such as diesel or gasoline.

The fuel preferably contains alcohols having from 1 to 8 carbon atoms, more preferably methanol, ethanol, propanol, butanol or pentanol. Alcohols having at least three carbon atoms may be in their n-form, ie. linear and hydroxyl-terminated, or in their various iso-forms; in this case, the hydroxyl group may be primary, secondary or tertiary, preferably primary. More preferably, at least 80% by volume of the alcohols are linear hydrocarbons with a terminal hydroxyl group.

The fuels preferably contain at least 7% by volume, more preferably at least 10% by volume, particularly preferably at least 13% by volume, most preferably at least 16% by volume of alcohol.

The single-layer or multi-layer hollow body of the present invention is preferably a tube or vessel, preferably a component of a fuel supply system, preferably a fuel line or fuel tank.

The layer obtained from the molding composition of the present invention, which is preferably in contact with a liquid, is electrically conductive. The hollow body has a specific surface resistance of at most 10 ⁹ Ω/square and preferably at most 10 ⁹ Ω/square. Suitable testing methods are known in the prior art; preference is given to the determination of surface resistivity as specified in SAE J 2260 of November 2004.

A preferred multilayer hollow body according to the present invention has a so-called barrier layer. This barrier layer has a very low diffusion coefficient of the fuel components. Suitable materials for the barrier layer are hydrofluorocarbons and vinyl alcohol polymers. The multilayer hollow body preferably has a so-called EVOH barrier layer. EVOH is a copolymer of ethylene and vinyl alcohol. The ethylene content of the copolymer is preferably 20-45 mol% and in particular 25-35 mol%. A large number of types are commercially available. By way of example reference is made to the Kuraray EVAL Europe brochure "Introduction to Kuraray EVAL ^TM Resins", version 1.2/9810. In addition to prior art EVOH, the barrier layer may contain further additives, as is customary for use in barrier layer applications. Additives of this type are usually part of the know-how of the EVOH supplier.

The preferred multilayer hollow body of the present invention has a barrier layer (SpS) and as the innermost layer (Si) a layer obtained from the molding composition of the present invention, where the hollow body has a surface resistivity of not more than 10 ⁶ Ω/square according to SAE J 2260 November 2004

Between the barrier layer (SpS) and the innermost layer (Si) of the preferred multilayer hollow body, additional layers can be located, at least one layer (HVi), which provides adhesion between Si and SpS. Preferably, only the adhesion promoter layer is located between SpS and Si. If the adhesion between SpS and Si is to be sufficiently high, the adhesion promoting layer (HVi) can naturally be dispensed with.

Adhesion promoters between the barrier layer and the molding material layer of the present invention are known to those skilled in the art; preferred adhesion promoters are based on polyamides, preferably consisting of mixtures of PA 6.12 and PA 6, more preferably consisting of impact-resistant polyamides, and particularly preferably containing from 60 to 80% by weight of PA 6.12, from 10 to 25% by weight of PA 6 and from 5 % to 15% by weight of the impact modifier, where the mass proportions are chosen so as to add up to 100% by weight.

Preferably, the layers located on the inside of the barrier layer in the preferred hollow body of the present invention do not contain plasticizers as defined above. Also preferably, these layers include only the exact amount of additives needed, such as stabilizers and processing aids.

The preferred hollow body of the present invention preferably has at least one additional layer on the outside of the barrier layer. These outer layers are preferably likewise layers comprising at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 70% by weight, particularly preferably at least 80% by weight and most preferably at least 90% by weight of polyamides.

These polyamides are preferably PA homopolymers of the PA X.Y or PA Z type as described above. Preferably, the PA homopolymer of the outer layer (Sa) of the preferred hollow body is not identical to the inner layer (Si) homopolymer. Preferably, the outer layer PA homopolymer (Sa) is PA Z type PA, more preferably PA11 or PA12, most preferably PA12.

Between the outer layer (Sa) and the barrier layer (SpS) of the preferred hollow body of the present invention, additional layers can be placed, preferably at least one layer (HVa), which provides adhesion between Sa and SpS. Preferably, only the adhesion promoter layer is located between Sa and SpS. If the adhesion between Sa and SpS is to be sufficiently high, the adhesion promoting layer (HVa) can naturally be dispensed with.

The adhesion promoting layer (HVa) is preferably free of plasticizers as defined above. Also preferably, this layer includes only the exact amount of necessary additives, such as stabilizers and processing aids.

Preferably, the layers of adhesion promoters HVi and HVa are identical in terms of their chemical composition.

Also preference is given to multilayer hollow profiles having at least one layer consisting of the molding composition of the present invention, where this layer is in direct contact with the liquid and additionally has at least one barrier layer.

Also preference is given to multi-layer hollow profiles having at least one layer consisting of the molding composition of the present invention, and further having at least one barrier layer of hydrofluorocarbons or vinyl alcohol polymers; where the layers located on the inner side of the barrier layer in the hollow body do not contain plasticizers.

The hollow profile of the present invention can also be enclosed in an additional layer of elastomer. Both crosslinked rubber compositions and thermoplastic elastomers are suitable for sheathing. The sheath can be applied to the multilayer composite material either with or without the use of an additional adhesion promoter, for example, by co-extrusion, extrusion through a transverse die, or by stretching a prefabricated elastomeric hose over a preextruded multilayer tube. The sheath usually has a thickness of 0.1-4 mm and preferably 0.2-3 mm.

Examples of suitable elastomers include chloroprene rubber, ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), epichlorohydrin rubber (ECO), chlorinated polyethylene, acrylate rubber, chlorosulphonated polyethylene, silicone rubber, plasticized PVC, polyesteramides containing esters. groups, or polyetheramides.

The multilayer composite material can be produced in one or more stages, for example, using a one-step method by molding a multilayer structure, co-extrusion, co-extrusion blow molding (including, for example, 3D blow molding, extrusion of a preform for blowing into an open half-mold , 3D preform manipulation for blow molding, suction blow molding, 3D suction blow molding, sequential blow molding) or using multi-stage methods, which are described, for example, in patent document US5554425.

Further, the present invention is explained in the following experimental part using examples.

The following components/masses were used in these examples:

homopolymer PA 1 extrusion molding compound based on PA 6.12 from EVONIK Resource Efficiency GmbH (VESTAMID D22)

homopolymer PA 2 extrusion molding compound based on PA 10.10 from EVONIK Resource Efficiency GmbH (VESTAMID DS22)

homopolymer PA 3 extrusion molding compound based on PA 12 from EVONIK Resource Efficiency GmbH (VESTAMID L1901)

PEBA 1 extrusion molding composition based on PA 6.12 from EVONIK Resource Efficiency GmbH containing 25% by weight bisamino-terminated polyether having a molar mass of 400 g/mol (Elastamin RP-405, Huntsman)

PEBA 2 extrusion molding composition based on PA 10.10 from EVONIK Resource Efficiency GmbH containing 35.4% by weight of bisamino-terminated polyether having a molar mass of 650 g/mol

PEBA 3 extrusion molding composition based on PA 12 from EVONIK Resource Efficiency GmbH containing 29% by weight polyether with a bisamino-terminated group having a molar mass of 1000 g/mol

EVAL EVOH from Kuraray with 27 mol% ethylene (EVAL LA170B)

IM Impact modifier: Exxelor VA1803 (9%) + 1% Lotader AX8900

Stabilizer Blend of Irgafos and Irganox.

Adhesion promoter extrusion molding compound based on PA 6.12 from EVONIK Resource Efficiency GmbH (VESTAMID SX8002 or VESTAMID SX8080; SX8080 has the same performance as SX8002, but without plasticizer).

Example 1 Molding Compounds

The following molding compositions were formulated in a Haake kneader (HAAKE Rheomix 600 OS) by melt mixing the components.

Table 1. Composition containing molding masses from example 1

PEBA means PA copolymer, PE means polyester, CNT means carbon nanotubes;

the content of PE means the proportion of polyester by weight in the molding mass, without taking into account the mass of CNT;

the CNT content is a percentage by weight based on the total weight of the molding composition

molding compound Homopolymer PA PEBA PE content Contents of the CNT [% by weight] [% by weight] one one 0 0 0 eleven one 0 0 3 12 one one 4.25 0 13 one one 4.25 3 fourteen 0 one 25 0 fifteen one one 21 0 2 2 0 0 0 21 2 0 0 3 22 2 2 4.25 0 23 2 2 4.25 3 24 0 2 35.4 0 3 3 0 0 0 31 3 0 0 3 32 3 3 4.25 0 33 3 3 4.25 3 34 3 3 2.15 0 35 3 29 0

The molding masses 13, 23 and 33 are in accordance with the present invention.

Example 2 Determination of thermal properties

Via DSC according to ISO 11357 (Perkin-Elmer) at 20 K/min. the glass transition temperature T _g and the crystallite melting temperature T _m in the 1st heat test were determined, and the degree of crystallinity X _C was calculated from the determination of the melting enthalpy in the 2nd heat test.

Table 2. Determination of thermal properties according to example 2; n. in. means the value has not been defined

molding compound Tg Tm Xc [°C] [°C] [%] one 41 215 38 eleven 39 216 45 12 37 216 37 13 39 216 44 fourteen 43 0/163/197 32 fifteen 38 0/184/195/206 31 2 41 200 41 21 37 198 45 22 37 200 43 23 42 198 43 24 42 -23/186 32 3 38 178 32 31 40 179 37 32 37 179 36 33 40 179 36 34 40 177 32 35 35 -22/167 24

In all cases, it is observed that the degree of crystallinity X _C increases with the addition of carbon nanotubes to the base polymer. Moreover, in all cases, it is observed that the crystallinity of X _C can be reduced if a small part of the main polymer is replaced by PEBA. The molding compositions of the present invention are not characterized by a crystallite melting point of less than 50°C; this also applies to the molding composition 34 with a reduced polyester content.

Example 3 Production of hollow profiles

Five-layer tubes with an outer diameter of 8 mm and a total wall thickness of 1 mm were obtained by co-extrusion on a multi-layer Bellaform tube system.

The comparative example differs only in the composition of the inner layer (layer I).

Table 3 Layer configuration of hollow profiles according to example 3

According to the present invention Layer V VESTAMID LX9002; outer layer 0.45 mm Layer IV Adhesion promoter, external adhesive layer 0.1 mm Layer III EVAL barrier layer 0.15 mm Layer II Adhesion promoter, internal adhesive layer 0.1 mm Layer I Extrusion molding compound based on PEBA 1 The inner layer 0.2 mm Composition Molding material 13 89.5% by weight IM 10% by weight Stabilizer 0.5% by weight Comparison Layer I Extrusion molding compound based on PA 1 homopolymer The inner layer 0.2 mm Composition Molding material 11 89.5% by weight IM 10% by weight Stabilizer 0.5% by weight

Example 4 Testing

The tubes of example 3 were subjected to the following tests

a) Tensile test (with MLT). Single and multilayer tubes were tested according to DIN EN ISO 527-1 at a winding speed of 100 mm/min. The test specimens were approximately 200 mm long, the fixed length was 100 mm, and the strain gauge distance was 50 mm.

b) Impact test. The impact resistance of single-layer and multi-layer pipes was measured at 23°C according to DIN 73378.

The impact resistance of single-layer and multi-layer pipes was measured at -25°C according to VWTL52435 using an 880 g impact hammer.

The impact resistance of single-layer and multi-layer pipes was measured at -40°C according to J2260 using a 500 g impact hammer.

For all tests, 10 samples about 100 mm long were analyzed. After the load test, a visual check was made for damage.

c) Delamination test. The delamination test was carried out using a Zwick BZ 2.5/TN1S tensile tester, to which a tensile device and a rotating deflection roller made of metal are attached to be able to separate the individual layers of the test specimens from each other. The peel test according to DIN EN ISO 2411 was used to determine the adhesion between two layers by measuring the force required to separate the two layers from each other. For this purpose, tube segments of multilayer tubes 20 cm long were divided in the longitudinal direction into three parts using a cutting device.

Before starting the measurement, calipers were used to repeatedly measure the width of the sample at various points, and the average value was used for evaluation. The flaking end of one layer was then fixed in a clamp that continuously pulled said layer away from the second layer at an angle of 90°.

The layers were torn at a test speed of 50 mm/min while a plot of required force in Newtons versus displacement in millimeters was simultaneously recorded. This chart was used to determine the separation resistance in N/mm based on the width of the adhesive contact area.

d) Fuel permeability. The permeability measurement was used to determine how much fuel per day and meter of tube/square meter of internal area of the tube permeates through the fuel line when stored constant at 60°C. For this, pipe sections 300 mm long in each case were screwed at one end to a sealed container and weighed, then filled with 300 ml of CM 15, and the other end was closed. These test specimens were stored in an explosion-proof heated cabinet with forced ventilation at 60°C. The filled tubes were weighed again to determine the mass loss and hence the permeate mass of the fuel over time intervals. The effective seepage length was 285 mm.

e) Washout resistance. Using the washout determination, it was determined how much of the internal surface of the tube in g/m ² in the form of soluble and insoluble components is extracted from the multilayer composite material after exposure to fuel. To do this, a 2 m long section of the tube was completely filled with CM15 test fuel and sealed, and stored at 60°C for 96 hours. After cooling, the contents of the tube were poured into a beaker and washed with 20 ml of CM 15. for 24 hours. Thereafter, the test liquid was filtered under reduced pressure at 23°C and washed with 20 ml of CM 15. The filtered medium was left to evaporate in a fume hood at room temperature. Soluble extracts were thus obtained, the amount of which was determined by weighing. The filtrate was dried at 40°C for 24 hours and weighed. The difference from the initial weight of the filtrate was used to determine the amount of insoluble extracts.

The test is considered passed if less than 6 g/m ^{2 of} soluble constituents and less than 0.5 g/m ^{2 of} insoluble constituents have been washed out.

f) Heat aging characteristics of MLT (hot air circulation cabinet, 200 hours at 150°C and 1 hour at 170°C) are described.

In a heated cabinet with air circulation, sections of the respective single-layer or multi-layer pipes with a length of about 100 or 200 mm were stored at elevated temperatures for certain periods of time. In this case, it is necessary to ensure that the pipe sections are freely suspended in the furnace with air circulation, without touching each other or metal surfaces.

The length of the pipe segments depends on subsequent mechanical tests. As described in point b), specimens with a length of about 100 mm were used to test the impact resistance of the tube. After storage at 150°C for 200 h followed by conditioning under standard climatic conditions 23°C/50% r.h. humidity > 24 h, the tube impact test was carried out as described in point b). The strength test of the tube was carried out in a similar way on pieces of tube that had been previously stored at 170°C for 1 h.

g) Determination of insulation resistance and its change by storing fuel with CM15, CE10 and FAM B at 60°C.

The electrical resistance was determined on at least three sections of the tube with a length of 42 cm according to SAE J2260-1996. To do this, the inner surfaces of the tube were brought into contact at the ends of the tube with plugs of a certain length and diameter. Test voltages from 10 V to 500 V were used to measure electrical resistance in the range from 10 ² to 10 ¹⁴ Ω and converted using the internal area of the tube between the plugs to the required surface resistivity with the unit of measurement “Ohm per square”.

After that, the pipe sections were screwed at one end to the tank and weighed, then filled with 300 ml of test fuel (CM 15) and the other end was closed. The tube is located under the tank in such a way that the inner surface of the tube is completely filled with fuel during storage and electrical measurements. The inner layer was brought into contact through metal screw connections with support sleeves at the ends of the pipes, and the resistance was determined immediately after filling. The test specimens were stored in an explosion-proof heated cabinet with forced ventilation at 60°C and cooled to 23°C at regular intervals, and the change in electrical resistance was determined over a test time of about 1000 hours. In parallel with the electrical resistance, the absolute length of the free cross-section of the tube between the threaded connections was measured with a tape measure, and the change in length was determined by means of a dial indicator in the range from 0% to 5%.

The test is passed if the resistance is less than 10 ⁶ ohms/area.

The fuel composition for testing CE 10 and CM 15 and FAM B is specified in reference documents SAE J2260-1996; CM 15 meets ASTM D471-15, “Standard Fuel I” (isooctane/toluene, methanol); FAM B corresponds to test fluid according to DIN 51604-2 (1984); CE10 corresponds to “Fuel C” blend according to ASTM D471-15 plus 10 ± 1% ethanol by volume.

The results are shown in Table 4.

Table 4. Test results of pipes according to example 3

Trial According to the present invention Comparative Aging resistance 150°C for 200 h (DIN 53497), then pendulum hammer according to ISO 179-1 at r.t. no cracks 10 out of 10 destroyed Cold shock at -25°C/880 g no cracks 1 out of 10
destroyed Cold shock at -40°C/500 g no cracks 2 out of 10
destroyed Washout resistance according to point e) passed not installed Insulation resistance according to item g) passed unsatisfactory result Permeability to fuel according to item d) 4.3 g / (m ² *d) undefined

Example 5: Molding compositions with different filler content

First of all, a filler-containing masterbatch was produced using a Nanocyl twin screw extruder based on polyamide modified polyether (PA612.6T, milled powder) having a concentration of 10% CNT.

Then the masterbatch is diluted in a twin screw extruder with the addition of polyamide, impact modifier, stabilizer and head. In this case, molding masses are obtained with the components and filler content shown in table 5.

Table 5. Compositions

Composition one 2 3 % by weight CNT (based on the total weight of the polyamide component and filler) 3.68 4.91 7.36 Plasticyl Masterbatch (10% by weight CNT) thirty 40 60 Vestamid Htplus 51.5 41.5 21.5 impact modifier fifteen fifteen fifteen Stabilizer 1.5 1.5 1.5 Vestamid FG schwarz 2 2 2

Molding masses are used to obtain test specimens. For the notch impact test, 170 x 10 x 4 mm ³ injection molded/multipurpose specimens are used. For the electrical test, strips 1 mm thick are extruded.

Table 6 below shows the results of the notch impact test and electrical test along with test conditions.

Table 6. Tests

Composition one 2 3 % by weight CNT (based on the total weight of the polyamide component and filler) 3.68 4.91 7.36 Notch impact resistance according to ISO179 1-eA at 23°C (in kJ/m ² ) 105.4(P) 102.31(P) 82.45(P) Resistivity in accordance with SAE J2260, measured on extruded tapes (in ohms/square) 1.51E+13 3.45E+10 1.73E+05

It is obvious that the impact resistance decreases with a notch of more than 6%. In addition, the resistivity is too high below 2.5%.

Claims (23)

1. A molding compound for producing single-layer or multi-layer hollow profiles, containing at least 50% by weight of a semi-crystalline polyamide component and containing a filler that affects the electrical conductivity of the molding compound, characterized in that the molding composition is not characterized by a crystallite melting point (Tm) of less than 50°C, where the polyamide component contains components A and B: A is a PA homopolymer of type PA X.Y or PA Z, where X is a diamine residue (DA), Y is a dicarboxylic residue (DC), and Z is an alpha, omega amino acid residue; B PA copolymer type PA X'.Y', where X' is a diamine residue (DA') and Y' is a dicarboxylic residue (DC'); where some of the diamine residues (DA') are replaced by a polyester having at least two amino ends or at least two hydroxy ends; where the proportion of polyester in the sum of components A and B is from 0.5% to 15% by weight, and where the proportion of the filler is from 2.5% to 6% by weight, based on the total weight of the polyamide component and the filler; where not more than 10 mol.% diamine residues (DA') can be replaced by a polyester having only one amino-terminus or only one hydroxy-terminus; where the PA copolymer component B is characterized by a polyester content of from 8% to 18% by weight, based on the total weight of the PA copolymer. 2. The molding compound according to claim 1, wherein the polyester has a number average molecular weight Mn of not more than 5000 g/mol. 3. Molding mass according to any one of paragraphs. 1 and 2, where the chain lengths of the PA copolymer and the PA homopolymer of the polyamide component differ from each other by no more than 10% on average with respect to the number of carbon atoms in the amide-forming units, where the difference is in terms of higher chain lengths. 4. Molding mass according to any one of paragraphs. 1-3, characterized in that it is characterized by a degree of crystallinity that is lower than the degree of crystallinity of a mixture comprising the same components A and an electrical conductivity filler in equal amounts, where any additional constituents of the molding composition are likewise the same in nature and quantity. 5. Molding mass according to any one of paragraphs. 1-4, characterized in that it does not contain plasticizers. 6. The use of molding mass according to any one of paragraphs. 1-5 for hollow profiles. 7. Single-layer hollow profiles, having at least one layer, consisting of a molding mass according to any one of paragraphs. 1-5. 8. Single-layer hollow profiles according to claim 7, having at least one barrier layer. 9. Single-layer hollow profiles according to any one of paragraphs. 7 and 8, where the layers located on the inside of the barrier layer in the hollow body do not contain plasticizers. 10. Multilayer hollow profiles having at least one layer consisting of a molding mass according to any one of paragraphs. 1-5. 11. Multilayer hollow profiles according to claim 10, having at least one barrier layer. 12. Multilayer hollow profiles according to any one of paragraphs. 10 and 11, where the layers located on the inside of the barrier layer in the hollow body do not contain plasticizers. 13. The method of obtaining a molding mass according to any one of paragraphs. 1-5, characterized in that the individual components are mixed by mixing in the melt. 14. The method according to claim 13, characterized in that components A and B and the filler are mixed together at the same time.