EP3728431A1

EP3728431A1 - Barrier layer for hoses

Info

Publication number: EP3728431A1
Application number: EP18792870.0A
Authority: EP
Inventors: Wolfram Herrmann; Dieter Borvitz; Steffen Wietzke; Frank Jungrichter; Hartmut Bangert
Original assignee: ContiTech Schlauch GmbH
Current assignee: ContiTech Schlauch GmbH
Priority date: 2017-12-21
Filing date: 2018-10-15
Publication date: 2020-10-28
Also published as: CN111511822A; WO2019120677A1; US11719364B2; DE102017223546A1; US20210080035A1

Abstract

The invention relates to a hose having at least one barrier layer as an inner layer and having an outer layer, wherein the barrier layer can be obtained by extrusion of a mixture, which comprises a) at least one thermoplastic fluoropolymer; b) at least one fluororubber and a crosslinking agent and/or at least one fluororubber elastomer; and c) at least one carbon filler selected from carbon black, in particular conductive carbon black, graphene, carbon nanofillers, in particular carbon nanotubes, carbon nanohorns, or a combination thereof, in a quantity of 0.05 wt% to 20 wt% of the carbon filler or carbon fillers, or irradiated PTFE, and vulcanization. The hose has a high degree of fuel, diesel and oil resistance and dynamic efficiency.

Description

description

Barrier layer for hoses

The invention relates to hoses with a barrier layer and a barrier layer and a

Process for their preparation.

For hoses used for the transport of aggressive media, e.g. Acids, fuels or oils used, possibly also at elevated temperatures, high demands on the durability of the hose materials used. For this purpose, the tube is usually provided with an inner layer which has a barrier or blocking function with respect to the medium to be transported.

For the inner layer with Sperrschichtfünktion against the medium to be transported are due to its media resistance and high temperature resistance

in particular fluorinated rubber mixtures used. These so-called FKM blends, also referred to as FPM blends, can be used with polyols and quaternary ones

Ammonium salts, e.g. in DE 43 11 549 A1 or in EP 1 096 190 B1, or bisphenolic and / or peroxidic, such as e.g. in EP 1 396 670 B1, be crosslinked.

Also, blends of fluorothermoplastic / crosslinked FPM are used as a low permeation material for inner layers of tubing. These mixtures are also referred to as FTPV (fluorothermoplastic vulcanizates).

When plastics are said to have electrical conductivity, electrically conductive fillers such as conductivity blacks are often used. Conductivity carbon blacks are also referred to as conductive carbon blacks. Hoses should also generally have a dynamic efficiency or elasticity. Dynamic ability and impermeability are interlinked

Material properties that are desired, but represent a conflict of objectives. The addition of carbon blacks enhances this conflict. This can lead to cracks in the hoses, which then fail. During processing, HF splitting may occur, damaging the polymer.

The object of the invention is to provide barrier layers for hoses which have both a dynamic efficiency or elasticity and are permeation-poor. In particular, hoses with electrical conductivity and high media resistance, e.g. to fuels or oils. The hoses obtained should have good crack resistance and damage to the plastics during the

Production should be avoided. This object has surprisingly been achieved in a first embodiment by a tube comprising at least one barrier layer as inner layer and one outer layer, wherein the barrier layer is obtainable by extrusion of a mixture comprising a) at least one thermoplastic fluoropolymer,

b) at least one fluororubber and a crosslinking agent and / or at least one fluororubber elastomer and

c) at least one carbon filler selected from carbon black, in particular

Conductivity carbon black, graphene, carbon nanofillers, especially carbon nanotubes, carbon nanohoms, or a combination thereof,

wherein the mixture contains from 0.05% to 20% by weight of the carbonaceous filler (s) and vulcanization.

In a second embodiment, this object has surprisingly been achieved by a tube which comprises at least one barrier layer as inner layer and one outer layer, wherein the barrier layer is obtainable by extrusion of a mixture comprising a) at least one thermoplastic fluoropolymer,

c) irradiated polytetrafluoroethylene (PTFE),

and vulcanization. The hoses according to the invention according to the first and second embodiments show both a good dynamic and crack resistance and a high

Resistance to media such as fuels and oils.

In the first embodiment, unlike barrier layers made correspondingly but containing no carbon filler, it has surprisingly been found that by the addition of the carbon filler as defined

lost thermoplastic properties in the barrier layer. This is evident from the dynamic-mechanical analysis (DMA) of the barrier layer. While in the case of the DMA a barrier layer made without the addition of carbon filler, the typical picture for a thermoplastic vulcanizate (TPV) also results

thermoplastic elastomer is used, melting of the thermoplastic can not be observed in the DMA of the carbon-filled barrier layer of the present invention. Not only is the storage modulus G 'significantly higher than the unfilled reference, but also at temperatures above 230 ° C, the storage and loss modulus G "changes in a similar manner, which makes the tan delta = G" / G 'even clearer. At 220 ° C, the unfilled material shows a tan delta> 1 (G "> G ') while the filled material has a Tan delta of 0.7.

Wikipedia: https://de.wikipedia.org/wiki/Viskoelastizit%C3%A4t) is after the

The reference fuses a liquid / melt while the filled material is a solid.

The transition between viscous and solid material behavior

(https: // en.wikipedia.org/wiki/V iscoelasticity% C3% A4t):

All liquids and solids can be considered as viscoelastic materials by their storage and loss modulus, G 'and G ", or their loss factor tan delta = G" / G' are given.For ideal viscous fluids (Newtonian fluid), the storage modulus is very small compared to the loss modulus, ideal-elastic

Solids that obey Hooke's Law, the loss modulus is very small compared to the memory module. Viscoelastic materials have both a measurable storage modulus and a measurable loss modulus. If the storage modulus is greater than the loss modulus, it is called solids, otherwise liquids.

Without wishing to be bound by theory, it is believed that the carbon filler in the thermoplastic will cause or promote cross-linking. Thus, in the barrier layer as the end product preferably no thermoplastic elastomer is present, but probably a crosslinked thermoplastic. In particular, the barrier layer produced according to the invention is no longer fusible.

In the second embodiment, it has surprisingly been found that the addition of irradiated PTFE powder produces an at least 3-phase material.

Additional advantages are a further reduced permeation and a reduction of the shear forces in the processing. The latter leads to a reduced polymer degradation of the fluoropolymers, so that stress corrosion cracking is avoided. It is particularly advantageous to use electron beam-modified PTFE powder. In

Rubber Rubber Plastics 5, 2005, 226 these additives are described. PTFE powder has no free radicals as inert polymer. Only by the irradiation long-lived radicals are formed which are detectable with ESR (electron spin resonance). Preferably, the PTFE has less than lxl 0 ¹⁸ spins / g, more preferably 1c10 ¹⁷ - 1c10 ¹⁴ spins / g. The size of the particles is preferably 500 μm to 0.01 μm, more preferably about 0.2 μm. The free radicals make it possible to couple the PTFE to the matrix.

Preferred embodiments of the method are given in the dependent claims. In the following, the invention will be explained in detail. Preferably, the vulcanization is carried out at 150 ° C to 200 ° C. Particularly preferably, the vulcanization takes place at the hose construction formed, comprising at least the barrier layer as the inner layer and the outer layer.

The hose according to the invention comprises at least one barrier layer as the inner layer and an outer layer. The barrier layer is obtainable by extrusion of a mixture as defined above. The following information applies to the first and the second

Embodiment, unless stated otherwise.

The blend used for the extrusion comprises at least one thermoplastic fluoropolymer. One, two or more thermoplastic fluoropolymers can be used. Thermoplastic fluoropolymers are generally semicrystalline, meltable and melt-processible fluoropolymers.

For the purposes of the present invention, the thermoplastic fluoropolymer may be any thermoplastic fluoropolymer except for irradiated PTFE. Irradiated PTFE may be included in the mixture as an optional additional component in the first embodiment. In the second embodiment, irradiated PTFE is included as a compulsory additional component in the mixture.

Examples of suitable thermoplastic fluoropolymers are poly (chlorotrifluoroethylene-co-vinylidene fluoride) (CTFE / VDF), polyethylene-co-chlorotrifluoroethylene (ECTFE), poly (ethylene-co-tetrafluoroethylene) (ETFE), polychlorotrifluoroethylene (PCTFE), poly (tetrafluoroethylene -co-perfluoroalkylvinylether) (PFA or TFA), polyvinylidene fluoride (PVDF), polyvinylfluoride (PVF), poly (tetrafluoroethylene-co-hexafluoropropylene) (FEP) or poly (tetrafluoroethylene-co-hexafluoropropylene-co-vinylidene fluoride) (TFB), wherein FEP is preferred, since it is characterized by particularly good processing behavior and high elasticity with high barrier effect against fuel diffusion.

The mixture used for the extrusion further comprises at least one fluororubber and a crosslinking agent and / or at least one fluororubber elastomer. One, two or more fluororubbers or fluororubber elastomers can be used. In general, the mixture contains at least one fluororubber and a crosslinking agent for the crosslinking of the fluororubber. When networking or

Vulcanization of the fluororubber, which usually occurs during the formation of the barrier layer, forms a fluororubber elastomer. In the barrier layer obtained after extrusion, therefore, the crosslinked fluororubber, i. the fluororubber elastomer.

It may be possible that the crosslinking of the fluororubber occurs partially or completely already before the extrusion. In this case, the mixture already contains fluororubber elastomer, either without or in admixture with fluororubber and crosslinking agent.

As the fluororubber, all conventional fluororubbers can be used. Often, fluororubbers contain vinylidene fluoride (VDF) as a comonomer. Examples of suitable fluororubbers are poly (vinylidene fluoride-co-hexafluoropropylene) (VDF / HFP),

Poly (vinylidene fluoride-co-hexafluoropropylene-co-tetrafluoroethylene) (TFB),

Poly (vinylidene fluoride-co-tetrafluoroethylene-co-perfluoromethylvinyl ether) (VDF / TFE / PMVE), poly (tetrafluoroethylene-co-propylene) (TFE / P) and poly (vinylidene fluoride-co-chlorotrifluoroethylene) (VDF / CTFE). The fluororubber used in the mixture is preferably a co-polymer or ter-polymer.

Suitable cross-linking agents for the fluororubber are all cross-linking agents known from the prior art, which the person skilled in the art, taking into account the fluororubber used, can suitably select from the desired vulcanization. Typical crosslinking agents are e.g. Diamines, bisphenols, peroxides, polyols or quaternary ammonium salts.

The proportion of thermoplastic fluoropolymer in the mixture may be, for example, in the range of 60 to 90% by weight, preferably 70 to 80% by weight. The proportion of fluororubber and / or fluororubber elastomer in the mixture may be, for example, in the range from 10 to 40% by weight, preferably from 20 to 30% by weight. The total amount of thermoplastic fluoropolymer and fluororubber and / or fluororubber elastomer in the mixture may be, for example, in the range of 80 to 99.8% by weight, preferably 90 to 98% by weight. Blends of thermoplastic fluoropolymers and fluororubbers included

Crosslinking agents are commercially available as FTPV, e.g. Dai-EL Fluoro TPV SV-1020, Dai-EL Fluoro TPV SV-1030, Dai-EL Fluoro TPV SV-1032 from Daikin.

The mixture according to the first or second embodiment contains as component c) at least one carbon filler and / or irradiated PTFE.

In the first embodiment, the mixture further comprises, as component c), at least one carbon filler selected from carbon black, in particular conductive carbon black, graphene, carbon nano-fillers, in particular carbon nanotubes, or a combination thereof, the mixture being 0.05% by weight. to 20 wt .-%, preferably 0.2 wt .-% to 10 wt .-%, more preferably 0.2 wt .-% to 9 wt .-%, of the carbon filler or contains. In contrast to elastomers, the carbon black content in the mixture should be as low as possible.

In a first variant, only one or more carbon blacks, in particular conductive carbon black, are used as the carbon filler. The carbon black is preferably a conductivity black. When the at least one carbon filler is selected from carbon black, in particular conductivity carbon black, the mixture preferably contains from 1 to 20% by weight, more preferably from 2 to 10% by weight, particularly preferably from 3 to 9% by weight, of carbon black, in particular conductive carbon.

In a second variant, graphene, carbon nanofillers, in particular carbon nanotubes, or a combination thereof are selected as the carbon filler, with carbon nanotubes being preferred. When the at least one carbon filler is selected from graphene, carbon nanofillers, especially carbon nanotubes, or a combination thereof, with carbon nanotubes being preferred, the mixture preferably contains 0.05 to 10 wt%, preferably 0, 2 to 5 wt .-%, of the carbon or the fillers.

In a third variant, the carbon filler used is a combination of carbon black, in particular conductive carbon black, and at least one selected from graphene, carbon nanofillers, in particular carbon nanotubes, or a combination thereof, wherein a combination of carbon black, in particular conductive carbon black, and

Carbon nanotubes is particularly preferred. By adding graphene or Carbon nanofillers, especially carbon nanotubes, the proportion of carbon black can be significantly reduced, whereby a better dynamic behavior of the barrier layer is achieved. When the at least one carbon filler is a combination of carbon black, in particular conductive carbon black, and at least one selected from graphene, carbon nanofillers, in particular carbon nanotubes, or a combination thereof, wherein a combination of carbon black, in particular conductive carbon black, and carbon nanotubes more preferably, the mixture preferably contains from 0.2% to 7% by weight, more preferably from 1% to 5% by weight, of the carbon fillers.

In the third variant, the weight ratio of carbon black, in particular

Conductivity soot, to the total amount of graphene and carbon nanofillers, especially carbon nanotubes (preferably the weight ratio of carbon black, especially conductivity soot, to carbon nanotubes) in the mixture e.g. in the range of 7: 3 to 3: 0.05, preferably 4: 3 to 3: 0.5.

The carbon black, in particular the conductivity carbon black, preferably has an oil absorption number (OAN) according to ASTM D 2414-16 of greater than 140 ml / 100 g to 600 ml / 100 g, more preferably from 250 ml / 100 g to 550 ml / 100 g, and / or a specific surface area according to the BET method according to ASTM D6556-04 of 150 to 1400 m ² / g, preferably from 600 to 1200 m ² / g.

The carbon black is preferably a conductivity black or conductive black. Particularly suitable are highly conductive carbon blacks. Such are commercially available, such as the conductivity blacks of the Ketjenblack EC-600 and EC-300J series from Akzo-Nobel, Ensaco 250G, 260G and 350G from Imerys, Printex XE2-B, L6, XPB538 from Orion Engineered Carbons, Vulcan XC 72 from Cabot, CL-08, EH-02 from Continental Carbon India Limited or N472 conductive carbon black from various manufacturers. Graphene are formed from two-dimensional layers of covalently linked carbon atoms, which correspond approximately to a single graphite layer. Graphene production processes are based, for example, on comminution of graphite, for example by mechanical or chemical exfoliation, or on chemical vapor deposition (CVD). The graphene can be chemically modified. Graphenes have high electrical conductivity and excellent mechanical properties.

Examples of carbon nanofillers are e.g. Carbon nanofibres (CNF), carbon nanohy- namic (CNH) and carbon nanotubes (CNT), with CNT being particularly preferred.

Carbon nanotubes are in particular carbon tubes with a diameter of about 0.5 to 100 nm. The length can be a multiple of the diameter. These tubes may be formed of one or more ordered carbon atoms of substantially graphitic or graphene structure. Common structures of this CNT are of the cylinder type. In the case of the cylindrical structures, a distinction is made between the single-wall, double-walled carbon nanotubes and multi-walled cylindrical CNTs. Common methods for their preparation are for. Arc discharge, laser ablation, chemical vapor deposition, and catalytic chemical vapor deposition. The CNTs can be chemically modified. CNTs are lightweight, tensile and piping

electricity. CNT and its synthesis have been known in the literature for some time and are commercially available. The at least one carbon filler is preferably carbon black, in particular

Conductivity soot, and / or CNT selected.

The mixture according to the first embodiment may optionally be irradiated

Polytetrafluoroethylene (PTFE) included. Further details of irradiated PTFE are given below with respect to the second embodiment, which apply mutatis mutandis to the first embodiment, also in terms of quantities and the phases.

With regard to the first embodiment, it has already been stated above that preferably no thermoplastic elastomer is present in the resulting barrier layer as end product. The inventively produced barrier layer is at the first

Embodiment preferably no longer meltable.

In the second embodiment, the mixture as component c) does not comprise a carbon filler according to the first embodiment, but irradiated Polytetrafluoroethylene (PTFE), the mixture preferably containing from 1% to 30%, more preferably from 1% to 12%, by weight of irradiated PTFE.

Irradiated PTFE is PTFE which has been exposed by irradiation, e.g. by electron or gamma irradiation. Irradiated PTFE contains long-lived radicals, which can be detected by ESR measurements, which allow chemical binding of the irradiated PTFE to polymer chains in the mixture, e.g.

during the extrusion. The existence of persistent (long-lived) radicals in irradiated PTFE has been known for some time. The irradiation may e.g. with an absorbed dose in the range of 10 to 3000 kGy. The irradiation can be carried out in an inert gas. Upon irradiation in the presence of atmospheric oxygen, carboxyl groups on the

Form polymer chain.

High dosages of irradiated PTFE can be added to the mixture without reducing the other properties of the F-TPV. In particular, by the addition of irradiated PTFE, the barrier layer obtained contains at least three polymer phases: for example, an FKM elastomer phase, a FKM fluorothermoplastic blend phase, a

Fluorothermoplastic phase and PTFE phase which is chemically coupled to the matrix. The mixture according to the first and second embodiments may optionally contain further plastic polymers, such as thermoplastics or rubbers, and / or additives customary in this field, e.g. Accelerators that form a crosslinking system with the crosslinking agent. The proportion of other plastic polymers other than those mentioned above is preferably less than 10% by weight, more preferably less than 5% by weight.

Further examples of optional additives are fillers other than the carbon fillers listed above, and / or

Processing aids and / or plasticizers and / or anti-aging agents and optionally other additives, such. Fibers and color pigments.

Processing aids may in particular be carnauba waxes, pentaerythrityl tetrastearates, soaps, fatty acid esters, phosphoric acid esters, boric acid esters, acid amides, aliphatic and olefinic waxes and aliphatic and olefinic amines or mixtures thereof. In a preferred embodiment, the barrier layer, after extrusion and before vulcanization, over the temperature range 140 ° C to 300 ° C has a value of tan delta <1, calculated with the formula tan delta = G "/ G \ the memory module G ' and the

Loss modulus G "can be measured, for example, according to the method described in the examples.

As stated, the hose according to the invention comprises at least one barrier layer as the inner layer and an outer layer. The inner layer with barrier function is the inner layer of the tube which in use is in contact with the medium to be transported.

In the simplest case, the hose is a two-leg hose without embedded

Reinforcements, so formed exclusively of an inner layer and an outer layer. In this connection reference is made to the duplex extrusion method. In most cases, however, there is a strength element consisting of at least one reinforcement layer, which is arranged in one or more layers between the inner layer and the outer layer. In addition to the two-layer basic structure and the reinforcement, there may be further layers, in particular an intermediate layer.

In a preferred embodiment, at least one intermediate layer is arranged in the tube according to the invention between the barrier layer or inner layer and outer layer.

In a further preferred embodiment, a strength carrier is arranged in the tube according to the invention between the outer layer and the barrier layer or between the outer layer and the optionally present intermediate layer.

With regard to the outer layer and the other possible layers, the materials customary in the prior art can be used. Preferred variants are shown, with the following abbreviations: FKM (fluororubber), ACM (acrylate rubber), AEM (ethylene-acrylate rubber), CM (chlorinated polyethylene rubber), ECO (ethylene oxide-epichlorohydrin rubber), EPM (Ethylene-propylene rubber

(Mixed polymer)), EPDM (ethylene-propylene-diene rubber (copolymer)), HNBR (hydrogenated acrylonitrile-butadiene rubber), VMQ (silicone rubber). The outer layer is preferably formed from a crosslinked rubber compound or an elastomer. The rubber component of the rubber composition for the outer layer is preferably FKM, ACM, AEM, CM, EPM, ECO, EPDM, HNBR or VMQ or a blend of the aforementioned rubber components, optionally with at least one further rubber component, eg an AEM / EPDM blend. In most cases, however, waste-free rubber mixtures are used. Particularly preferred is the

Rubber component of the rubber composition for the outer layer ECO, AEM, ACM, CM and / or HNBR. Most preferably, the rubber component of

Rubber compound for the outer layer ECO, AEM, ACM, CM or HNBR. Although the outer layer is subjected to heavy loads, e.g. FKM

Standard mixtures are used according to the prior art. Rubber mixtures based on ACM and / or AEM are preferably diaminically crosslinked.

Rubber compounds based on EPM, EPDM and VMQ are preferably crosslinked peroxide.

The intermediate layer, if present, is preferably made of a vulcanizate of

Acrylonitrile-butadiene rubber (NBR), a vulcanizate of ethylene oxide-epichlorohydrin rubber (ECO) and / or bisphenol-crosslinked fluororubber (FKM), amine-crosslinked FKM and peroxide-crosslinked FKM, ethylene-acrylate rubber (AEM), acrylate Rubber (ACM), chlorinated polyethylene rubber (CM), hydrogenated acrylonitrile-butadiene rubber (HNBR), and combinations thereof. The intermediate layer can also serve as an adhesive layer between the inner layer and the outer layer and / or the reinforcement. The reinforcement, if present, is formed in particular from a woven, knitted or knitted fabric, in particular based on a textile material. Suitable materials for this purpose may be polyamide (PA), polyimide (PI), aramid, in particular para-aramid or meta-aramid, polyvinyl acetal (PVA), polyetheretherketone (PEEK), polyester, in particular polyethylene terephthalate (PET) or polyethylene 2,6-naphthalate (PEN), polysulfone (PSU), polyoxadiazole (POD), polyphenylene or polyphenylene derivative, in particular

Polyphenylene sulfide (PPS), or glass fibers. Particularly preferred are p-aramid, m-aramid, polyphenylene sulfide (PPS) and / or polyethylene terephthalate (PET). Also

Hybrid concepts, ie mixed forms of the mentioned, can be used, for example in the form of a mixed intermediate of m- and p-aramid or of PPS and PA. The PPS as High-performance material contributes to a high strength, while the PA contributes in addition to the strength carrier contribution on its Haftaktivierbarkeit to improved adhesion to the surrounding elastomeric material.

In a preferred embodiment is located between barrier layer and

Outer layer, preferably an elastomeric outer layer containing ethylene oxide-epichlorohydrin rubber (ECO), ethylene-acrylate rubber (AEM), acrylate rubber (ACM), chlorinated polyethylene rubber (CM) and / or hydrogenated acrylonitrile-butadiene rubber (HNBR) , at least one elastomeric intermediate layer, preferably containing ethylene oxide-epichlorohydrin rubber (ECO), ethylene-acrylate rubber (AEM), acrylate rubber (ACM), chlorinated polyethylene rubber (CM) and / or hydrogenated acrylonitrile-butadiene rubber (HNBR ), wherein between the at least one elastomeric

Intermediate layer and the outer layer is a strength carrier, preferably containing p-aramid, m-aramid, polyphenylene sulfide (PPS) and / or polyethylene terephthalate (PET), is arranged. In other words, there are four layers here.

In a further preferred embodiment, the tube has five layers. In this embodiment, between the barrier layer and the outer layer, there are two elastomeric intermediate layers, wherein a strength carrier is arranged between the two elastomeric intermediate layers and the outer layer, wherein the barrier layer preferably contains fluorothermoplastic vulcanizates (FTPV), wherein an inner elastomeric

Intermediate layer preferably contains fluororubber (FKM), wherein an outer elastomeric intermediate layer preferably contains ethylene oxide-epichlorohydrin rubber (ECO), wherein the reinforcement preferably contains m-aramid, and wherein the outer layer preferably contains acrylate rubber (ACM).

In a preferred embodiment, each elastomeric layer has one

Volume resistivity of <10 ⁹ ohms, measured according to DIN IEC 60093: 1993-12 and / or DIN IEC 167 1994-10. In other words, each elastomeric layer is electrically conductive.

The hose according to the invention is suitable e.g. for air-carrying hoses, e.g.

Charge air hoses, particulate filter hoses, control hoses, and in particular for fuel hoses, including diesel hoses, or oil hoses, such as Turbocharger cooling hoses. The hose according to the invention has a high fuel, diesel and oil resistance.

The invention also relates to a method for producing an inventive

A tube comprising at least one barrier layer as an inner layer and an outer layer, the method comprising:

1) extruding a mixture comprising

a) at least one thermoplastic fluoropolymer,

c) at least one carbon filler selected from carbon black, in particular

Carbon black, graphene, carbon nanofillers, especially carbon nanotubes, or a combination thereof, and / or

irradiated PTFE,

to form the barrier,

2) applying the outer layer, and

3) vulcanization of the formed hose assembly.

For the preparation of the barrier layer, the mixture according to the first or second

Extruded embodiment, preferably directly into the intended for the barrier tube shape.

The mixture is preferably extruded to form the barrier layer at a temperature in the range of 170 ° C to 300 ° C, preferably 240 to 270 ° C.

Preferably, the vulcanization is carried out at 150 ° C to 200 ° C.

Prior to extrusion to form the barrier layer, the mixture is preferably compounded by premixing the individual components a), b) and c), wherein the components a) and b), ie thermoplastic fluoropolymer and fluororubber / crosslinking agent and / or fluororubber elastomer, as already prefabricated compound can be used, for example in the form of the types 1020 or 1030 from Daikin. The premixing of components a), b) and c), for example a premix of components a) and b) with component c), for example carbon black, in particular conductive carbon black, can be effected, for example, by means of an extruder, for example a twin-screw extruder. The compounding can be done, for example, at a temperature in the range of 245 to 300 ° C. It is then the compounded mixture, eg as granules obtained. This is extrudable and can be used for extrusion to form the barrier layer.

The outer layer can be applied in a conventional manner over the inner layer, e.g. by extruding.

As stated above, before the application of the outer layer, a

Intermediate layer and / or a strength member are applied to the barrier layer. For example, the intermediate layer can be extruded onto the barrier layer. The strength member may be applied in a conventional manner to the barrier layer or the

Intermediate layer can be applied.

The invention will now be explained in more detail using an exemplary embodiment with reference to the figures. It shows:

1 shows a hose according to the invention, which additionally has an optional intermediate layer and an optional strength member.

2 recording of a fusion test on the barrier layer according to the invention or

Inner layer after extrusion and before vulcanization.

Fig. 3 recording a melt test on a reference.

4 shows results of a dynamic mechanical analysis (DMA) of the barrier layer or inner layer according to the invention after the extrusion and before the vulcanization.

5 shows results of the dynamic mechanical analysis (DMA) of a reference.

6 shows results of the dynamic mechanical analyzes (DMA) of all measured samples.

Fig. 1 shows a hose according to the invention with the following example

Material conception on:

The barrier layer or inner layer 1 was obtained by extrusion of a mixture containing Daikin FTPV SV-1020, a mixture of thermoplastic fluoropolymers and fluororubbers including crosslinking agent, and 7 wt .-%, based on the

Total weight of the mixture, Ketjenblack EC300J, a carbon black carbon filler, at 260 ° C and subsequent vulcanization of the illustrated hose assembly at 170 ° C. The barrier layer or inner layer 1 is bounded by the intermediate layer 2. The

Interlayer 2 is formed by a vulcanizate of ethylene oxide-epichlorohydrin rubber (ECO) and also serves as an adhesive layer between the inner layer 1 and the

Reinforcing member 3. The reinforcing member 3 is formed of m-aramid and is bounded by the outer layer 4. The outer layer 4 contains acrylate rubber (ACM).

A melt test was carried out on the barrier layer or inner layer after the extrusion and before the vulcanization. The barrier layer or inner layer, after extrusion and before vulcanization, was not meltable even at 280 ° C. (FIG. 2). The reference used was granules of Daikin FTPV SV-1020 without carbon filler. This reference was melted at 280 ° C (Figure 3).

At the barrier layer or inner layer, a dynamic mechanical analysis (DMA) was carried out after extrusion and before vulcanization. Dynamic Mechanical Analysis (DMA) was performed on a Mettler Toledo DMA / SDTA 861. Round samples were punched out and preloaded into the sample holder. A temperature scan in the range of - 140 ° C to 300 ° C at 10 Hz was selected as the measuring program, maximum force amplitude 10 N, maximum travel amplitude 2 mhi, heating rate 2 ° C / min.

FIG. 4 depicts the measurement profile of the barrier layer or inner layer according to the invention after extrusion and before vulcanization. The upper section shows the course of the memory module G 'and the loss module G ", each for a duplicate. At the bottom

The section for each of the two samples shows the corresponding course of tan delta. The value for tan delta remains below 1.0 even at temperatures above 220 ° C. 5 shows the course for two corresponding samples, only without carbon filler. At temperatures above 220 ° C., a value for tan delta greater than 1.0 is achieved. 6 shows the measurement curves for different barrier layers according to the invention or

Inner layers after extrusion and before vulcanization as well as not

Inventive samples without carbon filler in a graph. In the case of the barrier layers or inner layers according to the invention after extrusion and prior to vulcanization, it was surprisingly found that the thermoplastic properties in the barrier layer are lost as a result of the addition of the carbon filler, in contrast to barrier layers which have been produced accordingly but do not contain a carbon filler go. This is proven by dynamic-mechanical analysis (DMA). While the DMA of a barrier layer made without the addition of carbon filler gives the typical picture of a thermoplastic vulcanizate (TPV), which is also referred to as a thermoplastic elastomer, in the DMA of the barrier layer of the present invention made with carbon filler, the melting of the barrier layer Not only are thermoplastics observed: the storage modulus G 'is not only significantly higher than the unfilled reference, but it can also be seen that the storage and loss modulus G "changes in a similar manner at temperatures above 230 ° C. This is shown by the tan delta = G "/ G 'even clearer. At 220 ° C, the unfilled material exhibits a tan delta> 1 (G "> G ') while the filled material has a Tan delta of 0.7.

Wikipedia: https://de.wikipedia.org/wiki/Viskoelastizit%C3%A4t) is after the

The reference fuses a liquid / melt while the filled material is a solid.

LIST OF REFERENCE NUMBERS

1 barrier layer or inner layer 2 intermediate layer

3 reinforcements

4 outer layer

Claims

claims

A hose comprising at least one barrier layer as an inner layer and a

Outer layer, wherein the barrier layer is obtainable by extrusion of a mixture comprising

a) at least one thermoplastic fluoropolymer,

c) at least one carbon filler selected from carbon black, in particular

Carbon black, graphene, carbon nanofillers, especially carbon nanotubes, carbon nanohoms, or a combination thereof, the mixture containing from 0.05% to 20% by weight of the carbon filler (s),

and vulcanization.

2. A hose according to claim 1, wherein the at least one carbon filler is selected from carbon black, in particular carbon black, and the mixture is 1 to 20 wt .-%, preferably 2 to 10 wt .-%, more preferably 3 to 9 wt .-% , Soot, in particular

Füssfähigkeitsruß, contains.

3. The hose of claim 1 wherein the at least one carbon filler is made

Graphene, carbon nano-fillers, in particular carbon nanotubes, or a combination thereof is selected and the mixture contains 0.05 to 10 wt.%, Preferably 0.2 to 5 wt .-%, of the carbon or the fillers.

4. The hose of claim 1, wherein the at least one carbon filler is a combination of carbon black, especially carbon black, and at least one selected from graphene, carbon nanofillers, especially carbon nanotubes, or a combination thereof, and the mixture is preferably 0.2 Wt .-% to 7 wt .-% of carbon fillers.

5. Hose according to one of the preceding claims, wherein the barrier layer is not

is melted.

6. Hose according to one of the preceding claims, wherein the mixture contains irradiated polytetrafluoroethylene (PTFE).

7. Hose according to one of the preceding claims, wherein between the barrier layer and outer layer at least one intermediate layer is arranged, wherein the

Intermediate layer preferably a vulcanizate of acrylonitrile-butadiene rubber

(NBR), a vulcanizate of ethylene oxide-epichlorohydrin rubber (ECO) and / or bisphenol-crosslinked fluororubber (FKM), amine-crosslinked FKM and peroxide crosslinked FKM, and combinations thereof.

8. A hose as claimed in any one of the preceding claims, wherein in the mixture 60 wt% to 90 wt% of thermoplastic fluoropolymer and 10 wt% to 40 wt%

Fluororubber and / or fluororubber elastomer are included.

9. Hose according to one of the preceding claims, wherein between barrier layer and outer layer, preferably an elastomeric outer layer containing ethylene oxide epichlorohydrin rubber (ECO), ethylene acrylate rubber (AEM), acrylate rubber (ACM), chlorinated polyethylene rubber ( CM) and / or hydrogenated

Acrylonitrile butadiene rubber (HNBR), at least one elastomeric

Interlayer, preferably containing ethylene oxide-epichlorohydrin rubber (ECO), ethylene-acrylate rubber (AEM), acrylate rubber (ACM), chlorinated

Polyethylene rubber (CM) and / or hydrogenated acrylonitrile-butadiene rubber (HNBR), and wherein between the at least one elastomeric

Intermediate layer and the outer layer, a reinforcement, preferably containing p-aramid, m-aramid, polyphenylene sulfide (PPS) and / or polyethylene terephthalate (PET), is arranged.

10. Hose according to claim 9 with two elastomeric intermediate layers, wherein the

Fluorothermoplastic vulcanizate (FTPV) barrier layer, wherein an inner elastomeric interlayer contains fluororubber (FKM), an outer elastomeric interlayer comprising ethylene oxide-epichlorohydrin rubber (ECO), the reinforcing layer containing m-aramid, and the outer layer comprising acrylate rubber ( ACM).

11. Hose according to one of the preceding claims, in particular according to claim 9 or 10, wherein each elastomeric layer has a volume resistivity of <10 ⁹ ohms, measured according to DIN IEC 60093: 1993-12 and / or DIN IEC 167 1994-10.

12. Hose according to one of the preceding claims, wherein the hose is an air-leading

Hose, a fuel hose or an oil hose is.

13. A method of making a tube comprising at least one barrier layer as an inner layer and an outer layer, the method comprising:

1) extruding a mixture comprising

a) at least one thermoplastic fluoropolymer,

b) at least one fluororubber and a crosslinking agent and / or

at least one fluororubber elastomer and

c) at least one carbon filler selected from carbon black, in particular carbon black, graphene, carbon nanofillers, in particular carbon nanotubes, or a combination thereof, and / or irradiated PTFE

to form the barrier,

2) applying the outer layer, and

3) vulcanization of the formed hose assembly.

14. The method of claim 13, wherein the mixture is extruded at a temperature in the range of 170 ° C to 300 ° C, preferably 240 ° C to 270 ° C, extruded.

15. hose, comprising at least one barrier layer as inner layer and a

a) at least one thermoplastic fluoropolymer,

c) irradiated polytetrafluoroethylene (PTFE),

and vulcanization.