DE102004045775B4 - Use of stabilized, thermoplastic polyamide molding compositions as a coating of optical waveguides - Google Patents

Abstract

Use of thermoplastic polyamide molding compositions having a continuous temperature stability of at least 6000 hours at 125 ° C. as a coating of optical waveguides which comprise a cladding based on fluorine compounds or of fluoropolymers, comprising the following components:
(A) Polyamides which are polymers or polycondensates based on aliphatic lactams, preferably based on C ₆ to C ₁₂ lactams, or on ω-aminocarboxylic acids having 3 to 44 carbon atoms, preferably having 4 to 18 carbon atoms, more preferably having 12 carbon atoms , or on aromatic aminocarboxylic acids having 7 to 20 carbon atoms, or which are obtainable from the polycondensation of at least one diamine and at least one dicarboxylic acid having in each case 2 to 44 carbon atoms, wherein the at least one diamine is preferably selected from the group of aliphatic diamines with 2 to 18 C atoms, the cycloaliphatic diamines having 7 to 22 carbon atoms and the at least one dicarboxylic acid, preferably from the group consisting of aliphatic dicarboxylic acids having 3 to 44 carbon atoms, cycloaliphatic dicarboxylic acids having 8 to 24 carbon atoms and ...

Description

The The present invention relates to those specified in the claims Object.

The Invention particularly relates to the use of stabilized, thermoplastic polyamide molding compounds as a protective layer for coating of optical waveguides (in the following called LWL), which a Cladding based on fluorine compounds or fluoropolymers own.

The used according to the invention Polyamide molding compound has good adhesion to the cladding based of fluoropolymers or fluorine compounds. Also owns they have a high continuous temperature resistance of at least 3000 Hours at 125 ° C.

The The present invention further relates to optical strands having at least a fiber core, a single or multi-layered cladding and at least one LWL enclosing protective cover, which consists of stabilized thermoplastic polyamide molding compounds.

optical fiber are suitable for transmission of large amounts of data in the field of telecommunications and the others for trouble-free, d. H. by electromagnetic fields not influenceable data transmission. For data transmission over short Distances up to about 150 m will be out of the relatively expensive glass optics Fibers (GOF) also the cheap plastic optical fibers, d. H. Polymer optical fibers (POF) used.

Also in the areas of vehicle technology / vehicle construction (data and signal transmission in vehicles, planes, ships, etc.) are always the ones before mentioned POF used. The plastic fiber optic cables (K-LWL) have in general a structure made of a polymer optical fiber core, a cladding and a protective cladding.

The So far used polymer optical fibers are usually from a polymethyl methacrylate (PMMA) core. Due to the glass transition temperature PMMA's of 95 up to 100 ° C their use is limited to temperatures below 90 ° C. As alternative for higher temperatures glass optical fiber cores are single or multi-core, too in bundles, in development.

The cladding of the polymer optical fiber may be formed as a single layer or as a multilayer. The cladding material used is predominantly fluorine-containing plastics whose refractive index is in the range between 1.35 and 1.42. The refractive index is matched to the refractive index of the PMMA fiber core (refractive index η _PMMA = 1.49, ∅ _core = 980 nm). The optical attenuation of such a K-LWL is typically 130 to 150 dB / km (λ = 650 nm), the minimum bending radius is about 5 to 10 mm. The attenuation is defined or measured as follows: Usually, a transmitted light measurement is performed and the attenuation (a) of an optical fiber in dB is calculated from the ratio of the light energy with the level P ₁ in the beginning of the optical fiber and the level P ₂ at the end of the optical fiber the equation: (a) = 10 · log P 1 / P 2 ,

To measure the attenuation, both levels must be measured. P ₁ is easy to measure by attaching a sufficiently large receiver diode at the end of the fiber. P ₁ in the beginning of the optical fiber, not to be confused with P ₀ , which is to be coupled into the optical fiber and becomes P ₁ due to coupling losses, can only be measured by detours (for further details on the attenuation measurement, please refer to "Plastics in Cable Technology"). , Hans-J Maier, volume 111, 3rd edition, point 4.4.2).

In order to protect the sensitive K-LWL against mechanical, thermal and chemical effects, it is provided with a plastic encased, which can be single or multi-layered and acts as a protective cover (see. WO 99/12063 ). This protective cover may, for example, consist of polyethylene, polyvinyl chloride, ethylene-vinyl acetate copolymer or polyamide, depending on the intended use or purpose. It may also contain soot to prevent the penetration of extraneous light into the polymer optical fiber. The materials used for the protective cover, such as, for example, polyamide, polyurethane or polyoxymethylene, may be enriched with flame retardants (US Pat. DE 92 09 018 U ).

• a) 20 bis 95 Gew.-% eines Polyamids,
• b) 5 bis 45 Gew.-% eines Flammschutzmittels und
• c) 0 bis 60 Gew.-% eines Schlagzähmodifikators.

EP 1 376 156 A2 describes an optical fiber which has a fiber core and a single or multi-layer protective cover and additionally contains further layers: an inner outer layer which adheres firmly to the fiber sheath and consists of a molding compound containing a polyamide and which has a resting shear at 220 ° C in the range of 400 to 6000 Pa · s, and an outer outer layer which adheres to the inner outer layer with a peel force of a maximum of 30 N and consists of a polyamide molding composition containing the following components:

• a) 20 to 95% by weight of a polyamide,
• b) 5 to 45 wt .-% of a flame retardant and
• c) 0 to 60 wt .-% of an impact modifier.

The flame retardant contained in the molding compound of the outer skin layer according to EP 1376156 A2 may be any flame retardant commonly used for polyamide molding compositions.

In order to obtain polymer optical fibers having improved heat resistance, it is also known (cf. DE 38 43 310 C2 ) to produce the fiber core from a heat curable silicone resin, wherein the material for the fiber core is injected in an uncured state in a two-layered jacket tube during its manufacture. The two layers of the jacket tube, of which the outer is made opaque by enrichment with soot, are simultaneously extruded and firmly connected together by the extrusion process.

in the In the field of automotive engineering, polyamides are used as protective cover material Use, since they meet the requirements there in terms of mechanical Strength (primarily tensile strength and transverse compressive strength), the previous maximum operating temperature and the chemical resistance fulfill. However, the poor adhesion of the polyamide protective cover causes problems an optical waveguide, the cladding of a fluorine-containing Polymer exists.

Of the only weak adhesive seat of the protective cover affects in particular then disadvantageous if the optical fiber, d. H. Fiber core plus Cladding plus at least one protective cover, in a large temperature fluctuations Underlying environment, such as the passenger compartment or the engine compartment a motor vehicle, is laid and the fiber optic cable, so the fiber core plus cladding, due to its different thermal expansion behavior and the only poor adhesion of the polyamide on the fluoropolymer relative to the protective cover emotional. This has the consequence that, for example, the distance the face of the fiber to the transmitting and receiving elements (light emitting diode / PIN diode) in certain circumstances enlarged so far that inadmissible high, possibly leading to failure of the data transmission path intensity losses occur. Furthermore there is a risk of damage the transmitting or receiving elements, if the fiber is too far out of the cover migrates.

Around this as "Pistoning" of the LWL designated Suppress effect are used connectors, couplers or brackets, the large clamping or crimping forces on the protective cover exercise and thus increase the friction between the protective cover and the optical fiber. The consequent deformation of the boundary layer between the fiber core and cladding, however, results in increased signal attenuation.

The Although stripping the protective layer in the plug prevents the "Pistoning", but holds the danger of cladding during the assembly due to improper handling of the setter tool equipped with a pair of blades.

The Let clamp or crimp force exerted by the connector on the optical fiber also by a form-fitting Reduce the anchoring of the K-LWL in a conical bore of the connector housing. So it was suggested to use the face of the K-LWL be called Melt the plate, the resulting Schmelzwulst in the rejuvenating inward Push plug hole and anchor the K-LWL in this way firmly in the connector housing. Im melted and thus deformed area gives way to the geometry of the K-LWL however in certain circumstances significantly from the total reflection enabling cylinder geometry off, leaving in the connector housing increased intensity losses occur.

EP 0 649 738 A1 describes that one can produce a frictional connection of polyamide and polyvinylidene fluoride by adding a polyglutarimide to the polyamide. So z. Example, by a single-stage extrusion process, a two-layer composite of a polyamide and a polyvinylidene fluoride, a three-layer composite of a polyamide, a primer layer of a polyamide-polyglutarimide blend and a polyvinylidene fluoride are prepared. Polyglutarimides are also known as polymethacrylimides (PMMI).

For extrusion processing with K-LWL, it is important that the protective cover, which lies directly on the cladding, be applied at the lowest possible temperature. The glass transition temperatures of the fluorine-like Cladding polymers are close to those of the fiber core material (PMMA, 106 ° C), ie between 80 and 120 ° C. The cladding can be very thin (about 10 microns), its optical properties are precisely adjusted and can be easily influenced or changed by thermal or chemical influences. Therefore, the materials of the protective cover must be extruded at the lowest possible melting temperature.

The inventors of EP 1 171 786 reported tests with blends of PMMI (Pleximid 130, manufacturer: Röhm, Germany) and low-viscosity polyamide 12 (relative viscosity of 1.65, according to 0.5% in m-cresol), after which it was found that due to the high blend viscosity clearly too high melting temperatures resulted in the K-LWL cable extrusion and the optical attenuation of the fiber was irreversibly increased here. Polyamide 12 / PMMI blends are therefore unusable as protective cover materials.

Moreover, in the examples of the EP 0 649 738 A1 , Page 6, table, polyglutarimides very high viscosity and can not be used as an intermediate layer for a three-layer process or as a component in the blend with polyamide 12 for K-LWL extrusion.

EP 0 767 190 A1 describes the use of polyamide primers to make multilayer polymer or tubing, ie automobile or coolant piping for the automotive industry. The polyamides used here are usually not deep viscous. Furthermore, no optical properties of the layers are required. The in the EP 0 767 190 A1 described polyamides have an amino end group excess.

When carried out by the inventors of the present application K-LWL extrusion experiments with in the EP 0 767 190 A1 Although acceptable adhesion temperatures were achieved so that the fiber core was not thermally damaged. In the subsequent heat storage (80 °, 24 hours), however, the outer layer of the fiber, so the protective cover dyed brown. This appeared to be due to diffusion of the monomers into the protective shell and subsequent chemical reaction. The discoloration impaired the optical properties of the fiber. The polyamide molding compositions according to EP 0 767 190 A1 thus exude as a primer or protective layer for both K-LWL and glass optical fiber.

EP 0 239 935 B1 describes optical strands consisting essentially of a silica or optical glass core and a sheath of plastic material, the sheath being made of a plastic material obtained by curing a solvent-soluble copolymer of a fluoroolefin with an alkyl vinyl ether, the copolymer having cure sites and at least 10% by weight of fluorine, based on the fluoroolefin units.

EP 0 883 001 A1 describes an optical fiber having a quartz core and a core clad polymer cladding (PCF) which has a multilayer structure of a variety of different polymers. The in EP 0 883 001 A1 As a result, this PCF is used for data transmission, eg for ATM LAN, high-speed Ethernet connections.

EP 0 749 463 B1 describes a polyamide hot melt adhesive with fillers, wherein the hot melt adhesive contains as essential component a polyamide based on dimerized fatty acid and proportions of monomeric fatty acid having 12 to 22 carbon atoms and proportions of at least 2 primary supporting amines having 2 to 40 carbon atoms. It is essential in this polyamide hot melt adhesive that the polyamides predominantly have amino end groups. In the EP 0 749 463 B1 described hot melt adhesives lead to a higher peel strength on metals and to a greater resistance to petrolatum. Another advantage compared to the unfilled polyamide is the more favorable water vapor permeability, ie a lower water vapor permeability. Because of these properties, these hot melt adhesives are suitable for bonding metals to one another and with plastics, in particular with polyolefins and polyesters, and with polyvinyl chloride. Furthermore, there are applications in the bonding of multilayer cable, with concrete applications fiber optic cables and power cables.

GB 2 198 258 A1 describes the use of thermoplastically processable polyamide blends for the production of protective sheaths for optical waveguides. The protective cover consists essentially of a mixture of 0 to 95 wt .-% polyamide 12, 50 to 5 wt .-% polyamide elastomer and 0 to 95 wt .-% of another polyamide and / or copolyamide. The polyamide elastomer, which constitutes a substantial proportion of the mixture, may be a polyether amide which z. In DE-A-3006961 or in CH-A-0656135 be is written or a polyetheresteramide be, which z. In DE-A-2936977 or DE-A-3428404 is described.

JP 04 127107 describes an optical waveguide with a protective cover on the cladding to prevent the so-called "pistoning" effect, using a polymer consisting essentially of polyethylene as the primary coating material containing 0.1 to 10% by weight of an ethylene / vinyl acetate. Copolymers used.

The not yet published patent application CH-00000/03 The applicant of the present invention describes a thermoplastic multilayer composite of at least one first layer based on fluoropolymers, as well as at least one further, at least partially directly adjacent to the first layer second layer. In order to ensure the good adhesion to the layer of fluoropolymer is provided as a primer layer, a layer based on polyamide / polyamine. Astonishingly, such copolymers have been found to provide greatly improved adhesion. This thermoplastic multilayer composite can be used as a coating of optical conductors, in particular with an optical core based on PMMA.

EP 1 216 823 B1 describes multi-layer composites which a layer of a molding composition of polyamide, optionally admixed with a polyamide / polyamine copolymers and optionally subsequently contains thereon a layer of ethylene-vinyl alcohol copolymer. In the molding composition of polyamide, a polyamide / polyamine copolymer is provided as a compatibilizer, but there is no indication in the EP 1 216 823 B1 that a polyamide / polyamine copolymer without further polyamide blend proportions could have good adhesion to fluoropolymer layers.

EP 0 777 578 B1 describes a multi-layer composite comprising a first layer comprising a fluoropolymer, a second layer comprising a non-fluorinated polymer and an aliphatic di- or polyamine having a molecular weight of less than 1000, wherein the non-fluorinated polymer is a polyamide, polyimide, polyurethane, or a carboxyl , anhydride, or imide-functional polyolefin, and all of the amine is in the second layer. The amine should be present in an amount sufficient to increase adhesion between the layers as compared to compositions without di- or polyamine.

EP 0 955 326 B1 describes polyamides modified with dimerdiol and dimer diol-containing hydroxyl-terminated polyesters. In comparison to the unmodified polyamides, the described modified polyamides have increased flexibility and toughness even at low temperatures. A change in mechanical properties due to plasticizer loss or migration on contact with media or on exposure to heat does not occur because of the inherent plasticization. The flexible polyamides have excellent hydrolysis resistance compared with other diol-containing polyamides.

by virtue of the fact that the hitherto used in the prior art Polymer optical fibers usually consist of a PMMA core and this has a glass transition temperature of 95 to 100 ° C, the use of such polymer optical fibers limited to temperatures below 90 ° C, as already described above.

to Stabilization of polyamide molding compounds against thermooxidative or however, numerous systems are known for photooxidative degradation. Known stabilizer systems include phenolic antioxidants, for example from the group of hindered phenols, antioxidants based on aromatic amines, as well as copper compounds. Especially Mixtures of copper halides and alkali halides have become as effective stabilizers against thermooxidative aging proved. The mixtures of copper halides and alkali halides are in their stabilizing effect to the other stabilizer systems superior. Namely Polyamides are used permanently at temperatures above 120 ° C, organic stabilization systems fail mostly. In these Temperatures show stabilization based on copper salts Effectiveness when a thermo-oxidative resistance requires several thousand hours becomes. The stabilizers mentioned can the polyamides on various Be added, for example, before or during the Polymerization, powdering during drying, or by compounding.

Examples of a stabilization of polyamide molding compounds with copper compounds are disclosed in EP 0 745 642 B1 and EP 0 668 943 B1 mentioned. EP 0 745 642 B1 describes thermostable, weather-resistant polyamide molding compositions containing as stabilizer a mixture of a copper halide, one or more Halogen compounds and hypophosphorous acid or an alkali or alkaline earth metal salt of these acids in a certain molar ratio to each other. This stabilizer mixture should bring about a very good stabilization against thermooxidative and photooxidative aging.

EP 0 668 943 B1 describes stabilized polyamide filaments comprising polyphthalamide, a copper-containing stabilizer and a functionalized polyolefin synergist wherein the stabilizer comprises a polyphthalamide-soluble copper compound and an alkali metal halide and the synergist is present in an amount of from 1 to 20% by weight.

In addition to the systems mentioned, other mixtures have been described for the stabilization of polyamides against thermooxidative and photooxidative degradation. US-A-2,705,227 describes a ternary stabilizer system consisting of a copper compound, a halogen compound and a phosphoric acid or an alkali metal salt of a phosphoric acid.

GB-A-1 140 047 describes a ternary stabilizer system of a copper salt, phosphorous or hypophosphorous acid or a compound of these acids and an alkali halide. The claimed ternary stabilizer system is subject to the restriction that the phosphorus compound is used in at most half the molar amount of the copper salt used. If hypophosphorous acid is used as the phosphorus compound, according to the GB-A-1 140 047 these are used at most a quarter of the molar concentration of the copper salt used. The phosphorus compound is added in the quoted molar deficiency with respect to the amount of copper added to obtain a light color of the polyamide molding compositions.

DE-A-2 107 406 describes a ternary stabilizer system consisting of copper stearate, potassium iodide and manganese hypophosphite. The molding compositions stabilized with this mixture are described as colorless.

The EP-A-0 612 749 describes stabilized polyamide molding compositions containing as stabilizer both an ionic or complex copper stabilizer, and at the same time elemental, finely dispersed copper.

The known stabilizer systems retard the thermooxidative and the photooxidative aging of polyamide molding compounds. New applications increase the requirements for the stability of polyamide molding compounds to thermooxidative or photooxidative degradation. This applies, for example, to the application of Polyamide molding compounds in the engine compartment of automobiles. In this and In other areas, too, the polyamide molding compounds are strong Temperature load over long periods exposed. In these increased Temperatures are suitable for Polyamides, especially copper-based stabilizers.

The mechanism of stabilization of polyamides by the combination of metal salts such as copper halides and alkali halides is described, for example, by P. Gijsman et al. in Polymer Degradation and Stability 49 (1995), 127-133. The combination of copper salts with aromatic halogen compounds is in the DE-A-19847626 and with complexing agents such as mercaptans or phosphines is in the DE-A-19847627 mentioned. These systems are intended to reduce the discoloration of copper-based stabilizers.

Out It is well known in the art that metal deactivators with antioxidant activity, which through in the molecule contained sterically hindered phenols is used to use. Very often, these compounds are used to stabilize polyolefins, especially for Polyphenylene ether or for the constant use in contact with copper, for example at Cable applications, used.

For the type of stabilization (of polyolefins) metal deactivators are used, which according to the reference: "Plastics Additives Handbook, 4th Ed., 1993, Chapter 2.4, have the following chemical structures: amides of aliphatic and aromatic mono- and dicarboxylic acids and their N monosubstituted derivatives, cyclic amides such as barbituric acid, hydrazones and bishydrazones of aliphatic and aromatic aldehydes, hydrazides of aliphatic and aromatic mono- and dicarboxylic acids, bis-acylated hydrazine derivatives, heterocyclic compounds such as melamines, benzotriazoles, 8-oxo-quinolines , Hydrazones and acylated derivatives of hydrazine triazines, aminotriazoles and acylated derivatives thereof, polyhydrazides, molecular combinations of sterically hindered phenols and metal complexing groups, nickel salts of benzyl phosphonic acids, optionally in combination with other antioxidants or metal deactivators, pyridinethiol / Sn compounds, tertiary phosphoric acid esters of thiobisphenol. In the patent literature in this context, additional additional structural classes such as N, N'-bis-salicylal-ethylenediimides, salicylaloximines, derivatives of ethylenediaminetetraacetic acid, etc. mentioned. However, many of the above compounds can not be used in practice as metal deactivators in thermoplastics due to their low activity, insufficient thermal stability, or volatility.

Out EP 1 198 520 B1 However, it is also known to use sterically hindered phenols in polyamide molding compositions.

By phenolic antioxidants from the group of sterically hindered phenols, those skilled in the art will generally understand organic compounds containing at least one phenolic group wherein the aromatic moiety is substituted at least at one, preferably at both, positions directly adjacent to the carbon atom having the phenolic group. The substituents adjacent to the hydroxy group are alkyl radicals, preferably selected from the group of alkyl groups having 1 to 10 carbon atoms. They are preferably tertiary butyl groups. Suitable hindered phenols include, for example, tetrakis (methylene (3,5-di (tert-butyl-4-hydroxy-hydroxynoic acid)) methane, commercially known as Irganox 1010 (Ciba Specialty Chemicals). It is also known to add such antioxidants with hindered phenol group HT (high temperature) - polyamide injection molding compositions, so that they have improved thermal stability (see. EP 1 198 520 B1 ).

Therefore it is an object of the present invention stabilized thermoplastic Polyamide molding compositions to provide a long-term temperature resistance of at least 3000 Hours at 125 ° C own and for the coating of optical fibers, which a Cladding based on fluorine compounds or fluoropolymers have, are suitable.

A Another object of the present invention is to provide an optical To create vein, which has a long-term temperature resistance of at least 3000 hours at 125 ° C and which has a good Adhesion between the protective layer and the cladding based on Fluorine compounds or based on fluoropolymers, so one Fluorine cladding, possesses.

tries The inventors of the present application have shown that by the interaction between the amino end groups of the polyamide and the copper compounds, the viscosity of the polyamide molding compounds strong elevated becomes. This viscosity influence depends on from the concentration of amino end groups and the processing conditions, including drying temperature and drying time. The viscosity (Solution viscosity and melt viscosity) varies So with the processing conditions (temperature, duration) and increases usually more or less strong as a function of it. In industrial Manufacturing processes are not strong fluctuating viscosities acceptable.

On Reason of increased viscosity are higher Processing temperatures required, which additionally the Formation of tubers and gel particles is promoted, resulting in one irregular coating leads, which also not acceptable.

The The above objects are achieved by the use of the thermoplastic Polyamide molding compositions according to claim 1, which serves as a protective layer for coating optical waveguides, which have a Fluorcladding, should be used as well through the optical fiber according to claim 18 solved.

In the dependent claims are advantageous embodiments of the invention.

• (A) Polyamide, welche Polymerisate oder Polykondensate sind, basierend auf aliphatischen Lactamen, bevorzugt auf Basis von C₆ bis C₁₂ Lactamen, oder auf ω-Aminocarbonsäuren mit 3 bis 44 Kohlenstoffatomen, bevorzugt mit 4 bis 18 Kohlenstoffatomen, besonders bevorzugt mit 12 Kohlenstoffatomen, oder auf aromatischen Aminocarbonsäuren mit 7 bis 20 Kohlenstoffatomen, oder welche erhältlich sind aus der Polykondensation von mindestens einem Diamin und mindestens einer Dicarbonsäure mit jeweils 2 bis 44 C-Atomen, wobei das mindestens eine Diamin bevorzugt aus der Gruppe der aliphatischen Diamine mit 2 bis 18 C-Atomen, der cycloaliphatischen Diamine mit 7 bis 22 C-Atomen und die mindestens eine Dicarbonsäure, bevorzugt aus der Gruppe aus aliphatischen Dicarbonsäuren mit 3 bis 44 C-Atomen, cycloaliphatischen Dicarbonsäuren mit 8 bis 24 C-Atomen und aromatischen Dicarbonsäuren mit 8 bis 20 C-Atomen ausgewählt ist, und wobei die Polykondensate bzw. die Polymerisate einen Aminoendgruppenüberschuß aufweisen,
• (B) 0,01 Gew.-Teile bis 2 Gew.-Teile, bezogen auf den Polyamidanteil der Formmassen-Zusammensetzung, eines kupferhaltigen Stabilisierungsmittels,
• (C) 0,01 Gew.-Teile bis 3 Gew.-Teile, bezogen auf den Polyamidanteil der Formmassen-Zusammensetzung, mindestens einer organischen Verbindung mit Metall-komplexierenden Gruppen, ausgewählt aus der Gruppe der Säureamid-, Oxamid-, Oxalanilid-, Hydrazin-, Säurehydrazid- oder Hydrazon-Gruppen, der Gruppe der Benzotriazole, sowie der Gruppe der schwefelhaltigen Phosphite, wobei die Summe der Komponenten (A), (B) und gegebenenfalls (C) 100 Gew.-Teile ergibt,
• (D) 0 bis 45 Gew.-Teile, bevorzugt 0 bis 25 Gew.-Teile, eines oder mehrere funktionalisierte Polymere, bevorzugt aus der Gruppe der funktionalisierten Polyolefine und/oder der funktionalisierten Polyolefincopolymere, zusätzlich zur Summe der Komponenten (A), (B) und gegebenenfalls (C).

The thermoplastic polyamide molding compositions used according to the invention have a long-term temperature stability of at least 3000 hours at 125.degree. In a particular embodiment, the inventive material, ie, the thermoplastic molding compositions of the invention has a long-term temperature stability of at least 4000 hours at 125 ° C, more preferably of 5000 hours at 125 ° C and most preferably of 6000 hours at 125 ° C. The thermoplastic polyamide molding compositions used according to the invention contain the following components:

• (A) Polyamides which are polymers or polycondensates based on aliphatic lactams, preferably based on C ₆ to C ₁₂ lactams, or on ω-aminocarboxylic acids having 3 to 44 carbon atoms, preferably having 4 to 18 carbon atoms, more preferably having 12 carbon atoms , or on aromatic aminocarboxylic acids having 7 to 20 carbon atoms, or which are obtainable from the polycondensation of at least one diamine and at least one dicarboxylic acid having in each case 2 to 44 carbon atoms, wherein the at least one diamine is preferably selected from the group of aliphatic diamines with 2 to 18 C atoms, the cycloaliphatic diamines with 7 to 22 carbon atoms and the at least one dicar bonsäure, preferably selected from the group of aliphatic dicarboxylic acids having 3 to 44 carbon atoms, cycloaliphatic dicarboxylic acids having 8 to 24 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms, and wherein the polycondensates or the polymers have a Aminoendgruppenüberschuß .
• (B) 0.01 part by weight to 2 parts by weight, based on the polyamide content of the molding composition, of a copper-containing stabilizer,
• (C) from 0.01 parts by weight to 3 parts by weight, based on the polyamide content of the molding composition, of at least one organic compound having metal-complexing groups selected from the group of acid amide, oxamide, oxalanilide, Hydrazine, acid hydrazide or hydrazone groups, the group of benzotriazoles, and the group of sulfur-containing phosphites, where the sum of components (A), (B) and optionally (C) gives 100 parts by weight,
• (D) 0 to 45 parts by weight, preferably 0 to 25 parts by weight, of one or more functionalized polymers, preferably from the group of the functionalized polyolefins and / or the functionalized polyolefin copolymers, in addition to the sum of the components (A), ( B) and optionally (C).

Around to achieve high adhesion to fluorine compounds and fluoropolymers is an excess according to the invention at amino end groups in component (A) necessary. To achieve the temperature resistance According to the invention, a copper-containing material is suitable Stabilizing agent (B).

Around the disadvantages regarding to eliminate the processability resulting from the combination from amino terminal excess and copper stabilization is the addition of metal deactivators (C) required.

The according to the invention as a coating of polyamide molding compound used by LWL, which optionally also consist of polyamide / polyamine copolymers or contain such can, contains the following polycondensates or polymers:

- component (A):

As polyamides advantageously polycondensates with amino terminal excess of aliphatic lactams, preferably C ₆ to C ₁₂ lactams or ω-aminocarboxylic acids having 3 to 44 carbon atoms, preferably 4 to 18 carbon atoms, or those of aromatic ω-aminocarboxylic acids having 7 to 20 carbon atoms.

Also suitable polycondensates with amino terminal excess of at least one Diamine and at least one dicarboxylic acid having in each case 2 to 44 carbon atoms. examples for such diamines are ethyldiamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,10-diaminodecane, 1,12-diaminododecane, m- and p-xylylenediamine, cyclohexyldimethyleneamine, Bis (p-aminocyclohexyl) methane and its alkyl derivatives.

Examples for dicarboxylic acids Malon, amber, glutar, adipic, pimelin, cork, azelain and sebacic acid, dodecane, 1,6-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic and naphthalenedicarboxylic acid.

Especially suitable polyamides with amino terminal excess for the as coating of LWL used molding compounds are Homopolyamide, selected from the group consisting of PA 6, PA 11, PA 46, PA 66, PA 12, PA 1212, PA 1012, PA 610, PA 612, PA 69, PA 6T, PA 6I, PA 10T, PA 12T, PA 12I, mixtures thereof, or copolymers based on these homopolyamides, where PA 11, PA 12, PA 610, PA 612, PA 1212, PA 9T, PA 10T, PA 12T or copolymers, in particular PA 12T / 12, PA 10T / 12, PA 12T / 610, PA 12T / 106, PA 10T / 610 and PA 10T / 106 are preferred. Farther can According to the invention also polyamides such as PA 6/66, PA 6/612, PA 6/66/610, PA 6/66/12, PA 6 / 6T, PA 66 / 6T, PA 6/61 and PA 6I / 6T.

The Polymers or the polycondensates of component (A) are preferred an amino end group content in the range of 20 to 300 μeq / g, in particular in the range of 40 to 300 μeq / g and a carboxyl end group content of less than 20 μeq / g, in particular smaller 15 μeq / g, respectively based on the polyamide content.

The Polyamides of component (A) have a relative viscosity measured in 0.5% m-cresol at 20 ° C, of less than 2.0, in particular less than 1.8, more preferably in the Range from 1.4 to 1.8, up.

The polyamide portion of the polyamide / polyamine copolymers are polymers, based on aliphatic C ₆ to C ₁₂ lactams, or on ω-aminocarboxylic acids having 3 to 44 carbon atoms, preferably having 4 to 18 carbon atoms, more preferably having 12 carbon atoms, or on aromatic aminocarboxylic acids having 7 to 20 carbon atoms.

this (Co) polyamides can for certain Purpose also other, usual Be added polymers. The (co) polyamides used can be conventional additives such as UV stabilizers, crystallization accelerators, fillers, Flame retardants and lubricants.

at the flame retardants are flame retardants the group of halogen-free flame retardants, such as nitrogen or phosphorus based flame retardants. According to the invention are particularly preferably salts of phosphinic acid and / or melamine cyanurates and / or trialkyl phosphates. By the Use of salts of phosphinic acids as a flame retardant in the polyamide molding compounds is a fire classification according to UL-94 Tests (Underwriter Laboratories) of V0 at a specimen thickness of 0.4 mm achieved. Suitable phosphinic acids for the preparation of the used Phosphinic acid salts are for example dimethylphosphinic acid, ethylmethylphosphinic, diethylphosphinic, Methyl-n-propylphosphinic acid, Methandi (methylphosphinic acid), Ethane-1,2-di (methyl phosphinic acid), Hexane-1,6-di (methylphosphinic acid), Benzene-1,4-di (methyl phosphinic acid), Methyl-phenyl-phosphinic acid, Diphenylphosphinic.

The phosphinic acid salts can be prepared by known methods, such as in EP 0 699 708 A1 described, are produced. In this case, the phosphinic acids are reacted in aqueous solution with metal carbonates, metal hydroxides or metal oxides, essentially resulting in monomers, depending on the reaction conditions may also polymeric phosphinic salts.

The phosphinates can Ions of metals from the 2nd or 3rd main or subgroup of the periodic table are preferred, the calcium and aluminum salts of the phosphinic used. The phosphinic acid salts can also be used in the form of their mixtures. They are preferred in Powder form applied to when incorporated into the polymer a to achieve good dispersion.

at the invention used Polyamines used to make the polyamide / polyamine copolymers used are polyvinylamines, polyamines alternating polyketones, dendrimers, linear or branched ones Polyethyleneimines. Is it linear or branched polyethyleneimines, so dispose these preferably over a molecular weight in the range of 500 to 25,000 g / mol, in particular in the range of 800 to 5,000 g / mol. Furthermore, they are distinguished by a viscosity ranging from 1,200 to about 5,000 mPa · s at 20 ° C.

Typically, the polyamide / polyamine copolymers are characterized by an amino end group concentration in the range of 40 to 300 μeq / g. In particular, they have a volume-flow rate (MVR, Melt Volume Rate) of 10 to 1000 cm ^3/10 min at 275 ° C / 5 kg in accordance with ISO 1133. The MVR is the volume-flow index in cm ³ per 10 minutes, as measured after a melting time of 4 minutes at 275 ° C and a load of 5 kg using a standard MVR device.

The used according to the invention Polyamines, in particular the polyethyleneimine preferably used is in amounts of 0.2 to 5 wt .-%, more preferably in one Amount of 0.4 to 1.5 wt .-%, as co-component in the polyamide / polyamine copolymer used, with the remaining co-shares of the copolymer preferred Made of polyamide.

- component (B) (0.01-2 Parts by weight):

The Stabilizing component (B) may be used in 0.01 to 2 parts by weight in the polyamide molding compound and comprises a copper-containing stabilizer.

Prefers is a copper-containing stabilizer an alkali metal halide and a copper (I) halide and / or a copper (I) stearate and / or a cuprous oxide, in particular a weight ratio of alkali metal halide to the sum of copper (I) compounds from 2.5: 1 to 100: 1 complied becomes.

In a preferred embodiment According to the invention, the component (C) is in a molar ratio to Sum of copper (I) compounds from 0.5: 1 to 3: 1 before. Especially Preferably, component (C) is at least about equimolar Amount of copper amount of component (B) in the production of added thermoplastic molding compositions.

Metal deactivators (MD) suitable according to the invention are those compounds which are capable of complexing metals, especially copper ions. These metal-complexing compounds contain the following groups: acid amide, oxamide, oxalanilide, hydrazine, acid hydrazide or hydrazone units or benzotriazoles. Compounds with such structures act as metal deactivators (see Plastics Additives Handbook, 4 ^th , Ed., 1993, chapter 2.4).

Examples of metal deactivators (MD) used according to the invention are (compare component (C)):
1,2,3-benzotriazole, tolyltriazole, 3- (salycyloylamino) -1,2,4-triazole, dodecanedioic acid, bis [2- (2-hydroxybenzoyl) hydrazide], 2 ', 3-bis [[3- [3 , 5-di-tert-butyl-4-hydroxyphenyl] propionyl]] - propiono-hydrazide and tris [2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert-butyl) phenyl-5-methyl] phenyl-phosphite.

- component (D) (0-45 Parts by weight, preferably 0-25 Parts by weight):

The Compounds used as component (D) are preferred selected from the group of polyolefins and / or polyolefin copolymers, with acrylic acid, Succinic anhydride and / or maleic anhydride are grafted. For example, compounds are used according to the invention as adhesion promoters or impact modifiers for polyamides Such as functionalized polyethylene with medium, low or very low density or linear low density polyethylene (LLD-PE), functionalized copolymers of ethylene and linear, branched or cyclic alkenes, e.g. B. functionalized ethylene / propylene copolymers.

The Components (A), (B) and optionally (C) add up to 100 Parts by weight. Component (D) is optional and becomes in addition to the 100 parts by weight of the sum of the components (A), (B) and optionally (C) added.

The preparation of the polyamides used according to the invention will now be shown using the example of PA 12:
Polymerization of laurolactam in the presence of from 0.05 to 3% by weight of one or more amines, such as monoamine, preferably di- or polyamines, such as hexamethylenediamine, dodecanediamine, laromin or polyethyleneimines, in addition from 5 to 20% by weight of water.
Printing phase: 1 to 6 h at 290 to 330 ° C, 20 bar
Polymerization at atmospheric pressure under nitrogen flow 260 to 290 ° C, 0.5 to 6 h.

The produced polyamides to a relative viscosity under 2.0, especially below 1.8 (0.5% m-cresol at 20 ° C) and a Amino end group content in the range of 20 to 300 μEq / g, especially of 40 up to 300 μeq / g and a carboxyl end group content of less than 20 μeq / g, in particular smaller 15 μeq / g.

The Compounding this polyamide with amino terminal excess and the remaining components are carried out on conventional twin-screw extruders at temperatures of 200 to 280 ° C. There is a good distribution of the metal deactivator by use a usual one Mixing screw with kneading elements or other mixing devices necessary.

The Standard conditions for The drying of the resulting granules are 24 h at 110 ° C in vacuo.

The explain the following examples without limiting the present invention.

Polyamide used according to the invention:

Table 1: amine-terminated polyamide 12 (EMS-Chemie AG) Relative viscosity, 0.5% in m-cresol 1.65 MVR, 230 ° C / 2.16 kg cm ^3/10 min 65 Amino groups (ΜÄqu. / G) 100 Carboxyl end groups (ΜÄqu. / G) 10

Table 2: Behavior of the polyamide molding compound after different drying time and different residence time in the melt before the MVR measurement (see below)

Legend:

• MD1 = dodecanedioic acid bis [2- (2-hydroxybenzoyl) hydrazide]
• MD2 = 2 ', 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide
• MD = metal deactivator

At the granules dried with standard conditions became the reference values for the relative viscosity (0.5% m-cresol) and the MVR (230 ° C, 2.16 kg, after 4 minutes in the melt).

to Determination of change the melt polyamide molding material became the MVR even after 10 and measured in the melt for 20 minutes.

At the melting cones of the MVR measurements (granule drying with standard conditions) became the relative viscosity (0.5% m-cresol).

parts of the granules were additional 24 at 110 ° C dried and then both measurements (relative viscosity and MVR) carried out.

The Assessment of the polyamide molding compound under temperature load is in Table 2 below.

The Processability of the polyamide molding composition of the comparative example is bad because the processing temperature is raised because of the increased viscosity must be, tubers form and viscosity during the Processing varies.

at This is not the case with the polyamide molding compositions of Examples 1-3 and thus they show a good processability.

The Adhesion of all polyamide molding compounds without prior storage is good. After storage at 125 ° C over 3000 h only the polyamide molding compositions of Examples 1-3 the requirement.

The protective cover ( 4 ) From the polyamide molding composition of Comparative Example breaks in the buckling test after storage.

In the following 1 to 3 the tensile tensile strength after heat storage at 100, 120 and 140 ° C is shown. The figures show the change in the impact normalized to the starting value as a function of the storage time.

The Measurements of both materials start at the value 1. The Values of the comparative example (see Table 2) are in the beginning strong, so that the trend line of linear regression is not through the starting value leads. In the example of the invention 2, this is not due to the better stability of the composition the case.

The diagrams in the 1 to 3 show that the metal deactivator used according to the invention also positively influences the mechanical stability of the molding composition and not only improves its processability.

The present invention also relates to an optical fiber ( 1 ) with at least one fiber core ( 2 ) with a single or multi-layered cladding. ( 3 ) and at least one fiber optic cable ( 2 . 3 ) enclosing protective cover ( 4 ), whereby the cladding ( 3 ) or at least its outer layer of a layer based on fluorine compounds or of fluoropolymers and the protective cover ( 4 ) consist of polyamide, wherein the at least one protective cover ( 4 ) consists of a layer based on the polyamide molding compositions according to one or more of claims 1 to 17.

According to the invention, the protective cover adjacent to the cladding of fluorine compounds or fluoropolymers (US Pat. 4 ) also consist of a polyamide / polyamine copolymers.

In a particular embodiment of the invention, a further to the protective cover ( 4 ) adjacent protective cover ( 5 ) of polyamide molding compositions, but without Aminoendgruppenüberschuss the polycondensates or polymers may be arranged.

In another embodiment of the invention, the to the protective cover ( 4 ) adjacent protective cover ( 5 ) consist of a polymer other than polyamide. As materials for the protective cover ( 5 ) can be used in the present invention include: polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyurethane, polyoxymethylene, polyethylene, polyethylene copolymers, polypropylene, polypropylene copolymers, fluoropolymers, fluoropolymer compounds, ethylene tetrafluoroethylene copolymer, polyvinylidene fluoride or crosslinked polymers.

If necessary, for. B. when using a polyolefin as a protective cover ( 5 ), between the protective cover ( 4 ) and the protective cover ( 5 ) still a primer layer are arranged to realize the necessary adhesion of the protective cover ( 5 ) on the protective cover ( 4 ). For this purpose, known, conventional adhesion promoters can be used for polyamides which are stabilized with z. B. b ₁ , b ₂ or b ₃ (see claim 1, component B) may be equipped.

When according to the invention for the protective cover ( 5 ) polyethylene can also be functionalized with carboxyl, anhydride or imide polyethylene or polyethylene copolymer.

at crosslinked polymers can be crosslinked by peroxide, silane or radiation crosslinking done. As crosslinkable polymers come inter alia: polyethylene or polyethylene copolymers in each case with high, medium, low or very low density or linear low density polyethylene (LLD-PE) or metallocene polyethylene or polypropylene or polypropylene copolymers, such as polypropylene copolymers with Ethylene-propylene rubber or blends of polypropylene with ethylene-propylene rubber or Polyurethane.

In a particular embodiment, the protective cover ( 5 ) consist of a fluoropolymer, a fluoropolymer compound or a crosslinked polymer, in particular a radiation-crosslinked polymer.

The fiber core ( 2 ) According to the invention consists of glass, polycarbonate (PC), fluoropolymers, polyglutarimide or blends of polycarbonate and polymethylmethacrylate (PMMA).

In one embodiment of the invention, the optical cable contains both a protective cover ( 4 ) as well as a protective cover ( 5 ). The protective cover ( 5 ) may have color markings in the form of at least one strip or multiple strips. The color markers are temperature resistant and can be applied during extrusion.

The optical fiber according to the invention ( 1 ) is characterized in that the outer diameter of the optical waveguide (LWL) 2.3 is in the range of 75 to 3000 microns.

In general, the outer diameter of the cladding ( 3 ) 2000 ± 120 μm or 1000 ± 60 μm or 750 ± 45 μm or 500 ± 30 μm or 230 ± 20 μm or 125 ± 10 μm.

In the particular embodiment, the diameter of the fiber core ( 2 ) at least 8 microns, ma ximal 1000 microns, preferably 10 to 100 microns, more preferably 20 to 80 microns smaller than the corresponding outer diameter of the cladding ( 3 ).

The outer diameter of the optical fiber ( 1 ) may range between 0.15 and 5 mm.

In another embodiment, the optical fiber ( 1 ) contain a plurality of optical waveguides (LWL) 2.3.

The schematic structure of a wire according to the invention ( 1 ) is in 4 shown.

Under a core is the entire composite of fiber core, cladding and protective cover or Protective covers too understand. While the terms fiber, fiber, POF and GOF only on the fiber core with cladding.

As Hammam-protected polyamide for protective cover ( 5 ) include, for example, Hamm-protected polyamides, such as PA 12 or polyamide elastomers, such as polyetheramides, polyetheresteramides or polyesteramides.

Important in a vein is a defined liability.

• • Haftung von Schutzhülle (4) auf dem Cladding (bei ID₄ 1 mm und AD₄ 1,5 mm): ≥ 50 N bei Isolationslänge l_{Schutzhülle4} = 30 mm
• • Haftung von Schutzhülle (5) auf Schutzhülle (4) (bei ID₅ 1,5 mm und AD₅ 2,3 mm): 20 ± 10 N bei Isolationslänge l_{Schutzhülle5} = 30 mm

AD = Außendurchmesser, ID = InnendurchmesserThe requirements for the adhesion of the protective covers are:

• • adhesion of protective cover ( 4 ) on the cladding (for ID ₄ 1 mm and AD ₄ 1.5 mm): ≥ 50 N for insulation length l _{Protective cover4} = 30 mm
• • adhesion of protective cover ( 5 ) on protective cover ( 4 ) (for ID ₅ 1.5 mm and AD ₅ 2.3 mm): 20 ± 10 N for insulation length l _{Protective cover5} = 30 mm

AD = outer diameter, ID = inner diameter

• • Teilweises Abisolieren der Schutzhülle (4) einer 50 mm langen Ader derart, dass die Länge der verbleibenden Schutzhülle (4) ca. 30 mm beträgt.
• • Durchführung des abgesetzten Teils der Ader durch die Bohrung einer Messingplatte, wobei der Bohrungsdurchmesser in etwa 0,1 mm größer ist als der Außendurchmesser der Schutzhülle (4).
• • Einspannen des abgesetzten Endes der Ader in eine Zugprüfmaschine (Abzugsgeschwindigkeit 100 mm/min) und
• • Messung der Zugkraft, bei der sich die Schutzhülle (4) von dem darunter liegenden Cladding löst.

To check the adhesion of the protective cover on the cladding, the following test method was used:

• • Partial stripping of the protective cover ( 4 ) of a 50 mm long wire such that the length of the remaining protective cover ( 4 ) is about 30 mm.
• • Passing the remote part of the wire through the bore of a brass plate, the bore diameter is about 0.1 mm larger than the outer diameter of the protective cover ( 4 ).
• • Clamping the offset end of the wire in a tensile testing machine (withdrawal speed 100 mm / min) and
• • measurement of the tensile force at which the protective cover ( 4 ) releases from the underlying cladding.

Examples of the dimensions of different inventive wires:

Polymer optical fiber (POF)

• • POF-Kerndurchmesser 980 μm
• • Cladding Fluorpolymer WD: 20 μm, AD: 1 mm
• • Schutzhülle 1 WD: 0,25 mm, ID: 1 mm, AD: 1,5 mm
• • Schutzhülle 2 WD: 0,35 bis 0,4 mm, ID: 1,5 mm, AD: 2,3 mm

WD = WanddickeFrom the inside to the outside:

• • POF core diameter 980 μm
• • Cladding fluoropolymer WD: 20 μm, OD: 1 mm
• • Protective cover 1 WD: 0.25 mm, ID: 1 mm, OD: 1.5 mm
• • Protective cover 2 WD: 0.35 to 0.4 mm, ID: 1.5 mm, OD: 2.3 mm

WD = wall thickness

Glass Optical Fiber (GOF)

• a) Polymer Cladded Silica (PCS Fiber): From Inside to the outside: • Core diameter 200 μm • Cladding diameter 230 μm • Protective cover diameter 500 μm to 2000 μm
• b) Hard Cladded silica (HCS fiber): From inside to outside: • Core diameter 125 μm to 400 μm • Cladding diameter 140 μm to 430 μm • Protective cover diameter 250 μm to 730 μm

Production of the casing:

to optimal light transmission the vein must Core and cladding from external influences and damage protected become. For this purpose, the fiber is either individually or in a bundle with a coat, hereinafter referred to as a protective cover, made of plastic such as As polyethylene (PE), polyvinyl chloride (PVC), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-vinyl acetate copolymer (EVA), polyamide (PA), polytetrafluoroethylene (PTFE) or other material combinations sheathed. The protective cover can one or more layers and different wall thicknesses, also in the individual layers.

The cover is applied in a continuous extrusion process. Behind the unwinder is an extruder arranged, with which the material for the cover transferred to the fiber becomes. After the serving the vein is in a cooling tank chilled and fed to a rewinder (A. Weinert, Plastic Optical Fiber: Fundamentals, Components, Installation, Publicis MCD Verlag, Erlangen and Munich, 1998, P. 51).

• 1. in separaten Schritten auf die jeweils zuletzt hergestellte äußere Schicht erfolgen
• 2. in einer Extrusionslinie mit verschiedenen Extrudern nacheinander z. B. im sogenannten Tandemverfahren erfolgen, wie in 5 beschrieben ist.
• 3. durch Coextrusion von mehr als einer Schutzhülle gleichzeitig erfolgen.

The production of further sheathing can either:

• 1. take place in separate steps on the last produced outer layer
• 2. in an extrusion line with different extruders successively z. B. in the so-called tandem method, as in 5 is described.
• 3. take place simultaneously by coextrusion of more than one protective cover.

Special Attention in the production of the cladding of optical fibers must the Temperature, the pressure and the tensile forces are devoted. By these parameters can be the optical attenuation and the geometric Shape affects be what the light transmission quality of the wire impair can.

at the extrusion processing for the first protective cover, which is directly on the cladding, it is due to a POF the temperature sensitivity of the polymer important to the melt for the Materials of the protective cover if possible low temperature is extruded, approximately between 160-220 ° C, otherwise the Fiber damaged becomes. For GOF and other fibers can reach the processing temperature in the range from 160-250 ° C.

The Apply the protective covers with a hose coating tool (plastic technology, Cable and insulated cables, VDI-Verlag, Dusseldorf, 1984, p. 71). The Covers will be outside in this case of the tool on z. B. the cladding of the fiber core applied. In this method, no pressure on the supplied fiber core exercised with cladding. Even with coextrusion no pressure is applied.

About suitable Geometry choice of the tool (nozzle and core) can be the setting of a defined adhesion between POF and protective cover and this and other protective covers due to optimal heat transfer favored become.

The GOF and other protective covers can be, in contrast to POF, due to the lower temperature sensitivity additionally Preheat with a cylindrical heater to achieve the desired adhesion to achieve.

Claims (28)

Use of thermoplastic polyamide molding compositions having a continuous temperature resistance of at least 6000 hours at 125 ° C. as a coating of optical waveguides which comprise a cladding based on fluorine compounds or of fluoropolymers, comprising the following components: (A) Polyamides which are polymers or polycondensates on aliphatic lactams, preferably based on C ₆ to C ₁₂ lactams, or on ω-aminocarboxylic acids having 3 to 44 carbon atoms, preferably having 4 to 18 carbon atoms, more preferably having 12 carbon atoms, or on aromatic aminocarboxylic acids having 7 to 20 carbon atoms, or which are obtainable from the polycondensation of at least one diamine and at least one dicarboxylic acid having in each case 2 to 44 carbon atoms, where the at least one diamine is preferably selected from the group of aliphatic diamines having 2 to 18 carbon atoms, and cycloaliphatic diamines having 7 to 22 C atoms and the at least one Dica Rbonsäure, preferably from the Group of aliphatic dicarboxylic acids having 3 to 44 carbon atoms, cycloaliphatic dicarboxylic acids having 8 to 24 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms is selected, and wherein the polycondensates or the polymers have a Aminoendgruppenüberschuß, (B) 0 , 01 parts by weight to 2 parts by weight, based on the polyamide content of the molding composition, of a copper-containing stabilizing agent, (C) 0.01 parts by weight to 3 parts by weight, based on the polyamide content of the molding compositions Composition, at least one organic compound having metal-complexing groups selected from the group of the acid amide, oxamide, oxalanilide, hydrazine, acid hydrazide or hydrazone groups, the group of benzotriazoles, as well as the group of sulfur-containing phosphites, wherein the Total of components (A), (B) and optionally (C) 100 parts by weight, (D) 0 to 45 parts by weight, preferably 0 to 25 parts by weight, one or more functionalized polymers, bevo R ranges from the group of functionalized polyolefins and / or functionalized polyolefin copolymers, in addition to the sum of components (A), (B) and optionally (C). Use of the thermoplastic polyamide molding compounds according to claim 1, characterized in that the polymers or polycondensates of component (A) has an amino end group content in the range of 20 up to 300 μeq / g, in particular in the range of 40 to 300 μeq / g and a carboxyl end group content of less than 20 μeq / g, in particular smaller 15 μeq / g, respectively based on the polyamide content. Use of the thermoplastic polyamide molding compounds according to claim 1 or 2, characterized in that the polyamide of component (A) a relative viscosity, measured in 0.5% m-cresol at 20 ° C, of less than 2.0, in particular less than 1.8, more preferably in the Range from 1.4 to 1.8. Use of the thermoplastic polyamide molding compounds according to one of the preceding claims 1 to 3, characterized in that it is in the diamines to at least one or more selected from the group consisting ethyldiamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,10-diaminodecane, 1,12-Diaminododecane, m- and p-xylylenediamine, cyclohexyldimethyleneamine, bis (p-aminocyclohexyl) methane and / or their alkyl derivatives, and / or that it is at the dicarboxylic acids one or more, selected from the group consisting of malon, succinic, glutaric, adipic, Pimelic, cork, azelaic and sebacic acid, dodecanedicarboxylic acid, 1,6-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, is. Use of the thermoplastic polyamide molding compounds according to one of the preceding claims 1 to 4, characterized in that it is the polyamides of component (A) to homopolyamides selected from the group consisting made of PA 6, PA 11, PA 46, PA 66, PA 12, PA 1212, PA 1012, PA 610, PA 612, PA 69, PA 6T, PA 6I, PA 107, PA 127, PA 12I, mixtures thereof, or copolymers based on these homopolyamides, wherein PA 11, PA 12, PA610, PA612, PA 1212, PA 9T, PA 107, PA 127 or copolymers, in particular PA 127/12, PA 107/12, PA 127/610, PA 127/106, PA 107/610 and PA 107/106 are preferred. Use of the thermoplastic polyamide molding compounds according to one of the preceding claims 1 to 5, characterized in that it is the polyamides PA 6/66, PA 6/612, PA 6/66/610, PA 6/66/12, PA 6/67, PA 66/67, PA 6 / 6I and PA 6I / 6T. Use of the thermoplastic polyamide molding compositions according to one of the preceding claims 1 to 6, characterized in that the polyamides of component (A) are polyamide / polyamine copolymers whose polyamide component contains polymers which are based on aliphatic C ₆ to C ₁₂ Lactams, or based on ω-aminocarboxylic acids having 3 to 44 carbon atoms, preferably having 4 to 18 carbon atoms, more preferably having 12 carbon atoms, or based on aromatic aminocarboxylic acids having 7 to 20 carbon atoms. Use of the thermoplastic polyamide molding compounds according to one of the preceding claims 1 to 7, characterized in that it is the polyamides are polymers containing additives such as UV and heat stabilizers, Crystallization accelerators, plasticizers, flame retardants, impact modifiers, fillers and lubricants are added. Use of the thermoplastic polyamide molding compositions according to Claim 8, characterized in that the flame retardants are flame retardants from the group of halogen-free flame retardants, in particular nitrogen or phosphorus-based flame retardants, especially be Preferably, salts of phosphinic acids and / or melamine cyanurate and / or triaryl phosphates is. Use of the thermoplastic polyamide molding compounds according to one of the preceding claims 1 to 9, characterized in that it is the polyamines, used to make the polyamide / polyamine copolymers, polyvinylamines, polyamines of alternating polyketones, dendrimers, is linear or branched polyethyleneimines. Use of the thermoplastic polyamide molding compounds according to claim 10, characterized in that it is in the polyamines, the be used for the preparation of the polyamide / polyamine copolymers, linear or branched polyethyleneimines having a molecular weight in the range from 500 to 25,000 g / mol, preferably from 800 to 5,000 g / mol, preferably with a viscosity in the range of 1200 to 5000 mPa ∙ s, at 20 ° C, is. Use of the thermoplastic polyamide molding compounds according to one of the preceding claims 1 to 11, characterized in that the molding composition polyamine, in particular Polyethyleneimine, in an amount of 0.2 to 5 wt .-%, preferably in an amount of 0.4 to 1.5 wt .-%, as co-component in the polyamide / polyamine copolymer contains wherein the remaining Co contents of the copolymer consist of polyamide. Use of the thermoplastic polyamide molding compounds according to one of the preceding claims 1 to 12, characterized in that the copper-containing stabilizing agent (B) an alkali metal halide and a copper (I) halide and / or a copper (I) stearate, and / or a copper (I) oxide, in particular a weight ratio of alkali metal halide to the sum of the copper (I) compounds of 2.5: 1 to 100: 1 is present. Use of the thermoplastic polyamide molding compounds according to one of the preceding claims 1 to 13, characterized in that the compound is complexed with metal Groups (C) in a molar ratio to the sum of the copper (I) compounds from 0.5: 1 to 3: 1, in particular component (C) in at least about equimolar Amount of copper amount of component (B) is present. Use of the thermoplastic polyamide molding compounds according to one of the preceding claims 1 to 14, characterized in that as compound (C) N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazide and / or 2,2'-oxamido-bis [ethyl3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and / or 3- (Salycyloylamino) -1,2,4-triazole and / or 1,2,3-benzotriazole and / or tolyltriazole and / or dodecanedioic acid bis [2- (2-hydroxybenzoyl) hydrazide] and / or tris [2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert-butyl) -phenyl-5-methyl] -phenyl-phosphite is used. Use of the thermoplastic polyamide molding compounds according to one of the preceding claims 1 to 15, characterized in that component (D) is selected from the group of polyolefins and / or polyolefin copolymers, with acrylic acid, succinic anhydride or maleic anhydride grafted are. Optical wire ( 1 ) with at least one optical waveguide (LWL) ( 2 . 3 ), consisting of a fiber core and a single or multi-layered cladding ( 3 ) and at least one of the optical fibers (LWL) ( 2 . 3 ) enclosing protective cover ( 4 ), whereby the cladding ( 3 ) or at least its outer layer of a layer based on fluorine compounds or of fluoropolymers and the protective cover ( 4 ) consist of polyamide, characterized in that the at least one protective cover ( 4 ) consists of a layer based on the polyamide molding compositions according to one or more of claims 1 to 16. Optical wire ( 1 ) according to claim 17, characterized in that adjacent to the cladding of fluorine compounds or fluoropolymers protective cover ( 4 ) consists of a polyamide / polyamine copolymers. Optical wire ( 1 ) according to claim 17 or 18, characterized in that at least one further to the protective cover ( 4 ) adjacent protective cover ( 5 ) of polyamide molding compositions, according to any one of claims 1 to 19, but without Aminoendgruppenüberschuß the polycondensates or polymers, is arranged. Optical wire ( 1 ) according to claim 17 or 18, characterized in that the to the protective cover ( 4 ) adjacent protective cover ( 5 ) consists of a polymer other than polyamide. Optical wire ( 1 ) according to claim 20, characterized in that the to the protective cover ( 4 ) adjacent protective cover ( 5 ) consists of a fluoropolymer, a fluoropolymer compound or a crosslinked polymer, in particular a radiation-crosslinked polymer. Optical wire ( 1 ) according to claims 17 to 21, characterized in that the fiber core ( 2 ) made of glass, polycarbonate (PC), fluoropolymers, polyglutarimide or blends of polycarbonate (PC) and polymethylmethacrylate (PMMA). Optical wire ( 1 ) according to claims 17 to 22, characterized in that the outer diameter of the optical waveguide (LWL) ( 2 . 3 ) is in the range between 75 to 3000 microns. Optical wire ( 1 ) according to claims 17 to 23, characterized in that the outer diameter of the cladding ( 3 ) Is 2000 ± 120 μm or 1000 ± 60 μm or 750 ± 45 μm or 500 ± 30 μm or 230 ± 20 μm or 125 ± 10 μm. Optical wire ( 1 ) according to claims 17 to 24, characterized in that the diameter of the fiber core ( 2 ) is at least 8 microns, at most 1000 microns, preferably 10 to 100 microns, more preferably 20 to 80 microns smaller than the corresponding outer diameter of the cladding ( 3 ). Optical wire ( 1 ) according to one of the preceding claims 17 to 25, characterized in that the outer diameter of the optical fiber ( 1 ) is in the range between 0.15 mm and 5.0 mm. Optical wire ( 1 ) according to one of the preceding claims 17 to 26, characterized in that it comprises a plurality of optical waveguides (LWL) ( 2 . 3 ) contains. Optical wire ( 1 ) according to one of the preceding claims 17 to 27, containing both a protective cover ( 4 ) as well as a protective cover ( 5 ), characterized in that the protective cover ( 5 ) Has color markings in the form of at least one strip, wherein the color markers are temperature-resistant and have been applied during the extrusion.