CN101023137B

CN101023137B - Use of stabilized thermoplastic polyamide molding compounds as a coating for optical waveguides

Info

Publication number: CN101023137B
Application number: CN2005800318140A
Authority: CN
Inventors: 乔治·斯托普曼; 赛宾·贝里拉姆; 安德烈·斯特茨
Original assignee: EMS Chemie AG
Current assignee: EMS Chemie AG
Priority date: 2004-09-21
Filing date: 2005-09-20
Publication date: 2011-03-30
Anticipated expiration: 2025-09-20
Also published as: DE102004045775A1; DE102004045775B4; WO2006032465A1; CN101023137A; JP2008513818A; KR20070067158A

Abstract

The invention relates to the use of stabilized, thermoplastic polyamide molding compounds as a protective layer for coating optical waveguides possessing fluoride or fluoropolymer based cladding. The inventively used polyamide molding compound exhibits good adhesion to the fluoride or fluoropolymer based cladding. It also possesses a high permanent temperature resistance of at least 6000 hours at125 DEG C. The current invention also relates to optical strands comprising at least one fiber core, single-layered or multi-layered cladding and at least one protective sleeve which encompasses the optical waveguide and which is made of stabilized, thermoplastic polyamide molding compounds.

Description

Stable thermoplastic polyamide molding compounds is as the application of coating for optical waveguides

The present invention relates to the application of polyamide molding material; more particularly; relate to the application of stable thermoplastic polyamide mold material as the protective layer of optical waveguides (hereinafter to be referred as LWL) coating, described optical waveguides has a coating based on fluorine cpd or fluoropolymer.

The polyamide molding material used according to the present invention has good adhesion characteristics for described coating based on fluorine cpd or fluoropolymer.In addition, the used polyamide molding material of its present invention has under 125 ℃ of temperature at least 3000 hours high thermostability.

The invention still further relates to a kind of fiberguide cable, this cable comprises the fiber core of at least one coating that is arranged in single or multiple lift structure and at least one round LWL, the sleeve pipe of being made by stable thermoplastic polyamide mold material.

Fiber-optic cable is applicable to field of telecommunications great amount of data transmission and glitch-free data transmission, promptly is not subjected to the data transmission of electromagnetic field effects.When being used for distance and being no more than the transmission of about 150 meters short-range data, except using relatively costly glass optical fiber (GOF), also can use cheap plasticity-optical waveguides, i.e. polymer optical fiber (POF).

In automobile engineering/vehicle manufacturing (at vehicle, aircraft, the data in the steamer etc. and the transmission of signal) field, also always be to use above-mentioned POF.Plasticity-optical waveguides (K-LWL) is normally by a kind of polymer optical fibre core, and coating and sleeve pipe form.

Up to now, the polymer optical fiber that had used already is to be made of polymethylmethacrylate (PMMA) core.Because the second-order transition temperature of PMMA is 95-100 ℃, makes the use of this class material be limited in being lower than 90 ℃ temperature.The glass light fiber core of single line or multicore, just bundled glass light fiber core, the existing surrogate that uses when being developed to a kind of comparatively high temps.

The coating of polymer optical fiber can form one or more layers.Mainly by the material of fluorine-containing plastics as coating, its specific refractory power is between 1.33 to 1.42.This specific refractory power is suitable for specific refractory power (the specific refractory power η of PMMA fiber core _PMMA=1.49;

).The optical attenuator of this K-LWL adds up to 130 to 150dB/km usually, and (λ=650nm), minimum bending radius is about 5 to 10mm.Can define and/or measure this decay as follows: use a transmitted light to measure usually, then according to following formula, the energy level P when beginning by LWL ₁Energy level P when finishing with LWL ₂The radiometer of luminous energy calculate the attenuation decibel (dB) of a LWL.

(a)＝10·log?P ₁/P ₂.

In order to measure this decay, must measure two kinds of energy levels.P ₁Be easy to measure by annex at one of this fiber ends enough big receptor diode.Energy level P when LWL begins ₁Can not and P ₀Obscure P ₀Be to be access in LWL and to become P with the loss coupling ₁, P ₁Can only be to measure (about the further details of attenuation measurement, we roll up 111 at " Kunststoffe in der Kabeltechnik " Hans-J.Maier, 3.Edition, existing mentioning among the number 4.4.2) indirectly.

In order to protect sensitive K-LWL not to be subjected to mechanical effect, the influence of heat effect and chemical action needs to use a plastic material to encase it, and this plastic material can be one or more layers and have telescopic function (referring to WO 99/12063).According to needed use or application, this sleeve pipe is by for example polyethylene, polyvinyl chloride, and ethyl vinyl acetate multipolymer or polymeric amide are formed.In order to prevent that outside light from penetrating into this polymer optical fiber, also can comprise coal smoke (soot) in the sleeve pipe.Be used for this telescopic material, such as polymeric amide, urethane or polyoxymethylene and so on can add fire retardant (DE9209018U).

EP 1,376, a kind of optical fiber is disclosed among the 156A2, it has a fiber core and one or more layers sleeve pipe, comprise more layer in addition: the exterior layer of an inside, it sticks on the shell of fiber and by a kind of molding compounds firmly forms, and this compound comprises polymeric amide, and it has zero-shear viscosity under the condition of 400 to 6000Pas pressure and 220 ℃ of temperature; The exterior layer of an outside, it sticks on the exterior layer of above-mentioned inside, has the drawing force of maximum 30N, and it is made up of polyamide molding material, and comprises following component:

A) polymeric amide of 20-95% (weight)

B) fire retardant of 5-45% (weight) and

C) the modified impact agent of 0-60% (weight).

According to EP 1376156 A2, the fire retardant that comprises in the moulding material of the exterior layer of described outside can be any fire retardant that is usually used in polyamide molding material.

In order to obtain having the stable on heating polymer optical fiber of improvement, know (referring to DE 3843310C2) and can make this fiber core from a kind of silicone resin of heat setting type, the material that wherein is used for this fiber core is to be injected in the two-layer cage walls under uncured condition in its production process.Be extruded at the same time out and closely interconnecting by this two-layer cage walls of extrusion process, skin wherein becomes opaque owing to having added coal smoke.

In the automobile industry field, normally polymeric amide is used as shell material, because it has satisfied relevant mechanical stability (mainly being tensile strength and resistance to pressure), and realize the previous maximum operation (service) temperature and the requirement of chemical stability.Yet the problem that described polymeric amide sleeve pipe exists is that they are relatively poor for the adhesivity of the optical waveguides with coating of being made up of fluoropolymer.

(just fiber core adds superstratum when optical fiber; add one deck sleeve pipe at least) be in the environment of temperature generation great variety; for example at the passenger carriage (passenger compartment) of Motor vehicles or in nacelle; this only very weak adhesivity for protective casing can produce adverse influence; because different thermal expansion behavior and only be the very poor viscosity of polymeric amide to fluoropolymer; described LWL is that fiber core adds superstratum, can take place to move with respect to this telescopic.Its result is exactly that the front of for example LWL can increase to a certain extent to the distance that transmits and receives element (light emitting diode/scalp acupuncture diode), and produces the high strength loss that can not be allowed to, and also may cause the fault of data transfer path.In addition, too far away if LWL shifts out sleeve pipe, also there is the danger that causes emission or receiving element infringement.

In order to suppress " piston (pistoning) " effect of this LWL of being referred to as, use junctor, connecting rod or fixer, it acts on sleeve pipe and shows bigger clamping force or crimping power, has therefore increased the frictional force between sleeve pipe and the LWL.Yet, because the distortion in the frictional belt between fiber core and coating that this effect causes can cause the increase of signal attenuation.

The decomposition of the protective layer in the junctor has prevented this " piston " effect, and still, owing to use the unsuitable processing of the edger with a blade, it has hidden the danger of coating corrupted again when assembling.

Can also be by the suitable fixedly K-LWL of a conical boring on the connector shell, with clamping force or the crimping power that is reduced in this junctor in the optical fiber.Like this, suggestion can be by using the front of hot-plate fusion K-LWL, the boring that the fusion globule that forms is compressed into the junctor of taper, thus K-LWL is anchored on firmly in the shell of junctor.Yet in the zone of this fused and this distortion, the geometrical shape of K-LWL may deviate from the geometrical shape of the cylinder that can make its total reflection in fact, and therefore the rising of loss of strength has taken place in connector shell.

EP 0,649, and 738 A1 disclose by add poly-glutarimide to polymeric amide, can produce being connected of a kind of power of enforcement locking polymeric amide and fluorinated ethylene propylene.So, for example, by using a step extrusion process to make the veneer sheet (laminate) of pair of lamina and by polymeric amide by polymeric amide and fluorinated ethylene propylene, the viscosity promotor layer of forming by the mixture of the poly-glutarimide of polymeric amide, make trilaminar veneer sheet with fluorinated ethylene propylene, can, for example, poly-glutarimide (polyglutarimide) be exactly well-known Polymethacrylimide (polymethacrylimides) (PMMI).

For the expressing technique of K-LWL, this directly is locked in sleeve pipe on the coating to it is highly important that under alap temperature processing.The second-order transition temperature of fluoropolymer of forming this coating is near fiber core material (PMMA; 106 ℃) second-order transition temperature, just between 80 to 120 ℃.This coating extremely thin (about 10 μ m) can accurately adjust its optical property, and they is easy to be subjected to the influence and/or the change of heat or chemical action.Therefore, the extrusion coated of carrying out this shell material under its degree of depth fused temperature must be made as far as possible.

EP 1,171,786 contriver reported PMMI (pleximide130, manufacturers: German) and low-viscosity polyamides 12 (relative viscosity 1.65, according to 0.5% in meta-cresol) combined experiments, find in view of the above because high mixing viscosity causes the optical attenuator of very high melt temperature and this fiber irreversibly to increase at this when the K-LWL-Ka cable is extruded.Therefore, polymeric amide 12/PMMI mixture is for being useless as the telescopic material.

In all others, at EP 0,649, the embodiment part of 738 A1, the 6th page, the poly-glutarimide of enumerating in the form has very high viscosity, can not be as the middle layer of three layer process, or conduct and polymeric amide 12 blended compositions and be used for extruding of K-LWL.

EP 0,767, and 190A1 discloses polymeric amide viscosity promotor and has been applied to produce multiple layer polymer or multitube road (pipings), promptly is used for the gasoline or the cooling line of automobile industry.Polymeric amide used herein is not low-viscosity usually.In addition, do not need this layer to have optical property.At EP 0,767, disclosed polymeric amide has excess of ammonia base terminal group among 190 A1.

Have at EP 0,767, in the K-LWL extrusioning experiment of the disclosed viscosity promotor of 190 A1 (this patent is finished by the present inventor), reached the extrusion temperature of allowing, this fiber core just can be by thermal damage like this.Yet when thermmal storage (80 ℃, 24 hours) subsequently, the skin of this fiber is that sleeve pipe can the browning look.This obviously is because monomer diffuses into sleeve pipe and taken place due to the chemical reaction.This painted optical characteristics of fiber that makes weakens.Thereby according to EP 0,767, the polyamide molding material of 190 A1 is excluded as the viscosity promotor or the protective layer that are used for K-LWL and glass optics LWL.

At EP 0,239, disclosed optical fiber among 935 B1, basically form by the core of a silica glass or opticglass and the interlayer of a plastic material, this interlayer is made by plastic material, the soluble multipolymer curing of its solvent for fluoroolefin and alkyl vinyl ether gets, and wherein said multipolymer has curable site and comprises the fluorine relevant with the fluoroolefin unit of 10wt% at least.

At EP 0,883, a kind of optical fiber is disclosed among 001 A1, it has a quartzy core and a core that coats polymer coating (PCF), and it demonstrates the multilayered structure of multiple different polymkeric substance.Compare with the junctor of curved (" crimp type "), at EP 0,883, disclosed broadband P CF shows obvious less consumption among 001 A1.Therefore, this PCF can be used for data corresponding, for example, has ATM-LAN, the connection of Fast Ethernet.

At EP 0,749, a kind of polymeric amide fusion cellulosic binder is disclosed among 463 B1, wherein this fusion tackiness agent comprises based on the polymeric amide as the dimer (fatty acid) yl of main component, with the fatty acid monomer part that contains 12 to 22 carbon atoms with contain 2 at least 2 alkaline primary amine parts to 40 carbon atoms.It all is the polymeric amide that mainly contains the N-terminal base that the tackiness agent that is used for this polyamide thermoplastic is gone up substantially.At EP0, disclosed fusion tackiness agent causes a higher metal-stripping intensity and the anti-vaseline of an enhanced among 749,463 B1.Compare with the polymeric amide that does not have to fill, its further advantages are more to help vapour permeability, just lower vapour permeability.Because these features, these thermoplastic binder are suitable for to each other can be as the bonding between metal and plastics with metal, especially with polyolefine and polyester with the same with polyvinyl chloride.Further use the coating that is on the bonding cable, concrete whereby application is fiber optic cable and cable.

At GB 2,198, the application of the machinable polyamide compound of telescopic thermoplasticity that is used for the production optical waveguides is disclosed among 258 A1.This sleeve pipe is made up of the mixture of 0-95wt% polymeric amide 12 and 50-5wt% polyamide elastomer and another polymeric amide of 0-95% and/or copolyamide basically.This polyamide elastomer has been represented the integral part of this mixture, can be polyetheramides, for example at DE-A-3006961 or disclosed in CH-A-0656135, or a kind of polyester ether acid amides, for example disclosed in DE-A-2936977 or DE-A-3428404.

In JP 04127107, disclose a kind of telescopic optical waveguides that on coating, has, can prevent so-called " piston " effect.At this moment, this polymkeric substance is gone up by polyethylene substantially and is formed, and ethyl acetate/vinyl acetate copolymer that it has comprised 0.1-10wt% is used for main coating material.

The present patent application people also do not have a kind of thermoplastic multilayer veneer sheet has been described among the disclosed patent application CH-00000/03, be made up of based on fluoropolymer the first layer and at least one second layer at least one, the second layer to small part directly is connected on the first layer.In order to ensure with the good adhesivity of fluoropolymer interlayer, provide a layer based on polymeric amide/polyamine as the adhesion promoter layer.Find that this multipolymer provides a kind of adhesive power of strong improvement unexpectedly.This thermoplastic multilayer veneer sheet can be used for the coating of optical wire, particularly has the optics core based on PMMA.

At EP 1,216, a kind of multilayer layer pressing plate is disclosed among 823 B1, it has comprised a polyamide molding material layer, randomly adds polymeric amide/polyamine multipolymer and randomly adds the adjoining course of an ethyl vinyl alcohol copolymer.In this polyamide molding material, a kind of polymeric amide/polyamine multipolymer media compatibility is provided, but at EP 1,216, do not mention not having the polymeric amide/polyamine multipolymer of other polymeric amide mixing portion can have this fact of good adhesive power among 823 B1 to fluoroplymer layer.

At EP 0, disclose a kind of multilayer layer pressing plate among 777,578 B1, it has a first layer that comprises fluoropolymer, having comprised does not a kind ofly have fluorizated polymkeric substance and a kind of molecular weight less than 1000 the aliphatic diamines or the second layer of polyamine, wherein said not have the fluorizated polymkeric substance be a kind of polymeric amide, polyimide, urethane, or contain carboxyl, acid anhydrides, or the polyolefine of imide functional group, and whole amine all is in the second layer.Compare during with the existing of the component that does not have diamines or polyamine, the amount of described amine should be the adhesive power that is enough to increase interlayer.

At EP0, disclose by dimer diol among 955,326 B1 and comprised the polymeric amide of the dimer diol modification of the predetermined polyester of hydroxyl.Do not have the polymeric amide of modification to compare with described, even at low temperatures, the polymeric amide of modification also shows an enhanced flexibility and toughness.Because inherent plasticising performance own, so variation along with the mechanical property that contacts with medium or cause owing to softening agent loss and/or migration during heat effect can not take place.Compare with other polymeric amide that contains glycol, this flexible polymeric amide has good anti-hydrolytic performance.

As mentioned above, the used so far polymer optical fiber of Miao Shuing has comprised the PMMA core usually in the prior art, from 95 to 100 ℃ of its second-order transition temperatures, and the use of this polymer optical fiber can only be limited in being lower than 90 ℃.

But, be used for the thermal oxidation resistance of polyamide molding material or the stabilization that anti-photooxidation decomposes, known a lot of systems.The phenolic aldehyde antioxidant belongs to well-known stabiliser system, for example, the hindered phenol group, based on the antioxidant of aromatic amine, and copper compound.Particularly the halogenide of copper and alkali-metal halid mixture have been proved to be thermal oxidation resistance aged effective stabilizer.The halogenide of copper and the stabilization of alkali-metal halid mixture are better than other stabiliser system.If be higher than 120 ℃ of permanent use polymeric amide, organically stabiliser system can lose efficacy mostly.Even thermo-oxidative stability need surpass several thousand hours, the stablizer based on copper bearing salt under this temperature also is effective.Described stablizer can add in the polymeric amide in a different manner, as an example, can at the Cheng Fenzhong of drying process, or add in mixing before polymerization or in the polymerization process.

At EP 0,745, mentioned among 642 B1 and EP 0,668,943 B1 and used copper compound polyamide molding material to be carried out the example of stabilization.EP 0,745, and 642 B1 have described as stablizer, heat-staple, the polyamide molding material of weather, it is for having comprised by copper halide, one or more halogen compounds and phospho acid or its an alkali metal salt or alkaline earth salt are formed, with a definite molar ratio blended mixture.This stabilizer blend has brought the aging or aging very advantages of excellent stability of anti-photooxidation of thermal oxidation resistance.

In EP 0668943 B1, stable polyamide filament has been described, it has comprised polyphtalamide, the polyolefine synergistic agent of cupric stablizer and functionalization, wherein said stablizer has comprised soluble copper compound and alkali metal halide in polyphtalamide, and the amount of described synergistic agent is 1 to 20wt%.

Except the system of having mentioned, other material blends of the stabilization that is used for polymeric amide thermal oxidation resistance and anti-photooxidation decomposition has been described also.US-A-2,705,227 have described a kind of ternary stabiliser system, and by copper compound, an alkali metal salt of halogen compounds and phosphoric acid or phosphoric acid is formed.

GB-A-1140047 has described a kind of ternary stabiliser system, and it is by copper bearing salt, phosphorous acid or phospho acid, or form by the compound of these bronsted lowry acids and bases bronsted lowry metal halides.Being limited in of the ternary stabiliser system of this pressurized, the consumption of described phosphorus compound are at most half of the used molar weight that contains mantoquita.According to GB-A-1140047, if use phospho acid as P contained compound, its consumption is at most 1/4th of the used volumetric molar concentration that contains mantoquita.In order to obtain the polyamide molding material of light colour, the molar weight of the phosphorus compound that is added should be than it with respect to the copper amount that is added and the reference quantity of setting usually is lower.

DE-A-2107,406 have described a kind of ternary stabiliser system, and it is by copper stearate, and potassiumiodide and phospho acid manganese are formed.Moulding material with this stabilized with mixture is colourless.

EP-A-0612,749 have described stable polyamide molding material, and it comprises the stablizer of cupric ion or complex copper, also comprises elemental copper, and the copper of fine dispersion is as stablizer.

Existing known stabiliser system has stoped the thermal-oxidative ageing of polyamide molding material and photoxidation to be worn out.New application has increased the demand of this polyamide molding material to the stability of thermooxidizing or photoxidation decomposition.For example, in the nacelle of automobile, use this polyamide molding material.At this and in other field, polyamide molding material is in the high-temperature load for a long time.Under the temperature of these risings, be specially adapted to polymeric amide based on the stabilization of copper.

People such as P.Gijsman are at Polymer Degradation and Stability 49 (1995), described for example among the 127-133 polymeric amide by and the mechanism of metal-salt (as the halogenide and the alkali metal halide of copper) bonded stabilization.In DE-A19847626, also mentioned the combination that contains mantoquita and aromatic halides and in DE-A19847627, mentioned the combination that contains mantoquita and complexing agent, as mercaptan or phosphuret-(t)ed hydrogen.The painted of stabilization based on copper in these systems also will be alleviated.

From the description of prior art, to have known and used metal negative catalyst with antioxygenation, this effect is to be caused by the sterically hindered phenol that is included in the molecule.Often use this compounds to be used for the stabilization polyolefine, especially for polyphenylene ether (polyphenylenethers) or be used for continuous use when contacting, for example be used for cable application with copper.

For the employed metal negative catalyst of this class static stabilization (polyolefinic); it is according to following quoted passage: Plastics Additives Handbook; the 4th edition; 1993; 2.4 chapters and sections; has the following chemical structure: the acid amides of aliphatics and aromatic monocarboxylic acid and dicarboxylic acid and the mono-substituted derivative of N-thereof; cyclic amide, malonylurea for example, the hydrazone of alkanoic and aromatic aldehyde and dihydrazone; the hydrazides of aliphatics and aromatic monocarboxylic acid and dicarboxylic acid; two propylene hydrazide derivatives, heterogeneous ring compound, for example trimeric cyanamide; benzotriazole; 8-oxygen-quinoline, the acylated derivatives of hydrazone and hydrazine and triazine, aminotriazole and its acylated derivatives; polyhydrazide; the molecule binding substances of sterically hindered phenol and metal complex base, any combination thereof of phenmethyl nickelous phosphate and other antioxidant or metal negative catalyst; pyrimidine mercaptan/Sn compound, the triguaiacyl phosphate of thiobisphenol (tertiaryphosphoric acid esters of thiobisphenol).In patent document, also mention other textural classification in the context, as N, N '-two-salicylic aldehyde-second diimine (N, N '-bis-salicylal-ethylendiimide), salicyl oxygen imines (salicylaloximine), the derivative of second diamino tetraacethyl (derivatives ofethylendiaminotetraacetic acid) etc.Yet, because its low activity, insufficient thermostability or because easy volatile, above-named a lot of compounds can not be used to the metal negative catalyst of thermoplastics in practice.

From EP 1,198,520 B1 can also be known, usage space sterically hindered phenol in polyamide molding material.

Those skilled in the art is from selecting the phenolic aldehyde antioxidant for use the serial sterically hindered phenol as organic compound usually, it comprises a phenolic groups at least, wherein Fang Xiang half preferably is substituted in position, two places at least at a place, and carbon atom direct and described phenolic groups is adjacent.This substituent adjacent with oh group is alkyl group, preferably is selected from the alkyl group of 1 to 10 carbon atom.Its preferred tertiary butyl group.Suitable hindered phenol comprises, four (methyl (3 for example, 5-two (uncle)-butyl-4-hydroxyl stannate) ((methylen (3 for tetrakis for methane, 5-di (tert)-butyl-4-hydroxyhydrostannic acid)) methane), the commercial trade mark is Irganox 1010 (Ciba Specialty chemicals).Known this antioxidant and hindered phenol have been joined in the injection-molded compound of HT (high temperature) polymeric amide, can demonstrate improved thermostability (referring to EP 1,198,520 B1) like this.

Therefore, one object of the present invention is the thermoplastic polyamide mold material that provides stable, it has 125 ℃ of thermostabilitys of 3000 hours at least, and is applicable to that the coating of optical waveguides, this optical waveguides have one based on fluorine cpd or based on the coating of fluoropolymer.

Another object of the present invention is to prepare a kind of optical fiber, and it has 125 ℃ of thermostabilitys of at least 3000 hours and has at protective layer and good adhesivity between based on the coating (as the fluorine coating) of fluorine cpd or fluoropolymer.

The present inventor attempts the viscosity that N-terminal base and the interaction between the copper compound by polymeric amide improve this polyamide molding material greatly.This viscosity effect depends on the concentration and the processing conditions of N-terminal base, and it has also comprised drying temperature and exsiccant time length.Like this, viscosity (soltion viscosity and melt viscosity) changes along with processing conditions (temperature and time length), normally rises to a bigger or lesser extent as its function.In industrial manufacturing processed the viscosity that can not accept to change significantly.

Owing to the viscosity that increases needs higher processing temperature, promoted the formation of block and gel particle whereby extraly, cause forming an irregular coating, this also is unacceptable.

Thermoplastic polyamide mold material of the application of the invention and optical fiber can be realized above-mentioned purpose, and this thermoplastic polyamide mold material is used as protective layer used coating in the optical waveguides with fluorine coating.

Used thermoplastic polyamide mold material has 125 ℃ of thermostabilitys of 3000 hours at least according to the present invention.In a specific embodiment, according to material of the present invention, Themoplastic molding materials just of the present invention, have under 125 ℃ at least 4000 hours thermostability, particularly preferably be 125 ℃ of following thermostabilitys of 5000 hours with especially preferably 125 ℃ of following thermostabilitys of 6000 hours.The used thermoplastic polyamide mold material of the present invention comprises following component:

(A) polymeric amide, its polymkeric substance or polycondensation product for being made by following compound promptly by the aliphatics lactan, is preferably based on C ₆To C ₁₂Lactan, or by omega-amino-carboxylic acid with 3 to 44 carbon atoms, preferably have 4 to 18 carbon atoms, the omega-amino-carboxylic acid that more preferably has 12 carbon atoms, or make by the aromatic amine yl carboxylic acid with 7 to 20 carbon atoms, perhaps by at least a diamines that all has 2 to 44 carbon atoms and at least a dicarboxylic acid polycondensation and, wherein at least a diamines is preferably selected from the aliphatie diamine of in 2 to 18 carbon atoms, cycloaliphatic diamine with 7 to 22 carbon atoms, be preferably selected from aliphatic dicarboxylic acid with at least a dicarboxylic acid with 3 to 44 carbon atoms, have the cycloaliphatic dicarboxylic acid and the aromatic dicarboxylic acid with 8 to 20 carbon atoms of 8 to 24 carbon atoms, wherein said polycondensation product and/or polymkeric substance have excess of ammonia base terminal group.

(B) polymeric amide with respect to described moulding material composition partly is a kind of copper bearing stablizer (b of 0.01 weight part to 2 weight parts ₁), or sterically hindered phenol and HALS stablizer (b ₂) binding substances, or sterically hindered phenol (b ₃),

(C) partly be 0 to 3 weight part with respect to the polymeric amide of described moulding material composition, preferred 0.01 weight part is to 3 weight parts, at least a organic compound that has the metal complex group, described metal complex group is selected from the acid amides of acid, oxamide, diphenyl oxalate acid amides (oxalanilide), hydrazine, the hydrazides of acid or the group of hydrazone, the phosphite group of the group of benzotriazole and sulfur-bearing, at this, component (A), (B) and optionally component (C) adds up to 100 weight parts

(D) except component (A), 0 to 45 weight part outside the sum of component (C) (B) and optionally, preferred 0 to 25 weight part, the polymkeric substance of one or more functionalization, the polyolefine of preferred functionization and/or the polyolefin copolymer of functionalization.

In order to realize high adhesivity,, must need excess of ammonia base terminal group for component (A) according to the present invention to fluorine cpd and fluoropolymer.In order to reach temperature stability, according to the present invention, cupric stablizer (b ₁) or sterically hindered phenol is suitable and HALS stablizer (b ₂) or sterically hindered phenol (b ₃) combination.

Particularly, at using cupric stablizer (b among the present invention ₁) situation.In order to eliminate because the defective relevant with processing characteristics that the combination of excess of ammonia base terminal group and copper stablizer causes must will be added metal negative catalyst (C) in an embodiment of the present invention.

Optionally formed or comprised this polyamide molding material that is used as the LWL coating among the present invention of polymeric amide/polyamine multipolymer and comprised following polycondensation product or polymkeric substance by polymeric amide/polyamine multipolymer:

Component (A):

As polymeric amide, the preferred polycondensation product that has excessive amino terminal group that generates by the aliphatics lactan that uses, wherein preferred C ₆To C ₁₂Lactan or have the omega-amino-carboxylic acid of 3 to 44 carbon atoms, preferred 4 to 18 carbon atoms, or preferably have the aromatic omega-amino-carboxylic acid of 7 to 20 carbon atoms.

Same be suitable for be, by all having the polycondensation product that has excessive amino terminal group 2 to 44 carbon atoms, that at least a diamines and at least a dicarboxylic acid generate.The example of this diamines is a quadrol, 1, and the 4-butanediamine, 1, the 6-hexanediamine, 1,1,12-diamino dodecane ,-and right-benzene dimethylamine, cyclohexyl dimethylamine, two-(right-aminocyclohexyl) methane and its alkyl derivative.

The example of this dicarboxylic acid is a propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and sebacic acid, dodecyl diacid, 1,6-cyclohexane diacid, terephthalic acid, m-phthalic acid and naphthalene diacid.

The polymeric amide that has excessive amino terminal group that is especially suitable for use as the LWL coating and is used for moulding material is to be selected from following group equal polyester-polyamide: PA 6, and PA 11, and PA 46, PA 66, and PA 12, and PA 1212, PA1012, PA 610, and PA 612, PA 69, PA 6T, PA 6I, PA 10T, PA 12T, PA 12I, their mixture, or the multipolymer that makes by these equal polyester-polyamides, wherein preferred PA 11, PA 12, and PA 610, and PA 612, PA 1212, PA 9T, PA 10T, PA 12T or multipolymer, preferred especially PA 12T/12, PA10T/12, PA 12T/610, PA 12T/106, PA 10T/610 and PA 10T/106.In addition, also can use such as PA 6/66 according to the present invention, PA 6/612, and PA 6/66/610, and PA 6/66/12, PA 6/6T, and PA66/6T, PA 6/6I and PA 6I/6T are at interior polymeric amide.

In each related polymeric amide part, the content that the polymkeric substance of component (A) and/or polycondensation product preferably contain the N-terminal base is 20 to 300 μ equ./g, particularly the content of 40 to 300 μ equ./g and C-terminal base particularly is less than 15 μ equ./g for being less than 20 μ equ./g.

The relative viscosity of the polymeric amide of component (A) (20 ℃ record in 0.5% meta-cresol) is less than 2.0, preferably less than 1.8, more preferably in 1.4 to 1.8 scope.

The polymeric amide of polymeric amide/polyamine multipolymer partly is by aliphatics C ₆To C ₁₂The polymkeric substance that lactan makes, or by having 3 to 44 carbon atoms (preferred 4 to 18 carbon atoms, preferred especially 12 carbon atoms) polymkeric substance that omega-amino-carboxylic acid makes, or the polymkeric substance that makes by aromatic amine yl carboxylic acid with 7 to 20 carbon atoms.

The difference that these (being total to) polymeric amide also have is, for some purposes can be added polymkeric substance commonly used therein.Used (being total to) polymeric amide can include additive commonly used, as the UV stablizer, and crystallization promoter, filler, fire retardant and lubricant.

Described fire retardant is the fire retardant that is selected from halogen-free flame retardants series, as the fire retardant based on nitrogen or phosphorus.According to the present invention, preferred especially phosphinates and/or melamine cyanurate and/or triaryl phosphate.Use the fire retardant of phosphinates as polyamide molding material, according to UL-94 test (Underwriter Laboratories Inc., Underwriter Laboratories), when the thickness of specimen was 0.4mm, the burning that obtains was classified as V0.The phospho acid that are suitable for that are used to prepare used phosphinates are, for example, and the dimethyl phospho acid, the ethyl-methyl phospho acid, diethyl phospho acid, methyl-n-propylphosphinic acid, dimethyl phospho acid methane, 1,2-two (methyl phospho acid) ethane, 1,6-two (methyl phospho acid) hexane, 1,4-two (methyl phospho acid) benzene, the aminomethyl phenyl phospho acid, diphenyl phosphonic acid.

Described phosphinates is synthetic in accordance with known methods, for example at EP 0,699, and disclosed method among 708 A1.Described phospho acid are by metal carbonate, and the oxyhydroxide of metal or the oxide compound of metal react in the aqueous solution and mainly be converted into the monomer phosphinates, also may form the polymeric phosphinates according to reaction conditions.

Described phosphinates can comprise the second or the 3rd main group or the metal ion of subgroup in the periodictable, preferably uses the calcium salt of phospho acid and the aluminium salt of phospho acid.Described phosphinates also can its mixture form use.When itself and mixed with polymers,, preferably use pulverous phosphinates in order to obtain better dispersiveness.

The polyamine that is used to prepare polymeric amide/polyamine multipolymer according to the present invention is a polyvinylamine, with the polyamine of polyketone alternating polymerization, and dendrimer (dendrimeres), linear or grafted polymine.If it is linear or the grafted polymine, preferably have mole 500 to 25, the 000g/mol scope, more preferably 800 to 5, the 000g/mol scope.This polyamine has 1200 to about 5000mPa*s viscosity at 20 ℃ in addition.

Typically, the amino end group concentration of described polymeric amide/polyamine multipolymer is 40 to 300 μ equ./g.Preferably, according to ISO 1133, at 275 ℃/5kg, its melt volume rate (MVR) is 10 to 1000cm ³/ 10min.MVR is per 10 minutes cm ³The melt volume rate, it is the MVR equipment of use standard, measures on time after 4 minutes 275 ℃ and load 5kg fusion.

The polyamine that the present invention is used, preferably used polymine with 0.2 to the consumption of 5wt%, preferred especially 0.4 to 1.5wt% consumption uses, and as the copolymerization component of polymeric amide/polyamine multipolymer, wherein remaining copolymerization part preferentially is made up of polymeric amide in this multipolymer.

Component (B) (0.01-2 weight part)

Comprise the stabilizer component (B) of 0.01 to 2 weight part in polyamide molding material, it comprises the possibility of three kinds of stabilizations, promptly

(b ₁) a kind of copper bearing stablizer

(b ₂) at least a and HALS bonded sterically hindered phenol,

(b ₃) at least a sterically hindered phenol.

If use the cupric stablizer as stablizer of the present invention, need in this moulding material, add metal complex, this metal complex preferably adds with the amount with respect to 0.01 to 3 weight part of polymeric amide part in the described composition.

The halogenide of preferred as alkali and cuprous halide (I) and/or stearic acid cuprous (I) and/or Red copper oxide (I) are as copper bearing stablizer (b ₁), wherein especially the weight ratio of alkali metal halide and copper (I) total amount of compound was remained on 2.5: 1 to 100: 1.

In a preferred embodiment of the invention, the mol ratio of component (C) and cupric (I) total amount of compound is between 0.5: 1 to 3: 1.When producing described Themoplastic molding materials, more preferably add at least with component (B) in the component (C) of the about equimolar amount of copper content.

For example, following compounds can be used as the HALS stablizer according to the present invention: two (2,2,6,6-tetramethyl--4-piperidyl) sebate and/or two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate and/or poly-[1-(2 '-hydroxyethyl)-2,2,6,6-tetramethyl--4-hydroxy piperidine base succinate] and/or poly-[[6-(1,1,3, the 3-tetramethyl butyl) amino]-1,3,5-triazine-2,4-two] [(2,2,6,6-tetramethyl--4-piperidyl) imido grpup]-1,6-dihexyl [(2,2,6,6-tetramethyl--4-piperidyl) imines].

According to the present invention, suitable metal negative catalyst (MD) is some energy and metal ion, especially compounds of cupric ion complexing.It is following that but the compound of these complexing metals comprises: the acid amides of acid, oxamide, diphenyl oxalate acid amides (oxalanilide), hydrazine, the hydrazides of acid or the unit or the benzotriazole of hydrazone.Compound with these structures can be used for the metal negative catalyst (referring to Plastics Additives Handbook, 4 ^ThEd., 1993, chapter.2.4).

The example of used metal negative catalyst (MD) is (referring to component (C)) according to the present invention:

1,2, the 3-benzotriazole, tolyl-triazole, 3-(salicylyl amino)-1,2, the 4-triazole, laurostearic acid two [2-(2-hydroxybenzene first) hydrazides], 2 ', 3-two [[3-[3,5-two-tertiary butyl-4-hydroxyphenyl] propionyl]]-propionyl hydrazine and three [the 2-tertiary butyl-4 '-sulphur (2 '-methyl-4 '-hydroxyl-the 5 '-tertiary butyl)-phenyl-5-methyl] phenyl-phosphorous acid ester.

Component (D) (0-45 weight part, preferred 0-25 weight part)

Be used for the compound of component (D), be preferably selected from: polyolefine and/or polyolefin copolymer, it is a vinylformic acid, Succinic anhydried and/or maleic anhydride graft.For example, as viscosity promotor that is used for polymeric amide or modified impact agent, the compound used according to the present invention is, as polyethylene with media featureization, low density or extra-low density or linear low density polyethylene (LLD-PE), by ethene and linear, the multipolymer of the functionalization of grafted or cyclic olefin-copolymerization is as the ethylene/propene copolymer of functionalization.

Component (A), the summation of component (B) and component (C) is 100 weight parts.Component (D) is optionally, and it joins the component (A) of 100 weight parts extraly, component (B) and optionally in the summation of component (C).

Be example now, the preparation method of the polymeric amide that the present invention is used be described with PA12:

The polymerization of laurolactam (laurinlactam) is monoamine or the polyamines 0.05 to 3wt%, for example monoamine, preferably diamines or polyamine, as the cyclohexyl diamines, the dodecyl diamines carries out under the existence of lactone diamines (laromine) or polymine and 5 to 20% water.

The pressure phase: at 290 to 330 ℃, 20bar, 1 to 6 hour

In 260 to 290 ℃ of polymerizations of carrying out 0.5 to 6 hour under normal pressure nitrogen.

The relative viscosity of prepared polymeric amide is less than 2.0, preferably less than 1.8 (in 0.5% meta-cresol at 20 ℃), its N-terminal base content is at 20 to 300 μ equ./g, preferably at 40 to 300 μ equ./g, its C-terminal base content is less than 20 μ equ./g, preferably is less than 15 μ equ./g.

Under on the common duplex forcing machine in 200 to 280 ℃, this polymeric amide and all the other components that contains excessive amino terminal group mixed.As use common mixing screw (usualmixing screw with kneading elements) or other mixing equipment with kneading member, then must use a kind of metal negative catalyst with good dispersion.

The standard conditions of the drying process of resulting granules are under 110 ℃ in vacuum, dry 24 hours.The following examples have been described the present invention, but the present invention is not limited to these embodiment.

The polymeric amide that the present invention is used:

Table 1: amino-terminated polymeric amide 12 (EMS Chemie AG)

Relative viscosity, 0.5% in meta-cresol		1,65
			MVR，230℃/2,16kg	cm ³/10min	65
The N-terminal base	(μequ./g)	100
			The C-terminal base	(μequ./g)	10

Table 2: stay deposit time handle after the behavior of polyamide molding material (further referring to following) with different in melt the different time of drying of carrying out before MVR measures

Title

MD1=dodecyl diacid two [2-(2-(2-hydroxybenzoyl)) hydrazine]

MD2=2 ', 3-two [[3-[3,5-di-t-butyl-4-hydroxyphenyl]-propionyl]] the propionyl hydrazine

MD=metal negative catalyst

The reference volume that is used for relative viscosity (0.5% meta-cresol) and MVR (230 ℃, 2.16kg is in melt behind the 4minutes) is measured under standard conditions dried particle and is obtained.

For the mensuration of the variation of polyamide molding material in melt, can also in melt, measure MVR after 10 and 20 minutes.

In the melt cone of MVR method of masurement (dried particles under the standard conditions), measure relative viscosity (0.5% meta-cresol).

Particulate fraction 110 ℃ extra dry 24 hours, carry out the measurement of the two (relative viscosity and MVR) then.

Under temperature load, the evaluation of polyamide molding material is summarized in following table 2.

Along with because the viscosity that increases, block forms and in the variation of course of processing medium viscosity, must raise adds the temperature in man-hour, so the processing characteristics of the polyamide molding material in the comparative example is very poor.

Polyamide molding material among the embodiment 1-3 does not then have this situation, and it shows good processibility.

The adhesivity of all polyamide molding materials that store in advance is all not very good.After 3000 hours, have only the polyamide molding material of embodiment 1-3 to satisfy the demands 125 ℃ of storages.

Through after storing, the sleeve pipe (4) that is made by the polyamide molding material of comparative example breaks in bursting test.

Among Fig. 1 to 3 below, show the impact traction toughness after 100,120 and 140 ℃ of thermmal storages.There is shown of the variation of the standardized impact traction of initial value toughness with the storage time.

The measurement of two kinds of materials is respectively in value 1 beginning.The decline that the numerical value of comparative example (referring to watch 2) is promptly very fast in early days, thereby the Trendline of linear decline can not be passed through initial value.According to the composition of the embodiment of the invention 2 because its stability does not preferably just have this problem.

There is shown of Fig. 1 to 3, not only improved the processibility of described moulding material according to the used metal negative catalyst of the present invention, also improved its mechanical stability.

The invention still further relates to a kind of optical fiber (1), has at least one fiber core that has one or more layers coating (3) (2), with at least one encapsulation LWL (2,3) sleeve pipe (4), wherein said coating (3) or at least its skin formed by a kind of layer institute that forms by fluorine cpd or fluoropolymer, described sleeve pipe (4) is made up of polymeric amide, and wherein at least one sleeve pipe (4) is made up of a kind of layer that is formed by one or several the described polyamide molding material in the claim 1 to 17.

According to the present invention, also can form by a kind of multipolymer of polymeric amide/polyamine in abutting connection with the described sleeve pipe (4) of the coating of fluorine cpd or fluoropolymer.

In a specific embodiment of the present invention, the sleeve pipe (5) of another kind of polyamide molding material also can be set, it does not still have the excess of ammonia base terminal group of polycondensation product or polymkeric substance in abutting connection with sleeve pipe (4).

In another embodiment of the present invention, can form by the another kind of polymkeric substance except that polymeric amide in abutting connection with the sleeve pipe (5) of sleeve pipe (4).According to the present invention, the material that can be used for sleeve pipe (5) is selected from: polyvinyl chloride, polyvinyl acetate, the acetate copolymer of ethyl vinyl, urethane, polyoxymethylene, polyethylene, polyethylene and ethylene copolymers, polypropylene, polypropylene copolymer, fluoropolymer, the compound of fluoropolymer, vinyl tetrafluoroethylene base co-polymer, fluorinated ethylene propylene (polyvinilyden fluoride), or crosslinked polymkeric substance.

If desired, for example, when using polyolefine, between sleeve pipe (4) and sleeve pipe (5), can arrange an adhesion promoter layer, to realize the adherent demand of sleeve pipe (5) to sleeve pipe (4) as sleeve pipe (5).When being used for this purpose, can use the adhesion promotor that is used for polymeric amide of known routine, its may with stablizer dispensing together, for example, b ₁, b ₂Or b ₃(referring to claim 1, B component).

The polyethylene that is used for sleeve pipe (5) according to the present invention can also be to use carboxyl, the polyethylene of acid anhydrides or imide group functionalization or poly multipolymer.

Described cross-linked polymer is by superoxide, silane or radiation crosslinking.Applicable interlacing polymkeric substance is selected from: have height respectively, in, the polyethylene or the poly multipolymer of low or extra-low density, or linear low density polyethylene (LLD-PE), or metallocene PE, or polypropylene or polyacrylic multipolymer, as the multipolymer of polypropylene and ethylene-propylene rubber(EPR), or the mixture of polypropylene and ethylene-propylene rubber(EPR) or urethane.

In a specific embodiment, sleeve pipe (5) is by a kind of fluoropolymer, and the polymkeric substance of a kind of fluoropolymer compound or crosslinked polymkeric substance, particularly radiation crosslinking is formed.

According to the present invention, fiber core (2) is by glass, polycarbonate (PC), and fluoropolymer, poly-glutarimide, or form by the mixture that polycarbonate and polymethylmethacrylate (PMMA) make.

In one embodiment of the invention, described optical fiber has comprised sleeve pipe (4) and sleeve pipe (5).Described sleeve pipe (5) has at least one or several color mark.Described color mark is a heatproof, and can be used for expressing technique.

Optical fiber of the present invention (1) is characterised in that the external diameter of described optical waveguides (LWL) 2,3 is in 75 to 3000 mu m ranges.

Usually, the external diameter of described coating (3) can be 2000 ± 120 μ m or 1000 ± 60 μ m or 750+ ± 45 μ m or 500 ± 30 μ m or 230 ± 20 μ m or 125 ± 10 μ m.

In a specific embodiment, the diameter of fiber core (2) is 8 μ m at least, maximum 1000 μ m, and preferred 10 to 100 μ m, more preferably 20 to 80 μ m are less than the external diameter of corresponding coating (3).

The external diameter of described optical fiber (1) between 0.15 and 5mm between.

In another embodiment, described optical fiber (1) has comprised several 2,3 optical waveguidess of forming (LWL).

Structural representation according to a kind of fiber of the present invention (1) is as follows:

Fiber can be understood that it is fiber core, coating and sleeve pipe and/or telescopic integrally combined.The term fiber, LWL, POF and GOF only relate to the fiber core that has coating.

Fire-retardant polymeric amide (as PA 12) or polyamide elastomer (as polyetheramides, polyether ester amides or polyesteramide) all are applicable to sleeve pipe (5) as fire-retardant polymeric amide.

For a kind of fiber, a kind of definite adhesive power is important.

The prerequisite of described telescopic adhesive power is:

The adhesive power of the sleeve pipe on coating (4) is (by ID ₄1mm and AD ₄1.5mm):

〉=50N and insulated lengths 1 _{Sleeve pipe 4}=30mm

The adhesive power of the sleeve pipe (5) on sleeve pipe (4) is (by ID ₅1.5mm and AD ₅2,3mm):

20 ± 10N and insulated lengths 1 _{Sleeve pipe 5}=30mm

The AD=external diameter, the ID=internal diameter

In order to detect the adhesive power of sleeve pipe on coating, used following testing method:

The sleeve pipe (4) of the fiber of a 50mm length of part peeling, the about 30mm of length of remaining sleeve pipe like this (4).

Control the classification part of described fiber by the boring on the sheet brass, wherein said borehole diameter is greater than the about 0.1mm of sleeve pipe (4) external diameter.

The classification end that clamps described fiber enter a pull test machine (pulling speed is 100mm/min) and

Measure described tractive force, make sleeve pipe (4) peel off from the coating of below.

The example of the dimensions of different fibers according to the present invention:

Polymer optical fibre (POF)

From inside to outside:

The POF core, diameter 980 μ m

Coating fluoropolymer WT:20 μ m, AD:1mm

Sleeve pipe 1WT:0.25mm, ID:1mm, AD:1,5mm

Sleeve pipe 2WT:0.35to 0.4mm, ID:1.5mm, AD:2.3mm

The WT=wall thickness

Glass fiber (GOF)

A) silicon-dioxide of polymer overmold (Polymere cladded silica) (PCS fiber):

From inside to outside:

Core, diameter 200 μ m

Coating, diameter 230 μ m

Sleeve pipe, diameter 500 μ m are to 2000 μ m

B) silicon-dioxide (Hard cladded silica) (HCS fiber) that covers of Hard Roll:

From inside to outside:

Core, diameter 125 μ m are to 400 μ m

Coating, diameter 140 μ m are to 430 μ m

Sleeve pipe, diameter 250 μ m are to 730 μ m

The preparation of coating

For the light transmission of the best of described fiber core and coating, must prevent outside interference and loss.For this purpose, described fiber or individually, or the coated layer in bundled ground coats, then be to coat with sleeve pipe, described sleeve pipe is to make by being selected from following plastic material: polyethylene (PE), polyvinyl chloride (PVC), ethylene tetrafluoroethylene copolymer (ETFE), the acetate copolymer of ethyl vinyl (EH), polyamide (PA), polytetrafluoroethylene (PTFE) or other combinations of materials.Described sleeve pipe can form one or more layers, and it has different wall thickness, even also can have different wall thickness in independent one deck.

Make this sleeve pipe by continuous expressing technique.In the reeler back forcing machine is set, will be used for the telescopic material thus and be moved to described fiber.After coating, this fiber is cooled in cooling pool, supplies with rewinding machine (A.Winert then, Kunststofflichtwellenleiter:Grundlagen, Komponenten, Installation Publicis MCD Verlag, Erlangen and Munich, 1998, the 51 pages).

Further the preparation of coating can by following the two one of method implement:

1. the step to separate is carried out the preparation of described further coating on the skin that in the end makes

2. on an extrudate flow waterline with different forcing machines, carry out the preparation of described further coating continuously, for example, so-called series connection method (referring to key diagram) (face as follows)

Use series connection method to apply 2 layers key diagram

3. pass through extrusion moulding simultaneously more than a kind of multiple sleeve pipe

When the coating of the described optical waveguides of preparation, must pay special attention to temperature, the tractive force of pressure and rising.Described optical attenuator and geometric shape can be subjected to the influence of these parameters, thereby weaken the light transmission quality of this fiber.

In directly adhering to the first telescopic extrusion of coating, it is highly important that for POF, because the temperature sensitivity of this polymkeric substance, the melt of this shell material need to extrude in an alap temperature (about 160-220 ℃), otherwise can damage this fiber.For GOF and other fiber, processing temperature can be 160-250 ℃ scope.

Use a kind of pipe box coating equipment (Kunststofftechnik, Kabel und isolierte Leitungen, VDI-Verlag, D ü sseldorf, 1984, the 71 pages) to prepare described sleeve pipe.In this case, described sleeve pipe is that external application at described equipment is to the coating of for example this fiber core.This method need not apply any pressure to the fiber core of the band coating of being supplied with.When extrusion, also need not to exert pressure.

By suitable design-selection equipment (nozzle and core), because best heat transfer, can advantageously be adjusted between POF and the sleeve pipe and their (POF and sleeve pipes) and other add the bounding force of determining between the sleeve pipe in addition.

Opposite with POF is, because GOF and other add sleeve pipe in addition and have less temperature sensitivity, in order to reach required viscosity, it can use cylindrical radiation heater to come preheating.

Claims

1. a thermoplastic polyamide mold material application, it has at least 6000 hours thermostability under 125 ℃, as the coating of optical waveguides, described optical waveguides has the coating that is formed by fluorine cpd or fluoropolymer, and described thermoplastic polyamide mold material comprises following component:

(A) polymeric amide, its polymkeric substance or polycondensation product for making by following compound, promptly by the aliphatics lactan, or by omega-amino-carboxylic acid with 3 to 44 carbon atoms, or make by the aromatic amine yl carboxylic acid with 7 to 20 carbon atoms, perhaps by at least a diamines that all has 2 to 44 carbon atoms and at least a dicarboxylic acid polycondensation and, wherein said polycondensation product and/or polymkeric substance have excess of ammonia base terminal group

(C) polymeric amide with respect to described moulding material composition partly is at least a organic compound that has the metal complex group of 0 to 3 weight part, described metal complex group is selected from the acid amides of acid, oxamide, the diphenyl oxalate acid amides, hydrazine, the hydrazides of acid or the group of hydrazone, the group of benzotriazole, phosphite group with sulfur-bearing

At this, component (A), (B) and optionally component (C) add up to 100 weight parts,

(D) except component (A), (B) and optionally the polymkeric substance of one or more functionalization of 0 to 45 weight part outside the sum of component (C) is selected from polyolefine and/or polyolefin copolymer, and it is grafted with vinylformic acid, Succinic anhydried and/or maleic anhydride.

2. thermoplastic polyamide mold material's according to claim 1 application is characterized in that, described aliphatics lactan is C ₆To C ₁₂Lactan.

3. thermoplastic polyamide mold material's according to claim 1 application is characterized in that, described omega-amino-carboxylic acid is the omega-amino-carboxylic acid with 4 to 18 carbon atoms.

4. thermoplastic polyamide mold material's according to claim 3 application is characterized in that, described omega-amino-carboxylic acid is the omega-amino-carboxylic acid with 12 carbon atoms.

5. thermoplastic polyamide mold material's according to claim 1 application is characterized in that, described at least a diamines is selected from the aliphatie diamine of 2 to 18 carbon atoms, has the cycloaliphatic diamine of 7 to 22 carbon atoms; And/or at least a dicarboxylic acid is selected from the aliphatic dicarboxylic acid with 3 to 44 carbon atoms, has the cycloaliphatic dicarboxylic acid of 8 to 24 carbon atoms and has the aromatic dicarboxylic acid of 8 to 20 carbon atoms.

6. thermoplastic polyamide mold material's according to claim 1 application is characterized in that, comprises that described component (C) 0.01 weight part is to 3 weight parts.

7. thermoplastic polyamide mold material's according to claim 1 application is characterized in that, comprises described component (D) 0 to 25 weight part.

8. thermoplastic polyamide mold material's according to claim 1 application, it is characterized in that, in each related polymeric amide part, the content that the polymkeric substance of described component (A) or polycondensation product contain the N-terminal base is that the content of 20 to 300 μ equ./g and C-terminal base is less than 20 μ equ./g.

9. thermoplastic polyamide mold material's according to claim 8 application is characterized in that, the content of described N-terminal base is 40 to 300 μ equ./g; And/or the content of described C-terminal base is less than 15 μ equ./g.

10. according to claim 1 or 8 described thermoplastic polyamide mold materials' application, it is characterized in that the relative viscosity of the polymeric amide of described component (A) is measured as less than 2.0 in 0.5% meta-cresol at 20 ℃.

11. thermoplastic polyamide mold material's according to claim 10 application is characterized in that, the relative viscosity of the polymeric amide of described component (A) is measured as less than 1.8 in 0.5% meta-cresol at 20 ℃.

12. thermoplastic polyamide mold material's according to claim 10 application is characterized in that, the relative viscosity of the polymeric amide of described component (A) is measured as in 1.4 to 1.8 scope in 0.5% meta-cresol at 20 ℃.

13. the application according to claim 1 or 8 described thermoplastic polyamide mold materials is characterized in that at least a diamines is to be selected from quadrol, 1,4-butanediamine, 1, the 6-hexanediamine, 1,1,12-diamino dodecane ,-and right-benzene dimethylamine, the cyclohexyl dimethylamine, two-(right-aminocyclohexyl) methane and/or its alkyl derivative, and/or at least a dicarboxylic acid is to be selected from propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and sebacic acid, dodecyl diacid, 1,6-cyclohexane diacid, terephthalic acid, m-phthalic acid and naphthalene diacid.

14. the application according to claim 1 or 8 described thermoplastic polyamide mold materials is characterized in that, the polymeric amide of described component (A) is a homopolyamide, is selected from PA 6, PA 11, and PA 46, and PA 66, PA12, PA 1212, PA 9T, and PA 1012, and PA 610, PA 612, and PA 69, PA 6T, PA 6I, PA 10T, PA 12T, PA 12I, their mixture, or the multipolymer that makes by these homopolyamides.

15. thermoplastic polyamide mold material's according to claim 14 application is characterized in that, the polymeric amide of described component (A) is to be selected from PA 11, PA 12, and PA 610, and PA 612, PA 1212, PA 9T, PA 10T, the homopolyamide of PA 12T, or be selected from PA 12T/12, PA 10T/12, PA 12T/610, PA12T/106, the multipolymer of PA 10T/610 and PA 10T/106.

16. according to claim 1 or 8 described thermoplastic polyamide mold materials' application, it is characterized in that described polymeric amide is PA 6/66, PA 6/612, PA 6/66/610, and PA 6/66/12, PA 6/6T, PA66/6T, PA 6/6I and PA 6I/6T.

17. the application according to claim 1 or 8 described thermoplastic polyamide mold materials is characterized in that, the polymeric amide of described component (A) is polymeric amide/polyamine multipolymer, and its polymeric amide has partly comprised by aliphatics C ₆To C ₁₂The polymkeric substance that lactan makes, or the polymkeric substance that makes by omega-amino-carboxylic acid, or the polymkeric substance that makes by aromatic amine yl carboxylic acid with 7 to 20 carbon atoms with 3 to 44 carbon atoms.

18. thermoplastic polyamide mold material's according to claim 17 application is characterized in that, described omega-amino-carboxylic acid is the omega-amino-carboxylic acid of 4 to 18 carbon atoms.

19. thermoplastic polyamide mold material's according to claim 17 application is characterized in that, the omega-amino-carboxylic acid that described omega-amino-carboxylic acid is 12 carbon atoms.

20. the application according to claim 1 or 8 described thermoplastic polyamide mold materials is characterized in that, described polymeric amide is the polymkeric substance that has wherein added additive.

21. thermoplastic polyamide mold material's according to claim 20 application is characterized in that, described additive is selected from the UV stablizer, thermo-stabilizer, crystallization promoter, softening agent, fire retardant, modified impact agent, filler and lubricant.

22. thermoplastic polyamide mold material's according to claim 21 application is characterized in that, described fire retardant is selected from the fire retardant of halogen-free flame retardants series.

23. thermoplastic polyamide mold material's according to claim 22 application is characterized in that, described fire retardant is based on the fire retardant of nitrogen or phosphorus.

24. thermoplastic polyamide mold material's according to claim 22 application is characterized in that, described fire retardant is phosphinates and/or melamine cyanurate and/or triaryl phosphate.

25. application according to claim 1 or 8 described thermoplastic polyamide mold materials, it is characterized in that the described polyamine that is used to prepare polymeric amide/polyamine multipolymer is a polyvinylamine, with the polyamine of polyketone alternating polymerization, dendrimer, linear or grafted polymine.

26. thermoplastic polyamide mold material's according to claim 25 application, it is characterized in that the described polyamine that is used to prepare polymeric amide/polyamine multipolymer is linear or grafted polymine, it has mole 500 to 25, in the 000g/mol scope.

27. thermoplastic polyamide mold material's according to claim 26 application, it is characterized in that the described polyamine that is used to prepare polymeric amide/polyamine multipolymer is linear or grafted polymine, it has mole 800 to 5, in the 000g/mol scope.

28. thermoplastic polyamide mold material's according to claim 26 application is characterized in that the described polyamine that is used to prepare polymeric amide/polyamine multipolymer has 1200 to 5000mPa*s viscosity under 20 ℃.

29. the application according to claim 1 or 8 described thermoplastic polyamide mold materials is characterized in that described moulding material has comprised polyamine, the consumption with 0.2 to 5wt% uses, as the copolymerization component of polymeric amide/polyamine multipolymer.

30. application according to claim 1 or 8 described thermoplastic polyamide mold materials, it is characterized in that, described moulding material has comprised polyamine, consumption with 0.2 to 5wt% uses, as the copolymerization component of polymeric amide/polyamine multipolymer, wherein remaining copolymerization part is made up of polymeric amide in this multipolymer.

31. thermoplastic polyamide mold material's according to claim 29 application is characterized in that, described copolymerization component is a polymine.

32. thermoplastic polyamide mold material's according to claim 29 application is characterized in that, described moulding material has comprised polyamine, and the consumption with 0.4 to 1.5wt% uses, as the copolymerization component of polymeric amide/polyamine multipolymer.

33. thermoplastic polyamide mold material's according to claim 29 application, it is characterized in that, described moulding material has comprised polyamine, consumption with 0.4 to 1.5wt% uses, as the copolymerization component of polymeric amide/polyamine multipolymer, wherein remaining copolymerization part is made up of polymeric amide in this multipolymer.

34. the application according to claim 1 or 8 described thermoplastic polyamide mold materials is characterized in that, described copper bearing stablizer (b ₁) comprised alkali-metal halogenide and cuprous halide (I) and/or stearic acid cuprous (I) and/or Red copper oxide (I).

35. thermoplastic polyamide mold material's according to claim 34 application is characterized in that, the weight ratio of described alkali metal halide and copper (I) total amount of compound is 2.5: 1 to 100: 1.

36. the application according to claim 1 or 8 described thermoplastic polyamide mold materials is characterized in that, the described compound (C) that has a metal complex group is 0.5: 1 to 3: 1 with the mol ratio of cupric (I) total amount of compound.

37. thermoplastic polyamide mold material's according to claim 36 application is characterized in that, described component (C) waits mole in component (b at least ₁) middle copper content.

38. application according to claim 1 or 8 described thermoplastic polyamide mold materials, it is characterized in that described compound (C) is N, [3-(3 for N '-two, 5-di-t-butyl-4-hydroxyphenyl) propionyl]-hydrazides and/or 2,2 '-[ethyl-3-(3 for oxalyl amido-two, 5-di-t-butyl-4-hydroxyphenyl) propionic ester] and/or 3-(salicylyl amino)-1,2,4-triazole and/or 1,2,3-benzotriazole and/or tolyl-triazole and/or 12 diacid two [2-(2-hydroxybenzene first) hydrazides] and/or three [the 2-tertiary butyl-4-sulphur (2 '-methyl-4 '-hydroxyl-the 5 '-tertiary butyl)-phenyl-5-methyl] phenyl-phosphorous acid esters.

39. the application according to claim 1 or 8 described thermoplastic polyamide mold materials is characterized in that, described HALS stablizer is two (2,2,6,6-tetramethyl--4-piperidyl) sebate and/or two (1,2,2,6,6-pentamethyl--4-piperidyl sebate and/or poly-[1-(2 '-hydroxyethyl)-2,2,6,6-tetramethyl--4-hydroxy piperidine base succinate] and/or poly-[[6-(1,1,3, the 3-tetramethyl butyl) amino]-1,3,5-triazines-2,4-two bases] [(2,2,6,6-tetramethyl--4-piperidyl) imido grpup]-1,6-dihexyl [(2,2,6,6-tetramethyl--4-piperidyl) imines].

40. optical fiber (1), it has an optical waveguides (2 at least, 3), this optical fiber is by a fiber core, with one or more layers coating (3), with at least one with described optical waveguides (2,3) Feng Zhuan sleeve pipe (4) is formed, wherein said coating (3) or at least its skin formed by a kind of layer institute that forms by fluorine cpd or fluoropolymer, described sleeve pipe (4) is made up of polymeric amide, it is characterized in that at least one sleeve pipe (4) is made up of a kind of layer based on any the described polyamide molding material in the claim 1 to 39.

41. according to the described optical fiber of claim 40 (1), it is characterized in that, form by a kind of multipolymer of polymeric amide/polyamine with the described sleeve pipe (4) of the described coating adjacency of described fluorine cpd or fluoropolymer.

42. according to claim 40 or 41 described optical fibers (1), it is characterized in that, at least one other sleeve pipe (5) in abutting connection with sleeve pipe (4) is installed, it is for making according to any the polyamide molding material in the claim 1 to 39, but described polycondensation product or polymkeric substance do not have excess of ammonia base terminal group.

43., it is characterized in that described sleeve pipe in abutting connection with sleeve pipe (4) (5) is made up of the another kind of polymkeric substance except that polymeric amide according to claim 40 or 41 described optical fibers (1).

44. according to the described optical fiber of claim 43 (1), it is characterized in that described sleeve pipe (5) by fluoropolymer in abutting connection with sleeve pipe (4), the compound of fluoropolymer, or crosslinked polymkeric substance is formed.

45., it is characterized in that described sleeve pipe (5) is made up of a kind of radiation crosslinking polymkeric substance according to the described optical fiber of claim 44 (1).

46., it is characterized in that described fiber core (2) is by glass according to claim 40 or 41 described optical fibers (1), polycarbonate, fluoropolymer, poly-glutarimide, or form by the mixture that polycarbonate and polymethylmethacrylate make.

47., it is characterized in that the external diameter of described optical waveguides (2,3) is in 75 to 3000 mu m ranges according to claim 40 or 41 described optical fibers (1).

48. according to claim 40 or 41 described optical fibers (1), the external diameter that it is characterized in that described coating (3) is 2000 ± 120 μ m or 1000 ± 60 μ m or 750 ± 45 μ m or 500 ± 30 μ m or 230 ± 20 μ m or 125 ± 10 μ m.

49. according to claim 40 or 41 described optical fibers (1), it is characterized in that the external diameter of described fiber core (2) is at least 8 μ m, maximum 1000 μ m are less than the external diameter of corresponding coating (3).

50. according to the described optical fiber of claim 49 (1), the external diameter that it is characterized in that described fiber core (2) is 10 to 100 μ m, less than the external diameter of corresponding coating (3).

51. according to the described optical fiber of claim 49 (1), the external diameter that it is characterized in that described fiber core (2) is 20 to 80 μ m, less than the external diameter of corresponding coating (3).

52. according to claim 40 or 41 described optical fibers (1), the external diameter that it is characterized in that described optical fiber (1) between 0.15 and 5mm between.

53., it is characterized in that it has comprised a plurality of optical waveguidess (2,3) according to claim 40 or 41 described optical fibers (1).

54., comprise a sleeve pipe (4) and a sleeve pipe (5) according to the described optical fiber of claim 42 (1), it is characterized in that described sleeve pipe (5) has at least one color mark, wherein said color mark is a heatproof, and can be used for expressing technique.