JP2008513818A - Use of stabilized thermoplastic polyamide molding materials as coatings for optical waveguides - Google Patents

Abstract

The present invention relates to a stable thermoplastic polyamide molding material which is protected by coating an optical waveguide having a cladding based on a fluorine compound or a fluorine-based polymer. The polyamide molding material of the present invention exhibits excellent adhesion to a clad based on a fluorine compound or a fluorine-based polymer. Moreover, it has durability at 125 ° C. and a high temperature of 6000 hours or more. Furthermore, the present invention relates to an optical fiber comprising at least one fiber core, one or more claddings, and one or more protective sleeves enclosing the optical waveguide, comprising a stabilized thermoplastic polyamide molding material.
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Description

  The present invention relates to the main object shown in the claims, and is used as a protective film for an optical waveguide (hereinafter simply referred to as OW), which is particularly stabilized and uses a thermoplastic polyamide molding material as a cladding region of a fluorine-based material or a fluorine-based polymer. Related to.

  The polyamide molding material according to the present invention has suitable adhesion to a cladding region of a fluorine-based material or a fluorine-based polymer. Furthermore, it has a high heat resistance of at least 3000 hours at 125 ° C.

  The present invention also relates to an optical cable having a sleeve enclosing at least one fiber core and a surrounding single or multilayer clad and OW, and to a thermoplastic polyamide molding material in which the sleeve is stabilized.

  The optical fiber cable can transmit a large amount of data in the field of telecommunications, has no noise, and transmits data without being affected by electromagnetic waves. For data transmission over a short distance of up to 150 m, an inexpensive plastic optical waveguide such as a polymer optical fiber (POF) is used in addition to a relatively expensive glass optical fiber (GOF).

  The POF is widely used in the field of automobile technology / communication means (transmission of data and signals between automobiles, airplanes, ships, etc.). POF-OW is generally formed from a polymer optical fiber core, cladding, and sleeve. POF is usually formed from polymethyl methacrylate (PMMA). Since the glass transition point of PMMA is 95-100 degreeC, it is restrict | limited to 90 degrees C or less use. Bundled single-wire or multi-core glass optical fiber cores are progressing to withstand high temperatures.

The cladding of POF can be formed in a single layer or multiple layers. Fluorine-containing plastics are mainly used as cladding materials and have a refractive index of 1.35 to 1.42. This refractive index conforms to the refractive index of the fiber core of _PMMA (η _PMMA = 1.49; φ _Kern = 980 nm). Such POF-OW light attenuation is typically 130-150 dB / km (λ = 650 nm) with a minimum bend radius of 5-10 mm. The normal optical transmission measurement is expressed by the following equation, where P _{1 is} the optical energy of the first OW and P ₂ is the optical energy of the terminal OW.
(A) = 10 · logP ₁ / P ₂

In order to measure the attenuation, both levels must be measured. P ₁ is easy to measure with a sufficiently large receiving diode attachment at the end of the fiber. The initial P ₁ of the OW is measured indirectly, taking into account the loss when combined with the OW, so as not to be confused with P ₀ (for details, see “Kunststoffe in der Kabeltechnik” Hands-J. Meyer, 111, 3rd edition, see No. 4.4.2).

  In order to protect the delicate POF-OW mechanically, thermally and chemically, there is a method in which it is coated with plastic and formed as a single or multilayer sleeve (WO99 / 12063). This sleeve is made of polyethylene, polyvinyl chloride, ethylene vinyl acetate copolymer, polyamide, or the like. Then, it must be blackened so that light from the outside does not enter the POF. The use of materials such as polyamide, polyurethane, polyoxymethylene for the sleeve improves the fire resistance (DE 9209018U).

EP 1 376 156 A2 discloses an optical fiber and has an additional layer in addition to a fiber core and a single or multi-layer sleeve: the layer is made of a molding material whose inner layer is made of molding material as a fiber coating and has a zero shear viscosity of 400 ° C. at 400 ° C. ~ 6000 Pas. On the other hand, the outer layer adheres to the inner layer, has a maximum tensile strength of 30 N, is made of a polyamide molding material, and has the following composition.
Polyamide; 20-95% by weight
Fire-resistant component; 5-45% by weight
Impact resistant component: 0 to 60% by weight

  The refractory component described in EP 1376156A2 includes a molding material for the outer layer, suitably a polyamide molding material is described.

  As for POF with improved heat resistance, there is a fiber core made of a thermosetting silicone resin, which is injected in a two-layer coated tube in an uncured state during production. The two-layer coated tube is formed of a black opaque material on the outer side and is firmly bonded to each other by the molding method because it is simultaneously molded.

  In the field of automobile manufacture, polyamide is used as a sleeve material, satisfies the requirements of mechanical stability (tensile strength, fracture resistance, etc.), and is stable in heat resistance and chemicals during the previous use. However, polyamides are problematic because they have poor adhesion to optical waveguides having a clad made of a fluorine-containing polymer.

  Especially when the adhesive strength of the protective sleeve is weak, an optical fiber (for example, consisting of a fiber core, a cladding and at least one sleeve) is subjected to a large temperature change (for example, the interior of an automobile and an engine room, etc.) in the environment. Further, since the thermal expansion coefficient is different from that of the clad and the sleeve and the low adhesion between the fluoropolymer and the polyamide is observed, it is not preferable. For example, the transmission and reception elements (LEDs and pin diodes) are affected by the distance from the surface of the OW, and a loss exceeding the allowable range occurs, leading to a loss of data transfer. In addition, if the OW outer sleeve changes significantly, it will damage the transmitting and receiving elements.

  In order to suppress this (referred to as “positioning” of the OW), the connector, coupler, and retainer form the sleeve with a large clamping force and clipping force, so that the frictional force between the sleeve and the OW becomes large. In addition, deformation occurs at the interface between the fiber core and the clad, which increases signal attenuation.

  While disassembly of the protective layer in the connector prevents "positioning", there is a risk of cladding damage during assembly due to improper handling of the trimming tool with a set of blades.

  The clamping or clipping force from the connector on the optical fiber can be reduced by securing the POF-OW in the cone shape of the connector housing. Using a hot plate, a taper is formed toward the connector hole by surface melting of the POF-OW, and the POF-OW is firmly bonded to the connector by an anchor effect. However, the loss into the connector housing is increased because the POF-OW geometry totally deviates from the cylinder geometry during melting or molding.

  EP 0 649 731 A1 discloses forming a polyamide and polyvinylidene fluoride by adding polyglutarimide to the polyamide. The two-layer laminate is made from polyamide and polyvinylidene fluoride, and the three-layer laminate is formed in one step by extrusion molding by blending polyamide, polyamide-polyglutarimide with polyvinylidene fluoride as an adhesion promoter layer. Polyglutarimide is well known as polymethacrylimide (PMMI).

  POF-OW extrusion is performed at the lowest possible temperature, although the sleeve is directly bonded to the cladding. The glass transition point of the clad fluoride is 80 to 120 ° C., which is close to the fiber core material (PMMA; 106 ° C.). The cladding is very thin (about 10 μm) and the optical features are precisely prepared and are susceptible to being affected or changed by the heat or chemical environment. Accordingly, the sleeve material must be coated at a temperature that melts and penetrates as deeply as possible.

  The inventors of EP1171786 blended from PMMI (pleximide 130, manufacturer Rohm, Germany) and low viscosity polyamide 12 (relative viscosity 1.65 in 0.5% metacresol solution) to determine the melting temperature of the POF-OW cable. Molded at higher blend viscosities and lost almost no optical attenuation of the fiber. Polyamide 12 / PMMI mixtures are not used as sleeve material.

  As another document, an example of polyglutarimide is disclosed in page 6 of EP0649738A1 in the table, and it is very high viscosity and cannot be applied as a three-layer intermediate layer. A molded part of POF-OW as a blend with polyamide 12 It is used as

  EP 0 767 190 A1 describes the use of polyamide adhesive promoters for multi-layer polymer or pipe (eg gasoline and coolant products for automobile production) products. The polyamide used here is usually not of low viscosity. Furthermore, no optical features are required for the layer. The polyamide described in EP0767190A1 has many amide end groups. The acceptable molding temperature is achieved by a POF-OW molding test using an adhesive promoter as described in EP 0767190A1, and the fiber core is not damaged by heat. However, the outer layer of fiber (eg sleeve) turns brown while maintaining the temperature (80 ° C., 24 hours). This is apparently due to monomer diffusion and chemical reaction within the sleeve. This coloring reduces the optical characteristics of the fiber. The polyamide molding material of EP0767190A1 is not suitable for POF-OW and glass OW as an adhesion promoter or protective layer.

  EP0239935B1 describes an optical fiber, which consists of a quartz glass or optical glass core and a plastic material coating, which is obtained by curing a solvent-soluble copolymer of a fluorinated olefin and an alkyl vinyl ether. The copolymer contains at least 10% by weight of a curable part and fluorine derived from fluorinated olefin units.

  EP 0883001 A1 describes an optical fiber consisting of a quartz core and a polymer cladding (PCF) covering it, and discloses a multilayer structure of a plurality of different polymers. The broadband PCF described in EP 0883001 A1 shows significant low losses associated with “crimp type” connectors. Therefore, this PCF is used for high-speed and large-capacity connection such as data communication such as ATM-LAN.

  EP 0 494 463 B1 describes polyamide fusion fillers which contain not only C12-22 fatty acid monomers but also polyamides based on fatty acid dimers and at least two C2-40 amines as main components. This polyamide is a thermoplastic adhesive polyamide having terminal amino groups. The fusion described in EP0749463B1 means high peel strength to metal and has high oil resistance. Furthermore, the vapor permeability is higher than when no polyamide is used. From these characteristics, the thermoplastic adhesive is suitable for bonding not only plastic but also metal, and particularly suitable for bonding not only polyvinyl chloride but also polyester and polyolefin. Furthermore, the present invention is applied to adhesion of a coating layer of a cable, specifically, an optical fiber cable or an electric cable.

  GB2198258A1 describes the use of thermoplastic polyamides for optical waveguide sleeves. The sleeve basically comprises 0 to 95% by weight polyamide 12, 50 to 5% by weight polyamide elastomer and 0 to 95% by weight other polyamides and / or copolyamides. The polyamide elastomer occupying a substantial part of the mixture is a polyetheramide as described in DE-A-3006961, CH-A-0656135, and a polyetherester polyamide as described in DE-A-293697 or DE-A-3428404. .

  JP 04-127107 describes an optical waveguide having a sleeve on the clad and shows that the “pistoning phenomenon” is avoided. As the polymer, polyethylene containing 0.1 to 10% by weight of ethylene vinyl acetate copolymer is basically used as a coating material.

  Application No. CH-00000 / 03 includes a thermoplastic multilayer of at least a first layer based on a fluorinated polymer, at least one second layer, and at least a layer partially adjacent to the first layer. The laminate is described. In order to ensure good adhesion to the fluorinated polymer, a polyamide / polyamine-based layer is provided as an adhesive promoter layer. Such a copolymer appears to have a strong adhesion. This thermoplastic multilayer laminate can be used in particular as a coating for photoconductors with PMMA as the core.

  EP1216823B1 describes a multilayer laminate and optionally includes a layer of polyamide molding material and a layer of polyamide / polyamine copolymer as well as a layer of ethylene vinyl alcohol copolymer. In polyamide molding materials, polyamide / polyamine copolymer compatible intermediates are given, but EP1216823B1 provides good adhesion to fluoropolymer layers without the polyamide / polyamine copolymer mixing with polyamide. There is no description that it has characteristics.

  EP 0 777 578 B1 describes that the first layer is a fluorinated polymer, the second layer is not a fluorinated polymer but an aliphatic di- or polyamide having a molecular weight of at least 1000 or more, and is not a fluorinated polymer such as polyamide, polyimide, polyurethane, carboxyl or anhydrous Alternatively, a multilayer laminate is described in which a polyolefin having an imide group, an amine or the like constitutes the second layer. The amine is a quaternary amine and sufficiently enhances the adhesion between layers without the use of di- or polyamines.

  EP 0955326 B1 describes polyamides modified with dimer diols, including dimer diols and polyesters with hydroxyl groups. Compared to unmodified polyamides, modified polyamides are flexible and sticky even at low temperatures. The change in mechanical properties due to migration due to loss of flexibility and / or contact with the media does not occur due to inherent plasticity. This flexible polyamide has superior resistance to hydrolysis compared to diols containing other polyamides.

  Since polymer optical fibers usually have a PMMA core and a glass transition temperature of 95-100 ° C., such polymer optical fibers are limited to use at temperatures below 90 ° C. as described above.

  However, polyamide molding materials are stable to oxidation by heat and oxidative decomposition by light, and are known in many systems. In addition to copper compounds, phenolic antioxidants known as stabilizer systems, such as sterically hindered phenols, are based on aromatic amines for antioxidant capacity. In particular, a mixture of copper halide and alkali metal halide has a stabilizing effect against oxidation by heat. Mixtures of copper halides and alkali metal halides are also effective for other stabilization systems. If the polyamide is continuously used above 120 ° C, most organic stabilizers are ineffective. If heat-resistant oxidation stability of several thousand hours or more is required, a salt containing copper is effective. The stabilizer can be added to the polyamide by different methods, such as before or during polymerization, or when powdered, during the drying process, and further during mixing.

  The stability of the polyamide molding material and the copper compound is described in EP0745642B1 and EP066843B1. EP 0745642 B1 describes a heat-stable, water-resistant polyamide molding material containing copper halide, with one or more halides and hypophosphoric acid or alkali or alkaline earth metal salts as stabilizers Contains in molar ratio. This stabilizer mixture is excellent in heat oxidation resistance and light oxidation resistance.

  EP 0 668 934 B1 describes stabilized polyamide filaments which contain polyphthalamide and are synergistic with copper stabilizers and functional polyolefins. The copper compound fuses with polyphthalamide and contains a stabilizer in the range of 1 to 20% by weight due to synergy with the alkali halide.

  In addition to the above systems, there are also documents describing further mixed materials for stabilizing the heat-resistant and light-oxidized polyamide. US-A-2705227 describes a ternary stabilizer comprising a copper compound, a halogen compound, phosphoric acid or an alkali salt of phosphoric acid.

  GB-A-1140047 describes a stabilizer consisting of three components: a copper-containing salt, phosphorous acid or phosphoric acid or an acid mixture thereof, and an alkali halide. There is a limitation that phosphorous acid is contained in an amount of 1/2 mol or more of the copper-containing salt. If phosphoric acid is used in place of the phosphite compound, there is a description that it is used in an amount of 1/4 mole or more of the copper-containing salt. The phosphorous acid compound is added to compensate for the shortage of the copper addition amount and to express the bright color of the polyamide molding material.

  DE-A-2107406 describes a three-component stabilizer of copper stearate, calcium iodide and manganese hyposphite. Molding materials stabilized by this mixture are said to be colorless.

  EP-A-0612749 describes stabilized polyamide molding materials. This includes ionic and composite copper stabilizers, and further includes copper with finely dispersed elements as stabilizers.

  Stabilization systems that inhibit the thermal and photo-oxidation properties of polyamide molding materials are also known. There is an increasing demand for the stability of polyamide molding materials related to thermal and photo-oxidation properties. For example, a case where a polyamide molding material used for an engine part of an automobile is applied. In other fields, polyamide molding materials are used in an environment where a temperature load is applied for a long time. Under these temperatures, copper-based stability is particularly suitable for polyamides.

  The stabilization mechanism of polyamides by a combination of copper halide and alkali halide metal salts is described, for example, in P. Gijsman et al., Polymer Degradation and Stability 49 (1995), 127-133. Combinations of aromatic halides and copper-containing salts are described in DE-A 19844762 and also disclosed in mixtures with mercaptans or phosphine. The technology for these copper-based stabilizers will decrease.

  Metal use weight loss techniques for antioxidant effects are also known, for example, with molecules containing sterically hindered phenols. Often these mixtures are used, for example, for stabilizing polyolefins for cables, especially when used continuously in contact with polyphenylene ether or copper.

  According to the cited literature (Plastics Additives Handbook, 4th Ed., 1993, chapter 2.4), the following chemical structure is described regarding stabilization by metal. Aliphatic amides and aromatic mono-dicarboxylic acids, N-monosubstituted derivatives, cyclic amides, barbituric acids, aliphatic and aromatic aldehyde hydrazones and bishydrazones, aliphatic and aromatic mono-dicarboxylic acid hydrazides, bisacrylates Hydrazine derivatives, heterocyclic compounds such as melamine, benzotriazole, 8-oxoquinoline, hydrazone, acrylate derivatives of hydrazinotriazine, aminotriazole and its acrylate derivatives, polyhydrazides, sterically hindered phenol molecular conjugates, metal complexes, benzyl phosphorus Nickel acid salts, other antioxidants and metal derivatives, pyridine thiol / tin mixtures, thiobisphenol triphosphates, etc. The patent literature further describes N, N ′ bis-salicyl-ethylenediimide, salicyloxyamine, ethylenediaminetetraacetic acid derivatives and the like. However, many of the above compounds cannot actually be used as metal stabilizers for thermoplastics. This is because the activity is low, sufficient heat stability is not provided, and there is a problem in volatility.

  EP 1198520B1 describes the use of sterically hindered phenols in polyamide molding materials.

  A person skilled in the art, as an organic mixture, includes a homologue of a sterically hindered phenol, at least a phenol group, at least one half of an aromatic ring, preferably two or more positions substituted, and the phenol group directly bonded to a carbon atom Is said to have antioxidant properties. The substituent of the hydroxy group is an alkyl group, preferably selected from C1-10 alkyl groups. Preferably, it is a t-butyl group. A preferred sterically hindered phenol is tetrakis (methylene (3,5-di (tertiary) -butyl-4-hydroxystannic acid)) methane, commercially available from Irganox® 1010 (Ciba Specialty Chemicals). ) HT (high temperature) polyamide molding materials to which an antioxidant having a sterically hindered phenol group is added are well known and have been shown to have high thermal stability (EP1198520B1).

  An object of the present invention is to provide a stable thermoplastic polyamide molding material, particularly suitable for coating a light guide having a thermal stability of at least 3000 hours at 125 ° C. and a clad of a fluorinated compound or a fluoropolymer. It is to provide a polyamide molding material.

  Yet another object is to provide an optical fiber that provides a protective layer with excellent thermal stability at 125 ° C. for at least 3000 hours and adhesion to a fluorinated compound or fluoropolymer clad.

  In the present specification, the inventors clarify the following. The viscosity of the polyamide molding material is increased by the interaction between the terminal amino group of the polyamide and the copper compound. This viscosity effect depends on the relationship between terminal amino groups and processing conditions (for example, drying temperature and drying period). As described above, the viscosity (the viscosity of the solution and the viscosity in the molten state) varies depending on the processing conditions (drying temperature and drying period), and the function is improved or decreased. In the manufacturing process, large changes in viscosity are unacceptable.

  In order to form tubes and gel parts, increasing viscosity requires processing at higher temperatures. It will form an irregular coating and is therefore unacceptable.

  The object is solved by using the thermoplastic molding material according to claim 1 and is used not only as an optical fiber according to claim 18 but also as a covering protective layer of an optical waveguide having a clad of a fluorine compound. The dependent claims show preferred examples of the invention.

  The thermoplastic polyamide molding material according to the invention has a thermal stability of at least 3000 hours at 125 ° C. In another preferred example according to the invention, the thermoplastic molding material has a thermal stability of at least 4000 hours at 125 ° C, more preferably a thermal stability of 5000 hours at 125 ° C, particularly preferably 125 ° C. Has a thermal stability of 6000 hours. The thermoplastic polyamide molding material according to the present invention has the following composition.

(A) A polyamide which is a polymer or a polycondensate and is an aliphatic lactam (preferably C6-12) or ω-aminocarboxylic acid (C3-44, preferably C4-18, more preferably C12), or Said polyamides based on C7-20 aromatic aminocarboxylic acids,
Or a polycondensate of at least one diamine of C2 to 44 and at least one dicarboxylic acid of C2 to 44,
The diamine is preferably selected from C2-18 aliphatic diamines, C7-22 cycloaliphatic diamines,
The dicarboxylic acid is selected from C3-44 aliphatic dicarboxylic acids, C8-24 cycloaliphatic dicarboxylic acids, C8-20 aromatic dicarboxylic acids,
The polyamide which is a polymer or polycondensate having many terminal amino groups;
(B) 0.01-2% by weight of a copper-containing stabilizer (b ₁ ), or a combination of a sterically hindered phenol and a HALS stabilizer (b ₂ ), or a sterically hindered phenol (b ₃ ), based on the polyamide, (C) 0 to 3% by weight, preferably 0.01 to 3% by weight based on the polyamide, forming a complex with a metal (acid amide, oxyamide, oxalanilide, hydrazine, acid hydrazide, benzotriazole, etc. And at least one organic compound selected from sulfur-containing phosphorous acid,
The sum of (A), (B) and (C) is 100% by weight. (D) One or more functional polymers (preferably functional polyolefins, functional polyolefin copolymers) It is characterized by adding 0 to 45% by weight, preferably 0 to 25% by weight, based on the total of B) and (C).

One or more terminal amino groups are required for the component (A) of the present invention so as to have a high adhesion to the fluorine compound and the fluorine polymer. In order to improve heat resistance, a copper-containing stabilizer (b ₁ ), a combination of a sterically hindered phenol and a HALS stabilizer (b ₂ ), or a sterically hindered phenol (b ₃ ) is added.

In particular, a copper-containing stabilizer (b ₁ ) is required in the present invention. The addition of the metal moderator component (C) is important in the present invention in order to eliminate the processability penalty resulting from the combination of the terminal amino group and the copper stabilizer.

These polyamide molding materials are used for coating OWs, which are polyamide / polyamine copolymers or the following polycondensates or polymers:
Component (A):
Polyamide is preferably a polycondensation component having many terminal amino groups, and is an aliphatic lactam (preferably C6-12), ω-aminocarboxylic acid (C3-44, preferably C4-18), or aromatic ω-aminocarboxylic acid (C7-20),
Or there exists a polycondensation component with many terminal amino groups which consists of at least 1 type of diamine of C2-44 and at least 1 type of dicarboxylic acid of C2-44. For example, ethylenediamine, 1,4 diaminobutane, 1,6 diaminohexane, 1,10 diaminodecane, 1,12 diaminododecane, m-, p-xylenediamine, cyclohexyldimethylenediamine, bis- (p- Aminocyclohexyl) methane, and their alkyl derivatives.

  Dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 1,6 cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc. There is.

  Particularly preferred polyamides having a large terminal amino group (hereinafter abbreviated as PA) for molding materials for OW coating include PA6, PA11, PA46, PA66, PA12, PA1212, PA1012, PA610, PA612, PA69, PA6T, PA61, PA10T. Homopolyamides selected from PA12T, PA12I, or mixtures thereof, or copolymers based on homopolyamides such as PA11, PA12, PA610, PA612, PA1212, PA9T, PA10T, PA12T, in particular as copolymers PA12T and PA12, PA10T and PA12, PA12T and PA610, PA12T and PA106, PA10T and PA610, and PA10T and PA106 copolymers. Further, PA6 and PA66, PA6 and PA612, PA6 and PA66 and PA610, PA6 and PA66 and PA12, PA6 and PA6T, PA66 and PA6T, PA6 and PA6I, PA6I and PA6T, and the like are also preferable.

  As the polymer and / or polycondensate of component (A), the amount of terminal amino groups is 20 to 300 μequ. / G, preferably 40 to 300 μequ. / G, based on the polyamide main chain, and the terminal carboxyl group is Polyamides less than 20 μequ. / G are preferred, preferably less than 15 μequ. / G.

  The relative viscosity of the polyamide component (A) is 0.5% m-cresol solution, the value at 20 ° C. is less than 1.8, more preferably in the range of 1.4 to 1.8.

  The polyamide of the polyamide / polyamine copolymer is a C6-12 fatty acid lactam, an ω-aminocarboxylic acid (C3-44, preferably C4-18, more preferably C12), or a C7-20 aromatic aminocarboxylic acid. The polymer.

  Depending on the purpose, different or ordinary polymers can be added to these (co) polymers. For example, UV stabilizers, crystallization accelerators, fillers, flame retardants, lubricants and the like.

  Flame retardants include halogen-free flame retardants based on nitrogen or phosphorus. In the present invention, hypophosphorous acid, melamine cyanurate, triallyl phosphate and the like are particularly preferable. Hypophosphite as a flame retardant added to the polyamide molding material has a test piece thickness of 0.4 mm and a UL-94 test (American Insurer Safety Laboratory) V0. As preferred hypophosphorous acid or a salt thereof, dimethyl hypophosphorous acid, ethylmethyl hypophosphorous acid, diethyl hypophosphorous acid, methyl n-propyl hypophosphorous acid, methandi (methyl hypophosphorous acid), ethane 1 , 2-di (methyl hypophosphorous acid), hexane 1,6-di (methyl hypophosphorous acid), benzene 1,4-di (methyl hypophosphorous acid), methylphenyl hypophosphorous acid, diphenyl hypophosphite A phosphoric acid is mentioned.

  Hypophosphite can be synthesized by known methods and is described, for example, in EP0699708A1. Hypophosphite reacts with metal carbonate, metal hydroxide, and metal oxide in an aqueous solution to form a monomer, and polymer type hypophosphite is produced depending on the reaction conditions.

  Hypophosphite contains a few metal ions in the periodic table, and preferably a salt such as calcium or aluminum is used. Hypophosphite can be used as a mixture thereof. In order to achieve a good dispersion when mixed with the polymer, they are used in powder form.

  As the polyamide according to the present invention, polyvinylamine, polyamine derived from polyketone, dendrimer, linear or branched polyethyleneimine, and the like can be used for the polyamide / polyamine copolymer. For example, when linear or branched polyethyleneimine is used, the molecular weight is 500 to 25000 g / mol, preferably 800 to 5000 g / mol. Furthermore, the viscosity is 1200 to 5000 mPa · s at 20 ° C.

A typical polyamide / polyamine copolymer has a terminal amino group content of 40-300 μequ. / G. In particular melt flow rate according to ISO1133 (melt volume rate: MVR) is 10~1000cm ^3/10 min when 275 ° C. / 5 kg. MVR is measured after melting for 4 minutes at 275 ° C. in a volume that melts and flows for 10 minutes. In the standard measurement, a load of 5 kg is applied.

  The polyamine of the present invention is particularly preferably polyethyleneimine, and can be used in an amount of 0.2 to 5% by weight, more preferably 0.4 to 1.5% by weight as a component of the polyamide / polyamine copolymer, with the balance Is a polyamide.

About component (B) (0.01-2 weight%) Stabilization component (B) is used in the ratio of 0.01-2 weight% of a polyamide molding material. And the following three components are included.
(B ₁ ) copper-containing stabilizer (b ₂ ) composition of HALS and at least one sterically hindered phenol (b ₃ ) at least one sterically hindered phenol

  When using a copper containing stabilizer, it adds as a metal composite in a molding material, and the quantity is 0.01 to 3 weight% with respect to polyamide.

A combination of an alkali halide salt and any one of copper (I) halide, copper (I) stearate and copper (I) oxide is a preferred component (b ₁ ), and an alkali halide salt and copper ( I) The ratio to the total of the compounds is preferably in the range of 2.5: 1 to 100: 1.

  As a specific example of the present invention, component (C) is used in a molar ratio of 0.5: 1 to 3: 1 with respect to the copper (I) compound. In the production of the thermoplastic molding material, it is more preferable that the component (C) is used in an equimolar amount with the component (B).

  For example, the following composition is mentioned as a HALS stabilizer. : Bis (2,2,6,6-tetramethyl-4-piperidinyl) sebastate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebastate, poly [1- (2′-hydroxyethyl) ) -2,2,6,6-tetramethyl-4-hydroxypiperidinyl succinate], poly [[6- (1,1,3,3-tetramethylbutyl) amino] -1,3,5- Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] -1,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl) ) Imino]].

  Preferred metal moderators (MM) according to the present invention are compounds capable of forming a complex with metals, particularly copper. The metal forms a complex with the following groups: Acid amide, oxamide, oxalanilide, hydrazine, hydrazide acid, hydrazone, benzotriazole and the like. For the structure of metal moderators, see Plastics Additives Handbook, 4th Ed., 1993, chapter. 2.4.

Specific examples of MM as component (C) are:
1,2,3-benzotriazole, triallyltriazole, 3- (salicyloylamino) -1,2,4-triazole, bis [2- (2-hydroxybenzoyl) hydrazide] dodecanoate, 2 ′, 3- Bis [[3- [3,5-di-t-butyl-4-hydroxyphenyl] propionyl]]-propion hydrazide, tris [2-t-butyl-4′-thio (2′-methyl-4′-hydroxy) -5'-t-butyl) -phenyl-5-methyl] phenyl phosphate and the like.

Component (D) (0 to 45% by weight, preferably 0 to 25% by weight)
The component (D) is preferably a polyolefin copolymer grafted with polyolefin, acrylic acid, succinic anhydride, or maleic anhydride. This component is used to enhance the adhesion and impact absorption of polyamides, for example, functional polyethylene, low density or linear low density polyethylene (LLD-PE), linear, branched, cyclic alkene and ethylene. There are polymers (for example, ethylene / propylene copolymers).

  If the components (A), (B), and (C) are 100 in total, the component (D) is arbitrarily added thereto.

  Here, PA12 will be described as a polyamide used in the present invention. Polymerize by adding 0.05 to 3% by weight of lauric lactam and one or more amines, for example, monoamines, preferably hexamethylenediamine, dodecanediamine, lauromine, polyethyleneimine, etc. as di- or polyamines and adding 5 to 20% by weight of water. Can be obtained. The polymerization conditions are 290 to 330 ° C., 20 bar for 1 to 6 hours, or usually under a nitrogen stream at 260 to 290 ° C. for 0.5 to 6 hours.

  The obtained polyamide has a relative viscosity (measured with a 0.5% cresol solution at 20 ° C.) of 2.0 or less, preferably 1.8 or less, and a terminal amino group of 20 to 300 μequ. / G, preferably 40 to 300 μequ. The terminal carboxyl group is 20 μequ. / g or less, preferably 15 μequ. / g or less.

  This polyamide has many terminal amino groups and can be molded by a double screw type extrusion molding at a temperature of 200 to 280 ° C. In order to disperse the metal moderator satisfactorily, it is added during the screw mixing and kneaded with other additives.

  The conditions for drying the granular product are 110 ° C. and 24 hours. Examples of the present invention will be described below.

Polyamide according to the present invention Table 1 shows polyamide 12 having a terminal amino group (manufactured by EMS Chemie AG).

  Table 2 shows physical property values of MVR of the polyamide molding material measured under dry conditions and melt conditions. In Table 2, MM1 is dodecanedioic acid bis [2- (2-hydroxybenzoyl) hydrazide]. MM2 represents 2 ′, 3-bis [[3- [3,5-di-t-butyl-4-hydroxyphenyl] propionyl]]-propion hydrazide, and MM is a metal moderator.

  Relative viscosity (0.5% m-cresol solution), MVR (230 ° C., 2.16 kg, 4 minutes after melting) were measured using granules dried under standard conditions. In MVR measurement, the value measured 10 minutes or 20 minutes after melting is also shown.

  The relative viscosity (0.5% m-cresol solution) was measured using the material obtained after MVR measurement (using granules dried under standard conditions).

  Granules dried at 110 ° C. for 24 hours were used for measurement of relative viscosity and MVR.

  Table 2 shows the evaluation of polyamide by heat load. The polyamide of the comparative example is inferior in workability because the viscosity increases during the process such as forming a small lump as the temperature rises, and the viscosity changes during the treatment. On the other hand, Examples 1-3 do not have such a thing, and it turns out that it is excellent in workability.

  All polyamides in the table are excellent in adhesion before storage. However, after storage at 125 ° C. for 3000 hours, only Examples 1 to 3 can satisfy the requirements. The sleeve (4) made of the comparative polyamide was broken in the destructive test after storage.

  1 to 3 show the impact tensile strength when stored at 100 ° C, 120 ° C, and 140 ° C. From the graph, it can be seen that the impact tensile strength changes according to the storage period.

  From the initial value of the measurement, it can be seen that the comparative example (in Table 2) is considerably low and decreases with a considerable slope. On the other hand, in the case of Example 2, there is no such thing and it turns out that it has the outstanding storage durability.

  According to FIGS. 1-3, it turns out that it is excellent not only in the process characteristic which was excellent by using the metal moderator of this invention but in mechanical stability.

  The optical fiber (1) of the present invention has at least a core (2), one or more multilayer clads (3), and at least one sleeve (4) so as to cover the OW (2, 3). The clad (3) is a multilayer clad based on a fluorinated compound or a fluoropolymer, the sleeve (4) is made of polyamide, and at least one layer of the sleeve (4) is a polyamide according to claims 1 to 17 of the present invention. Based on molding material.

  The sleeve (4) of the present invention may be a polyamide / polyamine copolymer adhered to a fluorinated compound or a clad of a fluoropolymer.

  In another embodiment, a sleeve (5) of polyamide molding material can also be adhered to the sleeve (4), which material may not be rich in polycondensates or polymer terminal amino groups.

  In another specific example, the sleeve (5) may be a polymer other than polyamide. As the material of the sleeve (5) of the present invention, polyvinyl chloride, polyvinyl acetate, ethyl-vinyl acetate copolymer, polyurethane, polyoxymethylene, polyethylene, polyethylene copolymer, polypropylene, polypropylene copolymer, fluorine polymer, Fluoropolymer compounds, ethylene-tetrafluoroethylene copolymers, polyvinylidene fluoride, crosslinkable polymers, and the like.

When the polyolefin sleeve (5) is used, a material for increasing the adhesive force between the sleeve (4) and the sleeve (5) can be used if necessary. For this purpose, known polyamide adhesion enhancers can be used, and b ₁ , b ₂ , b ₃ (the component (B)) can also be used as stabilizers.

  The polyethylene used for the sleeve (5) may have a substituent such as a carboxyl group, an anhydrous group, or an imide group, and may be a polyethylene copolymer.

  The crosslinkable polymer has crosslink points such as peroxide, silane, and radical generating group. Other polymers can be combined, for example, polyethylene, polyethylene copolymer, high density, intermediate density, low density, linear low density polyethylene (LLD-PE), metallocene polyethylene, polypropylene, polypropylene copolymer, Examples thereof include a copolymer of ethylene propylene rubber and polypropylene, and a blend of polypropylene and ethylene propylene rubber or polyurethane.

  As another specific example, the sleeve (5) may be a fluorine-based polymer, a compound of a fluorine-based polymer, a crosslinkable polymer, a radically polymerizable polymer, or the like.

  The fiber core (2) according to the present invention is made of glass, polycarbonate (PC), fluorine-based polymer, polyglutarimide, a blend of polycarbonate and polymethyl methacrylate, or the like.

  As a specific example of the optical fiber of the present invention, both the sleeve (4) and the sleeve (5) are provided. The sleeve (5) may be formed in at least one line that is color-marked. Color marking has heat resistance and can be applied during molding.

  In the optical fiber (1) of the present invention, the optical waveguide (OW2, 3) portion has a diameter of 75 to 3000 μm. The diameter of the clad (3) is usually 2000 ± 120 μm, 1000 ± 60 μm, 750 ± 45 μm, 500 ± 30 μm, 230 ± 20 μm, 125 ± 10 μm.

  As a special example, the fiber core (2) is at least 8 μm, at most 1000 μm, preferably 10-100 μm, more preferably 20-80 μm, which is smaller than the corresponding diameter of the cladding (3).

  The outer diameter of the optical fiber (1) is in the range of 0.15 to 5 mm.

  Other specific examples of the optical fiber (1) can include a plurality of optical waveguides (OW).

  The specific structure of the fiber (1) according to the present invention is shown in FIG.

  It is understood that the fiber as a whole consists of a fiber core, a cladding, and one or more sleeves. The term fiber includes any fiber core and clad such as OW, POF, and GOF.

  A flame retardant polyamide such as PA12 or a polyamide elastomer such as polyether amide, polyether ester amide, or polyester amide is effective for making the sleeve (5) flame retardant.

Here, the fiber bonding is defined. The adhesive force required for the sleeve is as follows.
・ Adhesive strength of sleeve (4) to clad (inner diameter 1mm, outer diameter 1.5mm)
≧ 50N (per 30mm length of sleeve 4)
・ Adhesive strength of sleeve (5) to sleeve (4) (inner diameter 1.5 mm, outer diameter 2.3 mm)
20 ± 10N (per 30mm length of sleeve 5)

The method for measuring the adhesion of the sleeve to the clad is as follows.
・ Peel a part of the 50 mm long sleeve. However, 30 mm is left as an adhesive part.
-Pass the fiber directly through a brass plate with holes. The hole diameter is about 0.1 mm larger than the outer diameter of the sleeve (4).
• Clip the end of the fiber to a tensile tester. (Tensile speed is 100 mm / min)
-Measure the tensile stress when peeling the sleeve (4) from the clad.

Another specific example is shown about the fiber of this invention.
(Optical fiber polymer (POF))
・ POF core has a diameter of 980μm
-Cladding layer thickness of fluoropolymer: 20 μm, outer diameter: 1 mm
-Layer thickness of sleeve 1: 0.25 mm, inner diameter 1 mm, outer diameter 1.5 mm
-Layer thickness of sleeve 2: 0.35 to 0.4 mm, inner diameter 1.5 mm, outer diameter 2.3 mm

(Glass optical fiber (GOF))
a) Polymer clad silica (PCS fiber): From inside to outside-Core diameter 200 μm
・ Clad diameter 230μm
・ Sleeve diameter 500-2000μm
b) Hard clad silica (HCS fiber): From inside to outside-Core diameter 125-400 μm
・ Clad diameter 140 ~ 430μm
・ Sleeve diameter 250 ~ 730μm

(When used for product coating)
The light transmitting material having the fiber core and the cladding needs to be affected by the external environment and prevented from being damaged. Therefore, the fibers are individually or collectively coated, and the following plastics can be used as the sleeve. Polyethylene (PE), polyvinyl chloride (PVC), ethylene tetrafluoroethylene copolymer (ETFE), ethylene vinyl acetate copolymer (EH), polyamide (PA), polytetrafluoroethylene (PTFE), or other materials In combination. The sleeve can be formed in a single layer or multiple layers and can have different thicknesses.

  The sleeve can be continuously extruded. An extruder is provided after the unwinder to extrude the sleeve material as fibers. The fiber is cooled with a chiller, and this is wound up by a rewinder. (A. Winert, Kunststofflichtwellenleiter: Grundlagen, Komponenten, Installation Publicis MCD Verlag, Erlangen and Munich, 1998, page 51)

Further, the coated product is manufactured as follows.
1. 1. Step of manufacturing an outermost layer provided separately 2. Steps of continuous extrusion by different extruders by the so-called tandem method (FIG. 5 shows the formation of a two-layer coating by the tandem method) At the same time, one or more sleeves are formed.

  When manufacturing optical waveguide coatings, special attention must be paid to temperature, pressure, and traction. This is because light attenuation and geometry are affected by these parameters, which degrades the light transmission of the fiber.

  During extrusion of the first sleeve, which adheres directly to the cladding, the temperature is better as low as possible, for example 160-, since the polymer material of the sleeve is melted and POF is sensitive to temperature and damages the fiber. It is good to carry out between 220 degreeC. For example, for GOF and other fibers, the processing temperature is in the range of 160-250 ° C.

  Sleeves can also be used for tube coverings (Kunststofftechnik, Kabel und isolierte Leitungen, VDI-Verlag, Dusseldorf, 1984, page 71). In this case, the sleeve is applied further out of the tool outside the cladding of the fiber core. This method does not apply extra pressure to the fiber core and cladding. Similarly, no pressure is applied during extrusion molding.

  By selecting an appropriate tool (nozzle, core, etc.), the adhesive force between the POF and the sleeve can be adjusted, and the sleeve can be provided with optimum thermal conductivity.

  Since GOF has a lower influence on heat than POF, when a sleeve is formed, it can be preheated by a cylindrical heater to achieve a desired adhesive force.

FIG. 1 is a diagram showing the impact tensile strength after heat storage at 140 ° C. FIG. 2 is a diagram showing the impact tensile strength after heat storage at 100 ° C. FIG. 3 is a diagram showing the impact tensile strength after heat storage at 120 ° C. FIG. 4 is a view showing the structure of the fiber according to the present invention. FIG. 5 is a main conceptual diagram of a two-layer coat by the tandem method.

Claims (29)

A coating agent for an optical waveguide having a clad based on a fluorine compound or a fluorine-based polymer, wherein the polyamide molding material is used for heat resistance stability of at least 125 ° C. for 6000 hours,
(A) A polyamide which is a polymer or a polycondensate and is an aliphatic lactam (preferably C6-12) or ω-aminocarboxylic acid (C3-44, preferably C4-18, more preferably C12), or Said polyamides based on C7-20 aromatic aminocarboxylic acids,
Or a polycondensate of at least one diamine of C2 to 44 and at least one dicarboxylic acid of C2 to 44,
The diamine is preferably selected from C2-18 aliphatic diamines, C7-22 cycloaliphatic diamines,
The dicarboxylic acid is selected from C3-44 aliphatic dicarboxylic acids, C8-24 cycloaliphatic dicarboxylic acids, C8-20 aromatic dicarboxylic acids,
The polyamide which is a polymer or polycondensate having many terminal amino groups;
(B) 0.01-2% by weight of a copper-containing stabilizer (b ₁ ), or a combination of a sterically hindered phenol and a HALS stabilizer (b ₂ ), or a sterically hindered phenol (b ₃ ), based on the polyamide, (C) 0 to 3% by weight, preferably 0.01 to 3% by weight with respect to the polyamide, forming a complex with a metal (acid amide, oxyamide, oxalanilide, hydrazine, acid hydrazide, benzotriazole, etc. And at least one organic compound selected from sulfur-containing phosphorous acid,
The sum of (A), (B), and (C) is 100% by weight, and (D) one or more functional polymers (preferably functional polyolefin, functional polyolefin copolymer) (B) and (C) were added in an amount of 0 to 45% by weight, preferably 0 to 25% by weight,
Use method of the polyamide molding material containing each said component. The polymer or polycondensate of the component (A) contains 20 to 300 μequ. / G, particularly 40 to 300 μequ. / G, of terminal amino groups with respect to the polyamide.
The terminal carboxyl group is contained in the polyamide in an amount of 20 μequ. / G or less, particularly 15 μequ. / G or less.
A method for using the polyamide molding material according to claim 1.   The relative viscosity of the component (A) polyamide measured at 20 ° C. in a 0.5% m-cresol solution is 2.0 or less, particularly 1.8 or less, more preferably 1.4 to 1.8. The method of using a polyamide molding material according to claim 1 or 2, which is a range. The diamine is ethylenediamine, 1,4 diaminobutane, 1,6 diaminohexane, 1,10 diaminodecane, 1,12 diaminododecane, m- or p-xylenediamine, cyclohexyldimethylenediamine, bis- (p-aminocyclohexyl). ) One or more selected from methane and alkyl derivatives thereof,
The dicarboxylic acid is selected from malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 1,6 cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid. More than one kind selected,
The use method of the polyamide molding material in any one of Claims 1 thru | or 3. A homopolyamide selected from PA6, PA11, PA46, PA66, PA12, PA1212, PA1012, PA610, PA612, PA69, PA6T, PA6I, PA10T, PA12T, PA12I, or a mixture thereof;
Alternatively, copolymers based on homopolyamides selected from PA11, PA12, PA610, PA612, PA1212, PA9T, PA10T, PA12T, in particular, copolymers include PA12T and PA12, PA10T and PA12, PA12T and PA610, PA12T and PA106, PA10T and PA610, PA10T and PA106 copolymers are preferred,
The use method of the polyamide molding material in any one of Claims 1 thru | or 4. The polyamide is PA6 and PA66, PA6 and PA612, PA6 and PA66 and PA610, PA6 and PA66 and PA12, PA6 and PA6T, PA66 and PA6T, PA6 and PA6I, PA6I and PA6T,
The use method of the polyamide molding material in any one of Claims 1 thru | or 5. The polyamide of component (A) is a polyamide / polyamine copolymer, and the polyamide portion of the copolymer is a C6-12 fatty acid lactam, ω-aminocarboxylic acid (C3-44, preferably C4 -18, more preferably C12), or based on C7-20 aromatic aminocarboxylic acids,
The use method of the polyamide molding material in any one of Claims 1 thru | or 6. As an additive to the polyamide, one or more of a UV stabilizer, a heat stabilizer, a crystallization accelerator, a plasticizer, a flame retardant, a shock absorber, a filler, a lubricant,
The use method of the polyamide molding material in any one of Claims 1 thru | or 7. The flame retardant is selected from halogen-free flame retardants, in particular based on nitrogen or phosphorus;
Preferably, it is one of hypophosphorous acid, melamine cyanurate, triallyl phosphate,
A method for using the polyamide molding material according to claim 8. The polyamide used in the preparation of the polyamide / polyamine copolymer uses polyvinylamine, polyamines derived from polyketones, dendrimers, linear or branched polyethyleneimines,
The use method of the polyamide molding material in any one of Claims 1 thru | or 9. The polyamine used to produce the polyamide / polyamine copolymer is either linear or branched polyethyleneimine;
The molecular weight of the imine is 500 to 25000 g / mol, preferably 800 to 5000 g / mol, and its viscosity is 1200 to 5000 mPa · s at 20 ° C.
The use method of the polyamide molding material of Claim 10. The polyamide molding material contains a polyamine, and polyethyleneimine is particularly suitable as the polyamine, and 0.2 to 5% by weight, more preferably 0.4 to 1.5% by weight as a component of the polyamide / polyamine copolymer. The balance is polyamide,
The use method of the polyamide molding material in any one of Claims 1 thru | or 11. The copper-containing stabilizer (b ₁ ) is an alkali halide salt;
It is a combination with at least one of copper (I) halide, copper (I) stearate, copper (I) oxide,
The ratio of the alkali halide salt to the sum of the copper (I) compounds ranges from 2.5: 1 to 100: 1.
The use method of the polyamide molding material in any one of Claims 1 thru | or 12. The complex component (C) with the metal is in a range of a molar ratio of 0.5: 1 to 3: 1 with respect to the total of the copper (I) compound,
The component (C) is at least equimolar with the amount of copper of the component (b ₁ ).
The use method of the polyamide molding material in any one of Claims 1 thru | or 13. The component (C) is N, N′-bis [3- (3,5) -di-t-butyl-4-hydroxyphenyl) propionyl] -hydrazide, 2,2′-oxamido-bis [ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3- (salicyloylamino) -1,2,4-triazole, 1,2,3-benzotriazole, triallyltriazole, dodecanni Acid bis [2- (2-hydroxybenzoyl) hydrazide], tris [2-t-butyl-4'-thio (2'-methyl-4'-hydroxy-5'-t-butyl) -phenyl-5-methyl Including one or more selected from phenyl-phosphate,
The use method of the polyamide molding material in any one of Claims 1 thru | or 14. The HALS stabilizer is bis (2,2,6,6-tetramethyl-4-piperidinyl) sebastate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebastate, poly [1- ( 2'-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidinyl succinate], poly [[6- (1,1,3,3-tetramethylbutyl) amino] -1 , 3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] -1,6-hexanediyl [(2,2,6,6-tetra Methyl-4-piperidinyl) imino]].
The use method of the polyamide molding material in any one of Claims 1 thru | or 15. The component (D) is at least one of a polyolefin and a polyolefin copolymer,
Grafted with at least one of acrylic acid, succinic anhydride, maleic anhydride,
The use method of the polyamide molding material in any one of Claims 1 thru | or 15. At least one optical waveguide (OW) (2, 3) comprising a fiber core (2), one or more claddings (3), and at least one sleeve (4) covering the optical waveguide (2, 3). An optical fiber (1) having
The cladding (3) or its outermost layer is based on a fluorine compound or a fluorine-based polymer,
The sleeve (4) comprises polyamide;
Optical fiber (1), characterized in that the at least one sleeve (4) is based on one or more polyamide molding materials according to any of the preceding claims.   The optical fiber (1) according to claim 18, wherein the sleeve (4) that adheres to a cladding of a fluorine compound or a fluorine-based polymer comprises a polyamide / polyamine copolymer.   20. A polyamide condensate according to claim 1, which is a polycondensate or polymer that does not have many terminal amino groups, and is bonded to the sleeve (4) to form at least one sleeve (5). An optical fiber (1) according to claim 18 or 19.   20. Optical fiber (1) according to claim 18 or 19, wherein the sleeve (5) which adheres to the sleeve (4) is another polymer other than polyamide.   The optical fiber (1) according to claim 21, wherein the sleeve (5) that adheres to the sleeve (4) comprises any one of a fluorine-based polymer, a fluorine-based polymer compound, and a crosslinkable polymer (particularly a radically crosslinkable polymer).   The fiber core (2) is made of any one or more of glass, polycarbonate (PC), fluoropolymer, polyglutarimide, and a blend of polycarbonate and polymethyl methacrylate (PMMA). Optical fiber (1).   The optical fiber (1) according to claim 18 to 23, wherein the outer diameter of the optical waveguide (OW) (2, 3) is 75 to 3000 µm.   25. Optical fiber according to claim 18-24, wherein the outer diameter of the cladding (3) is either 2000 ± 120 μm, or 1000 ± 60 μm, or 750 ± 45 μm, 500 ± 30 μm, 230 ± 20 μm, 125 ± 10 μm. 1).   26. Optical fiber (1) according to claim 18-25, wherein the outer diameter of the fiber core (2) is 8 to 1000 [mu] m, preferably 10 to 100 [mu] m, more preferably 20 to 80 [mu] m and smaller than the outer diameter of the cladding (3).   27. Optical fiber (1) according to claims 18 to 26, wherein the outer diameter of the optical fiber (1) is 0.15 to 5 mm.   28. Optical fiber (1) according to claims 18 to 27, comprising a plurality of optical waveguides (OW) (2, 3).   A sleeve (4) and a sleeve (5), wherein the sleeve (5) is one or more stripes forming a color mark, and the color mark is heat resistant to the temperature during extrusion. Optical fiber (1) according to 18 to 28.

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