WO2014148609A1 - 光ファイバケーブル及び移動媒体 - Google Patents
光ファイバケーブル及び移動媒体 Download PDFInfo
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- WO2014148609A1 WO2014148609A1 PCT/JP2014/057788 JP2014057788W WO2014148609A1 WO 2014148609 A1 WO2014148609 A1 WO 2014148609A1 JP 2014057788 W JP2014057788 W JP 2014057788W WO 2014148609 A1 WO2014148609 A1 WO 2014148609A1
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- optical fiber
- polyamide
- fiber cable
- mass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
- C09D177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
- C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02033—Core or cladding made from organic material, e.g. polymeric material
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
- G02B6/4401—Optical cables
- G02B6/4402—Optical cables with one single optical waveguide
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
- G02B6/4401—Optical cables
- G02B6/4429—Means specially adapted for strengthening or protecting the cables
- G02B6/4436—Heat resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
Definitions
- the present invention relates to an optical fiber cable and a moving medium.
- Optical fibers are used in data communication and sensor applications.
- the types of optical fibers are glass optical fibers made of glass such as quartz and plastic optical fibers made of plastic (hereinafter referred to as “POF”). .)
- POF has a structure in which a highly transparent resin such as polymethyl methacrylate is mainly used as a core, and a resin having a refractive index lower than that of the resin constituting the core is provided on the outer periphery thereof.
- POF has a shorter transmission distance than glass optical fibers, but has advantages such as easy end face processing and handling, light weight, low cost, and a large aperture. Therefore, POF is used in a wide variety of applications such as lighting, sensors, and communication, and the production amount of POF is on an increasing trend.
- the coating material for the optical fiber cable is required to have high heat resistance and high heat dimensional stability.
- optical fiber cables are used as wiring for in-car communication, they are used in an environment where flammable materials such as oil, electrolyte, gasoline, etc. are present nearby, so they have high chemical resistance and high flame resistance. Sex is also required.
- Polyamide resins are known to have excellent heat resistance and dimensional stability, and are often used as coating materials for optical fibers. However, when an optical fiber cable coated with a polyamide resin or a polyamide elastomer resin is used for a long time at a high temperature, the optical characteristics are lowered, and the mechanical strength of the optical fiber cable is lowered.
- Patent Documents 1 and 2 In order to improve performance such as heat resistance, a polymer containing fluorine atoms is used for the cladding of POF (Patent Documents 1 and 2), or a specific polyester is used for the core of POF (or for the core and the cladding). (Patent Documents 3 and 4), various improvements have been made.
- the present inventors have completed the present invention capable of achieving the above object by using a specific resin in combination.
- an optical fiber cable having an optical fiber and a coating layer provided on the outer periphery of the optical fiber and including at least a coating inner layer and a coating outer layer,
- the material constituting the coating inner layer includes a polyamide resin (A)
- An optical fiber cable is provided in which the material constituting the outer coating layer includes a polyamide resin (C), and the material includes at least one of a polyphenylene ether resin (B) and a semi-aromatic polyamide resin (C1).
- a moving medium including the above-described optical fiber cable is provided.
- an optical fiber cable having long-term heat resistance can be provided.
- the optical fiber cable which has sufficient flame retardance and mechanical characteristics can be provided.
- the coating layer of the optical fiber cable according to the embodiment of the present invention includes at least a coating inner layer and a coating outer layer, and the material constituting the coating inner layer (coating inner layer material) is a polyamide (PA) resin (A).
- the material constituting the coating outer layer (coating outer layer material) includes a polyamide (PA) resin (C), and the coating outer layer material is composed of a polyphenylene ether (PPE) resin (B) and a semi-aromatic polyamide resin (C1). Contains at least one.
- this coating outer layer material a material containing PPE resin (B) and PA resin (C) as main components can be used as the first form.
- This coating outer layer material contains PPE resin (B) and PA resin (C) as the main components, so that it can impart particularly long-term heat resistance to optical fiber cables, and impart mechanical properties such as sufficient mechanical strength. be able to.
- PPE alloy resin which consists of PPE resin (B) and PA resin (C) as a main component can be used.
- Such a coating outer layer material may be composed of only PPE resin (B) and PA resin (C), or may be composed only of PPE alloy resin, or may be composed of these resins (B) and (C) or It may be a composition in which various additives such as flame retardants and antioxidants and other resins are added to the PPE alloy resin.
- a material containing a semi-aromatic polyamide resin (C1) as the PA resin (C) can be used as the second form.
- this coating outer layer material contains the semi-aromatic polyamide resin (C1), particularly long-term heat resistance can be imparted to the optical fiber cable.
- This coating outer layer material may consist only of the semi-aromatic polyamide resin (C1), or various additives such as flame retardants and antioxidants and other resins (aliphatic) to the semi-aromatic polyamide resin (C1). It may be a composition to which a polyamide resin (G) is added.
- a semi-aromatic polyamide alloy resin composed of a semi-aromatic polyamide resin (C1) and an aliphatic polyamide resin (G) can be used as the resin component of the coating outer layer material.
- PPE resin (B) Polyphenylene ether (PPE) resin
- B The kind of PPE resin (B) in embodiment of this invention is not specifically limited, A well-known PPE resin can be used.
- Examples of the PPE resin (B) include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6- Ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-) 6-propyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2,6 -Dibromomethyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-ditolyl-1,4-phenylene) ether Poly (2,6-dichloro-1,4-pheny
- Such PPE resin can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- poly (2,6-dimethyl-1,4-phenylene) ether is particularly preferable because it is easily available for general use.
- PA resin (C) Polyamide (PA) resin (C)
- PA resin (C) has good compatibility with PPE resin (B), or alloy resin with PPE resin (B). What can form is preferable.
- long-term heat resistance can be imparted to the optical fiber cable, and sufficient mechanical strength can be imparted.
- the outer layer material containing PA resin (C) is coated on the outer periphery of an optical fiber coated with a polyamide resin, the adhesion between the formed outer layer and the coating layer made of the polyamide resin thereunder is good. Become.
- the type of PA resin (C) is not particularly limited, and a known polyamide resin can be used.
- the PA resin (C) include polyamide 11, polyamide 12, polyamide 612, polyamide 1010; aliphatic polyamide such as polyamide 6 and polyamide 66; polyamide 6T, polyamide MXD6 including an aromatic ring in a part of the main chain skeleton, Aromatic polyamides such as polyamide 9T can be mentioned.
- Such PA resin can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- polyamide 6, polyamide 66, and polyamide MXD6 having high heat resistance and low oxygen permeability are preferable.
- the coating outer layer material in the embodiment of the present invention comprises PPE resin (B) and PA resin (C) as main components, or A PPE alloy resin composed of these resins (B) and (C) can be the main component.
- the main component indicates that the total content of PPE resin (B) and PA resin (C) in the coating outer layer material (or the content of PPE alloy resin) is 50% by mass or more, and 55% by mass. % Or more is preferable, 60 mass% or more is more preferable, and 70 mass% or more is more preferable.
- the mixing ratio of the PPE resin (B) and the PA resin (C) is not particularly limited as long as long-term heat resistance and sufficient mechanical properties are obtained.
- PA resin (C) is preferably mixed at a ratio of 10 to 300 parts by mass, more preferably 35 to 200 parts by mass, and further preferably 50 to 100 parts by mass with respect to 100 parts by mass of PPE resin (B). be able to. That is, the mass ratio (C / B) of the PA resin (C) to the PPE resin (B) is preferably in the range of 10/100 to 300/100, more preferably in the range of 35/100 to 200/100. The range of 50/100 to 100/100 is more preferable.
- the mixing ratio of the PA resin (C) is 10 parts by mass or more, sufficient long-term heat resistance and sufficient mechanical strength can be imparted to the PPE alloy resin.
- the mixing ratio of the PA resin (C) is 300 parts by mass or less, the melt viscosity of the PPE alloy resin can be lowered, and an optical fiber cable having appropriate flexibility when coated on an optical fiber can be obtained. it can.
- the method is not particularly limited as long as both resins can be sufficiently mixed or evenly dispersed.
- it can be alloyed using a compatibilizing agent capable of uniformly dispersing both resins.
- the compatibilizer is dispersed at the interface between the PPE resin (B) and the PA resin (C), the interfacial tension of the resin can be reduced, and the resins can be dispersed with each other.
- the type of the compatibilizing agent is not particularly limited, but for example, it is preferable to use a compatibilizing agent having a polar reactive functional group such as a carboxyl group, an epoxy group, or an amino group.
- a compatibilizing agent having a polar reactive functional group such as a carboxyl group, an epoxy group, or an amino group.
- compatibilizing agent having a carboxyl group examples include unsaturated carboxylic acids such as maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, acrylic acid, and methacrylic acid; esters of the unsaturated carboxylic acid, acids Amides, anhydrides and the like can be used.
- compatibilizer having an epoxy group epichlorohydrin, 2-methylepichlorohydrin, 2,2-bis (4-glycidylphenyl ether) propane, epoxy resin, or the like can be used.
- compatibilizers having amino groups include aliphatic amine compounds such as hexamethylenediamine and tetramethylenediamine; fats such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide.
- Aromatic compounds such as N, N-dimethylaminostyrene; morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, N-vinylpyrrole, N-vinylpyrrolidone, N-vinylthiopyrrolidone
- a heterocyclic compound such as can be used.
- the amount of the compatibilizer used is not particularly limited as long as the PPE resin (B) and the PA resin (C) are sufficiently dispersed.
- the amount of the compatibilizing agent used is 0.5 to 20% by mass, preferably 1 to 15% by mass, more preferably 2 to It can be 10 mass%.
- the PPE resin and the PA resin can be sufficiently dispersed, and long-term heat resistance and sufficient mechanical strength can be obtained.
- a compatibilizing agent 20 mass% or less By making the usage-amount of a compatibilizing agent 20 mass% or less, a high softness
- the PPE alloy resin in the embodiment of the present invention can be manufactured by itself, or can be a known or commercially available one.
- the method for producing the PPE alloy resin is not particularly limited as long as the PPE resin and the PA resin can be sufficiently dispersed.
- the PA resin can be added after adding the compatibilizer to the PPE resin and mixing well, or the PPE resin can be added after adding the compatibilizer to the PA resin and mixing well. It is also possible to add a compatibilizing agent after mixing the PPE resin and the PA resin.
- the coating outer layer material in the embodiment of the present invention can contain a semi-aromatic polyamide-based resin (C1) as a main component.
- the main component means that the content of the semi-aromatic polyamide resin (C1) in the coating outer layer material is 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more. 70 mass% or more is more preferable.
- a semi-aromatic polyamide-based resin (C1) can be used alone as a resin material contained in the coating outer layer material.
- the semi-aromatic polyamide resin (C1) in the embodiment of the present invention is a polyamide containing an aromatic ring in a part of the main chain skeleton, and is a polyamide resin, diamine and aromatic obtained by condensation polymerization of an aromatic diamine and a dicarboxylic acid. And a polyamide resin obtained by condensation polymerization with an aromatic dicarboxylic acid.
- a polyamide resin having a meta-substituted benzene ring is preferable because the crystallinity is not too high and the melting point is suitable for coating.
- the meta-substituted benzene ring corresponds to a structure derived from one having two substituents on the benzene ring at the 1-position and the 3-position.
- Examples of the polyamide resin having a meta-substituted benzene ring include polyamide MXD6 and polyamide 6I.
- aliphatic diamine constituting the semi-aromatic polyamide resin (C1) a linear aliphatic diamine represented by 1, x-alkanediamine (x is an integer of 2 to 20) can be used. Specifically, 1,2-ethylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine Is mentioned.
- Examples of the aromatic diamine constituting the semi-aromatic polyamide resin (C1) include ortho-xylylenediamine, meta-xylylenediamine, and para-xylylenediamine.
- Examples of the aliphatic dicarboxylic acid constituting the semi-aromatic polyamide resin (C1) include oxalic acid (ethanedioic acid), malonic acid (propanedioic acid), succinic acid (butanedioic acid), and glutaric acid (pentanedioic acid). , Adipic acid (hexanedioic acid), pimelic acid (heptanedioic acid), suberic acid (octanedioic acid), azelaic acid (nonanedioic acid), and sebacic acid (decanedioic acid).
- oxalic acid ethanedioic acid
- malonic acid propanedioic acid
- succinic acid butanedioic acid
- glutaric acid penentanedioic acid
- Adipic acid hexanedioic acid
- pimelic acid heptaned
- Examples of the aromatic dicarboxylic acid constituting the semi-aromatic polyamide resin (C1) include phthalic acid, isophthalic acid, and terephthalic acid in which two carboxyl groups are substituted on the benzene ring.
- polyamide 4T (a copolymer of 1,4-butanediamine and terephthalic acid)
- polyamide 6T a copolymer of 1,6-hexanediamine and terephthalic acid
- Polyamide MXD6 copolymer of meta-xylylenediamine and adipic acid
- polyamide 6I copolymer of 1,6-hexanediamine and isophthalic acid
- polyamide 6T / I (1,6-hexanediamine and terephthalate) Acid / isophthalic acid mixture
- polyamide 9T copolymer of 1,9-nonanediamine and terephthalic acid
- the semi-aromatic polyamide resin (C1) is preferably polyamide MXD6, polyamide 6T, polyamide 6T / I, polyamide 6I or polyamide 9T from the viewpoint of heat resistance or oxygen permeability.
- the coating outer layer material in the embodiment of the present invention is mainly composed of a semi-aromatic polyamide alloy resin comprising a semi-aromatic polyamide resin (C1) and an aliphatic polyamide resin (G). It can be.
- the aliphatic polyamide resin (G) used for alloying with the semi-aromatic polyamide resin (C1) has good compatibility with the semi-aromatic polyamide (C1), and the alloy resin with the semi-aromatic polyamide resin (C1). When this is formed and used for the coating layer of the optical fiber, it becomes possible to impart moderate flexibility.
- Known aliphatic polyamide resins can be used. Examples thereof include polyamide 11, polyamide 12, polyamide 612, polyamide 1010, polyamide 6, and polyamide 66. Among these, polyamide 6 and polyamide 66 are preferable from the viewpoints of heat resistance and oxygen permeability.
- the above-mentioned semi-aromatic polyamide alloy resin as a main component means that the content of the semi-aromatic polyamide alloy resin in the coating outer layer material is 50% by mass or more, and 55% by mass.
- the above is preferable, 60 mass% or more is more preferable, and 70 mass% or more is more preferable.
- the mixing ratio of the semi-aromatic polyamide resin (C1) and the aliphatic polyamide resin (G) is not particularly limited as long as long-term heat resistance is obtained.
- the aliphatic polyamide resin (G) can be mixed at a ratio of, for example, 300 parts by mass or less with respect to 100 parts by mass of the semi-aromatic polyamide resin (C1), preferably in the range of 5 to 300 parts by mass.
- the range of ⁇ 200 parts by mass is more preferable, and the range of 30 ⁇ 100 parts by mass is more preferable. That is, the mass ratio (G / C1) of the fatty polyamide resin (G) to the semi-aromatic polyamide resin (C1) is preferably in the range of 5/100 to 300/100. A range is more preferable, and a range of 30/100 to 100/100 is more preferable.
- the polyamide alloy resin provides more sufficient long-term heat resistance and sufficient mechanical strength. Can be made.
- the mixing ratio of the aliphatic polyamide resin (G) is 300 parts by mass or less with respect to 100 parts by mass of the semi-aromatic polyamide resin, the melt viscosity of the polyamide alloy resin can be reduced, and when the optical fiber is coated In addition, an optical fiber cable having moderate flexibility can be obtained.
- both resins can be sufficiently mixed or uniformly dispersed.
- both resins can be uniformly melt-kneaded and dispersed, or alloyed with a compatibilizing agent capable of uniformly dispersing both resins.
- the compatibilizer is dispersed at the interface between the semi-aromatic polyamide resin and the aliphatic polyamide resin, the interfacial tension of the resin can be lowered, and the resins can be dispersed with each other.
- the type of the compatibilizing agent is not particularly limited, but for example, it is preferable to use a compatibilizing agent having a polar reactive functional group such as a carboxyl group, an epoxy group, or an amino group.
- a compatibilizing agent having a polar reactive functional group such as a carboxyl group, an epoxy group, or an amino group.
- compatibilizing agent having a carboxyl group examples include unsaturated carboxylic acids such as maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, acrylic acid, methacrylic acid; esters of the unsaturated carboxylic acid, acid amides , Anhydrides and the like can be used.
- unsaturated carboxylic acids such as maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, acrylic acid, methacrylic acid
- esters of the unsaturated carboxylic acid, acid amides , Anhydrides and the like can be used.
- compatibilizer having an epoxy group epichlorohydrin, 2-methylepichlorohydrin, 2,2-bis (4-glycidylphenyl ether) propane, epoxy resin, or the like can be used.
- compatibilizers having amino groups include aliphatic amine compounds such as hexamethylenediamine and tetramethylenediamine; fats such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide.
- Aromatic compounds such as N, N-dimethylaminostyrene; morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, N-vinylpyrrole, N-vinylpyrrolidone, N-vinylthiopyrrolidone
- a heterocyclic compound such as can be used.
- the amount of the compatibilizer used is not particularly limited as long as the semi-aromatic polyamide resin (C1) and the aliphatic polyamide resin (G) are sufficiently dispersed.
- the amount of the compatibilizer used is 0.5 to 20% by mass, preferably 1 to 15% by mass, based on the total amount of the semi-aromatic polyamide resin (C1) and the aliphatic polyamide resin (G). More preferably, it can be 2 to 10% by mass.
- the compatibilizer in an amount of 0.5% by mass or more, the semi-aromatic polyamide resin (C1) and the aliphatic polyamide resin (G) can be sufficiently dispersed, and the long-term heat resistance and sufficient machinery can be obtained. Strength can be obtained.
- a compatibilizer 20 mass% or less By making the usage-amount of a compatibilizer 20 mass% or less, a high softness
- the semi-aromatic polyamide resin (C1) and the aliphatic polyamide resin (G) used in the embodiment of the present invention can be produced by themselves, or those known or commercially available can be used.
- the method for producing the semi-aromatic polyamide alloy resin is not particularly limited as long as the semi-aromatic polyamide resin (C1) and the aliphatic polyamide resin (G) can be sufficiently dispersed. For example, it can be obtained by melt-kneading the semi-aromatic polyamide resin (C1) and the aliphatic polyamide resin (G), or after adding a compatibilizer to the semi-aromatic polyamide (C1) and mixing them well.
- An aliphatic polyamide resin can be added, a compatibilizer can be added to the aliphatic polyamide resin (G) and mixed thoroughly, and then the semi-aromatic polyamide resin (C1) can be added.
- the compatibilizer can be added after mixing the aromatic polyamide resin (C1) and the aliphatic polyamide resin (G).
- the coating outer layer material in the embodiment of the present invention only the PPE resin (B) and the PA resin (C) (for example, only the PPE alloy resin described above) or the semi-aromatic polyamide resin (C1) only. Can be used, and semi-aromatic polyamide resin (C1) and other resin only (for example, only the above-mentioned semi-aromatic polyamide alloy resin) can be used.
- the additive according to the purpose can be contained in
- (1-6) Flame Retardant It is preferable to add a flame retardant to the coating layer of the optical fiber cable according to the embodiment of the present invention, and it is more preferable to add it to the coating outer layer material.
- a flame retardant a nitrogen-based flame retardant having a high interaction with the flame retardant of PA resin is preferable.
- nitrogen flame retardants include nitrogen compounds such as melamine compounds, triazine compounds, urea compounds, guanidine compounds, and tetrazole compounds.
- a flame retardant composed of at least one selected from these nitrogen-based compounds can be suitably used.
- a compound having a melamine skeleton can be used, for example, melamine; melamine derivatives such as melam, melem, and melon which are condensates of melamine; cyanuric acid; a salt of melamine and cyanuric acid Mention may be made of melamine cyanurate; melamine sulfate; a mixture of melamine and melamine cyanurate.
- a compound having a triazine skeleton can be used as the triazine compound.
- urea compound a compound having a urea skeleton and a salt thereof can be used, and examples thereof include guanyl urea phosphate.
- guanidine compound a compound having a guanidine skeleton and a salt thereof can be used, and examples thereof include guanidine sulfamate and guanidine phosphate.
- tetrazole compound a compound having a tetrazole skeleton, a metal salt or an amine salt of a tetrazole compound, or the like can be used.
- a compound having a tetrazole skeleton a metal salt or an amine salt of a tetrazole compound, or the like can be used.
- These nitrogen compounds can be used alone or in combination of two or more.
- melamine compounds melamine compounds, triazine compounds, and tetrazole compounds are preferable, and melamine compounds are more preferable because the dispersibility of the flame retardant is improved by interaction with the polyamide resin.
- melamine compounds melamine cyanurate, melamine sulfate, a salt of melamine sulfate, a mixture of melamine and melamine cyanurate, and the like are more preferable. This is because these nitrogen compounds are decomposed during combustion and generate an inert gas, so that the flame retardancy (self-extinguishing property) is increased.
- Such melamine compounds may be commercially available.
- STABIACE MC-2010N (trade name, manufactured by Sakai Chemical Industry Co., Ltd.)
- MELAPUR MC 25 (trade name, manufactured by BASF)
- MELAPUR 200/70 (trade name, manufactured by BASF)
- Apinon-901 (trade name, manufactured by Sanwa Chemical Co., Ltd.)
- the content of a flame retardant such as a nitrogen compound is preferably added in the range of 5 to 50% by mass in the material constituting the coating layer (for example, the coating outer layer material), more preferably 10 to 40% by mass, and 20 to 30%. More preferred is mass%.
- a flame retardant such as a nitrogen compound
- the reason why the content of the nitrogen compound is 50% by mass or less is that it is difficult to recognize a dramatic increase in the effect according to the increase in the amount of addition.
- a flame retardant aid may be added to the coating material in the embodiment of the present invention as long as desired characteristics are not impaired.
- the type of flame retardant aid is not particularly limited, but it is preferable to use a phosphorus compound having good compatibility with PPE.
- phosphorus compounds examples include aromatic phosphates such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate; resorcinol bis-diphenyl phosphate, resorcinol bis- Examples thereof include organic phosphorus compounds such as aromatic condensed phosphate esters such as dixylenyl phosphate and bisphenol A bis-diphenyl phosphate. These phosphorus compounds can be used alone or in combination of two or more. Among these, phosphate ester, condensed phosphate ester, phosphate, and condensed phosphate are preferable.
- the amount of the flame retardant aid such as a phosphorus compound is not particularly limited. For example, it is preferably added in the range of 0.1 to 30% by mass in the material constituting the coating layer (for example, the coating outer layer material). More preferably, it is ⁇ 20% by mass, and further preferably 5 ⁇ 15% by mass. By making the addition amount of the phosphorus compound 0.1% by mass or more, sufficient flame retardancy can be imparted to the coating material. The reason why the addition amount of the phosphorus compound is 30% by mass or less is that it is difficult to recognize a dramatic increase in the effect according to the increase in the addition amount.
- the total amount of these flame retardants and flame retardant aids is preferably added in the range of 5 to 50% by mass in the material constituting the coating layer (for example, coating outer layer material), and 7 to 40% by mass. Is more preferably 10 to 30% by mass.
- a total of 5% by mass or more of a flame retardant and a flame retardant aid it is possible to impart flame retardancy that can pass DIN72551-5, which is a flame retardance standard for electric wires and the like described later.
- the reason why the total amount of the flame retardant and the flame retardant auxiliary is less than 50% by mass is that it is difficult to recognize a dramatic increase in the effect according to the increase in the amount added.
- An antioxidant may be added to the coating layer of the optical fiber cable according to the embodiment of the present invention, and it is preferably added to the coating outer layer material. By adding the antioxidant, it is possible to suppress deterioration of the PA resin due to thermal oxidation in a high temperature environment.
- the type of the antioxidant is not particularly limited, and for example, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, an amine-based antioxidant, and the like can be used. Among these, phenol-based antioxidants and sulfur-based antioxidants are preferable, and at least one of these is preferably used.
- the phenolic antioxidant is not particularly limited, and examples thereof include hindered phenol compounds.
- examples of the hindered phenol compound include N, N ′-(1,6-hexanediyl) bis [3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanamide], pentaerythritol tetrakis [3- [3,5-di (t-butyl) -4-hydroxyphenyl] propionate], 2,2thio [diethylbis-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3- ( Octadecyl 3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4 ′, 4 ′′-[(2,4,6-trimethylbenzene-1,3,5-triyl) tris (methylene ]] Tris (2,6-di-tert-butylphenol), bis (3-tert-butyl-4-hydroxy-5
- N, N ′-(1,6-hexanediyl) bis [3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanamide] (molecular weight 636; for example, IRGANOX 1098 (trade name) ), BASF), pentaerythritol tetrakis [3- [3,5-di (t-butyl) -4-hydroxyphenyl] propionate] (molecular weight 1176; for example, IRGANOX 1010 (trade name), BASF), and 3, 9-bis [2- [3- (3-tert-butyl-4-hydroxy-S-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro (5 5) Undecane (molecular weight 741; for example, ADK STAB AO-80 (trade name), ADEKA Co., Ltd.) It preferred because s
- the addition amount of the phenolic antioxidant is preferably in the range of 0.01 to 5% by mass, more preferably 0.5 to 3% by mass in the material constituting the coating layer (for example, the coating outer layer material), and 0 More preferably, the content is 1 to 1% by mass.
- the addition amount 0.01% by mass or more it is possible to impart further sufficient long-term heat resistance.
- the addition amount 5% by mass or less it is possible to suppress a decrease in the mechanical strength of the coating material in the embodiment of the present invention.
- sulfur-based antioxidant examples include a thioether compound in which a propionic acid ester is bonded to divalent sulfur. These compounds include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, 4,6-bis (octylthio) And methyl) -o-cresol.
- dimyristyl-3,3′-thiodipropionate (molecular weight 571; for example, Yoshitomi DMTP (trade name), API Corporation), distearyl-3,3′-thiodipropionate (molecular weight 683; for example, Yoshitomi DSTP (trade name), API Corporation) and the like are preferable.
- the addition amount of the sulfur-based antioxidant is preferably in the range of 0.01 to 15% by mass, more preferably 0.5 to 10% by mass in the material constituting the coating layer (for example, the coating outer layer material). More preferably, the content is 1 to 3% by mass.
- the addition amount 0.01% by mass or more it is possible to impart further sufficient long-term heat resistance.
- the addition amount 15% by mass or less it is possible to suppress a decrease in the mechanical strength of the coating material in the embodiment of the present invention.
- phosphorus antioxidants include trisnonylphenyl phosphate, tris (2,4-di-t-butylphenyl) phosphate, distearyl pentaerythritol diphosphate, bis (2,4-di-t-butylphenyl).
- Pentaerythritol phosphate bis (2,6-di-t-butyl 4-methylphenyl) pentaerythritol phosphate, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphate, tetrakis (2,4 -Di-t-butylphenyl) -4,4′biphenylene-diphosphate.
- amine-based antioxidants include N, N′-diphenyl-p-phenylenediamine, N-cyclohexyl lu N′phenyl-p-phenylenediamine, P-isopropoxydiphenylamine, N-phenyl-2-naphthylamine, N , N, N ′, N′-tetramethyl-p-phenylenediamine, N, N, N ′, N′-tetramethyl-p, p′-diaminodiphenylmethane, N, N-dimethyl-2-naphthylamine, N, N'-diphenylquinone diimine and the like.
- antioxidants compounds having a molecular weight of 500 or more are preferable.
- the mechanical properties of the optical fiber can be attributed to the fact that the antioxidant itself bleeds out to the surface of the optical fiber cable or migrates to the optical fiber over a long period of use. This is because the optical characteristics can be prevented from deteriorating.
- one kind of antioxidant can be used alone, or two or more kinds of antioxidants can be used in combination.
- two or more kinds of antioxidants can be used in combination.
- a phenolic antioxidant and a sulfurous antioxidant in combination include the following effects.
- the decomposed radicals are combined with oxygen atoms in the air to generate peroxide radicals (ROO.) (R is an alkyl group), and the deterioration proceeds.
- the phenol-based antioxidant has a function of capturing the generated peroxide radical and converting it into hydroxyperoxide (ROOH).
- sulfur-based antioxidants can decompose hydroxy peroxides into stable alcohol components. For this reason, the synergistic effect of two types of antioxidant can be acquired.
- the total addition amount may be in the range of 0.01 to 10% by mass in the material constituting the coating layer (for example, the coating outer layer material). Preferably, it is 0.05 to 7% by mass, and more preferably 0.1 to 5% by mass. Heat resistance stability can be further improved by adding 0.01% by mass or more of the total amount of the phenolic antioxidant and the sulfur-based antioxidant. The fall of the mechanical strength of an optical fiber cable can be suppressed by making the total addition amount of a phenolic antioxidant and sulfur type antioxidant into 10 mass% or less. Further, the addition ratio of the phenol-based antioxidant and the sulfur-based antioxidant is not particularly limited, and is preferably about 1: 1 to 1: 3, for example.
- a material constituting the coating layer for example, a coating inner layer material within the range that does not impair the characteristics of the optical fiber for the purpose of improving designability and distinguishability.
- a pigment can be added in the coating outer layer material.
- the kind of pigment is not limited, and either an inorganic pigment or an organic pigment can be used.
- titanium dioxide, zinc oxide, etc. as white pigments
- azo organic pigments, yellow lead, chromium yellow, zinc yellow, etc. as yellow pigments
- ultramarine blue, cobalt blue, etc. as blue pigments
- chromium oxides, etc. as green pigments
- the addition amount of the pigment is not particularly limited, and is preferably 0.5 to 10% by mass, more preferably 1 to 7% by mass in the material constituting the coating layer (for example, the coating inner layer material and the coating outer layer material). 5 mass% is still more preferable.
- a sufficient coloring effect can be exhibited by setting the amount of pigment added to 0.5% by mass or more. By making the addition amount of the pigment 10% by mass or less, it is possible to prevent the mechanical strength of the optical fiber cable from being lowered, and it is possible to prevent the pigment from moving to the optical fiber and the optical characteristics from being lowered. .
- optical fiber cable (2-1) Optical Fiber
- an optical fiber made of glass can be used, and an optical fiber made of plastic (POF) can also be used.
- POF optical fiber made of plastic
- the type of the optical fiber made of glass is not limited, and a silica glass fiber (PCS) in which both the core and the clad are made of quartz glass, the core is made of quartz glass, and the clad is made of a resin such as a fluororesin. Etc., known ones can be used.
- PCS silica glass fiber
- the type of POF is not limited, and a known or newly developed POF can be used.
- the optical fiber cable according to the embodiment of the present invention preferably uses POF. When it is assumed to be used in a moving medium such as an automobile, it is preferable because of easy handling.
- a GI POF in which the refractive index of the core continuously decreases from the center to the outer periphery for example, a multi-layer POF in which the refractive index of the core gradually decreases from the center to the outer periphery, and a plurality of cores are clad Multi-core POF etc. that are enclosed in a single box.
- a multi-layer POF from the viewpoint of widening the POF and performing high-speed signal transmission.
- the material used for the core is not particularly limited, and can be appropriately selected according to the purpose of use. For example, it is preferable to use a highly transparent polymer.
- a polymer containing a methacrylate unit is preferable.
- examples of such a polymer include a methyl methacrylate homopolymer, a copolymer having a methyl methacrylate unit as a main constituent unit, and a polymer having a fluorinated alkyl methacrylate unit as a main constituent unit.
- a methyl methacrylate homopolymer and a copolymer having a methyl methacrylate unit as a main constituent unit are preferable.
- a methyl methacrylate unit contains 50 mass% or more, it is more preferable that 60 mass% or more is included, and it is further more preferable that 70 mass% or more is included.
- Methyl methacrylate homopolymer is particularly preferable from the viewpoint of excellent heat resistance and transparency.
- the clad formed on the outer periphery of the core may be formed from one layer or may be formed from two or more layers.
- a sheath material used for the POF cladding a sheath material having a refractive index smaller than that of the material used for the core (core material) is used.
- the sheath material may be a fluorine polymer such as vinylidene fluoride polymer, a perfluoroalkyl methacrylate polymer, a methacrylate polymer, A copolymer of a fluoroalkyl methacrylate compound and a (meth) acrylate compound is used.
- a fluorine polymer such as vinylidene fluoride polymer, a perfluoroalkyl methacrylate polymer, a methacrylate polymer, A copolymer of a fluoroalkyl methacrylate compound and a (meth) acrylate compound is used.
- vinylidene fluoride polymer examples include polyvinylidene fluoride, copolymers containing vinylidene fluoride units, such as vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, fluoride Vinylidene-hexafluoroacetone copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, other ternary or more copolymers containing vinylidene fluoride units Etc. can be used.
- copolymers containing vinylidene fluoride units such as vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, fluoride Vinylidene-hexafluoroacetone copo
- Such POF can be produced by a known method such as a melt spinning method.
- a melt spinning method such as a melt spinning method.
- the diameter is preferably set in the range of, for example, 500 ⁇ m to 1200 ⁇ m, more preferably in the range of 700 ⁇ m to 1100 ⁇ m, and further in the range of 750 to 1000 ⁇ m, from the viewpoint of transmission characteristics and handling properties. preferable.
- the thickness of the POF cladding is preferably in the range of 3 to 30 ⁇ m, more preferably in the range of 4 to 20 ⁇ m, and even more preferably in the range of 5 to 15 ⁇ m in order to totally reflect the light passing through the core.
- the thickness of the clad is 3 ⁇ m or more, the light in the core can be fully reflected.
- the reason why the thickness of the clad is 30 ⁇ m or less is that a decrease in the amount of light that propagates can be suppressed, and even if the thickness is further increased, it is difficult to recognize a dramatic increase in light propagation.
- the coating layer provided on the outer periphery of the optical fiber includes a coating inner layer provided on the inner side and a coating outer layer provided on the outer side.
- a two-layer structure made of these coating layers may be used, or another layer made of another material may be further provided.
- the other layer may be provided inside the coated inner layer (on the optical fiber side), may be provided outside the coated outer layer (on the side far from the optical fiber), or between the coated inner layer and the coated outer layer. May be provided.
- a configuration in which a coating inner layer is first provided on the outer periphery of the optical fiber and a coating outer layer is provided on the outer periphery of the coating inner layer is preferable.
- a coating inner layer is first provided on the outer periphery of the optical fiber and a coating outer layer is provided on the outer periphery of the coating inner layer.
- the coated inner layer in the embodiment of the present invention preferably uses a polyamide (PA) resin (A) as a main component.
- PA polyamide
- the main component means that the content of the PA resin (A) in the coating inner layer material is 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more, and 70% by mass. The above is more preferable.
- PA resin (A) is excellent in that it has a relatively low melting point and is easy to coat (good workability). Also, when POF containing vinylidene fluoride resin in the cladding is used as the optical fiber, the amide bond in the PA resin constituting the coating inner layer and the CF bond in the vinylidene fluoride resin constituting the cladding By this interaction, the adhesion between the clad and the coating inner layer can be improved.
- PA resin (A) examples include homopolymers such as polyamide 11, polyamide 12, polyamide 612, and polyamide 1010, polyamide copolymers composed of combinations of monomer units constituting these polymers, and polymers.
- polyamide 11, polyamide 12, and polyamide 1010 homopolymers that are excellent in heat resistance, flex resistance, chemical resistance, and the like are particularly preferable.
- the homopolymers of polyamide 11, polyamide 12, and polyamide 1010 have good moldability in the coating process and have an appropriate melting point. Therefore, the polymethyl methacrylate homopolymer or methyl methacrylate is the main component.
- the POF can be easily coated without deteriorating the transmission performance of the POF having the copolymer as a core material.
- these resins are also excellent in dimensional stability, the use of these resins in the coating inner layer is effective in generating heat shrinkage and pistoning, which are particularly problematic when optical fiber cables are used for automotive LAN applications. Can be prevented.
- polyamide 11, polyamide 12, and polyamide 1010 homopolymers have particularly excellent battery fluid resistance among polyamide resins. preferable.
- Additives such as carbon black and other black pigments are added to the coating inner layer to prevent light leakage from the optical fiber to the coating layer and to prevent external light from entering the optical fiber. can do.
- the addition amount of the additive is not particularly limited, but for example, it is preferably in the range of 0.15 to 5% by mass, more preferably in the range of 0.2 to 2.5% by mass in the coating inner layer material, 0.3 The range of ⁇ 1.5% by mass is more preferable.
- the additive amount 0.15% by mass or more By making the additive amount 0.15% by mass or more, the effect of suppressing the entrance of external light into the optical fiber can be enhanced, and the stability during communication, which is the original purpose of use of the optical fiber, can be improved. Can be increased.
- the additive amount By setting the additive amount to be 5% by mass or less, light leakage from the bent portion can be suppressed even when the optical fiber is laid in a bent state.
- (2-2-2) Coated outer layer In the optical fiber cable according to the embodiment of the present invention, it is preferable to provide a coated outer layer made of the above-described coated outer layer material on the outer periphery of the coated inner layer. By adopting such a configuration, the optical fiber cable can have excellent long-term heat resistance.
- a known method such as an extrusion coating method using a known device such as a crosshead type coating device equipped with an extruder can be employed.
- the melting temperature is preferably set in the range of 150 ° C to 230 ° C.
- the thermal effect on the optical fiber can be suppressed by the coating inner layer when coating a high temperature resin material, and the melting temperature of the coating material Even if the thickness is high, it is possible to form the outer coating layer without impairing the optical characteristics of the optical fiber.
- the coating inner layer is formed by coating the PA resin (A), and then the coating outer layer is formed by coating the high temperature resin material. did it.
- the outer diameter of the optical fiber cable according to the embodiment of the present invention is set to, for example, a general 2.2 mm
- the outer diameter of the POF is set to, for example, 1.0 mm which is the same as the outer diameter of the POF used for general purposes
- the total thickness of the coating layer can be set to 0.6 mm.
- the thickness ratio of the coating inner layer to the coating outer layer may be in the range of 50:50 (for example, coating inner layer 300 ⁇ m, coating outer layer 300 ⁇ m) to 10:90 (for example coating inner layer 60 ⁇ m, coating outer layer 540 ⁇ m).
- the thickness ratio of the inner coating layer to the outer coating layer is in the range of 40:60 (for example, inner coating layer 240 ⁇ m, outer coating layer 360 ⁇ m) to 15:85 (for example inner coating layer 90 ⁇ m, outer coating layer 510 ⁇ m), and 30:70 (for example inner coating layer 180 ⁇ m, outer coating layer 420 ⁇ m) )
- 20:80 for example, a coating inner layer of 120 ⁇ m, a coating outer layer of 480 ⁇ m
- desired heat resistance and flame retardancy can be obtained.
- the optical fiber cable according to the embodiment of the present invention can be provided with long-term heat resistance and high sufficient mechanical strength, it is particularly suitably used for a moving medium that can be exposed to a high temperature environment such as an automobile, a ship, and a railway. be able to.
- the evaluation method of the optical fiber cable performed for the examples is as follows.
- Transmission loss (dB / km) was measured by the 25m-1m cutback method. Light having a measurement wavelength of 550 nm and an incident light NA (numerical aperture) of 0.1 was used.
- the pass / fail criteria were determined by applying a burner flame to an optical fiber cable for 10 seconds, igniting the flame, keeping the flame away from the sample, and passing the flame that disappeared within 30 seconds. Things were rejected. And such a test was done with respect to ten samples. The number of passes for 10 samples is shown in Table 1 as the result of the combustion test.
- Impact resistance test A test based on JIS C6861 was performed. The sample was placed on a flat steel plate, a 1 kg weight was dropped from a predetermined height, the sample and the steel plate were impacted, and the potential energy of the weight at that time was measured. This was repeated, and the test was terminated when a 1 dB loss increase from the initial value occurred, and the potential energy at that time was shown as a test result (impact resistance).
- Example 1 A POF having the following configuration was used as the optical fiber.
- Second clad (second clad located on the outer periphery of the first clad): vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer (refractive index 1.374).
- An optical fiber cable was manufactured by coating the above POF as follows. First, using a crosshead type coating device, the outer peripheral part of the POF was coated with a polyamide resin to form a coated inner layer having a thickness of 260 ⁇ m. A cable having an outer diameter of 1.52 mm was obtained. At this time, polyamide 12 (trade name: Daiamide L1640, manufactured by Daicel Evonik) was used as the polyamide resin, and the temperature of the crosshead die of the crosshead type coating apparatus was set to 220 ° C.
- a coating outer layer material is coated on the outer peripheral portion of the obtained cable using a crosshead cable coating apparatus, a coating outer layer having a thickness of 390 ⁇ m is formed, and an optical fiber cable having an outer diameter of 2.3 mm having a two-layer coating structure Got.
- an outer layer material 100 parts by mass of an alloy resin of polyamide 66 and poly (2,6-dimethyl-1,4-phenylene) ether (trade name: Noryl GTX951, manufactured by Subic Innovative Plastics) A compound containing 30 parts by mass of a nitrogen-based flame retardant (trade name: melamine cyanurate MC6000) manufactured by Chemical Industry Co., Ltd. was used.
- Example 2 The resin of the coating outer layer material was changed to an alloy resin of polyamide 6 and poly (2,6-dimethyl-1,4-phenylene) ether (trade name: Noryl GTX600, manufactured by Subic Innovative Plastics), and this alloy resin 100 parts by mass of nitrogen-based flame retardant (product name: melamine cyanurate MC6000) manufactured by Nissan Chemical Industries, Ltd. as a flame retardant, and ADEKA's hindered phenol antioxidant (product) as an antioxidant
- a cable was produced. Table 1 shows the test results of the obtained optical fiber cable.
- Examples 3 to 7 The optical fiber cable was the same as in Example 1 except that the coating outer layer material was resin, flame retardant, hindered phenolic antioxidant, sulfurous antioxidant, and the mixing ratio thereof as shown in Table 1. Was made. Table 1 shows the test results of the obtained optical fiber cable.
- Example 8 to 12 Except for the coating outer layer material, resin, flame retardant, hindered phenol-based antioxidant, sulfur-based antioxidant and pigment, and the mixing ratio thereof as shown in Table 2, light was obtained in the same manner as in Example 1. A fiber cable was prepared. Table 2 shows the test results of the obtained optical fiber cable.
- Example 1 As the coating outer layer material, the resin was changed to polyamide 6 (trade name: Unitika Nylon 6 A1020BRL, manufactured by Unitika), and a nitrogen-based flame retardant (product of Nissan Chemical Industries, Ltd.) as a flame retardant for 100 parts by mass of the resin. Name: Melamine Cyanurate MC6000) Same as Example 1 except that 30 parts by weight and 3 parts by weight of ADEKA phenolic antioxidant (trade name: ADK STAB AO-80) were added as an antioxidant Thus, an optical fiber cable was produced. Table 1 shows the test results of the obtained optical fiber cable.
- polyamide 6 trade name: Unitika Nylon 6 A1020BRL, manufactured by Unitika
- a nitrogen-based flame retardant product of Nissan Chemical Industries, Ltd.
- ADEKA phenolic antioxidant trade name: ADK STAB AO-80
- Example 1 except that the resin of the coating inner layer material, the resin of the coating outer layer material, the flame retardant, the hindered phenol antioxidant, the sulfur antioxidant and the pigment, and the mixing ratio thereof are as shown in Table 2.
- An optical fiber cable was produced in the same manner as described above. The test results of the obtained optical fiber cable are shown in Table 2.
- A-1) Polyamide 12 resin (trade name: Daiamide L1640, manufactured by Daicel Evonik)
- A-2 Polyamide 6 resin (trade name “UBE Nylon 1011B”, manufactured by Ube Industries, Ltd.)
- A-3) Polyamide 66 resin (Brand name: Maranyl nylon 66 A226, manufactured by Unitika Ltd.)
- A-4) Polyamide 66 resin (trade name “Leona 1300S”, manufactured by Asahi Kasei Chemicals Corporation)
- A-5) Polyamide 12 elastomer resin (trade name: Grillamide XE3833, manufactured by EMS)
- BC-1 An alloy resin (trade name: Noryl GTX951, manufactured by Subic Innovative Plastics) of polyamide 66 resin and PPE resin (poly (2,6-dimethyl-1,4-phenylene) ether), alloy resin
- the total content of polyamide 66 resin and PPE resin is 70% by mass or more
- the optical fiber cables of Examples 1 to 7 using PA resin as the resin for the coating inner layer and the alloy resin of PA resin and PPE resin as the resin for the coating outer layer are excellent in long-term heat resistance, Moreover, the flame retardancy was excellent, and sufficient impact resistance and hydrolysis resistance were exhibited.
- the optical fiber cables of Comparative Examples 1 to 4 in which an alloy resin of PA resin and PPE resin was not used as the coating material of the optical fiber cable were inferior in long-term heat resistance (Condition A). It was. Further, in the optical fiber cables of Comparative Examples 1 and 2, the coating layer deteriorated and cracked in the hydrolysis test, and cracks were observed. In addition, the optical fiber cable of Comparative Example 5 using alloy resin for both the inner coating layer and the outer coating layer was inferior in long-term heat resistance (conditions A and B). Further, Comparative Examples 1 to 3 were inferior in flame retardancy.
- the optical fiber cable was excellent in long-term heat resistance and flame resistance.
- the optical fiber cables of Comparative Examples 6 and 7 in which the semi-aromatic polyamide resin was not used as the coating material of the optical fiber cable were inferior in long-term heat resistance (condition A).
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Abstract
Description
前記被覆内層を構成する材料が、ポリアミド樹脂(A)を含み、
前記被覆外層を構成する材料が、ポリアミド樹脂(C)を含み、該材料はポリフェニレンエーテル樹脂(B)及び半芳香族ポリアミド樹脂(C1)の少なくとも1種を含む、光ファイバケーブルが提供される。
本発明の実施形態による光ファイバケーブルの被覆層は、被覆内層と被覆外層を少なくとも含み、被覆内層を構成する材料(被覆内層材料)は、ポリアミド(PA)樹脂(A)を含み、被覆外層を構成する材料(被覆外層材料)は、ポリアミド(PA)樹脂(C)を含み、この被覆外層材料はポリフェニレンエーテル(PPE)樹脂(B)及び半芳香族ポリアミド樹脂(C1)の少なくとも1種を含む。
本発明の実施形態におけるPPE樹脂(B)の種類は特には限定されず、公知のPPE樹脂を使用することができる。
被覆外層材料がPPE樹脂(B)とPA樹脂(C)を含む場合、PA樹脂(C)は、PPE樹脂(B)との相溶性が良好であり、あるいはPPE樹脂(B)とのアロイ樹脂を形成できるものが好ましい。このような被覆外層材料を用いると、光ファイバケーブルに長期耐熱性を付与することができ、十分な機械的強度も付与することができる。また、PA樹脂(C)含む被覆外層材料を、ポリアミド樹脂で被覆された光ファイバの外周に被覆する場合、形成された被覆外層とその下のポリアミド樹脂からなる被覆層との密着性が良好となる。
本発明の実施形態における被覆外層材料は、PPE樹脂(B)とPA樹脂(C)を主成分とし、あるいはこれらの樹脂(B)及び(C)からなるPPEアロイ樹脂を主成分とすることができる。ここで、主成分とは、被覆外層材料中のPPE樹脂(B)とPA樹脂(C)の合計含有量(あるいはPPEアロイ樹脂の含有量)が50質量%以上であることを示し、55質量%以上が好ましく、60質量%以上がより好ましく、70質量%以上がさらに好ましい。
本発明の実施形態における被覆外層材料は、半芳香族ポリアミド系樹脂(C1)を主成分として含むことができる。ここで、主成分とは、被覆外層材料中の半芳香族ポリアミド系樹脂(C1)の含有量が50質量%以上であることを示し、55質量%以上が好ましく、60質量%以上がより好ましく、70質量%以上がさらに好ましい。被覆外層材料に含まれる樹脂材料として半芳香族ポリアミド系樹脂(C1)を単独で使用することができる。
本発明の実施形態における被覆外層材料は、半芳香族ポリアミド樹脂(C1)と脂肪族ポリアミド樹脂(G)とからなる半芳香族ポリアミドアロイ樹脂を主成分とすることができる。
本発明の実施形態による光ファイバケーブルの被覆層には難燃剤を添加することが好ましく、被覆外層材料に添加することがより好ましい。難燃剤の種類としては、PA樹脂の難燃化に高い相互作用を示す窒素系難燃剤が好ましい。このような窒素系難燃剤としては、例えば、メラミン系化合物、トリアジン系化合物、尿素系化合物、グアニジン系化合物、テトラゾール系化合物等の窒素系化合物を挙げることができる。これらの窒素系化合物から選ばれる少なくとも一種からなる難燃剤を好適に用いることができる。
本発明の実施形態による光ファイバケーブルの被覆層には、酸化防止剤を添加することもでき、被覆外層材料に添加することが好ましい。酸化防止剤を添加することにより、PA樹脂の高温環境下での熱酸化による劣化を抑制することができる。
また、本発明の実施形態において、意匠性、識別性を高める目的で、光ファイバの特性を損なわない範囲で、被覆層を構成する材料(例えば被覆内層材料、被覆外層材料)中に顔料を添加することができる。顔料の種類は限定されず、無機系顔料又は有機系顔料のいずれも使用することができる。
光ファイバの外周に上述の被覆層(被覆内層、被覆外層)を設けることにより、長期耐熱性、十分な機械特性等を有する光ファイバケーブルを得ることができる。
本発明の実施形態による光ファイバケーブルにおいて使用する光ファイバの種類は限定されない。例えば、ガラス製の光ファイバを使用することもできるし、プラスチック製の光ファイバ(POF)を使用することもできる。
本発明の実施形態による光ファイバケーブルにおいて、光ファイバの外周に設ける被覆層は、内側に設けられる被覆内層と、外側に設けられる被覆外層を含む。これらの被覆層からなる2層構造でもよいし、他の材料からなる別の層をさらに設けることもできる。当該別の層は、被覆内層の内側(光ファイバ側)に設けられてもよいし、被覆外層の外側(光ファイバから遠い側)に設けられていてもよいし、被覆内層と被覆外層の間に設けられていてもよい。
本発明の実施形態における被覆内層は、ポリアミド(PA)樹脂(A)を主成分として使用することが好ましい。ここで、主成分とは、被覆内層材料中のPA樹脂(A)の含有量が50質量%以上であることを示し、55質量%以上が好ましく、60質量%以上がより好ましく、70質量%以上がさらに好ましい。
本発明の実施形態による光ファイバケーブルでは、前記被覆内層の外周に、前述の被覆外層材料からなる被覆外層を設けることが好ましい。このような構成を取ることにより、光ファイバケーブルが優れた長期耐熱性を備えることができる。
25m-1mカットバック法により伝送損失(dB/km)を測定した。測定波長が550nm、入射光のNA(開口数)が0.1の光を用いた。
第1の長期耐熱試験(条件A)として、105℃10%RH以下の温度条件下で5000時間後の伝送損失を測定した。
難燃性試験は、DIN72551-5に準拠して行った。なお、この試験では、電線用の難燃性測定法であるDIN72551-5を、光ファイバケーブルの難燃性を測定するために、次のように若干変更している。
(1)加水分解試験
85℃95%の湿熱環境下で1000時間保持したケーブルを直径10mmの金属棒に隙間なく巻きつけ24時間後の被覆層の割れ、亀裂等の劣化の有無を目視で観察した。表中において、被覆層の表面に割れがなかったものを○、割れがあったものを×と記載した。
JIS C6861に準拠した試験を実施した。試料を平たんな鋼板に設置し、1kgのおもりを所定の高さから落下させ、試料と鋼板に衝撃を与え、その際のおもりの位置エネルギーを測定した。これを繰り返し行い、初期値より1dB損失増加が生じた時点で試験を終了し、その際の位置エネルギーを試験結果(耐衝撃性)として示した。
光ファイバとして、以下の構成を有するPOFを使用した。
第1クラッド(コアの外周に位置する1層目のクラッド):2,2,2-トリフルオロエチルメタクリレート(3FM)/2-(パーフルオロオクチル)エチルメタクリレート(17FM)/メタクリル酸メチル/メタクリル酸=51/31/17/1(質量比))共重合体;
第2クラッド(第1クラッドの外周に位置する2層目のクラッド):ビニリデンフルオライド/テトラフルオロエチレン/ヘキサフルオロプロピレン共重合体(屈折率1.374)。
被覆外層材料の樹脂を、ポリアミド6とポリ(2,6-ジメチル-1,4-フェニレン)エーテルとのアロイ樹脂(商品名:ノリルGTX600、サビックイノベーティブプラスチック社製)に変更し、このアロイ樹脂100質量部に対して、難燃剤として日産化学工業社製の窒素系難燃剤(商品名:メラミンシアヌレート MC6000)を30質量部、酸化防止剤としてADEKA社のヒンダードフェノール系酸化防止剤(商品名:アデカスタブ AO-80)を1質量部、APIコーポレーション社の硫黄系酸化防止剤(商品名:ヨシトミDSTP)を3質量部添加したものを使用した以外は、実施例1と同様にして光ファイバケーブルを作製した。得られた光ファイバケーブルの試験結果を表1に示す。
被覆外層材料について、樹脂、難燃剤、ヒンダードフェノール系酸化防止剤および硫黄系酸化防止剤、並びにそれらの混合比を表1に示す通りとした以外は、実施例1と同様にして光ファイバケーブルを作製した。得られた光ファイバケーブルの試験結果を表1に示す。
被覆外層材料について、樹脂、難燃剤、ヒンダードフェノール系酸化防止剤、硫黄系酸化防止剤および顔料、並びにそれらの混合比を表2に示す通りとした以外は、実施例1と同様にして光ファイバケーブルを作製した。得られた光ファイバケーブルの試験結果を表2に示す。
被覆外層材料として、樹脂をポリアミド6(商品名:ユニチカナイロン6 A1020BRL、ユニチカ社製)に変更し、この樹脂100質量部に対して、難燃剤として日産化学工業社製の窒素系難燃剤(商品名:メラミンシアヌレート MC6000)30質量部、酸化防止剤としてADEKA社のフェノール系酸化防止剤(商品名:アデカスタブ AO-80)を3質量部添加したものを使用した以外は、実施例1と同様にして光ファイバケーブルを作製した。得られた光ファイバケーブルの試験結果を表1に示す。
被覆内層材料の樹脂、被覆外層材料の樹脂、難燃剤、ヒンダードフェノール系酸化防止剤および硫黄系酸化防止剤、並びにそれらの混合比を表1に示す通りとした以外は、実施例1と同様にして光ファイバケーブルを作製した。得られた光ファイバケーブルの試験結果について表1に示す。
被覆内層材料の樹脂、被覆外層材料の樹脂、難燃剤、ヒンダードフェノール系酸化防止剤、硫黄系酸化防止剤および顔料、並びにそれらの混合比を表2に示す通りとした以外は、実施例1と同様にして光ファイバケーブルを作製した。得られた光ファイバケーブルの試験結果について表2に示す。
(A-1):ポリアミド12樹脂(商品名:ダイアミド L1640、ダイセル・エボニック(株)製)
(A-2):ポリアミド6樹脂(商品名「UBEナイロン 1011B」、宇部興産(株)製)
(A-3):ポリアミド66樹脂(商品名:マラニールナイロン66 A226、ユニチカ(株)製)
(A-4):ポリアミド66樹脂(商品名「レオナ1300S」、旭化成ケミカルズ(株)製)
(A-5):ポリアミド12エラストマー樹脂(商品名:グリルアミドXE3833、EMS社製)
(BC-1):ポリアミド66樹脂とPPE樹脂(ポリ(2,6-ジメチル-1,4-フェニレン)エーテル)とのアロイ樹脂(商品名:ノリルGTX951、サビックイノベーティブプラスチック社製)、アロイ樹脂中のポリアミド66樹脂とPPE樹脂の合計の含有量は70質量%以上
(BC-2):ポリアミド66樹脂とPPE樹脂(ポリ(2,6-ジメチル-1,4-フェニレン)エーテル)とのアロイ樹脂(商品名:ノリルGTX9400W、サビックイノベーティブプラスチック社製)、アロイ樹脂中のポリアミド66樹脂とPPE樹脂の合計の含有量は70質量%以上
(BC-3):ポリアミド6樹脂とPPE樹脂(ポリ(2,6-ジメチル-1,4-フェニレン)エーテル)とのアロイ樹脂(商品名:ノリルGTX600、サビックイノベーティブプラスチック社製)、アロイ樹脂中のポリアミド6樹脂とPPE樹脂の合計の含有量は70質量%以上
(C1-1):ポリアミドMXD6樹脂(商品名:ナイロンMXD6 S6001、三菱ガス化学(株)製)
(C1-2):ポリアミド9T樹脂(商品名:ジェネスタ N1000A、(株)クラレ製)
(C1-3):(C1-1)と(A-4)とのアロイ樹脂((C1-1):(A-4)=70:30(質量比))
(C1-4):(C1-1)と(A-4)とのアロイ樹脂((C1-1):(A-4)=60:40(質量比))
(C1-5):(C1-1)と(A-2)とのアロイ樹脂((C1-1):(A-2)=70:30(質量比))
(C1-6):(C1-2)と(A-3)とのアロイ樹脂((C1-2):(A-3)=70:30(質量比))
(D-1):メラミンシアヌレート(商品名:メラミンシアヌレート MC6000、日産化学工業(株)製)
(D-2):臭素化ポリスチレン(商品名:HP-3010、アルベマール日本(株)製、臭素原子の含有率68.5質量%)
(E-1):ヒンダードフェノール系酸化防止剤(商品名:アデカスタブ AO-80、(株)ADEKA製)
(E-2):ヒンダードフェノール系酸化防止剤(商品名:IRGANOX1010、BASF社製)
(E-3):ヒンダードフェノール系酸化防止剤(商品名:IRGANOX1098、BASF社製)
(E-4):硫黄系酸化防止剤(商品名:ヨシトミDSTP、(株)エーピーアイコーポレーション製)
(F-1):群青色顔料(商品名:強化群青 AP-205、第一化成工業(株)製)
条件A:温度105℃、相対湿度10%以下で5000時間暴露
条件B:温度85℃、相対湿度85%で3000時間暴露。
Claims (16)
- 光ファイバと、該光ファイバの外周に設けられ少なくとも被覆内層及び被覆外層からなる被覆層とを有する光ファイバケーブルであって、
前記被覆内層を構成する材料が、ポリアミド樹脂(A)を含み、
前記被覆外層を構成する材料が、ポリアミド樹脂(C)を含み、該材料はポリフェニレンエーテル樹脂(B)及び半芳香族ポリアミド樹脂(C1)の少なくとも1種を含む、光ファイバケーブル。 - 前記被覆外層を構成する材料が、ポリフェニレンエーテル樹脂(B)を含む、請求項1に記載の光ファイバケーブル。
- ポリアミド樹脂(C)が、ポリアミド6、ポリアミド66及びポリアミドMXD6から選ばれる少なくとも1種からなる、請求項2に記載の光ファイバケーブル。
- 前記被覆外層を構成する材料中、ポリフェニレンエーテル樹脂(B)とポリアミド樹脂(C)の合計の含有率が50質量%以上である、請求項2又は3に記載の光ファイバケーブル。
- 前記被覆外層を構成する材料中、ポリフェニレンエーテル樹脂(B)に対するポリアミド樹脂(C)の質量比率(C/B)が、10/100~300/100の範囲にある、請求項2から4のいずれか一項に記載の光ファイバケーブル。
- 前記被覆外層を構成する材料が、半芳香族ポリアミド樹脂(C1)を含む、請求項1に記載の光ファイバケーブル。
- 前記被覆外層を構成する材料中、半芳香族ポリアミド樹脂(C1)の含有率が50質量%以上である、請求項6に記載の光ファイバケーブル。
- 半芳香族ポリアミド樹脂(C1)が、ポリアミドMXD6、ポリアミド6T、ポリアミド6I、ポリアミド6T/I及びポリアミド9Tから選ばれる少なくとも1種からなる、請求項6又は7に記載の光ファイバケーブル。
- 半芳香族ポリアミド樹脂(C1)が、メタ位置換のベンゼン環を有するポリアミド樹脂である、請求項6から8のいずれか一項に記載の光ファイバケーブル。
- ポリアミド樹脂(A)が、ポリアミド11、ポリアミド12及びポリアミド1010から選ばれる少なくとも1種からなる、請求項1から9のいずれか一項に記載の光ファイバケーブル。
- 前記被覆内層を構成する材料中、ポリアミド樹脂(A)の含有率が50質量%以上である、請求項1から10のいずれか一項に記載の光ファイバケーブル。
- 前記被覆外層を構成する材料が、更に難燃剤(D)を含む、請求項1から11のいずれか一項に記載の光ファイバケーブル。
- 難燃剤(D)が、窒素系化合物である、請求項12に記載の光ファイバケーブル。
- 前記被覆外層を構成する材料が、更に酸化防止剤(E)を含む、請求項1から13のいずれか一項に記載の光ファイバケーブル。
- 酸化防止剤(E)が、ヒンダードフェノール系酸化防止剤及び硫黄系酸化防止剤の少なくとも1種からなる、請求項14に記載の光ファイバケーブル。
- 請求項1から15のいずれか一項に記載の光ファイバケーブルを含む、移動媒体。
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JPWO2014148609A1 (ja) | 2017-02-16 |
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