WO2022009529A1 - 樹脂組成物、光ファイバのセカンダリ被覆材料、光ファイバ、及び光ファイバの製造方法 - Google Patents

樹脂組成物、光ファイバのセカンダリ被覆材料、光ファイバ、及び光ファイバの製造方法 Download PDF

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Publication number
WO2022009529A1
WO2022009529A1 PCT/JP2021/018824 JP2021018824W WO2022009529A1 WO 2022009529 A1 WO2022009529 A1 WO 2022009529A1 JP 2021018824 W JP2021018824 W JP 2021018824W WO 2022009529 A1 WO2022009529 A1 WO 2022009529A1
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Prior art keywords
resin composition
optical fiber
meth
acrylate
resin layer
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PCT/JP2021/018824
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English (en)
French (fr)
Japanese (ja)
Inventor
勝史 浜窪
隆志 藤井
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Priority to JP2022534929A priority Critical patent/JP7647753B2/ja
Priority to US18/008,997 priority patent/US20230312778A1/en
Priority to CN202180040930.8A priority patent/CN115668021A/zh
Priority to EP21837399.1A priority patent/EP4170401A4/en
Publication of WO2022009529A1 publication Critical patent/WO2022009529A1/ja
Anticipated expiration legal-status Critical
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/104—Coating to obtain optical fibres
    • C03C25/1065—Multiple coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • G02B6/02395—Glass optical fibre with a protective coating, e.g. two layer polymer coating deposited directly on a silica cladding surface during fibre manufacture
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length

Definitions

  • the present disclosure relates to a resin composition, a secondary coating material for an optical fiber, an optical fiber, and a method for manufacturing the optical fiber.
  • the optical fiber has a coating resin layer for protecting the glass fiber which is an optical transmitter.
  • the coating resin layer is composed of, for example, a primary resin layer and a secondary resin layer.
  • the resin composition according to one aspect of the present disclosure is a resin composition for coating an optical fiber, which comprises a photopolymerizable compound containing urethane (meth) acrylate, a photopolymerization initiator, and an antistatic material. It is a resin composition having a surface resistance ⁇ s of a cured product of the resin composition of 10 15 ⁇ or less.
  • FIG. 1 is a schematic cross-sectional view showing an example of an optical fiber according to the present embodiment.
  • An object of the present disclosure is to provide a resin composition for coating an optical fiber, which can suppress charging of the optical fiber and reduce disconnection due to adhesion of foreign matter or the like.
  • the present disclosure is also intended to provide a secondary coating material for an optical fiber, an optical fiber, and a method for manufacturing the optical fiber.
  • the resin composition according to one aspect of the present disclosure is a resin composition for coating an optical fiber, which comprises a photopolymerizable compound containing urethane (meth) acrylate, a photopolymerization initiator, and an antistatic material. It is a resin composition having a surface resistance ⁇ s of a cured product of the resin composition of 10 15 ⁇ or less.
  • the Young's modulus of the cured product of the resin composition may be 1000 MPa or more and 3000 MPa or less at 23 ° C.
  • the cured product of the resin composition has appropriate strength and toughness, and it becomes easier to suppress disconnection of the optical fiber.
  • the antistatic material may include at least one carbon nanotube selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled carbon nanotubes. By using these carbon nanotubes, it becomes easier to suppress the charge of the optical fiber.
  • the content of the antistatic material may be 0.001 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the photopolymerizable compound. This makes it easier to obtain an antistatic effect and also makes it easier to secure strength.
  • the average diameter of the carbon nanotubes may be 1 nm or more and 5 nm or less, and the average length of the carbon nanotubes may be 50 ⁇ m or more and 700 ⁇ m or less.
  • the secondary coating material for the optical fiber according to one aspect of the present disclosure includes the above resin composition. By forming a secondary resin layer using the above resin composition, an optical fiber having excellent antistatic properties can be obtained.
  • the optical fiber according to one aspect of the present disclosure is an optical fiber including a glass fiber including a core and a clad and a coated resin layer covering the outer periphery of the glass fiber, and the coated resin layer is in contact with the glass fiber.
  • a primary resin layer covering a glass fiber and a secondary resin layer covering the outer periphery of the primary resin layer are included, and the secondary resin layer is made of a cured product of the above resin composition.
  • Such an optical fiber has excellent antistatic properties.
  • the method for producing an optical fiber according to one aspect of the present disclosure includes a coating step of applying the above resin composition to the outer periphery of a glass fiber including a core and a clad, and a coating step of applying ultraviolet rays after the coating step to apply the resin composition. Includes a curing step to cure. This makes it possible to manufacture an optical fiber having excellent antistatic properties.
  • the resin composition contains a base resin containing a photopolymerizable compound and a photopolymerization initiator, and an antistatic material.
  • the base resin can contain a photopolymerizable compound containing an oligomer and a monomer containing a urethane (meth) acrylate, and a photopolymerization initiator.
  • the (meth) acrylate means an acrylate or a methacrylate corresponding thereto. The same applies to (meth) acrylic acid and the like.
  • urethane (meth) acrylate an oligomer obtained by reacting a polyol compound, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound can be used.
  • polyol compound examples include polytetramethylene glycol, polypropylene glycol and bisphenol A / ethylene oxide-added diol.
  • polyisocyanate compound examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane 4,4'-diisocyanate.
  • hydroxyl group-containing (meth) acrylate compound examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, and pentaerythritol tri (meth) acrylate. Examples thereof include 2-hydroxypropyl (meth) acrylate and tripropylene glycol mono (meth) acrylate.
  • the number average molecular weight of the polyol compound may be 400 or more and 1000 or less.
  • An organotin compound is generally used as a catalyst for synthesizing urethane (meth) acrylate.
  • the organotin compound include dibutyltin dilaurate, dibutyltin diacetate, dibutyltinmalate, dibutyltinbis (2-ethylhexyl mercaptoacetate), dibutyltinbis (isooctyl mercaptoacetate) and dibutyltin oxide. From the viewpoint of easy availability or catalytic performance, it is preferable to use dibutyltin dilaurate or dibutyltin diacetate as the catalyst.
  • a lower alcohol having 5 or less carbon atoms may be used when synthesizing urethane (meth) acrylate.
  • the lower alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol and 3-pentanol.
  • Examples thereof include 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol and 2,2-dimethyl-1-propanol.
  • the oligomer may further contain an epoxy (meth) acrylate.
  • an epoxy (meth) acrylate an oligomer obtained by reacting an epoxy resin having two or more glycidyl groups with a compound having a (meth) acryloyl group can be used.
  • the epoxy (meth) acrylate for example, bisphenol A type epoxy (meth) acrylate can be used.
  • the content of epoxy (meth) acrylate is preferably 10% by mass or more and 55% by mass or less, and more preferably 15% by mass or more and 50% by mass or less, based on the total amount of oligomers and monomers, in order to increase the toughness of the optical fiber. , 20% by mass or more and 45% by mass or less is more preferable.
  • the monomer at least one selected from the group consisting of a monofunctional monomer having one polymerizable group and a polyfunctional monomer having two or more polymerizable groups can be used. Two or more kinds of monomers may be mixed and used.
  • Examples of the monofunctional monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, and tert-butyl (meth) acrylate.
  • -Maleimide-based monomers such as phenylmaleimide; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-methyl (meth) acrylamide, N -N-substituted amide-based monomers such as butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide; aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, (meth).
  • Aminoalkyl (meth) acrylate monomers such as N, N-dimethylaminoethyl acrylate, tert-butylaminoethyl (meth) acrylate; N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl- Examples thereof include succinimide-based monomers such as 6-oxyhexamethylene succinimide and N- (meth) acryloyl-8-oxyoctamethylene succinimide.
  • polyfunctional monomer examples include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate.
  • Di (meth) acrylate of alkylene oxide adduct of bisphenol A tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,16-hexadecane EO addition of diol di (meth) acrylate, 1,20-eicosane diol di (meth) acrylate, isopentyl diol di (meth) acrylate, 3-ethyl-1,8-octane diol di (meth) acrylate, bisphenol A
  • the monomer preferably contains a polyfunctional monomer, and more preferably contains a monomer having two polymerizable groups.
  • the photopolymerization initiator it can be appropriately selected from known radical photopolymerization initiators and used.
  • the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone (Omnirad 184, manufactured by IGM Resins), 2,2-dimethoxy-2-phenylacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-.
  • the antistatic material examples include carbon nanotubes, low molecular weight surfactants (low molecular weight antistatic agents), conductive polymers (high molecular weight antistatic agents) and the like.
  • the antistatic material may be carbon nanotubes from the viewpoint of suppressing coloring of the optical fiber and easily obtaining an antistatic effect with a small amount.
  • the carbon nanotubes may include at least one carbon nanotube selected from the group consisting of single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs) and multi-walled carbon nanotubes (MWCNTs).
  • the average diameter of carbon nanotubes may be 1 nm or more and 5 nm or less. Further, the average length of the carbon nanotubes may be 50 ⁇ m or more and 700 ⁇ m or less. Since carbon nanotubes have such characteristics, it is easy to obtain an antistatic effect with a small amount. Such carbon nanotubes having a small diameter, a large specific surface area, and a long length (high aspect ratio) can be obtained, for example, by the super growth method.
  • the average diameter of carbon nanotubes can be measured by a transmission electron microscope (TEM).
  • the average length of carbon nanotubes can be measured by a scanning electron microscope (SEM), an atomic force microscope (AFM), or the like.
  • the content of the antistatic material may be 0.001 part by mass or more, 0.003 part by mass or more, and 0 by mass with respect to 100 parts by mass of the photopolymerizable compound from the viewpoint of easily obtaining the antistatic effect. It may be .005 parts by mass or more. Further, the content of the antistatic material may be 1 part by mass or less, and 0.5 part by mass or less with respect to 100 parts by mass of the photopolymerizable compound, from the viewpoint of easily suppressing deterioration of strength and scratch resistance. It may be present, and may be 0.1 parts by mass or less.
  • the resin composition may further contain a silane coupling agent, a leveling agent, a defoaming agent, an antioxidant, a sensitizer, inorganic oxide particles and the like.
  • the silane coupling agent is not particularly limited as long as it does not interfere with the curing of the resin composition.
  • examples of the silane coupling agent include tetramethyl silicate, tetraethyl silicate, mercaptopropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris ( ⁇ -methoxy-ethoxy) silane, and ⁇ - (3,4-epoxycyclohexyl).
  • -Ethyltrimethoxysilane dimethoxydimethylsilane, diethoxydimethylsilane, 3-acryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -methacryloxypropyl Trimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -Chloropropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, bis- [3- (triethoxysilyl) prop
  • the inorganic oxide particles are not particularly limited, but silicon dioxide (silica), zirconium dioxide (zirconia), aluminum oxide (alumina), from the viewpoint of excellent dispersibility in the resin composition and easy preparation of the young ratio, Examples thereof include particles containing at least one selected from the group consisting of magnesium oxide (magnesia), titanium oxide (titania), tin oxide and zinc oxide.
  • the surface resistivity ⁇ s (that is, substantially the surface resistivity of the secondary resin layer described later) of the cured product of the resin composition is 10 15 ⁇ ( ⁇ / sq. Or ⁇ / ⁇ ) or less.
  • the antistatic effect can be sufficiently obtained, and it is considered that the charging of the optical fiber can be suppressed and the disconnection of the optical fiber due to the adhesion of foreign matter or the like can be reduced.
  • the surface resistivity may be 10 14 ⁇ or less, and may be 10 13 ⁇ or less.
  • the lower limit of the surface resistivity can be adjusted as appropriate, but may be from easily viewpoint to suppress the reduction in strength and abrasion resistance 10 6 Omega.
  • the surface resistivity of the cured product of the resin composition can be measured using, for example, a resin film obtained by curing the resin composition with an integrated light amount of 900 mJ / cm 2 or more and 1100 mJ / cm 2 or less.
  • the Young's modulus of the cured product of the resin composition may be 1000 MPa or more and 3000 MPa or less at 23 ° C., and may be 1200 MPa or more and 2800 MPa or less, 1300 MPa. It may be 2700 MPa or less.
  • the Young's modulus of the cured product is 1000 MPa or more, the strength of the optical fiber is likely to be improved, and when it is 3000 MPa or less, appropriate toughness can be imparted to the cured product, so that the optical fiber is less likely to break.
  • the Young's modulus of the cured product of the resin composition can be measured using, for example, a resin film obtained by curing the resin composition with an integrated light amount of 900 mJ / cm 2 or more and 1100 mJ / cm 2 or less.
  • the Young's modulus is measured using the resin film in this way, the value tends to be slightly higher (generally about 100 MPa higher) than the Young's modulus of the secondary resin layer formed by the resin composition.
  • the secondary coating material of the optical fiber contains the above resin composition. By forming a secondary resin layer using the above resin composition, an optical fiber having excellent antistatic properties can be produced.
  • FIG. 1 is a schematic cross-sectional view showing an example of an optical fiber according to the present embodiment.
  • the optical fiber 10 includes a glass fiber 13 including a core 11 and a clad 12, and a coated resin layer 16 including a primary resin layer 14 and a secondary resin layer 15 provided on the outer periphery of the glass fiber 13.
  • the clad 12 surrounds the core 11.
  • the core 11 and the clad 12 mainly contain glass such as quartz glass.
  • glass such as quartz glass.
  • quartz glass or pure quartz glass to which germanium is added can be used for the core 11, and pure quartz glass or pure quartz glass or pure quartz glass can be used for the clad 12. Quartz glass to which fluorine is added can be used.
  • the outer diameter (D2) of the glass fiber 13 is about 100 ⁇ m to 125 ⁇ m, and the diameter (D1) of the core 11 constituting the glass fiber 13 is about 7 ⁇ m to 15 ⁇ m.
  • the thickness of the coating resin layer 16 is usually about 22 ⁇ m to 70 ⁇ m.
  • the thickness of each of the primary resin layer 14 and the secondary resin layer 15 may be about 5 ⁇ m to 50 ⁇ m.
  • the thickness of each layer of the primary resin layer 14 and the secondary resin layer 15 is about 10 ⁇ m to 50 ⁇ m.
  • the thickness of the primary resin layer 14 may be 35 ⁇ m
  • the thickness of the secondary resin layer 15 may be 25 ⁇ m.
  • the outer diameter of the optical fiber 10 may be about 245 ⁇ m to 265 ⁇ m.
  • the thickness of each layer of the primary resin layer 14 and the secondary resin layer 15 is about 10 ⁇ m to 38 ⁇ m.
  • the thickness of the primary resin layer 14 may be 25 ⁇ m
  • the thickness of the secondary resin layer 15 may be 10 ⁇ m.
  • the outer diameter of the optical fiber 10 may be about 179 ⁇ m to 221 ⁇ m.
  • the thickness of each layer of the primary resin layer 14 and the secondary resin layer 15 is about 5 ⁇ m to 32 ⁇ m.
  • the thickness of the primary resin layer 14 may be 25 ⁇ m
  • the thickness of the secondary resin layer 15 may be 10 ⁇ m.
  • the outer diameter of the optical fiber 10 may be about 144 ⁇ m to 174 ⁇ m.
  • the secondary resin layer 15 is charged with a photopolymerizable compound containing urethane (meth) acrylate and a base resin containing a photopolymerization initiator. It can be formed by curing the above resin composition containing an inhibitory material. That is, the secondary resin layer 15 may contain a cured product of the above resin composition containing a photopolymerizable compound containing urethane (meth) acrylate, a base resin containing a photopolymerization initiator, and an antistatic material.
  • the Young's modulus of the secondary resin layer may be 1000 MPa or more and 3000 MPa or less at 23 ° C., may be 1200 MPa or more and 2800 MPa or less, and may be 1300 MPa or more and 2700 MPa or less.
  • the Young's modulus of the secondary resin layer is 1000 MPa or more, the lateral pressure characteristics are easily improved, and when it is 3000 MPa or less, appropriate toughness can be imparted to the secondary resin layer, so that it is difficult to break the wire.
  • the primary resin layer 14 can be formed by curing, for example, a resin composition containing a photopolymerizable compound containing urethane (meth) acrylate, a photopolymerization initiator and a silane coupling agent.
  • a resin composition containing a photopolymerizable compound containing urethane (meth) acrylate, a photopolymerization initiator and a silane coupling agent Conventionally known techniques can be used for the resin composition for the primary resin layer.
  • the oligomer, monomer, photopolymerization initiator and silane coupling agent containing urethane (meth) acrylate may be appropriately selected from the compounds exemplified in the above base resin.
  • the resin composition forming the primary resin layer has a composition different from that of the base resin forming the secondary resin layer.
  • the Young's modulus of the primary resin layer is preferably 0.04 MPa or more and 1.0 MPa or less, and 0.05 MPa or more and 0.9 MPa or less at 23 ° C. Is more preferable, and more preferably 0.05 MPa or more and 0.8 MPa or less.
  • the method for manufacturing an optical fiber includes a coating step of applying the above resin composition to the outer periphery of a glass fiber including a core and a clad, and a curing step of curing the resin composition by irradiating ultraviolet rays after the coating step. including. More specifically, the resin composition for the primary resin layer is applied to the outer periphery of the glass fiber to form the primary resin layer by irradiating with ultraviolet rays, and the resin composition for the secondary resin layer is further applied to the outer periphery thereof. Then, by irradiating with ultraviolet rays, a secondary resin layer can be formed and an optical fiber can be obtained. The irradiation of ultraviolet rays can be carried out with an integrated light intensity of 1000 ⁇ 100 mJ / cm 2.
  • urethane acrylate (UA) obtained by reacting polypropylene glycol having a number average molecular weight of 600, 2,4-tolylene diisocyanate and 2-hydroxyethyl acrylate, and bisphenol A type epoxy acrylate (EA) are used. Got ready.
  • TPGDA Tripropylene glycol diacrylate
  • PO-A 2-phenoxyethyl acrylate
  • Photopolymerization initiator As a photopolymerization initiator, 1-hydroxycyclohexylphenyl ketone (Omnirad 184) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO) were prepared.
  • Antistatic material As an antistatic material, a single-walled carbon nanotube (SWCNT), powdered carbon nanotube, single-walled (brand name: Aldrich, obtained from Sigma-Aldrich, product name) was prepared.
  • the SWCNT is manufactured by the super growth method, has an average diameter of 3 nm to 5 nm, and an average length of 300 ⁇ m to 500 ⁇ m.
  • the above oligomer, monomer and photopolymerization initiator were mixed to prepare a base resin.
  • the photopolymerization initiator 1.5 parts by mass of 1-hydroxycyclohexylphenylketone and 1.5 parts by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide are used for 100 parts by mass of the total amount of oligomers and monomers. board.
  • the carbon nanotubes were mixed with the base resin so that the content of the carbon nanotubes was the amount shown in Table 1.
  • most of the dispersion medium methanol was removed under reduced pressure to prepare a resin composition for the secondary resin layer.
  • the content of methanol remaining in the resin composition was 5% by mass or less.
  • the amount of the oligomer and the monomer is the content based on the total amount of the oligomer and the monomer
  • the amount of the carbon nanotube is the amount with respect to 100 parts by mass of the photopolymerizable compound (oligomer and the monomer).
  • this urethane acrylate 75 parts by mass of this urethane acrylate, 12 parts by mass of nonylphenol EO modified acrylate, 6 parts by mass of N-vinylcaprolactam, 2 parts by mass of 1,6-hexanediol diacrylate, 1 part by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, And 1 part by mass of ⁇ -mercaptopropyltrimethoxysilane were mixed to obtain a resin composition for a primary resin layer.
  • a resin composition for a primary resin layer was applied to the outer periphery of a glass fiber having a diameter of 125 ⁇ m composed of a core and a clad and irradiated with ultraviolet rays to form a primary resin layer having a thickness of 20 ⁇ m. Further, a resin composition for a secondary resin layer was applied to the outer periphery thereof and irradiated with ultraviolet rays to form a secondary resin layer having a thickness of 15 ⁇ m, thereby producing an optical fiber.
  • Ultraviolet irradiation was carried out using an electrodeless UV lamp system (“VPS600 (D bulb)” manufactured by Heraeus) under the condition of 1000 ⁇ 100 mJ / cm 2. The line speed was 1500 m / min.
  • the resin film is punched into a JIS K 7127 type 5 dumbbell shape, and pulled under the conditions of 23 ⁇ 2 ° C, 50 ⁇ 10% RH, a tensile speed of 1 mm / min, and a distance between marked lines of 25 mm using a tensile tester. , A stress-strain curve was obtained. Then, the Young's modulus of the resin film was obtained by the secant method of 2.5% strain. The measurement was performed 5 times, and the average value was taken as Young's modulus. When the Young's modulus is measured using the resin film in this way, the value tends to be slightly higher (generally about 100 MPa higher) than the Young's modulus of the secondary resin layer formed by the resin composition.
  • the optical fiber obtained in each example was immersed in a mixed solvent of acetone and ethanol, and only the coating resin layer was pulled out in a tubular shape. Next, after removing the solvent by vacuum drying, the mixture was allowed to stand in a constant temperature room maintained at 23 ⁇ 2 ° C. and 50 ⁇ 10% RH for 16 hours or more, and then the tensile speed was 1 mm / min using a tensile tester. A stress-strain curve was obtained by pulling under the condition of 25 mm between marked lines. Then, the Young's modulus of the coated resin layer was obtained by a secant method with a 2.5% strain. The measurement was performed 5 times, and the average value was taken as Young's modulus. The Young's modulus obtained by this can be regarded as substantially the Young's modulus of the secondary resin layer.
  • a resin film (cured product) was obtained from the resin compositions obtained in each example by the same procedure as the above-mentioned "Measurement of Young's modulus: Film Young's modulus". This was cut into 10 cm ⁇ 10 cm and used as a measurement sample. Then, the surface resistivity was measured under the following devices and conditions.
  • Measuring method 3-terminal method
  • Measuring device Advantest Co., Ltd., Ultra-high resistance / micro ammeter R8340, and ADC Co., Ltd., Resistivity Chamber 120704A
  • Applied voltage DC 500V
  • Charging time 1 minute
  • Measurement atmosphere In air Measurement temperature and humidity: 21 ° C, 34% RH to 35%
  • Electrode size Electrode 1 with a diameter of 5.0 cm, electrode 2 with an inner diameter of 7.0 cm Number of measured n: 3

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PCT/JP2021/018824 2020-07-09 2021-05-18 樹脂組成物、光ファイバのセカンダリ被覆材料、光ファイバ、及び光ファイバの製造方法 Ceased WO2022009529A1 (ja)

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US18/008,997 US20230312778A1 (en) 2020-07-09 2021-05-18 Resin composition, optical fiber secondary coating material, optical fiber, and optical fiber production method
CN202180040930.8A CN115668021A (zh) 2020-07-09 2021-05-18 树脂组合物、光纤的次级被覆材料、光纤及光纤的制造方法
EP21837399.1A EP4170401A4 (en) 2020-07-09 2021-05-18 RESIN COMPOSITION, OPTICAL FIBER SECONDARY COATING MATERIAL, OPTICAL FIBER AND OPTICAL FIBER PRODUCTION METHOD

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CN115916721B (zh) * 2020-06-24 2025-04-08 住友电气工业株式会社 树脂组合物、光纤以及光纤的制造方法
WO2023210461A1 (ja) * 2022-04-27 2023-11-02 株式会社フジクラ 光ファイバ素線、および光ファイバリボンの製造方法
CN118206904A (zh) * 2024-04-19 2024-06-18 江苏亨通光纤科技有限公司 一种聚合物接枝碳纳米管改性的高性能光纤涂料的制备方法及应用方法

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JP2013018562A (ja) 2011-07-07 2013-01-31 Sumitomo Electric Ind Ltd 光ファイバの巻取り方法及び巻取り装置
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JP2013018562A (ja) 2011-07-07 2013-01-31 Sumitomo Electric Ind Ltd 光ファイバの巻取り方法及び巻取り装置
JP2015195143A (ja) * 2014-03-31 2015-11-05 戸田工業株式会社 カーボンナノチューブ分散液および非水電解質二次電池
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JP7647753B2 (ja) 2025-03-18
TW202204284A (zh) 2022-02-01
JPWO2022009529A1 (https=) 2022-01-13

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