WO2024154414A1 - Resin composition for optical fiber color coating, optical fiber, and optical fiber ribbon - Google Patents

Resin composition for optical fiber color coating, optical fiber, and optical fiber ribbon Download PDF

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Publication number
WO2024154414A1
WO2024154414A1 PCT/JP2023/040101 JP2023040101W WO2024154414A1 WO 2024154414 A1 WO2024154414 A1 WO 2024154414A1 JP 2023040101 W JP2023040101 W JP 2023040101W WO 2024154414 A1 WO2024154414 A1 WO 2024154414A1
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Prior art keywords
resin layer
meth
acrylate
optical fiber
resin composition
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PCT/JP2023/040101
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French (fr)
Japanese (ja)
Inventor
勝史 浜窪
矩章 岩口
未歩 池川
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住友電気工業株式会社
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Publication of WO2024154414A1 publication Critical patent/WO2024154414A1/en

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    • 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
    • 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
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/285—Acrylic resins
    • 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
    • C03C25/465—Coatings containing composite materials
    • C03C25/475—Coatings containing composite materials containing colouring agents
    • 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
    • C03C25/62—Surface treatment of fibres or filaments made from glass, minerals or slags by application of electric or wave energy; by particle radiation or ion implantation
    • C03C25/6206—Electromagnetic waves
    • C03C25/6226—Ultraviolet
    • 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

Definitions

  • the present disclosure relates to a resin composition for colored coating of optical fibers, an optical fiber, and an optical fiber ribbon.
  • optical fibers have a coating resin layer to protect the glass fiber that transmits light.
  • the coating resin layer has, for example, a primary resin layer and a secondary resin layer.
  • the outermost layer of the coating resin layer is composed of a colored resin layer for identifying the optical fiber (see, for example, Patent Documents 1 to 3).
  • the resin composition for optical fiber coloring coating contains a photopolymerizable compound, a polymer dispersant having an acidic functional group, a photopolymerization initiator, and surface-treated titanium oxide particles, the content of the polymer dispersant being 0.01% by mass or more and 18% by mass or less based on the content of the surface-treated titanium oxide particles, and the acid value of the polymer dispersant being 25 mgKOH/g or more and 180 mgKOH/g or less.
  • FIG. 1 is a schematic cross-sectional view showing an example of an optical fiber according to the present embodiment.
  • FIG. 2 is a schematic cross-sectional view showing an example of the optical fiber according to the present embodiment.
  • FIG. 3 is a schematic cross-sectional view showing an example of an optical fiber ribbon according to the present embodiment.
  • the resin composition for forming the colored resin layer contains an inorganic pigment such as titanium oxide. Since the inorganic pigment has a larger specific gravity than the resin component, the inorganic pigment may settle during storage of the prepared resin composition. Therefore, the resin composition for colored coating of optical fiber is required to have excellent storage stability.
  • the present disclosure aims to provide a resin composition for colored coating of optical fibers that has excellent storage stability, an optical fiber, and an optical fiber ribbon.
  • a resin composition for coloring and coating optical fibers contains a photopolymerizable compound, a polymer dispersant having an acidic functional group, a photopolymerization initiator, and surface-treated titanium oxide particles, the content of the polymer dispersant being 0.01% by mass or more and 18% by mass or less based on the content of the surface-treated titanium oxide particles, and the acid value of the polymer dispersant being 25 mgKOH/g or more and 180 mgKOH/g or less.
  • Such a resin composition can have excellent storage stability by containing a polymer dispersant having an acidic functional group in a specific range and by setting the acid value of the polymer dispersant in a specific range.
  • the acidic functional group may be a phosphoric acid group or a carboxyl group in order to further improve the storage stability of the resin composition.
  • the surface-treated titanium oxide particles may have a surface treatment layer containing at least one selected from the group consisting of aluminum oxide, silicon dioxide, and zirconium dioxide.
  • the photopolymerizable compound may contain epoxy di(meth)acrylate in order to increase the strength of the resin layer.
  • An optical fiber according to one aspect of the present disclosure comprises a glass fiber including a core and a cladding, a primary resin layer that contacts the glass fiber and covers the glass fiber, a secondary resin layer that covers the primary resin layer, and a colored resin layer that covers the secondary resin layer, the colored resin layer containing a cured product of the resin composition described in any one of (1) to (4) above.
  • An optical fiber according to one aspect of the present disclosure comprises a glass fiber including a core and a cladding, a primary resin layer that contacts the glass fiber and covers the glass fiber, and a secondary resin layer that covers the primary resin layer, the secondary resin layer containing a cured product of the resin composition described in any one of (1) to (4) above.
  • an optical fiber ribbon In an optical fiber ribbon according to one aspect of the present disclosure, a plurality of optical fibers as described in (5) or (6) above are arranged in parallel and coated with a ribbon resin. Such an optical fiber ribbon is less likely to peel off when the optical fibers are removed, and the optical fibers can be easily identified.
  • the resin composition for coloring and coating an optical fiber contains a photopolymerizable compound, a polymer dispersant having an acidic functional group, a photopolymerization initiator, and surface-treated titanium oxide particles, and the content of the polymer dispersant is 0.01 mass % or more and 18 mass % or less based on the content of the surface-treated titanium oxide particles, and the acid value of the polymer dispersant is 25 mg KOH/g or more and 180 mg KOH/g or less.
  • the polymer dispersant adsorbs to the surface of the surface-treated titanium oxide particles via the acidic functional groups, dispersing the surface-treated titanium oxide particles in the resin composition and suppressing the aggregation of the surface-treated titanium oxide particles.
  • acidic functional groups examples include phosphate groups and carboxy groups.
  • the acidic functional group is a phosphate group or a carboxy group, the storage stability of the resin composition can be further improved.
  • the structure of the polymer dispersant may be a straight-chain type having an acidic functional group at the end, or a comb-shaped type having multiple acidic functional groups in the side chain. By using a comb-shaped polymer dispersant, the storage stability of the resin composition can be further improved.
  • the polymer dispersant may be a random copolymer, a block copolymer, or a graft copolymer.
  • polymeric dispersants examples include polyurethane-based dispersants, polyether-based dispersants, and polyester-based dispersants.
  • a comb-shaped polyester-based dispersant having a phosphate group on the side chain may be used.
  • the content of the polymer dispersant may be 0.05 mass% or more, 0.08 mass% or more, 0.1 mass% or more, or 0.3 mass% or more based on the content of the surface-treated titanium oxide particles, and may be 16 mass% or less, 15 mass% or less, or 12 mass% or less.
  • the acid value of the polymer dispersant may be 30 mgKOH/g or more, 35 mgKOH/g or more, 45 mgKOH/g or more, or 50 mgKOH/g or more, and may be 160 mgKOH/g or less, 150 mgKOH/g or less, 140 mgKOH/g or less, or 120 mgKOH/g or less.
  • the acid value of the polymer dispersant can be measured, for example, in accordance with DIN EN ISO 2114.
  • the photopolymerizable compound is not particularly limited, but may contain epoxy di(meth)acrylate from the viewpoint of increasing the strength of the resin layer.
  • epoxy di(meth)acrylate a reaction product of a diglycidyl ether compound having a bisphenol skeleton and a compound having a (meth)acryloyl group such as (meth)acrylic acid can be used.
  • epoxy di(meth)acrylates examples include (meth)acrylic acid adducts of bisphenol A diglycidyl ether, (meth)acrylic acid adducts of bisphenol AF diglycidyl ether, and (meth)acrylic acid adducts of bisphenol F diglycidyl ether.
  • the content of the epoxy di(meth)acrylate may be 30 parts by mass or more, 40 parts by mass or more, or 45 parts by mass or more, and may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less, relative to 100 parts by mass of the total amount of the photopolymerizable compound.
  • the photopolymerizable compound may further contain a urethane (meth)acrylate from the viewpoint of adjusting the Young's modulus of the resin layer.
  • a urethane (meth)acrylate for example, a urethane oligomer obtained by reacting a polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate compound can be used.
  • the urethane (meth)acrylate may be used alone or in combination of two or more types.
  • polyol compounds include polytetramethylene glycol, polypropylene glycol, and bisphenol A-ethylene oxide addition diol.
  • polyisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane 4,4'-diisocyanate.
  • hydroxyl group-containing (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 1,6-hexanediol mono(meth)acrylate, pentaerythritol tri(meth)acrylate, 2-hydroxypropyl (meth)acrylate, and tripropylene glycol mono(meth)acrylate.
  • the number average molecular weight (Mn) of the polyol compound may be 300 or more and 3000 or less, 400 or more and 3000 or less, or 500 or more and 2500 or less.
  • Organotin compounds are generally used as catalysts in the synthesis of urethane (meth)acrylates.
  • organotin compounds include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate, dibutyltin bis(2-ethylhexyl mercaptoacetate), dibutyltin bis(isooctyl mercaptoacetate) and dibutyltin oxide. From the standpoint of easy availability or catalytic performance, dibutyltin dilaurate or dibutyltin diacetate may be used as the catalyst.
  • a lower alcohol having 5 or less carbon atoms may be used.
  • lower alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, and 2,2-dimethyl-1-propanol.
  • the photopolymerizable compound according to this embodiment may further contain a photopolymerizable compound (hereinafter referred to as "monomer") other than epoxy di(meth)acrylate.
  • a photopolymerizable compound hereinafter referred to as "monomer”
  • a monofunctional monomer having one polymerizable group or a polyfunctional monomer having two or more polymerizable groups can be used. Two or more types of monomers may be mixed and used.
  • monofunctional monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, s-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 3-phenoxyethyl (meth)acrylate, (Meth)acrylate mono
  • carboxy group-containing monomers such as N-(meth)acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, 3-(3-pyridine)propyl(meth)acrylate, and cyclic trimethylolpropane formal acrylate; heterocycle-containing monomers such as maleimide, N-cyclohexylmaleimide, and N-phenylmaleimide; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-hexyl(meth)acrylamide, N Amide monomers such as N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, and N-methylolpropane(meth
  • polyfunctional monomers examples include polyethylene glycol di(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, ethylene oxide modified bisphenol F di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, polypropylene glycol di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, propylene oxide modified neopentyl glycol di(meth)acrylate, polytetraethylene glycol di(meth)acrylate, p) acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, 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(me
  • the photopolymerizable compound according to this embodiment may contain an alkylene oxide-modified polyfunctional monomer from the viewpoint of adjusting the Young's modulus of the resin layer.
  • the alkylene oxide-modified polyfunctional monomer may have at least one selected from the group consisting of an ethylene oxide (EO) chain and a propylene oxide (PO) chain.
  • EO ethylene oxide
  • PO propylene oxide
  • the ethylene oxide chain can be represented as "(EO)n” and the propylene oxide chain as "(PO)n".
  • n is an integer of 1 or more, and may be 2 or more or 3 or more, and may be 30 or less, 25 or less, or 20 or less.
  • alkylene oxide modified di(meth)acrylates examples include polyethylene glycol di(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, ethylene oxide modified bisphenol F di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate polypropylene glycol di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, and propylene oxide modified neopentyl glycol di(meth)acrylate.
  • alkylene oxide modified tri(meth)acrylates include trimethylolpropane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, trimethylolpropane polypropoxy tri(meth)acrylate, trimethylolpropane polyethoxy polypropoxy tri(meth)acrylate, tris[(meth)acryloyloxyethyl]isocyanurate, and pentaerythritol tri(meth)acrylate.
  • the photopolymerization initiator can be appropriately selected from known radical photopolymerization initiators.
  • photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resins), 2,2-dimethoxy-2-phenylacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2-methyl-1-[4- (methylthio)phenyl]-2-morpholino-propan-1-one (Omnirad 907, IGM Resins), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO, IGM Resins), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, IGM Resins).
  • the content of the photopolymerization initiator may be 1 part by mass or more and 10 parts by mass or less, 2 parts by mass or more and 8 parts by mass or less, or 3 parts by mass or more and 7 parts by mass or less, relative to 100 parts by mass of the total amount of the photopolymerizable compounds.
  • the resin composition according to this embodiment contains surface-treated titanium oxide particles in order to color the resin layer.
  • the surface-treated titanium oxide particles are particles in which titanium oxide has been surface-treated with an inorganic substance, and have excellent dispersibility in the resin composition.
  • Examples of inorganic substances used for surface treatment include aluminum oxide, silicon dioxide, and zirconium dioxide.
  • a surface treatment layer containing at least one selected from the group consisting of aluminum oxide, silicon dioxide, and zirconium dioxide the dispersibility can be further improved.
  • the surface treatment layer may be formed on at least a portion of the surface of the titanium oxide particles, or may be formed on the entire surface of the titanium oxide particles.
  • the surface treatment layer is formed by surface treatment of the titanium oxide particles.
  • the amount of the surface treatment layer in the surface-treated titanium oxide particles may be 1 mass% or more, 1.5 mass% or more, or 2 mass% or more from the viewpoint of further improving dispersibility, and may be 10 mass% or less, 9 mass% or less, or 8 mass% or less from the viewpoint of increasing hiding power.
  • the amount of the surface treatment layer can be calculated by measuring the amount of titanium element and inorganic elements other than titanium contained in the surface-treated titanium oxide particles using inductively coupled mass spectrometry (ICP-MS).
  • the average primary particle size of the surface-treated titanium oxide particles may be 300 nm or less, 295 nm or less, or 290 nm or less, from the viewpoint of improving the lateral pressure resistance of the coating resin layer.
  • the average primary particle size of the surface-treated titanium oxide particles may be 100 nm or more, 150 nm or more, or 200 nm or more, or may be 200 nm or more and 300 nm or less, from the viewpoint of improving hiding power.
  • the average primary particle size can be measured, for example, by image analysis of electron microscope photographs, light scattering method, BET method, etc.
  • the content of the surface-treated titanium oxide particles may be 0.6 mass% or more, 1 mass% or more, 2 mass% or more, or 3 mass% or more based on the total amount of the resin composition from the viewpoint of improving the visibility of the resin layer.
  • the content of the surface-treated titanium oxide particles may be 20 mass% or less, 15 mass% or less, 10 mass% or less, or 8 mass% or less based on the total amount of the resin composition from the viewpoint of improving the curability of the resin composition.
  • the resin composition according to this embodiment may further contain a silane coupling agent, a leveling agent, an antifoaming agent, an antioxidant, a sensitizer, etc.
  • silane coupling agent is not particularly limited as long as it does not interfere with the curing of the resin composition.
  • silane coupling agents include tetramethyl silicate, tetraethyl silicate, mercaptopropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris( ⁇ -methoxy-ethoxy)silane, ⁇ -(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, dimethoxydimethylsilane, diethoxydimethylsilane, 3-acryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N
  • the viscosity of the resin composition according to this embodiment at 25°C may be 1000 mPa ⁇ s or more, 1500 mPa ⁇ s or more, or 2000 mPa ⁇ s or more from the viewpoint of storage stability, and may be less than 10000 mPa ⁇ s, 8000 mPa ⁇ s or less, or 6000 mPa ⁇ s or less from the viewpoint of coatability.
  • the Young's modulus of the resin film may be 500 MPa or more, 600 MPa or more, or 700 MPa or more at 23°C. From the viewpoint of forming a resin layer with excellent toughness, the Young's modulus of the resin film may be 1500 MPa or less, 1300 MPa or less, or 1200 MPa or less at 23°C.
  • the resin composition according to this embodiment can be suitably used as a colored coating material for optical fibers.
  • the outermost layer of the coating resin layer using a colored coating material containing the resin composition according to this embodiment, the single-core separation property of the optical fiber can be improved.
  • Fig. 1 is a schematic cross-sectional view showing the configuration of an optical fiber according to an embodiment.
  • the optical fiber 1 of the present embodiment includes a glass fiber 10 and a coating resin layer 20 that contacts the glass fiber 10 and covers the outer periphery of the glass fiber 10.
  • the glass fiber 10 is a light-guiding optical transmission body that transmits light introduced into the optical fiber 1.
  • the glass fiber 10 is a glass member, and is configured, for example, with silica (SiO 2 ) glass as a base material (main component).
  • the glass fiber 10 includes a core 12 and a clad 14 that covers the core 12.
  • the glass fiber 10 transmits light introduced into the optical fiber 1.
  • the core 12 is provided, for example, in a region that includes the central axis of the glass fiber 10.
  • the core 12 is made of, for example, pure SiO 2 glass, or SiO 2 glass containing germanium dioxide (GeO 2 ), fluorine element, or the like.
  • the clad 14 is provided in a region that surrounds the core 12.
  • the clad 14 has a refractive index lower than that of the core 12.
  • the clad 14 is made of, for example, pure SiO 2 glass, or SiO 2 glass to which fluorine element is added.
  • the outer diameter of the glass fiber 10 is about 100 ⁇ m to 125 ⁇ m, and the diameter of the core 12 constituting the glass fiber 10 is about 7 ⁇ m to 15 ⁇ m.
  • the coating resin layer 20 is an ultraviolet-curable resin layer that covers the clad 14.
  • the coating resin layer 20 includes a primary resin layer 22 that coats the outer periphery of the glass fiber 10, a secondary resin layer 24 that coats the outer periphery of the primary resin layer 22, and a colored resin layer 26 that coats the outer periphery of the secondary resin layer 24.
  • the primary resin layer 22 is in contact with the outer periphery of the clad 14 and coats the entire clad 14.
  • the secondary resin layer 24 is in contact with the outer periphery of the primary resin layer 22 and coats the entire primary resin layer 22.
  • the colored resin layer 26 is in contact with the outer periphery of the secondary resin layer 24 and coats the outer periphery of the secondary resin layer 24.
  • the thickness of the primary resin layer 22 is, for example, 10 ⁇ m or more and 50 ⁇ m or less.
  • the thickness of the secondary resin layer 24 is, for example, 10 ⁇ m or more and 40 ⁇ m or less.
  • the thickness of the colored resin layer 26 is, for example, 3 ⁇ m or more and 10 ⁇ m or less.
  • the primary resin layer 22 may be formed using a resin composition for primary resin layers that is conventionally known.
  • the primary resin layer 22 may be formed, for example, by curing a resin composition that includes urethane (meth)acrylate, a monomer, a photopolymerization initiator, and a silane coupling agent.
  • the secondary resin layer 24 may be formed using a conventionally known resin composition for secondary resin layers.
  • the secondary resin layer 24 can be formed, for example, by curing a resin composition containing urethane (meth)acrylate, a monomer, and a photopolymerization initiator.
  • the resin composition according to this embodiment can be applied to the colored resin layer 26.
  • the colored resin layer 26 can be formed by curing the resin composition.
  • the colored resin layer 26 contains the cured product of the resin composition according to this embodiment, thereby improving the single-core separation property of the optical fiber.
  • the colored resin layer 26 and the secondary resin layer 24 are less likely to peel off when the ribbon material is removed.
  • FIG. 2 is a schematic cross-sectional view showing the configuration of an optical fiber according to one embodiment.
  • the optical fiber 1A includes a glass fiber 10 and a coating resin layer 20A that contacts the glass fiber 10 and covers the outer periphery of the glass fiber 10.
  • the coating resin layer 20A includes a primary resin layer 22 and a secondary resin layer 24.
  • the resin composition according to this embodiment can be applied to the secondary resin layer 24.
  • the secondary resin layer 24 can be formed by curing the resin composition.
  • the secondary resin layer 24 functions as a colored secondary resin layer.
  • the secondary resin layer 24 contains a cured product of the resin composition according to this embodiment, thereby improving the single-core separation property of the optical fiber.
  • optical fiber ribbon The optical fiber according to this embodiment can be used to fabricate an optical fiber ribbon, which is made up of a plurality of the optical fibers arranged in parallel and coated with a ribbon resin.
  • FIG. 3 is a schematic cross-sectional view showing an optical fiber ribbon according to this embodiment.
  • the optical fiber ribbon 100 has a plurality of optical fibers 1 and a connecting resin layer 40 in which the optical fibers 1 are coated and connected with a ribbon resin.
  • the connecting resin layer 40 is formed from a ribbon resin.
  • four optical fibers are shown as an example, but the number is not particularly limited.
  • the ribbon resin resin materials generally known as ribbon materials can be used.
  • the ribbon resin may contain a thermosetting resin such as silicone resin, epoxy resin, or urethane resin, or an ultraviolet-curing resin such as epoxy acrylate, urethane acrylate, or polyester acrylate.
  • the optical fiber ribbon of this embodiment uses the above optical fiber, so that the optical fiber can be easily identified without color peeling when removing the connecting resin layer from the optical fiber ribbon to extract the optical fiber.
  • Photopolymerizable Compound As photopolymerizable compounds, bisphenol A epoxy diacrylate (EA), polypropylene glycol diacrylate (PPGDA), and the following alkylene oxide modified acrylate compound were prepared.
  • TMP(EO) 3TA Trimethylolpropane EO adduct triacrylate (EO number: 3)
  • TMP(EO) 15 TA Trimethylolpropane EO adduct triacrylate (EO number: 15)
  • BPA(EO) 30 DA EO-modified bisphenol A di(meth)acrylate (EO number: 30)
  • Photopolymerization initiator As photoinitiators, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO) and 1-hydroxycyclohexyl phenyl ketone (Omnirad 184) were prepared.
  • Surface-treated titanium oxide particles having a surface treatment layer containing aluminum oxide (Al 2 O 3 ) were prepared as surface-treated titanium oxide particles.
  • the average primary particle size of the surface-treated titanium oxide particles was 200 to 300 nm, and the amount of Al 2 O 3 calculated by ICP-MS measurement was 2.5 mass %.
  • Test Examples 1 to 7 Resin compositions were prepared by mixing the photopolymerizable compound and photopolymerization initiator in the amounts (parts by mass) shown in Table 2 with the polymer dispersant and surface-treated titanium oxide particles in the contents (% by mass) shown in Table 2.
  • the content of the polymer dispersant is a value based on the content of the surface-treated titanium oxide particles
  • the content of the surface-treated titanium oxide particles is a value based on the total amount of the resin composition.
  • Test Examples 1 to 6 correspond to Examples
  • Test Example 7 corresponds to a Comparative Example.
  • Test Examples 8 to 13 Resin compositions were prepared by mixing the photopolymerizable compound and photopolymerization initiator in the amounts (parts by mass) shown in Table 3 with the polymer dispersant and surface-treated titanium oxide particles in the contents (% by mass) shown in Table 3. Test Examples 8 to 11 correspond to Examples, and Test Examples 12 and 13 correspond to Comparative Examples.
  • viscosity The viscosity of the resin composition at 25° C. was measured using a rheometer ("MCR-102" manufactured by Anton Paar) under conditions of cone plate CP25-2 and a shear rate of 10 s ⁇ 1 .
  • the resin composition was applied onto a polyethylene terephthalate (PET) film using a spin coater, and then cured using an electrodeless UV lamp system (Heraeus's "VPS600 (D bulb)") at 1000 ⁇ 100 mJ/ cm2 to form a resin layer with a thickness of 50 ⁇ 5 ⁇ m on the PET film.
  • the resin layer was peeled off from the PET film to obtain a resin film.
  • the resin film was punched out into a dumbbell shape conforming to JIS K 7127 Type 5, and pulled using a tensile tester at 23 ⁇ 2°C, 50 ⁇ 10% RH, with a pulling speed of 1 mm/min and a gauge distance of 25 mm, to obtain a stress-strain curve.
  • the film Young's modulus was calculated using the 2.5% secant line.
  • Resin composition for primary resin layer A urethane acrylate obtained by reacting polypropylene glycol having a molecular weight of 4000, isophorone diisocyanate, hydroxyethyl acrylate, and methanol was prepared. 75 parts by mass of this urethane acrylate, 12 parts by mass of nonylphenol EO-modified acrylate, 6 parts by mass of N-vinyl caprolactam, 2 parts by mass of 1,6-hexanediol diacrylate, 1 part by mass of Omnirad TPO, and 1 part by mass of 3-mercaptopropyltrimethoxysilane were mixed to prepare a resin composition P.
  • Resin composition for secondary resin layer A urethane acrylate obtained by reacting polypropylene glycol having a molecular weight of 600, 2,4-tolylene diisocyanate, and 2-hydroxyethyl acrylate was prepared. Resin composition S was prepared by mixing 40 parts by mass of this urethane acrylate, 35 parts by mass of isobornyl acrylate, 24 parts by mass of epoxy acrylate which is an acrylic acid adduct of bisphenol A diglycidyl ether, 1 part by mass of Omnirad TPO, and 1 part by mass of Omnirad 184.
  • Urethane acrylate A obtained by reacting bisphenol A-ethylene oxide adduct diol, tolylene diisocyanate, and hydroxyethyl acrylate
  • urethane acrylate B obtained by reacting polytetramethylene glycol, tolylene diisocyanate, and hydroxyethyl acrylate were prepared.
  • Resin composition R was prepared by mixing 18 parts by weight of urethane acrylate A, 10 parts by weight of urethane acrylate B, 15 parts by weight of tricyclodecane dimethanol diacrylate, 10 parts by weight of N-vinylpyrrolidone, 10 parts by weight of isobornyl acrylate, 5 parts by weight of bisphenol A-ethylene oxide adduct diol diacrylate, 0.7 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (Omnirad 907), and 1.3 parts by weight of Omnirad TPO.
  • a primary resin layer having a thickness of 17.5 ⁇ m was formed on the outer circumference of a glass fiber having a diameter of 125 ⁇ m, which was composed of a core and a clad, using resin composition P, and a secondary resin layer having a thickness of 15 ⁇ m was further formed on the outer circumference of the primary resin layer using resin composition S, to produce an optical fiber.
  • a colored resin layer having a thickness of 5 ⁇ m was formed on the outer circumference of the secondary resin layer using the resin compositions of Test Examples 1 to 13 while the optical fiber was reeled out using a coloring machine, thereby producing an optical fiber having a diameter of 200 ⁇ m and a colored resin layer (hereinafter referred to as "colored optical fiber").
  • the linear speed when forming each resin layer was 1500 m/min.

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Abstract

The resin composition for optical fiber color coating contains a photopolymerizable compound, a polymer dispersant having an acidic functional group, a photopolymerization initiator, and surface-treated titanium oxide particles. The content of the polymer dispersant is 0.01-18 mass% inclusive based on the content of the surface-treated titanium oxide particles, and the acid value of the polymer dispersant is 25-180 mg KOH/g inclusive.

Description

光ファイバ着色被覆用の樹脂組成物、光ファイバ、および光ファイバリボンResin composition for colored coating of optical fiber, optical fiber, and optical fiber ribbon
　本開示は、光ファイバ着色被覆用の樹脂組成物、光ファイバ、および光ファイバリボンに関する。
　本出願は、２０２３年１月１８日出願の日本出願第２０２３－００６０１９号に基づく優先権を主張し、前記日本出願に記載された全ての記載内容を援用するものである。 The present disclosure relates to a resin composition for colored coating of optical fibers, an optical fiber, and an optical fiber ribbon.
This application claims priority based on Japanese Application No. 2023-006019 filed on January 18, 2023, and incorporates by reference all of the contents of the above-mentioned Japanese application.
　一般に、光ファイバは、光伝送体であるガラスファイバを保護するための被覆樹脂層を有している。被覆樹脂層は、例えば、プライマリ樹脂層およびセカンダリ樹脂層を有している。被覆樹脂層の最外層は、光ファイバの識別のための着色樹脂層から構成される（例えば、特許文献１～３参照。）。 Generally, optical fibers have a coating resin layer to protect the glass fiber that transmits light. The coating resin layer has, for example, a primary resin layer and a secondary resin layer. The outermost layer of the coating resin layer is composed of a colored resin layer for identifying the optical fiber (see, for example, Patent Documents 1 to 3).
特開平６－２４２３５５号公報Japanese Patent Application Publication No. 6-242355 特開２００３－２７９８１１号公報JP 2003-279811 A 国際公開第２０１６／０４７００２号International Publication No. 2016/047002
　本開示の一態様に係る光ファイバ着色被覆用の樹脂組成物は、光重合性化合物と、酸性官能基を有する高分子分散剤と、光重合開始剤と、表面処理酸化チタン粒子と、を含有し、高分子分散剤の含有量が、表面処理酸化チタン粒子の含有量を基準として、０．０１質量％以上１８質量％以下であり、高分子分散剤の酸価が、２５ｍｇＫＯＨ／ｇ以上１８０ｍｇＫＯＨ／ｇ以下である。 The resin composition for optical fiber coloring coating according to one embodiment of the present disclosure contains a photopolymerizable compound, a polymer dispersant having an acidic functional group, a photopolymerization initiator, and surface-treated titanium oxide particles, the content of the polymer dispersant being 0.01% by mass or more and 18% by mass or less based on the content of the surface-treated titanium oxide particles, and the acid value of the polymer dispersant being 25 mgKOH/g or more and 180 mgKOH/g or less.
図１は、本実施形態に係る光ファイバの一例を示す概略断面図である。FIG. 1 is a schematic cross-sectional view showing an example of an optical fiber according to the present embodiment. 図２は、本実施形態に係る光ファイバの一例を示す概略断面図である。FIG. 2 is a schematic cross-sectional view showing an example of the optical fiber according to the present embodiment. 図３は、本実施形態に係る光ファイバリボンの一例を示す概略断面図である。FIG. 3 is a schematic cross-sectional view showing an example of an optical fiber ribbon according to the present embodiment.
［本開示が解決しようとする課題］
　着色樹脂層を形成するための樹脂組成物は、酸化チタン等の無機顔料を含んでいる。無機顔料は、樹脂成分に比べて比重が大きいため、調製後の樹脂組成物を保存している間に無機顔料の沈降等が生じてしまうことがある。そのため、光ファイバの着色被覆用の樹脂組成物には、保存安定性に優れることが求められる。 [Problem to be solved by this disclosure]
The resin composition for forming the colored resin layer contains an inorganic pigment such as titanium oxide. Since the inorganic pigment has a larger specific gravity than the resin component, the inorganic pigment may settle during storage of the prepared resin composition. Therefore, the resin composition for colored coating of optical fiber is required to have excellent storage stability.
　本開示は、保存安定性に優れる光ファイバの着色被覆用の樹脂組成物、光ファイバ、および光ファイバリボンを提供することを目的とする。 The present disclosure aims to provide a resin composition for colored coating of optical fibers that has excellent storage stability, an optical fiber, and an optical fiber ribbon.
［本開示の効果］
　本開示によれば、保存安定性に優れることができる光ファイバの着色被覆用の樹脂組成物、光ファイバ、および光ファイバリボンを提供することができる。 [Effects of the present disclosure]
According to the present disclosure, it is possible to provide a resin composition for coloring coating of an optical fiber, an optical fiber, and an optical fiber ribbon, which have excellent storage stability.
［本開示の実施形態の説明］
　最初に、本開示の実施形態の内容を列記して説明する。 [Description of the embodiments of the present disclosure]
First, the contents of the embodiments of the present disclosure will be listed and described.
　（１）本開示の一態様に係る光ファイバ着色被覆用の樹脂組成物は、光重合性化合物と、酸性官能基を有する高分子分散剤と、光重合開始剤と、表面処理酸化チタン粒子と、を含有し、高分子分散剤の含有量が、表面処理酸化チタン粒子の含有量を基準として、０．０１質量％以上１８質量％以下であり、高分子分散剤の酸価が、２５ｍｇＫＯＨ／ｇ以上１８０ｍｇＫＯＨ／ｇ以下である。 (1) A resin composition for coloring and coating optical fibers according to one embodiment of the present disclosure contains a photopolymerizable compound, a polymer dispersant having an acidic functional group, a photopolymerization initiator, and surface-treated titanium oxide particles, the content of the polymer dispersant being 0.01% by mass or more and 18% by mass or less based on the content of the surface-treated titanium oxide particles, and the acid value of the polymer dispersant being 25 mgKOH/g or more and 180 mgKOH/g or less.
　このような樹脂組成物は、酸性官能基を有する高分子分散剤を特定の範囲で含有し、該高分子分散剤の酸価を特定の範囲とすることで、保存安定性に優れることができる。 Such a resin composition can have excellent storage stability by containing a polymer dispersant having an acidic functional group in a specific range and by setting the acid value of the polymer dispersant in a specific range.
　（２）上記（１）において、樹脂組成物の保存安定性をより向上する観点から、酸性官能基が、リン酸基またはカルボキシ基であってもよい。 (2) In the above (1), the acidic functional group may be a phosphoric acid group or a carboxyl group in order to further improve the storage stability of the resin composition.
　（３）上記（１）または（２）において、樹脂組成物の保存安定性をより向上する観点から、表面処理酸化チタン粒子が、酸化アルミニウム、二酸化ケイ素、および二酸化ジルコニウムからなる群より選ばれる少なくとも１種を含む表面処理層を有してもよい。 (3) In the above (1) or (2), in order to further improve the storage stability of the resin composition, the surface-treated titanium oxide particles may have a surface treatment layer containing at least one selected from the group consisting of aluminum oxide, silicon dioxide, and zirconium dioxide.
　（４）上記（１）から（３）のいずれかにおいて、樹脂層の強度を高める観点から、光重合性化合物が、エポキシジ（メタ）アクリレートを含んでもよい。 (4) In any of the above (1) to (3), the photopolymerizable compound may contain epoxy di(meth)acrylate in order to increase the strength of the resin layer.
　（５）本開示の一態様に係る光ファイバは、コアおよびクラッドを含むガラスファイバと、ガラスファイバに接してガラスファイバを被覆するプライマリ樹脂層と、プライマリ樹脂層を被覆するセカンダリ樹脂層と、セカンダリ樹脂層を被覆する着色樹脂層と、を備え、着色樹脂層が、上記（１）から（４）のいずれかに記載の樹脂組成物の硬化物を含む。本実施形態に係る樹脂組成物を着色樹脂層に適用することで、断線等の生じ難い光ファイバを作製することができる。 (5) An optical fiber according to one aspect of the present disclosure comprises a glass fiber including a core and a cladding, a primary resin layer that contacts the glass fiber and covers the glass fiber, a secondary resin layer that covers the primary resin layer, and a colored resin layer that covers the secondary resin layer, the colored resin layer containing a cured product of the resin composition described in any one of (1) to (4) above. By applying the resin composition according to this embodiment to the colored resin layer, an optical fiber that is less prone to breakage can be produced.
　（６）本開示の一態様に係る光ファイバは、コアおよびクラッドを含むガラスファイバと、ガラスファイバに接してガラスファイバを被覆するプライマリ樹脂層と、プライマリ樹脂層を被覆するセカンダリ樹脂層と、を備え、セカンダリ樹脂層が、上記（１）から（４）のいずれかに記載の樹脂組成物の硬化物を含む。本実施形態に係る樹脂組成物をセカンダリ樹脂層に適用することで、断線等の生じ難い光ファイバを作製することができる。 (6) An optical fiber according to one aspect of the present disclosure comprises a glass fiber including a core and a cladding, a primary resin layer that contacts the glass fiber and covers the glass fiber, and a secondary resin layer that covers the primary resin layer, the secondary resin layer containing a cured product of the resin composition described in any one of (1) to (4) above. By applying the resin composition according to this embodiment to the secondary resin layer, an optical fiber that is less prone to breakage can be produced.
　（７）本開示の一態様に係る光ファイバリボンは、上記（５）または（６）に記載の光ファイバが複数並列され、リボン用樹脂で被覆されている。このような光ファイバリボンは、光ファイバを取り出す作業をする際に色剥がれが生じ難く、光ファイバを容易に識別することができる。 (7) In an optical fiber ribbon according to one aspect of the present disclosure, a plurality of optical fibers as described in (5) or (6) above are arranged in parallel and coated with a ribbon resin. Such an optical fiber ribbon is less likely to peel off when the optical fibers are removed, and the optical fibers can be easily identified.
［本開示の実施形態の詳細］
　本開示の実施形態に係る樹脂組成物および光ファイバの具体例を、必要により図面を参照しつつ説明する。なお、本開示はこれらの例示に限定されず、特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。以下の説明では、図面の説明において同一の要素には同一の符号を付し、重複する説明を省略する。本明細書における（メタ）アクリレートとは、アクリレートまたはそれに対応するメタクリレートを意味する。（メタ）アクリロイル等の他の類似表現についても同様である。 [Details of the embodiment of the present disclosure]
Specific examples of the resin composition and optical fiber according to the embodiment of the present disclosure will be described with reference to the drawings as necessary. The present disclosure is not limited to these examples, but is indicated by the claims, and is intended to include all modifications within the meaning and scope equivalent to the claims. In the following description, the same elements in the description of the drawings are given the same reference numerals, and duplicated descriptions are omitted. In this specification, (meth)acrylate means acrylate or the corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl.
（樹脂組成物）
　本実施形態に係る光ファイバ着色被覆用の樹脂組成物は、光重合性化合物と、酸性官能基を有する高分子分散剤と、光重合開始剤と、表面処理酸化チタン粒子と、を含有し、高分子分散剤の含有量が、表面処理酸化チタン粒子の含有量を基準として、０．０１質量％以上１８質量％以下であり、高分子分散剤の酸価が、２５ｍｇＫＯＨ／ｇ以上１８０ｍｇＫＯＨ／ｇ以下である。 (Resin composition)
The resin composition for coloring and coating an optical fiber according to this embodiment contains a photopolymerizable compound, a polymer dispersant having an acidic functional group, a photopolymerization initiator, and surface-treated titanium oxide particles, and the content of the polymer dispersant is 0.01 mass % or more and 18 mass % or less based on the content of the surface-treated titanium oxide particles, and the acid value of the polymer dispersant is 25 mg KOH/g or more and 180 mg KOH/g or less.
　高分子分散剤は、酸性官能基を介して表面処理酸化チタン粒子の表面に吸着することで、表面処理酸化チタン粒子を樹脂組成物中に分散させ、表面処理酸化チタン粒子の凝集を抑制することができる。 The polymer dispersant adsorbs to the surface of the surface-treated titanium oxide particles via the acidic functional groups, dispersing the surface-treated titanium oxide particles in the resin composition and suppressing the aggregation of the surface-treated titanium oxide particles.
　酸性官能基としては、例えば、リン酸基およびカルボキシ基が挙げられる。酸性官能基がリン酸基またはカルボキシ基であると、樹脂組成物の保存安定性をより向上することができる。 Examples of acidic functional groups include phosphate groups and carboxy groups. When the acidic functional group is a phosphate group or a carboxy group, the storage stability of the resin composition can be further improved.
　高分子分散剤の構造は、酸性官能基を末端に有する直鎖型であってもよく、複数の酸性官能基を側鎖に有する櫛型であってもよい。櫛型の高分子分散剤を用いることで、樹脂組成物の保存安定性をより向上することができる。高分子分散剤は、ランダム共重合体、ブロック共重合体、またはグラフト共重合体であってもよい。 The structure of the polymer dispersant may be a straight-chain type having an acidic functional group at the end, or a comb-shaped type having multiple acidic functional groups in the side chain. By using a comb-shaped polymer dispersant, the storage stability of the resin composition can be further improved. The polymer dispersant may be a random copolymer, a block copolymer, or a graft copolymer.
　高分子分散剤としては、例えば、ポリウレタン系分散剤、ポリエーテル系分散剤、およびポリエステル系分散剤が挙げられる。樹脂組成物の保存安定性をより高める観点から、リン酸基を側鎖に有する櫛形のポリエステル系分散剤を用いてもよい。 Examples of polymeric dispersants include polyurethane-based dispersants, polyether-based dispersants, and polyester-based dispersants. In order to further improve the storage stability of the resin composition, a comb-shaped polyester-based dispersant having a phosphate group on the side chain may be used.
　高分子分散剤の含有量は、樹脂組成物の保存安定性をより向上する観点から、表面処理酸化チタン粒子の含有量を基準として、０．０５質量％以上、０．０８質量％以上、０．１質量％以上、または０．３質量％以上であってもよく、１６質量％以下、１５質量％以下、または１２質量％以下であってもよい。 From the viewpoint of further improving the storage stability of the resin composition, the content of the polymer dispersant may be 0.05 mass% or more, 0.08 mass% or more, 0.1 mass% or more, or 0.3 mass% or more based on the content of the surface-treated titanium oxide particles, and may be 16 mass% or less, 15 mass% or less, or 12 mass% or less.
　高分子分散剤の酸価は、樹脂組成物の保存安定性をより向上する観点から、３０ｍｇＫＯＨ／ｇ以上、３５ｍｇＫＯＨ／ｇ以上、４５ｍｇＫＯＨ／ｇ以上、または５０ｍｇＫＯＨ／ｇ以上であってもよく、１６０ｍｇＫＯＨ／ｇ以下、１５０ｍｇＫＯＨ／ｇ以下、１４０ｍｇＫＯＨ／ｇ以下、または１２０ｍｇＫＯＨ／ｇ以下であってもよい。高分子分散剤の酸価は、例えば、ＤＩＮ　ＥＮ　ＩＳＯ　２１１４に準拠して測定することができる。 From the viewpoint of further improving the storage stability of the resin composition, the acid value of the polymer dispersant may be 30 mgKOH/g or more, 35 mgKOH/g or more, 45 mgKOH/g or more, or 50 mgKOH/g or more, and may be 160 mgKOH/g or less, 150 mgKOH/g or less, 140 mgKOH/g or less, or 120 mgKOH/g or less. The acid value of the polymer dispersant can be measured, for example, in accordance with DIN EN ISO 2114.
　光重合性化合物は、特に限定されないが、光重合性化合物は、樹脂層の強度を高める観点から、エポキシジ（メタ）アクリレートを含んでもよい。エポキシジ（メタ）アクリレートとしては、ビスフェノール骨格を有するジグリシジルエーテル化合物と、（メタ）アクリル酸等の（メタ）アクリロイル基を有する化合物との反応物を用いることができる。 The photopolymerizable compound is not particularly limited, but may contain epoxy di(meth)acrylate from the viewpoint of increasing the strength of the resin layer. As the epoxy di(meth)acrylate, a reaction product of a diglycidyl ether compound having a bisphenol skeleton and a compound having a (meth)acryloyl group such as (meth)acrylic acid can be used.
　エポキシジ（メタ）アクリレートとしては、例えば、ビスフェノールＡジグリシジルエーテルの（メタ）アクリル酸付加物、ビスフェノールＡＦジグリシジルエーテルの（メタ）アクリル酸付加物、およびビスフェノールＦジグリシジルエーテルの（メタ）アクリル酸付加物が挙げられる。 Examples of epoxy di(meth)acrylates include (meth)acrylic acid adducts of bisphenol A diglycidyl ether, (meth)acrylic acid adducts of bisphenol AF diglycidyl ether, and (meth)acrylic acid adducts of bisphenol F diglycidyl ether.
　樹脂層の強度をより高める観点から、エポキシジ（メタ）アクリレートの含有量は、光重合性化合物の総量１００質量部に対して、３０質量部以上、４０質量部以上、または４５質量部以上であってもよく、７０質量部以下、６５質量部以下、または６０質量部以下であってもよい。 From the viewpoint of further increasing the strength of the resin layer, the content of the epoxy di(meth)acrylate may be 30 parts by mass or more, 40 parts by mass or more, or 45 parts by mass or more, and may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less, relative to 100 parts by mass of the total amount of the photopolymerizable compound.
　光重合性化合物は、樹脂層のヤング率を調整する観点から、ウレタン（メタ）アクリレートを更に含んでもよい。ウレタン（メタ）アクリレートとしては、例えば、ポリオール化合物、ポリイソシアネート化合物および水酸基含有（メタ）アクリレート化合物を反応させて得られるウレタンオリゴマーを用いることができる。ウレタン（メタ）アクリレートは、１種を単独でまたは２種以上混合して用いてもよい。 The photopolymerizable compound may further contain a urethane (meth)acrylate from the viewpoint of adjusting the Young's modulus of the resin layer. As the urethane (meth)acrylate, for example, a urethane oligomer obtained by reacting a polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate compound can be used. The urethane (meth)acrylate may be used alone or in combination of two or more types.
　ポリオール化合物としては、例えば、ポリテトラメチレングリコール、ポリプロピレングリコール、およびビスフェノールＡ・エチレンオキサイド付加ジオールが挙げられる。ポリイソシアネート化合物としては、例えば、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、イソホロンジイソシアネート、およびジシクロヘキシルメタン４，４’－ジイソシアナートが挙げられる。水酸基含有（メタ）アクリレート化合物としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、１，６－ヘキサンジオールモノ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、およびトリプロピレングリコールモノ（メタ）アクリレートが挙げられる。 Examples of polyol compounds include polytetramethylene glycol, polypropylene glycol, and bisphenol A-ethylene oxide addition diol. Examples of polyisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane 4,4'-diisocyanate. Examples of hydroxyl group-containing (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 1,6-hexanediol mono(meth)acrylate, pentaerythritol tri(meth)acrylate, 2-hydroxypropyl (meth)acrylate, and tripropylene glycol mono(meth)acrylate.
　樹脂層のヤング率を調整する観点から、ポリオール化合物の数平均分子量（Ｍｎ）は、３００以上３０００以下、４００以上３０００以下、または５００以上２５００以下であってもよい。 From the viewpoint of adjusting the Young's modulus of the resin layer, the number average molecular weight (Mn) of the polyol compound may be 300 or more and 3000 or less, 400 or more and 3000 or less, or 500 or more and 2500 or less.
　ウレタン（メタ）アクリレートを合成する際の触媒として、一般に有機スズ化合物が使用される。有機スズ化合物としては、例えば、ジブチルスズジラウレート、ジブチルスズジアセテート、ジブチルスズマレート、ジブチルスズビス（メルカプト酢酸２－エチルヘキシル）、ジブチルスズビス（メルカプト酢酸イソオクチル）およびジブチルスズオキシドが挙げられる。易入手性または触媒性能の点から、触媒としてジブチルスズジラウレートまたはジブチルスズジアセテートを使用してもよい。 Organotin compounds are generally used as catalysts in the synthesis of urethane (meth)acrylates. Examples of organotin compounds include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate, dibutyltin bis(2-ethylhexyl mercaptoacetate), dibutyltin bis(isooctyl mercaptoacetate) and dibutyltin oxide. From the standpoint of easy availability or catalytic performance, dibutyltin dilaurate or dibutyltin diacetate may be used as the catalyst.
　ウレタン（メタ）アクリレートを合成する際に炭素数５以下の低級アルコールを使用してもよい。低級アルコールとしては、例えば、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、２－メチル－２－プロパノール、１－ペンタノール、２－ペンタノール、３－ペンタノール、２－メチル－１－ブタノール、３－メチル－１－ブタノール、２－メチル－２－ブタノール、３－メチル－２－ブタノール、および２，２－ジメチル－１－プロパノールが挙げられる。 When synthesizing urethane (meth)acrylate, a lower alcohol having 5 or less carbon atoms may be used. Examples of lower alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, and 2,2-dimethyl-1-propanol.
　本実施形態に係る光重合性化合物は、エポキシジ（メタ）アクリレート以外の光重合性化合物（以下、「モノマー」という。）を更に含むことができる。 The photopolymerizable compound according to this embodiment may further contain a photopolymerizable compound (hereinafter referred to as "monomer") other than epoxy di(meth)acrylate.
　モノマーとしては、重合性基を１つ有する単官能モノマー、重合性基を２つ以上有する多官能モノマーを用いることができる。モノマーは、２種以上を混合して用いてもよい。 As the monomer, a monofunctional monomer having one polymerizable group or a polyfunctional monomer having two or more polymerizable groups can be used. Two or more types of monomers may be mixed and used.
　単官能モノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、へキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、イソアミル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、２－フェノキシエチル（メタ）アクリレート、３－フェノキシベンジルアクリレート、フェノキシジエチレングリコールアクリレート、フェノキシポリエチレングリコールアクリレート、４－ｔｅｒｔ－ブチルシクロヘキサノールアクリレート、テトラヒドロフルフリル（メタ）アクリレート、ベンジル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ノニルフェノールポリエチレングリコール（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレート、イソボルニル（メタ）アクリレート等の（メタ）アクリレート系モノマー；（メタ）アクリル酸、（メタ）アクリル酸ダイマー、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、ω－カルボキシ－ポリカプロラクトン（メタ）アクリレート等のカルボキシ基含有モノマー；Ｎ－（メタ）アクリロイルモルホリン、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－（メタ）アクリロイルピペリジン、Ｎ－（メタ）アクリロイルピロリジン、３－（３－ピリジン）プロピル（メタ）アクリレート、環状トリメチロールプロパンホルマールアクリレート等の複素環含有モノマー；マレイミド、Ｎ－シクロへキシルマレイミド、Ｎ－フェニルマレイミド等のマレイミド系モノマー；（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－ヘキシル（メタ）アクリルアミド、Ｎ－メチル（メタ）アクリルアミド、Ｎ－エチル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－メチロールプロパン（メタ）アクリルアミド等のアミド系モノマー；（メタ）アクリル酸アミノエチル、（メタ）アクリル酸アミノプロピル、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノエチル、（メタ）アクリル酸ｔｅｒｔ－ブチルアミノエチル等の（メタ）アクリル酸アミノアルキル系モノマー；Ｎ－（メタ）アクリロイルオキシメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－６－オキシヘキサメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－８－オキシオクタメチレンスクシンイミド等のスクシンイミド系モノマーが挙げられる。 Examples of monofunctional monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, s-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 3-phenoxyethyl (meth)acrylate, (Meth)acrylate monomers such as dibenzyl acrylate, phenoxy diethylene glycol acrylate, phenoxy polyethylene glycol acrylate, 4-tert-butylcyclohexanol acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, nonylphenol polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, and isobornyl (meth)acrylate; (meth)acrylic acid, (meth)acrylic acid dimer, carboxyethyl (meth)acrylate, etc. carboxy group-containing monomers such as N-(meth)acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, 3-(3-pyridine)propyl(meth)acrylate, and cyclic trimethylolpropane formal acrylate; heterocycle-containing monomers such as maleimide, N-cyclohexylmaleimide, and N-phenylmaleimide; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-hexyl(meth)acrylamide, N Amide monomers such as N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, and N-methylolpropane(meth)acrylamide; aminoalkyl(meth)acrylate monomers such as aminoethyl(meth)acrylate, aminopropyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, and tert-butylaminoethyl(meth)acrylate; and succinimide monomers such as N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, and N-(meth)acryloyl-8-oxyoctamethylenesuccinimide.
　多官能モノマーとしては、例えば、ポリエチレングリコールジ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性ジ（メタ）アクリレート、エチレンオキサイド変性ビスフェノールＦジ（メタ）アクリレート、エチレンオキサイド変性ビスフェノールＡジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、プロピレンオキサイド変性ビスフェノールＡジ（メタ）アクリレート、プロピレンオキサイド変性ネオペンチルグリコールジ（メタ）アクリレート、ポリテトラエチレングリコールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１２－ドデカンジオールジ（メタ）アクリレート、１，１４－テトラデカンジオールジ（メタ）アクリレート、１，１６－ヘキサデカンジオールジ（メタ）アクリレート、１，２０－エイコサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、イソペンチルジオールジ（メタ）アクリレート、３－エチル－１，８－オクタンジオールジ（メタ）アクリレート；トリメチロールプロパントリ（メタ）アクリレート、トリメチロールオクタントリ（メタ）アクリレート、トリメチロールプロパンポリエトキシトリ（メタ）アクリレート、トリメチロールプロパンポリプロポキシトリ（メタ）アクリレート、トリメチロールプロパンポリエトキシポリプロポキシトリ（メタ）アクリレート、トリス［（メタ）アクリロイルオキシエチル］イソシアヌレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールポリエトキシテトラ（メタ）アクリレート、ペンタエリスリトールポリプロポキシテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、およびカプロラクトン変性トリス［（メタ）アクリロイルオキシエチル］イソシアヌレートが挙げられる。 Examples of polyfunctional monomers include polyethylene glycol di(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, ethylene oxide modified bisphenol F di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, polypropylene glycol di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, propylene oxide modified neopentyl glycol di(meth)acrylate, polytetraethylene glycol di(meth)acrylate, p) acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, 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-hexadecanediol di(meth)acrylate, 1,20-eicosanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, iso Pentyldiol di(meth)acrylate, 3-ethyl-1,8-octanediol di(meth)acrylate; trimethylolpropane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, trimethylolpropane polypropoxy tri(meth)acrylate, trimethylolpropane polyethoxy polypropoxy tri(meth)acrylate, tris[(meth)acryloyloxyethyl]isocyanurate, pentaerythritol tri(meth) acrylate, pentaerythritol polyethoxy tetra(meth)acrylate, pentaerythritol polypropoxy tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified tris[(meth)acryloyloxyethyl]isocyanurate.
　本実施形態に係る光重合性化合物は、樹脂層のヤング率を調整する観点から、アルキレンオキサイド変性された多官能モノマーを含んでもよい。アルキレンオキサイド変性された多官能モノマーは、エチレンオキサイド（ＥＯ）鎖およびプロピレンオキサイド（ＰＯ）鎖からなる群より選ばれる少なくとも１種を有してもよい。エチレンオキサイド鎖を「（ＥＯ）ｎ」、プロピレンオキサイド鎖を「（ＰＯ）ｎ」と表すことができる。ｎは１以上の整数であり、２以上または３以上であってもよく、３０以下、２５以下、または２０以下であってもよい。 The photopolymerizable compound according to this embodiment may contain an alkylene oxide-modified polyfunctional monomer from the viewpoint of adjusting the Young's modulus of the resin layer. The alkylene oxide-modified polyfunctional monomer may have at least one selected from the group consisting of an ethylene oxide (EO) chain and a propylene oxide (PO) chain. The ethylene oxide chain can be represented as "(EO)n" and the propylene oxide chain as "(PO)n". n is an integer of 1 or more, and may be 2 or more or 3 or more, and may be 30 or less, 25 or less, or 20 or less.
　アルキレンオキサイド変性ジ（メタ）アクリレートとしては、例えば、ポリエチレングリコールジ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性ジ（メタ）アクリレート、エチレンオキサイド変性ビスフェノールＦジ（メタ）アクリレート、エチレンオキサイド変性ビスフェノールＡジ（メタ）アクリレートポリプロピレングリコールジ（メタ）アクリレート、プロピレンオキサイド変性ビスフェノールＡジ（メタ）アクリレート、およびプロピレンオキサイド変性ネオペンチルグリコールジ（メタ）アクリレートが挙げられる。 Examples of alkylene oxide modified di(meth)acrylates include polyethylene glycol di(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, ethylene oxide modified bisphenol F di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate polypropylene glycol di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, and propylene oxide modified neopentyl glycol di(meth)acrylate.
　アルキレンオキサイド変性トリ（メタ）アクリレートとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールオクタントリ（メタ）アクリレート、トリメチロールプロパンポリエトキシトリ（メタ）アクリレート、トリメチロールプロパンポリプロポキシトリ（メタ）アクリレート、トリメチロールプロパンポリエトキシポリプロポキシトリ（メタ）アクリレート、トリス［（メタ）アクリロイルオキシエチル］イソシアヌレート、およびペンタエリスリトールトリ（メタ）アクリレートが挙げられる。 Examples of alkylene oxide modified tri(meth)acrylates include trimethylolpropane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, trimethylolpropane polypropoxy tri(meth)acrylate, trimethylolpropane polyethoxy polypropoxy tri(meth)acrylate, tris[(meth)acryloyloxyethyl]isocyanurate, and pentaerythritol tri(meth)acrylate.
　光重合開始剤は、公知のラジカル光重合開始剤の中から適宜選択して使用することができる。光重合開始剤としては、例えば、１－ヒドロキシシクロヘキシルフェニルケトン（Ｏｍｎｉｒａｄ　１８４、ＩＧＭ　Ｒｅｓｉｎｓ社製）、２，２－ジメトキシ－２－フェニルアセトフェノン、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルホスフィンオキサイド、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－プロパン－１－オン（Ｏｍｎｉｒａｄ　９０７、ＩＧＭ　Ｒｅｓｉｎｓ社製）、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド（Ｏｍｎｉｒａｄ　ＴＰＯ、ＩＧＭ　Ｒｅｓｉｎｓ社製）、およびビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキシド（Ｏｍｎｉｒａｄ　８１９、ＩＧＭ　Ｒｅｓｉｎｓ社製）が挙げられる。 The photopolymerization initiator can be appropriately selected from known radical photopolymerization initiators. Examples of photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resins), 2,2-dimethoxy-2-phenylacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2-methyl-1-[4- (methylthio)phenyl]-2-morpholino-propan-1-one (Omnirad 907, IGM Resins), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO, IGM Resins), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, IGM Resins).
　光重合開始剤の含有量は、光重合性化合物の総量１００質量部に対して、１質量部以上１０質量部以下、２質量部以上８質量部以下、または３質量部以上７質量部以下であってもよい。 The content of the photopolymerization initiator may be 1 part by mass or more and 10 parts by mass or less, 2 parts by mass or more and 8 parts by mass or less, or 3 parts by mass or more and 7 parts by mass or less, relative to 100 parts by mass of the total amount of the photopolymerizable compounds.
　本実施形態に係る樹脂組成物は、樹脂層を着色する観点から、表面処理酸化チタン粒子を含有する。表面処理酸化チタン粒子は、酸化チタンが無機物により表面処理が施された粒子であり、樹脂組成物中の分散性に優れている。 The resin composition according to this embodiment contains surface-treated titanium oxide particles in order to color the resin layer. The surface-treated titanium oxide particles are particles in which titanium oxide has been surface-treated with an inorganic substance, and have excellent dispersibility in the resin composition.
　表面処理に用いる無機物としては、例えば、酸化アルミニウム、二酸化ケイ素、および二酸化ジルコニウムが挙げられる。表面処理酸化チタン粒子が、酸化アルミニウム、二酸化ケイ素、および二酸化ジルコニウムからなる群より選ばれる少なくとも１種を含む表面処理層を有することで、分散性をより向上することができる。表面処理層は、酸化チタン粒子の表面の少なくとも一部に形成されてよく、酸化チタン粒子の全表面に形成されていてもよい。表面処理層は、酸化チタン粒子の表面処理によって形成されたものである。 Examples of inorganic substances used for surface treatment include aluminum oxide, silicon dioxide, and zirconium dioxide. By having a surface treatment layer containing at least one selected from the group consisting of aluminum oxide, silicon dioxide, and zirconium dioxide, the dispersibility can be further improved. The surface treatment layer may be formed on at least a portion of the surface of the titanium oxide particles, or may be formed on the entire surface of the titanium oxide particles. The surface treatment layer is formed by surface treatment of the titanium oxide particles.
　表面処理酸化チタン粒子における表面処理層の量は、分散性をより向上する観点から、１質量％以上、１．５質量％以上、または２質量％以上であってもよく、隠蔽力を高める観点から、１０質量％以下、９質量％以下、または８質量％以下であってもよい。表面処理層の量は、誘導結合質量分析（ＩＣＰ－ＭＳ）を用いて、表面処理酸化チタン粒子に含まれるチタン元素およびチタン以外の無機物の元素の量を測定することで算出することができる。 The amount of the surface treatment layer in the surface-treated titanium oxide particles may be 1 mass% or more, 1.5 mass% or more, or 2 mass% or more from the viewpoint of further improving dispersibility, and may be 10 mass% or less, 9 mass% or less, or 8 mass% or less from the viewpoint of increasing hiding power. The amount of the surface treatment layer can be calculated by measuring the amount of titanium element and inorganic elements other than titanium contained in the surface-treated titanium oxide particles using inductively coupled mass spectrometry (ICP-MS).
　表面処理酸化チタン粒子の平均一次粒径は、被覆樹脂層の側圧耐性を向上する観点から、３００ｎｍ以下、２９５ｎｍ以下、または２９０ｎｍ以下であってもよい。表面処理酸化チタン粒子の平均一次粒径は、隠蔽力を高める観点から、１００ｎｍ以上、１５０ｎｍ以上、または２００ｎｍ以上であってもよく、２００ｎｍ以上３００ｎｍ以下であってもよい。平均一次粒径は、例えば、電子顕微鏡写真の画像解析、光散乱法、ＢＥＴ法等によって測定することができる。 The average primary particle size of the surface-treated titanium oxide particles may be 300 nm or less, 295 nm or less, or 290 nm or less, from the viewpoint of improving the lateral pressure resistance of the coating resin layer. The average primary particle size of the surface-treated titanium oxide particles may be 100 nm or more, 150 nm or more, or 200 nm or more, or may be 200 nm or more and 300 nm or less, from the viewpoint of improving hiding power. The average primary particle size can be measured, for example, by image analysis of electron microscope photographs, light scattering method, BET method, etc.
　表面処理酸化チタン粒子の含有量は、樹脂層の視認性を向上する観点から、樹脂組成物の総量を基準として０．６質量％以上、１質量％以上、２質量％以上、または３質量％以上であってもよい。表面処理酸化チタン粒子の含有量は、樹脂組成物の硬化性を高める観点から、樹脂組成物の総量を基準として２０質量％以下、１５質量％以下、１０質量％以下、または８質量％以下であってもよい。 The content of the surface-treated titanium oxide particles may be 0.6 mass% or more, 1 mass% or more, 2 mass% or more, or 3 mass% or more based on the total amount of the resin composition from the viewpoint of improving the visibility of the resin layer. The content of the surface-treated titanium oxide particles may be 20 mass% or less, 15 mass% or less, 10 mass% or less, or 8 mass% or less based on the total amount of the resin composition from the viewpoint of improving the curability of the resin composition.
　本実施形態に係る樹脂組成物は、シランカップリング剤、レベリング剤、消泡剤、酸化防止剤、増感剤等を更に含有してもよい。 The resin composition according to this embodiment may further contain a silane coupling agent, a leveling agent, an antifoaming agent, an antioxidant, a sensitizer, etc.
　シランカップリング剤は、樹脂組成物の硬化の妨げにならなければ、特に限定されない。シランカップリング剤としては、例えば、テトラメチルシリケート、テトラエチルシリケート、メルカプトプロピルトリメトキシシラン、ビニルトリクロロシラン、ビニルトリエトキシシラン、ビニルトリス（β－メトキシ－エトキシ）シラン、β－（３，４－エポキシシクロヘキシル）－エチルトリメトキシシラン、ジメトキシジメチルシラン、ジエトキシジメチルシラン、３－アクリロキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、Ｎ－（β－アミノエチル）－γ－アミノプロピルトリメトキシシラン、Ｎ－（β－アミノエチル）－γ－アミノプロピルトリメチルジメトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン、γ－クロロプロピルトリメトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－アミノプロピルトリメトキシシラン、ビス－［３－（トリエトキシシリル）プロピル］テトラスルフィド、ビス－［３－（トリエトキシシリル）プロピル］ジスルフィド、γ－トリメトキシシリルプロピルジメチルチオカルバミルテトラスルフィド、およびγ－トリメトキシシリルプロピルベンゾチアジルテトラスルフィドが挙げられる。 The silane coupling agent is not particularly limited as long as it does not interfere with the curing of the resin composition. Examples of silane coupling agents include tetramethyl silicate, tetraethyl silicate, mercaptopropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxy-ethoxy)silane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, dimethoxydimethylsilane, diethoxydimethylsilane, 3-acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ -aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, bis-[3-(triethoxysilyl)propyl]tetrasulfide, bis-[3-(triethoxysilyl)propyl]disulfide, γ-trimethoxysilylpropyldimethylthiocarbamyltetrasulfide, and γ-trimethoxysilylpropylbenzothiazyltetrasulfide.
　本実施形態に係る樹脂組成物の２５℃での粘度は、保存安定性の観点から、１０００ｍＰａ・ｓ以上、１５００ｍＰａ・ｓ以上、または２０００ｍＰａ・ｓ以上であってもよく、塗布性の観点から、１００００ｍＰａ・ｓ未満、８０００ｍＰａ・ｓ以下、または６０００ｍＰａ・ｓ以下であってもよい。 The viscosity of the resin composition according to this embodiment at 25°C may be 1000 mPa·s or more, 1500 mPa·s or more, or 2000 mPa·s or more from the viewpoint of storage stability, and may be less than 10000 mPa·s, 8000 mPa·s or less, or 6000 mPa·s or less from the viewpoint of coatability.
　光ファイバの単心分離性を向上する観点から、樹脂フィルムのヤング率は、２３℃で５００ＭＰａ以上、６００ＭＰａ以上、または７００ＭＰａ以上であってもよい。靱性に優れる樹脂層を形成する観点から、樹脂フィルムのヤング率は、２３℃で１５００ＭＰａ以下、１３００ＭＰａ以下、または１２００ＭＰａ以下であってもよい。 From the viewpoint of improving the single-core separation of the optical fiber, the Young's modulus of the resin film may be 500 MPa or more, 600 MPa or more, or 700 MPa or more at 23°C. From the viewpoint of forming a resin layer with excellent toughness, the Young's modulus of the resin film may be 1500 MPa or less, 1300 MPa or less, or 1200 MPa or less at 23°C.
　本実施形態に係る樹脂組成物は、光ファイバの着色被覆材料として好適に用いることができる。本実施形態に係る樹脂組成物を含む着色被覆材料を用いて被覆樹脂層の最外層を形成することで、光ファイバの単心分離性を向上することができる。 The resin composition according to this embodiment can be suitably used as a colored coating material for optical fibers. By forming the outermost layer of the coating resin layer using a colored coating material containing the resin composition according to this embodiment, the single-core separation property of the optical fiber can be improved.
（光ファイバ）
　図１は、一実施形態に係る光ファイバの構成を示す概略断面図である。図１に示されるように、本実施形態の光ファイバ１は、ガラスファイバ１０と、ガラスファイバ１０に接してガラスファイバ１０の外周を覆う被覆樹脂層２０とを備えている。 (Optical fiber)
Fig. 1 is a schematic cross-sectional view showing the configuration of an optical fiber according to an embodiment. As shown in Fig. 1, the optical fiber 1 of the present embodiment includes a glass fiber 10 and a coating resin layer 20 that contacts the glass fiber 10 and covers the outer periphery of the glass fiber 10.
　ガラスファイバ１０は、光ファイバ１に導入された光を伝送する導光性の光伝送体である。ガラスファイバ１０は、ガラス製の部材であって、例えば、シリカ（ＳｉＯ２）ガラスを基材（主成分）として構成される。ガラスファイバ１０は、コア１２と、コア１２を覆うクラッド１４とを備えている。ガラスファイバ１０は、光ファイバ１に導入された光を伝送する。コア１２は、例えば、ガラスファイバ１０の中心軸線を含む領域に設けられている。コア１２は、例えば、純ＳｉＯ２ガラス、または、ＳｉＯ２ガラスに二酸化ゲルマニウム（ＧｅＯ２）、フッ素元素等が含まれたものからなっている。クラッド１４は、コア１２を囲む領域に設けられている。クラッド１４は、コア１２の屈折率より低い屈折率を有している。クラッド１４は、例えば、純ＳｉＯ２ガラス、またはフッ素元素が添加されたＳｉＯ２ガラスからなっている。ガラスファイバ１０の外径は１００μｍから１２５μｍ程度であり、ガラスファイバ１０を構成するコア１２の直径は、７μｍから１５μｍ程度である。 The glass fiber 10 is a light-guiding optical transmission body that transmits light introduced into the optical fiber 1. The glass fiber 10 is a glass member, and is configured, for example, with silica (SiO 2 ) glass as a base material (main component). The glass fiber 10 includes a core 12 and a clad 14 that covers the core 12. The glass fiber 10 transmits light introduced into the optical fiber 1. The core 12 is provided, for example, in a region that includes the central axis of the glass fiber 10. The core 12 is made of, for example, pure SiO 2 glass, or SiO 2 glass containing germanium dioxide (GeO 2 ), fluorine element, or the like. The clad 14 is provided in a region that surrounds the core 12. The clad 14 has a refractive index lower than that of the core 12. The clad 14 is made of, for example, pure SiO 2 glass, or SiO 2 glass to which fluorine element is added. The outer diameter of the glass fiber 10 is about 100 μm to 125 μm, and the diameter of the core 12 constituting the glass fiber 10 is about 7 μm to 15 μm.
　被覆樹脂層２０は、クラッド１４を覆う紫外線硬化型の樹脂層である。被覆樹脂層２０は、ガラスファイバ１０の外周を被覆するプライマリ樹脂層２２と、プライマリ樹脂層２２の外周を被覆するセカンダリ樹脂層２４と、セカンダリ樹脂層２４の外周を被覆する着色樹脂層２６とを備えている。プライマリ樹脂層２２は、クラッド１４の外周面に接しており、クラッド１４の全体を被覆している。セカンダリ樹脂層２４は、プライマリ樹脂層２２の外周面に接しており、プライマリ樹脂層２２の全体を被覆している。着色樹脂層２６は、セカンダリ樹脂層２４の外周面に接しており、セカンダリ樹脂層２４の外周を被覆している。 The coating resin layer 20 is an ultraviolet-curable resin layer that covers the clad 14. The coating resin layer 20 includes a primary resin layer 22 that coats the outer periphery of the glass fiber 10, a secondary resin layer 24 that coats the outer periphery of the primary resin layer 22, and a colored resin layer 26 that coats the outer periphery of the secondary resin layer 24. The primary resin layer 22 is in contact with the outer periphery of the clad 14 and coats the entire clad 14. The secondary resin layer 24 is in contact with the outer periphery of the primary resin layer 22 and coats the entire primary resin layer 22. The colored resin layer 26 is in contact with the outer periphery of the secondary resin layer 24 and coats the outer periphery of the secondary resin layer 24.
　プライマリ樹脂層２２の厚さは、例えば、１０μｍ以上５０μｍ以下である。セカンダリ樹脂層２４の厚さは、例えば、１０μｍ以上４０μｍ以下である。着色樹脂層２６の厚さは、例えば、３μｍ以上１０μｍ以下である。 The thickness of the primary resin layer 22 is, for example, 10 μm or more and 50 μm or less. The thickness of the secondary resin layer 24 is, for example, 10 μm or more and 40 μm or less. The thickness of the colored resin layer 26 is, for example, 3 μm or more and 10 μm or less.
　プライマリ樹脂層２２は、従来公知のプライマリ樹脂層用の樹脂組成物を使用して形成してもよい。プライマリ樹脂層２２は、例えば、ウレタン（メタ）アクリレート、モノマー、光重合開始剤、およびシランカップリング剤を含む樹脂組成物を硬化させて形成することができる。 The primary resin layer 22 may be formed using a resin composition for primary resin layers that is conventionally known. The primary resin layer 22 may be formed, for example, by curing a resin composition that includes urethane (meth)acrylate, a monomer, a photopolymerization initiator, and a silane coupling agent.
　セカンダリ樹脂層２４は、従来公知のセカンダリ樹脂層用の樹脂組成物を使用して形成してもよい。セカンダリ樹脂層２４は、例えば、ウレタン（メタ）アクリレート、モノマー、および光重合開始剤を含む樹脂組成物を硬化させて形成することができる。 The secondary resin layer 24 may be formed using a conventionally known resin composition for secondary resin layers. The secondary resin layer 24 can be formed, for example, by curing a resin composition containing urethane (meth)acrylate, a monomer, and a photopolymerization initiator.
　本実施形態に係る樹脂組成物は、着色樹脂層２６に適用することができる。着色樹脂層２６は、上記樹脂組成物を硬化させて形成することができる。着色樹脂層２６は、本実施形態に係る樹脂組成物の硬化物を含むことにより、光ファイバの単心分離性を向上することができる。光ファイバの被覆樹脂層の最外層として、本実施形態に係る樹脂組成物の硬化物を含む着色樹脂層を有することによって、リボン材を除去する際に着色樹脂層２６およびセカンダリ樹脂層２４が剥がれ難くなる。 The resin composition according to this embodiment can be applied to the colored resin layer 26. The colored resin layer 26 can be formed by curing the resin composition. The colored resin layer 26 contains the cured product of the resin composition according to this embodiment, thereby improving the single-core separation property of the optical fiber. By having a colored resin layer containing the cured product of the resin composition according to this embodiment as the outermost layer of the coating resin layer of the optical fiber, the colored resin layer 26 and the secondary resin layer 24 are less likely to peel off when the ribbon material is removed.
　図２は、一実施形態に係る光ファイバの構成を示す概略断面図である。図２に示されるように、光ファイバ１Ａは、ガラスファイバ１０と、ガラスファイバ１０に接してガラスファイバ１０の外周を覆う被覆樹脂層２０Ａとを備えている。被覆樹脂層２０Ａは、プライマリ樹脂層２２と、セカンダリ樹脂層２４とを備えている。 FIG. 2 is a schematic cross-sectional view showing the configuration of an optical fiber according to one embodiment. As shown in FIG. 2, the optical fiber 1A includes a glass fiber 10 and a coating resin layer 20A that contacts the glass fiber 10 and covers the outer periphery of the glass fiber 10. The coating resin layer 20A includes a primary resin layer 22 and a secondary resin layer 24.
　本実施形態に係る樹脂組成物は、セカンダリ樹脂層２４に適用することができる。セカンダリ樹脂層２４は、上記樹脂組成物を硬化させて形成することができる。この場合、セカンダリ樹脂層２４は、着色セカンダリ樹脂層として機能する。セカンダリ樹脂層２４は、本実施形態に係る樹脂組成物の硬化物を含むことにより、光ファイバの単心分離性を向上することができる。光ファイバの被覆樹脂層の最外層として、本実施形態に係る樹脂組成物の硬化物を含む着色セカンダリ樹脂層を有することによって、リボン材を除去する際にセカンダリ樹脂層２４が剥がれ難くなる。 The resin composition according to this embodiment can be applied to the secondary resin layer 24. The secondary resin layer 24 can be formed by curing the resin composition. In this case, the secondary resin layer 24 functions as a colored secondary resin layer. The secondary resin layer 24 contains a cured product of the resin composition according to this embodiment, thereby improving the single-core separation property of the optical fiber. By having a colored secondary resin layer containing a cured product of the resin composition according to this embodiment as the outermost layer of the coating resin layer of the optical fiber, the secondary resin layer 24 becomes less likely to peel off when the ribbon material is removed.
（光ファイバリボン）
　本実施形態に係る光ファイバを用いて光ファイバリボンを作製することができる。光ファイバリボンは、上記光ファイバが複数並列され、リボン用樹脂で被覆されている。 (Optical fiber ribbon)
The optical fiber according to this embodiment can be used to fabricate an optical fiber ribbon, which is made up of a plurality of the optical fibers arranged in parallel and coated with a ribbon resin.
　図３は、本実施形態に係る光ファイバリボンを示す概略断面図である。光ファイバリボン１００は、複数の光ファイバ１と、光ファイバ１がリボン用樹脂により被覆されて連結された連結樹脂層４０とを有している。連結樹脂層４０はリボン用樹脂により形成されている。図３では、一例として４本の光ファイバが示されているが、その本数は特に限定されるものではない。 FIG. 3 is a schematic cross-sectional view showing an optical fiber ribbon according to this embodiment. The optical fiber ribbon 100 has a plurality of optical fibers 1 and a connecting resin layer 40 in which the optical fibers 1 are coated and connected with a ribbon resin. The connecting resin layer 40 is formed from a ribbon resin. In FIG. 3, four optical fibers are shown as an example, but the number is not particularly limited.
　リボン用樹脂としては、一般にリボン材として知られている樹脂材料を用いることができる。リボン用樹脂は、光ファイバの損傷防止性、分断容易性等の観点から、シリコーン樹脂、エポキシ樹脂、ウレタン樹脂等の熱硬化型樹脂、または、エポキシアクリレート、ウレタンアクリレート、ポリエステルアクリレート等の紫外線硬化型樹脂を含有してもよい。 As the ribbon resin, resin materials generally known as ribbon materials can be used. From the viewpoint of preventing damage to the optical fiber and ease of cutting, the ribbon resin may contain a thermosetting resin such as silicone resin, epoxy resin, or urethane resin, or an ultraviolet-curing resin such as epoxy acrylate, urethane acrylate, or polyester acrylate.
　本実施形態に係る光ファイバリボンは、上記光ファイバを用いることで、光ファイバリボンから連結樹脂層を除去して光ファイバを取り出す作業をする際に色剥がれが生じることがなく、光ファイバを容易に識別することができる。 The optical fiber ribbon of this embodiment uses the above optical fiber, so that the optical fiber can be easily identified without color peeling when removing the connecting resin layer from the optical fiber ribbon to extract the optical fiber.
　以下、本開示に係る実施例および比較例を用いた評価試験の結果を示し、本開示を更に詳細に説明する。なお、本発明はこれら実施例に限定されない。 Below, the results of evaluation tests using examples and comparative examples related to this disclosure will be presented, and this disclosure will be explained in more detail. Note that the present disclosure is not limited to these examples.
［着色樹脂層用の樹脂組成物］
（高分子分散剤）
　表１に示す高分子分散剤を準備した。高分子分散剤の酸価は、水酸化カリウム水溶液を用いた高分子分散剤の中和滴定により測定した値である。 [Resin composition for colored resin layer]
(Polymer Dispersant)
The polymer dispersants shown in Table 1 were prepared. The acid value of the polymer dispersant was a value measured by neutralization titration of the polymer dispersant using an aqueous potassium hydroxide solution.
（光重合性化合物）
　光重合性化合物として、ビスフェノールＡエポキシジアクリレート（ＥＡ）、ポリプロピレングリコールジアクリレート（ＰＰＧＤＡ）と、以下のアルキレンオキサイド変性アクリレート化合物を準備した。
ＴＭＰ（ＥＯ）３ＴＡ：トリメチロールプロパンＥＯ付加トリアクリレート（ＥＯ数：３）
ＴＭＰ（ＥＯ）１５ＴＡ：トリメチロールプロパンＥＯ付加トリアクリレート（ＥＯ数：１５）
ＢＰＡ（ＥＯ）３０ＤＡ：ＥＯ変性ビスフェノールＡジ（メタ）アクリレート（ＥＯ数：３０） (Photopolymerizable Compound)
As photopolymerizable compounds, bisphenol A epoxy diacrylate (EA), polypropylene glycol diacrylate (PPGDA), and the following alkylene oxide modified acrylate compound were prepared.
TMP(EO) 3TA : Trimethylolpropane EO adduct triacrylate (EO number: 3)
TMP(EO) 15 TA: Trimethylolpropane EO adduct triacrylate (EO number: 15)
BPA(EO) 30 DA: EO-modified bisphenol A di(meth)acrylate (EO number: 30)
（光重合開始剤）
　光重合開始剤として、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド（Ｏｍｎｉｒａｄ　ＴＰＯ）および１－ヒドロキシシクロヘキシルフェニルケトン（Ｏｍｎｉｒａｄ　１８４）を準備した。 (Photopolymerization initiator)
As photoinitiators, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO) and 1-hydroxycyclohexyl phenyl ketone (Omnirad 184) were prepared.
（表面処理酸化チタン粒子）
　表面処理酸化チタン粒子として、酸化アルミニウム（Ａｌ２Ｏ３）を含む表面処理層を有する表面処理酸化チタン粒子を準備した。表面処理酸化チタン粒子の平均一次粒径は、２００～３００ｎｍであり、ＩＣＰ－ＭＳの測定により算出されるＡｌ２Ｏ３の量は、２．５質量％であった。 (Surface-treated titanium oxide particles)
Surface-treated titanium oxide particles having a surface treatment layer containing aluminum oxide (Al 2 O 3 ) were prepared as surface-treated titanium oxide particles. The average primary particle size of the surface-treated titanium oxide particles was 200 to 300 nm, and the amount of Al 2 O 3 calculated by ICP-MS measurement was 2.5 mass %.
（試験例１～７）
　表２に示す配合量（質量部）の光重合性化合物および光重合開始剤と、表２に示す含有量（質量％）の高分子分散剤および表面処理酸化チタン粒子とを混合して、樹脂組成物を調製した。なお、高分子分散剤の含有量は、表面処理酸化チタン粒子の含有量を基準とする数値であり、表面処理酸化チタン粒子の含有量は、樹脂組成物の総量を基準とする数値である。試験例１～６が実施例に相当し、試験例７が比較例に相当する。 (Test Examples 1 to 7)
Resin compositions were prepared by mixing the photopolymerizable compound and photopolymerization initiator in the amounts (parts by mass) shown in Table 2 with the polymer dispersant and surface-treated titanium oxide particles in the contents (% by mass) shown in Table 2. The content of the polymer dispersant is a value based on the content of the surface-treated titanium oxide particles, and the content of the surface-treated titanium oxide particles is a value based on the total amount of the resin composition. Test Examples 1 to 6 correspond to Examples, and Test Example 7 corresponds to a Comparative Example.
（試験例８～１３）
　表３に示す配合量（質量部）の光重合性化合物および光重合開始剤と、表３に示す含有量（質量％）の高分子分散剤および表面処理酸化チタン粒子とを混合して、樹脂組成物を調製した。試験例８～１１が実施例に相当し、試験例１２および１３が比較例に相当する。 (Test Examples 8 to 13)
Resin compositions were prepared by mixing the photopolymerizable compound and photopolymerization initiator in the amounts (parts by mass) shown in Table 3 with the polymer dispersant and surface-treated titanium oxide particles in the contents (% by mass) shown in Table 3. Test Examples 8 to 11 correspond to Examples, and Test Examples 12 and 13 correspond to Comparative Examples.
（粘度）
　樹脂組成物の２５℃における粘度を、レオメータ（Ａｎｔｏｎ　Ｐａａｒ社製の「ＭＣＲ－１０２」）を用いて、コーンプレートＣＰ２５－２、せん断速度１０ｓ－１の条件で測定した。 (viscosity)
The viscosity of the resin composition at 25° C. was measured using a rheometer ("MCR-102" manufactured by Anton Paar) under conditions of cone plate CP25-2 and a shear rate of 10 s −1 .
（ヤング率）
　スピンコータを用いて、樹脂組成物をポリエチレンテレフタレート（ＰＥＴ）フィルムの上に塗布した後、無電極ＵＶランプシステム（ヘレウス製の「ＶＰＳ６００（Ｄバルブ）」）を用いて、１０００±１００ｍＪ／ｃｍ２の条件で硬化させ、ＰＥＴフィルム上に厚み５０±５μｍの樹脂層を形成した。樹脂層をＰＥＴフィルムから剥がし、樹脂フィルムを得た。 (Young's modulus)
The resin composition was applied onto a polyethylene terephthalate (PET) film using a spin coater, and then cured using an electrodeless UV lamp system (Heraeus's "VPS600 (D bulb)") at 1000±100 mJ/ cm2 to form a resin layer with a thickness of 50±5 μm on the PET film. The resin layer was peeled off from the PET film to obtain a resin film.
　樹脂フィルムをＪＩＳ　Ｋ　７１２７　タイプ５号のダンベル形状に打ち抜き、２３±２℃、５０±１０％ＲＨの条件下で、引張試験機を用いて１ｍｍ／分の引張速度、標線間２５ｍｍの条件で引張り、応力－歪み曲線を得た。２．５％割線によりフィルムヤング率を求めた。 The resin film was punched out into a dumbbell shape conforming to JIS K 7127 Type 5, and pulled using a tensile tester at 23±2°C, 50±10% RH, with a pulling speed of 1 mm/min and a gauge distance of 25 mm, to obtain a stress-strain curve. The film Young's modulus was calculated using the 2.5% secant line.
（保存安定性）
　樹脂組成物を調製した後、３０℃の恒温槽に入れて保管した。３０日経過後に樹脂組成物の外観に変化がなかった場合を「Ａ」、１５日以内に樹脂組成物に沈降等の相分離が生じた場合を「Ｂ」、７日以内に樹脂組成物に沈降等の相分離が生じた場合を「Ｃ」と評価した。 (Storage stability)
After preparing the resin composition, it was stored in a thermostatic chamber at 30° C. If there was no change in the appearance of the resin composition after 30 days, it was rated as “A”, if phase separation such as precipitation occurred in the resin composition within 15 days, it was rated as “B”, and if phase separation such as precipitation occurred in the resin composition within 7 days, it was rated as “C”.
（プライマリ樹脂層用の樹脂組成物）
　分子量４０００のポリプロピレングリコール、イソホロンジイソシアネート、ヒドロキシエチルアクリレート、およびメタノールを反応して得られるウレタンアクリレートを準備した。このウレタンアクリレートを７５質量部、ノニルフェノールＥＯ変性アクリレートを１２質量部、Ｎ－ビニルカプロラクタムを６質量部、１，６－ヘキサンジオールジアクリレートを２質量部、Ｏｍｎｉｒａｄ　ＴＰＯを１質量部、および３－メルカプトプロピルトリメトキシシランを１質量部混合して、樹脂組成物Ｐを調製した。 (Resin composition for primary resin layer)
A urethane acrylate obtained by reacting polypropylene glycol having a molecular weight of 4000, isophorone diisocyanate, hydroxyethyl acrylate, and methanol was prepared. 75 parts by mass of this urethane acrylate, 12 parts by mass of nonylphenol EO-modified acrylate, 6 parts by mass of N-vinyl caprolactam, 2 parts by mass of 1,6-hexanediol diacrylate, 1 part by mass of Omnirad TPO, and 1 part by mass of 3-mercaptopropyltrimethoxysilane were mixed to prepare a resin composition P.
（セカンダリ樹脂層用の樹脂組成物）
　分子量６００のポリプロピレングリコール、２，４－トリレンジイソシアネートおよび２－ヒドロキシエチルアクリレートを反応して得られるウレタンアクリレートを準備した。このウレタンアクリレートを４０質量部、イソボルニルアクリレートを３５質量部、ビスフェノールＡジグリシジルエーテルのアクリル酸付加物であるエポキシアクリレートを２４質量部、およびＯｍｎｉｒａｄ　ＴＰＯを１質量部、Ｏｍｎｉｒａｄ　１８４を１質量部混合して、樹脂組成物Ｓを調製した。 (Resin composition for secondary resin layer)
A urethane acrylate obtained by reacting polypropylene glycol having a molecular weight of 600, 2,4-tolylene diisocyanate, and 2-hydroxyethyl acrylate was prepared. Resin composition S was prepared by mixing 40 parts by mass of this urethane acrylate, 35 parts by mass of isobornyl acrylate, 24 parts by mass of epoxy acrylate which is an acrylic acid adduct of bisphenol A diglycidyl ether, 1 part by mass of Omnirad TPO, and 1 part by mass of Omnirad 184.
（リボン用の樹脂組成物）
　ビスフェノールＡ・エチレンオキサイド付加ジオール、トリレンジイソシアネートおよびヒドロキシエチルアクリレートを反応して得られるウレタンアクリレートＡと、ポリテトラメチレングリコール、トリレンジイソシアネートおよびヒドロキシエチルアクリレートを反応して得られるウレタンアクリレートＢとを準備した。ウレタンアクリレートＡを１８質量部、ウレタンアクリレートＢを１０質量部、トリシクロデカンジメタノールジアクリレートを１５質量部、Ｎ－ビニルピロリドンを１０質量部、イソボルニルアクリレートを１０質量部、ビスフェノールＡ・エチレンオキサイド付加ジオールジアクリレートを５質量部、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－プロパン－１－オン（Ｏｍｎｉｒａｄ　９０７）を０．７質量部、およびＯｍｎｉｒａｄ　ＴＰＯを１．３質量部混合して、樹脂組成物Ｒを調製した。 (Resin composition for ribbon)
Urethane acrylate A obtained by reacting bisphenol A-ethylene oxide adduct diol, tolylene diisocyanate, and hydroxyethyl acrylate, and urethane acrylate B obtained by reacting polytetramethylene glycol, tolylene diisocyanate, and hydroxyethyl acrylate were prepared. Resin composition R was prepared by mixing 18 parts by weight of urethane acrylate A, 10 parts by weight of urethane acrylate B, 15 parts by weight of tricyclodecane dimethanol diacrylate, 10 parts by weight of N-vinylpyrrolidone, 10 parts by weight of isobornyl acrylate, 5 parts by weight of bisphenol A-ethylene oxide adduct diol diacrylate, 0.7 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (Omnirad 907), and 1.3 parts by weight of Omnirad TPO.
［光ファイバの作製］
　コアおよびクラッドから構成される直径１２５μｍのガラスファイバの外周に、樹脂組成物Ｐを用いて厚さ１７．５μｍのプライマリ樹脂層を形成し、更にその外周に樹脂組成物Ｓを用いて１５μｍのセカンダリ樹脂層を形成して、光ファイバを作製した。次いで、光ファイバを一旦巻き取った後に、着色機で光ファイバを改めて繰り出しながらセカンダリ樹脂層の外周に試験例１～１３の樹脂組成物により、厚さ５μｍの着色樹脂層を形成することで、着色樹脂層を有する直径２００μｍの光ファイバ（以下、「着色光ファイバ」という。）を作製した。各樹脂層を形成する際の線速は１５００ｍ／分とした。 [Fabrication of optical fiber]
A primary resin layer having a thickness of 17.5 μm was formed on the outer circumference of a glass fiber having a diameter of 125 μm, which was composed of a core and a clad, using resin composition P, and a secondary resin layer having a thickness of 15 μm was further formed on the outer circumference of the primary resin layer using resin composition S, to produce an optical fiber. Next, after the optical fiber was once wound up, a colored resin layer having a thickness of 5 μm was formed on the outer circumference of the secondary resin layer using the resin compositions of Test Examples 1 to 13 while the optical fiber was reeled out using a coloring machine, thereby producing an optical fiber having a diameter of 200 μm and a colored resin layer (hereinafter referred to as "colored optical fiber"). The linear speed when forming each resin layer was 1500 m/min.
［光ファイバリボンの作製］
　着色光ファイバを４本用意し、リボン用の樹脂組成物Ｒを被覆した後、紫外線を照射して硬化して連結樹脂層を形成し、光ファイバリボンを作製した。 [Fabrication of optical fiber ribbon]
Four colored optical fibers were prepared, coated with the resin composition R for ribbon, and then irradiated with ultraviolet light to harden the composition, thereby forming a connecting resin layer, thereby producing an optical fiber ribbon.
（色剥がれ試験）
　光ファイバリボンを８５℃８５％ＲＨの環境下（暗所）で９０日間保管した後、光ファイバリボンからＴｅｌｃｏｒｄｉａ　ＧＲ－２０　５．３．１に準拠し、光ファイバを単心分離した。その際の着色樹脂層の剥がれの有無を評価した。着色樹脂層に剥がれが無かった場合を「Ａ」、着色樹脂層にリボン用樹脂の一部が残った場合を「Ｂ」、着色樹脂層に剥がれが有った場合を「Ｃ」と評価した。 (Color peeling test)
After storing the optical fiber ribbon for 90 days in an environment of 85°C and 85% RH (in a dark place), the optical fibers were separated from the optical fiber ribbon in accordance with Telcordia GR-20 5.3.1. The presence or absence of peeling of the colored resin layer was evaluated. The case where there was no peeling of the colored resin layer was evaluated as "A", the case where a part of the ribbon resin remained in the colored resin layer was evaluated as "B", and the case where there was peeling of the colored resin layer was evaluated as "C".
　１，１Ａ…光ファイバ
　１０…ガラスファイバ
　１２…コア
　１４…クラッド
　２０，２０Ａ…被覆樹脂層
　２２…プライマリ樹脂層
　２４…セカンダリ樹脂層
　２６…着色樹脂層
　４０…連結樹脂層
　１００…光ファイバリボン Reference Signs List 1, 1A: Optical fiber 10: Glass fiber 12: Core 14: Cladding 20, 20A: Coating resin layer 22: Primary resin layer 24: Secondary resin layer 26: Colored resin layer 40: Connecting resin layer 100: Optical fiber ribbon

Claims (8)

  1. 　光重合性化合物と、酸性官能基を有する高分子分散剤と、光重合開始剤と、表面処理酸化チタン粒子と、を含有し、
    　前記高分子分散剤の含有量が、前記表面処理酸化チタン粒子の含有量を基準として、０．０１質量％以上１８質量％以下であり、
    　前記高分子分散剤の酸価が、２５ｍｇＫＯＨ／ｇ以上１８０ｍｇＫＯＨ／ｇ以下である、光ファイバ着色被覆用の樹脂組成物。     The composition contains a photopolymerizable compound, a polymer dispersant having an acidic functional group, a photopolymerization initiator, and surface-treated titanium oxide particles,
    the content of the polymer dispersant is 0.01% by mass or more and 18% by mass or less based on the content of the surface-treated titanium oxide particles,
    The resin composition for coloring and coating an optical fiber, wherein the acid value of the polymer dispersant is 25 mgKOH/g or more and 180 mgKOH/g or less.
  2. 　前記酸性官能基が、リン酸基またはカルボキシ基である、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the acidic functional group is a phosphoric acid group or a carboxyl group.
  3. 　前記表面処理酸化チタン粒子が、酸化アルミニウム、二酸化ケイ素、および二酸化ジルコニウムからなる群より選ばれる少なくとも１種を含む表面処理層を有する、請求項１または請求項２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the surface-treated titanium oxide particles have a surface treatment layer containing at least one selected from the group consisting of aluminum oxide, silicon dioxide, and zirconium dioxide.
  4. 　前記光重合性化合物が、エポキシジ（メタ）アクリレートを含む、請求項１から請求項３のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the photopolymerizable compound includes an epoxy di(meth)acrylate.
  5. 　コアおよびクラッドを含むガラスファイバと、
    　前記ガラスファイバに接して前記ガラスファイバを被覆するプライマリ樹脂層と、
    　前記プライマリ樹脂層を被覆するセカンダリ樹脂層と、
    　前記セカンダリ樹脂層を被覆する着色樹脂層と、を備え、
    　前記着色樹脂層が、請求項１から請求項４のいずれか一項に記載の樹脂組成物の硬化物を含む、光ファイバ。     a glass fiber including a core and a cladding;
    a primary resin layer that is in contact with and covers the glass fiber;
    a secondary resin layer that covers the primary resin layer;
    A colored resin layer that covers the secondary resin layer,
    An optical fiber, wherein the colored resin layer comprises a cured product of the resin composition according to any one of claims 1 to 4.
  6. 　コアおよびクラッドを含むガラスファイバと、
    　前記ガラスファイバに接して前記ガラスファイバを被覆するプライマリ樹脂層と、
    　前記プライマリ樹脂層を被覆するセカンダリ樹脂層と、を備え、
    　前記セカンダリ樹脂層が、請求項１から請求項４のいずれか一項に記載の樹脂組成物の硬化物を含む、光ファイバ。     a glass fiber including a core and a cladding;
    a primary resin layer that is in contact with and covers the glass fiber;
    A secondary resin layer that covers the primary resin layer,
    An optical fiber, wherein the secondary resin layer comprises a cured product of the resin composition according to claim 1 .
  7. 　請求項５に記載の光ファイバが複数並列され、リボン用樹脂で被覆された、光ファイバリボン。 An optical fiber ribbon comprising a plurality of optical fibers according to claim 5 arranged in parallel and coated with a ribbon resin.
  8. 　請求項６に記載の光ファイバが複数並列され、リボン用樹脂で被覆された、光ファイバリボン。 An optical fiber ribbon comprising a plurality of optical fibers according to claim 6 arranged in parallel and coated with a ribbon resin.
PCT/JP2023/040101 2023-01-18 2023-11-07 Resin composition for optical fiber color coating, optical fiber, and optical fiber ribbon WO2024154414A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016070966A (en) * 2014-09-26 2016-05-09 住友電気工業株式会社 Optical fiber core wire and optical fiber ribbon
WO2016088801A1 (en) * 2014-12-03 2016-06-09 住友電気工業株式会社 Optical fiber core and optical fiber tape core
JP2017095531A (en) * 2015-11-18 2017-06-01 サカタインクス株式会社 Ink composition for photosetting inkjet printing

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016070966A (en) * 2014-09-26 2016-05-09 住友電気工業株式会社 Optical fiber core wire and optical fiber ribbon
WO2016088801A1 (en) * 2014-12-03 2016-06-09 住友電気工業株式会社 Optical fiber core and optical fiber tape core
JP2017095531A (en) * 2015-11-18 2017-06-01 サカタインクス株式会社 Ink composition for photosetting inkjet printing

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