EP2222610A1 - Radiation curable cladding layer for polymer-clad optical fiber - Google Patents

Radiation curable cladding layer for polymer-clad optical fiber

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Publication number
EP2222610A1
EP2222610A1 EP08855289A EP08855289A EP2222610A1 EP 2222610 A1 EP2222610 A1 EP 2222610A1 EP 08855289 A EP08855289 A EP 08855289A EP 08855289 A EP08855289 A EP 08855289A EP 2222610 A1 EP2222610 A1 EP 2222610A1
Authority
EP
European Patent Office
Prior art keywords
meth
acrylate
resin composition
radiation
cladding layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08855289A
Other languages
German (de)
French (fr)
Inventor
Hiroyuki Ishii
Takahiko Kurosawa
Satoshi Kamo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
DSM IP Assets BV
Original Assignee
JSR Corp
DSM IP Assets BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JSR Corp, DSM IP Assets BV filed Critical JSR Corp
Publication of EP2222610A1 publication Critical patent/EP2222610A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C03C25/105—Organic claddings
    • 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
    • C08F220/00—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • the present invention relates to a curable liquid resin composition for forming a cladding layer of polymer-clad optical fibers.
  • Optical fibers suitable for high-capacity and high-speed digital signal communication have been widely used as information communication cables instead of metal electric wires.
  • Various optical fibers which differ in structure and configuration have been known.
  • Optical fibers have a basic structure including a core layer formed of glass, quartz, or a transparent resin, a cladding layer provided on the outer side of the core layer, and a polymer coating layer provided on the outer side of the cladding layer and formed of a radiation-curable resin or the like.
  • all-quartz optical fibers in which the core layer and the cladding layer are formed of quartz are widely used.
  • the diameter of the core layer is typically about 50 ⁇ m, and the total diameter of the core layer and the cladding layer is about 125 ⁇ m.
  • the total diameter of the core layer, the cladding layer, and the resin coating layer is from about 250 to about 500 ⁇ m.
  • Optical modules having optical signal transmission, reception, branching, and switching functions and the like have been developed for diverse optical information communications. It is important to connect an optical module and an optical fiber while aligning their optical axes in order to suppress the attenuation of optical signals. Since the diameter of the core layer of an optical fiber is small, as described above, it is difficult to achieve optical axis alignment when connecting an optical fiber to an optical module. Therefore, optical fibers of which the core diameter is increased to about 200 ⁇ m have been used. Optical fibers having such a large diameter normally have a cladding layer formed of a curable transparent resin, and are referred to as polymer-clad optical fibers (or plastic-clad optical fibers or polymer-clad fibers).
  • fluorine-containing UV-curable compositions containing a fluorine-containing urethane (meth)acrylate, a fluorine-containing (meth)acrylate oligomer, and the like have been known. See Patent Document 1: JP-A- 10- 10340,
  • Patent Document 2 JP-A-10-160947 and Patent Document 3: JP-A-11-119036.
  • Polymer-clad optical fibers having a core layer formed of glass or quartz are referred to as hard polymer-clad optical fibers
  • polymer-clad optical fibers having a core layer formed of a transparent resin are referred to as plastic fibers. Since the hard polymer-clad optical fibers exhibit high optical transmission efficiency, the hard polymer-clad optical fibers are used for communication over a relatively long distance. The plastic fibers are used for communication over a relatively short distance.
  • a curable transparent resin material used for the cladding layer of polymer-clad optical fibers is required to have a low refractive index and transparency that is stable over time; an appropriate viscosity for achieving excellent applicability; excellent adhesion to the core layer; and strength and flexibility represented by Young's modulus, breaking strength, elongation at break, and the like, for example.
  • the invention is directed to a radiation-curable resin composition
  • a radiation-curable resin composition comprising: (A) a fluorine-containing urethane (meth)acrylate;
  • R 1 represents a hydrogen atom or a methyl group
  • X represents a hydrogen atom or a fluorine atom
  • x represents 1 or 2
  • y represents an integer from 2 to 8;
  • the invention is directed to a cured film comprising a cured product of the radiation-curable resin composition according to the first aspect of the instant claimed invention.
  • the invention is directed to a polymer-clad optical fiber comprising a core layer formed of glass, quartz, or a transparent resin, and a cladding layer formed of the cured film according to the second aspect of the instant claimed invention, the cladding layer being in contact with the outer side of the core layer.
  • An object of the present invention is to provide a radiation-curable resin composition having properties (particularly a low refractive index, stable transparency, excellent adhesion to a core layer, excellent strength, and high flexibility) suitable as a cladding material for polymer-clad optical fibers.
  • the inventor of the present invention found that the above object can be achieved by a radiation-curable resin composition containing a fluorine-containing urethane (meth)acrylate, a specific fluorine-containing (meth)acrylate monomer, acrylic acid, and a silane coupling agent.
  • the present invention provides a radiation-curable resin composition comprising:
  • R 1 represents a hydrogen atom or a methyl group
  • X represents a hydrogen atom or a fluorine atom
  • x represents 1 or 2
  • y represents an integer from 2 to 8
  • the present invention also provides a cured film comprising a cured product of the above radiation-curable resin composition.
  • the present invention further provides a polymer-clad optical fiber comprising a core layer formed of glass, quartz, or a transparent resin, and a cladding layer formed of the above cured film, the cladding layer being in contact with the outer side of the core layer.
  • a polymer cladding layer obtained using the resin composition of the present invention has a low refractive index, stable transparency, excellent adhesion to a core layer, excellent strength, and high flexibility.
  • the fluorine-containing urethane (meth)acrylate (A) is not particularly limited insofar as the urethane (meth)acrylate contains a fluorine atom in the molecule. It is preferable to use a fluorine-containing urethane (meth)acrylate obtained by reacting a fluorine-containing polyol, a diisocyanate, and a hydroxyl group-containing (meth)acrylate.
  • the component (A) provides the composition of the present invention with basic properties necessary for a cladding layer material for polymer-clad optical fibers, such as a low refractive index, high mechanical strength, and excellent adhesion to a core layer formed of glass, quartz, or the like.
  • the fluorine-containing urethane (meth)acrylate (A) is produced by reacting a polyol, a diisocyanate, and a hydroxyl group-containing (meth)acrylate. Specifically, the fluorine-containing urethane (meth)acrylate (A) is produced by reacting isocyanate groups of the diisocyanate with hydroxyl groups of the polyol and the hydroxyl group-containing (meth)acrylate.
  • the fluorine-containing urethane (meth)acrylate (A) may be produced by reacting the polyol, the diisocyanate, and the hydroxyl group-containing (meth)acrylate all together; reacting the polyol with the diisocyanate, and reacting the resulting product with the hydroxyl group-containing (meth)acrylate; reacting the diisocyanate with the hydroxyl group-containing (meth)acrylate, and reacting the resulting product with the polyol; reacting the diisocyanate with the hydroxyl group-containing (meth)acrylate, reacting the resulting product with the polyol, and further reacting the resulting product with the hydroxyl group-containing (meth)acrylate; or the like.
  • fluorine-containing polyol examples include perfluoro polyethers shown by the following formula (2).
  • Z individually represents -CH 2 (OCH 2 CH 2 ) n OH (n represents an integer from 0 to 10, and preferably from 1 to 7), p represents an integer from 1 to 40, and q represents an integer from 1 to 70.
  • the molecular weight of the perfluoro polyether (2) is preferably 1000 to 5000, and particularly preferably 1000 to 3000.
  • a commercially available product such as Fluorolink E (manufactured by Solvay Solexis) may be used.
  • Examples of the diisocyanate include 2,4-tolylene diisocyanate,
  • 2,6-tolylene diisocyanate 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5- naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate),
  • 2,2,4-trimethylhexamethylene diisocyanate bis(2-isocyanatoethyl)fumarate, 6-isopropyl-l,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, and the like.
  • the aliphatic diisocyanates are preferable.
  • isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate), and the like are preferable.
  • hydroxyl group-containing (meth)acrylate examples include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, 2-hydroxyalkyl(meth)acryloyl phosphate, 4-hydroxycyclohexyl (meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylates shown by the following formulas (3) and (4), and the like.
  • CH 2 C(R 2 )-COOC
  • R 2 represents a hydrogen atom or a methyl group
  • m represents an integer from 1 to 15.
  • a compound obtained by subjecting (meth)acrylic acid and a glycidyl group-containing compound e.g., alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth)acrylate
  • a glycidyl group-containing compound e.g., alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth)acrylate
  • hydroxyl group-containing (meth)acrylates 2 -hydroxy ethyl
  • the proportion of the polyol, the diisocyanate, and the hydroxyl group-containing (meth)acrylate is determined so that isocyanate groups contained in the diisocyanate and hydroxyl groups contained in the hydroxyl group-containing (meth)acrylate are respectively 1 to 3 equivalents and 0.2 to 1.5 equivalents for one equivalent of hydroxyl groups contained in the polyol. It is preferable that the equivalent of hydroxyl groups contained in the polyol and the hydroxyl group-containing (meth)acrylate be almost equal to the equivalent of isocyanate groups contained in the diisocyanate.
  • a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, titanium tetraalkoxide, zirconium tetraalkoxide, or zirconium acetylacetonate in an amount of 0.01 to 1 part by mass based on 100 parts by mass of the reactants.
  • the reaction temperature is preferably 10 to 90 0 C, and particularly preferably 30 to 80 0 C.
  • the component (A) is normally incorporated in the composition in an amount of 30 to 70 mass%, preferably 40 to 70 mass%, and particularly preferably 50 to 65 mass% based on the total amount of the composition. If the amount of the component (A) is less than 30 mass%, applicability may be impaired due to a decrease in viscosity. If the amount of the component (A) is more than 30 mass%, applicability may be impaired due to an increase in viscosity.
  • Component (B) The component (B) is a compound shown by the following formula (1).
  • R 1 represents a hydrogen atom or a methyl group
  • X represents a hydrogen atom or a fluorine atom
  • x represents 1 or 2
  • y represents an integer from 2 to 8.
  • the component (B) is used to reduce the refractive index of the resulting cured product.
  • Specific examples of the component (B) include, but are not limited to, 2-perfluorooctylethyl (meth)acrylate,
  • 2,2,3,3-tetrafluoropropyl (meth)acrylate 2,2,3,3-tetrafluoropropyl (meth)acrylate, lH,lH,5H-octafluoropentyl (meth)acrylate, and the like.
  • Examples of commercially available products of these compounds include Viscoat 17F, 4F, 8F (manufactured by Osaka Organic Chemical Industry Ltd.), and the like.
  • 2-perfluorooctylethyl (meth)acrylate is preferable due to its excellent capability of dissolving the component (A) and its availability.
  • the component (B) is normally incorporated in the composition in an amount of 20 to 60 mass%, preferably 20 to 50 mass%, and particularly preferably 20 to 45 mass% based on the total amount of the composition. If the amount of the component (B) is less than 20 mass%, the refractive index of the resulting cured product may increase. If the amount of the component (B) is more than 60 mass%, applicability may be impaired due to an increase in viscosity of the composition.
  • the component (C) i.e., (meth)acrylic acid
  • the component (C) is normally used in an amount of 3 to 10 mass%, preferably 3 to 7 mass%, and particularly preferably 3 to 5 mass% based on the total amount of the composition. If the amount of the component (C) is within this range, an increase in refractive index occurs to only a small extent.
  • the component (D) i.e., silane coupling agent
  • the component (D) is not particularly limited.
  • vinyltrichloro silane, vinyltriethoxysilane, vinyltr is ( ⁇ - methoxyethoxy) silane , ⁇ -(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldietoxysilane, ⁇ -(meth)acryloxypropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane,
  • N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -chloropropyltrimetoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, bis-l,2-(trimethoxysilyl)ethane, or the like may be used as the component (D).
  • Examples of commercially available products of these compounds include SH6062, SZ6030 (manufactured by Dow Corning Toray Silicone Co., Ltd.), KBE 903, 603, 403 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
  • ⁇ -glycidoxypropyltrimetoxysilane, ⁇ -(meth)acryloxypropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, and ⁇ -aminopropyltrimethoxysilane are preferable.
  • These silane coupling agents may be used either individually or in combination.
  • the component (D) is normally incorporated in the composition in an amount of 0.5 to 1 mass% based on the total amount of the composition. If the amount of the component (D) is within this range, an increase in refractive index occurs to only a small extent.
  • the radiation-curable resin composition of the present invention may further include (E) a monofunctional acrylic monomer in order to increase the viscosity of the composition.
  • examples of the monofunctional acrylic monomer include diacetoneacrylamide and the like.
  • the component (E) is normally incorporated in the composition in an amount of 5 to 20 mass%, preferably 5 to 15 mass%, and particularly preferably 5 to 10 mass% based on the total amount of the composition. If the amount of the component (E) is within this range, an increase in refractive index occurs to only a small extent.
  • Examples of the photoinitiator (F) include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl methyl ketal,
  • a photosensitizer may be used in combination with the photoinitiator (F).
  • the photosensitizer include triethylamine, diethylamine, N-methyldiethanoleamine, ethanolamine,
  • the initiator (F) is incorporated in the composition of the present invention in an amount of 0.1 to 10 mass%, and particularly preferably 0.3 to 7 mass%.
  • Various additives such as an antioxidant, a coloring agent, a UV absorber, a light stabilizer, a silane coupling agent, a heat polymerization inhibitor, a leveling agent, a surfactant, a preservative, a plasticizer, a lubricant, a solvent, a filler, an aging preventive, a wettability improver, and a coating surface improver may optionally be added to the composition of the present invention insofar as the characteristics of the present invention are not adversely affected.
  • the viscosity (25 0 C) of the composition of the present invention is preferably 0.8 to 5 Pa-s, and particularly preferably 2 to 3 Pa-s.
  • the curable liquid resin composition of the present invention is normally cured by applying radiation. Note that heat may be applied in combination with radiation.
  • radiation refers to infrared rays, visible rays, UV rays, X-rays, electron beams, ⁇ -rays, ⁇ -rays, ⁇ -rays, and the like.
  • the curable liquid resin composition of the present invention preferably has a Young's modulus of 200 to 500 MPa. Since the composition of the present invention has a low refractive index, high transparency, and high adhesion to a core layer, the composition of the present invention is suitably used to form an optical fiber cladding layer.
  • a reaction vessel equipped with a stirrer was charged with 57.39 g of isophorone diisocyanate, 0.092 g of 2,6-di-t-butyl-p-cresol, 0.307 g of dibutyltin dilaurate, and 295.88 g of perfluoro polyether having a molecular weight of 2000.
  • the mixture was allowed to react at 40 0 C or less for two hours with stirring. After the dropwise addition of 29.98 g of hydroxyethyl acrylate, the mixture was stirred at 60 to 70 0 C for three hours. The reaction was determined to be completed when the residual isocyanate content became 0.1 mass% or less.
  • a reaction vessel equipped with a stirrer was charged with each component shown in Table 1. The mixture was stirred for one hour while controlling the liquid temperature at 50 0 C to obtain a curable liquid resin composition.
  • the curable liquid resin composition was applied to a glass plate using an applicator bar with a gap size of 250 ⁇ m, and was cured by applying UV rays at a dose of 1 J/cm 2 in a nitrogen atmosphere to obtain a Young's modulus measurement film.
  • the film was cut into a strip-shaped sample having a width of 6 mm and a length of 25 mm (portion to be pulled).
  • the sample was subjected to a tensile test at a temperature of 23 0 C and a humidity of 50%.
  • the Young's modulus of the sample was calculated from the tensile strength at a strain of 2.5% and a tensile rate of 1 mm/min.
  • the adhesion of the cured products of the compositions obtained in the example and comparative examples was measured. Specifically, the curable liquid resin composition was applied to a slide using an applicator with a gap size of 381 ⁇ m. UV rays were applied to the composition at a dose of 0.1 J/cm 2 in a nitrogen atmosphere to obtain a cured film having a thickness of about 200 ⁇ m. The cured film formed on the slide was allowed to stand at a temperature of 23 0 C and a relative humidity of 50% for 24 hours. A strip-shaped sample (width of a portion to be pulled: 10 mm) was prepared from the cured film. The sample was subjected to an adhesion test using a tensile tester in accordance with JIS Z0237. The adhesion of the sample was calculated from the tensile strength at a tensile rate of 50 mm/min.
  • the curable liquid resin composition was applied to a glass plate to a thickness of 200 ⁇ m using an applicator bar. UV rays were applied to the composition at a dose of 1.0 J/cm 2 in a nitrogen atmosphere to obtain a sample.
  • the refractive index (25 0 C) of the sample was measured using an Abbe refractometer (manufactured by Atago Co., Ltd.) in accordance with JIS K7105.
  • Viscoat 17F 2-perfluorooctylethyl (meth)acrylate (manufactured by Osaka Organic Chemical Industry, Ltd.)
  • Lucirin TPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF)
  • GA-80 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]- l,l-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane ("Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.)
  • the cured product of the curable liquid resin composition of Example 1 had an appropriate Young's modulus, refractive index, transparency (haze), and adhesion to glass.
  • the cured products of the comparative examples in which the component (C) and/or the component (D) was not used exhibited insufficient adhesion to glass.

Abstract

A liquid radiation curable coating composition suitable for use as a cladding layer on an optical fiber is described and claimed. The composition is as follows: (A) a fluorine-containing urethane (meth)acrylate; (B) a compound shown by the following formula (1), CH2=CR1COO(CH2)X(CF2)YX (1) wherein R1 represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a fluorine atom, x represents 1 or 2, and y represents an integer from 2 to 8; (C) (meth)acrylic acid; and (D) a silane coupling agent.

Description

Title: Radiation Curable Cladding Layer for Polymer-Clad Optical Fiber
Field of the invention
The present invention relates to a curable liquid resin composition for forming a cladding layer of polymer-clad optical fibers.
Background of the invention
Optical fibers suitable for high-capacity and high-speed digital signal communication have been widely used as information communication cables instead of metal electric wires. Various optical fibers which differ in structure and configuration have been known. Optical fibers have a basic structure including a core layer formed of glass, quartz, or a transparent resin, a cladding layer provided on the outer side of the core layer, and a polymer coating layer provided on the outer side of the cladding layer and formed of a radiation-curable resin or the like. In particular, all-quartz optical fibers in which the core layer and the cladding layer are formed of quartz are widely used. The diameter of the core layer is typically about 50 μm, and the total diameter of the core layer and the cladding layer is about 125 μm. The total diameter of the core layer, the cladding layer, and the resin coating layer is from about 250 to about 500 μm.
Optical modules having optical signal transmission, reception, branching, and switching functions and the like have been developed for diverse optical information communications. It is important to connect an optical module and an optical fiber while aligning their optical axes in order to suppress the attenuation of optical signals. Since the diameter of the core layer of an optical fiber is small, as described above, it is difficult to achieve optical axis alignment when connecting an optical fiber to an optical module. Therefore, optical fibers of which the core diameter is increased to about 200 μm have been used. Optical fibers having such a large diameter normally have a cladding layer formed of a curable transparent resin, and are referred to as polymer-clad optical fibers (or plastic-clad optical fibers or polymer-clad fibers). As the curable transparent resin that forms the cladding layer, fluorine-containing UV-curable compositions containing a fluorine-containing urethane (meth)acrylate, a fluorine-containing (meth)acrylate oligomer, and the like have been known. See Patent Document 1: JP-A- 10- 10340,
Patent Document 2: JP-A-10-160947 and Patent Document 3: JP-A-11-119036. Polymer-clad optical fibers having a core layer formed of glass or quartz are referred to as hard polymer-clad optical fibers, and polymer-clad optical fibers having a core layer formed of a transparent resin are referred to as plastic fibers. Since the hard polymer-clad optical fibers exhibit high optical transmission efficiency, the hard polymer-clad optical fibers are used for communication over a relatively long distance. The plastic fibers are used for communication over a relatively short distance.
A curable transparent resin material used for the cladding layer of polymer-clad optical fibers is required to have a low refractive index and transparency that is stable over time; an appropriate viscosity for achieving excellent applicability; excellent adhesion to the core layer; and strength and flexibility represented by Young's modulus, breaking strength, elongation at break, and the like, for example.
However, when using a known resin material for the cladding layer of polymer-clad optical fibers, it is difficult to obtain a polymer cladding layer having a low refractive index, transparency, excellent applicability, adhesion to the core layer, and excellent strength and flexibility. In particular, a resin composition that produces a polymer cladding layer exhibiting high adhesion to the core layer has been desired. Summary of the invention
In a first aspect the invention is directed to a radiation-curable resin composition comprising: (A) a fluorine-containing urethane (meth)acrylate;
(B) a compound shown by the following formula (1),
wherein R1 represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a fluorine atom, x represents 1 or 2, and y represents an integer from 2 to 8;
(C) (meth)acrylic acid; and
(D) a silane coupling agent. In a second aspect the invention is directed to a cured film comprising a cured product of the radiation-curable resin composition according to the first aspect of the instant claimed invention.
In a third aspect the invention is directed to a polymer-clad optical fiber comprising a core layer formed of glass, quartz, or a transparent resin, and a cladding layer formed of the cured film according to the second aspect of the instant claimed invention, the cladding layer being in contact with the outer side of the core layer.
Detailed description of the invention
An object of the present invention is to provide a radiation-curable resin composition having properties (particularly a low refractive index, stable transparency, excellent adhesion to a core layer, excellent strength, and high flexibility) suitable as a cladding material for polymer-clad optical fibers. The inventor of the present invention found that the above object can be achieved by a radiation-curable resin composition containing a fluorine-containing urethane (meth)acrylate, a specific fluorine-containing (meth)acrylate monomer, acrylic acid, and a silane coupling agent. Specifically, the present invention provides a radiation-curable resin composition comprising:
(A) a fluorine-containing urethane (meth)acrylate;
(B) a compound shown by the following formula (1),
wherein R1 represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a fluorine atom, x represents 1 or 2, and y represents an integer from 2 to 8; (C) (meth)acrylic acid; and
(D) a silane coupling agent.
The present invention also provides a cured film comprising a cured product of the above radiation-curable resin composition.
The present invention further provides a polymer-clad optical fiber comprising a core layer formed of glass, quartz, or a transparent resin, and a cladding layer formed of the above cured film, the cladding layer being in contact with the outer side of the core layer.
A polymer cladding layer obtained using the resin composition of the present invention has a low refractive index, stable transparency, excellent adhesion to a core layer, excellent strength, and high flexibility.
(A) Fluorine-containing urethane (meth)acrylate
The fluorine-containing urethane (meth)acrylate (A) is not particularly limited insofar as the urethane (meth)acrylate contains a fluorine atom in the molecule. It is preferable to use a fluorine-containing urethane (meth)acrylate obtained by reacting a fluorine-containing polyol, a diisocyanate, and a hydroxyl group-containing (meth)acrylate.
The component (A) provides the composition of the present invention with basic properties necessary for a cladding layer material for polymer-clad optical fibers, such as a low refractive index, high mechanical strength, and excellent adhesion to a core layer formed of glass, quartz, or the like.
The fluorine-containing urethane (meth)acrylate (A) is produced by reacting a polyol, a diisocyanate, and a hydroxyl group-containing (meth)acrylate. Specifically, the fluorine-containing urethane (meth)acrylate (A) is produced by reacting isocyanate groups of the diisocyanate with hydroxyl groups of the polyol and the hydroxyl group-containing (meth)acrylate.
The fluorine-containing urethane (meth)acrylate (A) may be produced by reacting the polyol, the diisocyanate, and the hydroxyl group-containing (meth)acrylate all together; reacting the polyol with the diisocyanate, and reacting the resulting product with the hydroxyl group-containing (meth)acrylate; reacting the diisocyanate with the hydroxyl group-containing (meth)acrylate, and reacting the resulting product with the polyol; reacting the diisocyanate with the hydroxyl group-containing (meth)acrylate, reacting the resulting product with the polyol, and further reacting the resulting product with the hydroxyl group-containing (meth)acrylate; or the like.
Examples of the fluorine-containing polyol include perfluoro polyethers shown by the following formula (2).
Z-CF2- KOCF2CF2)P-(OCF2)J-O-CF2-Z (2)
wherein Z individually represents -CH2(OCH2CH2)nOH (n represents an integer from 0 to 10, and preferably from 1 to 7), p represents an integer from 1 to 40, and q represents an integer from 1 to 70. The molecular weight of the perfluoro polyether (2) is preferably 1000 to 5000, and particularly preferably 1000 to 3000.
A commercially available product such as Fluorolink E (manufactured by Solvay Solexis) may be used. Examples of the diisocyanate include 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5- naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate),
2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanatoethyl)fumarate, 6-isopropyl-l,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, and the like.
Among these, the aliphatic diisocyanates are preferable. In particular, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate), and the like are preferable.
Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, 2-hydroxyalkyl(meth)acryloyl phosphate, 4-hydroxycyclohexyl (meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylates shown by the following formulas (3) and (4), and the like. CH2=C(R2)-COOCH2CH2-(OCOCH2CH2CH2CH2CH2)m-OH (3)
CH2=C(R2)-COOCH2CH(OH)CH2-O-(C6H5) (4)
wherein R2 represents a hydrogen atom or a methyl group, and m represents an integer from 1 to 15.
A compound obtained by subjecting (meth)acrylic acid and a glycidyl group-containing compound (e.g., alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth)acrylate) to an addition reaction may also be used. Among these hydroxyl group-containing (meth)acrylates, 2 -hydroxy ethyl
(meth)acrylate, 2-hydroxypropyl (meth)acrylate, and the like are preferable.
The proportion of the polyol, the diisocyanate, and the hydroxyl group-containing (meth)acrylate is determined so that isocyanate groups contained in the diisocyanate and hydroxyl groups contained in the hydroxyl group-containing (meth)acrylate are respectively 1 to 3 equivalents and 0.2 to 1.5 equivalents for one equivalent of hydroxyl groups contained in the polyol. It is preferable that the equivalent of hydroxyl groups contained in the polyol and the hydroxyl group-containing (meth)acrylate be almost equal to the equivalent of isocyanate groups contained in the diisocyanate. When reacting these compounds, it is preferable to use a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, titanium tetraalkoxide, zirconium tetraalkoxide, or zirconium acetylacetonate in an amount of 0.01 to 1 part by mass based on 100 parts by mass of the reactants. The reaction temperature is preferably 10 to 90 0C, and particularly preferably 30 to 80 0C.
The component (A) is normally incorporated in the composition in an amount of 30 to 70 mass%, preferably 40 to 70 mass%, and particularly preferably 50 to 65 mass% based on the total amount of the composition. If the amount of the component (A) is less than 30 mass%, applicability may be impaired due to a decrease in viscosity. If the amount of the component (A) is more than 30 mass%, applicability may be impaired due to an increase in viscosity.
Component (B) The component (B) is a compound shown by the following formula (1).
wherein R1 represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a fluorine atom, x represents 1 or 2, and y represents an integer from 2 to 8.
The component (B) is used to reduce the refractive index of the resulting cured product. Specific examples of the component (B) include, but are not limited to, 2-perfluorooctylethyl (meth)acrylate,
2,2,3,3-tetrafluoropropyl (meth)acrylate, lH,lH,5H-octafluoropentyl (meth)acrylate, and the like. Examples of commercially available products of these compounds include Viscoat 17F, 4F, 8F (manufactured by Osaka Organic Chemical Industry Ltd.), and the like. Among these, 2-perfluorooctylethyl (meth)acrylate is preferable due to its excellent capability of dissolving the component (A) and its availability.
The component (B) is normally incorporated in the composition in an amount of 20 to 60 mass%, preferably 20 to 50 mass%, and particularly preferably 20 to 45 mass% based on the total amount of the composition. If the amount of the component (B) is less than 20 mass%, the refractive index of the resulting cured product may increase. If the amount of the component (B) is more than 60 mass%, applicability may be impaired due to an increase in viscosity of the composition. Component (C)
The component (C) (i.e., (meth)acrylic acid) is normally used in an amount of 3 to 10 mass%, preferably 3 to 7 mass%, and particularly preferably 3 to 5 mass% based on the total amount of the composition. If the amount of the component (C) is within this range, an increase in refractive index occurs to only a small extent.
Component (D)
The component (D) (i.e., silane coupling agent) is not particularly limited. For example, vinyltrichloro silane, vinyltriethoxysilane, vinyltr is (β - methoxyethoxy) silane , β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldietoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane,
N-(β-aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, bis-l,2-(trimethoxysilyl)ethane, or the like may be used as the component (D). It is also possible to use bis-[3-(triethoxysilyl)propyl]tetrasulfide, bis- [3- (triethoxysilyl)propyl] disulfide, γ-trimethoxysilylpropyldimethylthiocarbamyl tetrasulfide, γ-trimethoxysilylpropylbenzothiazyl tetrasulfide, or the like. Examples of commercially available products of these compounds include SH6062, SZ6030 (manufactured by Dow Corning Toray Silicone Co., Ltd.), KBE 903, 603, 403 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Among these, γ-glycidoxypropyltrimetoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane are preferable. These silane coupling agents may be used either individually or in combination. The component (D) is normally incorporated in the composition in an amount of 0.5 to 1 mass% based on the total amount of the composition. If the amount of the component (D) is within this range, an increase in refractive index occurs to only a small extent.
The radiation-curable resin composition of the present invention may further include (E) a monofunctional acrylic monomer in order to increase the viscosity of the composition. Examples of the monofunctional acrylic monomer include diacetoneacrylamide and the like. The component (E) is normally incorporated in the composition in an amount of 5 to 20 mass%, preferably 5 to 15 mass%, and particularly preferably 5 to 10 mass% based on the total amount of the composition. If the amount of the component (E) is within this range, an increase in refractive index occurs to only a small extent. When the composition is cured by applying light such as UV rays, it is preferable to incorporate (F) a photoinitiator in the composition.
Examples of the photoinitiator (F) include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl methyl ketal,
1 - (4-isopropylphenyl) - 2-hydroxy- 2- methylpropan- 1 - one, 2-hydroxy-2-methyl-l-phenylpropan-l-one, thioxanethone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone,
2 - methyl- 1 - [4- (methylthio)phenyl] - 2- morpholino-pr opan- 1 - one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; Irgacure 184, 369, 651, 500, 907, CGI1700, CGI1750, CGI1850, CG24-61, Darocure 1116, 1173 (all manufactured by Ciba Specialty Chemicals Co.); Lucirin TPO (manufactured by BASF); Ubecryl P36 (manufactured by UCB); and the like.
A photosensitizer may be used in combination with the photoinitiator (F). Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanoleamine, ethanolamine,
4-dimethylaminobenzoic acid, 4-methyl dimethylaminobenzoate, 4-ethyl dimethylaminobenzoate, 4-isoamyl dimethylaminobenzoate; Ubecryl P102, 103, 104, 105 (all manufactured by UCB); and the like. When curing the curable liquid resin composition of the present invention by applying heat and UV rays, a heat polymerization initiator may be used in combination with the photoinitiator.
The initiator (F) is incorporated in the composition of the present invention in an amount of 0.1 to 10 mass%, and particularly preferably 0.3 to 7 mass%. Various additives such as an antioxidant, a coloring agent, a UV absorber, a light stabilizer, a silane coupling agent, a heat polymerization inhibitor, a leveling agent, a surfactant, a preservative, a plasticizer, a lubricant, a solvent, a filler, an aging preventive, a wettability improver, and a coating surface improver may optionally be added to the composition of the present invention insofar as the characteristics of the present invention are not adversely affected.
The viscosity (25 0C) of the composition of the present invention is preferably 0.8 to 5 Pa-s, and particularly preferably 2 to 3 Pa-s.
The curable liquid resin composition of the present invention is normally cured by applying radiation. Note that heat may be applied in combination with radiation. The term "radiation" used herein refers to infrared rays, visible rays, UV rays, X-rays, electron beams, α-rays, β-rays, γ-rays, and the like.
The curable liquid resin composition of the present invention preferably has a Young's modulus of 200 to 500 MPa. Since the composition of the present invention has a low refractive index, high transparency, and high adhesion to a core layer, the composition of the present invention is suitably used to form an optical fiber cladding layer.
Examples
The present invention is further described below by way of examples, which should not be construed as limiting the present invention.
Preparation Example 1 (synthesis of fluorine-containing urethane (meth)acrylate)
A reaction vessel equipped with a stirrer was charged with 57.39 g of isophorone diisocyanate, 0.092 g of 2,6-di-t-butyl-p-cresol, 0.307 g of dibutyltin dilaurate, and 295.88 g of perfluoro polyether having a molecular weight of 2000. The mixture was allowed to react at 40 0C or less for two hours with stirring. After the dropwise addition of 29.98 g of hydroxyethyl acrylate, the mixture was stirred at 60 to 70 0C for three hours. The reaction was determined to be completed when the residual isocyanate content became 0.1 mass% or less.
Example 1 and Comparative Examples 1 to 3
A reaction vessel equipped with a stirrer was charged with each component shown in Table 1. The mixture was stirred for one hour while controlling the liquid temperature at 50 0C to obtain a curable liquid resin composition.
Test Example 1
The curable liquid resin compositions obtained in the example and comparative examples were cured by the following method to prepare samples. The samples were evaluated as follows. The results are shown in Table 1. 1. Young's modulus
The curable liquid resin composition was applied to a glass plate using an applicator bar with a gap size of 250 μm, and was cured by applying UV rays at a dose of 1 J/cm2 in a nitrogen atmosphere to obtain a Young's modulus measurement film. The film was cut into a strip-shaped sample having a width of 6 mm and a length of 25 mm (portion to be pulled). The sample was subjected to a tensile test at a temperature of 23 0C and a humidity of 50%. The Young's modulus of the sample was calculated from the tensile strength at a strain of 2.5% and a tensile rate of 1 mm/min.
2. Adhesion
The adhesion of the cured products of the compositions obtained in the example and comparative examples was measured. Specifically, the curable liquid resin composition was applied to a slide using an applicator with a gap size of 381 μm. UV rays were applied to the composition at a dose of 0.1 J/cm2 in a nitrogen atmosphere to obtain a cured film having a thickness of about 200 μm. The cured film formed on the slide was allowed to stand at a temperature of 23 0C and a relative humidity of 50% for 24 hours. A strip-shaped sample (width of a portion to be pulled: 10 mm) was prepared from the cured film. The sample was subjected to an adhesion test using a tensile tester in accordance with JIS Z0237. The adhesion of the sample was calculated from the tensile strength at a tensile rate of 50 mm/min.
3. Refractive index
The curable liquid resin composition was applied to a glass plate to a thickness of 200 μm using an applicator bar. UV rays were applied to the composition at a dose of 1.0 J/cm2 in a nitrogen atmosphere to obtain a sample. The refractive index (25 0C) of the sample was measured using an Abbe refractometer (manufactured by Atago Co., Ltd.) in accordance with JIS K7105.
5. Transparency (haze) The total light transmittance of the cured film was measured in accordance with JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.).
[Table 1]
Viscoat 17F: 2-perfluorooctylethyl (meth)acrylate (manufactured by Osaka Organic Chemical Industry, Ltd.)
Lucirin TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF) GA-80: 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]- l,l-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane ("Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.)
As shown in Table 1, the cured product of the curable liquid resin composition of Example 1 had an appropriate Young's modulus, refractive index, transparency (haze), and adhesion to glass. On the other hand, the cured products of the comparative examples in which the component (C) and/or the component (D) was not used exhibited insufficient adhesion to glass.
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to,") unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non- claimed element as essential to the practice of the invention.
Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above- described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

Claims

Claims
1. A radiation-curable resin composition comprising:
(A) a fluorine-containing urethane (meth)acrylate;
(B) a compound shown by the following formula (1),
wherein R1 represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a fluorine atom, x represents 1 or 2, and y represents an integer from 2 to 8; (C) (meth)acrylic acid; and
(D) a silane coupling agent.
2. The radiation-curable resin composition according to claim 1, wherein the component (A) is obtained by reacting a fluorine-containing polyol, a diisocyanate, and a hydroxyl group-containing (meth)acrylate.
3. The radiation-curable resin composition according to claim 1 or 2, the radiation-curable resin composition further comprising (E) a monofunctional acrylic monomer.
4. The radiation-curable resin composition according to any one of claims 1 to 3, the radiation-curable resin composition being used to form an optical fiber cladding layer.
5. A cured film comprising a cured product of the radiation-curable resin composition according to any of claims 1 to 4.
6. A polymer-clad optical fiber comprising a core layer formed of glass, quartz, or a transparent resin, and a cladding layer formed of the cured film according to claim 5, the cladding layer being in contact with the outer side of the core layer.
EP08855289A 2007-11-30 2008-11-28 Radiation curable cladding layer for polymer-clad optical fiber Withdrawn EP2222610A1 (en)

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WO2012144005A1 (en) * 2011-04-18 2012-10-26 住友電気工業株式会社 Plastic-clad optical fiber core and optical fiber cable
JP2011154107A (en) 2010-01-26 2011-08-11 Sumitomo Electric Ind Ltd Plastic-cladding optical fiber
JP2012018258A (en) * 2010-07-07 2012-01-26 Furukawa Electric Co Ltd:The Optical fiber core wire
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WO2015125400A1 (en) 2014-02-19 2015-08-27 関西ペイント株式会社 Copolymer resin and coating composition
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