WO2023054140A1 - Procédé de production de fibre optique en plastique et appareil de production de fibre optique en plastique - Google Patents

Procédé de production de fibre optique en plastique et appareil de production de fibre optique en plastique Download PDF

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Publication number
WO2023054140A1
WO2023054140A1 PCT/JP2022/035273 JP2022035273W WO2023054140A1 WO 2023054140 A1 WO2023054140 A1 WO 2023054140A1 JP 2022035273 W JP2022035273 W JP 2022035273W WO 2023054140 A1 WO2023054140 A1 WO 2023054140A1
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raw material
manufacturing
melt extrusion
material resin
less
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PCT/JP2022/035273
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English (en)
Japanese (ja)
Inventor
匠 入江
竜弥 荒木
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日東電工株式会社
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Priority to CN202280045876.0A priority Critical patent/CN117615892A/zh
Priority to JP2023551396A priority patent/JPWO2023054140A1/ja
Publication of WO2023054140A1 publication Critical patent/WO2023054140A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/08—Conditioning or physical treatment of the material to be shaped by using wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating

Definitions

  • the present invention relates to a method and apparatus for manufacturing plastic optical fibers.
  • a type of optical fiber is a plastic optical fiber.
  • Plastic optical fibers are superior in flexibility and workability to optical fibers made of quartz glass, and can be manufactured at low cost. Plastic optical fibers are primarily used for short-distance (eg, 100 m or less) transmission media.
  • a plastic optical fiber is composed of multiple layers including a core and a cladding.
  • the core is the layer in the center of the optical fiber that transmits light.
  • the cladding is a layer that covers the core and is positioned outwardly of the core with respect to the central axis of the optical fiber.
  • the core has a relatively high refractive index and the cladding has a relatively low refractive index.
  • a coating layer may be arranged to cover the outer circumference of the clad.
  • a plastic optical fiber can be manufactured, for example, by a melt spinning method.
  • a raw material resin is melt-extruded to form each layer constituting the optical fiber.
  • Japanese Patent Laid-Open No. 2002-200000 discloses a melt extrusion device having an extrusion screw and a method of manufacturing a plastic optical fiber using the device.
  • Patent Literature 2 discloses a melt extrusion device using gas pressure and a method for manufacturing a plastic optical fiber using the device.
  • An object of the present invention is to provide a technique that enables further improvement in the quality of plastic optical fibers.
  • the water contained in the raw resin supplied to the melt extrusion mechanism causes hydrolysis of the raw resin and a decrease in melt viscosity, and the amount of water in the raw resin
  • the present invention A method of manufacturing a plastic optical fiber composed of multiple layers including a core and a cladding, comprising: Forming at least one layer selected from the plurality of layers by melt extrusion molding using a melt extrusion mechanism, A production method (first production method), wherein the water content of the raw material resin of the at least one layer is controlled to 400 ppm (by mass) or less at the time of supply to the melt extrusion mechanism; I will provide a.
  • the present invention provides A method of manufacturing a plastic optical fiber composed of multiple layers including a core and a cladding, comprising: Forming at least one layer selected from the plurality of layers by melt extrusion molding using a melt extrusion mechanism, The raw material resin of the at least one layer is accommodated in the raw material supply unit with a water content of 400 ppm (based on mass), and then supplied from the raw material supply unit to the melt extrusion mechanism, A manufacturing method (second manufacturing method) in which a gas having an absolute humidity of 0.03 g/m 3 or less is continuously or intermittently supplied to the interior of the raw material supply unit; I will provide a.
  • the present invention provides An apparatus for manufacturing a plastic optical fiber composed of multiple layers including a core and a clad, a melt extrusion mechanism for forming at least one layer selected from the plurality of layers by melt extrusion; a raw material supply unit that accommodates the raw material resin of the at least one layer and supplies the accommodated raw material resin to the melt extrusion mechanism; a moisture content control mechanism that maintains the atmosphere inside the raw material supply unit at an absolute humidity of 0.95 g/m 3 or less; manufacturing equipment, I will provide a.
  • the water content of the raw material resin supplied to the melt extrusion mechanism is controlled, thereby suppressing hydrolysis of the raw material resin and reduction in melt viscosity during melt extrusion molding. Therefore, according to the present invention, it is possible to further improve the quality of plastic optical fibers.
  • FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus capable of implementing the manufacturing method of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing an example of a plastic optical fiber manufactured by the manufacturing method of the present invention and/or the manufacturing apparatus of the present invention.
  • FIG. 3 is a graph showing the relationship between the nitrogen purge of the raw material supply section and the water content of the raw material resin accommodated in the raw material supply section, evaluated in the examples.
  • the manufacturing method according to the first aspect of the present invention comprises: A method of manufacturing a plastic optical fiber composed of multiple layers including a core and a cladding, comprising: Forming at least one layer selected from the plurality of layers by melt extrusion molding using a melt extrusion mechanism, The water content of the raw material resin of the at least one layer is controlled to 400 ppm (by mass) or less at the point of supply to the melt extrusion mechanism.
  • the raw material resin is accommodated, and the absolute humidity of the internal atmosphere is maintained at 0.95 g/m 3 or less.
  • the material is supplied to the melt extrusion mechanism from the raw material supply unit.
  • a gas having an absolute humidity of 0.03 g/m 3 or less is continuously or intermittently supplied to the interior of the raw material supply section.
  • a manufacturing method includes: A method of manufacturing a plastic optical fiber composed of multiple layers including a core and a cladding, comprising: Forming at least one layer selected from the plurality of layers by melt extrusion molding using a melt extrusion mechanism, The raw material resin of the at least one layer is accommodated in the raw material supply unit in a state where the water content is 400 ppm (based on mass) or less, and then supplied from the raw material supply unit to the melt extrusion mechanism, A gas having an absolute humidity of 0.03 g/m 3 or less is continuously or intermittently supplied to the inside of the raw material supply section.
  • the gas is an inert gas.
  • the gas is nitrogen.
  • the at least one layer is at least one layer selected from the core and the clad.
  • the raw material resin has hydrolyzability.
  • the raw material resin is polycarbonate.
  • the raw material resin supplied to the melt extrusion mechanism has a pellet shape, and the pellets has an average volume of 10.0 mm 3 or more.
  • the raw material resin supplied to the melt extrusion mechanism has a pellet shape, and the pellets is dried until the post-drying moisture content becomes 400 ppm (mass basis) or less, and then supplied to the melt extrusion mechanism.
  • the molding temperature of the raw material resin in the melt extrusion molding is the glass transition temperature (Tg ) +100° C. or higher.
  • the manufacturing apparatus includes An apparatus for manufacturing a plastic optical fiber composed of multiple layers including a core and a clad, a melt extrusion mechanism for forming at least one layer selected from the plurality of layers by melt extrusion; a raw material supply unit that accommodates the raw material resin of the at least one layer and supplies the accommodated raw material resin to the melt extrusion mechanism; a moisture content control mechanism that maintains the atmosphere inside the raw material supply unit at an absolute humidity of 0.95 g/m 3 or less; Prepare.
  • the moisture content control mechanism continuously or intermittently introduces gas having an absolute humidity of 0.03 g/m 3 or less into the raw material supply unit. Equipped with a gas supply mechanism for supplying to.
  • the gas is an inert gas.
  • the gas is nitrogen.
  • the at least one layer is at least one layer selected from the core and the clad.
  • the raw material resin has hydrolyzability.
  • the raw material resin is polycarbonate.
  • a first manufacturing method will be described with reference to the manufacturing apparatus of FIG.
  • a manufacturing apparatus 10 shown in FIG. 1 is a manufacturing apparatus for plastic optical fibers (hereinafter referred to as "POF").
  • the manufacturing apparatus 10 includes a plurality of melt extrusion mechanisms 1 (1a and 1b).
  • the melt extrusion mechanism 1 (each melt extrusion mechanism 1 a, 1 b) comprises an extrusion screw 11 and a gear pump 12 .
  • the extrusion screw 11 provided in the melt extrusion mechanism 1 of FIG. 1 is a single shaft.
  • the melt extrusion mechanism 1 of FIG. 1 comprises a screw cylinder 19 in which an extrusion screw 11 is accommodated.
  • the extrusion screw 11 and screw cylinder 19 constitute a single screw extruder 4 .
  • a hopper (raw material tank) as the raw material supply unit 2 is connected to the inlet 14 of the melt extrusion mechanism 1 .
  • a raw material resin 3 is accommodated inside a hopper connected to the melt extrusion mechanism 1 .
  • the contained raw material resin 3 usually has a pellet shape.
  • the raw material resin 3 is supplied from a hopper to the melt extruding mechanism 1 and heated to be softened or melted so that it can flow.
  • the raw material resin 3 in a fluid state passes through the gear pump 12 and is discharged from the discharge port 15 of the melt extrusion mechanism 1, and is melt-extruded into a predetermined layer constituting the POF.
  • the melt extrusion mechanism 1 utilizes mechanical pressure from an extrusion screw 11 . In the melt extrusion mechanism 1, kneading of the raw material resin 3 by the extrusion screw 11 may be performed.
  • the gear pump 12 is normally used for controlling the discharge amount of the raw material resin 3 .
  • Reference numeral 16 denotes a cooling block, which is arranged on the outer wall of the screw cylinder 19 in the vicinity of the inlet 14 and the connecting portion with the raw material supply section 2 in the melt extrusion mechanism 1 .
  • the cooling block 16 prevents the heat for making the raw material resin 3 flowable from being transferred to the raw material supply section 2 .
  • Reference numeral 17 is a band heater.
  • the band heater 17 is arranged on the outer wall of the screw cylinder 19 or the like on the downstream side of the connecting portion and the inlet 14 .
  • Reference numeral 18 is a screw head pressure gauge, which can be used to measure the discharge pressure of the raw material resin 3 .
  • Reference numeral 20 denotes a breaker plate, which prevents the raw material resin 3 in a solid state from being erroneously discharged.
  • Reference numeral 21 denotes a pipe through which the raw material resin 3 discharged from the discharge port 15 passes. A gear pump 12 is arranged along the path of the pipe 21 . The pipe 21 is provided inside and downstream of the block 23 .
  • Reference numeral 25 denotes a pipe for introducing gas 26 into the raw material supply section 2 .
  • the manufacturing apparatus 10 in FIG. 1 can manufacture the POF 101 composed of two layers, the core 102 and the clad 103 (see FIG. 2).
  • POF 101 is typically of the gradient index (GI) type.
  • the POF 101 is not limited to the GI type.
  • a core 102 and a clad 103 are formed by melt extrusion molding using the respective melt extrusion mechanisms 1a and 1b.
  • the clad 103 is formed by molding the raw material resin 3 discharged from the melt extrusion mechanism 1b in the first chamber 40 so as to cover the outer periphery of the core 102 .
  • the clad 103 is formed while the core 102 formed by melt extrusion molding using the melt extrusion mechanism 1 a passes through the first chamber 40 .
  • At least one layer selected from a plurality of layers constituting the POF 101 is formed by melt extrusion molding using a melt extrusion mechanism, and the moisture content of the raw material resin of the at least one layer is , and controlled to 400 ppm (based on mass; "ppm” shown below is based on mass) at the time of supply to the melt extrusion mechanism.
  • ppm based on mass
  • Hydrolysis causes the layers constituting the POF 101 to fluctuate or deteriorate in optical properties and, in some cases, to foam.
  • a decrease in melt viscosity causes variation or deterioration in optical properties of the layers constituting the POF 101 . Therefore, it is possible to further improve the quality of the POF 101 by controlling the amount of water in the raw material resin.
  • the moisture content to be controlled may be 350 ppm or less, 300 ppm or less, or even 250 ppm or less.
  • the lower limit of the water content to be controlled is not limited, it may be, for example, 50 ppm or more in consideration of industrial production costs and the like.
  • the control of the water content should be performed for at least one layer selected from the multiple layers that make up the POF 101 .
  • At least one layer is, for example, at least one layer selected from core 102 and clad 103 .
  • the moisture content can be controlled for at least one layer selected from the core 102 and the clad 103 .
  • the melt extrusion mechanism 1 in FIG. 1 is a mechanism that uses mechanical pressure from an extrusion screw 11. It is possible to control the water content as described above for mechanisms other than the melt-extrusion mechanism using mechanical pressure, for example, the melt-extrusion mechanism using gas pressure. However, in the production of POF 101, which usually has a very small wire diameter and therefore the extrusion rate of the raw material resin per unit time is negligible, the raw material is generally non-sealed and in communication with the external environment. It is preferable to apply the control of the water content to the melt extrusion molding using the melt extrusion mechanism 1 in which the raw material resin 3 can be accommodated in the supply unit 2 for a long period of time.
  • the water content of the raw resin can be evaluated using a chemical reaction moisture meter (for example, Brabender's Aquatrack series). This moisture meter heats the raw resin, reacts the moisture released from the raw resin by heating with a measurement reagent (calcium hydride), and detects the amount of carbon dioxide generated by the reaction. Moisture content can be evaluated.
  • the sample is, for example, started at room temperature and heated to 160°C.
  • the time of supply to the melt-extrusion mechanism 1 typically means the time of supply to the melt-extrusion mechanism 1 from the raw material supply section 2 connected to the melt-extrusion mechanism 1 . In the example of FIG. 1, it is the point of passage through the inlet 14 of the melt extrusion mechanism 1 .
  • the raw material resin 3 is fed from the raw material supply unit 2 in which the raw material resin 3 is accommodated and the internal absolute humidity is maintained at 0.95 g/m 3 or less, and then through the melt extrusion mechanism 1. may be supplied to
  • the absolute humidity maintained may be 0.60 g/m 3 or less, or even 0.50 g/m 3 or less.
  • the lower limit of the retained absolute humidity is not limited, it may be, for example, 0.04 g/m 2 or more in consideration of industrial manufacturing costs.
  • the raw material supply unit 2 may contain the raw material resin 3 which already has a water content of 400 ppm or less (or the water content range is smaller), in which case the water content can be more reliably controlled.
  • a gas having an absolute humidity of 0.03 g/m 3 or less may be continuously or intermittently supplied to the inside of the raw material supply unit 2.
  • the interior of the raw material supply section 2 may be continuously or intermittently purged (replaced) with a gas having a humidity of 0.03 g/m 3 or less.
  • Continuous means performing continuously for a predetermined period of time, and "intermittently” means performing for a predetermined period of time with interruptions in between.
  • the gas can be supplied to the raw material supply section 2 from a gas supply mechanism such as a nozzle arranged inside the raw material supply section 2, for example.
  • the pipe 25 may be used for gas supply.
  • the absolute humidity of the gas may be 0.02 g/m 3 or less.
  • the lower limit of the absolute humidity of the gas is not limited, it may be, for example, 0.01 g/m 3 or more in consideration of industrial production costs and the like. Absolute humidity can be evaluated with a hygrometer.
  • the gas may contain or be nitrogen.
  • the gas may be an inert gas. Examples of inert gases are nitrogen, carbon dioxide, helium and argon.
  • the gas may be substantially free of oxygen. In the present specification, substantially free of oxygen means that the oxygen content is 0.20% by volume or less, preferably 0.10% by volume or less, more preferably 0.05% by volume or less. do.
  • a dehumidifying member may be arranged inside the raw material supply section 2 in order to maintain the absolute humidity inside the raw material supply section 2 .
  • the dehumidifying member includes, for example, a hygroscopic material.
  • the gas supply mechanism and the dehumidification member may be a moisture content control mechanism that maintains the atmosphere inside the raw material supply section 2 at an absolute humidity of 0.95 g/m 3 or less (furthermore, the range described above).
  • the moisture content control mechanism is not limited to the above example.
  • the melt extrusion mechanism 1 in FIG. 1 includes a single screw extruder 4.
  • the melt extrusion mechanism 1 may comprise a multi-screw extruder with two or more extrusion screws 11 .
  • the melt extrusion mechanism 1 is not limited to the above example.
  • the melt extrusion mechanism 1 may not use gas pressure for melt extrusion.
  • An example of the raw material supply unit 2 is a hopper.
  • the raw material supply unit 2 is not limited to the above example.
  • the raw material resin 3 supplied to the melt extrusion mechanism 1 may have the shape of pellets and the average volume of the pellets may be 10.0 mm 3 or more. In this case, absorption of water by the raw material resin 3 in the raw material supply unit 2 can be suppressed.
  • the average volume may be 11.0 mm 3 or more.
  • the upper limit of the average volume is, for example, 20.0 mm 3 or less.
  • the average volume of the pellets (mm 3 ) is, for example, the weight of at least 50 pellets is measured, and the number N (grains) and weight W (g) of the measured pellets, and the specific gravity SG (g/cm 3 ), it can be obtained from the formula: ⁇ W(g)/SG(g/cm 3 ) ⁇ /N ⁇ 1000. From the viewpoint of minimizing the error, it is preferable to use an electronic balance capable of measuring 1/10000 g for the measurement of the weight W.
  • the raw material resin 3 (typically in the form of pellets) may be supplied to the melt extrusion mechanism 1 after being dried until the water content after drying is 400 ppm or less.
  • the destination of supply of the dried raw material resin 3 may be the raw material supply unit 2 .
  • the moisture content after drying may be 350 ppm or less, and the lower limit of the moisture content after drying is, for example, 10 ppm or more.
  • the moisture content after drying can be evaluated in the same manner as the moisture content of the raw material resin using a chemical reaction type moisture meter.
  • a POF having a multilayer structure of three or more layers may be manufactured by the first manufacturing method.
  • An example of a POF having a multi-layer structure of three or more layers includes a core, a clad, and a coating layer covering the clad arranged outside the clad with respect to the central axis of the POF.
  • the at least one layer that controls the water content of the raw material resin may be a coating layer.
  • the covering layer is also referred to by those skilled in the art as an overcladding.
  • a hydrolyzable resin such as polycarbonate is often used as a raw material resin.
  • the molding temperature of the raw material resin in melt extrusion molding in the melt extrusion mechanism 1 may be the glass transition temperature (Tg) of the raw material resin + 100°C or higher, or may be Tg + 130°C or higher.
  • the upper limit of the molding temperature is, for example, Tg+180° C. or less. In this case, the volatile components contained in the raw material resin can be more reliably removed during molding, thereby further improving the quality of the POF 101 .
  • the manufacturing apparatus that can implement the first manufacturing method is not limited to the example in FIG.
  • At least one layer selected from a plurality of layers constituting the POF 101 is formed by melt extrusion molding using the melt extrusion mechanism 1, and the raw material resin of the at least one layer contains water.
  • the raw material supply section 2 After being accommodated in the raw material supply section 2 in a state where the amount is 400 ppm or less, it is supplied from the raw material supply section 2 to the melt extrusion mechanism 1 .
  • a gas having an absolute humidity of 0.03 g/m 3 or less is continuously or intermittently supplied to the interior of the raw material supply unit 2 .
  • the moisture content of the raw material resin is already 400 ppm or less at the time it is accommodated in the raw material supply unit 2, and is maintained at 400 ppm or below while being accommodated in the raw material supply unit 2 by the gas supply. This suppresses hydrolysis of the raw material resin and a decrease in melt viscosity in melt extrusion molding.
  • the water content of the raw material resin accommodated in the raw material supply unit 2 may be 350 ppm or less, 300 ppm or less, or even 250 ppm or less.
  • the lower limit of the water content is not limited, it may be, for example, 50 ppm or more in consideration of industrial production costs and the like.
  • the gas supply and type are the same as in the first manufacturing method.
  • the absolute humidity of the supplied gas can take the range described above in the description of the first manufacturing method.
  • the melt extrusion mechanism in the second manufacturing method is usually the melt extrusion mechanism 1 using mechanical pressure.
  • the control of the water content of the raw material resin may be performed for at least one layer selected from a plurality of layers forming the POF 101 .
  • the at least one layer that controls the water content of the raw material resin is, for example, at least one layer selected from the core 102 and the clad 103, and may be a coating layer.
  • the manufacturing apparatus that can implement the second manufacturing method is not limited to the example in FIG.
  • the present invention provides a method for manufacturing a plastic optical fiber composed of a plurality of layers including a core and a clad, wherein at least one layer selected from the plurality of layers is melted.
  • a manufacturing method ( A third manufacturing method) is provided.
  • the third production method also suppresses hydrolysis of the raw material resin and reduction in melt viscosity in melt extrusion molding.
  • the water content of the raw material resin discharged from the melt extrusion mechanism may be 350 ppm or less, 300 ppm or less, or even 250 ppm or less.
  • the lower limit of the water content is not limited, it may be, for example, 50 ppm or more in consideration of industrial production costs and the like.
  • the time of discharge is, for example, the time of inflow into the first chamber 40 .
  • the water content of the raw material resin in the gear pump 12 may be evaluated. Since the path of the raw material resin from the gear pump 12 to the first chamber 40 is normally closed, it is considered that the water content of the raw material resin does not change substantially along the path.
  • the third manufacturing method can be implemented, for example, by controlling the amount of water in the resin raw material as described above in the description of the first manufacturing method and/or the second manufacturing method.
  • descriptions of matters common to the first manufacturing method and/or the second manufacturing method will be omitted.
  • the third manufacturing method can be implemented, for example, by the manufacturing apparatus shown in FIG.
  • the manufacturing apparatus capable of implementing the third manufacturing method is not limited to the example of FIG.
  • Raw material resins for the core 102 and the clad 103 are, for example, fluorine-containing resins, acrylic resins such as methyl methacrylate, styrene resins, and carbonate resins.
  • the refractive index of the material resin forming the clad 103 is generally lower than the refractive index of the material resin forming the core 102 .
  • Raw material resins for the coating layer are, for example, polycarbonate, various engineering plastics, cycloolefin polymers, polytetrafluoroethylene (PTFE), modified PTFE, and perfluoroalkoxyalkane (PFA).
  • the raw material resin may contain an additive such as a refractive index adjuster.
  • the raw material resin is not limited to the above examples.
  • a known resin that can form each layer of the POF may be selected as the raw material resin.
  • the raw material resin may be hydrolyzable.
  • the hydrolyzable resin may have at least one selected from an ester structure, carbonate structure, urethane structure, amide structure, ether structure and acetal structure.
  • the hydrolyzable resin is, for example, polycarbonate.
  • the fluorine-containing resin (polymer (P)) is shown below.
  • Polymers (P) shown below are suitable for use in core 102 .
  • the polymer (P) preferably contains substantially no hydrogen atoms from the viewpoint of suppressing light absorption due to stretching energy of C—H bonds, and all hydrogen atoms bonded to carbon atoms are fluorine atoms. Substitution is particularly preferred.
  • that the polymer (P) does not substantially contain hydrogen atoms means that the content of hydrogen atoms in the polymer (P) is 1 mol % or less.
  • the polymer (P) preferably has a fluorine-containing alicyclic structure.
  • the fluorine-containing alicyclic structure may be contained in the main chain of the polymer (P) or may be contained in the side chain of the polymer (P).
  • the polymer (P) has, for example, a structural unit (A) represented by the following formula (1).
  • R ff 1 to R ff 4 each independently represent a fluorine atom, a C 1-7 perfluoroalkyl group, or a C 1-7 perfluoroalkyl ether group.
  • R ff1 and R ff2 may combine to form a ring .
  • Perfluoro means that all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms.
  • the number of carbon atoms in the perfluoroalkyl group is preferably 1-5, more preferably 1-3, and even more preferably 1.
  • a perfluoroalkyl group may be linear or branched.
  • the perfluoroalkyl group includes trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group and the like.
  • the perfluoroalkyl ether group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.
  • a perfluoroalkyl ether group may be linear or branched.
  • a perfluoromethoxymethyl group etc. are mentioned as a perfluoroalkyl ether group.
  • the ring may be a 5-membered ring or a 6-membered ring.
  • This ring includes a perfluorotetrahydrofuran ring, a perfluorocyclopentane ring, a perfluorocyclohexane ring, and the like.
  • structural unit (A) include structural units represented by the following formulas (A1) to (A8).
  • the structural unit (A) is preferably a structural unit (A2), that is, a structural unit represented by the following formula (2).
  • the polymer (P) may contain one or more of the structural units (A).
  • the content of the structural unit (A) is preferably 20 mol% or more, more preferably 40 mol% or more, based on the total of all structural units. By containing 20 mol % or more of the structural unit (A), the polymer (P) tends to have higher heat resistance. When the structural unit (A) is contained in an amount of 40 mol % or more, the polymer (P) tends to have high heat resistance as well as higher transparency and higher mechanical strength.
  • the content of the structural unit (A) is preferably 95 mol% or less, more preferably 70 mol% or less, based on the total of all structural units.
  • the structural unit (A) is derived from, for example, a compound represented by the following formula (3).
  • R ff 1 to R ff 4 are the same as in formula (1).
  • the compound represented by formula (3) can be obtained by a known production method including, for example, the production method disclosed in Japanese Patent Publication No. 2007-504125.
  • Specific examples of the compound represented by the formula (3) include compounds represented by the following formulas (M1) to (M8).
  • the polymer (P) may further contain other structural units in addition to the structural unit (A).
  • Other structural units include the following structural units (B) to (D).
  • the structural unit (B) is represented by the following formula (4).
  • R 1 to R 3 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 7 carbon atoms.
  • R 4 represents a perfluoroalkyl group having 1 to 7 carbon atoms.
  • a perfluoroalkyl group may have a ring structure.
  • a portion of fluorine atoms may be substituted with halogen atoms other than fluorine atoms.
  • Some of the fluorine atoms in the perfluoroalkyl group may be substituted with halogen atoms other than fluorine atoms.
  • the polymer (P) may contain one or more of the structural units (B).
  • the content of the structural unit (B) is preferably 5 to 10 mol% of the total of all structural units.
  • the content of the structural unit (B) may be 9 mol% or less, or may be 8 mol% or less.
  • the structural unit (B) is derived, for example, from a compound represented by the following formula (5).
  • R 1 to R 4 are the same as in formula (4).
  • the compound represented by formula (5) is a fluorine-containing vinyl ether such as perfluorovinyl ether.
  • the structural unit (C) is represented by the following formula (6).
  • R 5 to R 8 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 7 carbon atoms.
  • a perfluoroalkyl group may have a ring structure.
  • a portion of fluorine atoms may be substituted with halogen atoms other than fluorine atoms.
  • Some of the fluorine atoms in the perfluoroalkyl group may be substituted with halogen atoms other than fluorine atoms.
  • the polymer (P) may contain one or more of the structural units (C).
  • the content of the structural unit (C) is preferably 5 to 10 mol% of the total of all structural units.
  • the content of the structural unit (C) may be 9 mol% or less, or may be 8 mol% or less.
  • the structural unit (C) is derived from, for example, a compound represented by the following formula (7).
  • R 5 to R 8 are the same as in formula (6).
  • Compounds represented by formula (7) are fluorine-containing olefins such as tetrafluoroethylene and chlorotrifluoroethylene.
  • the structural unit (D) is represented by the following formula (8).
  • Z represents an oxygen atom, a single bond or —OC(R 19 R 20 )O—
  • each of R 9 to R 20 independently represents a fluorine atom or perfluoroalkyl having 1 to 5 carbon atoms. group, or a perfluoroalkoxy group having 1 to 5 carbon atoms.
  • a portion of fluorine atoms may be substituted with halogen atoms other than fluorine atoms.
  • Some of the fluorine atoms in the perfluoroalkyl group may be substituted with halogen atoms other than fluorine atoms.
  • fluorine atoms in the perfluoroalkoxy group may be substituted with halogen atoms other than fluorine atoms.
  • s and t each independently represents an integer of 0 to 5 and s+t is 1 to 6 (provided that s+t may be 0 when Z is —OC(R 19 R 20 )O—); .
  • the structural unit (D) is preferably represented by the following formula (9).
  • the structural unit represented by the following formula (9) is the case where Z is an oxygen atom, s is 0, and t is 2 in the above formula (8).
  • R 141 , R 142 , R 151 and R 152 each independently represents a fluorine atom, a perfluoroalkyl group having 1 to 5 carbon atoms, or a perfluoroalkoxy group having 1 to 5 carbon atoms. .
  • a portion of fluorine atoms may be substituted with halogen atoms other than fluorine atoms.
  • Some of the fluorine atoms in the perfluoroalkyl group may be substituted with halogen atoms other than fluorine atoms.
  • Some of the fluorine atoms in the perfluoroalkoxy group may be substituted with halogen atoms other than fluorine atoms.
  • the polymer (P) may contain one or more of the structural units (D).
  • the content of the structural unit (D) is preferably 30 to 67 mol% of the total of all structural units.
  • the content of the structural unit (D) is, for example, 35 mol% or more, may be 60 mol% or less, or may be 55 mol% or less.
  • the structural unit (D) is derived, for example, from a compound represented by the following formula (10).
  • Z, R 9 -R 18 , s and t are the same as in formula (8).
  • the compound represented by formula (10) is a fluorine-containing compound having two or more polymerizable double bonds and capable of cyclic polymerization.
  • Structural unit (D) is preferably derived from a compound represented by the following formula (11).
  • R 141 , R 142 , R 151 and R 152 are the same as in formula (9).
  • the polymer (P) may further contain structural units other than the structural units (A) to (D), but substantially contains structural units other than the structural units (A) to (D). preferably not included. Note that the polymer (P) does not substantially contain other structural units other than the structural units (A) to (D) means that the total of all structural units in the polymer (P), the structural unit (A ) to (D) is 95 mol % or more, preferably 98 mol % or more.
  • the method of polymerizing the polymer (P) is not particularly limited, and for example, a general polymerization method such as radical polymerization can be used.
  • a polymerization initiator for polymerizing the polymer (P) may be a perfluorinated compound.
  • the glass transition temperature (Tg) of the polymer (P) is not particularly limited, and is, for example, 100° C. to 140° C., may be 105° C. or higher, or may be 120° C. or higher.
  • Tg means the midpoint glass transition temperature (T mg ) determined according to the Japanese Industrial Standards (JIS) K7121:1987.
  • the manufacturing apparatus 10 of FIG. 1 is an apparatus capable of carrying out the manufacturing method of the present invention, and is also an example of the manufacturing apparatus of the present invention.
  • the manufacturing apparatus 10 matters other than those described above in the description of the first to third manufacturing methods will be described.
  • the manufacturing apparatus 10 may include a moisture content control mechanism that maintains the atmosphere inside the raw material supply unit 2 at an absolute humidity of 0.95 g/m 3 or less.
  • the moisture content control mechanism may include a gas supply mechanism that continuously or intermittently supplies gas with an absolute humidity of 0.03 g/m 3 or less to the inside of the raw material supply unit 2. It may be a dehumidifying member arranged in.
  • the absolute humidity to be held and the absolute humidity of the supplied gas can each take the range described above in the description of the first manufacturing method.
  • a known pump can be used for the gear pump 12.
  • the manufacturing apparatus 10 may further include a control mechanism (not shown).
  • the control mechanism includes, for example, a DSP (Digital Signal Processor) including an A/D conversion circuit, an input/output circuit, an arithmetic circuit, a storage device, and the like.
  • the control mechanism may store a program for properly operating the manufacturing apparatus 10 .
  • the control mechanism may, for example, control a moisture content control mechanism.
  • the manufacturing apparatus 10 may include a hygrometer that measures the absolute humidity of the atmosphere inside the raw material supply unit 2, and the control mechanism and the hygrometer may be connected.
  • the POF 101 shown in FIG. 2 can be manufactured by the manufacturing method or manufacturing apparatus of the present invention.
  • the manufactured POF is not limited to the example of FIG.
  • melt viscosity (melt viscosity) at that temperature was evaluated with a twin capillary viscometer (RH-7 manufactured by Malvern). The shear rate during evaluation was 100 sec -1 .
  • the melt viscosity was almost constant (3200 to 3300 Pa s) for samples with a water content of 400 ppm or less, but began to decrease linearly when it exceeded 400 ppm, and was 3000 Pa s for a sample with a water content of 800 ppm and 3000 ppm for a water content.
  • the sample was 2150 Pa ⁇ s.
  • Example 2 Relationship between water content and hydrolyzability of raw material resin
  • Experimental Example 2 the relationship between the water content of the starting resin and its hydrolyzability was evaluated. 5 g of each sample prepared in Experimental Example 1 was placed in a heating bath maintained at 230° C. and heated for 2 hours. ) (% by weight relative to the weight of the sample before heating) was evaluated. The proportion was almost constant (0.1 to 0.15% by weight) for samples with a water content of 400 ppm or less, but began to increase linearly above 400 ppm, reaching 0.21 weight for samples with a water content of 800 ppm. %, and a sample with a water content of 3000 ppm was 0.42% by weight.
  • Example 3 Relationship between Nitrogen Purge and Moisture Content of Raw Resin
  • the relationship between the nitrogen purge of the raw material supply section and the water content of the raw material resin accommodated in the raw material supply section was evaluated. 1000 g of the sample prepared in Experimental Example 1 and having a water content of 200 ppm was placed in a hopper having an inner volume of 5 L. The ambient temperature was 22.1° C. and the relative humidity was 53%. Next, the change in the moisture content of the sample when the interior of the hopper was continuously purged with nitrogen at an absolute humidity of 0.8 g/m 3 and the moisture content of the sample when the sample was left standing without purging with nitrogen. We evaluated the changes in The evaluation results are shown in FIG. As shown in FIG.
  • Example 1 Polymethyl methacrylate (PMMA) pellets (manufactured by Mitsubishi Chemical, ACRYPET, the average volume of pellets evaluated by the above method is 17.8 mm 3 (however, the number of pellets N when evaluating the average volume was 50; hereinafter the same)) was dried in a dry atmosphere at 100° C. for 10 hours. After drying, the water content (water content after drying) was evaluated using a chemical reaction moisture meter (Aquatrac 3E, manufactured by Brabender) and found to be 84 ppm.
  • PMMA Polymethyl methacrylate
  • PC/PET Polycarbonate/polyethylene terephthalate copolymer resin
  • the water content of each resin at the point of supply from the hopper to the melt extruder was 92 ppm for PMMA and 85 ppm for PC/PET.
  • the water content of each resin was evaluated by the method described above using the moisture meter.
  • an optical microscope Keyence VHX-300, 200x magnification
  • no air bubbles were observed, so it was judged to be good (A).
  • B unsatisfactory
  • Example 2 A POF having a length of 100 m was produced in the same manner as in Example 1, except that the PC/PET pellets were dried for 6 hours. The moisture content of the pellets after drying was 136 ppm, and the moisture content of the pellets at the screw inlet was 139 ppm.
  • Example 3 A POF having a length of 100 m was produced in the same manner as in Example 1, except that the PC/PET pellet molding temperature was changed to 210°C. The moisture content of the pellets after drying was 40 ppm, and the moisture content of the pellets at the screw inlet was 43 ppm.
  • Example 4 A POF having a length of 100 m was produced in the same manner as in Example 1, except that the PC/PET pellet molding temperature was changed to 250°C. The moisture content of the pellets after drying was 34 ppm, and the moisture content of the pellets at the screw inlet was 40 ppm.
  • Example 5 A POF having a length of 100 m was produced in the same manner as in Example 1, except that the PMMA pellets were dried for 6 hours. The moisture content of the pellets after drying was 136 ppm, and the moisture content of the pellets at the screw inlet was 141 ppm.
  • Example 6 A POF having a length of 100 m was produced in the same manner as in Example 1 except that the PMMA pellet molding temperature was changed to 210° C., and the presence or absence of bubbles in the produced POF was checked.
  • the moisture content of the pellets after drying was 40 ppm, and the moisture content of the pellets at the screw inlet was 42 ppm.
  • Example 7 A POF having a length of 100 m was produced in the same manner as in Example 1 except that the PMMA pellet molding temperature was changed to 250° C., and the presence or absence of bubbles in the produced POF was checked.
  • the moisture content of the pellets after drying was 34 ppm, and the moisture content of the pellets at the screw inlet was 41 ppm.
  • Example 1 A POF having a length of 100 m was produced in the same manner as in Example 1, except that the drying time of the PC/PET pellets was changed to 1 hour. Air bubbles were confirmed. The moisture content of the pellets after drying was 739 ppm, and the moisture content of the pellets at the screw inlet was 750 ppm.
  • Example 2 A POF having a length of 100 m was produced in the same manner as in Example 1, except that the PC/PET pellet molding temperature was changed to 250° C. and the drying time was changed to 1 hour. Air bubbles were confirmed in the clad (PC/PET layer). The moisture content of the pellets after drying was 820 ppm, and the moisture content of the pellets at the screw inlet was 840 ppm.
  • Example 3 A POF having a length of 100 m was produced in the same manner as in Example 1, except that the PMMA pellets were dried for 1 hour. rice field. The moisture content of the pellets after drying was 739 ppm, and the moisture content of the pellets at the screw inlet was 753 ppm.
  • Example 4 A POF having a length of 100 m was produced in the same manner as in Example 1, except that the PMMA pellet molding temperature was changed to 250° C. and the drying time was changed to 1 hour. Air bubbles were confirmed in the PMMA layer). The moisture content of the pellets after drying was 820 ppm, and the moisture content of the pellets at the screw inlet was 840 ppm.
  • Example 5 A POF having a length of 100 m was produced in the same manner as in Example 1, except that nitrogen was not supplied to the inside of the hopper containing the PC/PET pellets. Air bubbles were confirmed in the clad (PC/PET layer). The moisture content of the pellets at the screw inlet was 450 ppm.
  • Comparative Example 6 A POF with a length of 100 m was produced in the same manner as in Comparative Example 5 except that PC/PET pellets with an average volume of 4.8 mm 3 (same resin composition) were used, and the presence or absence of bubbles in the produced POF was checked. Air bubbles were found in the clad (PC/PET layer). The moisture content of the pellets after drying was 85 ppm, and the moisture content of the pellets at the screw inlet was 900 ppm.
  • Comparative Example 7 A POF having a length of 100 m was produced in the same manner as in Comparative Example 5 except that PC/PET pellets with an average volume of 4.8 mm 3 (same resin composition) were used and the drying time of the pellets was set to 1 hour. When the presence or absence of air bubbles in the manufactured POF was checked, air bubbles were confirmed in the clad (PC/PET layer). The moisture content of the pellets after drying was 680 ppm, and the moisture content of the pellets at the screw inlet was 900 ppm.
  • Table 1 The evaluation results of each example and comparative example are summarized in Table 1 below.
  • the upper row corresponds to the core, and the lower row corresponds to the clad.
  • the manufacturing method and manufacturing apparatus of the present invention can be used for manufacturing plastic optical fibers.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention concerne une technologie qui permet une amélioration supplémentaire de la qualité d'une fibre optique en plastique. La technologie est un procédé de production d'une fibre optique en plastique qui est composée d'une âme et d'une pluralité de couches comprenant une gaine; ce procédé de production comprend la formation d'au moins une couche qui est sélectionnée parmi la pluralité de couches au moyen d'un moulage par extrusion à l'état fondu qui utilise un mécanisme d'extrusion à l'état fondu; et la teneur en eau d'une résine de départ de la/des couche(s) est régulée à 400 ppm ou moins (par rapport à la masse) au moment où la résine de départ est fournie au mécanisme d'extrusion à l'état fondu.
PCT/JP2022/035273 2021-09-30 2022-09-21 Procédé de production de fibre optique en plastique et appareil de production de fibre optique en plastique WO2023054140A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0592422A (ja) * 1991-10-01 1993-04-16 Teijin Chem Ltd 光学成形品用成形材料の製造方法
JP2006163031A (ja) * 2004-12-08 2006-06-22 Fuji Photo Film Co Ltd プラスチック光学部材の製造方法及び製造装置
JP2007517235A (ja) * 2003-06-13 2007-06-28 ファースト クオリティ ファイバーズ リミテッド ライアビリティ カンパニー 扁平なプラスチック光ファイバおよびこのようなファイバを用いる照明装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0592422A (ja) * 1991-10-01 1993-04-16 Teijin Chem Ltd 光学成形品用成形材料の製造方法
JP2007517235A (ja) * 2003-06-13 2007-06-28 ファースト クオリティ ファイバーズ リミテッド ライアビリティ カンパニー 扁平なプラスチック光ファイバおよびこのようなファイバを用いる照明装置
JP2006163031A (ja) * 2004-12-08 2006-06-22 Fuji Photo Film Co Ltd プラスチック光学部材の製造方法及び製造装置

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