Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
  • G02B6/02—Optical fibres with cladding with or without a coating
  • G02B6/02033—Core or cladding made from organic material, e.g. polymeric material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
  • G02B6/02—Optical fibres with cladding with or without a coating
  • G02B6/036—Optical fibres with cladding with or without a coating core or cladding comprising multiple layers
  • G02B6/03616—Optical fibres characterised both by the number of different refractive index layers around the central core segment, i.e. around the innermost high index core layer, and their relative refractive index difference
  • G02B6/03622—Optical fibres characterised both by the number of different refractive index layers around the central core segment, i.e. around the innermost high index core layer, and their relative refractive index difference having 2 layers only
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
  • G02B6/02—Optical fibres with cladding with or without a coating
  • G02B6/036—Optical fibres with cladding with or without a coating core or cladding comprising multiple layers
  • G02B6/03616—Optical fibres characterised both by the number of different refractive index layers around the central core segment, i.e. around the innermost high index core layer, and their relative refractive index difference
  • G02B6/03622—Optical fibres characterised both by the number of different refractive index layers around the central core segment, i.e. around the innermost high index core layer, and their relative refractive index difference having 2 layers only
  • G02B6/03633—Optical fibres characterised both by the number of different refractive index layers around the central core segment, i.e. around the innermost high index core layer, and their relative refractive index difference having 2 layers only arranged - -
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
  • A61B1/00—Instruments for performing medical examinations of the interior of cavities or tubes of the body by visual or photographical inspection, e.g. endoscopes; Illuminating arrangements therefor
  • A61B1/00163—Optical arrangements
  • A61B1/00165—Optical arrangements with light-conductive means, e.g. fibre optics
  • A61B1/0017—Details of single optical fibres, e.g. material or cladding
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
  • A61B1/00—Instruments for performing medical examinations of the interior of cavities or tubes of the body by visual or photographical inspection, e.g. endoscopes; Illuminating arrangements therefor
  • A61B1/06—Instruments for performing medical examinations of the interior of cavities or tubes of the body by visual or photographical inspection, e.g. endoscopes; Illuminating arrangements therefor with illuminating arrangements
  • A61B1/07—Instruments for performing medical examinations of the interior of cavities or tubes of the body by visual or photographical inspection, e.g. endoscopes; Illuminating arrangements therefor with illuminating arrangements using light-conductive means, e.g. optical fibres

Definitions

• the present invention relates to a plastic optical fiber, a medical lighting device using the plastic optical fiber, a medical sensor device, a medical phototherapy device, and a plastic optical fiber cord.
• Plastic optical fiber is superior to glass-based optical fiber in terms of workability, handleability, manufacturing cost, etc., so it is used for short-distance optical signal transmission, light guide, etc.
• a plastic optical fiber is usually composed of two layers of a core and a clad, and the core generally has excellent transparency as represented by polymethylmethacrylate (hereinafter abbreviated as PMMA).
• PMMA polymethylmethacrylate
• a polymer having good weather resistance is used.
• the clad needs to have a lower refractive index than the core in order to confine light inside the core, and a fluorine-containing polymer is widely used.
• PMMA has high hygroscopicity
• the plastic optical fiber using PMMA as a core has a problem that the translucency is lowered in the visible long wave region near 800 nm due to moisture absorption.
• the core is an optical fiber made of a fluorine-substituted styrene / dehydride (meth) acrylate copolymer.
• styrene is brittle and has low elongation
• a plastic optical fiber using polystyrene as a core has a problem of insufficient bending resistance.
• a plastic optical fiber having excellent bending resistance it is an all-plastic optical fiber having a core-sheath-protective layer structure, and is characterized by being composed of a polymer having a breaking elongation of 30% or more as a protective material.
• Optical fibers have been proposed (see, for example, Patent Document 2).
• plastic optical fibers for endoscope lighting used in medical applications are required to have flexibility and durability against repeated bending in order to pass through internal organs having a complicated structure. Further, also in the light guide sensor for robots and the photoelectric sensor for industrial equipment, since the bending drive unit is large, excellent flexibility is required. Moisture resistance is also required in an environment where the plastic optical fiber comes into contact with water, such as inside or outdoors.
• Patent Document 2 Even if the technique described in Patent Document 2 is applied to a plastic optical fiber using polystyrene as a core, there is still a problem that the high bending resistance required in recent years is still insufficient.
• a main object of the present invention is to provide a plastic optical fiber having excellent moisture resistance and bending resistance.
• the plastic optical fiber of the present invention has the following configuration. That is, A multi-layered plastic optical fiber having a core and a first clad and a second clad, wherein the core has a water absorption rate of 0.001% or more and 0.29% or less, a total light transmittance of 80% or more, and a plasticizer of 0.
• the medical lighting device of the present invention has the following configuration. That is, A medical lighting device having the plastic optical fiber.
• the medical sensor device of the present invention has the following configuration. That is, A medical sensor device having the plastic optical fiber.
• the medical phototherapy device of the present invention has the following configuration. That is, it is a medical phototherapy device having the plastic optical fiber.
• the plastic optical fiber cord of the present invention has the following configuration. That is, it is a plastic optical fiber cord having at least one coating layer on the outer layer of the plastic optical fiber.
• the plastic optical fiber of the present invention preferably satisfies the following formulas (1) and (2).
• Equation (1) first clad thickness ⁇ 100 / fiber diameter [%] 0.5 ⁇ y equation (2)
• y second clad thickness ⁇ 100 / fiber diameter [%].
• the plastic optical fiber of the present invention preferably has a polymer whose core is any one of styrene, cycloolefin, methylpentene, and carbonate as a main component.
• the plastic optical fiber of the present invention has at least one type in which the first clad is selected from the group consisting of a polymer composed of methyl methacrylate and / or a polymer composed of methyl methacrylate as a main component, methyl acrylate, ethyl acrylic rate, and butyl acrylate. It is preferable that the copolymer contains 0.1% by weight to 12% by weight of the copolymerization component of the above.
• the water absorption rate of the second clad is 0.001% or more and 0.29% or less, and the elastic modulus of the second clad is 100 MPa or more and 2000 MPa or less.
• the second clad contains 0.03 wt% or more and 5.0 wt% or less of carbon black.
• the light transmission loss R (dB / km) at a wavelength of 660 nm and the light transmission loss I (dB / km) at a wavelength of 800 nm satisfy R ⁇ I.
• the light transmission loss R (dB / km) at a wavelength of 660 nm and the light transmission loss I (dB / km) at a wavelength of 800 nm satisfy 0.2 ⁇ R / I ⁇ 1. Is preferable.
• the melt flow rate (230 ° C., load 3.8 kg) of the core is preferably 1 g / 10 minutes or more and 200 g / 10 minutes or less.
• the plastic optical fiber of the present invention preferably has a fiber diameter of 100 ⁇ m or more and 500 ⁇ m or less.
• the plastic optical fiber of the present invention has a core, a first clad, and a second clad in this order.
• the clad may have three or more layers.
• the innermost clad in contact with the core is located outside the first clad and the first clad, and the clad in contact with the first clad is referred to as the second clad.
• the core is preferably a polymer containing any one of styrene, cycloolefin, methylpentene, and carbonate as a main component, and more preferably composed of a polymer containing a styrene residue as a main component. preferable.
• the permeability is stabilized.
• the polymerization component (monomer) of such a polymer include styrene; substituted styrene such as methylstyrene and ⁇ -methylstyrene; (meth) acrylic acid ester; (meth) acrylic acid; and N-substituted maleimide.
• (Meta) acrylic acid ester is a general term for acrylic acid and methacrylic acid, and for example, methyl acrylate, ethyl methacrylate, butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, Bornyl methacrylate, and adamantyl methacrylate. And so on.
• Examples of the N-substituted maleimide include N-isopropylmaleimide, N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, and NO-methylphenylmaleimide. Two or more of these may be used.
• the polymer containing a styrene residue as a main component refers to a polymer in which 50 mol% or more of the repeating units constituting the polymer are derived from styrene.
• the repeating unit constituting the polymer preferably contains 70 mol% or more of styrene residues, and more preferably 90 mol% or more. Moisture resistance can be improved by selecting a polymer containing a styrene residue as a main component.
• the core contains 0.01 wt% or more and 10 wt% or less of the plasticizer.
• the plasticizer By containing the plasticizer, the moldability and flexibility of the core can be improved, and the bending resistance can be further improved. If the content of the plasticizer in the core is less than 0.01 wt%, the moldability and flexibility of the core will be poor. On the other hand, if the content of the plasticizer in the core is larger than 10 wt%, the heat resistance deteriorates. It is preferably 0.05 wt% or more and 7 wt% or less, and more preferably 0.1 wt% or more and 7 wt% or less.
• the core plasticizer consists of a compound that imparts flexibility, weather resistance, and processability to the resin.
• the plasticizer include, but are not limited to, epoxy-based plasticizers, phthalate-based plasticizers, polyester-based plasticizers, hydrocarbons such as paraffin and polyethylene oxide.
• epoxidized soybean oil ESBO
• epoxidized flaxseed oil ELSO
• DOA dioctyl adipate
• DINA diisononyl adipate
• TCP tricresyl phosphate
• ATBC tributyl acetylcitrate
• TOTM Trimellitic acid trioctyl
• sebacic acid ester azelaic acid ester
• solid paraffin solid paraffin
• light liquid paraffin heavy liquid paraffin
• bis (2-ethylhexyl) phthalate DEHP
• butyl benzyl phthalate BBP
• phthalate examples thereof include, but are not limited to, dibutyl acid (DBP), diisobutyl phthalate, diisodecyl phthalate (DIDP), dioctyl phthalate (DOP), polyethylene oxide (PEO), polyethylene glycol (PEG) and the like.
• the core may contain stabilizers such as antioxidants and heat-resistant stability to the extent that it does not affect the translucency.
• the water absorption rate of the core is 0.001% or more and 0.29% or less. If it is larger than 0.29%, it is easy to absorb water and the permeability changes with time. It is preferably 0.002 or more and 0.20% or less, and more preferably 0.003% or more and 0.1% or less.
• the total light transmittance of the core is 80% or more. If the total light transmittance is less than 80%, the transmittance is poor, and even if the length of the fiber is short, light does not pass through and the sensor cannot be used. It is preferably 85% or more, and more preferably 87% or more.
• the relationship between the refractive index (X) of the core and the refractive index (Y) of the first clad is XY> 0.01. If XY ⁇ 0.01, light cannot be confined in the core.
• the melt flow rate of the core (230 ° C., load 3.8 kg) is preferably 1 g / 10 minutes or more and 200 g / 10 minutes or less. Within this range, spinning, which is a process of forming a core, is stable.
• a more preferable melt flow rate (230 ° C., load 3.8 kg) is 1 g / 10 minutes or more and 100 g / min or less.
• the plastic optical fiber of the present invention has at least two layers of cladding.
• the first clad is at least one selected from the group consisting of a polymer composed of methyl methacrylate and / or a polymer composed of methyl methacrylate as a main component, methyl acrylate, ethyl acrylic rate, and butyl acrylate. It is preferable that the copolymer contains 0.1% by weight or more and 12% by weight or less of the copolymerization component.
• the polymer containing methyl methacrylate as a main component refers to a polymer in which 50 mol% or more of the repeating units constituting the polymer are derived from methyl methacrylate.
• the first clad material preferably has a low refractive index with respect to the core and is excellent in interfacial adhesion with the core.
• Examples of the copolymerization component of the copolymer containing methyl methacrylate as a main component include (meth) acrylic acid ester, (meth) acrylic acid, styrene, substituted styrene, and N-substituted maleimide.
• Examples of the (meth) acrylic acid ester, substituted styrene, and N-substituted maleimide include those exemplified as the polymerization component of the core. Two or more of these may be used.
• the copolymer may contain at least one copolymer component selected from the group consisting of methyl acrylate, ethyl acrylate and butyl acrylate with methyl methacrylate as a main component in an amount of 0.1% by weight or more and 12% by weight or less. preferable.
• methyl acrylate, ethyl acrylate, and butyl acrylate as a copolymer component, heat resistance can be imparted and the melt viscosity can be adjusted. Methyl acrylate is preferred. In this case, the interfacial adhesion with the core can be further improved, and the breaking strength of the plastic optical fiber can be increased.
• the content of the copolymerization component is more preferably 0.3% by weight or more and 10% by weight or less. Even more preferably, it is 0.8% by weight or more and 6% by weight or less.
• the plastic optical fiber of the present invention preferably satisfies the following formula (1). 0.01 ⁇ x ⁇ 20 Equation (1)
• x 0.01% or more
• the interfacial adhesion between the core / first clad and the first clad / second clad becomes good, and the bending resistance is improved. It is more preferably 0.05% or more, and even more preferably 0.1% or more.
• x 20% or less, the proportion of the second clad having relatively excellent bending resistance increases, so that the bending resistance is improved. It is more preferably 10% or less, and even more preferably 8% or less.
• the thickness and fiber diameter of the first clad are cut perpendicular to the stretching direction at five locations randomly selected from the plastic optical fiber so that the core / first clad / second clad interface can be observed.
• After polishing the cross section it can be measured by magnifying observation using a digital microscope VHX-7000 (manufactured by KEYENCE CORPORATION). The magnification of magnified observation is between 10 and 200 times, and the range in which the entire cross section is within the visual field range and the interface can be observed is selected.
• the thickness of the thinnest portion of the first clad is measured and used as the thickness of the first clad.
• the diameter of the optical fiber is measured as the fiber diameter.
• the shortest diameter of the optical fiber is the fiber diameter.
• the fiber diameter and the thickness of the first clad are measured for each of the five cross sections, and the average values are taken as the fiber diameter and the thickness of the first clad, respectively.
• the relationship between the refractive index (Y) of the first clad and the refractive index (Z) of the second clad is YZ> 0.05.
• YZ ⁇ 0.05 light easily leaks from the second clad.
• the water absorption rate of the second clad is preferably 0.001% or more and 0.29% or less. Within this range, the absorption of water can be suppressed. It is preferably 0.002% or more and 0.20% or less, and more preferably 0.003% or more and 0.1% or less.
• the flexural modulus of the second clad is preferably 100 MPa or more and 2,000 MPa or less. When the flexural modulus is 100 MPa or more, the protective effect of the first clad by the second clad becomes good, and the bending resistance is improved. On the other hand, when the flexural modulus is 2,000 MPa or less, the stress on the first clad during bending is relaxed, and the bending resistance is improved.
• the flexural modulus is measured by ASTM D790 (2010). A test piece of 127 mm ⁇ 13 mm ⁇ 3.1 mm is used, and the measurement unit is kg / cm 2 . The flexural modulus is obtained from the tangent line of the slope with the largest slope at the beginning of the bending load-deflection curve. If it is difficult to collect the clad and directly measure the flexural modulus, if the composition of the clad is known, a clad having the same composition can be prepared and the flexural modulus can be measured.
• the second clad contains a polymer containing fluorine.
• the polymerization component of the polymer containing fluorine include vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, hexafluoroacetone, perfluoroalkyl methacrylate, hexafluoropropyl methacrylate, and tetrafluoropropyl methacrylate. Examples include pentafluoropropyl methacrylate. Two or more of these may be used.
• the fluorine content of the second clad is preferably 50% by weight or more.
• the fluorine content By setting the fluorine content to 50% by weight or more, the proportion of monomer residues having a low fluorine content such as acrylate and methacrylate is reduced, and the flexural modulus of the second clad is easily adjusted to the above-mentioned preferable range, and the resistance to resistance is reduced. Flexibility can be further improved.
• ethylene is preferable to further use ethylene as a polymerization component of the polymer containing fluorine of the second clad.
• ethylene By copolymerizing ethylene, the formability can be improved and the breaking strength of the plastic optical fiber can be increased.
• the second clad contains 0.03 wt% or more and 5.0 wt% or more of carbon black.
• it is 0.03 wt% or more, external light can be shielded and the sensor sensitivity is stable. It is more preferably 0.05 wt% or more, and even more preferably 0.1 wt% or more.
• it is less than 5.0 wt%, the workability of the second clad becomes good. It is more preferably less than 3.0 wt% and even more preferably 1.0 wt% or more.
• the second clad may contain pigments such as titanium dioxide, zinc oxide and chromium oxide, and other additives in addition to carbon black, as long as the characteristics are not impaired.
• the copolymer of the second clad has a carbonyl group-containing functional group at the end of the polymer chain or the side chain.
• a carbonyl group-containing functional group By having a carbonyl group-containing functional group, solvent resistance can be improved.
• RF and RF' represent a group having fluorine, for example, an alkyl fluoride group, a vinylidene fluoride group, and the like.
• the plastic optical fiber of the present invention preferably satisfies the following formula (2).
• y is in the above-mentioned preferable range, the ratio of the second clad to the plastic optical fiber can be secured, so that the deterioration of the bending resistance can be prevented. It is more preferably 1% or more, and even more preferably 5% or more.
• the thickness and fiber diameter of the second clad are measured in the same manner as the above-mentioned first clad thickness and fiber diameter.
• the light transmission loss R (dB / km) at a wavelength of 660 nm and the light transmission loss I (dB / km) at a wavelength of 800 nm satisfy R ⁇ I. More preferably, 0.2 ⁇ R / I ⁇ 1.
• wavelengths of 660 nm and 800 nm are wavelengths that easily pass through a living body and are therefore used as an index of sensor sensitivity.
• the reflectance of the wavelength of 660 nm changes greatly depending on the oxygen content of hemoglobin
• the wavelength of 800 nm is the value obtained by dividing R by I, taking advantage of the property that it is hardly affected by the oxygen content.
• a certain R / I index is often used as sensor sensitivity. When it is larger than 0.2, the transparency due to the wavelength of 660 nm is good, so that the sensor sensitivity is improved. Further, when it is less than 1, the transparency of 800 nm is good, so that the sensor sensitivity is stable.
• the fiber diameter of the plastic optical fiber of the present invention is preferably 100 ⁇ m or more and 500 ⁇ m or less.
• the fiber diameter of the plastic optical fiber of the present invention is preferably 100 ⁇ m or more and 500 ⁇ m or less.
• a core material and a clad material are discharged from a composite base for a concentric composite under a heated and melted state to form a core / first clad / second clad three-layer core sheath structure.
• the composite spinning method for forming the above is preferably used.
• a stretching treatment of about 1.2 to 3 times is generally performed to obtain a plastic optical fiber.
• the temperature at the time of spinning is better, preferably 250 ° C. or lower, and more preferably 240 ° C. or lower.
• the plastic optical fiber cord according to the embodiment of the present invention has at least one coating layer on the outer layer of the above-mentioned plastic optical fiber.
• the material forming the coating layer include polyethylene, polypropylene or a copolymer thereof, a blended product, an olefin polymer containing an organic silane group, ethylene-vinyl acetate, polyvinyl chloride, polyfluorinated vinylidene, and nylon 12.
• examples thereof include polyamide resins such as, polyester resins, nylon elastomers, polyester elastomers, urethane resins, fluororesins, and rubbers such as EPM and EPDM.
• the coating layer may be one layer or multiple layers, and in the case of multiple layers, a tension member such as "Kevlar” (registered trademark) may be inserted between the coating layers.
• these coating layers may contain stabilizers such as antioxidants, aging resistant agents, and UV stabilizers.
• the coating layer can be formed by a known method such as a melt extrusion molding method using a crosshead die.
• the endoscope lighting device has the above-mentioned plastic optical fiber and can be used in combination with the endoscope.
• the probe for ophthalmic surgery lighting according to the embodiment of the present invention has the above-mentioned plastic optical fiber as ophthalmic surgery lighting.
• the vascular catheter according to the embodiment of the present invention has the above-mentioned plastic optical fiber as a catheter illumination or an optical sensor.
• Core water absorption rate Adopted the value announced by the supplier. When the published value of the supplier was unknown, a sample was prepared based on the information obtained by analyzing the composition of the core in accordance with JIS K7209, and the water absorption rate was calculated.
• Core composition ratio For the core materials used in each Example and Comparative Example, the amount of styrene residue of the polymer was determined using GC / MS (GC: 7890A, manufactured by Agilent; MS: JMS-Q1050GC, manufactured by JEOL). ..
• Clad composition ratio For the clad material used in each Example and Comparative Example, a composition ratio (FT-IR manufactured by Bio-Rad Digilab) and solid 19 F-NMR (AVANCE NEO 400 manufactured by Bruker) was used. Weight%) was calculated.
• a 127 mm ⁇ 13 mm ⁇ 3.1 mm test piece was prepared from the second clad material used in each Example and Comparative Example, and the measurement unit was kg / cm 2 .
• the flexural modulus was calculated from the tangent line of the slope with the largest slope at the beginning of the bending load-deflection curve.
• Light loss (moisture resistance) in the flooded state of the plastic optical fiber The light amount of the plastic optical fiber obtained in each Example and Comparative Example was measured using an 820 nm LED (light emitting diode). Further, the plastic optical fibers obtained in each Example and Comparative Example were immersed in water at 23 ° C. for 10 m, and the amount of light was measured in the same manner after 100 hours. The amount of decrease (light loss) obtained by subtracting the initial light amount from the light amount in the flooded state was used as an index of moisture resistance. A negative value of light loss means that the amount of light in the bent state is lower than the initial amount of light. The smaller the absolute value of the light loss, the better the moisture resistance.
• Light loss (bending resistance) in the bent state of the plastic optical fiber The light amount of the plastic optical fiber obtained in each Example and Comparative Example was measured using an 820 nm LED (light emitting diode). Further, the plastic optical fibers obtained in each Example and Comparative Example were wound around a metal rod having a radius of 5 mm at 360 degrees, and the amount of light was measured in the same manner. The amount of decrease (light loss) obtained by subtracting the initial light amount from the light amount in the bent state was used as an index of bending resistance. A negative value of light loss means that the amount of light in the bent state is lower than the initial amount of light. The smaller the absolute value of the light loss, the better the bending resistance.
• Breaking strength of plastic optical fiber The plastic optical fiber obtained in each example and comparative example was subjected to a tensile test under the condition of tensile speed: 100 mm / min in accordance with JIS C 6637 (2015), and the plastic optical fiber. The strength at the time of breaking (breaking strength) was measured. Each of the three samples was measured and the average value was adopted.
• Translucency loss of plastic optical fiber For the plastic optical fiber obtained in each example and comparative example, wavelengths of 660 nm and 800 nm were selected from the light source of the halogen lamp, and the translucency loss (translucency loss) with a cutback of 5 m-2 m. dB / km) was measured.
• the first clad material the methyl methacrylate / methyl acrylate copolymer having the composition ratios shown in Table 1 was supplied to the composite spinning machine, and as the second clad material, the vinylidene fluoride polymer was supplied to the composite spinning machine.
• polystyrene having a styrene residue content of 100 mol% produced by continuous soul polymerization was supplied as a core material to 95% by weight and liquid paraffin to 5% by weight, and the core was supplied at 220 ° C.
• the clad was subjected to core-sheath composite melt spinning to obtain a plastic optical fiber having a fiber diameter of 300 ⁇ m (core diameter 228 ⁇ m, first clad thickness 6 ⁇ m, second clad thickness 30 ⁇ m).
• Example 2 A plastic optical fiber was obtained in the same manner as in Example 1 except that the clad material of the first clad was changed to the polymer having the composition shown in Table 1. Table 2 shows the results of the same evaluation as in Example 1 for the obtained plastic optical fiber.
• Example 3 A plastic optical fiber was obtained in the same manner as in Example 1 except that the clad thickness of the second clad was changed so that y had the values shown in Table 1. Table 2 shows the results of the same evaluation as in Example 1 for the obtained plastic optical fiber.
• Example 4 A plastic optical fiber was obtained in the same manner as in Example 1 except that the clad material of the second clad was changed to the copolymer having the composition ratio shown in Table 1.
• Table 2 shows the results of the same evaluation as in Example 1 for the obtained plastic optical fiber.
• Example 5 A plastic optical fiber was obtained in the same manner as in Example 1 except that the ratio of polystyrene and liquid paraffin of the core material was changed to the values shown in Table 1.
• Table 2 shows the results of the same evaluation as in Example 1 for the obtained plastic optical fiber.
• Example 6 A plastic optical fiber was obtained in the same manner as in Example 1 except that the clad material of the second clad was changed to the copolymer having the composition ratio shown in Table 1.
• Table 2 shows the results of the same evaluation as in Example 1 for the obtained plastic optical fiber.
• Examples 7 to 9 A plastic optical fiber was obtained in the same manner as in Example 1 except that the clad material of the first clad was changed to the polymer having the composition shown in Table 1.
• Table 2 shows the results of the same evaluation as in Example 1 for the obtained plastic optical fiber.
• Example 10 A plastic optical fiber was obtained in the same manner as in Example 7 except that liquid paraffin was not used as the core material.
• Table 2 shows the results of the same evaluation as in Example 1 for the obtained plastic optical fiber.
• Examples 11 and 12 A plastic optical fiber was obtained in the same manner as in Example 1 except that the clad material of the first clad was changed to the polymer shown in Table 1.
• Table 2 shows the results of the same evaluation as in Example 1 for the obtained plastic optical fiber.
• Examples 13 and 14 A plastic optical fiber was obtained in the same manner as in Example 1 except that the thicknesses of the first clad and the second clad were changed to the values shown in Table 1.
• Table 2 shows the results of the same evaluation as in Example 1 for the obtained plastic optical fiber.
• Examples 15 to 17 A plastic optical fiber was obtained in the same manner as in Example 1 except that liquid paraffin or PEO was used as the core material and carbon black was used for the second clad.
• Table 2 shows the results of the same evaluation as in Example 1 for the obtained plastic optical fiber.
• Example 18 to 20 A plastic optical fiber was obtained in the same manner as in Example 1 except that the core material was as shown in Table 1. Table 2 shows the results of the same evaluation as in Example 1 for the obtained plastic optical fiber.
• Example 21 As a core material, a plastic optical fiber was obtained in the same manner as in Example 10 except that the spinning temperature was 250 ° C. Table 2 shows the results of the same evaluation as in Example 1 for the obtained plastic optical fiber.
• Comparative Examples 1 to 4 A plastic optical fiber was obtained in the same manner as in Example 1 except that the core material and the clad material were changed to the copolymers having the composition ratios shown in Table 3. Table 4 shows the results of the same evaluation as in Example 1 for these plastic optical fibers.
• LP liquid paraffin
• St polystyrene
• PEO polyethylene oxide
• TPX polymethylpentene
• PC polycarbonate
• PC polycarbonate
• COP polycycloolefin
• MMA methylmethacrylate
• MA methylacrylate
• 2F vinylidene fluoride
• 4F Tetrafluoroethylene
• 6F Hexafluoropropylene
• FVE Heptafluorovinyl ether
• 4FM Tetrafluoropropyl methacrylate
• 5FM Pentafluoropropyl methacrylate.
• the plastic optical fiber and the plastic optical fiber cord of the present invention are wiring in a moving body such as an automobile, an aircraft, a ship, and a train, wiring for short-distance communication such as AV equipment, home equipment, and office equipment, and medical endoscope lighting.
• Ophthalmic surgery lighting, laparoscopic surgery lighting, catheter lighting, microscope lighting, light guide sensor for robots, photoelectric sensor for industrial equipment, automobile collision sensor, wall decoration lighting, interior lighting, etc. Can be done.
• it is suitable for lighting of medical equipment and industrial sensor applications because it has a high aperture ratio, moderate flexibility, and a property that it is difficult to reduce transmission loss even when bending, and more specifically.

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• Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2021
  • 2021-06-21 US US18/087,788 patent/US12449587B2/en active Active
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