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WO2002046811A1 - Fibre optique plastique - Google Patents

Fibre optique plastique Download PDF

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Publication number
WO2002046811A1
WO2002046811A1 PCT/JP2001/010734 JP0110734W WO0246811A1 WO 2002046811 A1 WO2002046811 A1 WO 2002046811A1 JP 0110734 W JP0110734 W JP 0110734W WO 0246811 A1 WO0246811 A1 WO 0246811A1
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WO
WIPO (PCT)
Prior art keywords
polymer
fluorine
amorphous fluororesin
refractive index
monomer
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.)
Ceased
Application number
PCT/JP2001/010734
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English (en)
Japanese (ja)
Inventor
Hidenobu Murofushi
Norihide Sugiyama
Kimiaki Kashiwagi
Masakuni Sato
Gen Ogawa
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AGC Inc
Original Assignee
Asahi Glass Co Ltd
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 Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2002548490A priority Critical patent/JPWO2002046811A1/ja
Priority to AU2002221082A priority patent/AU2002221082A1/en
Publication of WO2002046811A1 publication Critical patent/WO2002046811A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
    • 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
    • C08F34/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
    • C08F34/02—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring in a ring containing oxygen

Definitions

  • the present invention relates to a step index type plastic optical fiber (hereinafter referred to as an SI type optical fiber), and more particularly to an SI type optical fiber capable of transmitting a wide range of light from the visible to the near-infrared region and having a large numerical aperture. .
  • An ordinary plastic optical fiber has a basic structural unit consisting of a core made of a transparent resin such as methyl methyl acrylate and polycarbonate, and a clad made of a resin such as a fluoropolymer that has a smaller refractive index and is transparent. .
  • Japanese Patent Publication No. 28221935 discloses an SI type optical fiber using a perfluoropolymer for the core and cladding materials.
  • the conventional plastic optical fiber using perfluoropolymer for the core and cladding has a problem that the numerical aperture (NA) is small because the refractive index difference between the core and the cladding is small.
  • NA numerical aperture
  • the present invention solves this problem, and provides a plastic optical fiber suitable for use in optical communication media such as various sensors for industrial use and medical use, which has a small loss during bending and can receive light in a wide range. With the goal. Disclosure of the invention
  • the present invention provides an amorphous fluororesin (A-1) in which a core is substantially composed of a fluoropolymer having substantially no hydrogen atom and having a chlorine atom in a side chain;
  • An SI type light comprising an amorphous fluororesin (B) composed of a fluorine-containing polymer having substantially no hydrogen atoms, wherein the refractive index difference between the core and the clad is 0.020 or more.
  • the core is made of an amorphous fluororesin (A) composed of a fluoropolymer containing a high refractive index agent and having substantially no hydrogen atoms
  • the cladding is substantially made of hydrogen.
  • An SI type optical fiber comprising an amorphous fluororesin (B) composed of a fluorine-containing polymer having no atoms and having a refractive index difference of 0.020 or more between the core and the clad. is there.
  • the present invention provides an amorphous fluororesin (A) whose core is composed of a fluoropolymer having substantially no hydrogen atoms, or an amorphous fluororesin (A) containing a high refractive index agent.
  • the cladding is made of an amorphous fluororesin (B-2) composed of a fluorine-containing polymer having a refractive index of less than 1.300, which has substantially no hydrogen atoms, and the refractive index difference between the core and the cladding is 0. 020 or more, characterized in that it is not less than 020.
  • the present invention provides an amorphous fluororesin (A) in which the core is composed of a fluorine-containing polymer represented by the following formula (1) and having a repeating unit in which the monomer (a) is cyclopolymerized.
  • the core is composed of a fluorine-containing polymer represented by the following formula (1) and having a repeating unit in which the monomer (a) is cyclopolymerized.
  • the cladding is made of a fluoropolymer having a repeating unit obtained by polymerizing a monomer (b-1) represented by the following formula (4).
  • An SI type optical fiber Composed of an amorphous fluororesin (B-3) or an amorphous fluororesin (B-3) containing a fluorinated plasticizer having substantially no hydrogen atoms, and the refractive index of the core and the clad.
  • An SI type optical fiber characterized in that the difference is 0.020 or more.
  • R 1 R 2 , R 3 and R 4 are each independently a perfluoroalkyl group having 1 to 9 carbon atoms, a chlorine atom or a fluorine atom, and R 13 is 2 to 5 carbon atoms.
  • R 14 represents a Perufuruoroaru kill group or a fluorine atom of one to 9 carbon atoms.
  • the present invention provides an amorphous fluororesin (A) whose core is composed of a fluoropolymer having substantially no hydrogen atoms, or an amorphous fluororesin (A) containing a high refractive index agent.
  • the present invention also provides an optical member characterized by using perfluoro (2-pentyl-1,3-dioxole), a fluorine-containing polymer having a repeating unit obtained by polymerizing perfluoro (2-pentyl-1,3-dioxole), and the polymer. is there.
  • FIG. 1 is a graph showing the transmission loss (wavelength 500 000 nm) of the SI optical fiber of Example 43. BEST MODE FOR CARRYING OUT THE INVENTION
  • the amorphous fluororesin in the present invention is composed of only one kind or a mixed two or more kinds of specific fluoropolymers which become amorphous, and the fluoropolymers as other constituents. In addition, a small amount of additives may be contained. Further, the amorphous fluororesin may contain a small amount of a crystalline fluoropolymer (a fluoropolymer which becomes crystalline by itself) as long as it is entirely amorphous.
  • Certain fluoropolymers are also polymers having substantially no hydrogen atoms.
  • the other polymer is a polymer having substantially no hydrogen atom. That is, the polymer constituting the amorphous fluororesin in the present invention is composed of a polymer having substantially no hydrogen atoms. Is done.
  • the polymer constituting the amorphous fluororesin means a polymer having substantially no hydrogen atom.
  • the term “polymer” refers particularly to
  • homopolymer or “copolymer”, it may be a homopolymer or a copolymer.
  • SI type optical fibers consist of a core and a cladding having a relatively lower refractive index.
  • Amorphous fluoroplastics are inherently low-refractive-index resins, and when they are used as the core material, the cladding material that must have a lower refractive index than that of the resin has a smaller range of choices. It was difficult to increase the difference.
  • the present invention uses an amorphous fluororesin in the same category as the core as the material of the clad, increases the refractive index difference between the core and the clad as compared with the conventional one, and improves the optical properties and the physical properties of each material. The purpose is to enhance mechanical properties.
  • One aspect of the present invention is to increase the refractive index of the core by using an amorphous fluororesin composed of a fluorine-containing polymer having a chlorine atom, which has the effect of increasing the refractive index, as a material of the core. This is to increase the difference in the refractive index between them.
  • This chlorine atom must be a chlorine atom bonded to the side chain of the polymer, and if the chlorine atom is bonded to a carbon atom of the main chain, the polymerizability of the monomer deteriorates and the polymer becomes stable. There are problems such as the inability to obtain a high molecular weight polymer having physical properties, or the increase in crystallinity and the increase in scattering loss.
  • the main chain of the fluorinated polymer constituting the amorphous fluororesin is composed of a chain of only carbon atoms, and the main chain is composed of two carbon atoms constituting a polymerizable double bond. Formed from a chain. Further, in a polymer obtained by cyclopolymerization of a monomer having two polymerizable double bonds (hereinafter also referred to as fluorine-containing gens), four carbon atoms constituting two polymerizable double bonds are used.
  • the main chain is formed from the chain of Therefore, having a chlorine atom in the side chain means having a chlorine atom directly bonded to another carbon atom without having a chlorine atom directly bonded to a carbon atom constituting these polymerizable double bonds.
  • the present invention is also to increase the refractive index of the core by using an amorphous fluororesin containing a high refractive index agent as the material of the core, thereby increasing the refractive index difference from the cladding.
  • This high refractive index agent is a fluorine-containing polymer that constitutes the compounded amorphous fluorine resin. It is a compound having a higher refractive index than the body, and the refractive index of the amorphous fluororesin containing it is higher than that of the amorphous fluororesin not containing it.
  • the refractive index of the amorphous fluororesin increases with the amount of the high refractive index agent.
  • ⁇ As the refractive index-imparting agent, a fluorine-containing aromatic compound having substantially no hydrogen atom is particularly preferable. Further, in the present invention, the refractive index difference from the core is increased by using a fluorine-containing polymer having a lower refractive index than the conventional one as the fluorine-containing polymer constituting the cladding amorphous fluorine resin.
  • Perfluoro (2,2-dimethyl-1,3-dioxol) (formula (5) below, hereinafter referred to as PDD) polymer is known as a fluorine-containing polymer constituting the amorphous fluorine resin of the clad.
  • a fluoropolymer having a lower refractive index is used.
  • a core comprising a combination of a fluorine-containing polymer having a chlorine atom and a high-refractive index agent, and a combination of this core and a clad comprising a fluoropolymer having a lower refractive index
  • a combination of a core made of an amorphous fluororesin and a clad made of a fluoropolymer having a lower refractive index can be made of an amorphous fluororesin containing a fluorine-containing plasticizer.
  • the fluoropolymer having a low refractive index which is a material of the clad, usually has high rigidity and is brittle, so it is preferable to increase the flexibility by blending a plasticizer.
  • the plasticizer must be a fluorine compound in order to enhance the affinity with the fluoropolymer, and preferably has substantially no hydrogen atom.
  • the fluorine-containing plasticizer is a compound having a high fluorine content, it also has the effect of lowering the refractive index of the clad.
  • increasing the refractive index difference between the core and the clad that is, the numerical aperture Increasing the (NA) suppresses the increase in transmission loss when the SI-type optical fiber is bent, and when used in a sensor, it can collect light from a wide range, improving sensor sensitivity. I like it.
  • the refractive index difference between the amorphous fluorine-containing resin of the core and the amorphous fluorine-containing resin of the clad must be 0.020 or more. is necessary.
  • the difference in refractive index is preferably at least 0.030, more preferably at least 0.040, further preferably at least 0.045, particularly preferably at least 0.050. And most preferably 0.060 or more.
  • the upper limit of the refractive index difference is not particularly limited, but is usually 0.2.
  • the numerical aperture of the SI optical fiber of the present invention is preferably 0.280 or more. It is more preferably at least 0.325, further preferably at least 0.364, particularly preferably at least 0.380, most preferably at least 0.415. Although there is no particular upper limit for the numerical aperture, it is usually 0.75.
  • a method using a core material having a higher refractive index as compared with the conventional method a method using a clad material having a lower refractive index as compared with the conventional method
  • a method using a clad material having a lower refractive index as compared with the conventional method There is a method of combining a core material having a higher refractive index with a clad material having a lower refractive index as compared with the conventional one.
  • the amorphous fluororesin of the core and the amorphous fluororesin of the clad are used in these methods. It can be applied to any of
  • the amorphous fluororesin of the core and the amorphous fluororesin of the clad in the present invention are amorphous fluororesins in the same category except that the refractive index is different.
  • the amorphous fluororesin of the core is hereinafter referred to as amorphous fluororesin (A)
  • the amorphous fluorine resin of the clad is referred to as amorphous fluorine resin jS (B).
  • the fluorinated polymer constituting these amorphous fluororesins is a polymer having substantially no hydrogen atom and having no carbon-hydrogen bond. Since the amorphous fluororesin is composed of a fluorine-containing polymer having substantially no hydrogen atoms, transmission loss in the near-infrared region is reduced, and light from visible light to near-infrared light is favorably transmitted. An SI optical fiber that can be transmitted is obtained. The fact that the fluororesin is amorphous reduces the scattering loss of the SI optical fiber, particularly in the short wavelength region.
  • the amorphous fluororesin may be composed only of a fluoropolymer, and may contain an additive as long as the optical transmission performance, the mechanical performance and the like are not substantially impaired.
  • the additives include a plasticizer, a refractive index adjuster, various stabilizers, and a crosslinking agent. These are preferably fluorine compounds having a high affinity for the fluoropolymer in order not to substantially impair the optical transmission performance or to improve the performance.
  • a high refractive index agent as a refractive index adjusting agent in the amorphous fluororesin (A) of the core in order to increase the NA of the SI optical fiber.
  • a plasticizer in the amorphous fluorine resin (B) of the clad in order to impart flexibility to the optical fiber.
  • Examples of the fluorine-containing polymer constituting the amorphous fluororesin in the present invention include a polymer having a repeating unit obtained by cyclopolymerization of a fluorine-containing compound (hereinafter, also referred to as a “cyclized polymer”) and a fluorine-containing dioxole
  • a polymer having a repeating unit obtained by polymerizing hereinafter also referred to as a dioxo-based polymer
  • the cyclized polymer may be a copolymer of two or more fluorogens, or may be a copolymer of a fluorogen and another copolymerizable monomer. Polymerizable monomers are suitable as other copolymerizable monomers.
  • the dioxol-based polymer may also be a copolymer of two or more fluorine-containing dioxols, or may be a copolymer of a fluorine-containing dioxole and another copolymerizable monomer. Further, the fluoropolymer constituting the amorphous fluororesin may be a copolymer of a fluorogen and a dioxole.
  • dioxol-based polymers tend to have a particularly low refractive index as compared with the cyclized polymer, so that the fluorinated polymer constituting the cladding amorphous fluororesin (B) is used.
  • a dioxol-based polymer is preferable as the coalescence, and a cyclized polymer is preferable as the fluorine-containing polymer constituting the amorphous fluororesin (A) of the core.
  • the copolymer can be used for both the core and the clad due to the difference in refractive index from other amorphous fluororesins to be combined, but is usually suitable as a material for the clad. It is.
  • the above-mentioned polymer can be obtained by using any of the known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization using the monomers described below.
  • a radical generator is usually used as a polymerization initiator.
  • Post-treatment such as fluorination of the obtained polymer can also be performed.
  • the viscosity of the above-mentioned fluoropolymer in the molten state is preferably 1 ⁇ 10 2 to 1 ⁇ 10 5 Pa ⁇ s at a melting temperature of 200 to 300 ° C. If the melt viscosity is too high, melt spinning becomes difficult. Further, if the melt viscosity is too low, it is not practically preferable. That is, it is softened at a high temperature when used as an optical transmission body in electronic devices and automobiles, and the transmission performance as an SI type optical fiber is deteriorated.
  • the number average molecular weight M n of the fluorine-containing polymer 1 X 10 4 ⁇ 5X 10 6 is rather preferred, more preferably 5 X 10 4 ⁇ 1 X 10 6. If the molecular weight is too small, the heat resistance may be deteriorated, and if it is too large, the melt viscosity becomes high and molding becomes difficult, which is not preferable.
  • the cyclized polymer is a repeating unit obtained by cyclizing and polymerizing a monomer represented by the following formula (1) (hereinafter referred to as monomer (a)). Polymers having a position are preferred.
  • m is an integer of 0 to 5
  • RR 2 , R 3 and R 4 are each independently carbon Represents a perfluoroalkyl group of the numbers 1 to 9, a chlorine atom or a fluorine atom.
  • m is particularly preferably an integer of 0 to 3.
  • the R ⁇ R 2, R 3 and R 4 is preferably also three many a pel full O b alkyl group or a chlorine atom other fluorine atom.
  • the monomer (a) having a Perufuruo port alkyl group or a chlorine atom 1 ⁇ and 1 2 of the least one is a pel full O b alkyl group or a chlorine atom, in all others fluorine atom Certain compounds are preferred.
  • the perfluoroalkyl group a perfluoroalkyl group having 1 to 2 carbon atoms is preferable.
  • the repeating unit obtained by cyclopolymerization of the monomer (a) usually has a structure represented by the following formula (la) or (lb).
  • Examples of the monomer (a) having no chlorine atom (hereinafter referred to as monomer (a-2)) among the monomers (a) include the following monomers. Methods for synthesizing these monomers are disclosed in JP-A-11-131215, JP-A-4-346957, and the like.
  • Examples of the monomer having a chlorine atom (hereinafter referred to as monomer (a-1)) among monomers (a) include the following monomers.
  • the copolymerizable monomer may include a repeating unit obtained by polymerizing another copolymerizable monomer.
  • the other copolymerizable monomer is preferably a monoene, and the monoene has substantially no hydrogen atom. When it has a chlorine atom, it is a compound having no chlorine atom directly bonded to a carbon atom constituting a polymerizable double bond.
  • a monomer (c) which is a monomer represented by the following formula (2), a monomer (b) which is a monomer represented by the following formula (4), Perfluoroolefins such as perfluoroethylene (hereinafter referred to as TFE) and perfluoro (alkyl) such as perfluoro (3-ox-111-hexene) (CF 3 -CF 2 -CF 2 -0-CF CF 2 ) Vinyl ethers) and perfluoro (methylenedioxolanes) such as perfluoro (2-methylene-4-methyl-1,3-dioxolane) (formula (6), hereinafter referred to as MMD).
  • TFE perfluoroethylene
  • Vinyl ethers and perfluoro (methylenedioxolanes) such as per
  • the proportion of the repeating unit in which the monomer (a) is cyclopolymerized with respect to all the repeating units in the cyclized polymer is suitably from 20 to 100 mol%. , 40 to 100% by mole, and particularly preferably 50 to 100% by mole. If this ratio is too small, it is difficult to obtain a polymer having good optical and mechanical properties.
  • the ratio of the repeating unit in which the monomer (a) is cyclopolymerized is not particularly limited.
  • a monomer represented by the following formula (2) (hereinafter referred to as monomer (c)) is a preferable monomer for producing a cyclized polymer having a chlorine atom in a side chain.
  • This monomer is polymerized Having two chlorine atoms at a position distant from the acidic double bond, the cyclized polymer obtained by copolymerizing this monomer (c) and monomer (a) 'has a high refractive index and It becomes a cyclized polymer with good physical properties.
  • CF 2 CF-O-CR 5 R 6 — (CR 7 R 8 ) n — CFC1-CF 2 C1 (2)
  • n is an integer of 0 to 5
  • R 5 , R 6 , R 7 and R 8 are Each independently represents a perfluoroalkyl group having 1 to 9 carbon atoms, a chlorine atom or a fluorine atom.
  • n is 2 or more, a plurality of R 7 (same for R 8 ) may be different from each other.
  • n is preferably an integer of 0 to 3
  • R 5 , 6 , R 7 and R 8 are preferably all fluorine atoms.
  • R 5 and R 6 are all other fluorine atoms per full O b alkyl group.
  • the perfluoroalkyl group a perfluoroalkyl group having 1 to 2 carbon atoms is preferable.
  • a method for synthesizing the monomer (c) is disclosed in, for example, JP-A-11-131215.
  • the dioxo-based polymer is a polymer of one or more fluorine-containing dioxoles or a copolymer of a fluorine-containing dioxole and another copolymerizable monomer.
  • a monomer represented by the following formula (3) hereinafter referred to as a monomer (b) is preferable.
  • R 11 and R 12 are each independently carbon number 1-9.
  • at least one of R 11 and R 12 is a perfluoroalkyl group.
  • perfluoroalkyl-based charcoal The prime number is more preferably 1 to 6.
  • the dioxol-based polymer may be one or more polymers of the monomer (b), but usually a copolymer with another copolymerizable monomer is preferred. That is, the dioxyl-based polymer preferably contains a repeating unit in which another copolymerizable monomer is polymerized in addition to the repeating unit in which the monomer (b) is polymerized.
  • the other copolymerizable monomer is preferably a monoene or a cyclizable polymer, and is preferably a monomer having substantially no hydrogen atom, and preferably having no chlorine atom.
  • the monomer (a) perfluoroolefins such as TFE,
  • the proportion of the repeating unit in which the monomer (b) is polymerized to all the repeating units in the dioxole polymer is suitably 20 to 95 mol%. It is preferably from 90 to 90 mol%, particularly preferably from 35 to 85 mol%. If the ratio is too small or too large, it is difficult to obtain a polymer having good optical and mechanical properties.
  • the obtained fluoropolymer is used as a constituent of the amorphous fluororesin (A) or the amorphous fluororesin (B)
  • the copolymerization ratio is selected depending on whether or not the component is used (that is, depending on whether it is used for a fluorine-containing polymer having a high refractive index or a fluorine-containing polymer having a low refractive index).
  • the monomer (a) is a polymer having a high ratio of repeating units obtained by cyclopolymerization, and in the case of a low-refractive-index fluoropolymer, the monomer (b) is polymerized.
  • the polymer has a high proportion of repeating units.
  • the proportion of the repeating unit in which the monomer (b) is polymerized is preferably more than 0 mol% to 40 mol%, and particularly preferably 1 to 30 mol%.
  • the proportion of the repeating unit in which the monomer (b) is polymerized is preferably from 30 mol% to less than 100 mol%, particularly preferably from 40 mol% to 95 mol%.
  • the fluorine-containing polymer having a repeating unit in which a monomer represented by the following formula (4) (hereinafter referred to as monomer (b-1)) is polymerized has a lower refractive index . That is, a polymer having a repeating unit obtained by polymerizing PDD and PD Compared to the same polymer except that monomer (b-1) has a polymerized repeating unit instead of polymerized repeating unit, the latter has a lower refractive index.
  • R 13 represents a perfluoroalkyl group having 2 to 9 carbon atoms
  • R 14 represents a perfluoroalkyl group having 9 or less carbon atoms or a fluorine atom.
  • R 13 is preferably pel full O b alkyl group from 2 to 6 carbon
  • R 14 is preferably Perufuruoroaru kill group or a fluorine atom of one to 6 carbon.
  • monomer (b-1) examples include the following.
  • Examples of the monomer (b) other than the monomer (b-1) (8) include PDD, perfluoro (2-methyl-1,3-dioxol) and the like.
  • the amorphous fluorine resin (A) of the core preferably contains a high refractive index agent.
  • the high refractive index agent must have a higher refractive index than the fluoropolymer constituting the amorphous fluororesin (A) and have a high affinity for the fluoropolymer. Having high affinity means that it is sufficiently dissolved in the fluoropolymer, has no insoluble matter, and has no possibility of generating a micro phase-separated structure. If such an insoluble matter-mic phase separation structure exists, that part causes light scattering.
  • the high refractive index agent a compound which is blended with the core fluoropolymer in an amount equal to or less than its saturation solubility and which can sufficiently increase the refractive index of the amorphous fluororesin (A) in the core is used. Is done.
  • the high refractive index agent has a high affinity, a fluorine compound having a relatively low molecular weight is preferred. Further, it preferably has a chlorine atom, an aromatic nucleus, a metal component, and the like because of a high refractive index. Particularly, a compound having a chlorine atom and / or an aromatic nucleus is preferable. Further, the high refractive index agent is preferably a compound having substantially no hydrogen atom as in the case of the fluoropolymer. Thereby, the transmission loss reduction in the near infrared region of the amorphous fluororesin containing the high refractive index agent is maintained.
  • the high-refractive-index agent is a relatively low-molecular-weight fluorine compound having substantially no hydrogen atom and having a chlorine atom and Z or an aromatic nucleus.
  • the molecular weight of the high refractive index agent is preferably 2000 or less, and for polymers such as oligomers, the average molecular weight is preferably 2000 or less. Examples thereof include a fluorinated compound having a chlorine atom, a fluorinated aromatic compound, a fluorinated condensed polycyclic compound, and a metal chelate compound.
  • Preferred high refractive index agents are a fluorine compound having substantially no hydrogen atom and having a chlorine atom, and a fluorine-containing aromatic compound having substantially no hydrogen atom. More preferred are fluorine-containing aromatic compounds having substantially no hydrogen atoms, and among them, perfluoroaromatic compounds having 3 to 5 benzene nuclei in one molecule are particularly preferred. These high refractive index agents can be used alone or in combination of two or more.
  • fluorinated condensed polycyclic compound examples include perfluoroanthracene, perfluorinated fluorene, perfluorophenalene, perfluorophenanthrene and the like.
  • metal chelate compound examples include perfluoro (tetraphenyltin).
  • Examples of the fluorine compound having a chlorine atom include pentafluorobenzene, chloroperfluoronaphthalene, and trifluoroethylene oligomer having an average molecular weight of 200 or less.
  • the trifluoroethylene oligomer commercially available one having an average molecular weight of 2000 or less can be used, or it can be obtained by collecting a fraction having an average molecular weight of 2000 or less by distillation.
  • Perfluoro triphenylphosphine
  • perfluorobenzophenone perfluorobiphenyl
  • perfluoroterphenyl perfluoro (diphenylsulfide)
  • perfluoro (2,4) 6-trifluorene 1,3,5-triazine
  • perfluoro (1,3,5-triphenylbenzene) hereinafter referred to as TPB.
  • perfluoro (2,4,6-triphenyl 1,3,5-triazine) or TPB is preferable, and TPB is particularly preferable because of its high affinity with the fluoropolymer.
  • the ratio of the high refractive index agent in the amorphous fluororesin (A) is preferably such that the amorphous fluororesin ( ⁇ ) Is it not less than the amount that reaches the refractive index and not more than the solubility of the high refractive index agent in the fluoropolymer?
  • the amorphous fluororesin ( ⁇ ) Is it not less than the amount that reaches the refractive index and not more than the solubility of the high refractive index agent in the fluoropolymer?
  • it can be contained in the amorphous fluororesin (A) in an amount of 30% by mass or less.
  • the preferred content is 1 to 20% by mass, and particularly preferably contains 5 to 20% by mass of a high refractive index agent.
  • the amorphous fluorine resin (B) of the clad contains a fluorine-containing plasticizer having substantially no hydrogen atoms.
  • Fluorine-containing plasticizers soften the amorphous fluororesin in the clad to improve the workability of SI-type optical fibers, and also provide features such as making cracks less likely to occur in large-diameter fibers.
  • the addition of a fluorine-containing plasticizer having a high fluorine content has an effect of further lowering the refractive index of the amorphous fluorine resin of the clad.
  • perfluoropolyethers As the fluorinated plasticizer, perfluoropolyethers and the like are preferable.
  • perfluoropolyethers include perfluoro (polyoxyalkylene alkyl ether).
  • Specific examples of perfluoropolyethers include Crytox (trade name, manufactured by Dupont), Demnum (trade name, manufactured by Daikin Industries), Fomblin (trade name, manufactured by Audimont), and the like.
  • the average molecular weight is preferably at least 100, from the viewpoint that it is difficult to volatilize during molding or use.
  • the upper limit of the molecular weight is not particularly limited, but is preferably 20000 or less from the viewpoint of compatibility with the fluoropolymer of the clad.
  • the ratio of the fluorine-containing plasticizer in the amorphous fluorine-containing resin (B) is such that the amorphous plasticizer (B) has a desired plasticizing effect.
  • the amount is not particularly limited as long as it is an amount that achieves the above and is not more than the amount of solubility of the fluoroplastic in the fluoropolymer. Usually, it can contain 50% by mass or less in the amorphous fluorine-containing resin (B).
  • the preferred content is 1 to 40% by mass, particularly preferably 5 to 40% by mass of a fluorinated plasticizer.
  • the amorphous fluororesin (A) is preferably composed of a cyclized polymer as described above.
  • the refractive index of the cyclized polymer itself constituting the amorphous fluororesin (A) is preferably at least 1.330, particularly preferably at least 1.335. There is no particular upper limit for the refractive index of the cyclized polymer itself, but it is usually 1.45.
  • the amorphous fluorinated resin (A) can be composed of the cyclized polymer alone without including a high refractive index agent. Refraction of the cyclized polymer itself When the refractive index is not sufficiently high or when the refractive index of the amorphous fluororesin (B) is relatively high and the refractive index difference with the cyclized polymer is not large, the amorphous fluororesin containing a high refractive index agent is used. It is preferable to use (A).
  • the refractive index of the amorphous fluororesin (A) which may contain a high refractive index agent is preferably 1.340 or more, more preferably 1.345 or more, still more preferably 1.350 or more, and most preferably 1.355 or more. preferable.
  • the upper limit of the refractive index of the amorphous fluororesin (A) is not particularly limited, but is usually 1.5.
  • the amorphous fluororesin (A-1) composed of a fluoropolymer substantially having no hydrogen atom and having a chlorine atom in a side chain is the same as that of the amorphous fluororesin (A). Of these, it is composed of a fluoropolymer having a chlorine atom in the side chain. Since the amorphous fluororesin (A) is preferably a cyclized polymer, the amorphous fluororesin (A-1) is also preferably a cyclized polymer.
  • the fluorine-containing polymer having a chlorine atom in its side chain has a refractive index of 1.345 or more, preferably 1.350 or more. Similarly, the refractive index of the amorphous fluororesin (A-1) is preferably 1.345 or more, particularly preferably 1.350 or more.
  • Examples of the fluorine-containing polymer having a chlorine atom in a side chain, which constitutes the amorphous fluororesin (A-1), include a polymer containing a cyclic unit of a monomer (a-1) (see below).
  • the monomer (a-2) may have a cyclically polymerized repeating unit), and other carbons having no chlorine atom directly bonded to the carbon atom constituting the polymerizable double bond
  • monomer (c) is particularly preferred.
  • the monomer having no chlorine atom among the monomers (a) is hereinafter referred to as a monomer (a-2).
  • Particularly preferred fluorine-containing polymers having a chlorine atom in the side chain are polymers having a repeating unit in which the monomer (a-1) is cyclopolymerized (provided that the monomer (a-2) is a cyclopolymer. And a polymer having a repeating unit in which the monomer (a-1) is cyclopolymerized and a repeating unit in which the monomer (a-2) is cyclopolymerized, and And a polymer having a repeating unit in which the monomer ( a ) is cyclopolymerized and a repeating unit in which the monomer (c) is polymerized.
  • the amorphous fluororesin (A-1) is composed of a fluorine-containing polymer having a chlorine atom, it has a sufficiently high refractive index without containing a high refractive index agent. However, in some cases, a high refractive index agent may be included.
  • the amorphous fluororesin (A) includes the amorphous fluororesin (A-1) as a category, but particularly when it is composed of a fluoropolymer having no chlorine atom, a high refractive index agent is used. It is preferred to include.
  • the amorphous fluororesin (A) is composed of a fluorine-containing polymer having no chlorine atom, the refractive index difference between the amorphous fluororesin (B) and the amorphous fluororesin (B) combined as a clad is large. In some cases, it is not necessary to include a high refractive index agent.
  • the amorphous fluororesin (B) is preferably composed of a dioxo-based polymer as described above.
  • the refractive index of the dioxole polymer is not particularly limited as long as the refractive index difference between the dioxole polymer constituting the amorphous fluororesin (B) and the amorphous fluororesin (A) is large. It is preferable that the refractive index of the dioxole polymer constituting the crystalline fluororesin (B) is less than 1.330, particularly less than 1.310.
  • the refractive index of the dioxol-based polymer itself must be less than 1.300, particularly less than 1.296. Is more preferred.
  • the lower limit of the refractive index of the dioxyl polymer itself is not particularly limited, but is usually 1.290.
  • an amorphous fluororesin composed of a fluoropolymer having a refractive index of less than 1.300 is hereinafter referred to as an amorphous fluororesin (B-2).
  • the fluorine-containing polymer having a repeating unit in which the monomer (b-1) is polymerized is a fluorine-containing polymer having a repeating unit in which the monomer (b) other than the monomer (b-1) is polymerized. It has a lower refractive index than the base polymer.
  • the amorphous fluororesin (B) composed of a fluoropolymer having a repeating unit in which the monomer (b-1) is polymerized is hereinafter referred to as an amorphous fluororesin (B-3).
  • more preferable polymers have a refractive index of less than 1.300, particularly less than 1.296. It is a polymer.
  • the amorphous fluororesin (B-2) and the fluoropolymer constituting the amorphous fluororesin (B-3) have a repeating unit in which the monomer (b-1) is polymerized and A fluoropolymer having a refractive index of less than 1.300 is preferred.
  • This fluoropolymer has a copolymerization molar ratio of the monomer (b-1) and TFE of 99 to 2
  • the refractive index of the amorphous fluororesin (B) which may contain a fluorinated plasticizer is 1.3.
  • Particularly preferred refractive index of the amorphous fluororesin (B) is less than 1.300, most preferably less than 1.296.
  • the lower limit of the refractive index of the amorphous fluororesin (B) is not particularly limited, but is usually 1.28.
  • the SI optical fiber of the present invention can be manufactured by a known method for manufacturing an SI optical fiber. For example, it can be produced by the method described in the above-mentioned Japanese Patent No. 2821935. Further, the method of producing a graded index type plastic optical fiber described in Japanese Patent Application Laid-Open No. 8-58488 and Japanese Patent Application Laid-Open No. Molded optical fibers can also be manufactured. For example, an SI type optical fiber manufacturing preform (hereinafter simply referred to as a preform) is manufactured and spun from the preform to form an SI type optical fiber, or an SI type optical fiber is extruded according to a multicolor spinning method. There is a method for producing a fiber.
  • the SI optical fiber of the present invention does not increase transmission loss due to water absorption due to the water and oil repellency of fluorine atoms, and has high solvent resistance.
  • the optical fiber has low transmission loss over a wide wavelength range from the visible region to the near infrared region.
  • the difference in the refractive index between the core and the clad can be made sufficiently large, so that the numerical aperture (NA) can be made 0.415 or more.
  • SI type optical fiber with a large numerical aperture allows light to enter from a wide angle, that is, it can detect signals from a wide angle as a sensor, and can increase the coupling efficiency between the light source and the fiber. Energy can be input and transmitted, and bending loss during transmission can be kept small.
  • the SI type optical fiber of the present invention can be further used in the form of an optical fiber cord-to-optical fiber cable with a coating, or a bundled optical fiber cable.
  • the SI optical fiber of the present invention can have a transmission loss of 100 db or less (less than or equal to 50 dB / km) at a wavelength of 600 to 160 nm.
  • Such a low level transmission loss in a wide wavelength range of 600 to 160 nm Losing is very advantageous.
  • connection with the quartz optical fiber is easy, and compared with the conventional plastic optical fiber, which has to use a wavelength shorter than 600 to 1,600 nm. There is an advantage that an inexpensive light source is required.
  • plastic optical fibers have a large fiber diameter and are easy to connect to light sources and light-receiving elements or to fibers. Therefore, expectations for construction of inexpensive short-distance communication systems are increasing. Since the SI type optical fiber of the present invention has remarkably improved heat resistance, it has high thermal stability and can prevent a reduction in transmission loss even when exposed to a high temperature above room temperature for a long time.
  • Examples 1 to 3 are examples of monomer synthesis in which fluorine-containing dioxols were synthesized.
  • Examples 4 to 27 are polymer production examples for producing a fluorinated polymer constituting an amorphous fluororesin.
  • Examples 28 to 41 are examples of producing an amorphous fluororesin for producing an SI optical fiber.
  • Examples 42 to 58 are examples of producing an SI optical fiber.
  • PMPROD (Hereinafter referred to as PMPROD).
  • thermocouple temperature 77 g of the above dioxolane compound was placed in a 50 OmL glass four-necked flask equipped with a degree meter, and chlorine gas introduction was started at 5 ° C.
  • chlorine gas introduction was started at 5 ° C.
  • chlorine was introduced slowly because the reaction was intense.
  • the temperature was gradually raised, and the reaction was continued at 78 ° C at the end, and the reaction was terminated when the chlorine was no longer consumed.
  • PMPEND (Hereinafter referred to as PMPEND).
  • the collected matter was poured into cold water, the lower fluorocarbon phase was separated, and 22 g (yield 35%) of the target PPD (formula (9)) having a purity of 99.7% was obtained by distillation under reduced pressure. This was used for the following polymerization.
  • the glass transition temperature T g of the fluoropolymer or the amorphous fluororesin was measured using differential scanning calorimetry (based on JI S_K7121). .
  • the refractive index was measured using an Abbe refractometer.
  • the molecular weight was measured as a number average molecular weight Mn in terms of polymethyl methacrylate by gel permeation chromatography (GPC) using a dichloro-opening pen-fluorfluoropropane solvent (hereinafter referred to as R225).
  • the intrinsic viscosity [77] (unit: dlZg) was measured at 30 ° C. by dissolving in PBTHF (R 225 for the polymer P-4 obtained in Example 7).
  • the fluorination treatment of the polymer is basically performed by treating the polymer in an atmosphere of a mixed gas of fluorine and nitrogen (fluorine gas concentration: 20% by volume) at 250 ° C for 5 hours. Yes (specify if the conditions are changed).
  • a 5 L glass flask was charged with 750 g of BVE, 4 kg of ion-exchanged water (hereinafter also referred to as water), 260 g of methanol, and 3.7 g of diisopropylperoxydicarbonate. After purging the system with nitrogen, suspension polymerization was carried out at 40 ° C. for 22 hours to obtain 690 g of a polymer having an Mn of about 5 ⁇ 10 4 . By subjecting this polymer to fluorination treatment, a polymer having good light transmittance and thermal stability (hereinafter referred to as polymer P-1) was obtained. Of the polymer P- 1 [] is 0. 25, T g is 108 ° C, the refractive index 1. a 342 was a transparent vitreous polymer tough at room temperature.
  • polymer P-2 a polymer having good light transmittance and thermal stability (hereinafter referred to as polymer P-2) was obtained.
  • [??] of the polymer P-2 was 0.44, Mn was 131,500, the refractive index was 1.33, and T g was 124 ° C.
  • the tensile properties of polymer P-2 are tensile modulus of elasticity of 14 3 OMPa yield stress of 36 MPa, elongation at break of 4.2%, and zero shear viscosity at 230 ° C of 89,000 Pa ⁇ was s
  • polymer P-4 a polymer having good light transmittance and thermal stability (hereinafter referred to as polymer P-4) was obtained.
  • [77] of the polymer P- 4 is 0.5 is 20, M n 121500, the refractive index is 1. 372, T g was 126 ° C.
  • the tensile properties of the polymer P-4 were a tensile modulus of 170 OMPa, a yield stress of 5 OMPa, and a yield elongation of 3.8%.
  • a 20 OmL autoclave was charged with 80 g of water, 20 g of BVE-4CL, 15 g of BVE, 8 Omg of perfluorobenzoylperoxide, and 2.O g of methanol. After the autoclave was replaced with nitrogen, the autoclave was heated until the internal temperature reached 70 ° C., and polymerization was carried out for 24 hours. The obtained polymer was washed with water and methanol, and then dried at 200 ° C for 1 hour. The yield of the obtained polymer was 80%. By subjecting this polymer to a fluorination treatment, a polymer having good light transmittance and thermal stability (hereinafter referred to as polymer P-5) was obtained. The polymer P- 5 [] is 0.30, the refractive index 1. 36, T g was 120.
  • a 10 OmL stainless steel autoclave was charged with 50 g of trichloro- mouth trifluoroethane, 30 g of BVE-4DCL, and 0.1 g of diisopropylperoxydicarbonate.
  • the autoclave was heated and stirred at 50 ° C for 3 days. After that, the autoclave was opened and washed with methanol.
  • the obtained polymer was taken out, and the solvent and the residual monomer were distilled off under reduced pressure to obtain 29 g of a colorless and transparent polymer.
  • the yield of the obtained polymer was 96%.
  • the tensile properties of the polymer P-6 were a tensile modulus of 1690 MPa, a yield stress of 50 MPa, and a yield elongation of 3.6%.
  • a 20 OmL autoclave was charged with 80 g of water, 22 g of BVE-4 DCL, 15 g of BVE, 75 mg of perfluorobenzoylperoxide, and 2.0 g of methanol. After the autoclave was replaced with nitrogen, the autoclave was heated until the internal temperature reached 70 ° C., and polymerization was carried out for 28 hours. The obtained polymer was washed with water and methanol, and then dried at 200 ° C for 2 hours. The yield of the obtained polymer was 80%. By subjecting this polymer to a fluorination treatment, a polymer having excellent light transmittance and thermal stability (hereinafter referred to as polymer P-7) was obtained. [ ⁇ ] of the polymer P-7 was 0.28, the refractive index was 1.38, and the T g was 145.
  • a 20 OmL autoclave was charged with 80 g of water, 12 g of 2 CLBVE, 15 g of BVE, 75 mg of perfluorobenzoylperoxide, and 1.0 g of methanol. After the autoclave was replaced with nitrogen, the autoclave was heated until the internal temperature reached 75 ° C., and polymerization was carried out for 40 hours. The obtained polymer was washed with water and methanol, and then dried at 200 for 2 hours. The yield of the obtained polymer was 70%. By subjecting this polymer to a fluorination treatment, a polymer having good light transmittance and thermal stability (hereinafter referred to as polymer P-8) was obtained. [??] of the polymer P_8 is 0.25, the refractive index is 1. 35, T g was 98 ° C.
  • T g is the M n in 160 ° C to obtain a polymer of about 1. 7X 10 5.
  • polymer a polymer having good light transmittance and heat stability
  • Coalescence P-9 Polymer P-9 was colorless and transparent, and had a refractive index of 1. SO 5.
  • T g is the M n in 200 ° C to obtain a polymer of about 1. 5 X 10 5.
  • polymer P-10 was colorless and transparent, and had a refractive index of 1.298.
  • T g is the M n in 190 ° C to obtain a polymer of about l 3X 10 5.
  • Polymer P-15 was obtained.
  • Polymer P_15 was colorless and transparent, and had a refractive index of 1.310.
  • PH VE Radical polymerization of CF-0-CF (CF 3 ) -CF 2 -0-CF 2 -CF 2 -CF 3 ) (hereinafter referred to as PH VE) at a mass ratio of 85:15 using PBTHF as a solvent, A polymer having g of 182 and [] of 0.38 was obtained. By subjecting this polymer to a fluorination treatment, a polymer having good light transmittance and thermal stability (hereinafter referred to as polymer P- 16) was obtained. Polymer P-16 was colorless and transparent, and had a refractive index of 1.300.
  • polymer P-17 a polymer having good light transmittance and thermal stability (hereinafter referred to as polymer P-17) was obtained.
  • Polymer P-17 is colorless and transparent, and has a refractive index of 1.
  • polymer P_20 a polymer having good light transmittance and thermal stability (hereinafter referred to as polymer P_20) was obtained.
  • Polymer P-20 was colorless and transparent, and had a refractive index of 1.325.
  • polymer P-21 a polymer having good light transmittance and thermal stability (hereinafter referred to as polymer P-21) was obtained.
  • Polymer P-21 was colorless and transparent, and had a refractive index of 1.324.
  • polymer P-24 a polymer having good light transmittance and thermal stability (hereinafter referred to as polymer P-24) was obtained.
  • Polymer P-24 was colorless and transparent, and had a refractive index of 1.307.
  • polymer P-25 a polymer having good light transmittance and thermal stability (hereinafter referred to as polymer P-25) was obtained.
  • polymer P-4 was 0.87, Mn was 105000, the refractive index was 1.320, and T g was 105 ° C.
  • the tensile properties of the polymer P-4 were a tensile modulus of 500 MPa and an elongation at break of 63%.
  • Resin R-1 had a refractive index of 1.357 and a T g of 90 ° C.
  • the resulting mixtures were named Resin R-2 to Resin R-15, and Table 1 shows the composition, refractive index, and Tg (° C) including Resin R_1.
  • “Amount of additive” in Table 1 represents the ratio (% by mass) of the additive in the mixture.
  • the additives used are as follows.
  • CFE Clos trifluoroethylene oligomer having an average molecular weight of 2,000.
  • PPE Perfluoropolyether having an average molecular weight of 4000 (trade name “Fonbulin Z 03” manufactured by Audimont). (table 1 )
  • the numerical aperture (NA) of the obtained S-type optical fiber was measured by the far-field pattern method (based on J13-66862).
  • the transmission loss was measured by the cut-back method at a wavelength of 500 to 160 nm.
  • Fibers were created by the following two methods. Preform method: Cylinder polymer (or resin) is melt-molded at 250 ° C to produce a cylindrical tube, and core polymer (or resin) is melt-molded with 2501: To produce a cylinder having an outer diameter slightly smaller than the inner diameter of the cylindrical tube. A preform is manufactured by inserting the cylindrical body into the hollow portion of the cylindrical tube and heating to 230 ° C to combine the two, and the preform is melt-spun at 250 ° C to form the SI type. Obtain an optical fiber.
  • Two-layer extrusion spinning method Using an extruder, the core polymer (or resin) is placed at the center Then, the polymer (or resin) to be the clad is arranged on the outer periphery, and is extruded concentrically at 250T: to obtain the SI type optical fiber.
  • FIG. 1 shows the results of measuring the transmission loss of the obtained SI optical fiber.
  • the transmission loss of this SI optical fiber is 62 dB / km at 650 nm, 20 dBZkm at 850 nm, and 22 dBZkm at 1300 nm.
  • the NA was 0.34.
  • Example 44 In the same manner as in Example 44, an SI type optical fiber was prepared by the preform method. Table 2 shows the types of core and cladding materials, outer diameter and core diameter, transmission loss, and NA of the obtained SI optical fiber. In addition, when a heat resistance test was performed under the same conditions as in Example 44, the transmission loss did not change for any of the SI type optical fibers, and the heat resistance was good.
  • an SI optical fiber having a clad of resin R-12 and a core of polymer P-1, an outer diameter of 1000 m and a core diameter of 900 im was obtained.
  • the optical transmission loss of this SI optical fiber is 146 dBZkm at 650 nm, 85 dBZkm at 850 nm, and 71 dB / km at 1300 nm, and can transmit light from visible light to near-infrared light well.
  • Optical fiber. NA was 0.35. After storing this optical fiber in an oven at 80 ° C for 3000 hours, a heat resistance test was performed to measure the transmission loss again. No change was observed, and the heat resistance was good.
  • Example 44 In the same manner as in Example 44, an SI type optical fiber was prepared by the preform method. Table 3 shows the types of core and cladding materials, outer diameter and core diameter, transmission loss, and NA of the obtained SI optical fiber. In addition, when a heat resistance test was performed under the same conditions as in Example 44, the transmission loss did not change for any of the SI type optical fibers, and the heat resistance was good. (Table 3)
  • Example 4 In the same manner as in Example 4, an SI type optical fiber was prepared by the preform method. Table 4 shows the types of core and cladding materials, outer diameter and core diameter, transmission loss, and NA of the obtained SI optical fiber. In addition, when a heat resistance test was performed under the same conditions as in Example 44, the transmission loss did not change for any of the SI optical fibers, and the heat resistance was good.
  • an SI optical fiber having a core of resin R-8 and a clad of resin R_12, an outer diameter of 1000 Aim, and a core diameter of 950 / zm was obtained.
  • the optical transmission loss of this SI type optical fiber is 146 dB / km at 650 nm, 85 dBZkm at 85011111, and 71 dBZkm at 1300 nm, and is an optical fiber that can transmit light from visible light to near-infrared light well. there were. NA was 0.58. When a heat resistance test was performed under the same conditions as in Example 57, the transmission loss did not change and the heat resistance was good. Industrial applicability
  • the SI optical fiber of the present invention can increase the numerical aperture by increasing the refractive index difference between the core and the cladding without deteriorating the light transmission performance. As a result, the transmission loss during bending is not increased, and when used in a sensor or the like, the light can be collected from a wide range, so that the sensor sensitivity is improved. Also, it can give low level transmission loss over a wide wavelength range of 600 to 1600 nm. In other words, since the same wavelength as the quartz optical fiber can be used, the connection with the quartz optical fiber is easy, and the wavelength of 600 to We have to use shorter wavelengths than 160 nm,
  • the SI type optical fiber of the present invention has a large fiber diameter like ordinary plastic optical fiber and can be connected to a light source and a light receiving element or easily connected to each other, so that an inexpensive short distance communication system can be constructed.
  • the SI type optical fiber of the present invention has dramatically improved heat resistance as compared with ordinary plastic optical fibers, it has high thermal stability and is exposed to high temperatures above room temperature for a long time. In this case, the transmission loss can be prevented from lowering. Also, since the cladding can have flexibility, a fiber that is less likely to crack can be obtained.

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Abstract

L'invention concerne une fibre optique plastique du type à saut d'indice et à grande ouverture numérique (NA), à faible perte de transmission sur une large gamme de longueurs d'ondes et à faible perte par courbure, dans laquelle les matériaux d'un coeur et d'une gaine se composent d'une fluororésine amorphe ne présentant sensiblement aucun atome d'hydrogène, et le matériau de coeur utilise une fluororésine amorphe présentant un indice de réfraction supérieur ayant jamais été atteint, et/ou le matériau de gain utilise une fluororésine amorphe présentant un indice de réfraction inférieur à ceux atteints auparavant, augmentant ainsi la différence d'indice de réfraction entre les deux matériaux.
PCT/JP2001/010734 2000-12-07 2001-12-07 Fibre optique plastique Ceased WO2002046811A1 (fr)

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WO2005037818A1 (fr) * 2003-10-16 2005-04-28 Asahi Glass Company, Limited Nouveau compose dioxolane fluore et nouveau polymere fluore
WO2005085303A1 (fr) * 2004-03-08 2005-09-15 Asahi Glass Company, Limited Composition vulcanisable et procede de fabrication de produit chimique fluoré vulcanisé
JP2022117348A (ja) * 2021-01-29 2022-08-10 日東電工株式会社 プラスチック光ファイバーおよびその製造方法

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EP0907088A2 (fr) * 1997-10-02 1999-04-07 Asahi Glass Company Ltd. Matière plastique pour l'optique avec indice de réfraction à gradient et méthode pour sa préparation
EP0950672A1 (fr) * 1998-04-17 1999-10-20 Asahi Glass Company Ltd. Procédé de préparation de polymères contenant du fluor
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US5080508A (en) * 1990-04-19 1992-01-14 Mitsubishi Rayon Co., Ltd. Plastic optical fibers
EP0488390A1 (fr) * 1990-11-30 1992-06-03 Mitsubishi Rayon Co., Ltd. Fibres optiques en matières synthétiques
EP0907088A2 (fr) * 1997-10-02 1999-04-07 Asahi Glass Company Ltd. Matière plastique pour l'optique avec indice de réfraction à gradient et méthode pour sa préparation
EP0950672A1 (fr) * 1998-04-17 1999-10-20 Asahi Glass Company Ltd. Procédé de préparation de polymères contenant du fluor
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005037818A1 (fr) * 2003-10-16 2005-04-28 Asahi Glass Company, Limited Nouveau compose dioxolane fluore et nouveau polymere fluore
JPWO2005037818A1 (ja) * 2003-10-16 2006-12-28 旭硝子株式会社 新規な含フッ素ジオキソラン化合物、および新規な含フッ素重合体
CN100412072C (zh) * 2003-10-16 2008-08-20 旭硝子株式会社 含氟二氧戊环化合物及新型含氟聚合物
JP4696914B2 (ja) * 2003-10-16 2011-06-08 旭硝子株式会社 新規な含フッ素ジオキソラン化合物、および新規な含フッ素重合体
WO2005085303A1 (fr) * 2004-03-08 2005-09-15 Asahi Glass Company, Limited Composition vulcanisable et procede de fabrication de produit chimique fluoré vulcanisé
US7252886B2 (en) 2004-03-08 2007-08-07 Asahi Glass Company, Limited Curable composition and process for producing cured fluorinated product
JP2022117348A (ja) * 2021-01-29 2022-08-10 日東電工株式会社 プラスチック光ファイバーおよびその製造方法

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