WO2004070435A1 - Materiau optique resistant a la chaleur et support pour transmission optique obtenu a partir de ce dernier - Google Patents

Materiau optique resistant a la chaleur et support pour transmission optique obtenu a partir de ce dernier Download PDF

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Publication number
WO2004070435A1
WO2004070435A1 PCT/JP2004/000691 JP2004000691W WO2004070435A1 WO 2004070435 A1 WO2004070435 A1 WO 2004070435A1 JP 2004000691 W JP2004000691 W JP 2004000691W WO 2004070435 A1 WO2004070435 A1 WO 2004070435A1
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Prior art keywords
structural unit
heat
formula
polymer
optical material
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PCT/JP2004/000691
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English (en)
Japanese (ja)
Inventor
Yoshito Tanaka
Takayuki Araki
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Daikin Industries, Ltd.
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Publication of WO2004070435A1 publication Critical patent/WO2004070435A1/fr

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    • 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
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/122—Basic optical elements, e.g. light-guiding paths
    • G02B6/1221—Basic optical elements, e.g. light-guiding paths made from organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/045—Light guides
    • G02B1/046—Light guides characterised by the core material
    • 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
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B2006/12083—Constructional arrangements
    • G02B2006/121—Channel; buried or the like

Definitions

  • the present invention relates to an optical material having excellent heat resistance in addition to optical characteristics.
  • the optical material of the present invention is suitable, for example, as an optical transmission medium, more specifically, as a material for a plastic optical fiber or a waveguide element, particularly as a core material.
  • Acrylic resins are transparent to light in the visible region.
  • PMMA polymethyl methacrylate
  • they are commonly used in the core of plastic optical fibers for communications using LEDs as a light source (wavelength: 65 nm).
  • LEDs as a light source
  • PMMA has insufficient heat resistance (Tg: 105 ° C), so it may change its shape or impair its properties in applications or places where heat resistance is required. It can only be used in environments up to about 70.
  • Attempts to improve the heat resistance of PMMA include a method of copolymerizing ⁇ -methylstyrene and a method of copolymerizing maleic anhydride / styrene. In this case, the heat resistance is improved, but the mechanical strength is accordingly reduced, so that the fiber is easily broken when bent after being formed.
  • polycarbonate resin is excellent in heat resistance (Tg: 145.C), but when this is used for the core material of one optical fiber, the optical transmission loss is extremely large, Transmission, for example, transmission over 20 m is problematic.
  • Amorphous polyolefins (T g: 171 ° C, refractive index: 1.5 1) have particularly high heat resistance, but when exposed to air at high temperatures, coloring and gelling due to the effect of oxygen molecules may occur. It is easy to proceed, and as a result, when used as a core material of an optical fiber, there is a problem that transmission loss of an optical signal increases.
  • the LAN communication cables for these vehicles are required to have heat resistance in high-temperature areas such as the engine room and ceiling.
  • a plastic optical fiber for automobiles that has both heat resistance and signal transmission capability is required, but such an optical fiber has not yet been obtained for the aforementioned reasons. You.
  • An object of the present invention is to provide an optical material having both heat resistance and signal transmission ability in view of the above-mentioned conventional technology.
  • Another object of the present invention is to obtain an optical transmission medium, more specifically, an optical material having a signal transmission capability that can be used as a core material of a plastic optical fiber or a waveguide element.
  • the present inventors have conducted intensive studies to solve the above problems, and found that a specific polymer having an alicyclic hydrocarbon moiety in the side chain is excellent in heat resistance.
  • polymers having hydrocarbon moieties polymers having a heat distortion temperature of a specific temperature or higher are useful as heat-resistant optical materials.
  • optical polymers used in plastic optical fibers for automotive LAN as described above have found that they are useful as materials and have completed the present invention.
  • the heat-resistant optical material of the present invention is a heat-resistant optical material comprising a polymer having an alicyclic hydrocarbon moiety in a side chain, and a polymer having an alicyclic hydrocarbon moiety in the side chain.
  • the heat distortion temperature is 1 15 or more, and the equation (M 1)
  • the structural unit Ml has the formula (1): X
  • Structural unit derived from at least one of the monomers represented by the formula structural unit A is a structural unit derived from at least one of the monomers copolymerizable with the monomer of the formula (1)], It consists of a polymer containing 1 to 100 mol% of the structural unit Ml and 0 to 99 mol% of the structural unit A.
  • the polymer of the formula (M-1) according to the present invention comprises, as an essential component, a structural unit (Ml) derived from an acryl-based monomer of the formula (1) having an alicyclic hydrocarbon moiety in a side chain. It is a polymer, and it is preferable as a heat-resistant optical material because it is transparent to light in the visible region and has a high glass transition temperature by introducing an alicyclic hydrocarbon into a side chain.
  • the above-mentioned polymer has a heat distortion temperature of 115 ° C or higher, and is an optical material usable even in a high-temperature environment of 70 or higher, for example, a material useful for a plastic optical fiber for a vehicle-mounted LAN.
  • FIG. 1 is a schematic cross-sectional view of a main part structure of an optical waveguide device.
  • the structural unit M 1 which is an essential component in the polymer of the formula (M-1) of the present invention has a general formula (M_2):
  • Structural unit M 1-1 is represented by formula (2):
  • Z 1 is a monovalent organic group having 330 carbon atoms having an alicyclic hydrocarbon moiety
  • Structural unit Ml—2 is the formula (3):
  • X 3 is at least one member selected from the group consisting of H CH 3 C 1 and CF 3 ;
  • Z 2 is a monovalent organic group having 330 carbon atoms having an alicyclic hydrocarbon moiety
  • Structural unit derived from at least one of the monomers represented by the following formulas] may be a structural unit containing 199 mol% of the structural unit M1-1 and 199 mol% of the structural unit M1_2. preferable.
  • the first of the preferable polymers of the present invention is that the above-mentioned M1-1 power is 199 mol%, the structural unit Ml-2 is 199 mol%, and the arbitrary structural unit A in the formula (M-1) is 098 mol% % Polymer.
  • ⁇ -fluoroacrylic acid-derived structural unit ⁇ 1-1 having an aliphatic alicyclic hydrocarbon moiety in the side chain and ⁇ -fluoroacrylic acid represented by the formula (2) among the monomers of the formula (1) It is a polymer that has structural unit ⁇ 1-2 as an essential component derived from a monomer other than a single unit.
  • heat resistance and transparency can be imparted by introducing the structural unit Ml-2,
  • it is possible to adjust the refractive index for example, to set PMMA or higher by increasing the refractive index).
  • the structural unit Ml-2 is a structural unit derived from methacrylate in which X 3 in the formula (3) is CH 3 , and the above-mentioned heat resistance, transparency and refractive index adjustment functions can be more effectively achieved. Can be granted.
  • Structural unit A_1 is represented by formula (4):
  • X 1 is at least one selected from the group consisting of H, CH 3 , F, C 1 and CF 3 ; R 1 is a hydrogen atom, a linear or branched ether bond having 1 to 30 carbon atoms) At least one selected from the group consisting of an alkyl group that may be contained and a fluorinated alkyl group that may contain a linear or branched ether bond having 1 to 30 carbon atoms) Structural unit derived from one kind and Z or formula (5): X 2 CH 2 ⁇ C
  • X 2 is the same as X 1 in the formula (4); a monovalent hydrocarbon group having 6 to 30 carbon atoms comprising R 2 is an aromatic ring structure (aromatic ring), provided that R 2 A part or all of the hydrogen atoms in the monomer may be substituted with a fluorine atom); a structural unit derived from at least one of the following monomers; structural unit A-2 is represented by the formula (1), (1) 4) and a structural unit derived from a monomer copolymerizable with the monomer shown in (5)], wherein 1 to 99 mol% of the structural unit A-1 and the structural unit A are contained in the polymer.
  • the structural unit contains 0 to 98 mol% of —2.
  • the second of the preferable polymers of the present invention is that the structural unit M1 having an alicyclic hydrocarbon site in the side chain in the formula (M-1) is 1 to 99 mol%, and the alicyclic hydrocarbon site is It is a polymer containing 1 to 99 mol% of structural unit A-1 not containing, and 0 to 98 mol% of arbitrary structural unit A-2.
  • the refractive index can be adjusted (for example, set to PMMA or higher by increasing the refractive index). It is.
  • the refractive index can be adjusted (for example, PMMA or more by increasing the refractive index). Is set to).
  • X 1 and X 2 in the structural unit A-1 are structural units derived from methacrylate, which is CH 3 , it is preferable in that heat resistance, transparency, and a function of adjusting a refractive index can be more effectively imparted.
  • X 1 and X 2 in the structural unit A-1 are structural units derived from ⁇ -fluoroacrylate, which is an F atom, heat resistance and mechanical strength, particularly bending It is preferable in that it can impart strength and further flexibility.
  • the structural unit A-1 is a structural unit derived from at least one monomer selected from methyl methacrylate and methyl- ⁇ -fluoroacrylate. Can be granted.
  • the structural unit A-1 is a structural unit derived from at least one monomer selected from phenyl methacrylate and phenyl ⁇ -fluoroacrylate, it is preferable in that it can impart further heat resistance and low water absorption.
  • the ratio of Ml / A-1 is 5/95 to 90/10 mol%, more preferably 595 to 60/40 mol%, particularly preferably 10 ⁇ 90 to 50/50 mol%.
  • the ratio is 10/90 to 40/60 mol%.
  • X in the structural unit Ml derived from the monomer of the formula (1) is preferably an F atom.
  • heat resistance and mechanical strength, particularly bending strength, and further flexibility can be imparted.
  • Z forming a side chain in the polymer of the present invention containing the structural unit of the formula (M-1) and the polymer containing the structural unit of the formula (M-3), the side in the polymer containing the structural unit of the formula (M-2) ZZ 2 forming a chain is an organic group having 3 to 30 carbon atoms and having an alicyclic hydrocarbon moiety therein.
  • the alicyclic hydrocarbon moiety may be a monocyclic hydrocarbon moiety, a multicyclic hydrocarbon moiety, or a hydrocarbon moiety containing any of them.
  • alicyclic hydrocarbon moiety includes a monocyclic hydrocarbon moiety, ⁇ , ⁇
  • Zeta 2 is preferably a number of 7 or more organic groups carbon, it'll connexion than effective As a result, heat resistance can be imparted.
  • ⁇ and ⁇ 2 are preferably an organic group containing a hydrocarbon moiety having a double ring structure, and can more effectively impart heat resistance and transparency.
  • ⁇ 2 when containing a hydrocarbon moiety having a monocyclic structure, ⁇ 2 is, specifically,
  • hydrogen atoms of these exemplified hydrocarbon groups may be substituted with an alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a functional group.
  • hydrogen atoms of these exemplified hydrocarbon groups may be substituted with an alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a functional group.
  • double ring structure consisting Adamanta down and its derivatives, Noruporunan and its derivatives or Ranaru double ring structure, tricyclo [5 .. 2. 1.0 2 ' 6 ]
  • Those containing a double ring structure composed of decane and a derivative thereof are preferable, and these can particularly effectively impart heat resistance and transparency to the polymer.
  • Polymer and the formula (M- 2) and (M- 3) structure 3 ⁇ 4 side chains that have a hydrocarbon moiety of alicyclic structure in the polymer containing structural units of the formula (M- 1) of the present invention monomer capable of forming the unit (formula (1) (2) and (3)) is specifically the Z, in Akuriru monomer which have at least one side chain structure selected from the ZZ 2 There are, for example, the following.
  • R la , R 2a , R 3a , R 4a , R 5a , R 6a , R 7a , R 8a , R 9a , R 10a are the same Or different, H, F, C 1 or an alkyl group which may be substituted by a halogen atom having 1 to 14 carbon atoms; R 11a has 1 to 6 carbon atoms which may include a bond or a branched chain; Alkylene group; n is 0, an integer of 1-2)
  • R 1 R 2b is a substituent bonded to the ring, CH 3 C 2 H 5 or OH; R 4b R 5b has a bond or a branched chain.
  • R 3b is HCH 3 or C 2 H 5 ; n is an integer of 0 or 12), and more specifically,
  • X is H, F, C 1, CH 3 or CF 3; R 1 'R 2C , R 3C, R
  • R 14C and R 15E are the same or different, and may be an alkyl group having 1 to 14 carbon atoms which may be substituted with H, F, CI or a halogen atom; R 16C may have a bond or a branched chain. (Good alkylene group with 1 to 6 carbon atoms)
  • R ld , R 2d , R 3d , R 4d , R 5d , R 6d , R 7d , R 8d 3 ⁇ 4 R 9d 3 ⁇ 4 R 10d , R lld 3 ⁇ 4 R 12d and R 13d are the same or different and are an alkyl group having 1 to 14 carbon atoms which may be substituted with H, F, C 1 or a halogen atom; R 14 d includes a bond or a branched chain (Alkylene group having 1 to 6 carbon atoms which may be present)
  • n is an integer of 16 and m is an integer of up to 0 29.
  • Y is H or F; R le R 2e R 3e is the same or different, and H is an alkyl which may contain an ether bond of 129 carbon atoms.
  • H is an alkyl which may contain an ether bond of 129 carbon atoms.
  • fluorine-containing alkyl group which may contain an ether bond having 1 to 29 carbon atoms
  • methacrylic acid, ⁇ -fluoroacrylic acid, acrylic acid, methyl methacrylate ( ⁇ ), and methyl ⁇ -fluoroacrylate are excellent in the effects of improving transparency, heat resistance, and mechanical strength. preferable.
  • ⁇ is excellent in improving optical and mechanical properties.
  • monomer having a hydrocarbon group containing an aromatic cyclic structure (aromatic ring) of the formula (5) in the side chain include:
  • R 5 f is the same or different and is an alkyl group having 1 to 14 carbon atoms which may be substituted by H, F, C 1 or a halogen atom; R 6 f may have a bond or a branched chain A good alkylene group having 1 to 6 carbon atoms) and the like.
  • the aromatic cyclic structure contained in R 2 is not only an aromatic monocyclic structure such as a benzene ring, but also a multiple cyclic structure such as a naphthylene ring or an anthracene cyclic structure, or a pyridine ring. It may be a structure in which two or more aromatic cyclic structures such as phenyl are continuously connected.
  • phenyl methacrylate .. phenyl methacrylate is preferred from the viewpoint of improving heat resistance.
  • the molecular weight of the polymer used in the heat-resistant optical material of the present invention is generally in the range of 2000 to 1,000,000 in number average molecular weight, preferably 10,000 to 500,000, particularly preferably 50,000 to 300,000. Low An excessively high molecular weight is not preferable because mechanical properties, particularly, bending strength and flexibility are reduced. On the other hand, a molecular weight that is too high is not preferred because moldability is reduced and transparency is reduced due to an increase in light scattering.
  • the polymer used in the heat-resistant optical material of the present invention has a heat distortion temperature of 115 ° C. or higher, which suppresses softening even in a high-temperature environment. Signal transmission (transmission with little loss of optical signal over long distances) becomes possible.
  • the heat distortion temperature in the present invention means a deflection temperature under load (HDT), and uses a value measured by a method standardized by ASTM D684.
  • the heat distortion temperature is preferably 12 Ot: or more, especially 130 ° C or more, and more preferably 140 ° C or more.
  • the high heat deformation temperature makes it possible to control automobiles, especially around engine parts, and aircraft. It is advantageous for optical components, optical communication media, plastic optical fibers, etc. used in high-temperature environments, such as for controlling air conditioners and controlling industrial mouth pots.
  • the heat-resistant optical material of the present invention needs to have high transparency to light in the visible region, and particularly preferably has high transparency to light having a wavelength of 650 nm.
  • the heat-resistant optical material of the present invention preferably has an extinction coefficient at 65 Onm wavelength light of 0.015 cm- 1 or less, particularly 0.014 cm- 1 or less, and more preferably 0.015 cm- 1 or less. It is preferably cm- 1 or less.
  • the extinction coefficient means that a plastic optical fiber having a length of 10 Omm is manufactured by using a heat-resistant optical material of the present invention as a core material by melt-spinning with a clad material having an appropriate refractive index and a wavelength of 650 nm. Measure transmitted light intensity with light at nm. The incident light intensity iota beta, when the transmitted light intensity, the absorption coefficient under Refers to the value calculated by the formula.
  • the heat-resistant optical material of the present invention can adjust the refractive index in a wide range. Thus, it can be used for optical transmission media or cladding.
  • the heat-resistant optical material of the present invention since the heat-resistant optical material of the present invention has high transparency and can be adjusted to a high refractive index, it can be used for an optical transmission medium, for example, a core of a plastic optical fiber / optical waveguide element.
  • heat resistant optical material refractive index of the present invention n D 1. 45 or more der Rukoto are preferred.
  • the refractive index uses the value measured using an Abbe's refractometer at 25 using sodium D line as a light source.
  • the refractive index is preferably 1.47 or more, more preferably 1.48 or more, and the most preferred range is 1.48 to 1.52. If the refractive index is too low, it is not preferable because the choice of the material on the cladding material side is restricted when fabricating the plastic optical fiber. If the refractive index is too high, the transmission loss due to light scattering increases, and the coupling loss increases when joining the plastic optical fibers.
  • Structural unit A—1a is a structural unit derived from methyl methacrylate], and 1 to 100 mol% of structural unit Ml—1a; From 0 to 99 mol%.
  • This polymer is preferred because it has high transparency and excellent mechanical strength, particularly excellent bending strength and flexibility.
  • the structural units Ml-1a and A-1a are the same as those in the above formula (M-4); the structural unit A-2a is a structural unit derived from phenyl methacrylate or phenyl-1-a-fluoroacrylate).
  • This polymer is preferred because it has excellent heat resistance and low water absorption.
  • z 4 is Adamantan and its derivatives, Noruporunan and derivatives thereof, tricyclo [5.2.2 1.0 2'6] hydrocarbon moiety of decane and at least one double ring structure derivatives or selected Monovalent organic group containing 10 to 30 carbon atoms)
  • a polymer comprising 1 to 99 mol% of a structural unit M 1-la, 1 to 99 mol% of a structural unit M 1-2a, and 0 to 98 mol% of a structural unit A-1a.
  • This polymer is preferred because it has excellent heat resistance and mechanical strength, particularly excellent bending strength, and is easy to adjust the refractive index.
  • additives may be mixed within a range that does not impair heat resistance or signal transmission performance.
  • benzyl phthalate-n-butyl (refractive index: 1.575), 1-methoxyphenyl-2-phenylene (refractive index: 1.571), benzyl benzoate (refractive index: 1.568), bromobenzene (refractive index: 1.557), o-dichlorobenzene (refractive index: 1.551) m-dichlorobenzene (refractive index: 1.543) 3 ⁇ 4 1, 2'-dibromoethane (Refractive index: 1.538), 3-phenyl-1-propanol (refractive index: 1.532), diphenylphthalic acid (C 6 H 4 (COOC 6 H 5 ) 2 ), triphenyl phosphine ((C 6 H 5) 3 P) and dibenzyl phosphate Feto ((C 6 H 5 CH 2 ⁇ ) 2 PH0 2), 4, 4, one dibromobenzyl, 4, 4 'single dibro
  • These low molecular weight compounds not only simply adjust the refractive index of the heat-resistant optical material of the present invention uniformly, but also, for example, a refractive index distribution (graded grade) described in JP-A-8-110420. It functions as a dopant for obtaining an index-type optical fiber.
  • the heat resistant optical material of the present invention is also useful for obtaining a heat resistant refractive index distribution (graded index) type optical fiber.
  • the heat-resistant optical material of the present invention as an optical transmission medium and a core material of a plastic optical fiber formed of a core and a clad.
  • the above plastic optical fiber using the heat resistant optical material of the present invention has high heat resistance, it is useful when 100 or more heat resistance is required.
  • heat resistance is required in a light guide.
  • heat resistance is required to detect the parts where the atmosphere becomes hot, such as the detection of headlight illumination of a car and the positioning sensor of a melting press. The same applies to sensors in industrial lopots.
  • heat resistance of 100 ° C or more is required, for example, when wiring in the engine room, the ceiling of a car, or the instrument panel where the temperature is high in an in-vehicle LAN. The same applies to the case where it is mounted on an aircraft.
  • Plastic optical fibers in factory-automation (FA) applications also require heat resistance when exposed to high-temperature environments.
  • heat resistance is required due to the environment where there is no ordinary air conditioning equipment such as a distribution panel room on the roof of a pill or a communication base station.
  • the heat-resistant optical material of the present invention can be effectively used for these uses.
  • optical materials used for the plastic optical fiber cladding using the heat-resistant optical material have a glass transition temperature of 10 ° C. or more and a refractive index (n D ) of 1.44 or less.
  • the optical material used for the clad preferably has a glass transition temperature of 105 or more, more preferably 110 ° C or more, further preferably 120 ° C or more, particularly 130 ° C or more.
  • Heat resistance can be improved by having a high glass transition temperature, and it is preferable in that a high heat-resistant plastic optical fiber can be formed in combination with the heat-resistant optical material of the present invention used for the core. It can be used more effectively in applications where
  • the preferred polymer used as the heat-resistant cladding has a refractive index of 1.
  • a fluorinated acryl-based resin of 44 or less is usually used, and a methacrylate having a fluoroacrylyl group in a side chain, a (co) copolymer of CK-fluoroacrylate and the like are preferable.
  • a fluorine-containing acrylate having both heat resistance (high glass transition temperature) and low refractive index formula (6):
  • a fluorine-containing copolymer composed of the structural unit of the above formula (6) and a structural unit derived from methyl methacrylate is preferable.
  • a structural unit (a) of the above formula (6) and a structural unit (b) derived from methyl methacrylate are preferred.
  • a fluorine-containing copolymer having a ratio of (a) / (b) 32 68 to 64/36 mol% is preferred.
  • the layer structure of the plastic optical fiber is generally composed of a core layer and a cladding layer from the inside.
  • the caliber is not particularly limited, but usually from 125 l mm.
  • a protective layer may be provided on the outer periphery.
  • This protective layer is mainly used for the purpose of improving heat resistance, reducing bending loss, and improving impact resistance.
  • a vinylidene fluoride copolymer is used. Among them, a vinylidene fluoride Z tetrafluoroethylene copolymer is preferable.
  • the thickness of the protective layer is almost the same as that of the cladding layer.
  • a coating layer is further arranged on the outer periphery.
  • the coating layer conventionally used nylon 12, polyvinyl chloride, polyethylene, polyurethane, polypropylene and the like can be used.
  • the one in which the core layer has a single refractive index is called an SI (step index) type plastic optical fiber, which is the most common.
  • the one in which the refractive index of the core layer decreases stepwise from the inner circumference to the outer circumference is called a multi-step plastic optical fiber.
  • a fiber whose refractive index decreases smoothly from the inner circumference to the outer circumference is called a GI (graded index) plastic optical fiber.
  • the core material polymer and the clad material polymer are arranged concentrically using a composite spinning nozzle, and melt composite spinning is performed.
  • a method of forming into a par and then performing a stretching treatment under heating for the purpose of improving the mechanical strength is used.
  • the heat-resistant optical material of the present invention can be preferably used also as a core of an optical waveguide element, and specific examples of the same polymer as the core material and the clad material can be similarly preferably exemplified.
  • FIG. 1 illustrates a main structure of a typical optical waveguide device.
  • 1 is the base A plate
  • 2 is a core portion
  • 3 and 4 are clad portions.
  • Such an optical waveguide device is used to connect between optical functional devices, and light transmitted from a terminal of one of the optical functional devices passes through the core portion 2 of the optical waveguide device, for example, the core portion 2 and the clad portion. While repeating total reflection at the interface with 3 and 4, it is propagated to the other optical functional device terminal.
  • the type of the optical waveguide element can be an appropriate type such as a planar type, a strip type, a ridge type, and a buried type.
  • optical material of the present invention can be used for the core portion and the clad portion of the above-mentioned optical functional device.
  • the optical material of the present invention may be used only for the core portion or only the clad portion.
  • various functional compounds for example, a nonlinear optical material, a functional organic dye having a fluorescent property, a photorefractive material, and the like are contained in the optical material of the present invention, and are used for a core portion of a waveguide type optical functional element. It is also possible.
  • Optical waveguide devices include, for example, devices that perform operations such as switching, amplification, wavelength conversion, optical multiplexing / demultiplexing, and wavelength selection on optical communication signals, such as optical switches, optical routers, ONUs, and media converters. Available.
  • the heat-resistant optical material of the present invention may be used for other purposes other than the above, for example, for lenses (pickup lenses, lenses for glasses, lenses for cameras, Fresnel lenses for projects, contact lenses), sealing for luminous bodies such as LEDs. Materials, anti-reflective materials, optical disc substrates, cover materials for lighting equipment, display protection plates, transparent cases, display boards, automotive parts, etc.
  • MMA methyl methacrylate
  • n-laurylmercapone 0.1 g
  • azoisobutyronitrile 0.02 5 8 5 0 0111 Inside the glass flask The mixture was dissolved and mixed in, degassing and nitrogen substitution were repeated, and after sealing, polymerization was carried out at 70 ° C for 16 hours.
  • the physical property values are measured by the following methods.
  • MI Melt index
  • Each of the copolymers was mounted on a 9.5 mm inner diameter cylinder and maintained at a temperature of 230 for 5 minutes using a drop-down type flow tester manufactured by Shimadzu Corporation. Extruded through an lmm, 8 mm long orifice and expressed in grams of copolymer extruded in 10 minutes.
  • the composite fiber is spun at 230 to produce a plastic optical fiber with a diameter of 300 m (cladding material thickness 15) and a length of 100 mm.
  • the transmittance of the optical fiber is measured with light at a wavelength of 650 nm.
  • Incident light intensity I When the transmitted light intensity is, the extinction coefficient and ⁇ are calculated by the following formula.
  • the tensile strength is measured using a universal tester manufactured by Shimadzu Corporation according to ASTM D638.
  • a copolymer was obtained in the same manner as in Example 1, except that 15 g of isobornyl a-fluoroacrylate, 15 g of phenyl Q! -Fluoroacrylate, and 70 g of MMA were used as monomers.
  • the composition and various physical properties of the obtained copolymer were measured in the same manner as in Example 1. Table 1 shows the results.
  • Example 1 Same as Example 1 except that 40 g of tricyclodecanyl monofluoroacrylate and 60 g of methyl monofluoroacrylate were used as monomers To obtain a copolymer. The composition and various physical properties of the obtained copolymer were measured in the same manner as in Example 1. Table 1 shows the results.
  • a copolymer was obtained in the same manner as in Example 1 except that 25 g of 2-methyl-2 adamantyl ⁇ -fluoroacrylate, 25 g of isopolnyl methacrylate and 50 g of MMA were used as monomers.
  • the composition and various physical properties of the obtained copolymer were measured in the same manner as in Example 1. Table 1 shows the results.
  • Example 5
  • Example 1 In the same manner as in Example 1 except that 15 g of cyclohexyl ⁇ -fluoroacrylate, 25 g of phenyl ⁇ -fluoroacrylate and 60 g of methyl ⁇ -fluoroacrylate were used as monomers. A copolymer was obtained. The composition and various physical properties of the obtained copolymer were measured in the same manner as in Example 1. Table 1 shows the results.
  • a homopolymer of MMA was obtained in the same manner as in Example 1 except that only 100 g of MMA was used as a monomer.
  • Various physical properties of the obtained polymer were measured in the same manner as in Example 1. Table 1 shows the results.
  • a copolymer was obtained in the same manner as in Example 1, except that 30 g of phenylmethyl acrylate and 70 g of MMA were used as monomers.
  • the composition and various physical properties of the obtained copolymer were measured in the same manner as in Example 1. Table 1 shows the results. Comparative Example 3
  • a copolymer was obtained in the same manner as in Example 1 except that 25 g of 2,2,2-trifluoroethyl ⁇ -fluoroacrylate and 75 g of maraudal A were used as monomers.
  • the composition and various physical properties of the obtained copolymer were measured in the same manner as in Example 1. Table 1 shows the results. Comparative Example 4
  • the copolymer was prepared in the same manner as in Example 1 except that 50 g of 2,2,3,3,3-pentanofluoropropyl ⁇ -fluoroacrylate and 50 g of phenyl methacrylate were used as monomers. Got. The composition and various physical properties of the obtained copolymer were measured in the same manner as in Example 1. Table 1 shows the results.
  • Example 2 The same procedure as in Example 1 was repeated except that 50 g of 2,2-bis (trifluoromethyl) propanyl methacrylate, 20 g of MMA, and 30 g of 1H, 1H, 3H-tetrafluoropropyl methacrylate were used as monomers. A polymer was obtained. The glass transition temperature of the obtained polymer was 110 ° C, the MI was 37 g / 10 min, and the refractive index was 1.419.
  • a plastic optical fiber 1 was obtained in the same manner as in Example 6, except that the polymer of Example 4 was used as the core material and the polymer of Synthesis Example 1 was used as the clad material. Table 2 shows the characteristics of the obtained plastic optical fiber.
  • a plastic optical fiber was obtained in the same manner as in Example 6, except that the polymer of Comparative Example 3 was used as the core material.
  • Table 2 shows the characteristics of the obtained plastic optical fiber. Table 2
  • an optical material having both heat resistance and signal transmission ability can be provided.
  • optical transmission media specifically optical materials with signal transmission capabilities that can be used as core materials for plastic optical fibers and waveguide devices, especially the 125 ° C environment required in automobile engine rooms Or a plastic optical fiber made of an optical material that can be used in a 150 ° C environment required in an engine room of a diesel car.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Optical Integrated Circuits (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)

Abstract

L'invention concerne un matériau optique qui contient un polymère présentant une température de résistance à la déformation à chaud supérieure ou égale à 115 °C, comportant des fractions hydrocarbures alicycliques en tant que chaînes latérales. Ce matériau optique présente non seulement une résistance à la chaleur mais également une capacité de transmission de signaux de sorte qu'il peut être utilisé comme matériau de coeur dans des supports de transmission optique, en particulier dans une fibre optique en plastique et un élément guide d'ondes.
PCT/JP2004/000691 2003-02-03 2004-01-27 Materiau optique resistant a la chaleur et support pour transmission optique obtenu a partir de ce dernier WO2004070435A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003-026359 2003-02-03
JP2003026359A JP2006188544A (ja) 2003-02-03 2003-02-03 耐熱性光学材料およびそれを用いた光伝送用媒体

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WO2004070435A1 true WO2004070435A1 (fr) 2004-08-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8648160B2 (en) 2004-11-09 2014-02-11 Idemitsu Kosan Co., Ltd. Optical semiconductor sealing material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58125742A (ja) * 1982-01-20 1983-07-26 Konishiroku Photo Ind Co Ltd 光学用樹脂組成物および光学用素子
JPH02308202A (ja) * 1989-05-24 1990-12-21 Hitachi Ltd 光学部品及びその製造方法とその応用装置
JPH06333405A (ja) * 1993-05-20 1994-12-02 Matsushita Electric Works Ltd 照明装置
JPH0735929A (ja) * 1993-07-19 1995-02-07 Mitsubishi Rayon Co Ltd 屈折率分布型光伝送体
JPH08304634A (ja) * 1995-05-12 1996-11-22 Sumitomo Electric Ind Ltd プラスチック光ファイバ母材の製造方法及びプラスチック光ファイバ
EP1116577A2 (fr) * 2000-01-11 2001-07-18 Samsung Electronics Co., Ltd. Procédé pour la fabrication d'une ébauche pour une fibre optique et l'ébauche obtenue

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58125742A (ja) * 1982-01-20 1983-07-26 Konishiroku Photo Ind Co Ltd 光学用樹脂組成物および光学用素子
JPH02308202A (ja) * 1989-05-24 1990-12-21 Hitachi Ltd 光学部品及びその製造方法とその応用装置
JPH06333405A (ja) * 1993-05-20 1994-12-02 Matsushita Electric Works Ltd 照明装置
JPH0735929A (ja) * 1993-07-19 1995-02-07 Mitsubishi Rayon Co Ltd 屈折率分布型光伝送体
JPH08304634A (ja) * 1995-05-12 1996-11-22 Sumitomo Electric Ind Ltd プラスチック光ファイバ母材の製造方法及びプラスチック光ファイバ
EP1116577A2 (fr) * 2000-01-11 2001-07-18 Samsung Electronics Co., Ltd. Procédé pour la fabrication d'une ébauche pour une fibre optique et l'ébauche obtenue

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8648160B2 (en) 2004-11-09 2014-02-11 Idemitsu Kosan Co., Ltd. Optical semiconductor sealing material

Also Published As

Publication number Publication date
JP2006188544A (ja) 2006-07-20

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