JPH05112635A - Totally fluorinated wholly aromatic polyester and optical part using the same polyester - Google Patents
Totally fluorinated wholly aromatic polyester and optical part using the same polyesterInfo
- Publication number
- JPH05112635A JPH05112635A JP3302753A JP30275391A JPH05112635A JP H05112635 A JPH05112635 A JP H05112635A JP 3302753 A JP3302753 A JP 3302753A JP 30275391 A JP30275391 A JP 30275391A JP H05112635 A JPH05112635 A JP H05112635A
- Authority
- JP
- Japan
- Prior art keywords
- optical
- polymer
- polyester
- optical component
- wholly aromatic
- 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.)
- Pending
Links
Landscapes
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規な高分子化合物に係
り、特に、近赤外光を用いる光伝送用の材料として有用
な全フッ素化全芳香族ポリエステルとその用途に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymer compound, and more particularly to a perfluorinated wholly aromatic polyester useful as a material for optical transmission using near infrared light and its use.
【０００２】[0002]
【従来の技術】現在、光伝送システムとしては８５０ｎ
ｍ以上の近赤外光を用いた無機系光学部品が実用化され
ている。これに対して取扱いの容易なポリマーを光伝送
部に使用した光学部品は、８５０ｎｍ以上の近赤外領域
でのポリマー固有の吸収損失が大きいため、吸収損失の
小さな６６０ｎｍ帯を中心とする可視光でのシステムを
独立して構築していた。そこで８５０ｎｍ以上の近赤外
光でも使用可能なポリマー製光学部品が切望されてい
る。この目的で、ポリマー エンジニアリング アンド
サイエンス，２９，１２０９（１９８９）に記載のよ
うに、フッ素化あるいは重水素化したポリメチルメタク
リレートあるいはポリスチレンをコアに用いた光ファイ
バ等が提案されている。2. Description of the Related Art Currently, as an optical transmission system, 850n
Inorganic optical components using near-infrared light of m or more have been put into practical use. On the other hand, the optical parts that use a polymer that is easy to handle in the optical transmission section have a large absorption loss peculiar to the polymer in the near infrared region of 850 nm or more, so visible light centered on the 660 nm band where absorption loss is small. I was building the system independently. Therefore, a polymer optical component that can be used even in near infrared light of 850 nm or more has been earnestly desired. For this purpose, as described in Polymer Engineering and Science, 29 , 1209 (1989), an optical fiber using a fluorinated or deuterated polymethylmethacrylate or polystyrene as a core has been proposed.
【０００３】[0003]
【発明が解決しようとする課題】上記従来技術では、８
５０ｎｍ以上の近赤外光での透明性は向上したが、ポリ
マーの耐熱性が不足しており、また水分の影響も大きく
受けるなど信頼性に欠けるため、長期信頼性を要求され
る光通信系に適用できない等の問題を有していた。そこ
で、本発明では、前記従来技術の問題点を解決し、既存
の無機系光伝送システムで用いられている８５０ｎｍ以
上の近赤外光を伝送可能な耐熱性を有する有機高分子化
合物を開発し、それを用いた光学部品を提供することを
目的とする。In the above-mentioned prior art, 8
Transparency in near-infrared light of 50 nm or more is improved, but the heat resistance of the polymer is insufficient and it is also unreliable because it is greatly affected by moisture, so optical communication systems that require long-term reliability. There was a problem that it could not be applied to. Therefore, the present invention solves the above-mentioned problems of the prior art, and develops a heat-resistant organic polymer compound capable of transmitting near-infrared light of 850 nm or more, which is used in existing inorganic optical transmission systems. , And to provide an optical component using the same.
【０００４】[0004]
【課題を解決するための手段】上記目的を達成するため
に、本発明では、全フッ素化全芳香族ポリエステルを得
たものであり、該ポリエステルは下記化１の繰り返し構
造を有する高分子化合物である。In order to achieve the above object, in the present invention, a perfluorinated wholly aromatic polyester is obtained, which is a polymer compound having a repeating structure of the following chemical formula 1. is there.
【化１】 （式中、−ＣＯＯ−基とフェニル基の結合はメタ位かパ
ラ位であり、ＸはＦ又はＣＦ3 で、同一又は異っていて
もよい。） 上記高分子化合物の重合度は特に制限されないが、成形
性に影響する。特に好適には重合度１００〜２５００で
ある。重合度が１００より小さい場合、成形品の寸法安
定性が低下し、また重合度が２５００より大きい場合、
成形時の流動性が低下する等のデメリットが生ずる。[Chemical 1] (In the formula, the bond between the -COO- group and the phenyl group is at the meta position or the para position, X is F or CF 3 , and may be the same or different.) The degree of polymerization of the polymer compound is not particularly limited. Not affected, but it affects formability. Particularly preferably, the degree of polymerization is 100 to 2500. If the degree of polymerization is less than 100, the dimensional stability of the molded article is reduced, and if the degree of polymerization is more than 2500,
There are disadvantages such as a decrease in fluidity during molding.
【０００５】上記本発明の全フッ素化全芳香族ポリエス
テルは、伝送波長８５０ｎｍ以上で低損失かつ耐熱性に
優れている。特に、従来は有機系ポリマーでは使用でき
なかった１．３ミクロン以上の長波長領域で、本発明の
ポリマーを用いれば光を数十メートル伝送することが可
能となった。このポリマーは製膜あるいは成形材料とし
ても有効であり、光ファイバから薄膜光導波路まで適用
できる。光伝送部にクラッドを必要とする場合でも、ク
ラッド用ポリマーの材料としては特に制限されず、光伝
送部（コア）よりも屈折率の低い従来公知の材料を使用
することができる。本発明のポリマーにより製造した光
学部品は、例えば受光器内蔵車載コンピュータと光源内
蔵操作スイッチとを有し、これらを光ファイバで接続し
た自動車内光ＬＡＮにおいて、該光ファイバとして用い
ることができる。The above-mentioned perfluorinated wholly aromatic polyester of the present invention has low loss and excellent heat resistance at a transmission wavelength of 850 nm or more. In particular, in the long wavelength region of 1.3 μm or more, which could not be used in the conventional organic polymers, it became possible to transmit light of several tens of meters by using the polymer of the present invention. This polymer is also effective as a film-forming or molding material, and can be applied from optical fibers to thin-film optical waveguides. Even when a clad is required in the optical transmission part, the material of the polymer for the clad is not particularly limited, and a conventionally known material having a lower refractive index than that of the optical transmission part (core) can be used. The optical component manufactured from the polymer of the present invention has, for example, an in-vehicle computer with a built-in light receiver and an operation switch with a built-in light source, and can be used as the optical fiber in an in-vehicle optical LAN in which these are connected by an optical fiber.
【０００６】[0006]
【作用】近赤外領域におけるポリマーの吸収損失は、水
素原子を含む化学結合の分子振動吸収の高調波に起因す
る。そこでこの水素原子をフッ素で置換すると、この高
調波吸収強度は大幅に低減する。しかしながら主鎖中に
メチレン結合が存在するとフッ素化してもポリマーの耐
熱性はメチレン結合の無いものに比べ低いため、全芳香
族系ポリマーであることが望ましい。そこで主鎖に含ま
れる化学結合としては、全フッ素化フェニレンの他は最
低限のエーテル結合及びエステル結合に限定される。さ
らに全フッ素化フェニレンの全てがパラ位で結合してい
ると、ミクロな領域でのポリマーの結晶化あるいは光学
異方性の増大による光散乱損失の増加が顕著となるた
め、メタ置換の全フッ素化フェニレンを含む必要があ
る。The absorption loss of the polymer in the near-infrared region is due to the harmonic of the molecular vibration absorption of the chemical bond containing the hydrogen atom. Therefore, if this hydrogen atom is replaced with fluorine, this harmonic absorption intensity is significantly reduced. However, if a methylene bond is present in the main chain, the heat resistance of the polymer is lower than that without a methylene bond even if it is fluorinated. Therefore, a wholly aromatic polymer is preferable. Therefore, the chemical bond contained in the main chain is limited to the minimum ether bond and ester bond other than perfluorinated phenylene. Furthermore, if all of the perfluorinated phenylenes are bound in the para position, the meta-substitution of all-fluorinated fluorescein will be remarkable because the light scattering loss will increase remarkably due to the crystallization of the polymer in the microscopic region or the increase of the optical anisotropy. Must contain phenylene chloride.
【０００７】[0007]
【実施例】以下、実施例を用いて本発明を詳細に説明す
る。 実施例１ テトラフルオロハイドロキノン５．５ｇ、テトラフルオ
ロイソフタロイルクロライド８．３ｇをメタ及びターフ
ェニル等重量混合体７０ｇ中に加え、攪拌しながら１８
０℃で加熱した。反応中は塩酸ガスが発生する。約２０
分間反応後塩酸ガスの発生はかなり減少した。３４０℃
でさらに５０分間加熱還流すると、粘稠な淡黄色溶液が
得られた。混合物を室温にまで冷却後、反応混合物より
繰返し単位の化学構造が化２の構造を有するポリマーを
分離し、熱アセトンで精製、ろ過し、減圧乾燥した（収
量９ｇ）。The present invention will be described in detail below with reference to examples. Example 1 Tetrafluorohydroquinone (5.5 g) and tetrafluoroisophthaloyl chloride (8.3 g) were added to a mixture of meta and terphenyl (70 g) by weight, and the mixture was stirred while stirring.
Heated at 0 ° C. Hydrochloric acid gas is generated during the reaction. About 20
After the reaction for a minute, the generation of hydrochloric acid gas was considerably reduced. 340 ° C
When heated at reflux for another 50 minutes, a viscous pale yellow solution was obtained. After cooling the mixture to room temperature, a polymer having a chemical structure of a repeating unit represented by Chemical Formula 2 was separated from the reaction mixture, purified with hot acetone, filtered, and dried under reduced pressure (yield 9 g).
【化２】 このポリマーの分子量は数平均分子量で１２６，００
０、重量平均分子量で４８６，０００であった。[Chemical 2] The number average molecular weight of this polymer is 126,00.
It was 0 and the weight average molecular weight was 486,000.
【０００８】次に、このポリマーをコア用ポリマーとし
て用い、クラッド用ポリマーとして４フッ化エチレン−
６フッ化プロピレン共重合体（ＦＥＰ）を用いて、図１
に示すような直径０．５ｍｍのコア１及び外形１．０ｍ
ｍのクラッド２からなる構造の光ファイバを二重ノズル
構造を有する溶融押出紡糸装置により３８０℃で作製し
た。この光ファイバの伝送損失スペクトルを図２に示
す。図２に示すように波長８５０、１３００、１５５０
ｎｍにおける伝送損失値はそれぞれ０．８５、０．７
０、０．８１ｄＢ／ｍであり、波長８５０ｎｍ以上では
短距離光通信には十分な光伝送性能を有していた。さら
に、１８０℃で２日間加熱後も伝送損失はほとんど変化
しておらず、耐熱特性が優れていた。Next, this polymer was used as a core polymer, and as a clad polymer, tetrafluoroethylene-
Using a hexafluoropropylene copolymer (FEP), FIG.
Core 1 with a diameter of 0.5 mm and outer diameter of 1.0 m
An optical fiber having a structure composed of m of clad 2 was produced at 380 ° C. by a melt extrusion spinning device having a double nozzle structure. The transmission loss spectrum of this optical fiber is shown in FIG. As shown in FIG. 2, wavelengths 850, 1300, 1550
The transmission loss values in nm are 0.85 and 0.7, respectively.
It was 0, 0.81 dB / m, and had a sufficient optical transmission performance for short-distance optical communication at a wavelength of 850 nm or more. Furthermore, the transmission loss was hardly changed even after heating at 180 ° C. for 2 days, and the heat resistance was excellent.
【０００９】実施例２ 実施例１と同様にして繰返し単位の化学構造が化３の構
造を有するポリマーを得た。Example 2 In the same manner as in Example 1, a polymer having the chemical structure of the repeating unit of the formula 3 was obtained.
【化３】 このポリマーをコア用ポリマーとして用い、クラッド用
ポリマーとして４フッ化エチレン−６フッ化プロピレン
共重合体（ＦＥＰ）を用いて、図１に示すような直径
０．５ｍｍのコア１及び外形１．０ｍｍのクラッド２か
らなる構造の光ファイバを得た。この光ファイバの波長
８５０、１３００、１５５０ｎｍにおける伝送損失値は
それぞれ０．６９、０．６０、０．７０ｄＢ／ｍであ
り、短距離光通信には十分な光伝送性能を有していた。
さらに、１８０℃で２日間加熱後も伝送損失はほとんど
変化しておらず、耐熱特性が優れていた。[Chemical 3] Using this polymer as a core polymer and a tetrafluoroethylene-6-fluoropropylene copolymer (FEP) as a clad polymer, a core 1 having a diameter of 0.5 mm and an outer diameter of 1.0 mm as shown in FIG. An optical fiber having a structure including the clad 2 was obtained. The transmission loss values at wavelengths of 850, 1300, and 1550 nm of this optical fiber were 0.69, 0.60, and 0.70 dB / m, respectively, and had sufficient optical transmission performance for short-distance optical communication.
Furthermore, the transmission loss was hardly changed even after heating at 180 ° C. for 2 days, and the heat resistance was excellent.
【００１０】実施例３ コア用ポリマーとして化２に示す繰返し単位のポリマー
を用いて、クラッド用ポリマーとして２，２，２−トリ
フルオロエチルメタクリレートポリマーを用いて図３に
示すような直径０．５ｍｍのコア１及び全長３０ｍｍの
クラッド２からなる構造の光分岐器（６分岐路：最大分
岐角１０度）を得た。まずコアを射出温度３８０℃で射
出成形法により作製し、クラッドの原料となるモノマー
をベンゾイルパーオキシド０．５重量パーセントを重合
開始剤として約８０℃で注型法にて重合した。この６分
岐路の波長８５０ｎｍにおける過剰損失は２ｄＢと小さ
く、また分岐光強度も全ての出射光でほぼ等しかった。Example 3 A polymer having a repeating unit shown in Chemical formula 2 was used as a core polymer, and 2,2,2-trifluoroethylmethacrylate polymer was used as a clad polymer, and the diameter was 0.5 mm as shown in FIG. An optical branching device (6 branching paths: maximum branching angle of 10 degrees) having a structure including the core 1 and the clad 2 having a total length of 30 mm was obtained. First, a core was prepared by an injection molding method at an injection temperature of 380 ° C., and a monomer as a raw material for a clad was polymerized by a casting method at about 80 ° C. using 0.5% by weight of benzoyl peroxide as a polymerization initiator. The excess loss at the wavelength of 850 nm in the 6-branch path was as small as 2 dB, and the branched light intensity was almost the same for all the emitted lights.
【００１１】実施例４ 石英ガラス基板上に膜厚１０ミクロンの実施例１で得た
ポリマー膜をプレス成形にて４２０℃で作製した。この
膜をエッチングして、図４に示したような導波回路層３
（導波路幅７ミクロン）を形成した。波長１．３ミクロ
ンのシングルモード石英光ファイバ出射光を入射したと
ころ、良好に伝送した。Example 4 A polymer film having a thickness of 10 μm obtained in Example 1 was formed on a quartz glass substrate by press molding at 420 ° C. This film is etched to form the waveguide circuit layer 3 as shown in FIG.
(Waveguide width 7 microns) was formed. When the light emitted from the single-mode quartz optical fiber with a wavelength of 1.3 microns was incident, it was transmitted satisfactorily.
【００１２】実施例５ 実施例１で得た光ファイバ４を用い、図４に示す自動車
内光ＬＡＮを行った。受光器内蔵車載コンピュータ５は
運転席下部に設置されており、８５０ｎｍの光源内蔵操
作スイッチ６はそれぞれ４個所のドアに取付けられてい
る。車載コンピュータ５と操作スイッチ６とは光ファイ
バ４により接続されている。操作スイッチ６により車載
コンピュータ５を介してオーディオ、空調機構等の制御
を行った結果、良好に動作することを確認した。Example 5 Using the optical fiber 4 obtained in Example 1, an in-vehicle optical LAN shown in FIG. 4 was performed. The on-vehicle computer 5 with a built-in light receiver is installed in the lower part of the driver's seat, and the operation switch 6 with a built-in light source of 850 nm is installed on each of the four doors. The vehicle-mounted computer 5 and the operation switch 6 are connected by the optical fiber 4. As a result of controlling the audio system, the air-conditioning system, etc. through the vehicle-mounted computer 5 by the operation switch 6, it was confirmed that the operation was good.
【００１３】比較例１ ハイドロキノン５ｇ、イソフタロイルクロライド９ｇを
メタ及びターフェニル等重量混合体８０ｇ中に加え、攪
拌しながら１６０℃で加熱した。約１２分間反応後塩酸
ガスの発生はかなり減少した。３１０℃でさらに３０分
間加熱還流すると、粘稠な濃黄色溶液が得られた。混合
物を室温にまで冷却後、反応混合物より繰返し単位の化
学構造が化４の構造を有するポリマーを分離し、熱アセ
トンで精製、ろ過し、減圧乾燥した。Comparative Example 1 5 g of hydroquinone and 9 g of isophthaloyl chloride were added to 80 g of a weight mixture of meta and terphenyl and heated at 160 ° C. with stirring. After reacting for about 12 minutes, generation of hydrochloric acid gas was considerably reduced. Heating at reflux at 310 ° C. for a further 30 minutes gave a viscous dark yellow solution. After cooling the mixture to room temperature, a polymer having a repeating unit with a chemical structure of chemical formula 4 was separated from the reaction mixture, purified with hot acetone, filtered, and dried under reduced pressure.
【化４】 [Chemical 4]
【００１４】このポリマーをコア用ポリマーとして用
い、クラッド用ポリマーとして４フッ化エチレン−６フ
ッ化プロピレン共重合体（ＦＥＰ）を用いて図１に示す
ような直径０．５ｍｍのコア１及び外形１．０ｍｍのク
ラッド２からなる構造の光ファイバを二重ノズル構造を
有する溶融押出紡糸装置により作製した。しかしなが
ら、この光ファイバは波長８５０ｎｍ以上での近赤外光
を全く伝送しなかった。Using this polymer as a core polymer and a tetrafluoroethylene-6-fluoropropylene copolymer (FEP) as a clad polymer, a core 1 having a diameter of 0.5 mm and an outer shape 1 as shown in FIG. An optical fiber having a structure of 0.0 mm clad 2 was produced by a melt extrusion spinning device having a double nozzle structure. However, this optical fiber did not transmit near infrared light at a wavelength of 850 nm or more.
【００１５】[0015]
【発明の効果】本発明によれば、伝送波長８５０ｎｍ以
上での近赤外領域において、取扱性及び信頼性に優れた
ポリマー製光学部品を得ることができ、無機系光伝送シ
ステムに適用することが可能となる。According to the present invention, it is possible to obtain a polymer optical component having excellent handleability and reliability in the near infrared region at a transmission wavelength of 850 nm or more, and to apply it to an inorganic optical transmission system. Is possible.
【図１】本発明のポリマー製光学部品である光ファイバ
の構造図を示す。FIG. 1 shows a structural diagram of an optical fiber which is a polymer optical component of the present invention.
【図２】実施例１で得た光ファイバの伝送損失スペクト
ル図を示す。2 shows a transmission loss spectrum diagram of the optical fiber obtained in Example 1. FIG.
【図３】本発明のポリマー製光学部品である光分岐器
（６分岐路）の模式図を示す。FIG. 3 is a schematic diagram of an optical branching device (six branching paths) which is a polymer optical component of the present invention.
【図４】本発明のポリマー製光学部品である導波型光回
路の模式図を示す。FIG. 4 is a schematic view of a waveguide type optical circuit which is a polymer optical component of the present invention.
【図５】本発明のポリマー製光学部品を用いた自動車内
光ＬＡＮの構成図を示す。FIG. 5 is a configuration diagram of an in-vehicle optical LAN using the polymer optical component of the present invention.
１：コア、２：クラッド、３：基板、４：光ファイバ、
５：車載コンピュータ、６：操作スイッチ1: core, 2: clad, 3: substrate, 4: optical fiber,
5: In-vehicle computer, 6: Operation switch
───────────────────────────────────────────────────── フロントページの続き (72)発明者 竹谷 則明 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 (72)発明者 赤坂 伸一 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noriaki Takeya 4026 Kuji Town, Hitachi City, Hitachi, Ibaraki Prefecture, Hitachi Research Institute, Ltd. (72) Shinichi Akasaka 4026 Kuji Town, Hitachi City, Ibaraki, Hitachi Corporation Hitachi Research Laboratory
Claims (6)
素化全芳香族ポリエステル。 【化１】 （式中、−ＣＯＯ−基とフェニレン基の結合はメタ位か
パラ位であり、ＸはＦ又はＣＦ3 で、同一又は異ってい
てもよい。）1. A perfluorinated wholly aromatic polyester having a repeating structure of the following chemical formula 1. [Chemical 1] (Wherein, -COO- bond group and a phenylene group is meta- or para-position, X is may be in F or CF 3, the same or different.)
５００である請求項１記載の全フッ素化全芳香族ポリエ
ステル。2. The degree of polymerization of the polyester is 100 to 2
The fully fluorinated wholly aromatic polyester according to claim 1, which is 500.
族ポリエステルを、中心光源波長８５０ｎｍ以上の近赤
外光による光学部品用の材料として用いることを特徴と
するポリマー製光学部品。3. A polymer optical component, wherein the perfluorinated wholly aromatic polyester according to claim 1 or 2 is used as a material for an optical component by near infrared light having a central light source wavelength of 850 nm or more.
アとクラッドからなる光ファイバであることを特徴とす
る請求項３記載のポリマー製光学部品。4. The polymer optical component according to claim 3, wherein the material for the optical component is an optical fiber including at least a core and a clad.
であることを特徴とする請求項３記載のポリマー製光学
部品。5. The polymer optical component according to claim 3, wherein the material for the optical component is a waveguide type optical circuit.
操作スイッチとを有し、これらを光ファイバで接続した
自動車内光ＬＡＮにおいて、該光ファイバが請求項３記
載のポリマー製光学部品であることを特徴とする自動車
内光ＬＡＮ。6. An optical LAN in a vehicle, comprising an on-vehicle computer with a built-in light receiver and an operation switch with a built-in light source, which are connected by an optical fiber, wherein the optical fiber is the polymer optical component according to claim 3. Characteristic optical LAN in a car.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3302753A JPH05112635A (en) | 1991-10-23 | 1991-10-23 | Totally fluorinated wholly aromatic polyester and optical part using the same polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3302753A JPH05112635A (en) | 1991-10-23 | 1991-10-23 | Totally fluorinated wholly aromatic polyester and optical part using the same polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05112635A true JPH05112635A (en) | 1993-05-07 |
Family
ID=17912738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3302753A Pending JPH05112635A (en) | 1991-10-23 | 1991-10-23 | Totally fluorinated wholly aromatic polyester and optical part using the same polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05112635A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995028660A1 (en) * | 1994-04-18 | 1995-10-26 | Yasuhiro Koike | Refractive index distribution type optical resin and production method thereof |
| WO2001099323A1 (en) * | 2000-06-21 | 2001-12-27 | Mitsubishi Denki Kabushiki Kaisha | Data transmission system |
| US6470131B1 (en) | 2000-11-03 | 2002-10-22 | Corning Incorporated | Highly-halogenated low optical loss polymer |
| US7352967B1 (en) | 2000-06-21 | 2008-04-01 | Mitsubishi Denki Kabushiki Kaisha | Data transmission system |
| WO2010095678A1 (en) | 2009-02-20 | 2010-08-26 | セントラル硝子株式会社 | Fluorinated dicarboxylic acid derivative and polymer obtained therefrom |
| WO2020175671A1 (en) * | 2019-02-28 | 2020-09-03 | 富士フイルム株式会社 | Polymer, method for producing same, gas separation membrane using this polymer, gas separation module, gas separation device and m-phenylenediamine compound |
-
1991
- 1991-10-23 JP JP3302753A patent/JPH05112635A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995028660A1 (en) * | 1994-04-18 | 1995-10-26 | Yasuhiro Koike | Refractive index distribution type optical resin and production method thereof |
| WO2001099323A1 (en) * | 2000-06-21 | 2001-12-27 | Mitsubishi Denki Kabushiki Kaisha | Data transmission system |
| US7352967B1 (en) | 2000-06-21 | 2008-04-01 | Mitsubishi Denki Kabushiki Kaisha | Data transmission system |
| US6470131B1 (en) | 2000-11-03 | 2002-10-22 | Corning Incorporated | Highly-halogenated low optical loss polymer |
| WO2002036659A3 (en) * | 2000-11-03 | 2003-02-13 | Corning Inc | Highly-halogenated low optical loss polyester |
| US6610813B2 (en) | 2000-11-03 | 2003-08-26 | Corning Incorporated | Highly-halogenated low optical loss polymer |
| WO2010095678A1 (en) | 2009-02-20 | 2010-08-26 | セントラル硝子株式会社 | Fluorinated dicarboxylic acid derivative and polymer obtained therefrom |
| JP2010215904A (en) * | 2009-02-20 | 2010-09-30 | Central Glass Co Ltd | Fluorinated dicarboxylic acid derivative and high-molecular compound obtained by using the same |
| US8809451B2 (en) | 2009-02-20 | 2014-08-19 | Central Glass Company, Limited | Fluorinated dicarboxylic acid derivative and polymer obtained therefrom |
| WO2020175671A1 (en) * | 2019-02-28 | 2020-09-03 | 富士フイルム株式会社 | Polymer, method for producing same, gas separation membrane using this polymer, gas separation module, gas separation device and m-phenylenediamine compound |
| US11806661B2 (en) | 2019-02-28 | 2023-11-07 | Fujifilm Corporation | Polymer and method for producing the same, gas separation membrane, gas separation module, and gas separation apparatus using the polymer, and m-phenylenediamine compound |
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