JP3719898B2 - Optical polyimide monomer, polyimide compound and production method thereof - Google Patents
Optical polyimide monomer, polyimide compound and production method thereof Download PDFInfo
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- JP3719898B2 JP3719898B2 JP2000064045A JP2000064045A JP3719898B2 JP 3719898 B2 JP3719898 B2 JP 3719898B2 JP 2000064045 A JP2000064045 A JP 2000064045A JP 2000064045 A JP2000064045 A JP 2000064045A JP 3719898 B2 JP3719898 B2 JP 3719898B2
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- 229920001721 polyimide Polymers 0.000 title claims description 91
- 239000004642 Polyimide Substances 0.000 title claims description 84
- 150000001875 compounds Chemical class 0.000 title claims description 44
- 239000000178 monomer Substances 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 230000003287 optical effect Effects 0.000 title claims description 25
- 238000000034 method Methods 0.000 claims description 43
- 229920005575 poly(amic acid) Polymers 0.000 claims description 30
- -1 dinitro compound Chemical class 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 21
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- 238000004090 dissolution Methods 0.000 claims description 12
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical group 0.000 claims description 9
- 239000002861 polymer material Substances 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- HQROXDLWVGFPDE-UHFFFAOYSA-N 1-chloro-4-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(C(F)(F)F)=C1 HQROXDLWVGFPDE-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- DLDIDQIZPBIVNQ-UHFFFAOYSA-N hydron;2-methylpropan-2-amine;chloride Chemical compound Cl.CC(C)(C)N DLDIDQIZPBIVNQ-UHFFFAOYSA-N 0.000 claims description 7
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- STOSPPMGXZPHKP-UHFFFAOYSA-N tetrachlorohydroquinone Chemical compound OC1=C(Cl)C(Cl)=C(O)C(Cl)=C1Cl STOSPPMGXZPHKP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000005530 etching Methods 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- LACZRKUWKHQVKS-UHFFFAOYSA-N 4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F LACZRKUWKHQVKS-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004891 communication Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DFSUKONUQMHUKQ-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound OC(=O)C1=CC=CC(C(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)(C(F)(F)F)C(F)(F)F)=C1C(O)=O DFSUKONUQMHUKQ-UHFFFAOYSA-N 0.000 description 4
- DIWFGFLMMAYPRW-UHFFFAOYSA-N 4-[4-[4-amino-2-(trifluoromethyl)phenoxy]-2,3,5,6-tetrafluorophenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC(C(=C1F)F)=C(F)C(F)=C1OC1=CC=C(N)C=C1C(F)(F)F DIWFGFLMMAYPRW-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000012792 core layer Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- GRLQBYQELUWBIO-UHFFFAOYSA-N 4,6-dichlorobenzene-1,3-diol Chemical compound OC1=CC(O)=C(Cl)C=C1Cl GRLQBYQELUWBIO-UHFFFAOYSA-N 0.000 description 3
- KOYZQFHTKXPFRM-UHFFFAOYSA-N 4-[5-[4-amino-2-(trifluoromethyl)phenoxy]-2,4-dichlorophenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC1=CC(OC=2C(=CC(N)=CC=2)C(F)(F)F)=C(Cl)C=C1Cl KOYZQFHTKXPFRM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 3
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 3
- 229910052805 deuterium Chemical group 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- SOZFIIXUNAKEJP-UHFFFAOYSA-N 1,2,3,4-tetrafluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1F SOZFIIXUNAKEJP-UHFFFAOYSA-N 0.000 description 2
- ZSDAMBJDFDRLSS-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-diol Chemical compound OC1=C(F)C(F)=C(O)C(F)=C1F ZSDAMBJDFDRLSS-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 0 *c(cc1*)ccc1OCOc(cc1)c(*)cc1N Chemical compound *c(cc1*)ccc1OCOc(cc1)c(*)cc1N 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000013308 plastic optical fiber Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は光学用の線形(linear)高分子材料に係り、特に、光学用のポリイミド単量体、ポリイミド化合物及びその製造方法に関する。
【０００２】
【従来の技術】
通常、光学用の線形高分子材料は次世代の高速、大容量情報通信事業の核心部品である各種の光学素子に用いられる材料であり、光電集積回路、光電混合配線管、ハイブリッド集積化素子、光多重基板素子及びプラスチック光ファイバなどを導波させるための光学素子の製作に用いられる。
今までの光学素子の材料としてはＬｉＮｂＯ3のような無機結晶を用いてきたが、前記無機結晶はその特性上製造及び加工が困難で大量生産には限界があるため、現在では材料設計及び加工が容易な有機高分子材料に対する研究が行われつつある。
【０００３】
このような有機高分子材料のうち、ポリイミドは優れた熱的、機械的性質により半導体保護用の緩衝剤として用いられており、前記ポリイミドを光学用の高分子材料として活用するためにＣ−Ｈ結合の水素の代わりにフッ素や重水素を置換して光の吸収損失を低減するための研究が行われている。一般に高分子材料は１０００−１７００nmの近赤外線領域で光の吸収が発生する。このような光の吸収損失は高分子の主鎖にあるＣ−Ｈ結合の伸縮振動と変形振動による高周波の倍音により発生する。これを低減するためには光の吸収波長を近赤外線領域よりは長波長や短波長側に移動させるべきである。このため、Ｃ−Ｈ結合の水素をフッ素や重水素に置換する。
【０００４】
前記水素を重水素に置換したポリイミドの場合、１５５０nm波長帯で光の吸収が発生するため、光通信素子用の材料には不向きである。しかしながら、前記水素をフッ素に置換したポリイミドの場合は１０００−１７００nm波長帯の光吸収損失を最少化することができて光通信素子用の材料として開発されている。前記フッ素に置換したポリイミドを用いて光導波路を製作するときはコア層及びクラッド層の屈折率の差を満たすため、フッ素を含む単量体及びフッ素を含まない単量体の混合比率を適宜に調節して共重合させてコア層及びクラッド層を製作する。
【０００５】
しかしながら、従来のフッ素に置換したポリイミド、すなわち、フルオロ化ポリイミド化合物はフッ素の含有により屈折率が低いため、これを用いてコア層を形成する場合、コア層より低い屈折率を有するクラッド層を形成するために使用する材料の選択幅は制限される。かつ、前記フッ素に置換したポリイミドを用いてクラッド層を形成する場合にも、フッ素含有量の減少によりＣ−Ｈ結合の含有量が増えるため、光の吸収損失は増加するという問題点がある。
かつ、従来のポリイミドは低い複屈折率を有する柔軟な鎖構造を備えるが、このような鎖構造のポリイミドは食刻工程でその深さが深くなる場合、シリコン基板とポリイミドとの熱膨張係数の差により薄膜がきれるという問題点も発生する。
【０００６】
【発明が解決しようとする課題】
従って、本発明の目的は、従来のフルオロ化ポリイミド化合物の低い光吸収損失及び高い耐熱特性をそのまま維持しながら、食刻工程時の薄膜のきれ現象を防止することのできる光学用のポリイミド単量体、ポリイミド化合物及びその製造方法を提供することにある。
本発明の他の目的は、１３００−１５５０nmの光通信波長帯域で低い光吸収損失を有することにより、比較的広い領域で様々な屈折率の調節によりコアとクラッドの材料選択幅を広げる光学用のポリイミド単量体、ポリイミド化合物及びその製造方法を提供することにある。
【０００７】
【課題を解決するための手段】
前記目的を達成するための本発明は光学用の高分子材料として活用するためのポリイミド単量体、ポリイミド化合物及びその製造方法を提供する。本発明によるポリイミド単量体はポリイミド化合物を製造するための食刻工程でその食刻深さが深くなる場合、シリコン基板とポリイミドの熱膨張係数の差により発生する薄膜のきれ現象を防止するために提供される。本発明のポリイミド化合物は前記ポリイミド単量体とジアンヒドリドを溶媒に溶解させて中間体であるポリアミック酸(amic acid)を合成し、そのポリアミック酸をシリコン基板にコーティングして熱処理することにより製造される。
【０００８】
【発明の実施の形態】
以下、光学用のポリイミド単量体及びその製造方法、ポリイミド化合物及びその製造方法を説明する。
１．ポリイミド単量体及びその製造方法
本発明によるポリイミド単量体はポリイミド化合物を製造するための食刻工程で食刻の深さが深くなる場合、シリコン基板とポリイミドの熱膨張係数の差により発生する薄膜のきれ現象を防止するために提供される。
本発明のポリイミド単量体は下記の化学式１のように定義される。
【０００９】
【化７】
【００１０】
図１は本発明の実施形態によるポリイミド単量体の製造方法を示した流れ図である。図１に示したように、前記ポリイミド単量体は溶解過程(１１０)、加熱過程(１２０)、再結晶過程(１３０)及び還元過程(１４０)を含む工程により製造される。
前記溶解過程(１１０)はジオール(diol)と２−クロロ−５−ニトロベンゾトリフルオライドをＮ，Ｎ−ジメチルアセトアミドに溶解させる過程である。前記ジオールとしては、２，２−ビス(４−ヒドロキシフェニル)−１，１，１，３，３，３−ヘキサフルオロプロパン、テトラフルオロ−１，４，ヒドロキノン、テトラクロロ−１，４，ヒドロキノン、ヒドロキノン及び４，６−ジクロロレゾルシノールなどを用いることができる。
【００１１】
前記加熱過程(１２０)は前記溶解過程(１１０)による生成物に炭酸カリウム、第三ブチルアンモニウムクロライド及び銅パウダーを入れて熱を加える過程である。前記加熱過程(１２０)の加熱温度及び加熱時間は実施形態に応じて可変値を有する。
前記再結晶過程(１３０)は前記加熱過程(１２０)による生成物で銅を取り除いて沈殿させた後、アセト酸(acetic acid)で再結晶してジニトロ化合物を得る過程である。前記再結晶過程(１３０)の沈殿に用いられる溶媒は前記溶解過程に用いられるジオールの種類に応じて決められる。すなわち、前記ジオールとして２，２−ビス(４−ヒドロキシフェニル)−１，１，１，３，３，３−ヘキサフルオロプロパン、テトラフルオロ−１，４−ヒドロキノン及びヒドロキノンを用いる場合にはメタノール−水の１：１混合物を、前記ジオールとしてテトラクロロ−１，４−ヒドロキノンを用いる場合には濃い硫酸を、前記ジオールとして４，６−ジクロロレゾルシノールを用いる場合には塩酸を添加した水をそれぞれ沈殿用の溶媒として用いる。
【００１２】
前記還元過程(１４０)は前記ジニトロ化合物をテトラヒドロフランに溶解させた後、触媒を用いて還元させることにより、ジアミン化合物を生成する過程である。前記還元過程(１４０)は水素気体雰囲気下で行われるが、前記触媒としてはパラジウムを用いる。前記パラジウム及び水素はＮＯ2をＮＨ2に還元させる役目を果たす。
本発明のポリイミド単量体はポリイミド化合物からなるコアとクラッドの複屈折の変化問題点を改善することができる。かつ、本発明のポリイミド単量体は前記化学式１のＡｒ部分に様々なハロゲン化芳香族環基を置換させて広い範囲の屈折率を調節してコアとクラッド材料の選択幅を広げることができる。
【００１３】
［実施形態１−１］
２，２−ビス(４−ヒドロキシフェニル)−１，１，１，３，３，３−ヘキサフルオロプロパン５．１ｇ、０．０１５２モルと２−クロロ−５−ニトロベンゾトリフルオライド７．５１８ｇ、０．０３３３モルとを溶媒であるＮ−Ｎ−ジメチルアセトアミド６３ｍｌ(約２０％の固形粉含量)に溶解させた後、炭酸カリウム６．９１ｇ、０．０５モルと第三ブチルアンモニウムクロライド０．０９７５ｇ及び銅パウダー０．１９５ｇを入れた後、１００℃で２時間加熱反応させた。その後、前記反応溶液を濾過して銅を取り除いた後、メタノール−水の１：１混合溶媒に入れて沈殿物が生成されると、アセト酸で再結晶して黄色のジニトロ化合物８．４９７ｇ(７８．５％の収率)を得た。この化合物５．０ｇをテトラヒドロフランに溶解させた後、水素気体雰囲気でパラジウム(活性炭素内１０％)触媒を用いて還元させて前記化学式１により定義されるジアミン化合物２．６３３ｇ(６０．０％の収率)を製造した。
【００１４】
［実施形態１−２］
テトラフルオロ−１，４−ヒドロキノン２．７６１ｇ、０．０１５２モルと２−クロロ−５−ニトロベンゾトリフルオライド７．５１８ｇ、０．０３３３モルとを溶媒であるＮ−Ｎ−ジメチルアセトアミド５１ｍｌ(約２０％の固形粉含量)に溶解させた後、炭酸カリウム６．９１ｇ、０．０５モルと第三ブチルアンモニウムクロライド０．０９７５ｇ及び銅パウダー０．１９５ｇを入れた後、１１０℃で１６時間加熱反応させた。その後、前記反応溶液を濾過して銅を取り除いた後、メタノール−水の１：１混合溶媒に入れて沈殿物が生成されると、アセト酸で再結晶して肌色のジニトロ化合物５．５０５ｇ(６４．８％の収率)を得た。この化合物５．０ｇをテトラヒドロフランに溶解させた後、水素気体雰囲気でパラジウム(活性炭素内１０％)触媒を用いて還元させて前記化学式１により定義されるジアミン化合物３．４０７ｇ(７６．３％の収率)を製造した。
【００１５】
［実施形態１−３］
テトラクロロ−１，４−ヒドロキノン３．７６８ｇ、０．０１５２モルと２−クロロ−５−ニトロベンゾトリフルオライド７．５１８ｇ、０．０３３３モルとを溶媒であるＮ−Ｎ−ジメチルアセトアミド５６ｍｌ(約２０％の固形粉含量)に溶解させた後、炭酸カリウム６．９１ｇ、０．０５モルと第三ブチルアンモニウムクロライド０．０９７５ｇ及び銅パウダー０．１９５ｇを入れた後、８０℃で２４時間加熱反応させた。その後、前記反応溶液を濾過して銅を取り除いた後、濃い硫酸に入れて沈殿物が生成されると、アセト酸で再結晶して黄色のジニトロ化合物５．９０ｇ(６２．０％の収率)を得た。この化合物５．０ｇをテトラヒドロフランに溶解させた後、水素気体雰囲気でパラジウム(活性炭素内１０％)触媒を用いて還元させて前記化学式１により定義されるジアミン化合物３．１４８ｇ(６９．６％の収率)を製造した。
【００１６】
［実施形態１−４］
ヒドロキノン１．６７４ｇ、０．０１５２モルと２−クロロ−５−ニトロベンゾトリフルオライド７．５１８ｇ、０．０３３３モルとを溶媒であるＮ−Ｎ−ジメチルアセトアミド４６ｍｌ(約２０％の固形粉含量)に溶解させた後、炭酸カリウム６．９１ｇ、０．０５モルと第三ブチルアンモニウムクロライド０．０９７５ｇ及び銅パウダー０．１９５ｇを入れた後、１１０℃で３時間加熱反応させた。その後、前記反応溶液を濾過して銅を取り除いた後、メタノール−水の１：１混合溶媒に入れて沈殿物が生成されると、アセト酸で再結晶して黄色のジニトロ化合物５．３３７ｇ(７１．９％の収率)を得た。この化合物５．０ｇをテトラヒドロフランに溶解させた後、水素気体雰囲気でパラジウム(活性炭素内１０％)触媒を用いて還元させて前記化学式１により定義されるジアミン化合物３．３１３ｇ(７５．５％の収率)を製造した。
【００１７】
［実施形態１−５］
４，６−ジクロロレゾルシノール２．７２１ｇ、０．０１５２モルと２−クロロ−５−ニトロベンゾトリフルオライド７．５１８ｇ、０．０３３３モルとを溶媒であるＮ−Ｎ−ジメチルアセトアミド４６ｍｌ(約２０％の固形粉含量)に溶解させた後、炭酸カリウム６．９１ｇ、０．０５モルと第三ブチルアンモニウムクロライド０．０９７５ｇ及び銅パウダー０．１９５ｇを入れた後、８０℃で１５時間加熱反応させた。その後、前記反応溶液を濾過して銅を取り除いた後、塩酸を添加した水に入れて沈殿物が生成されると、アセト酸で再結晶して黄色のジニトロ化合物５．２８７ｇ(６２．４％の収率)を得た。この化合物５．０ｇをテトラヒドロフランに溶解させた後、水素気体雰囲気でバラジウム(活性炭素内１０％)触媒を用いて還元させて前記化学式１により定義されるジアミン化合物２．３４７ｇ(５３．５％の収率)を製造した。
【００１８】
２．ポリイミド化合物及びその製造方法
本発明のポリイミド化合物は上述したように製造されるポリイミド単量体とジアンヒドリドを溶媒に溶解させて中間体のポリアミック酸を合成し、前記合成ポリアミック酸をシリコン基板にコーティングした後、熱処理することにより製造される。この際、前記ジアンヒドリドは下記の化学式２により定義され、本発明のポリイミド化合物は下記の化学式３により定義される。
【００１９】
【化８】
【００２０】
【化９】
【００２１】
図２は本発明の実施形態によるポリイミド化合物の製造方法を示した流れ図である。図２に示したように、本発明のポリイミド化合物は溶解過程(２１０)、中間体形成過程(２２０)、コーティング過程(２３０)及び熱処理過程(２４０)を含む工程により製造される。
前記溶解過程(２１０)は化学式１によるポリイミド単量体と化学式２によるジアンヒドリドをジメチルアセトアミドに溶解させる過程である。前記ポリイミド単量体としては１，４−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)テトラフルオロベンゼン、１，４−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)ベンゼン、１，３−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)−４，６−ジクロロベンゼンなどを用いることができ、前記ジアンヒドリドとしては２，２−ビス(ジカルボキシフェニル)ヘキサフルオロプロパンジアンヒドリド及び１，２，４，５−ベンゼンテトラカルボキシアンヒドリドを用いる。
【００２２】
前記中間体形成過程(２２０)は前記溶解過程(２１０)による生成物を窒素雰囲気で攪拌させて中間体のポリアミック酸を形成する過程である。
前記コーティング過程(２３０)は前記中間体形成過程(２２０)で形成したポリアミック酸溶液をシリコン基板にコーティングする過程である。
前記熱処理過程(２４０)は前記ポリアミック酸コーティング基板を熱処理して最終的にポリイミド化合物を生成する過程である。前記熱処理過程(２４０)は窒素雰囲気のオーブンで行われるが、前記窒素はポリイミド化合物の内部への水分浸透を防止して高分子構造の鎖連結破壊を防止する。
【００２３】
３．共重合ポリイミド化合物及びその製造方法
本発明の共重合ポリイミド化合物は化学式１により定義される相異なるポリイミド単量体を相異なる比率で化学式２のジアンヒドリドと共重合させることにより製造され、このように製造された共重合ポリイミド化合物は相異なる屈折率を有する。
【００２４】
(１) 第１の共重合ポリイミド化合物及びその製造方法
本発明の実施形態による第１の共重合ポリイミド化合物は相異なるポリイミド単量体、すなわち、１，４−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)テトラフルオロベンゼン、１，４−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)ベンゼン、１，３−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)−４，６−ジクロロベンゼンなどを２，２−ビス(ジカルボキシフェニル)ヘキサフルオロプロパンジアンヒドリド(６ＦＤＡ)と共重合させることにより生成され、化学式４により定義される。
【００２５】
【化１０】
【００２６】
本発明の第１の共重合ポリイミド化合物の製造過程を調べると、同じモル数のポリイミド単量体と２，２−ビス(ジカルボキシフェニル)ヘキサフルオロプロパンジアンヒドリド(６ＦＤＡ)をジメチルアセトアミドに溶解させる。前記溶解過程による生成物を窒素雰囲気で攪拌させて中間体のポリアミック酸を形成させる。その後、前記ポリアミック酸をシリコン基板にスピンコーティングした後、前記ポリアミック酸コーティングのシリコン基板をオーブンなどで熱処理すると、前記化学式４のような第１の共重合ポリイミド化合物を得ることができる。
【００２７】
［実施形態２−１］
同じモル数の１，４−ビス（４−アミノ−２−トリフルオロメチルフェノキシ）テトラフルオロベンゼン４．５０３ｇ、０．００９モルと２，２−ビス（ジカルボキシフェニル）ヘキサフルオロプロパンジヒドリド４ｇ、０．００９モルとを溶媒であるジメチルアセトアミド４２．５ｇに溶解させた後、窒素雰囲気で２４時間攪拌させてポリアミック酸を合成した。その後、前記ポリアミック酸溶液をシリコン基板にスピンコーティングし、これを窒素雰囲気のオーブンで１００℃／３０分、２００℃／１時間、３５０℃／１時間熱処理して透明なポリイミドフィルムを得た。この際、前記ポリイミドの屈折率は１５５０nmでＴＥモードの場合は１．５０９９、ＴＭモードの場合は１．５０２４である。
【００２８】
［実施形態２−２］
同じモル数の１，４−ビス（４−アミノ−２−トリフルオロメチルフェノキシ）ベンゼン３．８５５ｇ、０．００９モルと２，２−ビス（ジカルボキシフェニル）ヘキサフルオロプロパンジヒドリド４ｇ、０．００９モルとを溶媒であるジメチルアセトアミド４２．５ｇに溶解させた後、窒素雰囲気で２４時間攪拌させてポリアミック酸を合成した。その後、前記ポリアミック酸溶液をシリコン基板にスピンコーティングし、これを窒素雰囲気のオーブンで１００℃／３０分、２００℃／１時間、３５０℃／１時間熱処理して透明なポリイミドフィルムを得た。この際、前記ポリイミドの屈折率は１５５０nmでＴＥモードの場合は１．５２８９、ＴＭモードの場合は１．５２２４である。
【００２９】
［実施形態２−３］
同じモル数の１，３−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)−４，６−ジクロロベンゼン４．４７５ｇ、０．００９モルと２，２−ビス(ジカルボキシフェニル)ヘキサフルオロプロパンジヒドリド４ｇ、０．００９モルとを溶媒であるジメチルアセトアミド４２．４ｇに溶解させた後、窒素雰囲気で２４時間攪拌させてポリアミック酸を合成した。その後、前記ポリアミック酸溶液をシリコン基板にスピンコーティングし、これを窒素雰囲気のオーブンで１００℃／３０分、２００℃／１時間、３５０℃／１時間熱処理して透明なポリイミドフィルムを得た。この際、前記ポリイミドの屈折率は１５５０nmでＴＥモードの場合は１．５３４４、ＴＭモードの場合は１．５３０３である。
【００３０】
(２) 第２の共重合ポリイミド化合物及びその製造方法
本発明の実施形態による第２の共重合ポリイミド化合物は相異なるポリイミド単量体、すなわち、１，４−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)テトラフルオロベンゼン、１，４−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)ベンゼン、１，３−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)−４，６−ジクロロベンゼンのうち、いずれか一つを１，２，４，５−ベンゼンテトラカルボキシアンヒドリド(ＰＤＭＡ)と共重合させることにより生成され、化学式５により定義される。
【００３１】
【化１１】
【００３２】
本発明の第２の共重合ポリイミド化合物の製造過程を調べると、ポリイミド単量体と１，２，４，５−ベンゼンテトラカルボキシアンヒドリドをジメチルアセトアミドに溶解させる。次に、前記溶解過程による生成物を窒素雰囲気で攪拌させて中間体のポリアミック酸を形成させる。その後、前記ポリアミック酸をシリコン基板にスピンコーティングした後、前記ポリアミック酸コーティングのシリコン基板をオーブンなどで熱処理すると、前記化学式５のような第２共重合ポリイミド化合物を得ることができる。
【００３３】
［実施形態３−１］
同じモル数の１，４−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)テトラフルオロベンゼン４．５０３ｇ、０．００９モルと１，２，４，５−ベンゼンテトラカルボキシアンヒドリド１．９６３ｇ、０．００９モルとを溶媒であるジメチルアセトアミド３２．３ｇに溶解させた後、窒素雰囲気で２４時間攪拌させてポリアミック酸を合成した。その後、前記ポリアミック酸溶液をシリコン基板にスピンコーティングし、これを窒素雰囲気のオーブンで１００℃／３０分、２００℃／１時間、３５０℃／１時間熱処理して透明なポリイミドフィルムを得た。この際、前記ポリイミドの屈折率は１５５０nmでＴＥモードの場合は１．５３９７、ＴＭモードの場合は１．５２３９である。
【００３４】
［実施形態３−２］
同じモル数の１，４−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)ベンゼン３．８５５ｇ、０．００９モルと１，２，４，５−ベンゼンテトラカルボキシアンヒドリド１．９６３ｇ、０．００９モルとを溶媒であるジメチルアセトアミド２９．１ｇに溶解させた後、窒素雰囲気で２４時間攪拌させてポリアミック酸を合成した。その後、前記ポリアミック酸溶液をシリコン基板にスピンコーティングし、これを窒素雰囲気のオーブンで１００℃／３０分、２００℃／１時間、３５０℃／１時間熱処理して透明なポリイミドフィルムを得た。この際、前記ポリイミドの屈折率は１５５０nmでＴＥモードの場合は１．５６７１、ＴＭモードの場合は１．５５１３である。
【００３５】
［実施形態３−３］
同じモル数の１，３−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)−４，６−ジクロロベンゼン４．４７５ｇ、０．００９モルと１，２，４，５−ベンゼンテトラカルボキシアンヒドリド１．９６３ｇ、０．００９モルとを溶媒であるジメチルアセトアミド３２．３ｇに溶解させた後、窒素雰囲気で２４時間攪拌させてポリアミック酸を合成した。その後、前記ポリアミック酸溶液をシリコン基板にスピンコーティングし、これを窒素雰囲気のオーブンで１００℃／３０分、２００℃／１時間、３５０℃／１時間熱処理して透明なポリイミドフィルムを得た。この際、前記ポリイミドの屈折率は１５５０nmでＴＥモードの場合は１．５７２７、ＴＭモードの場合は１．５６７０である。
【００３６】
［実施形態３−４］
二種のジアミン、１，４−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)テトラフルオロベンゼン１．５７６ｇ、０．００３１５モル及び１，４−ビス(４−アミノ−２−トリフルオロメチルフェノキシ)ベンゼン２．５０６ｇ、０．００５８５モルを１，２，４，５−ベンゼンテトラカルボキシアンヒドリドとともに溶媒であるジメチルアセトアミド３０．２ｇに溶解させた後、窒素雰囲気で２４時間攪拌させてポリアミック酸を合成した。その後、前記ポリアミック酸溶液をシリコン基板にスピンコーティングし、これを窒素雰囲気のオーブンで１００℃／３０分、２００℃／１時間、３５０℃／１時間熱処理して透明なポリイミドフィルムを得た。この際、前記ポリイミドの屈折率は１５５０nmでＴＥモードの場合は１．５５９７、ＴＭモードの場合は１．５４００である。
【００３７】
【発明の効果】
上述したように、本発明の実施形態による光学用のポリイミド単量体、ポリイミド化合物及びその製造方法はフルオロ化ポリイミド化合物の低い光吸収損失及び高い耐熱特性はそのまま維持しながら、食刻工程時の薄膜のきれ現象を防止することができる。
かつ、本発明の実施形態による光学用のポリイミド単量体、ポリイミド化合物及びその製造方法は１３００−１５５０nmの光通信波長帯域で低い光吸収損失を示すため、比較的広い領域で様々な屈折率の調節によりコアとクラッドの材料選択幅を広げることができる。
【図面の簡単な説明】
【図１】本発明の実施形態によるポリイミド単量体の製造方法を示した流れ図である。
【図２】本発明の実施形態によるポリイミド化合物の製造方法を示した流れ図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an optical linear polymer material, and more particularly to an optical polyimide monomer, a polyimide compound, and a method for producing the same.
[0002]
[Prior art]
In general, linear polymer materials for optics are materials used for various optical elements that are the core components of the next generation high-speed, large-capacity information and communications business. Photoelectric integrated circuits, photoelectric mixed wiring tubes, hybrid integrated elements, It is used to manufacture an optical element for guiding an optical multi-substrate element and a plastic optical fiber.
In the past, inorganic crystals such as LiNbO 3 have been used as the material of optical elements. However, since the inorganic crystals are difficult to manufacture and process due to their characteristics and there is a limit to mass production, material design and processing are currently limited. Research on organic polymer materials that are easy to handle is underway.
[0003]
Among these organic polymer materials, polyimide is used as a buffer for protecting semiconductors due to excellent thermal and mechanical properties. In order to utilize the polyimide as an optical polymer material, C—H Research has been conducted to reduce light absorption loss by substituting fluorine or deuterium for hydrogen instead of bonding hydrogen. In general, a polymer material absorbs light in the near infrared region of 1000 to 1700 nm. Such light absorption loss occurs due to high-frequency overtones caused by stretching and deformation vibrations of CH bonds in the main chain of the polymer. In order to reduce this, the absorption wavelength of light should be moved to a longer wavelength or shorter wavelength side than the near infrared region. For this reason, the hydrogen of the C—H bond is replaced with fluorine or deuterium.
[0004]
In the case of the polyimide in which hydrogen is substituted with deuterium, light absorption occurs in the 1550 nm wavelength band, so that it is not suitable for a material for an optical communication element. However, in the case of polyimide in which hydrogen is replaced with fluorine, light absorption loss in the wavelength band of 1000 to 1700 nm can be minimized, and it has been developed as a material for optical communication elements. When manufacturing an optical waveguide using polyimide substituted with fluorine, the mixing ratio of the monomer containing fluorine and the monomer not containing fluorine is appropriately set in order to satisfy the difference in refractive index between the core layer and the cladding layer. The core layer and the clad layer are manufactured by adjusting and copolymerizing.
[0005]
However, since conventional polyimide substituted with fluorine, ie, fluorinated polyimide compound, has a low refractive index due to the inclusion of fluorine, a clad layer having a lower refractive index than the core layer is formed when a core layer is formed using this. The choice of materials used to do so is limited. In addition, when the clad layer is formed using the polyimide substituted with fluorine, there is a problem that the absorption loss of light increases because the content of C—H bonds increases due to the decrease in fluorine content.
In addition, the conventional polyimide has a flexible chain structure having a low birefringence, but when the depth of the polyimide having such a chain structure becomes deep during the etching process, the thermal expansion coefficient between the silicon substrate and the polyimide is low. There is also a problem that the thin film is broken due to the difference.
[0006]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide an optical polyimide unit that can prevent the thin film cracking phenomenon during the etching process while maintaining the low light absorption loss and high heat resistance of the conventional fluorinated polyimide compound. It is in providing a body, a polyimide compound, and its manufacturing method.
Another object of the present invention is for optical use that has a low optical absorption loss in the optical communication wavelength band of 1300 to 1550 nm, thereby expanding the material selection range of the core and the clad by adjusting various refractive indexes in a relatively wide region. It is providing the polyimide monomer, a polyimide compound, and its manufacturing method.
[0007]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a polyimide monomer, a polyimide compound and a method for producing the same for use as an optical polymer material. The polyimide monomer according to the present invention prevents a thin film cracking phenomenon caused by a difference in thermal expansion coefficient between the silicon substrate and the polyimide when the etching depth is deep in the etching process for manufacturing the polyimide compound. Provided to. The polyimide compound of the present invention is manufactured by dissolving the polyimide monomer and dianhydride in a solvent to synthesize an intermediate polyamic acid (amic acid), coating the polyamic acid on a silicon substrate, and heat-treating it. The
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the polyimide monomer for optics, its manufacturing method, a polyimide compound, and its manufacturing method are demonstrated.
1. Polyimide monomer and manufacturing method thereof The polyimide monomer according to the present invention is generated due to a difference in thermal expansion coefficient between the silicon substrate and the polyimide when the etching depth becomes deep in the etching process for manufacturing the polyimide compound. Provided to prevent thin film breakage.
The polyimide monomer of the present invention is defined as the following chemical formula 1.
[0009]
[Chemical 7]
[0010]
FIG. 1 is a flowchart illustrating a method for producing a polyimide monomer according to an embodiment of the present invention. As shown in FIG. 1, the polyimide monomer is manufactured through processes including a dissolution process (110), a heating process (120), a recrystallization process (130), and a reduction process (140).
The dissolution process (110) is a process of dissolving diol and 2-chloro-5-nitrobenzotrifluoride in N, N-dimethylacetamide. Examples of the diol include 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, tetrafluoro-1,4, hydroquinone, and tetrachloro-1,4, hydroquinone. Hydroquinone and 4,6-dichlororesorcinol can be used.
[0011]
The heating process (120) is a process in which potassium carbonate, tert-butylammonium chloride and copper powder are added to the product of the dissolution process (110) and heat is applied. The heating temperature and the heating time of the
The
[0012]
The reduction process (140) is a process of forming a diamine compound by dissolving the dinitro compound in tetrahydrofuran and then reducing it using a catalyst. The
The polyimide monomer of the present invention can improve the problem of change in birefringence between a core and a clad made of a polyimide compound. In addition, the polyimide monomer of the present invention can expand the selection range of the core and clad material by substituting various halogenated aromatic ring groups in the Ar portion of the chemical formula 1 to adjust the refractive index in a wide range. .
[0013]
[Embodiment 1-1]
2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (5.1 g), 0.0152 mol and 2-chloro-5-nitrobenzotrifluoride (7.518 g), 0.0333 mol was dissolved in 63 ml of NN-dimethylacetamide (about 20% solid powder content) as a solvent and then 6.91 g, 0.05 mol of potassium carbonate and 0.0975 g of tert-butylammonium chloride. And after adding 0.195 g of copper powder, it was made to heat-react at 100 degreeC for 2 hours. Thereafter, the reaction solution was filtered to remove copper, and then put into a 1: 1 mixed solvent of methanol and water, and when a precipitate was formed, it was recrystallized with aceto acid and 8.497 g of a yellow dinitro compound ( 78.5% yield). After dissolving 5.0 g of this compound in tetrahydrofuran, it was reduced with a palladium (10% in activated carbon) catalyst in a hydrogen gas atmosphere to obtain 2.633 g (60.0% of diamine compound) defined by the above chemical formula 1. Yield).
[0014]
[Embodiment 1-2]
51 ml (about 20) of NN-dimethylacetamide as a solvent was prepared by using 2.761 g of tetrafluoro-1,4-hydroquinone, 0.0152 mol and 7.518 g of 2-chloro-5-nitrobenzotrifluoride, 0.0333 mol. % Solid powder content), potassium carbonate 6.91 g, 0.05 mol, tert-butylammonium chloride 0.0975 g and copper powder 0.195 g were added, followed by heating at 110 ° C. for 16 hours. It was. Thereafter, the reaction solution was filtered to remove copper, and then put into a 1: 1 mixed solvent of methanol-water, and when a precipitate was formed, it was recrystallized with aceto acid to give 5.505 g of skin-colored dinitro compound ( 64.8% yield). After dissolving 5.0 g of this compound in tetrahydrofuran and reducing it with a palladium (10% in activated carbon) catalyst in a hydrogen gas atmosphere, 3.407 g (76.3% of diamine compound) defined by the above chemical formula 1 was used. Yield).
[0015]
[Embodiment 1-3]
56 ml of NN-dimethylacetamide (about 20 ml) containing 3.768 g of tetrachloro-1,4-hydroquinone and 0.0152 mol and 7.518 g of 2-chloro-5-nitrobenzotrifluoride and 0.0333 mol as a solvent. % Solid powder content), potassium carbonate 6.91 g, 0.05 mol, tert-butylammonium chloride 0.0975 g and copper powder 0.195 g were added, followed by heating at 80 ° C. for 24 hours. It was. Thereafter, the reaction solution was filtered to remove copper, and then added to concentrated sulfuric acid to form a precipitate, which was recrystallized with aceto acid to give 5.90 g of a yellow dinitro compound (62.0% yield). ) After dissolving 5.0 g of this compound in tetrahydrofuran, it was reduced using a palladium (10% in activated carbon) catalyst in a hydrogen gas atmosphere to obtain 3.148 g (69.6% of diamine compound) defined by Formula 1 above. Yield).
[0016]
[Embodiment 1-4]
Hydroquinone (1.674 g, 0.0152 mol) and 2-chloro-5-nitrobenzotrifluoride (7.518 g, 0.0333 mol) in 46 ml of NN-dimethylacetamide (about 20% solid powder content) as a solvent After dissolution, 6.91 g, 0.05 mol of potassium carbonate, 0.0975 g of tert-butylammonium chloride and 0.195 g of copper powder were added, followed by heating at 110 ° C. for 3 hours. Thereafter, the reaction solution was filtered to remove copper, and then put into a 1: 1 mixed solvent of methanol and water, and when a precipitate was formed, it was recrystallized with aceto acid to give 5.337 g of a yellow dinitro compound ( 71.9% yield). After 5.0 g of this compound was dissolved in tetrahydrofuran, it was reduced with a palladium (10% in activated carbon) catalyst in a hydrogen gas atmosphere to obtain 3.313 g (75.5% of diamine compound) defined by Formula 1 above. Yield).
[0017]
Embodiment 1-5
46 ml of NN-dimethylacetamide (about 20%) was prepared by using 2.721 g of 4,6-dichlororesorcinol, 0.0152 mol and 7.518 g of 2-chloro-5-nitrobenzotrifluoride, 0.0333 mol as solvent. After being dissolved in (solid powder content), 6.91 g of potassium carbonate, 0.05 mol, 0.0975 g of tert-butylammonium chloride and 0.195 g of copper powder were added, followed by heating at 80 ° C. for 15 hours. Thereafter, the reaction solution was filtered to remove copper, and then added to water to which hydrochloric acid had been added. When a precipitate was formed, it was recrystallized from aceto acid to give 5.287 g (62.4%) of a yellow dinitro compound. Yield). After dissolving 5.0 g of this compound in tetrahydrofuran, it was reduced using a catalyst of palladium (10% in activated carbon) in a hydrogen gas atmosphere to obtain 2.347 g (53.5% of diamine compound) defined by Formula 1 above. Yield).
[0018]
2. Polyimide compound and production method thereof The polyimide compound of the present invention is prepared by dissolving the polyimide monomer and dianhydride produced as described above in a solvent to synthesize an intermediate polyamic acid, and coating the synthetic polyamic acid on a silicon substrate. Then, it is manufactured by heat treatment. At this time, the dianhydride is defined by the following chemical formula 2, and the polyimide compound of the present invention is defined by the following chemical formula 3.
[0019]
[Chemical 8]
[0020]
[Chemical 9]
[0021]
FIG. 2 is a flowchart illustrating a method for manufacturing a polyimide compound according to an embodiment of the present invention. As shown in FIG. 2, the polyimide compound of the present invention is manufactured through processes including a dissolution process (210), an intermediate formation process (220), a coating process (230), and a heat treatment process (240).
The dissolution process (210) is a process of dissolving the polyimide monomer according to Chemical Formula 1 and the dianhydride according to Chemical Formula 2 in dimethylacetamide. Examples of the polyimide monomer include 1,4-bis (4-amino-2-trifluoromethylphenoxy) tetrafluorobenzene, 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 1,3 -Bis (4-amino-2-trifluoromethylphenoxy) -4,6-dichlorobenzene and the like can be used, and as the dianhydride, 2,2-bis (dicarboxyphenyl) hexafluoropropane dianhydride and 1 2,4,5-benzenetetracarboxyanhydride is used.
[0022]
The
The
The
[0023]
3. Copolymerized polyimide compound and production method thereof The copolymerized polyimide compound of the present invention is produced by copolymerizing different polyimide monomers defined by Chemical Formula 1 with dianhydride of Chemical Formula 2 in different ratios, as described above. The produced copolymer polyimide compound has different refractive indexes.
[0024]
(1) First Copolymerized Polyimide Compound and Method for Producing the Same The first copolymerized polyimide compound according to the embodiment of the present invention includes different polyimide monomers, that is, 1,4-bis (4-amino-2-trimethyl). Fluoromethylphenoxy) tetrafluorobenzene, 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 1,3-bis (4-amino-2-trifluoromethylphenoxy) -4,6-di It is produced by copolymerizing chlorobenzene or the like with 2,2-bis (dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), and is defined by Chemical Formula 4.
[0025]
[Chemical Formula 10]
[0026]
When the production process of the first copolymerized polyimide compound of the present invention is examined, the same number of moles of polyimide monomer and 2,2-bis (dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) are dissolved in dimethylacetamide. . The product resulting from the dissolution process is stirred in a nitrogen atmosphere to form an intermediate polyamic acid. Then, after spin-coating the polyamic acid on a silicon substrate, the silicon substrate coated with the polyamic acid is heat-treated in an oven or the like to obtain the first copolymer polyimide compound represented by the chemical formula 4.
[0027]
[Embodiment 2-1]
4.53 g of 1,4-bis (4-amino-2-trifluoromethylphenoxy) tetrafluorobenzene of the same number of moles, 0.009 mol and 4 g of 2,2-bis (dicarboxyphenyl) hexafluoropropane dihydride, After dissolving 0.009 mol in 42.5 g of dimethylacetamide as a solvent, the mixture was stirred in a nitrogen atmosphere for 24 hours to synthesize a polyamic acid. Thereafter, the polyamic acid solution was spin-coated on a silicon substrate, and this was heat-treated in an oven in a nitrogen atmosphere at 100 ° C./30 minutes, 200 ° C./1 hour, 350 ° C./1 hour to obtain a transparent polyimide film. At this time, the refractive index of the polyimide is 1550 nm and is 1.5099 in the TE mode and 1.5024 in the TM mode.
[0028]
[Embodiment 2-2]
1.855 g of 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene of the same number of moles, 0.009 mol and 4 g of 2,2-bis (dicarboxyphenyl) hexafluoropropane dihydride; 009 mol was dissolved in 42.5 g of dimethylacetamide as a solvent, and then stirred for 24 hours in a nitrogen atmosphere to synthesize a polyamic acid. Thereafter, the polyamic acid solution was spin-coated on a silicon substrate, and this was heat-treated in an oven in a nitrogen atmosphere at 100 ° C./30 minutes, 200 ° C./1 hour, 350 ° C./1 hour to obtain a transparent polyimide film. At this time, the refractive index of the polyimide is 1550 nm, 1.5289 in the TE mode, and 1.5224 in the TM mode.
[0029]
[Embodiment 2-3]
1.475 of 1,3-bis (4-amino-2-trifluoromethylphenoxy) -4,6-dichlorobenzene of the same mole number, 0.009 mole and 2,2-bis (dicarboxyphenyl) hexafluoropropane 4 g of dihydride and 0.009 mol were dissolved in 42.4 g of dimethylacetamide as a solvent, and then stirred for 24 hours in a nitrogen atmosphere to synthesize a polyamic acid. Thereafter, the polyamic acid solution was spin-coated on a silicon substrate, and this was heat-treated in an oven in a nitrogen atmosphere at 100 ° C./30 minutes, 200 ° C./1 hour, 350 ° C./1 hour to obtain a transparent polyimide film. At this time, the refractive index of the polyimide is 1550 nm, 1.5344 for the TE mode, and 1.5303 for the TM mode.
[0030]
(2) Second Copolymerized Polyimide Compound and Method for Producing the Same The second copolymerized polyimide compound according to the embodiment of the present invention is a different polyimide monomer, that is, 1,4-bis (4-amino-2-trimethyl). Fluoromethylphenoxy) tetrafluorobenzene, 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 1,3-bis (4-amino-2-trifluoromethylphenoxy) -4,6-di It is produced by copolymerizing any one of chlorobenzene with 1,2,4,5-benzenetetracarboxyanhydride (PDMA), and is defined by Chemical Formula 5.
[0031]
Embedded image
[0032]
When the production process of the second copolymerized polyimide compound of the present invention is examined, the polyimide monomer and 1,2,4,5-benzenetetracarboxyanhydride are dissolved in dimethylacetamide. Next, the product resulting from the dissolution process is stirred in a nitrogen atmosphere to form an intermediate polyamic acid. Thereafter, the polyamic acid is spin-coated on a silicon substrate, and then the silicon substrate coated with the polyamic acid is heat-treated in an oven or the like, whereby a second copolymerized polyimide compound represented by Formula 5 can be obtained.
[0033]
[Embodiment 3-1]
4.503 g of 1,4-bis (4-amino-2-trifluoromethylphenoxy) tetrafluorobenzene of the same number of moles, 0.009 mol and 1.963 g of 1,2,4,5-benzenetetracarboxyanhydride, 0.009 mol was dissolved in 32.3 g of dimethylacetamide as a solvent, and then stirred for 24 hours in a nitrogen atmosphere to synthesize a polyamic acid. Thereafter, the polyamic acid solution was spin-coated on a silicon substrate, and this was heat-treated in an oven in a nitrogen atmosphere at 100 ° C./30 minutes, 200 ° C./1 hour, 350 ° C./1 hour to obtain a transparent polyimide film. At this time, the refractive index of the polyimide is 1550 nm, 1.5397 for the TE mode, and 1.5239 for the TM mode.
[0034]
[Embodiment 3-2]
1.855 g, 0.009 mol of 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene of the same mole number, 1.963 g of 1,9,4,5-benzenetetracarboxyanhydride; 009 mol was dissolved in 29.1 g of dimethylacetamide as a solvent, and then stirred for 24 hours in a nitrogen atmosphere to synthesize a polyamic acid. Thereafter, the polyamic acid solution was spin-coated on a silicon substrate, and this was heat-treated in an oven in a nitrogen atmosphere at 100 ° C./30 minutes, 200 ° C./1 hour, 350 ° C./1 hour to obtain a transparent polyimide film. At this time, the refractive index of the polyimide is 1550 nm, 1.5671 in the TE mode, and 1.5513 in the TM mode.
[0035]
[Embodiment 3-3]
1.475 g of 1,3-bis (4-amino-2-trifluoromethylphenoxy) -4,6-dichlorobenzene of the same number of moles, 0.009 mol and 1,2,4,5-benzenetetracarboxyanhydride 1.963 g and 0.009 mol were dissolved in 32.3 g of dimethylacetamide as a solvent, and then stirred for 24 hours in a nitrogen atmosphere to synthesize a polyamic acid. Thereafter, the polyamic acid solution was spin-coated on a silicon substrate, and this was heat-treated in an oven in a nitrogen atmosphere at 100 ° C./30 minutes, 200 ° C./1 hour, 350 ° C./1 hour to obtain a transparent polyimide film. At this time, the refractive index of the polyimide is 1550 nm, 1.5727 in the TE mode, and 1.5670 in the TM mode.
[0036]
[Embodiment 3-4]
Two diamines, 1,4-bis (4-amino-2-trifluoromethylphenoxy) tetrafluorobenzene 1.576 g, 0.00315 mol and 1,4-bis (4-amino-2-trifluoromethylphenoxy) ) After dissolving 2.506 g of benzene and 0.00585 mol in 30.2 g of dimethylacetamide as a solvent together with 1,2,4,5-benzenetetracarboxyanhydride, the mixture was stirred in a nitrogen atmosphere for 24 hours to give a polyamic acid. Synthesized. Thereafter, the polyamic acid solution was spin-coated on a silicon substrate, and this was heat-treated in an oven in a nitrogen atmosphere at 100 ° C./30 minutes, 200 ° C./1 hour, 350 ° C./1 hour to obtain a transparent polyimide film. At this time, the refractive index of the polyimide is 1550 nm, 1.5597 for the TE mode, and 1.5400 for the TM mode.
[0037]
【The invention's effect】
As described above, the optical polyimide monomer, the polyimide compound, and the manufacturing method thereof according to the embodiment of the present invention maintain the low light absorption loss and the high heat resistance of the fluorinated polyimide compound as they are, while the etching process is performed. Thin film breakage can be prevented.
In addition, since the optical polyimide monomer, the polyimide compound, and the manufacturing method thereof according to the embodiment of the present invention exhibit low optical absorption loss in the optical communication wavelength band of 1300 to 1550 nm, various refractive indexes are obtained in a relatively wide region. Adjustments can expand the material selection range for the core and cladding.
[Brief description of the drawings]
FIG. 1 is a flowchart illustrating a method for producing a polyimide monomer according to an embodiment of the present invention.
FIG. 2 is a flowchart illustrating a method for producing a polyimide compound according to an embodiment of the present invention.
Claims (6)
により定義される、光学用高分子材料用のポリイミド単量体。The following chemical formula 1:
Polyimide monomer for optical polymer material , defined by
前記溶解過程による生成物に炭酸カリウム、第三ブチルアンモニウムクロライド及び銅パウダーを入れて熱を加える過程と、
前記加熱過程による生成物で銅を取り除いて沈殿させた後、アセト酸で再結晶してジニトロ化合物を得る過程と、
前記ジニトロ化合物をテトラヒドロフランに溶解させた後、触媒を用いて還元させることにより、ジアミン化合物を生成する過程とを備えることを特徴とする光学用のポリイミド単量体の製造方法。Dissolving a compound selected from the group consisting of tetrafluoro- 1,3 -hydroquinone and tetrachloro- 1,4 -hydroquinone and 2-chloro-5-nitrobenzotrifluoride in N, N-dimethylacetamide;
Adding potassium carbonate, tert-butylammonium chloride and copper powder to the product of the dissolution process and applying heat;
Removing and precipitating copper from the product of the heating process, and then recrystallizing with aceto acid to obtain a dinitro compound;
A process for producing a diamine compound by dissolving the dinitro compound in tetrahydrofuran and then reducing the dinitro compound using a catalyst.
により定義される、ポリイミド化合物からなる光学用高分子。 The following chemical formula 3:
An optical polymer comprising a polyimide compound defined by
によるポリイミド単量体と下記の化学式２：
によるジアンヒドリドをジメチルアセトアミドに溶解させる過程と、
前記溶解過程による生成物を窒素雰囲気で攪拌させてポリアミック酸を形成する中間体形成過程と、
前記中間体形成過程によるポリアミック酸をシリコン基板にコーティングする過程と、
前記ポリアミック酸でコーティングされた基板を熱処理してポリイミド化合物を生成する過程とを備えることを特徴とする光学用のポリイミド化合物の製造方法。In a method for producing an optical polymer material, the following chemical formula 1:
And the following chemical formula 2:
A process of dissolving dianhydride by dimethylacetamide,
An intermediate formation process in which the product of the dissolution process is stirred in a nitrogen atmosphere to form a polyamic acid;
A process of coating a silicon substrate with polyamic acid by the intermediate formation process;
A process for producing a polyimide compound by heat-treating the substrate coated with the polyamic acid.
により定義されることを特徴とする光学用のポリイミド化合物。The following chemical formula 4:
An optical polyimide compound characterized by the above.
により定義される、ポリイミド化合物からなる光学用高分子。 The following chemical formula 5:
An optical polymer comprising a polyimide compound defined by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000064045A JP3719898B2 (en) | 2000-03-08 | 2000-03-08 | Optical polyimide monomer, polyimide compound and production method thereof |
Applications Claiming Priority (1)
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| KR101912738B1 (en) * | 2017-05-23 | 2018-10-30 | 주식회사 대림코퍼레이션 | High Transparency polyimide precursor resin composition having excellent Optical Characteristics and phase Retardation, method for manufacturing polyimide film using the same, and polyimide film thereof |
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