JP4955877B2 - Polyaminofluorene derivative - Google Patents
Polyaminofluorene derivative Download PDFInfo
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- JP4955877B2 JP4955877B2 JP2001301076A JP2001301076A JP4955877B2 JP 4955877 B2 JP4955877 B2 JP 4955877B2 JP 2001301076 A JP2001301076 A JP 2001301076A JP 2001301076 A JP2001301076 A JP 2001301076A JP 4955877 B2 JP4955877 B2 JP 4955877B2
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000002837 carbocyclic group Chemical group 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims 2
- 239000003610 charcoal Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 59
- 239000000126 substance Substances 0.000 description 42
- 230000009477 glass transition Effects 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005259 measurement Methods 0.000 description 10
- -1 biphenylyl group Chemical group 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005019 vapor deposition process Methods 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000262 chemical ionisation mass spectrometry Methods 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- OGNSDRMLWYNUED-UHFFFAOYSA-N 1-cyclohexyl-4-[4-[4-(4-cyclohexylcyclohexyl)cyclohexyl]cyclohexyl]cyclohexane Chemical group C1CCCCC1C1CCC(C2CCC(CC2)C2CCC(CC2)C2CCC(CC2)C2CCCCC2)CC1 OGNSDRMLWYNUED-UHFFFAOYSA-N 0.000 description 1
- RINOYHWVBUKAQE-UHFFFAOYSA-N 1-iodo-2-methylbenzene Chemical compound CC1=CC=CC=C1I RINOYHWVBUKAQE-UHFFFAOYSA-N 0.000 description 1
- NHPPIJMARIVBGU-UHFFFAOYSA-N 1-iodonaphthalene Chemical compound C1=CC=C2C(I)=CC=CC2=C1 NHPPIJMARIVBGU-UHFFFAOYSA-N 0.000 description 1
- CWNJSSNWLUIMDP-UHFFFAOYSA-N 1-iodopyrene Chemical compound C1=C2C(I)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 CWNJSSNWLUIMDP-UHFFFAOYSA-N 0.000 description 1
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000003336 coronenyl group Chemical group C1(=CC2=CC=C3C=CC4=CC=C5C=CC6=CC=C1C1=C6C5=C4C3=C21)* 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000002192 heptalenyl group Chemical group 0.000 description 1
- 125000001633 hexacenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC5=CC6=CC=CC=C6C=C5C=C4C=C3C=C12)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000006384 methylpyridyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000003933 pentacenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C12)* 0.000 description 1
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000001828 phenalenyl group Chemical group C1(C=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 125000001388 picenyl group Chemical group C1(=CC=CC2=CC=C3C4=CC=C5C=CC=CC5=C4C=CC3=C21)* 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は蒸着プロセス耐熱性に優れた化合物、およびその化合物を用いた電荷輸送材料、有機電界発光素子に関するものである。
【０００２】
【従来の技術】
電子製品の材料化合物、特に有機電界発光素子の電荷輸送材料として、分子中にトリフェニルアミンの４量体の構造を部分的に含む多様な構造の化合物が提案されている。（特開平7-126226号公報、特開平7-126615号公報）
【０００３】
またフルオレンの部分構造を有するトリフェニルアミンの二量体が、有機電界発光素子の材料として提案されている。（特許第３０７９９０９号）
【０００４】
【発明が解決しようとする課題】
有機電界発光素子の応用分野が拡大してきたことに伴い、製品の素子性能として１００℃を越える耐熱性が求められるようになってきたが（有機ＬＥＤ素子の残された重要課題と実用化技術、ｐ４、有機エレクトロニクス材料研究会、1999）、１００℃を越える耐熱性を満足させるためにはおおむね１４０℃を越えるガラス転移点を有する化合物が必要とされる。
【０００５】
また有機電界発光素子の製造に際しては、蒸着温度を上げることによって蒸着時間を短縮することが可能なので、蒸着プロセス時の耐熱性が高いことが材料化合物に求められている。化合物が分解する温度付近で蒸着プロセスを行うと、化学的に均一な機能性膜が作製できず、有機電界発光素子の特性は大きく低下する。
【０００６】
本発明はガラス転移点が高く、しかも蒸着プロセス時の耐熱性が高い化合物を耐熱性電荷輸送材料として提供すること、またその材料の使用によって優れた特性を有する耐熱性有機電界発光素子を提供することを目的としている。
【０００７】
【課題を解決するための手段】
本発明者らは前記した二つの要件を同時に満足する化合物を探索した結果、一般式［１］で表される化合物が１５０℃を越える高いガラス転移点を有し、しかも熱的に安定であることを見出して本発明を完成するに至った。すなわち本発明は、一般式［１］で表されるポリアミノフルオレン誘導体である。
【０００８】
【化３】
〔式中、Ａr１、Ａr２はそれぞれ独立に置換もしくは無置換の炭素環式芳香族環基（炭素数６以上）、置換もしくは無置換の複素環式芳香族環基または置換もしくは無置換の炭素環式脂肪族環基（環を構成する炭素数５以上）を表す。Ｒ１、Ｒ２、Ｒ３はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基（炭素数１〜８）、アルコキシ基（炭素数１〜８）を表し、Ｒ４は水素原子、ハロゲン原子、アルキル基（炭素数１〜８）、アルコキシ基（炭素数１〜８）、アミノ基、モノアルキル（炭素数１〜４）アミノ基、モノアリール（炭素数６〜１８）アミノ基、ジアルキル（炭素数１〜４）アミノ基またはジアリール（炭素数６〜１８）アミノ基を表し、Ｒ５は水素原子、ハロゲン原子、アルキル基（炭素数１〜８）、アルコキシ基（炭素数１〜８）、無置換の炭素環式芳香族環基またはジアルキル（炭素数１〜４）アミノ基もしくはジアリール（炭素数６〜１８）アミノ基で置換された炭素環式芳香族環基を表す。〕
【００１０】
また、本発明は一般式［１］で表される構造を有することを特徴とする耐熱性電荷輸送材料であり、さらに、その耐熱性電荷輸送材料を用いたことを特徴とする耐熱性有機電界発光素子である。
【００１１】
本発明の一般式［１］で表されるポリアミノフルオレン誘導体中、Ａr１、Ａr２で表される基としては次のような基が挙げられる。置換もしくは無置換の炭素環式芳香族環基としては、フェニル基、ビフェニリル基、トリフェニリル基、テトラフェニリル基、クロロフェニル基、ニトロフェニル基、シアノフェニル基、メトキシフェニル基、トリル基、キシリル基、クメニル基、メシチル基、ペンタレニル基、インデニル基、ナフチル基、アズレニル基、ヘプタレニル基、アセナフチレニル基、フェナレニル基、フルオレニル基、アントリル基、アントラキノニル基、メチルアントリル基、フェナントリル基、トリフェニレニル基、ピレニル基、クリセニル基、ピセニル基、ペリレニル基、ペンタフェニル基、ペンタセニル基、テトラフェニレニル基、ヘキサフェニル基、ヘキサセニル基、ルビセニル基、コロネニル基等がある。
【００１２】
次に、置換もしくは無置換の複素環式芳香族環基としては、チエニル基、フリル基、ピロリル基、イミダゾリル基、ピラゾリル基、オキサゾリル基、チアゾリル基、イミダゾリル基、ピリジル基、ピラジニル基、ピリミジニル基、ピリダジニル基、インドリル基、キノリル基、イソキノリル基、フタラジニル基、キノキサリニル基、キナゾリニル基、カルバゾリル基、アクリジニル基、フェナジニル基、フルフリル基、イソチアゾリル基、イソキサゾリル基、フラザニル基、フェノキサジニル基、ベンゾチエニル基、ベンゾチアゾリル基、ベンゾオキサゾリル基、ベンゾイミダゾリル基、メチルピリジル基、シアノピリジル基等がある。
【００１３】
また、置換もしくは無置換の炭素環式脂肪族環基としては、シクロペンチル基、シクロヘキシル基、ノルボレニル基、アダマンチル基等がある。
【００１４】
本発明のポリアミノフルオレン誘導体の一般式［１］中、Ａr１、Ａr２で表される基のうちの少なくとも一方が無置換の炭素環式芳香族環基（炭素数６〜１０）である場合には、Ｒ１、Ｒ２、Ｒ３のうちの少なくとも一つがアルキル基（炭素数１〜８）またはアルコキシ基（炭素数１〜８）であることが好ましく、またＲ４およびＲ５のうちの少なくとも一方がジアリール（炭素数６〜１８）アミノ基であることが好ましい。
【００１５】
また、より好ましいものは一般式［１］中のＡr１およびＡr２のうちの少なくとも一方が、置換もしくは無置換の炭素環式芳香族環基（炭素数１１〜１８）である場合である。
【００１６】
本発明の一般式［１］で表される誘導体の具体的化合物である、［化２］式で表される無置換のトリフェニルアミンの４量体は、
【００１７】
【化４】
分解耐熱性が４７０℃という高い温度を有しながら、１６１℃という高いガラス転移点を示す。［化２］式は特開平７−１２６２２６号公報に例示されているが、合成方法や物性値、さらには分解耐熱性やガラス転移点についての記載は無い。この高いガラス転移点については、［化３］式で表されるフルオレン部分構造を含むトリフェニルアミンの２量体の化合物、
【００１９】
【化５】
のガラス転移点文献値（IEEE TRANSACTIONS ON ELECTRON DEVICES,1302-1306,VOL.44,NO.8,AUGUST 1997）である１１１℃や、フルオレン構造を含まない［化４］式で表される単純なトリフェニルアミンの４量体化合物、
【００２１】
【化６】
のガラス転移点１４２℃や、同じく５量体の１４５℃よりも高く勝っている。
【００２３】
さらに本発明においては、［化２］式で表される化合物のフェニル基を、置換フェニル基、炭素数の多い炭素環式芳香族環基または複素環式芳香族環基に換えることによって、ガラス転移点をさらに上げることができる。
【００２４】
例えば［化２］式の化合物のフェニル基４個をナフチル基に換えた、本発明の［化５］式で表される化合物のガラス転移点は１７１℃であり、［化２］式の化合物よりさらに高いガラス転移点を示した。
【００２５】
【化７】
本発明の化合物はウルマン反応をおこなうことで合成できる。さらに晶析や吸着、カラムクロマトグラフィーを行うことによって精製でき、高純度品を得ることができる。
【００２７】
本発明の一般式［１］で表されるポリアミノフルオレン誘導体の具体的化合物を［表１］〜［表３］に示した。
ただし、化合物［化２］、［化５］、［化８］〜［化１３］、［化１５］〜［化１８］、［化２０］〜［化３３］、［化３５］〜［化３７］、［化４０］を参考例とする。
【００２８】
【表１】
【表２】
【表３】
本発明のポリアミノフルオレン誘導体の仕事関数は５．１〜５．６ｅＶであり、電荷輸送材料として使用するのに十分な特性を有している。
【００３２】
本発明のポリアミノフルオレン誘導体が、単純なトリフェニルアミンの４量体を顕著に上回る高いガラス転移点を示す理由、また本発明の化合物がヘテロな骨格構造を有する化合物の中では顕著に熱的に安定である理由は、本発明の化合物がフルオレン構造を有しているためと考えられる。その結果、蒸着プロセス時の高温に耐えることができ、容易に有機電界発光素子を作製することができる。 またガラス転移点が高いために、電荷輸送材料として形成された機能膜は安定である。さらに有機電界発光素子や電子写真用感光体に使用された場合は、高温環境下や発熱環境下において優れた安定性を発揮することが可能になる。
【００３３】
【発明の実施の形態】
以下本発明のポリアミノフルオレン誘導体の製造方法および物性について、実施例により具体的に説明する。
なお、実施例１、２および７は、それぞれ、参考例１、２および７と読替えるものとする。
【００３４】
【実施例】
〔実施例１〕
４，４’−（９−フルオレニリデン）ビス（Ｎ−（４'''−フェニルアミノ−４”−ビフェニリル）アニリン）８．４ｇ（１０mmol）、ヨードベンゼン１０．２ｇ（５０mmol）、無水炭酸カリウム８．３ｇ（６０mmol）、銅粉０．６４ｇ（１０mmol）、トリデカン１００ｍｌを混合し、窒素雰囲気下で還流して１０時間反応させた。反応生成物をトルエン１２０ｍｌで抽出し、不溶分を濾別した。濾液を濃縮乾固して粗製物を得て、シリカゲルを用いたカラムクロマトグラフィーによって精製した。精製によって得られた白色粉体は５．４ｇで、収率は４７％、融点は１８６〜２２０℃であった。
【００３５】
得られた白色粉体について、ＮＭＲで化学構造を同定した。測定結果は［図１］１３Ｃ−ＮＭＲの通りであった。
【００３６】
［図１］の１３Ｃ−ＮＭＲにおいて、化合物を構成する８４個の芳香族炭素に相当する２６ピークのうち、２４個の芳香族炭素ピーク（１２０．０３，１２２．７１、１２３．２０，１２３．９７，１２４．１３，１２４．２１，１２４．４１，１２５．２０，１２６．１４，１２７．１６，１２７．２９，１２７．５１，１２８．１２，１２８．８３，１２８．９２，１２９．１３，１３４．６２，１３９．７７，１３９．９４，１４５．９１，１４６．４５，１４６．５８，１４７．５８，１５１．４０ｐｐｍ）と、フルオレンの９位の脂肪族炭素ピーク（６４．５６ｐｐｍ）を検出した。
【００３７】
さらに、得られた白色粉体について元素分析を実施した結果は次の通りであった。
理論値（炭素８９．６％）（水素５．５％）（窒素４．９％）
実測値（炭素８９．５％）（水素５．６％）（窒素４．４％）
以上の１３Ｃ−ＮＭＲおよび元素分析の結果を総合して、［化２］式の構造を同定した。
【００３８】
〔実施例２〕
実施例１と同様な方法で、４，４’−（９−フルオレニリデン）ビス（Ｎ−（４'''−フェニルアミノ−４”−ビフェニリル）アニリン）に１−ヨードナフタレンを反応させ、融点１８４〜２１５℃の淡黄白色の粉体として、［化５］式で表される化合物を得た。
【００３９】
この化合物の赤外線吸収スペクトル（ＫＢｒ錠剤法）測定結果を［図２］に示す。
【００４０】
〔比較例１〕
特許第３０７９９０９号公報の実施例１に記載された［化３］式の化合物を、実施例１と同様な方法で４，４’−（９−フルオレニリデン）ジアニリンにヨードトルエンを反応させて得た。得られた白色粉体について、マススペクトル（島津製作所）で分子量を測定した。ＣＩ−ＭＳ測定の結果は［図３］の通りであった。
【００４１】
［図３］のＣＩ−ＭＳ測定により、分子量７０９に相当する親ピ−クを検出して得られた白色紛体が［化３］式の構造であると同定した。
【００４２】
〔比較例２〕
特開平７−１２６２２６号公報の実施例１の化合物を、その実施例に記載された方法で合成し、融点２４０〜２４４℃の淡黄白色の粉体として、［化４］式の化合物を得た。
【００４３】
〔比較例３〕
特開平７−１２６２２６号公報の実施例３の化合物を、その実施例に記載された方法で合成して、融点１６０〜１８３℃の白色粉体として［化６］式の化合物を得た。
【００４４】
【化８】
〔実施例３〕
本発明のポリアミノフルオレン誘導体と、比較例で合成したトリフェニルアミン４量体構造を有する類似の電荷輸送材料化合物について、ＤＳＣ（示差走査熱量計、マックサイエンス製）によってガラス転移点を測定し、比較した。［化２］式の化合物の測定結果を［図４］に、［化５］式の化合物の測定結果を［図５］に、［化３］式の化合物の測定結果を［図６］に示した。
【００４６】
［図６］に示したように、比較例１で合成した、特許第３０７９９０９号公報実施例１記載の化合物は、融解後の冷却時に結晶化を起こしてガラス転移を示さなかった。他の化合物については、ＤＳＣの測定結果よりガラス転移点を求めた。ガラス転移点測定結果は次の通りである。
【００４７】
［化２］式の本発明実施例１の化合物 ガラス転移点 ： １６１℃
［化５］式の本発明実施例２の化合物 ガラス転移点 ： １７１℃
［化４］式の比較例２の化合物 ガラス転移点 ： １４２℃
［化６］式の比較例３の化合物 ガラス転移点 ： １３８℃
【００４８】
以上の結果から本発明のポリアミノフルオレン誘導体が、比較例で合成した類似のトリフェニルアミン４量体群に比べて、高いガラス転移点を有することが明白である。
【００４９】
［実施例４］
本発明のポリアミノフルオレン誘導体について窒素気流シリンダ−と電気炉、液体クロマトグラフィ−を用いて、分解耐熱性を測定した。比較のために非共役型の分子構造を有する類似の電荷輸送材料についても測定を行った。分解耐熱性は、３０分間に化合物の１％が分解する最低温度で示した。
［化２］式の本発明実施例１の化合物 分解耐熱性 ： ４７０℃
［化６］式の比較例３の化合物 分解耐熱性 ： ２７９℃
【００５０】
以上の結果から本発明のフルオレン構造を含む化合物が、特開平７−１２６２２６号公報実施例３記載の類似のヘテロな骨格構造を有する化合物と比べて、研著に高い分解耐熱性を有することが明白である。
【００５１】
［実施例５］
本発明のポリアミノフルオレン誘導体について、表面分析計ＡＣ１（理研計器製）で仕事関数を測定し、一般的な正孔輸送材料と比較した。測定結果を次に示す。
［化２］式の本発明実施例１の化合物 仕事関数 ： ５．４ｅＶ
［化４］式の比較例２の化合物 仕事関数 ： ５．３ｅＶ
［化６］式の比較例３の化合物 仕事関数 ： ５．４ｅＶ
この結果から、本発明の化合物は従来の正孔輸送材料と同程度の仕事関数を有しており、正孔輸送材料として適性であるといえる。
【００５２】
〔実施例６〕
実施例１と同様な方法で、４，４’−（９−フルオレニリデン）ビス（Ｎ−（４'''−フェニルアミノ−４”−ビフェニリル）トルイジン）にヨードベンゼンを反応させて［化７］式の化合物を得た。
【００５３】
【化９】
〔実施例７〕
実施例１と同様な方法で、４，４’−（９−フルオレニリデン）ビス（Ｎ−（４'''−フェニルアミノ−４”−ビフェニリル）アニリン）に１−ヨ−ドピレンを反応させ融点３００℃以上の黄色粉体として、［化８］式の化合物を得た。
【００５５】
【化１０】
この化合物の赤外線吸収スペクトル（ＫＢｒ錠剤法）を［図７］に示す。
【００５７】
【発明の効果】
本発明のポリアミノフルオレン誘導体は分解耐熱性が高いため蒸着プロセスが行いやすく、有機電界発光素子用の材料として適している。またガラス転移点が従来の電荷輸送材料化合物より高いので、作製した機能膜が電気的・化学的に安定である。したがって、本発明の耐熱性電荷輸送材料を使用した耐熱性有機電界発光素子は、優れた環境安定性を発揮する。
【図面の簡単な説明】
【図１】［化２］式の実施例１の化合物を測定した１３Ｃ−ＮＭＲ図である。
【図２】［化５］式の実施例２の化合物を測定した赤外線吸収スペクトル図である。
【図３】［化３］式の比較例１の化合物を測定したＣＩ−ＭＳ図である。
【図４】［化２］式の実施例１の化合物を測定したＤＳＣ図である。
【図５】［化５］式の実施例２の化合物を測定したＤＳＣ図である。
【図６】［化３］式の比較例１の化合物を測定したＤＳＣ図である。
【図７】［化８］式の実施例７の化合物を測定した赤外線吸収スペクトル図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a compound excellent in heat resistance of a vapor deposition process, a charge transport material using the compound, and an organic electroluminescent element.
[0002]
[Prior art]
As compounds for electronic products, in particular, as charge transport materials for organic electroluminescent devices, compounds having various structures in which a molecule partially includes a triphenylamine tetramer structure have been proposed. (Japanese Patent Laid-Open Nos. 7-126226 and 7-26615)
[0003]
Further, a diphenylamine having a partial structure of fluorene has been proposed as a material for an organic electroluminescence device. (Patent No. 3079909)
[0004]
[Problems to be solved by the invention]
With the expansion of the application field of organic electroluminescent devices, heat resistance exceeding 100 ° C. has been required as the device performance of products (remaining important issues and practical technologies of organic LED devices, p4, Organic Electronics Materials Research Group, 1999), a compound having a glass transition point exceeding 140 ° C. is generally required to satisfy heat resistance exceeding 100 ° C.
[0005]
In the production of an organic electroluminescent element, since the deposition time can be shortened by raising the deposition temperature, the material compound is required to have high heat resistance during the deposition process. When the vapor deposition process is performed near the temperature at which the compound decomposes, a chemically uniform functional film cannot be produced, and the characteristics of the organic electroluminescent device are greatly deteriorated.
[0006]
The present invention provides a compound having a high glass transition point and high heat resistance during the vapor deposition process as a heat-resistant charge transport material, and also provides a heat-resistant organic electroluminescent device having excellent characteristics by using the material. The purpose is that.
[0007]
[Means for Solving the Problems]
As a result of searching for a compound that simultaneously satisfies the above two requirements, the present inventors have found that the compound represented by the general formula [1] has a high glass transition point exceeding 150 ° C. and is thermally stable. As a result, the present invention has been completed. That is, the present invention is a polyaminofluorene derivative represented by the general formula [1].
[0008]
[Chemical 3]
[Wherein Ar 1 and Ar 2 are each independently a substituted or unsubstituted carbocyclic aromatic ring group (having 6 or more carbon atoms), a substituted or unsubstituted heterocyclic aromatic ring group, or a substituted or unsubstituted group. A carbocyclic aliphatic ring group (5 or more carbon atoms constituting the ring) is represented. R 1 , R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, an alkyl group (1 to 8 carbon atoms), an alkoxy group (1 to 8 carbon atoms), R 4 represents a hydrogen atom, a halogen atom, Alkyl group (1 to 8 carbon atoms), alkoxy group (1 to 8 carbon atoms), amino group, monoalkyl (1 to 4 carbon atoms) amino group, monoaryl (6 to 18 carbon atoms) amino group, dialkyl (carbon) C1-4) amino group or a diaryl (represents the number 6-18) amino group carbons, R 5 is a hydrogen atom, a halogen atom, an alkyl group (1-8 carbon atoms), an alkoxy group (1-8 carbon atoms), It represents an unsubstituted carbocyclic aromatic ring group or a carbocyclic aromatic ring group substituted with a dialkyl (C1-4) amino group or diaryl (C6-18) amino group. ]
[0010]
The present invention also relates to a heat-resistant charge transport material having a structure represented by the general formula [1], and further using the heat-resistant charge transport material. It is a light emitting element.
[0011]
In the polyaminofluorene derivative represented by the general formula [1] of the present invention, groups represented by Ar 1 and Ar 2 include the following groups. As the substituted or unsubstituted carbocyclic aromatic ring group, phenyl group, biphenylyl group, triphenylyl group, tetraphenylyl group, chlorophenyl group, nitrophenyl group, cyanophenyl group, methoxyphenyl group, tolyl group, xylyl group, Cumenyl group, mesityl group, pentalenyl group, indenyl group, naphthyl group, azulenyl group, heptalenyl group, acenaphthylenyl group, phenalenyl group, fluorenyl group, anthryl group, anthraquinonyl group, methylanthryl group, phenanthryl group, triphenylenyl group, pyrenyl group, Examples include a chrycenyl group, a picenyl group, a perylenyl group, a pentaphenyl group, a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexacenyl group, a rubicenyl group, and a coronenyl group.
[0012]
Next, as the substituted or unsubstituted heterocyclic aromatic ring group, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, oxazolyl group, thiazolyl group, imidazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group , Pyridazinyl group, indolyl group, quinolyl group, isoquinolyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, carbazolyl group, acridinyl group, phenazinyl group, furfuryl group, isothiazolyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, benzothienyl group, Examples include a benzothiazolyl group, a benzoxazolyl group, a benzimidazolyl group, a methylpyridyl group, and a cyanopyridyl group.
[0013]
Examples of the substituted or unsubstituted carbocyclic aliphatic ring group include a cyclopentyl group, a cyclohexyl group, a norborenyl group, and an adamantyl group.
[0014]
In the general formula [1] of the polyaminofluorene derivative of the present invention, when at least one of the groups represented by Ar 1 and Ar 2 is an unsubstituted carbocyclic aromatic ring group (having 6 to 10 carbon atoms) It is preferable that at least one of R 1 , R 2 and R 3 is an alkyl group (1 to 8 carbon atoms) or an alkoxy group (1 to 8 carbon atoms), and among R 4 and R 5 It is preferable that at least one of is a diaryl (C6-C18) amino group.
[0015]
More preferred is a case where at least one of Ar 1 and Ar 2 in the general formula [1] is a substituted or unsubstituted carbocyclic aromatic ring group (having 11 to 18 carbon atoms).
[0016]
The tetramer of unsubstituted triphenylamine represented by the formula [Chemical Formula 2], which is a specific compound of the derivative represented by the general formula [1] of the present invention,
[0017]
[Formula 4]
Decomposition heat resistance has a high glass transition point of 161 ° C. while having a high temperature of 470 ° C. The formula [Chemical Formula 2] is exemplified in JP-A-7-126226, but there is no description about the synthesis method, physical properties, further decomposition heat resistance or glass transition point. About this high glass transition point, a diphenyl compound of triphenylamine containing a fluorene partial structure represented by the formula [3]
[0019]
[Chemical formula 5]
The glass transition point literature value (IEEE TRANSACTIONS ON ELECTRON DEVICES, 1302-1306, VOL.44, NO.8, AUGUST 1997) is a simple expression represented by the formula [4] that does not include the fluorene structure. A tetrameric compound of triphenylamine,
[0021]
[Chemical 6]
The glass transition point is 142 ° C., which is higher than the 145 ° C. of the pentamer.
[0023]
Furthermore, in the present invention, by replacing the phenyl group of the compound represented by the formula [Chemical Formula 2] with a substituted phenyl group, a carbocyclic aromatic ring group having a large number of carbon atoms, or a heterocyclic aromatic ring group, The transition point can be further increased.
[0024]
For example, the compound represented by [Chemical Formula 5] of the present invention, in which four phenyl groups of the compound represented by [Chemical Formula 2] are replaced with naphthyl groups, has a glass transition point of 171 ° C. An even higher glass transition point was exhibited.
[0025]
[Chemical 7]
The compound of the present invention can be synthesized by performing an Ullmann reaction. Furthermore, it can refine | purify by performing crystallization, adsorption | suction, and column chromatography, and can obtain a highly purified product.
[0027]
Specific compounds of the polyaminofluorene derivative represented by the general formula [1] of the present invention are shown in [Table 1] to [Table 3].
However, the compounds [Chemical Formula 2], [Chemical Formula 5], [Chemical Formula 8] to [Chemical Formula 13], [Chemical Formula 15] to [Chemical Formula 18], [Chemical Formula 20] to [Chemical Formula 33], and [Chemical Formula 35] to [Chemical Formula]. 37] and [Chemical 40] are taken as reference examples.
[0028]
[Table 1]
[Table 2]
[Table 3]
The work function of the polyaminofluorene derivative of the present invention is 5.1 to 5.6 eV, and has sufficient characteristics to be used as a charge transport material.
[0032]
The reason why the polyaminofluorene derivative of the present invention exhibits a high glass transition point that is significantly higher than that of a simple triphenylamine tetramer, and the compound of the present invention is significantly more thermally among the compounds having a hetero skeleton structure. The reason why it is stable is considered that the compound of the present invention has a fluorene structure. As a result, it can withstand high temperatures during the vapor deposition process, and an organic electroluminescent device can be easily produced. Moreover, since the glass transition point is high, the functional film formed as a charge transport material is stable. Further, when used in an organic electroluminescent device or an electrophotographic photosensitive member, it is possible to exhibit excellent stability in a high temperature environment or a heat generation environment.
[0033]
DETAILED DESCRIPTION OF THE INVENTION
The production method and physical properties of the polyaminofluorene derivative of the present invention will be specifically described below with reference to examples.
In addition, Examples 1, 2, and 7 shall be read as Reference Examples 1, 2, and 7, respectively.
[0034]
【Example】
[Example 1]
8.4 g (10 mmol) of 4,4 ′-(9-fluorenylidene) bis (N- (4 ′ ″-phenylamino-4 ″ -biphenylyl) aniline), 10.2 g (50 mmol) of iodobenzene, anhydrous potassium carbonate 8 .3 g (60 mmol), copper powder 0.64 g (10 mmol), and tridecane 100 ml were mixed and refluxed under a nitrogen atmosphere for 10 hours, the reaction product was extracted with 120 ml of toluene, and the insoluble matter was filtered off. The filtrate was concentrated to dryness to obtain a crude product, which was purified by column chromatography using silica gel.The white powder obtained by the purification was 5.4 g, the yield was 47%, and the melting point was 186-220. ° C.
[0035]
About the obtained white powder, the chemical structure was identified by NMR. The measurement results were as shown in [FIG. 1] 13C-NMR.
[0036]
In 13C-NMR of [FIG. 1], 24 aromatic carbon peaks (120.03, 122.71, 123.20, 123.123) out of 26 peaks corresponding to 84 aromatic carbons constituting the compound. 97, 124.13, 124.21, 124.41, 125.20, 126.14, 127.16, 127.29, 127.51, 128.12, 128.83, 128.92, 129.13, 134.62, 139.77, 139.94, 145.91, 146.45, 146.58, 147.58, 151.40 ppm) and the 9th position aliphatic carbon peak (64.56 ppm) of fluorene was detected. did.
[0037]
Further, the results of elemental analysis of the obtained white powder were as follows.
Theoretical value (carbon 89.6%) (hydrogen 5.5%) (nitrogen 4.9%)
Measured value (carbon 89.5%) (hydrogen 5.6%) (nitrogen 4.4%)
By combining the above 13C-NMR and elemental analysis results, the structure of the formula [2] was identified.
[0038]
[Example 2]
In the same manner as in Example 1, 4,4 ′-(9-fluorenylidene) bis (N- (4 ′ ″-phenylamino-4 ″ -biphenylyl) aniline) was reacted with 1-iodonaphthalene to obtain a melting point of 184. A compound represented by the formula [5] was obtained as a pale yellowish white powder at 215 ° C.
[0039]
The infrared absorption spectrum (KBr tablet method) measurement result of this compound is shown in FIG.
[0040]
[Comparative Example 1]
The compound of the formula [Chemical Formula 3] described in Example 1 of Japanese Patent No. 3079909 was obtained by reacting 4,4 ′-(9-fluorenylidene) dianiline with iodotoluene in the same manner as in Example 1. . About the obtained white powder, the molecular weight was measured by mass spectrum (Shimadzu Corporation). The result of CI-MS measurement was as shown in FIG.
[0041]
By the CI-MS measurement of [FIG. 3], the white powder obtained by detecting the parent peak corresponding to the molecular weight 709 was identified as having the structure of [Chemical Formula 3].
[0042]
[Comparative Example 2]
The compound of Example 1 of JP-A-7-126226 was synthesized by the method described in that Example to obtain a compound of the formula [Chemical Formula 4] as a pale yellowish white powder having a melting point of 240 to 244 ° C. It was.
[0043]
[Comparative Example 3]
The compound of Example 3 of JP-A-7-126226 was synthesized by the method described in the Example to obtain a compound of the formula [6] as a white powder having a melting point of 160 to 183 ° C.
[0044]
[Chemical 8]
Example 3
For the polyaminofluorene derivative of the present invention and a similar charge transport material compound having a triphenylamine tetramer structure synthesized in Comparative Example, the glass transition point was measured by DSC (differential scanning calorimeter, manufactured by Mac Science), and compared. did. The measurement result of the compound of formula [2] is shown in [FIG. 4], the measurement result of the compound of formula [5] is shown in [FIG. 5], and the measurement result of the compound of formula [3] is shown in [FIG. 6]. Indicated.
[0046]
As shown in FIG. 6, the compound described in Example 1 of Japanese Patent No. 3079909 synthesized in Comparative Example 1 did not show glass transition due to crystallization upon cooling after melting. About other compounds, the glass transition point was calculated | required from the measurement result of DSC. The glass transition point measurement results are as follows.
[0047]
[Chemical Formula 2] Compound of the Example 1 of the present invention Glass transition point: 161 ° C.
[Chemical Formula 5] Compound of the present invention Example 2 having the formula Glass transition point: 171 ° C.
[Chemical Formula 4] Compound of Comparative Example 2 in Formula: Glass Transition Point: 142 ° C.
[Chemical Formula 6] Compound of Comparative Example 3 in Formula: Glass Transition Point: 138 ° C.
[0048]
From the above results, it is clear that the polyaminofluorene derivative of the present invention has a higher glass transition point than the similar triphenylamine tetramer group synthesized in the comparative example.
[0049]
[Example 4]
The decomposition heat resistance of the polyaminofluorene derivative of the present invention was measured using a nitrogen stream cylinder, an electric furnace, and liquid chromatography. For comparison, a similar charge transport material having a non-conjugated molecular structure was also measured. The decomposition heat resistance was shown at the lowest temperature at which 1% of the compound decomposes in 30 minutes.
[Chemical Formula 2] Compound of the present invention Example 1 Decomposition heat resistance: 470 ° C.
[Chemical Formula 6] Compound of Comparative Example 3 of formula Decomposition heat resistance: 279 ° C
[0050]
From the above results, the compound containing the fluorene structure of the present invention has significantly higher decomposition heat resistance than the compound having a similar hetero skeleton structure described in Example 3 of JP-A-7-126226. It is obvious.
[0051]
[Example 5]
The work function of the polyaminofluorene derivative of the present invention was measured with a surface analyzer AC1 (manufactured by Riken Keiki Co., Ltd.) and compared with a general hole transport material. The measurement results are shown below.
Compound of the formula of the present invention represented by the formula [Formula 2] Work function: 5.4 eV
[Chemical Formula 4] Compound of Comparative Example 2 of Formula Work Function: 5.3 eV
[Chemical Formula 6] Compound of Comparative Example 3 in Formula: Work Function: 5.4 eV
From this result, it can be said that the compound of the present invention has a work function comparable to that of a conventional hole transport material and is suitable as a hole transport material.
[0052]
Example 6
In the same manner as in Example 1, iodobenzene was reacted with 4,4 ′-(9-fluorenylidene) bis (N- (4 ′ ″-phenylamino-4 ″ -biphenylyl) toluidine). The compound of formula was obtained.
[0053]
[Chemical 9]
Example 7
In the same manner as in Example 1, 4,4 ′-(9-fluorenylidene) bis (N- (4 ′ ″-phenylamino-4 ″ -biphenylyl) aniline) was reacted with 1-iodopyrene, melting point 300 A compound of the formula [8] was obtained as a yellow powder having a temperature of 0 ° C. or higher.
[0055]
[Chemical Formula 10]
The infrared absorption spectrum (KBr tablet method) of this compound is shown in FIG.
[0057]
【Effect of the invention】
Since the polyaminofluorene derivative of the present invention has high decomposition heat resistance, it is easy to perform a vapor deposition process and is suitable as a material for an organic electroluminescence device. In addition, since the glass transition point is higher than that of the conventional charge transport material compound, the prepared functional film is electrically and chemically stable. Therefore, the heat-resistant organic electroluminescent element using the heat-resistant charge transport material of the present invention exhibits excellent environmental stability.
[Brief description of the drawings]
FIG. 1 is a 13C-NMR diagram obtained by measuring the compound of Example 1 of the formula [Chemical Formula 2].
FIG. 2 is an infrared absorption spectrum obtained by measuring the compound of Example 2 of the formula [Chemical Formula 5].
FIG. 3 is a CI-MS diagram obtained by measuring the compound of Comparative Example 1 of the formula [Chemical Formula 3].
FIG. 4 is a DSC diagram obtained by measuring the compound of Example 1 of the formula [Chemical Formula 2].
FIG. 5 is a DSC diagram obtained by measuring the compound of Example 2 of the formula [Chemical Formula 5].
FIG. 6 is a DSC diagram obtained by measuring the compound of Comparative Example 1 of the formula [Chemical Formula 3].
7 is an infrared absorption spectrum obtained by measuring the compound of Example 7 of the formula [Chemical Formula 8]. FIG.
Claims (7)
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| JP4078961B2 (en) * | 2002-11-21 | 2008-04-23 | 三菱化学株式会社 | Bisaminophenylmethane compounds and charge transport materials, organic electroluminescent device materials and organic electroluminescent devices using the same |
| JP4905445B2 (en) * | 2003-05-27 | 2012-03-28 | 株式会社デンソー | Tertiary amine compound, organic EL device material and organic EL device |
| TW200517469A (en) * | 2003-10-30 | 2005-06-01 | Nissan Chemical Ind Ltd | Charge-transporting compound, charge-transporting material, charge-transporting varnish, charge-transporting thin film, and organic electroluminescent device |
| US7807274B2 (en) * | 2003-12-26 | 2010-10-05 | Hodogaya Chemical Co., Ltd. | Tetramine compound and organic EL device |
| US7365230B2 (en) | 2004-02-20 | 2008-04-29 | E.I. Du Pont De Nemours And Company | Cross-linkable polymers and electronic devices made with such polymers |
| WO2005099312A2 (en) | 2004-03-31 | 2005-10-20 | E. I. Du Pont De Nemours And Company | Triarylamine compounds for use as charge transport materials |
| JP5103727B2 (en) * | 2005-11-16 | 2012-12-19 | 東ソー株式会社 | Fluorene compound and organic EL device using the same |
| JP4765589B2 (en) * | 2005-12-02 | 2011-09-07 | 東洋インキＳｃホールディングス株式会社 | Fluorene compound having carbazolyl group and use thereof |
| EP2299509B1 (en) | 2008-05-16 | 2016-06-29 | Hodogaya Chemical Co., Ltd. | Organic electroluminescent device |
| WO2010137601A1 (en) | 2009-05-29 | 2010-12-02 | Semiconductor Energy Laboratory Co., Ltd. | Fluorene derivative, light-emitting element, light-emitting device, electronic device, and lighting device |
| US8642190B2 (en) * | 2009-10-22 | 2014-02-04 | Semiconductor Energy Laboratory Co., Ltd. | Fluorene derivative, light-emitting element, light-emitting device, electronic device, and lighting device |
| TWI557113B (en) | 2010-08-27 | 2016-11-11 | 半導體能源研究所股份有限公司 | Fluorene derivative, organic compound, and light-emitting element, light-emitting device, and electronic device using the compound |
| WO2016052252A1 (en) * | 2014-09-29 | 2016-04-07 | 日産化学工業株式会社 | Charge-transporting varnish |
| JP7325731B2 (en) | 2018-08-23 | 2023-08-15 | 国立大学法人九州大学 | organic electroluminescence element |
| CN114751832B (en) * | 2022-06-14 | 2022-10-04 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent compound, preparation method and application thereof |
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| JP3220950B2 (en) * | 1993-11-01 | 2001-10-22 | 保土谷化学工業株式会社 | Benzidine compound |
| JP3194657B2 (en) * | 1993-11-01 | 2001-07-30 | 松下電器産業株式会社 | EL device |
| JPH07331238A (en) * | 1994-06-15 | 1995-12-19 | Matsushita Electric Ind Co Ltd | Electroluminescent element |
| JPH083122A (en) * | 1994-06-15 | 1996-01-09 | Hodogaya Chem Co Ltd | Hexaamine compound |
| JPH08292586A (en) * | 1995-04-21 | 1996-11-05 | Hodogaya Chem Co Ltd | Electrophotographic photoreceptor |
| WO2001056091A2 (en) * | 2000-01-28 | 2001-08-02 | Siemens Aktiengesellschaft | Charge transport material having an increased glass transition temperature and the use of said material |
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