JP4562884B2 - Organic electroluminescence device - Google Patents
Organic electroluminescence device Download PDFInfo
- Publication number
- JP4562884B2 JP4562884B2 JP2000255141A JP2000255141A JP4562884B2 JP 4562884 B2 JP4562884 B2 JP 4562884B2 JP 2000255141 A JP2000255141 A JP 2000255141A JP 2000255141 A JP2000255141 A JP 2000255141A JP 4562884 B2 JP4562884 B2 JP 4562884B2
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- Prior art keywords
- compound
- organic
- layer
- residue
- film
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- 238000005401 electroluminescence Methods 0.000 title claims description 39
- 239000010410 layer Substances 0.000 claims description 86
- 150000001875 compounds Chemical class 0.000 claims description 48
- 238000002347 injection Methods 0.000 claims description 43
- 239000007924 injection Substances 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- -1 diphenylamino group Chemical group 0.000 claims description 34
- 150000002430 hydrocarbons Chemical class 0.000 claims description 25
- 150000002894 organic compounds Chemical class 0.000 claims description 13
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002356 single layer Substances 0.000 claims description 7
- 150000002484 inorganic compounds Chemical class 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001769 aryl amino group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical group C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 claims 1
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical group C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 claims 1
- FBTOLQFRGURPJH-UHFFFAOYSA-N 1-phenyl-9h-carbazole Chemical group C1=CC=CC=C1C1=CC=CC2=C1NC1=CC=CC=C12 FBTOLQFRGURPJH-UHFFFAOYSA-N 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 125000006617 triphenylamine group Chemical group 0.000 claims 1
- 239000010408 film Substances 0.000 description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000000463 material Substances 0.000 description 31
- 239000007787 solid Substances 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 15
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000012300 argon atmosphere Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
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- 229920005989 resin Polymers 0.000 description 9
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- 239000000126 substance Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- 230000032258 transport Effects 0.000 description 8
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- 230000005525 hole transport Effects 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- DCDDBMVMARYAGR-UHFFFAOYSA-N 3-(10-fluoranthen-3-ylanthracen-9-yl)fluoranthene Chemical compound C12=CC=CC=C2C(C2=C3C=CC=C4C=5C(C(C=C2)=C43)=CC=CC=5)=C(C=CC=C2)C2=C1C1=CC=C2C3=C1C=CC=C3C1=CC=CC=C12 DCDDBMVMARYAGR-UHFFFAOYSA-N 0.000 description 5
- KKQFMFGEULOVDU-UHFFFAOYSA-N 3-[3,5-di(fluoranthen-3-yl)phenyl]fluoranthene Chemical compound C12=CC=CC=C2C2=CC=CC3=C2C1=CC=C3C1=CC(C=2C=3C=CC=C4C5=CC=CC=C5C(C=34)=CC=2)=CC(C2=C3C=CC=C4C=5C(C(C=C2)=C43)=CC=CC=5)=C1 KKQFMFGEULOVDU-UHFFFAOYSA-N 0.000 description 5
- GDYWWULLVRYHEP-UHFFFAOYSA-N 8-(4-fluoranthen-8-ylphenyl)fluoranthene Chemical compound C1=CC(C2=CC=C(C=C22)C3=CC=C(C=C3)C3=CC=C4C=5C=CC=C6C=CC=C(C=56)C4=C3)=C3C2=CC=CC3=C1 GDYWWULLVRYHEP-UHFFFAOYSA-N 0.000 description 5
- VOEQABZWJKRFRW-UHFFFAOYSA-N C1SC=NN1C1=CC=C(C=CC=C2C3=C(C=C4)C5=CC=CC=C5)C2=C1C3=C4C1=CC=CC=C1 Chemical compound C1SC=NN1C1=CC=C(C=CC=C2C3=C(C=C4)C5=CC=CC=C5)C2=C1C3=C4C1=CC=CC=C1 VOEQABZWJKRFRW-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 5
- 238000000859 sublimation Methods 0.000 description 5
- 230000008022 sublimation Effects 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- CNRNNPZITWDZGC-UHFFFAOYSA-N (7,10-diphenylfluoranthen-3-yl)boronic acid Chemical compound C=12C3=CC=CC=1C(B(O)O)=CC=C2C1=C3C(C=2C=CC=CC=2)=CC=C1C1=CC=CC=C1 CNRNNPZITWDZGC-UHFFFAOYSA-N 0.000 description 3
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
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- 125000006165 cyclic alkyl group Chemical group 0.000 description 3
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- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- MKZHJJQCUIZEDE-UHFFFAOYSA-N 1-[(2-hydroxy-3-naphthalen-1-yloxypropyl)-propan-2-ylamino]-3-naphthalen-1-yloxypropan-2-ol Chemical compound C1=CC=C2C(OCC(O)CN(CC(O)COC=3C4=CC=CC=C4C=CC=3)C(C)C)=CC=CC2=C1 MKZHJJQCUIZEDE-UHFFFAOYSA-N 0.000 description 2
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 1
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- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- KWQNQSDKCINQQP-UHFFFAOYSA-K tri(quinolin-8-yloxy)gallane Chemical compound C1=CN=C2C(O[Ga](OC=3C4=NC=CC=C4C=CC=3)OC=3C4=NC=CC=C4C=CC=3)=CC=CC2=C1 KWQNQSDKCINQQP-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- HTPBWAPZAJWXKY-UHFFFAOYSA-L zinc;quinolin-8-olate Chemical compound [Zn+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 HTPBWAPZAJWXKY-UHFFFAOYSA-L 0.000 description 1
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- 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】
本発明は新規炭化水素化合物及び有機エレクトロルミネッセンス素子に関し、特に、耐熱性が高く、高発光効率の有機エレクトロルミネッセンス素子及びそれを実現する新規炭化水素化合物に関するものである。
【０００２】
【従来の技術】
有機物質を使用した有機エレクトロルミネッセンス（ＥＬ）素子は、壁掛テレビの平面発光体やディスプレイのバックライト等の光源として使用され、盛んに開発が行われている。特に、最近では、高耐熱性と高効率を両立させる有機エレクトロルミネッセンス素子及びそれを実現する化合物が開発されている。
例えば、特開平８−１２６００号公報にはフェニルアントラセン化合物及びこれを利用した素子が開示され、ガラス転移温度を１４０℃以上とすることにより耐熱性を改良しているが、輝度／電波密度／１０で算出される発光効率が２ｃｄ／Ａ程度と低く、改良が求められていた。また、特開平１０−７２５７９号公報には、アミノアントラセン化合物及びそれを用いた素子が開示され、発光効率が改善されているが、耐熱性が十分ではなかった。さらに、特開平１０−１８９２４７号公報には、フルオランテン系化合物を用いた素子が開示されているが、フルオランテン系化合物の単量体からなる化合物であるため、耐熱性の改良が不十分であった。
【０００３】
【発明が解決しようとする課題】
本発明は、前記の課題を解決するためになされたもので、耐熱性が高く、高発光効率の有機エレクトロルミネッセンス素子及びそれを実現する新規炭化水素化合物を提供することを目的とするものである。
【０００４】
【課題を解決するための手段】
本発明者らは、前記の好ましい性質を有する有機エレクトロルミネッセンス素子（以下、有機ＥＬ素子）を開発すべく鋭意研究を重ねた結果、フルオランテン構造にアリール構造が結合した新規炭化水素化合物を有機化合物膜に添加すると有機エレクトロルミネッセンス素子の耐熱性が向上し、さらに正孔輸送性及び電子輸送性が向上して高発光効率となることを見出し本発明を完成するに至った。
【０００５】
すなわち、本発明は、下記一般式（１）で表される新規炭化水素化合物、
Ｘn −Ａｒ1 ・・・（１）
（式中、Ａｒ1 は、置換もしくは未置換の炭素原子数６〜４０の芳香族環基、置換もしくは未置換の炭素原子数６〜４０のアリールアミノ基、置換もしくは未置換の炭素原子数６〜６０のジアミノアリール基、置換もしくは未置換の炭素原子数６〜６０のトリアミノアリール基、置換もしくは未置換の炭素原子数３〜４０の複素環基又は置換もしくは未置換のエテニレン、Ｘはフルオランテン構造を有する一価の基、ｎは２〜４の整数である。）
を提供するものである。
また、本発明は、一対の電極間に、少なくとも発光層を有する単層又は複数層からなる有機化合物膜を有する有機エレクトロルミネッセンス素子（有機ＥＬ素子）であって、該有機化合物膜の少なくとも一層が前記新規炭化水素化合物を含有することを特徴とする有機エレクトロルミネッセンス素子をも提供するものである。
【０００６】
【発明の実施の形態】
本発明の新規炭化水素化合物は、上記一般式（１）で表される。
式中、Ａｒ1 は、置換もしくは未置換の炭素原子数６〜４０の芳香族環基、置換もしくは未置換の炭素原子数６〜４０のアリールアミノ基、置換もしくは未置換の炭素原子数６〜６０のジアミノアリール基、置換もしくは未置換の炭素原子数６〜６０のトリアミノアリール基、置換もしくは未置換の炭素原子数３〜４０の複素環基又は置換もしくは未置換のエテニレンである。
Ｘはフルオランテン構造を有する一価の基、ｎは２〜４の整数である。
【０００７】
該Ｘは、下記一般式〔１〕〜〔３〕に示す構造を有する化合物の一価の基であることが好ましい。
【化２】
一般式〔１〕〜〔３〕式中、Ｘ1 〜Ｘ16は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは未置換の直鎖、分岐もしくは環状の炭素原子数１〜３０のアルキル基、置換もしくは未置換の直鎖、分岐もしくは環状の炭素原子数１〜３０のアルコキシ基、置換もしくは未置換の直鎖、分岐もしくは環状の炭素原子数１〜３０のアルキルチオ基、置換もしくは未置換の直鎖、分岐もしくは環状の炭素原子数２〜３０のアルケニル基、置換もしくは未置換の直鎖、分岐もしくは環状の炭素原子数２〜３０のアルケニルオキシ基、置換もしくは未置換の直鎖、分岐もしくは環状の炭素原子数２〜３０のアルケニルチオ基、置換もしくは未置換の炭素原子数７〜３０のアラルキル基、置換もしくは未置換の炭素原子数７〜３０のアラルキルオキシ基、置換もしくは未置換の炭素原子数７〜３０のアラルキルチオ基、置換もしくは未置換の炭素原子数６〜２０のアリール基、置換もしくは未置換の炭素原子数６〜２０のアリールオキシ基、置換もしくは未置換の炭素原子数６〜２０のアリールチオ基、置換もしくは未置換の炭素原子数２〜３０のアミノ基、シアノ基、水酸基、−ＣＯＯＲ1 基（基中、Ｒ1 は水素原子、置換もしくは未置換の直鎖、分岐もしくは環状の炭素原子数１〜３０のアルキル基、置換もしくは未置換の直鎖、分岐もしくは環状の炭素原子数２〜３０のアルケニル基、置換もしくは未置換の炭素原子数７〜３０のアラルキル基、又は置換もしくは未置換の炭素原子数６〜３０のアリール基を表す）、−ＣＯＲ2 基（基中、Ｒ2 は水素原子、置換もしくは未置換の直鎖、分岐もしくは環状の炭素原子数１〜３０のアルキル基、置換もしくは未置換の直鎖、分岐もしくは環状の炭素原子数２〜３０のアルケニル基、置換もしくは未置換の炭素原子数７〜３０のアラルキル基、置換もしくは未置換の炭素原子数６〜３０のアリール基、又はアミノ基を表す）、−ＯＣＯＲ3 基（基中、Ｒ3 は、置換もしくは未置換の直鎖、分岐もしくは環状の炭素原子数１〜３０のアルキル基、置換もしくは未置換の直鎖、分岐もしくは環状の炭素原子数２〜３０のアルケニル基、置換もしくは未置換の炭素原子数７〜３０のアラルキル基、置換もしくは未置換の炭素原子数６〜３０のアリール基を表す）を表し、さらにＸ1 〜Ｘ16のうち、隣接する基及び各基の置換基は、互いに結合して、置換もしくは未置換の炭素環を形成していてもよい。
【０００９】
本発明の有機ＥＬ素子は、一対の電極間に、少なくとも発光層を有する単層又は複数層からなる有機化合物膜を有する有機エレクトロルミネッセンス素子であって、該有機化合物膜の少なくとも一層が前記新規炭化水素化合物を含有する。
前記発光層が、前記新規炭化水素化合物を含有することが好ましい。また、電子注入層又は正孔注入層が前記新規炭化水素化合物を含有することも好ましい。
前記発光層と電極との間に無機化合物層を設けても良い。
前記発光層に、発光中心として縮合多環芳香族誘導体を含有するとさらに好ましい。
前記新規炭化水素化合物を、有機化合物膜の少なくとも一層に含有させると耐熱性及び発光効率が向上するのは、フルオランテン構造の蛍光性が高く、さらに上記一般式（１）の化合物において、ｎ＝２〜４とすることで、該化合物のガラス転移温度が高くなるからである。
【００１０】
以下に、本発明の新規炭化水素化合物の代表例（Ａ１）〜（Ａ２４）を例示するが、本発明はこれらの代表例に限定されるものではない。
【００１１】
【化３】
【化４】
【化５】
【化６】
【化７】
本発明の有機ＥＬ素子は、陽極と陰極間に単層もしくは多層の有機化合物膜を形成した素子である。単層型の場合、陽極と陰極との間に発光層を設けている。発光層は、発光材料を含有し、それに加えて陽極から注入した正孔、もしくは陰極から注入した電子を発光材料まで輸送させるために、正孔注入材料もしくは電子注入材料を含有しても良い。しかしながら、発光材料は、極めて高い蛍光量子効率、高い正孔輸送能力および電子輸送能力を併せ持ち、均一な薄膜を形成することが好ましい。多層型の有機ＥＬ素子は、（陽極／正孔注入層／発光層／陰極）、（陽極／発光層／電子注入層／陰極）、（陽極／正孔注入層／発光層／電子注入層／陰極）の多層構成で積層したものがある。
【００１７】
発光層には、必要に応じて、本発明の新規炭化水素化合物に加えてさらなる公知の発光材料、ドーピング材料、正孔注入材料や電子注入材料を使用することもできる。この新規炭化水素化合物の好ましい使用法としては、発光層、電子注入層、正孔輸送層又は正孔注入層のいずれかの層に、濃度０．５〜５０重量％で添加する。さらに好ましくは、濃度１〜２０重量％である。
有機ＥＬ素子は、多層構造にすることにより、クエンチングによる輝度や寿命の低下を防ぐことができる。必要があれば、発光材料、他のドーピング材料、正孔注入材料や電子注入材料を組み合わせて使用することができる。また、他のドーピング材料により、発光輝度や発光効率の向上、赤色や白色の発光を得ることもできる。また、正孔注入層、発光層、電子注入層は、それぞれ二層以上の層構成により形成されても良い。その際には、正孔注入層の場合、電極から正孔を注入する層を正孔注入層、正孔注入層から正孔を受け取り発光層まで正孔を輸送する層を正孔輸送層と呼ぶ。同様に、電子注入層の場合、電極から電子を注入する層を電子注入層、電子注入層から電子を受け取り発光層まで電子を輸送する層を電子輸送層と呼ぶ。これらの各層は、材料のエネルギー準位、耐熱性、有機化合物膜もしくは金属電極との密着性等の各要因により選択されて使用される。
【００１８】
前記新規炭化水素化合物と共に有機化合物膜に使用できる発光材料またはホスト材料としては、縮合多環芳香族があり、例えばアントラセン、ナフタレン、フェナントレン、ピレン、テトラセン、ペンタセン、コロネン、クリセン、フルオレセイン、ペリレン、ルブレン及びそれらの誘導体がある。さらに、フタロペリレン、ナフタロペリレン、ペリノン、フタロペリノン、ナフタロペリノン、ジフェニルブタジエン、テトラフェニルブタジエン、クマリン、オキサジアゾール、アルダジン、ビスベンゾキサゾリン、ビススチリル、ピラジン、シクロペンタジエン、キノリン金属錯体、アミノキノリン金属錯体、ベンゾキノリン金属錯体、イミン、ジフェニルエチレン、ビニルアントラセン、ジアミノカルバゾール、ピラン、チオピラン、ポリメチン、メロシアニン、イミダゾールキレート化オキシノイド化合物、キナクリドン、ルブレン、スチルベン系誘導体及び蛍光色素等が挙げられるが、これらに限定されるものではない。
【００１９】
正孔注入材料としては、正孔を輸送する能力を持ち、陽極からの正孔注入効果、発光層または発光材料に対して優れた正孔注入効果を有し、発光層で生成した励起子の電子注入層または電子注入材料への移動を防止し、かつ薄膜形成能力の優れた化合物が好ましい。具体的には、フタロシアニン誘導体、ナフタロシアニン誘導体、ポルフィリン誘導体、オキサゾール、オキサジアゾール、トリアゾール、イミダゾール、イミダゾロン、イミダゾールチオン、ピラゾリン、ピラゾロン、テトラヒドロイミダゾール、オキサゾール、オキサジアゾール、ヒドラゾン、アシルヒドラゾン、ポリアリールアルカン、スチルベン、ブタジエン、ベンジジン型トリフェニルアミン、スチリルアミン型トリフェニルアミン、ジアミン型トリフェニルアミン等と、それらの誘導体、およびポリビニルカルバゾール、ポリシラン、導電性高分子等の高分子材料が挙げられるが、これらに限定されるものではない。
【００２０】
本発明の有機ＥＬ素子において使用できる正孔注入材料の中で、さらに効果的な正孔注入材料は、芳香族三級アミン誘導体もしくはフタロシアニン誘導体である。
芳香族三級アミン誘導体の具体例は、トリフェニルアミン、トリトリルアミン、トリルジフェニルアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−（３−メチルフェニル）−１，１’−ビフェニル−４，４’−ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−（４−メチルフェニル）−１，１’−フェニル−４，４’−ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−（４−メチルフェニル）−１，１’−ビフェニル−４，４’−ジアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ジナフチル−１，１’−ビフェニル−４，４’−ジアミン、Ｎ，Ｎ’−（メチルフェニル）−Ｎ，Ｎ’−（４−ｎ−ブチルフェニル）−フェナントレン−９，１０−ジアミン、Ｎ，Ｎ−ビス（４−ジ−４−トリルアミノフェニル）−４−フェニル−シクロヘキサン等、もしくはこれらの芳香族三級アミン骨格を有したオリゴマーもしくはポリマーであるが、これらに限定されるものではない。
フタロシアニン（Ｐｃ）誘導体の具体例は、Ｈ2 Ｐｃ、ＣｕＰｃ、ＣｏＰｃ、ＮｉＰｃ、ＺｎＰｃ、ＰｄＰｃ、ＦｅＰｃ、ＭｎＰｃ、ＣｌＡｌＰｃ、ＣｌＧａＰｃ、ＣｌＩｎＰｃ、ＣｌＳｎＰｃ、Ｃｌ2 ＳｉＰｃ、（ＨＯ）ＡｌＰｃ、（ＨＯ）ＧａＰｃ、ＶＯＰｃ、ＴｉＯＰｃ、ＭｏＯＰｃ、ＧａＰｃ−Ｏ−ＧａＰｃ等のフタロシアニン誘導体およびナフタロシアニン誘導体であるが、これらに限定されるものではない。
【００２１】
電子注入材料としては、電子を輸送する能力を持ち、陰極からの電子注入効果、発光層または発光材料に対して優れた電子注入効果を有し、発光層で生成した励起子の正孔注入層への移動を防止し、かつ薄膜形成能力の優れた化合物が好ましい。具体的には、フルオレノン、アントラキノジメタン、ジフェノキノン、チオピランジオキシド、オキサゾール、オキサジアゾール、トリアゾール、イミダゾール、ペリレンテトラカルボン酸、フレオレニリデンメタン、アントラキノジメタン、アントロン等とそれらの誘導体が挙げられるが、これらに限定されるものではない。また、正孔注入材料に電子受容物質を、電子注入材料に電子供与性物質を添加することにより電荷注入性を向上させることもできる。
【００２２】
本発明の有機ＥＬ素子において、さらに効果的な電子注入材料は、金属錯体化合物もしくは含窒素五員環誘導体である。
金属錯体化合物の具体例は、８−ヒドロキシキノリナートリチウム、ビス（８−ヒドロキシキノリナート）亜鉛、ビス（８−ヒドロキシキノリナート）銅、ビス（８−ヒドロキシキノリナート）マンガン、トリス（８−ヒドロキシキノリナート）アルミニウム、トリス（２−メチル−８−ヒドロキシキノリナート）アルミニウム、トリス（８−ヒドロキシキノリナート）ガリウム、ビス（１０−ヒドロキシベンゾ［ｈ］キノリナート）ベリリウム、ビス（１０−ヒドロキシベンゾ［ｈ］キノリナート）亜鉛、ビス（２−メチル−８−キノリナート）クロロガリウム、ビス（２−メチル−８−キノリナート）（ｏ−クレゾラート）ガリウム、ビス（２−メチル−８−キノリナート）（１−ナフトラート）アルミニウム、ビス（２−メチル−８−キノリナート）（２−ナフトラート）ガリウム等が挙げられるが、これらに限定されるものではない。
【００２３】
また、含窒素五員誘導体は、オキサゾール、チアゾール、オキサジアゾール、チアジアゾールもしくはトリアゾール誘導体が好ましい。具体的には、２，５−ビス（１−フェニル）−１，３，４−オキサゾール、ジメチルＰＯＰＯＰ、２，５−ビス（１−フェニル）−１，３，４−チアゾール、２，５−ビス（１−フェニル）−１，３，４−オキサジアゾール、２−（４’−ｔｅｒｔ−ブチルフェニル）−５−( ４”−ビフェニル) １，３，４−オキサジアゾール、２，５−ビス（１−ナフチル）−１，３，４−オキサジアゾール、１，４−ビス［２−( ５−フェニルオキサジアゾリル) ］ベンゼン、１，４−ビス［２−( ５−フェニルオキサジアゾリル) −４−ｔｅｒｔ−ブチルベンゼン］、２−（４’−ｔｅｒｔ−ブチルフェニル）−５−( ４”−ビフェニル) −１，３，４−チアジアゾール、２，５−ビス（１−ナフチル）−１，３，４−チアジアゾール、１，４−ビス［２−( ５−フェニルチアジアゾリル) ］ベンゼン、２−（４’−ｔｅｒｔ−ブチルフェニル）−５−( ４”−ビフェニル) −１，３，４−トリアゾール、２，５−ビス（１−ナフチル）−１，３，４−トリアゾール、１，４−ビス［２−( ５−フェニルトリアゾリル) ］ベンゼン等が挙げられるが、これらに限定されるものではない。
本発明においては、発光層と電極との間に無機化合物層を電荷注入性向上のために設けてもよい。このような無機化合物層としては、アルカリ金属化合物（フッ化物、酸化物など）、アルカリ土類金属化合物などがあり、具体的にはＬｉＦ、Ｌｉ2 Ｏ、ＢａＯ、ＳｒＯ、ＢａＦ2 、ＳｒＦ2 などが挙げられる。
【００２４】
有機ＥＬ素子の陽極に使用される導電性材料としては、４ｅＶより大きな仕事関数を持つものが適しており、炭素、アルミニウム、バナジウム、鉄、コバルト、ニッケル、タングステン、銀、金、白金、パラジウム等およびそれらの合金、ＩＴＯ基板、ＮＥＳＡ基板に使用される酸化スズ、酸化インジウム等の酸化金属、さらにはポリチオフェンやポリピロール等の有機導電性樹脂が用いられる。陰極に使用される導電性物質としては、４ｅＶより小さな仕事関数を持つものが適しており、マグネシウム、カルシウム、錫、鉛、チタニウム、イットリウム、リチウム、ルテニウム、マンガン、アルミニウム等およびそれらの合金が用いられるが、これらに限定されるものではない。合金としては、マグネシウム／銀、マグネシウム／インジウム、リチウム／アルミニウム等が代表例として挙げられるが、これらに限定されるものではない。合金の比率は、蒸着源の温度、雰囲気、真空度等により制御され、適切な比率に選択される。陽極および陰極は、必要があれば二層以上の層構成により形成されていても良い。
【００２５】
有機ＥＬ素子では、効率良く発光させるために、少なくとも一方の面は素子の発光波長領域において充分透明にすることが望ましい。また、基板も透明であることが望ましい。透明電極は、上記の導電性材料を使用して、蒸着やスパッタリング等の方法で所定の透光性が確保されるように設定する。発光面の電極は、光透過率を１０％以上にすることが望ましい。基板は、機械的、熱的強度を有し、透明性を有するものであれば限定されるものではないが、ガラス基板および透明性樹脂フィルムが挙げられる。透明性樹脂フィルムとしては、ポリエチレン、エチレン−酢酸ビニル共重合体、エチレン−ビニルアルコール共重合体、ポリプロピレン、ポリスチレン、ポリメチルメタアクリレート、ポリ塩化ビニル、ポリビニルアルコール、ポリビニルブチラール、ナイロン、ポリエーテルエーテルケトン、ポリサルホン、ポリエーテルサルフォン、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体、ポリビニルフルオライド、テトラフルオロエチレン−エチレン共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、ポリクロロトリフルオロエチレン、ポリビニリデンフルオライド、ポリエステル、ポリカーボネート、ポリウレタン、ポリイミド、ポリエーテルイミド、ポリイミド、ポリプロピレン等が挙げられる。
【００２６】
本発明の有機ＥＬ素子は、温度、湿度、雰囲気等に対する安定性の向上のために、素子の表面に保護層を設けたり、シリコンオイル、樹脂等により素子全体を保護することも可能である。
有機ＥＬ素子の各層の形成は、真空蒸着、スパッタリング、プラズマ、イオンプレーティング等の乾式成膜法やスピンコーティング、ディッピング、フローコーティング等の湿式成膜法のいずれの方法を適用することができる。膜厚は特に限定されるものではないが、適切な膜厚に設定する必要がある。膜厚が厚すぎると、一定の光出力を得るために大きな印加電圧が必要になり効率が悪くなる。膜厚が薄すぎるとピンホール等が発生して、電界を印加しても充分な発光輝度が得られない。通常の膜厚は５ｎｍから１０μｍの範囲が適しているが、１０ｎｍから０．２μｍの範囲がさらに好ましい。
【００２７】
湿式成膜法の場合、各層を形成する材料を、エタノール、クロロホルム、テトラヒドロフラン、ジオキサン等の適切な溶媒に溶解または分散させて薄膜を形成するが、その溶媒はいずれであっても良い。また、いずれの有機薄膜層においても、成膜性向上、膜のピンホール防止等のため適切な樹脂や添加剤を使用しても良い。使用の可能な樹脂としては、ポリスチレン、ポリカーボネート、ポリアリレート、ポリエステル、ポリアミド、ポリウレタン、ポリスルフォン、ポリメチルメタクリレート、ポリメチルアクリレート、セルロース等の絶縁性樹脂およびそれらの共重合体、ポリ−Ｎ−ビニルカルバゾール、ポリシラン等の光導電性樹脂、ポリチオフェン、ポリピロール等の導電性樹脂を挙げられる。また、添加剤としては、酸化防止剤、紫外線吸収剤、可塑剤等を挙げられる。
【００２８】
本発明の有機ＥＬ素子は、例えば壁掛けテレビのフラットパネルディスプレイ等の平面発光体、複写機、プリンター、液晶ディスプレイのバックライト又は計器類等の光源、表示板、標識灯等に利用できる。
【００２９】
【実施例】
以下、本発明を合成例及び実施例に基づいてさらに詳細に説明する。
合成例１（化合物（Ａ１））
以下に示す反応経路によって化合物（Ａ１）を製造した。
【化８】
（１）７，１０−ジフェニルフルオランテン−３−ボロン酸の合成
アルゴン雰囲気下、３−ブロモ−７，１０−ジフェニルフルオランテン(25g, 58mmol) を無水エーテル(150ml) に溶かし、ドライアイス／メタノール浴で−35℃に冷却した。これにｎ−ブチルリチウム／ヘキサン溶液(1.50mol/l,43ml,65mmol) を滴下し、−20℃で１時間攪拌した。反応混合物を−70℃に冷却し、トリイソプロポキシシラン(37ml,0.16mol,2.8eq)の無水エーテル溶液(30ml)を加えて、−65℃で１時間、室温で２時間攪拌し、一晩放置した。反応混合物に10％塩酸水溶液(150ml) を加えて室温で１時間撹拌後、有機層を分取し、飽和食塩水(50ml)で洗浄、無水硫酸マグネシウムで乾燥、溶媒留去して得られた固体をヘキサンで洗浄して白色固体(19g,48mmol,収率83%)を得た。
【００３１】
（２）１，４’−ビス（３−（７，１０−ジフェニル) フルオランテニル）ベンゼン（Ａ１）の合成
アルゴン雰囲気下、７，１０−ジフェニルフルオランテン−３−ボロン酸(18g,45mmol,2.8eq)、１，４−ジブロモベンゼン(3.8g,16mmol) 、テトラキス（トリフェニルホスフィン）パラジウム(0)(0.37g, 0.32mmol,2%Pd) をトルエン(200ml) に懸濁し、炭酸ナトリウム水溶液(10g, 94mmol,5.8eq/48ml)を加えて10時間還流し、一晩放置した。反応混合物をろ別し、水、メタノール、アセトンで洗浄して灰色固体(11g,14mmol,収率88%)を得、さらに昇華精製により黄色固体(9.1g,11mmol) を得た。
得られた固体は、４００ＭＨｚＮＭＲスペクトル、プロトンＮＭＲスペクトル及びＦＤ−ＭＳ（フィールドディソプーションマススペクトル）の測定により化合物（Ａ１）であることが確認された。
【００３２】
合成例２（化合物（Ａ２））
以下に示す反応経路によって化合物（Ａ２）を製造した。
【化９】
（１）Ｎ，Ｎ’−ビス（７，１０−ジフェニル−３−フルオラントイル）ヒドラジンの合成
フラスコ中で、ヒドラジンサルフェート(2.2g,17mmol) を蒸留水(40ml)に加え、さらに水酸化ナトリウム(1.5g,38mmol) を溶かした水溶液を氷浴で冷やしながら撹拌する。次に水酸化ナトリウム(1.6g,40mmol) を蒸留水(30ml)に溶かし、７，１０−ジフェニル−３−フルオラントイルクロライド(15g,36mmol)を加えた溶液を前記フラスコ中に１時間かけて滴下した。さらに、10℃で２時間攪拌した後、ろ過して白色の残さを得た。この残さを50％含水アセトンで洗浄し、再びろ過、乾燥して白色固体(8.7g,11mmol, 収率65%)を得た。
【００３４】
（２）２，５−ビス（３−（７，１０−ジフェニル) フルオランテニル）−１，３，４−チアジアゾール（Ａ２）の合成
アルゴン雰囲気下、フオスフォラペンタスルフィド(3.2g,14mmol) 、Ｎ，Ｎ’−ビス（７，１０−ジフェニル−３−フルオラントイル）ヒドラジン(8.7g,11mmol) を無水クロロホルム(50ml)に加え４０時間還流した。その後、10％水酸化カリウム水溶液(50ml)で２回洗浄後、蒸留水でさらに２回洗浄し、硫酸マグネシウムで乾燥、溶媒を留去し、カラムクロマトグラフィーで精製して黄色結晶(4.0g,5.0mmol,収率45%)を得た。
得られた結晶は、４００ＭＨｚＮＭＲスペクトル、プロトンＮＭＲスペクトル及びＦＤ−ＭＳの測定により化合物（Ａ２）であることが確認された。
【００３５】
合成例３（化合物（Ａ３））
以下に示す反応経路によって化合物（Ａ３）を製造した。
【化１０】
（１）４，７−ビス（３−（７，１０−ジフェニル) フルオランテニル）−２，１，３−ベンゾチアゾール（Ａ３）の合成
アルゴン雰囲気下、７，１０−ジフェニルフルオランテン−３−ボロン酸(18g,45mmol,2.8eq)、４，７−ジブロモ−２，１，３−ベンゾチアゾール(4.7g,16mmol) 、テトラキス（トリフェニルホスフィン）パラジウム(0)(0.37g,0.32mmol, 2%Pd) をトルエン(200ml) に懸濁し、炭酸ナトリウム水溶液(10g,94mmol,5.8eq/48ml) を加えて１０時間還流し、一晩放置した。反応混合物をろ別し、水、メタノール、アセトンで洗浄し、カラムクロマトグラフィーで精製して、やまぶき色固体(9.7g,12mmol, 収率72%)を得た。
得られた固体は、４００ＭＨｚＮＭＲスペクトル、プロトンＮＭＲスペクトル及びＦＤ−ＭＳの測定により化合物（Ａ３）であることが確認された。
【００３７】
合成例４（化合物（Ａ６））
以下に示す反応経路によって化合物（Ａ６）を製造した。
【化１１】
（１）フルオランテン−３−ボロン酸の合成
アルゴン雰囲気下、３−ブロモフルオランテン(15g,53mmol)を無水エーテル(120ml) に溶かし、ドライアイス／メタノール浴で−35℃に冷却した。これにｎ−ブチルリチウム／ヘキサン溶液(1.50mol/l,38ml,58mmol) を滴下し、−20℃で１時間攪拌した。反応混合物を−70℃に冷却し、トリイソプロポキシシラン(28ml,0.12mol,2.3eq)の無水エーテル溶液(25ml)を加えて、−65℃で１時間、室温で２時間攪拌し、一晩放置した。反応混合物に10％塩酸水溶液(120ml) を加えて、室温で１時間撹拌後、有機層を分取し、飽和食塩水(40ml)で洗浄、無水硫酸マグネシウムで乾燥、溶媒留去して得られた固体をヘキサンで洗浄して白色固体(11g,45mmol,収率85%)を得た。
【００３９】
（２）１，３，５−トリス（３−フルオランテニル）ベンゼン（Ａ６）の合成
アルゴン雰囲気下、フルオランテン−３−ボロン酸(10g,41mmol,3.8eq)、１，３，５−トリブロモベンゼン(3.5g,11mmol) 、テトラキス（トリフェニルホスフィン）パラジウム(0)(0.29g,0.25mmol,2.3%Pd)をトルエン(150ml) に懸濁し、炭酸ナトリウム水溶液(9g,86mmol,7.8eq/43ml)を加えて10時間還流し、一晩放置した。反応混合物をろ別し、水、メタノール、アセトンで洗浄して灰色固体(6.5g,9.6mmol,収率87%)を得、さらに昇華精製により黄色固体(4.3g,6.4mmol)を得た。得られた固体は、４００ＭＨｚＮＭＲスペクトル、プロトンＮＭＲスペクトル及びＦＤ−ＭＳの測定により化合物（Ａ６）であることが確認された。
【００４０】
合成例５（化合物（Ａ９））
以下に示す反応経路によって化合物（Ａ９）を製造した。
【化１２】
（１）９，１０−ビス（３−フルオランテニル）アントラセン（Ａ９）の合成
アルゴン雰囲気下、フルオランテン−３−ボロン酸(10g,41mmol,2.2eq)、９，１０−ジブロモアントラセン(6.3g,19mmol) 、テトラキス（トリフェニルホスフィン）パラジウム(0)(0.44g,0.38mmol,2%Pd)をトルエン(150ml) に懸濁し、炭酸ナトリウム水溶液(8.6g,82mmol,4.4eq/40ml)を加えて10時間還流し、一晩放置した。反応混合物をろ別し、水、メタノール、アセトンで洗浄して灰色固体(10g,17mmol,収率91%)を得、さらに昇華精製により黄色固体(8.4g,14mmol) を得た。得られた固体は、４００ＭＨｚＮＭＲスペクトル、プロトンＮＭＲスペクトル及びＦＤ−ＭＳの測定により化合物（Ａ９）であることが確認された。
【００４２】
合成例６（化合物（Ａ１５））
以下に示す反応経路によって化合物（Ａ１５）を製造した。
【化１３】
（１）Ｎ，Ｎ’−ビス（３−（７，１０−ジフェニル) フルオランテニル）アニリン（Ａ１５）の合成
アルゴン雰囲気下、３−ブロモ−７，１０−ジフェニルフルオランテン(5g,12mmol) 、酢酸パラジウム(2)(0.06g,0.3mmol)、トリ−ｔ−ブチルホスフィン(0.23g,1.1mmol) 、ｔ−ブトキシナトリウム(1.6g,16mmol) 、アニリン(0.5g,6mmol)を無水トルエン(50ml)に加え、30分室温で撹拌後、７時間還流した。析出した結晶をろ別し、トルエン、水で洗浄後、減圧乾燥して黄色固体を得た。さらにカラムクロマトグラフィーで精製して、淡黄色固体(4.5g,5.7mmol,収率96%)を得た。
得られた固体は、４００ＭＨｚＮＭＲスペクトル、プロトンＮＭＲスペクトル及びＦＤ−ＭＳの測定により化合物（Ａ１５）であることが確認された。
【００４４】
合成例７（化合物（Ａ１６））
以下に示す反応経路によって化合物（Ａ１６）を製造した。
【化１４】
（１）３，６−ビス（３−（７，１０−ジフェニル) フルオランテニル）−９−フェニルカンバゾール（Ａ１６）の合成
アルゴン雰囲気下、７，１０−ジフェニルフルオランテン−３−ボロン酸(9g,22mmol,2.4eq) 、３，６−ジブロモ−９−カンバゾール(3.7g,9.2mmol)、テトラキス（トリフェニルホスフィン）パラジウム(0)(0.21g,0.18mmol,2%Pd)をトルエン(100ml) に懸濁し、炭酸ナトリウム水溶液(6.9g,65mmol,7.0eq/33ml)を加えて１４時間還流し、一晩放置した。反応混合物をろ別し、水、メタノール、アセトンで洗浄し、カラムクロマトグラフィーで精製して、淡黄色固体(8.1g,8.5mmol,収率92%)を得た。
得られた固体は、４００ＭＨｚＮＭＲスペクトル、プロトンＮＭＲスペクトル及びＦＤ−ＭＳの測定により化合物（Ａ１６）であることが確認された。
【００４６】
合成例８（化合物（Ａ１８））
以下に示す反応経路によって化合物（Ａ１８）を製造した。
【化１５】
（１）フルオランテン−８−ボロン酸の合成
アルゴン雰囲気下、８−ブロモフルオランテン(15g,53mmol)を無水エーテル(120ml) に溶かし、ドライアイス／メタノール浴で−35℃に冷却した。これにｎ−ブチルリチウム／ヘキサン溶液(1.50mol/l,38ml,58mmol) を滴下し、−20℃で１時間攪拌した。反応混合物を−70℃に冷却し、トリイソプロポキシシラン(28ml,0.12mol,2.3eq)の無水エーテル溶液(25ml)を加えて、−65℃で１時間、室温で２時間攪拌し、一晩放置した。反応混合物に10％塩酸水溶液(120ml) を加えて室温で１時間撹拌後、有機層を分取し、飽和食塩水(40ml)で洗浄、無水硫酸マグネシウムで乾燥、溶媒留去して得られた固体をヘキサンで洗浄して白色固体(12g,49mmol,収率92%)を得た。
【００４８】
（２）１，４−ビス（８−フルオランテニル）ベンゼン（Ａ１８）の合成
アルゴン雰囲気下、フルオランテン−８−ボロン酸(9g,37mmol,2.3eq) 、１，４−ジブロモベンゼン(3.8g,16mmol) 、テトラキス（トリフェニルホスフィン）パラジウム(0)(0.37g,0.32mmol,2%Pd)をトルエン(200ml) に懸濁し、炭酸ナトリウム水溶液(10g,94mmol,5.8eq/48ml) を加えて10時間還流し、一晩放置した。反応混合物をろ別し、水、メタノール、アセトンで洗浄して灰色固体(7.4g,15mmol, 収率94%)を得、さらに昇華精製により淡黄色固体(6.0g,12mmol) を得た。
得られた固体は、４００ＭＨｚＮＭＲスペクトル、プロトンＮＭＲスペクトル及びＦＤ−ＭＳの測定により化合物（Ａ１８）であることが確認された。
【００４９】
合成例９（化合物（Ａ２０））
以下に示す反応経路によって化合物（Ａ２０）を製造した。
【化１６】
（１）３−Ｎ，Ｎ’−ジフェニルアミノフルオランテン−８−ボロン酸の合成
アルゴン雰囲気下、３−Ｎ，Ｎ’−ジフェニルアミノフルオランテン(12g, 27mmol) を無水エーテル(100ml) に溶かし、ドライアイス／メタノール浴で−35℃に冷却した。これにｎ−ブチルリチウム／ヘキサン溶液(1.50mol/l,19ml,29mmol) を滴下し、−20℃で１時間攪拌した。反応混合物を−70℃に冷却し、トリイソプロポキシシラン(14ml,60mmol,2.2eq) の無水エーテル溶液(20ml)を加えて、−65℃で１時間、室温で３時間攪拌し、一晩放置した。反応混合物に10％塩酸水溶液(100ml) を加えて室温で１時間撹拌後、有機層を分取し、飽和食塩水(36ml)で洗浄、無水硫酸マグネシウムで乾燥、溶媒留去して得られた固体をヘキサンで洗浄して白色固体(9.2g,23mmol, 収率85%)を得た。
【００５１】
（２）１，４−ビス（８−（３−Ｎ，Ｎ’−ジフェニルアミノ）フルオランテニル）ベンゼン（Ａ２０）の合成
アルゴン雰囲気下、３−Ｎ，Ｎ’−ジフェニルアミノフルオランテン−８−ボロン酸(9g,22mmol,2.2eq) 、１，４−ジブロモベンゼン(2.4g,10mmol) 、テトラキス（トリフェニルホスフィン）パラジウム(0)(0.23g,0.20mmol,2%Pd)をトルエン(150ml) に懸濁し、炭酸ナトリウム水溶液(6.4g,60mmol,6.0eq/31ml)を加えて12時間還流し、一晩放置した。反応混合物をろ別し、水、メタノール、アセトンで洗浄して灰色固体(6.9g,8.5mmol,収率85%)を得、さらに昇華精製により淡黄色固体(5.2g,6.4mmol)を得た。
得られた固体は、４００ＭＨｚＮＭＲスペクトル、プロトンＮＭＲスペクトル及びＦＤ−ＭＳの測定により化合物（Ａ２０）であることが確認された。
【００５２】
実施例１
25mm×75mm×1.1mm 厚のＩＴＯ透明電極付きガラス基板（ジオマティック社製）をイソプロピルアルコール中で超音波洗浄を５分間行なった後、ＵＶオゾン洗浄を30分間行なった。洗浄後の透明電極ライン付きガラス基板を真空蒸着装置の基板ホルダーに装着し、まず透明電極ラインが形成されている側の面上に、前記透明電極を覆うようにして膜厚60nmのＮ，Ｎ' −ビス（Ｎ，Ｎ' −ジフェニル−４−アミノフェニル）−Ｎ，Ｎ’−ジフェニル−４，４' −ジアミノ−１，１' −ビフェニル膜（以下、ＴＰＤ２３２膜）を成膜した。このＴＰＤ２３２膜は、正孔注入層として機能する。次に、ＴＰＤ２３２膜上に膜厚20nmの４，４' −ビス［Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ］ビフェニル膜（以下、ＮＰＤ膜）を成膜した。このＮＰＤ膜は正孔輸送層として機能する。さらに、ＮＰＤ膜上に膜厚40nmの上記化合物（Ａ１）を蒸着し成膜した。この膜は、発光層として機能する。この膜上に膜厚20nmのトリス（８−キノリノール）アルミニウム膜（以下、Ａｌｑ膜）を成膜した。このＡｌｑ膜は、電子注入層として機能する。この後Ｌｉ（Ｌｉ源：サエスゲッター社製）とＡｌｑを二元蒸着させ、電子注入層（陰極）としてＡｌｑ：Ｌｉ膜を形成した。このＡｌｑ：Ｌｉ膜上に金属Ａｌを蒸着させ金属陰極を形成し有機ＥＬ素子を作製した。この素子は直流電圧6Vで発光輝度150cd/m2、最大発光輝度43000cd/m2、発光効率3.0cd/A の青色発光が得られた。
【００５３】
実施例２〜８
実施例１において、化合物（Ａ１）の代わりに表１に示す化合物を使用したことを除き同様にして、有機ＥＬ素子を作製し、直流電圧6Vで、発光輝度、発光効率、ガラス転移温度を測定し、発光色を観察し、さらに耐熱性テストとして85℃の温度下に500 時間保存した後に、初期輝度からの発光減少率を測定した。その結果を表１に示す。
【００５４】
比較例１
実施例１において、化合物（Ａ１）の代わりに、７，１０−ジフェニルフルオランテン（ＤＰＦ）を使用したことを除き同様にして、有機ＥＬ素子を作製し、直流電圧5Vで、発光輝度、発光効率を測定し、発光色を観察し、さらに耐熱性テストとして85℃の温度下に500 時間保存した後に、初期輝度からの発光減少率を測定した。その結果を表１に示す。
【００５５】
【表１】
表１に示したように、本発明の新規炭化水素化合物を利用した有機ＥＬ素子は、発光効率が高く、耐熱性に優れている。これは、本発明の新規炭化水素化合物のガラス転移温度が１００℃超と高く、青色〜緑色領域にわたる蛍光性を保持するためである。
【００５７】
実施例９
25mm×75mm×1.1mm 厚のＩＴＯ透明電極付きガラス基板（ジオマティック社製）をイソプロピルアルコール中で超音波洗浄を５分間行なった後、ＵＶオゾン洗浄を30分間行なった。洗浄後の透明電極ライン付きガラス基板を真空蒸着装置の基板ホルダーに装着し、まず透明電極ラインが形成されている側の面上に、前記透明電極を覆うようにして膜厚60nmのＴＰＤ２３２膜を成膜した。このＴＰＤ２３２膜は、正孔注入層として機能する。次に、ＴＰＤ２３２膜上に膜厚20nmに上記化合物（Ａ１５）からなる膜を成膜した。この（Ａ１５）膜は正孔輸送層として機能する。さらに、（Ａ１５）膜上に膜厚40nmのＡｌｑ及びルブレンを重量比30：１で蒸着し成膜した。この膜は、発光層として機能する。この膜上に膜厚20nmのＡｌｑ膜を成膜した。このＡｌｑ膜は、電子注入層として機能する。この後Ｌｉ（Ｌｉ源：サエスゲッター社製）とＡｌｑを二元蒸着させ、電子注入層（陰極）としてＡｌｑ：Ｌｉ膜を形成した。このＡｌｑ：Ｌｉ膜上に金属Ａｌを蒸着させ金属陰極を形成し有機ＥＬ素子を作製した。この素子は直流電圧6Vで発光輝度150cd/m2、最大発光輝度73000cd/m2、発光効率10.0cd/Aと極めて高い発光効率の黄色発光が得られた。また、初期輝度を1000cd/m2 として定電流駆動して寿命試験を行ったところ半減寿命6200時間と極めて長かった。
以上のことから、本発明の新規炭化水素化合物は、正孔輸送性の化合物として極めて優れている。
【００５８】
実施例１０
25mm×75mm×1.1mm 厚のＩＴＯ透明電極付きガラス基板（ジオマティック社製）をイソプロピルアルコール中で超音波洗浄を５分間行なった後、ＵＶオゾン洗浄を30分間行なった。洗浄後の透明電極ライン付きガラス基板を真空蒸着装置の基板ホルダーに装着し、まず透明電極ラインが形成されている側の面上に、前記透明電極を覆うようにして膜厚60nmのＴＰＤ２３２膜を成膜した。このＴＰＤ２３２膜は、正孔注入層として機能する。次に、ＴＰＤ２３２膜上に膜厚20nmにＮＰＤ膜を成膜した。このＮＰＤ膜は正孔輸送層として機能する。さらに、ＮＰＤ膜上に膜厚40nmのＡｌｑ及びルブレンを重量比３０：１で蒸着し成膜した。この膜は、発光層として機能する。この膜上に膜厚20nmの上記化合物（Ａ３）からなる膜を成膜した。この（Ａ３）膜は、電子注入層として機能する。この後、無機化合物膜として、膜厚１nmのＬｉＦ膜を形成した。このＬｉＦ膜上に金属Ａｌを蒸着させ金属陰極を形成し有機ＥＬ素子を作製した。この素子は直流電圧5.5Vで発光輝度250cd/m2、最大発光輝度93000cd/m2、発光効率12.0cd/Aと極めて高い発光効率の黄色発光が得られた。また、初期輝度を1000cd/m2 として定電流駆動して寿命試験を行ったところ半減寿命5000時間と極めて長かった。
以上のことから、本発明の新規炭化水素化合物は、電子輸送性の化合物として極めて優れている。
【００５９】
実施例１１
実施例１０において、ＬｉＦ膜の無機化合物膜を形成する代わりに、上記化合物（Ａ３）とＣｓ（セシウム）をモル比１：１で混合した電子輸送性化合物と還元性化合物との混合型電子注入層を形成した有機ＥＬ素子を作製した。この素子は直流電圧4.5Vで発光輝度1020cd/m2 とさらに低電圧駆動となり、最大発光輝度123000cd/m2 、発光効率13.0cd/Aと極めて高い発光効率の黄色発光が得られた。
また、初期輝度を1000cd/m2 として定電流駆動して寿命試験を行ったところ半減寿命5800時間と極めて長かった。
【００６０】
【発明の効果】
以上、詳細に説明したように、本発明の新規炭化水素化合物を利用した有機エレクトロルミネッセンス素子は、耐熱性が高く、発光効率も高く、さらには長寿命である。
このため、本発明の有機エレクトロルミネッセンス素子は、壁掛テレビの平面発光体やディスプレイのバックライト等の光源として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel hydrocarbon compound and an organic electroluminescence device, and more particularly to an organic electroluminescence device having high heat resistance and high luminous efficiency and a novel hydrocarbon compound for realizing the same.
[0002]
[Prior art]
An organic electroluminescence (EL) element using an organic substance is used as a light source such as a flat light emitter of a wall-mounted television and a backlight of a display, and has been actively developed. In particular, recently, an organic electroluminescence device that achieves both high heat resistance and high efficiency and a compound that realizes the same have been developed.
For example, Japanese Patent Application Laid-Open No. 8-12600 discloses a phenylanthracene compound and a device using the same, and the heat resistance is improved by setting the glass transition temperature to 140 ° C. or higher. The light emission efficiency calculated by (2) was as low as about 2 cd / A, and improvement was demanded. Japanese Patent Application Laid-Open No. 10-72579 discloses an aminoanthracene compound and a device using the same, and the light emission efficiency is improved, but the heat resistance is not sufficient. Further, Japanese Patent Application Laid-Open No. 10-189247 discloses a device using a fluoranthene compound, but since the compound is composed of a monomer of a fluoranthene compound, the heat resistance has not been improved sufficiently. .
[0003]
[Problems to be solved by the invention]
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide an organic electroluminescence device having high heat resistance and high luminous efficiency and a novel hydrocarbon compound that realizes the organic electroluminescence device. .
[0004]
[Means for Solving the Problems]
As a result of intensive research to develop an organic electroluminescence device (hereinafter referred to as an organic EL device) having the above-mentioned preferable properties, the present inventors have developed a novel hydrocarbon compound in which an aryl structure is bonded to a fluoranthene structure as an organic compound film. When added to the above, the heat resistance of the organic electroluminescence device is improved, and further, the hole transport property and the electron transport property are improved and high luminous efficiency is obtained, and the present invention has been completed.
[0005]
That is, the present invention provides a novel hydrocarbon compound represented by the following general formula (1):
X n -Ar 1 (1)
(In the formula, Ar 1 represents a substituted or unsubstituted aromatic ring group having 6 to 40 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 40 carbon atoms, a substituted or unsubstituted carbon atom number of 6; -60 diaminoaryl group, substituted or unsubstituted triaminoaryl group having 6 to 60 carbon atoms, substituted or unsubstituted heterocyclic group having 3 to 40 carbon atoms, or substituted or unsubstituted ethenylene, X is fluoranthene A monovalent group having a structure, n is an integer of 2 to 4.)
Is to provide.
The present invention also provides an organic electroluminescence element (organic EL element) having an organic compound film composed of a single layer or a plurality of layers having at least a light emitting layer between a pair of electrodes, wherein at least one layer of the organic compound film is formed. The present invention also provides an organic electroluminescence device comprising the novel hydrocarbon compound.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The novel hydrocarbon compound of the present invention is represented by the above general formula (1).
In the formula, Ar 1 represents a substituted or unsubstituted aromatic ring group having 6 to 40 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 40 carbon atoms, a substituted or unsubstituted carbon atom having 6 to 6 carbon atoms. 60 diaminoaryl groups, substituted or unsubstituted triaminoaryl groups having 6 to 60 carbon atoms, substituted or unsubstituted heterocyclic groups having 3 to 40 carbon atoms, or substituted or unsubstituted ethenylene.
X is a monovalent group having a fluoranthene structure, and n is an integer of 2 to 4.
[0007]
The X is preferably a monovalent group of a compound having a structure represented by the following general formulas [1] to [3].
[Chemical 2]
In the general formulas [1] to [3], X 1 to X 16 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. Substituted or unsubstituted linear, branched or cyclic alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted linear, branched or cyclic alkylthio groups having 1 to 30 carbon atoms, substituted or unsubstituted Straight chain, branched or cyclic alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted straight chain, branched or cyclic alkenyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted straight chain, branched or Cyclic alkenylthio group having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms Group, substituted or unsubstituted aralkylthio group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, substituted Alternatively, an unsubstituted arylthio group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group having 2 to 30 carbon atoms, a cyano group, a hydroxyl group, a —COOR 1 group (wherein R 1 is a hydrogen atom, substituted or Unsubstituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted linear, branched or cyclic alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms A 7 to 30 aralkyl group or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a —COR 2 group (wherein R 2 is a hydrogen atom, a substituted or unsubstituted straight chain, Branched or cyclic alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted straight chain, branched or cyclic alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms , Represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or an amino group), -OCOR 3 group (wherein R 3 is a substituted or unsubstituted linear, branched or cyclic carbon atom number) 1-30 alkyl groups, substituted or unsubstituted linear, branched or cyclic alkenyl groups having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted carbons Represents an aryl group having 6 to 30 atoms, and among X 1 to X 16 , adjacent groups and substituents of each group are bonded to each other to form a substituted or unsubstituted carbocycle. May be.
[0009]
The organic EL device of the present invention is an organic electroluminescence device having an organic compound film composed of a single layer or a plurality of layers having at least a light emitting layer between a pair of electrodes, wherein at least one layer of the organic compound film is the above-mentioned novel carbonized film. Contains hydrogen compounds.
The light emitting layer preferably contains the novel hydrocarbon compound. Moreover, it is also preferable that an electron injection layer or a hole injection layer contains the novel hydrocarbon compound.
An inorganic compound layer may be provided between the light emitting layer and the electrode.
More preferably, the light emitting layer contains a condensed polycyclic aromatic derivative as a light emission center.
When the novel hydrocarbon compound is contained in at least one layer of the organic compound film, the heat resistance and the luminous efficiency are improved because the fluorescence of the fluoranthene structure is high, and in the compound of the general formula (1), n = 2 It is because the glass transition temperature of this compound becomes high by setting it as -4.
[0010]
Hereinafter, representative examples (A1) to (A24) of the novel hydrocarbon compound of the present invention will be exemplified, but the present invention is not limited to these representative examples.
[0011]
[Chemical 3]
[Formula 4]
[Chemical formula 5]
[Chemical 6]
[Chemical 7]
The organic EL device of the present invention is a device in which a single-layer or multilayer organic compound film is formed between an anode and a cathode. In the case of a single layer type, a light emitting layer is provided between the anode and the cathode. The light-emitting layer contains a light-emitting material, and may further contain a hole-injecting material or an electron-injecting material in order to transport holes injected from the anode or electrons injected from the cathode to the light-emitting material. However, it is preferable that the light emitting material has extremely high fluorescence quantum efficiency, high hole transport ability and electron transport ability, and forms a uniform thin film. Multi-layer type organic EL elements are (anode / hole injection layer / light emitting layer / cathode), (anode / light emitting layer / electron injection layer / cathode), (anode / hole injection layer / light emitting layer / electron injection layer / There is a laminated structure of a cathode).
[0017]
If necessary, in addition to the novel hydrocarbon compound of the present invention, further known light-emitting materials, doping materials, hole-injecting materials, and electron-injecting materials can be used for the light-emitting layer. As a preferred method of using this novel hydrocarbon compound, it is added at a concentration of 0.5 to 50% by weight to any one of the light emitting layer, the electron injection layer, the hole transport layer and the hole injection layer. More preferably, the concentration is 1 to 20% by weight.
By making the organic EL element have a multi-layer structure, it is possible to prevent a decrease in luminance and lifetime due to quenching. If necessary, a light emitting material, another doping material, a hole injection material, and an electron injection material can be used in combination. Further, with other doping materials, it is possible to improve light emission luminance and light emission efficiency and to obtain red or white light emission. Further, the hole injection layer, the light emitting layer, and the electron injection layer may each be formed with a layer configuration of two or more layers. In that case, in the case of a hole injection layer, the layer that injects holes from the electrode is a hole injection layer, and the layer that receives holes from the hole injection layer and transports holes to the light emitting layer is a hole transport layer. Call. Similarly, in the case of an electron injection layer, a layer that injects electrons from an electrode is referred to as an electron injection layer, and a layer that receives electrons from the electron injection layer and transports electrons to a light emitting layer is referred to as an electron transport layer. Each of these layers is selected and used depending on factors such as the energy level of the material, heat resistance, and adhesion to the organic compound film or metal electrode.
[0018]
Examples of the light emitting material or host material that can be used in the organic compound film together with the novel hydrocarbon compound include condensed polycyclic aromatics such as anthracene, naphthalene, phenanthrene, pyrene, tetracene, pentacene, coronene, chrysene, fluorescein, perylene, rubrene. And their derivatives. Further, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline Examples include, but are not limited to, metal complexes, imines, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, imidazole chelating oxinoid compounds, quinacridone, rubrene, stilbene derivatives and fluorescent dyes. is not.
[0019]
As a hole injection material, it has the ability to transport holes, has a hole injection effect from the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and excitons generated in the light emitting layer. A compound that prevents movement to the electron injection layer or the electron injection material and has an excellent thin film forming ability is preferable. Specifically, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acyl hydrazone, polyaryl Examples include alkane, stilbene, butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, and their derivatives, and polymer materials such as polyvinylcarbazole, polysilane, and conductive polymers. However, it is not limited to these.
[0020]
Among the hole injection materials that can be used in the organic EL device of the present invention, a more effective hole injection material is an aromatic tertiary amine derivative or a phthalocyanine derivative.
Specific examples of the aromatic tertiary amine derivative are triphenylamine, tolylamine, tolyldiphenylamine, N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4 '-Diamine, N, N, N', N '-(4-methylphenyl) -1,1'-phenyl-4,4'-diamine, N, N, N', N '-(4-methylphenyl) ) -1,1′-biphenyl-4,4′-diamine, N, N′-diphenyl-N, N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine, N, N ′-( Methylphenyl) -N, N ′-(4-n-butylphenyl) -phenanthrene-9,10-diamine, N, N-bis (4-di-4-tolylaminophenyl) -4-phenyl-cyclohexane, etc. Or these oligomers having an aromatic tertiary amine skeleton Properly is a polymer, but is not limited thereto.
Specific examples of phthalocyanine (Pc) derivatives are H 2 Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl 2 SiPc, (HO) AlPc, (HO) GaPc, Although it is a phthalocyanine derivative and a naphthalocyanine derivative such as VOPc, TiOPc, MoOPc, and GaPc-O-GaPc, it is not limited thereto.
[0021]
The electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect for the light emitting layer or the light emitting material, and a hole injection layer of excitons generated in the light emitting layer The compound which prevents the movement to and is excellent in thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, and their derivatives However, it is not limited to these. Further, the charge injection property can be improved by adding an electron accepting material to the hole injecting material and an electron donating material to the electron injecting material.
[0022]
In the organic EL device of the present invention, a more effective electron injection material is a metal complex compound or a nitrogen-containing five-membered ring derivative.
Specific examples of the metal complex compound include 8-hydroxyquinolinate lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, tris ( 8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium, bis ( 10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (o-cresolate) gallium, bis (2-methyl-8-quinolinato) ) (1-Naphtholate) aluminum, bis (2-methyl-8-) Norinato) (2-naphtholato) gallium and the like, but not limited thereto.
[0023]
The nitrogen-containing five-membered derivative is preferably an oxazole, thiazole, oxadiazole, thiadiazole or triazole derivative. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, dimethyl POPOP, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5- Bis (1-phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5 -Bis (1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxa) Diazolyl) -4-tert-butylbenzene], 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) ) -1,3,4-thiadiazole, 1,4-bis [2- ( -Phenylthiadiazolyl)] benzene, 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1 , 3,4-triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like, but are not limited thereto.
In the present invention, an inorganic compound layer may be provided between the light emitting layer and the electrode for improving the charge injection property. Examples of such inorganic compound layers include alkali metal compounds (fluorides, oxides, etc.), alkaline earth metal compounds, and the like. Specifically, LiF, Li 2 O, BaO, SrO, BaF 2 , SrF 2, etc. Is mentioned.
[0024]
As a conductive material used for an anode of an organic EL element, a material having a work function larger than 4 eV is suitable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, etc. Further, metal oxides such as tin oxide and indium oxide used for alloys thereof, ITO substrates and NESA substrates, and organic conductive resins such as polythiophene and polypyrrole are used. As the conductive material used for the cathode, those having a work function smaller than 4 eV are suitable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, and alloys thereof are used. However, it is not limited to these. Examples of alloys include magnesium / silver, magnesium / indium, lithium / aluminum, and the like, but are not limited thereto. The ratio of the alloy is controlled by the temperature of the vapor deposition source, the atmosphere, the degree of vacuum, etc., and is selected to an appropriate ratio. If necessary, the anode and the cathode may be formed of two or more layers.
[0025]
In an organic EL element, in order to emit light efficiently, it is desirable that at least one surface is sufficiently transparent in the light emission wavelength region of the element. The substrate is also preferably transparent. The transparent electrode is set using the above-described conductive material so that predetermined translucency is ensured by a method such as vapor deposition or sputtering. The electrode on the light emitting surface preferably has a light transmittance of 10% or more. The substrate is not limited as long as it has mechanical and thermal strength and is transparent, and examples thereof include a glass substrate and a transparent resin film. Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone. , Polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, polyimide, polypropylene, etc. It is.
[0026]
The organic EL device of the present invention can be provided with a protective layer on the surface of the device, or the entire device can be protected with silicon oil, resin, or the like in order to improve stability against temperature, humidity, atmosphere, and the like.
Each layer of the organic EL element can be formed by any of dry film forming methods such as vacuum deposition, sputtering, plasma, and ion plating, and wet film forming methods such as spin coating, dipping, and flow coating. The film thickness is not particularly limited, but must be set to an appropriate film thickness. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, pinholes and the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied. The normal film thickness is suitably in the range of 5 nm to 10 μm, but more preferably in the range of 10 nm to 0.2 μm.
[0027]
In the case of the wet film forming method, the material for forming each layer is dissolved or dispersed in an appropriate solvent such as ethanol, chloroform, tetrahydrofuran, dioxane or the like to form a thin film, and any solvent may be used. In any organic thin film layer, an appropriate resin or additive may be used for improving film formability and preventing pinholes in the film. Usable resins include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and copolymers thereof, poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole. Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.
[0028]
The organic EL device of the present invention can be used, for example, as a flat light emitter such as a flat panel display of a wall-mounted television, a light source such as a copying machine, a printer, a backlight of a liquid crystal display or instruments, a display board, a marker lamp, and the like.
[0029]
【Example】
Hereinafter, the present invention will be described in more detail based on synthesis examples and examples.
Synthesis Example 1 (Compound (A1))
Compound (A1) was produced according to the reaction route shown below.
[Chemical 8]
(1) Synthesis of 7,10-diphenylfluoranthene-3-boronic acid Under an argon atmosphere, 3-bromo-7,10-diphenylfluoranthene (25 g, 58 mmol) was dissolved in anhydrous ether (150 ml) and dried ice / Cooled to -35 ° C in a methanol bath. An n-butyllithium / hexane solution (1.50 mol / l, 43 ml, 65 mmol) was added dropwise thereto, and the mixture was stirred at -20 ° C for 1 hour. The reaction mixture was cooled to −70 ° C., triisopropoxysilane (37 ml, 0.16 mol, 2.8 eq) in anhydrous ether (30 ml) was added, and the mixture was stirred at −65 ° C. for 1 hour and at room temperature for 2 hours, overnight. I left it alone. A 10% aqueous hydrochloric acid solution (150 ml) was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The organic layer was separated, washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and evaporated. The solid was washed with hexane to give a white solid (19 g, 48 mmol, yield 83%).
[0031]
(2) Synthesis of 1,4′-bis (3- (7,10-diphenyl) fluoranthenyl) benzene (A1) Under an argon atmosphere, 7,10-diphenylfluoranthene-3-boronic acid (18 g, 45 mmol) , 2.8eq), 1,4-dibromobenzene (3.8 g, 16 mmol), tetrakis (triphenylphosphine) palladium (0) (0.37 g, 0.32 mmol, 2% Pd) suspended in toluene (200 ml) and sodium carbonate An aqueous solution (10 g, 94 mmol, 5.8 eq / 48 ml) was added, and the mixture was refluxed for 10 hours and left overnight. The reaction mixture was filtered and washed with water, methanol, and acetone to obtain a gray solid (11 g, 14 mmol, yield 88%), and further, a yellow solid (9.1 g, 11 mmol) was obtained by sublimation purification.
The obtained solid was confirmed to be the compound (A1) by measurement of 400 MHz NMR spectrum, proton NMR spectrum, and FD-MS (field desorption mass spectrum).
[0032]
Synthesis Example 2 (Compound (A2))
Compound (A2) was produced by the reaction route shown below.
[Chemical 9]
(1) Synthesis of N, N′-bis (7,10-diphenyl-3-fluorantyl) hydrazine In a flask, hydrazine sulfate (2.2 g, 17 mmol) was added to distilled water (40 ml), and sodium hydroxide was further added. An aqueous solution in which (1.5 g, 38 mmol) is dissolved is stirred while being cooled in an ice bath. Next, sodium hydroxide (1.6 g, 40 mmol) was dissolved in distilled water (30 ml), and 7,10-diphenyl-3-fluorantyl chloride (15 g, 36 mmol) was added to the flask over 1 hour. It was dripped. Further, the mixture was stirred at 10 ° C. for 2 hours and then filtered to obtain a white residue. The residue was washed with 50% water-containing acetone, filtered and dried again to obtain a white solid (8.7 g, 11 mmol, yield 65%).
[0034]
(2) Synthesis of 2,5-bis (3- (7,10-diphenyl) fluoranthenyl) -1,3,4-thiadiazole (A2) Under argon atmosphere, phosphorapentasulfide (3.2 g, 14 mmol), N, N′-bis (7,10-diphenyl-3-fluoranthyl) hydrazine (8.7 g, 11 mmol) was added to anhydrous chloroform (50 ml) and refluxed for 40 hours. Then, after washing twice with 10% aqueous potassium hydroxide solution (50 ml), further washing twice with distilled water, drying over magnesium sulfate, distilling off the solvent, purification by column chromatography and purification of yellow crystals (4.0 g, 5.0 mmol, yield 45%) was obtained.
The obtained crystal was confirmed to be the compound (A2) by measurement of 400 MHz NMR spectrum, proton NMR spectrum and FD-MS.
[0035]
Synthesis Example 3 (Compound (A3))
Compound (A3) was produced by the reaction route shown below.
[Chemical Formula 10]
(1) Synthesis of 4,7-bis (3- (7,10-diphenyl) fluoranthenyl) -2,1,3-benzothiazole (A3) 7,10-diphenylfluoranthene-3 under an argon atmosphere -Boronic acid (18 g, 45 mmol, 2.8 eq), 4,7-dibromo-2,1,3-benzothiazole (4.7 g, 16 mmol), tetrakis (triphenylphosphine) palladium (0) (0.37 g, 0.32 mmol, 2% Pd) was suspended in toluene (200 ml), an aqueous sodium carbonate solution (10 g, 94 mmol, 5.8 eq / 48 ml) was added, and the mixture was refluxed for 10 hours and left overnight. The reaction mixture was filtered, washed with water, methanol and acetone, and purified by column chromatography to obtain a bright yellow solid (9.7 g, 12 mmol, yield 72%).
The obtained solid was confirmed to be the compound (A3) by measurement of 400 MHz NMR spectrum, proton NMR spectrum and FD-MS.
[0037]
Synthesis Example 4 (Compound (A6))
Compound (A6) was produced according to the reaction route shown below.
Embedded image
(1) Synthesis of fluoranthene-3-boronic acid 3-bromofluoranthene (15 g, 53 mmol) was dissolved in anhydrous ether (120 ml) under an argon atmosphere and cooled to -35 ° C. in a dry ice / methanol bath. An n-butyllithium / hexane solution (1.50 mol / l, 38 ml, 58 mmol) was added dropwise thereto, and the mixture was stirred at -20 ° C for 1 hour. The reaction mixture was cooled to −70 ° C., triisopropoxysilane (28 ml, 0.12 mol, 2.3 eq) in anhydrous ether (25 ml) was added, and the mixture was stirred at −65 ° C. for 1 hour and at room temperature for 2 hours, overnight. I left it alone. To the reaction mixture was added 10% aqueous hydrochloric acid (120 ml), and the mixture was stirred at room temperature for 1 hour. The organic layer was separated, washed with saturated brine (40 ml), dried over anhydrous magnesium sulfate, and evaporated. The obtained solid was washed with hexane to obtain a white solid (11 g, 45 mmol, yield 85%).
[0039]
(2) Synthesis of 1,3,5-tris (3-fluoranthenyl) benzene (A6) Under an argon atmosphere, fluoranthene-3-boronic acid (10 g, 41 mmol, 3.8 eq), 1,3,5-tribromo Benzene (3.5 g, 11 mmol), tetrakis (triphenylphosphine) palladium (0) (0.29 g, 0.25 mmol, 2.3% Pd) are suspended in toluene (150 ml), and aqueous sodium carbonate solution (9 g, 86 mmol, 7.8 eq / 43 ml) ) Was added, refluxed for 10 hours, and allowed to stand overnight. The reaction mixture was filtered, washed with water, methanol and acetone to obtain a gray solid (6.5 g, 9.6 mmol, yield 87%), and further purified by sublimation to obtain a yellow solid (4.3 g, 6.4 mmol). The obtained solid was confirmed to be the compound (A6) by measurement of 400 MHz NMR spectrum, proton NMR spectrum and FD-MS.
[0040]
Synthesis Example 5 (Compound (A9))
Compound (A9) was produced according to the reaction route shown below.
Embedded image
(1) Synthesis of 9,10-bis (3-fluoranthenyl) anthracene (A9) Under an argon atmosphere, fluoranthene-3-boronic acid (10 g, 41 mmol, 2.2 eq), 9,10-dibromoanthracene (6.3 g, 19 mmol), tetrakis (triphenylphosphine) palladium (0) (0.44 g, 0.38 mmol, 2% Pd) was suspended in toluene (150 ml), and an aqueous sodium carbonate solution (8.6 g, 82 mmol, 4.4 eq / 40 ml) was added. Refluxed for 10 hours and left overnight. The reaction mixture was filtered and washed with water, methanol and acetone to obtain a gray solid (10 g, 17 mmol, yield 91%), and further a yellow solid (8.4 g, 14 mmol) was obtained by sublimation purification. The obtained solid was confirmed to be the compound (A9) by measurement of 400 MHz NMR spectrum, proton NMR spectrum and FD-MS.
[0042]
Synthesis Example 6 (Compound (A15))
Compound (A15) was produced according to the reaction route shown below.
Embedded image
(1) Synthesis of N, N′-bis (3- (7,10-diphenyl) fluoranthenyl) aniline (A15) Under an argon atmosphere, 3-bromo-7,10-diphenylfluoranthene (5 g, 12 mmol) Palladium acetate (2) (0.06 g, 0.3 mmol), tri-t-butylphosphine (0.23 g, 1.1 mmol), t-butoxy sodium (1.6 g, 16 mmol), aniline (0.5 g, 6 mmol) in anhydrous toluene ( The mixture was stirred at room temperature for 30 minutes and then refluxed for 7 hours. The precipitated crystals were separated by filtration, washed with toluene and water, and then dried under reduced pressure to obtain a yellow solid. Further purification by column chromatography gave a pale yellow solid (4.5 g, 5.7 mmol, yield 96%).
The obtained solid was confirmed to be the compound (A15) by measurement of 400 MHz NMR spectrum, proton NMR spectrum and FD-MS.
[0044]
Synthesis Example 7 (Compound (A16))
Compound (A16) was produced according to the reaction route shown below.
Embedded image
(1) Synthesis of 3,6-bis (3- (7,10-diphenyl) fluoranthenyl) -9-phenylcampazole (A16) 7,10-diphenylfluoranthene-3-boronic acid under argon atmosphere (9 g, 22 mmol, 2.4 eq), 3,6-dibromo-9-campazole (3.7 g, 9.2 mmol), tetrakis (triphenylphosphine) palladium (0) (0.21 g, 0.18 mmol, 2% Pd) in toluene ( 100 ml), an aqueous sodium carbonate solution (6.9 g, 65 mmol, 7.0 eq / 33 ml) was added, and the mixture was refluxed for 14 hours and allowed to stand overnight. The reaction mixture was separated by filtration, washed with water, methanol and acetone, and purified by column chromatography to obtain a pale yellow solid (8.1 g, 8.5 mmol, yield 92%).
The obtained solid was confirmed to be the compound (A16) by measurement of 400 MHz NMR spectrum, proton NMR spectrum and FD-MS.
[0046]
Synthesis Example 8 (Compound (A18))
Compound (A18) was produced according to the reaction route shown below.
Embedded image
(1) Synthesis of fluoranthene-8-boronic acid Under an argon atmosphere, 8-bromofluoranthene (15 g, 53 mmol) was dissolved in anhydrous ether (120 ml) and cooled to -35 ° C. in a dry ice / methanol bath. An n-butyllithium / hexane solution (1.50 mol / l, 38 ml, 58 mmol) was added dropwise thereto, and the mixture was stirred at -20 ° C for 1 hour. The reaction mixture was cooled to −70 ° C., triisopropoxysilane (28 ml, 0.12 mol, 2.3 eq) in anhydrous ether (25 ml) was added, and the mixture was stirred at −65 ° C. for 1 hour and at room temperature for 2 hours, overnight. I left it alone. A 10% aqueous hydrochloric acid solution (120 ml) was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The organic layer was separated, washed with saturated brine (40 ml), dried over anhydrous magnesium sulfate, and evaporated. The solid was washed with hexane to obtain a white solid (12 g, 49 mmol, yield 92%).
[0048]
(2) Synthesis of 1,4-bis (8-fluoranthenyl) benzene (A18) Under an argon atmosphere, fluoranthene-8-boronic acid (9 g, 37 mmol, 2.3 eq), 1,4-dibromobenzene (3.8 g, 16 mmol), tetrakis (triphenylphosphine) palladium (0) (0.37 g, 0.32 mmol, 2% Pd) was suspended in toluene (200 ml), and an aqueous sodium carbonate solution (10 g, 94 mmol, 5.8 eq / 48 ml) was added. Refluxed for hours and left overnight. The reaction mixture was filtered and washed with water, methanol, and acetone to obtain a gray solid (7.4 g, 15 mmol, yield 94%), and further sublimation purification gave a pale yellow solid (6.0 g, 12 mmol).
The obtained solid was confirmed to be the compound (A18) by measurement of 400 MHz NMR spectrum, proton NMR spectrum and FD-MS.
[0049]
Synthesis Example 9 (Compound (A20))
Compound (A20) was produced according to the reaction route shown below.
Embedded image
(1) Synthesis of 3-N, N′-diphenylaminofluoranthene-8-boronic acid 3-N, N′-diphenylaminofluoranthene (12 g, 27 mmol) was added to anhydrous ether (100 ml) under an argon atmosphere. Dissolved and cooled to −35 ° C. in a dry ice / methanol bath. An n-butyllithium / hexane solution (1.50 mol / l, 19 ml, 29 mmol) was added dropwise thereto, and the mixture was stirred at -20 ° C for 1 hour. The reaction mixture is cooled to −70 ° C., triisopropoxysilane (14 ml, 60 mmol, 2.2 eq) in anhydrous ether (20 ml) is added, and the mixture is stirred at −65 ° C. for 1 hour, at room temperature for 3 hours, and allowed to stand overnight. did. A 10% aqueous hydrochloric acid solution (100 ml) was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The organic layer was separated, washed with saturated brine (36 ml), dried over anhydrous magnesium sulfate, and evaporated to obtain the solvent. The solid was washed with hexane to give a white solid (9.2 g, 23 mmol, 85% yield).
[0051]
(2) Synthesis of 1,4-bis (8- (3-N, N′-diphenylamino) fluoranthenyl) benzene (A20) 3-N, N′-diphenylaminofluoranthene-8 under argon atmosphere -Boronic acid (9 g, 22 mmol, 2.2 eq), 1,4-dibromobenzene (2.4 g, 10 mmol), tetrakis (triphenylphosphine) palladium (0) (0.23 g, 0.20 mmol, 2% Pd) in toluene (150 ml) ), An aqueous sodium carbonate solution (6.4 g, 60 mmol, 6.0 eq / 31 ml) was added, and the mixture was refluxed for 12 hours and allowed to stand overnight. The reaction mixture was filtered and washed with water, methanol, and acetone to obtain a gray solid (6.9 g, 8.5 mmol, yield 85%), and further sublimation purification gave a pale yellow solid (5.2 g, 6.4 mmol). .
The obtained solid was confirmed to be the compound (A20) by measurement of 400 MHz NMR spectrum, proton NMR spectrum and FD-MS.
[0052]
Example 1
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 1.1 mm (manufactured by Geomatic) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 30 minutes. A glass substrate with a transparent electrode line after cleaning is mounted on a substrate holder of a vacuum deposition apparatus. First, N, N with a film thickness of 60 nm is formed on the surface where the transparent electrode line is formed so as to cover the transparent electrode. A '-bis (N, N'-diphenyl-4-aminophenyl) -N, N'-diphenyl-4,4'-diamino-1,1'-biphenyl film (hereinafter referred to as TPD232 film) was formed. This TPD232 film functions as a hole injection layer. Next, a 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl film (hereinafter referred to as an NPD film) having a thickness of 20 nm was formed on the TPD232 film. This NPD film functions as a hole transport layer. Further, the compound (A1) having a thickness of 40 nm was deposited on the NPD film to form a film. This film functions as a light emitting layer. A tris (8-quinolinol) aluminum film (hereinafter referred to as an Alq film) having a thickness of 20 nm was formed on this film. This Alq film functions as an electron injection layer. Thereafter, Li (Li source: manufactured by SAES Getter Co., Ltd.) and Alq were vapor-deposited, and an Alq: Li film was formed as an electron injection layer (cathode). Metal Al was vapor-deposited on this Alq: Li film to form a metal cathode to produce an organic EL device. This device emitted blue light with a direct current voltage of 6 V and an emission luminance of 150 cd / m 2 , a maximum emission luminance of 43000 cd / m 2 and an emission efficiency of 3.0 cd / A.
[0053]
Examples 2-8
In Example 1, an organic EL device was prepared in the same manner except that the compound shown in Table 1 was used instead of the compound (A1), and the luminance, luminous efficiency, and glass transition temperature were measured at a DC voltage of 6V. Then, the luminescent color was observed, and after storing for 500 hours at a temperature of 85 ° C. as a heat resistance test, the reduction rate of luminescence from the initial luminance was measured. The results are shown in Table 1.
[0054]
Comparative Example 1
In Example 1, an organic EL device was prepared in the same manner except that 7,10-diphenylfluoranthene (DPF) was used in place of the compound (A1), and the luminance and light emission were measured at a DC voltage of 5V. The efficiency was measured, the luminescent color was observed, and after storing for 500 hours at a temperature of 85 ° C. as a heat resistance test, the rate of decrease in luminescence from the initial luminance was measured. The results are shown in Table 1.
[0055]
[Table 1]
As shown in Table 1, the organic EL device using the novel hydrocarbon compound of the present invention has high luminous efficiency and excellent heat resistance. This is because the novel hydrocarbon compound of the present invention has a high glass transition temperature of more than 100 ° C. and retains fluorescence in the blue to green region.
[0057]
Example 9
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 1.1 mm (manufactured by Geomatic) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 30 minutes. A glass substrate with a transparent electrode line after cleaning is mounted on a substrate holder of a vacuum deposition apparatus, and a TPD232 film having a thickness of 60 nm is first formed on the surface where the transparent electrode line is formed so as to cover the transparent electrode. A film was formed. This TPD232 film functions as a hole injection layer. Next, a film made of the above compound (A15) was formed to a thickness of 20 nm on the TPD232 film. This (A15) film functions as a hole transport layer. Further, Alq and rubrene having a thickness of 40 nm were deposited on the (A15) film at a weight ratio of 30: 1 to form a film. This film functions as a light emitting layer. An Alq film having a thickness of 20 nm was formed on this film. This Alq film functions as an electron injection layer. Thereafter, Li (Li source: manufactured by SAES Getter Co., Ltd.) and Alq were vapor-deposited, and an Alq: Li film was formed as an electron injection layer (cathode). Metal Al was vapor-deposited on this Alq: Li film to form a metal cathode to produce an organic EL device. This device produced yellow light with extremely high light emission efficiency at a direct current voltage of 6 V, with a light emission luminance of 150 cd / m 2 , a maximum light emission luminance of 73000 cd / m 2 , and a light emission efficiency of 10.0 cd / A. In addition, when the lifetime test was performed by driving at a constant current with an initial luminance of 1000 cd / m 2 , the half-life was 6200 hours, which was extremely long.
From the above, the novel hydrocarbon compound of the present invention is extremely excellent as a hole transporting compound.
[0058]
Example 10
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 1.1 mm (manufactured by Geomatic) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 30 minutes. A glass substrate with a transparent electrode line after cleaning is mounted on a substrate holder of a vacuum deposition apparatus, and a TPD232 film having a thickness of 60 nm is first formed on the surface where the transparent electrode line is formed so as to cover the transparent electrode. A film was formed. This TPD232 film functions as a hole injection layer. Next, an NPD film was formed to a thickness of 20 nm on the TPD232 film. This NPD film functions as a hole transport layer. Further, Alq and rubrene having a thickness of 40 nm were deposited on the NPD film at a weight ratio of 30: 1. This film functions as a light emitting layer. A film made of the compound (A3) having a thickness of 20 nm was formed on this film. This (A3) film functions as an electron injection layer. Thereafter, a LiF film having a thickness of 1 nm was formed as an inorganic compound film. Metal Al was vapor-deposited on this LiF film to form a metal cathode, thereby producing an organic EL device. This device emission luminance 250 cd / m 2 at a direct current voltage 5.5V, the maximum emission luminance 93000cd / m 2, the yellow light emission of extremely high luminous efficiency and luminous efficiency 12.0 cd / A was obtained. In addition, when the lifetime test was performed by driving at a constant current with an initial luminance of 1000 cd / m 2 , the half-life was 5000 hours, which was extremely long.
From the above, the novel hydrocarbon compound of the present invention is extremely excellent as an electron transporting compound.
[0059]
Example 11
In Example 10, instead of forming an inorganic compound film of LiF film, mixed electron injection of an electron transporting compound and a reducing compound in which the compound (A3) and Cs (cesium) are mixed at a molar ratio of 1: 1 is used. An organic EL element having a layer was produced. This device was driven at a lower voltage of 4.520 V and a luminance of 1020 cd / m 2, and yellow light emission with a maximum luminance of 123000 cd / m 2 and a luminous efficiency of 13.0 cd / A was obtained.
In addition, when the lifetime test was performed by driving at a constant current with an initial luminance of 1000 cd / m 2 , the half-life was 5800 hours, which was extremely long.
[0060]
【The invention's effect】
As described above in detail, the organic electroluminescence device using the novel hydrocarbon compound of the present invention has high heat resistance, high luminous efficiency, and long life.
For this reason, the organic electroluminescence element of the present invention is useful as a light source such as a flat light emitter of a wall-mounted television or a backlight of a display.
Claims (7)
Ｘn−Ａｒ1 ・・・（１）
（式中、ｎは２〜４の整数であり、Ａｒ 1 は、ベンゼン残基、ビフェニル残基、炭素原子数６のアリールアミノ基、トリフェニルアミン残基、チアジアゾール残基、ベンゾチアゾール残基、ベンゾチアジアゾール残基又はフェニルカルバゾール残基である。） It has 2 to 4 monovalent residues X formed by removing any one of X 1 to X 16 from the compounds represented by the following general formulas [1] to [3] , and the following general formula ( A novel hydrocarbon compound represented by 1).
X n -Ar 1 (1)
(In the formula, n is an integer of 2 to 4, Ar 1 is a benzene residue, a biphenyl residue, an arylamino group having 6 carbon atoms, a triphenylamine residue, a thiadiazole residue, a benzothiazole residue, Benzothiadiazole residue or phenylcarbazole residue. )
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