JP4186758B2 - Polymer compound, hole injecting / transporting material, organic electroluminescent device material and organic electroluminescent device - Google Patents
Polymer compound, hole injecting / transporting material, organic electroluminescent device material and organic electroluminescent device Download PDFInfo
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- JP4186758B2 JP4186758B2 JP2003308956A JP2003308956A JP4186758B2 JP 4186758 B2 JP4186758 B2 JP 4186758B2 JP 2003308956 A JP2003308956 A JP 2003308956A JP 2003308956 A JP2003308956 A JP 2003308956A JP 4186758 B2 JP4186758 B2 JP 4186758B2
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- organic electroluminescent
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- 150000001875 compounds Chemical class 0.000 title claims description 114
- 229920000642 polymer Polymers 0.000 title claims description 107
- 239000000463 material Substances 0.000 title claims description 64
- 125000001424 substituent group Chemical group 0.000 claims description 120
- 238000002347 injection Methods 0.000 claims description 56
- 239000007924 injection Substances 0.000 claims description 56
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 26
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000000304 alkynyl group Chemical group 0.000 claims description 18
- 125000002252 acyl group Chemical group 0.000 claims description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 16
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims description 8
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 8
- 125000005647 linker group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 134
- 125000004432 carbon atom Chemical group C* 0.000 description 41
- 239000000758 substrate Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 26
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- 239000010408 film Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000000151 deposition Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
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- 238000003786 synthesis reaction Methods 0.000 description 11
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- 239000011248 coating agent Substances 0.000 description 10
- 125000001624 naphthyl group Chemical group 0.000 description 10
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 10
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 238000004528 spin coating Methods 0.000 description 9
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 8
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 8
- 125000002950 monocyclic group Chemical group 0.000 description 8
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000004982 aromatic amines Chemical class 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
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- 125000004076 pyridyl group Chemical group 0.000 description 6
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 6
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
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- 239000002841 Lewis acid Substances 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
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- 238000004140 cleaning Methods 0.000 description 5
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 229910001507 metal halide Inorganic materials 0.000 description 5
- 150000005309 metal halides Chemical class 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229960003540 oxyquinoline Drugs 0.000 description 5
- 125000005493 quinolyl group Chemical group 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- MRDGZSKYFPGAKP-UHFFFAOYSA-N para-methoxyphenylpiperazine Chemical compound C1=CC(OC)=CC=C1N1CCNCC1 MRDGZSKYFPGAKP-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 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
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
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- 125000005843 halogen group Chemical group 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
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- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 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 2
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- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
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Images
Description
本発明は新規の高分子化合物、およびこれを用いた有機電界発光素子に関するものである。該有機電界発光素子は、有機化合物から成る発光層に電界をかけて光を放出する薄膜型デバイスに関するものである。 The present invention relates to a novel polymer compound and an organic electroluminescence device using the same. The organic electroluminescent element relates to a thin film device that emits light by applying an electric field to a light emitting layer made of an organic compound.
従来、薄膜型の電界発光（ＥＬ）素子としては、無機材料のＩＩ−ＶＩ族化合物半導体であるＺｎＳ、ＣａＳ、ＳｒＳ等に、発光中心であるＭｎや希土類元素（Ｅｕ、Ｃｅ、Ｔｂ、Ｓｍ等）をドープしたものが一般的であるが、上記の無機材料から作製したＥＬ素子は、
１）交流駆動が必要（５０〜１０００Ｈｚ）、
２）駆動電圧が高い（〜２００Ｖ）、
３）フルカラー化が困難、
４）周辺駆動回路のコストが高い、
という問題点を有している。
Conventionally, as a thin film type electroluminescent (EL) element, ZnS, CaS, SrS, etc., which are inorganic material II-VI compound semiconductors, Mn or rare earth elements (Eu, Ce, Tb, Sm, etc.) that are emission centers. ) Is generally used, but an EL element made from the above inorganic material is
1) AC drive is required (50-1000Hz),
2) High driving voltage (~ 200V),
3) Full color is difficult,
4) The cost of the peripheral drive circuit is high.
Has the problem.
しかし、近年、上記問題点の改良のため、有機薄膜を用いたＥＬ素子の開発が行われるようになった。特に、発光効率を高めるため、電極からのキャリアー注入の効率向上を目的として電極の種類の最適化を行い、芳香族ジアミンから成る正孔輸送層と８−ヒドロキシキノリンのアルミニウム錯体から成る発光層とを設けた有機電界発光素子の開発（Ａｐｐｌ． Ｐｈｙｓ． Ｌｅｔｔ．， ５１巻， ９１３頁，１９８７年）により、従来のアントラセン等の単結晶を用いたＥＬ素子と比較して発光効率の大幅な改善がなされ、実用化されつつある。 However, in recent years, EL devices using organic thin films have been developed to improve the above problems. In particular, in order to improve luminous efficiency, the type of electrode is optimized for the purpose of improving the efficiency of carrier injection from the electrode, and a hole transporting layer made of aromatic diamine and a light emitting layer made of 8-hydroxyquinoline aluminum complex, (Appl. Phys. Lett., 51, 913, 1987) significantly improves luminous efficiency compared to conventional EL devices using single crystals such as anthracene. Has been put into practical use.
上記の様な低分子材料を用いた電界発光素子の他にも、発光層の材料として、ポリ（ｐ−フェニレンビニレン）、ポリ［２−メトキシ−５−（２−エチルヘキシルオキシ）−１，４−フェニレンビニレン］、ポリ（３−アルキルチオフェン）、ポリフルオレン等の高分子材料を用いた電界発光素子の開発や、ポリビニルカルバゾール等の高分子に低分子の発光材料と電子移動材料を混合分散した素子の開発も行われている。 In addition to the electroluminescent device using the low molecular weight material as described above, as the material of the light emitting layer, poly (p-phenylene vinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4 -Phenylene vinylene], poly (3-alkylthiophene), development of electroluminescent devices using polymer materials such as polyfluorene, and low molecular light emitting materials and electron transfer materials mixed and dispersed in polymers such as polyvinyl carbazole Devices are also being developed.
ところで、有機電界発光素子の最大の課題は、駆動寿命である。素子の駆動を不安定にする具体的な現象としては、発光輝度の低下、定電流駆動時の電圧上昇、非発光部分（ダークスポット）の発生等が挙げられる。これらの現象の原因はいくつか存在するが、主な原因の一つとして有機層の薄膜形状の劣化が挙げられる。この薄膜形状の劣化は、素子駆動時の発熱による有機非晶質膜の結晶化（または凝集）等に起因すると考えられている。特に、駆動電圧の上昇抑制については陽極と正孔輸送層のコンタクトが重要である。 By the way, the biggest problem of the organic electroluminescent element is the driving life. Specific phenomena that destabilize the driving of the element include a decrease in light emission luminance, a voltage increase during constant current driving, generation of a non-light emitting portion (dark spot), and the like. There are several causes of these phenomena, but one of the main causes is the deterioration of the thin film shape of the organic layer. It is considered that the deterioration of the thin film shape is caused by crystallization (or aggregation) of the organic amorphous film due to heat generated when the element is driven. In particular, the contact between the anode and the hole transport layer is important for suppressing the increase in driving voltage.
そこで、陽極と正孔輸送層のコンタクトを向上させるため両層の間に正孔注入層を設け、駆動電圧を低下させることが検討されている。正孔注入層に用いられる材料に要求される条件としては、陽極とのコンタクトがよく均一な薄膜が形成でき、熱的に安定、すなわち、融点及びガラス転移温度（Ｔｇ）が高いこと、具体的には３００℃以上の融点と１２０℃以上のガラス転移温度を有すること好ましい。さらに、イオン化ポテンシャルが低く陽極からの正孔注入が容易なこと、正孔移動度が大きいこと等も重要である。 Therefore, in order to improve the contact between the anode and the hole transport layer, it has been studied to provide a hole injection layer between the two layers to lower the drive voltage. The conditions required for the material used for the hole injection layer include that the contact with the anode is good and a uniform thin film can be formed, and that the material is thermally stable, that is, the melting point and the glass transition temperature (Tg) are high. It preferably has a melting point of 300 ° C. or higher and a glass transition temperature of 120 ° C. or higher. Furthermore, it is important that the ionization potential is low, hole injection from the anode is easy, hole mobility is high, and the like.
正孔注入層の材料としても種々のものが検討されており、例えばポルフィリン誘導体やフタロシアニン化合物、スターバースト型芳香族トリアミン、スパッタ・カーボン膜や、
バナジウム酸化物、ルテニウム酸化物、モリブデン酸化物等の金属酸化物などが報告されている。
しかしながら、陽極と正孔輸送層の間に正孔注入層を挿入する方法において、ポルフィリン誘導体やフタロシアニン化合物を正孔注入層として用いた場合、これらの膜自体による光吸収のためにスペクトルが変化する、外観上着色して透明でなくなるという問題がある。
Various materials for the hole injection layer have been studied, such as porphyrin derivatives, phthalocyanine compounds, starburst aromatic triamines, sputtered carbon films,
Metal oxides such as vanadium oxide, ruthenium oxide, and molybdenum oxide have been reported.
However, in the method of inserting a hole injection layer between the anode and the hole transport layer, when a porphyrin derivative or a phthalocyanine compound is used as the hole injection layer, the spectrum changes due to light absorption by these films themselves. There is a problem that it is colored in appearance and is not transparent.
また、スターバースト型芳香族トリアミンでは、イオン化ポテンシャルが低く透明性がよいという利点はあるものの、ガラス転移点や融点が低いために耐熱性に難点がある。
一方、共役・非共役の各種高分子化合物を含む正孔注入層も多数提案されている。通常、有機電界発光素子の陽極として用いられるインジウム・スズ酸化物（ＩＴＯ）は、１０ｎｍ程度の表面粗さ（Ｒａ）を有するのに加えて、局所的に突起を有することが多く、素子作製時に短絡欠陥を生じるという問題があったが、該陽極上に、高分子化合物を含む溶液を塗布して正孔注入層を設けることにより、該欠陥の低減ももたらされるため好ましい。
In addition, although the starburst type aromatic triamine has an advantage that the ionization potential is low and the transparency is good, the glass transition point and the melting point are low, so that the heat resistance is difficult.
On the other hand, many hole injection layers containing various conjugated and non-conjugated polymer compounds have been proposed. In general, indium tin oxide (ITO) used as an anode of an organic electroluminescence device has a surface roughness (Ra) of about 10 nm and often has local protrusions. Although there was a problem of causing a short circuit defect, it is preferable to apply a solution containing a polymer compound on the anode to provide a hole injection layer, thereby reducing the defect.
しかし、単一の繰り返し単位しか有さないポリマー（ホモポリマー）では、同一の繰り返し単位が主鎖に沿って配列されており、立体科学的な不規則性もないため、ポリマー鎖が折りたたまれて高分子結晶の元となる核が形成されやすく、十分な溶解性が得られない場合があり、また、短絡欠陥を低減させる効果について更なる改善が求められている。
また、例えばポリチエニレンビニレン、ポリチオフェン、ポリアニリン等の共役系ポリマーの使用が提案されている。しかしこれらは、溶剤への溶解性に問題があり、製造プロセス面での問題がある。
However, in a polymer having only a single repeating unit (homopolymer), the same repeating unit is arranged along the main chain, and there is no stereochemical irregularity, so the polymer chain is folded. Nuclei serving as the basis of polymer crystals are likely to be formed, and sufficient solubility may not be obtained, and further improvement is required for the effect of reducing short-circuit defects.
In addition, the use of conjugated polymers such as polythienylene vinylene, polythiophene and polyaniline has been proposed. However, these have a problem in solubility in a solvent and have a problem in terms of manufacturing process.
更に、非共役系の直鎖型正孔輸送性ポリマーに電子受容性化合物を混合し、正孔注入層として使用することにより、素子の低電圧駆動が可能なことが開示されているが（特許文献１参照）、ここで開示されるポリマーはガラス転移温度Ｔｇが低く、耐熱性に難点がある。
なお、特許文献２には、例えば実施例１０に２種のシロキサン系連結基を含む２種の繰り返し単位を有するポリマーが記載されている。しかし、該ポリマーの連結基の一方は−ＳｉＭｅＭｅＯ−が４つ繰り返されるテトラシロキサン構造であるため、正孔注入・輸送におけるトラップになりやすく、さらに、結晶化の起点になりやすいと考えられる。
Furthermore, it is disclosed that a device can be driven at a low voltage by mixing an electron-accepting compound with a non-conjugated linear hole transporting polymer and using it as a hole injection layer (patent) Reference 1), the polymer disclosed here has a low glass transition temperature Tg and has a disadvantage in heat resistance.
Patent Document 2 describes, for example, a polymer having two types of repeating units containing two types of siloxane-based linking groups in Example 10. However, since one of the linking groups of the polymer has a tetrasiloxane structure in which -SiMeMeO- is repeated four times, it is likely to be a trap in hole injection / transport, and more likely to be a starting point for crystallization.
ところで、有機電界発光素子においてポリマーを含む層を形成する場合、生産性の面では印刷法を使用することが好ましい。具体的には、オフセット印刷、スクリーン印刷、フレキソ印刷、インクジェット印刷などが挙げられる。これらの印刷法にて効率良く層形成する場合、塗布液となるポリマー含有組成物には、ある程度の固形分濃度が必要とされる。このため、ポリマーには溶剤への高い可溶性が要求される。
このように有機電界発光素子の駆動時における電圧が高く、耐熱性を含めた安定性が低いことは、ファクシミリ、複写機、液晶ディスプレイのバックライト等の光源としては大きな問題であり、特にフルカラーフラットパネル・ディスプレイ等の表示素子としても望ましくない。
本発明は、上記従来の問題点を解決し、低電圧、高発光効率で駆動させることができ、かつ良好な耐熱性を有し、長期間にわたって安定な発光特性を維持することができ、前述の陽極の表面粗さに起因する素子作製時の短絡欠陥を防止した有機電界発光素子を提供す
るものである。また、印刷法を用いた有機電界発光素子の製造プロセスに適した正孔注入・輸送材料と、この有機電界発光素子の正孔注入・輸送材料に好適な新規高分子化合物を提供することを目的とする。
The high voltage at the time of driving the organic electroluminescent element and the low stability including heat resistance are serious problems as light sources for facsimiles, copiers, liquid crystal display backlights, etc. It is not desirable as a display element such as a panel display.
The present invention solves the above-mentioned conventional problems, can be driven with low voltage and high luminous efficiency, has good heat resistance, and can maintain stable luminous characteristics over a long period of time. The organic electroluminescent element which prevented the short circuit defect at the time of element preparation resulting from the surface roughness of this anode is provided. Another object of the present invention is to provide a hole injection / transport material suitable for a manufacturing process of an organic electroluminescence device using a printing method, and a novel polymer compound suitable for a hole injection / transport material of the organic electroluminescence device. And
本発明者らは、上記課題を解決すべく鋭意検討した結果、ｐ−フェニレン構造を介して主鎖に連なるアリールアミン構造と、ｍ−フェニレン構造を介して連なるアリールアミン構造との共重合体が、充分な正孔注入性・輸送性と、溶剤への溶解性や非晶質性を両立できることを見出し、本発明に至った。
すなわち本発明は、下記一般式（Ｉ）で表される繰り返し単位、および下記一般式（ＩＩ）で表されるくり返し単位を含有する、重量平均分子量が１，０００〜１，０００，０００である高分子化合物、該高分子化合物を含有する正孔注入・輸送材料、該高分子化合物を含有する有機電界発光素子材料およびこれを用いた有機電界発光素子に存する。
As a result of intensive studies to solve the above problems, the present inventors have found that a copolymer of an arylamine structure connected to the main chain via a p-phenylene structure and an arylamine structure connected via an m-phenylene structure is obtained. As a result, the inventors have found that sufficient hole injection / transport properties, solubility in a solvent, and amorphous properties can be compatible, and the present invention has been achieved.
That is, the present invention includes a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II), and has a weight average molecular weight of 1,000 to 1,000,000. The present invention resides in a polymer compound, a hole injection / transport material containing the polymer compound, an organic electroluminescent device material containing the polymer compound, and an organic electroluminescent device using the same.
（式中、Ａｒ1、Ａｒ2、Ａｒ6およびＡｒ7は各々独立に、置換基を有していてもよい芳香族炭化水素基、または置換基を有していてもよい芳香族複素環基を表す。
Ａｒ3およびＡｒ8は各々独立に、ｐ−フェニレン基、ｍ−フェニレン基、または４，４’−ビフェニレン基を表し、これらはいずれも、置換基を有していてもよい。
(In the formula, Ar 1 , Ar 2 , Ar 6 and Ar 7 are each independently an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. Represents.
Ar 3 and Ar 8 each independently represent a p-phenylene group, an m-phenylene group, or a 4,4′-biphenylene group, and any of these may have a substituent.
環Ａ４、環Ａ５、環Ａ９および環Ａ１０は各々独立して、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアラルキル基、置換基を有していてもよいアシル基、置換基を有していてもよい芳香族炭化水素基、および置換基を有していてもよい芳香族複素環基よりなる群から選ばれる１種または２種以上の置換基で置換されていてもよいベンゼン環を示す。 Ring A4, Ring A5, Ring A9 and Ring A10 each independently have an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An alkynyl group, an aralkyl group which may have a substituent, an acyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a substituent; The benzene ring which may be substituted by the 1 type (s) or 2 or more types of substituent chosen from the group which consists of a good aromatic heterocyclic group is shown.
ＸおよびＹは各々独立して、２価の連結基を表す。）
上記一般式（Ｉ）および一般式（ＩＩ）で表される繰り返し単位を含み、通常１００℃以上のＴｇを有する高分子化合物を用いることで、これを用いた有機電界発光素子の発光
特性と耐熱性を同時に改善することを可能とした。
また、本発明の正孔注入・輸送材料の場合、上記高分子由来の利点に加え、電子供与性である本発明の高分子化合物に電子受容性化合物を併用することにより、系内で電荷移動が起こり、結果としてフリーキャリアである正孔が生成し、該材料を用いて形成された層の電気電導度が高くなる。このような層を、例えば有機電界発光素子の発光層と陽極との間に設けることで、発光層と陽極との電気的接合が改善され、駆動電圧が低下すると同時に連続駆動時の安定性も向上する。
X and Y each independently represent a divalent linking group. )
By using a polymer compound containing a repeating unit represented by the above general formula (I) and general formula (II) and usually having a Tg of 100 ° C. or higher, the emission characteristics and heat resistance of an organic electroluminescence device using the same It was possible to improve the sex at the same time.
In the case of the hole injecting / transporting material of the present invention, in addition to the advantages derived from the above-mentioned polymer, charge transfer in the system can be achieved by using an electron accepting compound in combination with the polymer compound of the present invention that is electron donating. As a result, holes that are free carriers are generated, and the electric conductivity of the layer formed using the material is increased. By providing such a layer, for example, between the light emitting layer and the anode of the organic electroluminescent element, the electrical connection between the light emitting layer and the anode is improved, and the driving voltage is lowered and the stability during continuous driving is also improved. improves.
しかも有機電界発光素子において、本発明の高分子化合物を主成分とする層を、塗布プロセスにて陽極上に形成することにより、前述の陽極の表面粗さが緩和され、良好な表面平滑化効果が得られ、素子作製時の短絡欠陥が防止されるという効果も奏される。
本発明の高分子化合物は、上記一般式（Ｉ）および一般式（ＩＩ）で表される二種類の繰り返し単位をもち、幾何構造の異なる繰り返し単位がランダムに分布しているため、高分子結晶の元となる核が形成され難いと考えられ、また高分子鎖の規則性がくずれるため、単一の繰り返し単位のみで表される高分子化合物に比べ、非晶質性が高く、種々の有機溶剤に対して高い溶解性を示す。
In addition, in the organic electroluminescent device, the surface roughness of the anode is reduced by forming a layer mainly composed of the polymer compound of the present invention on the anode by a coating process, and a good surface smoothing effect is achieved. Is obtained, and the effect of preventing short circuit defects during device fabrication is also achieved.
The polymer compound of the present invention has two types of repeating units represented by the above general formula (I) and general formula (II), and repeating units having different geometric structures are randomly distributed. It is thought that nuclei that form the basis of nuclei are difficult to form, and the regularity of the polymer chain is broken, so that it is highly amorphous compared to a polymer compound represented by only a single repeating unit, and various organic High solubility in solvents.
つまり本発明の高分子化合物は、非晶質性が高いために、素子作製時の短絡欠陥を防止する効果が大きく、また、高い溶解性を示すため、容易に塗布液の固形分濃度を高めることが可能であり、印刷法にて効率良く層形成することが可能である。
なお、本発明の高分子化合物を含む正孔注入・輸送材料または有機電界発光素子材料を用いて形成された層は、通常、正孔輸送性を示す層である。後述するように、例えば有機電界発光素子を構成する層として用いられる場合、該層は陽極と発光層との間であればどこに在っても良く、後掲の図１〜３に示す如く、陽極上に直接設けるものに何ら限定されないが、陽極（無機材料）との電気的接合が良く、耐熱性が高いというこの層の長所を十分に生かすためには、陽極と接する位置に正孔注入層として形成するのが最も有利である。
That is, since the polymer compound of the present invention is highly amorphous, it has a large effect of preventing short-circuit defects during device fabrication, and because it exhibits high solubility, it easily increases the solid content concentration of the coating solution. It is possible to form a layer efficiently by a printing method.
In addition, the layer formed using the hole injection / transport material or organic electroluminescent element material containing the polymer compound of the present invention is usually a layer exhibiting hole transport properties. As will be described later, for example, when used as a layer constituting an organic electroluminescent element, the layer may be present anywhere between the anode and the light emitting layer, as shown in FIGS. Although it is not limited to what is directly provided on the anode, in order to make full use of the advantages of this layer, which is good electrical connection with the anode (inorganic material) and high heat resistance, hole injection is made at the position in contact with the anode. Most advantageously, it is formed as a layer.
本発明の高分子化合物を電子受容性化合物と併用する場合には、該高分子化合物のイオン化ポテンシャルから電子受容性化合物の電子親和力を引いた値は０．７ｅＶ以下であることが好ましく、また、これらを含有する層中の電子受容性化合物の含有量は、芳香族アミン含有高分子化合物に対して０．１〜５０重量％の範囲であることが好ましい。 When the polymer compound of the present invention is used in combination with an electron-accepting compound, the value obtained by subtracting the electron affinity of the electron-accepting compound from the ionization potential of the polymer compound is preferably 0.7 eV or less. The content of the electron-accepting compound in the layer containing these is preferably in the range of 0.1 to 50% by weight with respect to the aromatic amine-containing polymer compound.
本発明の高分子化合物は、塗布プロセスに有利な、特定の高分子共重合体と電子受容性化合物を含有する正孔注入層を有するために、低電圧で駆動可能かつ耐熱性の向上した有機電界発光素子を得ることができる。
本発明による有機電界発光素子はフラットパネル・ディスプレイ（例えばＯＡコンピュータ用や壁掛けテレビ）や面発光体としての特徴を生かした光源（例えば、複写機の光源、液晶ディスプレイや計器類のバックライト光源）、表示板、標識灯への応用が考えられ、特に、高耐熱性が要求される車載用表示素子としては、その技術的価値は大きいものである。
Since the polymer compound of the present invention has a hole injection layer containing a specific polymer copolymer and an electron-accepting compound, which is advantageous for the coating process, it can be driven at a low voltage and has improved heat resistance. An electroluminescent element can be obtained.
The organic electroluminescent device according to the present invention is a light source (for example, a light source of a copying machine, a backlight source of a liquid crystal display or an instrument) utilizing characteristics of a flat panel display (for example, for an OA computer or a wall-mounted television) or a surface light emitter. Application to display panels and marker lamps is conceivable, and the technical value is particularly great as an in-vehicle display element that requires high heat resistance.
以下に本発明の実施の形態を詳細に説明する。
まず、本発明の高分子化合物について説明する。
本発明の高分子化合物は前記一般式（Ｉ）および前記一般式（ＩＩ）で表されるくり返し単位を有するものである。
一般式（Ｉ）におけるＡｒ1およびＡｒ2、並びに一般式（ＩＩ）におけるＡｒ6および
Ａｒ7は、各々独立に、置換基を有していてもよい芳香族炭化水素基、または置換基を有
していてもよい芳香族複素環基を表す。
Hereinafter, embodiments of the present invention will be described in detail.
First, the polymer compound of the present invention will be described.
The polymer compound of the present invention has a repeating unit represented by the general formula (I) and the general formula (II).
Ar 1 and Ar 2 in the general formula (I) and Ar 6 and Ar 7 in the general formula (II) each independently have an aromatic hydrocarbon group which may have a substituent, or a substituent. Represents an aromatic heterocyclic group which may be substituted.
該芳香族炭化水素基および芳香族複素環基として、好ましくは５または６員環の単環または２〜４縮合環が挙げられる。具体的には、
フェニル基、ナフチル基、フェナントリル基、アントリル基、ナフタセニル基、ピレニル基、フルオレニル基、ベンゾフルオレニル基
などの芳香族炭化水素環、および
チェニル基、ベンゾチェニル基、ジベンゾチェニル基、フリル基、ベンゾフリル基、ピロリル基、インドリル基、ベンゾインドリル基、イソインドリル基、ベンゾイソインドリル基、カルバゾリル基、ベンゾカルバゾリル基、ピリジル基、キノリル基、ナフトピリジル基、キノキサリニル基、フェナントリジル基、フェナントロリニル基、フェノキサジニル基、フェノチアジニル基
などの芳香族複素環が挙げられる。
The aromatic hydrocarbon group and the aromatic heterocyclic group are preferably a 5- or 6-membered monocyclic ring or a 2-4 condensed ring. In particular,
Aromatic hydrocarbon rings such as phenyl group, naphthyl group, phenanthryl group, anthryl group, naphthacenyl group, pyrenyl group, fluorenyl group, benzofluorenyl group, and phenyl group, benzocenyl group, dibenzocenyl group, furyl group, benzofuryl Group, pyrrolyl group, indolyl group, benzoindolyl group, isoindolyl group, benzoisoindolyl group, carbazolyl group, benzocarbazolyl group, pyridyl group, quinolyl group, naphthopyridyl group, quinoxalinyl group, phenanthridyl group, phenanthroli Aromatic heterocycles such as nyl group, phenoxazinyl group, phenothiazinyl group and the like can be mentioned.
中でも、溶解性および耐熱性に優れ、かつ、合成が容易であるという理由から、一般式（Ｉ）および（ＩＩ）における窒素原子に結合する部分がベンゼン環である場合、すなわち、一般式（Ｉ）で表される繰り返し単位は、後述する一般式（Ｉ’）で表される構造である場合が好ましく、同様に、一般式（ＩＩ）で表される繰り返し単位は、後述する一般式（ＩＩ’）で表される構造である場合が好ましい。なお、一般式（Ｉ）で表される繰り返し単位が一般式（Ｉ’）で表される構造であり、かつ一般式（ＩＩ）で表される繰り返し単位が、一般式（ＩＩ’）で表される構造である場合がより好ましい。 Among these, when the moiety bonded to the nitrogen atom in the general formulas (I) and (II) is a benzene ring because of excellent solubility and heat resistance and easy synthesis, that is, the general formula (I The repeating unit represented by formula (II) is preferably a structure represented by the general formula (I ′) described later. Similarly, the repeating unit represented by the general formula (II) is represented by the general formula (II) described later. The structure represented by ') is preferred. The repeating unit represented by the general formula (I) has a structure represented by the general formula (I ′), and the repeating unit represented by the general formula (II) is represented by the general formula (II ′). More preferred is the structure.
一般式（Ｉ）におけるＡｒ1およびＡｒ2、並びに一般式（ＩＩ）におけるＡｒ6および
Ａｒ7における、芳香族炭化水素基および芳香族複素環基が有しうる置換基は、本発明化
合物の性能を損なわない限り、任意の基であってよい。好ましくは、一般式（Ｉ’）における環Ａ１及び環Ａ２、並びに一般式（ＩＩ’）における環Ａ６及び環Ａ７、におけるベンゼン環およびその縮合環が有しうる基として後述する基と同様の基が挙げられる。
The substituent that the aromatic hydrocarbon group and the aromatic heterocyclic group may have in Ar 1 and Ar 2 in the general formula (I) and Ar 6 and Ar 7 in the general formula (II) is the performance of the compound of the present invention. As long as the above is not impaired, any group may be used. Preferably, a group similar to the group described below as a group that can be possessed by the benzene ring and its condensed ring in ring A1 and ring A2 in general formula (I ′), and ring A6 and ring A7 in general formula (II ′) Is mentioned.
一般式（Ｉ）におけるＡｒ3、および一般式（ＩＩ）におけるＡｒ8は、各々独立に、ｐ−フェニレン基、ｍ−フェニレン基、または４，４’−ビフェニレン基を表し、これらはいずれも置換基を有していてもよい。
該置換基は、本発明化合物の性能を損なわない限り、任意の基であってよい。好ましくは、例えばメチル基、エチル基等の炭素数１〜６のアルキル基；ビニル基等の炭素数２〜６のアルケニル基；エチニル基等の炭素数２〜６のアルキニル基；ベンジル基、フェネチル基等の炭素数７〜２０のアラルキル基；アセチル基、ベンゾイル基等の炭素数２〜７のアシル基；フェニル基、ナフチル基等の炭素数６〜２０の炭素数芳香族炭化水素基；チエニル基、ピリジル基、カルバゾリル基等の５または６員環の単環または２〜４縮合環からなる芳香族複素環基、またはこれらが更に置換されてなる基などが挙げられる。
Ar 3 in the general formula (I) and Ar 8 in the general formula (II) each independently represent a p-phenylene group, an m-phenylene group, or a 4,4′-biphenylene group, both of which are substituted. It may have a group.
The substituent may be any group as long as the performance of the compound of the present invention is not impaired. Preferably, for example, an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; an alkenyl group having 2 to 6 carbon atoms such as a vinyl group; an alkynyl group having 2 to 6 carbon atoms such as an ethynyl group; a benzyl group or a phenethyl group An aralkyl group having 7 to 20 carbon atoms such as a group; an acyl group having 2 to 7 carbon atoms such as an acetyl group and a benzoyl group; an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; Group, a pyridyl group, a carbazolyl group or the like, a 5- or 6-membered monocyclic ring or an aromatic heterocyclic group composed of 2 to 4 condensed rings, or a group in which these are further substituted.
上記「更なる置換基」としては、後述する置換基群Ｚから選ばれた１種または２種以上が挙げられる。
一般式（Ｉ）におけるＡｒ3、および一般式（ＩＩ）におけるＡｒ8としては、各種溶剤への溶解性に優れる点、及び該高分子化合物を有機電界発光素子に適用した場合に駆動寿命がより優れると予想される点からは、ｐ−フェニレン基またはｍ−フェニレン基であることが好ましい。
Examples of the “further substituent” include one or more selected from the substituent group Z described later.
Ar 3 in the general formula (I) and Ar 8 in the general formula (II) are superior in solubility in various solvents, and have a longer driving life when the polymer compound is applied to an organic electroluminescence device. A p-phenylene group or an m-phenylene group is preferable from the point that it is expected to be excellent.
一般式（Ｉ）における環Ａ４及び環Ａ５、並びに一般式（ＩＩ）における環Ａ９及び環Ａ１０は、各々独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアラルキル基、置換基を有していてもよいアシル基、置換基を有していてもよい芳香族炭化
水素基、および置換基を有していてもよい芳香族複素環基よりなる群から選ばれる１種または２種以上で置換されていてもよいベンゼン環を表す。
Ring A4 and Ring A5 in General Formula (I) and Ring A9 and Ring A10 in General Formula (II) may each independently have an alkyl group which may have a substituent or a substituent. A good alkenyl group, an alkynyl group which may have a substituent, an aralkyl group which may have a substituent, an acyl group which may have a substituent, an aromatic which may have a substituent Represents a benzene ring which may be substituted with one or two or more selected from the group consisting of an aromatic hydrocarbon group and an aromatic heterocyclic group which may have a substituent.
より具体的には、メチル基、エチル基等の炭素数１〜６のアルキル基；ビニル基、アリル基等の炭素数２〜６のアルケニル基；エチニル基等の炭素数２〜６のアルキニル基；ベンジル基、フェネチル基等の炭素数７〜２０のアラルキル基；アセチル基、ベンゾイル基等の炭素数２〜７のアシル基；フェニル基、ナフチル基等の炭素数６〜２０の芳香族炭化水素基；チエニル基、ピリジル基、キノリル基、カルバゾリル基等の５または６員環の単環または２〜４縮合環から成る芳香族複素環基、あるいはこれらが更に置換されてなる基、を有していても良いベンゼン環である。 More specifically, an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; an alkenyl group having 2 to 6 carbon atoms such as a vinyl group or an allyl group; an alkynyl group having 2 to 6 carbon atoms such as an ethynyl group; An aralkyl group having 7 to 20 carbon atoms such as a benzyl group or a phenethyl group; an acyl group having 2 to 7 carbon atoms such as an acetyl group or a benzoyl group; an aromatic hydrocarbon having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; A group; an aromatic heterocyclic group composed of a 5- or 6-membered monocyclic ring or a condensed ring of 2 to 4 such as a thienyl group, a pyridyl group, a quinolyl group, a carbazolyl group, or a group in which these are further substituted It may be a benzene ring.
これら「更なる置換基」としては、例えば後述の置換基群Ｚの１種または２種以上が挙げられる。
環Ａ４、環Ａ５、環Ａ９および環Ａ１０としては、無置換のベンゼン環であるか、或いはメチル基、エチル基等の炭素数１〜６のアルキル基；ビニル基、アリル基等の炭素数２〜６のアルケニル基；エチニル基等の炭素数２〜６のアルキニル基；ベンジル基、フェネチル基等の炭素数７〜２０のアラルキル基；アセチル基、ベンゾイル基等の炭素数２〜７のアシル基；フェニル基、ナフチル基等の炭素数６〜２０の芳香族炭化水素基；チエニル基、ピリジル基、キノリル基、カルバゾリル基等の５または６員環の単環または２〜４縮合環から成る芳香族複素環基がより好ましく、無置換のベンゼン環が特に好ましい。
Examples of these “further substituents” include one or more of the substituent group Z described below.
Ring A4, ring A5, ring A9 and ring A10 are unsubstituted benzene rings, or alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; 2 carbon atoms such as vinyl group and allyl group An alkynyl group having 2 to 6 carbon atoms such as an ethynyl group; an aralkyl group having 7 to 20 carbon atoms such as a benzyl group or a phenethyl group; an acyl group having 2 to 7 carbon atoms such as an acetyl group or a benzoyl group; An aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a fragrance comprising a 5- or 6-membered monocyclic ring or a 2-4 condensed ring such as a thienyl group, pyridyl group, quinolyl group, carbazolyl group, etc. A group heterocyclic group is more preferred, and an unsubstituted benzene ring is particularly preferred.
一般式（Ｉ）におけるＸ、および一般式（ＩＩ）におけるＹは、各々独立に、任意の２価の連結基を表す。ＸおよびＹは、本発明化合物の性能を損なわない限り、特に制限はないが、好ましくは、例えば下記部分構造から選ばれた２価の連結基が挙げられる。 X in general formula (I) and Y in general formula (II) each independently represent any divalent linking group. X and Y are not particularly limited as long as they do not impair the performance of the compound of the present invention, and preferred examples thereof include a divalent linking group selected from the following partial structures.
上記式中、Ａｒ11ないしＡｒ20は各々独立して、置換基を有していてもよい芳香族環、好ましくは置換基を有していてもよい、５または６員環の単独または２〜３縮合環の芳香族環基（芳香族炭化水素環および芳香族複素環）であり、具体的にはベンゼン環、ナフタレン環、フェナントレン環、アントラセン環、ピリジン環、キノリン環、チオフェン環、ベンゾチオフェン環、ピロール環、インドール環、ベンゾフラン環、カルバゾール環等が挙げられる。 In the above formula, each of Ar 11 to Ar 20 is independently an aromatic ring which may have a substituent, preferably a 5- or 6-membered ring which may have a substituent, 3 condensed ring aromatic ring groups (aromatic hydrocarbon ring and aromatic heterocycle), specifically benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, pyridine ring, quinoline ring, thiophene ring, benzothiophene Ring, pyrrole ring, indole ring, benzofuran ring, carbazole ring and the like.
このような芳香族環が有しうる置換基としては、以下にＲ21およびＲ22の例として挙げ
るものと同様の基が挙げられる。
Ｒ21およびＲ22は各々独立して、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアラルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアミノ基、置換基を有してもよい芳香族炭化水素基、置換基を有してもよい芳香族複素環基を表す。より具体的には、水素原子；メチル基、エチル基等の炭素数１〜６のアルキル基；ビニル基、アリル基等の炭素数２〜６のアルケニル基；エチニル基等の炭素数２〜６のアルキニル基；ベンジル基等の炭素数７〜２０のアラルキル基；アセチル基、ベンゾイル基等の炭素数２〜２０のアシル基；ジフェニルアミノ基、ジメチルアミノ基等の、炭素数１〜６のアルキル基および／または芳香族炭化水素基を有するアミノ基；フェニル基、ナフチル基等の炭素数６〜２０の芳香族炭化水素基；チエニル基、ピリジル基等の、５または６員環の単環または２〜４縮合環からなる芳香族複素環基、またはこれらが更に置換されて成る基が挙げられる。
Examples of the substituent that such an aromatic ring may have include the same groups as those exemplified below for R 21 and R 22 .
R 21 and R 22 each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an aralkyl group that may have a substituent, or a substituent. An alkoxy group that may have, an aryloxy group that may have a substituent, an amino group that may have a substituent, an aromatic hydrocarbon group that may have a substituent, and a substituent Represents an aromatic heterocyclic group which may be substituted. More specifically, a hydrogen atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an alkenyl group having 2 to 6 carbon atoms such as a vinyl group and an allyl group; and 2 to 6 carbon atoms such as an ethynyl group. An alkynyl group having 7 to 20 carbon atoms such as a benzyl group; an acyl group having 2 to 20 carbon atoms such as an acetyl group and a benzoyl group; an alkyl having 1 to 6 carbon atoms such as a diphenylamino group and a dimethylamino group An amino group having a group and / or an aromatic hydrocarbon group; an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a monocyclic 5- or 6-membered ring such as a thienyl group or a pyridyl group; Examples thereof include an aromatic heterocyclic group composed of 2 to 4 condensed rings, or a group obtained by further substituting these.
これらの「更なる置換基」としては、後述する置換基群Ｚから選ばれた１種または２種以上が挙げられる。
Ａｒ11ないしＡｒ20の置換基、Ｒ21、およびＲ22として特に好ましいものは、水素原子（即ち、無置換）、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、メトキシ基、フェニル基、トリル基である。
Examples of these “further substituents” include one or more selected from the substituent group Z described later.
Particularly preferred as the substituents for Ar 11 to Ar 20 , R 21 , and R 22 are a hydrogen atom (ie, unsubstituted), a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a methoxy group, and a phenyl group. , A tolyl group.
ＸおよびＹとして、好ましくは X and Y are preferably
であり、特に、 And in particular,
であることが好ましい。なお、Ｒ31〜Ｒ37は、Ａｒ11〜Ａｒ18が有しうる置換基として前述したものであり、好ましい基についても同様であり、Ｒ38はＲ21、Ｒ22の置換基として前述したものである。 It is preferable that R 31 to R 37 are those described above as the substituents that Ar 11 to Ar 18 may have, and the same applies to the preferred groups, and R 38 is the same as the substituents for R 21 and R 22. It is.
本発明の高分子化合物において、一般式（Ｉ）で表される繰り返し単位は、下記一般式（Ｉ’）で表される構造である場合が好ましく、また一般式（ＩＩ）で表される繰り返し単位は下記一般式（ＩＩ’）で表される構造である場合が好ましい。また、一般式（Ｉ）で表される繰り返し単位が、下記一般式（Ｉ’）で表される構造であり、かつ、一般式（ＩＩ）で表される繰り返し単位が下記一般式（ＩＩ’）で表される構造である場合が特に好ましい。 In the polymer compound of the present invention, the repeating unit represented by the general formula (I) is preferably a structure represented by the following general formula (I ′), and the repeating unit represented by the general formula (II) The unit is preferably a structure represented by the following general formula (II ′). The repeating unit represented by the general formula (I) has a structure represented by the following general formula (I ′), and the repeating unit represented by the general formula (II) is represented by the following general formula (II ′). ) Is particularly preferable.
上記式中、環Ａ１、環Ａ２、環Ａ６および環Ａ７は各々独立して、ベンゼン環、或いは任意の環が縮合したベンゼン環であり、このベンゼン環および縮合環は、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアラルキル基、置換基を有していてもよいアシル基、置換基を有していてもよいアミノ基、置換基を有していてもよい芳香族炭化水素基、および置換基を有していてもよい芳香族複素環基よりなる群から選ばれる１種または２種以上の基で置換されていてもよい。 In the above formula, ring A1, ring A2, ring A6 and ring A7 are each independently a benzene ring or a benzene ring condensed with an arbitrary ring, and the benzene ring and the condensed ring have a substituent. An alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. From the group consisting of a good acyl group, an amino group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and an aromatic heterocyclic group which may have a substituent It may be substituted with one or more selected groups.
Ａｒ3およびＡｒ8は各々独立に、ｐ−フェニレン基、ｍ−フェニレン基、または４，４’−ビフェニレン基を表し、これらはいずれも、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアラルキル基、置換基を有していてもよいアシル基、置換基を有していてもよい芳香族炭化水素基、および置換基を有していてもよい芳香族複素環基よりな
る群から選ばれる１種または２種以上の置換基で置換されていてもよい。
Ar 3 and Ar 8 each independently represent a p-phenylene group, an m-phenylene group, or a 4,4′-biphenylene group, and any of these may have an alkyl group or a substituent which may have a substituent. An alkynyl group which may have a substituent, an alkynyl group which may have a substituent, an aralkyl group which may have a substituent, an acyl group which may have a substituent, and a substituent. It may be substituted with one or more substituents selected from the group consisting of an aromatic hydrocarbon group which may be substituted and an aromatic heterocyclic group which may have a substituent.
環Ａ４、環Ａ５、環Ａ９、環Ａ１０、ＸおよびＹは各々、前記一般式（Ｉ）および（ＩＩ）におけると同義である。
一般式（Ｉ’）における環Ａ１および環Ａ２、並びに一般式（ＩＩ）における環Ａ６および環Ａ７は各々独立して、ベンゼン環（フェニル基）、或いは任意の環が縮合したベンゼン環を表す。該ベンゼン環に縮合する環は、芳香族炭化水素環または芳香族複素環が好ましく、これらのうち、５または６員環の単環または２〜３縮合環がより好ましい。中でも、耐熱性および化学的安定性の観点から芳香族炭化水素環が好ましい。
Ring A4, Ring A5, Ring A9, Ring A10, X and Y are as defined above in general formulas (I) and (II).
Ring A1 and ring A2 in general formula (I ′), and ring A6 and ring A7 in general formula (II) each independently represent a benzene ring (phenyl group) or a benzene ring condensed with an arbitrary ring. The ring condensed with the benzene ring is preferably an aromatic hydrocarbon ring or an aromatic heterocycle, and more preferably a 5- or 6-membered monocyclic ring or a 2-3 condensed ring. Among these, an aromatic hydrocarbon ring is preferable from the viewpoint of heat resistance and chemical stability.
この環Ａ１、環Ａ２、環Ａ６および環Ａ７が有しうる置換基は、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアラルキル基、置換基を有していてもよいアシル基、置換基を有していてもよいアミノ基、置換基を有していてもよい芳香族炭化水素基、および置換基を有していてもよい芳香族複素環基よりなる群から選ばれる１種または２種以上であり、より具体的にはメチル基、エチル基等の炭素数１〜６のアルキル基；ビニル基、アリル基等の炭素数２〜６のアルケニル基；エチニル基等の炭素数２〜６のアルキニル基；ベンジル基、フェネチル基等の炭素数７〜２０のアラルキル基；アセチル基、ベンゾイル基等の炭素数２〜７のアシル基；ジフェニルアミノ基、ジメチルアミノ基等の、炭素数１〜６のアルキル基または芳香族炭化水素基を有するアミノ基；フェニル基、ナフチル基等の炭素数６〜２０の芳香族炭化水素基；チエニル基、キノリル基、カルバゾリル基等の５または６員環の単環または２〜４縮合環からなる芳香族複素環基、あるいはこれらが更に置換されてなる基である。 The substituent that the ring A1, the ring A2, the ring A6, and the ring A7 may have an alkyl group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. An alkynyl group which may have a substituent, an aralkyl group which may have a substituent, an acyl group which may have a substituent, an amino group which may have a substituent, and a substituent which may have 1 type or 2 types or more selected from the group consisting of a good aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group, and more specifically carbon such as methyl group and ethyl group An alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms such as a vinyl group and an allyl group; an alkynyl group having 2 to 6 carbon atoms such as an ethynyl group; and a 7 to 20 carbon atom such as a benzyl group and a phenethyl group. Aralkyl group: Acetyl group, benzoyl group, etc. having 2 to 7 carbon atoms An amino group having an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group such as a diphenylamino group or a dimethylamino group; an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group An aromatic heterocyclic group composed of a 5- or 6-membered monocyclic ring or a 2-4 condensed ring such as a thienyl group, a quinolyl group, a carbazolyl group, or a group in which these are further substituted.
これら「更なる置換基」としては、例えば、下記の置換基群Ｚから選ばれた１種または２種以上が挙げられる。
［置換基群Ｚ］
メチル基、エチル基等の炭素数１〜６のアルキル基；ビニル基等の炭素数２〜６のアルケニル基；エチニル基等の炭素数２〜６のアルキニル基、メトキシカルボニル基、エトキシカルボニル基等の炭素数２〜７のアルコキシカルボニル基；ジメチルアミノ基、ジエチルアミノ基等の炭素数２〜１０のジアルキルアミノ基；ジフェニルアミノ基、ジトリルアミノ基、カルバゾリル基等のジアリールアミノ基；フェニルメチルアミノ基等のアリールアルキルアミノ基；アセチル基、ベンゾイル基等のアシル基、フッ素原子等のハロゲン原子；トリフルオロメチル基等のハロアルキル基；フェノキシ基等のアリールオキシ基；シアノ基；フェニル基、ナフチル基等の芳香族炭化水素基；チエニル基等の芳香族複素環基
環Ａ１、環Ａ２、環Ａ６および環Ａ７の置換基としては、メチル基、エチル基等の炭素数１〜６のアルキル基；ビニル基、アリル基等の炭素数２〜６のアルケニル基；エチニル基等の炭素数２〜６のアルキニル基；ベンジル基、フェネチル基等の炭素数７〜２０のアラルキル基；アセチル基、ベンゾイル基等の炭素数２〜７のアシル基；ジフェニルアミノ基、ジメチルアミノ基等の、炭素数１〜６のアルキル基または芳香族炭化水素基を有するアミノ基；フェニル基、ナフチル基等の炭素数６〜２０の芳香族炭化水素基；チエニル基、キノリル基、カルバゾリル基等の５または６員環の単環または２〜４縮合環からなる芳香族複素環基、あるいはこれらが更に置換されてなるがより好ましく、無置換である場合が更に好ましい。
Examples of these “further substituents” include one or more selected from the following substituent group Z.
[Substituent group Z]
C1-C6 alkyl groups such as methyl and ethyl groups; C2-C6 alkenyl groups such as vinyl groups; C2-C6 alkynyl groups such as ethynyl groups, methoxycarbonyl groups, ethoxycarbonyl groups, etc. An alkoxycarbonyl group having 2 to 7 carbon atoms; a dialkylamino group having 2 to 10 carbon atoms such as a dimethylamino group and a diethylamino group; a diarylamino group such as a diphenylamino group, a ditolylamino group and a carbazolyl group; a phenylmethylamino group and the like Arylalkylamino group; acyl group such as acetyl group and benzoyl group; halogen atom such as fluorine atom; haloalkyl group such as trifluoromethyl group; aryloxy group such as phenoxy group; cyano group; aromatic such as phenyl group and naphthyl group Aromatic hydrocarbon group such as thienyl group, ring A1, ring A2, ring A6 and Examples of the substituent for ring A7 include alkyl groups having 1 to 6 carbon atoms such as a methyl group and an ethyl group; alkenyl groups having 2 to 6 carbon atoms such as a vinyl group and an allyl group; and 2 to 6 carbon atoms such as an ethynyl group. Alkynyl group; Aralkyl group having 7 to 20 carbon atoms such as benzyl group and phenethyl group; Acyl group having 2 to 7 carbon atoms such as acetyl group and benzoyl group; 1 to 6 carbon atoms such as diphenylamino group and dimethylamino group An amino group having an alkyl group or an aromatic hydrocarbon group; an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a single 5- or 6-membered ring such as a thienyl group, a quinolyl group or a carbazolyl group. An aromatic heterocyclic group consisting of a ring or a condensed ring of 2 to 4 or these are further substituted, more preferably, more preferably unsubstituted.
一般式（Ｉ’）のＡｒ3、および一般式（ＩＩ’）のＡｒ8は、ｐ−フェニレン基、ｍ−フェニレン基、４，４’−ビフェニレン基から選ばれる２価の芳香族基であり、これらはいずれも、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアラルキル基、置換基を有していてもよいアシル基、置換基を有していてもよい芳香族炭化水素基、およ
び置換基を有していてもよい芳香族複素環基よりなる群から選ばれる１種または２種以上の置換基で置換されていてもよい。上記各基の具体例としては、一般式（Ｉ）におけるＡｒ3、および（ＩＩ）におけるＡｒ8の項で述べたものと同様の基が挙げられ、好ましい基も前述と同様である。また、一般式（Ｉ）におけるＡｒ3、および（ＩＩ）におけるＡｒ8の項で述べたと同様に、ｐ−フェニレン基またはｍ−フェニレン基であることが好ましい。
Ar 3 in the general formula (I ′) and Ar 8 in the general formula (II ′) are divalent aromatic groups selected from a p-phenylene group, an m-phenylene group, and a 4,4′-biphenylene group. Any of these may have an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent. From the group consisting of a good aralkyl group, an optionally substituted acyl group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group It may be substituted with one or more selected substituents. Specific examples of each of the above groups include the same groups as those described in the section of Ar 3 in the general formula (I) and Ar 8 in (II), and preferred groups are also the same as described above. Further, as Ar 3 in the general formula (I), and in (II) and described in the section of Ar 8, is preferably a p- phenylene or m- phenylene group.
電子分布が偏りなく非局在化するため電荷移動度に優れることと、合成が容易であるとの理由から、本発明の高分子化合物において、同一分子中のＡｒ1とＡｒ6、およびＡｒ2
とＡｒ7は、各々、同一の構造であることが好ましい。またＡｒ1とＡｒ6が同一の構造で
あり、かつＡｒ2とＡｒ7が同一である場合がより好ましく、Ａｒ1、Ａｒ2、Ａｒ6および
Ａｒ7がいずれも同一の構造である場合が更に好ましい。
同様に、同一分子中に前記一般式（Ｉ’）で表される繰り返し単位と、前記一般式（ＩＩ’）で表される繰り返し単位を含む場合、同一分子中の環Ａ１と環Ａ６、および環Ａ２と環Ａ７は、各々、同一の構造であることが好ましい。また環Ａ１と環Ａ６が同一の構造であり、かつ環Ａ２と環Ａ７が同一である場合がより好ましく、環Ａ１、環Ａ２、環Ａ６および環Ａ７がいずれも同一の構造である場合が更に好ましい。
さらに、同一分子中の環Ａ４と環Ａ５、および環Ａ９と環Ａ１０は、各々、同一の構造であることが好ましい。また環Ａ４と環Ａ５が同一の構造であり、かつ環Ａ９と環Ａ１０が同一である場合がより好ましく、環Ａ４、環Ａ５、環Ａ９および環Ａ１０がいずれも同一の構造である場合が更に好ましい。これは、同一分子中に前記一般式（Ｉ’）で表される繰り返し単位と、前記一般式（ＩＩ’）で表される繰り返し単位を含む場合も同様である。
以下に本発明の高分子化合物の繰り返し単位の好ましい具体例を示すが、本発明はこれにより限定されるものではない。
In the polymer compound of the present invention, Ar 1 , Ar 6 , and Ar 2 in the same molecule are used because the electron distribution is delocalized without unevenness and the charge mobility is excellent and the synthesis is easy.
And Ar 7 preferably have the same structure. More preferably, Ar 1 and Ar 6 have the same structure, and Ar 2 and Ar 7 are the same, and Ar 1 , Ar 2 , Ar 6 and Ar 7 all have the same structure. preferable.
Similarly, when the same molecule contains the repeating unit represented by the general formula (I ′) and the repeating unit represented by the general formula (II ′), ring A1 and ring A6 in the same molecule, and Ring A2 and ring A7 each preferably have the same structure. More preferably, ring A1 and ring A6 have the same structure, and ring A2 and ring A7 are the same, and ring A1, ring A2, ring A6 and ring A7 all have the same structure. preferable.
Furthermore, it is preferable that ring A4 and ring A5, and ring A9 and ring A10 in the same molecule each have the same structure. More preferably, ring A4 and ring A5 have the same structure, and ring A9 and ring A10 are the same, and ring A4, ring A5, ring A9 and ring A10 all have the same structure. preferable. The same applies to the case where the same molecule contains the repeating unit represented by the general formula (I ′) and the repeating unit represented by the general formula (II ′).
Preferred specific examples of the repeating unit of the polymer compound of the present invention are shown below, but the present invention is not limited thereby.
本発明の高分子化合物において、一般式（Ｉ）で表される繰り返し単位と、一般式（ＩＩ）で表される繰り返し単位の含有量比（モル比）は、（Ｉ）／（ＩＩ）＝０．２〜５程度であることが好ましい。 In the polymer compound of the present invention, the content ratio (molar ratio) of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) is (I) / (II) = It is preferable that it is about 0.2-5.
更に、本発明の高分子化合物の性能を損なわない範囲で、他の種々のモノマー由来の繰り返し単位を含有していてもよい。他のモノマー由来の繰り返し単位としては、例えば前記一般式（Ｉ）における−Ｏ−Ｘ−Ｏ−構造部分、および／または（ＩＩ）における−Ｏ−Ｙ−Ｏ−構造部分を、 Furthermore, it may contain repeating units derived from other various monomers as long as the performance of the polymer compound of the present invention is not impaired. Examples of the repeating unit derived from another monomer include, for example, the —O—X—O— structure moiety in the general formula (I) and / or the —O—Y—O— structure moiety in (II).
とした繰り返し単位が挙げられるが、有機電界発光素子の製造に有用な化合物としては、前記一般式（Ｉ）または（ＩＩ）で表される繰り返し単位の含有量合計が、１分子あたり２０モル％以上のものが好ましく、より好ましくは５０モル％以上、さらに好ましくは８０モル％以上のものである。 As a compound useful for the production of an organic electroluminescent device, the total content of the repeating units represented by the general formula (I) or (II) is 20 mol% per molecule. The above is preferable, more preferably 50 mol% or more, and still more preferably 80 mol% or more.
本発明の高分子化合物の中、重量平均分子量が１，０００〜１，０００，０００のものが有機電界発光素子の製造に有用である。また、この高分子化合物を含む層を、塗布法により形成する場合には、溶解性および耐熱性の点から重量平均分子量が１０，０００以上である場合が好ましく、また２００，０００以下のものが好ましい。
本発明の高分子化合物は、例えば、先ず４−位にヒドロキシ基を有する芳香族ジアミン化合物と３−位にヒドロキシ基を有する芳香族ジアミン化合物を合成し、それらと、４，４'−ジフルオロベンゾフェノン、ビス（４−フルオロフェニル）スルホン等の芳香族二
ハロゲン化物、または、メチルフェニルジクロロシラン等の二ハロゲン化ケイ素化合物と反応させることにより得られる。
Among the polymer compounds of the present invention, those having a weight average molecular weight of 1,000 to 1,000,000 are useful for producing an organic electroluminescent device. When the layer containing the polymer compound is formed by a coating method, the weight average molecular weight is preferably 10,000 or more from the viewpoint of solubility and heat resistance, and those having a molecular weight of 200,000 or less. preferable.
The polymer compound of the present invention is prepared, for example, by first synthesizing an aromatic diamine compound having a hydroxy group at the 4-position and an aromatic diamine compound having a hydroxy group at the 3-position, and 4,4′-difluorobenzophenone. It can be obtained by reacting with an aromatic dihalide such as bis (4-fluorophenyl) sulfone or a silicon dihalide compound such as methylphenyldichlorosilane.
本発明の高分子化合物は、適度な正孔輸送性を有するため、正孔注入・輸送材料として電子写真感光体、有機電界発光素子、光電変換素子、有機太陽電池、有機整流素子等に好適に使用できる。
また、各種溶媒への溶解性が高く、結晶化し難く、ガラス転移温度が高くて薄膜形成性に優れるため、耐熱性に優れ、長期間安定に駆動（発光）する有機電界発光素子を提供することが可能であり、有機電界発光素子材料として好適である。
Since the polymer compound of the present invention has an appropriate hole transport property, it is suitable as a hole injection / transport material for an electrophotographic photoreceptor, an organic electroluminescence device, a photoelectric conversion device, an organic solar cell, an organic rectifying device, and the like. Can be used.
Also, to provide an organic electroluminescence device that has high solubility in various solvents, is difficult to crystallize, has a high glass transition temperature, and is excellent in thin film formation, and thus has excellent heat resistance and can be stably driven (emitted) for a long period of time. And is suitable as an organic electroluminescent element material.
本発明の高分子化合物をこれらの用途に供する場合、電子受容性化合物を併用することにより、電荷注入・輸送のバランスを適切に調整できるため好ましい。
なお、本発明の高分子化合物を電子受容性化合物と併用する場合には、該高分子化合物のイオン化ポテンシャルから電子受容性化合物の電子親和力を引いた値は０．７ｅＶ以下であることが好ましく、また、これらを含有する層中の電子受容性化合物の含有量は、芳香族アミン含有高分子化合物に対して０．１〜５０重量％の範囲であることが好ましい。該電子受容性化合物の種類および併用割合については、本発明の高分子化合物を有機電界発光素子を構成する層に適用した場合を例に、後に詳述する。
When the polymer compound of the present invention is used in these applications, it is preferable to use an electron-accepting compound in combination because the charge injection / transport balance can be appropriately adjusted.
When the polymer compound of the present invention is used in combination with an electron accepting compound, the value obtained by subtracting the electron affinity of the electron accepting compound from the ionization potential of the polymer compound is preferably 0.7 eV or less, Moreover, it is preferable that content of the electron-accepting compound in the layer containing these is the range of 0.1 to 50 weight% with respect to an aromatic amine containing polymer compound. The type and ratio of the electron-accepting compound will be described in detail later, taking as an example the case where the polymer compound of the present invention is applied to a layer constituting an organic electroluminescent device.
次に、本発明の化合物を用いた有機電界発光素子について説明する。
本発明の有機電界発光素子は、陽極、陰極、およびこれら両極間に設けられた発光層を有し、該発光層として、または該発光層と陽極又は陰極との間に有する層として、本発明の高分子化合物を含む有機電界発光素子材料を用いて形成された層を有することを特徴とする。
Next, an organic electroluminescence device using the compound of the present invention will be described.
The organic electroluminescent element of the present invention has an anode, a cathode, and a light emitting layer provided between the two electrodes, and the present invention as the light emitting layer or as a layer between the light emitting layer and the anode or cathode. It has the layer formed using the organic electroluminescent element material containing the high molecular compound.
本発明の有機電界発光素子において、同一の層内に２種以上の本発明の高分子化合物が含有されていても良い。また、２以上の層に本発明の高分子化合物が含有されている場合、これらの層に含有される該化合物は同一のものであっても異なるものであってもよい。
本発明の高分子化合物は正孔注入・輸送性に優れるため、発光層と陽極との間に設けられた層中に含まれる場合が好ましく、特に陽極（無機材料）との電気的接合が良く、耐熱性が高いというこの層の長所を十分に生かすためには、後掲の図１〜３に示す如く、陽極と接する正孔注入層として形成するのが最も有利であるが、これに限定されるものではない。
In the organic electroluminescent element of the present invention, two or more polymer compounds of the present invention may be contained in the same layer. When the polymer compound of the present invention is contained in two or more layers, the compounds contained in these layers may be the same or different.
Since the polymer compound of the present invention is excellent in hole injection / transport properties, it is preferably contained in a layer provided between the light-emitting layer and the anode, and particularly has good electrical junction with the anode (inorganic material). In order to make full use of the advantages of this layer having high heat resistance, it is most advantageous to form it as a hole injection layer in contact with the anode, as shown in FIGS. Is not to be done.
以下に、添付図面を参照して、本発明の高分子化合物（を含む有機電界発光素子材料）を、陽極上に設けられた正孔注入層に含有する場合を例に、本発明の有機電界発光素子の実施の形態を詳細に説明する。
図１〜３は本発明の有機電界発光素子の実施の形態を示す模式的な断面図であ
り、１は基板、２は陽極、３は正孔注入層、４は正孔輸送層、５は発光層、６は電子輸送層、７は陰極を各々表わす。
Hereinafter, with reference to the accompanying drawings, the organic electric field of the present invention is taken as an example when the polymer compound of the present invention (including the organic electroluminescent element material) is contained in a hole injection layer provided on the anode. Embodiments of the light-emitting element will be described in detail.
1 to 3 are schematic cross-sectional views showing an embodiment of the organic electroluminescence device of the present invention, wherein 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, The light emitting layer, 6 represents an electron transport layer, and 7 represents a cathode.
基板１は有機電界発光素子の支持体となるものであり、石英やガラスの板、金属板や金属箔、プラスチックフィルムやシートなどが用いられる。特にガラス板や、ポリエステル、ポリメタクリレート、ポリカーボネート、ポリスルホンなどの透明な合成樹脂の板が好ましい。合成樹脂基板を使用する場合にはガスバリア性に留意する必要がある。基板のガスバリア性が低すぎると、基板を通過する外気により有機電界発光素子が劣化することがあるので好ましくない。このため、合成樹脂基板のどちらか片側もしくは両側に緻密なシリコン酸化膜等を設けてガスバリア性を確保してもよい。 The substrate 1 serves as a support for the organic electroluminescent element, and a quartz or glass plate, a metal plate or a metal foil, a plastic film, a sheet, or the like is used. In particular, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polysulfone is preferable. When using a synthetic resin substrate, it is necessary to pay attention to gas barrier properties. If the gas barrier property of the substrate is too low, the organic electroluminescent element may be deteriorated by the outside air passing through the substrate, which is not preferable. For this reason, a dense silicon oxide film or the like may be provided on one side or both sides of the synthetic resin substrate to ensure gas barrier properties.
基板１上には陽極２が設けられるが、陽極２は正孔注入層３への正孔注入の役割を果たすものである。この陽極２は、通常、アルミニウム、金、銀、ニッケル、パラジウム、白金等の金属、インジウムおよび／またはスズの酸化物などの金属酸化物、ヨウ化銅などのハロゲン化金属、カーボンブラック等により構成される。陽極２の形成は通常、スパッタリング法、真空蒸着法などにより行われることが多い。また、銀などの金属微粒子、ヨウ化銅などの微粒子、カーボンブラック、導電性の金属酸化物微粒子等を適当なバインダー樹脂溶液に分散し、基板１上に塗布することにより陽極２を形成することもできる。陽極２は異なる物質で積層して形成することも可能である。陽極２の厚みは、必要とされる透明性により異なる。透明性が必要とされる場合は、可視光の透過率を、通常、60％以上、好ましくは80％以上とすることが望ましく、この場合、陽極２の厚みは、通常、1000nm以下、好ましくは 500nm以下であり、下限は10nm程度、好ましくは20nm程度である。不透明でよい場合には陽極２は基板１と同一でもよい。また、さらには上記の陽極２の上に異なる導電材料を積層することも可能である。 An anode 2 is provided on the substrate 1, and the anode 2 plays a role of hole injection into the hole injection layer 3. The anode 2 is usually composed of a metal such as aluminum, gold, silver, nickel, palladium, or platinum, a metal oxide such as an oxide of indium and / or tin, a metal halide such as copper iodide, or carbon black. Is done. In general, the anode 2 is often formed by sputtering, vacuum deposition, or the like. Also, the anode 2 is formed by dispersing fine particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, etc. in an appropriate binder resin solution and applying the solution onto the substrate 1. You can also. The anode 2 can also be formed by stacking different materials. The thickness of the anode 2 varies depending on the required transparency. When transparency is required, the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness of the anode 2 is usually 1000 nm or less, preferably The lower limit is about 10 nm, preferably about 20 nm. If it may be opaque, the anode 2 may be the same as the substrate 1. Furthermore, it is also possible to laminate different conductive materials on the anode 2 described above.
本発明では、図１の素子構造においては、陽極２の上に正孔注入層３が設けられる。この正孔注入層３に用いられる材料に要求される条件としては、陽極２からの正孔注入効率が高く、かつ、注入された正孔を効率よく輸送することができる材料であることが挙げられる。そのためには、イオン化ポテンシャルが小さく、可視光の光に対して透明性が高く、しかも正孔移動度が大きく、さらに安定性に優れ、トラップとなる不純物が製造時や使用時に発生しにくいことが要求される。上記の一般的要求以外に、車載表示用の応用を考えた場合、素子にはさらに１００℃以上の耐熱性を有することが好ましい。 In the present invention, the hole injection layer 3 is provided on the anode 2 in the element structure of FIG. Conditions required for the material used for the hole injection layer 3 include a material having high hole injection efficiency from the anode 2 and capable of efficiently transporting the injected holes. It is done. For this purpose, the ionization potential is small, the transparency to visible light is high, the hole mobility is high, the stability is high, and impurities that become traps are less likely to be generated during manufacturing and use. Required. In addition to the above general requirements, when considering application for in-vehicle display, it is preferable that the element further has heat resistance of 100 ° C. or higher.
本発明の有機電界発光素子は、正孔注入層が前記一般式（Ｉ）および（ＩＩ）で表わされる繰り返し単位を有する高分子化合物を含むことを特徴とする。該高分子化合物のみからなる層であってもよいが、更に、電子受容性化合物をも含有する場合が、より好ましい。
本発明においては、通常、１００℃以上のＴｇを有する高分子化合物と電子受容性化合物を混合して用いることで、素子の発光特性と耐熱性を同時に改善することを可能とした。電子供与性の高分子化合物に電子受容性化合物を混合することにより、電荷移動が起こり、結果としてフリーキャリアである正孔が生成し、正孔注入層の電気電導度が高くなる。発光層と陽極との電気的接合が、本発明による正孔注入層を設けることで改善され、駆動電圧が低下すると同時に連続駆動時の安定性も向上する。また、１００℃以上のＴｇを有する高分子化合物を正孔注入層の母体とすることにより、素子の耐熱性も大きく改善される。
The organic electroluminescent element of the present invention is characterized in that the hole injection layer contains a polymer compound having a repeating unit represented by the general formulas (I) and (II). Although it may be a layer composed only of the polymer compound, it is more preferable that the layer further contains an electron accepting compound.
In the present invention, usually, a mixture of a polymer compound having a Tg of 100 ° C. or higher and an electron accepting compound can be used to simultaneously improve the light emission characteristics and heat resistance of the device. By mixing the electron-accepting compound with the electron-donating polymer compound, charge transfer occurs, and as a result, holes that are free carriers are generated, and the electrical conductivity of the hole-injecting layer is increased. The electrical junction between the light emitting layer and the anode is improved by providing the hole injection layer according to the present invention, and the driving voltage is lowered and the stability during continuous driving is also improved. Further, by using a polymer compound having a Tg of 100 ° C. or higher as the base material of the hole injection layer, the heat resistance of the device is greatly improved.
本発明の高分子化合物と組み合わせて用いる電子受容性化合物としては、該高分子化合物との間で電荷移動を起こすものであればよいが、本発明者が鋭意検討した結果、本発明の高分子化合物のイオン化ポテンシャル、ＩＰ（ポリマー）、と電子受容性化合物（アクセプタ）の電子親和力、ＥＡ（アクセプタ）の２つの物性値が、
ＩＰ（ポリマー）−ＥＡ（アクセプタ）≦ ０．７ｅＶ、
の関係式で表される時に本発明の目的に特に有効であることを見出した。
このことを図４のエネルギー準位図を用いて説明する。一般に、イオン化ポテンシャル及び電子親和力は真空準位を基準として決定される。イオン化ポテンシャルは物質のＨＯＭＯ（最高被占分子軌道）レベルにある電子を真空準位に放出するのに必要なエネルギーで定義され、電子親和力は真空準位にある電子が物質のＬＵＭＯ（最低空分子軌道）レベルに落ちて安定化するエネルギーで定義される。図４に示す高分子化合物のＨＯＭＯレベルのイオン化ポテンシャルと、電子受容性化合物のＬＵＭＯレベルの電子親和力の差が ０．７ｅＶ以下であることが好ましい。イオン化ポテンシャルは光電子分光法で直接測定されるか、電気化学的に測定した酸化電位を基準電極に対して補正しても求められる。後者の方法の場合は、例えば、飽和甘コウ電極（ＳＣＥ）を基準電極として用いたとき、
イオン化ポテンシャル＝酸化電位（ｖｓ．ＳＣＥ）＋４．３ ｅＶ、
で表される（“Ｍｏｌｅｃｕｌａｒ Ｓｅｍｉｃｏｎｄｕｃｔｏｒｓ”， Ｓｐ
ｒｉｎｇｅｒ−Ｖｅｒｌａｇ， １９８５年、９８頁）。電子親和力は、上述のイオン化ポテンシャルから光学的バンドギャップを差し引いて求められるか、電気化学的な還元電位から上記の式で同様に求められる。
As the electron-accepting compound used in combination with the polymer compound of the present invention, any compound that causes charge transfer with the polymer compound may be used. Two physical property values of the ionization potential of the compound, IP (polymer), electron affinity of the electron accepting compound (acceptor), and EA (acceptor)
IP (polymer) -EA (acceptor) ≦ 0.7 eV,
It has been found that the present invention is particularly effective for the purpose of the present invention.
This will be described with reference to the energy level diagram of FIG. In general, the ionization potential and the electron affinity are determined based on the vacuum level. The ionization potential is defined by the energy required to release electrons at the HOMO (highest occupied molecular orbital) level of the material to the vacuum level, and the electron affinity is the LUMO (lowest empty molecule) of the electron at the vacuum level. Defined by the energy that falls to the orbital level and stabilizes. The difference between the ionization potential at the HOMO level of the polymer compound shown in FIG. 4 and the electron affinity at the LUMO level of the electron accepting compound is preferably 0.7 eV or less. The ionization potential can be directly measured by photoelectron spectroscopy or can be obtained by correcting the electrochemically measured oxidation potential with respect to the reference electrode. In the case of the latter method, for example, when a saturated sweet potato electrode (SCE) is used as a reference electrode,
Ionization potential = oxidation potential (vs. SCE) + 4.3 eV,
("Molecular Semiconductors", Sp
ringer-Verlag, 1985, p. 98). The electron affinity can be obtained by subtracting the optical band gap from the above-mentioned ionization potential, or similarly obtained by the above formula from the electrochemical reduction potential.
前記イオン化ポテンシャルと電子親和力の関係式は、酸化電位と還元電位を用いて、
高分子化合物の酸化電位−アクセプタの還元電位≦ ０．７Ｖ、
と表現することもできる。
電子受容性化合物の含有量は、本発明の高分子化合物に対して０．１〜５０重量％の範囲にあることが好ましい。さらに好ましくは、０．５〜３０重量％の濃度範囲が実用特性上望ましい。
The relational expression between the ionization potential and the electron affinity uses an oxidation potential and a reduction potential,
Oxidation potential of polymer compound−reduction potential of acceptor ≦ 0.7V,
It can also be expressed as
The content of the electron-accepting compound is preferably in the range of 0.1 to 50% by weight with respect to the polymer compound of the present invention. More preferably, a concentration range of 0.5 to 30% by weight is desirable in practical characteristics.
このような電子受容性化合物としては、例えば、トリアリールホウ素化合物、ハロゲン化金属、ルイス酸、有機酸、アリールアミンとハロゲン化金属との塩、アリールアミンとルイス酸との塩よりなる群から選ばれる１種又は２種以上の化合物等が挙げられる。これらの電子受容性化合物は、正孔輸送材料と混合して用いられ、正孔輸送材料を酸化することにより正孔注入層の導電率を向上させることができる。 Examples of such electron-accepting compounds are selected from the group consisting of triarylboron compounds, metal halides, Lewis acids, organic acids, salts of arylamines and metal halides, and salts of arylamines and Lewis acids. 1 type, or 2 or more types of compounds etc. which are mentioned. These electron-accepting compounds are used by mixing with a hole transport material, and the conductivity of the hole injection layer can be improved by oxidizing the hole transport material.
電子受容性化合物として、トリアリールホウ素化合物としては、下記一般式（III）に
示したホウ素化合物が挙げられる。一般式（III）で表されるホウ素化合物は、ルイス酸
であることが好ましい。また、ホウ素化合物の電子親和力は、通常、４ｅＶ以上、好ましく、５ｅＶ以上である。
Examples of the triarylboron compound as the electron-accepting compound include boron compounds represented by the following general formula (III). The boron compound represented by the general formula (III) is preferably a Lewis acid. Further, the electron affinity of the boron compound is usually 4 eV or more, preferably 5 eV or more.
一般式（III）において、Ａｒ41〜Ａｒ43は、各々独立に、置換基を有していてもよい
フェニル基、ナフチル基、アントリル基、ビフェニル基等の５または６員環の単環、またはこれらが２〜３個縮合及び／または直接結合してなる芳香族炭化水素環基；或いは置換基を有していてもよいチエニル基、ピリジル基、トリアジル基、ピラジル基、キノキサリル基等の５または６員環の単環、またはこれらが２〜３個縮合及び／または直接結合してなる芳香族複素環基を表す。
In the general formula (III), Ar 41 to Ar 43 are each independently a monocyclic 5- or 6-membered ring such as a phenyl group, a naphthyl group, an anthryl group, or a biphenyl group, which may have a substituent, or An aromatic hydrocarbon ring group formed by condensing 2 or 3 of these and / or directly bonding; or 5 or a thienyl group, pyridyl group, triazyl group, pyrazyl group, quinoxalyl group and the like which may have a substituent It represents a 6-membered monocycle or an aromatic heterocyclic group formed by condensing and / or directly bonding 2 to 3 of these.
このような置換基としては、例えば、フッ素原子等のハロゲン原子；メチル基、エチル基等の炭素数１〜６の直鎖または分岐のアルキル基；ビニル基等のアルケニル基；メトキシカルボニル基、エトキシカルボニル基等の炭素数１〜６の直鎖または分岐のアルコキシカルボニル基；メトキシ基、エトキシ基等の炭素数１〜６の直鎖または分岐のアルコキシ基；フェノキシ基、ベンジルオキシ基等のアリールオキシ基；ジメチルアミノ基、ジエチルアミノ基等のジアルキルアミノ基、アセチル基等のアシル基、トリフルオロメチル基等のハロアルキル基、シアノ基等が挙げられる。 Examples of such a substituent include a halogen atom such as a fluorine atom; a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an alkenyl group such as a vinyl group; a methoxycarbonyl group and an ethoxy group. C1-C6 linear or branched alkoxycarbonyl group such as carbonyl group; C1-C6 linear or branched alkoxy group such as methoxy group and ethoxy group; Aryloxy such as phenoxy group and benzyloxy group Groups; dialkylamino groups such as dimethylamino group and diethylamino group; acyl groups such as acetyl group; haloalkyl groups such as trifluoromethyl group; and cyano groups.
このような置換基として、Ａｒ41ないしＡｒ43の少なくとも１つが、ハメット定数（σｍおよび／またはσｐ）が正の値を示す置換基を有する化合物であることが好ましく、Ａｒ41ないしＡｒ43が、いずれもハメット定数（σｍおよび／またはσｐ）が正の値を示す置換基を有する化合物であることが特に好ましい。このような、電子吸引性の置換基を有することにより、これらの化合物の電子受容性が向上する。また、Ａｒ41ないしＡｒ43がいずれも、ハロゲン原子で置換された芳香族炭化水素基または芳香族複素環基を表す化合物であることがさらに好ましい。 As such substituents, at least one of from Ar 41 Ar 43, preferably Hammett constants (sigma m and / or sigma p) is a compound having a substituent having a positive value, to no Ar 41 Ar 43 Are particularly preferably compounds having a substituent with a positive Hammett constant (σ m and / or σ p ). By having such an electron-withdrawing substituent, the electron acceptability of these compounds is improved. Further, it is more preferable that Ar 41 to Ar 43 are compounds each representing an aromatic hydrocarbon group or an aromatic heterocyclic group substituted with a halogen atom.
一般式（III）で表されるホウ素化合物の好ましい具体例を以下に示すが、これらに限
定するものではない。
Although the preferable specific example of the boron compound represented by general formula (III) is shown below, it is not limited to these.
これらの中、以下に示す化合物が特に好ましい。 Of these, the following compounds are particularly preferred.
また、電子受容性化合物として、ハロゲン化金属、ルイス酸、有機酸、アリールアミンとハロゲン化金属との塩、アリールアミンとルイス酸との塩よりなる群から選ばれる１種又は２種以上の化合物の具体例として、以下に示す化合物が挙げられる Further, as the electron-accepting compound, one or more compounds selected from the group consisting of metal halides, Lewis acids, organic acids, salts of arylamines and metal halides, and salts of arylamines and Lewis acids Specific examples of these include the following compounds:
本発明の高分子化合物と電子受容性化合物から成る正孔注入層３は、通常、公知の湿式成膜法により前記陽極２上に形成される。前記一般式（Ｉ）および（ＩＩ）で表される繰り返し単位を有する高分子化合物と電子受容性化合物の所定量を、必要により正孔のトラップにならないバインダー樹脂や塗布性改良剤などの添加剤とを添加し、溶解して塗布溶液を調製し、スプレー法、スピンコート法、ディップコート法などの塗布法やインクジェット法など印刷法等の各種湿式成膜法により陽極２上に塗布し、乾燥して正孔注入層３を形成する。 The hole injection layer 3 composed of the polymer compound of the present invention and the electron accepting compound is usually formed on the anode 2 by a known wet film forming method. Additives such as a binder resin and a coating property improving agent that do not become a hole trap if necessary for a predetermined amount of the polymer compound having the repeating units represented by the general formulas (I) and (II) and the electron accepting compound. And dissolved to prepare a coating solution, which is applied onto the anode 2 by various wet film forming methods such as a coating method such as a spray method, a spin coating method, a dip coating method or a printing method such as an ink jet method, and then dried. Thus, the hole injection layer 3 is formed.
正孔注入層３の膜厚の上限は、通常１０００ｎｍ程度、好ましくは５００ｎｍ程度であり、また下限は通常５ｎｍ程度、好ましくは１０ｎｍ程度である。
正孔注入層３の上には発光層５が設けられる。発光層５は、電界を与えられた電極間において陰極７からの注入された電子と正孔注入層３から輸送された正孔を効率よく再結合し、かつ、再結合により効率よく発光する材料から形成される。
The upper limit of the thickness of the hole injection layer 3 is usually about 1000 nm, preferably about 500 nm, and the lower limit is usually about 5 nm, preferably about 10 nm.
A light emitting layer 5 is provided on the hole injection layer 3. The light-emitting layer 5 is a material that efficiently recombines electrons injected from the cathode 7 and holes transported from the hole injection layer 3 between electrodes to which an electric field is applied, and efficiently emits light by recombination. Formed from.
このような条件を満たす材料としては、８−ヒドロキシキノリンのアルミニウム錯体などの金属錯体（特開昭５９−１９４３９３号公報）、１０−ヒドロキシベンゾ〔ｈ〕キノリンの金属錯体（特開平６−３２２３６２号公報）、ビススチリルベンゼン誘導体（特開平１−２４５０８７号公報、同２−２２２４８４号公報）、ビススチリルアリーレン誘導体（特開平２−２４７２７８号公報）、（２−ヒドロキシフェニル）ベンゾチアゾールの金属錯体（特開平８−３１５９８３号公報）、シロール誘導体等が挙げられる。これらの発光層材料は、通常は真空蒸着法により正孔注入層３上に積層される。 Materials satisfying such conditions include metal complexes such as aluminum complexes of 8-hydroxyquinoline (JP 59-194393), metal complexes of 10-hydroxybenzo [h] quinoline (JP 6-322362 A). Gazette), bisstyrylbenzene derivatives (JP-A-1-245087, JP-A-2-222484), bisstyrylarylene derivatives (JP-A-2-247278), metal complexes of (2-hydroxyphenyl) benzothiazole ( JP-A-8-315983), silole derivatives and the like. These light emitting layer materials are usually laminated on the hole injection layer 3 by a vacuum deposition method.
素子の発光効率を向上させるとともに発光色を変える目的で、例えば、８−ヒドロキシキノリンのアルミニウム錯体をホスト材料として、クマリン等のレーザ用蛍光色素をドープすること（J. Appl. Phys., 65巻, 3610頁, 1989年）等が行われている。
素子の駆動寿命を改善する目的においても、前記発光層材料をホスト材料として、蛍光色素をドープすることは有効である。例えば、８−ヒドロキシキノリンのアルミニウム錯体などの金属錯体をホスト材料として、ルブレンに代表されるナフタセン誘導体（特開平４−３３５０８７号公報）、キナクリドン誘導体（特開平５−７０７７３号公報）、ペリレン等の縮合多環芳香族炭化水素環（特開平５−１９８３７７号公報）を、ホスト材料に対して 0.1〜10重量％ドープすることにより、素子の発光特性、特に駆動安定性を大きく向上させることができる。発光層のホスト材料に上記ナフタセン誘導体、キナクリドン誘導体、ペリレン等の蛍光色素をドープする方法としては、共蒸着による方法と蒸着源を予め所定の濃度で混合しておく方法がある。
For the purpose of improving the luminous efficiency of the device and changing the emission color, for example, doping a fluorescent dye for lasers such as coumarin with an aluminum complex of 8-hydroxyquinoline as a host material (J. Appl. Phys., Volume 65) , 3610, 1989).
In order to improve the driving life of the device, it is effective to dope a fluorescent dye using the light emitting layer material as a host material. For example, using a metal complex such as an aluminum complex of 8-hydroxyquinoline as a host material, a naphthacene derivative represented by rubrene (JP-A-4-335087), a quinacridone derivative (JP-A-5-70773), perylene, etc. By doping a condensed polycyclic aromatic hydrocarbon ring (Japanese Patent Laid-Open No. 5-198377) with 0.1 to 10% by weight with respect to the host material, the light emission characteristics of the device, particularly the driving stability, can be greatly improved. . As a method of doping the host material of the light emitting layer with a fluorescent dye such as the naphthacene derivative, quinacridone derivative, or perylene, there are a method by co-evaporation and a method in which a deposition source is mixed in advance at a predetermined concentration.
高分子系の発光層材料としては、先に挙げたポリ（ｐ−フェニレンビニレン）、ポリ［２−メトキシ−５−（２−エチルヘキシルオキシ）−１，４−フェニレンビニレン］、ポリ（３−アルキルチオフェン）等の高分子材料や、ポリビニルカルバゾール等の高分子に発光材料と電子移動材料を混合した系等が挙げられる。これらの材料は正孔注入層３と同様にスピンコートやディップコート等の方法により正孔注入層３上に塗布して薄膜化される。 Examples of the polymer light emitting layer material include poly (p-phenylene vinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene], poly (3-alkyl) mentioned above. Examples thereof include a polymer material such as thiophene) and a system in which a light emitting material and an electron transfer material are mixed with a polymer such as polyvinylcarbazole. These materials are coated on the hole injection layer 3 by a method such as spin coating or dip coating in the same manner as the hole injection layer 3 to form a thin film.
発光層５の膜厚の上限は、通常200 nm、好ましくは100 nmであり、下限は通常10nm、好ましくは30nmである。
素子の発光特性を向上させるために、図２に示す様に、正孔輸送層４を正孔注入層３と発光層５との間に設けたり、さらには、図３に示す様に電子輸送層６を発光層５と陰極７の間に設けるなどして機能分離型の有機電解発光素子とすることが行われる。
The upper limit of the thickness of the light emitting layer 5 is usually 200 nm, preferably 100 nm, and the lower limit is usually 10 nm, preferably 30 nm.
In order to improve the light emitting characteristics of the device, a hole transport layer 4 is provided between the hole injection layer 3 and the light emitting layer 5 as shown in FIG. 2, and further, as shown in FIG. The layer 6 is provided between the light emitting layer 5 and the cathode 7 to form a function-separated organic electroluminescent device.
図２および図３の機能分離型素子において、正孔輸送層４の材料としては、正孔注入層３からの正孔注入効率が高く、かつ、注入された正孔を効率よく輸送することができる材料であることが必要である。そのためには、イオン化ポテンシャルが小さく、しかも正孔移動度が大きく、さらに安定性に優れ、トラップとなる不純物が製造時や使用時に発生しにくいことが要求される。また、発光層５と直接接する層であるために、発光を消光する物質が含まれていないことが望ましい。 2 and 3, the material for the hole transport layer 4 has high hole injection efficiency from the hole injection layer 3 and can efficiently transport the injected holes. It must be a material that can be made. For this purpose, it is required that the ionization potential is low, the hole mobility is high, the stability is high, and impurities that become traps are not easily generated during production or use. In addition, since the layer is in direct contact with the light emitting layer 5, it is desirable that no substance that quenches light emission is contained.
このような正孔輸送材料としては、例えば、４，４’−ビス［Ｎ−（９−ナフチル）−Ｎ−フェニルアミノ］ビフェニルで代表される２個以上の３級アミンを含み２個以上の縮合芳香族炭化水素環が窒素原子に置換した芳香族ジアミン（特開平５−２３４６８１号公報）、４，４’，４”−トリス（１−ナフチルフェニルアミノ）トリフェニルアミン等のスターバースト構造を有する芳香族アミン化合物（J. Lumin., 72-74巻、985頁、1997年
）、トリフェニルアミンの四量体から成る芳香族アミン化合物（Chem.Commun., 2175頁
、1996年）、２，２’，７，７’−テトラキス−（ジフェニルアミノ）−９，９’−スピロビフルオレン等のスピロ化合物（Synth. Metals, 91巻、209頁、1997年）等が挙げられる。これらの化合物は、単独で用いてもよいし、必要に応じて２種以上を混合して用いてもよい。
Examples of such a hole transport material include two or more tertiary amines represented by 4,4′-bis [N- (9-naphthyl) -N-phenylamino] biphenyl, and two or more A starburst structure such as an aromatic diamine in which a condensed aromatic hydrocarbon ring is substituted with a nitrogen atom (Japanese Patent Laid-Open No. 5-234681), 4,4 ′, 4 ″ -tris (1-naphthylphenylamino) triphenylamine, etc. Aromatic amine compound (J. Lumin., 72-74, 985, 1997), aromatic amine compound composed of tetraphenylamine tetramer (Chem. Commun., 2175, 1996), 2 , 2 ', 7,7'-tetrakis- (diphenylamino) -9,9'-spirobifluorene (Synth. Metals, 91, 209, 1997) and the like. May be used alone or as needed It may be mixed up.
上記の化合物以外に、正孔輸送層４の材料として、ポリビニルカルバゾール、ポリビニルトリフェニルアミン（特開平７−５３９５３号公報）、テトラフェニルベンジジンを含有するポリアリーレンエーテルサルホン（Polym. Adv. Tech.,
7巻、33頁、1996年）等の高分子材料が挙げられる。
正孔輸送層４は、上記の正孔輸送材料を塗布法あるいは真空蒸着法により前記正孔注入層３上に積層することにより形成される。
In addition to the above-mentioned compounds, polyarylene ether sulfone (Polym. Adv. Tech.) Containing polyvinylcarbazole, polyvinyltriphenylamine (Japanese Patent Laid-Open No. 7-53953), and tetraphenylbenzidine as materials for the hole transport layer 4. ,
(7, 33, 1996).
The hole transport layer 4 is formed by laminating the above hole transport material on the hole injection layer 3 by a coating method or a vacuum deposition method.
塗布法の場合は、正孔輸送材料の１種または２種以上と、必要により正孔のトラップにならないバインダー樹脂や塗布性改良剤などの添加剤とを添加し、適当な溶媒に溶解して塗布溶液を調製し、スピンコート法などの方法により陽極２上に塗布し、乾燥して正孔輸送層４を形成する。この場合、バインダー樹脂としては、ポリカーボネート、ポリアリレート、ポリエステル等を用いることができる。バインダー樹脂は添加量が多いと正孔移動度を低下させるので、少ない方が望ましく、通常、正孔輸送層４中の割合で５０重量％以下が好ましい。 In the case of the coating method, one or more of the hole transport materials and, if necessary, additives such as a binder resin and a coating property improving agent that do not trap holes are added and dissolved in a suitable solvent. A coating solution is prepared, applied onto the anode 2 by a method such as spin coating, and dried to form the hole transport layer 4. In this case, polycarbonate, polyarylate, polyester or the like can be used as the binder resin. When the amount of the binder resin added is large, the hole mobility is lowered. Therefore, it is desirable that the binder resin is small, and the amount in the hole transport layer 4 is generally preferably 50% by weight or less.
真空蒸着法の場合には、正孔輸送材料を真空容器内に設置されたルツボに入れ、真空容器内を適当な真空ポンプで１０-4Ｐａ程度にまで排気した後、ルツボを加熱して、正孔輸送材料を蒸発させ、ルツボと向き合って置かれた、正孔注入層３が形成された基板１上に正孔輸送層４を形成させる。
正孔輸送層４の膜厚の上限は、通常300 nm、好ましくは100 nmであり、下限は通常10nm、好ましくは30nmである。このように薄い膜を一様に形成するためには、一般に真空蒸着法がよく用いられる。
In the case of the vacuum evaporation method, the hole transport material is put in a crucible installed in a vacuum vessel, the inside of the vacuum vessel is evacuated to about 10 −4 Pa with a suitable vacuum pump, and then the crucible is heated, The hole transport material is evaporated, and the hole transport layer 4 is formed on the substrate 1 on which the hole injection layer 3 is formed, which is placed facing the crucible.
The upper limit of the thickness of the hole transport layer 4 is usually 300 nm, preferably 100 nm, and the lower limit is usually 10 nm, preferably 30 nm. In order to uniformly form such a thin film, a vacuum deposition method is often used in general.
有機電界発光素子の発光効率をさらに向上させる方法として、図３に示すように発光層４の上にさらに電子輸送層６を積層することもできる。この電子輸送層６に用いられる化合物には、陰極７からの電子注入が容易で、電子の輸送能力がさらに大きいことが要求される。この様な電子輸送材料としては、既に発光層材料として挙げた８−ヒドロキシキノリンのアルミ錯体、オキサジアゾール誘導体（Appl. Phys. Lett., 55巻, 1489頁, 1989
年） やそれらをポリメタクリル酸メチル（ＰＭＭＡ）等の樹脂に分散した系、フェナン
トロリン誘導体（特開平５−３３１４５９号公報）、２−ｔ−ブチル−９，１０−Ｎ，Ｎ’−ジシアノアントラキノンジイミン、ｎ型水素化非晶質炭化シリコン、ｎ型硫化亜鉛、ｎ型セレン化亜鉛等が挙げられる。
As a method for further improving the light emission efficiency of the organic electroluminescence device, an electron transport layer 6 may be further laminated on the light emitting layer 4 as shown in FIG. The compound used for the electron transport layer 6 is required to be easy to inject electrons from the cathode 7 and to have a larger electron transport capability. Examples of such an electron transport material include 8-hydroxyquinoline aluminum complexes and oxadiazole derivatives (Appl. Phys. Lett., 55, 1489, 1989) already mentioned as the light emitting layer material.
And a system in which they are dispersed in a resin such as polymethyl methacrylate (PMMA), a phenanthroline derivative (Japanese Patent Laid-Open No. 5-331459), 2-t-butyl-9,10-N, N′-dicyanoanthraquinone dii Min, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zinc selenide and the like.
電子輸送層６の膜厚の上限は、通常200 nm、好ましくは100 nmであり、下限は通常5nm
、好ましくは10nmである。
陰極７は、発光層５に電子を注入する役割を果たす。陰極７の形成材料としては、前記陽極２に使用される材料を用いることが可能であるが、効率よく電子注入を行なうには、仕事関数の低い金属が好ましく、スズ、マグネシウム、インジウム、カルシウム、アルミニウム、銀等の適当な金属またはそれらの合金が用いられる。具体例としては、マグネシウム−銀合金、マグネシウム−インジウム合金、アルミニウム−リチウム合金等の低仕事関数合金電極が挙げられる。さらに、陰極７と発光層５または電子輸送層６の界面にＬｉＦ、ＭｇＦ2、Ｌｉ2Ｏ等の極薄絶縁膜（0.1〜5nm）を挿入することも、素子の効率を向上させる有効な方法である（Appl. Phys. Lett., 70巻，152頁，1997年；特開平１０−７４５８６号公報；IEEE Trans. Electron. Devices，44巻，1245頁，1997年）。
The upper limit of the thickness of the electron transport layer 6 is usually 200 nm, preferably 100 nm, and the lower limit is usually 5 nm.
, Preferably 10 nm.
The cathode 7 serves to inject electrons into the light emitting layer 5. As a material for forming the cathode 7, the material used for the anode 2 can be used. However, in order to perform electron injection efficiently, a metal having a low work function is preferable, and tin, magnesium, indium, calcium, A suitable metal such as aluminum or silver or an alloy thereof is used. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy. Furthermore, inserting an ultra-thin insulating film (0.1-5 nm) such as LiF, MgF 2 , Li 2 O at the interface between the cathode 7 and the light emitting layer 5 or the electron transport layer 6 is also an effective method for improving the efficiency of the device. (Appl. Phys. Lett., 70, 152, 1997; JP-A-10-74586; IEEE Trans. Electron. Devices, 44, 1245, 1997).
陰極７の膜厚は通常、陽極２と同様である。低仕事関数金属から成る陰極を保護する目的で、この上にさらに、仕事関数が高く大気に対して安定な金属層を積層することは素子の安定性を増す。この目的のために、アルミニウム、銀、銅、ニッケル、クロム、金、白金等の金属が使われる。
図１〜３は、本発明で採用される素子構造の一例であって、本発明は何ら図示のものに限定されるものではない。例えば、図１とは逆の構造、即ち、基板上に陰極７、発光層５、正孔注入層３、陽極２の順に積層することも可能であり、既述したように少なくとも一方が透明性の高い２枚の基板の間に本発明の有機電界発光素子を設けることも可能である。同様に、図２および図３に示した前記各層構成とは逆の構造に積層することも可能である。また、図１〜３
のいずれの層構成においても、本発明の趣旨を逸脱しない範囲で、助９宇述以外の層を有していても良く、また上記複数の層の機能を併有する層を採用することにより、層構成を簡略化する等、適宜変更を加えることができる。
The film thickness of the cathode 7 is usually the same as that of the anode 2. For the purpose of protecting the cathode made of a low work function metal, further laminating a metal layer having a high work function and stable to the atmosphere on the cathode increases the stability of the device. For this purpose, metals such as aluminum, silver, copper, nickel, chromium, gold, platinum are used.
1-3 are examples of the element structure employed in the present invention, and the present invention is not limited to the illustrated one. For example, a structure opposite to that shown in FIG. 1, that is, a cathode 7, a light emitting layer 5, a hole injection layer 3, and an anode 2 can be laminated in this order on a substrate, and at least one of them is transparent as described above. It is also possible to provide the organic electroluminescence device of the present invention between two high-height substrates. Similarly, it is also possible to laminate in a structure opposite to that of each of the layers shown in FIGS. 1 to 3
In any of the layer configurations, within a range not departing from the gist of the present invention, it may have a layer other than the auxiliary 9 statement, and by adopting a layer having the functions of the plurality of layers, Changes can be made as appropriate, such as simplifying the layer structure.
或いはまた、トップエミッション構造や、陰極・陽極共に透明電極を用いることにより、透過型ディスプレイとすることも可能である。
このような本発明の有機電界発光素子は、単一の素子、アレイ状に配置された構造からなる素子、陽極と陰極がＸ−Ｙマトリックス状に配置された構造のいずれにも適用することができる。
Alternatively, a transmissive display can be obtained by using a top emission structure or using a transparent electrode for both the cathode and the anode.
Such an organic electroluminescent element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix. it can.
次に、本発明を原料合成例、合成例、実施例および比較例によって更に具体的に説明するが、本発明はその要旨を越えない限り、以下の実施例の記載に限定されるものではない。
まず、一般式（Ｉ）および（ＩＩ）で表される繰り返し単位を有する高分子を、以下の原料を用いて合成した。
〔原料合成例〕
（１−１）Ｎ，Ｎ′−ジフェニル−Ｎ，Ｎ′−ビス（４−メトキシフェニル）−１，４−フェニレンジアミン（４−ＭＰＰ）の合成
Next, the present invention will be described more specifically with reference to raw material synthesis examples, synthesis examples, examples and comparative examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist. .
First, polymers having repeating units represented by the general formulas (I) and (II) were synthesized using the following raw materials.
[Raw material synthesis example]
(1-1) Synthesis of N, N′-diphenyl-N, N′-bis (4-methoxyphenyl) -1,4-phenylenediamine (4-MPP)
Ｎ，Ｎ′−ジフェニル−１，４−フェニレンジアミン（７７．０ミリモル）と４−ヨードアニソール（２３１ミリモル）とをテトラグライム１５０ミリリットルに溶かし、銅粉末（１５４ミリモル）および炭酸カリウム（１１２ミリモル）の存在下、窒素雰囲気中２００℃で８時間反応を行った。その結果、式（Ｍ１）で示される４−ＭＰＰ（３４．８ｇ、収率９６％）を得た。
（１−２）Ｎ，Ｎ′−ジフェニル−Ｎ，Ｎ′−（４−ヒドロキシフェニル）−１，４−フェニレンジアミン（４−ＨＰＰ）の合成
N, N'-diphenyl-1,4-phenylenediamine (77.0 mmol) and 4-iodoanisole (231 mmol) are dissolved in 150 ml of tetraglyme, and copper powder (154 mmol) and potassium carbonate (112 mmol) are dissolved. The reaction was carried out in a nitrogen atmosphere at 200 ° C. for 8 hours. As a result, 4-MPP represented by the formula (M1) (34.8 g, yield 96%) was obtained.
(1-2) Synthesis of N, N′-diphenyl-N, N ′-(4-hydroxyphenyl) -1,4-phenylenediamine (4-HPP)
４−ＭＰＰ（５０．０ミリモル）を３６０ミリリットルの塩化メチレンに溶かし、窒素雰囲気下、ドライアイス−エタノールバスで系内を−６５℃以下に冷やし、これに三臭化ほう素（１００ミリモル）の塩化メチレン溶液（１００ミリリットル）を滴下した。滴下終了後、冷媒バスを外し２時間撹拌した後、酢酸エチルで抽出し、シリカゲルカラムクロマトフラフィーによって精製した。その結果、式（Ｍ２）で示される４−ＨＰＰ（１６．２ｇ、収率７３％）を得た。以下に４−ＨＰＰの１Ｈ−ＮＭＲを示す。 4-MPP (50.0 mmol) was dissolved in 360 ml of methylene chloride, and the inside of the system was cooled to −65 ° C. or less with a dry ice-ethanol bath in a nitrogen atmosphere, and boron tribromide (100 mmol) was added thereto. Methylene chloride solution (100 ml) was added dropwise. After completion of the dropping, the refrigerant bath was removed and the mixture was stirred for 2 hours, extracted with ethyl acetate, and purified by silica gel column chromatography. As a result, 4-HPP (16.2 g, yield 73%) represented by the formula (M2) was obtained. The 1H-NMR of 4-HPP is shown below.
δ（ＤＭＳＯ，４００ＭＨｚ）
９．３６ （１Ｈ， ｓ）
７．１９ （４Ｈ， ｄｄ， Ｊ＝８．０， ７．９）
６．９４ （４Ｈ， ｄｄ， Ｊ＝６．９， ２．１）
６．８８ （４Ｈ， ｓ）
６．８７−６．８３ （６Ｈ， ｍ）
６．７５ （４Ｈ， ｄｄ， Ｊ＝６．９， ２．１）
（２−１）Ｎ，Ｎ′−ジフェニル−Ｎ，Ｎ′−ビス（３−メトキシフェニル）−１，４−フェニレンジアミン（３−ＭＰＰ）の合成
δ (DMSO, 400 MHz)
9.36 (1H, s)
7.19 (4H, dd, J = 8.0, 7.9)
6.94 (4H, dd, J = 6.9, 2.1)
6.88 (4H, s)
6.87-6.83 (6H, m)
6.75 (4H, dd, J = 6.9, 2.1)
(2-1) Synthesis of N, N′-diphenyl-N, N′-bis (3-methoxyphenyl) -1,4-phenylenediamine (3-MPP)
Ｎ，Ｎ′−ジフェニル−１，４−フェニレンジアミン（３８．５ミリモル）と３−ヨードアニソール（１００ミリモル）とをテトラグライム５０ミリリットルに溶かし、銅粉末（７６．９ミリモル）および炭酸カリウム（５７．７ミリモル）の存在下、窒素雰囲気中２００℃で８時間反応を行った。その結果、式（Ｍ３）で示される４−ＭＰＰ（１２．０ｇ、収率６６％）を得た。
（２−２）Ｎ，Ｎ′−ジフェニル−Ｎ，Ｎ′−（３−ヒドロキシフェニル）−１，４−フェニレンジアミン（３−ＨＰＰ）の合成
N, N'-diphenyl-1,4-phenylenediamine (38.5 mmol) and 3-iodoanisole (100 mmol) are dissolved in 50 ml of tetraglyme, and copper powder (76.9 mmol) and potassium carbonate (57 .7 mmol) in the presence of nitrogen at 200 ° C. for 8 hours. As a result, 4-MPP represented by the formula (M3) (12.0 g, yield 66%) was obtained.
(2-2) Synthesis of N, N′-diphenyl-N, N ′-(3-hydroxyphenyl) -1,4-phenylenediamine (3-HPP)
３−ＭＰＰ（１３．４ミリモル）を３６０ミリリットルの塩化メチレンに溶かし、窒素雰囲気下、ドライアイス−エタノールバスで系内を−６５℃以下に冷やし、これに三臭化ほう素（２７ミリモル）の塩化メチレン溶液（２７ミリリットル）を滴下した。滴下終了後、冷媒バスを外し２時間撹拌した後、酢酸エチルで抽出し、シリカゲルカラムクロマトフラフィーによって精製した。その結果、式（Ｍ４）で示される３−ＨＰＰ（５．６８ｇ、収率９５％）を得た。以下に３−ＨＰＰの１Ｈ−ＮＭＲを示す。 3-MPP (13.4 mmol) was dissolved in 360 ml of methylene chloride, and the inside of the system was cooled to −65 ° C. or lower with a dry ice-ethanol bath in a nitrogen atmosphere, and boron tribromide (27 mmol) was added thereto. Methylene chloride solution (27 milliliters) was added dropwise. After completion of the dropping, the refrigerant bath was removed and the mixture was stirred for 2 hours, extracted with ethyl acetate, and purified by silica gel column chromatography. As a result, 3-HPP (5.68 g, yield 95%) represented by the formula (M4) was obtained. The 1H-NMR of 3-HPP is shown below.
ｄ （ＤＭＳＯ，４００ＭＨｚ）
９．３６ （１Ｈ， ｓ）
７．１９ （４Ｈ， ｄｄ， Ｊ＝８．０， ７．９）
６．９４ （４Ｈ， ｄｄ， Ｊ＝６．９， ２．１）
６．８８ （４Ｈ， ｓ）
６．８７−６．８３ （６Ｈ， ｍ）
６．７５ （４Ｈ， ｄｄ， Ｊ＝６．９， ２．１）
〔合成例１〕
d (DMSO, 400MHz)
9.36 (1H, s)
7.19 (4H, dd, J = 8.0, 7.9)
6.94 (4H, dd, J = 6.9, 2.1)
6.88 (4H, s)
6.87-6.83 (6H, m)
6.75 (4H, dd, J = 6.9, 2.1)
[Synthesis Example 1]
４−ＨＰＰ（６．４ミリモル）と３−ＨＰＰ（１．６ミリモル）と４，４′−ジフルオロベンゾフェノン（８．０ミリモル）とを８０ミリリットルのＮＭＰに溶かし、炭酸カリウム（４８ミリモル）の存在下、窒素雰囲気中１４０℃で２０時間、縮合反応させた。放冷後、酢酸４ミリリットルを反応系に加え、メタノール中に放出し、得られたポリマーを水洗いし、無機塩を除いた。６０℃で減圧乾燥させた後、ポリマーをクロロホルムに溶か
し、メタノールに放出し再沈殿させた。最後に、アセトンで懸洗することにより、低分子量成分を除き、式（Ｕ１）および式（Ｕ２）で表される繰り返し単位を有するポリマー（Ｐ１）（４．２３ｇ，８５％）を得た。
4-HPP (6.4 mmol), 3-HPP (1.6 mmol) and 4,4'-difluorobenzophenone (8.0 mmol) are dissolved in 80 ml of NMP and the presence of potassium carbonate (48 mmol). Under the nitrogen atmosphere, the condensation reaction was carried out at 140 ° C. for 20 hours. After allowing to cool, 4 ml of acetic acid was added to the reaction system and released into methanol, and the resulting polymer was washed with water to remove inorganic salts. After drying at 60 ° C. under reduced pressure, the polymer was dissolved in chloroform and released into methanol for reprecipitation. Finally, by washing with acetone, a polymer (P1) (4.23 g, 85%) having repeating units represented by the formula (U1) and the formula (U2) was obtained by removing the low molecular weight component.
このポリマー（Ｐ１）のＴｇは１６７℃、重量平均分子量（Ｍｗ）は１６，５００、数平均分子量（Ｍｎ）６，０００であり、分子量はＴＨＦ中でＧＰＣ測定により、ポリスチレンを標準試料として求めた。
合成例２
The polymer (P1) had a Tg of 167 ° C., a weight average molecular weight (Mw) of 16,500, and a number average molecular weight (Mn) of 6,000, and the molecular weight was determined by GPC measurement in THF using polystyrene as a standard sample. .
Synthesis example 2
４−ＨＰＰ（３．０ミリモル）と３−ＨＰＰ（２．０ミリモル）を１２ミリリットルのトルエンおよび１．２ミリリットルのピリジン中に溶解させ、窒素雰囲気下、内温６５℃に加温し、これに３．０ミリリットルのトルエンで希釈したメチルフェニルジクロロシラン（５．０ミリモル）を滴下した。滴下後、６５℃で４時間攪拌し反応させた。得られたポリマーを、ポリマーをクロロホルムに溶かし、メタノールに放出し再沈殿させた。減圧乾
燥した後、もう一度、ポリマーをクロロホルムに溶かし、メタノールに放出し再沈殿させ、式（Ｕ３）および式（Ｕ４）で表される繰り返し単位を有するポリマー（Ｐ２）（１．０３ｇ，３７％）を得た。
4-HPP (3.0 mmol) and 3-HPP (2.0 mmol) were dissolved in 12 ml of toluene and 1.2 ml of pyridine and heated to an internal temperature of 65 ° C. under a nitrogen atmosphere. Was added dropwise methylphenyldichlorosilane (5.0 mmol) diluted with 3.0 ml of toluene. After dropping, the mixture was stirred at 65 ° C. for 4 hours to be reacted. The polymer obtained was dissolved in chloroform and released into methanol for reprecipitation. After drying under reduced pressure, the polymer was once again dissolved in chloroform, released into methanol and reprecipitated, and the polymer (P2) (1.03 g, 37%) having repeating units represented by the formulas (U3) and (U4) Got.
このポリマー（Ｐ２）のＴｇは１１９℃、重量平均分子量（Ｍｗ）は３９，１００、数平均分子量（Ｍｎ）５，９００であり、分子量はＴＨＦ中でＧＰＣ測定により、ポリスチレンを標準試料として求めた。
〔実施例１〕
上記ポリマー（Ｐ１）のＮＭＰ（Ｎ−メチルピロリドン）およびテトラリン（１，２，３，４−テトラヒドロナフタレン）に溶解させた。その結果を表３に示す。表３に示すようにポリマー（Ｐ１）は対応する単一の繰り返し単位を有するポリマー（Ｐ３）に比較して高い溶解性を示した。
〔比較例１〕
上記ポリマー（Ｐ１）の繰り返し単位の一つである式（Ｕ１）のみが繰り返された下記ポリマー（Ｐ３）のＮＭＰ（Ｎ−メチルピロリドン）およびテトラリン（１，２，３，４−テトラヒドロナフタレン）に溶解させた。その結果を表３に示す。
The polymer (P2) had a Tg of 119 ° C., a weight average molecular weight (Mw) of 39,100, and a number average molecular weight (Mn) of 5,900. The molecular weight was determined by GPC measurement in THF using polystyrene as a standard sample. .
[Example 1]
The polymer (P1) was dissolved in NMP (N-methylpyrrolidone) and tetralin (1,2,3,4-tetrahydronaphthalene). The results are shown in Table 3. As shown in Table 3, the polymer (P1) showed higher solubility than the polymer (P3) having a corresponding single repeating unit.
[Comparative Example 1]
NMP (N-methylpyrrolidone) and tetralin (1,2,3,4-tetrahydronaphthalene) of the following polymer (P3) in which only the formula (U1) which is one of the repeating units of the polymer (P1) is repeated Dissolved. The results are shown in Table 3.
（Ｍｗ＝１７３００、Ｍｎ＝５８７０） (Mw = 17300, Mn = 5870)
〔実施例２〕
上記ポリマー（Ｐ２）のＮＭＰ（Ｎ−メチルピロリドン）およびトルエンへに溶解させた。その結果を表４に示す。表４に示すようにポリマー（Ｐ２）は対応する単一の繰り返し単位を有するポリマー（Ｐ４）に比較して高い溶解性を示した。
〔比較例２〕
上記ポリマー（Ｐ２）の繰り返し単位の一つである式（Ｕ３）のみが繰り返された下記
ポリマー（Ｐ４）のＮＭＰ（Ｎ−メチルピロリドン）およびトルエンに溶解させた。その結果を表４に示す。
[Example 2]
The polymer (P2) was dissolved in NMP (N-methylpyrrolidone) and toluene. The results are shown in Table 4. As shown in Table 4, the polymer (P2) showed higher solubility than the polymer (P4) having a corresponding single repeating unit.
[Comparative Example 2]
It was dissolved in NMP (N-methylpyrrolidone) and toluene of the following polymer (P4) in which only the formula (U3) which is one of the repeating units of the polymer (P2) was repeated. The results are shown in Table 4.
（Ｍｗ＝１０９００、Ｍｎ＝４３００） (Mw = 10900, Mn = 4300)
〔実施例３〕
ガラス基板をアセトンで超音波洗浄、純水で水洗、イソプロピルアルコールで超音波洗浄、乾燥窒素で乾燥、ＵＶ／オゾン洗浄を行った後、既述の方法により合成したポリマー（Ｐ１）を下記の条件で、上記ガラス基板上にスピンコートした：
溶媒 安息香酸エチル
塗布液濃度 ２０．０［ｍｇ／ｍｌ］
スピナ回転数 １５００［ｒｐｍ］
スピナ回転時間 ３０［秒］
乾燥条件 １００℃−１ｈ
上記のスピンコートにより３０ｎｍの膜厚の均一な薄膜が形成された。この薄膜試料のイオン化ポテンシャルを理研計器（株）製の紫外線電子分析装置（ＡＣ−１）を用いて測定した値を表５に示す。表５に示すようにポリマー（Ｐ１）は対応する単一の繰り返し単位を有するポリマー（Ｐ３）とほぼ等しいイオン化ポテンシャルを与えた。
〔比較例３〕
ガラス基板をアセトンで超音波洗浄、純水で水洗、イソプロピルアルコールで超音波洗
浄、乾燥窒素で乾燥、ＵＶ／オゾン洗浄を行った後、ポリマー（Ｐ３）を下記の条件で、上記ガラス基板上にスピンコートした：
溶媒 安息香酸エチル
塗布液濃度 ２０．０［ｍｇ／ｍｌ］
スピナ回転数 １５００［ｒｐｍ］
スピナ回転時間 ３０［秒］
乾燥条件 １００℃−１ｈ
上記のスピンコートにより３０ｎｍの膜厚の均一な薄膜が形成された。この薄膜試料のイオン化ポテンシャルを理研計器（株）製の紫外線電子分析装置（ＡＣ−１）を用いて測定した値を表５に示す。
〔実施例４〕
ガラス基板をアセトンで超音波洗浄、純水で水洗、イソプロピルアルコールで超音波洗浄、乾燥窒素で乾燥、ＵＶ／オゾン洗浄を行った後、既述の方法により合成したポリマー（Ｐ２）を下記の条件で、上記ガラス基板上にスピンコートした：
溶媒 安息香酸エチル
塗布液濃度 ５．０［ｍｇ／ｍｌ］
スピナ回転数 １５００［ｒｐｍ］
スピナ回転時間 ３０［秒］
乾燥条件 １００℃−１ｈ
上記のスピンコートにより３０ｎｍの膜厚の均一な薄膜が形成された。この薄膜試料のイオン化ポテンシャルを理研計器（株）製の紫外線電子分析装置（ＡＣ−１）を用いて測定した値を表５に示す。表５に示すようにポリマー（Ｐ２）は対応する単一の繰り返し単位を有するポリマー（Ｐ４）とほぼ等しいイオン化ポテンシャルを与えた。
〔比較例４〕
ガラス基板をアセトンで超音波洗浄、純水で水洗、イソプロピルアルコールで超音波洗浄、乾燥窒素で乾燥、ＵＶ／オゾン洗浄を行った後、既述の方法により合成したポリマー（Ｐ４）を下記の条件で、上記ガラス基板上にスピンコートした：
溶媒 安息香酸エチル
塗布液濃度 ２０．０［ｍｇ／ｍｌ］
スピナ回転数 １５００［ｒｐｍ］
スピナ回転時間 ３０［秒］
乾燥条件 １００℃−１ｈ
上記のスピンコートにより３０ｎｍの膜厚の均一な薄膜が形成された。この薄膜試料のイオン化ポテンシャルを理研計器（株）製の紫外線電子分析装置（ＡＣ−１）を用いて測定した値を表５に示す。
Example 3
The glass substrate was subjected to ultrasonic cleaning with acetone, water with pure water, ultrasonic cleaning with isopropyl alcohol, drying with dry nitrogen, and UV / ozone cleaning, and then the polymer (P1) synthesized by the method described above was subjected to the following conditions: Was spin coated onto the glass substrate:
Solvent ethyl benzoate
Coating solution concentration 20.0 [mg / ml]
Spinner speed 1500 [rpm]
Spinner rotation time 30 [seconds]
Drying conditions 100 ° C-1h
A uniform thin film with a thickness of 30 nm was formed by the above spin coating. Table 5 shows values obtained by measuring the ionization potential of this thin film sample using an ultraviolet electron analyzer (AC-1) manufactured by Riken Keiki Co., Ltd. As shown in Table 5, polymer (P1) gave an ionization potential approximately equal to polymer (P3) having a corresponding single repeating unit.
[Comparative Example 3]
The glass substrate was subjected to ultrasonic cleaning with acetone, water with pure water, ultrasonic cleaning with isopropyl alcohol, drying with dry nitrogen, and UV / ozone cleaning, and then the polymer (P3) was deposited on the glass substrate under the following conditions. Spin coated:
Solvent ethyl benzoate
Coating solution concentration 20.0 [mg / ml]
Spinner speed 1500 [rpm]
Spinner rotation time 30 [seconds]
Drying conditions 100 ° C-1h
A uniform thin film with a thickness of 30 nm was formed by the above spin coating. Table 5 shows values obtained by measuring the ionization potential of this thin film sample using an ultraviolet electron analyzer (AC-1) manufactured by Riken Keiki Co., Ltd.
Example 4
The glass substrate was subjected to ultrasonic cleaning with acetone, pure water, ultrasonic cleaning with isopropyl alcohol, drying with dry nitrogen, and UV / ozone cleaning, and then the polymer (P2) synthesized by the method described above was subjected to the following conditions. Was spin coated onto the glass substrate:
Solvent ethyl benzoate
Coating solution concentration 5.0 [mg / ml]
Spinner speed 1500 [rpm]
Spinner rotation time 30 [seconds]
Drying conditions 100 ° C-1h
A uniform thin film with a thickness of 30 nm was formed by the above spin coating. Table 5 shows values obtained by measuring the ionization potential of this thin film sample using an ultraviolet electron analyzer (AC-1) manufactured by Riken Keiki Co., Ltd. As shown in Table 5, polymer (P2) gave an ionization potential approximately equal to polymer (P4) having a corresponding single repeat unit.
[Comparative Example 4]
The glass substrate was subjected to ultrasonic cleaning with acetone, water with pure water, ultrasonic cleaning with isopropyl alcohol, drying with dry nitrogen, UV / ozone cleaning, and the polymer (P4) synthesized by the above-described method was subjected to the following conditions. Was spin coated onto the glass substrate:
Solvent ethyl benzoate
Coating solution concentration 20.0 [mg / ml]
Spinner speed 1500 [rpm]
Spinner rotation time 30 [seconds]
Drying conditions 100 ° C-1h
A uniform thin film with a thickness of 30 nm was formed by the above spin coating. Table 5 shows values obtained by measuring the ionization potential of this thin film sample using an ultraviolet electron analyzer (AC-1) manufactured by Riken Keiki Co., Ltd.
〔実施例５〕
図３に示す構造を有する有機電界発光素子を以下の方法で作製した。
ガラス基板上にインジウム・スズ酸化物（ＩＴＯ）透明導電膜を １２０ｎｍ堆積したもの（ジオマテック社製；電子ビーム成膜品；シート抵抗１５Ω／ｓｑ）を通常のフォトリソグラフィ技術と塩酸エッチングを用いて ２ｍｍ幅のストライプにパターニングして陽極を形成した。パターン形成したＩＴＯ基板を、アセトンによる超音波洗浄、純水による水洗、イソプロピルアルコールによる超音波洗浄の順で洗浄後、窒素ブローで乾燥させ、最後に紫外線オゾン洗浄を行った。
Example 5
An organic electroluminescent element having the structure shown in FIG. 3 was produced by the following method.
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate with a thickness of 120 nm (manufactured by Geomat Corp .; electron beam film-formed product; sheet resistance 15 Ω / sq) is 2 mm using ordinary photolithography technology and hydrochloric acid etching. An anode was formed by patterning into a stripe having a width. The patterned ITO substrate was cleaned in the order of ultrasonic cleaning with acetone, water with pure water, and ultrasonic cleaning with isopropyl alcohol, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.
このＩＴＯガラス基板上に、本発明の高分子化合物（Ｐ２）とＰＰＢの混合物を下記の条件で、上記ＩＴＯガラス基板上にスピンコートした：
溶媒 安息香酸エチル
（Ｐ２） ２０．０［ｍｇ／ｍｌ］
ＰＰＢ ２．０ ［ｍｇ／ｍｌ］
スピナ回転数 １５００［ｒｐｍ］
スピナ回転時間 ３０［秒］
乾燥条件 １００℃−１ｈ
上記のスピンコートにより３０ｎｍの膜厚の均一な薄膜形状を有する正孔注入層３を形成した。
A mixture of the polymer compound (P2) of the present invention and PPB was spin-coated on the ITO glass substrate on the ITO glass substrate under the following conditions:
Solvent Ethyl benzoate (P2) 20.0 [mg / ml]
PPB 2.0 [mg / ml]
Spinner speed 1500 [rpm]
Spinner rotation time 30 [seconds]
Drying conditions 100 ° C-1h
The hole injection layer 3 having a uniform thin film shape with a thickness of 30 nm was formed by the above spin coating.
次に、上記正孔注入層を塗布成膜した基板を真空蒸着装置内に設置した。上記装置の粗排気を油回転ポンプにより行った後、装置内の真空度が２×１０-6Ｔｏｒｒ（約２．７×１０-4Ｐａ）以下になるまで液体窒素トラップを備えた油拡散ポンプを用いて排気した。上記装置内に配置されたセラミックるつぼに入れた以下に示す芳香族ジアミン化合物、４，４′−ビス［Ｎ−（１−フェナントリル）−Ｎ−フェニルアミノ］ビフェニルを加熱して蒸着を行った。蒸着時の真空度は１．３×１０-6Ｔｏｒｒ（約１．７×１０-4Ｐａ）、蒸着速度は０．１−０．２ｎｍ／秒で、膜厚４０ｎｍの膜を本発明の高分子化合物（Ｐ２）からなる正孔注入層の上に積層して正孔輸送層４を完成させた。 Next, the substrate on which the hole injection layer was applied and formed was placed in a vacuum evaporation apparatus. An oil diffusion pump equipped with a liquid nitrogen trap until the degree of vacuum in the apparatus becomes 2 × 10 −6 Torr (about 2.7 × 10 −4 Pa) or less after rough exhaust of the above apparatus by an oil rotary pump Was evacuated. The following aromatic diamine compound, 4,4′-bis [N- (1-phenanthryl) -N-phenylamino] biphenyl, placed in a ceramic crucible placed in the above apparatus was heated for vapor deposition. The degree of vacuum during deposition is 1.3 × 10 −6 Torr (about 1.7 × 10 −4 Pa), the deposition rate is 0.1-0.2 nm / second, and a 40 nm-thick film is formed according to the present invention. The hole transport layer 4 was completed by laminating on the hole injection layer made of the molecular compound (P2).
引続き、発光層５の材料として、以下の構造式に示すアルミニウムの８−ヒドロキシキノリン錯体、Ａｌ（Ｃ9Ｈ6ＮＯ）3、とルブレンとを同時に蒸着した。アルミニウムの８
−ヒドロキシキノリン錯体に対するルブレンの割合は２．０ｖｏｌ．％になるようにした。この時のアルミニウムの８−ヒドロキシキノリン錯体のるつぼ温度は ２７５〜２８５℃の範囲で制御し、蒸着時の真空度は１．２×１０-6Ｔｏｒｒ（約１．６×１０-4Ｐａ蒸着速度は０．１−０．２ｎｍ／秒であった。またルブレンのるつぼ温度は ２４０〜２５０℃の範囲で制御し、蒸着速度は０．００２−０．００４ｎｍ／秒であった。このように蒸着された発光層の膜厚は３０ｎｍであった。続いて、電子輸送層（６）としてアルミニウムの８−ヒドロキシキノリン錯体、Ａｌ（Ｃ9Ｈ6ＮＯ）3、を正孔輸送層と同様にして
蒸着を行った。この時のアルミニウムの８−ヒドロキシキノリン錯体のるつぼ温度は ２７５〜２８５℃の範囲で制御し、蒸着時の真空度は１．１×１０-6Ｔｏｒｒ（約１．５×１０-4Ｐａ）、蒸着速度は０．１−０．２ｎｍ／秒で、蒸着された電子輸送層の膜厚は３０ｎｍであった。
Subsequently, as a material for the light-emitting layer 5, an 8-hydroxyquinoline complex of aluminum represented by the following structural formula, Al (C 9 H 6 NO) 3 , and rubrene were vapor-deposited at the same time. 8 of aluminum
The ratio of rubrene to the hydroxyquinoline complex is 2.0 vol. %. At this time, the crucible temperature of the aluminum 8-hydroxyquinoline complex was controlled in the range of 275 to 285 ° C., and the degree of vacuum during the deposition was 1.2 × 10 −6 Torr (about 1.6 × 10 −4 Pa deposition rate). The crucible temperature of rubrene was controlled in the range of 240 to 250 ° C., and the deposition rate was 0.002 to 0.004 nm / second. The film thickness of the light emitting layer was 30 nm, and subsequently, an 8-hydroxyquinoline complex of aluminum, Al (C 9 H 6 NO) 3 , was used as the electron transport layer (6) in the same manner as the hole transport layer. At this time, the crucible temperature of the aluminum 8-hydroxyquinoline complex was controlled in the range of 275 to 285 ° C., and the degree of vacuum during the deposition was 1.1 × 10 −6 Torr (about 1.5 × 10 -4 Pa), deposition rate 0.1 In 0.2 nm / sec, thickness of the deposited electron transport layer was 30 nm.
なお、上記の正孔輸送層４及び発光層５、電子輸送層６を真空蒸着する時の基板温度は室温に保持した。
ここで、電子輸送層６までの蒸着を行った素子を一度前記真空蒸着装置内より大気中に取り出して、陰極蒸着用のマスクとして２ｍｍ幅のストライプ状シャドーマスクを、陽極２のＩＴＯストライプとは直交するように素子に密着させて、別の真空蒸着装置内に設置して有機層と同様にして装置内の真空度が２×１０-6Ｔｏｒｒ（約２．７×１０-4Ｐａ）以下になるまで排気した。陰極７として、先ず、フッ化リチウム（ＬｉＦ）をモリブデンボートを用いて、蒸着速度０．０２ｎｍ／秒、真空度７．０×１０-6Ｔｏｒｒ（約９．３×１０-4Ｐａ）で、０．５ ｎｍの膜厚で発光層５あるいは電子輸送層６の上に成膜した。次に、アルミニウムを同様にモリブデンボートにより加熱して、蒸着速度０．３ｎｍ／秒、真空度１×１０-5Ｔｏｒｒ（約１．３×１０-3Ｐａ）で膜厚８０ｎｍのアルミニウム層を形成して陰極７を完成させた。以上の３層型陰極７の蒸着時の基板温度は室温に保持した。
In addition, the substrate temperature at the time of vacuum-depositing said positive hole transport layer 4, the light emitting layer 5, and the electron carrying layer 6 was hold | maintained at room temperature.
Here, the element on which the electron transport layer 6 has been deposited is once taken out from the vacuum deposition apparatus into the atmosphere, and a 2 mm wide stripe-shaped shadow mask is used as a cathode deposition mask. The element is in close contact with each other at right angles and installed in a separate vacuum deposition apparatus, and the degree of vacuum in the apparatus is 2 × 10 −6 Torr (about 2.7 × 10 −4 Pa) or less as in the organic layer It exhausted until it became. As the cathode 7, first, lithium fluoride (LiF) was deposited at a deposition rate of 0.02 nm / second and a degree of vacuum of 7.0 × 10 −6 Torr (about 9.3 × 10 −4 Pa) using a molybdenum boat. The film was formed on the light emitting layer 5 or the electron transport layer 6 with a film thickness of 0.5 nm. Next, aluminum is similarly heated by a molybdenum boat to form an aluminum layer having a thickness of 80 nm at a deposition rate of 0.3 nm / second and a degree of vacuum of 1 × 10 −5 Torr (about 1.3 × 10 −3 Pa). Thus, the cathode 7 was completed. The substrate temperature at the time of vapor deposition of the above three-layered cathode 7 was kept at room temperature.
以上の様にして、２ｍｍ×２ｍｍのサイズの発光面積部分を有する有機電界発光素子が得られた。この素子の発光特性を表６にに示す。表６において、発光輝度は２５０ｍＡ／ｃｍ2の電流密度での値、発光効率は１００ｃｄ／ｍ2での値、輝度／電流は輝度−電流密度特性の傾きを、電圧は１００ｃｄ／ｍ2での値を各々示す。表６より、対応する単一の
繰り返し単位を有するポリマー（Ｐ３）と同等の特性をもつ、駆動電圧の低い、高輝度かつ高発光効率で発光する素子が得られたことが明らかである。
〔比較例５〕
本発明のポリマー（Ｐ２）の代わりに、対応する単一の繰り返し単位のみを有するポリマー（Ｐ４）を用い、正孔注入層３を形成する際の、ＩＴＯガラス基板上へのスピンコートの条件を：
溶媒 安息香酸エチル
（Ｐ４） ２０．０［ｍｇ／ｍｌ］
ＰＰＢ ２．０ ［ｍｇ／ｍｌ］
スピナ回転数 １５００［ｒｐｍ］
スピナ回転時間 ３０［秒］
乾燥条件 １００℃−１ｈ
とした他は、実施例５と同様に素子を作成した。この素子の発光特性を表６に示す。
As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. The light emission characteristics of this device are shown in Table 6. In Table 6, the light emission luminance is a value at a current density of 250 mA / cm 2 , the light emission efficiency is a value at 100 cd / m 2 , the luminance / current is the slope of the luminance-current density characteristic, and the voltage is 100 cd / m 2 . Each value is shown. From Table 6, it is clear that a device having characteristics equivalent to those of the polymer (P3) having a corresponding single repeating unit and having a low driving voltage, high luminance and high luminous efficiency was obtained.
[Comparative Example 5]
Instead of the polymer (P2) of the present invention, the polymer (P4) having only a single repeating unit is used, and the conditions for spin coating on the ITO glass substrate when forming the hole injection layer 3 are as follows: :
Solvent Ethyl benzoate (P4) 20.0 [mg / ml]
PPB 2.0 [mg / ml]
Spinner speed 1500 [rpm]
Spinner rotation time 30 [seconds]
Drying conditions 100 ° C-1h
A device was fabricated in the same manner as in Example 5 except that. The light emission characteristics of this device are shown in Table 6.
１ 基板
２ 陽極
３ 正孔注入層
４ 正孔輸送層
５ 発光層
６ 電子輸送層
７ 陰極
DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Electron transport layer 7 Cathode
Claims (12)
種以上の基で置換されていてもよい。
Ａｒ3およびＡｒ8は各々独立に、ｐ−フェニレン基、ｍ−フェニレン基、または４，４’−ビフェニレン基を表し、これらはいずれも、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアラルキル基、置換基を有していてもよいアシル基、置換基を有していてもよい芳香族炭化水素基、および置換基を有していてもよい芳香族複素環基よりなる群から選ばれる１種または２種以上の置換基で置換されていてもよい。
環Ａ４、環Ａ５、環Ａ９および環Ａ１０は各々独立して、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアラルキル基、置換基を有していてもよいアシル基、置換基を有していてもよい芳香族炭化水素基、および置換基を有していてもよい芳香族複素環基よりなる群から選ばれる１種または２種以上の置換基で置換されていてもよいベンゼン環を示す。
ＸおよびＹは各々独立に、下記構造式で表される部分構造からなる群より選ばれた２価の連結基である。）
It may be substituted with more than one group.
Ar 3 and Ar 8 each independently represent a p-phenylene group, an m-phenylene group, or a 4,4′-biphenylene group, and any of these may have an alkyl group or a substituent which may have a substituent. An alkynyl group which may have a substituent, an alkynyl group which may have a substituent, an aralkyl group which may have a substituent, an acyl group which may have a substituent, and a substituent. It may be substituted with one or more substituents selected from the group consisting of an aromatic hydrocarbon group which may be substituted and an aromatic heterocyclic group which may have a substituent.
Ring A4, Ring A5, Ring A9 and Ring A10 are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. A good alkynyl group, an aralkyl group which may have a substituent, an acyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a substituent The benzene ring which may be substituted by the 1 type (s) or 2 or more types of substituent chosen from the group which consists of an aromatic heterocyclic group which may be shown.
X and Y are each independently a divalent linking group selected from the group consisting of partial structures represented by the following structural formula. )
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003308956A JP4186758B2 (en) | 2003-09-01 | 2003-09-01 | Polymer compound, hole injecting / transporting material, organic electroluminescent device material and organic electroluminescent device |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003308956A JP4186758B2 (en) | 2003-09-01 | 2003-09-01 | Polymer compound, hole injecting / transporting material, organic electroluminescent device material and organic electroluminescent device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005075948A JP2005075948A (en) | 2005-03-24 |
| JP4186758B2 true JP4186758B2 (en) | 2008-11-26 |
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| WO2010140553A1 (en) | 2009-06-01 | 2010-12-09 | 日立化成工業株式会社 | Organic electronic material, ink composition containing same, and organic thin film, organic electronic element, organic electroluminescent element, lighting device, and display device formed therewith |
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|---|---|---|---|---|
| WO2010140553A1 (en) | 2009-06-01 | 2010-12-09 | 日立化成工業株式会社 | Organic electronic material, ink composition containing same, and organic thin film, organic electronic element, organic electroluminescent element, lighting device, and display device formed therewith |
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| JP2005075948A (en) | 2005-03-24 |
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