JP2013036023A - Material for organic electroluminescent element and application of the same - Google Patents
Material for organic electroluminescent element and application of the same Download PDFInfo
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- JP2013036023A JP2013036023A JP2012032257A JP2012032257A JP2013036023A JP 2013036023 A JP2013036023 A JP 2013036023A JP 2012032257 A JP2012032257 A JP 2012032257A JP 2012032257 A JP2012032257 A JP 2012032257A JP 2013036023 A JP2013036023 A JP 2013036023A
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- 239000003550 marker Substances 0.000 description 1
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- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
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- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
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- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
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- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
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Abstract
Description
本発明は新規な有機エレクトロルミネッセンス素子用材料に関する。さらに詳しくは、有機エレクトロルミネッセンス素子（以下有機ＥＬ素子と略記）に用いた場合、塗布による製膜が可能である正孔輸送層、および正孔注入層用材料として有用なアリールアミンポリマーを含有する有機エレクトロルミネッセンス素子用材料に関する。 The present invention relates to a novel material for an organic electroluminescence device. More specifically, when it is used for an organic electroluminescence device (hereinafter abbreviated as an organic EL device), it contains an arylamine polymer that is useful as a material for a hole transport layer and a hole injection layer that can be formed by coating. The present invention relates to a material for an organic electroluminescence element.
近年、有機ＥＬ素子においては、素子の長寿命化が求められている。素子の寿命に影響を及ぼす原因は様々な因子が考えられるが、その一つとして、素子を構成する材料のガラス転移温度(Ｔｇ)が、素子の寿命に大きな影響を及ぼすものと考えられている。すなわち、素子の使用環境や駆動時の発熱などにより、素子の温度が構成する材料のＴｇを上回ると、構成する材料の結晶化が起こり、ダークスポットと呼ばれる非発光領域が発生することが指摘されている。そのため、より高いＴｇを示す材料が求められてきた（非特許文献１、２）。
In recent years, organic EL elements have been required to have a long lifetime. There are various factors that can affect the lifetime of the device. One of the factors is considered to be that the glass transition temperature (Tg) of the material constituting the device has a significant effect on the lifetime of the device. . That is, it is pointed out that when the temperature of the element exceeds the Tg of the constituent material due to the use environment of the element or the heat generated during driving, the constituent material is crystallized and a non-light emitting region called a dark spot is generated. ing. For this reason, materials having higher Tg have been demanded (Non-Patent
また、有機ＥＬ素子の成膜方法も、高真空中での蒸着法の他、湿式成膜法も多く検討されてきた。特に、湿式成膜法は、太面積化が容易であり、将来有望と考えられているが、正孔注入層にＰＥＤＯＴ・ＰＳＳを用い、その上に発光層が直接接すると、有機ＥＬ素子の寿命が著しく短くなるという問題点があった。また、有機層を塗布で成膜する場合、水系溶媒での塗布と、有機溶媒系での塗布は積層可能であるが同一溶媒系での積層は困難である。よって、ＰＥＤＯＴ・ＰＳＳと発光層の間に正孔輸送層を塗布法で成膜することは、困難であった。 In addition to the deposition method in a high vacuum, many wet deposition methods have been studied as a method for forming an organic EL element. In particular, the wet film formation method is easy to increase in area and is considered promising in the future. However, when PEDOT / PSS is used for the hole injection layer and the light emitting layer is in direct contact with the hole injection layer, the organic EL element There was a problem that the lifetime was significantly shortened. In addition, when an organic layer is formed by coating, coating with an aqueous solvent and coating with an organic solvent system can be stacked, but stacking with the same solvent system is difficult. Therefore, it has been difficult to form a hole transport layer between the PEDOT / PSS and the light emitting layer by a coating method.
また、塗布型の正孔輸送材料として、アミン含有ポリマー材料が開発されてきた。しかしながら、発光層と同一溶媒で塗布するとことが困難であるという欠点があった。（特許文献１〜５、非特許文献３）。
Also, amine-containing polymer materials have been developed as coating-type hole transport materials. However, there is a drawback that it is difficult to apply with the same solvent as the light emitting layer. (
本発明の課題は、有機ＥＬ素子用材料に有用な化合物を提供すること、および、特に正孔注入層もしくは正孔輸送層用材料として好適に用いることができる化合物を提供することにある。さらには、この有機エレクトロルミネッセンス素子用材料を用いることにより、高い発光効率、低電圧駆動、色純度、長寿命、耐熱性などの優れた特性を示す有機ＥＬ素子を提供することである。 An object of the present invention is to provide a compound useful for a material for an organic EL device, and particularly to provide a compound that can be suitably used as a material for a hole injection layer or a hole transport layer. Furthermore, it is to provide an organic EL element exhibiting excellent characteristics such as high luminous efficiency, low voltage driving, color purity, long life, heat resistance, and the like by using the material for organic electroluminescence element.
本発明者らは、前記諸問題を解決するために、鋭意研究を重ねた結果、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention.
すなわち本発明は、下記一般式［１］で表される重合性化合物、または、下記一般式［２］で表される重合性化合物に関する。 That is, the present invention relates to a polymerizable compound represented by the following general formula [1] or a polymerizable compound represented by the following general formula [2].
一般式［１］
一般式［２］
（一般式［１］及び一般式［２］中、
Ａは、下記一般式［３］を、
Ｂは、下記一般式［４］を、
Ｅは、下記一般式［５］、または一般式［６］を、
Ｆは、水素原子、下記一般式［７］、もしくは、ハロゲン原子を表し、
ｎ及びｍは、それぞれ独立に、１以上の整数を表す。）
(In general formula [1] and general formula [2],
A represents the following general formula [3]:
B represents the following general formula [4]:
E represents the following general formula [5] or general formula [6]:
F represents a hydrogen atom, the following general formula [7], or a halogen atom,
n and m each independently represent an integer of 1 or more. )
一般式［３］
（一般式［３］中、Ｒ1およびＲ2は、それぞれ独立に、水素原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基を表す。）
(In General Formula [3], R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, Represents a substituted or unsubstituted monovalent aliphatic heterocyclic group or a substituted or unsubstituted monovalent aromatic heterocyclic group.)
一般式［４］
（一般式［４］中、Ｒ3〜Ｒ7は、それぞれ独立に、水素原子、ハロゲン原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、Ｒ3〜Ｒ7は、隣接した基が互いに結合して環を形成しても良い。） (In General Formula [4], R 3 to R 7 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic carbonization. Hydrogen group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted silyl group, alkoxyl group, aryloxy group, or substituted amino group R 3 to R 7 may represent a group, and adjacent groups may be bonded to each other to form a ring.
一般式［５］
（一般式［５］中、Ｒ8は、置換または未置換の２価の脂肪族炭化水素基、置換もしくは未置換の２価の芳香族炭化水素基、置換もしくは未置換の２価の脂肪族複素環基、または、置換もしくは未置換の２価の芳香族複素環基を表し、
Ｒ9は、水素原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、または、置換もしくは未置換の１価の芳香族複素環基を表し、
Ｘは、直接結合、酸素原子、または、硫黄原子を表す。）
(In the general formula [5], R 8 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic group. Represents a heterocyclic group, or a substituted or unsubstituted divalent aromatic heterocyclic group,
R 9 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or Represents a substituted or unsubstituted monovalent aromatic heterocyclic group,
X represents a direct bond, an oxygen atom, or a sulfur atom. )
一般式［６］
（一般式［６］中、Ｒ10は、置換または未置換の２価の脂肪族炭化水素基、置換もしくは未置換の２価の芳香族炭化水素基、置換もしくは未置換の２価の脂肪族複素環基、または、置換もしくは未置換の２価の芳香族複素環基を表し、
Ｒ11は、水素原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、または、置換もしくは未置換の１価の芳香族複素環基を表し、
Ｘは、直接結合、酸素原子、または、硫黄原子を表す。）
(In the general formula [6], R 10 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic group. Represents a heterocyclic group, or a substituted or unsubstituted divalent aromatic heterocyclic group,
R 11 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or Represents a substituted or unsubstituted monovalent aromatic heterocyclic group,
X represents a direct bond, an oxygen atom, or a sulfur atom. )
一般式［７］
（一般式［７］中、Ｒ12〜Ｒ16は、それぞれ独立に、水素原子、ハロゲン原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、Ｒ12〜Ｒ16は、隣接した基が互いに結合して環を形成しても良い。） (In the general formula [7], R 12 to R 16 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic carbonization. Hydrogen group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted silyl group, alkoxyl group, aryloxy group, or substituted amino group R 12 to R 16 may represent a group, and adjacent groups may be bonded to each other to form a ring.
また、本発明は、上記の重合性化合物を重合してなる高分子化合物に関する。 Moreover, this invention relates to the high molecular compound formed by superposing | polymerizing said polymeric compound.
また、本発明は、上記の高分子化合物を含有する、有機エレクトロルミネッセンス素子用材料に関する。 Moreover, this invention relates to the material for organic electroluminescent elements containing said high molecular compound.
また、本発明は、一対の電極間に複数層の有機層を形成してなる有機エレクトロルミネッセンス素子において、前記有機層の少なくとも一層が、上記有機エレクトロルミネッセンス素子用材料を含んでなる有機エレクトロルミネッセンス素子に関する。 In addition, the present invention provides an organic electroluminescence device comprising a plurality of organic layers formed between a pair of electrodes, wherein at least one of the organic layers comprises the material for an organic electroluminescence device. About.
また、本発明は、一対の電極間に正孔注入層、正孔輸送層を含む複数層の有機層を形成してなる有機エレクトロルミネッセンス素子において、前記有機層の少なくとも一層が、上記有機エレクトロルミネッセンス素子用材料を含んでなる有機エレクトロルミネッセンス素子に関する。 Further, the present invention provides an organic electroluminescence device comprising a plurality of organic layers including a hole injection layer and a hole transport layer between a pair of electrodes, wherein at least one of the organic layers is the above organic electroluminescence. The present invention relates to an organic electroluminescence element comprising an element material.
また、本発明は、正孔注入層、正孔輸送層が湿式成膜法により形成されてなる層である上記有機エレクトロルミネッセンス素子に関する。 Moreover, this invention relates to the said organic electroluminescent element which is a layer in which a positive hole injection layer and a positive hole transport layer are formed by the wet film-forming method.
また、本発明は、上記有機エレクトロルミネッセンス素子用材料と、有機溶剤とからなる有機エレクトロルミネッセンス素子用インキ組成物に関する。 Moreover, this invention relates to the ink composition for organic electroluminescent elements which consists of the said organic electroluminescent element material and an organic solvent.
本発明の有機ＥＬ素子用材料を用いた有機ＥＬ素子は、低い電圧で駆動し、かつ、長寿命であるため、壁掛けテレビ等のフラットパネルディスプレイや平面発光体として好適に使用することができ、複写機やプリンター等の光源、液晶ディスプレイや計器類等の光源、表示板、標識灯等への応用が可能である。 Since the organic EL element using the organic EL element material of the present invention is driven at a low voltage and has a long life, it can be suitably used as a flat panel display such as a wall-mounted TV or a flat light emitter, It can be applied to light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display panels, and indicator lights.
以下、詳細にわたって本発明を説明する。 Hereinafter, the present invention will be described in detail.
まず、一般式［３］における、Ｒ1およびＲ2は、それぞれ独立に、水素原子、または、置換または未置換の１価の脂肪族炭化水素基、または、置換もしくは未置換の１価の芳香族炭化水素基、または、置換もしくは未置換の１価の脂肪族複素環基、または、置換もしくは未置換の１価の芳香族複素環基を表す First, R 1 and R 2 in the general formula [3] are each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, or a substituted or unsubstituted monovalent aromatic. Represents a hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or a substituted or unsubstituted monovalent aromatic heterocyclic group
ここで、１価の脂肪族炭化水素基としては、炭素数１〜１８の１価の脂肪族炭化水素基を指し、そのようなものとしては、アルキル基、アルケニル基、アルキニル基、シクロアルキル基が挙げられる。 Here, the monovalent aliphatic hydrocarbon group refers to a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group. Is mentioned.
ここで、アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、イソペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基、ドデシル基、ペンタデシル基、オクタデシル基といった炭素数１〜１８のアルキル基が挙げられる。 Here, as the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group , An alkyl group having 1 to 18 carbon atoms such as a decyl group, a dodecyl group, a pentadecyl group and an octadecyl group.
また、アルケニル基としては、ビニル基、１−プロペニル基、２−プロペニル基、イソプロペニル基、１−ブテニル基、２−ブテニル基、３−ブテニル基、１−オクテニル基、１−デセニル基、１−オクタデセニル基といった炭素数２〜１８のアルケニル基が挙げられる。 Examples of the alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1-decenyl group, 1 -C2-C18 alkenyl groups, such as an octadecenyl group, are mentioned.
また、アルキニル基としては、エチニル基、１−プロピニル基、２−プロピニル基、１−ブチニル基、２−ブチニル基、３−ブチニル基、１−オクチニル基、１−デシニル基、１−オクタデシニル基といった炭素数２〜１８のアルキニル基が挙げられる。 Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group and 1-octadecynyl group. Examples include alkynyl groups having 2 to 18 carbon atoms.
また、シクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロオクタデシル基、２−インデノ基といった炭素数３〜１８のシクロアルキル基が挙げられる。 Examples of the cycloalkyl group include cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, and 2-indeno group. .
さらに、１価の芳香族炭化水素基としては、１価の単環、縮合環、環集合芳香族炭化水素基が挙げられる。 Furthermore, examples of the monovalent aromatic hydrocarbon group include a monovalent monocyclic ring, a condensed ring, and a ring assembly aromatic hydrocarbon group.
ここで、１価の単環芳香族炭化水素基としては、フェニル基、ｏ−トリル基、ｍ−トリル基、ｐ−トリル基、２，４−キシリル基、ｐ−クメニル基、メシチル基等の炭素数６〜１８の１価の単環芳香族炭化水素基が挙げられる。 Here, examples of the monovalent monocyclic aromatic hydrocarbon group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,4-xylyl group, a p-cumenyl group, and a mesityl group. Examples thereof include monovalent monocyclic aromatic hydrocarbon groups having 6 to 18 carbon atoms.
また、１価の縮合環芳香族炭化水素基としては、１−ナフチル基、２−ナフチル基、１−アンスリル基、２−アンスリル基、５−アンスリル基、１−フェナンスリル基、９−フェナンスリル基、１−アセナフチル基、２−アズレニル基、１−ピレニル基、２−トリフェニレル基等の炭素数１０〜１８の１価の縮合環芳香族炭化水素基が挙げられる。 Examples of the monovalent condensed ring aromatic hydrocarbon group include 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, C1-C18 monovalent | monohydric condensed ring aromatic hydrocarbon groups, such as 1-acenaphthyl group, 2-azurenyl group, 1-pyrenyl group, 2-triphenylyl group, are mentioned.
また、１価の環集合芳香族炭化水素基としては、ｏ−ビフェニリル基、ｍ−ビフェニリル基、ｐ−ビフェニリル基等の炭素数１２〜１８の１価の環集合芳香族炭化水素基が挙げられる。 Examples of the monovalent ring-assembled aromatic hydrocarbon group include monovalent ring-assembled aromatic hydrocarbon groups having 12 to 18 carbon atoms such as o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group. .
さらに、１価の脂肪族複素環基としては、２−ピラゾリノ基、ピペリジノ基、モルホリノ基、２−モルホリニル基といった炭素数３〜１８の１価の脂肪族複素環基が挙げられる。 Furthermore, examples of the monovalent aliphatic heterocyclic group include monovalent aliphatic heterocyclic groups having 3 to 18 carbon atoms such as a 2-pyrazolino group, a piperidino group, a morpholino group, and a 2-morpholinyl group.
さらに、１価の芳香族複素環基としては、トリアゾリル基、３−オキサジアゾリル基、２−フラニル基、３−フラニル基、２−フリル基、３−フリル基、２−チエニル基、３−チエニル基、１−ピロ−リル基、２−ピロ−リル基、３−ピロ−リル基、２−ピリジル基、３−ピリジル基、４−ピリジル基、２−ピラジル基、２−オキサゾリル基、３−イソオキサゾリル基、２−チアゾリル基、３−イソチアゾリル基、２−イミダゾリル基、３−ピラゾリル基、２−キノリル基、３−キノリル基、４−キノリル基、５−キノリル基、６−キノリル基、７−キノリル基、８−キノリル基、１−イソキノリル基、２−キノキサリニル基、２−ベンゾフリル基、２−ベンゾチエニル基、Ｎ−インドリル基、Ｎ−カルバゾリル基、Ｎ−アクリジニル基、２−チオフェニル基、３−チオフェニル基、ビピリジル基、フェナントロリル基といった炭素数２〜１８の１価の芳香族複素環基が挙げられる。 Furthermore, as the monovalent aromatic heterocyclic group, triazolyl group, 3-oxadiazolyl group, 2-furanyl group, 3-furanyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazyl group, 2-oxazolyl group, 3-isoxazolyl Group, 2-thiazolyl group, 3-isothiazolyl group, 2-imidazolyl group, 3-pyrazolyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group Group, 8-quinolyl group, 1-isoquinolyl group, 2-quinoxalinyl group, 2-benzofuryl group, 2-benzothienyl group, N-indolyl group, N-carbazolyl group, N-acridinyl group, 2 Thiophenyl group, 3-thiophenyl group, bipyridyl group, and monovalent aromatic heterocyclic group having 2 to 18 carbon atoms such phenanthrolyl group.
一般式［４］における、Ｒ3〜Ｒ7は、それぞれ独立に、水素原子、または、ハロゲン原子、または、置換または未置換の１価の脂肪族炭化水素基、または、置換もしくは未置換の１価の芳香族炭化水素基、または、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基、または、シアノ基、または、置換シリル基、または、アルコキシル基、または、アリ−ルオキシ基、または、置換アミノ基を表し、Ｒ3〜Ｒ7は、隣接した基が互いに結合して環を形成しても良い。 In the general formula [4], R 3 to R 7 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, or a substituted or unsubstituted 1 A monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, a cyano group, or a substituted silyl group, or Represents an alkoxyl group, an aryloxy group, or a substituted amino group, and R 3 to R 7 may be bonded to each other to form a ring.
ここで、置換もしくは未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、および置換もしくは未置換の１価の芳香族複素環基は前述のものが挙げられる。 Here, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, and a substituted or unsubstituted Examples of the monovalent aromatic heterocyclic group include those described above.
また、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
さらに、置換シリル基としては、置換もしくは未置換のアルキル基、または、置換もしくは未置換のアリール基によって置換されたシリル基であり、モノアルキルシリル基、モノアリールシリル基、ジアルキルシリル基、ジアリールシリル基、トリアルキルシリル基、トリアリールシリル基等といった置換シリル基が挙げられる。 Furthermore, the substituted silyl group is a substituted or unsubstituted alkyl group, or a silyl group substituted by a substituted or unsubstituted aryl group. A monoalkylsilyl group, a monoarylsilyl group, a dialkylsilyl group, a diarylsilyl group And substituted silyl groups such as a group, a trialkylsilyl group, and a triarylsilyl group.
ここで、モノアルキルシリル基としては、モノメチルシリル基、モノエチルシリル基、モノブチルシリル基、モノイソプロピルシリル基、モノデカンシリル、モノイコサンシリル基、モノトリアコンタンシリル基等のモノアルキルシリル基が挙げられる。 Here, as the monoalkylsilyl group, a monoalkylsilyl group such as a monomethylsilyl group, a monoethylsilyl group, a monobutylsilyl group, a monoisopropylsilyl group, a monodecanesilyl, a monoicosanesilyl group, or a monotriacontanesilyl group Is mentioned.
また、モノアリールシリル基としては、モノフェニルシリル基、モノトリルシリル基、モノナフチルシリル基、モノアンスリルシリル基等のモノアリールシリルが挙げられる。 Examples of the monoarylsilyl group include monoarylsilyl such as monophenylsilyl group, monotolylsilyl group, mononaphthylsilyl group, and monoanthrylsilyl group.
また、ジアルキルシリル基としては、ジメチルシリル基、ジエチルシリル基、ジメチルエチルシリル基、ジイソプロピルシリル基、ジブチルシリル基、ジオクチルシリル基、ジデカンシリル基等のジアルキルシリル基が挙げられる。 Examples of the dialkylsilyl group include dialkylsilyl groups such as dimethylsilyl group, diethylsilyl group, dimethylethylsilyl group, diisopropylsilyl group, dibutylsilyl group, dioctylsilyl group, and didecanesilyl group.
また、ジアリールシリル基としては、ジフェニルシリル基、ジトリルシリル基等のジアリールシリルが挙げられる。 Examples of the diarylsilyl group include diarylsilyl such as diphenylsilyl group and ditolylsilyl group.
また、トリアルキルシリル基としては、トリメチルシリル基、トリエチルシリル基、ジメチルエチルシリル基、トリイソプロピルシリル基、トリブチルシリル基、トリオクチルシリル基等のトリアルキルシリル基が挙げられる。 Examples of the trialkylsilyl group include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, dimethylethylsilyl group, triisopropylsilyl group, tributylsilyl group, and trioctylsilyl group.
また、トリアリールシリル基としては、トリフェニルシリル基、トリトリルシリル基等のトリアリールシリル基が挙げられる。 Examples of the triarylsilyl group include triarylsilyl groups such as a triphenylsilyl group and a tolylsilylsilyl group.
また、アルコキシル基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ｔｅｒｔ−ブトキシ基、オクチルオキシ基、ｔｅｒｔ−オクチルオキシ基といった炭素数１〜８のアルコキシル基が挙げられる。 Moreover, as an alkoxyl group, C1-C8 alkoxyl groups, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, an octyloxy group, a tert-octyloxy group, are mentioned.
また、アリールオキシ基としては、フェノキシ基、４−ｔｅｒｔ−ブチルフェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、９−アンスリルオキシ基といった炭素数６〜１４のアリ−ルオキシ基が挙げられる。 Examples of the aryloxy group include aryloxy groups having 6 to 14 carbon atoms such as phenoxy group, 4-tert-butylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, and 9-anthryloxy group. It is done.
ここで、置換アミノ基としては、Ｎ−メチルアミノ基、Ｎ−エチルアミノ基、Ｎ，Ｎ−ジエチルアミノ基、Ｎ，Ｎ−ジイソプロピルアミノ基、Ｎ，Ｎ−ジブチルアミノ基、Ｎ−ベンジルアミノ基、Ｎ，Ｎ−ジベンジルアミノ基、Ｎ−フェニルアミノ基、Ｎ−フェニル−Ｎ−メチルアミノ基、Ｎ，Ｎ−ジフェニルアミノ基、Ｎ，Ｎ−ビス（ｍ−トリル）アミノ基、Ｎ，Ｎ−ビス（ｐ−トリル）アミノ基、Ｎ，Ｎ−ビス（ｐ−ビフェニリル）アミノ基、ビス［４−（４−メチル）ビフェニリル］アミノ基、Ｎ−α−ナフチル−Ｎ−フェニルアミノ基、Ｎ−β−ナフチル−Ｎ−フェニルアミノ基等の炭素数２〜２６の置換アミノ基が挙げられる。 Here, as the substituted amino group, N-methylamino group, N-ethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N-benzylamino group, N, N-dibenzylamino group, N-phenylamino group, N-phenyl-N-methylamino group, N, N-diphenylamino group, N, N-bis (m-tolyl) amino group, N, N- Bis (p-tolyl) amino group, N, N-bis (p-biphenylyl) amino group, bis [4- (4-methyl) biphenylyl] amino group, N-α-naphthyl-N-phenylamino group, N- Examples thereof include substituted amino groups having 2 to 26 carbon atoms such as β-naphthyl-N-phenylamino group.
一般式［５］中、Ｒ8は、置換もしくは未置換の２価の脂肪族炭化水素基、置換もしくは未置換の２価の芳香族炭化水素基、置換もしくは未置換の２価の脂肪族複素環基、または、置換もしくは未置換の２価の芳香族複素環基を表し、Ｒ9は、水素原子、置換もしくは未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、または、置換もしくは未置換の１価の芳香族複素環基を表し、Ｘは、直接結合、酸素原子、または、硫黄原子を表す。 In the general formula [5], R 8 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic complex. Represents a cyclic group or a substituted or unsubstituted divalent aromatic heterocyclic group, and R 9 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent Represents an aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or a substituted or unsubstituted monovalent aromatic heterocyclic group, and X represents a direct bond, an oxygen atom, or sulfur. Represents an atom.
また、一般式［６］中、Ｒ10は、置換もしくは未置換の２価の脂肪族炭化水素基、置換もしくは未置換の２価の芳香族炭化水素基、置換もしくは未置換の２価の脂肪族複素環基、または、置換もしくは未置換の２価の芳香族複素環基を表し、Ｒ11は、水素原子、置換もしくは未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、または、置換もしくは未置換の１価の芳香族複素環基を表し、Ｘは、直接結合、酸素原子、または、硫黄原子を表す。 In the general formula [6], R 10 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent fat. Represents a heterocyclic group, or a substituted or unsubstituted divalent aromatic heterocyclic group, and R 11 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted 1 Represents a divalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or a substituted or unsubstituted monovalent aromatic heterocyclic group, and X represents a direct bond, an oxygen atom, or Represents a sulfur atom.
ここで、２価の脂肪族炭化水素基としては、炭素数１〜１８の２価の脂肪族炭化水素基を指し、そのようなものとしては、アルキレン基、アルケニレン基、アルキニレン基、シクロアルキレン基が挙げられる。 Here, the divalent aliphatic hydrocarbon group refers to a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, such as an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group. Is mentioned.
ここで、アルキレン基としては、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、ｓｅｃ−ブチレン基、ｔｅｒｔ−ブチレン基、ペンチレン基、イソペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、デシレン基、ドデシレン基、ペンタデシレン基、オクタデシレン基といった炭素数１〜１８のアルキレン基が挙げられる。 Here, as the alkylene group, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, pentylene group, isopentylene group, hexylene group, heptylene group, octylene. And an alkylene group having 1 to 18 carbon atoms such as a group, a decylene group, a dodecylene group, a pentadecylene group, and an octadecylene group.
また、アルケニレン基としては、エチレニレン基、１−プロペニレン基、２−プロペニレン基、イソプロペニレン基、１−ブテニレン基、２−ブテニレン基、３−ブテニレン基、１−オクテニレン基、１−デセニレン基、１−オクタデセニレン基といった炭素数２〜１８のアルケニレン基が挙げられる。 Examples of the alkenylene group include an ethylenylene group, a 1-propenylene group, a 2-propenylene group, an isopropenylene group, a 1-butenylene group, a 2-butenylene group, a 3-butenylene group, a 1-octenylene group, a 1-decenylene group, C2-C18 alkenylene groups, such as 1-octadecenylene group, are mentioned.
また、アルキニレン基としては、エチニレン基、１−プロピニレン基、２−プロピニレン基、１−ブチニレン基、２−ブチニレン基、３−ブチニレン基、１−オクチニレン基、１−デシニレン基、１−オクタデシニレン基といった炭素数２〜１８のアルキニレン基が挙げられる。 Examples of the alkynylene group include ethynylene group, 1-propynylene group, 2-propynylene group, 1-butynylene group, 2-butynylene group, 3-butynylene group, 1-octynylene group, 1-decynylene group, and 1-octadecynylene group. Examples thereof include alkynylene groups having 2 to 18 carbon atoms.
また、シクロアルキレン基としては、シクロプロピレン基、シクロブチレン基、シクロペンチレン基、シクロヘキシレン基、シクロヘプチレン基、シクロオクチレン基、シクロオクタデシレン基、２−インデニレン基といった炭素数３〜１８のシクロアルキレン基が挙げられる。 The cycloalkylene group has 3 to 18 carbon atoms such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclooctadecylene group, and a 2-indenylene group. A cycloalkylene group is mentioned.
さらに、２価の芳香族炭化水素基としては、２価の単環、縮合環、環集合芳香族炭化水素基が挙げられる。 Further, examples of the divalent aromatic hydrocarbon group include a divalent monocyclic ring, a condensed ring, and a ring assembly aromatic hydrocarbon group.
ここで、２価の単環芳香族炭化水素基としては、フェニレニル基、ｏ−トリレニル基、ｍ−トリレニル基、ｐ−トリレニル基、２，４−キシリレニル基、ｐ−クメニレニル基、メシチレニル基等の炭素数６〜１８の２価の単環芳香族炭化水素基が挙げられる。 Here, examples of the divalent monocyclic aromatic hydrocarbon group include a phenylenyl group, an o-tolylenyl group, an m-tolylenyl group, a p-tolylenyl group, a 2,4-xylylenyl group, a p-cumenylenyl group, and a mesityrenyl group. Examples thereof include a bivalent monocyclic aromatic hydrocarbon group having 6 to 18 carbon atoms.
また、２価の縮合環芳香族炭化水素基としては、１−ナフチレニル基、２−ナフチレニル基、１−アンスリレニル基、２−アンスリレニル基、５−アンスリレニル基、１−フェナンスレニル基、９−フェナンスレニル基、１−アセナフチレニル基、２−アズレニレニル基、１−ピレニレニル基、２−トリフェニレニル基等の炭素数１０〜１８の２価の縮合環芳香族炭化水素基が挙げられる。 Examples of the divalent condensed ring aromatic hydrocarbon group include 1-naphthylenyl group, 2-naphthylenyl group, 1-anthrylenyl group, 2-anthrylenyl group, 5-anthrylenyl group, 1-phenanthrenyl group, 9-phenanthrenyl group, Examples thereof include C10-18 divalent condensed ring aromatic hydrocarbon groups such as 1-acenaphthylenyl group, 2-azurenylenyl group, 1-pyrenylenyl group, 2-triphenylenyl group and the like.
また、２価の環集合芳香族炭化水素基としては、ｏ−ビフェニレニル基、ｍ−ビフェニレニル基、ｐ−ビフェニレニル基等の炭素数１２〜１８の２価の環集合芳香族炭化水素基が挙げられる。 Moreover, as a bivalent ring assembly aromatic hydrocarbon group, C12-18 bivalent ring assembly aromatic hydrocarbon groups, such as o-biphenylenyl group, m-biphenylenyl group, p-biphenylenyl group, are mentioned. .
さらに、２価の脂肪族複素環基としては、２−ピラゾリニレン基、ピペリジニレン基、モルホリニレン基、２−モルホリニレン基といった炭素数３〜１８の２価の脂肪族複素環基が挙げられる。 Furthermore, as a bivalent aliphatic heterocyclic group, C3-C18 bivalent aliphatic heterocyclic groups, such as 2-pyrazolinylene group, piperidinylene group, morpholinylene group, and 2-morpholinylene group, are mentioned.
さらに、２価の芳香族複素環基としては、トリアゾレニル基、３−オキサジアゾレニル基、２−フラニレニル基、３−フラニレニル基、２−フリレニル基、３−フリレニル基、２−チエニレニル基、３−チエニレニル基、１−ピロ−リレニル基、２−ピロ−リレニル基、３−ピロ−リレニル基、２−ピリジレニル基、３−ピリジレニル基、４−ピリジレニル基、２−ピラジレニル基、２−オキサゾリレニル基、３−イソオキサゾリレニル基、２−チアゾリレニル基、３−イソチアゾリレニル基、２−イミダゾリレニル基、３−ピラゾリレニル基、２−キノリレニル基、３−キノリレニル基、４−キノリレニル基、５−キノリレニル基、６−キノリレニル基、７−キノリレニル基、８−キノリレニル基、１−イソキノリレニル基、２−キノキサリニレニル基、２−ベンゾフリレニル基、２−ベンゾチエニレニル基、Ｎ−インドリレニル基、Ｎ−カルバゾリレニル基、Ｎ−アクリジニレニル基、２−チオフェニレニル基、３−チオフェニレニル基、ビピリジレニル基、フェナントロリレニル基といった炭素数２〜１８の２価の芳香族複素環基が挙げられる。 In addition, examples of the divalent aromatic heterocyclic group include triazolenyl group, 3-oxadiazorenyl group, 2-furanylenyl group, 3-furanylenyl group, 2-furylenyl group, 3-furylenyl group, 2-thienylenyl group, 3 -Thienylenyl group, 1-pyro-rylenyl group, 2-pyrrole-relenyl group, 3-pyrrole-ylenyl group, 2-pyridylenyl group, 3-pyridylenyl group, 4-pyridylenyl group, 2-pyrazylenyl group, 2-oxazolylenyl group, 3-isoxazolylenyl group, 2-thiazolylenyl group, 3-isothiazolylenyl group, 2-imidazolylenyl group, 3-pyrazolylenyl group, 2-quinolylenyl group, 3-quinolylenyl group, 4-quinolylenyl group, 5-quinolylenyl group Group, 6-quinolylenyl group, 7-quinolylenyl group, 8-quinolylenyl group, 1-isoquinolylenyl group, 2-quinoxa Nylenyl group, 2-benzofurenyl group, 2-benzothienylenyl group, N-indolinylenyl group, N-carbazolylenyl group, N-acridinylenyl group, 2-thiophenylenyl group, 3-thiophenylenyl group, bipyridylenyl group, phenanthrylylenyl group And a divalent aromatic heterocyclic group having 2 to 18 carbon atoms.
さらに、一般式［７］中、Ｒ12〜Ｒ16は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、Ｒ12〜Ｒ16は、隣接した基が互いに結合して環を形成しても良い Further, in the general formula [7], R 12 to R 16 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic. Hydrocarbon group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted silyl group, alkoxyl group, aryloxy group, or substituted Represents an amino group, and R 12 to R 16 may form a ring by bonding adjacent groups to each other.
ここで、一般式［５］〜［７］における、ハロゲン原子、置換もしくは未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、および置換もしくは未置換の１価の芳香族複素環基は前述のものが挙げられる。 Here, in the general formulas [5] to [7], a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted Examples of the monovalent aliphatic heterocyclic group and the substituted or unsubstituted monovalent aromatic heterocyclic group include those described above.
ここで、１価の脂肪族炭化水素基、１価の芳香族炭化水素基、１価の脂肪族複素環基、１価の芳香族複素環基、２価の脂肪族炭化水素基、２価の芳香族炭化水素基、２価の脂肪族複素環基、および、２価の芳香族複素環基は置換されていても良い。その場合の置換基としては、前述の１価の脂肪族炭化水素基、１価の芳香族炭化水素基、１価の脂肪族複素環基、１価の芳香族複素環基、ハロゲン原子、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、置換アミノ基が挙げられる。 Here, monovalent aliphatic hydrocarbon group, monovalent aromatic hydrocarbon group, monovalent aliphatic heterocyclic group, monovalent aromatic heterocyclic group, divalent aliphatic hydrocarbon group, divalent The aromatic hydrocarbon group, divalent aliphatic heterocyclic group and divalent aromatic heterocyclic group may be substituted. In this case, examples of the substituent include the aforementioned monovalent aliphatic hydrocarbon group, monovalent aromatic hydrocarbon group, monovalent aliphatic heterocyclic group, monovalent aromatic heterocyclic group, halogen atom, cyano Group, substituted silyl group, alkoxyl group, aryloxy group, substituted amino group.
また、一般式［１］および［２］における、ｎおよびｍは、それぞれ独立に、１以上の整数を表す。ここで、ｎおよびｍは好ましくは１〜１０００であり、特に好ましくは１〜１００である。この理由として、分子量が大きいと、汎用性有機溶媒に溶解しづらくなる懸念があるためである。 In general formulas [1] and [2], n and m each independently represent an integer of 1 or more. Here, n and m are preferably 1-1000, particularly preferably 1-100. This is because if the molecular weight is large, there is a concern that it is difficult to dissolve in a general-purpose organic solvent.
本発明で用いられる一般式［１］で表される化合物の代表例を、以下の表１に示すが、本発明は、この代表例に限定されるものではない。 Representative examples of the compound represented by the general formula [1] used in the present invention are shown in the following Table 1, but the present invention is not limited to these representative examples.
本発明で用いられる一般式［２］で表される化合物の代表例を、以下の表２に示すが、本発明は、この代表例に限定されるものではない。 Representative examples of the compound represented by the general formula [2] used in the present invention are shown in Table 2 below, but the present invention is not limited to these representative examples.
尚、本発明における、湿式成膜法とは、塗布法、インクジェット法、ディップコート法、ダイコート法、スプレーコート法、スピンコート法、ロールコーター法、湿漬塗布法、スクリーン印刷法、フレキソ印刷、スクリーン印刷法、ＬＢ法等などにより、組成物を塗布して成膜するものである。 In the present invention, the wet film forming method is a coating method, an inkjet method, a dip coating method, a die coating method, a spray coating method, a spin coating method, a roll coater method, a dipping coating method, a screen printing method, flexographic printing, The composition is applied to form a film by a screen printing method, an LB method, or the like.
次に、有機ＥＬ素子用インキ組成物について説明する。 Next, the ink composition for organic EL elements will be described.
本発明における有機ＥＬ素子用インキ組成物は、少なくとも本発明の有機ＥＬ素子用材料と溶剤を含有する。 The ink composition for organic EL elements in the present invention contains at least the material for organic EL elements of the present invention and a solvent.
上記、有機ＥＬ素子用インキ組成物に含まれる溶剤としては種々の溶剤が適用可能であり、特に限定されない。例えば、トルエン、キシレン、メチシレン、シクロヘキシルベンゼン、テトラリン等の芳香族炭化水素；クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン等のハロゲン化芳香族炭化水素；１，２−ジメトキシベンゼン、１，３−ジメトキシベンゼン、アニソール、フェネトール、２−メトキシトルエン、３−メトキシトルエン、４−メトキシトルエン、２，３−ジメチルアニソール、２，４−ジメチルアニソール等の芳香族エーテル；酢酸フェニル、プロピオン酸フェニル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸ｎ−ブチル等の芳香族エステル；シクロヘキサノン、シクロオクタノン等の脂環を有するケトン；メチルエチルケトン、ジブチルケトン等の脂肪族ケトン；メチルエチルケトン、シクロヘキサノール、シクロオクタノール等の脂環を有するアルコール；ブタノール、ヘキサノール等の脂肪族アルコール；エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコール−１−モノメチルエーテルアセタート（ＰＧＭＥＡ）等の脂肪族エーテル；酢酸エチル、酢酸ｎ−ブチル、乳酸エチル、乳酸ｎ−ブチル等の脂肪族エステル等が挙げられる。 Various solvents are applicable as the solvent contained in the above-mentioned ink composition for organic EL elements, and are not particularly limited. For example, aromatic hydrocarbons such as toluene, xylene, methicylene, cyclohexylbenzene and tetralin; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and anisole , Phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and other aromatic ethers; phenyl acetate, phenyl propionate, methyl benzoate, benzoic acid Aromatic esters such as ethyl, propyl benzoate and n-butyl benzoate; ketones having an alicyclic ring such as cyclohexanone and cyclooctanone; aliphatic ketones such as methyl ethyl ketone and dibutyl ketone; methyl ethyl ketone and cyclohexano Alcohol having an alicyclic ring such as ruthenium or cyclooctanol; Aliphatic alcohol such as butanol or hexanol; Aliphatic ether such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether or propylene glycol-1-monomethyl ether acetate (PGMEA); Ethyl acetate And aliphatic esters such as n-butyl acetate, ethyl lactate and n-butyl lactate.
これらのうち、水の溶解度が低い点、容易には変質しない点で、トルエン、キシレン、メチシレン、シクロヘキシルベンゼン、テトラリン等の芳香族炭化水素が好ましい。 Of these, aromatic hydrocarbons such as toluene, xylene, methicylene, cyclohexylbenzene, tetralin and the like are preferable in that they have low water solubility and are not easily altered.
また、これらの溶媒は単独で使用しても複数混合して用いてもよい。尚、使用可能な溶媒はこれらに限定されるものではない。 These solvents may be used alone or in combination. In addition, the solvent which can be used is not limited to these.
有機電界発光素子には、陰極等の水分により著しく劣化する材料が多く使用されているため、組成物中の水分の存在は、乾燥後の膜中に水分が残留し、素子の特性を低下させる可能性が考えられ好ましくない。 Since organic electroluminescent devices use many materials such as cathodes that deteriorate significantly due to moisture, the presence of moisture in the composition causes moisture to remain in the dried film, degrading the device characteristics. The possibility is considered and it is not preferable.
また、湿式成膜時における組成物からの溶剤蒸発による、成膜安定性の低下を低減するためには、有機ＥＬ素子用組成物の溶剤として、沸点が１００℃以上、好ましくは沸点が１５０℃以上、より好ましくは沸点が２００℃以上の溶剤を用いることが効果的である。 Further, in order to reduce a decrease in film formation stability due to solvent evaporation from the composition during wet film formation, the boiling point is 100 ° C. or higher, preferably 150 ° C. as the solvent of the composition for organic EL elements. As described above, it is more effective to use a solvent having a boiling point of 200 ° C. or higher.
本発明の有機ＥＬ素子用インキ組成物は、発光材料が低分子材料であって、湿式成膜法によりこの発光材料を含有する層が形成される有機ＥＬ発光素子に用いられることが好ましい。 The ink composition for an organic EL element of the present invention is preferably used for an organic EL light emitting element in which a light emitting material is a low molecular material and a layer containing the light emitting material is formed by a wet film forming method.
本発明の有機ＥＬ素子用インキ組成物は、主に、発光材料を含有させ、発光層を形成するために用いられるが、正孔輸送層などの他の層に用いてもよい。 The ink composition for organic EL elements of the present invention is mainly used for containing a light emitting material and forming a light emitting layer, but may be used for other layers such as a hole transport layer.
本発明においては、本発明の目的が損なわれない範囲で、所望により発光層に本発明のインキ組成物に、他の公知の発光材料を含有させても良く、また、本発明の組成物を湿式成膜法により成膜した発光層に、他の公知の発光材料を含む発光層を積層しても良い。尚、この場合、他の公知の発光材料を含む発光層は真空蒸着法等の乾式法で形成してもよい。 In the present invention, as long as the object of the present invention is not impaired, the ink composition of the present invention may optionally contain other known light-emitting materials in the light emitting layer. A light-emitting layer containing another known light-emitting material may be stacked on the light-emitting layer formed by a wet film formation method. In this case, the light emitting layer containing another known light emitting material may be formed by a dry method such as a vacuum evaporation method.
本発明の有機ＥＬ素子用インキ組成物は、本発明の有機ＥＬ素子用材料の含有量が０．５ｗｔ％以上であることが好ましい。通常、有機ＥＬ素子の発光層膜厚は１０〜１００ｎｍであるが、一般的には５０ｎｍ以上の場合が多い。５０ｎｍよりも薄い膜厚になると発光性能の低下や大幅な色調のずれ等の不具合を生じてしまう。５０ｎｍ以上の膜厚を容易に形成するには０．５ｗｔ％以上の溶液濃度であることが好ましい。０．５ｗｔ％よりも濃度が低い場合は厚膜形成が困難となる。 In the organic EL element ink composition of the present invention, the content of the organic EL element material of the present invention is preferably 0.5 wt% or more. Usually, the thickness of the light-emitting layer of the organic EL element is 10 to 100 nm, but generally it is often 50 nm or more. When the film thickness is less than 50 nm, problems such as a decrease in light emission performance and a large color tone deviation occur. In order to easily form a film thickness of 50 nm or more, the solution concentration is preferably 0.5 wt% or more. When the concentration is lower than 0.5 wt%, it is difficult to form a thick film.
本発明の有機ＥＬ素子用インキ組成物には、上述した有機ＥＬ素子用材料と溶剤の他に、必要に応じて公知の添加剤を添加してもよい。 In addition to the organic EL element material and solvent described above, a known additive may be added to the ink composition for an organic EL element of the present invention as necessary.
本発明の有機ＥＬ素子用インキ組成物は、公知の湿式成膜法、例えば、塗布法、インクジェット法、ディップコート法、ダイコート法、スプレーコート法、スピンコート法、ロールコーター法、湿漬塗布法、スクリーン印刷法、フレキソ印刷、スクリーン印刷法、ＬＢ法等により成膜できる。 The ink composition for an organic EL device of the present invention is a known wet film forming method, for example, a coating method, an inkjet method, a dip coating method, a die coating method, a spray coating method, a spin coating method, a roll coater method, a dipping coating method. The film can be formed by a screen printing method, a flexographic printing method, a screen printing method, an LB method, or the like.
ここで、本発明の化合物からなる有機エレクトロルミネッセンス素子用材料を用いて作成することができる有機ＥＬ素子について詳細に説明する。 Here, the organic EL element which can be produced using the organic electroluminescent element material comprising the compound of the present invention will be described in detail.
有機ＥＬ素子は、陽極と陰極間に一層または多層の有機層を形成した素子から構成されるが、ここで、一層型有機ＥＬ素子とは、陽極と陰極との間に発光層のみからなる素子を指す。一方、多層型有機ＥＬ素子とは、発光層の他に、発光層への正孔や電子の注入を容易にしたり、発光層内での正孔と電子との再結合を円滑に行わせたりすることを目的として、正孔注入層、正孔輸送層、正孔阻止層、電子注入層などを積層させたものを指す。また、発光層と陽極との間で発光層に隣接して存在し、発光層と陽極、又は発光層と、正孔注入層若しくは正孔輸送層とを隔離する役割をもつ層であるインターレイヤー層を挿入しても良い。したがって、多層型有機ＥＬ素子の代表的な素子構成としては、（１）陽極／正孔注入層／発光層／陰極、（２）陽極／正孔注入層／正孔輸送層／発光層／陰極、（３）陽極／正孔注入層／発光層／電子注入層／陰極、（４）陽極／正孔注入層／正孔輸送層／発光層／電子注入層／陰極、（５）陽極／正孔注入層／発光層／正孔阻止層／電子注入層／陰極、（６）陽極／正孔注入層／正孔輸送層／発光層／正孔阻止層／電子注入層／陰極、（７）陽極／発光層／正孔阻止層／電子注入層／陰極、（８）陽極／発光層／電子注入層／陰極（９）陽極／正孔注入層／正孔輸送層／インターレイヤー層／発光層／陰極、（１０）陽極／正孔注入層／インターレイヤー層／発光層／電子注入層／陰極、（１１）陽極／正孔注入層／正孔輸送層／インターレイヤー層／発光層／電子注入層／陰極、等の多層構成で積層した素子構成が考えられる。 The organic EL element is composed of an element in which a single layer or a multilayer organic layer is formed between an anode and a cathode. Here, the single layer type organic EL element is an element composed of only a light emitting layer between an anode and a cathode. Point to. On the other hand, the multilayer organic EL element facilitates injection of holes and electrons into the light emitting layer in addition to the light emitting layer, and facilitates recombination of holes and electrons in the light emitting layer. For the purpose of this, it refers to a layer in which a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, and the like are laminated. Further, an interlayer that is adjacent to the light emitting layer between the light emitting layer and the anode and has a role of separating the light emitting layer and the anode or the light emitting layer from the hole injection layer or the hole transport layer. Layers may be inserted. Therefore, typical element configurations of the multilayer organic EL element include (1) anode / hole injection layer / light emitting layer / cathode, and (2) anode / hole injection layer / hole transport layer / light emitting layer / cathode. (3) Anode / hole injection layer / light emitting layer / electron injection layer / cathode, (4) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, (5) Anode / positive Hole injection layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (6) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (7) Anode / light emitting layer / hole blocking layer / electron injection layer / cathode, (8) anode / light emitting layer / electron injection layer / cathode (9) anode / hole injection layer / hole transport layer / interlayer layer / light emitting layer / Cathode, (10) anode / hole injection layer / interlayer layer / light emitting layer / electron injection layer / cathode, (11) anode / hole injection layer / hole transport layer / inter layer Layer / light emitting layer / electron injection layer / cathode, an element formed by laminating a multilayer structure etc. can be considered.
また、上述した各有機層は、それぞれ二層以上の層構成により形成されても良く、いくつかの層が繰り返し積層されていても良い。そのような例として、近年、光取り出し効率の向上を目的に、上述の多層型有機ＥＬ素子の一部の層を多層化する「マルチ・フォトン・エミッション」と呼ばれる素子構成が提案されている。これは例えば、ガラス基板／陽極／正孔輸送層／電子輸送性発光層／電子注入層／電荷発生層／発光ユニット／陰極から構成される有機ＥＬ素子に於いて、電荷発生層と発光ユニットの部分を複数層積層するといった方法が挙げられる。 Moreover, each organic layer mentioned above may be formed by the layer structure of two or more layers, respectively, and several layers may be laminated | stacked repeatedly. As such an example, an element configuration called “multi-photon emission” in which a part of the above-described multilayer organic EL element is multilayered has been proposed in recent years for the purpose of improving light extraction efficiency. For example, in an organic EL device composed of a glass substrate / anode / hole transport layer / electron transporting light emitting layer / electron injection layer / charge generating layer / light emitting unit / cathode, the charge generating layer and the light emitting unit There is a method of laminating a plurality of portions.
本発明の有機ＥＬ素子を作製する方法については、上記の材料および方法により陽極、発光層、必要に応じて正孔注入層、および必要に応じて電子注入層を形成し、最後に陰極を形成すればよい。また、陰極から陽極へ、前記と逆の順序で有機ＥＬ素子を作製することもできる。 Regarding the method for producing the organic EL device of the present invention, an anode, a light emitting layer, a hole injection layer as necessary, and an electron injection layer as necessary are formed by the above materials and methods, and finally a cathode is formed. do it. Moreover, an organic EL element can also be produced from the cathode to the anode in the reverse order.
この有機ＥＬ素子は、透光性の基板上に作製する。この透光性基板は有機ＥＬ素子を支持する基板であり、その透光性については、４００〜７００ｎｍの可視領域の光の透過率が５０％以上、好ましくは９０％以上であるものが望ましく、さらに平滑な基板を用いるのが好ましい。 This organic EL element is manufactured on a translucent substrate. This translucent substrate is a substrate that supports the organic EL element, and for the translucency, it is desirable that the transmittance of light in the visible region of 400 to 700 nm is 50% or more, preferably 90% or more, Further, it is preferable to use a smooth substrate.
これら基板は、機械的、熱的強度を有し、透明であれば特に限定されるものではないが、例えば、ガラス板、合成樹脂板などが好適に用いられる。ガラス板としては、特にソーダ石灰ガラス、バリウム・ストロンチウム含有ガラス、鉛ガラス、アルミノケイ酸ガラス、ホウケイ酸ガラス、バリウムホウケイ酸ガラス、石英などで成形された板が挙げられる。また、合成樹脂板としては、ポリカーボネート樹脂、アクリル樹脂、ポリエチレンテレフタレート樹脂、ポリエーテルサルファイド樹脂、ポリサルフォン樹脂などの板が挙げられる。 These substrates have mechanical and thermal strengths and are not particularly limited as long as they are transparent. For example, glass plates, synthetic resin plates and the like are preferably used. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the synthetic resin plate include plates such as polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, and polysulfone resin.
本発明の有機ＥＬ素子の各層の形成方法としては、真空蒸着、電子線ビーム照射、スパッタリング、プラズマ、イオンプレーティング等の乾式成膜法、もしくはスピンコーティング、ディッピング、フローコーティング等の湿式成膜法のいずれかの方法を適用することができる。また、特表２００２−５３４７８２や、Ｓ．Ｔ．Ｌｅｅ， ｅｔ ａｌ．， Ｐｒｏｃｅｅｄｉｎｇｓ ｏｆ ＳＩＤ’０２， ｐ．７８４（２００２）に記載されているＬＩＴＩ（Ｌａｓｅｒ Ｉｎｄｕｃｅｄ Ｔｈｅｒｍａｌ Ｉｍａｇｉｎｇ、レーザー熱転写）法や、印刷（オフセット印刷、フレキソ印刷、グラビア印刷、スクリーン印刷）、インクジェット等の方法を適用することもできる。 As a method for forming each layer of the organic EL element of the present invention, a dry film forming method such as vacuum deposition, electron beam irradiation, sputtering, plasma, ion plating, or a wet film forming method such as spin coating, dipping, or flow coating is used. Either method can be applied. In addition, Special Table 2002-53482, S.I. T.A. Lee, et al. , Proceedings of SID'02, p. LITI (Laser Induced Thermal Imaging) method described in 784 (2002), printing (offset printing, flexographic printing, gravure printing, screen printing), inkjet, and the like can also be applied.
有機層は、特に分子堆積膜であることが好ましい。ここで分子堆積膜とは、気相状態の材料化合物から沈着され形成された薄膜や、溶液状態または液相状態の材料化合物から固体化され形成された膜のことであり、通常この分子堆積膜は、ＬＢ法により形成された薄膜（分子累積膜）とは凝集構造、高次構造の相違や、それに起因する機能的な相違により区分することができる。また特開昭５７−５１７８１号公報に開示されているように、樹脂等の結着剤と材料化合物とを溶剤に溶かして溶液とした後、これをスピンコート法等により薄膜化することによっても、有機層を形成することができる。各層の膜厚は特に限定されるものではないが、膜厚が厚すぎると一定の光出力を得るために大きな印加電圧が必要となり効率が悪くなり、逆に膜厚が薄すぎるとピンホール等が発生し、電界を印加しても充分な発光輝度が得にくくなる。したがって、各層の膜厚は、１ｎｍから１μｍの範囲が適しているが、１０ｎｍから０．２μｍの範囲がより好ましい。 The organic layer is particularly preferably a molecular deposited film. Here, the molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidifying from a material compound in a solution state or a liquid phase state. Can be classified from a thin film (accumulated film) formed by the LB method according to a difference in an agglomerated structure and a higher-order structure and a functional difference resulting therefrom. Further, as disclosed in JP-A-57-51781, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, which is then thinned by a spin coat method or the like. An organic layer can be formed. The film thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Conversely, if the film thickness is too thin, pinholes, etc. And it becomes difficult to obtain sufficient light emission luminance even when an electric field is applied. Accordingly, the thickness of each layer is suitably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.
また、有機ＥＬ素子の温度、湿度、雰囲気等に対する安定性向上のために、素子の表面に保護層を設けたり、樹脂等により素子全体を被覆や封止を施したりしても良い。特に素子全体を被覆や封止する際には、光によって硬化する光硬化性樹脂が好適に使用される。 Further, in order to improve the stability of the organic EL element with respect to temperature, humidity, atmosphere and the like, a protective layer may be provided on the surface of the element, or the entire element may be covered or sealed with a resin or the like. In particular, when the entire element is covered or sealed, a photocurable resin that is cured by light is preferably used.
本発明の有機ＥＬ素子に印加する電流は通常、直流であるが、パルス電流や交流を用いてもよい。電流値、電圧値は、素子破壊しない範囲内であれば特に制限はないが、素子の消費電力や寿命を考慮すると、なるべく小さい電気エネルギーで効率良く発光させることが望ましい。 The current applied to the organic EL element of the present invention is usually a direct current, but a pulse current or an alternating current may be used. The current value and the voltage value are not particularly limited as long as the element is within a range not destroying the element. However, considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electrical energy as possible.
本発明の有機ＥＬ素子の駆動方法は、パッシブマトリクス法のみならず、アクティブマトリックス法での駆動も可能である。また、本発明の有機ＥＬ素子から光を取り出す方法としては、陽極側から光を取り出すボトム・エミッションという方法のみならず、陰極側から光を取り出すトップ・エミッションという方法にも適用可能である。これらの方法や技術は、城戸淳二著、「有機ＥＬのすべて」、日本実業出版社（２００３年発行）に記載されている。 The organic EL device driving method of the present invention can be driven not only by the passive matrix method but also by the active matrix method. Further, the method for extracting light from the organic EL device of the present invention is applicable not only to the method of bottom emission for extracting light from the anode side but also to the method of top emission for extracting light from the cathode side. These methods and techniques are described in Shinji Kido, “All about organic EL”, published by Nihon Jitsugyo Shuppansha (published in 2003).
本発明の有機ＥＬ素子のフルカラー化方式の主な方式としては、３色塗り分け方式、色変換方式、カラーフィルター方式が挙げられる。３色塗り分け方式では、シャドウマスクを使った蒸着法や、インクジェット法や印刷法が挙げられる。また、特表２００２−５３４７８２や、Ｓ．Ｔ．Ｌｅｅ， ｅｔ ａｌ．， Ｐｒｏｃｅｅｄｉｎｇｓ ｏｆ ＳＩＤ’０２， ｐ．７８４（２００２）に記載されているレーザー熱転写法（Ｌａｓｅｒ Ｉｎｄｕｃｅｄ Ｔｈｅｒｍａｌ Ｉｍａｇｉｎｇ、ＬＩＴＩ法ともいわれる）も用いることができる。色変換方式では、青色発光の発光層を使って、蛍光色素を分散した色変換（ＣＣＭ）層を通して、青色より長波長の緑色と赤色に変換する方法である。カラーフィルター方式では、白色発光の有機ＥＬ素子を使って、液晶用カラーフィルターを通して３原色の光を取り出す方法であるが、これら３原色に加えて、一部白色光をそのまま取り出して発光に利用することで、素子全体の発光効率をあげることもできる。 Examples of the main method of full colorization of the organic EL device of the present invention include a three-color coating method, a color conversion method, and a color filter method. In the three-color coating method, an evaporation method using a shadow mask, an ink jet method, and a printing method can be used. In addition, Special Table 2002-53482, S.I. T.A. Lee, et al. , Proceedings of SID'02, p. 784 (2002) can also be used. The laser thermal transfer method (also referred to as Laser Induced Thermal Imaging, LITI method) can also be used. In the color conversion method, a blue light emitting layer is used to convert green and red having a longer wavelength than blue through a color conversion (CCM) layer in which fluorescent dyes are dispersed. The color filter method uses a white light emitting organic EL element to extract light of three primary colors through a color filter for liquid crystal. In addition to these three primary colors, a part of white light is directly extracted and used for light emission. Thus, the luminous efficiency of the entire device can be increased.
さらに、本発明の有機ＥＬ素子は、マイクロキャビティ構造を採用しても構わない。これは、有機ＥＬ素子は、発光層が陽極と陰極との間に挟持された構造であり、発光した光は陽極と陰極との間で多重干渉を生じるが、陽極及び陰極の反射率、透過率などの光学的な特性と、これらに挟持された有機層の膜厚とを適当に選ぶことにより、多重干渉効果を積極的に利用し、素子より取り出される発光波長を制御するという技術である。これにより、発光色度を改善することも可能となる。この多重干渉効果のメカニズムについては、Ｊ．Ｙａｍａｄａ等によるＡＭ−ＬＣＤ Ｄｉｇｅｓｔ ｏｆ Ｔｅｃｈｎｉｃａｌ Ｐａｐｅｒｓ，ＯＤ−２，ｐ．７７〜８０（２００２）に記載されている。 Furthermore, the organic EL element of the present invention may adopt a microcavity structure. This is because the organic EL element has a structure in which the light emitting layer is sandwiched between the anode and the cathode, and the emitted light causes multiple interference between the anode and the cathode, but the reflectance and transmission of the anode and the cathode. This is a technology that actively uses the multiple interference effect and controls the emission wavelength extracted from the device by appropriately selecting the optical characteristics such as the rate and the film thickness of the organic layer sandwiched between them. . Thereby, it is also possible to improve the emission chromaticity. For the mechanism of this multiple interference effect, see J.A. Yamada et al., AM-LCD Digest of Technical Papers, OD-2, p. 77-80 (2002).
以上述べたように、本発明の有機エレクトロルミネッセンス素子用材料を用いた有機ＥＬ素子は、低い駆動電圧で長時間の青色発光を得ることが可能である。故に、本有機ＥＬ素子は、壁掛けテレビ等のフラットパネルディスプレイや各種の平面発光体として、さらには、複写機やプリンター等の光源、液晶ディスプレイや計器類等の光源、表示板、標識灯等への応用が考えられる。 As described above, the organic EL element using the organic electroluminescence element material of the present invention can obtain long-term blue light emission at a low driving voltage. Therefore, this organic EL device can be used as a flat panel display such as a wall-mounted television and various flat light emitters, as well as a light source such as a copying machine or a printer, a light source such as a liquid crystal display or an instrument, a display board, a marker lamp, etc. Can be applied.
以下、本発明を実施例で説明するが、本発明はこれら実施例になんら限定されるものではない。なお、以下の製造例、実施例、比較例の説明中、部は重量部、％ は重量％ を表す。また、以下の製造例においては、赤外線吸収スペクトル（ＩＲ）は、パーキンエルマー社製Ｓｐｅｃｔｒｕｍ Ｏｎｅ Ｖｅｒ．Ａ フーリエ変換赤外線分光分析装置を用いて測定した。また、ＮＭＲスペクトルは、日本電子社製ＧＳＸ２７０ ＦＴ−ＮＭＲ分析装置を用いて測定した。さらに、ＧＰＣ分析は、東ソー社製ＧＰＣ−８０２０（カラム：ＴＳＫｇｅｌ Ｍｕｌｔｉｐｏｒｅ−Ｈ）を用いて測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples at all. In the following description of production examples, examples and comparative examples, parts represent parts by weight and% represents% by weight. Further, in the following production examples, infrared absorption spectrum (IR) is measured by Perkin Elmer Spectrum One Ver. A It measured using the Fourier-transform infrared spectroscopy analyzer. Further, the NMR spectrum was measured using a GSX270 FT-NMR analyzer manufactured by JEOL. Furthermore, GPC analysis was measured using GPC-8020 (column: TSKgel Multipore-H) manufactured by Tosoh Corporation.
実施例１
化合物（１）の合成方法
反応式（１−１）〜（１−３）を用いて化合物（１）を合成した。
Example 1
Method for Synthesizing Compound (1) Compound (1) was synthesized using reaction formulas (1-1) to (1-3).
反応式（１−１）
Reaction formula (1-1)
（反応式（１−１）中、Ｒ1およびＲ2は、それぞれ独立に、水素原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基を表し、Ｒ3〜Ｒ7は、それぞれ独立に、水素原子、ハロゲン原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、Ｒ3〜Ｒ7は、隣接した基が互いに結合して環を形成しても良い。ｎは、それぞれ独立に、１以上の整数を表す。） (In Reaction Formula (1-1), R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon. Represents a group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, and R 3 to R 7 each independently represents a hydrogen atom, a halogen atom, a substituted Or an unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic Represents a heterocyclic group, a cyano group, a substituted silyl group, an alkoxyl group, an aryloxy group, or a substituted amino group, and R 3 to R 7 may be bonded to each other to form a ring. N independently represents an integer of 1 or more.)
反応式（１−２）
Reaction formula (1-2)
（反応式（１−２）中、Ｒ1およびＲ2は、それぞれ独立に、水素原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基を表し、Ｒ3〜Ｒ7は、それぞれ独立に、水素原子、ハロゲン原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、Ｒ8は、置換または未置換の２価の脂肪族炭化水素基、置換もしくは未置換の２価の芳香族炭化水素基、置換もしくは未置換の２価の脂肪族複素環基、置換もしくは未置換の２価の芳香族複素環基を表し、Ｒ9は、水素原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基を表し、Ｘは、直接結合、酸素原子、硫黄原子を表し、Ｒ3〜Ｒ7は、隣接した基が互いに結合して環を形成しても良い。ｎは、それぞれ独立に、１以上の整数を表す。） (In Reaction Formula (1-2), R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon. Represents a group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, and R 3 to R 7 each independently represents a hydrogen atom, a halogen atom, a substituted Or an unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic Represents a heterocyclic group, a cyano group, a substituted silyl group, an alkoxyl group, an aryloxy group, or a substituted amino group, and R 8 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, substituted or unsubstituted A divalent aromatic hydrocarbon group, substituted or unsubstituted 2 Aliphatic heterocyclic group, a divalent aromatic heterocyclic group or a substituted or unsubstituted, R 9 is a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted 1 Represents a divalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, and X represents a direct bond, an oxygen atom, or a sulfur atom. And each of R 3 to R 7 may be bonded to each other to form a ring, and each n independently represents an integer of 1 or more.)
反応式（１−３）
（反応式（１−３）中、Ｒ1およびＲ2は、それぞれ独立に、水素原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基を表し、Ｒ3〜Ｒ7は、それぞれ独立に、水素原子、ハロゲン原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、Ｒ8は、置換または未置換の２価の脂肪族炭化水素基、置換もしくは未置換の２価の芳香族炭化水素基、置換もしくは未置換の２価の脂肪族複素環基、置換もしくは未置換の２価の芳香族複素環基を表し、Ｒ9は、水素原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基を表し、Ｘは、直接結合、酸素原子、硫黄原子を表し、Ｒ10〜Ｒ14は、それぞれ独立に、水素原子、ハロゲン原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、Ｒ3〜Ｒ7、Ｒ10〜Ｒ14は、隣接した基が互いに結合して環を形成しても良い。ｎは、それぞれ独立に、１以上の整数を表す。） (In the reaction formula (1-3), R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon. Represents a group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, and R 3 to R 7 each independently represents a hydrogen atom, a halogen atom, a substituted Or an unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic Represents a heterocyclic group, a cyano group, a substituted silyl group, an alkoxyl group, an aryloxy group, or a substituted amino group, and R 8 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, substituted or unsubstituted A divalent aromatic hydrocarbon group, substituted or unsubstituted 2 Aliphatic heterocyclic group, a divalent aromatic heterocyclic group or a substituted or unsubstituted, R 9 is a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted 1 Represents a divalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, and X represents a direct bond, an oxygen atom, or a sulfur atom. R 10 to R 14 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, substituted or unsubstituted monovalent aliphatic heterocyclic group substituted, substituted or unsubstituted monovalent aromatic heterocyclic group, a cyano group, a substituted silyl group, an alkoxyl group, ant - aryloxy group, or a substituted amino group, R 3 to R 7, R 10 to R 14 are joined to the adjacent groups from one another May be formed .n each independently represents an integer of 1 or more.)
実施例２
化合物（４１）の合成方法
反応式（２−１）〜（２−２）を用いて化合物（２）を合成した。
Example 2
Method for Synthesizing Compound (41) Compound (2) was synthesized using reaction formulas (2-1) to (2-2).
反応式（２−１）
（反応式（２−１）中、Ｒ1およびＲ2は、それぞれ独立に、水素原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基を表し、Ｒ3〜Ｒ7は、それぞれ独立に、水素原子、ハロゲン原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、Ｒ3〜Ｒ7は、隣接した基が互いに結合して環を形成しても良い。ｍは、それぞれ独立に、１以上の整数を表す。） (In Reaction Formula (2-1), R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon. Represents a group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, and R 3 to R 7 each independently represents a hydrogen atom, a halogen atom, a substituted Or an unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic Represents a heterocyclic group, a cyano group, a substituted silyl group, an alkoxyl group, an aryloxy group, or a substituted amino group, and R 3 to R 7 may be bonded to each other to form a ring. M represents an integer of 1 or more independently.)
反応式（２−２）
（反応式（２−２）中、Ｒ1およびＲ2は、それぞれ独立に、水素原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基を表し、Ｒ3〜Ｒ7は、それぞれ独立に、水素原子、ハロゲン原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、Ｒ10は、置換または未置換の２価の脂肪族炭化水素基、置換もしくは未置換の２価の芳香族炭化水素基、置換もしくは未置換の２価の脂肪族複素環基、置換もしくは未置換の２価の芳香族複素環基を表し、Ｒ11は、水素原子、置換または未置換の１価の脂肪族炭化水素基、置換もしくは未置換の１価の芳香族炭化水素基、置換もしくは未置換の１価の脂肪族複素環基、置換もしくは未置換の１価の芳香族複素環基を表し、Ｘは、直接結合、酸素原子、硫黄原子を表し、Ｒ3〜Ｒ7は、隣接した基が互いに結合して環を形成しても良い。ｍは、それぞれ独立に、１以上の整数を表す。） (In Reaction Formula (2-2), R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, or a substituted or unsubstituted monovalent aromatic hydrocarbon. Represents a group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, and R 3 to R 7 each independently represents a hydrogen atom, a halogen atom, a substituted Or an unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic Represents a heterocyclic group, a cyano group, a substituted silyl group, an alkoxyl group, an aryloxy group, or a substituted amino group, and R 10 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, substituted or unsubstituted A divalent aromatic hydrocarbon group, substituted or unsubstituted 2 Aliphatic heterocyclic group, a divalent aromatic heterocyclic group or a substituted or unsubstituted, R 11 is a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted 1 Represents a divalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, and X represents a direct bond, an oxygen atom, or a sulfur atom. And each of R 3 to R 7 may be bonded to each other to form a ring, and each m independently represents an integer of 1 or more.)
実施例３〜４０ Examples 3-40
上記に示す反応式（１−１）〜（１−３）または、反応式（２−１）〜（２−２）を組み合わせて、表３および表４に示す化合物を合成した。 The compounds shown in Table 3 and Table 4 were synthesized by combining the reaction formulas (1-1) to (1-3) or the reaction formulas (2-1) to (2-2) shown above.
実施例１〜４０のＧＰＣによる分子量測定結果を表３および表４に示す。また、実施例１の化合物のＩＲスペクトルを図１に示す。 The results of molecular weight measurement by GPC in Examples 1 to 40 are shown in Table 3 and Table 4. The IR spectrum of the compound of Example 1 is shown in FIG.
有機ＥＬ素子の実施例
以下、本発明の化合物を有機ＥＬ素子用材料として用いた有機ＥＬ素子について下記実施例により説明するが、本発明は下記実施例に限定されるものではない。実施例においては、特に断りのない限り、混合比は全て重量比を示す。蒸着（真空蒸着）は１０-6Ｔｏｒｒの真空中にて、基板の加熱や冷却といった温度制御はしない条件下で行った。また、素子の発光特性は、発光素子面積２ｍｍ×２ｍｍの有機ＥＬ素子を用いて特性を測定した。
Examples of Organic EL Device Hereinafter, organic EL devices using the compound of the present invention as a material for organic EL devices will be described with reference to the following examples, but the present invention is not limited to the following examples. In the examples, all mixing ratios are weight ratios unless otherwise specified. Vapor deposition (vacuum deposition) was performed in a vacuum of 10 −6 Torr under conditions where temperature control such as heating and cooling of the substrate was not performed. The light emission characteristics of the element were measured using an organic EL element having a light emitting element area of 2 mm × 2 mm.
実施例８１
洗浄したＩＴＯ電極付きガラス板上に、ＰＥＤＯＴ／ＰＳＳ（ポリ(３，４−エチレンジオキシ)−２，５−チオフェン／ポリスチレンスルホン酸、Ｂａｙｅｒ社製ＢＡＹＴＲＯＮ Ｐ ＶＰ ＣＨ８０００）をスピンコート法にて製膜し、２００℃乾燥により、膜厚６０ｎｍの正孔注入層を得た。次いで、本発明の表３中の実施例（１）を０．５ｗｔ％の濃度でトルエンに溶解させ、スピンコーティング法により２０ｎｍの膜厚の正孔輸送層を製膜し、２００℃にて重合させた。ついで、以下に示す化合物（Ａ）を、１．０ｗｔ％の濃度でトルエンに溶解させ、スピンコーティング法により４０ｎｍの膜厚の発光層を製膜し、１００℃にて乾燥させた。さらにその上に、以下に示す化合物（Ｂ）を、真空蒸着して膜厚２０ｎｍの電子注入層を作成し、その上に、まずフッ化リチウムを１ｎｍ、次いでアルミニウム（Ａｌ）を１５０ｎｍ蒸着して電極を形成し、有機ＥＬ素子を得た。この素子について通電試験を行ったところ、最大発光輝度３５０ｃｄ／ｍ2の青色発光が得られた。この素子を６Ｖに駆動させた際の色度は、ＣＩＥ（ｘ，ｙ）＝（０．１４，０．１０）の青色発光であった。この素子を発光輝度５００（ｃｄ／ｍ2）で室温にて定電流駆動したときの輝度半減寿命を測定した。また、電流密度１２．５ｍＡ／ｃｍ2で駆動させた時の初期輝度、および６０℃の環境で１００時間連続駆動させた後の輝度を測定した。結果を表５に示す。
Example 81
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid, BAYTRON P VP CH8000 manufactured by Bayer) manufactured on a cleaned glass plate with an ITO electrode by a spin coating method Then, a hole injection layer having a film thickness of 60 nm was obtained by drying at 200 ° C. Next, Example (1) in Table 3 of the present invention was dissolved in toluene at a concentration of 0.5 wt%, a 20 nm thick hole transport layer was formed by spin coating, and polymerized at 200 ° C. I let you. Next, the compound (A) shown below was dissolved in toluene at a concentration of 1.0 wt%, a light emitting layer having a thickness of 40 nm was formed by spin coating, and dried at 100 ° C. Further, a compound (B) shown below is vacuum-deposited thereon to form an electron injection layer having a film thickness of 20 nm, and then 1 nm of lithium fluoride and then 150 nm of aluminum (Al) are vapor-deposited thereon. An electrode was formed to obtain an organic EL element. When this device was subjected to a current test, blue light emission with a maximum light emission luminance of 350 cd / m 2 was obtained. The chromaticity when this device was driven to 6 V was blue light emission of CIE (x, y) = (0.14, 0.10). The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ) was measured. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 5.
実施例８２〜１２０
表３中の実施例１のかわりに、表３、表４に示す実施例化合物を用いて発光層を作成した以外は実施例８１と同様に素子を作成した。この素子を発光輝度５００（ｃｄ／ｍ2）で室温にて定電流駆動したときの輝度半減寿命を測定した。また、電流密度１２．５ｍＡ／ｃｍ2で駆動させた時の初期輝度、および６０℃の環境で１００時間連続駆動させた後の輝度を測定した。結果を表５に示す。
Examples 82-120
A device was prepared in the same manner as in Example 81 except that a light emitting layer was prepared using the example compounds shown in Tables 3 and 4 instead of Example 1 in Table 3. The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ) was measured. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 5.
比較例１
実施例１において、正孔輸送層を製膜しない以外は、実施例１と同様に素子を作成した。この素子を６Ｖに駆動させた際の色度は、ＣＩＥ（ｘ，ｙ）＝（０．１５，０．１３）の青色発光であった。この素子を発光輝度５００（ｃｄ／ｍ2）で室温にて定電流駆動したときの輝度と半減寿命を測定した。また、電流密度１２．５ｍＡ／ｃｍ2で駆動させた時の初期輝度、および６０℃の環境で１００時間連続駆動させた後の輝度を測定した。結果を表５に示す。
Comparative Example 1
In Example 1, an element was prepared in the same manner as in Example 1 except that the hole transport layer was not formed. The chromaticity when this device was driven to 6 V was blue light emission of CIE (x, y) = (0.15, 0.13). The device was measured for luminance and half-life when the device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ). Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 5.
表５
表５から明らかなように、本発明の化合物はいずれも、比較例１で作成した素子よりも、長寿命で且つ、高い輝度が得られた。 As is apparent from Table 5, all the compounds of the present invention had a longer lifetime and higher luminance than the device prepared in Comparative Example 1.
実施例１２１
洗浄したＩＴＯ電極付きガラス板上に、ＰＥＤＯＴ／ＰＳＳ（ポリ(３，４−エチレンジオキシ)−２，５−チオフェン／ポリスチレンスルホン酸、Ｂａｙｅｒ社製ＢＡＹＴＲＯＮ Ｐ ＶＰ ＣＨ８０００）をスピンコート法にて製膜し、２００℃乾燥により、膜厚６０ｎｍの正孔注入層を得た。次いで、本発明の表３中の実施例（１）を０．５ｗｔ％の濃度でトルエンに溶解させ、スピンコーティング法により２０ｎｍの膜厚の正孔輸送層を製膜し、２００℃にて重合させた。ついで、以下に示す化合物（Ｃ）と化合物（Ｄ）を、９８：２の割合で１．０ｗｔ％の濃度でトルエンに溶解させ、スピンコーティング法により４０ｎｍの膜厚の発光層を製膜し、１００℃にて乾燥させた。さらにその上に、以下に示す化合物（Ｂ）を、真空蒸着して膜厚２０ｎｍの電子注入層を作成し、その上に、まずフッ化リチウムを１ｎｍ、次いでアルミニウム（Ａｌ）を１５０ｎｍ蒸着して電極を形成し、有機ＥＬ素子を得た。この素子について通電試験を行ったところ、最大発光輝度６９０ｃｄ／ｍ2の青色発光が得られた。この素子を６Ｖに駆動させた際の色度は、ＣＩＥ（ｘ，ｙ）＝（０．１４，０．１２）の青色発光であった。この素子を発光輝度５００（ｃｄ／ｍ2）で室温にて定電流駆動したときの輝度半減寿命を測定した。また、電流密度１２．５ｍＡ／ｃｍ2で駆動させた時の初期輝度、および６０℃の環境で１００時間連続駆動させた後の輝度を測定した。結果を表６に示す。
Example 121
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid, BAYTRON P VP CH8000 manufactured by Bayer) manufactured on a cleaned glass plate with an ITO electrode by a spin coating method Then, a hole injection layer having a film thickness of 60 nm was obtained by drying at 200 ° C. Next, Example (1) in Table 3 of the present invention was dissolved in toluene at a concentration of 0.5 wt%, a 20 nm thick hole transport layer was formed by spin coating, and polymerized at 200 ° C. I let you. Next, the compound (C) and the compound (D) shown below were dissolved in toluene at a concentration of 1.0 wt% at a ratio of 98: 2, and a light emitting layer having a thickness of 40 nm was formed by a spin coating method. Dried at 100 ° C. Further, a compound (B) shown below is vacuum-deposited thereon to form an electron injection layer having a film thickness of 20 nm, and then 1 nm of lithium fluoride and then 150 nm of aluminum (Al) are vapor-deposited thereon. An electrode was formed to obtain an organic EL element. When this device was subjected to an energization test, blue light emission with a maximum light emission luminance of 690 cd / m 2 was obtained. The chromaticity when this element was driven to 6 V was blue light emission of CIE (x, y) = (0.14, 0.12). The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ) was measured. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 6.
実施例１２２〜１６０
表３中の実施例１のかわりに、表３、表４に示す実施例化合物を用いて発光層を作成した以外は実施例１２１と同様に素子を作成した。この素子を発光輝度５００（ｃｄ／ｍ2）で室温にて定電流駆動したときの輝度半減寿命を測定した。また、電流密度１２．５ｍＡ／ｃｍ2で駆動させた時の初期輝度、および６０℃の環境で１００時間連続駆動させた後の輝度を測定した。結果を表６に示す。
Examples 122-160
A device was prepared in the same manner as in Example 121 except that a light emitting layer was prepared using the example compounds shown in Tables 3 and 4 instead of Example 1 in Table 3. The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ) was measured. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 6.
比較例２
実施例１２１において、正孔輸送層を製膜しない以外は、実施例１２１と同様に素子を作成した。この素子を６Ｖに駆動させた際の色度は、ＣＩＥ（ｘ，ｙ）＝（０．１５，０．１３）の青色発光であった。この素子を発光輝度５００（ｃｄ／ｍ2）で室温にて定電流駆動したときの輝度と半減寿命を測定した。また、電流密度１２．５ｍＡ／ｃｍ2で駆動させた時の初期輝度、および６０℃の環境で１００時間連続駆動させた後の輝度を測定した。結果を表６に示す。
Comparative Example 2
In Example 121, an element was prepared in the same manner as in Example 121 except that the hole transport layer was not formed. The chromaticity when this device was driven to 6 V was blue light emission of CIE (x, y) = (0.15, 0.13). The device was measured for luminance and half-life when the device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ). Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 6.
表６
表６から明らかなように、本発明の化合物はいずれも、比較例２で作成した素子よりも、長寿命で且つ、高い輝度が得られた。 As is apparent from Table 6, all the compounds of the present invention had a longer lifetime and higher luminance than the device prepared in Comparative Example 2.
実施例１６１
洗浄したＩＴＯ電極付きガラス板上に、本発明の表３中の実施例１と以下に示す化合物（Ｅ）を９０：１０の割合で混合し、０．５ｗｔ％の濃度でトルエンに溶解させ、スピンコーティング法により２０ｎｍの膜厚の正孔注入層を製膜し、２００℃にて重合させた。ついで、以下に示した化合物（Ｆ）と化合物（Ｇ）を、９８：２の割合で１．０ｗｔ％の濃度でトルエンに溶解させ、スピンコーティング法により４０ｎｍの膜厚の発光層を製膜し、１００℃にて乾燥させた。さらにその上に、以下に示す化合物（Ｂ）を、真空蒸着して膜厚２０ｎｍの電子注入層を作成し、その上に、まずフッ化リチウムを１ｎｍ、次いでアルミニウム（Ａｌ）を１５０ｎｍ蒸着して電極を形成し、有機ＥＬ素子を得た。この素子について通電試験を行ったところ、最大発光輝度７５０ｃｄ／ｍ2の青色発光が得られた。この素子を６Ｖに駆動させた際の色度は、ＣＩＥ（ｘ，ｙ）＝（０．１４，０．１２）の青色発光であった。この素子を発光輝度５００（ｃｄ／ｍ2）で室温にて定電流駆動したときの輝度半減寿命を測定した。また、電流密度１２．５ｍＡ／ｃｍ2で駆動させた時の初期輝度、および６０℃の環境で１００時間連続駆動させた後の輝度を測定した。結果を表７に示す。
Example 161
On the washed glass plate with an ITO electrode, Example 1 in Table 3 of the present invention and the compound (E) shown below were mixed at a ratio of 90:10 and dissolved in toluene at a concentration of 0.5 wt%, A hole injection layer having a thickness of 20 nm was formed by spin coating and polymerized at 200 ° C. Next, the compound (F) and the compound (G) shown below were dissolved in toluene at a concentration of 1.0 wt% at a ratio of 98: 2, and a light-emitting layer having a thickness of 40 nm was formed by spin coating. And dried at 100 ° C. Further, a compound (B) shown below is vacuum-deposited thereon to form an electron injection layer having a film thickness of 20 nm, and then 1 nm of lithium fluoride and then 150 nm of aluminum (Al) are vapor-deposited thereon. An electrode was formed to obtain an organic EL element. When this device was subjected to an energization test, blue light emission with a maximum light emission luminance of 750 cd / m 2 was obtained. The chromaticity when this element was driven to 6 V was blue light emission of CIE (x, y) = (0.14, 0.12). The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ) was measured. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 7.
実施例１６２〜１８０
表３中の実施例１のかわりに、表３、表４に示す実施例化合物を用いて発光層を作成した以外は実施例１６１と同様に素子を作成した。この素子を発光輝度５００（ｃｄ／ｍ2）で室温にて定電流駆動したときの輝度半減寿命を測定した。また、電流密度１２．５ｍＡ／ｃｍ2で駆動させた時の初期輝度、および６０℃の環境で１００時間連続駆動させた後の輝度を測定した。結果を表７に示す。
Examples 162-180
A device was prepared in the same manner as in Example 161 except that a light emitting layer was prepared using the example compounds shown in Tables 3 and 4 instead of Example 1 in Table 3. The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ) was measured. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 7.
比較例３
実施例１６１において、正孔注入層にＰＥＤＯＴ・ＰＳＳを製膜する以外は、実施例１６１と同様に素子を作成した。この素子を６Ｖに駆動させた際の色度は、ＣＩＥ（ｘ，ｙ）＝（０．１５，０．１３）の青色発光であった。この素子を発光輝度５００（ｃｄ／ｍ2）で室温にて定電流駆動したときの輝度と半減寿命を測定した。また、電流密度１２．５ｍＡ／ｃｍ2で駆動させた時の初期輝度、および６０℃の環境で１００時間連続駆動させた後の輝度を測定した。結果を表７に示す。
Comparative Example 3
In Example 161, an element was prepared in the same manner as in Example 161 except that PEDOT / PSS was formed on the hole injection layer. The chromaticity when this device was driven to 6 V was blue light emission of CIE (x, y) = (0.15, 0.13). The device was measured for luminance and half-life when the device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ). Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 7.
表７
表７から明らかなように、本発明の化合物はいずれも、比較例３で作成した素子よりも、長寿命で且つ、高い輝度が得られた。 As is apparent from Table 7, all the compounds of the present invention had a longer lifetime and higher luminance than the device prepared in Comparative Example 3.
以上のように、本発明で示された有機エレクトロルミネッセンス素子用材料を用いることにより、高い性能のＥＬ素子が作成できる。比較化合物に対して格段に高い性能が発揮されることは明らかであり、有機ＥＬ素子の高い発光効率、低駆動電圧化、長寿命化、高色純度な青色発光が達成できる。 As described above, a high-performance EL element can be created by using the organic electroluminescence element material shown in the present invention. It is clear that remarkably high performance is exhibited with respect to the comparative compound, and high emission efficiency, low drive voltage, long life, and high color purity blue light emission of the organic EL element can be achieved.
Claims (7)
一般式［１］
Ｂは、下記一般式［４］を、
Ｅは、下記一般式［５］、または一般式［６］を、
Ｆは、水素原子、下記一般式［７］もしくは、ハロゲン原子を表し、
ｎおよびｍは、それぞれ独立に、１以上の整数を表す。）
一般式［３］
一般式［４］
一般式［５］
一般式［６］
一般式［７］
General formula [1]
B represents the following general formula [4]:
E represents the following general formula [5] or general formula [6]:
F represents a hydrogen atom, the following general formula [7] or a halogen atom,
n and m each independently represents an integer of 1 or more. )
General formula [3]
General formula [4]
General formula [5]
General formula [6]
General formula [7]
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