JPWO2016190014A1 - Method for producing material for organic electroluminescence device and organic electroluminescence device - Google Patents
Method for producing material for organic electroluminescence device and organic electroluminescence device Download PDFInfo
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- JPWO2016190014A1 JPWO2016190014A1 JP2017520298A JP2017520298A JPWO2016190014A1 JP WO2016190014 A1 JPWO2016190014 A1 JP WO2016190014A1 JP 2017520298 A JP2017520298 A JP 2017520298A JP 2017520298 A JP2017520298 A JP 2017520298A JP WO2016190014 A1 JPWO2016190014 A1 JP WO2016190014A1
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- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical class C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- DLJHXMRDIWMMGO-UHFFFAOYSA-N quinolin-8-ol;zinc Chemical compound [Zn].C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1 DLJHXMRDIWMMGO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000001022 rhodamine dye Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- WTGQALLALWYDJH-WYHSTMEOSA-N scopolamine hydrobromide Chemical compound Br.C1([C@@H](CO)C(=O)OC2C[C@@H]3N([C@H](C2)[C@@H]2[C@H]3O2)C)=CC=CC=C1 WTGQALLALWYDJH-WYHSTMEOSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- LAYPMCGIWDGYKX-UHFFFAOYSA-N trichloromethyl hydrogen carbonate Chemical compound OC(=O)OC(Cl)(Cl)Cl LAYPMCGIWDGYKX-UHFFFAOYSA-N 0.000 description 1
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 1
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical compound FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
Abstract
本発明の課題は、有機エレクトロルミネッセンス素子用材料となる化合物の合成の途中段階又は最終段階で、シアン化合物を使用せずにシアノ基を導入したシアン化合物を高収率で得る方法を提供することである。本発明の有機エレクトロルミネッセンス素子用材料の製造方法は、シアノ基を有する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の製造方法であって、前記シアノ基を有する化合物が、下記官能基群に含まれるいずれかの官能基からシアノ基へと変換することにより製造されることを特徴とする。官能基群：【化１】（Ｒは、アルキル基又はアリール基を表す。）An object of the present invention is to provide a method for obtaining a cyanide compound having a cyano group introduced in a high yield without using a cyanide compound in the middle or final stage of synthesis of a compound to be a material for an organic electroluminescence device. It is. The method for producing an organic electroluminescent element material of the present invention is a method for producing an organic electroluminescent element material containing a compound having a cyano group, and the compound having the cyano group is included in the following functional group group. It is produced by converting any functional group into a cyano group. Functional group group: ## STR1 ## (R represents an alkyl group or an aryl group)
Description
本発明は、有機エレクトロルミネッセンス素子用材料の製造方法及び有機エレクトロルミネッセンス素子に関する。より詳しくは、シアン化合物を使用せずにシアノ基を導入したシアン化合物を高収率で得ることができる有機エレクトロルミネッセンス素子用材料の製造方法等に関する。 The present invention relates to a method for producing an organic electroluminescent element material and an organic electroluminescent element. More specifically, the present invention relates to a method for producing a material for an organic electroluminescence element that can obtain a cyan compound having a cyano group introduced in a high yield without using a cyan compound.
有機エレクトロルミネッセンス素子（以下、「有機ＥＬ素子」ともいう。）は、陽極と陰極の間を、有機発光物質が含有された有機薄膜層（単層部又は多層部）で構成する薄膜型の全固体素子である。有機ＥＬ素子に電圧を印加すると、有機薄膜層に陰極から電子が、陽極から正孔が注入され、これらが発光層（有機発光物質含有層）において再結合して励起子が生じる。有機ＥＬ素子はこれら励起子からの光の放出（蛍光・リン光）を利用した発光素子であり、次世代の平面ディスプレイや照明として期待されている技術である。 An organic electroluminescence element (hereinafter also referred to as “organic EL element”) is an all-film thin film type composed of an organic thin film layer (single layer portion or multilayer portion) containing an organic light-emitting substance between an anode and a cathode. It is a solid element. When a voltage is applied to the organic EL element, electrons are injected from the cathode into the organic thin film layer and holes are injected from the anode, and these are recombined in the light emitting layer (organic light emitting substance-containing layer) to generate excitons. The organic EL element is a light-emitting element using light emission (fluorescence / phosphorescence) from these excitons, and is a technology expected as a next-generation flat display and illumination.
さらに、蛍光発光を利用する有機ＥＬ素子に比べ、原理的に約４倍の発光効率が実現可能である励起三重項からのリン光発光を利用する有機ＥＬ素子がプリンストン大学から報告されて以来、室温でリン光を示す材料の開発を始めとし、発光素子の層構成や電極の研究開発が世界中で行われている。
このように、リン光発光方式は大変ポテンシャルの高い方式であるが、リン光発光を利用する有機ＥＬデバイスにおいては、蛍光発光を利用する場合とは大きく異なり、発光中心の位置をコントロールする方法、とりわけ発光層の内部で再結合を行い、いかに発光を安定に行わせることができるかが、素子の効率・寿命を捕らえる上で重要な技術的課題となっている。Furthermore, since an organic EL element using phosphorescence emission from an excited triplet, which can realize a luminous efficiency of about 4 times in principle in comparison with an organic EL element using fluorescence emission, has been reported from Princeton University, Starting with the development of materials that exhibit phosphorescence at room temperature, research and development of light-emitting element layer configurations and electrodes are being carried out around the world.
As described above, the phosphorescence emission method is a method with a very high potential. However, in the organic EL device using phosphorescence emission, a method for controlling the position of the emission center is greatly different from the case of using fluorescence emission. In particular, how to stabilize the light emission by recombination inside the light emitting layer is an important technical issue in terms of capturing the efficiency and lifetime of the device.
そこで近年は発光層に隣接する形で、発光層の陽極側に位置する正孔輸送層や、発光層の陰極側に位置する電子輸送層等を備えた多層積層型の素子がよく知られている。また、発光層には発光ドーパントとしてのリン光発光性化合物とホスト化合物とを用いた混合層が多く用いられている。 Therefore, in recent years, multilayer stacked devices having a hole transport layer located on the anode side of the light emitting layer and an electron transport layer located on the cathode side of the light emitting layer in a form adjacent to the light emitting layer are well known. Yes. In addition, a mixed layer using a phosphorescent compound as a light emitting dopant and a host compound is often used for the light emitting layer.
これらの多層積層型素子では、発光層での再結合の頻度を高めるために、陽極から注入される正孔と、陰極から注入される電子とを、それぞれ効率よく発光層まで輸送することが重要となる。そのためには、隣接する層と層の間の最高被占分子軌道（ＨＯＭＯ）準位及び最低空分子軌道（ＬＵＭＯ）準位の相互関係、すなわち各層を構成する化合物のＨＯＭＯ準位及びＬＵＭＯ準位の高低を適切に制御することが必要である。 In these multilayer stacked devices, it is important to efficiently transport holes injected from the anode and electrons injected from the cathode to the light emitting layer, respectively, in order to increase the frequency of recombination in the light emitting layer. It becomes. For that purpose, the mutual relationship between the highest occupied molecular orbital (HOMO) level and the lowest unoccupied molecular orbital (LUMO) level between adjacent layers, that is, the HOMO level and the LUMO level of the compound constituting each layer. It is necessary to appropriately control the height of the.
ＨＯＭＯ準位及びＬＵＭＯ準位を制御する方法のうち、特にエネルギー準位を深く（低く）する方法としては、２つの方法が挙げられる。
第一の方法は、電子求引性の窒素原子を含んだ芳香族複素環を含んだ化合物を用いる方法である。窒素原子を含んだ芳香族複素環として具体的には、ピリジン、ピリミジン、トリアジン及びキノリン等が挙げられる。
第二の方法は、電子求引性官能基を導入した化合物を用いる方法である。この方法では、既存の有機ＥＬ材料に対して電子求引性官能基を導入することにより、ＨＯＭＯ準位及びＬＵＭＯ準位を目的の値に調整できるため、設計が容易であるという利点がある。電子求引性基としては特にシアノ基がよく用いられる（例えば、特許文献１参照。）。Of the methods for controlling the HOMO level and the LUMO level, there are two methods for deepening (lowering) the energy level.
The first method is a method using a compound containing an aromatic heterocycle containing an electron-withdrawing nitrogen atom. Specific examples of the aromatic heterocycle containing a nitrogen atom include pyridine, pyrimidine, triazine and quinoline.
The second method is a method using a compound into which an electron withdrawing functional group is introduced. This method has an advantage that the design is easy because the HOMO level and the LUMO level can be adjusted to target values by introducing an electron withdrawing functional group into an existing organic EL material. In particular, a cyano group is often used as the electron-withdrawing group (see, for example, Patent Document 1).
有機ＥＬ用材料に用いられるシアノ基を有する化合物は多く知られているが、それらの合成方法は、シアノベンゼン誘導体のように、シアノ基が置換された化合物を原料として用いるものがほとんどである（例えば、特許文献２参照。）。 Many compounds having a cyano group used for organic EL materials are known, but most of the synthesis methods thereof use a compound substituted with a cyano group as a raw material, such as a cyanobenzene derivative ( For example, see Patent Document 2.)
一方で、合成ルートの途中段階や最終段階でシアノ基を導入する方法も知られている（例えば、特許文献３参照。）。この場合、用いられる反応試薬は、シアン化銅やシアン化亜鉛といった、いわゆるシアン化合物である。 On the other hand, a method of introducing a cyano group at an intermediate stage or final stage of the synthesis route is also known (see, for example, Patent Document 3). In this case, the reaction reagent used is a so-called cyanide compound such as copper cyanide or zinc cyanide.
シアン化合物は、青酸カリウムに代表されるように猛毒であるものが多く、使用中はもとより処理中及び処理後にも青酸ガスが発生しないように適切かつ慎重に取り扱わなければならない。またその上で、シアン化合物の取り扱い時には、局所排気装置などの大がかりな設備が必要となる。さらには法律で定められているとおり、保存中にもその所在や在庫量を厳重に管理する必要がある。すなわち、シアン化合物は取り扱いが極めて煩雑であり、またその使用には危険を伴う。 Many cyanide compounds are extremely toxic, as represented by potassium cyanide, and must be handled appropriately and carefully so that the cyanide gas is not generated not only during use but also during and after treatment. In addition, when handling cyanide compounds, a large facility such as a local exhaust device is required. Furthermore, as required by law, it is necessary to strictly control the location and inventory during storage. That is, the cyanide compound is extremely complicated to handle, and its use is dangerous.
本発明は、上記問題・状況に鑑みてなされたものであり、その解決課題は、有機エレクトロルミネッセンス素子用材料となる化合物の合成の途中段階又は最終段階で、シアン化合物を使用せずにシアノ基を導入したシアン化合物を高収率で得る方法を提供することである。 The present invention has been made in view of the above problems and situations, and the solution is to solve the problem in the middle or final stage of the synthesis of a compound to be a material for an organic electroluminescence element without using a cyanide compound. The present invention provides a method for obtaining a cyanide compound in which is introduced in high yield.
本発明者は、上記課題を解決すべく上記問題の原因等について検討した結果、シアン化合物を用いずに、特定の官能基をシアノ基へと変換する過程を含んだ製造方法によって得られる化合物が、シアン化合物を用いて製造した同一化合物よりも有機ＥＬ素子に用いた際に高い性能を発揮することを見いだし、本発明に至った。
すなわち、本発明の上記課題は、下記の手段により解決される。As a result of examining the cause of the above-mentioned problem in order to solve the above-mentioned problems, the present inventor has found a compound obtained by a production method including a process of converting a specific functional group into a cyano group without using a cyanide compound. The present inventors have found that it exhibits higher performance when used in an organic EL device than the same compound produced using a cyanide compound, and has led to the present invention.
That is, the said subject of this invention is solved by the following means.
１．シアノ基を有する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の製造方法であって、
前記シアノ基を有する化合物が、下記官能基群に含まれるいずれかの官能基からシアノ基へと変換することにより製造されることを特徴とする有機エレクトロルミネッセンス素子用材料の製造方法。
官能基群：
A method for producing a material for an organic electroluminescent element, wherein the compound having a cyano group is produced by converting any functional group included in the functional group group below into a cyano group.
Functional group group:
２．前記官能基群に含まれるいずれかの官能基からシアノ基へと変換する際に、五酸化二リン、五塩化リン、オキシ塩化リン、三塩化リン、三臭化リン、塩化チオニル、硫酸、有機スルホン酸、有機スルホン酸無水物、有機スルホン酸クロリド、有機カルボン酸、有機カルボン酸無水物、有機カルボン酸クロリド、ジホスゲン及びトリホスゲンから選ばれる化合物を用いることを特徴とする第１項に記載の有機エレクトロルミネッセンス素子用材料の製造方法。 2. When converting any of the functional groups included in the functional group into a cyano group, diphosphorus pentoxide, phosphorous pentachloride, phosphorous oxychloride, phosphorous trichloride, phosphorous tribromide, thionyl chloride, sulfuric acid, organic 2. The organic material according to item 1, wherein a compound selected from sulfonic acid, organic sulfonic acid anhydride, organic sulfonic acid chloride, organic carboxylic acid, organic carboxylic acid anhydride, organic carboxylic acid chloride, diphosgene and triphosgene is used. A method for producing a material for an electroluminescence element.
３．前記官能基群に含まれるいずれかの官能基からシアノ基へと変換する際に、五酸化二リン、オキシ塩化リン、三塩化リン、三臭化リン及び塩化チオニルから選ばれる化合物を用いることを特徴とする第１項又は第２項に記載の有機エレクトロルミネッセンス素子用材料の製造方法。 3. A compound selected from diphosphorus pentoxide, phosphorous oxychloride, phosphorous trichloride, phosphorous tribromide and thionyl chloride is used when converting any functional group included in the functional group into a cyano group. The manufacturing method of the material for organic electroluminescent elements of 1st term | claim or 2nd term | claim characterized by the above-mentioned.
４．第１項から第３項までのいずれか一項に記載の有機エレクトロルミネッセンス素子用材料の製造方法により製造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たことを特徴とする有機エレクトロルミネッセンス素子。 4). An organic electroluminescence device comprising an organic electroluminescence device material produced by the method for producing an organic electroluminescence device material according to any one of items 1 to 3.
本発明の上記手段により、有機エレクトロルミネッセンス素子用材料となる化合物の合成の途中段階又は最終段階で、シアン化合物を使用せずにシアノ基を導入したシアン化合物を高収率で得る方法を提供することができる。 By the above-mentioned means of the present invention, there is provided a method for obtaining a cyanide compound introduced with a cyano group in a high yield without using a cyanide compound in the middle or final stage of synthesis of a compound to be a material for an organic electroluminescence device. be able to.
本発明の効果の発現機構又は作用機構については、明確にはなっていないが、以下のように推察している。
前述のとおり、シアン化合物は、青酸カリウムに代表されるように猛毒であるものが多く、取り扱いが極めて煩雑であり、使用には危険を伴う。さらには、有機ＥＬ素子用材料となる化合物にシアン化物イオンが微量でも混入した場合には、有機ＥＬ素子の性能が大きく損なわれることもわかってきた。これは、基本的には絶縁性である有機化合物からなる薄膜中に、導電性のシアン化物イオンがコンタミネーションすることで、電子及び正孔の輸送性が大きく変化したり、絶縁破壊がおきたりするためであると考えられる。
そこで、脱水反応を利用してシアノ基を導入した化合物を合成し、有機ＥＬ素子に用いることで、発光効率や寿命の低下の原因となる不具合の発生確率を下げることができるものと推察している。The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
As described above, many cyanide compounds are extremely toxic as represented by potassium cyanate, and are extremely complicated to handle, and are dangerous to use. Furthermore, it has been found that when a cyanide ion is mixed even in a trace amount into a compound as a material for an organic EL element, the performance of the organic EL element is greatly impaired. This is due to the fact that conductive cyanide ions are contaminated in a thin film made of an organic compound that is basically insulative, so that the transport properties of electrons and holes change greatly, or dielectric breakdown occurs. It is thought that it is to do.
Therefore, by synthesizing a compound having a cyano group introduced using a dehydration reaction and using it in an organic EL device, it is assumed that the probability of occurrence of defects that cause a reduction in luminous efficiency and lifetime can be reduced. Yes.
本発明の有機ＥＬ素子用材料の製造方法は、シアノ基を有する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の製造方法であって、前記シアノ基を有する化合物が、前記官能基群に含まれるいずれかの官能基からシアノ基へと変換することにより製造されることを特徴とする。この特徴は、各請求項に係る発明に共通する又は対応する技術的特徴である。 The method for producing an organic EL element material of the present invention is a method for producing an organic electroluminescent element material containing a compound having a cyano group, wherein the compound having the cyano group is included in the functional group group. It is produced by converting the functional group into a cyano group. This feature is a technical feature common to or corresponding to the claimed invention.
本発明の実施態様としては、前記官能基群に含まれるいずれかの官能基からシアノ基へと変換する際に、五酸化二リン、五塩化リン、オキシ塩化リン、三塩化リン、三臭化リン、塩化チオニル、硫酸、有機スルホン酸、有機スルホン酸無水物、有機スルホン酸クロリド、有機カルボン酸、有機カルボン酸無水物、有機カルボン酸クロリド、ジホスゲン及びトリホスゲンから選ばれる化合物を用いることが、変換反応の効率の観点から好ましい。 As an embodiment of the present invention, when any functional group included in the functional group group is converted to a cyano group, diphosphorus pentoxide, phosphorous pentachloride, phosphorous oxychloride, phosphorous trichloride, tribromide. Conversion using a compound selected from phosphorus, thionyl chloride, sulfuric acid, organic sulfonic acid, organic sulfonic acid anhydride, organic sulfonic acid chloride, organic carboxylic acid, organic carboxylic acid anhydride, organic carboxylic acid chloride, diphosgene and triphosgene It is preferable from the viewpoint of reaction efficiency.
また、前記官能基群に含まれるいずれかの官能基からシアノ基へと変換する際に、五酸化二リン、オキシ塩化リン、三塩化リン、三臭化リン及び塩化チオニルから選ばれる化合物を用いることが、化合物入手の容易性の観点から好ましい。 Further, when converting any functional group included in the functional group into a cyano group, a compound selected from diphosphorus pentoxide, phosphorous oxychloride, phosphorous trichloride, phosphorous tribromide and thionyl chloride is used. Is preferable from the viewpoint of easy availability of the compound.
本発明の有機エレクトロルミネッセンス素子用材料の製造方法により製造された有機エレクトロルミネッセンス素子用材料は、有機エレクトロルミネッセンス素子に好適に用いられる。これにより、有機エレクトロルミネッセンス素子の発光効率及び寿命の低下を抑制する効果が得られる。 The organic electroluminescent element material produced by the method for producing an organic electroluminescent element material of the present invention is suitably used for an organic electroluminescent element. Thereby, the effect which suppresses the luminous efficiency of an organic electroluminescent element and the fall of a lifetime is acquired.
以下、本発明とその構成要素、及び本発明を実施するための形態・態様について詳細な説明をする。なお、以下の説明において示す「〜」は、その前後に記載される数値を下限値及び上限値として含む意味で使用する。 Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, "-" shown in the following description is used with the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.
《有機ＥＬ素子用材料の製造方法》
本発明の有機エレクトロルミネッセンス（以下、有機ＥＬともいう。）素子用材料の製造方法は、シアノ基を有する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の製造方法であって、前記シアノ基を有する化合物が、下記官能基群に含まれるいずれかの官能基からシアノ基へと変換することにより製造されることを特徴とする。
官能基群：
The method for producing an organic electroluminescent (hereinafter also referred to as organic EL) device material of the present invention is a method for producing an organic electroluminescent device material containing a compound having a cyano group, the compound having a cyano group. Is produced by converting any functional group included in the following functional group group into a cyano group.
Functional group group:
前記官能基群に含まれるいずれかの官能基からシアノ基へと変換する際に、五酸化二リン（Ｐ４Ｏ１０；１〜２当量）、五塩化リン（ＰＣｌ５）、オキシ塩化リン（ＰＯＣｌ３）、三塩化リン（ＰＣｌ３）、三臭化リン（ＰＢｒ３）、塩化チオニル（ＳＯＣｌ２；１〜２当量）、濃硫酸（Ｈ２ＳＯ４）、有機スルホン酸（Ｒ１ＳＯ３Ｈ；例えば、メタンスルホン酸、ベンゼンスルホン酸及びｐ−トルエンスルホン酸等、１〜２当量）、有機スルホン酸無水物（（Ｒ２ＳＯ２）２Ｏ；例えば、メタンスルホン酸無水物及びトリフルオロメタンスルホン酸無水物、１〜２当量）、有機スルホン酸クロリド（Ｒ３ＳＯ２Ｃｌ；例えば、メタンスルホニルクロリド、１〜２当量）、有機カルボン酸（Ｒ４ＣＯＯＨ；例えば、トリフルオロ酢酸）、有機カルボン酸無水物（Ｒ５−ＣＯ−Ｏ−ＣＯ−Ｒ６；例えば、無水酢酸、無水トリフルオロ酢酸、１〜２当量）、有機カルボン酸クロリド（Ｒ７−Ｃ（＝Ｏ）−Ｃｌ；例えば、トリフルオロアセチルクロリド、１〜２当量）、ジホスゲン（クロロギ酸トリクロロメチル）及びトリホスゲン（炭酸ビス(トリクロロメチル)）から選ばれる化合物を用いることが好ましく、特に、五酸化二リン、オキシ塩化リン、三塩化リン、三臭化リン及び塩化チオニルから選ばれる化合物を用いることが好ましい。具体的な合成方法については実施例に記載する方法で合成することができ、前記官能基群を有する化合物は同様の方法でシアノ基へと変換することができる。When converting any functional group included in the functional group into a cyano group, diphosphorus pentoxide (P 4 O 10 ; 1 to 2 equivalents), phosphorus pentachloride (PCl 5 ), phosphorus oxychloride ( POCl 3 ), phosphorus trichloride (PCl 3 ), phosphorus tribromide (PBr 3 ), thionyl chloride (SOCl 2 ; 1 to 2 equivalents), concentrated sulfuric acid (H 2 SO 4 ), organic sulfonic acid (R 1 SO 3) H; for example, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc., 1-2 equivalents), organic sulfonic acid anhydride ((R 2 SO 2 ) 2 O; for example, methanesulfonic acid anhydride and trifluoromethane Sulfonic acid anhydride, 1-2 equivalents), organic sulfonic acid chloride (R 3 SO 2 Cl; eg, methanesulfonyl chloride, 1-2 equivalents), organic carboxylic acid (R 4 COOH; eg, Trifluoroacetic acid), organic carboxylic acid anhydride (R 5 —CO—O—CO—R 6 ; for example, acetic anhydride, trifluoroacetic anhydride, 1 to 2 equivalents), organic carboxylic acid chloride (R 7 —C (═O ) -Cl; for example, a compound selected from trifluoroacetyl chloride, 1 to 2 equivalents), diphosgene (trichloromethyl chloroformate) and triphosgene (bis (trichloromethyl carbonate)) is preferably used. It is preferable to use a compound selected from phosphorus oxychloride, phosphorus trichloride, phosphorus tribromide and thionyl chloride. About the specific synthesis method, it can synthesize | combine by the method described in an Example, The compound which has the said functional group group can be converted into a cyano group by the same method.
《有機ＥＬ素子の構成層》
本発明の有機ＥＬ素子は、前記有機ＥＬ素子用材料の製造方法により製造された有機ＥＬ素子用材料を用いることが好ましい。
本発明の有機ＥＬ素子における代表的な素子構成としては、以下の構成を挙げることができるが、これらに限定されるものではない。
（１）陽極／発光層／陰極
（２）陽極／発光層／電子輸送層／陰極
（３）陽極／正孔輸送層／発光層／陰極
（４）陽極／正孔輸送層／発光層／電子輸送層／陰極
（５）陽極／正孔輸送層／発光層／電子輸送層／電子注入層／陰極
（６）陽極／正孔注入層／正孔輸送層／発光層／電子輸送層／陰極
（７）陽極／正孔注入層／正孔輸送層／（電子阻止層／）発光層／（正孔阻止層／）電子輸送層／電子注入層／陰極<< Constituent layers of organic EL elements >>
The organic EL element of the present invention preferably uses an organic EL element material produced by the method for producing an organic EL element material.
As typical element structures in the organic EL element of the present invention, the following structures can be exemplified, but the invention is not limited thereto.
(1) Anode / light emitting layer / cathode (2) Anode / light emitting layer / electron transport layer / cathode (3) Anode / hole transport layer / light emitting layer / cathode (4) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (6) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode ( 7) Anode / hole injection layer / hole transport layer / (electron blocking layer /) light emitting layer / (hole blocking layer /) electron transport layer / electron injection layer / cathode
上記の中で（７）の構成が好ましく用いられるが、これに限定されるものではない。
本発明に係る発光層は、単層又は複数層で構成されており、発光層が複数の場合は各発光層の間に非発光性の中間層を設けてもよい。
必要に応じて、発光層と陰極との間に正孔阻止層（正孔障壁層ともいう。）や電子注入層（陰極バッファー層ともいう。）を設けてもよく、また、発光層と陽極との間に電子阻止層（電子障壁層ともいう。）や正孔注入層（陽極バッファー層ともいう。）を設けてもよい。Among the above, the configuration (7) is preferably used, but is not limited thereto.
The light emitting layer according to the present invention is composed of a single layer or a plurality of layers, and when there are a plurality of light emitting layers, a non-light emitting intermediate layer may be provided between the light emitting layers.
If necessary, a hole blocking layer (also referred to as a hole blocking layer) or an electron injection layer (also referred to as a cathode buffer layer) may be provided between the light emitting layer and the cathode. An electron blocking layer (also referred to as an electron barrier layer) or a hole injection layer (also referred to as an anode buffer layer) may be provided therebetween.
本発明に係る電子輸送層とは、電子を輸送する機能を有する層であり、広い意味で電子注入層、正孔阻止層も電子輸送層に含まれ、複数層で構成されていてもよい。
本発明に係る正孔輸送層とは、正孔を輸送する機能を有する層であり、広い意味で正孔注入層、電子阻止層も正孔輸送層に含まれ、複数層で構成されていてもよい。
上記の代表的な素子構成において、陽極と陰極を除いた層を「有機層」という。The electron transport layer according to the present invention is a layer having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer, and may be composed of a plurality of layers.
The hole transport layer according to the present invention is a layer having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer, and are composed of a plurality of layers. Also good.
In the above-described typical element configuration, a layer excluding the anode and the cathode is referred to as an “organic layer”.
（タンデム構造）
本発明の有機ＥＬ素子は、少なくとも１層の発光層を含む発光ユニットを複数積層した、いわゆるタンデム構造の素子であってもよい。
タンデム構造の代表的な素子構成としては、例えば以下の構成を挙げることができる。
陽極／第１発光ユニット／中間層／第２発光ユニット／中間層／第３発光ユニット／陰極
ここで、上記複数の発光ユニットは全て同じであっても異なっていてもよい。また二つの発光ユニットが同じであり、残る一つが異なっていてもよい。複数の発光ユニットは直接積層されていても、中間層（中間電極、中間導電層、電荷発生層、電子引抜層、接続層、中間絶縁層とも呼ばれる。）を介して積層されていてもよく、陽極側の隣接層に電子を、陰極側の隣接層に正孔を供給する機能を持った層であれば、公知の材料構成を用いることができる。(Tandem structure)
The organic EL element of the present invention may be a so-called tandem structure element in which a plurality of light emitting units including at least one light emitting layer are stacked.
As typical element configurations of the tandem structure, for example, the following configurations can be given.
Anode / first light emitting unit / intermediate layer / second light emitting unit / intermediate layer / third light emitting unit / cathode Here, the plurality of light emitting units may all be the same or different. Two light emitting units may be the same, and the remaining one may be different. The plurality of light emitting units may be laminated directly or via an intermediate layer (also referred to as an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate insulating layer), A known material structure can be used as long as it has a function of supplying electrons to the anode-side adjacent layer and holes to the cathode-side adjacent layer.
中間層に用いられる材料としては、例えば、ＩＴＯ（インジウム・スズ酸化物）、ＩＺＯ（インジウム・亜鉛酸化物）、ＺｎＯ２、ＴｉＮ、ＺｒＮ、ＨｆＮ、ＴｉＯ２、Ｖ２Ｏ５、ＣｕＩ、ＩｎＮ、ＧａＮ、ＣｕＡｌＯ２、ＣｕＧａＯ２、ＳｒＣｕ２Ｏ２、ＬａＢ６、ＲｕＯ２、Ａｌ等の導電性無機化合物層、これら導電性無機化合物の２層膜や多層膜、またＣ６０等のフラーレン類、オリゴチオフェン等の導電性有機物層、金属フタロシアニン類、無金属フタロシアニン類、ポルフィリン類等の導電性有機化合物層等が挙げられるが、本発明はこれらに限定されない。
発光ユニット内の好ましい構成としては、例えば上記の代表的な素子構成で挙げた（１）〜（７）の構成から、陽極と陰極を除いたもの等が挙げられるが、本発明はこれらに限定されない。Examples of the material used for the intermediate layer include ITO (indium tin oxide), IZO (indium zinc oxide), ZnO 2 , TiN, ZrN, HfN, TiO 2 , V 2 O 5 , CuI, InN, Conductive inorganic compound layers such as GaN, CuAlO 2 , CuGaO 2 , SrCu 2 O 2 , LaB 6 , RuO 2 , and Al, two-layer films and multilayer films of these conductive inorganic compounds, and fullerenes such as C 60 , oligos Examples include conductive organic material layers such as thiophene, conductive organic compound layers such as metal phthalocyanines, metal-free phthalocyanines, and porphyrins, but the present invention is not limited thereto.
Examples of a preferable configuration in the light emitting unit include those obtained by removing the anode and the cathode from the configurations (1) to (7) described in the above representative element configurations, but the present invention is not limited thereto. Not.
タンデム型有機ＥＬ素子の具体例としては、例えば、米国特許第７４２０２０３号明細書、米国特許第７４７３９２３号明細書、米国特許第６８７２４７２号明細書、米国特許第６１０７７３４号明細書、米国特許第６３３７４９２号明細書、特開２０１１−９６６７９号公報、特開２０１０−１９２７１９号公報、特開２００９−０７６９２９号公報、特開２００８−０７８４１４号公報、特開２００７−０５９８４８号公報、国際公開第２００５／０９４１３０号等に記載の素子構成や構成材料等が挙げられるが、本発明はこれらに限定されない。
以下、本発明の有機ＥＬ素子を構成する各層について説明する。Specific examples of the tandem organic EL element include, for example, US Pat. No. 7,420,203, US Pat. No. 7,473,923, US Pat. No. 6,872,472, US Pat. No. 6,107,734, US Pat. No. 6,337,492. Description, JP 2011-96679 A, JP 2010-192719 A, JP 2009-076929 A, JP 2008-078414 A, JP 2007-059848 A, International Publication No. 2005/094130. However, the present invention is not limited to these.
Hereinafter, each layer which comprises the organic EL element of this invention is demonstrated.
《発光層》
本発明に係る発光層は、電極又は電子輸送層及び正孔輸送層から注入されてくる電子及び正孔が再結合して発光する層であり、発光する部分は発光層の層内であっても発光層と隣接層との界面であってもよい。
発光層の層厚の総和は特に制限はないが、層を構成する膜の均質性や、発光時に不必要な高電圧を印加することを防止し、かつ、駆動電流に対する発光色の安定性向上の観点から、好ましくは２ｎｍ〜５μｍの範囲内に調整され、更に好ましくは２〜２００ｎｍの範囲内に調整され、特に好ましくは５〜１００ｎｍの範囲内に調整される。<Light emitting layer>
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode or the electron transport layer and the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.
The total thickness of the light-emitting layers is not particularly limited, but the uniformity of the films that make up the layers and the prevention of applying unnecessary high voltages during light emission, as well as improving the stability of the emission color against the drive current In view of the above, it is preferably adjusted within the range of 2 nm to 5 μm, more preferably adjusted within the range of 2 to 200 nm, and particularly preferably within the range of 5 to 100 nm.
発光層の作製には、後述する発光ドーパントやホスト化合物を用いて、例えば、真空蒸着法、湿式法（ウェットプロセスともいい、例えば、スピンコート法、キャスト法、ダイコート法、ブレードコート法、ロールコート法、インクジェット法、印刷法、スプレーコート法、カーテンコート法、ＬＢ法（ラングミュア・ブロジェット（Ｌａｎｇｍｕｉｒ Ｂｌｏｄｇｅｔｔ法））等を挙げることができる。）等により成膜して形成することができる。
本発明の有機ＥＬ素子の発光層が、発光ドーパント（リン光発光性ドーパントや蛍光発光性ドーパント等）と、ホスト化合物とを含有することが好ましい。For the production of the light-emitting layer, a light-emitting dopant or a host compound, which will be described later, is used. Or the like, the ink jet method, the printing method, the spray coating method, the curtain coating method, the LB method (Langmuir Brodgett method, etc.).
It is preferable that the light emitting layer of the organic EL device of the present invention contains a light emitting dopant (such as a phosphorescent light emitting dopant or a fluorescent light emitting dopant) and a host compound.
（１）シアノ基を有する化合物
本発明に係るシアノ基を有する化合物は、有機ＥＬ素子用材料として用いることができ、特にホスト化合物として用いられることが好ましい。以下、本発明に係るシアノ基を有する化合物の具体例を挙げるが、本発明はこれらに限定されない。なお、以下に示した化合物については機能を阻害しない程度に更に置換基を有することも好ましい。(1) Compound having a cyano group The compound having a cyano group according to the present invention can be used as a material for an organic EL device, and is particularly preferably used as a host compound. Hereinafter, although the specific example of the compound which has a cyano group concerning this invention is given, this invention is not limited to these. In addition, about the compound shown below, it is also preferable to have a substituent further to such an extent that a function is not inhibited.
本発明に用いることができるホスト化合物（発光ホスト、発光ホスト化合物ともいう。）は、発光層に含有される化合物の内で、その層中での質量比が２０％以上であり、かつ室温（２５℃）においてリン光発光のリン光量子効率が、０．１未満の化合物と定義される。好ましくはリン光量子効率が０．０１未満である。また、発光層に含有される化合物の中で、その層中での質量比が２０％以上であることが好ましい。 A host compound (also referred to as a light-emitting host or a light-emitting host compound) that can be used in the present invention has a mass ratio in the layer of 20% or more among the compounds contained in the light-emitting layer, and a room temperature ( 25 ° C.) is defined as a compound having a phosphorescence quantum efficiency of phosphorescence of less than 0.1. Preferably, the phosphorescence quantum efficiency is less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.
また、本発明においては、従来公知のホスト化合物を一つ又は複数種併用して用いてもよい。ホスト化合物を複数種用いることで、電荷の移動を調整することが可能であり、有機ＥＬ素子を高効率化することができる。また、後述するリン光ドーパントとして用いられるイリジウム錯体及び／又は従来公知の化合物を複数種用いることで、異なる発光を混ぜることが可能となり、これにより任意の発光色を得ることができる。 In the present invention, one or a plurality of conventionally known host compounds may be used in combination. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. Moreover, it becomes possible to mix different light emission by using multiple types of iridium complexes and / or conventionally well-known compounds used as a phosphorescence dopant mentioned later, and can thereby obtain arbitrary luminescent colors.
本発明に併用することができる公知のホスト化合物としては正孔輸送能、電子輸送能を有しつつ、かつ、発光の長波長化を防ぎ、なおかつ高Ｔｇ（ガラス転移温度）である化合物が好ましい。
また、本発明に用いられるホスト化合物としては、低分子化合物でも、繰り返し単位をもつ高分子化合物でもよく、ビニル基やエポキシ基のような重合性基を有する低分子化合物（重合性ホスト化合物）でもよく、このような化合物を１種又は複数種用いてもよい。As the known host compound that can be used in combination with the present invention, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being long-wavelength, and has a high Tg (glass transition temperature) is preferable. .
The host compound used in the present invention may be a low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound (polymerizable host compound) having a polymerizable group such as a vinyl group or an epoxy group. Of course, one or more of such compounds may be used.
公知のホスト化合物の具体例としては、以下の文献に記載の化合物が挙げられる。
特開２００１−２５７０７６号公報、同２００２−３０８８５５号公報、同２００１−３１３１７９号公報、同２００２−３１９４９１号公報、同２００１−３５７９７７号公報、同２００２−３３４７８６号公報、同２００２−８８６０号公報、同２００２−３３４７８７号公報、同２００２−１５８７１号公報、同２００２−３３４７８８号公報、同２００２−４３０５６号公報、同２００２−３３４７８９号公報、同２００２−７５６４５号公報、同２００２−３３８５７９号公報、同２００２−１０５４４５号公報、同２００２−３４３５６８号公報、同２００２−１４１１７３号公報、同２００２−３５２９５７号公報、同２００２−２０３６８３号公報、同２００２−３６３２２７号公報、同２００２−２３１４５３号公報、同２００３−３１６５号公報、同２００２−２３４８８８号公報、同２００３−２７０４８号公報、同２００２−２５５９３４号公報、同２００２−２６０８６１号公報、同２００２−２８０１８３号公報、同２００２−２９９０６０号公報、同２００２−３０２５１６号公報、同２００２−３０５０８３号公報、同２００２−３０５０８４号公報、同２００２−３０８８３７号公報等である。Specific examples of known host compounds include compounds described in the following documents.
JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.
（２）発光性ドーパント
発光性ドーパント（発光ドーパント、ドーパント化合物、単にドーパントともいう。）について説明する。
発光性ドーパントとしては、蛍光発光性ドーパント（蛍光ドーパント、蛍光性化合物、蛍光発光性化合物ともいう。）、リン光発光性ドーパント（リン光ドーパント、リン光性化合物、リン光発光性化合物等ともいう。）を用いることができる。(2) Luminescent dopant A luminescent dopant (a luminescent dopant, a dopant compound, or simply referred to as a dopant) will be described.
As the luminescent dopant, a fluorescent luminescent dopant (also referred to as a fluorescent dopant, a fluorescent compound, or a fluorescent luminescent compound), a phosphorescent dopant (also referred to as a phosphorescent dopant, a phosphorescent compound, a phosphorescent compound, or the like). .) Can be used.
（２．１）リン光ドーパント
リン光ドーパントは、励起三重項からの発光が観測される化合物であり、具体的には室温（２５℃）にてリン光発光する化合物であり、リン光量子効率が、２５℃において０．０１以上の化合物であると定義されるが、好ましいリン光量子効率は０．１以上である。
上記リン光量子効率は、第４版実験化学講座７の分光IIの３９８頁（１９９２年版、丸善）に記載の方法により測定できる。溶液中でのリン光量子効率は種々の溶媒を用いて測定できるが、本発明で用いられるリン光ドーパントは、任意の溶媒のいずれかにおいて上記リン光量子効率（０．０１以上）が達成されればよい。(2.1) Phosphorescent dopant A phosphorescent dopant is a compound in which light emission from an excited triplet is observed, specifically a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescent quantum efficiency of The phosphorescence quantum efficiency is preferably 0.1 or more, although it is defined as a compound of 0.01 or more at 25 ° C.
The phosphorescence quantum efficiency can be measured by the method described in Spectra II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum efficiency in a solution can be measured using various solvents, the phosphorescence dopant used in the present invention can be obtained as long as the phosphorescence quantum efficiency (0.01 or more) is achieved in any solvent. Good.
リン光ドーパントの発光は原理としては２種挙げられ、一つはキャリアが輸送されるホスト化合物上でキャリアの再結合が起こって発光性ホスト化合物の励起状態が生成し、このエネルギーをリン光ドーパントに移動させることでリン光ドーパントからの発光を得るというエネルギー移動型である。もう一つはリン光ドーパントがキャリアトラップとなり、リン光ドーパント上でキャリアの再結合が起こり、リン光ドーパントからの発光が得られるというキャリアトラップ型である。いずれの場合においても、リン光ドーパントの励起状態のエネルギーはホスト化合物の励起状態のエネルギーよりも低いことが条件である。 There are two types of light emission of the phosphorescent dopant in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate the excited state of the luminescent host compound, and this energy is used as the phosphorescent dopant. It is an energy transfer type in which light emission from a phosphorescent dopant is obtained by moving to. The other is a carrier trap type in which a phosphorescent dopant becomes a carrier trap, and carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained. In any case, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.
以下、一般式（ＤＰ）で表され、本発明において好適に用いられるリン光発光性化合物（リン光発光性ドーパント）について説明する。 Hereinafter, the phosphorescent compound (phosphorescent dopant) represented by the general formula (DP) and suitably used in the present invention will be described.
式中、Ｍは、Ｉｒ、Ｐｔ、Ｒｈ、Ｒｕ、Ａｇ、Ｃｕ又はＯｓを表す。Ａ１、Ａ２、Ｂ１及びＢ２は、それぞれ、炭素原子又は窒素原子を表す。環Ｚ１は、Ａ１及びＡ２とともに形成される６員の芳香族炭化水素環又は５員若しくは６員の芳香族複素環を表す。環Ｚ２は、Ｂ１及びＢ２とともに形成される５員又は６員の芳香族複素環を表す。環Ｚ１及び環Ｚ２は置換基を有していてもよく、さらに置換基同士が結合して縮環構造を形成していてもよい。また、各々の配位子の置換基が、互いに結合して、配位子同士が連結していてもよい。Ｌ′は、Ｍに配位したモノアニオン性の二座配位子を表す。ｍ′は、０〜２の整数を表す。ｎ′は、１〜３の整数を表す。ｍ′＋ｎ′は、２又は３である。ｍ′及びｎ′が２以上の場合、環Ｚ１及び環Ｚ２で表される配位子及びＬ′は、各々、同じでも異なっていてもよい。In the formula, M represents Ir, Pt, Rh, Ru, Ag, Cu, or Os. A 1 , A 2 , B 1 and B 2 each represent a carbon atom or a nitrogen atom. Ring Z 1 represents a 6-membered aromatic hydrocarbon ring or 5-membered or 6-membered aromatic heterocycle formed together with A 1 and A 2 . Ring Z 2 represents a 5-membered or 6-membered aromatic heterocycle formed together with B 1 and B 2 . Ring Z 1 and ring Z 2 may have a substituent, and the substituents may be bonded to each other to form a condensed ring structure. Moreover, the substituent of each ligand may couple | bond together and the ligands may connect. L ′ represents a monoanionic bidentate ligand coordinated to M. m ′ represents an integer of 0 to 2. n ′ represents an integer of 1 to 3. m ′ + n ′ is 2 or 3. When m ′ and n ′ are 2 or more, the ligands represented by the ring Z 1 and the ring Z 2 and L ′ may be the same or different.
一般式（ＤＰ）において、Ｍは、Ｉｒ、Ｐｔ、Ｒｈ、Ｒｕ、Ａｇ、Ｃｕ又はＯｓを挙げることができ、Ｉｒ、Ｐｔ、Ｒｈ、Ｒｕ又はＯｓであることがより好ましく、Ｉｒ、Ｐｔ又はＯｓであることがより好ましい。
Ａ１、Ａ２、Ｂ１及びＢ２は、各々炭素原子又は窒素原子を表し、環Ｚ１は、Ａ１及びＡ２とともに形成される６員の芳香族炭化水素環、又は５員又は６員の芳香族複素環を表し、環Ｚ２は、Ｂ１及びＢ２とともに形成される５員又は６員の芳香族複素環を表す。In the general formula (DP), M can include Ir, Pt, Rh, Ru, Ag, Cu or Os, more preferably Ir, Pt, Rh, Ru or Os, and Ir, Pt or Os. It is more preferable that
A 1 , A 2 , B 1 and B 2 each represent a carbon atom or a nitrogen atom, and ring Z 1 is a 6-membered aromatic hydrocarbon ring formed together with A 1 and A 2 , or 5 or 6 Represents a membered aromatic heterocycle, and ring Z 2 represents a 5-membered or 6-membered aromatic heterocycle formed together with B 1 and B 2 .
環Ｚ２は、５員の芳香族複素環であることが好ましく、Ｂ１及びＢ２は、少なくとも一方が窒素原子であることが好ましい。
環Ｚ１及び環Ｚ２は、置換基を有していてもよく、置換基として好ましくは、アリール基、ヘテロアリール基、シリル基、アルキル基であり、さらに好ましくはフェニル基、カルバゾリル基、ジベンゾフラニル基、ジベンゾチオフェニル基、トリフェニルシリル基、メチル基、イソプロピル基であって、より好ましくはフェニル基、カルバゾリル基、ジベンゾフラニル基、ジベンゾチオフェニル基、トリフェニルシリル基が挙げられる。また、環Ｚ１及び環Ｚ２の置換基は、さらに置換基同士が結合して縮環構造を形成していてもよい。また、各々の配位子の置換基が互いに結合して、配位子同士が連結していてもよい。Ring Z 2 is preferably a 5-membered aromatic heterocyclic ring, and at least one of B 1 and B 2 is preferably a nitrogen atom.
Ring Z 1 and ring Z 2 may have a substituent, and the substituent is preferably an aryl group, heteroaryl group, silyl group, or alkyl group, more preferably a phenyl group, a carbazolyl group, or a dibenzo group. A furanyl group, a dibenzothiophenyl group, a triphenylsilyl group, a methyl group, and an isopropyl group, more preferably a phenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, and a triphenylsilyl group. Moreover, the substituents of the ring Z 1 and the ring Z 2 may be further bonded to each other to form a condensed ring structure. Moreover, the substituent of each ligand may mutually couple | bond together and the ligands may connect.
Ｌ′は、Ｍに配位したモノアニオン性の二座配位子を表す。
ｍ′は０〜２の整数を表し、ｎ′は１〜３の整数を表し、ｍ′＋ｎ′は２又は３である。
ｍ′及びｎ′が２以上のとき、環Ｚ１及び環Ｚ２で表される配位子及びＬ′は各々同じでも異なっていてもよい。
一般式（ＤＰ）の構造は、好ましくは下記一般式（ＤＰ−１）又は（ＤＰ−２）の構造で表される。L ′ represents a monoanionic bidentate ligand coordinated to M.
m ′ represents an integer of 0 to 2, n ′ represents an integer of 1 to 3, and m ′ + n ′ is 2 or 3.
When m ′ and n ′ are 2 or more, the ligands represented by ring Z 1 and ring Z 2 and L ′ may be the same or different.
The structure of the general formula (DP) is preferably represented by the following general formula (DP-1) or (DP-2).
一般式（ＤＰ−１）において、Ｍ、Ａ１、Ａ２、Ｂ１、Ｂ２、環Ｚ１、Ｌ′、ｍ′及びｎ′は、一般式（ＤＰ）におけるＭ、Ａ１、Ａ２、Ｂ１、Ｂ２、環Ｚ１、Ｌ′、ｍ′及びｎ′と同義である。
Ｂ３〜Ｂ５は、芳香族複素環を形成する原子群であり、水素原子又は置換基を有していてもよい炭素原子、窒素原子、酸素原子又は硫黄原子を表す。Ｂ３〜Ｂ５が有する置換基としては、前述の一般式（ＤＰ）における環Ｚ１及び環Ｚ２が有する置換基と同義の基が挙げられる。In the general formula (DP-1), M, A 1 , A 2 , B 1 , B 2 , ring Z 1 , L ′, m ′ and n ′ are M, A 1 , A 2 in the general formula (DP). , B 1 , B 2 , ring Z 1 , L ′, m ′ and n ′.
B 3 to B 5 are an atomic group forming an aromatic heterocyclic ring, and represent a hydrogen atom or a carbon atom, nitrogen atom, oxygen atom or sulfur atom which may have a substituent. Examples of the substituent that B 3 to B 5 have include the same groups as the substituents that the ring Z 1 and the ring Z 2 have in the general formula (DP).
一般式（ＤＰ−１）においてＢ１〜Ｂ５で形成される芳香族複素環は、下記一般式（ＤＰ−１ａ）、（ＤＰ−１ｂ）及び（ＤＰ−１ｃ）の構造のいずれかで表されることが好ましく、一般式（ＤＰ−１ｃ）の構造で表されることがより好ましい。The aromatic heterocycle formed by B 1 to B 5 in the general formula (DP-1) is represented by any one of the structures of the following general formulas (DP-1a), (DP-1b), and (DP-1c). It is preferable to be represented by the structure of the general formula (DP-1c).
一般式（ＤＰ−１ａ）、（ＤＰ−１ｂ）及び（ＤＰ−１ｃ）において、＊１は一般式（ＤＰ−１）のＡ２との結合部位を表し、＊２はＭとの結合部位を表す。
Ｒｂ３〜Ｒｂ５は水素原子又は置換基を表し、Ｒｂ３〜Ｒｂ５で表される置換基としては、前述の一般式（ＤＰ）における環Ｚ１及び環Ｚ２が有する置換基と同義の基が挙げられる。
一般式（ＤＰ−１ａ）におけるＢ４及びＢ５は、炭素原子又は窒素原子であり、より好ましくは少なくとも一つが炭素原子である。
一般式（ＤＰ−１ｂ）におけるＢ３〜Ｂ５は、炭素原子又は窒素原子であり、より好ましくは少なくとも一つが炭素原子である。
一般式（ＤＰ−１ｃ）におけるＢ３及びＢ４は、炭素原子又は窒素原子であり、より好ましくは少なくとも一つが炭素原子であり、Ｒｂ３とＲｂ４で表される置換基がさらに互いに結合して縮環構造を形成していることがより好ましく、このとき新たに形成される縮環構造は芳香族環であることが好ましく、ベンゾイミダゾール環、イミダゾピリジン環、イミダゾピラジン環又はプリン環のいずれかであることが好ましい。Ｒｂ５はアルキル基、アリール基であることが好ましく、フェニル基であることがより好ましい。In the general formulas (DP-1a), (DP-1b), and (DP-1c), * 1 represents a binding site with A 2 in the general formula (DP-1), and * 2 represents a binding site with M. Represent.
Rb 3 ~Rb 5 represents a hydrogen atom or a substituent, as the substituent represented by Rb 3 ~Rb 5, the same as the substituents possessed by the ring Z 1 and the ring Z 2 in the above general formula (DP) Groups.
B 4 and B 5 in the general formula (DP-1a) are a carbon atom or a nitrogen atom, and more preferably at least one is a carbon atom.
B 3 to B 5 in the general formula (DP-1b) are a carbon atom or a nitrogen atom, and more preferably at least one is a carbon atom.
B 3 and B 4 in formula (DP-1c) are a carbon atom or a nitrogen atom, more preferably at least one is a carbon atom, and the substituents represented by Rb 3 and Rb 4 are further bonded to each other. It is more preferable that a condensed ring structure is formed, and the newly formed condensed ring structure is preferably an aromatic ring, and any of a benzimidazole ring, an imidazopyridine ring, an imidazopyrazine ring, and a purine ring is preferable. It is preferable that Rb 5 is preferably an alkyl group or an aryl group, and more preferably a phenyl group.
一般式（ＤＰ−２）において、Ｍ、Ａ１、Ａ２、Ｂ１、Ｂ２、環Ｚ１、Ｌ′、ｍ′及びｎ′は、一般式（ＤＰ）におけるＭ、Ａ１、Ａ２、Ｂ１、Ｂ２、環Ｚ１、Ｌ′、ｍ′及びｎ′と同義である。
環Ｚ２は、Ｂ１〜Ｂ３とともに形成される５員の芳香族複素環を表す。
Ａ３及びＢ３は炭素原子又は窒素原子を表し、Ｌ″は２価の連結基を表す。Ｌ″で表される２価の連結基としては、例えば、アルキレン基、アルケニレン基、アリーレン基、ヘテロアリーレン基、２価の複素環基、−Ｏ−、−Ｓ−、又はこれらを任意に組み合わせた連結基等が挙げられる。
一般式（ＤＰ−２）は、さらに一般式（ＤＰ−２ａ）で表されることが好ましい。In the general formula (DP-2), M, A 1 , A 2 , B 1 , B 2 , ring Z 1 , L ′, m ′ and n ′ are M, A 1 , A 2 in the general formula (DP). , B 1 , B 2 , ring Z 1 , L ′, m ′ and n ′.
Ring Z 2 represents a 5-membered aromatic heterocycle formed together with B 1 to B 3 .
A 3 and B 3 represent a carbon atom or a nitrogen atom, L ″ represents a divalent linking group. Examples of the divalent linking group represented by L ″ include an alkylene group, an alkenylene group, an arylene group, Examples include a heteroarylene group, a divalent heterocyclic group, —O—, —S—, or a linking group in which these are arbitrarily combined.
The general formula (DP-2) is preferably further represented by the general formula (DP-2a).
一般式（ＤＰ−２ａ）において、Ｍ、Ａ１、Ａ２、Ａ３、Ｂ１、Ｂ２、Ｂ３、環Ｚ１、環Ｚ２、Ｌ′、ｍ′及びｎ′は、一般式（ＤＰ−２）におけるＭ、Ａ１、Ａ２、Ａ３、Ｂ１、Ｂ２、Ｂ３、環Ｚ１、環Ｚ２、Ｌ′、ｍ′及びｎ′と同義である。
Ｌ″１及びＬ″２はＣ−Ｒｂ６又は窒素原子を表し、Ｒｂ６は水素原子又は置換基を表す。Ｌ″１及びＬ″２がＣ−Ｒｂ６の場合はＲｂ６同士が互いに結合し環を形成してもよい。
一般式（ＤＰ）、（ＤＰ−１）、（ＤＰ−２）及び（ＤＰ−２ａ）において、Ａ２が炭素原子であることが好ましく、さらにＡ１が炭素原子であることが好ましい。より好ましくは環Ｚ１が置換又は無置換のベンゼン環又はピリジン環であり、さらに好ましくはベンゼン環である。In the general formula (DP-2a), M, A 1 , A 2 , A 3 , B 1 , B 2 , B 3 , ring Z 1 , ring Z 2 , L ′, m ′ and n ′ are represented by the general formula ( It is synonymous with M, A 1 , A 2 , A 3 , B 1 , B 2 , B 3 , ring Z 1 , ring Z 2 , L ′, m ′ and n ′ in DP-2).
L ″ 1 and L ″ 2 represent C—Rb 6 or a nitrogen atom, and Rb 6 represents a hydrogen atom or a substituent. When L ″ 1 and L ″ 2 are C—Rb 6 , Rb 6 may be bonded to each other to form a ring.
In the general formulas (DP), (DP-1), (DP-2), and (DP-2a), A 2 is preferably a carbon atom, and A 1 is preferably a carbon atom. More preferably, the ring Z 1 is a substituted or unsubstituted benzene ring or pyridine ring, and more preferably a benzene ring.
（２．２）蛍光ドーパント
蛍光ドーパントとしては、クマリン系色素、ピラン系色素、シアニン系色素、クロコニウム系色素、スクアリウム系色素、オキソベンツアントラセン系色素、フルオレセイン系色素、ローダミン系色素、ピリリウム系色素、ペリレン系色素、スチルベン系色素、ポリチオフェン系色素、又は希土類錯体系蛍光体等や、レーザー色素に代表される蛍光量子効率が高い化合物が挙げられる。(2.2) Fluorescent dopant Examples of fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, Examples include perylene dyes, stilbene dyes, polythiophene dyes, rare earth complex phosphors, and compounds having high fluorescence quantum efficiency, such as laser dyes.
［従来公知のドーパントとの併用］
また、本発明に用いられる発光ドーパントは、複数種の化合物を併用して用いてもよく、構造の異なるリン光ドーパント同士の組み合わせや、リン光ドーパントと蛍光ドーパントを組み合わせて用いてもよい。
本発明に使用できる公知のリン光ドーパントの具体例としては、以下の文献に記載されている化合物等が挙げられる。
Ｎａｔｕｒｅ，３９５，１５１（１９９８）、Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，７８，１６２２（２００１）、Ａｄｖ．Ｍａｔｅｒ．，１９，７３９（２００７）、Ｃｈｅｍ．Ｍａｔｅｒ．，１７，３５３２（２００５）、Ａｄｖ．Ｍａｔｅｒ．，１７，１０５９（２００５）、国際公開第２００９／１００９９１号、国際公開第２００８／１０１８４２号、国際公開第２００３／０４０２５７号、米国特許出願公開第２００６／８３５４６９号明細書、米国特許出願公開第２００６／０２０２１９４号明細書、米国特許出願公開第２００７／００８７３２１号明細書、米国特許出願公開第２００５／０２４４６７３号明細書、Ｉｎｏｒｇ．Ｃｈｅｍ．，４０，１７０４（２００１）、Ｃｈｅｍ．Ｍａｔｅｒ．，１６，２４８０（２００４）、Ａｄｖ．Ｍａｔｅｒ．，１６，２００３（２００４）、Ａｎｇｅｗ．Ｃｈｅｍ．ｌｎｔ．Ｅｄ．，２００６，４５，７８００、Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，８６，１５３５０５（２００５）、Ｃｈｅｍ．Ｌｅｔｔ．，３４，５９２（２００５）、Ｃｈｅｍ．Ｃｏｍｍｕｎ．，２９０６（２００５）、Ｉｎｏｒｇ．Ｃｈｅｍ．，４２，１２４８（２００３）、国際公開第２００９／０５０２９０号、国際公開第２００２／０１５６４５号、国際公開第２００９／０００６７３号、米国特許出願公開第２００２／００３４６５６号明細書、米国特許第７３３２２３２号明細書、米国特許出願公開第２００９／０１０８７３７号明細書、米国特許出願公開第２００９／００３９７７６号明細書、米国特許第６９２１９１５号明細書、米国特許第６６８７２６６号明細書、米国特許出願公開第２００７／０１９０３５９号明細書、米国特許出願公開第２００６／０００８６７０号明細書、米国特許出願公開第２００９／０１６５８４６号明細書、米国特許出願公開第２００８／００１５３５５号明細書、米国特許第７２５０２２６号明細書、米国特許第７３９６５９８号明細書、米国特許出願公開第２００６／０２６３６３５号明細書、米国特許出願公開第２００３／０１３８６５７号明細書、米国特許出願公開第２００３／０１５２８０２号明細書、米国特許第７０９０９２８号明細書、Ａｎｇｅｗ．Ｃｈｅｍ．ｌｎｔ．Ｅｄ．，４７，１（２００８）、Ｃｈｅｍ．Ｍａｔｅｒ．，１８，５１１９（２００６）、Ｉｎｏｒｇ．Ｃｈｅｍ．，４６，４３０８（２００７）、Ｏｒｇａｎｏｍｅｔａｌｌｉｃｓ，２３，３７４５（２００４）、Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，７４，１３６１（１９９９）、国際公開第２００２／００２７１４号、国際公開第２００６／００９０２４号、国際公開第２００６／０５６４１８号、国際公開第２００５／０１９３７３号、国際公開第２００５／１２３８７３号、国際公開第２００７／００４３８０号、国際公開第２００６／０８２７４２号、米国特許出願公開第２００６／０２５１９２３号明細書、米国特許出願公開第２００５／０２６０４４１号明細書、米国特許第７３９３５９９号明細書、米国特許第７５３４５０５号明細書、米国特許第７４４５８５５号明細書、米国特許出願公開第２００７／０１９０３５９号明細書、米国特許出願公開第２００８／０２９７０３３号明細書、米国特許第７３３８７２２号明細書、米国特許出願公開第２００２／０１３４９８４号明細書、米国特許第７２７９７０４号明細書、米国特許出願公開第２００６／０９８１２０号明細書、米国特許出願公開第２００６／１０３８７４号明細書、国際公開第２００５／０７６３８０号、国際公開第２０１０／０３２６６３号、国際公開第２００８／１４０１１５号、国際公開第２００７／０５２４３１号、国際公開第２０１１／１３４０１３号、国際公開第２０１１／１５７３３９号、国際公開第２０１０／０８６０８９号、国際公開第２００９／１１３６４６号、国際公開第２０１２／０２０３２７号、国際公開第２０１１／０５１４０４号、国際公開第２０１１／００４６３９号、国際公開第２０１１／０７３１４９号、米国特許出願公開第２０１２／２２８５８３号明細書、米国特許出願公開第２０１２／２１２１２６号明細書、特開２０１２−０６９７３７号公報、特開２０１１−１８１３０３号公報、特開２００９−１１４０８６号公報、特開２００３−８１９８８号公報、特開２００２−３０２６７１号公報、特開２００２−３６３５５２号公報等である。
中でも、好ましいリン光ドーパントとしてはＩｒを中心金属に有する有機金属錯体が挙げられる。さらに好ましくは、金属−炭素結合、金属−窒素結合、金属−酸素結合、金属−硫黄結合のうち少なくとも一つの配位様式を含む錯体が好ましい。
ここで、本発明に使用できる公知のリン光ドーパントの具体例を挙げるが、本発明はこれらに限定されない。[Combination with conventionally known dopants]
In addition, the light emitting dopant used in the present invention may be used in combination of a plurality of types of compounds, a combination of phosphorescent dopants having different structures, or a combination of a phosphorescent dopant and a fluorescent dopant.
Specific examples of known phosphorescent dopants that can be used in the present invention include compounds described in the following documents.
Nature, 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. , 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. , 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Application Publication No. 2006/835469, US Patent Application Publication No. 2006. No. 0202194, U.S. Patent Application Publication No. 2007/0087321, U.S. Patent Application Publication No. 2005/0244673, Inorg. Chem. , 40, 1704 (2001), Chem. Mater. 16, 2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. lnt. Ed. , 2006, 45, 7800, Appl. Phys. Lett. 86, 153505 (2005), Chem. Lett. , 34, 592 (2005), Chem. Commun. , 2906 (2005), Inorg. Chem. , 42, 1248 (2003), International Publication No. 2009/050290, International Publication No. 2002/015645, International Publication No. 2009/000673, US Patent Application Publication No. 2002/0034656, and US Pat. No. 7,332,232. United States Patent Application Publication No. 2009/0108737, United States Patent Application Publication No. 2009/0039776, United States Patent No. 6921915, United States Patent No. 6,687,266, United States Patent Application Publication No. 2007/0190359. No., US Patent Application Publication No. 2006/0008670, US Patent Application Publication No. 2009/0165846, US Patent Application Publication No. 2008/0015355, US Pat. No. 7,250,226, US Patent No. 7396598 Writing, U.S. Patent Application Publication No. 2006/0263635, U.S. Patent Application Publication No. 2003/0138657, U.S. Patent Application Publication No. 2003/0152802, U.S. Patent No. 7090928, Angew. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. , 18, 5119 (2006), Inorg. Chem. 46, 4308 (2007), Organometallics, 23, 3745 (2004), Appl. Phys. Lett. , 74, 1361 (1999), International Publication No. 2002/002714, International Publication No. 2006/009024, International Publication No. 2006/056418, International Publication No. 2005/019373, International Publication No. 2005/123873, International Publication. No. 2007/004380, International Publication No. 2006/082742, US Patent Application Publication No. 2006/0251923, US Patent Application Publication No. 2005/0260441, US Pat. No. 7,393,599, US Pat. No. 7,534,505. No. 7, U.S. Pat. No. 7,445,855, U.S. Patent Application Publication No. 2007/0190359, U.S. Patent Application Publication No. 2008/0297033, U.S. Pat. No. 7,338,722, U.S. Patent Application Publication No. 2002. / 013498 No. 7, U.S. Pat. No. 7,279,704, U.S. Patent Application Publication No. 2006/098120, U.S. Patent Application Publication No. 2006/103874, WO 2005/076380, WO 2010/032663 No., International Publication No. 2008/140115, International Publication No. 2007/052431, International Publication No. 2011/134013, International Publication No. 2011/157339, International Publication No. 2010/086089, International Publication No. 2009/113646, International Publication No. 2012/020327, International Publication No. 2011/051404, International Publication No. 2011/004639, International Publication No. 2011/073149, US Patent Application Publication No. 2012/228583, US Patent Application Publication No. 2012 / 21212 , JP2012-069737, JP2011-181303, JP2009-1114086, JP2003-81988, JP2002-302671, JP2002-363552. For example, a gazette.
Among these, a preferable phosphorescent dopant includes an organometallic complex having Ir as a central metal. More preferably, a complex containing at least one coordination mode among a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is preferable.
Here, although the specific example of the well-known phosphorescence dopant which can be used for this invention is given, this invention is not limited to these.
《電子輸送層》
電子輸送層とは、電子を輸送する機能を有する材料からなり、広い意味で電子注入層、正孔阻止層も電子輸送層に含まれる。電子輸送層は単層若しくは複数層を設けることができる。
電子輸送層は、陰極より注入された電子を発光層に伝達する機能を有していればよく、電子輸送層の構成材料としては従来公知の化合物の中から任意のものを選択し併用することも可能である。《Electron transport layer》
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided with a single layer or a plurality of layers.
The electron transport layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and as a constituent material of the electron transport layer, any one of conventionally known compounds may be selected and used in combination. Is also possible.
電子輸送層に用いられる従来公知の材料（以下、電子輸送材料という。）の例としては、ニトロ置換フルオレン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、ナフタレンペリレン等の多環芳香族炭化水素、複素環テトラカルボン酸無水物、カルボジイミド、フレオレニリデンメタン誘導体、アントラキノジメタン及びアントロン誘導体、オキサジアゾール誘導体、カルボリン誘導体又は該カルボリン誘導体のカルボリン環を構成する炭化水素環の炭素原子の少なくとも一つが窒素原子で置換されている環構造を有する誘導体、ヘキサアザトリフェニレン誘導体等が挙げられる。
更に、上記オキサジアゾール誘導体において、オキサジアゾール環の酸素原子を硫黄原子に置換したチアジアゾール誘導体、電子求引性基として知られているキノキサリン環を有するキノキサリン誘導体も電子輸送材料として用いることができる。
これらの材料を高分子鎖に導入した、又はこれらの材料を高分子の主鎖とした高分子材料を用いることもできる。Examples of conventionally known materials used for the electron transport layer (hereinafter referred to as electron transport materials) include polycyclic aromatic hydrocarbons such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, Heterocyclic tetracarboxylic anhydride, carbodiimide, fluorenylidenemethane derivative, anthraquinodimethane and anthrone derivative, oxadiazole derivative, carboline derivative or at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative And derivatives having a ring structure in which one is substituted with a nitrogen atom, hexaazatriphenylene derivatives and the like.
Furthermore, in the above oxadiazole derivatives, thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. .
It is also possible to use a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain.
また、８−キノリノール誘導体の金属錯体、例えば、トリス（８−キノリノール）アルミニウム（Ａｌｑ）、トリス（５，７−ジクロロ−８−キノリノール）アルミニウム、トリス（５，７−ジブロモ−８−キノリノール）アルミニウム、トリス（２−メチル−８−キノリノール）アルミニウム、トリス（５−メチル−８−キノリノール）アルミニウム、ビス（８−キノリノール）亜鉛（Ｚｎｑ）等、及びこれらの金属錯体の中心金属がＩｎ、Ｍｇ、Ｃｕ、Ｃａ、Ｓｎ、Ｇａ又はＰｂに置き替わった金属錯体も電子輸送材料として用いることができる。
その他、メタルフリー若しくはメタルフタロシアニン、又はそれらの末端がアルキル基やスルホン酸基等で置換されているものも電子輸送材料として用いることができる。
また、ｎ型−Ｓｉ、ｎ型−ＳｉＣ等の無機半導体も電子輸送材料として用いることができる。In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga, or Pb can also be used as the electron transport material.
In addition, metal-free or metal phthalocyanine, or those having a terminal substituted with an alkyl group or a sulfonic acid group can be used as the electron transport material.
In addition, inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the electron transport material.
電子輸送層は、電子輸送材料を、例えば、真空蒸着法、湿式法（ウェットプロセスともいい、例えば、スピンコート法、キャスト法、ダイコート法、ブレードコート法、ロールコート法、インクジェット法、印刷法、スプレーコート法、カーテンコート法、ＬＢ法（ラングミュア・ブロジェット（Ｌａｎｇｍｕｉｒ Ｂｌｏｄｇｅｔｔ法）等を挙げることができる。））等により、薄膜化することで形成することが好ましい。 The electron transport layer is made of, for example, a vacuum deposition method, a wet method (also referred to as a wet process, such as a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method, an inkjet method, a printing method, The film is preferably formed by thinning by a spray coating method, a curtain coating method, an LB method (such as Langmuir-Blodgett method)).
電子輸送層の層厚については特に制限はないが、通常は５〜５０００ｎｍ程度、好ましくは５〜２００ｎｍの範囲内である。この電子輸送層は上記材料の１種又は２種以上からなる１層構造であってもよい。
また、金属錯体やハロゲン化金属など金属化合物等のｎ型ドーパントをドープして用いてもよい。Although there is no restriction | limiting in particular about the layer thickness of an electron carrying layer, Usually, about 5-5000 nm, Preferably it exists in the range of 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.
Further, an n-type dopant such as a metal compound such as a metal complex or a metal halide may be doped.
本発明の有機ＥＬ素子の電子輸送層の形成に好ましく用いられる従来公知の電子輸送材料の一例として、国際公開第２０１３／０６１８５０号に記載の化合物を好適に用いることができるが、本発明はこれらに限定されない。 As an example of a conventionally known electron transport material preferably used for forming the electron transport layer of the organic EL device of the present invention, the compounds described in International Publication No. 2013/061850 can be preferably used. It is not limited to.
《陰極》
一方、陰極としては、仕事関数の小さい（４ｅＶ以下）金属（電子注入性金属と称する。）、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが用いられる。このような電極物質の具体例としては、ナトリウム、ナトリウム−カリウム合金、マグネシウム、リチウム、マグネシウム／銅混合物、マグネシウム／銀混合物、マグネシウム／アルミニウム混合物、マグネシウム／インジウム混合物、アルミニウム／酸化アルミニウム（Ａｌ２Ｏ３）混合物、インジウム、リチウム／アルミニウム混合物、希土類金属等が挙げられる。これらの中で、電子注入性及び酸化等に対する耐久性の点から、電子注入性金属とこれより仕事関数の値が大きく安定な金属である第二金属との混合物、例えば、マグネシウム／銀混合物、マグネシウム／アルミニウム混合物、マグネシウム／インジウム混合物、アルミニウム／酸化アルミニウム（Ａｌ２Ｏ３）混合物、リチウム／アルミニウム混合物、アルミニウム等が好適である。"cathode"
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
陰極は、これらの電極物質を蒸着やスパッタリング等の方法で薄膜を形成させることにより、作製することができる。また、陰極としてのシート抵抗は数百Ω／□以下が好ましく、膜厚は通常１０ｎｍ〜５μｍ、好ましくは５０〜２００ｎｍの範囲内で選ばれる。
なお、発光した光を透過させるため、有機ＥＬ素子の陽極又は陰極のいずれか一方が透明又は半透明であれば発光輝度が向上し好都合である。
また、陰極に上記金属を１〜２０ｎｍの膜厚で作製した後に、後述する陽極の説明で挙げる導電性透明材料をその上に作製することで、透明又は半透明の陰極を作製することができ、これを応用することで陽極と陰極の両方が透過性を有する素子を作製することができる。The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected within the range of 10 nm to 5 μm, preferably 50 to 200 nm.
In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the emission luminance is advantageously improved.
In addition, a transparent or translucent cathode can be produced by producing a conductive transparent material mentioned in the explanation of the anode described later on the cathode after producing the metal with a thickness of 1 to 20 nm on the cathode. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.
《注入層：電子注入層（陰極バッファー層）、正孔注入層》
注入層は必要に応じて設け、電子注入層と正孔注入層があり、上記のように陽極と発光層又は正孔輸送層の間、及び陰極と発光層又は電子輸送層との間に存在させてもよい。
注入層とは、駆動電圧低下や発光輝度向上のために電極と有機層間に設けられる層のことで、「有機ＥＬ素子とその工業化最前線（１９９８年１１月３０日エヌ・ティー・エス社発行）」の第２編第２章「電極材料」（１２３〜１６６頁）に詳細に記載されており、正孔注入層（陽極バッファー層）と電子注入層（陰極バッファー層）とがある。<< Injection layer: electron injection layer (cathode buffer layer), hole injection layer >>
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, exists between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport layer. You may let them.
An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).
陽極バッファー層（正孔注入層）は、特開平９−４５４７９号公報、同９−２６００６２号公報、同８−２８８０６９号公報等にもその詳細が記載されており、具体例として、銅フタロシアニンに代表されるフタロシアニンバッファー層、特表２００３−５１９４３２号公報や特開２００６−１３５１４５号公報等に記載されているようなヘキサアザトリフェニレン誘導体バッファー層、酸化バナジウムに代表される酸化物バッファー層、アモルファスカーボンバッファー層、ポリアニリン（エメラルディン）やポリチオフェン等の導電性高分子を用いた高分子バッファー層、トリス（２−フェニルピリジン）イリジウム錯体等に代表されるオルトメタル化錯体層等が挙げられる。 The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Representative phthalocyanine buffer layer, hexaazatriphenylene derivative buffer layer, oxide buffer layer typified by vanadium oxide, amorphous carbon as described in JP-T-2003-519432 and JP-A-2006-135145 Examples thereof include a buffer layer, a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) and polythiophene, and an orthometalated complex layer represented by tris (2-phenylpyridine) iridium complex.
陰極バッファー層（電子注入層）は、特開平６−３２５８７１号公報、同９−１７５７４号公報、同１０−７４５８６号公報等にもその詳細が記載されており、具体的にはストロンチウムやアルミニウム等に代表される金属バッファー層、フッ化リチウム、フッ化カリウムに代表されるアルカリ金属化合物バッファー層、フッ化マグネシウム、フッ化セシウムに代表されるアルカリ土類金属化合物バッファー層、酸化アルミニウムに代表される酸化物バッファー層等が挙げられる。上記バッファー層（注入層）はごく薄い膜であることが望ましく、素材にもよるがその膜厚は０．１ｎｍ〜５μｍの範囲内が好ましい。 The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by, alkali metal compound buffer layer typified by lithium fluoride and potassium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride and cesium fluoride, typified by aluminum oxide Examples thereof include an oxide buffer layer. The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm, although it depends on the material.
《阻止層：正孔阻止層、電子阻止層》
阻止層は、上記のごとく有機化合物薄膜の基本構成層の他に必要に応じて設けられるものである。例えば、特開平１１−２０４２５８号公報、同１１−２０４３５９号公報、及び「有機ＥＬ素子とその工業化最前線（１９９８年１１月３０日エヌ・ティー・エス社発行）」の２３７頁等に記載されている正孔阻止（ホールブロック）層がある。<Blocking layer: hole blocking layer, electron blocking layer>
As described above, the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.
正孔阻止層とは、広い意味では電子輸送層の機能を有し、電子を輸送する機能を有しつつ正孔を輸送する能力が著しく小さい正孔阻止材料からなり、電子を輸送しつつ正孔を阻止することで電子と正孔の再結合確率を向上させることができる。
また、前述する電子輸送層の構成を必要に応じて、正孔阻止層として用いることができる。
本発明の有機ＥＬ素子の正孔阻止層は、発光層に隣接して設けられていることが好ましい。
正孔阻止層には、前述のホスト化合物として挙げた、カルバゾール誘導体、カルボリン誘導体、ジアザカルバゾール誘導体（ここで、ジアザカルバゾール誘導体とは、カルボリン環を構成する炭素原子のいずれか一つが窒素原子で置き換わったものをいう。）を含有することが好ましい。The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material having a function of transporting electrons and a very small ability to transport holes. By blocking the holes, the probability of recombination of electrons and holes can be improved.
Moreover, the structure of the electron carrying layer mentioned above can be used as a hole-blocking layer as needed.
The hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.
The hole blocking layer includes a carbazole derivative, a carboline derivative, a diazacarbazole derivative (the diazacarbazole derivative is a nitrogen atom in which any one of carbon atoms constituting the carboline ring is cited as the host compound described above. It is preferable to contain the thing replaced by.
一方、電子阻止層とは、広い意味では正孔輸送層の機能を有し、正孔を輸送する機能を有しつつ電子を輸送する能力が著しく小さい材料からなり、正孔を輸送しつつ電子を阻止することで電子と正孔の再結合確率を向上させることができる。
また、後述する正孔輸送層の構成を必要に応じて電子阻止層として用いることができる。本発明に係る正孔阻止層、電子輸送層の層厚としては、好ましくは３〜１００ｎｍであり、更に好ましくは５〜３０ｎｍの範囲内である。On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material having a function of transporting holes while having a remarkably small ability to transport electrons. The probability of recombination of electrons and holes can be improved by blocking.
Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. The layer thickness of the hole blocking layer and the electron transport layer according to the present invention is preferably 3 to 100 nm, more preferably 5 to 30 nm.
《正孔輸送層》
正孔輸送層とは、正孔を輸送する機能を有する正孔輸送材料からなり、広い意味で正孔注入層、電子阻止層も正孔輸送層に含まれる。正孔輸送層は単層又は複数層設けることができる。
正孔輸送材料としては、正孔の注入又は輸送、電子の障壁性のいずれかを有するものであり、有機物、無機物のいずれであってもよい。例えば、トリアゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体及びピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、オキサゾール誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、アニリン系共重合体、導電性高分子オリゴマー、特にチオフェンオリゴマー等が挙げられる。
また、特表２００３−５１９４３２号公報や特開２００６−１３５１４５号公報等に記載されているようなアザトリフェニレン誘導体も同様に正孔輸送材料として用いることができる。《Hole transport layer》
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.
The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, particularly thiophene oligomers.
Further, azatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as a hole transport material.
正孔輸送材料としては、上記のものを使用することができるが、ポルフィリン化合物、芳香族第３級アミン化合物及びスチリルアミン化合物、特に芳香族第３級アミン化合物を用いることが好ましい。
芳香族第３級アミン化合物及びスチリルアミン化合物の代表例としては、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラフェニル−４，４′−ジアミノフェニル；Ｎ，Ｎ′−ジフェニル−Ｎ，Ｎ′−ビス（３−メチルフェニル）−〔１，１′−ビフェニル〕−４，４′−ジアミン（ＴＰＤ）；２，２−ビス（４−ジ−ｐ−トリルアミノフェニル）プロパン；１，１−ビス（４−ジ−ｐ−トリルアミノフェニル）シクロヘキサン；Ｎ，Ｎ，Ｎ′，Ｎ′−テトラ−ｐ−トリル−４，４′−ジアミノビフェニル；１，１−ビス（４−ジ−ｐ−トリルアミノフェニル）−４−フェニルシクロヘキサン；ビス（４−ジメチルアミノ−２−メチルフェニル）フェニルメタン；ビス（４−ジ−ｐ−トリルアミノフェニル）フェニルメタン；Ｎ，Ｎ′−ジフェニル−Ｎ，Ｎ′−ジ（４−メトキシフェニル）−４，４′−ジアミノビフェニル；Ｎ，Ｎ，Ｎ′，Ｎ′−テトラフェニル−４，４′−ジアミノジフェニルエーテル；４，４′−ビス（ジフェニルアミノ）クオードリフェニル；Ｎ，Ｎ，Ｎ−トリ（ｐ−トリル）アミン；４−（ジ−ｐ−トリルアミノ）−４′−〔４−（ジ−ｐ−トリルアミノ）スチリル〕スチルベン；４−Ｎ，Ｎ−ジフェニルアミノ−（２−ジフェニルビニル）ベンゼン；３−メトキシ−４′−Ｎ，Ｎ−ジフェニルアミノスチルベン；Ｎ−フェニルカルバゾール、更には米国特許第５０６１５６９号明細書に記載されている２個の縮合芳香族環を分子内に有するもの、例えば、４，４′−ビス〔Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ〕ビフェニル（ＮＰＤ）、特開平４−３０８６８８号公報に記載されているトリフェニルアミンユニットが三つスターバースト型に連結された４，４′，４″−トリス〔Ｎ−（３−メチルフェニル）−Ｎ−フェニルアミノ〕トリフェニルアミン（ＭＴＤＡＴＡ）等が挙げられる。Although the above-mentioned thing can be used as a positive hole transport material, It is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styryl amine compound, especially an aromatic tertiary amine compound.
Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbene; N-phenylcarbazole, and also two fused aromatic rings described in US Pat. No. 5,061,569. What is contained in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), Japanese Patent Laid-Open No. 4-308688 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA), etc., in which three triphenylamine units described in 1 are linked in a starburst type Is mentioned.
更にこれらの材料を高分子鎖に導入した、又はこれらの材料を高分子の主鎖とした高分子材料を用いることもできる。
また、ｐ型−Ｓｉ、ｐ型−ＳｉＣ等の無機化合物も正孔注入材料、正孔輸送材料として使用することができる。
また、特開平１１−２５１０６７号公報、Ｊ．Ｈｕａｎｇ ｅｔ．ａｌ．著文献（Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ Ｌｅｔｔｅｒｓ ８０（２００２），ｐ．１３９）に記載されているような、いわゆるｐ型正孔輸送材料を用いることもできる。本発明においては、より高効率の発光素子が得られることからこれらの材料を用いることが好ましい。Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, these materials are preferably used because a light-emitting element with higher efficiency can be obtained.
正孔輸送層は、上記正孔輸送材料を、例えば、真空蒸着法、スピンコート法、キャスト法、インクジェット法を含む印刷法、ＬＢ法等の公知の方法により、薄膜化することにより形成することができる。
正孔輸送層の層厚については特に制限はないが、通常は５ｎｍ〜５μｍ程度、好ましくは５〜２００ｎｍである。この正孔輸送層は上記材料の１種又は２種以上からなる１層構造であってもよい。The hole transport layer is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Can do.
Although there is no restriction | limiting in particular about the layer thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. This hole transport layer may have a single layer structure composed of one or more of the above materials.
また、不純物をドープしたｐ性の高い正孔輸送層を用いることもできる。その例としては、特開平４−２９７０７６号公報、特開２０００−１９６１４０号公報、同２００１−１０２１７５号公報の各公報、Ｊ．Ａｐｐｌ．Ｐｈｙｓ．，９５，５７７３（２００４）等に記載されたものが挙げられる。
本発明においては、このようなｐ性の高い正孔輸送層を用いることが、より低消費電力の素子を作製することができるため好ましい。Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.
In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced.
《陽極》
有機ＥＬ素子における陽極としては、仕事関数の大きい（４ｅＶ以上）金属、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが好ましく用いられる。このような電極物質の具体例としては、Ａｕ等の金属、ＣｕＩ、ＩＴＯ、ＳｎＯ２、ＺｎＯ等の導電性透明材料が挙げられる。
また、ＩＤＩＸＯ（Ｉｎ２Ｏ３−ＺｎＯ）等非晶質で透明導電膜を作製可能な材料を用いてもよい。陽極はこれらの電極物質を蒸着やスパッタリング等の方法により薄膜を形成させ、フォトリソグラフィー法で所望の形状のパターンを形成してもよく、又はパターン精度を余り必要としない場合は（１００μｍ以上程度）、上記電極物質の蒸着やスパッタリング時に所望の形状のマスクを介してパターンを形成してもよい。"anode"
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such an electrode substance include metals such as Au, and conductive transparent materials such as CuI, ITO, SnO 2 , and ZnO.
Alternatively, an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used. For the anode, a thin film may be formed by vapor deposition or sputtering of these electrode materials, and a pattern of a desired shape may be formed by photolithography, or when pattern accuracy is not required (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
または、有機導電性化合物のように塗布可能な物質を用いる場合には、印刷方式、コーティング方式等の湿式成膜法を用いることもできる。この陽極より発光を取り出す場合には、透過率を１０％より大きくすることが望ましく、また陽極としてのシート抵抗は数百Ω／□以下が好ましい。更に膜厚は材料にもよるが、通常１０〜１０００ｎｍ、好ましくは１０〜２００ｎｍの範囲内で選ばれる。 Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected within the range of 10 to 1000 nm, preferably 10 to 200 nm.
《支持基板》
本発明の有機ＥＬ素子に用いることのできる支持基板（以下、基体、基板、基材、支持体等ともいう。）としては、ガラス、プラスチック等の種類には特に限定はなく、また透明であっても不透明であってもよい。支持基板側から光を取り出す場合には、支持基板は透明であることが好ましい。好ましく用いられる透明な支持基板としては、ガラス、石英、透明樹脂フィルムを挙げることができる。特に好ましい支持基板は、有機ＥＬ素子にフレキシブル性を与えることが可能な樹脂フィルムである。《Support substrate》
The support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc., and is transparent. Or opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.
樹脂フィルムとしては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）等のポリエステル、ポリエチレン、ポリプロピレン、セロファン、セルロースジアセテート、セルローストリアセテート（ＴＡＣ）、セルロースアセテートブチレート、セルロースアセテートプロピオネート（ＣＡＰ）、セルロースアセテートフタレート、セルロースナイトレート等のセルロースエステル類又はそれらの誘導体、ポリ塩化ビニリデン、ポリビニルアルコール、ポリエチレンビニルアルコール、シンジオタクティックポリスチレン、ポリカーボネート、ノルボルネン樹脂、ポリメチルペンテン、ポリエーテルケトン、ポリイミド、ポリエーテルスルホン（ＰＥＳ）、ポリフェニレンスルフィド、ポリスルホン類、ポリエーテルイミド、ポリエーテルケトンイミド、ポリアミド、フッ素樹脂、ナイロン、ポリメチルメタクリレート、アクリル又はポリアリレート類、アートン（商品名ＪＳＲ社製）又はアペル（商品名三井化学社製）といったシクロオレフィン系樹脂等のフィルムを挙げることができる。 Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Can be mentioned.
樹脂フィルムの表面には、無機物、有機物の被膜又はその両者のハイブリッド被膜が形成されていてもよく、ＪＩＳ Ｋ ７１２９−１９９２に準拠した方法で測定された、水蒸気透過度（２５±０．５℃、相対湿度（９０±２）％）が０．０１ｇ／ｍ２・２４ｈ以下のガスバリアー性フィルムであることが好ましく、更には、ＪＩＳ Ｋ ７１２６−１９８７に準拠した方法で測定された酸素透過度が、１×１０−３ｍｌ／ｍ２・２４ｈ・ａｔｍ以下、水蒸気透過度が、１×１０−５ｇ／ｍ２・２４ｈ以下の高ガスバリアー性フィルムであることが好ましい。An inorganic film, an organic film, or a hybrid film of both may be formed on the surface of the resin film, and the water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. , And a relative humidity (90 ± 2)%) of 0.01 g / m 2 · 24 h or less is preferable. Further, the oxygen permeability measured by a method according to JIS K 7126-1987 is preferable. However, it is preferable that it is a high gas-barrier film whose 1 * 10 < -3 > ml / m < 2 > * 24h * atm or less and water vapor permeability are 1 * 10 < -5 > g / m < 2 > * 24h or less.
ガスバリアー層を形成する材料としては、水分や酸素等の素子の劣化をもたらすものの浸入を抑制する機能を有する材料であればよく、例えば、酸化ケイ素、二酸化ケイ素、窒化ケイ素等を用いることができる。更に該膜の脆弱性を改良するために、これら無機層と有機材料からなる層の積層構造を持たせることがより好ましい。無機層と有機層の積層順については特に制限はないが、両者を交互に複数回積層させることが好ましい。 The material for forming the gas barrier layer may be any material as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. . Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and organic material layers. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.
ガスバリアー層の形成方法については特に限定はなく、例えば、真空蒸着法、スパッタリング法、反応性スパッタリング法、分子線エピタキシー法、クラスターイオンビーム法、イオンプレーティング法、プラズマ重合法、大気圧プラズマ重合法、プラズマＣＶＤ法、レーザーＣＶＤ法、熱ＣＶＤ法、コーティング法等を用いることができるが、特開２００４−６８１４３号公報に記載されているような大気圧プラズマ重合法によるものが特に好ましい。
不透明な支持基板としては、例えば、アルミ、ステンレス等の金属板、フィルムや不透明樹脂基板、セラミック製の基板等が挙げられる。The method for forming the gas barrier layer is not particularly limited. For example, the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.
本発明の有機ＥＬ素子の発光の室温における外部取り出し量子効率は、１％以上であることが好ましく、５％以上であるとより好ましい。
ここで、外部取り出し量子効率（％）＝有機ＥＬ素子外部に発光した光子数／有機ＥＬ素子に流した電子数×１００である。
また、カラーフィルター等の色相改良フィルター等を併用しても、有機ＥＬ素子からの発光色を、蛍光体を用いて多色へ変換する色変換フィルターを併用してもよい。色変換フィルターを用いる場合においては、有機ＥＬ素子の発光のλｍａｘは４８０ｎｍ以下が好ましい。The external extraction quantum efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, and more preferably 5% or more.
Here, external extraction quantum efficiency (%) = number of photons emitted to the outside of the organic EL element / number of electrons flowed to the organic EL element × 100.
In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.
《有機ＥＬ素子の作製方法》
有機ＥＬ素子の作製方法の一例として、陽極／正孔注入層／正孔輸送層／発光層／正孔阻止層／電子輸送層／陰極バッファー層（電子注入層）／陰極からなる素子の作製方法について説明する。
まず、適当な基体上に所望の電極物質、例えば、陽極用物質からなる薄膜を１μｍ以下、好ましくは１０〜２００ｎｍの範囲内の膜厚になるように形成させ、陽極を作製する。
次に、この上に素子材料である正孔注入層、正孔輸送層、発光層、正孔阻止層、電子輸送層、陰極バッファー層等の有機化合物を含有する薄膜を形成させる。<< Method for producing organic EL element >>
As an example of a method for producing an organic EL device, a device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode Will be described.
First, a thin film made of a desired electrode material, for example, an anode material, is formed on a suitable substrate so as to have a thickness of 1 μm or less, preferably in the range of 10 to 200 nm, to produce an anode.
Next, a thin film containing an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, or a cathode buffer layer, which is an element material, is formed thereon.
薄膜の形成方法としては、例えば、真空蒸着法、湿式法（ウェットプロセスともいう。）等により成膜して形成することができる。
湿式法としては、スピンコート法、キャスト法、ダイコート法、ブレードコート法、ロールコート法、インクジェット法、印刷法、スプレーコート法、カーテンコート法、ＬＢ法等があるが、精密な薄膜が形成可能で、かつ高生産性の点から、ダイコート法、ロールコート法、インクジェット法、スプレーコート法などのロールｔｏロール方式適性の高い方法が好ましい。また、層ごとに異なる成膜法を適用してもよい。As a method for forming a thin film, for example, a thin film can be formed by a vacuum deposition method, a wet method (also referred to as a wet process), or the like.
Wet methods include spin coating, casting, die coating, blade coating, roll coating, ink jet, printing, spray coating, curtain coating, and LB, but precise thin films can be formed. From the viewpoint of high productivity, a method having high suitability for the roll-to-roll method such as a die coating method, a roll coating method, an ink jet method, and a spray coating method is preferable. Different film formation methods may be applied for each layer.
本発明に用いられる発光ドーパント等の有機ＥＬ素子用材料を溶解又は分散する液媒体としては、例えば、メチルエチルケトン、シクロヘキサノン等のケトン類、酢酸エチル等の脂肪酸エステル類、ジクロロベンゼン等のハロゲン化炭化水素類、トルエン、キシレン、メシチレン、シクロヘキシルベンゼン等の芳香族炭化水素類、シクロヘキサン、デカリン、ドデカン等の脂肪族炭化水素類、ジメチルホルムアミド（ＤＭＦ）、ＤＭＳＯ等の有機溶媒を用いることができる。
また、分散方法としては、超音波、高剪断力分散やメディア分散等の分散方法により分散することができる。Examples of the liquid medium for dissolving or dispersing the organic EL device material such as a light-emitting dopant used in the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, and halogenated hydrocarbons such as dichlorobenzene. , Aromatic hydrocarbons such as toluene, xylene, mesitylene, and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as dimethylformamide (DMF) and DMSO can be used.
Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.
これらの層の形成後、その上に陰極用物質からなる薄膜を１μｍ以下、好ましくは５０〜２００ｎｍの範囲内の膜厚になるように形成させ、陰極を設けることにより所望の有機ＥＬ素子が得られる。
また、順序を逆にして、陰極、陰極バッファー層、電子輸送層、正孔阻止層、発光層、正孔輸送層、正孔注入層、陽極の順に作製することも可能である。
本発明の有機ＥＬ素子の作製は、一回の真空引きで一貫して正孔注入層から陰極まで作製するのが好ましいが、途中で取り出して異なる成膜法を施しても構わない。その際、作業を乾燥不活性ガス雰囲気下で行うことが好ましい。After the formation of these layers, a thin film made of a cathode material is formed thereon so as to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm, and a desired organic EL device is obtained by providing a cathode. It is done.
Further, the order can be reversed, and the cathode, cathode buffer layer, electron transport layer, hole blocking layer, light emitting layer, hole transport layer, hole injection layer, and anode can be formed in this order.
The organic EL device of the present invention is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but it may be taken out halfway and subjected to different film forming methods. At that time, it is preferable to perform the work in a dry inert gas atmosphere.
《その他の構成》
本発明に用いることができる封止手段、保護膜、保護板、光取り出し効率を向上させる技術及び集光シートとしては、特開２０１４−１５２１５１号公報等に記載の公知の技術を用いることができる。<Other configuration>
As a sealing means, a protective film, a protective plate, a technique for improving light extraction efficiency, and a light collecting sheet that can be used in the present invention, a known technique described in JP 2014-152151 A can be used. .
《用途》
本発明の有機ＥＬ素子は、電子デバイス、表示装置、ディスプレイ、各種発光装置として用いることができる。発光装置として、例えば、照明装置（家庭用照明、車内照明）、時計や液晶用バックライト、看板広告、信号機、光記憶媒体の光源、電子写真複写機の光源、光通信処理機の光源、光センサーの光源等が挙げられるがこれに限定するものではないが、特に液晶表示装置のバックライト、照明用光源としての用途に有効に用いることができる。<Application>
The organic EL element of the present invention can be used as an electronic device, a display device, a display, and various light emitting devices. Examples of light-emitting devices include lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light Although the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.
本発明の有機ＥＬ素子においては、必要に応じ成膜時にメタルマスクやインクジェットプリンティング法等でパターニングを施してもよい。パターニングする場合は、電極のみをパターニングしてもよいし、電極と発光層をパターニングしてもよいし、素子全層をパターニングしてもよく、素子の作製においては、従来公知の方法を用いることができる。 In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.
本発明の有機ＥＬ素子や本発明で用いられる化合物の発光する色は、「新編色彩科学ハンドブック」（日本色彩学会編、東京大学出版会、１９８５）の１０８頁の図７．１６において、分光放射輝度計ＣＳ−１０００（コニカミノルタ（株）製）で測定した結果をＣＩＥ色度座標に当てはめたときの色で決定される。
また、本発明の有機ＥＬ素子が白色素子の場合には、白色とは、２度視野角正面輝度を上記方法により測定した際に、１０００ｃｄ／ｍ２でのＣＩＥ１９３１表色系における色度がＸ＝０．３３±０．０７、Ｙ＝０．３３±０．１の領域内にあることをいう。The light emission color of the organic EL device of the present invention and the compound used in the present invention is shown in FIG. 7.16 on
When the organic EL element of the present invention is a white element, white means that the chromaticity in the CIE1931 color system at 1000 cd / m 2 is X when the 2 ° viewing angle front luminance is measured by the above method. = 0.33 ± 0.07 and Y = 0.33 ± 0.1.
《表示装置・照明装置》
本発明の有機ＥＬ素子は、特開２０１４−１５２１５１号公報等に記載の公知の技術を用いて表示装置及び照明装置に具備することができる。
具体的には、本発明の有機ＥＬ素子の非発光面をガラスケースで覆い、厚さ３００μｍのガラス基板を封止用基板として用いて、周囲にシール材として、エポキシ系光硬化型接着剤（東亞合成社製ラックストラックＬＣ０６２９Ｂ）を適用し、これを陰極上に重ねて透明支持基板と密着させ、ガラス基板側からＵＶ光を照射して、硬化させて、封止し、図１及び図２に示すような照明装置を形成することができる。《Display device / Lighting device》
The organic EL element of the present invention can be provided in a display device and a lighting device using a known technique described in Japanese Patent Application Laid-Open No. 2014-152151.
Specifically, the non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a glass substrate having a thickness of 300 μm is used as a sealing substrate, and an epoxy photocurable adhesive ( Tokusei Co., Ltd. LUX TRACK LC0629B) is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured, and sealed. A lighting device as shown in FIG.
図１は、照明装置の概略図を示し、本発明の有機ＥＬ素子（照明装置内の有機ＥＬ素子１０１）はガラスカバー１０２で覆われている（なお、ガラスカバーでの封止作業は、照明装置内の有機ＥＬ素子１０１を大気に接触させることなく窒素雰囲気下のグローブボックス（純度９９．９９９％以上の高純度窒素ガスの雰囲気下）で行った。）。
図２は、照明装置の断面図を示し、図２において、１０５は陰極、１０６は有機層、１０７は透明電極付きガラス基板を示す。なお、ガラスカバー１０２内には窒素ガス１０８が充填され、捕水剤１０９が設けられている。FIG. 1 shows a schematic diagram of a lighting device, and the organic EL element of the present invention (
FIG. 2 is a cross-sectional view of the lighting device. In FIG. 2,
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例において「％」の表示を用いるが、特に断りがない限り「体積％」を表す。なお、合成方法１〜５において、Ａｒ及びＡｒ′とは以下の構造を示す。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "volume%" is represented. In synthesis methods 1 to 5, Ar and Ar ′ represent the following structures.
［実施例１］
《合成方法１》
−７８℃に冷却したアリールブロミドＩ（１０．０ｇ、１４．０ｍｍｏｌ）の無水テトラヒドロフラン（ＴＨＦ）溶液（３００ｍＬ）に、ｎ−ブチルリチウム（１．６Ｍヘキサン溶液、１０ｍＬ、１６ｍｍｏｌ）を１０分かけて滴下し、さらに３０分撹拌した。続いてこの溶液に二酸化炭素ガスを１０分間吹き込み、その後反応溶液を室温まで昇温した。水を加えて反応を停止したのち、塩酸を加えて溶液を酸性として酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過し、溶媒を減圧下で除去した。トルエンで再結晶を行い、カルボン酸IIを得た（７．８３ｇ、１１．５ｍｍｏｌ、収率８２％）。[Example 1]
<< Synthesis Method 1 >>
To an anhydrous tetrahydrofuran (THF) solution (300 mL) of aryl bromide I (10.0 g, 14.0 mmol) cooled to −78 ° C., n-butyllithium (1.6 M hexane solution, 10 mL, 16 mmol) was added over 10 minutes. The solution was added dropwise and further stirred for 30 minutes. Subsequently, carbon dioxide gas was blown into this solution for 10 minutes, and then the reaction solution was heated to room temperature. Water was added to stop the reaction, and hydrochloric acid was added to make the solution acidic, followed by extraction with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over magnesium sulfate. Magnesium sulfate was filtered and the solvent was removed under reduced pressure. Recrystallization from toluene gave carboxylic acid II (7.83 g, 11.5 mmol, yield 82%).
カルボン酸II（７．０ｇ、１０．３ｍｍｏｌ）をトルエン（１００ｍＬ）に溶解し、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）（３ｍＬ）を加えた。続いて塩化チオニル（０．９ｍＬ、１２ｍｍｏｌ）を加え、６０℃で２時間撹拌した。系内を減圧して揮発物を留去し、トルエン（１００ｍＬ）を加えた。この操作を２回繰り返した後、トルエン（１００ｍＬ）及びトリエチルアミン（２．２ｍＬ、１５．４ｍｏｌ）を加えた。続いてこの溶液にアンモニアガスを３０分間吹き込んだ。反応溶液に水を加えたのち、酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過し、溶媒を減圧下で除去した。ジオキサンで再結晶を行い、アミドIIIを得た（６．５９ｇ、９．６８ｍｍｏｌ、収率９４％）。 Carboxylic acid II (7.0 g, 10.3 mmol) was dissolved in toluene (100 mL), and N, N-dimethylformamide (DMF) (3 mL) was added. Subsequently, thionyl chloride (0.9 mL, 12 mmol) was added, and the mixture was stirred at 60 ° C. for 2 hours. The system was decompressed to remove volatiles, and toluene (100 mL) was added. After this operation was repeated twice, toluene (100 mL) and triethylamine (2.2 mL, 15.4 mol) were added. Subsequently, ammonia gas was blown into this solution for 30 minutes. Water was added to the reaction solution, followed by extraction with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over magnesium sulfate. Magnesium sulfate was filtered and the solvent was removed under reduced pressure. Recrystallization from dioxane gave amide III (6.59 g, 9.68 mmol, 94% yield).
アミドIII（６．００ｇ、８．８２ｍｍｏｌ）のトルエン溶液（１００ｍＬ）に五酸化二リン（３．１３ｇ、２２．１ｍｍｏｌ）を加え、１００℃にて８時間撹拌した。放冷後、反応溶液を氷水に注ぎ、トルエンで抽出した。このときの洗浄液を洗浄液Ａとして、後に分析を行った。一方、得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過し、溶媒を減圧下で除去した。シリカゲルクロマトグラフィーにて精製し、シアン化合物IVを得た（５．４４ｇ、８．２１ｍｍｏｌ、収率９３％）。得られた化合物の１Ｈ−ＮＭＲ及び質量分析を測定し、目的物であると同定した。To a toluene solution (100 mL) of amide III (6.00 g, 8.82 mmol) was added diphosphorus pentoxide (3.13 g, 22.1 mmol), and the mixture was stirred at 100 ° C. for 8 hours. After allowing to cool, the reaction solution was poured into ice water and extracted with toluene. The cleaning liquid at this time was used as the cleaning liquid A, and the analysis was performed later. On the other hand, the obtained organic layer was washed with saturated saline, and dried by adding magnesium sulfate. Magnesium sulfate was filtered and the solvent was removed under reduced pressure. Purification by silica gel chromatography gave cyanide compound IV (5.44 g, 8.21 mmol, 93% yield). 1 H-NMR and mass spectrometry of the obtained compound were measured and identified as the target product.
《合成方法２》
−７８℃に冷却したアリールブロミドＩ（１０．０ｇ、１４．０ｍｍｏｌ）の無水ＴＨＦ溶液（１００ｍＬ）に、ｎ−ブチルリチウム（１．６Ｍヘキサン溶液、１０ｍＬ、１６ｍｍｏｌ）を１０分かけて滴下し、さらに３０分撹拌した。続いてこの溶液にＤＭＦ（１．５ｍＬ、２０ｍｍｏｌ）を１０分かけて滴下し、その後反応溶液を室温まで昇温した。飽和塩化アンモニウム水溶液を加えて反応を停止したのち、酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過し、溶媒を減圧下で除去した。トルエンで再結晶を行い、ホルミル化体Ｖを得た（６．８０ｇ、１０．２ｍｍｏｌ、収率７３％）。<< Synthesis Method 2 >>
N-Butyllithium (1.6 M hexane solution, 10 mL, 16 mmol) was added dropwise to an anhydrous THF solution (100 mL) of aryl bromide I (10.0 g, 14.0 mmol) cooled to −78 ° C. over 10 minutes, Stir for another 30 minutes. Subsequently, DMF (1.5 mL, 20 mmol) was added dropwise to this solution over 10 minutes, and then the reaction solution was warmed to room temperature. Saturated aqueous ammonium chloride solution was added to stop the reaction, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over magnesium sulfate. Magnesium sulfate was filtered and the solvent was removed under reduced pressure. Recrystallization with toluene gave formyl compound V (6.80 g, 10.2 mmol, yield 73%).
ヒドロキシアミン塩酸塩（０．７５ｇ、１０．７ｍｏｌ）及び水酸化ナトリウム（０．４３ｇ、１０．７ｍｍｏｌ）を水／エタノール（１：１、５０ｍＬ）に溶解した。続いてホルミル化体Ｖ（６．５０ｇ、９．７６ｍｍｏｌ）のＴＨＦ溶液（５０ｍＬ）を加え、室温で１２時間撹拌した。反応終了後、酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過し、溶媒を減圧下で除去した。トルエンで再結晶を行い、アルドキシムVIを得た（５．３８ｇ、７．９１ｍｍｏｌ、収率８１％）。 Hydroxyamine hydrochloride (0.75 g, 10.7 mol) and sodium hydroxide (0.43 g, 10.7 mmol) were dissolved in water / ethanol (1: 1, 50 mL). Subsequently, a formyl compound V (6.50 g, 9.76 mmol) in THF (50 mL) was added, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, extraction was performed with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over magnesium sulfate. Magnesium sulfate was filtered and the solvent was removed under reduced pressure. Recrystallization with toluene gave aldoxime VI (5.38 g, 7.91 mmol, 81% yield).
０℃に冷却したアルドキシムVI（５．００ｇ、７．３４ｍｏｌ）のジクロロメタン溶液（３０ｍＬ）に、塩化チオニル（０．８０ｍＬ、１１．０ｍｍｏｌ）を加えて２時間撹拌し、その後反応溶液を室温まで昇温した。再び０℃まで冷却したのち、飽和炭酸水素ナトリウム水溶液を加えて反応を停止したのち、トルエンで抽出した。このときの洗浄液を洗浄液Ｂとして、後に分析を行った。一方、得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過し、溶媒を減圧下で除去した。シリカゲルクロマトグラフィーにて精製し、シアン化合物IVを得た（４．２８ｇ、６．４６ｍｍｏｌ、収率８８％）。得られた化合物の１Ｈ−ＮＭＲ及び質量分析を測定し、目的物であると同定した。Thionyl chloride (0.80 mL, 11.0 mmol) was added to a dichloromethane solution (30 mL) of aldoxime VI (5.00 g, 7.34 mol) cooled to 0 ° C., and the mixture was stirred for 2 hours. Warm up. After cooling again to 0 ° C., a saturated aqueous sodium hydrogen carbonate solution was added to stop the reaction, and the mixture was extracted with toluene. The analysis was conducted later with the cleaning liquid at this time as the cleaning liquid B. On the other hand, the obtained organic layer was washed with saturated saline, and dried by adding magnesium sulfate. Magnesium sulfate was filtered and the solvent was removed under reduced pressure. Purification by silica gel chromatography gave cyanide compound IV (4.28 g, 6.46 mmol, 88% yield). 1 H-NMR and mass spectrometry of the obtained compound were measured and identified as the target product.
《合成方法３》
アリールブロミドＩ（１０．０ｇ、１４．０ｍｏｌ）のＮＭＰ溶液（１００ｍＬ）に、シアン化銅（Ｉ）（２．４９ｇ、２８．０ｍｏｌ）を加え、２００℃で６時間撹拌した。放冷後、アンモニア水溶液を加えて１時間撹拌したのちにトルエンを加えてさらに撹拌し、不溶物を濾別した。濾液をトルエンで抽出し、このときの洗浄液を洗浄液Ｃとして、後に分析を行った。一方、得られた有機層を飽和食塩水で洗浄した後に、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過し、溶媒を減圧下で除去した。シリカゲルクロマトグラフィーにて精製し、シアン化合物IVを得た（５．６６ｇ、８．５４ｍｍｏｌ、収率６１％）。得られた化合物の１Ｈ−ＮＭＲ及び質量分析を測定し、目的物であると同定した。<< Synthesis Method 3 >>
Copper cyanide (I) (2.49 g, 28.0 mol) was added to an NMP solution (100 mL) of aryl bromide I (10.0 g, 14.0 mol), and the mixture was stirred at 200 ° C. for 6 hours. After allowing to cool, an aqueous ammonia solution was added and the mixture was stirred for 1 hour. Toluene was added and the mixture was further stirred, and insoluble matters were filtered off. The filtrate was extracted with toluene, and the washing liquid at this time was designated as washing liquid C, and later analysis was performed. On the other hand, the obtained organic layer was washed with a saturated saline solution and then dried by adding magnesium sulfate. Magnesium sulfate was filtered and the solvent was removed under reduced pressure. Purification by silica gel chromatography gave cyanide compound IV (5.66 g, 8.54 mmol, 61% yield). 1 H-NMR and mass spectrometry of the obtained compound were measured and identified as the target product.
《合成方法４》
−７８℃に冷却した化合物VII（１２．８ｇ、１６．０ｍｍｏｌ）の無水ＴＨＦ溶液（３００ｍＬ）に、ｎ−ブチルリチウム（１．６Ｍヘキサン溶液、１０ｍＬ、１６ｍｍｏｌ）を１０分かけて滴下し、さらに３０分撹拌した。続いてこの溶液に二酸化炭素ガスを１０分間吹き込み、その後反応溶液を室温まで昇温した。水を加えて反応を停止したのち、塩酸を加えて溶液を酸性として酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過し、溶媒を減圧下で除去した。トルエンで再結晶を行い、カルボン酸VIIIを得た（９．６０ｇ、１１．３ｍｍｏｌ、収率７１％）。<< Synthesis Method 4 >>
To an anhydrous THF solution (300 mL) of compound VII (12.8 g, 16.0 mmol) cooled to −78 ° C., n-butyllithium (1.6 M hexane solution, 10 mL, 16 mmol) was added dropwise over 10 minutes, and further Stir for 30 minutes. Subsequently, carbon dioxide gas was blown into this solution for 10 minutes, and then the reaction solution was heated to room temperature. Water was added to stop the reaction, and hydrochloric acid was added to make the solution acidic, followed by extraction with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over magnesium sulfate. Magnesium sulfate was filtered and the solvent was removed under reduced pressure. Recrystallization from toluene gave carboxylic acid VIII (9.60 g, 11.3 mmol, 71% yield).
カルボン酸VIII（９．０ｇ、１０．６ｍｍｏｌ）のＤＭＦ溶液（２０ｍＬ）に、１，１′−カルボニルジイミダゾール（１．７２ｇ、１０．６ｍｏｌ）のＤＭＦ溶液（２０ｍＬ）を加えた。２時間撹拌したのちに、この溶液にヒドロキシアミン塩酸塩（１．４７ｇ、２１．２ｍｏｌ）を加え、２４時間撹拌した。反応溶液に水を加えたのち、酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過し、溶媒を減圧下で除去した。ジオキサンで再結晶を行い、アミドIXを得た（５．９４ｇ、６．８９ｍｍｏｌ、収率６５％）。 To a DMF solution (20 mL) of carboxylic acid VIII (9.0 g, 10.6 mmol), a DMF solution (20 mL) of 1,1′-carbonyldiimidazole (1.72 g, 10.6 mol) was added. After stirring for 2 hours, hydroxyamine hydrochloride (1.47 g, 21.2 mol) was added to the solution and stirred for 24 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over magnesium sulfate. Magnesium sulfate was filtered and the solvent was removed under reduced pressure. Recrystallization from dioxane afforded amide IX (5.94 g, 6.89 mmol, 65% yield).
アミドIX（５．５０ｇ、６．３８ｍｍｏｌ）のクロロベンゼン溶液（１００ｍＬ）に三臭化リン（１．２ｍＬ、１２．８ｍｍｏｌ）を加え、８０℃にて１６時間撹拌した。放冷後、反応溶液を氷水に注ぎ、飽和炭酸水素ナトリウム水溶液で中和したのちにトルエンで抽出し、このときの洗浄液を洗浄液Ｄとして、後に分析を行った。一方、得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過し、溶媒を減圧下で除去した。シリカゲルクロマトグラフィーにて精製し、シアン化合物Ｘを得た（４．１７ｇ、５．０４ｍｍｏｌ、収率７９％）。得られた化合物の１Ｈ−ＮＭＲ及び質量分析を測定し、目的物であると同定した。Phosphorus tribromide (1.2 mL, 12.8 mmol) was added to a chlorobenzene solution (100 mL) of amide IX (5.50 g, 6.38 mmol), and the mixture was stirred at 80 ° C. for 16 hours. After standing to cool, the reaction solution was poured into ice water, neutralized with a saturated aqueous sodium hydrogen carbonate solution, and extracted with toluene. On the other hand, the obtained organic layer was washed with saturated saline, and dried by adding magnesium sulfate. Magnesium sulfate was filtered and the solvent was removed under reduced pressure. Purification by silica gel chromatography gave cyanide compound X (4.17 g, 5.04 mmol, yield 79%). 1 H-NMR and mass spectrometry of the obtained compound were measured and identified as the target product.
《合成方法５》
−３０℃に冷却した化合物VII（１２．８ｇ、１６．０ｍｍｏｌ）の無水ＴＨＦ溶液（３００ｍＬ）に、ｎ−ブチルリチウム（１．６Ｍヘキサン溶液、１２ｍＬ、１９ｍｍｏｌ）を３０分かけて滴下し、さらに室温で１時間撹拌した。この溶液を再度−３０℃に冷却したのちに１，２−ジブロモエタン（２０ｍＬ、２４ｍｍｏｌ）を３０分かけて滴下し、室温まで昇温したのちに１８時間撹拌した。水を加えて反応を停止したのち、酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過し、溶媒を減圧下で除去した。トルエンで再結晶を行い、アリールブロミドXIを得た（９．０３ｇ、１０．２ｍｍｏｌ、収率６４％）。<< Synthesis Method 5 >>
To an anhydrous THF solution (300 mL) of Compound VII (12.8 g, 16.0 mmol) cooled to −30 ° C., n-butyllithium (1.6 M hexane solution, 12 mL, 19 mmol) was added dropwise over 30 minutes, and further Stir at room temperature for 1 hour. The solution was cooled again to −30 ° C., 1,2-dibromoethane (20 mL, 24 mmol) was added dropwise over 30 minutes, and the mixture was warmed to room temperature and stirred for 18 hours. The reaction was stopped by adding water, followed by extraction with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over magnesium sulfate. Magnesium sulfate was filtered and the solvent was removed under reduced pressure. Recrystallization from toluene gave aryl bromide XI (9.03 g, 10.2 mmol, 64% yield).
アリールブロミドXI（８．０ｇ、９．０７ｍｏｌ）のＮＭＰ溶液（１００ｍＬ）に、シアン化銅（Ｉ）（１．６１ｇ、１８．１ｍｏｌ）を加え、２００℃で６時間撹拌した。放冷後、アンモニア水溶液を加えて１時間撹拌したのちにトルエンを加えてさらに撹拌し、不溶物を濾別した。濾液をトルエンで抽出し、このときの洗浄液を洗浄液Ｅとして、後に分析を行った。一方、得られた有機層を飽和食塩水で洗浄した後に、硫酸マグネシウムを加えて乾燥した。硫酸マグネシウムをろ過し、溶媒を減圧下で除去した。シリカゲルクロマトグラフィーにて精製し、シアン化合物Ｘを得た（４．３６ｇ、５．２６ｍｍｏｌ、収率５８％）。得られた化合物の１Ｈ−ＮＭＲ及び質量分析を測定し、目的物であると同定した。Copper cyanide (I) (1.61 g, 18.1 mol) was added to an NMP solution (100 mL) of aryl bromide XI (8.0 g, 9.07 mol), and the mixture was stirred at 200 ° C. for 6 hours. After allowing to cool, an aqueous ammonia solution was added and the mixture was stirred for 1 hour. Toluene was added and the mixture was further stirred, and insoluble matters were filtered off. The filtrate was extracted with toluene, and the washing liquid at this time was used as the washing liquid E, which was later analyzed. On the other hand, the obtained organic layer was washed with a saturated saline solution and then dried by adding magnesium sulfate. Magnesium sulfate was filtered and the solvent was removed under reduced pressure. Purification by silica gel chromatography gave cyanide compound X (4.36 g, 5.26 mmol, yield 58%). 1 H-NMR and mass spectrometry of the obtained compound were measured and identified as the target product.
《洗浄液中のシアン化物イオン濃度の測定》
合成方法１〜５で発生した洗浄液Ａ〜Ｅに対して、パックテスト（共立理化学研究所製）を用いて、シアン化物イオン濃度の半定量測定を行った。結果を表１に示した。<Measurement of cyanide ion concentration in cleaning solution>
Semi-quantitative measurement of the cyanide ion concentration was performed on the cleaning liquids A to E generated in the synthesis methods 1 to 5 using a pack test (manufactured by Kyoritsu Riken). The results are shown in Table 1.
以上より、シアン化合物を使用していない合成方法１、２及び４では、洗浄液のシアン化物イオン濃度が検出限界以下であったのに対し、シアン化銅を使用した合成方法３及び５の洗浄液からはシアン化物イオンが検出されたことが分かった。すなわち、その取り扱いや処理が煩雑である、シアン化物イオンを含んだ廃液を排出しない、合成方法１、２及び４の合成法がより好ましい。 As described above, in the synthesis methods 1, 2 and 4 in which no cyanide compound is used, the cyanide ion concentration of the cleaning solution was below the detection limit, whereas from the cleaning solutions of the synthesis methods 3 and 5 using copper cyanide. Found that cyanide ions were detected. That is, the synthesis methods 1, 2, and 4 are more preferable because they are complicated to handle and process and do not discharge waste liquid containing cyanide ions.
［実施例２］
《有機ＥＬ素子評価》
（１）有機ＥＬ素子１−１の作製
（陽極の形成）
５０ｍｍ×５０ｍｍ、厚さ０．７ｍｍのガラス基板上に、陽極としてＩＴＯ（インジウム・スズ酸化物）を１５０ｎｍの厚さで成膜し、パターニングを行った後、このＩＴＯ透明電極を付けた透明基板をイソプロピルアルコールで超音波洗浄し、乾燥窒素ガスで乾燥し、ＵＶオゾン洗浄を５分間行った。[Example 2]
<< Evaluation of organic EL elements >>
(1) Production of organic EL element 1-1 (formation of anode)
A transparent substrate with an ITO (Indium Tin Oxide) film having a thickness of 150 nm formed on a glass substrate of 50 mm × 50 mm and a thickness of 0.7 mm, patterned, and this ITO transparent electrode was attached Was subjected to ultrasonic cleaning with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
（正孔注入層の形成）
さらにこの基板上に、ポリ（３，４−エチレンジオキシチオフェン）−ポリスチレンスルホネート（ＰＥＤＯＴ／ＰＳＳと略記、Ｂａｙｅｒ製、Ｂａｙｔｒｏｎ Ｐ Ａｌ ４０８３）を純水で希釈した溶液をスピンコート法により成膜した後、１４０℃にて１時間乾燥し、層厚５０ｎｍの正孔注入層を設けた。この透明基板を市販の真空蒸着装置の基板ホルダーに固定した。(Formation of hole injection layer)
Further, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (abbreviated as PEDOT / PSS, manufactured by Bayer, Baytron P Al 4083) with pure water was formed on this substrate by spin coating. Then, it dried at 140 degreeC for 1 hour, and provided the positive hole injection layer with a layer thickness of 50 nm. This transparent substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus.
（正孔輸送層の形成）
真空蒸着装置内の蒸着用るつぼの各々に、各層の構成材料を、各々素子作製に最適の量を充填した。蒸着用るつぼはモリブデン製又はタングステン製の抵抗加熱用材料で作製されたものを用いた。
真空度１×１０−４Ｐａまで減圧した後、化合物ＨＴ−１の入った蒸着用るつぼに通電して加熱し、蒸着速度０．１ｎｍ／秒で正孔注入層上に蒸着し、層厚１０ｎｍの正孔輸送層を形成した。(Formation of hole transport layer)
Each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the constituent material of each layer in an amount optimal for device fabrication. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
After depressurizing to a vacuum of 1 × 10 −4 Pa, the deposition crucible containing compound HT-1 was energized and heated, deposited on the hole injection layer at a deposition rate of 0.1 nm / second, and a layer thickness of 10 nm. The hole transport layer was formed.
（発光層の形成）
次いで、ホスト化合物として合成方法１で合成した化合物（Ｈ−２８）及びリン光発光性化合物としてＤ−６３がそれぞれ９４％、６％の体積％になるように蒸着速度０．１ｎｍ／秒で共蒸着し、層厚３０ｎｍの発光層を形成した。(Formation of light emitting layer)
Next, the compound (H-28) synthesized by the synthesis method 1 as the host compound and D-63 as the phosphorescent compound were simultaneously used at a deposition rate of 0.1 nm / second so that the volume percentage was 94% and 6%, respectively. Evaporation was performed to form a light emitting layer with a layer thickness of 30 nm.
（正孔阻止層・電子輸送層・陰極の形成）
次いで、化合物ＨＢ−１を蒸着速度０．１ｎｍ／秒で蒸着し、層厚５ｎｍの正孔阻止層を形成し、続いて化合物Ａｌｑ（ｔｒｉｓ（８−ｈｙｄｒｏｘｙｑｕｉｎｏｌｉｎａｔｏ）ａｌｕｍｉｎｉｕｍ）を蒸着速度０．１ｎｍ／秒で蒸着し、層厚３０ｎｍの電子輸送層を形成した。さらに、フッ化カリウムを膜厚２ｎｍで形成した後に、アルミニウム１００ｎｍを蒸着して陰極を形成した。(Formation of hole blocking layer, electron transport layer, cathode)
Next, compound HB-1 was deposited at a deposition rate of 0.1 nm / second to form a hole blocking layer having a layer thickness of 5 nm, and subsequently compound Alq (tris (8-hydroxyquinolinato) aluminum) was deposited at a deposition rate of 0.1 nm / second. Vapor deposition was performed in seconds to form an electron transport layer having a layer thickness of 30 nm. Furthermore, after forming potassium fluoride with a film thickness of 2 nm, 100 nm of aluminum was vapor-deposited to form a cathode.
上記素子の非発光面側を、窒素雰囲気下、ＵＶ硬化樹脂を用いてガラスカバーを接着し、有機ＥＬ素子１を作製した。なお、本実施例において使用される化合物は、下記のとおりの化学構造式を有するものである。 A glass cover was adhered to the non-light-emitting surface side of the above element using a UV curable resin in a nitrogen atmosphere to produce an organic EL element 1. In addition, the compound used in a present Example has the following chemical structural formula.
（２）有機ＥＬ素子２〜５の作製
有機ＥＬ素子１の作製において、合成方法１で合成したホスト化合物（Ｈ−２８）を、表１に記載の化合物に変えた以外は有機ＥＬ素子１の作製と同様にして有機ＥＬ素子２〜５を作製した。(2) Preparation of organic EL element 2-5 In preparation of the organic EL element 1, the host compound (H-28) synthesize | combined with the synthesis method 1 of the organic EL element 1 except having changed into the compound of Table 1. Organic EL elements 2 to 5 were produced in the same manner as the production.
《有機ＥＬ素子の評価》
各有機ＥＬ素子について下記の評価を行った。評価結果を表１に示す。
（１）発光効率（ＥＱＥ、外部取出し量子効率）
有機ＥＬ素子を室温（２５℃）、２．５ｍＡ／ｃｍ２の定電流条件下による通電を行い、発光開始直後の発光輝度（Ｌ０）［ｃｄ／ｍ２］を測定することにより、外部取出し量子効率（η）を算出した。
ここで、発光輝度の測定はＣＳ−２０００（コニカミノルタ製）を用いて行い、外部取出し量子効率は有機ＥＬ素子１を１００とする相対値で表した。
なお、値が大きいほうが比較例に対して効率が優れていることを示す。
（２）半減寿命
下記に示す測定法に従って、半減寿命の評価を行った。
各有機ＥＬ素子を初期輝度４０００ｃｄ／ｍ２を与える電流で定電流駆動して、初期輝度の１／２になる時間を求め、これを半減寿命の尺度とした。なお、半減寿命は有機ＥＬ素子１を１００とする相対値で表した。
なお、値が大きいほうが比較例に対して耐久性が優れていることを示す。<< Evaluation of organic EL elements >>
The following evaluation was performed for each organic EL element. The evaluation results are shown in Table 1.
(1) Luminous efficiency (EQE, external extraction quantum efficiency)
The organic EL device was energized under a constant current condition of room temperature (25 ° C.) and 2.5 mA / cm 2 , and the light emission luminance (L 0 ) [cd / m 2 ] immediately after the start of light emission was measured. The quantum efficiency (η) was calculated.
Here, the measurement of emission luminance was performed using CS-2000 (manufactured by Konica Minolta), and the external extraction quantum efficiency was expressed as a relative value with the organic EL element 1 as 100.
In addition, the one where a value is large shows that efficiency is excellent with respect to a comparative example.
(2) Half-life The half-life was evaluated according to the measurement method shown below.
Each organic EL element was driven at a constant current with a current giving an initial luminance of 4000 cd / m 2 , and a time during which the initial luminance was ½ was obtained. The half life was expressed as a relative value with the organic EL element 1 as 100.
In addition, the one where a value is larger shows that durability is excellent with respect to a comparative example.
以上より、比較例で用いた化合物に対し、本発明の製造方法にて製造した化合物を用いると発光効率が高く、半減寿命が長くなることがわかり、本発明の方法にて製造した化合物を用いた有機ＥＬ素子は高い発光効率と耐久性を両立していることが分かった。 From the above, it can be seen that when the compound produced by the production method of the present invention is used in comparison with the compound used in the comparative example, the luminous efficiency is high and the half-life is prolonged, and the compound produced by the method of the present invention is used. It was found that the conventional organic EL device has both high luminous efficiency and durability.
本発明の有機エレクトロルミネッセンス素子用材料の製造方法により、高い発光効率と耐久性を両立する有機エレクトロルミネッセンス素子を得ることができ、当該有機ＥＬ素子は、表示デバイス、ディスプレイ、各種発光光源に好適に利用することができる。 According to the method for producing a material for an organic electroluminescent element of the present invention, an organic electroluminescent element having both high luminous efficiency and durability can be obtained, and the organic EL element is suitable for a display device, a display, and various light emitting light sources. Can be used.
１０１ 照明装置内の有機ＥＬ素子
１０２ ガラスカバー
１０５ 陰極
１０６ 有機ＥＬ層
１０７ 透明電極付きガラス基板
１０８ 窒素ガス
１０９ 捕水剤
Ｌ 発光光DESCRIPTION OF
Claims (4)
前記シアノ基を有する化合物が、下記官能基群に含まれるいずれかの官能基からシアノ基へと変換することにより製造されることを特徴とする有機エレクトロルミネッセンス素子用材料の製造方法。
官能基群：
A method for producing a material for an organic electroluminescent element, wherein the compound having a cyano group is produced by converting any functional group included in the functional group group below into a cyano group.
Functional group group:
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