WO2006103916A1

WO2006103916A1 - Organic electroluminescent device

Info

Publication number: WO2006103916A1
Application number: PCT/JP2006/304999
Authority: WO
Inventors: Takashi Arakane; Toshihiro Iwakuma; Mineyuki Kubota; Masakazu Funahashi
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 2005-03-25
Filing date: 2006-03-14
Publication date: 2006-10-05
Also published as: TW200643142A

Abstract

Disclosed is an organic electroluminescent device wherein an organic thin film composed of one or more layers including at least a light-emitting layer is interposed between a cathode and an anode, and at least one layer in the organic thin film contains a compound (A) having a specific terminal substituent and a compound (B) of an asymmetric structure which has a fused aromatic ring having 12-50 nuclear carbon atoms. This organic electroluminescent device is capable of emitting red light of high color purity while having high luminous efficiency and long life.

Description

Specification

Organic electoluminescence device

Technical field

TECHNICAL FIELD [0001] The present invention relates to an organic electoluminescence (EL) device, and more particularly to an organic EL device capable of obtaining red light emission with high color efficiency while having high luminous efficiency and long life.

Background art

An organic EL element is a self-luminous element that utilizes the principle that a fluorescent substance emits light by recombination energy of holes injected from an anode and electrons injected from a cathode when an electric field is applied.

Eastman's Kodak's CW Tang et al. Reported a low-voltage driven organic EL device using stacked devices (CW Tang, SA Vanslyke, Applied Physics Letters, 51 卷, page 913, 1987, etc.) Since then, research on organic EL devices using organic materials as constituent materials has been actively conducted.

Tnag et al. Employ a layered structure using tris (8-quinolinol) aluminum for the light-emitting layer and triphenyldiamin derivative for the hole-transporting layer. The advantages of the stacked structure are that the efficiency of hole injection into the light-emitting layer can be increased, the efficiency of excitons generated by recombination by blocking electrons injected into the cathode can be increased, and light emission For example, the excitons generated in the layer can be confined. As shown in this example, the device structure of an organic EL device is a two-layer type of a hole transport (injection) layer and an electron transport light-emitting layer, or a hole transport (injection) layer, a light-emitting layer, and an electron transport (injection) layer. A three-layer structure is well known. In such a multilayer structure element, various improvements have been made to the element structure and formation method in order to increase the recombination efficiency of injected holes and electrons.

[0003] Further, as light-emitting elements used for organic EL elements, light-emitting materials such as chelate complexes such as tris (8-quinolinol) aluminum complex, coumarin complexes, tetraphenylbutadiene derivatives, bisstyrinylene arylene derivatives, and oxaziazole derivatives are known. It has been reported that light emission in the visible region from blue to red can be obtained. Although the realization of a child is expected (for example, Patent Documents:! To 3 etc.), the luminous efficiency and lifetime have not reached a practical level and are insufficient. In addition, full-color displays require three primary colors (blue, green, and red), but high-efficiency red elements are particularly required.

In order to meet such demand, recently, for example, Patent Document 4 discloses a red light emitting device in which a naphthacene or pentacene derivative is added to a light emitting layer. However, although this device is excellent in red purity, the half-life of the brightness when the applied voltage is as high as 1 IV is about 150 hours, which is insufficient. Patent Document 5 discloses a device in which a dicyanomethylene (DCM) compound is added to a light emitting layer, but the red purity is insufficient. Patent Document 6 discloses a red light-emitting device in which an amine-based aromatic compound is added to a light-emitting layer. Although this device has good CIE chromaticity (0.64, 0.33) and color purity, The drive voltage was high. Patent Documents 7 and 8 disclose an element using an amine-based aromatic compound and Alq as a light emitting layer. This element emits red light but has low efficiency and a short life. Patent Document 9 discloses a device using an amine-based aromatic compound and DPVDPAN (see the comparative example below for the chemical structure) in the light-emitting layer, but a highly efficient device emits red light and emits red light. The element to perform was low efficiency.

Patent Document 1 Japanese Patent Application Laid-Open No. 8-239655

Patent Document 2 Japanese Patent Laid-Open No. 7-138561

Patent Document 3 Japanese Patent Laid-Open No. 3-200289

Patent Document 4 Japanese Patent Application Laid-Open No. 8-311442

Patent Document 5 Japanese Patent Laid-Open No. 3-162481

Patent Document 6 Japanese Unexamined Patent Publication No. 2001-81451

Patent Document 7 International Publication WO01Z23497

Patent Document 8 Japanese Patent Application Laid-Open No. 2003 — 40845

Patent Document 9 Japanese Unexamined Patent Application Publication No. 2003-81924

Disclosure of the invention

Problems to be solved by the invention

The present invention has been made to solve the above problems, and has high luminous efficiency and long life. Nevertheless, an object is to provide an organic EL device capable of emitting red light with high color purity.

Means for solving the problem

[0006] As a result of intensive studies to achieve the above object, the present inventors have found that an organic thin film layer that forms an organic EL element is (A) the following general formula (1) and / or (1 ') And a compound having (B) a condensed aromatic ring having a nuclear carbon number of 12 to 50 and an asymmetric structure. The invention has been completed. That is, the present invention provides an organic EL device in which an organic thin film layer composed of one or more layers including at least a light emitting layer is sandwiched between a cathode and an anode, and at least one layer of the organic thin film layer comprises (A) Provided is an organic EL device comprising a compound represented by (1) and / or (1 ′) and (B) a compound having a condensed aromatic ring having 12 to 50 nuclear carbon atoms and an asymmetric structure It is.

[0007] [Chemical 1]

[In General Formula (1), Ai ^ Ar ⁴ is each independently a group represented by the following General Formula (2), (3) or (4). However, at least one of Ar ^{1 to} Ar ⁴ is a group represented by the following general formula (2) or (3).

[Chemical 2]

(In the general formula (2), at least two of R ^{1 to} R ³ are substituted or unsubstituted linear or branched alkyl groups having from 30 to 30 carbon atoms, and the rest are hydrogen atoms.

In general formula (3), at least one of R ^{4 to} R ⁶ is a substituted or unsubstituted cycloalkyl group having 3 to 50 nuclear carbon atoms, and the remainder is a hydrogen atom.

In the general formula (4), R ⁷ ~R ^U are each independently a hydrogen atom, a substituted or Mu置conversion linear or branched alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon atoms 1 50 alkoxy groups, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 50 nuclear carbon atoms, substituted or unsubstituted aromatic heterocyclic groups having 5 to 50 nuclear carbon atoms, substituted or unsubstituted nuclear carbon numbers A 5- to 50-aryloxy group, a substituted or unsubstituted aralkyl group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 nuclear carbon atoms, or a halogen atom. R ^{7 to} R "may be bonded to each other in contact with P to form a saturated or unsaturated cyclic structure.

The invention's effect

[0010] The organic EL device of the present invention can produce red light with high color purity while having high luminous efficiency and long life.

BEST MODE FOR CARRYING OUT THE INVENTION

[0011] The organic EL device of the present invention is an organic electroluminescent device in which an organic thin film layer comprising a single layer or a plurality of layers including at least a light emitting layer is sandwiched between a cathode and an anode. , (A) a compound represented by the following general formula (1) and / or (1 ′), and (B) a compound having a condensed aromatic ring having 12 to 50 nuclear carbon atoms and an asymmetric structure .

Hereinafter, the general formulas (1) and (1 ′) of the component (A) will be described.

[0012] [Chemical 3]

In the general formula (1), 8 to 8 !: ⁴ are each independently a group represented by the following general formula (2), (3) or (4). However, at least one of Ar ^{1 to} Ar ⁴ is a group represented by the following general formula (2) or (3).

[Chemical 4]

In the general formula (2), at least two of R ¹ to are substituted or unsubstituted linear or branched alkyl groups having from 30 to 30 carbon atoms, and the remainder is a hydrogen atom. In the general formula (2), at least two of R ^{1 to} R ³ are each independently a methinole group, an ethyl group, an isopropylinole group, a 1_butyl group, a 2_methylpropyl group, or 1,1-dimethylethyl. A group, dimethyl group or trimethyl group is preferred.

[0015] R ¹ ~: Examples of the alkyl group of R ³ include, for example, a methinole group, an ethyl group, a propyl group, an isopropylinole group, an n_butyl group, an s_butyl group, an isobutyl group, a t_butyl group, an n_ Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2-dihydroxyethyl group, 1 , 3 Dihydroxyisopropyl group, 2,3 dihydroxy-t-butyl group, 1,2,3 trihydroxypropyl group, chloromethyl group, 1 chloroethyl group, 2 chloroethyl group, 2 chloroethyl isobutyl group, 1,2 dichloro Diethyl group, 1,3 Group, 2, 3 dichloro-t-butyl group, 1, 2, 3 trichloropropyl group, bromomethyl group, 1-bromoethinole group, 2-bromoethynole group, 2-bromoisobutynole group, 1,2-dibromoethyl group, 1, 3-Dibromoisopropyl group, 2, 3-Dibu-mouthed tert-butyl group, 1, 2, 3-Tribromopropyl group, Eodomethyl group, 1-Edoethinole group, 2-Edoethinole group, 2-Odoisobutyl group, 1, 2 _ Jodoethyl group, 1, 3—Jodoisopropyl group, 2, 3—Jodo—_Butyl group, 1, 2, 3 _Triodopropyl group, Aminomethyl group, 1 _Aminoethyl group, 2 _Aminoethyl group, 2 —Aminoisobutyl group, 1,2-Diaminoethyl group, 1,3_Diaminoisopropinole group, 2,3_Diamino-t-butynole group, 1,2,3_Triaminopropyl group, Cyanmethinole group , 1— Fanoethyl group, 2-Cyanoethyl group, 2_Cyanoisobutyl group, 1,2_Dicanoethyl group, 1,3-Dicanoisopropyl group, 2,3-Dicanoyl t_butyl group, 1, 2, 3_tricyano Propyl group, Nitromethyl group, 1_Nitroethyl group, 2-Nitroethyl group, 2_Nitroisobutyl group, 1,2-Dinitroethyl group, 1,3-Dinitroisopropyl group, 2,3 Dinitro-tbutyl group, 1, 2, 3 And trinitropropyl group.

Among these, a methyl group, an ethyl group, an isopropyl group, a 1-butyl group, a 2-methylpropyl group, a 1,1-dimethylethyl group, a dimethyl group, and a trimethyl group are preferable.

In the general formula (3), at least one of R ^{4 to} R ⁶ is a substituted or unsubstituted cycloalkyl group having 3 to 50 nuclear carbon atoms, and the remaining is a hydrogen atom. In the general formula (3), at least one of R ⁴ to R ⁶ is preferably a cyclohexyl group.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 1_norbornyl group, and a 2_norbornyl group. And a cyclohexyl group is preferable.

[0017] In the general formula (4), R ⁷ ~R ^U are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 50 carbon atoms substituted or Mu置conversion, a substituted or unsubstituted carbon An alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear carbon atoms, a substituted or unsubstituted group; Nuclear carbon number 5 to 50 aryloxy group, substituted or unsubstituted aralkyl having 6 to 50 nuclear carbon atoms Group, a substituted or unsubstituted cycloalkyl group having 3 to 50 nuclear carbon atoms, or a halogen atom.

[0018] The alkyl group for R ⁷ to R ^U, for example, a methyl group, Echiru group, propyl group, isopropyl Pinore group, n_ butyl group, s_ butyl group, an isobutyl group, t_ butyl group, n_ pentyl Group, n-hexyl group, n-heptyl group, n-octyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2-dihydroxyethyl group, 1, 3-dihydroxyisopropyl group, 2,3-dihydroxyt-butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1_chloroethyl group, 2_chloroethylol group, 2_chloroisobutyl group Group, 1,2-Dichlorodiethyl group, 1,3-Dicyclodiethylpropylene group, 2,3-Dichlorodi-butyl group, 1,2,3_Trichlorodipropyl group, Bromomethyl group, 1_Bromochinole group , 2_ Bromoec Group, 2_bromoisobutynol group, 1,2_dibromoethyl group, 1,3_dibromoisopropyl group, 2,3_dibromo-_butyl group, 1,2,3-tribromopropyl group, odomethyl group 1-yodoethyl group, 2-yodoethyl group, 2-jodoisobutyl group, 1,2 jodoethyl group, 1,3 jodoisopropyl group, 2,3-jodo tert-butylol group, 1,2,3-tridopropinole group, Aminomethylol group, 1-aminoethylinole group, 2--minominoethinole group, 2--aminominobutynole group, 1,2-di-aminominochinole group, 1,3-diaminoisopropyl group, 2,3-diamino-tert-butyl group, 1,2 , 3 Triaminopropyl group, Cyanomethyl group, 1-Cyanoethyl group, 2-Cyanoethyl group, 2-Cyanoisobutyl group, 1,2-Dicanoethyl group, 1,3-Dicanoisopropyl group, 2, 3-Di Cyanate butyl group, 1, 2, 3 tricyanopropyl group, nitromethyl group, 1 1 2 troethyl group, 2 1 2 troethyl group, 2 2 troisobutyl group, 1, 2 dinitroethyl group, 1, 3 dinitro isopropyl group, 2 , 3-dinitro_butyl group, 1, 2, 3_trinitropropyl group and the like.

[0019] R ⁷ ~: The alkoxy group of R ¹¹ is a group represented by 10 Y, and examples of Υ include the same examples as those described for the alkyl group.

Examples of the aromatic hydrocarbon group represented by R ^{7 to} R ^U include a phenyl group, a 1_naphthyl group, a 2_naphthyl group, a 1_anthrinol group, a 2_anthrinol group, a 9 anthryl group, and a 9- (10-phenolo group. ) Anthryl group, 9 _ (10_ naphthyl _ 1—yl) Anthryl group, 9 _ (10 naphthyl) —2—yl) anthryl group, 1-phenanthryl group, 2 phenanthryl group, 3 phenanthryl group, 4 phenanthrinol group, 9 phenanthryl group, 6-chrycenyl group, 1 naphthacenyl group, 2 naphthacenyl group, 9 naphthacenyl group, 1 -Pyrenyl group, 2 pyrenyl group, 4 —pyrenyl group, 2_biphenyldiyl group, 3_biphenyldiyl group, 4_biphenyldiyl group, p-terphenyl _4-yl group, p-terphenyl _ 3— Group, p-terphenyl _ 2 —inole group, m-terfeninore _4—inole group, m-terfeninore _ 3—inole group, m-ter feninole _ 2-inole group, o_trinore Group, m-trinole group, ρ-trinole group, p_t_butynolezinole group, 3_methyl_2_naphthyl group, 4_methyl_1_naphthyl group, 4_methyl_1_anthryl group and the like.

Examples of the aromatic heterocyclic group represented by R ^{7 to} R ^U include 1_pyrrolyl group, 2_pyrrolyl group, 3_pyrrolyl group, pyradyl group, 2_pyridinyl group, 1_imidazolyl group, 2_imidazolyl group, 1 —Pyrazolinole group, 1_Indolizinyl group, 2_Indolizinyl group, 3_Indolizinyl group, 5-Indolizinyl group, 6-Indolizinyl group, 7-Indolizinyl group, 8-Indolizinyl group, 2Imidazopyridinyl group, 3Imidazopyridinyl group Group, 5 imidazopyridinyl group, 6 imidazopyridinyl group, 7-imidazopyridinyl group, 8-imidazopyridinyl group, 3-pyridinyl group, 4 pyridinyl group, 1 indolinole group, 2 indolinole group , 3 indolyl group, 4 indolyl group, 5—indolyl group, 6—indolyl group, 7—indolyl group, 1 isoindolyl group, 2 isoindolyl group, 3 isodolyl group , 4-isoindolyl group, 5 isoindolyl group, 6 isoindolyl group, 7 isoindolyl group, 2 frinole group, 3 frinole group, 2 benzofuranyl group, 3-benzofuranyl group, 4 monobenzofuranyl group, 5-benzofuranyl group, 6-Benzofuranyl group, 7-Benzofuranyl group, 1 Isobenzofuranyl group, 3-Isobenzofuranyl group, 4_Isobenzofuranyl group, 5 _Isobenzofuranyl group, 6 _Isobenzofuranyl group, 7_ Isobenzofuranyl group, 2_quinolyl group, 3_quinolyl group, 4_quinolyl group, 5_quinolyl group, 6_quinolyl group, 7-quinolinol group, 8-quinolinol group, 1_isoquinolyl group, 3_isoquinolyl group, 4_isoquinolinol group, 5_isoquinolyl group, 6_isoquinolinol group, 7-soquinolyl group, 8_isoquinolinol group, 2_quinoxalinyl group, 5_ki Xalinyl group, 6-quinoxalinyl group, 1_carbazolyl group, 2_carbazolyl group, 3_carbazolyl group, 4_force norevazolyl group, 9_carbazolyl group, / 3-carbinyl 1_yl, / 3-carboline 3 _ 3-in-force, 4-inole, 1-in-one evoline 5-in-nore, 1-in-one evoline- 6-in-nore, 1-in-one-revolin 7-inole-in-one-no-revolin 6--in-no-le, 1-in-one-revolin 9-in-nore, 1 Group, 2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinyl group, 9_ Phenanthridinyl group, 10-phenanthridinyl group, 1-acridinino group, 2-ataridinino group, 3-ataridinyl group, 4-ataridinolin group, 9-ataridinino group, 1,7_phenanthroline_2— Inole group, 1, 7_phenanthroline _3—Innole group, 1, 7_Phenanthroline _4—Inole group, 1, 7_Phenanthroline _5-—Inole group, 1,7—Fenance Lorin 1 6-yl group, 1, 7-Phenanthrololin 1--8 group, 1, 7-Phenanthrin 1 9-Inole group, 1, 7-Phenanthroline 1 10-Inole group, 1,8-Phenanthroline 1 2-Inole group, 1,8_Phenanthroline group 3-Inole group, 1,8_Phenanthroline group 4-Inole group, 1,8_Phenanthhroline group _5--Inole group, 1,8_Phenanthroline group _6-Inole group, 1,8 Phenanthroline-7-inore group, 1,8-phenanthroline-9-inole group, 1,8-phenanthroline 10-inore group, 1,9 phenanthroline-2-inole group, 1,9 phenanthroline 3-Inole group, 1, 9-Phenanthroline 1 4-Inole group, 1, 9-Phenanthuroline 1- 5-Inole group, 1, 9-Phenanthuroline 1-6-Inole group, 1, 9-Phenanthroline 1-Inole group, 1 , 9—Phenanthuroline 1—Inole 1, 9-phenanthroline 1 10-inole group, 1, 10-phenanthroline 1 2-inole group, 1, 10-phenanthroline 1-inole group, 1, 10-phenanthroline 1- 4-yl group, 1, 10 —Phoenanthroline 1—yl group, 2, 9 Phenol 1—yl group, 2, 9 Phenolthroline 3—yl group, 2, 9 Phenanthroline 4 —Zyl group, 2, 9 Phenanthroline 1 5 —Yl group, 2, 9 phenanthroline 1—6-yl group, 2, 9—phenanthroline 1—7-inole group, 2, 9—phenanthroline 1—8-inole group, 2, 9—phenanthroline 1—10-yl group, 2,8-phenanthroline 1-yl group, 2,8-phenanthroline 3-yl group, 2,8-phenanthroline 4-yl group, 2,8-phenanthroline 5-5-yl group, 2 , 8—Phenanthhroline 6—yl group, 2, 8—Phenanthhroline 7 Group, 2, 8_phenanthroline _9—yl group, 2, 8_phenanthroline 10-yl group, 2, 7_phenanthroline _1—inore group, 2, 7_phenanthroline _3—inole group, 2, 7 _Phenanthuroline 4-yl group, 2, 7-Phenanthuroline 5-yl group, 2, 7-Phenanthuro Phosphorus 6-yl group, 2, 7 Phenylthroline 1-8-yl group, 2, 7 Phenylthroline 9-yl group, 2, 7 Phenylthroline 10-yl group, 1 Phenadinyl group, 2 Phenyladinyl group, 1-Fuee Notiazinyl group, 2 Phenothiazinyl group, 3 Phenothiazinyl group, 4_Phinothiazinyl group, 10-Phonothiazinyl group, 1-Phenoxazinyl group, 2-Phenoxazinyl group, 3_Phenoxazinyl group, 4_Phenoxazinyl group, 10-Phenoxazinyl group Nyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5_oxadiazolyl group, 3-furazanyl group, 2_chenyl group, 3_phenyl group, 2-methylpyrrole— 1—yl group, 2 methyl pyrrole— 3—yl group, 2 methinore pyrrolinore _4—inore group, 2 methinorepyrroloinole _ 5—inore group, 3 1-yl group, 3-methylpyrrole-2-yl group, 3 methylpyrrole-4-yl group, 3 methylolpyrrole-5-yl group, 2_t-butylpyrrole-4-yl group , 3 _ (2-phenylpropyl) pyrrole-1-yl group, 2 _ methyl _ 1 _ yndolyl group, 4 _ methyl _ 1 _ indolyl group, 2-methyl -3- indolyl group, 4-methyl -3- indolyl group 2 t-butyl 1 indolyl group, 4 t butyl 1 indolyl group, 2 t butyl 3 indolyl group, 4 t butyl 3 indolyl group, and the like.

The aryloxy group of R ^{7 to} R ″ is represented as OY ′, and examples of Y ′ include the same examples as the aromatic hydrocarbon group and aromatic heterocyclic group.

Examples of the aralkyl group of R ^{7 to} R ″ include, for example, benzyl group, 1 phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-tbutyl group, α-naphthylmethyl group 1 α-naphthylethyl, 2 a-naphthylethyl, 1 α-naphthylisopropyl, 2 a-naphthylisopropyl, β-naphthylmethyl, 1 _β-naphthylethyl, 2-β-naphthylethyl, 1-β-naphthyl Isopropyl group, 2-β-naphthylisopropyl group, 1_pyrrolylmethyl group, 2_ (1_pyrrolyl) ethyl group, ρ_methylbenzyl group, m_methylbenzyl group, o-methenolevendinore group, p-black port Benzinore group, m-black benzylene group, o_black benzyl group, ρ_bromobenzyl group, m_bromobenzyl group, o_bromobenzyl group Group, p-odobenzyl group, m_odobenzyl group, o_odobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group, m -Aminobenzil group, o Aminobenzil group, p-Nitrobenzyl group, m-Nitrobenzyl group, o-Nitrobenzyl group, p-Cyanobenzyl group, m-Cyanobenzyl group, o-Cyanobenzilole group, 1-hydroxy-2- Examples thereof include a phenolinoisopropinole group and a 1 chloro-2-phenenoylisopropyl group.

R ⁷ ~: Examples of the cycloalkyl group R ^11, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4 hexyl group methylcyclohexyl, 1-Adamanchi group, 2-Adamanchiru group, 1 _ norbornyl Group, 2_norbornyl group and the like. Examples of the halogen atom of R ⁷ to R ^U, for example, a fluorine atom, a chlorine atom, a bromine atom and an ® © iodine atom.

[0022] In the general formula (4), R ^{7 to} R ^U may be bonded to each other in contact with P to form a saturated or unsaturated cyclic structure.

Examples of the cyclic structure include, for example, cycloalkanes having 4 to 12 carbon atoms such as cyclobutane, cyclopentane, cyclohexane, adamantane, norbornane, cyclobutene, cyclobenten, cyclohexene, cycloheptene, and cyclootaten. C 4-12 cycloalkadiene, cyclohexadiene, cyclohexadiene, cyclooctagen, etc. Examples include 50 aromatic rings, heterocyclic rings having 5 to 50 carbon atoms such as imidazole, pyrrole, furan, thiophene and pyridine.

In addition, as a substituent of each group of the general formulas (2) to (4), a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted nuclear atom number of 5 to 50 Aromatic heterocyclic group, substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 50 nuclear carbon atoms, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms Group, substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 nucleus atoms, substituted or unsubstituted aryloxy group having 5 to 50 nucleus atoms, substituted or unsubstituted Examples thereof include a substituted alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, and a hydroxyl group.

[0023] The following are examples of combinations of 8 to 8 in the general formulas (1) and (1 ') of the component (A) Although shown below, it is not limited to these.

[Chemical 5]

/: O 1 £ AV

^ §0024 Next, the compound (B) having a condensed aromatic ring having 12 to 50 nuclear carbon atoms and having an asymmetric structure (hereinafter sometimes referred to as a condensed aromatic ring-containing compound) will be described.

Examples of the condensed aromatic ring having 12 to 50 nuclear carbon atoms include anthracene, phenanthrene, pyrene, taricene, triphenylene, perylene and the like, and anthracene and pyrene are preferable.

In addition, the condensed aromatic ring-containing compound has an asymmetric structure. For example, it is represented by an asymmetric anthracene derivative represented by the following general formula (5), an asymmetric anthracene derivative represented by the general formula (6), or a general formula (7). Preferred examples include asymmetric pyrene derivatives and asymmetric diphenylanthracene derivatives represented by the general formula (8).

[0026] [Chemical 7]

(Five)

[In general formula (5), X represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aromatic group having 5 to 50 nuclear atoms. Heterocyclic group, substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 50 nuclear carbon atoms, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted Or an unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted An alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, and a hydroxyl group.

Ar ⁵¹ and Ar ⁵² are each independently a substituted or unsubstituted condensed aromatic ring group having 10 to 50 nuclear carbon atoms, and at least one of Ar ⁵¹ and Ar ⁵² is represented by the following general formula (i): 1_naphthyl group or 2_naphthyl group represented by the following general formula (式). [0028] [Chemical 8]

(In the general formulas (i) and Gi), R ^{51 to} R ⁵⁷ are a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and at least one pair of adjacent R ^{51 to} R ⁵⁷ is These are bonded together to form a ring structure. )

a, b and c are each an integer of 0 to 4, and d is an integer of 1 to 3. When d is 2 or more, the groups in [] may be the same or different. ]

[0029] Examples of the aromatic hydrocarbon group, aromatic heterocyclic group, alkyl group, cycloalkyl group, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, aralkyl group, and aryloxy group of X include same examples as those mentioned R ⁷ to R ^U in the general formula (4) below.

The arylthio group of X is represented by —SY ′, and examples of Y ′ include the same examples as the aromatic hydrocarbon group and aromatic heterocyclic group.

The alkoxycarbonyl group of X is a group represented by _C0OY, and examples of Y include the same examples as those described above for the alkyl group.

Examples of the silyl group of X include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a butyldimethylsilyl group, and a propyldimethylsilyl group.

Examples of the condensed aromatic ring group of Ar ⁵¹ and Ar ⁵² include naphthalene, anthracene, phenanthrene, pyrene, taricene, triphenylene, perylene and the like.

Examples of the alkyl group of R ^{51 to} R ⁵⁷ include the same examples as those described for R ^{7 to} R ″ in the general formula (4). Examples of the cyclic structure formed by R ^{51 to} R ⁵⁷ include Examples thereof include cycloalkanes having 4 to 12 carbon atoms such as cyclobutane, cyclopentane, cyclohexane, adamantane and norbornane.

[0030] [Chemical 9]

(6)

[In General Formula (6), A ⁶¹ and A ⁶² are each independently a substituted or unsubstituted condensed aromatic ring group having 10 to 20 nuclear carbon atoms.

Ar ⁶¹ and Ar ⁶² are each independently a hydrogen atom or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms.

R ^{61 to} R ⁷ ° each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms. Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted Substituted aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, substituted or unsubstituted carbon atoms 1 to 50 alkoxycarbonyl groups, substituted or unsubstituted silyl group, carboxyl group, halogen atom, cyano group, nitro group or hydroxyl group.

Ar ⁶¹ , Ar ⁶² , R ⁶⁹ and R ™ may be plural or adjacent to each other to form a saturated or unsaturated cyclic structure.

However, in the general formula (6), a symmetric group with respect to the XY axis shown on the anthracene is bonded to the 9th and 10th positions of the central anthracene. ]

Examples of the condensed aromatic ring of A ⁶¹ and A ⁶² include the examples given for Ar ⁵¹ and Ar ⁵² in the general formula (5). Among them, the ones with suitable carbon numbers are listed.

Examples of each group of Ar ⁶¹ , Ar ⁶² and R ^{61 to} R ^7Q , and examples of the cyclic structure that Ar ⁶¹ , Ar ⁶² , R ⁶⁹ and R ⁷ ° may form include those represented by the general formula (4). Examples similar to those mentioned are given.

[Chemical 10]

[In the general formula (7), Ar and Ar ′ are substituted or unsubstituted aromatic hydrocarbon groups having 6 to 50 nuclear carbon atoms, or substituted or unsubstituted aromatic heterocyclic rings having 5 to 50 nuclear atoms, respectively. It is a group.

L and L ′ are each a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalenylene group, a substituted or unsubstituted fluorenylene group, or a substituted or unsubstituted dibenzosilolylene group.

m is an integer from 0 to 2, n is an integer from 1 to 4, s is an integer from 0 to 2, and t is an integer from 0 to 4. In addition, L or Ar is bonded to any one of 1 to 5 positions of pyrene, and L ′ or Ar is bonded to any of 6 to 10 positions of pyrene.

However, when n + t is an even number, Ar, Ar ′, L, and V satisfy the following (1) or (2).

(1) Ar ≠ Ar ′ and / or L ≠ L ′ (where ≠ represents a group having a different structure)

(2) When Ar = Ar 'and L = L

(2-1) m ≠ s and / or n ≠ t, or

(2-2) When m = s and n = t,

(2-2-1) L and L ', or pyrene force, Ar and Ar, respectively, the force that binds to different bonding positions on (2-2-2) L and L', or pyrene force Ar and At the same bond position on Ar ' In the case of bonding, the substitutional force in pyrene of L and L ′ or Ar and Ar, Si position and 6 position, or 2 and 7 position, ]

Examples of the aromatic hydrocarbon group and aromatic heterocyclic group for Ar and Ar ′ include the same examples as those given in the general formula (5).

[0035] [Chemical 11]

[0036] [In the general formula (8), each of Αΐ ΆΧ Ί 独立 is independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms, and e and f are each an integer of 1 to 4 It is. However, when e = f = 1 and the bonding position of Ar ⁸¹ and Ar ^{82 to} the benzene ring is symmetrical, Ar ⁸¹ and Ar ⁸² are not the same e or f is an integer of 2 to 4 E and f are different integers.

R ^{81 to} R ⁹ ° each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms. Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted Substituted aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, substituted or unsubstituted carbon atoms 1 to 50 alkoxycarbonyl groups, substituted or unsubstituted silyl group, carboxyl group, halogen atom, cyano group, nitro group, hydroxyl group. ]

Examples of each group of Ar ⁸¹ , Ar ⁸² and R ^{81 to} R ^9Q include the same examples as those given in the general formula (5). [0037] The substituents of the groups of the general formulas (5) to (8) are substituted or unsubstituted aromatic hydrocarbon groups having 6 to 50 nuclear carbon atoms, substituted or unsubstituted nuclear atoms. 5 to 50 aromatic heterocyclic group, substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, substituted or unsubstituted carbon number 1 to 50 A substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 nucleus atoms, Examples thereof include a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, and a hydroxyl group.

[0038] In the organic EL device of the present invention, it is preferable that the organic thin film layer contains the compound represented by the general formula (1):! To 70% by weight, more preferably! To 20% by weight. .

Further, in the organic EL device of the present invention, the compound of the component (A) which is preferably contained when the light emitting layer contains the compound of the component (A) and the compound of the component (B) is a dopant, More preferably, the compound of component (B) is a host material.

[0039] In the organic EL device of the present invention, by combining the component (A) and the component (B),

A compound having a specific terminal substituent represented by the general formula (1) or (1 ′) of the component (A), in particular, a plurality of linear or branched alkyl groups or cycloalkyl groups are introduced on the diphenylamino group. Red light emission with high color purity can be obtained without impairing the effect of emitting long wavelengths by the compound. In addition, a compound having a condensed aromatic ring having 12 to 50 nuclear carbon atoms and having an asymmetric structure, such as component (B), particularly a compound having a specific terminal substituent as described above, is steric hindrance between compounds. As a result, the concentration quenching due to molecular association can be prevented and the lifetime can be further extended, so that red emission with high color purity can be obtained while having high emission efficiency and long lifetime.

The red emission color of organic EL elements can be divided by the maximum emission wavelength of the emission spectrum, orange (585 to 595 nm), red (maximum emission wavelength: 595 to 620 nm), pure red (maximum emission wavelength: 620). ~ 700nm).

In red light-emitting elements showing yellow to orange or red, red light emission means that CIEx value in CIE chromaticity coordinates is 0.62 or more (preferably 0.62 or more and less than 0.73), orange Luminescence is a CIEx value between 0 · 54 and less than 0 · 62.

[0040] In the organic EL device of the present invention, various intermediate layers are preferably interposed between the pair of electrodes and the light emitting layer. Examples of the intermediate layer include a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer.

As a typical element configuration of such an organic EL element,

(1) Anode / light emitting layer / cathode

(2) Anode / hole injection layer / light emitting layer / cathode

(3) Anode / light emitting layer / electron injection layer / cathode

(4) Anode / hole injection layer / light emitting layer / electron injection layer / cathode

(5) Anode / organic semiconductor layer / light emitting layer / cathode

(6) Anode / organic semiconductor layer / electron barrier layer / light emitting layer / cathode

(7) Anode / organic semiconductor layer / light emitting layer / adhesion improving layer / cathode

(8) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode

(9) Anode / insulating layer / light emitting layer / insulating layer / cathode

(10) Anode / inorganic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode

(11) Anode / organic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode

(12) Anode / insulating layer / hole injection layer / hole transport layer / light emitting layer / insulating layer / cathode

(13) Structures such as anode / insulating layer / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode can be mentioned.

Among these, the force for which the configuration of (8) is preferably used is not limited to these.

[0041] This organic EL element is usually produced on a translucent substrate. This translucent substrate is a substrate that supports organic EL elements, and the translucency is 50 for light in the visible region of 400 to 700 nm. It is preferable to use a smoother substrate that is more than / o.

As such a translucent substrate, for example, a glass plate, a synthetic resin plate, or the like is preferably used. Examples of glass plates include soda-lime glass, glass containing strontium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. A plate formed with a throat. Examples of the synthetic resin plate include polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, and polysulfone resin.

[0042] Next, as the anode, a material having a large work function (4 eV or more) metal, alloy, electrically conductive compound or a mixture thereof is preferably used. Specific examples of such electrode materials include metals such as Au, Cul, IT〇 (indium tinoxide), Sn〇,

Examples include conductive materials such as ZnO and In-Zn-O. In order to form this anode, a thin film can be formed from these electrode materials by a method such as vapor deposition or sputtering. The anode desirably has such a characteristic that when light emitted from the light emitting layer is extracted from the anode, the transmittance for light emission from the anode is greater than 10%. The sheet resistance of the anode is preferably several hundred Ω or less. Further, although the film thickness of the anode depends on the material, it is usually selected in the range of 10 nm to l x m, preferably 10 to 200 nm.

[0043] Next, as the cathode, those having a low work function, (4 eV or less) metal, an alloy, an electrically conductive compound, and a mixture thereof as an electrode material are used. Examples of such electrode materials are sodium, sodium-potassium alloy, magnesium, lithium, magnesium silver alloy, aluminum / aluminum oxide, Al / Li 0, Al / LiO, Al / LiF, aluminum. Examples include lithium alloys, indium, and rare earth metals.

This cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.

Here, when the light emission from the light emitting layer is taken out by the cathode power, the transmittance for the light emission of the cathode is preferably larger than 10%. The sheet resistance as the cathode is preferably several hundred Ω / b or less, and the film thickness is usually 10 nm to l zm, preferably 50 to 200 nm.

[0044] In the organic EL device of the present invention, at least one surface selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer (hereinafter, referred to as a "metal oxide layer") is formed on at least one surface of the pair of electrodes thus prepared. These are sometimes referred to as surface layers). Specifically, a chalcogenide (including oxide) layer of metal such as silicon or aluminum is formed on the anode surface on the light emitting layer side, and a metal halide layer or metal oxide layer is formed on the cathode surface on the light emitting layer side. It is good to arrange. Thereby, the drive can be stabilized. Preferred examples of the chalcogenide include SiOx (l≤X≤2), AlOx (l≤X≤1.5), Si ON, SiAlON, etc., and examples of the metal halide include LiF, MgF

, CaF, rare earth metal fluoride and the like are preferable, and examples of the metal oxide include Cs.

Preferred are O, LiO, MgO, SrO, BaO, CaO.

[0045] In the organic EL device of the present invention, both the electron transport property and the hole transport property of the light emitting layer are improved by the use ratio of the component (A) and the component (B). It is possible to omit intermediate layers such as layers, hole transport layers, and electron injection layers. The surface layer can be provided also in this case and is preferable.

Further, in the organic EL device of the present invention, the mixed region of the electron transfer compound and the reducing dopant or the mixed region of the hole transfer compound and the oxidizing dopant is formed on at least one surface of the pair of electrodes thus prepared. Is also preferable. In this way, the electron transfer compound is reduced and becomes an anion, and the mixed region more easily injects and transfers electrons to the light emitting layer. In addition, the hole transfer compound is oxidized and becomes a cation, so that the mixed region more easily injects and transfers holes to the light emitting layer. As a preferable oxidizing dopant, there are various Lewis acid acceptor compounds. Preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals and their compounds.

In the organic EL device of the present invention, the light emitting layer is

(i) Injection function; function that can inject holes from the anode or hole injection layer when an electric field is applied, and can inject electrons from the negative electrode or electron injection layer

(ii) Transport function: Function to move injected charges (electrons and holes) by the force of electric field

(iii) Luminescent function; provides a field for recombination of electrons and holes, and has a function to connect this to light emission.

As a method for forming the light emitting layer, known methods such as vapor deposition, spin coating, and LB method can be applied. The light emitting layer is particularly preferably a molecular deposited film. Here, the molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidification from a material compound in a solution state or a liquid phase state. This molecular deposited film has an agglomerated structure and a high structure compared to the thin film (molecular accumulation film) formed by the LB method It can be classified by the difference in the next structure and the functional difference resulting therefrom.

[0047] Further, as disclosed in JP-A-57-51781, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, which is then thin-filmed by spin coating or the like. The light emitting layer can also be formed by annealing.

In the present invention, as long as the object of the present invention is not impaired, if desired, the light emitting layer may contain other known light emitting materials other than the component (A) and the component (B). A light emitting layer containing another known light emitting material may be laminated on the light emitting layer containing the compound according to the present invention.

[0048] Next, the hole injecting / transporting layer is a layer that helps injecting holes into the light emitting layer and transports them to the light emitting region, and has a high hole mobility and usually has an ion energy of 5.5 eV or less. And small les. For such a hole injection / transport layer, a material that transports holes to the light-emitting layer with a lower electric field strength is preferred. Further, the mobility force of holes is small, for example, when an electric field of 10 ⁴ to 10 ⁶ VZcm is applied. even without those which are 10- ⁶ cm ² / V * s is preferable. As such a material, a material that has been conventionally used as a hole transport material in an optical material, or a known medium-powered material used for a hole injection layer of an organic EL element is selected. Can be used.

In order to form this hole injection 'transport layer, the hole injection' transport material may be formed into a thin film by a known method such as vacuum deposition, spin coating, casting, or LB. ,. In this case, the thickness of the hole injecting / transporting layer is not particularly limited, but is usually 5 nm to 5 μm.

[0049] Next, the electron injection layer 'transport layer is a layer that assists the injection of electrons into the light emitting layer and transports it to the light emitting region, and has a high electron mobility, and the adhesion improving layer is the electron injection layer. Among these, it is a layer made of a material that particularly adheres well to the cathode. The material used for the electron injection layer is preferably a metal complex of 8-hydroxyquinoline or a derivative thereof. Specific examples of the above-mentioned metal complexes of 8-hydroxyquinoline or its derivatives include metal chelate oxinoid compounds containing a chelate of oxine (generally 8-quinolinol or 8-hydroxyquinoline) such as tris (8-quinolinol) aluminum. It can be used as an electron injection material. In addition, since the organic EL device of the present invention applies an electric field to the ultrathin film, pixel defects due to leakage or short-circuiting are likely to occur. In order to prevent this, an insulating thin film layer may be inserted between the pair of electrodes.

[0050] Examples of the material used for the insulating layer include aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesium oxide, magnesium oxide, magnesium fluoride, oxidizing power, normesium, calcium fluoride, aluminum nitride, Examples thereof include titanium oxide, silicon oxide, germanium oxide, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, and vanadium oxide. A mixture or laminate of these may be used.

Next, regarding the method for producing the organic EL device of the present invention, for example, an anode, a light emitting layer, a hole injection layer as necessary, and an electron injection layer as necessary are formed by the above-described materials and methods. A cathode may be formed on the substrate. In addition, the organic EL element can be fabricated in the reverse order from the cathode to the anode.

Hereinafter, as an example, an example of manufacturing an organic EL element having a structure in which an anode / a hole injection layer / a light emitting layer / an electron injection layer / a cathode are sequentially provided on a translucent substrate will be described.

First, a thin film having an anode material strength is formed on a suitable translucent substrate by vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 10 to 200 nm, and used as an anode. Next, a hole injection layer is provided on the anode. As described above, the hole injection layer can be formed by a method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. A homogeneous film can be obtained immediately and pinholes are not easily generated. In view of the above, it is preferable to form the film by a vacuum evaporation method. When forming a hole injection layer by vacuum deposition, the deposition conditions vary depending on the compound used (material of the hole injection layer), the crystal structure and recombination structure of the target hole injection layer, etc. deposition source temperature 50 to 450 ° C, vacuum degree of 10- 7~: 10- ³ torr, vapor deposition rate 0. 01~50nm / sec, a substrate temperature of _ 50 to 300 ° C, in the range of thickness of 5 nm to 5 mu m It is preferable to select appropriately.

Next, a light emitting layer is provided on the hole injection layer. This light-emitting layer is also formed by thinning the film using a material comprising the compounds of the components (A) and (B) according to the present invention by a method such as vacuum deposition, sputtering, spin coating, or casting. However, it can be formed by vacuum deposition from the standpoint that a homogeneous film is obtained and pinholes are not easily generated. It is preferable. When forming a light emitting layer by vacuum deposition, the deposition conditions vary depending on the compound used, but in general, it is possible to select from the same condition range as the formation of the hole injection layer. The film thickness is preferably in the range of 10 to 40 nm.

Next, an electron injection layer is provided on the light emitting layer. Also in this case, like the hole injection layer and the light emitting layer, it is preferable to form by a vacuum evaporation method because it is necessary to obtain a homogeneous film. The vapor deposition conditions can be selected from the same condition ranges as those for the hole injection layer and the light emitting layer.

Finally, a cathode is laminated to obtain an organic EL element. The cathode is made of metal, and vapor deposition or sputtering can be used. However, vacuum deposition is preferred to protect the underlying organic layer from damage during film formation.

The above organic EL device is preferably manufactured from the anode to the cathode consistently by a single vacuum.

When a direct current voltage is applied to the organic EL element, light emission can be observed by applying a voltage of 3 to 40 V with the anode as + and the cathode as-polarity. In addition, even when a voltage is applied with the opposite polarity, no current flows and no light is emitted. Furthermore, when AC voltage is applied, uniform light emission is observed only when the anode is + and the cathode is of the same polarity. In this case, the AC waveform to be applied is arbitrary.

Example

[0054] Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1

25 mm X 75 mm X O. A transparent electrode made of indium oxide having a thickness of 120 nm was provided on a 7 mm size glass substrate. This glass substrate was ultrasonically cleaned in isopropyl alcohol for 5 minutes, then UV ozone cleaned for 30 minutes, and this substrate was placed in a vacuum evaporation system.

First, 正孔 ', Ν "—bis [4- (diphenylamino) phenol] -Ν', Ν"-diphenylbiphenyl4,4'-diamin is added to the substrate as a hole injection layer at 60 nm. After vapor deposition to a thickness, N, N, —bis [4'— {N— (naphthyl-1-yl) — N—phenyl} aminobiphenol 1— Nil]-N-phenylamine deposited to a thickness of 20nm did. Next, when forming the light emitting layer, the following compound (B) -1 as a host material and the following compound (A) -5 as a dopant were co-deposited at a weight ratio of 40: 4, and then deposited to a thickness of 40 nm. In addition, tris (8-hydroxyquinonato) aluminum (hereinafter referred to as Alq) is used as an electron injection layer.

Three

Evaporated to a thickness of 20 nm. Next, lithium fluoride was evaporated to a thickness of 0.3 nm, and then aluminum was evaporated to a thickness of 150 nm. This aluminum / lithium fluoride acts as the cathode. In this way, an organic EL device was produced.

When a current test was performed on the obtained device, a red light emission with an emission luminance of 767 cdZm ² was obtained at a current density of lOmAZcm ² , the chromaticity coordinates were (0.62 and 0.38), and the efficiency was 7.67 cd. / A. In addition, a half-life was 4200 hours when a DC continuous energization test was performed at an initial luminance of 5000 cdZm ² .

[Chemical 12]

Examples 2-8

An organic EL device was produced in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the host material and dopant of the light emitting layer. The compounds used in Examples 2 to 8 shown in Table 1 are shown below.

The obtained device was energized at a current density of 10 mA / cm ^{2 in the same} manner as in Example 1. Table 1 shows the results of a DC continuous energization test with an initial luminance of 5000 cd / m ² .

[0057] [Chemical 13]

(D) — 1 (E)-1

[0058] Comparative Example:! ~ 10

An organic EL device was produced in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the host material and dopant of the light emitting layer. The compounds used in Comparative Examples 1 to 10 shown in Table 1 are shown below.

The obtained device was subjected to an energization test at a current density of 10 mA / cm ² in the same manner as in Example 1, and the results of a DC continuous energization test with an initial luminance of 5000 cd / m ² are shown in Table 1.

[0059] [Chemical 14]

[table 1]

As shown in Table 1, in the organic EL devices of Examples:! To 8, red light emission with high color purity was obtained while having high luminous efficiency and long life, whereas the above-mentioned general formula was used as a dopant. (1) and / or (1 ′), Comparative Examples 1 to 4 using a compound and Comparative Examples 5 to 7 using a condensed aromatic ring compound having a symmetrical structure as a host material have high color purity. In Comparative Examples 8 to 10 in which red light emission was not obtained and a compound that was not the condensed aromatic ring-containing compound was used as a dopant, the lifetime was significantly short. Industrial applicability

As described in detail above, the organic EL device of the present invention can emit red light with high color purity while having high luminous efficiency and long life. Therefore, it is useful as a practical organic EL device, and is particularly suitable for a full-color display.

Claims

[Claims] In an organic electoluminescence device in which an organic thin film layer composed of one or more layers including at least a light emitting layer is sandwiched between a cathode and an anode, at least one layer of the organic thin film layer comprises (A) the following general formula: An organic electroluminescent device comprising a compound represented by (1) and / or (1 ') and (B) a compound having a condensed aromatic ring having 12 to 50 nuclear carbon atoms and having an asymmetric structure. [In the general formula (1), Ai ^ Ar4 is each independently a group represented by the following general formula (2), (3) or (4). However, at least one of Ar1 to Ar4 is a group represented by the following general formula (2) or (3). [In the general formula (2), at least two of R1˜ are substituted or unsubstituted carbon: straight chain or branched alkyl group having 30 to 30 carbon atoms, and the remainder is a hydrogen atom. In (3), at least one of R4 to R6 is a substituted or unsubstituted cycloalkyl group having 3 to 50 nuclear carbon atoms, and the remainder is a hydrogen atom. In general formula (4), R7 to R "are Each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, or a substituted or unsubstituted nuclear carbon number. 6-50 aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group having 5 to 50 carbon atoms, substituted or unsubstituted nuclear carbon number 5 to 50 aryloxy group, substituted or unsubstituted nucleus C 6-50 aralkyl group, substituted or unsubstituted C 3-50 C A chloroalkyl group or a halogen atom R7 to RU may be bonded to each other in contact with P to form a saturated or unsaturated cyclic structure. The asymmetric anthracene derivative represented by the general formula (5), the asymmetric anthracene derivative represented by the general formula (6), the asymmetric pyrene derivative represented by the general formula (7), or the asymmetric diphenyl derivative represented by the general formula (8). The organic electoluminescence device according to claim 1, which is a luanthracene derivative [Chemical formula 3] (5) [In the general formula (5), X is a hydrogen atom, a substituted or unsubstituted nuclear carbon number of 6 to 50. Aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted nuclear carbon number 3 to 5 0 cycloalkyl group, substituted or unsubstituted Substituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 carbon atoms, substituted or unsubstituted nuclear atoms An arylcarbonyl group having 5 to 50, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, and a hydroxyl group. Ar52 is independently a substituted or unsubstituted condensed aromatic ring group having 10 to 50 nuclear carbon atoms, and at least one of Ar51 and Ar52 is a 1 naphthyl group represented by the following general formula (i) or It is a 2-naphthyl group represented by the general formula (ii). (!) (Ii) (In the general formulas (i) and (ii), RU to R17 are a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms. At least one pair adjacent to each other is bonded to each other to form a cyclic structure.) A, b and c are each an integer of 0 to 4, and d is an integer of 1 to 3. When d is 2 or more, the groups in [] may be the same or different. [In the general formula (6), A61 and A62 are each independently a substituted or unsubstituted condensed aromatic ring group having 10 to 20 nuclear carbon atoms. Ar61 and Ar62 are each independently a hydrogen atom or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms. Rbl to R7 "each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 50 nuclear carbon atoms, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted Aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, substituted or unsubstituted carbon atoms having 1 to 50 carbon atoms An alkoxycarbonyl group, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group or a hydroxyl group Ar61, Ar62, R69 and R7Q may be plural or adjacent to each other; Mutual It may be bonded to form a saturated or unsaturated cyclic structure, provided that in the general formula (6), X-Y shown on the anthracene is located at the 9th and 10th positions of the central anthracene. In the case where a group that is symmetric with respect to the axis is bonded,] [Chemical Formula 6] [In the general formula (7), Ar and Ar ′ are substituted or unsubstituted nuclear carbon atoms of 6 to 50, respectively. An aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, L and L ′ are each a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalenylene group, A substituted or unsubstituted fluorenylene group or a substituted or unsubstituted dibenzosilolylene group, m is an integer from 0 to 2, n is an integer from 1 to 4, s is an integer from 0 to 2, and t is from 0 to 4 L or Ar is bonded to any one of 1 to 5 positions of pyrene, and L ′ or Ar Is bound to any one of the 6th to 10th positions of pyrene, provided that when n + t is an even number, Ar, Ar ', L, and L satisfy (1) or (2) below.

(1) Ar ≠ Ar ′ and Z or L ≠ L ′ (where ≠ indicates a group having a different structure)

(2) When Ar = Ar 'and L = L'

(2-1) m ≠ s and / or n ≠ t, or

(2-2) When m = s and n = t,

(2-2-1) L and L ', or pyrene force, Ar and Ar, respectively, the force that binds to different bonding positions on (2-2-2) L and L', or pyrene force Ar and In the case of bonding at the same bonding position on Ar ', L and L' or Ar and Ar, the substitution position force position in pyrene and 6th position, or 2nd and 7th position, ]

[Chemical 7]

[In the general formula (8), Ar ⁸¹ and ΑΛ are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms, and e and f are integers of 1 to 4 respectively. is there. However, when e = f = 1 and the bonding position of Ar ⁸¹ and Ar ^{82 to} the benzene ring is symmetrical, Ar ⁸¹ and Ar ⁸² are not the same e or f is an integer of 2 to 4 E and f are different integers.

R ^{81 to} R ⁹ ° each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms. , Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted carbon number 3 -50 cycloalkyl group, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 nucleus atoms Substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, substituted or unsubstituted silyl group, carboxyl group, halogen atom, cyano group, nitro Group, a hydroxyl group. ]

[3] In the general formula (2), at least two of R ^{1 to} R ³ are each independently a methyl group, an ethyl group, an isopropyl group, a 1-butyl group, a 2_methylpropyl group, 2. The organic electroluminescent element according to claim 1, which is a 1-dimethylethyl group, a dimethyl group or a trimethyl group.

[4] The organic electoluminescence device according to [1], wherein in the general formula (3), at least one of R ^{4 to} R ⁶ is a cyclohexyl group.

[5] The organic electroluminescent device according to claim 1, wherein the organic thin-film layer contains:! To 70% by weight of the compound represented by the general formula (1).

6. The organic electroluminescent device according to claim 1, wherein the light emitting layer contains a compound of component (A) and a compound of component (B).

7. The organic electroluminescent device according to claim 1, wherein the compound of component (A) is a dopant and the compound of component (B) is a host material.

8. The organic electoluminescence device according to claim 1, which emits red light.