JP2006056841A - Amine compound and organic electroluminescent element containing the amine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an amine compound and to provide an organic electroluminescent element containing the compound. <P>SOLUTION: The amine compound is represented by formula (1) [wherein R<SB>1</SB>and R<SB>2</SB>are each a hydrogen atom, a straight chain, branched, or cyclic alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic-heterocyclic group; Z<SB>1</SB>to Z<SB>4</SB>are each a substituent; n<SB>1</SB>to n<SB>4</SB>are each an integer of 0 to 3; and A<SB>1</SB>, A<SB>2</SB>, and A<SB>3</SB>are each a group represented by formula (2) (wherein Ar<SB>1</SB>and Ar<SB>2</SB>are each a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic-heterocyclic group, provided that Ar<SB>1</SB>and Ar<SB>2</SB>may be combined with each other to form a ring structure), provided that the groups A<SB>1</SB>, A<SB>2</SB>, and A<SB>3</SB>, represented by formula (2) may be the same or different from each other]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel amine compound and an organic electroluminescent device containing the amine compound.

Conventionally, amine compounds have been used as production intermediates for various dyes or various functional materials. As a functional material, for example, it has been used as a charge transport material for an electrophotographic photoreceptor. Recently, it has been proposed to be useful as a hole injecting and transporting material of an organic electroluminescent device (organic electroluminescent device: organic EL device) using an organic material as a luminescent material [for example, Appl. Phys. Lett. , 51, 913 (1987)]

  Electroluminescent devices that use electroluminescence are self-luminous compared to liquid crystal displays and thus have high visibility and high-speed responsiveness, so that they can display clear images when used in displays. In addition, since it is an all solid-state device, it has characteristics such as excellent impact resistance. Therefore, in recent years, it is expected to be widely used for thin displays, liquid crystal display backlights, flat light sources, and the like.

  Here, the electroluminescent element can be roughly classified into an inorganic electroluminescent element and an organic electroluminescent element according to the constituent materials. The inorganic electroluminescent device is a dispersive electroluminescent device using an inorganic material such as zinc sulfide. The driving method of this dispersive electroluminescent device is that an accelerated electron collides and excites the emission center by applying a high electric field. Therefore, it is necessary to drive with a high AC voltage. Therefore, there are problems such as a complicated driving circuit and low luminance.

  On the other hand, an organic electroluminescence device (organic electroluminescence device: organic EL device) emits light by recombining charges (holes and electrons) injected from an electrode in a light emitting layer made of an organic compound. Because it is “light emission”, it can be driven at a low voltage (Non-patent Document 1 and Patent Document 1). Further, there is an advantage that an arbitrary emission color and characteristics can be easily changed by changing the molecular design of the organic compound. For this reason, various materials and element configurations have been proposed at present, and research and development has been activated.

  On the other hand, various problems and problems still remain in the organic electroluminescent devices using the materials proposed so far. For example, there is a problem in the light emission life that the function of the element deteriorates and the light emission luminance decreases only by storing, regardless of the drive state or the non-drive state. In general, the emission luminance is still low, which is not sufficient for practical use.

  As a hole injecting and transporting material, 4,4′-bis [N-phenyl-N- (3 ″-) is used for the purpose of efficiently injecting and transporting holes to a thin film containing a fluorescent organic compound of an organic electroluminescence device. It has been proposed to use (methylphenyl) amino] biphenyl [Non-Patent Document 2].

  Moreover, as a hole injection transport material, for example, 9,9-dialkyl-2,7-bis (N, N-diphenylamino) fluorene derivative [for example, 9,9-dimethyl-2,7-bis (N, N It has also been proposed to use (diphenylamino) fluorene] (Patent Document 2).

  However, organic electroluminescent devices using these amine compounds as hole injecting and transporting materials also have problems such as low luminous efficiency, high driving voltage, poor stability and durability.

At present, there is a demand for an organic electroluminescent device excellent in luminous efficiency, driving voltage, stability, and durability. Therefore, a novel amine compound that exhibits excellent characteristics when used as an organic electroluminescent device is desired. ing.
Appl.Phys.Lett., 51,913 (1987) Jpn.J.Appl.Phys., 27, L269 (1988) Japanese Unexamined Patent Publication No. 63-264692 Japanese Patent Laid-Open No. 5-25473

  The subject of this invention is providing the organic electroluminescent element containing an amine compound and this compound. More specifically, it is an object to provide an amine compound suitable for a light emitting material of an organic electroluminescent element, and an organic electroluminescent element having excellent stability and durability and high heat resistance using the compound.

  In order to solve the above-mentioned problems, the present inventors have intensively studied various amine compounds and organic electroluminescent elements, and as a result, have completed the present invention. That is, the present invention provides <1>: an amine compound represented by the general formula (1) (chemical formula 1),

[Wherein R ₁ and R ₂ represent a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, Z _{1 to} Z ₄ represent a substituent, n _{1 to} n ₄ represent an integer of 0 to 3, and A ₁ , A _2, and A ₃ represent the general formula (2) (Chemical Formula 2)

(In the formula, Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group, and Ar ₁ and Ar ₂ are linked to each other to form a cyclic structure. The groups represented by general formula (2) of A ₁ , A ₂ and A ₃ may be the same or different.
<2>: The amine compound according to <1>, wherein Ar ₁ and Ar ₂ are substituted or unsubstituted aromatic hydrocarbon groups,
<3>: An organic electroluminescent device comprising at least one layer containing at least one amine compound described in <1> between a pair of electrodes,
<4>: The organic electroluminescence device according to <3>, wherein the layer containing the amine compound according to <1> is a hole injection layer,
<5>: The organic electroluminescence device according to <3>, wherein the layer containing the amine compound according to <1> is a hole transport layer;
<6>: The organic electroluminescent element according to <3>, wherein the layer containing the amine compound according to <1> is a light emitting layer.
<7>: The organic electroluminescent element according to any one of <3> to <6>, further having a light emitting layer between a pair of electrodes.
<8>: The organic electroluminescence device according to any one of <3> to <7>, further including an electron injecting and transporting layer between the pair of electrodes.

  According to the present invention, there is provided a novel amine compound and an organic electroluminescence device having high heat resistance, high luminous efficiency, low driving voltage, long emission life, excellent durability, and the use of the amine compound. It becomes possible.

Hereinafter, the present invention will be described in detail.
The amine compound of the present invention is a compound represented by the general formula (1) (chemical formula 3).

[Wherein R ₁ and R ₂ represent a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, Z _{1 to} Z ₄ represent a substituent, n _{1 to} n ₄ represent an integer of 0 to 3, and A ₁ , A _2, and A ₃ represent the general formula (2) (Chemical Formula 4)

(In the formula, Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group, and Ar ₁ and Ar ₂ are linked to each other to form a cyclic structure. And the groups represented by the general formula (2) of A ₁ , A ₂ and A ₃ may be the same or different.

In the amine compound represented by the general formula (1), R ₁ and R ₂ are a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted group. Represents an aromatic heterocyclic group, preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic group having 4 to 30 carbon atoms Represents a heterocyclic group, and more preferably a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or 4 to 20 carbon atoms. Represents an aromatic heterocyclic group.

Specific examples of the linear, branched or cyclic alkyl group represented by R ₁ and R ₂ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group 1-methylhexyl group, n-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4- Heptyl, 3,5,5-trimethylhexyl, n-decyl, 1-ethyloctyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tri Sil group, 1-hexyl heptyl group, n-tetradecyl group, n-pentadecyl group, 1-heptyloctyl group, n-hexadecyl group, n-heptadecyl group, 1-octylnonyl group, n-octadecyl group, 1-nonyldecyl group 1-decylundecyl group, n-eicosyl group, n-docosyl group, n-tetracosyl group, cyclohexylmethyl group, (1-isopropylcyclohexyl) methyl group, 2-cyclohexylethyl group, bornel group, isobornyl group, 1-norbornyl group 2-norbornanemethyl group, 1-bicyclo [2.2.2] octyl group, 1-adamantyl group, 3-noradamantyl group, 1-adamantylmethyl group, cyclobutyl group, cyclopentyl group, 1-methylcyclopentyl group, cyclohexyl Group, 4-methylcyclohexyl group, 3- Methylcyclohexyl group, 2-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, 2,6-diisopropylcyclohexyl group, 4-tert-butylcyclohexyl group, 3-tert-butylcyclohexyl group, 4-phenylcyclohexyl group, 2-phenylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclotetradecyl group,

  Methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-hexyloxymethyl group, (2-ethylbutyloxy) methyl group, n-octyloxymethyl group, n-decyloxymethyl group, 2-methoxyethyl group 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2′-ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropoxy Group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3- (n-butoxy) propyl group, 3- (n-pentyloxy) propyl group, 3- (n-hexyloxy) propyl group, 3- (2′-ethylbutoxy) propyl group, 3- (n-octyloxy) propyl group, 3- (2′-ethylhexyloxy) propyl group, 3- (n -Decyloxy) propyl group, 3- (n-dodecyloxy) propyl group, 3- (n-tetradecyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4- n-propoxybutyl group, 4-isopropoxybutyl group, 4-n-butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-o Tyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group, 5-n-propoxypentyl group, 6-ethoxyhexyl group, 6 -Isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group 8-methoxyoctyl group, 10-methoxydecyl group, 10-n-butoxydecyl group, 12-ethoxydodecyl group, 12-isopropoxide decyl group, tetrahydrofurfuryl group,

  2- (2′-methoxyethoxy) ethyl group, 2- (2′-ethoxyethoxy) ethyl group, 2- (2′-n-butoxyethoxy) ethyl group, 3- (2′-ethoxyethoxy) propyl group, 2-allyloxyethyl group, 2- (4′-pentenyloxy) ethyl group, 3-allyloxypropyl group, 3- (2′-hexenyloxy) propyl group, 3- (2′-heptenyloxy) propyl group, 3 -(1'-cyclohexenyloxy) propyl group, 4-allyloxybutyl group,

  Benzyloxymethyl group, 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4′-methylbenzyloxy) ethyl group, 2- (2′-methylbenzyloxy) ethyl group, 2- (4 ′) -Fluorobenzyloxy) ethyl group, 2- (4'-chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 3- (4'-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, 2- (Benzyloxymethoxy) ethyl group, 2- (4′-methylbenzyloxymethoxy) ethyl group,

  Phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 4-chlorophenyloxymethyl group Group, 2-chlorophenyloxymethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′-methoxyphenyl) Oxy) ethyl group, 2- (4′-chlorophenyloxy) ethyl group, 2- (4′-bromophenyloxy) ethyl group, 2- (1′-naphthyloxy) ethyl group, 2- (2′-naphthyloxy) ) Ethyl group, 3-phenyloxypropyl group, 3- (2′-naphthyloxy) propyl group, 4- Enyloxybutyl group, 4- (2′-ethylphenyloxy) butyl group, 5- (4′-tert-butylphenyloxy) pentyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl Group, 10-phenyloxydecyl group, 10- (3′-chlorophenyloxy) decyl group, 2- (2′-phenyloxyethoxy) ethyl group, 3- (2′-phenyloxyethoxy) propyl group, 4- ( 2'-phenyloxyethoxy) butyl group,

  n-butylthiomethyl group, n-hexylthiomethyl group, 2-methylthioethyl group, 2-ethylthioethyl group, 2-n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n-octyl Thioethyl group, 2-n-decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthiobutyl group 4-n-butylthiobutyl group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group, 6-n-butylthiohexyl group, 8-methylthiooctyl group, 2- (2 ′ -Methoxyethylthio) ethyl group, 4- (3'-ethoxypropylthio) butyl group, 2- (2'-ethylthioethylthio) ethyl group, 2-allylthioethyl group, -Benzylthioethyl group, 3- (4'-methylbenzylthio) propyl group, 4-benzylthiobutyl group, 2- (2'-benzyloxyethylthio) ethyl group, 3- (3'-benzylthiopropylthio) ) Propyl group,

  2-phenylthioethyl group, 2- (4'-methoxyphenylthio) ethyl group, 2- (2'-phenyloxyethylthio) ethyl group, 3- (2'-phenylthioethylthio) propyl group,

  Fluoromethyl group, 3-fluoropropyl group, 6-fluorohexyl group, 8-fluorooctyl group, difluoromethyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro -N-propyl group, 1,1,3-trihydro-perfluoro-n-propyl group, 1,1-dihydro-perfluoro-n-butyl group, 1,1-dihydro-perfluoro-n-pentyl group, 1,1-dihydro-perfluoro-n-hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl group, 1,1-dihydro-perfluoro-n-octyl group, 1,1-dihydro-perfluoro-n -Decyl group, 1,1-dihydro-perfluoro-n-dodecyl group, 1,1-dihydro-perfluoro-n-tetradecyl group, 1 1-dihydro-perfluoro-n-hexadecyl group, perfluoro-n-hexyl group, dichloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group, 8-chloro Octyl group, 2,2,2-trichloroethyl group,

  2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 6-hydroxyhexyl group, 5-hydroxyheptyl group, 8-hydroxyoctyl group, 10- Examples thereof include, but are not limited to, a substituted or unsubstituted linear, branched or cyclic alkyl group such as a hydroxydecyl group, a 12-hydroxydodecyl group and a 2-hydroxycyclohexyl group.

Specific examples of the substituted or unsubstituted aromatic hydrocarbon group or the substituted or unsubstituted aromatic heterocyclic group for R ₁ and R ₂ include, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, 4- Phenyl-1-naphthyl group, 6-phenyl-2-naphthyl group, 2-anthracenyl group, 9-anthracenyl group, 9-methyl-10-anthracenyl group, 9-phenyl-10-anthracenyl group, 1-phenanthryl group, 2 -Phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 9-methyl-10-phenanthryl group, 9-phenyl-10-phenanthryl group, 1-methyl-9-phenanthryl group, 1-phenyl- 9-phenanthryl group, 2-methyl-9-phenanthryl group, 2-phenyl-9-phenanthryl group, 1 8-dimethyl-9-phenanthryl group, 1,8-diphenyl-9-phenanthryl group, 2-chloro-9-phenanthryl group, 2-fluoro-9-phenanthryl group, 2,7-dichloro-9-phenanthryl group, 2 , 7-dimethyl-9-phenanthryl group, 2,7-diphenyl-9-phenanthryl group, 2,7,9-trimethyl-10-phenanthryl group, 2,7,9-triphenyl-10-phenanthryl group,

  1-pyrenyl group, 2-pyrenyl group, 1-phenyl-2-pyrenyl group, 1-methyl-2-pyrenyl group, 2-phenyl-1-pyrenyl group, 2-methyl-1-pyrenyl group, 4,5-dimethyl -1-pyrenyl group, 6-phenyl-1-pyrenyl group, 6-methyl-1-pyrenyl group, 6-tert-butyl-1-pyrenyl group, 6-cyclohexyl-1-pyrenyl group, 7-phenyl-1- Pyrenyl group, 7-methyl-1-pyrenyl group, 7-phenyl-2-pyrenyl group, 7-methyl-2-pyrenyl group, 7-tert-butyl-2-pyrenyl group, 1,8-diphenyl-2-pyrenyl group Group, 1,8-dimethyl-2-pyrenyl group, 5,9-dicyclohexyl-2-pyrenyl group, 3,6-diphenyl-1-pyrenyl group, 3,6-dimethyl-1-pyrenyl group, 3,6- Di-tert-butyl-1-pyre Nyl group, 8-methyl-1-pyrenyl group, 8-tert-butyl-1-pyrenyl group, 8-phenyl-1-pyrenyl group, 9-phenyl-1-pyrenyl group, 9-phenyl-2-pyrenyl group, 9-methyl-2-pyrenyl group, 10-phenyl-1-pyrenyl group, 10-methyl-1-pyrenyl group, 10-phenyl-2-pyrenyl group, 10-methyl-2-pyrenyl group, 9-methyl-1 -Pyrenyl group, 3,6,8-trimethyl-1-pyrenyl group, 3,6,8-triphenyl-1-pyrenyl group, 3,6-dimethyl-8-phenyl-1-pyrenyl group, 9,10- Dimethyl-1-pyrenyl group, 9,10-diphenyl-1-pyrenyl group, 4,9-dimethyl-1-pyrenyl group, 4,9-diphenyl-1-pyrenyl group, 9,5-dimethyl-2-pyrenyl group 4,5,9,10-tri Tyl-2-pyrenyl group, 4-quinolinyl group, 3-quinolinyl group, 2-quinolinyl group, 4-pyridinyl group, 3-pyridinyl group, 2-pyridinyl group, 2-pyrimidinyl group, 2-pyridazinyl group, 2-pyrazinyl group Group, 3-furanyl group, 2-furanyl group, 3-thienyl group, 2-thienyl group, 2-benzofuranyl group, 2-benzothiophenyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzooxazolyl Group, 2-benzothiazolyl group, 2-benzimidazolyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4- n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-iso Tilphenyl group, 4-sec-butylphenyl group, 2-sec-butylphenyl group, 4-tert-butylphenyl group, 3-tert-butylphenyl group, 2-tertbutylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 2-neopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4- (2′-ethylbutyl) phenyl group, 4-n-heptylphenyl group, 4 -N-octylphenyl group, 4- (2'-ethylhexyl) phenyl group, 4-tert-octylphenyl group, 4-n-decylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4- (4′-methylcyclohexyl) phenyl group, 4- (4′-tert-butylsilane) Cyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2,4-dimethylphenyl group, 3,5-dimethyl Phenyl group, 2,6-dimethylphenyl group, 2,4-diethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2 , 6-diethylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisobutylphenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 4,6 -Di-tert-butyl-2-methylphenyl group, 5-tert-butyl-2-methylphenyl group, 4-tert-butyl-2,6-dimethylphenyl group,

  4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl Group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, 2-isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4-n- Pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2-nepentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2 '-Ethylbutyloxy) phenyl group, 4-n-octyloxyphenyl group, 4-n- Siloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-methoxy-1-naphthyl group, 4-methoxy -1-naphthyl group, 4-n-butoxy-1-naphthyl group, 5-ethoxy-1-naphthyl group, 6-methoxy-2-naphthyl group, 6-ethoxy-2-naphthyl group, 6-n-butoxy- 2-naphthyl group, 6-n-hexyloxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 7-n-butoxy-2-naphthyl group, 2-methyl-4-methoxyphenyl group, 2-methyl -5-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 3-ethyl-5-methoxyphenyl group, 2-methoxy-4-methylphenyl 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy-6-ethoxyphenyl group, 3,4,5-trimethoxy Phenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4'-methylphenyl) phenyl group, 4- (3'-methylphenyl) phenyl group, 4- (4 ' -Methoxyphenyl) phenyl group, 4- (4'-n-butoxyphenyl) phenyl group, 2- (2'-methoxyphenyl) phenyl group, 4- (4'-chloro) Phenyl) phenyl group, 3-methyl-4-phenylphenyl group, 3-methoxy-4-phenylphenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 3- Chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 3-bromophenyl group, 2-bromophenyl group, 4-chloro-1-naphthyl group, 4-chloro-2-naphthyl group, 6-bromo-2- Naphthyl group, 2,3-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophene Group, 2,5-dibromophenyl group, 2,4,6-trichlorophenyl group, 2,4-dichloro-1-naphthyl group, 1,6-dichloro-2-naphthyl group, 2-fluoro-4-methyl Phenyl group, 2-fluoro-5-methylphenyl group, 3-fluoro-2-methylphenyl group, 3-fluoro-4-methylphenyl group, 2-methyl-4-fluorophenyl group, 2-methyl-5-fluoro Phenyl group, 3-methyl-4-fluorophenyl group, 2-chloro-4-methylphenyl group, 2-chloro-4-methylphenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methyl Phenyl group, 2-methyl-3-chlorophenyl group, 2-methyl-3-chlorophenyl group, 2-methyl-4-chlorophenyl group, 3-methyl-4-chlorophenyl group, 2- Loro-4,6-dimethylphenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group, 2-fluoro-4-ethoxyphenyl group, 2-fluoro-6-methoxyphenyl group, 3-fluoro-4-ethoxyphenyl group, 3-chloro-4-methoxyphenyl group, 2-methoxy-5-chlorophenyl group, 3-methoxy-6-chlorophenyl group, 5-chloro-2,4-dimethoxyphenyl group It can be mentioned, but is not limited to these.

In the amine compound represented by the general formula (1), Z _{1 to} Z ₄ represent a substituent, and the substituent includes a halogen atom, a substituted or unsubstituted amino group, or a — (γ) m-Φ group. (In the formula, Φ is a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted group. And γ represents an oxygen atom or a sulfur atom, and m represents 0 or 1).

Z _{1 to} Z ₄ are preferably a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon having 6 to 30 carbon atoms. Group, an aromatic heterocyclic group having 4 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or an unsubstituted amino group, or-(γ) m -Φ group (wherein Φ represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms) Represents a substituted or unsubstituted aromatic heterocyclic group having 4 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, γ represents an oxygen atom or a sulfur atom, and m represents Represents 0 or 1, more preferably, A primary atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, a substitution having 4 to 20 carbon atoms, or An unsubstituted aromatic heterocyclic group, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, or an unsubstituted amino group, or a-(γ) m-Φ group (wherein , Φ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, a substituted or unsubstituted group having 4 to 20 carbon atoms Or a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, γ represents an oxygen atom, and m represents 0 or 1.

Specific examples of the halogen atoms represented by Z _{1 to} Z ₄ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Specific examples of the substituted or unsubstituted amino group of Z _{1 to} Z ₄ include an amino group, N-methylamino group, N-ethylamino group, Nn-propylamino group, N-isopropylamino group, N- n-butylamino group, N-isobutylamino group, N-sec-butylamino group, N-tert-butylamino group, Nn-pentylamino group, N-cyclopentylamino group, Nn-hexylamino group, N-cyclohexylamino group, N-benzylamino group, N-phenethylamino group, N-phenylamino group, N- (1-naphthyl) amino group, N- (2-naphthyl) amino group, N- (4-phenyl) Phenyl) amino group, N- (3-phenylphenyl) amino group, N- (2-phenylphenyl) amino group, N- (4-methylphenyl) amino group, N- (2-methylphenyl) Mino group, N- (2-anthranyl) amino group, N- (9-anthranyl) amino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-propylamino group, N, N-di-isopropylamino group, N, N-di-n-butylamino group, N, N-di-isobutylamino group, N, N-di-sec-butylamino group, N, N-di- n-pentylamino group, N, N-dicyclopentylamino group, N, N-dicyclohexylamino group, N, N-dibenzylamino group, N, N-diphenethylamino group, N-methyl-N-ethylamino group N-methyl-Nn-propylamino group, N-methyl-N-isopropylamino group, N-methyl-Nn-butylamino group, N-methyl-N-tert-butylamino group, N-methyl -N-cyclopentylami Group, N-methyl-N-cyclohexylamino group, N-methyl-N-benzylamino group, N-methyl-N-phenethylamino group, N-ethyl-N-tert-butylamino group, N-ethyl-N- Cyclohexylamino group, N-ethyl-N-benzylamino group, N-isopropyl-N-cyclopentylamino group, N-isopropyl-N-cyclohexylamino group, N-isopropyl-N-benzylamino group, N-tert-butyl-N -Cyclohexylamino group, N-tert-butyl-N-benzylamino group, N-cyclopentyl-N-benzylamino group, N-cyclohexyl-N-benzylamino group, N, N-diphenylamino group, N, N-di (1-naphthyl) amino group, N, N-di (2-naphthyl) amino group, N, N-di (4-phenylphenyl) amino group, N , N- (4-methylphenyl) amino group, N, N-di (3-methylphenyl) amino group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) ) Amino group, N-phenyl-N- (4-phenylphenyl) amino group, N-phenyl-N- (3-phenylphenyl) amino group, N-phenyl-N- (2-phenylphenyl) amino group, N List substituted or unsubstituted amino groups such as -phenyl-N- (4-methylphenyl) amino group, N- (1-naphthyl) -N- (4'-phenylphenyl) amino group, N-carbazolyl group Can do.

Specific examples of the substituted or unsubstituted linear, branched or cyclic alkyl group which is Φ of the-(γ) m-Φ group of Z _{1 to} Z ₄ include, for example, a linear chain of R ₁ and R ₂ , The linear, branched or cyclic alkyl group mentioned as the specific example of the branched or cyclic alkyl group can be mentioned.

Specific examples of the substituted or unsubstituted aromatic hydrocarbon group or the substituted or unsubstituted aromatic heterocyclic group which is Φ of the-(γ) m-ZΦ group of Z _{1 to} Z ₄ include R ₁ and R _2. A substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group listed as specific examples of a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group Can be mentioned.

Specific examples of the substituted or unsubstituted aralkyl group [Phi of Z ₁ to Z ₄ of chromatography (γ) m-Φ group, e.g., benzyl, alpha-methylbenzyl group, alpha-ethylbenzyl group, a phenethyl group, α-methylphenethyl group, β-methylphenethyl group, α, α-dimethylbenzyl group, α, α-dimethylphenethyl group, 4-methylphenethyl group, 4-methylbenzyl group, 3-methylbenzyl group, 2-methylbenzyl Group, 4-ethylbenzyl group, 2-ethylbenzyl group, 4-isopropylbenzyl group, 4-tert-butylbenzyl group, 2-tert-butylbenzyl group, 4-tert-pentylbenzyl group, 4-cyclohexylbenzyl group, 4-n-octylbenzyl group, 4-tert-octylbenzyl group, 4-allylbenzyl group, 4-benzylbenzyl group, 4-phenethylbenzyl group, 4 Phenylbenzyl group, 4- (4′-methylphenyl) benzyl group, 4-methoxybenzyl group, 2-methoxybenzyl group, 2-ethoxybenzyl group, 4-n-butoxybenzyl group, 4-n-heptyloxybenzyl group 4-n-decyloxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-isobutoxymethyl Benzyl group, 4-allyloxybenzyl group, 4-vinyloxymethylbenzyl group, 4-benzyloxybenzyl group, 4-phenethyloxybenzyl group, 4-phenyloxybenzyl group, 3-phenyloxybenzyl group,

  4-hydroxybenzyl group, 3-hydroxybenzyl group, 2-hydroxybenzyl group, 4-hydroxy-3-methoxybenzyl group, 4-fluorobenzyl group, 2-fluorobenzyl group, 4-chlorobenzyl group, 3-chlorobenzyl And an aralkyl group such as a group, 2-chlorobenzyl group, 3,4-dichlorobenzyl group, 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group.

  In the-(γ) m-Φ group, γ represents an oxygen atom or a sulfur atom, and preferably represents an oxygen atom. M in the — (γ) m—Φ group represents 0 or 1, preferably 1.

In the amine compound represented by the general formula (1), n _{1 to} n ₄ represent an integer of 0 to 3, preferably an integer of 0 to 2, more preferably an integer of 0 to 1. If n ₁ ~n ₄ is 2 or more, each of _Z 1 to Z ₄ may be the same or may be different. When n _{1 to} n ₄ is 2 or more, adjacent Z _{1 to} Z ₄ may be bonded to each other to form a ring structure.

In the amine compound represented by the general formula (1), A ₁ , A ₂ and A ₃ are represented by the general formula (2) (chemical formula 5)

(In the formula, Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group, and Ar ₁ and Ar ₂ are linked to each other to form a cyclic structure. The groups represented by the general formula (2) of A ₁ , A ₂ and A ₃ may be the same or different.

In the general formula (2), Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group, and preferably substituted with 6 to 30 carbon atoms. Or an unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group having 4 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, or Represents a substituted or unsubstituted aromatic heterocyclic group having 4 to 20 carbon atoms.

Specific examples of the substituted or unsubstituted aromatic hydrocarbon group for Ar ₁ and Ar ₂ or the substituted or unsubstituted aromatic heterocyclic group include, for example, a substituted or unsubstituted aromatic group for R ₁ and R ₂ Specific examples of the hydrocarbon group or the substituted or unsubstituted aromatic heterocyclic group include the substituted or unsubstituted aromatic hydrocarbon group, or the substituted or unsubstituted aromatic heterocyclic group. .

Although it does not specifically limit as a specific example of group represented by General formula (2), For example,
N, N-diphenylamino group, N-phenyl-N- (4-methylphenyl) amino group, N-phenyl-N- (3-methylphenyl) amino group, N-phenyl-N- (2-methylphenyl) Amino group, N-phenyl-N- (4-methoxyphenyl) amino group, N-phenyl-N- (3-methoxyphenyl) amio group, N-phenyl-N- (2-methoxyphenyl) amino group, N- Phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group, N-phenyl-N- (4-phenyl-1-naphthyl) amino group, N-phenyl-N- (4-phenylphenyl) amino group, N-phenyl-N- (3-phenylphenyl) amino group, N-phenyl-N- (2-phenylphenyl) amino group, N-phenyl-N- (4-cyclo Xylphenyl) amino group, N-phenyl-N- (3-cyclohexylphenyl) amino group, N-phenyl-N- (2-cyclohexylphenyl) amino group, N-phenyl-N- [4- (2′-pyridinyl) ) Phenyl] amino group, N-phenyl-N- [4- (4′-pyridinyl) phenyl] amino group, N-phenyl-N- (4-phenoxyphenyl) amino group, N-phenyl-N- (3- Phenoxyphenyl) amino group, N-phenyl-N- (9-phenanthrenyl) amino group, N-phenyl-N- (9-phenyl-10-phenanthrenyl) amino group, N-phenyl-N- (9,9-dimethyl) -9H-fluoren-2-yl) amino group, N-phenyl-N- (2'-pyridinyl) amino group, N-phenyl-N- (3'-pyridinyl) amino group, -Phenyl-N- (4'-pyridinyl) amino group, N- (1-naphthyl) -N- (4'-phenylphenyl) amino group, N- (1-naphthyl) -N- (3'-phenylphenyl) ) Amino group, N- (1-naphthyl) -N- (2′-phenylphenyl) amino group, N- (2-naphthyl) -N- (4′-phenylphenyl) amino group, N- (2-naphthyl) ) -N- (3′-phenylphenyl) amino group, N- (2-naphthyl) -N- (2′-phenylphenyl) amino group,

  N, N-di (4-methylphenyl) amino group, N, N-di (3-methylphenyl) amino group, N, N-di (2-methylphenyl) amino group, N, N-di (4- Methoxyphenyl) amino group, N, N-di (3-methoxyphenyl) amino group, N, N-di (2-methoxyphenyl) amino group, N, N-di (1-naphthyl) amino group, N, N -Di (2-naphthyl) amino group, N- (1-naphthyl) -N- (2-naphthyl) amino group, N, N-di (4-phenylphenyl) amino group, N, N-di (3- Phenylphenyl) amino group, N, N-di (2-phenylphenyl) amino group, N, N-di (4-cyclohexylphenyl) amino group, N, N-di (3-cyclohexylphenyl) amino group, N, N-di (2-cyclohexylphenyl) amino group, N N- di (4-phenoxyphenyl) amino group, N, N- di (3-phenoxyphenyl) amino group, N, N- di (9-phenanthryl) amino group,

  N-carbazolyl group, 3,6-dimethyl-N-carbazolyl group, 3,6-diphenyl-N-carbazolyl group, 3,6-bis (N, N-diphenylamino) -N-carbazolyl group, 3,6- Bis [N-phenyl-N- (1′-naphthyl) amino] -N-carbazolyl group, 3,6-bis [N-phenyl-N- (4′-phenylphenyl) amino] -N-carbazolyl group, 3 , 6-Bis [N-carbazolyl] -N-carbazolyl group, 3- (N, N-diphenylamino) -N-carbazolyl group, 3- (N, N-diphenylamino) -6-phenyl-N-carbazolyl group 3- [N-phenyl-N- (1′-naphthyl) amino] -N-carbazolyl group, 1,8-diphenyl-3,6-bis (N, N-diphenylamino) -N-carbazolyl group, 3 -(N N- diphenylamino) -6- [N- phenyl-N-(1'-naphthyl) amino] carbazolyl group, N- phenothiazinyl group, and a N- phenoxazinyl group.

The amine compound represented by the general formula (1) of the present invention has the following general formulas (1-A) to (1) depending on the structure of the group represented by the general formula (2) of A ₁ , A ₂ and A _3. -F) It can be roughly divided into six types of structures represented by (Chemical formula 6).

[Wherein, R ₁ and R ₂ , Z _{1 to} Z ₄ , and n _{1 to} n ₄ represent the same meaning as in the general formula (1), and dA represents Ar ₁ and Ar ₂ in the general formula (2). And cyA represents a group in which Ar ₁ and Ar ₂ are bonded to each other to form a cyclic structure in the general formula (2)]

In the general formulas (1-A) to (1-F), dA represents a group in which Ar ₁ and Ar ₂ are not bonded to each other in the general formula (2) (for example, N, N-diphenylamino group), and cyA Represents a group (for example, N-carbazolyl group, N-phenothiazolyl group) in which Ar ₁ and Ar ₂ are bonded to each other to form a cyclic structure in the general formula (2).

The amine compound represented by the general formula (1) according to the present invention is preferably a compound represented by the general formula (1-A), (1-B), (1-D), or (1-F). It is. In the amine compound represented by the general formula (1-B) or (1-D), the cyA group bonded to the position of A _{1 in} the general formula (1) (the 2-position of the fluorene ring) is further It may be substituted with a substituted or unsubstituted amino group.

  Specific examples of the amine compound represented by the general formula (1) according to the present invention include, for example, the following compounds (Chemical Formula 7) to (Chemical Formula 19), but the present invention is not limited to these. It is not something.

The amine compound represented by the general formula (1) of the present invention can be produced by a method known per se.
Production of amine compound represented by general formula (1)

[Wherein, R ₁ and R ₂ , Z _{1 to} Z ₄ , n _{1 to} n ₄ and A _{1 to} A ₃ represent the same meaning as in general formula (1), and A ₁ and Ar ₂ represent general formula (2 And L ₁ and L ₂ represent a leaving group such as a halogen atom]

  That is, a halogenating agent (for example, bromine, iodine, potassium iodide / potassium periodate, N-bromosuccinimide, N-iodosuccinimide) is allowed to act on the compound represented by the general formula (A), and the general formula (B ), And then reacting the diarylamine represented by the general formula (C) to produce the amine compound represented by the general formula (1).

  The reaction of the compound represented by the general formula (B) and the compound represented by the general formula (C) is represented by [1] the compound represented by the general formula (B) and the general formula (C). Compounds such as palladium acetate [eg, palladium acetate / tri-tert-butylphosphine, tris (dibenzylideneacetone) dipalladium / dicyclohexylphenylphosphine] and bases (eg, potassium carbonate, sodium carbonate, cesium carbonate, tert-butoxysodium, tert A method of reacting in the presence of -butoxypotassium) [2] A compound represented by the general formula (B) and a compound represented by the general formula (C) are converted into a copper catalyst (for example, copper powder, copper chloride, odor Copper chloride) and a base (for example, sodium carbonate, potassium carbonate).

In addition, when L1 and L2 are different leaving groups, by sequentially reacting the compounds represented by the general formula (C), in the general formula (1), A ₁ is different from A ₂ and A ₃ Can also be produced.

Furthermore, a compound in which A ₁ is a 3,6-diamino-N-carbazolyl group in the general formula (1) can also be produced by the following steps (Chemical Formula 21).

[Wherein, R ₁ and R ₂ , Z _{1 to} Z ₄ , n _{1 to} n ₄ and A _{1 to} A ₃ represent the same meaning as in general formula (1), and A ₁ and Ar ₂ represent general formula (2 And L ₁ represents a leaving group such as a halogen atom]

That is, by using a compound represented by the general formula (A ′) as a starting material, halogenation with a halogenating agent is performed to produce a compound represented by the general formula (B ′). A compound in which A ₁ is a 3,6-diamino-N-carbazolyl group in the general formula (1) can also be produced by reacting the diarylamine represented by C).

  Next, the organic electroluminescent element of the present invention will be described. The organic electroluminescent element of the present invention comprises at least one layer containing at least one amine compound represented by the general formula (1) between a pair of electrodes. An organic electroluminescent element is usually formed by sandwiching at least one light emitting layer containing at least one light emitting component between a pair of electrodes. A hole injection / transport layer and / or an electron injection containing a hole injection component as desired, considering the functional level of the hole injection and hole transport, electron injection and electron transport of the compound used in the light emitting layer. A charge injection transport layer such as an electron injection transport layer containing a transport component can also be provided.

  For example, when the hole injection function, the hole transport function and / or the electron injection function, and the electron transport function of the compound used in the light emitting layer are good, the light emitting layer is a hole injection transport layer and / or an electron injection transport layer. As a type of element configuration that also serves as a single layer type element configuration. Further, when the light emitting layer is poor in the hole injection function and / or the hole transport function, a two-layer device configuration in which a hole injection transport layer is provided on the anode side of the light emitting layer, the light emitting layer has an electron injection function and / or Alternatively, when the electron transport function is poor, a two-layer device structure in which an electron injection transport layer is provided on the cathode side of the light emitting layer can be obtained. Furthermore, a three-layer device structure in which the light-emitting layer is sandwiched between a hole injecting and transporting layer and an electron injecting and transporting layer can be used.

  In addition, each of the hole injecting and transporting layer, the electron injecting and transporting layer, and the light emitting layer may have a single layer structure or a multilayer structure, and the hole injecting and transporting layer and the electron injecting and transporting layer The layer having an injection function and the layer having a transport function can be separately provided.

  In the organic electroluminescence device of the present invention, the amine compound represented by the general formula (1) is used as a component of the charge injection / transport layer (hole injection / transport layer and / or electron injection / transport layer) and / or the light-emitting layer. It is preferable to use it as a constituent of the light emitting layer.

  In the organic electroluminescent element of the present invention, the amine compound represented by the general formula (1) may be used alone or in combination.

  The configuration of the organic electroluminescent device of the present invention is not particularly limited. For example, (EL-1) anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode type device (FIG. 1). ), (EL-2) anode / hole injection transport layer / light emitting layer / cathode type device (FIG. 2), (EL-3) anode / light emitting layer / electron injection transport layer / cathode type device (FIG. 3), EL-4) Anode / light emitting layer / cathode type element (FIG. 4), and the like. Further, an EL (EL-5) anode / hole injection / transport layer / electron injection / transport layer / light-emitting layer / electron injection / transport layer / cathode-type device (FIG. 5) in which the light-emitting layer is sandwiched between electron injection / transport layers. You can also. The (EL-4) type element structure includes an element of a type in which a light emitting component is sandwiched between a pair of electrodes as a light emitting layer, (EL-6) a hole injection transport component as a light emitting layer, A device of a type in which a light emitting component and an electron injection component are mixed and sandwiched between a pair of electrodes (FIG. 6), (EL-7) a layer in which a hole injection transport component and a light emitting component are mixed as a light emitting layer Type element sandwiched between a pair of electrodes in a form (FIG. 7), (EL-8) type element sandwiched between a pair of electrodes in a single layer form in which a light emitting component and an electron injection component are mixed as a light emitting layer Any of (FIG. 8) may be sufficient.

  The organic electroluminescent device of the present invention is not limited to these device configurations, and each type of device can be provided with a plurality of hole injection / transport layers, light emitting layers, and electron injection / transport layers. Further, in each type of device, the hole injection / transport layer is disposed between the light emitting layer, the hole injection / transport component and the light emitting component mixed layer and / or the light emitting layer and the electron injection / transport layer between the light emitting component and the light emitting component. And a mixed layer of electron injecting and transporting components can be provided.

  A preferred organic electroluminescent element is an (EL-1) type element, an (EL-2) type element, an (EL-5) type element, an (EL-6) type element or an (EL-7) type element. More preferably, it is an (EL-1) type element, an (EL-2) type element or an (EL-7) type element.

  Hereinafter, the components of the organic electroluminescence device of the present invention will be described in detail. As an example, (EL-1) anode / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode type device shown in FIG. 1 will be described.

  In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injecting and transporting layer, 4 is a light emitting layer, 5 is an electron injecting and transporting layer, 6 is a cathode, and 7 is a power source.

  The organic electroluminescent element of the present invention is preferably supported by the substrate 1, and the substrate is not particularly limited, but a transparent or translucent substrate is preferable, and the material is soda lime glass, Examples thereof include glass such as borosilicate glass and transparent polymers such as polyester, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethyl methacrylate, polypropylene, and polyethylene. Further, a substrate made of a translucent plastic sheet, quartz, transparent ceramics, or a composite sheet in which these are combined can also be used. Furthermore, for example, a color filter film, a color conversion film, and a dielectric reflection film can be combined with the substrate to control the emission color.

As the anode 2, it is preferable to use a metal, an alloy or a conductive compound having a relatively large work function as an electrode material. Examples of the electrode material used for the anode include gold, platinum, silver, copper, cobalt, nickel, palladium, vanadium, tungsten, indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), zinc oxide, ITO ( Indium tin oxide (Indium Tin Oxide), polythiophene, polypyrrole, etc. can be mentioned. These electrode materials may be used alone or in combination.

  For the anode, these electrode materials can be formed on the substrate by a method such as vapor deposition or sputtering.

  Further, the anode may have a single layer structure or a multilayer structure. The sheet electrical resistance of the anode is preferably set to several hundred Ω / □ or less, more preferably about 5 to 50 Ω / □.

  The thickness of the anode is generally about 5 to 1000 nm, more preferably about 10 to 500 nm, although it depends on the material of the electrode material used.

  The hole injection transport layer 3 is a layer containing a compound having a function of facilitating the injection of holes from the anode and a function of transporting the injected holes.

  The hole injecting and transporting layer of the electroluminescent device of the present invention comprises a compound represented by the general formula (1) and / or other compounds having a hole injecting and transporting function (for example, phthalocyanine derivatives, triarylamine derivatives, triaryls) A methane derivative, an oxazole derivative, a hydrazone derivative, a stilbene derivative, a pyrazoline derivative, a polysilane derivative, polyphenylenevinylene and its derivative, polythiophene and its derivative, poly-N-vinylcarbazole, etc.).

  The compounds having a hole injecting and transporting function may be used alone or in combination.

  The organic electroluminescent element of the present invention preferably contains an amine compound represented by the general formula (1) in the hole injection transport layer. Examples of the compound having a hole injecting and transporting function other than the amine compound represented by the general formula (1) of the present invention that can be used in the organic electroluminescence device of the present invention include triarylamine derivatives (for example, 4, 4 '-Bis [N-phenyl-N- (4 "-methylphenyl) amino] -1,1'-biphenyl, 4,4'-bis [N-phenyl-N- (3" -methylphenyl) amino]- 1,1'-biphenyl, 4,4'-bis [N-phenyl-N- (3 "-methoxyphenyl) amino] -1,1'-biphenyl, 4,4'-bis [N-phenyl-N- (1 ″ -Naphtyl) amino] -1,1′-biphenyl, 3,3′-dimethyl-4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] -1,1 ′ -Biphenyl, 1,1-bis [4 '-[N, -Di (4 "-methylphenyl) amino] phenyl] cyclohexane, 9,10-bis [N- (4'-methylphenyl) -N- (4" -n-butylphenyl) amino] phenanthrene, 3,8- Bis (N, N-diphenylamino) -6-phenylphenanthridine, 4-methyl-N, N-bis [4 ", 4" '-bis [N', N'-di (4-methylphenyl) amino ] Biphenyl-4-yl] aniline, N, N'-bis [4- (diphenylamino) phenyl] -N, N'-diphenyl-1,3-diaminobenzene, N, N'-bis [4- (diphenyl) Amino) phenyl] -N, N′-diphenyl-1,4-diaminobenzene, 5,5 ″ -bis [4- (bis [4-methylphenyl] amino] phenyl-2,2 ′: 5 ′, 2 ″ -Terthiophene, 1 3,5-tris (diphenylamino) benzene, 4,4 ′, 4 ″ -tris (N-carbazolyl) triphenylamine, 4,4 ′, 4 ″ -tris [N, N-bis (4 ″ ′-tert -Butylbiphenyl-4 ""-yl) amino] triphenylamine, 1,3,5-tris [N- (4'-diphenylamino] benzene, etc., polythiophene and its derivatives, poly-N-vinylcarbazole and its derivatives Is more preferable.

  When the amine compound represented by the general formula (1) and another compound having a hole injection function are used in combination, the content of the amine compound represented by the general formula (1) in the hole injection / transport layer is: Preferably, it is 0.1% by weight or more, more preferably 0.5 to 99.9% by weight, still more preferably 3 to 97% by weight.

  The light emitting layer 4 is a layer containing a compound having a function of injecting holes and electrons, a function of transporting them, and a function of generating excitons by recombination of holes and electrons.

  The light emitting layer can be formed using at least one amine compound represented by the general formula (1) and / or another compound having a light emitting function.

  Examples of the compound having a light emitting function other than the amine compound represented by the general formula (1) include an acridone derivative, a quinacridone derivative, a diketopyrrolopyrrole derivative, a polycyclic aromatic compound [for example, rubrene, anthracene, tetracene, pyrene. Perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,4-bis (9′-ethynylanthcenyl) ) Benzene, 4,4′-bis (9 ″ -ethynylanthracenyl) biphenyl, dibenzo [f, f] diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene derivatives] , Triarylamine derivatives (for example, the compounds described above as compounds having a hole injecting and transporting function) Organometallic complexes [eg, tris (8-quinolinolato) aluminum, bis (10-benzo [h] quinolinolato) beryllium, zinc salt of 2- (2′-hydroxyphenyl) benzothiazole, 4- Zinc salt of hydroxyacridine, zinc salt of 3-hydroxyflavone, beryllium salt of 5-hydroxyflavone, aluminum salt of 5-hydroxyflavone], stilbene derivative [for example, 1,1,4,4-tetraphenyl-1,3 -Butadiene, 4,4'-bis (2,2-diphenylvinyl) biphenyl, 4,4'-bis [(1,1,2-triphenyl) ethenyl] biphenyl], coumarin derivatives (eg, coumarin 1, coumarin) 6, Coumarin 7, Coumarin 30, Coumarin 106, Coumarin 138, Coumarin 151, Marine 152, Coumarin 153, Coumarin 307, Coumarin 311, Coumarin 314, Coumarin 334, Coumarin 338, Coumarin 343, Coumarin 500), pyran derivatives (for example, DCM1, DCM2), oxazone derivatives (for example, Nile Red), benzothiazole derivatives Benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamic acid ester derivatives, poly-N-vinylcarbazole and derivatives thereof, polythiophene and derivatives thereof, polyphenylene and derivatives thereof, polyfluorene and derivatives thereof, polyphenylene vinylene and derivatives thereof, Polybiphenylene vinylene and its derivatives, polyterphenylene vinylene and its derivatives, polynaphthylene vinylene and its derivatives, polythieny Nbiniren and its derivatives, and the like. As the compound having a light emitting function other than the amine compound represented by the general formula (1), an acridone derivative, a quinacridone derivative, a polycyclic aromatic compound, a triarylamine derivative, an organometallic complex, and a stilbene derivative are preferable. More preferred are group compounds and organometallic complexes.

  In addition, a phosphorescent (triplet luminescent) compound can also be used in the light emitting layer of the organic electroluminescent device of the present invention as a compound having a light emitting function other than the amine compound represented by the general formula (1). It is.

  Here, examples of phosphorescent compounds include tris (2-phenylpyrimidyl) iridium complex, tris [2- (2′-fluorophenyl) pyridyl] iridium complex, and bis (2-phenylpyridyl) acetylacetonate. Iridium complex, bis [2- (2 ′, 4′-difluorophenyl) pyridyl] acetylacetonatoiridium complex, 2,3,7,8,12,13,17,18-octaethyl-21H, 23H porphyrin platinum complex, etc. Can be mentioned.

  The organic electroluminescent element of the present invention preferably contains an amine compound represented by the general formula (1) in the light emitting layer.

  When the amine compound represented by the general formula (1) and a compound having a light emitting function other than the amine compound represented by the general formula (1) are used in combination, the amine represented by the general formula (1) in the light emitting layer The proportion of the compound is preferably adjusted to 0.001 to 99.999% by weight.

The light-emitting layer can also be formed from a host compound and a guest compound (dopant) as described in J. Appl. Phys., 65 , 3610 (1989) and Japanese Patent Application Laid-Open No. 5-214332.

  The amine compound represented by the general formula (1) can be used as a host compound in the light emitting layer, and can also be used as a guest compound. When the light emitting layer is formed using the amine compound represented by the general formula (1) as a host compound, examples of the guest compound include the compounds having the above other light emitting functions, and among them, polycyclic aromatic compounds. Is preferred.

When the light emitting layer is formed using the amine compound represented by the general formula (1) as a host compound, the guest compound is preferably 0.001 to 40 weights with respect to the amine compound represented by the general formula (1). %, More preferably 0.01 to 30% by weight, still more preferably 0.1 to 20% by weight. The organic electroluminescent element of the present invention is preferably represented by the general formula (1) in the light emitting layer. An amine compound is contained as a host material.

  When the amine compound represented by the general formula (1) is used as a host material in combination with another compound having a light emitting function, the amine compound represented by the general formula (1) in the light emitting layer is preferably 40 It is 0.0% to 99.9%, and more preferably 60.0 to 99.9% by weight.

  The amount of the guest material used is 0.001 to 40% by weight, preferably 0.05 to 30% by weight, more preferably 0.1 to 20% by weight, based on the amine compound represented by the general formula (1). %. Moreover, a guest material may be used independently and may be used together.

  Further, when the light emitting layer is formed using the amine compound represented by the general formula (1) as a guest material, the host material includes a polycyclic aromatic compound, a triarylamine derivative, an organometallic complex, and a stilbene derivative. Preferably, a polycyclic aromatic compound and an organometallic complex are more preferable.

  When the amine compound represented by the general formula (1) is used as a guest material, the amine compound represented by the general formula (1) is preferably 0.001 to 40% by weight, more preferably 0.01 -30% by weight, more preferably 0.1-20% by weight.

  The electron injection / transport layer 5 is a layer containing a compound having a function of facilitating injection of electrons from the cathode and / or a function of transporting injected electrons.

  The organic electroluminescent element of the present invention preferably contains an amine compound represented by the general formula (1) in the electron injecting and transporting layer. Examples of the compound having an electron injecting and transporting function other than the amine compound represented by the general formula (1) of the present invention that can be used in the organic electroluminescent element of the present invention include, for example, organometallic complexes, oxadiazole derivatives, Examples thereof include triazole derivatives, triazine derivatives, perylene derivatives, quinoline derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted fluorenone derivatives, and thiopyrandioxide derivatives. Examples of the organometallic complex include an organoaluminum complex such as tris (8-quinolinolato) aluminum, an organic beryllium complex such as bis (10-benzo [h] quinolinolato) beryllium, a beryllium salt of 5-hydroxyflavone, 5- Examples thereof include an aluminum salt of hydroxyflavone. Preferably, it is an amine compound or organoaluminum complex represented by the general formula (1) of the present invention. Here, the organoaluminum complex is an organoaluminum complex having a substituted or unsubstituted 8-quinolinolato ligand.

  Examples of the organoaluminum complex having a substituted or unsubstituted 8-quinolylate ligand include compounds represented by general formula (a) to general formula (c).

(Q) ₃ -Al (a)
(Wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand)

(Q) ₂ -Al-OL '(b)
(In the formula, Q represents a substituted or unsubstituted 8-quinolinolate ligand, OL ′ represents a phenolate ligand, and L ′ represents a hydrocarbon group having 6 to 24 carbon atoms having a phenyl group. )

(Q) _2- Al-O-Al- (Q) ₂ (c)
(Wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand)

  Specific examples of the organoaluminum complex having a substituted or unsubstituted 8-quinolinolato ligand include, for example, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl- 8-quinolinolato) aluminum, tris (3,4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum,

  Bis (2-methyl-8-quinolinolato) (phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolate) ) Aluminum, bis (2-methyl-8-quinolinolato) (4-methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) ) (3-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, Bis (2-methyl-8-quinolinolate) ( , 6-Dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum Bis (2-methyl-8-quinolinolato) (3,5-di-tert-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolato) aluminum, bis (2 -Methyl-8-quinolinolato) (2,4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-trimethylphenolato) aluminum, bis (2-methyl- 8-quinolinolato) (2,4,5,6-tetramethylphenolate) aluminum, bi (2-methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenyl) Phenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2 , 4-dimethyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-di-tert-butylphenolate) aluminum,

  Bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2, 4-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-4-ethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-ethyl-8-quinolinolato) aluminum, bis (2- Methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano-8-quinolinolato) aluminum-μ- Oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bi (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum.

  A compound having an electron injection function may be used alone or in combination.

  As the cathode 6, it is preferable to use a metal, an alloy or a conductive compound having a relatively small work function as an electrode material. Examples of the electrode material used for the cathode include lithium salts of organic acids such as lithium, lithium-indium alloy, lithium fluoride, lithium benzoate, lithium acetate, sodium, sodium-potassium alloy, calcium, magnesium, magnesium-silver. Examples include alloys, magnesium-indium alloys, indium, ruthenium, titanium, manganese, yttrium, aluminum, aluminum-lithium alloys, aluminum-calcium alloys, aluminum-magnesium alloys, and graphite thin films. These electrode materials may be used alone or in combination.

  For the cathode, these electrode materials can be formed on the electron injecting and transporting layer by, for example, vapor deposition, sputtering, ion vapor deposition, ion plating, or cluster ion beam.

  The cathode may have a single layer structure or a multilayer structure. The sheet electrical resistance of the cathode is preferably several hundred Ω / □ or less. The thickness of the cathode is usually 5 to 1000 nm, preferably 10 to 500 nm, although it depends on the electrode material used. In order to take out light emitted from the organic electroluminescence device of the present invention with high efficiency, at least one of the anode and the cathode is preferably transparent or translucent, and generally has a transmittance of emitted light of 70% or more. Thus, it is preferable to set the material and thickness of the anode or cathode.

  The organic electroluminescent device of the present invention may contain a singlet oxygen quencher in at least one of the hole injection transport layer, the light emitting layer, and the electron injection transport layer. Although it does not specifically limit as a singlet oxygen quencher, For example, rubrene, a nickel complex, diphenylisobenzofuran is mentioned, Preferably it is rubrene.

  The layer containing the singlet oxygen quencher is not particularly limited, but is preferably a light emitting layer or a hole injection transport layer, and more preferably a hole injection transport layer. When a singlet oxygen quencher is contained in the hole injecting and transporting layer, it may be uniformly contained in the hole injecting and transporting layer, and a layer adjacent to the hole injecting and transporting layer (for example, a light emitting layer, a light emitting function). May be contained in the vicinity of the electron injecting and transporting layer).

  The content of the singlet oxygen quencher is 0.01 to 50% by weight, preferably 0.05 to 30% by weight, based on the total amount constituting the layer to be contained (for example, hole injection transport layer). Preferably, it is 0.1 to 20% by weight.

The formation method of the hole injection transport layer, the light emitting layer, and the electron injection transport layer is not particularly limited. For example, a vacuum deposition method, an ionization deposition method, a solution coating method (for example, a spin coating method, a casting method, A dip coat method, a bar coat method, a roll coat method, a Langmuir-Blodget method, an ink jet method) can be used. When forming each layer such as a hole injecting and transporting layer, a light emitting layer, and an electron injecting and transporting layer by a vacuum deposition method, the conditions for vacuum deposition are not particularly limited, but a vacuum of about 10 ⁻⁵ Torr or less is usually used. Below, it is preferable to carry out at a boating temperature (deposition source temperature) of about 50 to 500 ° C., a substrate temperature of about −50 to 300 ° C., and a deposition rate of about 0.005 to 50 nm / sec. In this case, each layer such as a hole injecting and transporting layer, a light emitting layer, and an electron injecting and transporting layer is preferably formed continuously under vacuum. It becomes possible to manufacture an organic electroluminescent element excellent in various characteristics by forming continuously. When each layer such as hole injection transport layer, light emitting layer, electron injection transport layer, etc. is formed using a plurality of compounds by vacuum deposition, the temperature of each boat containing the compounds is individually controlled and co-evaporated. It is preferable to do.

  When each layer is formed by a solution coating method, the component forming each layer or the component and a binder resin are dissolved or dispersed in a solvent to obtain a coating solution. Examples of the solvent include organic solvents (hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, and 1-methylnaphthalene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, dichloromethane, and chloroform. , Halogenated hydrocarbon solvents such as tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, methanol, propanol, butanol Alcohol solvents such as pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, dibutyl ether, tetrahydro Ether solvents such as ethylene, dioxane, dimethoxyethane, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide And polar solvents) and water. A solvent may be used independently and may be used together. When the components of the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer are dispersed in a solvent, for example, a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer or the like is used as a dispersion method. Can be used.

  Examples of binder resins that can be used in each layer such as a hole injecting and transporting layer, a light emitting layer, and an electron injecting and transporting layer include poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl methacrylate, poly Methyl acrylate, polyether, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, polyphenylene oxide, polyethersulfone, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, Examples thereof include polymer compounds such as polythienylene vinylene and its derivatives. Binder resins may be used alone or in combination. The concentration of the coating solution is not particularly limited, but can be set to a concentration range suitable for producing a desired thickness by the coating method to be carried out, usually 0.1 to 50% by weight, preferably 1 to 30% by weight. When a binder resin is used, the amount used is not particularly limited, but it is usually based on the total amount of components and binder resin that form each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer. It is used such that the content of the binder resin is 5 to 99.9% by weight, preferably 10 to 99% by weight (relative to the total amount of each component in the case of forming a single-layer element).

  The thickness of each layer such as the hole injection transport layer, the light emitting layer, and the electron injection transport layer is not particularly limited, but is usually 5 nm to 5 μm.

  The organic electroluminescent device of the present invention produced under the above conditions is preferably provided with a protective layer (sealing layer) for the purpose of preventing contact with oxygen, moisture, etc., and the device is made of an inert substance. It can also be protected by enclosing it in a medium (for example, paraffin, liquid paraffin, silicone oil, fluorocarbon oil, zeolite-containing fluorocarbon oil). Examples of the material used for the protective layer include organic polymer materials (for example, fluorine resin, epoxy resin, silicone resin, epoxy silicone resin, polystyrene, polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, Polyphenylene oxide), inorganic materials (for example, diamond thin film, amorphous silica, electrically insulating glass, metal oxide, metal nitride, metal carbide, metal sulfide), and photocurable resin. The material used for the protective layer may be used alone or in combination. The protective layer may have a single layer structure or a multilayer structure.

  Moreover, the organic electroluminescent element of this invention can also provide a metal oxide film (for example, aluminum oxide film) and a metal fluoride film as a protective film in an electrode.

  The organic electroluminescent element of the present invention can also be provided with an interface layer (intermediate layer) on the surface of the anode. Examples of the material for the interface layer include organic phosphorus compounds, polysilanes, aromatic amine derivatives, and phthalocyanine derivatives.

  Furthermore, the surface of an electrode, for example, an anode, can be used by treating the surface with acid, ammonia / hydrogen peroxide, or plasma.

  The organic electroluminescent element of the present invention can be usually used as a DC drive type element, but can also be used as an AC drive type element. Further, the organic electroluminescence device of the present invention may be a segment type, a passive drive type such as a simple matrix drive type, or an active drive type such as a TFT (thin film transistor) type or an MIM (metal-insulator-metal) type. It may be. The driving voltage is usually 2 to 30V. The organic electroluminescent element of the present invention includes a panel-type light source (for example, a backlight for a clock, a liquid crystal panel, etc.), various light-emitting elements (for example, an alternative to a light-emitting element such as an LED), and various display elements [for example, information display Element (PC monitor, mobile phone / mobile terminal display element)], various signs, various sensors, and the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to a following example.

Preparation of Exemplified Compound 4 [1] Preparation of 2-chloro-7- (3 ′, 6′-dibromo-N-carbazolyl) -9,9-dimethyl-9H-fluorene 2-chloro-7-N-carbazolyl-9 , 9-dimethyl-9H-fluorene (39.3 g, 0.1 mol) was dissolved in 150 g of N, N-dimethylformamide, this solution was cooled to 5 ° C. in an ice bath, and N-bromosuccinimide 35. A mixture consisting of 6 g and 150 g of N, N-dimethylformamide was added dropwise over 1 hour. Thereafter, the mixture was stirred at the same temperature for 12 hours, and the reaction mixture was warmed to room temperature and discharged into methanol. The resulting solid was recrystallized from N, N-dimethylformamide to give 43 g of 2-chloro-7- (3 ′, 6′-dibromo-N-carbazolyl) -9,9-dimethyl-9H-fluorene as colorless crystals. Obtained.

[2] Production of Exemplified Compound 4 2-Chloro-7- (3 ′, 6′-dibromo-N-carbazolyl) -9,9-dimethyl-9H-fluorene 5.49 g (10 mmol), N-phenylaniline A mixture consisting of 07 g (30 mmol), tert-butoxy sodium 4.02 g (42 mmol), palladium acetate 66 mg, dicyclohexylphenylphosphine 75 mg and toluene 50 g was heated to 100 ° C. under an argon stream and stirred at the same temperature for 8 hours. It was. Thereafter, the reaction mixture was cooled to room temperature, insolubles were filtered off, the filtrate was washed with water, and then toluene was distilled off from the filtrate under reduced pressure. The residue was purified by silica gel column chromatography and further recrystallized from toluene / n-hexane to obtain 3.80 g of the compound of Exemplary Compound 4 as colorless crystals.
Further, this compound was purified by sublimation at 430 ° C. and 2 × 10 ⁻⁴ Pa.
Glass transition point: 155 ° C
FD-MS: 860 (M ⁺ )
Elemental analysis: calculated (%); C, 87.87; H, 5.62; N, 6.51
Analytical value (%); C, 87.9; H, 5.6; N, 6.5

Production of Exemplary Compound 6 2-chloro-7- (3 ′, 6′-dibromo-N-carbazolyl) -9,9-dimethyl-9H-fluorene 5.49 g (10 mmol), N- (1-naphthyl) aniline 6 0.18 ml of tri-tert-butylphosphine was added to a mixture of 57 g (30 mmol), 4.02 g (42 mmol) of tert-butoxy sodium, 66 mg of palladium acetate, and 50 g of toluene under a stream of argon, and the mixture was heated to 100 ° C. Stirring was performed at the same temperature for 8 hours. Thereafter, the reaction mixture was cooled to room temperature, insolubles were filtered off, the filtrate was washed with water, and then toluene was distilled off from the filtrate under reduced pressure. The residue is purified by silica gel column chromatography, further subjected to heat extraction from toluene / n-hexane, the resulting solid is sludged with acetone, and then recrystallized from methyl cellosolve to give the compound of Exemplified Compound 6 as pale yellow crystals. As a result, 4.12 g was obtained.
Further, this compound was purified by sublimation at 430 ° C. and 1 × 10 ⁻⁴ Pa.
Glass transition point: 157 ° C
FD-MS: 1010 (M ⁺ )
Elemental analysis: calculated (%); C, 89.08; H, 5.38; N, 5.54
Analytical value (%); C, 89.1; H, 5.4; N, 5.5

Production of Illustrative Compound 8 In [2] of Example 1, instead of using 5.07 g (30 mmol) of N-phenylaniline, 8.07 g (30 mmol) of N- (9′-phenanthryl) aniline was used. According to the procedure described in [2] of Example 1, 5.15 g of the compound of Exemplary Compound 8 was obtained as pale yellow crystals.
Further, this compound was purified by sublimation at 450 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 1160 (M ⁺ )
Elemental analysis: calculated value (%); C, 89.97; H, 5.21; N, 4.82
Analytical value (%); C, 90.0; H, 5.2; N, 4.8

Production of Exemplary Compound 12 In [2] of Example 1, instead of using 5.07 g (30 mmol) of N-phenylaniline, 8.07 g (30 mmol) of N- (1′-naphthyl) -1-aminonaphthalene was used. Except that it was used, 6.20 g of the compound of Exemplary Compound 12 was obtained as pale yellow crystals according to the procedure described in [2] of Example 1.
Further, this compound was purified by sublimation at 450 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 1160 (M ⁺ )
Elemental analysis: calculated value (%); C, 89.97; H, 5.21; N, 4.82
Analytical value (%); C, 90.0; H, 5.2; N, 4.8

Production of Exemplified Compound 15 [1] Production of 2-chloro-7- (3 ′, 6′-dibromo-N-carbazolyl) -9,9-di-n-octyl-9H-fluorene 2-chloro-7-N -Carbazolyl-9,9-di-n-octyl-9H-fluorene (58.9 g, 0.1 mol) was dissolved in 150 g of N, N-dimethylformamide, and the solution was cooled to 5 ° C in an ice bath. A mixture consisting of 35.6 g of N-bromosuccinimide and 150 g of N, N-dimethylformamide was added dropwise over 1 hour. Thereafter, the mixture was stirred at the same temperature for 12 hours, and the reaction mixture was warmed to room temperature and discharged into methanol. The resulting solid was recrystallized from methyl cellosolve to give 2-chloro-7- (3 ′, 6′-dibromo-N-carbazolyl) -9,9-di-n-octyl-9H-fluorene as colorless crystals. .5 g was obtained.

[2] Production of Exemplified Compound 15 In [1] of Example 1, in 2-chloro-7- (3 ′, 6′-dibromo-N-carbazolyl) -9,9-dimethyl-9H-fluorene, 5.49 g ( 10 mmol), instead of using 2-chloro-7- (3 ′, 6′-dibromo-N-carbazolyl) -9,9-di-n-octyl-9H-fluorene, 7.47 g
Except for using (10 mmol), according to the procedure described in [2] of Example 1, 5.32 g of the compound of Exemplary Compound 15 was obtained as colorless crystals.
FD-MS: 1057 (M ⁺ )
Elemental analysis: calculated value (%); C, 88.46; H, 7.24; N, 5.30
Analytical value (%); C, 88.5; H, 7.2; N, 5.3

Production of Illustrative Compound 18 In [2] of Example 1, instead of using 5.07 g (30 mmol) of N-phenylaniline, 9.63 g (30 mmol) of N- (4′-phenylphenyl) -4-phenylaniline Except that was used, 6.20 g of the compound of Exemplified Compound 18 was obtained as pale yellow crystals according to the procedure described in [2] of Example 1.
Further, this compound was purified by sublimation at 470 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 1316 (M ⁺ )
Elemental analysis: calculated value (%); C, 90.24; H, 5.51; N, 4.25
Analytical value (%); C, 90.2; H, 5.5; N, 4.3

Production of Exemplified Compound 19 In [2] of Example 1, instead of using 5.07 g (30 mmol) of N-phenylaniline, 7.35 g (30 mmol) of N- (4′-phenylphenyl) aniline was used. In accordance with the operation described in [2] of Example 1, 4.86 g of the compound of Exemplified Compound 19 was obtained as colorless crystals.
Further, this compound was purified by sublimation at 440 ° C. and 2 × 10 ⁻⁴ Pa.
FD-MS: 1088 (M ⁺ )
Elemental analysis: calculated value (%); C, 89.31; H, 5.55; N, 5.14
Analytical value (%); C, 89.3; H, 5.5; N, 5.2

Production of Exemplary Compound 21 In [2] of Example 1, instead of using 5.07 g (30 mmol) of N-phenylaniline, 5.97 g (30 mmol) of N- (3′-methoxyphenyl) aniline was used. Produced 5.25 g of the compound of Exemplified Compound 21 as pale yellow crystals according to the procedure described in [2] of Example 1.
Further, this compound was purified by sublimation at 420 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 950 (M ⁺ )
Elemental analysis: calculated (%); C, 83.34; H, 5.72; N, 5.89; O, 5.05
Analytical value (%); C, 83.3; H, 5.7; N, 5.9

Production of Exemplified Compound 31 [1] Production of 2-chloro-7- (3 ′, 6′-dibromo-N-carbazolyl) -9,9-diethyl-9H-fluorene 2-chloro-7-N-carbazolyl-9 , 9-diethyl-9H-fluorene (42.2 g, 0.1 mol) was dissolved in 150 g of N, N-dimethylformamide, this solution was cooled to 5 ° C. in an ice bath, and N-bromosuccinimide 35. A mixture consisting of 6 g and 150 g of N, N-dimethylformamide was added dropwise over 1 hour. Thereafter, the mixture was stirred at the same temperature for 12 hours, and the reaction mixture was warmed to room temperature and discharged into methanol. The resulting solid was recrystallized from methyl cellosolve to give 2-chloro-7-N- (3 ′, 6′-dibromocarbazolyl) -9,9-di-nethyl-9H-fluorene as colorless crystals. 0.2 g was obtained.

[2] Production of Exemplary Compound 31 In [2] of Example 1, 2-chloro-7- (3 ′, 6′-dibromo-N-carbazolyl) -9,9-dimethyl-9H-fluorene 5.49 g ( 10 mmol) and 5.07 g (30 mmol) of N-phenylaniline, instead of using 2-chloro-7- (3 ′, 6′-dibromo-N-carbazolyl) -9,9-diethyl-9H-fluorene. Except that 77 g (10 mmol) and 6.57 g (30 mmol) of N- (1′-naphthyl) aniline were used, the compound of Exemplified Compound 31 was obtained as colorless crystals according to the procedure described in [2] of Example 1. 14 g was obtained.
Further, this compound was purified by sublimation at 430 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 1038 (M ⁺ )
Elemental analysis: calculated (%); C, 88.98; H, 5.62; N, 5.39
Analytical value (%); C, 89.0; H, 5.6; N, 5.4

Production of Exemplary Compound 35 In [2] of Example 1, [2] of Example 1 except that 5.01 g (30 mmol) of carbazole was used instead of 5.07 g (30 mmol) of N-phenylaniline. According to the procedure described in, 5.28 g of the compound of Exemplified Compound 35 was obtained as colorless crystals.
Further, this compound was purified by sublimation at 430 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 854 (M ⁺ )
Elemental analysis: calculated value (%); C, 88.50; H, 4.95; N, 6.55
Analytical value (%); C, 88.5; H, 5.0; N, 6.5

Production of Exemplary Compound 36 [1] Production of 2-chloro-7- (3 ′, 6′-bis-N-carbazolyl-N-carbazolyl) -9,9-dimethyl-9H-fluorene 2-chloro-7- ( 3 ', 6'-dibromo-N-carbazolyl) -9,9-dimethyl-9H-fluorene 10.98 g (20 mmol), carbazole 6.68 g (40 mmol), tert-butoxy sodium 5.36 g (56 mmol), palladium acetate A mixture consisting of 88 mg, 0.1 g of diphenylcyclohexylphosphine and 150 g of toluene was heated to 100 ° C. under an argon stream, and heated and stirred at the same temperature for 4 hours. Thereafter, the reaction mixture was cooled to room temperature, insolubles were filtered off, the filtrate was washed with water, and then toluene was distilled off from the filtrate under reduced pressure. The residue was purified by silica gel column chromatography, and further recrystallized from toluene / n-hexane to give 2-chloro-7- (3 ′, 6′-bis-N-carbazolyl-N-carbazolyl) -9,9- 8.22 g of dimethyl-9H-fluorene was obtained as colorless crystals.

[2] Production of Exemplified Compound 36 2-Chloro-7- (3 ′, 6′-bis-N-carbazolyl-N-carbazolyl) 9,9-dimethyl-9H-fluorene 7.24 g (10 mmol), N- ( 1-naphthyl) aniline 2.19 g (10 mmol), tert-butoxy sodium 1.34 g (14 mmol), palladium acetate 22 mg, tri-tert-butylphosphine 0.15 ml and toluene 40 g were mixed at 90 ° C. under an argon stream. The mixture was heated and stirred at the same temperature for 6 hours. Thereafter, the reaction mixture was cooled to room temperature, insoluble matters were filtered off, the filtrate was washed with water, and then toluene was distilled off from the filtrate under reduced pressure. The residue was purified by silica gel column chromatography and further recrystallized from toluene / n-hexane to obtain 3.98 g of the objective exemplified compound 36 as colorless crystals.
Further, this compound was purified by sublimation at 430 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 906 (M ⁺ )
Elemental analysis: calculated value (%); C, 88.71; H, 5.11; N, 6.18
Analytical value (%); C, 88.7; H, 5.1; N, 6.2

Production of Exemplified Compound 42 [1] Production of 2,7-bis (3 ′, 6′-bromo-N-carbazolyl) -9,9-dimethyl-9H-fluorene 2,7-bis-N-carbazolyl-9, 9-Dimethyl-9H-fluorene 52.4 g (0.1 mol)
Is dissolved in 150 g of N, N-dimethylformamide, the solution is cooled to 5 ° C. in an ice bath, and a mixture of 71.2 g of N-bromosuccinimide and 300 g of N, N-dimethylformamide is added over 1 hour. And dripped. Thereafter, the mixture was stirred at the same temperature for 12 hours, and the reaction mixture was warmed to room temperature and discharged into methanol. The resulting solid was recrystallized from N, N-dimethylformamide to give 70.14 g of 2,7-bis (3 ′, 6′-dibromo-N-carbazolyl) -9,9-dimethyl-9H-fluorene as colorless crystals. Obtained.

[2] Production of Exemplary Compound 42 2,7-bis (3 ′, 6′-dibromo-N-carbazolyl) -9,9-dimethyl-9H-fluorene 8.36 g (10 mmol), N-phenylaniline 6.76 g (40 mmol), 5.36 g (56 mmol) of tert-butoxy sodium, 88 mg of palladium acetate, 0.2 ml of tri-tert-butylphosphine and 100 g of toluene were heated to 100 ° C. under an argon stream, and the same temperature was maintained for 6 hours. Heating and stirring were performed. Thereafter, the reaction mixture was cooled to room temperature, insoluble matters were filtered off, the filtrate was washed with water, and then toluene was distilled off from the filtrate under reduced pressure. The residue was sludged with acetone and further recrystallized from toluene / n-hexane to obtain 6.38 g of the objective compound 42 as colorless crystals.
Further, this compound was purified by sublimation at 470 ° C. and 1 × 10 ⁻⁴ Pa.
FD-MS: 1192 (M ⁺ )
Elemental analysis: calculated value (%); C, 87.55; H, 5.41; N, 7.04
Analytical value (%); C, 87.6; H, 5.4; N, 7.0

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 150 nm was subjected to ultrasonic cleaning using a neutral detergent, Semico Clean (manufactured by Furuuchi Chemical), ultrapure water, acetone, and ethanol. The substrate was dried with nitrogen gas, further UV / ozone cleaned, fixed to a substrate holder of a vapor deposition apparatus, and the vapor deposition tank was depressurized to 3 × 10 ⁻⁴ Pa. First, the compound of Example Compound 4 was deposited on the ITO transparent electrode at a deposition rate of 0.2 nm / sec to a thickness of 60 nm to form a hole injecting and transporting layer. Next, tris (8-quinolinolato) aluminum was deposited at a deposition rate of 0.2 nm / sec to a thickness of 40 nm to form a light emitting layer that also served as an electron injecting and transporting layer. Furthermore, magnesium and silver were co-deposited to a thickness of 200 nm at a deposition rate of 0.2 nm / sec (weight ratio 10: 1) to form a cathode, and silver was deposited thereon at a deposition rate of 2.0 nm / sec. The organic electroluminescence device was fabricated by evaporating to a thickness of 200 nm as a cathode. In addition, vapor deposition was implemented, maintaining the pressure reduction state of a vapor deposition tank. A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at 50 ° C. Initially, green light emission of 5.9 V and luminance of 510 cd / m ² was confirmed. The half life of luminance was 610 hours.

  In Example 13, in forming the hole injection transport layer, instead of using the compound of Exemplified Compound 4, instead of using the compound of Exemplified Compound 8, an organic electroluminescent device was prepared in accordance with the operation described in Example 13. Produced. Green light emission was confirmed from the device. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1).

  In Example 13, in forming the hole injection transport layer, instead of using the compound of Exemplified Compound 4, instead of using the compound of Exemplified Compound 12, an organic electroluminescent device was prepared in accordance with the operation described in Example 13. Produced. Green light emission was confirmed from the element. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1).

  In Example 13, in forming the hole injection transport layer, instead of using the compound of Exemplified Compound 4, instead of using the compound of Exemplified Compound 19, an organic electroluminescent device was prepared according to the operation described in Example 13, except that the compound of Exemplified Compound 19 was used. Produced. Green light emission was confirmed from the device. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1).

  In Example 13, in forming the hole injecting and transporting layer, the organic electroluminescent device was prepared according to the procedure described in Example 13 except that the compound of Exemplified Compound 21 was used instead of the compound of Illustrated Compound 4. Produced. Green light emission was confirmed from the device. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1).

  In Example 13, in forming the hole injection transport layer, instead of using the compound of Exemplified Compound 4, instead of using the compound of Exemplified Compound 31, an organic electroluminescent device was prepared in accordance with the operation described in Example 13. Produced. Green light emission was confirmed from the device. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1).

  In Example 13, in forming the hole injecting and transporting layer, the organic electroluminescent device was prepared according to the procedure described in Example 13 except that the compound of Exemplified Compound 36 was used instead of the compound of Illustrated Compound 4. Produced. Green light emission was confirmed from the device. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1). In addition, the organic electroluminescence device was left at 100 ° C. for 1 hour, and it was confirmed that there was no significant change in the light emission characteristics.

Comparative Example 1:
In Example 13, N, N′-diphenyl-N, N′-di (1 ″ -naphthyl) -4,4′- was used instead of using the compound of Exemplary Compound 4 in forming the hole injecting and transporting layer. Except that diamino-1,1′-biphenyl was used, an organic electroluminescent device was produced in accordance with the procedure described in Example 13. The device was confirmed to emit green light. The results are shown in Table 1 (Table 1).

Comparative Example 2:
In Example 13, N, N′-diphenyl-N, N′-di (1 ″ -naphthyl) -2,7-diamino was used instead of using the compound of Exemplary Compound 4 in forming the hole injecting and transporting layer. Except for using -9,9-dimethyl-9H-fluorene, an organic electroluminescent device was produced in accordance with the procedure described in Example 13. Green light emission was confirmed from the device. The results are shown in Table 1 (Table 1).

A glass substrate having an ITO transparent electrode (anode) having a thickness of 150 nm was subjected to ultrasonic cleaning using a neutral detergent, semi-coclean (manufactured by Furuuchi Chemical), ultrapure water, acetone, and isopropanol, and further washed by boiling with isopropanol. . The substrate was dried with nitrogen gas, further UV / ozone cleaned, fixed to a substrate holder of a vapor deposition apparatus, and the vapor deposition tank was depressurized to 2 × 10 ⁻⁴ Pa.

First, the exemplary compound 42 was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec to a thickness of 60 nm to form a first hole injection transport layer. Subsequently, the exemplary compound 6 was deposited to a thickness of 10 nm at a deposition rate of 0.2 nm / sec to form a second hole injecting and transporting layer. Next, on the hole injecting and transporting layer, 9,10-di (2′-naphthyl) anthracene was evaporated to a thickness of 40 nm at a deposition rate of 0.2 nm / sec to form a light emitting layer. On the light-emitting layer, tris (8-quinolinolato) aluminum was deposited at a deposition rate of 0.2 nm / sec to a thickness of 20 nm to form a second electron injecting and transporting layer. An aluminum / lithium alloy was deposited thereon as a cathode to a thickness of 10 nm at a deposition rate of 2.0 nm / sec. Finally, aluminum was deposited to a thickness of 100 nm at a deposition rate of 2.0 nm / sec to form an electrode. A light emitting element was manufactured.
In addition, vapor deposition was implemented, maintaining the pressure reduction state of a vapor deposition tank. A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a current density of 10 mA / cm ² in a dry atmosphere. Initially, blue light emission of 5.1 V and luminance of 470 cd / m ² was confirmed. The half life of luminance was 950 hours. Note that no change in color tone was observed even after half-life.

Preparation of organic electroluminescence device A glass substrate having a 150 nm thick ITO transparent electrode (anode) was washed with a neutral detergent, semi-coclean (manufactured by Furuuchi Chemical), ultrapure water, and isopropanol boiling washing. The substrate was dried with nitrogen gas, further washed with U / V ozone, fixed to a substrate holder of a vapor deposition apparatus, and the vapor deposition tank was depressurized to 2 × 10 ⁻⁴ Pa.

Exemplified compound 8 was deposited on an ITO transparent substrate to a thickness of 50 nm at a deposition rate of 0.2 nm / sec to form a first hole injection transport layer. Next, the compound of Exemplified Compound 36 and coumarin 6 were co-evaporated from different deposition sources to a thickness of 40 nm at a deposition rate of 0.2 nm / sec and a deposition rate of 0.02 nm / sec to form a light emitting layer. Further, tris (8-quinolinolato) aluminum was deposited on the light emitting layer to a thickness of 30 nm at a deposition rate of 0.2 nm / sec to form an electron injecting and transporting layer. Thereafter, lithium fluoride is deposited to a thickness of 1 nm at a deposition rate of 0.2 nm / sec, and aluminum is deposited to a thickness of 150 nm at a deposition rate of 2.0 nm / sec to form a cathode. Was made. The vapor deposition was carried out while maintaining the reduced pressure in the vapor deposition tank. A direct current voltage was applied to the produced organic electroluminescent element, and it was continuously driven at a low current density of 10 mA / cm ² in a dry atmosphere at room temperature. Initially, green light emission of 5.4 V and 1200 cd / m ² was confirmed. The half life of luminance was 2300 hours. Note that no change in color tone was observed even after half-life.

Preparation of organic electroluminescence device A glass substrate having a 150 nm thick ITO transparent electrode (anode) was washed with a neutral detergent, semi-coclean (manufactured by Furuuchi Chemical), ultrapure water, and isopropanol boiling washing. The substrate was dried with nitrogen gas, further washed with U / V ozone, fixed to a substrate holder of a vapor deposition apparatus, and the vapor deposition tank was depressurized to 2 × 10 ⁻⁴ Pa.

A compound of exemplary compound 42 was deposited on an ITO transparent substrate at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form a first hole injecting and transporting layer. Next, N, N′-diphenyl-N, N′-di (1′-naphthyl) -4,4′-diamino-1,1′-biphenyl was deposited to a thickness of 10 nm at a deposition rate of 0.2 nm / sec. The second hole injecting and transporting layer was formed. The light emitting layer was formed by co-evaporating the compound of Exemplified Compound 36 and rubrene from different vapor deposition sources to a thickness of 40 nm at a vapor deposition rate of 0.2 nm / sec and a vapor deposition rate of 0.02 nm / sec. Further, the compound of the exemplified compound 35 is deposited on the light emitting layer at a deposition rate of 0.2 nm / sec to a thickness of 10 nm to form a first electron injecting and transporting layer, and tris (8-quinolinolate) is formed thereon. Aluminum was deposited to a thickness of 20 nm at a deposition rate of 0.2 nm / sec to form a second electron injecting and transporting layer. Thereafter, lithium fluoride is deposited to a thickness of 1 nm at a deposition rate of 0.2 nm / sec, and aluminum is deposited to a thickness of 150 nm at a deposition rate of 2.0 nm / sec to form a cathode. Was made. The vapor deposition was carried out while maintaining the reduced pressure in the vapor deposition tank. A direct current voltage was applied to the produced organic electroluminescent element, and it was continuously driven at a low current density of 10 mA / cm ² in a dry atmosphere at room temperature. Initially, yellow light emission of 5.3 V and 1300 cd / m ² was confirmed. The half life of luminance was 2500 hours. Note that no change in color tone was observed even after half-life.

Preparation of organic electroluminescence device A glass substrate having a 150 nm thick ITO transparent electrode (anode) was washed with a neutral detergent, semi-coclean (manufactured by Furuuchi Chemical), ultrapure water, and isopropanol boiling washing. The substrate was dried with nitrogen gas, further washed with U / V ozone, fixed to a substrate holder of a vapor deposition apparatus, and the vapor deposition tank was depressurized to 2 × 10 ⁻⁴ Pa.

4,4 ′, 4 ″ -tris (2 ″ ′-naphthylphenylamino) triphenylamine is deposited on an ITO transparent substrate to a thickness of 60 nm at a deposition rate of 0.1 nm / sec to form a first hole injecting and transporting layer. Formed. Subsequently, the compound of exemplary compound 18 was vapor-deposited at a vapor deposition rate of 0.2 nm / sec to a thickness of 20 nm to form a second hole transport layer. On top of that, 9,10-bis (2′-naphthyl) anthracene and 2,5,8,11-tetra-tert-butylperylene were deposited from different deposition sources at a deposition rate of 0.2 nm / sec and a deposition rate of 0.01 nm. The light emitting layer was formed by co-evaporation to a thickness of 40 nm at / sec. Further, tris (8-quinolinolato) aluminum was deposited on the light emitting layer to a thickness of 20 nm at a deposition rate of 0.2 nm / sec to form an electron injecting and transporting layer. Thereafter, lithium fluoride is deposited to a thickness of 1 nm at a deposition rate of 0.2 nm / sec, and aluminum is deposited to a thickness of 150 nm at a deposition rate of 2.0 nm / sec to form a cathode. Was made. The vapor deposition was carried out while maintaining the reduced pressure in the vapor deposition tank. A direct current voltage was applied to the produced organic electroluminescent element, and it was continuously driven at a low current density of 10 mA / cm ² in a dry atmosphere at room temperature. Initially, blue light emission of 5.6 V and 570 cd / m ² was confirmed. The half life of luminance was 1300 hours. Note that no change in color tone was observed even after half-life.

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 150 nm was subjected to ultrasonic cleaning using a neutral detergent, Semico Clean (manufactured by Furuuchi Chemical), ultrapure water, acetone, and ethanol. The substrate was dried with nitrogen gas and further UV / ozone cleaned. Next, 3 wt% dichloroethane containing polymethyl methacrylate (weight average molecular weight 25000), the compound of Exemplified Compound 15 and tris (8-quinolinolato) aluminum in a weight ratio of 100: 30: 40 on the ITO transparent electrode, respectively. A 120 nm light emitting layer was formed by spin coating using the solution. Next, the glass substrate having the light emitting layer was fixed to a substrate holder of a vapor deposition apparatus, and the vapor deposition layer was decompressed to 2 × 10 ⁻⁴ Pa. On the light emitting layer, magnesium and silver were co-deposited as a cathode at a deposition rate of 2.0 nm / sec to a thickness of 200 nm (weight ratio 10: 1) to form a cathode, thereby producing an organic electroluminescent device. When a DC voltage of 15 V was applied to the produced organic electroluminescent element at room temperature in a dry atmosphere, a current of 83 mA / cm ² flowed. Green light emission with a luminance of 510 cd / m ² was confirmed. The half life of luminance was 420 hours.

  According to the present invention, it is possible to provide a novel amine compound and an organic electroluminescence device having a long emission life and excellent durability.

It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element.

Explanation of symbols

1: Substrate 2: Anode 3: Hole injection / transport layer 3a: Hole injection / transport component 4: Light emitting layer 4a: Light emission component 5: Electron injection / transport layer 5 ″: Electron injection / transport layer 5a: Electron injection / transport component 6: Cathode 7: Power supply

Claims (8)

An amine compound represented by the general formula (1) (Chemical formula 1).

[Wherein R ₁ and R ₂ represent a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, Z ₁ to Z ₄ represents a _substituent, n 1 ~n ₄ represents an integer of _{0~3, a 1,} a ₂ and _{a 3} are the general formula (2)

(In the formula, Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group, and Ar ₁ and Ar ₂ are linked to each other to form a cyclic structure. The groups represented by general formula (2) of A ₁ , A ₂ and A ₃ may be the same or different. The amine compound according to claim 1, wherein Ar ₁ and Ar ₂ are substituted or unsubstituted aromatic hydrocarbon groups. An organic electroluminescence device comprising at least one layer containing at least one amine compound according to claim 1 sandwiched between a pair of electrodes. The organic electroluminescent element according to claim 3, wherein the layer containing the amine compound according to claim 1 is a hole injection layer. The organic electroluminescent element according to claim 3, wherein the layer containing the amine compound according to claim 1 is a hole transport layer. The organic electroluminescent element according to claim 3, wherein the layer containing the amine compound according to claim 1 is a light emitting layer. The organic electroluminescent element according to claim 3, further comprising a light emitting layer between the pair of electrodes. The organic electroluminescent element according to claim 3, further comprising an electron injecting and transporting layer between the pair of electrodes.

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