JP2005119994A - Fluorene compound, amine compound, method for producing the amine compound and organic electroluminescent element containing the amine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new fluorene compound, to provide an amine compound derived from the same, to provide a method for producing the amine compound, and to provide an organic electroluminescent element having the amine compound. <P>SOLUTION: This fluorene compound represented by formula (1) (X<SB>1</SB>and X<SB>2</SB>are each a halogen atom; Z<SB>1</SB>to Z<SB>5</SB>are each H, a substituted or un-substituted straight chain, branched chain or cyclic alkyl or a substituted or un-substituted aryl; R<SB>1</SB>to R<SB>5</SB>are each H, a substituted or un-substituted alkyl, an aryl, or the like). The method for producing a fluorene skeleton-having diamine compound represented by formula (1) [X<SB>1</SB>and X<SB>2</SB>are each -NAr<SB>1</SB>Ar<SB>2</SB>(Ar<SB>1</SB>and Ar<SB>2</SB>are each independently a substituted or un-substituted aryl), -N-carbazoyl or the like] comprises aminating the halogen atoms of the fluorene compound. The amine compound is used for the hole injection transport layers and luminescent layers of organic electroluminescent elements. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a fluorene compound which is a novel organic functional material intermediate, an amine compound produced from the intermediate, a method for producing the amine compound, and an organic electroluminescent device comprising the amine compound.

Conventionally, aromatic halogen compounds have been usefully used as production intermediates for various organic industrial materials and various organic functional materials. For example, a dihalogenofluorene compound is widely used as a raw material for producing a π-conjugated polymer compound used as a polymer organic electroluminescent element material (for example, Non-Patent Document 1). In addition, aromatic halogen compounds can be converted to aromatic amino compounds by, for example, an Ullmann reaction or an amination reaction in the presence of a palladium catalyst, and are widely used as intermediates for the production of various aromatic amine compounds. (For example, Non-Patent Document 2 and Patent Document 1) Thus, new development of aromatic halogen compounds is desired even now.
On the other hand, amine compounds have been used as production intermediates for various dyes or various functional materials.
As a functional material, for example, it is used as a charge transport material of an electrophotographic photosensitive member, and recently, a hole injection transport material of an organic electroluminescence device (organic electroluminescence device: organic EL device) using an organic material as a light emitting material. It is proposed that it is useful as [For example, nonpatent literature 3].
An organic electroluminescent device has a structure in which a thin film containing a fluorescent organic compound is sandwiched between an anode and a cathode, and electrons and holes are injected into the thin film and recombined to form an exciton (exington). ) And emits light using light emitted when the exciton is deactivated. The organic electroluminescent element can emit light at a low direct current voltage of several volts to several tens of volts, and various colors (for example, red, blue, green) can be selected by selecting the type of the fluorescent organic compound. ) Can be emitted. The organic electroluminescent element having such characteristics is expected to be applied to various light emitting elements, display elements and the like. However, in general, organic electroluminescent elements have drawbacks such as poor stability and durability. 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 4].
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 -Diphenylamino) fluorene] has also been proposed [Patent Document 2].
Patent Document 3 discloses at least one layer containing at least one compound represented by the following formula (a) (Chemical Formula 1) in order to provide an organic electroluminescent device having improved stability and durability. An organic electroluminescent element formed by sandwiching layers is disclosed.

However, an organic electroluminescent device having excellent stability, durability, and heat resistance has not been known so far, and therefore exhibits excellent characteristics when used as a constituent material of an organic electroluminescent device. New amine compounds are desired.
Macromolecules, 35, 6439-6445, (2002) J. et al. Am. Chem. Soc. , 120, 9722-9723, (1998) Appl.Phys.lett., 51,913 (1987) Jpn.J.Appl.Phys., 27, L269 (1988) Japanese Patent Laid-Open No. 11-322679 Japanese Patent Laid-Open No. 5-25473 Japanese Patent Laid-Open No. 11-144873

  The subject of this invention is providing the organic electroluminescent element containing an amine compound and this compound. More specifically, an amine compound with high heat resistance suitable for a hole injection transport material for an organic electroluminescence device, and organic electroluminescence with excellent stability and durability and excellent heat resistance using the compound. It is to provide an element.

    In order to solve the above-mentioned problems, the present inventors have intensively studied various fluorene compounds, amine compounds, and organic electroluminescent devices, and as a result, have completed the present invention. That is, the present invention provides <1>: a fluorene compound represented by the general formula (1) (chemical formula 2),

[Wherein, X ₁ and X ₂ represent a halogen atom, and Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ represent a hydrogen atom, a halogen atom or a — (O) nZ group (wherein Z is Represents a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted aryl group, and n represents 0 or 1, and represents R ₁ , R ₂ , R ₃ and R _4. Represents a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.
<2>: An amine compound represented by the general formula (2) (chemical formula 3),

[Wherein Y ₁ and Y ₂ are —NAr ₁ Ar ₂ groups (Ar ₁ and Ar ₂ each independently represents a substituted or unsubstituted aryl group), or —N-carbazolyl group, —N-phenoxazinyl group Or represents an —N-phenothiazinyl group, Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ are a hydrogen atom, a halogen atom or a — (O) nZ group (wherein Z is substituted or unsubstituted) Represents a linear, branched or cyclic alkyl group, or a substituted or unsubstituted aryl group, n represents 0 or 1, and R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, substituted Or an unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.
<3>: A process for producing an amine compound represented by the general formula (2) by aminating a halogen atom of the fluorene compound represented by the general formula (1),
<4>: An organic electroluminescent device comprising at least one layer containing at least one amine compound described in <2> between a pair of electrodes,
<5>: The organic electroluminescent device according to <4>, wherein the layer containing the amine compound according to <2> is a hole injection transport layer,
<6>: The organic electroluminescent device according to <4>, wherein the layer containing the amine compound according to <2> is a light emitting layer,
<7>: The organic electroluminescent element according to any one of <4> to <6>, further having a light emitting layer between a pair of electrodes.
<8>: The organic electroluminescence device according to any one of <4> to <7>, further comprising an electron injection / transport layer between the pair of electrodes.
It is about.

  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 using the amine compound. Further, according to the present invention, it is possible to provide a novel fluorene compound which is an intermediate suitable for the production of the amine compound, and a method for producing an amine compound using the fluorene compound as an intermediate.

Hereinafter, the present invention will be described in detail.
The fluorene compound of the present invention is a compound represented by the general formula (1) (Formula 4).

[Wherein, X ₁ and X ₂ represent a halogen atom, and Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ represent a hydrogen atom, a halogen atom or a — (O) nZ group (wherein Z is Represents a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted aryl group, and n represents 0 or 1, and represents R ₁ , R ₂ , R ₃ and R _4. Represents a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.
In the fluorene compound represented by the general formula (1), X ₁ and X ₂ each represent a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably a chlorine atom or a bromine atom.

In the fluorene compound represented by the general formula (1), Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ are each a hydrogen atom, a halogen atom or a — (O) nZ group (wherein Z is a substituent) Or an unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted aryl group, and n represents 0 or 1, preferably a hydrogen atom, a halogen atom or — (O) n-Z group (wherein Z represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted aryl group having 4 to 12 carbon atoms, n Represents 0 or 1, and more preferably a hydrogen atom, a halogen atom, or a — (O) nZ group (wherein Z is a substituted or unsubstituted straight chain or branched chain having 1 to 8 carbon atoms). Or a cyclic alkyl group, or substituted or unsubstituted Represents an aryl group having 6 to 12 carbon atoms, and n represents 0 or 1, more preferably a hydrogen atom, a halogen atom, a substituted or unsubstituted straight chain, branched chain or cyclic group having 1 to 8 carbon atoms. An alkyl group of 6 to 10 carbon atoms.
Specific examples of the halogen atoms of Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ include halogen atoms such as fluorine atom, chlorine atom and bromine atom.
Specific examples of the substituted or unsubstituted linear, branched or cyclic alkyl group which is Z in the-(O) nZ group 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 group, 3,5,5-trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-undecyl group, 1-methyldecyl group n-dodecyl group, n-tridecyl group, 1-hexylheptyl 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, Isobornel 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- Tylcyclohexyl 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-isopropoxidedecyl 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, 2- N-dithioethyl 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 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 aryl group that is Z in the-(O) nZ group include, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 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, -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,
4-quinolinyl 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, 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-pyrenyl 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- Renyl 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-trimethyl-2-pyrenyl group, 4-pyridinyl group, 3-pyridinyl group, 2-pyridinyl group, 3-furanyl group, 2-furanyl group, 3- Thienyl group, 2-thienyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl 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-isopropyl Pirufeniru group,

4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butylphenyl group, 2-sec-butylphenyl group, 4-tert-butylphenyl group, 3-tert-butylphenyl group, 2-tertbutyl Phenyl 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-dodecyl Phenyl group, 4-n-tetradecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4- (4′-methylcyclohexyl) Enyl group, 4- (4′-tert-butylcyclohexyl) 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-dimethylphenyl 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 A 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-trimethoxyphenyl 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′-chlorophenyl) 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-dichlorophenyl 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-methylphenyl group, 2-fluoro-5-methylphenyl group, 3-fluoro-2-methylphenyl group, 3-fluoro-4-methylphenyl group, 2-methyl-4- Fluorophenyl group, 2-methyl-5-fluorophenyl group, 3-methyl-4-fluorophenyl group, 2-chloro-4-methylphenyl group, 2-chloro-4-methylphenyl group, 2-chloro-5- Methylphenyl group, 2-chloro-6-methylphenyl group, 2-methyl-3-chlorophenyl group, 2-methyl-3-chlorophenyl group, 2-methyl-4-chlorophenyl Nyl group, 3-methyl-4-chlorophenyl group, 2-chloro-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 And a 5-chloro-2,4-dimethoxyphenyl group.

In the fluorene compound represented by the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, substituted or unsubstituted aryl. Group or a substituted or unsubstituted aralkyl group, preferably a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, a substituted or substituted group having 4 to 16 carbon atoms, or Represents an unsubstituted aryl group, or a substituted or unsubstituted aralkyl group having 5 to 16 carbon atoms, more preferably a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic group having 1 to 8 carbon atoms It represents an alkyl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms.
Specific examples of substituted or unsubstituted linear, branched or cyclic alkyl groups for R ₁ , R ₂ , R ₃ and R ₄ include substituted or unsubstituted Z which is Z in the — (O) nZ group. Specific examples of the linear, branched or cyclic alkyl group include substituted or unsubstituted linear, branched or cyclic alkyl groups.
Specific examples of the substituted or unsubstituted aryl group for R ₁ , R ₂ , R _3, and R ₄ are given as specific examples of the substituted or unsubstituted aryl group that is Z of the — (O) nZ group. Mention may be made of substituted or unsubstituted aryl groups.

Specific examples of the substituted or unsubstituted aralkyl group of R ₁ , R ₂ , R ₃ and R ₄ include, for example, benzyl group, α-methylbenzyl group, α-ethylbenzyl group, 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-ethyl Benzyl group, 2-ethylbenzyl group, 4-isopropylbenzyl group, 4-tert-butylbenzyl group, 2-tert-butylbenzyl group, 4-tert-pentylbenzyl group, 4-cyclohexylbenzyl group, 4-n-octyl Benzyl group, 4-tert-octylbenzyl group, 4-allylbenzyl group, 4-benzylbenzyl group, 4-phenethylbenzyl group, 4- An benzylbenzyl 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-isobutoxymethylbenzyl 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 aralkyl groups such as a group, 2-chlorobenzyl group, 3,4-dichlorobenzyl group, 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group.
In the fluorene compound represented by the general formula (1) of the present invention, the substitution position on the benzene ring that is the center of the two fluorene compounds is not particularly limited, and o-substitution, m-substitution, and Any of the p-substitutions can be preferably used. More preferred are m-substitution and p-substitution, and even more preferred is m-substitution.
Specific examples of the fluorene compound of the present invention include the following compounds (Chemical Formula 5 to Chemical Formula 16), but the present invention is not limited to these specific examples.

The fluorene compound of the present invention can be produced, for example, according to the following steps.
Production of fluorene compound represented by general formula (1)

[Wherein, X ₁ and X ₂ , Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ , R ₁ , R ₂ , R ₃ and R ₄ represent the same meaning as in general formula (1); ₁ and L ₂ represent a halogen atom or a boric acid group, L ₃ and L ₄ represent a halogen atom or a boric acid group, and when L ₁ and L ₂ are halogen atoms, L ₃ and L ₄ represent a boric acid group And when L ₁ and L ₂ are boric acid groups, L ₃ and L ₄ represent a halogen atom.

That is, the dihalogenated benzene derivative (or benzenediboronic acid derivative) represented by the general formula (A) is replaced with the fluoreneboronic acid derivative (or halogenated fluorene represented by the general formula (B) and / or (B ′). Derivatives) palladium catalysts [eg tetrakis (triphenylphosphine) palladium, palladium acetate / tri-tert-butylphosphine] and bases (eg inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, triethylamine) , A fluorene compound represented by the general formula (1) can be produced by reaction in the presence of an organic base such as diisopropylamine or pyridine.

The amine compound of the present invention is a compound represented by the general formula (2) (Chemical Formula 18).

[Wherein Y ₁ and Y ₂ are —NAr ₁ Ar ₂ groups (Ar ₁ and Ar ₂ each independently represents a substituted or unsubstituted aryl group), or —N-carbazolyl group, —N-phenoxazinyl group Or represents an —N-phenothiazinyl group, Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ are a hydrogen atom, a halogen atom or a — (O) nZ group (wherein Z is substituted or unsubstituted) Represents a linear, branched or cyclic alkyl group, or a substituted or unsubstituted aryl group, n represents 0 or 1, and R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, substituted Or an unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.

In General Formula (2), Y ₁ and Y ₂ represent —NAr ₁ Ar ₂ group, or —N-carbazolyl group, —N-phenoxazinyl group, or —N-phenothiazinyl group, preferably —NAr ₁ Ar ₂ groups or -N-carbazolyl group is represented.
Ar ₁ and Ar ₂ in the —NAr ₁ Ar ₂ group of Y ₁ and Y ₂ represent a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, More preferably, it represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
Specific examples of Ar ₁ and Ar ₂ include the substituted or unsubstituted aryl groups listed as specific examples of the substituted or unsubstituted aryl group of Z in the — (O) Z group.

Specific examples of —N-carbazolyl group, —N-phenoxazinyl group and —N-phenothiazinyl group for Y ₁ and Y ₂ include, for example, N-carbazolyl group, 2-methyl-N-carbazolyl group, 3-methyl- N-carbazolyl group, 4-methyl-N-carbazolyl group, 3-n-butyl-N-carbazolyl group, 3-n-hexyl-N-carbazolyl group, 3-n-octyl-N-carbazolyl group, 3-n -Decyl-N-carbazolyl group, 3,6-dimethyl-N-carbazolyl group, 2-methoxy-N-carbazolyl group, 3-ethoxy-N-carbazolyl group, 3-isopropyloxy-N-carbazolyl group, 3-n -Butyloxy-N-carbazolyl group, 3-n-octyloxy-N-carbazolyl group, 3-n-decyloxy-N-carbazolyl group, 3- Enyl-N-carbazolyl group, 3- (4′-methylphenyl) -N-carbazolyl group, 2,7-dimethyl-N-carbazolyl group, 2,7-diphenyl-N-carbazolyl group, 3,6-dimethyl- N-carbazolyl group, 3,6-diphenyl-N-carbazolyl group, 3,6-bis (4′-cyclohexylphenyl) -N-carbazolyl group, 3,6-bis (4′-phenylphenyl) -N-carbazolyl Group, 3-chloro-N-carbazolyl group, N-phenoxazinyl group, N-phenothiazinyl group, 2-trifluoromethyl-N-phenothiazinyl group, 2-methyl-N-phenothiazinyl group, 2-chloro-N- A phenothiazinyl group, a 3-chloro-N-phenothiazinyl group, and a 3-phenyl-N-phenothiazinyl group can be exemplified.

Specific examples of the amine compound represented by the general formula (2) according to the present invention include the following compounds (Chemical Formula 19 to Chemical Formula 38), but the present invention is limited to these. is not.

The amine compound represented by the general formula (2) of the present invention can be produced according to the following steps.
Production of amine compound represented by general formula (2)

[Wherein, X ₁ , X ₂ , Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ , R ₁ , R ₂ , R ₃ and R ₂ , Y ₁ and Y ₂ represent the general formula (1) and general It represents the same meaning as in formula (2).
That is, it can be produced by reacting the fluorene compound represented by the general formula (1) with the compound represented by the general formula (C) and / or the general formula (C ′). Here, the general formula (C) and the general formula (C ′) represent an amine compound in which a hydrogen atom is bonded to a group represented by Y ₁ or Y ₂ .
The reaction of the compound represented by the general formula (1) and the compound represented by the general formula (C) and / or the general formula (C ′)
[1] Optionally in the presence of a base (eg, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate) and a copper catalyst (eg, copper chloride, copper bromide, copper iodide) optionally in a polar solvent (eg, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N′-dimethylimidazolidinone, sulfolane, o-dichlorobenzene) and a compound represented by the general formula (1) A method of reacting a compound represented by the general formula (C) and / or the general formula (C ′),
[2] Base (eg, tert-butoxy sodium, tert-butoxy potassium, sodium carbonate, potassium carbonate) and palladium catalyst [eg, tetrakis (triphenylphosphine) palladium, palladium / carbon, palladium acetate / tri-tert-butylphosphine , Palladium acetate / dicyclohexylphenylphosphine, tris (dibenzylideneacetone) dipalladium / tri-tert-butylphosphine], a compound represented by general formula (1) and general formula (C) and / or general formula A method of reacting a compound represented by (C ′),
Can be implemented.

Moreover, the amine compound represented by General formula (2) can also be manufactured according to the process shown below as another method (Formula 40).

[Wherein Y ₁ , Y ₂ , Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ , R ₁ , R ₂ , R ₃ and R ₄ represent the same meaning as in general formula (1); ₁ and L ₂ represent a halogen atom or a boric acid group, L ₃ and L ₄ represent a boric acid group or a halogen atom, and when L ₁ and L ₂ are halogen atoms, L ₃ and L ₄ represent a boric acid group And when L ₁ and L ₂ are boric acid groups, L ₃ and L ₄ represent a halogen atom.

That is, a dihalogenobenzene derivative (phenyldiboronic acid derivative) represented by the general formula (D) and a fluoreneboronic acid derivative (halogenated) represented by the general formula (E) and / or the general formula (E ′). Fluorene derivatives) in the presence of a palladium catalyst [eg tetrakis (triphenylphosphine) palladium, palladium acetate / tri-tert-butylphosphine] and a base (eg potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate) It can be produced by reacting.

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 (2) 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. An electron injecting and transporting layer containing a transporting 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 electroluminescent device of the present invention, the amine compound represented by the amine compound represented by the general formula (2) is preferably used as a component of the hole injection transport layer and / or the light emitting layer. More preferably, it is used as a component of the injecting and transporting layer.
In the organic electroluminescent element of the present invention, the amine compound represented by the amine compound represented by the general formula (2) 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 (2) 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 (2) in the hole injecting and transporting layer. Examples of the compound having a hole injecting and transporting function other than the amine compound represented by the general formula (2) 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] tri More preferred are polythiophene and derivatives thereof, such as phenylamine, 1,3,5-tris [N- (4′-diphenylamino] benzene, and poly-N-vinylcarbazole and derivatives thereof.
When the amine compound represented by the general formula (2) and another compound having a hole injection function are used in combination, the content of the amine compound represented by the general formula (2) in the hole injection / transport layer is: Preferably, it is 0.1 mass% or more, More preferably, it is 0.5-99.9 mass%, More preferably, it is 3-97 mass%.
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 (2) 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 (2) 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, Coumarin 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 (eg Nile red), benzothiazole derivatives, benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamic acid ester derivatives, poly-N-vinylcarbazole and its derivatives, polythiophene and its derivatives, polyphenylene and Derivatives thereof, polyfluorene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polybiphenylene vinylene and derivatives thereof, polyterphenylene vinyl Ren and derivatives thereof, poly naphthylene vinylene and its derivatives, and polythienylenevinylene and derivatives thereof. As the compound having a light emitting function other than the amine compound represented by the general formula (2), 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.

The organic electroluminescent element of the present invention preferably contains an amine compound represented by the general formula (2) in the light emitting layer.
When an amine compound represented by the general formula (2) and a compound having a light emitting function other than the amine compound represented by the general formula (2) are used in combination, the amine represented by the general formula (2) in the light emitting layer The proportion of the compound is preferably adjusted to 0.001 to 99.999% by mass.
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 (2) can be used as a host compound of 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 (2) as a host compound, examples of the guest compound include compounds having other light emitting functions described above, and among them, polycyclic aromatic compounds. Is preferred.

When the light emitting layer is formed using the amine compound represented by the general formula (2) as a host compound, the guest compound is preferably 0.001 to 40 masses with respect to the amine compound represented by the general formula (2). %, More preferably 0.01 to 30% by mass, and still more preferably 0.1 to 20% by mass of the light-emitting layer using the amine compound represented by the general formula (2) as a host material. And a compound having a light emitting function other than the amine compound represented by (2) can be used as at least one guest material.
The organic electroluminescent element of the present invention preferably contains an amine compound represented by the general formula (2) as a host material in the light emitting layer.
When the amine compound host material represented by the general formula (2) is used in combination with another compound having a light emitting function, the amine compound represented by the general formula (2) in the light emitting layer is preferably 40. It is 0% to 99.9%, and more preferably 60.0 to 99.9% by mass.
The usage-amount of guest material is 0.001-40 mass% with respect to the amine compound represented by General formula (2), Preferably, it is 0.05-30 mass%, More preferably, it is 0.1-20 mass %. Moreover, a guest material may be used independently and may be used together.

When the light emitting layer is formed using the amine compound represented by the general formula (2) as a guest material, the host material is preferably a polycyclic aromatic compound, a triarylamine derivative, an organometallic complex, or a stilbene derivative. Polycyclic aromatic compounds and organometallic complexes are more preferred.
When the amine compound represented by the general formula (2) is used as a guest material, the amine compound represented by the general formula (2) is preferably 0.001 to 40% by mass, more preferably 0.01 -30 mass%, More preferably, 0.1-20 mass% is used.
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.
Examples of the compound having an electron injecting function used in the electron injecting and transporting layer include organometallic complexes, oxadiazole derivatives, triazole derivatives, triazine derivatives, perylene derivatives, quinoline derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted fluorenones. Derivatives, thiopyrandioxide derivatives and the like. 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. An organoaluminum complex is preferable, and an organoaluminum complex having a substituted or unsubstituted 8-quinolinolato ligand is more preferable. 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)
(Wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand, OL ′ represents an aryloxy ligand, and L ′ represents an aryl group having 6 to 24 carbon atoms)
(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-diphenylphenolate) 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, bis (2-methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholate) ) Aluminum, bis (2,4-dimethyl-8-quinolinolate) (2-phenylphenoler) ) Aluminum, bis (2,4-dimethyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolato) 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, lithium-indium alloy, sodium, sodium-potassium alloy, calcium, magnesium, magnesium-silver alloy, magnesium-indium alloy, indium, ruthenium, titanium, manganese, yttrium, and 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 efficiently extract light emitted from the organic electroluminescent device of the present invention, 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. 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).
As content of a singlet oxygen quencher, 0.01-50 mass% of the total quantity which comprises the layer (for example, hole injection transport layer) to contain, Preferably, 0.05-30 mass%, more Preferably, it is 0.1-20 mass%.

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 (hexane 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 for 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. Although the density | concentration of a coating liquid is not specifically limited, It can set to the density | concentration range suitable for producing desired thickness with the apply | coating method to implement, Usually, 0.1-50 mass%, Preferably 1 to 30% by mass. 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. The binder resin is used so that the content of the binder resin is 5 to 99.9% by mass, preferably 10 to 99% by mass (relative to the total amount of each component when a single-layer element is formed).
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 provided with a protective layer (sealing layer) for the purpose of preventing contact with oxygen, moisture, etc. For example, it can be protected by enclosing it in paraffin, liquid paraffin, silicon 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.

Production of Exemplified Compound A-10 7-chloro-9,9-dimethyl-9H-fluorene-2-boronic acid 10.1 g (0.037 mol), 1,4-diiodobenzene 6.10 g (0.0185 mol), To a mixture consisting of 4 g of sodium carbonate, 75 g of toluene and 38 g of water, 350 mg of tetrakis (triphenylphosphine) palladium was added under an argon stream, and the mixture was heated and stirred at 80 ° C. for 5 hours. Thereafter, the reaction mixture was cooled to room temperature, and the precipitated solid was filtered off. The obtained solid was dissolved in 400 ml of toluene, and then filtered through Celite, and the toluene solution was concentrated under reduced pressure. The residue was sludged with toluene to obtain 8.3 g of the target compound of Exemplified Compound A-10 as a colorless solid. The melting point of this compound was 266-270 ° C.

Preparation of Exemplified Compound A-18 In Example 1, instead of using 10.1 g (0.037 mol) of 7-chloro-9,9-dimethyl-9H-fluorene-2-boronic acid, 7-chloro-9, Except for using 15.3-g (0.037 mol) of 9-di-n-hexyl-9H-fluorene-2-boronic acid, Example Compound A-18 was obtained as colorless crystals according to the procedure described in Example 1. 0.1 g was obtained.

Preparation of Exemplified Compound A-20 In Example 1, instead of using 10.1 g (0.037 mol) of 7-chloro-9,9-dimethyl-9H-fluorene-2-boronic acid, 7-chloro-9, Except for using 15.1 g (0.037 mol) of 9-dicyclohexyl-9H-fluorene-2-boronic acid, 8.7 g of Exemplified Compound A-20 was obtained as unemployed crystals according to the procedure described in Example 1. .

Production of Illustrative Compound A-37 In Example 1, 10.1 g (0.037 mol) of 7-chloro-9,9-dimethyl-9H-fluorene-2-boronic acid and 6.10 g of 1.4-diiodobenzene Instead of using (0.0185 mol), 9.5 g (0.037 mol) of 7-chloro-9-methyl-9H-fluorene-2-boronic acid and 4.37 g (0.0185 mol) of 1.3-dibromobenzene 7.6 g of Exemplified Compound A-37 was obtained as colorless crystals according to the procedure described in Example 1 except that was used.

Production of Exemplified Compound A-45 In Example 1, instead of using 6.10 g (0.0185 mol) of 1,4-diiodomobenzene, 4.37 g (0.0185 mol) of 1,3-dibromobenzene was used. Except that, 8.0 g of Compound of Exemplified Compound A-45 was obtained as colorless crystals according to the procedure described in Example 1. The melting point of this compound was 244 to 246 ° C.

Production of Exemplified Compound A-46 In Example 1, instead of using 6.10 g (0.0185 mol) of 1,4-diiodobenzene, 5.80 g (0.0185 mol) of 1-phenyl-3,5-dibromobenzene ) Was used according to the procedure described in Example 1 to obtain 8.8 g of the compound of exemplary compound A-46 as colorless crystals.

Production of Exemplified Compound A-47 In Example 1, instead of using 6.10 g (0.0185 mol) of 1,4-diiodobenzene,
Except for using 4.60 g (0.0185 mol) of 3,5-dibromotoluene, 7.5 g of the compound of Exemplified Compound A-47 was obtained as colorless crystals according to the procedure described in Example 1.

Production of Exemplified Compound A-61 In Example 1, 7-chloro-9,9-dimethyl-9H-fluorene-2-boronic acid 10.1 g (0.037 mol) and 1.4-diiodobenzene 6.10 g Instead of using (0.0185 mol), 14.1 g (0.037 mol) of 7-chloro-9,9-dicyclopentyl-9H-fluorene-2-boronic acid and 4.37 g of 1.3-dibromobenzene (0 Except that 0.185 mol) was used, 7.6 g of Exemplified Compound A-61 was obtained as colorless crystals according to the procedure described in Example 1.

Production of Exemplified Compound A-78 In Example 1, instead of using 6.1 g (0.0185 mol) of 1,4-diiodobenzene, 4.37 g (0.0185 mol) of 1,2-dibromobenzene was used. 6.8 g of Exemplified Compound A-78 as colorless crystals was obtained according to the procedure described in Example 1.

Production of Exemplified Compound B-1 1,4-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3.98 g (7.5 mmol), N-phenyl To a mixture consisting of 2.54 g (15 mmol) of aniline, 2.3 g of sodium tert-butoxide, 26 mg of palladium acetate and 40 ml of xylene, 0.07 ml of tri-tert-butylphosphine is added under nitrogen atmosphere and at 120 ° C. for 15 hours. Stir with heating. Thereafter, 600 ml of toluene was added to the reaction mixture, dissolved by heating, and the insoluble matter was filtered through Celite. After the toluene phase is washed with water, toluene is distilled off from the toluene phase under reduced pressure, the residue is purified by silica gel column chromatography, and further recrystallized from toluene to give the desired compound of the exemplified compound B-1 as colorless. As a crystal, 3.2 g was obtained. Further, this compound was purified by sublimation at 390 ° C. and 2 × 10 ⁻⁴ Pa over 12 hours.

Production of Exemplary Compound B-2 In Example 10, except that 2.54 g (15 mmol) of N-phenylaniline was used, 3.29 g (15 mmol) of N- (1-naphthyl) aniline was used instead of using 2.54 g (15 mmol). According to the procedure described in 10, 2.9 g of the compound of exemplary compound B-2 was obtained as colorless crystals. Further, this compound was purified by sublimation at 430 ° C. and 2 × 10 ⁻⁴ Pa over 10 hours.

Production of Exemplified Compound B-3 In Example 10, except that 2.54 g (15 mmol) of N-phenylaniline was used, 4.04 g (15 mmol) of N- (9-phenanthryl) aniline was used. According to the procedure described in 10, 3.5 g of the compound of exemplary compound B-3 was obtained as colorless crystals. Further, this compound was purified by sublimation at 460 ° C. and 4 × 10 ⁻⁴ Pa for 12 hours.

Production Example 10 of Exemplified Compound B-7 In Example 10, 1,4-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3.98 g (7.5 mmol) ) And 2.54 g (15 mmol) of N-phenylaniline, instead of 1,4-bis (7′-chloro-9 ′, 9′-dicyclohexyl-9′H-fluoren-2′-yl) benzene 6 Except that 0.02 g (7.5 mmol) and 3.29 g (15 mmol) of N- (1-naphthyl) aniline were used, the compound of Exemplified Compound B-7 was obtained as colorless crystals according to the procedure described in Example 10. 6 g was obtained. Further, this compound was purified by sublimation at 460 ° C. and 1 × 10 ⁻⁴ Pa over 16 hours.

Preparation of Exemplified Compound B-29 According to the procedure described in Example 1, except that 2.51 g (15 mmol) of carbazole was used instead of 2.54 g (15 mmol) of N-phenylaniline in Example 10. 3.0 g of compound B-29 was obtained as colorless crystals. Further, this compound was purified by sublimation at 420 ° C. and 4 × 10 ⁻⁴ Pa for 8 hours.

Production of Exemplified Compound B-31 In Example 10, 1,4-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3.98 g (7.5 mmol) ) And 2.54 g (15 mmol) of N-phenylaniline, instead of 1,3-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3 According to the procedure described in Example 10 except that .98 g (7.5 mmol) and 3.29 g (15 mmol) of N- (1-naphthyl) aniline were used, the compound of Exemplified Compound B-31 as a colorless crystal was used. 2 g was obtained. Further, this compound was purified by sublimation at 430 ° C. and 2 × 10 ⁻⁴ Pa for 8 hours.

Preparation of Exemplified Compound B-32 In Example 10, 1,4-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3.98 g (7.5 mmol) ) And 2.54 g (15 mmol) of N-phenylaniline, instead of 1,3-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3 According to the procedure described in Example 10, except that .98 g (7.5 mmol) and N- (9-phenanthrenyl) aniline 4.04 g (15 mmol) were used, the compound of Exemplified Compound B-32 was obtained as colorless crystals. 6 g was obtained. Further, this compound was purified by sublimation at 450 ° C. and 2 × 10 ⁻⁴ Pa for 10 hours.

Preparation of Exemplified Compound B-50 In Example 10, 1,4-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3.98 g (7.5 mmol) ) And 2.54 g (15 mmol) of N-phenylaniline, instead of 1,3-bis (7′-chloro-9 ′, 9′-dicyclopentyl-9′H-fluoren-2′-yl) benzene Except that 5.60 g (7.5 mmol) and 3.29 g (15 mmol) of N- (1-naphthyl) aniline were used, the compound of Exemplified Compound B-50 was obtained as colorless crystals according to the procedure described in Example 10. .5 g was obtained. Further, this compound was purified by sublimation at 420 ° C. and 1 × 10 ⁻⁴ Pa for 8 hours.

Production of Exemplified Compound B-60 In Example 10, 1,4-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3.98 g (7.5 mmol) ) And 2.54 g (15 mmol) of N-phenylaniline, instead of 1,3-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3 Except for using .98 g (7.5 mmol) and 2.51 g (15 mmol) of carbazole, 3.2 g of Compound of Exemplified Compound B-60 was obtained as colorless crystals according to the procedure described in Example 10. Further, this compound was purified by sublimation at 450 ° C. and 2 × 10 ⁻⁴ Pa over 12 hours.

Production Example 10 of Exemplified Compound B-66 In Example 10, 1,4-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3.98 g (7.5 mmol) ) And N-phenylaniline 2.54 g (15 mmol), instead of 1,2-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3 According to the procedure described in Example 10, except that .98 g (7.5 mmol) and 3.29 g (15 mmol) of N- (1-naphthyl) aniline were used, the compound of Exemplified Compound B-66 was obtained as colorless crystals. 0.7 g was obtained. Further, this compound was purified by sublimation at 430 ° C. and 4 × 10 ⁻⁴ Pa over 12 hours.

Production Example 10 of Exemplified Compound B-99 In Example 10, 1,4-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3.98 g (7.5 mmol) ) And N-phenylaniline 2.54 g (15 mmol), instead of 1,2-bis (7′-chloro-9 ′, 9′-dimethyl-9′H-fluoren-2′-yl) benzene 3 2.9 g of Compound of Exemplified Compound B-99 was obtained as colorless crystals according to the procedure described in Example 10 except that .98 g (7.5 mmol) and 2.51 g (15 mmol) of carbazole were used. Further, this compound was purified by sublimation at 420 ° C. and 3 × 10 ⁻⁴ Pa for 12 hours.

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 200 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 using nitrogen gas, further washed with UV / ozone, fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition tank was depressurized to 3 × 10 ⁻⁶ Torr. First, the compound of Exemplified Compound B-2 was deposited on the ITO transparent electrode at a deposition rate of 0.2 nm / sec to a thickness of 75 nm to form a hole injecting and transporting layer. Next, tris (8-quinolinolato) aluminum was deposited on the hole injecting and transporting layer at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form a light emitting layer that also served as an electron injecting and transporting layer. Further, magnesium and silver were co-deposited as a cathode at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio 10: 1) to form an organic electroluminescent device. 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 5.7 V and luminance of 560 cd / m ² was confirmed. The half life of luminance was 880 hours.
Further, the device was allowed to stand at 100 ° C. for 1 hour, and it was confirmed that there was no significant change in light emission characteristics.

Preparation of Organic Electroluminescent Device In Example 21, in forming the hole injection transport layer, Example 21 except that the compound of Exemplary Compound B-3 was used instead of the compound of Exemplary Compound B-2. An organic electroluminescent element was produced according to the operation described. Green light emission was confirmed from the device. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1). Furthermore, no change was observed in the light emission characteristics of the device produced in the same manner even after being left at 100 ° C. for 1 hour.

Preparation of Organic Electroluminescent Device In Example 21, the hole injection / transport layer was prepared in the same manner as in Example 21 except that the compound of exemplary compound B-7 was used instead of the compound of exemplary compound B-2. An organic electroluminescent element was produced according to the operation described. Green light emission was confirmed from the device. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1). Furthermore, no change was observed in the light emission characteristics of the device produced in the same manner even after being left at 100 ° C. for 1 hour.

Production of Organic Electroluminescent Device In Example 21, the hole injection / transport layer was produced in the same manner as in Example 21 except that the compound of Illustrative Compound B-31 was used instead of the compound of Illustrative Compound B-2. An organic electroluminescent element was produced according to the operation described. Green light emission was confirmed from the device. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1). Furthermore, no change was observed in the light emission characteristics of the device produced in the same manner even after being left at 100 ° C. for 1 hour.

Production of Organic Electroluminescent Device In Example 21, in producing the hole injection transport layer, Example 21 except that the compound of Illustrative Compound B-32 was used instead of the Compound of Illustrative Compound B-2. An organic electroluminescent element was produced according to the operation described. Green light emission was confirmed from the device. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1). Furthermore, no change was observed in the light emission characteristics of the device produced in the same manner even after being left at 100 ° C. for 1 hour.

Production of Organic Electroluminescent Device In Example 21, in producing the hole injection transport layer, Example 21 except that the compound of Illustrative Compound B-50 was used instead of the Compound of Illustrative Compound B-2. An organic electroluminescent element was produced according to the operation described. Green light emission was confirmed from the device. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1). Furthermore, no change was observed in the light emission characteristics of the device produced in the same manner even after being left at 100 ° C. for 1 hour.

Production of Organic Electroluminescent Device In Example 21, in producing the hole injection transport layer, Example 21 except that the compound of Illustrative Compound B-66 was used instead of the Compound of Illustrative Compound B-2. An organic electroluminescent element was produced according to the operation described. Green light emission was confirmed from the device. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1). Furthermore, no change was observed in the light emission characteristics of the device produced in the same manner even after being left at 100 ° C. for 1 hour.

Comparative Example 1:
In Example 21, N, N′-diphenyl-N, N′-di (3 ″ -methylphenyl) -4, instead of using the compound of Exemplary Compound B-2 in forming the hole injecting and transporting layer, Except for using 4'-diaminobiphenyl, an organic electroluminescence device was produced according to the procedure described in Example 21. Green light emission was confirmed from the device, and the characteristics were examined. In addition, when the device was allowed to stand at 100 ° C. for 1 hour, light emission from the device was attenuated to the extent that it could not be confirmed.

Comparative Example 2:
In Example 21, in forming the hole injecting and transporting layer, N, N, N ′, N′-tetraphenyl-2,7-diamino-9,9- was used instead of using the compound of exemplary compound B-2. An organic electroluminescent element was produced according to the procedure described in Example 21 except that dimethyl-9H-fluorene was used. Green light emission was confirmed from each element. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1). Further, when the device was allowed to stand at 100 ° C. for 1 hour, it was confirmed that light emission from the device was attenuated.

Comparative Example 3:
In Example 21, N, N-diphenyl-2-amino-7 represented by the formula (a) (Chemical Formula 41) was used instead of using the compound of Exemplary Compound B-2 when forming the hole injecting and transporting layer. An organic electroluminescent element was produced according to the procedure described in Example 21 except that -N-carbazolyl-9,9-dimethyl-9H-fluorene was used. Green light emission was confirmed from each element. Further, the characteristics were examined, and the results are shown in Table 1 (Table 1). Further, when the device was allowed to stand at 100 ° C. for 1 hour, it was confirmed that light emission from the device was attenuated.

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 200 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 using nitrogen gas, further washed with UV / ozone, fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition tank was depressurized to 3 × 10 ⁻⁶ Torr.
First, poly (thiophene-2,5-diyl) was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a first hole injection transport layer. Subsequently, the compound of exemplary compound B-29 was deposited at a deposition rate of 0.2 nm / sec to a thickness of 55 nm to form a second hole injecting and transporting layer. Next, tris (8-quinolinolato) aluminum was deposited on the hole injecting and transporting layer at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form a light emitting layer that also served as an electron injecting and transporting layer. Further, magnesium and silver were co-deposited as a cathode at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio 10: 1) to form an organic electroluminescent device. 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. Initially, blue-green light emission of 5.7 V and luminance of 560 cd / m ² was confirmed. The half life of luminance was 1700 hours.
Further, the device was allowed to stand at 100 ° C. for 1 hour, and it was confirmed that there was no significant change in light emission characteristics.

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 200 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 using nitrogen gas, further washed with UV / ozone, fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition tank was depressurized to 3 × 10 ⁻⁶ Torr. First, 4,4 ′, 4 ″ -tris [N- (3 ″ -methylphenyl) -N-phenylamino] triphenylamine is deposited on an ITO transparent electrode at a deposition rate of 0.1 nm / sec and a thickness of 50 nm. To form a first hole injection transport layer. Next, the compound of Exemplified Compound B-60 and rubrene were co-evaporated from different vapor deposition sources to a thickness of 20 nm at a vapor deposition rate of 0.2 nm / sec (weight ratio 10: 1), and the second hole injection transport layer was formed. A combined light emitting layer was formed. Next, tris (8-quinolinolato) aluminum was vapor-deposited thereon to a thickness of 50 nm at a vapor deposition rate of 0.2 nm / sec to form a light-emitting layer also serving as an electron injecting and transporting layer. Further, magnesium and silver were co-deposited as a cathode at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio 10: 1) to form an organic electroluminescent device. 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. Initially, yellow light emission of 6.1 V and luminance of 590 cd / m ² was confirmed. The half life of luminance was 1400 hours. Further, the device was allowed to stand at 100 ° C. for 1 hour, and it was confirmed that there was no significant change in light emission characteristics.

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 200 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 using nitrogen gas, further washed with UV / ozone, fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition tank was depressurized to 3 × 10 ⁻⁶ Torr. First, poly (thiophene-2,5-diyl) was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a first hole injection transport layer. After returning the vapor deposition tank to atmospheric pressure, the vapor deposition tank was again decompressed to 3 × 10 ⁻⁶ Torr. Next, the compound of Exemplified Compound B-29 and rubrene were co-evaporated from different vapor deposition sources to a thickness of 55 nm at a vapor deposition rate of 0.2 nm / sec (weight ratio 10: 1), and the second hole injection transport layer was formed. A combined light emitting layer was formed. Next, while maintaining the reduced pressure state, tris (8-quinolinolato) aluminum was deposited thereon to a thickness of 50 nm at a deposition rate of 0.2 nm / sec to form an electron injecting and transporting layer. While maintaining the reduced pressure state, magnesium and silver were further co-deposited as a cathode to a thickness of 200 nm at a deposition rate of 0.2 nm / sec (weight ratio 10: 1) to form a cathode, and an organic electroluminescent device Was made. 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. Initially, yellow light emission of 6.0 V and luminance of 590 cd / m ² was confirmed. The half life of luminance was 1200 hours. Further, the device was allowed to stand at 100 ° C. for 1 hour, and it was confirmed that there was no significant change in light emission characteristics.

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 200 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 using nitrogen gas, further washed with UV / ozone, fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition tank was depressurized to 3 × 10 ⁻⁶ Torr. First, Exemplified Compound B-32 was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a first hole injection transport layer. After returning the vapor deposition tank to atmospheric pressure, the vapor deposition tank was again decompressed to 3 × 10 ⁻⁶ Torr. Next, the compound of Exemplified Compound B-60 and rubrene were co-deposited from different deposition sources to a thickness of 55 nm at a deposition rate of 0.2 nm / sec (weight ratio 10: 1), and the second hole injecting and transporting layer was formed. A combined light emitting layer was formed. Next, tris (8-quinolinolato) aluminum was deposited thereon to a thickness of 50 nm at a deposition rate of 0.2 nm / sec to form an electron injecting and transporting layer. Further, magnesium and silver were co-deposited as a cathode at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio 10: 1) to form an organic electroluminescent device. 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. Initially, yellow light emission of 5.7 V and luminance of 590 cd / m ² was confirmed. The half life of luminance was 1500 hours. Further, the device was allowed to stand at 100 ° C. for 1 hour, and it was confirmed that there was no significant change in light emission characteristics.

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 200 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 using nitrogen gas and further UV / ozone cleaned. Next, on an ITO transparent electrode, a spin coat method is used to spin-coat 40 nm of a 3% by mass dichloroethane solution containing a compound of polycarbonate (weight average molecular weight 39000) and exemplary compound B-31 at a weight ratio of 100: 50. A hole injection transport layer was formed. Next, the glass substrate having this hole injecting and transporting layer was fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition layer was decompressed to 3 × 10 ⁻⁶ Torr. Next, tris (8-quinolinolato) aluminum was vapor-deposited thereon to a thickness of 50 nm at a vapor deposition rate of 0.2 nm / sec to form a light-emitting layer also serving as an electron injecting and transporting layer. Further, magnesium and silver were co-deposited as a cathode at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio 10: 1) to form an organic electroluminescent device. When a DC voltage of 10 V was applied to the produced organic electroluminescent element in a dry atmosphere, a current of 84 mA / cm ² flowed. Green light emission with a luminance of 910 cd / m ² was confirmed. The half life of luminance was 380 hours.

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 200 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 using nitrogen gas and further UV / ozone cleaned. Next, on the ITO transparent electrode, polymethyl methacrylate (weight average molecular weight 25000), the compound of exemplary compound B-50, and tris (8-quinolinolato) aluminum are contained in a weight ratio of 100: 50: 0.5, respectively. A light emitting layer having a thickness of 100 nm was formed by spin coating using a 3% by mass dichloroethane 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 3 × 10 ⁻⁶ Torr. On the light emitting layer, magnesium and silver were co-deposited at a deposition rate of 0.2 nm / sec to a thickness of 200 nm as a cathode (weight ratio 10: 1) to form a cathode, and an organic electroluminescent device was produced. When a DC voltage of 15 V was applied to the produced organic electroluminescent element in a dry atmosphere, a current of 86 mA / cm ² flowed. Green light emission with a luminance of 540 cd / m ² was confirmed. The half life of luminance was 440 hours.

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

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)

A fluorene compound represented by the general formula (1) (Chemical formula 1).

[Wherein, X ₁ and X ₂ represent a halogen atom, and Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ represent a hydrogen atom, a halogen atom or a — (O) nZ group (wherein Z is Represents a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted aryl group, and n represents 0 or 1, and represents R ₁ , R ₂ , R ₃ and R _4. Represents a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. An amine compound represented by the general formula (2) (Chemical formula 2).

[Wherein Y ₁ and Y ₂ are —NAr ₁ Ar ₂ groups (Ar ₁ and Ar ₂ each independently represents a substituted or unsubstituted aryl group), or —N-carbazolyl group, —N-phenoxazinyl group Or represents an —N-phenothiazinyl group, Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ are a hydrogen atom, a halogen atom or a — (O) nZ group (wherein Z is substituted or unsubstituted) Represents a linear, branched or cyclic alkyl group, or a substituted or unsubstituted aryl group, n represents 0 or 1, and R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, substituted Or an unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. The manufacturing method of the amine compound represented by General formula (2) by aminating the halogen atom of the fluorene compound represented by General formula (1). An organic electroluminescence device comprising at least one layer containing at least one amine compound according to claim 2 sandwiched between a pair of electrodes. The organic electroluminescent element according to claim 4, wherein the layer containing the amine compound according to claim 2 is a hole injection transport layer. The organic electroluminescent device according to claim 4, wherein the layer containing the amine compound according to claim 2 is a light emitting layer. The organic electroluminescent device according to claim 4, further comprising a light emitting layer between the pair of electrodes. The organic electroluminescent element according to claim 4, further comprising an electron injecting and transporting layer between the pair of electrodes.

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