JP3983215B2 - 9,9-diphenylfluorene compound and organic electroluminescent device containing the 9,9-diphenylfluorene compound - Google Patents

Description

  The present invention relates to a novel 9,9-diphenylfluorene compound and an organic electroluminescence device comprising the 9,9-diphenylfluorene compound.

In recent years, with the development of displays, display materials with high definition, high brightness, high-speed response, low power consumption, and wide viewing angles are required. As one of them, it has been proposed that an organic electroluminescence element (organic electroluminescence element: organic EL element) using an organic material as a light emitting material is useful.
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. By injecting electrons and holes into the thin film and recombining them, an exciton (Exington) ) And emits light using light emitted when the exciton is deactivated [Non-Patent Document 1]. An organic electroluminescent element can emit light at a low direct current voltage of about several volts to several tens of volts, and is expected to be applied to various light emitting elements, display elements, and the like. However, in general, the light emission luminance is low and the light emission lifetime is short, which is not sufficient for practical use.
As a method for improving the light emission luminance and the light emission lifetime, for example, an organic electroluminescent element using a fluorene compound has been proposed (for example, see Patent Document 1 and Patent Document 2). However, it cannot be said that these light-emitting elements also have sufficiently satisfactory light emission luminance and light emission lifetime, and at present, new and improved compounds are desired.
Appl.Phys.lett., 51,913 (1987) Japanese Patent Laid-Open No. 11-144873 Japanese Patent Laid-Open No. 11-144875

An object of the present invention is to provide a novel 9,9-diphenylfluorene compound. More specifically, for example, it is to provide a 9,9-diphenylfluorene compound that can be suitably used for a hole injection / transport material of an organic electroluminescent device.

  In order to solve the above-mentioned problems, the present inventors have earnestly related to various 9,9-diphenylfluorene compounds, in particular, 9,9-diphenylfluorene compounds that can be suitably used as hole injection / transport materials for organic electroluminescence devices. As a result of studies, the present invention has been completed. That is, the present invention provides <1>: a 9,9-diphenylfluorene compound represented by the general formula (1),

Wherein the R1 ~ R3, each independently represent a hydrogen atom, a straight-chain, branched or cyclic alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group,, Z ₁ ~ Z ₆ Each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, or a substituted group. Or an unsubstituted aralkyl group, and Z ₇ represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, or a substituted group Alternatively, it represents an unsubstituted aralkyl group. ]
<2>: An organic electroluminescence device comprising at least one layer containing at least one 9, 9-diphenylfluorene compound represented by the general formula (1) described in <1> between a pair of electrodes,
<3>: The organic electroluminescent device according to <2>, wherein the layer containing the 9,9-diphenylfluorene compound represented by the general formula (1) according to <1> is a light emitting layer.
<4>: The organic electroluminescent device according to <2>, wherein the layer containing the 9,9-diphenylfluorene compound represented by the general formula (1) according to <1> is a hole injection transport layer,
<5>: The organic electroluminescence device according to <2>, <3>, and <4>, further having a hole injecting and transporting layer between the pair of electrodes.
<6>: The organic electroluminescence device according to any one of <2> to <5>, 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 9,9-diphenylfluorene compound and an organic electroluminescence device having a long emission lifetime and excellent durability.

Hereinafter, the present invention will be described in detail.
The 9,9-diphenylfluorene compound of the present invention is a compound represented by the general formula (1).

[ Wherein, R1 to R3 each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and Z _{1 to} Z ₆ Each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, or a substituted group. Or an unsubstituted aralkyl group, and Z ₇ represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, or a substituted group Alternatively, it represents an unsubstituted aralkyl group. ]

In the 9,9-diphenylfluorene compound represented by the general formula (1), R1 to R3 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted group. Alternatively, it represents an unsubstituted aralkyl group. The aryl group represents a carbocyclic aromatic group and a heterocyclic aromatic group. Similarly, the aryl group in the aralkyl group also represents a carbocyclic aromatic group and a heterocyclic aromatic group.
R1 to R3 are preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted aryl group having 3 to 25 carbon atoms, or a substituted or unsubstituted group having 5 to 16 carbon atoms. An unsubstituted aralkyl group, more preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or 7 carbon atoms A substituted or unsubstituted aralkyl group having ˜12, more preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. Or a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms.

Z _{1 to} Z ₆ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted group. It represents a substituted aryl group or a substituted or unsubstituted aralkyl group. When Z _{1 to} Z ₆ are amino groups, the amino group may have another substituent, and an alkyl group having 1 to 20 carbon atoms, an aryl group having 3 to 20 carbon atoms, or 4 carbon atoms. It may be monosubstituted or disubstituted with a substituent such as -20 aralkyl groups.
In the compound represented by the general formula (1), Z _{1 to} Z ₆ are preferably each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, A linear, branched or cyclic alkoxy group having 1 to 16 carbon atoms, an unsubstituted amino group, an amino group substituted with a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, and a carbon number of 6 to An amino group substituted with a substituted or unsubstituted aryl group having 25, an amino group substituted with a substituted or unsubstituted aralkyl group having 5 to 16 carbon atoms, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms Or a substituted or unsubstituted aralkyl group having 5 to 16 carbon atoms, more preferably a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Straight A branched or cyclic alkoxy group, an amino group substituted with a substituted or unsubstituted aryl group having 6 to 17 carbon atoms, or an amino group substituted with a substituted or unsubstituted aralkyl group having 6 to 17 carbon atoms, A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aralkyl group having 6 to 12 carbon atoms, more preferably a hydrogen atom, a halogen atom, a straight chain having 1 to 8 carbon atoms, A branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group having 1 to 8 carbon atoms, an amino group substituted with a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, and a carbon number of 6 to 10 A substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms.

Z ₇ represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. To express. In the compound represented by the general formula (1), Z ₇ is preferably a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, and a straight chain having 1 to 16 carbon atoms. A chain, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, or a substituted or unsubstituted aralkyl group having 5 to 16 carbon atoms, more preferably a hydrogen atom or a halogen atom. A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or A substituted or unsubstituted aralkyl group having 6 to 12 carbon atoms, more preferably a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and a straight chain having 1 to 8 carbon atoms. chain Branched or cyclic alkoxy group, a substituted or unsubstituted aralkyl group a substituted or unsubstituted aryl group or a 7 to 10 carbon atoms, 6 to 10 carbon atoms.

In the compound represented by the general formula (1), specific examples of the linear, branched or cyclic alkyl group represented by R1 to R3 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n- Butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 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-dimethyl group Heptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, 1-ethyloctyl, n-undecyl, 1-methyldecyl 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 Methylcyclohexyl group, 3-methylcyclohexyl group, 2-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3, 5-dimethylcyclohexyl group,

2,4,6-trimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, 2,6-diisopropylcyclohexyl group, 4-tert-butylcyclohexyl group, 3-tert-butylcyclohexyl group, 4-phenylcyclohexyl group, 2-phenylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclotetradecyl group, methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-hexyloxymethyl group, (2- Ethylbutyloxy) methyl group, n-octyloxymethyl group, n-decyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propyloxyethyl group, 2-isopropyloxyethyl group, 2 -N-butyloxyethyl group, 2-n-pent Oxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2′-ethylhexyl) Oxy) ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl Group, 3-ethoxypropyl group, 3-n-propyloxypropyl group, 3-isopropyloxypropyl group, 3- (n-butyloxy) propyl group, 3- (n-pentyloxy) propyl group, 3- (n- (Hexyloxy) propyl group, 3- (2′-ethylbutyloxy) 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-propyloxybutyl group, 4-isopropyloxybutyl group, 4-n-butyloxybutyl group, 4-n-hexyloxybutyl group, 4-n -Octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group, 5-n-propyloxypentyl group, 6-ethoxyhexyl group 6-isopropyloxyhexyl group, 6-n-butyloxyhexyl group, 6-n-hexyloxyhexyl group, -n- tetradecyloxy hexyl group, 4-methoxy cyclohexyl group,

7-ethoxyheptyl group, 7-isopropyloxyheptyl group, 8-methoxyoctyl group, 10-methoxydecyl group, 10-n-butyloxydecyl group, 12-ethoxydodecyl group, 12-isopropyloxidedecyl group, tetrahydrofurfuryl Group, 2- (2'-methoxyethoxy) ethyl group, 2- (2'-ethoxyethoxy) ethyl group, 2- (2'-n-butyloxyethoxy) 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′-fluorobenzyl) Oxy) ethyl group, 2- (4′-chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 3- (4′-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, 2- (benzyloxy) Methoxy) 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, 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-phenyloxybutyl group, 4- (2′-ethylphenyloxy) butyl group, 5- (4′-tert) -Butylphenyloxy) pentyl group, 6- (2'-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 1 -(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-octylthioethyl 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-ethylthio Pentyl 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-benzylthioethyl group, 3- (4′-methylbenzyl) Thio) 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, 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-chlorooctyl 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-hydroxydecyl And linear, branched or cyclic alkyl groups such as a group, 12-hydroxydodecyl group and 2-hydroxycyclohexyl group.

In the compound represented by the general formula (1), specific examples of the substituted or unsubstituted aryl group of R1 to R3 include, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 9 -Anthracenyl group, 9-phenanthryl group, 9-fluorenyl group, 4-quinolyl group, 5-pyridyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 2-pyrimidyl group, 4-pyrimidine group, 5 -Pyrimidyl group, 2-pyridazinyl group, 2-pyrazinyl group, 3-furyl group, 2-furyl group, 3-thienyl group, 2-thienyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzothiophenyl group 2-benzofuryl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzoimidazolyl group,
4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butylphenyl group, 2-sec-butylphenyl group, 4-tert-butylphenyl group, 3-tert-butylphenyl Group, 2-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4-n-heptylphenyl group, 4 -N-octylphenyl group, 4- (2'-ethylhexyl) phenyl group, 4-tert-octylphenyl group, 4-n-nonylphenyl group, 4 n- decyl phenyl group, 4-n- dodecyl phenyl group, 4-n- tetradecyl phenyl group, 4-n- hexadecyl phenyl group,

4-n-octadecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4- (4′-tert-butylcyclohexyl) phenyl group, 4- (4′-methylcyclohexyl) phenyl group, 3-cyclohexylphenyl Group, 2-cyclohexylphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 1-phenyl-2-naphthyl group, 9-methyl-10-anthracenyl group, 9-tert-butyl -10-anthracenyl group, 9-methyl-10-phenanthryl group, 9-tert-butyl-10-phenanthryl group, 9-phenyl-10-phenanthryl group, 1-pyrenyl group, 2,3-dimethylphenyl group, 2, 4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5- Methylphenyl group, 2,6-dimethylphenyl group, 2,3,5-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,4-diethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 2,6-diethylphenyl group, 2,6-diisopropylphenyl group, 2,6-diisobutylphenyl group, 2,4-di-tert-butylphenyl group, 2,5- Di-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 2,4-dineopentylphenyl group, 2,5-di-tert-pentylphenyl group, 4,6-di-tert- Butyl-2-methylphenyl group, 5-tert-butyl-2-methylphenyl group, 4-tert-butyl-2,6-dimethylphenyl group, 2,3,5,6-tetramethylphenyl group, 5-indanyl Base 1,2,3,4-tetrahydro-5-naphthyl, 1,2,3,4-tetrahydro-6-naphthyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group,

4-ethoxyphenyl group, 2-ethoxyphenyl group, 3-n-propyloxyphenyl group, 4-isopropyloxyphenyl group, 2-isopropyloxyphenyl group, 4-n-butyloxyphenyl group, 4-isobutyloxyphenyl group 2-isobutyloxyphenyl group, 2-sec-butyloxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2′-ethylbutyloxy) phenyl group, 4-n-octyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4 -N-tetradecyloxyphenyl group, 4-n-hexadecyloxyphenyl group 4-n-octadecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-methoxy-1-naphthyl group, 4-methoxy-1-naphthyl group, 4-n-butyloxy-1- Naphthyl group, 5-ethoxy-1-naphthyl group, 6-ethoxy-2-naphthyl group, 6-n-butyloxy-2-naphthyl group, 6-n-hexyloxy-2-naphthyl group, 7-methoxy-2- Naphthyl group, 7-n-butyloxy-2-naphthyl group, 2,3-dimethoxyphenyl 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-butyloxyphenyl group, -Methoxy-4-methylphenyl group, 2-methoxy-5-methylphenyl group, 2-methyl-4-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 3 -Ethyl-5-methoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy-6-ethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-fluorophenyl group, 3-fluorophenyl Group, 2-fluorophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 2-bromophenyl group, 4-chloro-1-naphthyl group, 4-chloro-2- Naphthyl group, 6-bromo-2-naphthyl group, 2,3-difluorophenyl group, 2,4-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, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,5-dibromophenyl group, 2,4,6-trichlorophenyl group, 2,3,6-tribromo Phenyl group, 3,4,5-trifluorophenyl 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, 4-fluoro-2-methylphenyl group 5-fluoro-2-methylphenyl group, 2-chloro-4-methylphenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 3-chloro-2-methylphenyl group, 4-chloro-2-methylphenyl group, 4-chloro-3-methylphenyl group, 2-chloro-4,6-dimethylphenyl group, 2-fluoro-4-methoxyphenyl group, 2-fluoro-6-methoxyphenyl Group, 3-fluoro-4-ethoxyphenyl group, 5-chloro-2-methoxyphenyl group, 6-chloro-3-methoxyphenyl group, 5-chloro-2,4-dimethoxyphenyl group, 2-chloro-4- Nitrophenyl group, 4-chloro-2-nitrophenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2-trifluoromethyl Phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 4-trifluoromethyloxyphenyl group, 4-allylphenyl group, 2-allylphenyl group, 2-isopropenylphenyl group, 4-benzylphenyl group, 2-benzylphenyl group, 4- (4′-methylbenzyl) phenyl group, 4-cumylphenyl group, 4- (4′-methoxycumyl) phenyl group,

4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4′-methylphenyl) phenyl group, 4- (4′-ethylphenyl) phenyl group, 4- (4′-isopropylphenyl) ) Phenyl group, 4- (4′-tert-butylphenyl) phenyl group, 4- (4′-n-hexylphenyl) phenyl group, 4- (4′-n-octylphenyl) phenyl group, 4- (4 '-Methoxyphenyl) phenyl group, 4- (4'-ethoxyphenyl) phenyl group, 4- (4'-n-butoxyphenyl) phenyl group, 2- (2'-methoxyphenyl) phenyl group, 4- (4 '-Fluorophenyl) phenyl group, 4- (4'-chlorophenyl) phenyl group, 3-methyl-4-phenyl group, 2-methoxy-5-phenylphenyl group, 3-methoxy -4-phenylphenyl group, 4-methoxymethylphenyl group, 4-ethoxymethylphenyl group, 4-n-butyloxymethylphenyl group, 3-methoxymethylphenyl group, 4- (2'-methoxyethyl) phenyl group, 4- (2′-ethoxyethyloxy) phenyl group, 4- (2′-n-butyloxyethyloxy) phenyl group, 4- (3′-ethoxypropyloxy) phenyl group, 4-vinyloxyphenyl group, 4 -Allyloxyphenyl group, 3-allyloxyphenyl group, 4- (4'-pentenyloxy) phenyl group, 4-allyloxy-1-naphthyl group, 4-allyloxymethylphenyl group, 4- (2'-allyloxy) Ethyloxy) phenyl group, 4-benzyloxyphenyl group, 2-benzyloxyphenyl group, 4-phenethyloxy Enyl group, 4- (4′-chlorobenzyloxy) phenyl group, 4- (4′-methylbenzyloxy) phenyl group, 4- (4′-methoxybenzyloxy) phenyl group, 4- (3′-ethoxybenzyl) Oxy) phenyl group, 4-benzyloxy-1-naphthyl group, 5- (4′-methylbenzyloxy) -1-naphthyl group, 6-benzyloxy-2-naphthyl group, 6- (4′-methylbenzyloxy) ) -2-naphthyl group, 7-benzyloxy-2-naphthyl group, 4- (benzyloxymethyl) phenyl group, 4- (2′-benzyloxyethyloxy) phenyl group, 4-phenyloxyphenyl group, 3- Phenyloxyphenyl group, 2-phenyloxyphenyl group, 4- (4′-methylphenyloxy) phenyl group,

4- (4′-methoxyphenyloxy) phenyl group, 4- (4′-chlorophenyloxy) phenyl group, 4-phenyloxy-1-naphthyl group, 6-phenyloxy-2-naphthyl group, 7-phenyloxy- 2-naphthyl group, 4-phenyloxymethylphenyl group, 4- (2′-phenyloxyethoxy) phenyl group, 4- [2 ′-(4′-methylphenyloxy) ethoxy] phenyl group, 4- [2 ′ -(4'-methoxyphenyloxy) ethoxy] phenyl group, 4- [2 '-(4'-chlorophenyloxy) ethoxy] phenyl group, 4-acetylphenyl group, 3-acetylphenyl group, 2-acetylphenyl group, 4-ethylcarbonylphenyl group, 2-ethylcarbonylphenyl group, 4-n-butylcarbonylphenyl group, 4-n-hexyl A carbonylphenyl group, a 4-n-octylcarbonylphenyl group, a 4-cyclohexylcarbonylphenyl group, a 4-acetyl-1-naphthyl group, a 6-acetyl-2-naphthyl group, a 6-n-butylcarbonyl-2-naphthyl group, 4-allylcarbonylphenyl group, 4-benzylcarbonylphenyl group, 4- (4′-methylbenzyl) carbonylphenyl group, 4-phenylcarbonylphenyl group, 4- (4′-methylphenyl) carbonylphenyl group, 4- ( 4'-chlorophenyl) carbonylphenyl group, 4-phenylcarbonyl-1-naphthyl group, 4-methoxycarbonylphenyl group, 2-methoxycarbonylphenyl group, 4-ethoxycarbonylphenyl group, 3-ethoxycarbonylphenyl group, 4-n -Propyloxycarbonylphenol Group, 4-n-butyloxycarbonylphenyl group, 4-n-hexyloxycarbonylphenyl group, 4-n-decyloxycarbonylphenyl group, 4-cyclohexyloxycarbonylphenyl group, 4-ethoxycarbonyl-1-naphthyl group 6-methoxycarbonyl-2-naphthyl group, 6-n-butyloxycarbonyl-2-naphthyl group, 4-allyloxycarbonylphenyl group, 4-benzyloxycarbonylphenyl group, 4- (4′-chlorobenzyl) oxy Carbonylphenyl group, 4-phenethyloxycarbonylphenyl group, 6-benzyloxycarbonyl-2-naphthyl group, 4-phenyloxycarbonylphenyl group,

4- (4′-ethylphenyl) oxycarbonylphenyl group, 4- (4′-chlorophenyl) oxycarbonylphenyl group, 4- (4′-ethoxyphenyl) oxycarbonylphenyl group, 6-phenyloxycarbonyl-2-naphthyl Group, 4-acetyloxyphenyl group, 3-acetyloxyphenyl group, 2-acetyloxyphenyl group, 4-ethylcarbonyloxyphenyl group, 2-ethylcarbonyloxyphenyl group, 4-n-propylcarbonyloxyphenyl group, 4 -N-pentylcarbonyloxyphenyl group, 4-n-octylcarbonyloxyphenyl group, 4-cyclohexylcarbonyloxyphenyl group, 3-cyclohexylcarbonyloxyphenyl group, 4-acetyloxy-1-naphthyl group, 4-n-butyl Carbonyl Xyl-1-naphthyl group, 5-acetyloxy-1-naphthyl group, 6-ethylcarbonyloxy-2-naphthyl group, 7-acetyloxy-2-naphthyl group, 4-allylcarbonyloxyphenyl group, 4-benzylcarbonyl Oxyphenyl group, 4-phenethylcarbonyloxyphenyl group, 6-benzylcarbonyloxy-2-naphthyl group, 4-phenylcarbonyloxyphenyl group, 4- (4′-methylphenyl) carbonyloxyphenyl group, 4- (2 ′ -Methylphenyl) carbonyloxyphenyl group, 4- (4'-chlorophenyl) carbonyloxyphenyl group, 4- (2'-chlorophenyl) carbonyloxyphenyl group, 4-phenylcarbonyloxy-1-naphthyl group, 6-phenylcarbonyl Oxy-2-naphthyl group, 7- Enylcarbonyloxy-2-naphthyl group, 4-methylthiophenyl group, 2-methylthiophenyl group, 2-ethylthiophenyl group, 3-ethylthiophenyl group, 4-n-propylthiophenyl group, 2-isopropylthiophenyl group 4-n-butylthiophenyl group, 2-isobutylthiophenyl group, 2-neopentylphenyl group, 4-n-hexylthiophenyl group, 4-n-octylthiophenyl group, 4-cyclohexylthiophenyl group, 4 -Benzylthiophenyl group,

3-benzylthiophenyl group, 2-benzylthiophenyl group, 4- (4′-chlorobenzylthio) phenyl group, 4-phenylthiophenyl group, 3-phenylthiophenyl group, 2-phenylthiophenyl group, 4- (4′-methylphenylthio) phenyl group, 4- (3′-methylphenylthio) phenyl group, 4- (4′-methoxyphenylthio) phenyl group, 4- (4′-chlorophenylthio) phenyl group, 2 -Ethylthio-1-naphthyl group, 4-methylthio-1-naphthyl group, 6-ethylthio-2-naphthyl group, 6-phenylthio-2-naphthyl group, 4-nitrophenyl group, 3-nitrophenyl group, 2-nitro Phenyl group, 3,5-dinitrophenyl group, 4-nitro-1-naphthyl group, 4-formylphenyl group, 3-formylphenyl group, 2- Rumylphenyl group, 4-formyl-1-naphthyl group, 1-formyl-2-naphthyl group, 4-pyrrolidinophenyl group, 4-piperidinophenyl group, 4-morpholinophenyl group, 4- (N-ethylpiperazino ) Phenyl group, 4-pyrrolidino-1-naphthyl group, 4-aminophenyl group, 3-aminophenyl group, 2-aminophenyl group, 4- (N-methylamino) phenyl group, 3- (N-methylamino) Phenyl group, 4- (N-ethylamino) phenyl group, 2- (N-isopropylamino) phenyl group, 4- (Nn-butylamino) phenyl group, 2- (Nn-butylamino) phenyl group 4- (Nn-octylamino) phenyl group, 4- (Nn-dodecylamino) phenyl group, 4- (N-benzylamino) phenyl group, 4- (N-phenyl) Amino) phenyl group, 2-(N-phenylamino) phenyl group, 4-(N, N-dimethylamino) phenyl group,

3- (N, N-dimethylamino) phenyl group, 4- (N, N-diethylamino) phenyl group, 2- (N, N-dimethylamino) phenyl group, 2- (N, N-diethylamino) phenyl group, 4- (N, N-di-n-butylamino) phenyl group, 4- (N, N-di-n-hexylamino) phenyl group, 4- (N-cyclohexyl-N-methylamino) phenyl group, 4 -(N, N-diethylamino) -1-naphthyl group, 4- (N-benzyl-N-phenylamino) phenyl group, 4- (N, N-diphenylamino) phenyl group, 4- [N-phenyl-N -(4-Methylphenyl) amino] phenyl group, 4- [N, N-di (3'-methylphenyl) amino] phenyl group, 4- [N, N-di (4'-methylphenyl) amino] phenyl Group, 4- [N, N- (4′-methoxyphenyl) amino] phenyl group, 2- (N, N-diphenylamino) phenyl group, 4-hydroxyphenyl group, 3-hydroxyphenyl group, 2-hydroxyphenyl group, 4-methyl-3-hydroxy Phenyl group, 6-methyl-3-hydroxyphenyl group, 2-hydroxy-1-naphthyl group, 8-hydroxy-1-naphthyl group, 4-hydroxy-1-naphthyl group, 1-hydroxy-2-naphthyl group, 6 Examples include substituted or unsubstituted aryl groups such as -hydroxy-2-naphthyl group, 4-cyanophenyl group, 2-cyanophenyl group, 4-cyano-1-naphthyl group, and 6-cyano-2-naphthyl group. it can.

  In the compound represented by the general formula (1), specific examples of the substituted or unsubstituted aralkyl group of R1 to R3 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-ethylbenzyl group, 2-ethylbenzyl group, 4-isopropylbenzyl group, 4-tert-butylbenzyl group, 2-tert-butylbenzyl group, 4-tert-pentylbenzyl group, 4-cyclohexylbenzyl group, 4 -N-octylbenzyl group, 4-tert-octylbenzyl group, 4-allylbenzyl group, 4-benzylbenzyl group, 4-phenethylbenzene Gil group, 4-phenylbenzyl group, 4- (4′-methylphenyl) benzyl group, 4-methoxybenzyl group, 2-methoxybenzyl group, 2-ethoxybenzyl group, 4-n-butoxybenzyl group, 4-n -Heptyloxybenzyl group, 4-n-decyloxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-isobutyloxymethylbenzyl 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-hydroxyben Zyl group, 4-hydroxy-3-methoxybenzyl group, 4-fluorobenzyl group, 2-fluorobenzyl group, 4-chlorobenzyl group, 3-chlorobenzyl group, 2-chlorobenzyl group, 3,4-dichlorobenzyl group And substituted or unsubstituted aralkyl groups such as 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group and 2-naphthylmethyl group.

In the compound represented by the general formula (1), examples of the halogen atom represented by Z _{1 to} Z ₇ include a fluorine atom, a chlorine atom, and a bromine atom.
In the compound represented by the general formula (1), specific examples of the linear, branched or cyclic alkyl group of Z _{1 to} Z ₇ include specific examples of the linear, branched or cyclic alkyl group of R 1 to R 3. The linear, branched or cyclic alkyl group mentioned as an example can be mentioned.
In the compound represented by the general formula (1), specific examples of the linear, branched or cyclic alkoxy group represented by Z _{1 to} Z ₇ include, for example, a linear, branched or cyclic alkyl group represented by R 1 to R 3. Specific examples include linear, branched or cyclic alkoxy groups containing a linear, branched or cyclic alkyl group.

In the compound represented by the general formula (1), examples of the substituted or unsubstituted amino group of Z _{1 to} Z ₆ include an amino group, an N-methylamino group, an N-ethylamino group, and an Nn-propyl group. Amino group, N-isopropylamino group, Nn-butylamino group, N-isobutylamino group, N-sec-butylamino group, N-tert-butylamino group, Nn-pentylamino group, N-cyclopentyl Amino group, Nn-hexylamino group, N-cyclohexylamino group, N-benzylamino group, N-phenethylamino group, N-phenylamino group, N- (1-naphthyl) amino group, N- (2- Naphthyl) amino group, N- (4-phenylphenyl) amino group, N- (3-phenylphenyl) amino group, N- (2-phenylphenyl) amino group, N- (4-methylphenyl) Mino group, N- (2-methylphenyl) amino group, N- (2-anthranyl) amino group, N- (9-anthranyl) amino group, N, N-dimethylamino group, N, N-diethylamino group, N , N-di-n-propylamino group, N, N-di-isopropylamino group, N, N-di-n-butylamino group, N, N-di-isobutylamino group, N, N-di-sec -Butylamino group, N, N-di-n-pentylamino group, N, N-dicyclopentylamino group, N, N-dicyclohexylamino group, N, N-dibenzylamino group, N, N-diphenethylamino Group, N-methyl-N-ethylamino group, N-methyl-Nn-propylamino group, N-methyl-N-isopropylamino group, N-methyl-Nn-butylamino group, N-methyl- N-tert-butylamino group, N-methyl-N-cyclopentylamino group, N-methyl-N-cyclohexylamino group,

N-methyl-N-benzylamino group, N-methyl-N-phenethylamino group, N-ethyl-N-tert-butylamino group, N-ethyl-N-cyclohexylamino group, N-ethyl-N-benzylamino Group, N-isopropyl-N-cyclopentylamino group, N-isopropyl-N-cyclohexylamino group, N-isopropyl-N-benzylamino group, N-tert-butyl-N-cyclohexylamino group, N-tert-butyl-N -Benzylamino group, N-cyclopentyl-N-benzylamino group, N-cyclohexyl-N-benzylamino group, N, N-diphenylamino group, N, N-di (1-naphthyl) amino group, N, N- Di (2-naphthyl) amino group, N, N-di (4-phenylphenyl) amino group, N, N- (4-methylphenyl) amino group, N, N Di (3-methylphenyl) amino group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group, N-phenyl-N- (4-phenylphenyl) Amino group, N-phenyl-N- (4-methylphenyl) amino group, N- (1-naphthyl) -N- (4′-phenylphenyl) amino group, N-phenyl-N- [4- (9 ′) -Fluorenyl) phenyl] amino group,

N- (2-tert-butyl-phenyl) -N- [4 ′-(9 ″ -fluorenyl) phenyl] amino group, N- (3-tert-butyl-phenyl) -N- [4 ′-(9 '' -Fluorenyl) phenyl] amino group, N- (4-tert-butyl-phenyl) -N- [4 '-(9' '-fluorenyl) phenyl] amino group, N- (1-naphthyl) -N- [4 '-(9' '-fluorenyl) phenyl] amino group, N- (2-naphthyl) -N- [4'-(9 ''-fluorenyl) phenyl] amino group, N- (9-anthracenyl)- N- [4 ′-(9 ″ -fluorenyl) phenyl] amino group, N- (10-methyl-9-anthracenyl) -N- [4 ′-(9 ″ -fluorenyl) phenyl] amino group, N- ( 10-phenyl-9-anthracenyl) -N- [4 ′-(9 ″ -fluorenyl) Enyl] amino group, N- (10-tert-butyl-9-anthracenyl) -N- [4 ′-(9 ″ -fluorenyl) phenyl] amino group, N- (9-phenanthryl) -N- [4′- (9 ″ -fluorenyl) phenyl] amino group, N- (10-methylphenanthren-9-yl) -N- [4 ′-(9 ″ -fluorenyl) phenyl] amino group, N- (10-tert- Butyl-phenanthren-9-yl) -N- [4 ′-(9 ″ -fluorenyl) phenyl] amino group, N- (10-phenylphenanthren-9-yl) -N- [4 ′-(9 ″ -Fluorenyl) phenyl] amino group, N- (2-methylphenyl) -N- [4 '-(9' '-fluorenyl) phenyl] amino group,

N- (3-methylphenyl) -N- [4 ′-(9 ″ -fluorenyl) phenyl] amino group, N- (4-methylphenyl) -N- [4 ′-(9 ″ -fluorenyl) phenyl ] Amino group, N- (2-methylphenyl) -N- [4 '-(9' '-fluorenyl) -2'-methylphenyl] amino group, N- (2-methoxyphenyl) -N- [4' -(9 ''-fluorenyl) phenyl] amino group, N- (3-methoxyphenyl) -N- [4 '-(9' '-fluorenyl) phenyl] amino group, N- (4-methoxyphenyl) -N -[4 '-(9' '-fluorenyl) phenyl] amino group, N- (2-fluorophenyl) -N- [4'-(9 ''-fluorenyl) phenyl] amino group, N- (3-fluoro Phenyl) -N- [4 ′-(9 ″ -fluorenyl) phenyl] a Examples include a mino group, N- (4-fluorophenyl) -N- [4 '-(9 "-fluorenyl) phenyl] amino group, N-carbazolyl group, and 3-tert-butyl-N-carbazolyl group.

In the compound represented by the general formula (1), as specific examples of the substituted or unsubstituted aryl group represented by Z _{1 to} Z ₇ , the substituted or non-substituted aryl groups represented by R1 to R3 are exemplified. An unsubstituted aryl group can be mentioned.
In the compound represented by the general formula (1), as specific examples of the substituted or unsubstituted aralkyl group of Z _{1 to} Z ₇ , the substituted or unsubstituted aralkyl groups exemplified as the substituted or unsubstituted aralkyl group of R 1 to R 3 can be used. An unsubstituted aralkyl group can be mentioned.
Specific examples of the 9,9-diphenylfluorene compound represented by the general formula (1) according to the present invention include the following compounds, but the present invention is not limited thereto. .

  The 9,9-diphenylfluorene compound represented by the general formula (1) of the present invention can be produced, for example, by the steps shown below.

  Production of 9,9-diphenylfluorene compound represented by general formula (1)

[Wherein, Z _{1 to} Z ₇ and R _{1 to} R 3 represent the same meaning as in general formula (1), and X represents a halogen atom]
That is, a 9,9-diphenylfluorene derivative represented by the general formula (A) and a halogenofluorene derivative represented by the general formula (B) are converted into a palladium catalyst [for example, palladium acetate / tri-tert-butylphosphine, palladium acetate / Produced by reacting in the presence of triphenylphosphine, tris (dibenzylideneacetone) dipalladium / tri-tert-butylphosphine] and a base (eg sodium-tert-butoxide, potassium carbonate, cesium carbonate, potassium-tert-butoxide) can do.
In addition, the compound represented by general formula (A) can be manufactured by the following processes (Formula 25), for example.

[Wherein, Z _{4 to} Z ₇ and R 3 represent the same meaning as in the general formula (1), and X represents a halogen atom. ]
That is, after reacting a fluorenone derivative represented by the general formula (C) with a Grignard reagent to produce a compound represented by the general formula (D), an aniline derivative and an acid [for example, p-toluenesulfonic acid, acetic acid, 35 % Hydrochloric acid aqueous solution, 50% sulfuric acid aqueous solution] and heating to obtain a compound represented by the general formula (E). The 9,9-diphenylfluorene derivative represented by the general formula (E) and the halogen compound represented by R3-X are converted into a palladium catalyst [for example, palladium acetate / tri-tert-butylphosphine, palladium acetate / triphenylphosphine, Tris (dibenzylideneacetone) dipalladium / tri-tert-butylphosphine, 1,1-bis (diphenylphosphinoferrocene) palladium dichloromethane complex / 1,1-bis (diphenylphosphinoferrocene)], and base (eg, sodium- By reacting in the presence of tert-butoxide, potassium carbonate, cesium carbonate, potassium-tert-butoxide), a 9,9-diphenylfluorene derivative represented by the general formula (A) can be produced.
Moreover, the halogen nofluorene derivative represented by general formula (B) can be manufactured according to the following process (Formula 26), for example.

[Wherein, Z _{1 to} Z ₃ and R _{1 to} R 2 represent the same meaning as in the general formula (1), X represents a halogen atom, and H represents hydrogen. ]
That is, [1-1] When R1 and R2 are the same linear, branched or cyclic alkyl group or a substituted or unsubstituted aralkyl group: a fluorene derivative represented by the general formula (F) and R1-X or The compound represented by the general formula (J) can be produced by reacting the halide represented by R2-X in the presence of a base (for example, n-butyllithium, sodium hydroxide, sodium hydride).
[1-2] When R1, R2 are different linear, branched or cyclic alkyl groups or substituted or unsubstituted aralkyl groups: fluorene derivatives represented by general formula (F) and R1-X A compound represented by the general formula (G) can be produced by reacting a halide in the presence of a base (for example, n-butyllithium, sodium hydroxide, sodium hydride). Similarly, a fluorene derivative represented by the general formula (J) is obtained by allowing a compound represented by the general formula (G) and a halide represented by R2-X to act in the presence of a base.
[2] When R1 or R2 is a substituted or unsubstituted aryl group: A fluorenone derivative represented by the general formula (H) is reacted with a Grignard reagent to produce a compound represented by the general formula (K), followed by substitution. A mixture of an aromatic compound represented by the group R2-H and an acid [for example, p-toluenesulfonic acid, acetic acid, 35% hydrochloric acid aqueous solution, 50% sulfuric acid aqueous solution], which is represented by the general formula (J) by heating. The fluorene derivative is obtained. Presence of a fluorene derivative represented by the general formula (J) with a copper compound [eg, copper powder, copper chloride, copper iodide] and a base (eg, sodium-tert-butoxide, potassium carbonate, cesium carbonate, potassium-tert-butoxide) Then, the halogenofluorene derivative represented by the general formula (B) can be produced by reacting with Z ₁ —H.

Next, the organic electroluminescent element of the present invention will be described. The organic electroluminescent element of the present invention is formed by sandwiching at least one layer containing at least one 9,9-diphenylfluorene compound represented by the general formula (1) between a pair of electrodes. An organic electroluminescent element is usually formed by sandwiching at least one light emitting layer containing at least one light emitting component between a pair of electrodes. A hole injection / transport layer and / or an electron injection containing a hole injection component, if 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 9,9-diphenylfluorene compound represented by the general formula (1) is preferably used as a component of the hole injection transport layer and / or the light emitting layer, and the hole injection transport. More preferably, it is used as a component of the layer.
In the organic electroluminescent element of the present invention, the 9,9-diphenylfluorene compound represented by the general formula (1) may be used alone or in combination.

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

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

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

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

In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injecting and transporting layer, 4 is a light emitting layer, 5 is an electron injecting and transporting layer, 6 is a cathode, and 7 is a power source.
The organic electroluminescent element of the present invention is preferably supported by the substrate 1, and the substrate is not particularly limited, but is preferably a transparent or translucent substrate, 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, and ITO (indium / tin / tin). Examples thereof include oxide (Indium Tin Oxide), polythiophene, and polypyrrole. 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 may be a 9,9-diphenylfluorene compound represented by the general formula (1) or another compound having a hole injecting and transporting function (for example, phthalocyanine derivatives, triarylamine derivatives, triarylmethane derivatives) Oxazole derivatives, hydrazone derivatives, stilbene derivatives, pyrazoline derivatives, polysilane derivatives, polyphenylene vinylene and derivatives thereof, polythiophene and derivatives thereof, poly-N-vinylcarbazole and the like.
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 a 9,9-diphenylfluorene compound represented by the general formula (1) in the hole injecting and transporting layer. As a compound having a hole injecting and transporting function other than the 9,9-diphenylfluorene compound represented by the general formula (1) of the present invention that can be used in the organic electroluminescence device of the present invention, a triarylamine derivative ( For example, 4,4′-bis [N-phenyl-N- (4 ″ -methylphenyl) amino] -1,1′-biphenyl, 4,4′-bis [N-phenyl-N- (3 ″ -methyl) Phenyl) amino] -1,1′-biphenyl, 4,4′-bis [N-phenyl-N- (3 ″ -methoxyphenyl) amino] -1,1′-biphenyl, 4,4′-bis [N -Phenyl-N- (1 "-naphthyl) amino] -1,1'-biphenyl, 3,3'-dimethyl-4,4'-bis [N-phenyl-N- (3" -methylphenyl) amino] -1,1'-biphenyl, 1, -Bis [4 '-[N, N-di (4 "-methylphenyl) amino] phenyl] cyclohexane, 9,10-bis [N- (4'-methylphenyl) -N- (4" -n-butyl) Phenyl) 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- (diphenylamino) phenyl] -N, N′-diphenyl-1,4-diaminobenzene, 5,5 ″ -bis [4- (bis [4-methylphenyl] amino] phenyl -2, 2 ': 5', "-Terthiophene, 1,3,5-tris (diphenylamino) benzene, 4,4 ', 4" -tris (N-carbazolyl) triphenylamine, 4,4', 4 "-tris [N, N- Bis (4 "'-tert-butylbiphenyl-4" "-yl) amino] triphenylamine, 1,3,5-tris [N- (4'-diphenylamino] benzene, polythiophene and its derivatives, poly- N-vinylcarbazole and its derivatives are more preferred.

When the 9,9-diphenylfluorene compound represented by the general formula (1) and another compound having a hole injection function are used in combination, the 9,9-diphenyl fluorene compound represented by the general formula (1) in the hole injection transport layer is used. The content of the 9-diphenylfluorene compound is preferably 0.1% by mass or more, more preferably 0.5 to 99.9% by mass, and still more preferably 3 to 97% by 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 includes at least a compound having a light emitting function other than the 9,9-diphenylfluorene compound represented by the general formula (1) using the 9,9-diphenylfluorene compound represented by the general formula (1) as a host material. A compound having a light emitting function other than the 9,9-diphenylfluorene compound represented by the general formula (1) can be used as at least one kind of host material. And a 9,9-diphenylfluorene compound represented by the above formula can be used as a guest material.
As a compound (guest material / host material) having a light emitting function other than the 9,9-diphenylfluorene compound represented by the general formula (1), for example, an acridone derivative, a quinacridone derivative, a diketopyrrolopyrrole derivative, a polycyclic aroma Group compounds [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 (eg, holes Examples of the compound having an in-transport function include the compounds described above), organometallic complexes [for example, tris (8-quinolinolato) aluminum, bis (10-benzo [h] quinolinolato) beryllium, 2- (2′-hydroxy Phenyl) benzothiazole zinc salt, zinc salt of 4-hydroxyacridine, zinc salt of 3-hydroxyflavone, beryllium salt of 5-hydroxyflavone, aluminum salt of 5-hydroxyflavone], stilbene derivatives [eg, 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 (eg DCM1, DCM2), oxazone derivatives (eg Nile Red), benzothiazole derivatives, benzo Oxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamic acid ester derivatives, poly-N-vinylcarbazole and its derivatives, polythiophene and its derivatives, polyphenylene and its derivatives, polyfluorene and Derivatives thereof, polyphenylene vinylene and derivatives thereof, poly-biphenylene vinylene and derivatives thereof, poly terpolymers phenylene vinylene and derivatives thereof, poly naphthylene vinylene and its derivatives, and polythienylenevinylene and derivatives thereof. As a compound having a light emitting function other than the 9,9-diphenylfluorene compound represented by the general formula (1) (guest material / host material), an acridone derivative, a quinacridone derivative, a polycyclic aromatic compound, a triarylamine derivative, Organometallic complexes and stilbene derivatives are preferred, and polycyclic aromatic compounds and organometallic complexes are more preferred.

The organic electroluminescent element of the present invention preferably contains a 9,9-diphenylfluorene compound represented by the general formula (1) as a host material in the light emitting layer.
When the 9,9-diphenylfluorene compound represented by the general formula (1) is used as a host material in combination with a compound having a light emitting function (guest material), it is represented by the general formula (1) occupied in the light emitting layer. The content of the 9,9-diphenylfluorene compound is preferably 99.9 to 80% by mass, and more preferably 99 to 90% by mass.
A host material may be used independently and may be used together.
Moreover, a guest material may be used independently and may be used together.
When a plurality of host materials are used in combination, the ratio of the 9,9-diphenylfluorene compound represented by the general formula (1) of the present invention to the entire host material is preferably 99 to 10% by mass, more preferably 90 to 20% by mass.
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 organoaluminum complexes such as tris (8-quinolinolato) aluminum, organic beryllium complexes such as bis (10-benzo [h] quinolinolato) beryllium, beryllium salts 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 a hole injecting and transporting layer, a light emitting layer, and an electron injecting and transporting layer is formed using a plurality of compounds by vacuum deposition, the temperature of each boat containing the compounds is individually controlled and co-evaporated. It is preferable to do.

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

Examples of binder resins that can be used in each layer such as a hole injecting and transporting layer, a light emitting layer, and an electron injecting and transporting layer include poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl methacrylate, poly Methyl acrylate, polyether, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, polyphenylene oxide, polyethersulfone, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, Examples thereof include polymer compounds such as polythienylene vinylene and its derivatives. Binder resins may be used alone or in combination. 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 Illustrative Compound 4 [1]: Production of 2-bromo-9,9-dimethylfluorene To a solution of 49 g (0.20 mol) of 2-bromofluorene in N, N-dimethylformamide (100 ml), 16 g of sodium hydride (40 % Liquid paraffin additive, 0.40 mol) was added. After stirring at 25 ° C. for 1 hour, 57 g (0.40 mol) of iodomethyl was added dropwise at 25 ° C. After stirring at 25 ° C. for 6 hours, 200 g of water was added and stirred for 3 hours. The precipitated crystals were separated by filtration and washed with water to obtain 47.2 g of crude crystals. Furthermore, the crude crystals were recrystallized with 500 ml of isopropanol to obtain 43.1 g of 2-bromo-9,9-dimethylfluorene.
[2]: Production of 9-hydroxy-9-phenylfluorene To a solution of 160 g (0.89 mol) of 9-fluorenone in tetrahydrofuran (800 ml), 750 g of phenylmagnesium bromide (32% tetrahydrofuran solution, 1.33 mol) was added dropwise at 0 ° C. After stirring for 8 hours at 25 ° C., a 10% aqueous hydrochloric acid solution (300 ml) was added. The organic layer was separated and concentrated, and the residue was dissolved in 1 L of ethyl acetate. After washing with water, it was dried over magnesium sulfate and concentrated to obtain 196 g of crude crystals. This was washed with 500 ml of hexane to obtain 185 g of 9-hydroxy-9-phenylfluorene.
[3]: Preparation of 9-phenyl-9- (4′-aminophenyl) fluorene 60 g (0.22 mol) of 9-hydroxy-9-phenylfluorene, 123 g (1.58 mol) of aniline, 250 ml of acetic acid (500 ml) of 35% aqueous hydrochloric acid ) The solution was stirred at 100 ° C. for 8 hours. After cooling, 200 ml of water was added, the precipitated crystals were filtered off, and the crystals were dissolved in 1 L of ethyl acetate. After adding 300 ml of 20% aqueous sodium hydroxide solution and stirring at 25 ° C. for 1 hour, the organic layer was separated and washed with water. By drying with magnesium sulfate and concentrating, 53 g of 9-phenyl-9- (4′-aminophenyl) fluorene was obtained.
[4]: Preparation of Exemplary Compound 4 9-phenyl-9- (4′-aminophenyl) fluorene 20 g (0.06 mol), 1,1-bis (diphenylphosphinoferrocene) palladium dichloromethane complex 0.24 g, 1,1 A solution of 0.53 g of bis (diphenylphosphinoferrocene), 6.9 g (0.07 mol) of sodium-tert-butoxide, 19.1 g (0.07 mol) of 2-bromo-9,9-dimethylfluorene in a tetrahydrofuran (48 ml) solution. Stir at 80 ° C. for 3 hours. After cooling to 25 ° C., 700 ml of ethyl acetate and 100 ml of water were added, and the organic layer was separated. By drying with magnesium sulfate and concentrating, 27.8 g of crude crystals were obtained. Furthermore, 24.6 g of the target exemplified compound 4 was obtained as colorless crystals by recrystallizing the crude crystals with 300 ml of isopropanol.

Production of Exemplified Compound 11 Exemplified Compound 4 4.73 g (0.009 mol), iodobenzene 1.84 g (0.009 mol), palladium acetate 0.004 g (0.002 mol), tri-tert-butylphosphine 0.1 ml, sodium A solution of 1.27 g (0.014 mol) of tert-butoxide in xylene (50 ml) was stirred at 110 ° C. for 3 hours. After cooling, toluene (500 ml) and water (100 ml) were added, and the organic layer was separated. It was dried over magnesium sulfate and concentrated to obtain 4.65 g of crude crystals. The crude crystals were washed with 100 ml of methanol, purified by silica gel column chromatography (eluent: toluene), and recrystallized with toluene to obtain 3.98 g of the target compound of Illustrative Compound 11 as colorless crystals. Further, this compound was purified by sublimation at 360 ° C. and 2 × 10 ⁻⁴ Pa.

Production of Exemplified Compound 12 According to the procedure described in Example 2, except that 1.29 g (0.009 mol) of 1-iodonaphthalene was used instead of 1.84 g (0.009 mol) of iodobenzene in Example 2. Thus, 2.76 g of the compound of Exemplary Compound 12 was obtained as colorless crystals. Further, this compound was purified by sublimation at 385 ° C. and 2 × 10 ⁻⁴ Pa.

Preparation of Exemplified Compound 31 [1]: Preparation of 7-chloro-2-iodo-9,9-dimethylfluorene 6.52 g (0.02 mol) of 7-chloro-2-iodofluorene was dissolved in 100 ml of N, N-dimethylformamide. To this solution, 1.6 g of sodium hydride (40% liquid paraffin additive, 0.04 mol) was added. After stirring at 25 ° C. for 1 hour, 5.68 g (0.04 mol) of iodomethyl was added dropwise at 25 ° C. After stirring at 25 ° C. for 6 hours, 200 g of water was added and stirred for 3 hours. The precipitated crystals were separated by filtration and washed with water to obtain 5.60 g of crude crystals. Further, the crude crystals were recrystallized with 50 ml of isopropanol to obtain 4.74 g of 7-chloro-2-iodo-9,9-dimethylfluorene.
[2]: Preparation of 7-chloro-2-N, N-diphenylamino-9,9-dimethylfluorene 7-chloro-2-iodo-9,9-dimethylfluorene 25 g (0.07 mol), copper iodide (I) 0.5 g (0.05 mol), 12 g (0.07 mol) of N, N-diphenylamine, 12.4 g (0.08 mol) of potassium carbonate, and 78 ml of o-dichlorobenzene were heated at 170 ° C. for 6 hours. The reaction solution was diluted with 100 ml of toluene and then filtered off, and the filtrate was concentrated to obtain 15.3 g of crude crystals. Further, the crude crystals were recrystallized with 30 ml of methyl cellosolve to obtain 5.60 g of 7-chloro-2-N, N-diphenylamino-9,9-dimethylfluorene.
[3]: Preparation of 9-phenyl-9- (N-phenyl-4′-aminophenyl) fluorene 20-g (0.06 mol) of 9-phenyl-9- (4′-aminophenyl) fluorene, 1,1-bis (diphenylphosphine) Finoferrocene) palladium dichloromethane complex 0.24g, 1,1-bis (diphenylphosphinoferrocene) 0.53g, sodium-tert-butoxide 6.9g (0.07mol), tetrahydrofuran 10.4g (0.07mol) tetrahydrofuran (48 ml) The solution was stirred at 80 ° C. for 3 hours. After cooling to 25 ° C., 700 ml of ethyl acetate and 100 ml of water were added, and the organic layer was separated. Drying with magnesium sulfate and concentration gave 30.2 g of crude crystals. Further, the crude crystals were recrystallized from 300 ml of isopropanol to obtain 16.4 g of 9-phenyl-9- (N-phenyl-4′-aminophenyl) fluorene.
[4]: Preparation of Exemplified Compound 31 9-phenyl-9- (N-phenyl-4′-aminophenyl) fluorene 3.85 g (0.009 mol), 7-chloro-2- (N, N-diphenyl) amino-9, 9-dimethylfluorene 3.56 g (0.009 mol), palladium acetate 0.004 g (0.002 mol), tri-tert-butylphosphine 0.1 g (0.005 mol), sodium-tert-butoxide 2.7 g (0.014 mol) ) In xylene (50 ml) was stirred at 110 ° C. for 3 hours. After cooling, toluene (500 ml) and water (100 ml) were added, and the organic layer was separated. By drying with magnesium sulfate and concentrating, 5.3 g of crude crystals were obtained. The crude crystals were washed with 100 ml of methanol, purified by silica gel column chromatography (eluent: toluene), and recrystallized with toluene to obtain 1.8 g of the target compound of exemplified compound 31 as colorless crystals. Further, this compound was purified by sublimation at 390 ° C. and 2 × 10 ⁻⁴ Pa.

Preparation of Exemplified Compound 32 In [4] of Example 4, instead of using 3.56 g (0.009 mol) of 7-chloro-2- (N, N-diphenyl) amino-9,9-dimethylfluorene, Exemplified according to the procedure described in [4] of Example 4 except that 4 g (0.009 mol) of chloro-2- [N-phenyl-N- (1′-naphthyl)] amino-9,9-dimethylfluorene was used. 1.77 g of compound 32 was obtained as colorless crystals. Further, this compound was purified by sublimation at 380 ° C. and 2 × 10 ⁻⁴ Pa.

Preparation of Exemplified Compound 33 In [4] of Example 4, instead of using 3.56 g (0.009 mol) of 7-chloro-2- (N, N-diphenyl) amino-9,9-dimethylfluorene, Except for using 3.54 g (0.009 mol) of chloro-2- (N-carbazolyl) -9,9-dimethylfluorene, following the procedure described in [4] of Example 4, the compound of Exemplified Compound 33 was colorless. 2.60 g of crystals were obtained. Further, this compound was purified by sublimation at 350 ° C. and 2 × 10 ⁻⁴ Pa.

Production of Exemplified Compound 41
[1] Preparation of 7-chloro-2-iodo 9-hydroxy-9-phenylfluorene 7-chloro-2-iodo 9-fluorenone 160 g (0.47 mol) in tetrahydrofuran (800 ml) in tetrahydrofuran (800 ml) 400 g of bromophenyl magnesium (32% tetrahydrofuran solution) , 0.71 mol) was added dropwise at 0 ° C. After stirring for 8 hours at 25 ° C., a 10% aqueous hydrochloric acid solution (300 ml) was added. The organic layer was separated and concentrated, and the residue was dissolved in 1 L of ethyl acetate. After washing with water, it was dried over magnesium sulfate and concentrated to obtain 190 g of crude crystals. This was washed with 500 ml of hexane to obtain 182 g of 7-chloro-2-iodo9-hydroxy-9-phenylfluorene.
[2]: Preparation of 7-chloro-2-iodo-9,9-diphenylfluorene 60-g (0.13 mol) of 7-chloro-2-iodo-9-hydroxy-9-phenylfluorene and 10 g (0.06 mol) of p-toluenesulfonic acid The benzene (500 ml) solution was stirred at 70 ° C. for 8 hours. After cooling, the reaction solution was concentrated and 200 ml of water was added. The precipitated crystals were separated by filtration to obtain 53 g of crude crystals. Further, the crude crystals were recrystallized with 400 ml of isopropanol to obtain 43.1 g of 7-chloro-2-iodo 9,9-diphenylfluorene.

[3]: Preparation of 7-chloro-2-N, N-diphenylamino-9,9-diphenylfluorene In [2] of Example 4, 7 g of 7-chloro-2-iodo-9,9-dimethylfluorene (0.07 mol) ), 7-chloro-2-N is prepared according to the procedure described in [2] of Example 4 except that 33 g (0.07 mol) of 7-chloro-2-iodo9,9-diphenylfluorene is used. N-diphenylamino-9,9-diphenylfluorene (28 g) was obtained.
[4] Preparation of Exemplified Compound 41 In [4] of Example 4, instead of using 3.56 g (0.009 mol) of 7-chloro-2- (N, N-diphenyl) amino-9,9-dimethylfluorene Exemplified compound 41 according to the procedure described in [4] of Example 4 except that 4.67 g (0.009 mol) of 7-chloro-2- (N, N-diphenyl) amino-9,9-diphenylfluorene was used. 4.01 g of the above compound was obtained as colorless crystals. Further, this compound was purified by sublimation at 420 ° C. and 2 × 10 ⁻⁴ Pa.

Preparation of Exemplified Compound 61 In [4] of Example 4, instead of using 3.56 g (0.009 mol) of 7-chloro-2- (N, N-diphenyl) amino-9,9-dimethylfluorene, 5- According to the procedure described in [4] of Example 4, except that 4.06 g (0.009 mol) of tert-butyl-7-chloro-2- (N, N-diphenyl) amino-9,9-dimethylfluorene was used, 3.34 g of the compound of exemplary compound 61 was obtained as colorless crystals. Further, this compound was purified by sublimation at 400 ° C. and 2 × 10 ⁻⁴ Pa.

Preparation of Exemplary Compound 65 In [4] of Example 4, instead of using 3.56 g (0.009 mol) of 7-chloro-2- (N, N-diphenyl) amino-9,9-dimethylfluorene, 5- [4] of Example 4 except that 5.00 g (0.009 mol) of tert-butyl-7-chloro-2- [N-phenyl-N- (9′-phenanthryl)] amino-9,9-dimethylfluorene was used. 2.86 g of the compound of Exemplified Compound 65 was obtained as colorless crystals. Further, this compound was purified by sublimation at 430 ° C. and 2 × 10 ⁻⁴ Pa.

Production of Exemplary Compound 91 In [4] of Example 4, 9-phenyl-9- (N-phenyl-4′-aminophenyl) fluorene 3.85 g (0.009 mol), 7-chloro-2- (N, N-diphenyl) ) Instead of using 3.59 g (0.009 mol) amino-9,9-dimethylfluorene, 0.004 g (0.002 mol) palladium acetate, 1.27 g (0.014 mol) sodium-tert-butoxide, 9-phenyl- 9- (N-phenyl-4′-aminophenyl) fluorene 10 g (0.024 mol), 2,7-diiodofluorene 5.17 g (0.012 mol), palladium acetate 0.26 g (0.002 mol), sodium-tert -The procedure described in [4] of Example 4 was repeated except that 2.67 g (0.028 mol) of butoxide was used. There was obtained 3.83g of the compound of Exemplary compound 91 as colorless crystals. Further, this compound was purified by sublimation at 320 ° C. and 2 × 10 ⁻⁴ Pa.

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 11 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. On top of this, tris (8-quinolinolato) aluminum was vapor-deposited to a thickness of 50 nm at a vapor deposition rate of 0.2 nm / sec to form a light-emitting layer that also served as an electron injection / transport 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 6.5 V and luminance of 460 cd / m ² was confirmed. The half life of luminance was 650 hours.

In Example 11, when forming the hole injecting and transporting layer, an organic electroluminescent device was prepared according to the procedure described in Example 11 except that the compound of exemplary compound 11 was used instead of the compound of exemplary compound 11. It was created. Further, in the same manner as in Example 11, a DC voltage was applied to the device, the characteristics of the device were measured, and the results are shown in Table 1 (Table 1).

In Example 11, when forming the hole injecting and transporting layer, the organic electroluminescent device was prepared according to the procedure described in Example 11 except that the compound of Exemplified Compound 31 was used instead of the compound of Illustrated Compound 11. Created. Further, in the same manner as in Example 11, a DC voltage was applied to the device, the characteristics of the device were measured, and the results are shown in Table 1 (Table 1).

In Example 11, when forming the hole injecting and transporting layer, the organic electroluminescent device was prepared according to the procedure described in Example 11 except that the compound of Exemplified Compound 32 was used instead of the compound of Illustrated Compound 11. Created. Further, in the same manner as in Example 11, a DC voltage was applied to the device, the characteristics of the device were measured, and the results are shown in Table 1 (Table 1).

In Example 11, when forming the hole injecting and transporting layer, the organic electroluminescent device was prepared according to the procedure described in Example 11 except that the compound of Exemplified Compound 33 was used instead of the compound of Illustrated Compound 11. Created. Further, in the same manner as in Example 11, a DC voltage was applied to the device, the characteristics of the device were measured, and the results are shown in Table 1 (Table 1).

In Example 11, when forming the hole injecting and transporting layer, the organic electroluminescent device was prepared according to the procedure described in Example 11 except that the compound of Exemplified Compound 41 was used instead of the compound of Illustrated Compound 11. Created. Further, in the same manner as in Example 11, a DC voltage was applied to the device, the characteristics of the device were measured, and the results are shown in Table 1 (Table 1).

In Example 11, when forming the hole injecting and transporting layer, an organic electroluminescent device was prepared according to the procedure described in Example 11 except that the compound of Exemplified Compound 61 was used instead of the compound of Illustrated Compound 11. Created. Further, in the same manner as in Example 11, a DC voltage was applied to the device, the characteristics of the device were measured, and the results are shown in Table 1 (Table 1).

In the formation of the hole injection / transport layer in Example 11, an organic electroluminescent device was prepared according to the procedure described in Example 11 except that the compound of exemplary compound 65 was used instead of the compound of exemplary compound 11 did. Further, in the same manner as in Example 11, a DC voltage was applied to the device, the characteristics of the device were measured, and the results are shown in Table 1 (Table 1).

In Example 11, when forming the hole injecting and transporting layer, the organic electroluminescent device was prepared according to the procedure described in Example 11 except that the compound of Exemplified Compound 91 was used instead of the compound of Illustrated Compound 11. Created. Further, in the same manner as in Example 11, a DC voltage was applied to the device, the characteristics of the device were measured, and the results are shown in Table 1 (Table 1).

Comparative Example 1:
In Example 11, when forming the hole injecting and transporting layer, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl was used instead of using the compound of Exemplary Compound 11. Except for the above, organic electroluminescent elements were produced in accordance with the procedure described in Example 11. Green light emission was confirmed from each element, and the characteristics were examined, and the results are shown in Table 1.
Comparative Example 2:
In Example 11, the formation of the hole injection transport layer was carried out except that 9,9-dimethyl-2,7-bis (N, N-diphenylamino) fluorene was used instead of using the compound of Exemplified Compound 11. According to the operation described in Example 11, an organic electroluminescent device was produced. Green light emission was confirmed from each element. Further, the characteristics were examined, and the results are shown in (Table 1).

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 the exemplary compound 33 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, green light emission of 6.0 V and luminance of 510 cd / m ² was confirmed. The half life of luminance was 1950 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, 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. Subsequently, the compound of Exemplified Compound 33 and rubrene were co-deposited to a thickness of 20 nm from different vapor deposition sources (weight ratio 10: 1) to form a light emitting layer that also served as the second hole injecting and transporting layer. 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 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 5.9 V and luminance of 500 cd / m ² was confirmed. The half life of luminance was 1900 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, 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 91 and rubrene were co-deposited 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 also provided. A 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 6.3 V and luminance of 510 cd / m ² was confirmed. The half life of luminance was 1700 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, Exemplified Compound 31 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 91 and rubrene were co-deposited 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 also provided. A 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 5.9 V and luminance of 540 cd / m ² was confirmed. The half life of luminance was 1700 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, a 40 nm hole is formed on the ITO transparent electrode by spin coating using a 3% by mass dichloroethane solution containing a compound of polycarbonate (weight average molecular weight 39000) and exemplary compound 91 in a weight ratio of 100: 50. An 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 98 mA / cm ² flowed. Green light emission with a luminance of 860 cd / m ² was confirmed. The luminance half-life 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), a mixture of compounds of the exemplary compound 91, 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 89 mA / cm ² flowed. Green light emission with a luminance of 610 cd / m ² was confirmed. The half life of luminance was 490 hours.

According to the present invention, it is possible to provide a novel 9,9-diphenylfluorene compound and an organic electroluminescence device having a long emission lifetime and excellent durability.

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

Explanation of symbols

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

Claims (6)

9,9-diphenylfluorene compound represented by the general formula (1).

[ Wherein, R1 to R3 each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and Z _{1 to} Z ₆ Each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, or a substituted group. Or an unsubstituted aralkyl group, and Z ₇ represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, or a substituted group Alternatively, it represents an unsubstituted aralkyl group. ] An organic electroluminescent device comprising at least one layer containing at least one 9,9-diphenylfluorene compound represented by the general formula (1) according to claim 1 interposed between a pair of electrodes. The organic electroluminescent element according to claim 2, wherein the layer containing the 9,9-diphenylfluorene compound represented by the general formula (1) according to claim 1 is a light emitting layer. The organic electroluminescence device according to claim 2, wherein the layer containing the 9,9-diphenylfluorene compound represented by the general formula (1) according to claim 1 is a hole injection transport layer. The organic electroluminescent element according to claim 2, further comprising a hole injecting and transporting layer between the pair of electrodes. The organic electroluminescent element according to claim 2, further comprising an electron injecting and transporting layer between the pair of electrodes.

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