JP4211869B2 - Diaminoarylene compound having carbazolyl group and use thereof - Google Patents

Description

  The present invention relates to a novel diaminoarylene compound having a carbazolyl group, and more specifically, when used in an organic electroluminescence device (hereinafter abbreviated as an organic EL device), the molecular crystallinity is low and the glass transition temperature (Tg). Therefore, the present invention relates to a diaminoarylene compound having a carbazolyl group that exhibits excellent performance (low voltage driving, long life, high stability).

 In recent years, organic EL elements have been required to have a long lifetime. There are various factors that may affect the lifetime of the element (see Non-Patent Document 1). As one of the factors, the glass transition temperature (Tg) of the material constituting the element has a large effect on the lifetime of the element. It is considered a thing. That is, it has been pointed out that when the temperature of the element exceeds the Tg of the constituent material due to the use environment of the element or the heat generated during driving, the material crystallizes and a non-light emitting region called a dark spot is generated. . For this reason, development of materials exhibiting higher Tg has been actively studied.

As a material constituting an organic EL element, a material containing a triphenylamine skeleton in a partial structure is well known, but a phenanthrene structure that is generally known to have high thermal stability in the field of the chemical industry is known. It is disclosed that the amine compound which can be used as an organic EL element material (refer patent document 1).
However, these materials are not so high in heat resistance (Tg), and the crystallinity of the material is also high, so that the film stability is insufficient, and the characteristics when an organic EL element is produced are not sufficient in the light emission lifetime. Also, the voltage (drive voltage) required for driving the element was high.

 On the other hand, application of carbazole derivatives to various functional materials and electronic materials has been studied. Utilizing the fact that the carbazole skeleton has a hole transporting property and a structure having high heat resistance, application to, for example, a charge transport material of an electrophotographic photosensitive member or a material for an organic EL element has been studied. ing. As typical examples, polyvinyl carbazole (PVK) and N, N′-dicarbazoyl-4,4′-biphenyl (CBP) are widely studied as materials for organic EL devices (Non-patent Documents 2 and 3). reference). Although carbazoles such as PVK and CBP have a relatively high Tg and heat resistance, they have a highly symmetrical structure. Therefore, when a thin film is formed by vacuum deposition or spin coating, the stability of the film is improved. However, it has a problem that it is easily crystallized and the lifetime of the device is extremely short.

A diamine compound having a 3-substituted carbazolyl group has been disclosed as a material that effectively utilizes the heat resistance of carbazole and has low molecular symmetry (see Patent Document 2). However, even with this compound, an EL element having high crystallinity and sufficient life characteristics has not been obtained.
In addition, in order to reduce the power consumption of EL elements, the hole injection layer and the hole transport layer are made of a material having an ionization potential suitable for hole injection and hole transport from the anode (ITO, etc.). Although demanded, there is no material having an appropriate ionization potential and all of the heat resistance and low crystallinity described above.

Toshito Shizushi, Chida Adachi, Hideyuki Murata, Organic EL Display, Ohmsha, 2004, 139 pages Applied Physics Letters, 2001, 78, 278 Journal of the American Chemical Society 2001, 123, 4304 Japanese Patent No. 3067469 JP 2004-536134 A

  The object of the present invention is to provide high characteristics such as low voltage drive, long life, and high stability when used as a material for an organic EL device, having high Tg, high heat resistance, and being difficult to crystallize molecules. It is to provide a diaminoarylene compound having a carbazolyl group having Another object of the present invention is to provide the above-described compound that can achieve a long lifetime of the device and a low voltage drive among the materials constituting the EL device, particularly when used as a hole injecting and transporting layer.

As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention.
That is, the present invention provides the following general formula [1]

(In the formula, Ar ^{1 to} Ar ⁴ are each independently a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms that may have a substituent, or 2 to carbon atoms that may have a substituent. 18 monovalent heterocyclic groups or the following general formula [2]

General formula [2]

(In the formula, Ar ⁵ is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms that may have a substituent, or a monovalent aromatic group having 2 to 18 carbon atoms that may have a substituent. Represents a heterocyclic group, and R ^{1 to} R ⁷ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic residue.
Wherein at least one of Ar ^{1 to} Ar ⁴ is a carbazolyl group represented by the general formula [2], and X represents the following general formula [3]

(In the formula, Q ^{9 to} Q ¹⁶ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic residue.)
A phenanthrene-diyl group which may have a substituent represented by the following general formula [4]

General formula [4]

^(Wherein, R 8 ^{to R 11} are each independently a hydrogen atom, or represents an organic residue of a halogen atom, or a monovalent or, ^{R 8} and ^R 9, ^{R 9} and ^{R 10} or ^{R 10,} And R ¹¹ may be bonded to each other between substituents to form a ring with adjacent carbon atoms.)
O-phenylene group which may have a substituent represented by the following general formula [5]

General formula [5]

(Wherein R ^{12 to} R ¹⁵ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic residue, or R ¹³ and R ¹⁴ , or R ¹⁴ and R ¹⁵ are substituents) They may be bonded together to form a ring with adjacent carbon atoms.)
The m-phenylene group which may have the substituent represented by this is represented. )
The diaminoarylene compound which has a carbazolyl group represented by these.

  In the present invention, the o-phenylene group represented by the general formula [4] is represented by the following general formula [6].

(In the formula, R ^{16 to} R ¹⁹ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic residue, or R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , or R ^18. And R ¹⁹ may be bonded to each other at a substituent to form a ring with an adjacent carbon atom, provided that when the newly formed ring is an aromatic ring, one of the above-mentioned three positions Only the position of.)
And a diaminoarylene compound having a carbazolyl group represented by the general formula [1], wherein the diaminoarylene compound is represented by the general formula [1].

  In the present invention, the m-phenylene group represented by the general formula [5] is represented by the following general formula [7].

(Wherein R ^{20 to} R ²³ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic residue, or R ²¹ and R ²² , or R ²² and R ²³ are substituents) They may be bonded to each other to form a ring with adjacent carbon atoms, provided that when the newly formed ring is an aromatic ring, it is only one of the two positions described above. )
And a diaminoarylene compound having a carbazolyl group represented by the general formula [1], wherein the diaminoarylene compound is represented by the general formula [1].
In the present invention, the o-phenylene group represented by the general formula [4] is represented by the following general formula [8].

(In the formula, R ^{24 to} R ²⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a monovalent aromatic having 6 to 12 carbon atoms that may have a substituent. Represents a hydrocarbon group or a monovalent heterocyclic group having 2 to 5 carbon atoms which may have a substituent.)
And a diaminoarylene compound having a carbazolyl group represented by the general formula [1], wherein the diaminoarylene compound is represented by the general formula [1].

  In the present invention, the o-phenylene group represented by the general formula [4] is represented by the following general formula [9].

(In formula, R < ²⁸ > -R < ³³ > is respectively independently a hydrogen atom, a halogen atom, a C1-C3 alkyl group, and a C6-C12 monovalent aromatic which may have a substituent. Represents a hydrocarbon group or a monovalent heterocyclic group having 2 to 5 carbon atoms which may have a substituent.)
And a diaminoarylene compound having a carbazolyl group represented by the general formula [1], which is an o-naphthalene-diyl group represented by formula (1).
In the present invention, the m-phenylene group represented by the general formula [5] is represented by the following general formula [10].

(In the formula, R ^{34 to} R ³⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a monovalent aromatic having 6 to 12 carbon atoms that may have a substituent. Represents a hydrocarbon group or a monovalent heterocyclic group having 2 to 5 carbon atoms which may have a substituent.)
And a diaminoarylene compound having a carbazolyl group represented by the general formula [1], wherein the diaminoarylene compound is represented by the general formula [1].

  Further, when the group X of the general formula [1] is a phenanthrene-diyl group which may have a substituent represented by the general formula [3], the following general formula [11]

(In formula, Ar < ¹ > -Ar < ⁴ > is respectively independently C1-C18 monovalent | monohydric aromatic hydrocarbon group which may have a substituent, and C2 which may have a substituent. Represents a monovalent heterocyclic group of ˜18 or a carbazolyl group represented by the above general formula [2], provided that at least one of Ar ^{1 to} Ar ⁴ is represented by the above general formula [2]. A carbazolyl group, and Q ^{9 to} Q ¹⁶ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic residue.)
The present invention relates to a phenanthrene compound having a carbazolyl group represented by the general formula [11]. The phenanthrene compound having a carbazolyl group represented by the general formula [11] is also included in the diaminoarylene compound having a carbazolyl group represented by the general formula [1]. 11] and a phenanthrene compound having a carbazolyl group, the diaminoarylene compound having a carbazolyl group.

In the present invention, Ar ¹ and Ar ² in the general formula [1] are each independently represented by the following general formula [12].

(Wherein, Ar ⁵ has the same meaning as Ar ⁵ in the general formula [2] described above.)
And Ar ³ and Ar ⁴ in the general formula [1] are each independently a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. The present invention relates to a diaminoarylene compound having a carbazolyl group represented by the general formula [1].

In the present invention, Ar ¹ in the above general formula [1] is represented by the above general formula [2] or [12], and Ar ² , Ar ³ in the above general formula [1], and Ar ⁴ is each independently a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and the carbazolyl group represented by the general formula [1] It has a diaminoarylene compound.

In the present invention, Ar ⁵ in the above general formula [2] or [12] is represented by the following general formula [13].

(In the formula, each R ³⁸ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. Or a monovalent heterocyclic group having 2 to 5 carbon atoms which may have a substituent.)
And a diaminoarylene compound having a carbazolyl group represented by the general formula [1].

  The present invention also relates to a diaminoarylene compound having a carbazolyl group represented by the above general formula [1] having a glass transition temperature (Tg) of 170 ° C. or higher.

The present invention also relates to a diaminoarylene compound having a carbazolyl group represented by the above general formula [1] having an ionization potential of 5.0 to 5.5 eV.
The present invention also relates to a material for an organic electroluminescence element comprising a diaminoarylene compound having a carbazolyl group represented by the general formula [1].
In addition, the present invention provides an organic electroluminescence device in which a light emitting layer or a plurality of organic layers including a light emitting layer is formed between a pair of electrodes, wherein at least one of the organic layers is the organic electroluminescence of the present invention described above. The present invention relates to an organic electroluminescence element comprising an element material.
Further, the present invention further includes a hole injection layer and / or a hole transport layer between the anode and the light emitting layer, and the hole injection layer and / or the hole transport layer is the above-described aspect of the present invention. It is related with the said organic electroluminescent element which comprises the material for organic electroluminescent elements.

Further, the present invention will be described in detail as follows.
(1) A diaminoarylene compound having a carbazolyl group represented by the general formula [1].
(2) Diaminoarylene having the carbazolyl group according to (1), wherein X in the general formula [1] is a phenanthrene-diyl group which may have a substituent represented by the general formula [3]. Compound.
(3) Diaminoarylene having the carbazolyl group according to (1), wherein X in the general formula [1] is an o-phenylene group which may have a substituent represented by the general formula [4]. Compound.
(4) The carbazolyl group according to (1) or (3), wherein the o-phenylene group represented by the general formula [4] is an o-phenylene group represented by the general formula [6]. A diaminoarylene compound having:
(5) Any of (1), (3), and (4) above, wherein the o-phenylene group represented by the general formula [4] is the o-phenylene group represented by the general formula [8]. A diaminoarylene compound having a carbazolyl group as described above.
(6) The (1), (3), or (4), wherein the o-phenylene group represented by the general formula [4] is the o-naphthalene-diyl group represented by the general formula [9]. A diaminoarylene compound having a carbazolyl group according to any one of the above.
(7) Diaminoarylene having the carbazolyl group according to (1), wherein X in the general formula [1] is an m-phenylene group which may have a substituent represented by the general formula [5]. Compound.
(8) The m-phenylene group represented by the general formula [5] has the carbazolyl group according to the above (1) or (7), which is the m-phenylene group represented by the general formula [7]. Diaminoarylene compounds.
(9) Any of (1), (7), or (8) above, wherein the m-phenylene group represented by the general formula [5] is the m-phenylene group represented by the general formula [10]. A diaminoarylene compound having a carbazolyl group as described above.
(10) The (1) or (2), wherein the diaminoarylene compound having a carbazolyl group represented by the general formula [1] is a phenanthrene compound having a carbazolyl group represented by the general formula [11]. A diaminoarylene compound having a carbazolyl group.
(11) The diaminoarylene having the carbazolyl group according to any one of (1) to (10), wherein the carbazolyl group represented by the general formula [2] is the carbazolyl group represented by the general formula [12]. Compound.
(12) Ar1 and Ar2 in the general formula [1] are each independently represented by the general formula [12], and Ar3 and Ar4 in the general formula [1] are each independently a substituent. The diaminoarylene compound which has a carbazolyl group as described in said (11) which is a C6-C18 monovalent | monohydric aromatic hydrocarbon group which may have.
(13) Ar1 in the general formula [1] is represented by the above general formula [2] or [12], and Ar2, Ar3, and Ar4 in the general formula [1] are each independently a substituent. The diaminoarylene compound having a carbazolyl group according to (11), which is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have.
(14) The diaminoarylene compound having a carbazolyl group according to any one of (1) to (13), wherein Ar5 in the general formula [2] is a phenyl group represented by the general formula [13].
(15) The diaminoarylene compound having a carbazolyl group according to any one of (1) to (14), which has a glass transition temperature (Tg) of 170 ° C. or higher.
(16) The diaminoarylene compound having a carbazolyl group according to any one of (1) to (15), which has an ionization potential of 5.0 to 5.5 eV.
(17) A material for an organic electroluminescence device comprising the diaminoarylene compound having a carbazolyl group according to any one of (1) to (16).
(18) In the organic electroluminescent element formed by forming a light emitting layer or a plurality of organic layers including a light emitting layer between a pair of electrodes, at least one of the organic layers is the organic electroluminescent element according to (17) An organic electroluminescence device comprising a material for use.
(19) Furthermore, it has a positive hole injection layer and / or a positive hole transport layer between an anode and a light emitting layer, The said positive hole injection layer and / or a positive hole transport layer are the organic as described in said (17). The organic electroluminescent device according to (18), comprising an electroluminescent device material.

  An organic EL device using the diaminoarylene compound having a carbazolyl group of the present invention as a material for an organic EL device has a very high thin film stability, emits light at a low driving voltage, and has a long lifetime. Can be suitably used as a flat panel display or a flat light emitter, and can be applied to a light source such as a copying machine or a printer, a light source such as a liquid crystal display or an instrument, a display plate, or a marker lamp.

Hereinafter, the present invention will be described in detail. First, the diaminoarylene compound having a carbazolyl group represented by the general formula [1] will be described.
The diaminoarylene compound having a carbazolyl group represented by the general formula [1] according to the present invention has at least one nitrogen atom of a diamine compound having an o-phenylene structure, an m-phenylene structure, or an o-phenanthrene-diyl structure. The 3-carbazolyl group is substituted. The phenanthrene-diyl group in the present invention is obtained by condensing two benzene rings with a phenylene group in an o-phenylene structure. In a broad sense, the phenanthrene-diyl group can be called a derivative of an o-phenylene structure. Since it has a high glass transition point (Tg) and has favorable properties as an organic EL material, it is particularly taken up. The phenylenediamine structure of the present invention is characterized by an ortho-phenylenediamine structure and a meta-phenylenediamine structure, and has structural features different from para-phenylenediamine. As described later, the 3-carbazolyl group is arranged so that the nitrogen atom of the carbazole ring and the nitrogen atom of the diamine are in the para position, but when the diamine has a p-phenylene structure, Furthermore, it has a para-position nitrogen atom, which is not preferable. In particular, it is not preferable from the viewpoint of maintaining amorphousness. Therefore, in this respect, the diamine compound having a p-phenylene structure and the diamine compound of the present invention are structurally different.
Ar ^{1 to} Ar ⁴ in the general formula [1] are each independently a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or a carbon number which may have a substituent. The monovalent heterocyclic group of 2-18, or the carbazolyl group represented by General formula [2] is represented. However, at least one of Ar ^{1 to} Ar ⁴ is a carbazolyl group represented by the general formula [2].

Examples of the monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms include monovalent monocyclic, condensed cyclic, or ring assembly (polycyclic) hydrocarbon groups having 6 to 18 carbon atoms.
Here, examples of the monovalent monocyclic aromatic hydrocarbon group having 6 to 18 carbon atoms include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,4-xylyl group, and p. -C6-C18 monovalent | monohydric monocyclic aromatic hydrocarbon groups, such as a cumenyl group and a mesityl group, are mention | raise | lifted.
Examples of the monovalent condensed ring hydrocarbon group include 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 9-phenanthryl group, Examples thereof include monovalent condensed ring hydrocarbon groups having 10 to 18 carbon atoms such as 1-acenaphthyl group, 2-azurenyl group, 1-pyrenyl group, and 2-triphenylenyl group .
Examples of the monovalent ring assembly hydrocarbon group include monovalent ring assembly hydrocarbon groups having 12 to 18 carbon atoms such as o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, and terphenyl group. can give.

Examples of the heterocyclic group of a monovalent heterocyclic group having 2 to 18 carbon atoms include a monovalent aliphatic heterocyclic group and a monovalent aromatic heterocyclic group. 3 to 8 member, preferably 5 to 7 membered monocyclic, polycyclic, or at least 1, preferably 1 to 3 hetero atoms selected from nitrogen atom, oxygen atom and sulfur atom A condensed heterocyclic ring may be mentioned.
Examples of the monovalent aliphatic heterocyclic group include monovalent aliphatic heterocyclic groups having 3 to 18 carbon atoms such as a 2-pyrazolino group, a piperidino group, a morpholino group, and a 2-morpholinyl group.
Examples of the monovalent aromatic heterocyclic group include a triazolyl group, 3-oxadiazolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 1-pyrrolyl group, 2- Pyrrolyl group, 3-pyrrolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazyl group, 2-oxazolyl group, 3-isoxazolyl group, 2-thiazolyl group, 3-isothiazolyl group, 2- Imidazolyl group, 3-pyrazolyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 2- Quinoxalinyl group, 2-benzofuryl group, 2-benzothienyl group, N-indolyl group, N-carbazolyl group, N-acridinyl group, (2,2′-bithienyl) -4- And monovalent aromatic heterocyclic groups having 2 to 18 carbon atoms such as yl groups.

When Ar ^{1 to} Ar ⁴ described above are an aromatic hydrocarbon group and a heterocyclic group, these aromatic hydrocarbon group and heterocyclic group may have a substituent. Examples of the substituent which may be bonded to these include a halogen atom and a monovalent organic residue.
As used herein, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The monovalent organic residue is not particularly limited, but may be a monovalent aliphatic hydrocarbon group that may have a substituent, a monovalent aromatic hydrocarbon group that may have a substituent, or a substituent. A monovalent aliphatic heterocyclic group which may have a monovalent aromatic heterocyclic group which may have a substituent, a cyano group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a substituted amino group Group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group and the like. Here, aryl in an aryloxy group or an arylthio group represents an aromatic hydrocarbon and an aromatic heterocyclic ring.
Here, the monovalent aliphatic hydrocarbon group refers to a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group. Is given.
Therefore, as the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, C1-C18 alkyl groups, such as a decyl group, a dodecyl group, a pentadecyl group, and an octadecyl group, are mentioned.
Examples of the alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1-decenyl group, 1 -An alkenyl group having 2 to 18 carbon atoms such as an octadecenyl group.
Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group and 1-octadecynyl group. Examples thereof include alkynyl groups having 2 to 18 carbon atoms.
Examples of the cycloalkyl group include cycloalkyl groups having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctadecyl group.
Furthermore, examples of the monovalent aromatic hydrocarbon group, monovalent aliphatic heterocyclic group, and monovalent aromatic heterocyclic group include those described above.

Examples of the alkoxy group include C1-C8 alkoxyl groups such as methoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group, octyloxy group, and tert-octyloxy group.
Examples of the aryloxy group include aryloxy groups having 6 to 14 carbon atoms such as phenoxy group, 4-tert-butylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, and 9-anthryloxy group. .
Examples of the alkylthio group include C1-C8 alkylthio groups such as a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, and an octylthio group.
Examples of the arylthio group include arylthio groups having 6 to 14 carbon atoms such as a phenylthio group, a 2-methylphenylthio group, and a 4-tert-butylphenylthio group.
The substituted amino group includes N-methylamino group, N-ethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N-benzylamino group, N , N-dibenzylamino group, N-phenylamino group, N-phenyl-N-methylamino group, N, N-diphenylamino group, N, N-bis (m-tolyl) amino group, N, N-bis (P-tolyl) amino group, N, N-bis (p-biphenylyl) amino group, bis [4- (4-methyl) biphenylyl] amino group, N-α-naphthyl-N-phenylamino group, N-β Examples thereof include substituted amino groups having 2 to 16 carbon atoms such as naphthyl-N-phenylamino group.
Examples of the acyl group include acyl groups having 2 to 14 carbon atoms such as an acetyl group, a propionyl group, a pivaloyl group, a cyclohexylcarbonyl group, a benzoyl group, a toluoyl group, an anisoyl group, and a cinnamoyl group.
Moreover, as an alkoxycarbonyl group, C2-C14 alkoxycarbonyl groups, such as a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group, are mention | raise | lifted.
Examples of the aryloxycarbonyl group include C2-C14 aryloxycarbonyl groups such as a phenoxycarbonyl group and a naphthyloxycarbonyl group.

Moreover, as an alkylsulfonyl group, C2-C14 alkylsulfonyl groups, such as a mesyl group, an ethylsulfonyl group, a propylsulfonyl group, are mention | raise | lifted.
Moreover, as an arylsulfonyl group, C2-C14 arylsulfonyl groups, such as a benzenesulfonyl group and p-toluenesulfonyl group, are mention | raise | lifted.
The monovalent aliphatic hydrocarbon group, monovalent aromatic hydrocarbon group, monovalent aliphatic heterocyclic group, and monovalent aromatic heterocyclic group described above are further substituted with other substituents. It may be. These substituents may be bonded to each other to form a ring together with adjacent atoms.
Preferred monovalent organic residues in the present invention include an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted alkenyl group having 2 to 18 carbon atoms, and a substituent. C2-C18 alkynyl group which may have, C3-C18 cycloalkyl group which may have a substituent, C6-C18 monovalent monovalent which may have a substituent. 3-8 membered aliphatic or aromatic heterocycle having 1 to 3 hetero atoms selected from a nitrogen atom, an oxygen atom, or a sulfur atom in the ring aromatic hydrocarbon group, which may have a substituent It may have a cyclic group, a cyano group, an alkoxyl group having 1 to 8 carbon atoms which may have a substituent, an aryloxy group having 6 to 14 carbon atoms which may have a substituent, or a substituent. C1-C8 alkylthio group, C2-C16 substituted amino group which may have a substituent, Substituent An optionally substituted acyl group having 2 to 14 carbon atoms, an optionally substituted alkoxycarbonyl group having 2 to 14 carbon atoms, and an optionally substituted aryloxycarbonyl group having 2 to 14 carbon atoms And a substituent selected from the group consisting of an alkylsulfonyl group having 2 to 14 carbon atoms which may have a substituent, or these substituents may be bonded to each other to form a ring with adjacent atoms. Good groups are mentioned.

Q ^{9 to} Q ¹⁶ in the general formula [3] or the general formula [11] each independently represent a hydrogen atom, a halogen atom, or a monovalent organic residue, and specific examples thereof are described above. I can give you. A particularly preferred example of Q ^{9 to} Q ¹⁶ is a hydrogen atom.

Next, Ar ⁵ in the general formula [2] is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent. Represents a monovalent aromatic heterocyclic group having 18 to 18 carbon atoms, or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.
Examples of the monovalent aromatic hydrocarbon group and monovalent aromatic heterocyclic group include those described above, and examples of the monovalent aliphatic hydrocarbon group include those having the corresponding carbon number among those described above. can give.
Moreover, R < ¹ > -R < ⁷ > in General formula [2] represents a hydrogen atom, a halogen atom, or a monovalent organic residue each independently. Examples of the halogen atom and monovalent organic residue include those described above.

Here, the 3-carbazoyl group of the general formula [2] is more preferably a 3-carbazoyl group represented by the general formula [12]. The carbazoyl group of the general formula [12] is a case where R ^{1 to} R ⁷ of the carbazoyl group of the general formula [2] are hydrogen atoms. When such a structure is adopted, the molecular weight is relatively small, and it is easy to form a thin film by sublimating a compound (material) by vapor deposition or the like, and is excellent in terms of stability. Because.
Furthermore, it is more preferable that Ar ⁵ in the general formula [2] or [12] has a structure of the general formula [13]. The reason will be described below.
In general, a carbazole compound has a stronger structure and higher thermal stability than a diphenylamino compound having no bond (see Chemical Formula 14).

Aromatic groups and heteroaromatic groups have a greater effect of increasing stability, and among them, the effect of increasing stability can be expected when Ar ⁵ is represented by the general formula [13].
R ³⁸ in the general formula [13] is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a monovalent aromatic having 6 to 12 carbon atoms which may have a substituent. It represents a hydrocarbon group or a monovalent heterocyclic group having 2 to 5 carbon atoms which may have a substituent.
Examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms and the monovalent heterocyclic group having 2 to 5 carbon atoms include those having the corresponding carbon number among those described above. Examples of the substituent that may be included include the aforementioned halogen atoms and monovalent organic residues. Particularly preferred examples of R ³⁸ include a hydrogen atom, phenyl group, biphenyl group, tolyl group, xylyl group, methyl group, ethyl group, cyano group, fluorine atom and the like.

In the diaminoarylene compound having a carbazolyl group of the general formula [1] described above, at least one of Ar ^{1 to} Ar ⁴ is represented by the general formula [2] or the general formula [12] 3. A carbazolyl group bonded at the position. The number of carbazolyl groups may be any of 1 to 4, but preferably, Ar ¹ and Ar ² are carbazolyl groups represented by the general formula [12], and Ar ³ and Ar ⁴ are A case where each is independently a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms is exemplified. As the number of carbazolyl groups increases, the heat resistance of the compound improves, but the increase in molecular weight makes it difficult to form a thin film using a vapor deposition process. For these reasons, when the deposition property is more important than the heat resistance, the number of carbazolyl groups is particularly preferably one or two.
Here, the monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms in Ar ³ and Ar ⁴ has the same meaning as described above, and particularly preferably a phenyl group, a tolyl group, a naphthyl group, and a biphenyl group. Terphenyl group.

  By the way, the effect of the carbazolyl group bonded at the 3-position will be mentioned. Usually, the amino group acts as an electron donor, but the nitrogen atom of carbazole has almost no donor property with respect to the ring-ring group bonded on the nitrogen atom. This is because the carbazole ring has planarity and is a very bulky substituent, and it is caused by difficulty in taking a planar structure with the substituent on the nitrogen atom. Conceivable. On the other hand, since the carbazole ring has ring planarity, it can be electron donor to the benzene ring portion (see Chemical Formula 15).

  Therefore, in the diaminoarylene compound having a carbazolyl group bonded at the 3-position of the present invention, both the amino group bonded to the carbazole ring and the nitrogen atom of the carbazole ring serve as electron donors to the benzene ring of the carbazole ring. Therefore, it is considered that an electron donor effect equivalent to or higher than that of the phenylenediamine structure can be exhibited (see Chemical formula 16).

For these reasons, the diaminoarylene compound having a carbazolyl group of the present invention tends to be a compound having a small ionization potential (a compound in which the ground state of the organic molecule is at a higher level), and when creating an organic EL device, A compound having a high hole injecting property or a high hole transporting property can be obtained.
Furthermore, since the carbazole ring bonded at the 3-position has a lower molecular symmetry than the carbazole ring bonded on the nitrogen atom, the crystallinity of the molecule is lowered and the amorphous property is increased, so that a thin film was formed. It is possible to greatly contribute to the improvement of stability.

Next, X in the general formula [1] will be described. X is a phenanthrene-diyl group which may have a substituent represented by the general formula [3], an o-phenylene group which may have a substituent represented by the general formula [4], or the general formula [ 5] represents an m-phenylene group optionally having a substituent.
When the group X of the general formula [1] is a phenanthrene-diyl group which may have a substituent represented by the general formula [3], a carbazolyl group represented by the general formula [11] is used. It becomes the phenanthrene compound which has. When the phenanthrene compound having a carbazolyl group represented by the general formula [11] of the present invention is used as a material for an organic EL device, the higher the Tg, the better. Preferable examples of the phenanthrene compound having a carbazolyl group represented by the general formula [11] of the present invention include Tg of 170 ° C. or higher.
In general, when the thermal load exceeding the Tg of the material is applied, the EL element is destroyed due to the crystallization of the film as described above. However, it is extremely high at 170 ° C. even in in-vehicle use and other high temperature environments. By having Tg, a stable and long-life EL element can be realized.
First, the carbazolyl group represented by the general formula [11] when the group X of the general formula [1] of the present invention is a phenanthrene-diyl group which may have a substituent represented by the general formula [3]. Although the phenanthrene compound having a carbazolyl group is used as the material for an organic EL device, the molecular weight of the compound is preferably 1500 or less, more preferably 1300 or less, and further 1200 or less. It is preferably 1100 or less. This is because, when the molecular weight is large, there is a concern that the vapor deposition property in the case of producing an element by vapor deposition is deteriorated.
Representative examples of phenanthrene compounds having a carbazolyl group represented by the general formula [11] of the present invention are shown in the following Table 1, but the present invention is not limited to these representative examples.

Next, X in the general formula [1] has an o-phenylene group which may have a substituent represented by the general formula [4], or a substituent represented by the general formula [5]. The case where it may be an m-phenylene group will be described.
Since these o-phenylene groups and m-phenylene groups have a structure with low symmetry compared to p-phenylene groups, the crystallinity of the molecules is low and the amorphousness is high. Can be formed.
In General Formula [4] or General Formula [5], R ^{8 to} R ¹¹ or R ^{12 to} R ¹⁵ represent a hydrogen atom, a halogen atom, or a monovalent organic residue. Examples of the halogen atom and monovalent organic residue include those described above.
In the general formula [4], R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , or R ¹⁰ and R ¹¹ may be bonded to each other at a substituent to form a ring with adjacent atoms. Similarly, in the general formula [5], R ¹³ and R ¹⁴ , or R ¹⁴ and R ¹⁵ may be bonded to each other with a substituent to form a ring with adjacent atoms.

A more preferable form of the general formula [4] is o-phenylene of the general formula [6]. R ^{16 to} R ¹⁹ in the general formula [6] have the same meanings as R ^{8 to} R ¹¹ in the general formula [4], but the substituents are bonded to each other to form a new ring. When it is an aromatic ring, it is limited to only one position.
A more preferable form of the general formula [5] is m-phenylene of the general formula [7]. R ^{20 to} R ²³ in the general formula [7] have the same meanings as R ^{12 to} R ¹⁵ in the general formula [5], but a new ring formed by bonding substituents to each other is When it is an aromatic ring, it is limited to only one position.
Of the general formula [4] and the general formula [5] described above, the most preferable embodiment is that an o-phenylene group which may have a substituent represented by the general formula [4] is represented by the general formula [8]. Examples thereof include o-phenylene, naphthylene represented by the general formula [9], and m-phenylene represented by the general formula [10].

In the formula, R ^{24 to} R ²⁷ , R ^{28 to} R ³³ , and R ^{34 to} R ³⁷ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a carbon number that may have a substituent. Represents a monovalent aromatic hydrocarbon group having 1 to 12 carbon atoms or a monovalent heterocyclic group having 2 to 5 carbon atoms which may have a substituent.
The halogen atom is the same as described above, and examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a normal propyl group, and an isopropyl group.
Examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms and the monovalent heterocyclic group having 2 to 5 carbon atoms include those having the corresponding carbon number among those described above.
Particularly preferred among R ^{24 to} R ²⁷ , R ^{28 to} R ³³ , and R ^{34 to} R ³⁷ are a hydrogen atom, a methyl group, and a phenyl group.

The diaminoarylene compound having a carbazolyl group represented by the general formula [1] used in the present invention has been described above. However, when these diaminoarylene compounds having a carbazolyl group are used as a material for an organic EL device, The molecular weight is preferably 1500 or less, more preferably 1300 or less, still more preferably 1200 or less, and particularly preferably 1100 or less. This is because, when the molecular weight is large, there is a concern that the vapor deposition property in the case of producing an element by vapor deposition is deteriorated.
Next, X in the general formula [1] of the present invention is an o-phenylene group which may have a substituent represented by the general formula [4], or a substitution represented by the general formula [5]. Table 2 below shows typical examples of diaminoarylene compounds having a carbazolyl group represented by the general formula [1] in the case of an m-phenylene group which may have a group. It is not limited to.

    The phenanthrene compound having a carbazolyl group of the present invention can be used for various applications. As a material that develops functions such as sensitizing effect, heat generation effect, coloring effect, fading effect, phosphorescence effect, phase change effect, photoelectric conversion effect, photomagnetic effect, photocatalytic effect, light modulation effect, optical recording effect, radical generation effect, etc. Or conversely, it can also be used as a material having a light emitting function under these effects. More specifically, light emitting materials, photoelectric conversion materials, optical recording materials, image forming materials, photochromic materials, organic EL materials, photoconductive materials, dichroic materials, radical generating materials, acid generating materials, base generating materials, phosphorescent materials Materials, nonlinear optical materials, second harmonic generation materials, third harmonic generation materials, photosensitive materials, light absorption materials, near infrared absorption materials, photochemical hole burning materials, optical sensing materials, optical marking materials, photochemical treatment Examples thereof include sensitizing materials, optical phase change recording materials, photosintered recording materials, magneto-optical recording materials, and dyes for photodynamic therapy.

  Of these various uses, the organic EL material (organic EL material, organic EL element material) is particularly preferably used.

  In the case of use as a material for an organic EL device, a high-purity material is particularly required. In such a case, the phenanthrene compound having a carbazolyl group of the present invention is a sublimation purification method, a recrystallization method, A reprecipitation method, a zone melting method, a column purification method, an adsorption method, or the like, or a combination of these methods can be used. Of these purification methods, the recrystallization method is preferred. For compounds having sublimation properties, it is preferable to employ a sublimation purification method. In the sublimation purification, it is preferable to employ a method in which the sublimation boat is maintained at a temperature lower than the temperature at which the target compound sublimates, and the sublimation impurities are removed in advance. In addition, it is desirable to apply a temperature gradient to the portion where the sublimate is collected so that the sublimate is dispersed in the impurities and the target product. Sublimation purification as described above is purification that separates impurities, and can be applied to the present invention. In addition, sublimation purification is useful for predicting the difficulty of the material vapor deposition.

  Here, the organic EL device that can be prepared using the phenanthrene compound having a carbazolyl group of the present invention will be described in detail.

  The organic EL element is composed of an element in which a single layer or a multilayer organic layer is formed between an anode and a cathode. Here, the single layer type organic EL element is an element composed of only a light emitting layer between an anode and a cathode. Point to. On the other hand, the multilayer organic EL element facilitates injection of holes and electrons into the light emitting layer in addition to the light emitting layer, and facilitates recombination of holes and electrons in the light emitting layer. For the purpose of this, it refers to a layer in which a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, and the like are laminated. Therefore, typical element configurations of the multilayer organic EL element include (1) anode / hole injection layer / light emitting layer / cathode, and (2) anode / hole injection layer / hole transport layer / light emitting layer / cathode. (3) Anode / hole injection layer / light emitting layer / electron injection layer / cathode, (4) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, (5) Anode / positive Hole injection layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (6) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (7) An element structure in which a multilayer structure of anode / light emitting layer / hole blocking layer / electron injection layer / cathode, (8) anode / light emitting layer / electron injection layer / cathode, etc., is considered.

  Moreover, each organic layer mentioned above may be formed by the layer structure of two or more layers, respectively, and several layers may be laminated | stacked repeatedly. As such an example, an element configuration called “multi-photon emission” in which a part of the above-described multilayer organic EL element is multilayered has been proposed in recent years for the purpose of improving light extraction efficiency. For example, in an organic EL device composed of a glass substrate / anode / hole transport layer / electron transporting light emitting layer / electron injection layer / charge generating layer / light emitting unit / cathode, the charge generating layer and the light emitting unit A method of laminating a plurality of layers is an example.

  The phenanthrene compound (organic EL device material) having a carbazolyl group of the present invention may be used in any of the above-mentioned layers, but it is particularly suitable for use in a hole injection layer, a hole transport layer, and a light emitting layer. it can. The organic EL device material of the present invention can be used not only as a single compound but also as a combination of two or more compounds, that is, mixed, co-evaporated, laminated, etc. is there. Further, in the above-described hole injection layer, hole transport layer, and light emitting layer, they may be used together with other materials.

For the hole injection layer, a hole injection material that exhibits an excellent hole injection effect with respect to the light emitting layer and that can form a hole injection layer excellent in adhesion to the anode interface and thin film formability is used. In addition, when such materials are laminated in multiple layers and a material having a high hole injection effect and a material having a high hole transport effect are laminated, the materials used for each are called a hole injection material and a hole transport material. Sometimes. The organic EL device material of the present invention can be suitably used for both hole injection materials and hole transport materials. These hole injection materials and hole transport materials need to have a high hole mobility and a small ionization energy of usually 5.5 eV or less. As such a hole injection layer, a material that transports holes to the light emitting layer with a lower electric field strength is preferable. Further, at the time of applying an electric field of, for example, 10 ⁴ to 10 ⁶ V / cm, those that are 10- ⁶ cm ² / V · sec is preferred. Other hole injection materials and hole transport materials that can be used by mixing with the organic EL device material of the present invention are not particularly limited as long as they have the above-mentioned preferable properties. Any material can be selected and used from those commonly used as charge transport materials for holes in a conductive material and known materials used for hole injection layers of organic EL devices.

  Specific examples of such hole injection materials and hole transport materials include triazole derivatives (see US Pat. No. 3,112,197) and oxadiazole derivatives (US Pat. No. 3,189,447). Imidazole derivatives (see Japanese Patent Publication No. 37-16096), polyarylalkane derivatives (US Pat. Nos. 3,615,402, 3,820,989, 3,542,544, JP-B-45-555, JP-A-51-10983, JP-A-51-93224, JP-A-55-17105, JP-A-56-4148, JP-A-55- No. 108667, No. 55-156953, No. 56-36656, etc.), pyrazoline derivatives and pyrazolone derivatives (US Pat. No. 3,180, No. 29, No. 4,278,746, JP-A 55-88064, No. 55-88065, No. 49-105537, No. 55-51086, No. 56-80051. No. 56-88141, No. 57-45545, No. 54-112437, No. 55-74546, etc.), phenylenediamine derivatives (US Pat. No. 3,615,404, Japanese Patent Publication Nos. 51-10105, 46-3712, 47-25336, JP 54-53435, 54-110536, 54-1119925, etc.), arylamine Derivatives (US Pat. Nos. 3,567,450, 3,180,703, 3,240,597, 3 No. 658,520, No. 4,232,103, No. 4,175,961, No. 4,012,376, JP-B 49-35702, No. 39 -27577, JP-A-55-144250, JP-A-56-119132, JP-A-56-22437, West German Patent No. 1,110,518, etc.), amino-substituted chalcone derivatives (US patents) No. 3,526,501), oxazole derivatives (disclosed in US Pat. No. 3,257,203, etc.), styryl anthracene derivatives (see JP 56-46234 A, etc.), Fluorenone derivatives (see JP-A-54-110837, etc.), hydrazone derivatives (US Pat. No. 3,717,462, JP-A-54-59143, 55-52063, 55-52064, 55-46760, 55-85495, 57-11350, 57-148749, JP-A-2-311591, etc. Stilbene derivatives (Japanese Patent Laid-Open Nos. 61-210363, 61-228451, 61-14642, 61-72255, 62-47646, 62-36674) 62-10652, 62-30255, 60-93455, 60-94462, 60-174749, 60-175052, etc.), silazane derivatives (US) Patent No. 4,950,950), polysilane (JP-A-2-204996), aniline copolymer (JP-A-2-282263), an electroconductive oligomer (particularly a thiophene oligomer) disclosed in JP-A-1-211399 and the like.

  As the hole injecting material and the hole transporting material, those described above can be used. Porphyrin compounds (Japanese Patent Laid-Open No. 63-295965), aromatic tertiary amine compounds and styrylamine compounds (US Pat. No. 4,127,412, JP-A-53-27033, 54-58445, 54-149634, 54-64299, 55-79450, 55-144250 No. 56-119132, No. 61-295558, No. 61-98353, No. 63-295695, etc.) can also be used. For example, 4,4′-bis (N- (1-naphthyl) -N-phenylamino) biphenyl having two condensed aromatic rings in the molecule described in US Pat. No. 5,061,569, etc. And 4,4 ′, 4 ″ -tris (N- (3-methylphenyl) -N-phenyl, in which three triphenylamine units described in JP-A-4-308688 are linked in a starburst type. Amino) triphenylamine, etc. In addition, examples of the hole injection material include phthalocyanine derivatives such as copper phthalocyanine and hydrogen phthalocyanine, and other aromatic dimethylidene compounds, p-type Si, p-type SiC, etc. These inorganic compounds can also be used as hole injection materials and hole transport materials.

  Specific examples of the aromatic tertiary amine derivative include, for example, N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4′-diamine, N, N , N ′, N ′-(4-methylphenyl) -1,1′-phenyl-4,4′-diamine, N, N, N ′, N ′-(4-methylphenyl) -1,1′- Biphenyl-4,4′-diamine, N, N′-diphenyl-N, N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine, N, N ′-(methylphenyl) -N, N '-(4-n-Butylphenyl) -phenanthrene-9,10-diamine, N, N-bis (4-di-4-tolylaminophenyl) -4-phenyl-cyclohexane, N, N'-bis (4 '-Diphenylamino-4-biphenylyl) -N, N'-diphenyl Nzine, N, N′-bis (4′-diphenylamino-4-phenyl) -N, N′-diphenylbenzidine, N, N′-bis (4′-diphenylamino-4-phenyl) -N, N ′ -Di (1-naphthyl) benzidine, N, N'-bis (4'-phenyl (1-naphthyl) amino-4-phenyl) -N, N'-diphenylbenzidine, N, N'-bis (4'- Phenyl (1-naphthyl) amino-4-phenyl) -N, N′-di (1-naphthyl) benzidine and the like can be mentioned, and these can be used for both hole injection materials and hole transport materials.

  As the hole injection material and hole transport material used together with the compound of the present invention (organic EL device material), the following general formulas [14] to [19] can be used.

General formula [14]

(In the formula, R ^{a11 to} R ^a14 each independently represents a hydrogen atom, an alkoxyl group, or a cyano group, but they are not all simultaneously hydrogen atoms.)
Here, as an alkoxyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, an octyloxy group, a tert-octyloxy group, a 2-bornyloxy group, a 2-isobornyloxy group, 1- Examples thereof include an alkoxyl group having 1 to 18 carbon atoms such as an adamantyloxy group. In particular, as a preferable combination of R ^{a11 to} R ^a14 of the general formula [5], it is preferable that all of R ^{a11 to} R ^a14 are a methoxy group, an ethoxy group, or a cyano group.

General formula [15]

(In the formula, Z ²¹ represents a linking group, and represents a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, an oxygen atom, or a sulfur atom. R ^{a21 to} R ^a26 represent And each independently represents a monovalent aromatic hydrocarbon group.)
In the general formula ^[15], the linking group ^{Z 21,} a single bond, a vinylene group, o- phenylene group, m- phenylene, p- phenylene, 1,4-naphthylene group, 2,6-naphthylene group, A 9,10-phenanthrylene group and a 9,10-anthrylene group are preferred, and a single bond, vinylene group, p-phenylene group, and 1,4-naphthylene group are more preferred. R ^{a21 to} R ^a26 include a monovalent aromatic hydrocarbon group selected from a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group. preferable.

Formula [16]

(In the formula, Z ³¹ is a linking group, and represents a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, an oxygen atom, or a sulfur atom. R ^{a31 to} R ^a36 represent And each independently represents a monovalent aromatic hydrocarbon group.)
As the linking group for Z ³¹ , a single bond, vinylene group, o-phenylene group, m-phenylene group, p-phenylene group, 1,4-naphthylene group, 2,6-naphthylene group, 9,10-phenanthrylene group, A 9,10-anthrylene group is preferable, and a single bond, vinylene group, p-phenylene group, and 1,4-naphthylene group are more preferable. R ^{a31 to} R ^a36 include a monovalent aromatic hydrocarbon group selected from a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group. preferable.

General formula [17]

(In the formula, R ^{a41 to} R ^a48 each independently represents a monovalent aromatic hydrocarbon group.)
R ^{a41 to} R ^a48 are preferably monovalent aromatic hydrocarbon groups selected from a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group.

General formula [18]

(In formula, R ^{< a51 >} -R ^{< a56 >} represents a monovalent ^| monohydric aromatic hydrocarbon group each independently.)
R ^{a51 to} R ^a56 are preferably monovalent aromatic hydrocarbon groups selected from a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group.

General formula [19]

(In the formula, R ^{a61 to} R ^a64 each independently represents a monovalent aromatic hydrocarbon group, and p represents an integer of 1 to 4.)
R ^{a61 to} R ^a64 are preferably a monovalent aromatic hydrocarbon group selected from a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group.
The compounds represented by the general formulas [14] to [19] described above are particularly preferably used as hole injection materials. Table 3 below shows particularly preferred examples.

  Moreover, as a hole transport material which can be used with the compound (organic EL element material) of this invention, the well-known compound shown in following Table 4 is mention | raise | lifted.

In order to form the hole injection layer described above, the above-described compound is thinned by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. Although there is no restriction | limiting in particular, Usually, they are 5 nm-5 micrometers.
On the other hand, for the electron injection layer, an electron injection material that exhibits an excellent electron injection effect with respect to the light emitting layer and that can form an electron injection layer excellent in adhesion to the cathode interface and thin film formability is used. Examples of such electron injection materials include metal complex compounds, nitrogen-containing five-membered ring derivatives, fluorenone derivatives, anthraquinodimethane derivatives, diphenoquinone derivatives, thiopyrandioxide derivatives, perylenetetracarboxylic acid derivatives, fluorenylidenemethane. Derivatives, anthrone derivatives, silole derivatives, triarylphosphine oxide derivatives, calcium acetylacetonate, sodium acetate and the like. In addition, inorganic / organic composite materials doped with metal such as cesium in bathophenanthroline (Proceedings of the Society of Polymer Science, Vol. 50, No. 4, 660, published in 2001), and the 50th Applied Physics Related Lecture Lecture Proceedings, No. Examples of electron injection materials include BCP, TPP, T5MPyTZ, etc. published on page 3, 1402, 2003. Electrons can be transported by forming a thin film necessary for device fabrication and injecting electrons from the cathode. If it is material, it will not specifically limit to these.

  Preferable examples of the electron injection material include metal complex compounds, nitrogen-containing five-membered ring derivatives, silole derivatives, and triarylphosphine oxide derivatives. As a preferable metal complex compound that can be used in the present invention, a metal complex of 8-hydroxyquinoline or a derivative thereof is suitable. Specific examples of the metal complex of 8-hydroxyquinoline or a derivative thereof include tris (8-hydroxyquinolinate) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (4-methyl-8- Hydroxyquinolinato) aluminum, tris (5-methyl-8-hydroxyquinolinato) aluminum, tris (5-phenyl-8-hydroxyquinolinato) aluminum, bis (8-hydroxyquinolinato) (1-naphtholate) ) Aluminum, bis (8-hydroxyquinolinate) (2-naphtholate) aluminum, bis (8-hydroxyquinolinate) (phenolate) aluminum, bis (8-hydroxyquinolinato) (4-cyano-1-naphtholate) ) Aluminum, bis (4-methyl-8) Hydroxyquinolinato) (1-naphtholato) aluminum, bis (5-methyl-8-hydroxyquinolinato) (2-naphtholato) aluminum, bis (5-phenyl-8-hydroxyquinolinato) (phenolate) aluminum, Bis (5-cyano-8-hydroxyquinolinate) (4-cyano-1-naphtholato) aluminum, bis (8-hydroxyquinolinato) chloroaluminum, bis (8-hydroxyquinolinato) (o-cresolate) Aluminum complex compounds such as aluminum, tris (8-hydroxyquinolinato) gallium, tris (2-methyl-8-hydroxyquinolinato) gallium, tris (4-methyl-8-hydroxyquinolinato) gallium, tris ( 5-Methyl-8-hydroxyquinolinate Gallium, tris (2-methyl-5-phenyl-8-hydroxyquinolinato) gallium, bis (2-methyl-8-hydroxyquinolinato) (1-naphtholato) gallium, bis (2-methyl-8-hydroxy) Quinolinate) (2-naphtholato) gallium, bis (2-methyl-8-hydroxyquinolinato) (phenolate) gallium, bis (2-methyl-8-hydroxyquinolinato) (4-cyano-1-naphtholate) ) Gallium, bis (2,4-dimethyl-8-hydroxyquinolinato) (1-naphtholate) gallium, bis (2,5-dimethyl-8-hydroxyquinolinato) (2-naphtholato) gallium, bis (2 -Methyl-5-phenyl-8-hydroxyquinolinate) (phenolate) gallium, bis (2-methyl-5- Cyano-8-hydroxyquinolinate) (4-cyano-1-naphtholate) gallium, bis (2-methyl-8-hydroxyquinolinate) chlorogallium, bis (2-methyl-8-hydroxyquinolinate) ( In addition to gallium complex compounds such as o-cresolate) gallium, 8-hydroxyquinolinate lithium, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, bis (10-hydroxybenzo [h And quinolinato) beryllium, bis (8-hydroxyquinolinato) zinc, and bis (10-hydroxybenzo [h] quinolinato) zinc.

Among the electron injection materials that can be used in the present invention, preferable nitrogen-containing five-membered ring derivatives include oxazole derivatives, thiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, and triazole derivatives. , 5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1-phenyl) -1, 3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5-bis (1-naphthyl) -1 , 3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butyl benzene], -(4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1,3,4-thiadiazole, 1,4 -Bis [2- (5-phenylthiadiazolyl)] benzene, 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4-triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like.
Among the electron injection materials that can be used in the present invention, particularly preferable oxadiazole derivatives include oxadiazole derivatives represented by the following general formula [20].
General formula [20]

(In the formula, Ar ^r1 and Ar ^r2 each independently represent a monovalent aromatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group which may have a substituent.)
Examples of the monovalent nitrogen-containing aromatic heterocyclic group include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 3-pyridyl group, 4-pyridazyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5- Monovalent nitrogen-containing monocyclic aromatic heterocyclic group such as pyrimidyl group, 2-pyrazyl group, 1-imidazolyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl Group, 7-quinolyl group, 8-quinolyl group, 2-quinazolyl group, 4-quinazolyl group, 5-quinazolyl group, 2-quinoxalyl group, 5-quinoxalyl group, 6-quinoxalyl group, 1-indolyl group, 9-caribazolyl Monovalent nitrogen-containing fused ring aromatic heterocyclic group such as a group, 2,2′-bipyridyl-3-yl group, 2,2′-bipyridyl-4-yl group, 3,3′-bipyridyl-2-yl The group 3,3′-bipyridyl-4- Monovalent nitrogen-containing ring-aggregated aromatic heterocyclic groups such as yl group, 4,4′-bipyridyl-2-yl group, 4,4′-bipyridyl-3-yl group, and the like. The hydrogen atom on the nitrogen-containing aromatic heterocyclic group may be substituted with a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group.

In general formula [20], as Ar ^r1 and Ar ^r2 , a preferable monovalent aromatic hydrocarbon group is substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group. 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group are preferable, and preferable monovalent nitrogen-containing aromatic heterocyclic groups are monovalent A 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2,2′-bipyridyl-3-yl group, which may be substituted with an aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group, and A 2,2′-bipyridyl-4-yl group can be mentioned.
Table 5 shows specific examples of oxadiazole derivatives that can be used in the present invention.

Among the electron injection materials that can be used in the present invention, a particularly preferred triazole derivative is a triazole derivative represented by the following general formula [21].
Formula [21]

(In the formula, Ar ^{t1 to} Ar ^t3 each independently represent a monovalent aromatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group which may have a substituent.)
Here, as Ar ^t1 and Ar ^t2, as a preferable monovalent aromatic hydrocarbon group, phenyl which may be substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group, Group, 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group. Preferred monovalent nitrogen-containing aromatic heterocyclic groups include monovalent aliphatic groups. 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2,2′-bipyridyl-3-yl group, and 2 which may be substituted with an aromatic hydrocarbon group or a monovalent aromatic hydrocarbon group , 2'-bipyridyl-4-yl group. In addition, as ^{Art 3} , preferred monovalent aromatic hydrocarbon groups include a phenyl group which may be substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group, 1- Examples thereof include a naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group. Preferred monovalent nitrogen-containing aromatic heterocyclic groups are monovalent aliphatic hydrocarbon groups. Or the 2-pyridyl group, 3-pyridyl group, and 4-pyridyl group which may be substituted by the monovalent | monohydric aromatic hydrocarbon group are mention | raise | lifted.
Table 6 shows specific examples of triazole derivatives that can be used in the present invention.

  Among the electron injection materials that can be used in the present invention, particularly preferred silole derivatives include silole derivatives represented by the following general formula [22].

General formula [22]

(Wherein R ^p1 and R ^p2 each independently represents a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or a monovalent nitrogen-containing aromatic complex that may have a substituent. Ar ^{p1 to} Ar ^p4 each independently represents a monovalent aromatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group which may have a substituent, R ^p1 , The adjacent groups of R ^p2 and Ar ^{p1 to} Ar ^p4 may be connected to each other to form a ring.
Here, as R ^p1 and R ^p2 , preferred monovalent aliphatic hydrocarbon group is methyl which may be substituted with a monovalent aromatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group. Group, ethyl group, propyl group, and butyl group. Preferred monovalent aromatic hydrocarbon groups are substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group. And a phenyl group, an m-biphenylyl group, and a p-biphenylyl group. Preferred monovalent nitrogen-containing aromatic heterocyclic groups include a monovalent aliphatic hydrocarbon group or a monovalent aromatic carbon group. Examples thereof include a 2-pyridyl group, a 3-pyridyl group and a 4-pyridyl group, which may be substituted with a hydrogen group. In addition, as Ar ^{p1 to} Ar ^p4 , a preferable monovalent aromatic hydrocarbon group is a phenyl group which may be substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group. , 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group, and preferable monovalent nitrogen-containing aromatic heterocyclic groups are monovalent aliphatic A 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2,2′-bipyridyl-3-yl group, which may be substituted with a hydrocarbon group or a monovalent aromatic hydrocarbon group, and 2, A 2'-bipyridyl-4-yl group is mentioned.
Table 7 shows specific examples of silole derivatives that can be used in the present invention.

Of the electron injecting materials that can be used in the present invention, preferred triarylphosphine oxide derivatives include those disclosed in JP-A-2002-63989, JP-A-2004-95221, JP-A-2004-203828, and JP-A-2004. -204140 and the triarylphosphine oxide derivative represented by the following general formula [23] can be shown.
General formula [23]

(In the formula, Ar ^{q1 to} Ar ^q3 each independently represent a monovalent aromatic hydrocarbon group which may have a substituent.)
Here, as Ar ^{q1 to} Ar ^q3 , a preferable monovalent aromatic hydrocarbon group is a phenyl group which may be substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group. 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group.
Table 8 shows specific examples of triarylphosphine oxide derivatives that can be used in the present invention.

Furthermore, a hole blocking material that can prevent holes from passing through the light emitting layer from reaching the electron injection layer and form a layer having excellent thin film formability is used for the hole blocking layer. Examples of such hole blocking materials include aluminum complex compounds such as bis (8-hydroxyquinolinate) (4-phenylphenolate) aluminum, and bis (2-methyl-8-hydroxyquinolinate) ( 4-phenylphenolate) gallium complex compounds such as gallium, and nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).
The light emitting layer of the organic EL device of the present invention preferably has the following functions.
Injection function: Function that can inject holes from the anode or hole injection layer when an electric field is applied, and can inject electrons from the cathode or electron injection layer:
Transport function: Function to move injected charges (electrons and holes) by the force of electric field Light emission function: Function to provide a field for recombination of electrons and holes and connect it to light emission However, holes are easily injected There may be a difference in the ease of injecting electrons and electrons, and the transport capability expressed by the mobility of holes and electrons may be large or small. preferable.
The light-emitting material of the organic EL element is mainly an organic compound, and specifically, the following compounds are used depending on a desired color tone.
For example, when obtaining violet emission from the ultraviolet region, a compound represented by the following general formula [24] is preferably used.

General formula [24]

(In the formula, X1 represents a group represented by the following general formula [25], and X2 represents any one of a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.]

Formula [25]

(In the formula, m represents an integer of 2 to 5)
The phenyl group, 1-naphthyl group, 2-naphthyl group, and phenylene group represented by X1 and X2 in the general formula [24] are one or more alkyl groups having 1 to 4 carbon atoms and 1 to 4 carbon atoms. It may be substituted with a substituent such as an alkoxyl group, a hydroxyl group, a sulfonyl group, a carbonyl group, an amino group, a dimethylamino group or a diphenylamino group. Moreover, when there are a plurality of these substituents, they may be bonded to each other to form a ring. Furthermore, the phenylene group represented by X1 is preferably bonded at the para position because it has good bonding properties and can easily form a smooth deposited film. Specific examples of the compound represented by the general formula [24] are as follows (where Ph represents a phenyl group).

Among these compounds, p-quaterphenyl derivatives and p-quinkphenyl derivatives are particularly preferable.
Further, in order to obtain light emission in the visible range, particularly blue to green, for example, a fluorescent brightener such as benzothiazole, benzimidazole, and benzoxazole, a metal chelated oxinoid compound, and a styrylbenzene compound may be used. it can. Specific examples of these compounds include compounds disclosed in, for example, JP-A-59-194393. Still other useful compounds are listed in Chemistry of Synthetic Soybean (1971) pages 628-637 and 640.
As the metal chelated oxinoid compound, for example, compounds disclosed in JP-A-63-295695 can be used. As typical examples, 8-hydroxyquinoline-based metal complexes such as tris (8-quinolinol) aluminum, dilithium ependridione and the like can be mentioned as suitable compounds.
As the styrylbenzene compound, for example, those disclosed in European Patent No. 0319881 and European Patent No. 0373582 can be used. And the distyrylpyrazine derivative currently disclosed by Unexamined-Japanese-Patent No. 2-252793 can also be used as a material of a light emitting layer. In addition, polyphenyl compounds disclosed in EP 0387715 can also be used as a material for the light emitting layer.
Further, in addition to the above-described fluorescent brightener, metal chelated oxinoid compound, styrylbenzene compound and the like, for example, 12-phthaloperinone (J. Appl. Phys., Vol. 27, L713 (1988)), 1,4- Diphenyl-1,3-butadiene, 1,1,4,4-tetraphenyl-1,3-butadiene (Appl. Phys. Lett., Vol. 56, L799 (1990)), naphthalimide derivatives No. 2-305886), perylene derivatives (Japanese Patent Laid-Open No. 2-189890), oxadiazole derivatives (Japanese Patent Laid-Open No. Hei 2-216791, or the 38th Applied Physics Related Conference) were disclosed by Hamada et al. Oxadiazole derivatives), aldazine derivatives (JP-A-2-220393), pyrazirine derivatives (JP-A-2-220394), cyclopentadiene derivative (JP-A-2-289675), pyrrolopyrrole derivative (JP-A-2-29691), styrylamine derivative (Appl. Phys. Lett., 56th). Vol. L799 (1990), coumarin compounds (Japanese Patent Laid-Open No. 2-191694), International Patent Publications WO 90/13148 and Appl. Phys. Lett., Vol 58, 18, P1982 (1991). Polymer compounds, 9,9 ′, 10,10′-tetraphenyl-2,2′-bianthracene, PPV (polyparaphenylene vinylene) derivatives, polyfluorene derivatives and copolymers thereof, for example, the following general formula [ 26] to the structure of the general formula [28]

General formula [26]

(In the formula, R ^X1 and R ^X2 each independently represent a monovalent aliphatic hydrocarbon group, and n1 represents an integer of 3 to 100.)

General formula [27]

(In the formula, R ^X3 and R ^X4 each independently represent a monovalent aliphatic hydrocarbon group, and n2 and n3 each independently represent an integer of 3 to 100.)

General formula [28]

(In the formula, R ^X5 and R ^X6 each independently represent a monovalent aliphatic hydrocarbon group, n4 and n5 each independently represent an integer of 3 to 100, and Ph represents a phenyl group.)
9,10-bis (N- (4- (2-phenylvinyl-1-yl) phenyl) -N-phenylamino) anthracene or the like can also be used as a material for the light emitting layer. Furthermore, a phenylanthracene derivative represented by the following general formula [20] as disclosed in JP-A-8-12600 can also be used as a light emitting material.
General formula [29]
A1-L-A2 [29]
(In the formula, A1 and A2 each independently represent a monophenylanthryl group or a diphenylanthryl group, which may be the same or different. L represents a single bond or a divalent linking group. )
Here, the divalent linking group represented by L is preferably a divalent monocyclic or condensed ring aromatic hydrocarbon group which may have a substituent. In particular, phenylanthracene derivatives represented by the following general formulas [30] to [31] are preferable.

General formula [30]

(In the formula, R ^{Z1 to} R ^Z4 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a monovalent aromatic hydrocarbon group, an alkoxyl group, an aryloxy group, a diarylamino group, or a monovalent group. The aliphatic heterocyclic group and monovalent aromatic heterocyclic group may be the same or different, and r1 to r4 each independently represents 0 or an integer of 1 to 5. ~r4 are each independently when an integer of 2 or ^{more, R Z1} each ^{other, R Z2} each ^{other, R Z3} each ^{other, R Z4} to each other may be different each be the ^{same, R Z1} each ^{other, R Z2} together , R ^Z3 and R ^Z4 may be bonded to form a ring, and L1 represents a single bond or a divalent monocyclic or condensed ring aromatic hydrocarbon group which may have a substituent. A divalent monocyclic ring which may have a group or Fused aromatic hydrocarbon group, an alkylene group, -O -, - S- or -NR- (wherein R represents an alkyl group or an aryl group) or may be mediated).

Formula [31]

Wherein R ^Z5 and R ^Z6 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a monovalent aromatic hydrocarbon group, an alkoxyl group, an aryloxy group, a diarylamino group, a monovalent group The aliphatic heterocyclic group and monovalent aromatic heterocyclic group may be the same or different, and r5 and r6 each independently represents 0 or an integer of 1 to 5. and r6 are each independently when it is 2 or more integer, each other R ^Z5 each other and R ^Z6 may also be different from each other could be identical, each other R ^Z5 each other and R ^Z6 are joined to form a ring L2 represents a single bond or a divalent monocyclic or condensed ring aromatic hydrocarbon group which may have a substituent, and a divalent monocyclic or condensed ring aromatic which may have a substituent. Group hydrocarbon group is an alkylene group, O -, - S- or -NR- (wherein R represents an alkyl group or an aryl group) or may be mediated).

  Of the general formula [30], phenylanthracene derivatives represented by the following general formula [32] to general formula [33] are more preferable.

General formula [32]

(In the formula, R ^{Z11 to} R ^Z30 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a monovalent aromatic hydrocarbon group, an alkoxyl group, an aryloxy group, a diarylamino group, a monovalent group. The aliphatic heterocyclic group and the monovalent aromatic heterocyclic group, which may be the same or different, and R ^{Z11 to} R ^Z30 are connected to each other to form a ring. (K1 represents an integer of 0 to 3)

Formula [33]

(In the formula, R ^{Z31 to} R ^Z50 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a monovalent aromatic hydrocarbon group, an alkoxyl group, an aryloxy group, a diarylamino group, or a monovalent group. And R ^{Z31 to} R ^Z50 may be the same or different, and R ^{Z31 to} R ^Z50 are connected to each other to form a ring. (K2 represents an integer of 0 to 3)

  Of the general formula [31], a phenylanthracene derivative represented by the following general formula [34] is more preferable.

General formula [34]

(In the formula, R ^{Z51 to} R ^Z60 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a monovalent aromatic hydrocarbon group, an alkoxyl group, an aryloxy group, a diarylamino group, a monovalent group. And R ^{Z51 to} R ^Z60 are connected to each other to form a ring, each of which may be the same or different. (K3 represents an integer of 0 to 3)
Specific examples of the general formula [32] to general formula [34] include the following compounds.

  Furthermore, the following compounds are also given as specific examples.

An amine compound represented by the following general formula [35] is also useful as a light emitting material.
General formula [35]

(In the formula, h is a valence and represents an integer of 1 to 6. E1 is an n-valent aromatic hydrocarbon group, E2 is an amino group selected from a dialkylamino group, a diarylamino group, and an alkylarylamino group. Represents a group.)
Here, as the base structure of the n-valent aromatic hydrocarbon group represented by E1, naphthalene, anthracene, 9-phenylanthracene, 9,10-diphenylanthracene, naphthacene, pyrene, perylene, biphenyl, binaphthyl, and bianthryl are preferable. , E1 is preferably a diarylamino group. N is preferably 1 to 4, and most preferably 2. Of the general formula [35], amine compounds represented by the following general formula [36] to general formula [45] are particularly preferable.

General formula [36]

(In the formula, R ^{y1 to} R ^y8 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic heterocyclic group. A cyclic group or an amino group selected from a dialkylamino group, a diarylamino group, and an alkylarylamino group, and at least one of R ^{y1 to} R ^y8 is a dialkylamino group, a diarylamino group, an alkylarylamino group. And represents an amino group selected from a group, R ^{y1 to} R ^y8 may be the same or different, and adjacent groups may be linked to form a ring.

General formula [37]

(In the formula, R ^{y11 to} R ^y20 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic heterocyclic group. A cyclic group or an amino group selected from a dialkylamino group, a diarylamino group, and an alkylarylamino group, and at least one of R ^{y11 to} R ^y20 is a dialkylamino group, a diarylamino group, an alkylarylamino group. And R ^{y11 to} R ^y20 may be the same or different, and adjacent groups may be connected to form a ring.

General formula [38]

( ^Wherein , R ^{y21 to} R ^y34 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic heterocyclic group. A cyclic group or an amino group selected from a dialkylamino group, a diarylamino group, and an alkylarylamino group, and at least one of R ^{y21 to} R ^y34 is a dialkylamino group, a diarylamino group, an alkylarylamino group. And R ^{y21 to} R ^y34 may be the same or different, and adjacent groups may be linked to form a ring.

General formula [39]

(In the formula, R ^{y35 to} R ^y52 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic heterocyclic group. A cyclic group or an amino group selected from a dialkylamino group, a diarylamino group, and an alkylarylamino group, and at least one of R ^{y35 to} R ^y52 is a dialkylamino group, a diarylamino group, an alkylarylamino group. Represents an amino group selected from a group, R ^{y35 to} R ^y52 may be the same or different, and adjacent groups may be linked to form a ring.)

General formula [40]

(In the formula, R ^{y53 to} R ^y64 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic heterocyclic group. ring group, or a dialkylamino group, a diarylamino group, represents an amino group selected from alkyl aryl amino group, of R ^y53 to R ^Y64, at least one, dialkylamino group, diarylamino group, an alkylarylamino Represents an amino group selected from the group, and R ^{y53 to} R ^y64 may be the same or different, and adjacent groups may be linked to form a ring.)

General formula [41]

( ^Wherein R ^{y65 to} R ^y74 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic heterocyclic group. ring group, or a dialkylamino group, a diarylamino group, represents an amino group selected from alkyl aryl amino group, of R ^Y65 to R ^Y74, at least one, dialkylamino group, diarylamino group, an alkylarylamino And R ^{y65 to} R ^y74 may be the same or different, and adjacent groups may be linked to form a ring.

General formula [42]

(In the formula, R ^{y75 to} R ^y86 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic heterocyclic group. A cyclic group or an amino group selected from a dialkylamino group, a diarylamino group, and an alkylarylamino group, and at least one of R ^{y75 to} R ^y86 is a dialkylamino group, a diarylamino group, an alkylarylamino group. Represents an amino group selected from the group, and R ^{y75 to} R ^y86 may be the same or different, and adjacent groups may be linked to form a ring.)

General formula [43]

(In the formula, R ^{y87 to} R ^y96 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic heterocyclic group. ring group, or a dialkylamino group, a diarylamino group, represents an amino group selected from alkyl aryl amino group, of ^R y87 ~R y96, at least one, dialkylamino group, diarylamino group, an alkylarylamino And R ^{y87 to} R ^y96 may be the same or different, and adjacent groups may be connected to form a ring.

General formula [44]

( ^Wherein R ^{y97 to} R ^y110 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic heterocyclic group. ring group, or a dialkylamino group, a diarylamino group, represents an amino group selected from alkyl aryl amino group, of R ^Y97 to R ^y110, at least one, dialkylamino group, diarylamino group, an alkylarylamino Represents an amino group selected from a group, R ^{y97 to} R ^y110 may be the same or different, and adjacent groups may be linked to form a ring.)

General formula [45]

( ^Wherein R ^{y111 to} R ^y128 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic heterocyclic group. ring group, or a dialkylamino group, a diarylamino group, represents an amino group selected from alkyl aryl amino group, of ^R y111 ~R y128, at least one, dialkylamino group, diarylamino group, an alkylarylamino Represents an amino group selected from a group, R ^{y111 to} R ^y128 may be the same or different, and adjacent groups may be linked to form a ring.)
The amine compounds of the general formula [40] and the general formula [42] described above can be preferably used when yellow to red light emission is obtained. Specific examples of the amine compounds represented by the general formulas [35] to [45] described above include compounds having the following structure (where Ph represents a phenyl group).

  In addition, in the above general formula [35] to general formula [45], a compound containing at least one styryl group represented by the following general formula [46] to general formula [47] instead of an amino group (for example, EP 0388768, JP-A-3-231970, etc.) can also be suitably used as the light emitting material.

General formula [46]

(In the formula, R ^{y129 to} R ^y131 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent aromatic hydrocarbon group. R ^{y129 to} R ^y131 are groups in which adjacent groups are connected to each other. And may form a ring.)

General formula [47]

( ^Wherein R ^{y132 to} R ^y138 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent aromatic hydrocarbon group. R ^{y134 to} R ^y138 each independently represents a hydrogen atom, An alkyl group, a cycloalkyl group, a monovalent aromatic hydrocarbon group, or an amino group selected from a dialkylamino group, a diarylamino group, and an alkylarylamino group, but at least one of R ^{y134 to} R ^y138 Is an amino group selected from a dialkylamino group, a diarylamino group, and an alkylarylamino group, and R ^{y132 to} R ^y138 may be linked to each other to form a ring.
Specific examples of the compound containing at least one styryl group represented by the general formulas [46] to [47] described above can include compounds having the following structure (where Ph represents a phenyl group): .

In addition, the general formula (Rs-Q) _2- Al-O-L3 (wherein L3 is a hydrocarbon having 6 to 24 carbon atoms including a phenyl moiety) described in JP-A-5-258862, etc. O-L3 is a phenolate ligand, Q represents a substituted 8-quinolinolato ligand, Rs sterically represents that two or more substituted 8-quinolinolato ligands are bonded to an aluminum atom. And a bis (2-methyl-8-quinolinolato) (para-phenylphenolato) aluminum (III) compound, which represents an 8-quinolinolato ring substituent selected to interfere. ), Bis (2-methyl-8-quinolinolato) (1-naphtholato) aluminum (III), and the like.

  In addition, there is a method for obtaining high-efficiency blue and green mixed light emission using doping described in JP-A-6-9953. In this case, examples of the host include the above-described light-emitting materials, and examples of the dopant include strong fluorescent dyes from blue to green, for example, coumarins or fluorescent dyes similar to those used as the host. Specifically, a light-emitting material having a distyrylarylene skeleton as a host, particularly preferably 4,4′-bis (2,2-diphenylvinyl) biphenyl, and diphenylaminovinylarylene as a dopant, particularly preferably, for example, N, N-diphenyl Amino vinyl benzene can be mentioned.

Although there is no restriction | limiting in particular as a light emitting layer which obtains white light emission, The following can be used.
The energy level of each layer of the organic EL laminated structure is defined and light is emitted using tunnel injection (European Patent No. 0390551). Similarly, a white light emitting element is described as an example of an element using tunnel injection (Japanese Patent Laid-Open No. 3-230584). A light-emitting layer having a two-layer structure is described (JP-A-2-220390 and JP-A-2-216790). A structure in which a light emitting layer is divided into a plurality of materials each having a different emission wavelength (Japanese Patent Laid-Open No. 4-51491). A structure in which a blue phosphor (fluorescence peak 380 to 480 nm) and a green phosphor (480 to 580 nm) are stacked and a red phosphor is further contained (Japanese Patent Laid-Open No. 6-207170). The blue light emitting layer contains a blue fluorescent dye, the green light emitting layer has a region containing a red fluorescent dye, and further contains a green phosphor (Japanese Patent Laid-Open No. 7-142169). Among these, those having the above-described configuration are particularly preferable.
Furthermore, for example, the following known compounds are preferably used as the light emitting material (where Ph represents a phenyl group).

  In the organic EL device of the present invention, a phosphorescent material can be used. Examples of the phosphorescent material or doping material that can be used in the organic EL device of the present invention include, for example, an organometallic complex, where the metal atom is usually a transition metal, and preferably has a period of 5th or 6th period. In the group, elements from Group 6 to Group 11, more preferably Group 8 to Group 10 are targeted. Specific examples include iridium and platinum. Examples of the ligand include 2-phenylpyridine and 2- (2'-benzothienyl) pyridine, and the carbon atom on these ligands is directly bonded to the metal. Another example is a porphyrin or tetraazaporphyrin ring complex, and the central metal is platinum. For example, the following known compounds are suitably used as the phosphorescent material (where Ph represents a phenyl group).

  Furthermore, the material used for the anode of the organic EL device of the present invention is preferably a material having a work function (4 eV or more) metal, alloy, electrically conductive compound or a mixture thereof as an electrode substance. Specific examples of such an electrode substance include metals such as Au, and conductive materials such as CuI, ITO, SnO2, and ZnO. In order to form this anode, a thin film can be formed from these electrode materials by a method such as vapor deposition or sputtering. The anode desirably has such a characteristic that when light emitted from the light emitting layer is extracted from the anode, the transmittance of the anode for light emission is greater than 10%. The sheet resistance of the anode is preferably several hundred Ω / □ or less. Further, although the film thickness of the anode depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.

  The material used for the cathode of the organic EL device of the present invention is a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof as an electrode substance. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / silver alloy, aluminum / aluminum oxide, aluminum / lithium alloy, indium, and rare earth metals. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Here, when light emitted from the light-emitting layer is extracted from the cathode, the transmittance of the cathode for light emission is preferably greater than 10%. The sheet resistance as a cathode is preferably several hundred Ω / □ or less, and the film thickness is usually 10 nm to 1 μm, preferably 50 to 200 nm.

  Regarding the method for producing the organic EL device of the present invention, an anode, a light emitting layer, a hole injection layer as necessary, and an electron injection layer as necessary are formed by the above materials and methods, and finally a cathode is formed. do it. Moreover, an organic EL element can also be produced from the cathode to the anode in the reverse order.

  This organic EL element is manufactured on a translucent substrate. This translucent substrate is a substrate that supports the organic EL element, and for the translucency, it is desirable that the transmittance of light in the visible region of 400 to 700 nm is 50% or more, preferably 90% or more, Further, it is preferable to use a smooth substrate.

  These substrates have mechanical and thermal strengths and are not particularly limited as long as they are transparent. For example, glass plates, synthetic resin plates and the like are preferably used. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the synthetic resin plate include plates made of polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, polysulfone resin, and the like.

  As a method for forming each layer of the organic EL element of the present invention, a dry film forming method such as vacuum deposition, electron beam irradiation, sputtering, plasma, ion plating, or a wet film forming method such as spin coating, dipping, or flow coating is used. Either method can be applied. The organic layer is particularly preferably a molecular deposited film. Here, the molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidifying from a material compound in a solution state or a liquid phase state. Can be classified from a thin film (accumulated film) formed by the LB method according to a difference in an agglomerated structure and a higher-order structure and a functional difference resulting therefrom. Further, as disclosed in JP-A-57-51781, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, which is then thinned by a spin coat method or the like. An organic layer can be formed. The film thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Conversely, if the film thickness is too thin, pinholes, etc. And it becomes difficult to obtain sufficient light emission luminance even when an electric field is applied. Accordingly, the thickness of each layer is suitably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.

  Further, in order to improve the stability of the organic EL element with respect to temperature, humidity, atmosphere and the like, a protective layer may be provided on the surface of the element, or the entire element may be covered or sealed with a resin or the like. In particular, when the entire element is covered or sealed, a photocurable resin that is cured by light is preferably used.

  The current applied to the organic EL element of the present invention is usually a direct current, but a pulse current or an alternating current may be used. The current value and the voltage value are not particularly limited as long as the element is within a range not destroying the element. However, considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electrical energy as possible.

  The organic EL device driving method of the present invention can be driven not only by the passive matrix method but also by the active matrix method. Further, the method for extracting light from the organic EL device of the present invention is applicable not only to the method of bottom emission for extracting light from the anode side but also to the method of top emission for extracting light from the cathode side. These methods and techniques are described in Shinji Kido, “All about organic EL”, published by Nihon Jitsugyo Shuppansha (published in 2003).

  Furthermore, the organic EL element of the present invention may adopt a microcavity structure. This is because the organic EL element has a structure in which the light emitting layer is sandwiched between the anode and the cathode, and the emitted light causes multiple interference between the anode and the cathode, but the reflectance and transmission of the anode and the cathode. This is a technology that actively uses the multiple interference effect and controls the emission wavelength extracted from the device by appropriately selecting the optical characteristics such as the rate and the film thickness of the organic layer sandwiched between them. . Thereby, it is also possible to improve the emission chromaticity. For the mechanism of this multiple interference effect, see J.A. Yamada et al., AM-LCD Digest of Technical Papers, OD-2, p. 77-80 (2002).

  As described above, the organic EL device using the phenanthrene compound having a carbazolyl group of the present invention can emit light for a long time with a low driving voltage. Therefore, this organic EL device can be used as a flat panel display such as a wall-mounted television and various flat light emitters, as well as a light source such as a copying machine or a printer, a light source such as a liquid crystal display or an instrument, a display board, a marker lamp, etc. Can be applied.

FIG. 1 is a mass spectrum of the compound (2). Calculated value: 842.34 (M ⁺ ), measured value: 842.361 FIG. 2 is ¹ HNMR of compound (2). (In THF-d ₈ ) FIG. 3 is a ¹³ C NMR of the compound (2). (In THF-d ₈ ) FIG. 4 is a mass spectrum of the compound (61). Calculated value: 742.309 (M ⁺ ), measured value: 742.291

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples at all.

Example 1
First, production examples of the phenanthrene compound having a carbazolyl group represented by the general formula [11] of the present invention will be described.
Method for Synthesizing Compound (2) The synthesis scheme is as in Reaction 1.
Reaction 1

Hereinafter, the reaction 1 will be described. Under a nitrogen atmosphere, 3.0 g (8.3 mmol) of (i), 7.0 g (21.6 mmol) of 3-bromo-9-phenylcarbazole (ii), 0.37 g of palladium acetate, tri-tert-butylphosphine 1 .4 g and sodium tert-butoxide 2.0 g were placed in a 100 ml four-necked flask, 20 ml of dehydrated xylene was added, and the mixture was heated to reflux for 1.5 hours. The reaction solution was poured into 400 ml of methanol, and the precipitated solid was collected by filtration and dried in a hot vacuum. As a crude product, (iii) (= compound (2)) was obtained in 8.2 g (yield 117%). The obtained crude product was purified by silica gel column chromatography, and further sublimation purification was performed. The glass transition temperature of this compound (2) was 171 ° C. (differential scanning calorimeter, manufactured by Seiko Instruments Inc.). The mass spectrum of the compound (manufactured by Bruker Daltonics, Autoflex II), ¹ H-NMR, and ¹³ C-NMR (manufactured by JEOL, GSX-270W) are shown in FIGS.
In addition, (i) used for the synthesis | combination of a compound (2) was able to be synthesize | combined using the method disclosed in Unexamined-Japanese-Patent No. 5-39248.
Further, 3-bromo-9-phenylcarbazole (ii) used for the synthesis of compound (2) was brominated at the 3-position of carbazole with reference to Industrial Chemical Journal, 1967, volume 70, page 63, Subsequently, the one synthesized by reacting iodobenzene by the Ullman method using a copper catalyst was used.

Examples 2-49
The compounds in Table 1 listed in Table 9 were synthesized. This will be described in detail below. In the synthesis method, the following reactions 2 to 6 were combined.
Reaction 2

Ar ^a is an aryl group necessary for synthesizing the compound of the present invention, and includes phenyl group, p-tolyl group, 4-biphenyl group, α-naphthyl group, β-naphthyl group, 9-anthryl group, and 9-phenanthryl. Group, 3-pyridyl group, 2-thienyl group, 2-furyl group, 4-cyanophenyl group, 4-methoxyphenyl group, 4-fluorophenyl group and the like. R is a substituent necessary for synthesizing the compound of the present invention, such as a hydrogen atom, phenyl group, methyl group, tert-butyl group, cyclohexyl group, thiophenyl group, phenoxy group, fluorine atom, diphenylamino group, etc. Is expressed. As a synthesis method, the method disclosed in JP-A-5-39248 was used.
Reaction 3

Ar ^a and R are as defined above, and Ar ^b is an aryl group necessary for synthesizing the compound of the present invention, and includes a phenyl group, a p-tolyl group, a 4-biphenyl group, an α-naphthyl group, β-naphthyl group, 3-pyridyl group, 2-thienyl group, 4-cyanophenyl group, 4-methoxyphenyl group, 4-fluorophenyl group, (4-diphenylamino) -phenyl group and the like are represented. R ′ is a substituent necessary for synthesizing the compound of the present invention, and represents a hydrogen atom, a fluorine atom, a phenyl group, a cyano group, a diphenylamino group, or the like. As a synthesis method, the monosubstituted target compound was easily obtained by the same operation as in Example 1 except that 1.1 equivalents of the corresponding carbazole derivative was reacted in place of (i) in Example 1. .
Reaction 4

Ar ^a , Ar ^b , R, and R ′ have the same meanings as described above. As a synthesis method, the target compound was similarly obtained by the same operation as in Example 1.
Reaction 5

Ar ^b and R ′ have the same meanings as described above. As a synthesis method, the target compound was obtained in the same manner as 3-bromo-9-phenylcarbazole (ii).
Reaction 6

Ar ^a , Ar ^b , R, and R ′ have the same meanings as described above. Ar ^c is an aryl group necessary for synthesizing the compounds of the present invention, a phenyl group, p- tolyl group, a 4-biphenyl group, alpha-naphthyl, beta-naphthyl, 3-pyridyl, 2-thienyl Group, 4-cyanophenyl group, 4-methoxyphenyl group, 4-fluorophenyl group, (4-diphenylamino) -phenyl group and the like. As the synthesis method, the target compound was obtained in the same manner as in Example 1 except that the starting material of reaction 6 was used instead of (i) and Arc-Br was used instead of (ii). It was.
The structure of the compound obtained by combining the above synthesis methods was confirmed by mass spectrum (manufactured by Bruker Daltonics, Autoflex II). The results are shown in Table 9. The compound numbers are the same as those in Table 1.

注：＊１ 番号は上記反応１−６に対応する。
＊２ ９，１０−ジアミノフェナントレンを原料とした。

Note: * 1 numbers correspond to reactions 1-6 above.
* 2 9,10-diaminophenanthrene was used as a raw material.

Next, X in the general formula [1] of the present invention is an o-phenylene group which may have a substituent represented by the general formula [4], or a substitution represented by the general formula [5]. A production example of a diaminoarylene compound having a carbazolyl group represented by the general formula [1] in the case of an m-phenylene group which may have a group will be described.
Each compound could be obtained by combining the reactions 7 to 13 shown below.
Reaction 7

Reaction 8

Reaction 9

Reaction 10

Reaction 11

Reaction 12

Reaction 13

3BrCz in reaction 7 was brominated at the 3-position of the carbazole derivative with reference to the Industrial Chemical Journal, published 1967, volume 70, page 63, and then reacted with the iodobenzene derivative by the Ullmann method using a copper catalyst. The synthesized one was used.
The Ullman method is a coupling reaction of aryl iodide and arylamine, in which a copper powder and a base such as anhydrous potassium carbonate are reacted at a temperature of about 100 to 180 ° C. in a high boiling point solvent such as nitrobenzene. The method known in the industry described in 7-126226 etc. was referred.
The synthesis of arylamine by the Ullmann method could also be used for the synthesis in Reaction Scheme 13.

In addition, the reaction of aryl bromide and arylamine in the reaction formulas 7 to 13 has a method in which a palladium compound and a phosphorus compound are used as a catalyst in the presence of a base instead of the copper powder and base used in the Ullman method. It was. Regarding this method, JP-A-10-81667, JP-A-10-139742, JP-A-10-310561, John F. Hartwig, Angew. Chem. Int. Ed., 37, 2046-2067 (1998), Bryant H. Yang, Stephen L Buchwald, J. Organomet. Chem., 576, 125-146 (1999), John P. Wolfe, Stephen L Buchwald, J. Org. Chem., 65, 1144 ˜1157 (2000), John P. Wolfe, Stephen L Buchwald, J. Org. Chem., 62, 1264-1267 (1997), Janis Louie, Michael S. Driver, Blake C. Hamann, John F. Hartwig, J. Org. Chem 62, pp. 1268 to 1273 (1997), JP-A 63-35548, JP-A 6-100503, JP 2001-515879, and re-published patent WO 2002/076922.
The conversion reaction from the nitro group to the amino group in the reaction 13 is a nitro group reduction reaction that has been well known for a long time, and is reduced with zinc or tin (II) chloride under acidic conditions, palladium black or By reduction with hydrogen in the presence of a catalyst such as Raney nickel and reduction using a reducing agent such as lithium aluminum hydride, the corresponding amine compound could be obtained from the nitro compound in good yield. This reduction reaction is carried out by Calvin A. Buehler and Donald E. Pearson, SURVEY OF ORGANIC SYNTHESES, 413-417, Wiley-Interscience (1970), The Chemical Society of Japan, New Experimental Chemistry Course 14, 1333-1335, The method known in the industry described in Maruzen (1978) etc. was referred.

Example 50
Synthesis Method of Compound (60) in Table 2 Under a nitrogen atmosphere, 1.1 g (10.2 mmol) of 1,2-diaminobenzene, 5.0 g (32 mmol) of bromobenzene, 0.12 g of palladium acetate, tri-tert-butyl 0.40 g of phosphine and 11.2 g of potassium carbonate were placed in a 50 ml four-necked flask, 20 ml of dehydrated xylene was added, and the mixture was heated to reflux for 3 hours. The reaction solution was neutralized with an aqueous ammonium chloride solution, and the organic layer was extracted with toluene. After drying with magnesium sulfate, the solvent was distilled off under reduced pressure. When a small amount of methanol is added to the residue and left to stand, crystals precipitate, and by filtration and drying, 0.8 g (yield 23%) of N, N, N′-triphenyl-1,2-phenylenediamine is obtained. It was. Next, 0.8 g (2.4 mmol) of the obtained N, N, N′-triphenyl-1,2-phenylenediamine, 3-bromo-9-phenylcarbazole 1, 0 g (3.1 mmol), palladium acetate 0 .05 g, 0.20 g of tri-tert-butylphosphine and 0.60 g of sodium tert-butoxide were placed in a 50 ml four-necked flask, 20 ml of dehydrated xylene was added, and the mixture was heated to reflux for 2 hours. The reaction solution was poured into 200 ml of methanol, and the precipitated solid was collected by filtration and dried in a hot vacuum. 1.2 g of compound (60) was obtained as a crude product. The obtained crude product was purified by silica gel column chromatography, and further sublimation purification was performed. The ionization potential of this compound (60) was 5.3 eV (AC-1 manufactured by Riken Keiki Co., Ltd.). The compound was identified by mass spectrum (manufactured by Bruker Daltonics, Autoflex II), ¹ H-NMR, ¹³ C-NMR.

Example 51
Synthesis Method of Compound (61) in Table 2 Under a nitrogen atmosphere, 2.4 g (10.2 mmol) of 1,2-dibromobenzene, 2.0 g (21 mmol) of aniline, 0.090 g of palladium acetate, tri-tert-butylphosphine 0.25 g and 8.6 g of potassium carbonate were placed in a 50 ml four-necked flask, 20 ml of dehydrated xylene was added, and the mixture was heated to reflux for 3 hours. The reaction solution was neutralized with an aqueous ammonium chloride solution, and the organic layer was extracted with toluene. After drying with magnesium sulfate, the solvent was distilled off under reduced pressure. When a small amount of methanol was added to the residue and left to stand, crystals were precipitated. By filtration and drying, 1.5 g (yield 56%) of N, N′-diphenyl-1,2-phenylenediamine was obtained. Next, 1.5 g (5.8 mmol) of the obtained N, N′-diphenyl-1,2-phenylenediamine, 4.8 g (15 mmol) of 3-bromo-9-phenylcarbazole, 0.26 g of palladium acetate, tri- 0.93 g of tert-butylphosphine and 1.4 g of sodium-tert-butoxide were placed in a 50 ml four-necked flask, 40 ml of dehydrated xylene was added, and the mixture was heated to reflux for 2 hours. The reaction solution was poured into 200 ml of methanol, and the precipitated solid was collected by filtration and dried in a hot vacuum. As a crude product, 4.7 g of compound (61) was obtained. The obtained crude product was purified by silica gel column chromatography, and further sublimation purification was performed. The ionization potential of this compound (61) was 5.3 eV (AC-1 manufactured by Riken Keiki Co., Ltd.). The compound was identified by mass spectrum (manufactured by Bruker Daltonics, Autoflex II), ¹ H-NMR, ¹³ C-NMR.

Example 52
Synthesis Method of Compound (92) in Table 2 Under a nitrogen atmosphere, 2.4 g (10.2 mmol) of 1,3-dibromobenzene, 2.0 g (21 mmol) of aniline, 0.090 g of palladium acetate, tri-tert-butylphosphine 0.25 g and 8.6 g of potassium carbonate were placed in a 50 ml four-necked flask, 20 ml of dehydrated xylene was added, and the mixture was heated to reflux for 3 hours. The reaction solution was neutralized with an aqueous ammonium chloride solution, and the organic layer was extracted with toluene. After drying with magnesium sulfate, the solvent was distilled off under reduced pressure. When a small amount of methanol was added to the residue and left to stand, crystals precipitated, and 1.9 g (yield 71%) of N, N′-diphenyl-1,3-phenylenediamine was obtained by filtration and drying. Next, 1.9 g (7.3 mmol) of N, N′-diphenyl-1,3-phenylenediamine and 6.1 g (19 mmol) of 3-bromo-9-phenylcarbazole obtained, 0.32 g of palladium acetate, tri- 1.2 g of tert-butylphosphine and 1.8 g of sodium tert-butoxide were placed in a 100 ml four-necked flask, 50 ml of dehydrated xylene was added, and the mixture was heated to reflux for 2 hours. The reaction solution was poured into 200 ml of methanol, and the precipitated solid was collected by filtration and dried in a hot vacuum. 5.5 g of compound (92) was obtained as a crude product. The obtained crude product was purified by silica gel column chromatography, and further sublimation purification was performed. The ionization potential of this compound (92) was 5.4 eV (AC-1 manufactured by Riken Keiki Co., Ltd.). The compound was identified by mass spectrum (manufactured by Bruker Daltonics, Autoflex II), ¹ H-NMR, ¹³ C-NMR.

Examples 53-110
The compounds of the present invention described in Table 10 could be synthesized in the same manner by combining the reactions 7 to 13 described above. The structure of the obtained compound was confirmed by mass spectrum (manufactured by Bruker Daltonics, Autoflex II). The results are shown in Table 10. The compound numbers are the same as those in Table 2. In addition, FIG. 4 shows the mass spectrum of the compound (61) (manufactured by Bruker Daltonics, Autoflex II).

    Note: * 1 numbers correspond to reactions 7-13 above.

Hereinafter, examples of preparing an organic EL device using the compound of the present invention will be described with reference to examples, but the present invention is not limited to the following examples. In the examples, all mixing ratios are weight ratios unless otherwise specified. Vapor deposition (vacuum vapor deposition) was performed in a vacuum of 10 ⁻⁶ Torr under conditions without temperature control such as substrate heating and cooling. In the evaluation of the light emission characteristics of the element, the characteristics of an organic EL element having an electrode area of 2 mm × 2 mm were measured.

Example 111
On the washed glass plate with an ITO electrode, the compound (1) of the present invention was vacuum-deposited to obtain a hole injection layer having a thickness of 60 nm. Next, N, N ′-(1-naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPD) was vacuum deposited to obtain a 20 nm hole transport layer. . Furthermore, a tris (8-hydroxyquinoline) aluminum complex is vacuum-deposited to form an electron-injection type light-emitting layer having a thickness of 60 nm, and then an electrode is formed by first depositing 1 nm of lithium fluoride and then 200 nm of aluminum. Thus, an organic EL element was obtained. The half life when this element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was measured. In addition, luminance was measured by continuously emitting light at a current density of 10 mA / cm ² for 100 hours in an environment of 100 ° C. The results are shown in Table 11.

Examples 112-120
A device similar to that of Example 111 was prepared, except that a hole injection layer was formed using the compounds shown in Table 11. The half life when this element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was measured. In addition, luminance was measured by continuously emitting light at a current density of 10 mA / cm ² for 100 hours in an environment of 100 ° C. The results are shown in Table 11.

Example 121
On the washed glass plate with an ITO electrode, the compound (44) in Table 1 of the present invention was vacuum-deposited to obtain a hole injection layer having a thickness of 60 nm. Subsequently, HTM9 in Table 4 was vacuum-deposited to obtain a 20 nm hole transport layer. Further, tris (8-hydroxyquinoline) aluminum complex (Alq3) was vacuum-deposited to prepare a 60 nm-thickness electron-injecting light-emitting layer, and first, 1 nm of lithium fluoride and then 200 nm of aluminum were evaporated. An electrode was formed to obtain an organic EL element. The half life when this element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was measured. In addition, luminance was measured by continuously emitting light at a current density of 10 mA / cm ² for 100 hours in an environment of 100 ° C. The results are shown in Table 11.

Examples 122-125
A device similar to that of Example 121 was formed except that a hole injection layer was formed using the compounds shown in Table 11. The half life when this element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2) was measured. In addition, luminance was measured by continuously emitting light at a current density of 10 mA / cm 2 for 100 hours in an environment of 100 ° C. The results are shown in Table 11.

Comparative Examples 1-2
A device similar to that of Example 111 was prepared, except that the hole injection layer was formed using the following compound (W) or compound (X). The half life when this element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was measured. In addition, luminance was measured by continuously emitting light at a current density of 10 mA / cm ² for 100 hours in an environment of 100 ° C. The results are also shown in Table 11.

  As is clear from Table 11, all of the compounds of the present invention are higher than the Tg of the compound (W) and the compound (X) of the comparative example, and the device prepared using them is longer in life and higher than the comparative example. Brightness was obtained.

Example 126
On the washed glass plate with an ITO electrode, the compound (60) of the present invention was vacuum-deposited to obtain a hole injection layer having a thickness of 60 nm. Next, N, N ′-(1-naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPD) was vacuum deposited to obtain a 20 nm hole transport layer. . Further, tris (8-hydroxyquinolinate) aluminum complex (Alq3) was vacuum-deposited to prepare a 60 nm-thickness electron-injection-type light-emitting layer, on which lithium fluoride (LiF) was first 1 nm, and then aluminum An electrode was formed by vapor-depositing (Al) at 200 nm to obtain an organic EL element. The half life when this element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was measured. In addition, luminance was measured by continuously emitting light at a current density of 10 mA / cm ² for 100 hours in an environment of 100 ° C. The results are shown in Table 12.

Examples 127-139
A device similar to that of Example 126 was formed except that a hole injection layer was formed using the compounds shown in Table 12. The half life when this element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2) was measured. In addition, luminance was measured by continuously emitting light at a current density of 10 mA / cm ² for 100 hours in an environment of 100 ° C. The results are shown in Table 12.

Comparative Examples 3-4
A device was prepared in the same manner as in Example 126 except that the hole injection layer was prepared using the following compound (Y) or compound (Z). The half life when this element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was measured. In addition, luminance was measured by continuously emitting light at a current density of 10 mA / cm ² for 100 hours in an environment of 100 ° C. The results are shown in Table 12.

  As is apparent from Table 12, the device prepared using the compound of the present invention can be driven at a lower voltage than the comparative example, and has a long lifetime and high luminance.

Example 140
Copper phthalocyanine was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 25 nm. Next, the compound (2) and the compound (A) in Table 1 were co-evaporated at a composition ratio of 100: 8 to form a light emitting layer having a thickness of 45 nm. Further, the compound (B) was deposited to form an electron injection layer having a thickness of 20 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide (Li ₂ O) and 100 nm of aluminum (Al) to obtain an organic EL device. This device showed an external quantum efficiency of 7.5% at a DC voltage of 10V. Further, the half-life when driven at a constant current with an emission luminance of 200 (cd / m ² ) was 5000 hours or more.

Examples 141-151
Instead of compound (2), compounds (3), (26), (27), (29), (31), (40), (42), (43), (47), (51) in Table 1 are used. ) And (59) were used, and an element was prepared in the same manner as in Example 140. These devices exhibited an external quantum efficiency of 7% or more at a DC voltage of 10 V, and had a half life of 5000 hours or more when driven at a constant current at an emission luminance of 200 (cd / m 2).

Example 152
Copper phthalocyanine was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 25 nm. Next, the compound (61) in Table 2 and the compound (A) described above were co-evaporated at a composition ratio of 100: 8 to form a light emitting layer having a thickness of 45 nm. Further, the above-described compound (B) was deposited to form an electron injection layer having a thickness of 20 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide (Li ₂ O) and 100 nm of aluminum (Al) to obtain an organic EL device. This device showed an external quantum efficiency of 7.5% at a DC voltage of 10V. Further, the half-life when driven at a constant current with an emission luminance of 200 (cd / m ² ) was 5000 hours or more.

Examples 153 to 163
Instead of the compound (61), the compounds (62), (74), (76), (88), (90), (99), (101), (102), (106), (110) in Table 1 are used. ) And (118) were used, and an element was produced in the same manner as in Example 152. These devices had an external quantum efficiency of 7% or more at a DC voltage of 10 V, and had a half life of 5000 hours or more when driven at a constant current at an emission luminance of 200 (cd / m ² ).

Example 164
A compound HIM16 in Table 3 was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 60 nm, and then a compound (32) in Table 1 was deposited to form a hole transport layer having a thickness of 20 nm. Formed. Next, Alq3 was deposited to form an electron injecting light emitting layer having a film thickness of 60 nm, and an electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride and 200 nm of aluminum to obtain an organic EL device. The light emission efficiency of this device at a DC voltage of 5 V was 1.9 (lm / W). Further, the half-life when driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Examples 165-169
A device was prepared in the same manner as in Example 164 except that HIM2, HIM4, HIM7, HIM9, and HIM15 in Table 3 were used. When these devices were driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ), all the half lives were 5000 hours or more.

Examples 170-179
Instead of compound (32) in Table 1, compounds (4), (5), (8), (30), (34), (36), (48), (53), (55) in Table 1 ) And (57) were used in the same manner as in Example 164, except that each was used. When these devices were driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ), all the half lives were 5000 hours or more.

Example 180
A compound HIM16 in Table 3 was deposited on a glass plate with an ITO electrode to form a 60 nm-thick hole injection layer, and then a compound (64) in Table 2 was deposited to form a 20-nm-thick hole transport layer. Formed. Next, Alq3 was deposited to form an electron injecting light emitting layer having a film thickness of 60 nm, and an electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride and 200 nm of aluminum to obtain an organic EL device. The light emission efficiency of this device at a DC voltage of 5 V was 1.9 (lm / W). Further, the half-life when driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Examples 181 to 185
A device was prepared in the same manner as in Example 180 except that HIM2, HIM4, HIM7, HIM9, and HIM15 in Table 3 were used. When these devices were driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ), all the half lives were 5000 hours or more.

Examples 186-195
Instead of the compound (64) in Table 2, the compounds (116), (117), (119), (125), (126), (127), (128), (129), (131) in Table 1 ) And (135) were used in the same manner as in Example 180 except that each of them was used. When these devices were driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ), all the half lives were 5000 hours or more.

Example 196
NPD was vacuum-deposited on a glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 40 nm. Next, the compound (17) in Table 1 and the following compound (C) were co-evaporated at a ratio of 98: 3 to prepare a light-emitting layer having a film thickness of 40 nm, and then Alq3 was vacuum-deposited to form a film having a film thickness of 30 nm. An electron injection layer was prepared. An electrode was formed thereon by vacuum-depositing lithium fluoride at 0.7 nm and then aluminum at 200 nm to obtain an organic EL element. This device emitted light with a luminance of 460 (cd / m ² ) and a maximum luminance of 92600 (cd / m ² ) at a DC voltage of 5V. Further, the half life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 4800 hours.

Examples 197-206
Instead of compound (17) in Table 1, compounds (10), (11), (14), (15), (18), (21), (25), (41), (49) in Table 1 ) And (56) were used in the same manner as in Example 196 except that each was used. When these devices were driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ), all the half lives were 5000 hours or more.

Example 207
NPD was vacuum-deposited on a glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 40 nm. Next, the compound (77) in Table 2 and the compound (C) described above were co-evaporated at a ratio of 98: 3 to prepare a light-emitting layer having a thickness of 40 nm, and then Alq3 was vacuum-deposited to form a film having a thickness of 30 nm. An electron injection layer was created. An electrode was formed thereon by vacuum-depositing lithium fluoride at 0.7 nm and then aluminum at 200 nm to obtain an organic EL element. This device emitted light with a luminance of 460 (cd / m ² ) and a maximum luminance of 92600 (cd / m ² ) at a DC voltage of 5V. Further, the half life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 4800 hours.

Examples 208-217
Instead of the compound (77) in Table 2, the compounds (69), (70), (73), (75), (79), (80), (84), (104), (108) in Table 1 ) And (115) were used in the same manner as in Example 207, except that each was used. When these devices were driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ), all the half lives were 5000 hours or more.

Example 218
On the glass plate with an ITO electrode, HIM9 in Table 3 was vapor-deposited to form a 50 nm-thick hole injection layer, and then compound (2) in Table 1 was vapor-deposited to 20 nm to form a hole transport layer. . Further, Alq3 was deposited to form a light emitting layer with a thickness of 20 nm. Further, Compound EX3 in Table 5 was deposited to form an electron injection layer having a thickness of 30 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide and 100 nm of aluminum to obtain an organic EL device. This device showed an emission luminance of 780 (cd / m ² ) at a DC voltage of 5.5V. In addition, the half-life when the element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was 5000 hours or more immediately after the element was created and after being stored in an oven at 100 ° C. for 1 hour. .

Examples 219-231
Instead of Compound EX3 in Table 5 used in Example 218, Compound EX4, Compound EX5, Compound EX7, Compound EX9, Compound EX10, Compound EX12 to Compound EX15, Compound EX17 to Compound EX20 in Table 5 as an electron injection layer A device was fabricated under the same conditions as in Example 218. The characteristics of the element were measured for the element immediately after the element preparation and after storage for 1 hour in an oven at 100 ° C. As a result, the device characteristics of all the devices when driven at a current density of 10 (mA / cm ² ) are as follows: voltage is 4.0 (V) or less, and luminance is 400 (cd / m 2) or more. The half-life when driven at a constant current at room temperature of 500 (cd / m 2) was 5000 hours or more.

Examples 232-242
Instead of the compound (2) in Table 1, the compounds (12), (13), (16), (20), (22), (24), (28), (35), ( 37), (50), and (52) were used, respectively, and the element was created on the same conditions as Example 218 except having used. The characteristics of the element were measured for the element immediately after the element preparation and after storage for 1 hour in an oven at 100 ° C. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 243
On the glass plate with an ITO electrode, HIM9 in Table 3 was vapor-deposited to form a hole injection layer having a film thickness of 50 nm, and then the compound (92) in Table 2 was vapor-deposited to 20 nm to form a hole transport layer. . Further, Alq3 was deposited to form a light emitting layer with a thickness of 20 nm. Further, Compound EX3 in Table 5 was deposited to form an electron injection layer having a thickness of 30 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide and 100 nm of aluminum to obtain an organic EL device. This device showed an emission luminance of 780 (cd / m ² ) at a DC voltage of 5.5V. In addition, the half-life when the element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was 5000 hours or more immediately after the element was created and after being stored in an oven at 100 ° C. for 1 hour. .

Examples 244-256
Instead of Compound EX3 in Table 5 used in Example 243, Compound EX4, Compound EX5, Compound EX7, Compound EX9, Compound EX10, Compound EX12 to Compound EX15, Compound EX17 to Compound EX20 in Table 5 are used as the electron injection layer. A device was fabricated under the same conditions as in Example 243. The characteristics of the element were measured for the element immediately after the element preparation and after storage for 1 hour in an oven at 100 ° C. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Examples 257-267
Instead of the compound (92) in Table 2, the compounds (63), (67), (71), (72), (81), (120), (121), (122), ( 124), (132), and (135) were used, and an element was produced under the same conditions as in Example 243 except that each was used. The characteristics of the element were measured for the element immediately after the element preparation and after storage for 1 hour in an oven at 100 ° C. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 268
A compound HIM10 in Table 3 is deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 55 nm, and then a compound (6) in Table 1 is deposited to 20 nm to form a hole transport layer. did. Further, Alq3 was deposited to form a light emitting layer with a thickness of 20 nm. Further, a compound ET3 in Table 6 was deposited to form an electron injection layer having a thickness of 30 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide and 100 nm of aluminum to obtain an organic EL device. This device had a light emission luminance of 750 (cd / m ² ) at a DC voltage of 5V. In addition, the half-life when the element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) for the element immediately after the element preparation and after being stored in an oven at 100 ° C. for 1 hour was 5000 hours for all elements. That was all.

Examples 269-281
Instead of compound ET3 in Table 6 used in Example 268, Compound ET4, Compound ET5, Compound ET7, Compound ET9, Compound ET10, Compound ET12 to Compound ET14, Compound ET16 to Compound ET20 in Table 6 were used as the electron injection layer. Each was used to fabricate a device under the same conditions as in Example 268. The characteristics of the element were measured for the element immediately after the element preparation and after storage for 1 hour in an oven at 100 ° C. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 282
On the glass plate with ITO electrode, the compound HIM11 in Table 3 was deposited to form a hole injection layer having a film thickness of 60 nm, and then the compound (2) in Table 1 was deposited to 15 nm to form a hole transport layer. did. Further, Alq3 was deposited to form a light emitting layer with a thickness of 20 nm. Furthermore, the compound ES5 in Table 7 was deposited to form an electron injection layer having a thickness of 30 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide and 100 nm of aluminum to obtain an organic EL device. This device showed a luminous efficiency of 2.5 (lm / W) at a DC voltage of 5.0 V. In addition, the half-life when the element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) for the element immediately after the element preparation and after being stored in an oven at 100 ° C. for 1 hour was 5000 hours for all elements. That was all.

Example 283
On a glass plate with an ITO electrode, the compound HIM10 in Table 3 is deposited to form a 55 nm-thick hole injection layer, and then the compound (65) in Table 2 is deposited to 20 nm to form a hole transport layer. did. Further, Alq3 was deposited to form a light emitting layer with a thickness of 20 nm. Further, a compound ET3 in Table 6 was deposited to form an electron injection layer having a thickness of 30 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide and 100 nm of aluminum to obtain an organic EL device. This device had a light emission luminance of 750 (cd / m ² ) at a DC voltage of 5V. In addition, the half-life when the element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) for the element immediately after the element preparation and after being stored in an oven at 100 ° C. for 1 hour was 5000 hours for all elements. That was all.

Examples 284-296
Instead of Compound ET3 in Table 6 used in Example 283, Compound ET4, Compound ET5, Compound ET7, Compound ET9, Compound ET10, Compound ET12 to Compound ET14, Compound ET16 to Compound ET20 in Table 6 were used as the electron injection layer. Each was used to create a device under the same conditions as in Example 283. The characteristics of the element were measured for the element immediately after the element preparation and after storage for 1 hour in an oven at 100 ° C. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 297
On a glass plate with an ITO electrode, the compound HIM11 in Table 3 is deposited to form a hole injection layer having a thickness of 60 nm, and then the compound (112) in Table 2 is deposited to 15 nm to form a hole transport layer. did. Further, Alq3 was deposited to form a light emitting layer with a thickness of 20 nm. Furthermore, the compound ES5 in Table 7 was deposited to form an electron injection layer having a thickness of 30 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide and 100 nm of aluminum to obtain an organic EL device. This device showed a luminous efficiency of 2.5 (lm / W) at a DC voltage of 5.0 V. In addition, the half-life when the element was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) for the element immediately after the element preparation and after being stored in an oven at 100 ° C. for 1 hour was 5000 hours for all elements. That was all.

Example 298
On a glass plate with an ITO electrode, the compound (52) in Table 1 of the present invention was dissolved in 1,2-dichloroethane, and a hole injection layer having a thickness of 50 nm was formed by a spin coating method. Next, Alq3 is deposited to form an electron injecting light emitting layer having a thickness of 30 nm, and an electrode having a thickness of 100 nm is formed thereon using an alloy in which magnesium and silver are mixed at a ratio of 10: 1. Got. The light emission efficiency of this device at a DC voltage of 8.4 V was 2.1 (lm / W). Further, the half-life when driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 299
On a glass plate with an ITO electrode, the compound (111) in Table 2 of the present invention was dissolved in 1,2-dichloroethane, and a hole injection layer having a thickness of 50 nm was formed by a spin coating method. Next, Alq3 is deposited to form an electron injecting light emitting layer having a thickness of 30 nm, and an electrode having a thickness of 100 nm is formed thereon using an alloy in which magnesium and silver are mixed at a ratio of 10: 1. Got. The light emission efficiency of this device at a DC voltage of 8.4 V was 2.1 (lm / W). Further, the half-life when driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 300
On the glass plate with an ITO electrode, the compound (48) in Table 1 of the present invention was deposited to form a hole injection layer having a thickness of 35 nm. Next, the following compound (D) and Alq3 were co-evaporated at a composition ratio of 1:20 to form a light emitting layer having a thickness of 35 nm. Further, Alq3 was deposited to form an electron injection layer with a thickness of 30 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a luminous efficiency of 0.61 (lm / W) at a DC voltage of 5.0V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 301
On the glass plate with an ITO electrode, the compound (94) in Table 2 of the present invention was deposited to form a hole injection layer having a thickness of 35 nm. Next, the compound (D) and Alq3 shown above were co-evaporated at a composition ratio of 1:20 to form a light emitting layer having a thickness of 35 nm. Further, Alq3 was deposited to form an electron injection layer with a thickness of 30 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a luminous efficiency of 0.61 (lm / W) at a DC voltage of 5.0V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 302
On the glass plate with an ITO electrode, the compounds (1) and (2) in Table 1 of the present invention were co-evaporated at a composition ratio of 1: 1 to form a hole injection layer having a thickness of 80 nm. Next, the compound (E) shown below was vapor-deposited to form a light-emitting layer having a thickness of 20 nm. Further, Alq3 was deposited to form an electron injection layer having a thickness of 20 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a luminous efficiency of 2.1 (lm / W) at a DC voltage of 5.3 V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 303
On the glass plate with an ITO electrode, the compounds (60) and (61) in Table 2 of the present invention were co-deposited at a composition ratio of 1: 1 to form a hole injection layer having a thickness of 80 nm. Next, the compound (E) shown above was vapor-deposited to form a 20 nm-thick luminescent layer. Further, Alq3 was deposited to form an electron injection layer having a thickness of 20 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a luminous efficiency of 2.1 (lm / W) at a DC voltage of 5.3 V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 304
On the glass plate with an ITO electrode, the compound (19) in Table 1 of the present invention was deposited to form a hole injection layer having a thickness of 60 nm. Next, the compound (F) shown below and the compound (G) shown below were co-evaporated at a composition ratio of 20: 1 to form a light emitting layer having a thickness of 30 nm. Further, Alq3 was deposited to form an electron injection layer having a thickness of 20 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a light emission efficiency of 5.7 (lm / W) at a DC voltage of 6.2 V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 305
On the glass plate with an ITO electrode, the compound (66) in Table 2 of the present invention was deposited to form a hole injection layer having a thickness of 60 nm. Next, the compound (F) shown above and the compound (G) shown below were co-evaporated at a composition ratio of 20: 1 to form a light emitting layer having a thickness of 30 nm. Further, Alq3 was deposited to form an electron injection layer having a thickness of 20 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a light emission efficiency of 5.7 (lm / W) at a DC voltage of 6.2 V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 306
On the glass plate with an ITO electrode, the compound (20) in Table 1 of the present invention was deposited to form a hole injection layer having a thickness of 35 nm. Next, the compound (H) shown below and the compound (I) shown below were co-evaporated at a composition ratio of 20: 1 to form a light emitting layer having a thickness of 35 nm. Further, Alq3 was deposited to form an electron injection layer with a thickness of 30 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a light emission efficiency of 3.1 (lm / W) at a DC voltage of 3.5V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 307
On the glass plate with an ITO electrode, the compound (95) in Table 2 of the present invention was deposited to form a hole injection layer having a thickness of 35 nm. The compound (H) shown above and the compound (I) shown below were co-evaporated at a composition ratio of 20: 1 to form a light emitting layer having a thickness of 35 nm. Further, Alq3 was deposited to form an electron injection layer with a thickness of 30 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a light emission efficiency of 3.1 (lm / W) at a DC voltage of 3.5V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 308
On the glass plate with an ITO electrode, the compound (44) in Table 1 of the present invention was deposited to form a 50 nm-thick hole injection layer. Next, the following compound (J) and Alq3 were co-evaporated at a composition ratio of 1: 1 to form an electron-transporting light-emitting layer having a thickness of 50 nm. Furthermore, an electrode having a thickness of 200 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 1: 3 to obtain an organic electroluminescence device. The light emission efficiency of this device at a DC voltage of 8 V was 1.0 (lm / W). Further, the half-life when driven at a constant current at room temperature with an emission luminance of 350 (cd / m ² ) was 5000 hours or more.

Example 309
On the glass plate with an ITO electrode, the compound (123) in Table 2 of the present invention was vapor-deposited to form a hole injection layer having a thickness of 50 nm. Next, the following compound (J) and Alq3 were co-evaporated at a composition ratio of 1: 1 to form an electron-transporting light-emitting layer having a thickness of 50 nm. Furthermore, an electrode having a thickness of 200 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 1: 3 to obtain an organic electroluminescence device. The light emission efficiency of this device at a DC voltage of 8 V was 1.0 (lm / W). Further, the half-life when driven at a constant current at room temperature with an emission luminance of 350 (cd / m ² ) was 5000 hours or more.

Example 310
On the glass plate with an ITO electrode, the compound (29) in Table 1 of the present invention was vapor-deposited to form a 50 nm-thick hole injection layer. Next, the above-described compound (H) and the following compound (K) were co-evaporated at a composition ratio of 100: 1 to form a light emitting layer having a thickness of 25 nm. Further, BCP was deposited to form an electron injection layer having a thickness of 25 nm. On top of this, 0.5 nm of lithium (Li) and 150 nm of silver were further deposited to obtain an organic electroluminescence device. This device showed a luminous efficiency of 0.87 (lm / W) at a DC voltage of 10V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 311
On the glass plate with an ITO electrode, the compound (136) in Table 2 of the present invention was deposited to form a hole injection layer having a thickness of 50 nm. Next, the compound (H) and the compound (K) shown above were co-evaporated at a composition ratio of 100: 1 to form a light emitting layer having a thickness of 25 nm. Further, BCP was deposited to form an electron injection layer having a thickness of 25 nm. On top of this, 0.5 nm of lithium (Li) and 150 nm of silver were further deposited to obtain an organic electroluminescence device. This device showed a luminous efficiency of 0.87 (lm / W) at a DC voltage of 10V. Also emission brightness
The half-life when driven at a constant current at 500 (cd / m ² ) was 5000 hours or more.

Example 312
On the glass plate with an ITO electrode, the compound (51) in Table 1 of the present invention was vapor-deposited to form a hole injection layer having a thickness of 40 nm. Next, a compound (L) shown below was deposited to a thickness of 10 nm to form a hole transport layer. Further, the compound (M) shown below and the compound (N) shown below were co-evaporated at a composition ratio of 1: 9 to form a light emitting layer having a thickness of 25 nm. Further, BCP was deposited to form a 15 nm hole blocking layer. Further, Alq3 was deposited to form an electron injection layer having a thickness of 25 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium fluoride (LiF) and 100 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed an external quantum efficiency of 7.1% at a DC voltage of 10V. Further, the half-life when driven at a constant current at an emission luminance of 100 (cd / m ² ) was 5000 hours or more.

Example 313
On the glass plate with an ITO electrode, the compound (113) in Table 2 of the present invention was vapor-deposited to form a 40 nm-thick hole injection layer. Next, the compound (L) shown above was deposited by 10 nm to form a hole transport layer. Further, the compound (M) shown above and the compound (N) shown above were co-evaporated at a composition ratio of 1: 9 to form a light emitting layer having a thickness of 25 nm. Further, BCP was deposited to form a 15 nm hole blocking layer. Further, Alq3 was deposited to form an electron injection layer having a thickness of 25 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium fluoride (LiF) and 100 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed an external quantum efficiency of 7.1% at a DC voltage of 10V. Further, the half-life when driven at a constant current at an emission luminance of 100 (cd / m ² ) was 5000 hours or more.

Example 314
On the glass plate with an ITO electrode, the compound (43) in Table 1 of the present invention was deposited by 60 nm to form a hole injection layer. Further, Alq3 was deposited to form a light emitting layer with a thickness of 20 nm. The following compound (O) was deposited to form an electron injection layer having a thickness of 30 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide (Li ₂ O) and 100 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a luminous efficiency of 2.1 (lm / W) at a DC voltage of 4.5 V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 315
On the glass plate with an ITO electrode, the compound (114) in Table 2 of the present invention was deposited by 60 nm to form a hole injection layer. Further, Alq3 was deposited to form a light emitting layer with a thickness of 20 nm. The compound (O) shown above was deposited to form an electron injection layer having a thickness of 30 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide (Li ₂ O) and 100 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a luminous efficiency of 2.1 (lm / W) at a DC voltage of 4.5 V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Examples 316-321
An experiment was performed under the same conditions as in Example 314 except that ES11 in Table 7 and EP2-4, EP10, and EP22 in Table 8 were used instead of the compound (O) as the electron injection layer. The characteristics of the device were measured in the same manner as in Example 314 for the device immediately after the device was created and after storage for 1 hour in an oven at 100 ° C. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Examples 322-327
Experiments were performed under the same conditions as in Example 315 except that ES11 in Table 7 and EP2-4, EP10, and EP22 in Table 8 were used instead of the compound (O) as the electron injection layer. The characteristics of the element were measured in the same manner as in Example 315 for the element immediately after element preparation and after storage for 1 hour in an oven at 100 ° C. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 328
On the glass plate with an ITO electrode, the compound (1) in Table 1 of the present invention was deposited to form a hole injection layer having a thickness of 35 nm. Further, NPD was deposited to form a 20 nm thick hole transport layer. Next, the compound (P) shown below and the compound (Q) shown below were co-evaporated at a composition ratio of 50: 1 to form a light emitting layer having a thickness of 35 nm. Further, the following compound (R) was deposited to form an electron injection layer having a thickness of 30 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a luminous efficiency of 4.1 (lm / W) at a DC voltage of 3.5V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Examples 329-335
Example except that compound (2), (5), (44), (46), (47), (49), (58) in Table 1 was used instead of compound (1). An element was prepared under the same conditions as in 328. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 336
On the glass plate with an ITO electrode, the compound (60) in Table 2 of the present invention was deposited to form a hole injection layer having a thickness of 35 nm. Further, NPD was deposited to form a 20 nm thick hole transport layer. Next, the compound (P) shown above and the compound (Q) shown above were co-evaporated at a composition ratio of 50: 1 to form a light emitting layer having a thickness of 35 nm. Further, the compound (R) shown above was deposited to form an electron injection layer having a thickness of 30 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a luminous efficiency of 4.1 (lm / W) at a DC voltage of 3.5V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Examples 337-343
Example 336 except that compound (61), (65), (83), (87), (89), (94), and (109) in Table 2 were used instead of compound (60), respectively. A device was created under the same conditions as in. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 344
On the glass plate with an ITO electrode, the compound (2) in Table 1 was vapor-deposited to form a 60 nm-thick hole injection layer, and then the compound (1) in Table 1 was vapor-deposited to form a positive 20-nm thick film. A hole transport layer was formed. Next, Alq3 was deposited to form an electron injecting light emitting layer having a film thickness of 60 nm, and an electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride and 200 nm of aluminum to obtain an organic EL device. The light emission efficiency of this device at a DC voltage of 5 V was 1.9 (lm / W). Further, the half-life when driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Examples 345-351
Example 344 except that compound (5), (44), (48), (49), (50), (52), and (58) in Table 1 were used instead of compound (1), respectively. A device was created under the same conditions as in. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Examples 352-358
Example 344 except that compound (6), (12), (18), (19), (27), (33), and (45) in Table 1 were used instead of compound (2), respectively. A device was created under the same conditions as in. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 359
A compound (61) in Table 2 was vapor-deposited on a glass plate with an ITO electrode to form a 60 nm-thick hole injection layer, and then the compound (60) in Table 2 was vapor-deposited to form a positive 20 nm-thick film. A hole transport layer was formed. Next, Alq3 was deposited to form an electron injecting light emitting layer having a film thickness of 60 nm, and an electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride and 200 nm of aluminum to obtain an organic EL device. The light emission efficiency of this device at a DC voltage of 5 V was 1.9 (lm / W). Further, the half-life when driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Examples 360-366
Example 359 except that compound (85), (96), (97), (114), (130), (133), and (134) in Table 2 were used instead of compound (60), respectively. A device was created under the same conditions as in. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Examples 367-373
Example except that the compound in Table 2 (63), (65), (71), (78), (86), (100), (98) was used instead of the compound (61). An element was prepared under the same conditions as in 359. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 374
On a glass plate with an ITO electrode, the compound (61) of the present invention was dissolved in 1,2-dichloroethane, and a 50 nm thick hole injection layer was formed by spin coating. Next, Alq3 is deposited to form an electron injecting light emitting layer having a thickness of 30 nm, and an electrode having a thickness of 100 nm is formed thereon using an alloy in which magnesium and silver are mixed at a ratio of 10: 1. Got. The light emission efficiency of this device at a DC voltage of 8.4 V was 2.1 (lm / W). Further, the half-life when driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 375
On the glass plate with an ITO electrode, the compound (62) of this invention was vapor-deposited and the 35-nm-thick hole injection layer was formed. Next, the compound (D) and Alq3 shown above were co-evaporated at a composition ratio of 1:20 to form a light emitting layer having a thickness of 35 nm. Further, Alq3 was deposited to form an electron injection layer with a thickness of 30 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a luminous efficiency of 0.61 (lm / W) at a DC voltage of 5.0V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 376
On the glass plate with an ITO electrode, the compound (61) of the present invention and the compound (93) of the present invention were co-evaporated at a composition ratio of 1: 1 to form a hole injection layer having a thickness of 80 nm. Next, the compound (E) shown above was vapor-deposited to form a 20 nm-thick luminescent layer. Further, Alq3 was deposited to form an electron injection layer having a thickness of 20 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a luminous efficiency of 2.1 (lm / W) at a DC voltage of 5.3 V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 377
On the glass plate with an ITO electrode, the compound (78) of this invention was vapor-deposited and the 60-nm-thick hole injection layer was formed. Next, the compound (F) shown above and the compound (G) shown above were co-evaporated at a composition ratio of 20: 1 to form a light emitting layer having a thickness of 30 nm. Further, Alq3 was deposited to form an electron injection layer having a thickness of 20 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a light emission efficiency of 5.7 (lm / W) at a DC voltage of 6.2 V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 378
On the glass plate with an ITO electrode, the compound (79) of the present invention was evaporated to form a hole injection layer having a thickness of 35 nm. Next, the compound (H) shown above and the compound (I) shown above were co-evaporated at a composition ratio of 20: 1 to form a light emitting layer having a thickness of 35 nm. Further, Alq3 was deposited to form an electron injection layer with a thickness of 30 nm. An electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a light emission efficiency of 3.1 (lm / W) at a DC voltage of 3.5V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 379
On the glass plate with an ITO electrode, the compound (80) of this invention was vapor-deposited and the 50-nm-thick hole injection layer was formed. Next, the compound (J) shown above and Alq3 were co-evaporated at a composition ratio of 1: 1 to form an electron-transporting light-emitting layer having a thickness of 50 nm. Furthermore, an electrode having a thickness of 200 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 1: 3 to obtain an organic electroluminescence device. The light emission efficiency of this device at a DC voltage of 8 V was 1.0 (lm / W). Further, the half-life when driven at a constant current at room temperature with an emission luminance of 350 (cd / m ² ) was 5000 hours or more.

Example 380
On the glass plate with an ITO electrode, the compound (88) of this invention was vapor-deposited and the 50-nm-thick hole injection layer was formed. Next, the compound (H) and the compound (K) shown above were co-evaporated at a composition ratio of 100: 1 to form a light emitting layer having a thickness of 25 nm. Further, BCP was deposited to form an electron injection layer having a thickness of 25 nm. On top of this, 0.5 nm of lithium (Li) and 150 nm of silver were further deposited to obtain an organic electroluminescence device. This device showed a luminous efficiency of 0.87 (lm / W) at a DC voltage of 10V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 381
On the glass plate with an ITO electrode, the compound (110) of this invention was vapor-deposited and the 40-nm-thick hole injection layer was formed. Next, the compound (L) shown above was deposited by 10 nm to form a hole transport layer. Further, the compound (M) shown above and the compound (N) shown above were co-evaporated at a composition ratio of 1: 9 to form a light emitting layer having a thickness of 25 nm. Further, BCP was deposited to form a 15 nm hole blocking layer. Further, Alq3 was deposited to form an electron injection layer having a thickness of 25 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium fluoride (LiF) and 100 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed an external quantum efficiency of 7.1% at a DC voltage of 10V. Further, the half-life when driven at a constant current at an emission luminance of 100 (cd / m ² ) was 5000 hours or more.

Example 382
On the glass plate with an ITO electrode, the compound (102) of the present invention was deposited by 60 nm to form a hole injection layer. Further, Alq3 was deposited to form a light emitting layer with a thickness of 20 nm. The compound (O) shown above was deposited to form an electron injection layer having a thickness of 30 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide (Li 2 O) and 100 nm of aluminum (Al) to obtain an organic electroluminescence device. This device showed a luminous efficiency of 2.1 (lm / W) at a DC voltage of 4.5 V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

Examples 383-388
The experiment was performed under the same conditions as in Example 382 except that ES11, EP2-4, EP10, and EP22 were used instead of the compound (O) as the electron injection layer. The characteristics of the element were measured in the same manner as in Example 382 for the element immediately after element preparation and after storage for 1 hour in an oven at 100 ° C. As a result, each of the elements has element characteristics when driven at a current density of 10 (mA / cm ² ), a voltage of 4.0 (V) or less, a luminance of 400 (cd / m ² ) or more, and light emission. The half-life when driven at a constant current at room temperature with a luminance of 500 (cd / m ² ) was 5000 hours or more.

Example 389
NPD was vacuum-deposited on a glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 40 nm. Next, the compound (93) of the present invention and the compound (C) shown above were co-evaporated at a ratio of 98: 3 to form a light-emitting layer having a thickness of 40 nm, and then Alq3 was vacuum-deposited to have a thickness of 30 nm. An electron injection layer was prepared. An electrode was formed thereon by vacuum-depositing lithium fluoride at 0.7 nm and then aluminum at 200 nm to obtain an organic phosphorescent device. This device emitted light having a light emission luminance of 360 (cd / m ² ) and a maximum light emission luminance of 87600 (cd / m ² ) at a DC voltage of 5V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 4500 hours.

Example 390
On a glass plate with an ITO electrode, the compound HIM16 in Table 3 was deposited to form a 60 nm-thick hole injection layer, and then the compound (92) of the present invention was deposited to form a 20-nm-thick hole transport layer. Formed. Next, Alq3 was deposited to form an electron injecting light emitting layer having a film thickness of 60 nm, and an electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride and 200 nm of aluminum to obtain an organic EL device. The light emission efficiency of this device at a DC voltage of 5 V was 1.8 (lm / W). Further, the half-life when driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was 5000 hours or more.

  As described above, by using the phenanthrene compound having a carbazolyl group shown in the present invention, an EL element with high performance can be produced. It is clear that remarkably high performance is exhibited with respect to the comparative compound, and it is possible to achieve a low driving voltage and a long life of the organic EL element.

Claims (19)

The following general formula [1]

(In the formula, Ar ^{1 to} Ar ⁴ are each independently a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms that may have a substituent, or 2 to carbon atoms that may have a substituent. 18 monovalent heterocyclic groups, or the following general formula [2],

(In the formula, Ar ⁵ is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms that may have a substituent, or a monovalent aromatic group having 2 to 18 carbon atoms that may have a substituent. ¹ represents a heterocyclic group, and R ^{1 to} R ⁷ are each independently selected from a hydrogen atom, a halogen atom, or an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a cyano group, or a diarylamino group. X represents an m-phenylene group which may have a substituent represented by the following general formula [5], and Ar ¹ and Ar ² are represented by the general formula [ 2], Ar ⁵ may have a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a halogen atom or a cyano group, or a substituent. Represents a monovalent aromatic heterocyclic group having 2 to 18 carbon atoms.)
Wherein at least one of Ar ^{1 to} Ar ⁴ is a carbazolyl group represented by the general formula [2], and X represents the following general formula [3]

(In the formula, Q ^{9 to} Q ¹⁶ are each independently a hydrogen atom, a halogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a diarylamino group, an aryl group. Represents a monovalent organic residue selected from an oxy group or an arylthio group.)
A phenanthrene-diyl group which may have a substituent represented by the following general formula [4]

Wherein R ^{8 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a diarylamino group, an aryl Represents a monovalent organic residue selected from an oxy group or an arylthio group, or R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , or R ¹⁰ and R ¹¹ are adjacent to each other by bonding to each other. And may form a ring with carbon atoms
O-phenylene group which may have a substituent represented by the following general formula [5]

(Wherein R ^{12 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a diarylamino group, an aryl Represents a monovalent organic residue selected from an oxy group or an arylthio group, or R ¹³ and R ¹⁴ , or R ¹⁴ and R ¹⁵ are bonded to each other by a substituent to form a ring with adjacent carbon atoms You may do it.)
The m-phenylene group which may have the substituent represented by this is represented. )
A diaminoarylene compound having a carbazolyl group represented by the formula: X in the general formula [1] is the following general formula [3]

(In the formula, Q ^{9 to} Q ¹⁶ are each independently a hydrogen atom, a halogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a diarylamino group, an aryl group. Represents a monovalent organic residue selected from an oxy group or an arylthio group.)
The diaminoarylene compound having a carbazolyl group according to claim 1, which is a phenanthrene-diyl group which may have a substituent represented by: X in the general formula [1] represents the following general formula [4]

Wherein R ^{8 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a diarylamino group, an aryl Represents a monovalent organic residue selected from an oxy group or an arylthio group, or R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , or R ¹⁰ and R ¹¹ are adjacent to each other by bonding to each other. And may form a ring with carbon atoms
The diaminoarylene compound having a carbazolyl group according to claim 1, which is an o-phenylene group which may have a substituent represented by the formula: The o-phenylene group represented by the general formula [4] is represented by the following general formula [6].

(In the formula, R ^{16 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a diarylamino group, an aryl group. Represents a monovalent organic residue selected from an oxy group or an arylthio group, or R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , or R ¹⁸ and R ¹⁹ are adjacent to each other by bonding to each other. (A ring may be formed together with a carbon atom. However, when the newly formed ring is an aromatic ring, it is only one of the above-mentioned three positions.)
The diaminoarylene compound having a carbazolyl group according to claim 1, which is an o-phenylene group represented by the formula: The o-phenylene group represented by the general formula [4] is represented by the following general formula [8].

^(Wherein, R 24 ^{to R 27} are each independently a hydrogen atom, a halogen atom, a monovalent aromatic hydrocarbon group of the alkyl group, carbon number 6 to 12 in 1 to 3 carbon atoms, or 2 carbon atoms Represents a monovalent aromatic heterocyclic group of ˜5.)
The diaminoarylene compound having a carbazolyl group according to claim 1, wherein the diaminoarylene compound is a o-phenylene group represented by the formula: The o-phenylene group represented by the general formula [4] is represented by the following general formula [9].

^(Wherein, R 28 ^{to R 33} each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a monovalent aromatic hydrocarbon group having a carbon number of 6 to 12, or 2 carbon atoms Represents a monovalent aromatic heterocyclic group of ˜5.)
The diaminoarylene compound having a carbazolyl group according to claim 1, which is an o-naphthalene-diyl group represented by: X in the general formula [1] is the following general formula [5]

(Wherein R ^{12 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a diarylamino group, an aryl Represents a monovalent organic residue selected from an oxy group or an arylthio group, or R ¹³ and R ¹⁴ , or R ¹⁴ and R ¹⁵ are bonded to each other by a substituent to form a ring with adjacent carbon atoms You may do it.)
The diaminoarylene compound having a carbazolyl group according to claim 1, which is an m-phenylene group which may have a substituent represented by the formula: The m-phenylene group represented by the general formula [5] is represented by the following general formula [7].

(Wherein R ^{20 to} R ²³ are each independently a hydrogen atom, a halogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a diarylamino group, an aryl Represents a monovalent organic residue selected from an oxy group or an arylthio group, or R ²¹ and R ²² , or R ²² and R ²³ are bonded to each other by a substituent to form a ring with adjacent carbon atoms (However, when the newly formed ring is an aromatic ring, it is only one of the two positions described above.)
The diaminoarylene compound having a carbazolyl group according to claim 1, wherein the diaminoarylene compound is a m-phenylene group represented by the formula: The m-phenylene group represented by the general formula [5] is represented by the following general formula [10].

^(Wherein, R 34 ^{to R 37} are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a monovalent aromatic hydrocarbon group having a carbon number of 6 to 12, or 2 carbon atoms Represents a monovalent aromatic heterocyclic group of ˜5.)
The diaminoarylene compound having a carbazolyl group according to claim 1, wherein the diaminoarylene compound is a m-phenylene group represented by the formula: A diaminoarylene compound having a carbazolyl group represented by the general formula [1] is represented by the following general formula [11].

(In formula, Ar < ¹ > -Ar < ⁴ > is respectively independently C1-C18 monovalent | monohydric aromatic hydrocarbon group which may have a substituent, and C2 which may have a substituent. Represents a monovalent heterocyclic group of ˜18 or a carbazolyl group represented by the above general formula [2], provided that at least one of Ar ^{1 to} Ar ⁴ is represented by the above general formula [2]. Each of Q ^{9 to} Q ¹⁶ independently represents a hydrogen atom, a halogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a diarylamino group, Represents a monovalent organic residue selected from an aryloxy group or an arylthio group.)
The diaminoarylene compound having a carbazolyl group according to claim 1, which is a phenanthrene compound having a carbazolyl group represented by the formula: The carbazolyl group represented by the general formula [2] is represented by the following general formula [12].

(Wherein, Ar ⁵ has the same meaning as Ar ⁵ in the general formula [2] described above.)
The diaminoarylene compound having a carbazolyl group according to any one of claims 1 to 10, which is represented by the formula: Ar ¹ and Ar ² in the general formula [1] are each independently represented by the following general formula [12]

(Wherein, Ar ⁵ has the same meaning as Ar ⁵ in the general formula [2] described above.)
And Ar ³ and Ar ^{4 in} the general formula [1] are each independently a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. 11. A diaminoarylene compound having a carbazolyl group according to 11. Ar ¹ in the general formula [1] is represented by the general formula [12] described above, and Ar ² , Ar ³ , and Ar ^{4 in} the general formula [1] each independently have a substituent. The diaminoarylene compound having a carbazolyl group according to claim 11, which is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Ar ⁵ in the general formula [2] is represented by the following general formula [13].

(In the formula, each R ³⁸ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. Or a monovalent heterocyclic group having 2 to 5 carbon atoms which may have a substituent.)
The diaminoarylene compound which has a carbazolyl group in any one of Claims 1-13 which are the phenyl groups represented by these. Glass transition temperature (Tg) is 170 degreeC or more, The diamino arylene compound which has a carbazolyl group in any one of Claims 1-14. The diaminoarylene compound having a carbazolyl group according to any one of claims 1 to 15, which has an ionization potential of 5.0 to 5.5 eV. The organic electroluminescent element material containing the diaminoarylene compound which has a carbazolyl group in any one of Claims 1-16. In the organic electroluminescent element formed by forming a light emitting layer or a plurality of organic layers including a light emitting layer between a pair of electrodes, at least one of the organic layers contains the material for an organic electroluminescent element according to claim 17. An organic electroluminescence device comprising: Furthermore, it has a positive hole injection layer and / or a positive hole transport layer between an anode and a light emitting layer, The said positive hole injection layer and / or a positive hole transport layer are for organic electroluminescent elements of Claim 17. The organic electroluminescent device according to claim 18, comprising a material.

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