KR20080064114A - Carbazole-containing amine compound and use thereof - Google Patents

Abstract

Disclosed is a carbazole-containing amine compound represented by the general formula [1] below. The carbazole-containing amine compound is likely to form a stable thin film since it has a high Tg and the molecule thereof hardly crystallizes. This carbazole-containing amine compound is useful as a chemical light-emitting material having excellent characteristics such as low-voltage driving and long life when it is used as a material for organic EL devices. (In the formula [1], A represents a phenylene group or a biphenylene group, and Ar1-Ar4 independently represent an optionally substituted monovalent aromatic group having 6-18 carbon atoms or the like. In this connection, at least one of Ar1-Ar4 is a carbazolyl group represented by the following general formula [4].)

Description

Carbazole-Containing Amine Compound and Uses thereof {CARBAZOLE-CONTAINING AMINE COMPOUND AND USE THEREOF}

The present invention relates to a novel carbazole-containing amine compound, and more particularly, when used as an organic electroluminescent device (hereinafter, abbreviated as organic EL device), because of low crystallinity of the molecule and high glass transition temperature (Tg) And a carbazole-containing amine compound having excellent performance (low voltage driving, long life, high stability).

Conventionally, the application of carbazole derivatives as various functional materials and electronic materials has been examined. Application of the charge transport material of an electrophotographic photosensitive member, the material for organic electroluminescent elements, etc. is examined using what the carbazole skeleton has a hole-transport property, and a structure with high heat resistance. As a typical example, polyvinylcarbazole (PVK) and N, N'-dicarbazoyl-4,4'-biphenyl (CBP) are widely studied as materials for organic EL devices (see Non-Patent Documents 1 and 2). . In general, when the organic EL element is driven or stored in a high temperature environment, adverse effects such as a change in the emission color, a decrease in the emission efficiency, an increase in the driving voltage, and a shortening of the emission lifetime are caused. In order to prevent this, it is necessary to increase the glass transition temperature (Tg) of the material. Carbazoles such as PVK and CBP have a relatively high Tg and heat resistance, but have a high symmetry structure, low stability of the film when forming a thin film by vacuum deposition or spin coating, easy crystallization, and long life of the device. The problem is that it is extremely short.

In such a situation, the diamine compound which substituted the 3 position of N-ethylcarbazole with an amino group is disclosed (refer nonpatent literature 3, 4 and patent document 1). Such a diamine compound has a suitable Ip as a hole injection material and a hole transport material, and becomes amorphous due to the asymmetry of the carbazole ring. However, the diamine compound has high film stability, but on the other hand, Tg is not very high and heat resistance is inferior to EL. Sufficient lifetime characteristics could not be obtained as an element.

Non-Patent Document 1: Applied Physics Letters, 2001, Vol. 78, p. 278

Non Patent Literature 2: Journal of the American Chemical Society, 2001, Vol. 123, p. 4304

Non-Patent Document 3: European Polymer Journal, 2005, vol. 41, p. 1821

Non-Patent Document 4: Environmental and Chemical Physics, 2002, Vol. 24, p. 30

Patent Document 1: Publication No. 2004-536134

An object of the present invention is to provide a carbazole-containing amine compound having a high Tg and difficult to crystallize molecules, and having excellent characteristics such as low voltage driving and long life when used as an organic EL device material.

MEANS TO SOLVE THE PROBLEM The present inventors came to this invention as a result of earnestly researching in order to solve the said problem.

That is, the present invention relates to a carbazole-containing amine compound represented by the following formula (1).

(Wherein A represents a phenylene group represented by the following formula (2) or a biphenylene group represented by the formula (3), and Ar ^{1 to} Ar ⁴ each independently represent a C 6-18 monovalent aromatic hydrocarbon group which may have a substituent; , A C2-C18 monovalent heterocyclic group which may have a substituent, or a carbazolyl group represented by the following general formula (4), provided that at least one of Ar ^{1 to} Ar ⁴ is a carbazolyl group represented by the general formula (4).

(In formula, one of R <^1> -R <^5> represents a bond and the other represents a hydrogen atom, a halogen atom, or monovalent organic residue each independently.)

(In formula, one of R <^6> -R <^10> and one of R <^11> -R <^15> represent a bond, and the remainder each independently represents a hydrogen atom, a halogen atom, or monovalent organic residue.)

Wherein Ar ⁵ represents a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a monovalent aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent, and each of R ¹⁶ to R ²² is independent Represents a hydrogen atom, a halogen atom or a monovalent organic residue.)

The present invention also relates to the carbazole-containing amine compound, wherein A is represented by the following formula (5) or (6).

(In formula, R <^1> -R <^4> represents a hydrogen atom, a halogen atom, or monovalent organic residue each independently.)

In the formula, R ⁶ to R ¹⁰ One represents a bond, the rest independently represent a hydrogen atom, a halogen atom or a monovalent organic residue, and each of R ¹² to R ¹⁵ independently represents a hydrogen atom, a halogen atom or a monovalent organic residue.)

In addition, the present invention is characterized in that Ar ¹ and Ar ² are each independently represented by the following formula (7), and Ar ³ and Ar ⁴ are each independently a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. To the carbazole-containing amine compound.

(Wherein, Ar ⁵ are as defined above by Ar ⁵ in the general formula (4).)

In addition, the present invention relates to the carbazole-containing amine compound, wherein Ar ⁵ is represented by the following formula (8).

(In formula, R <^23> is a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a C6-C12 monovalent aromatic hydrocarbon group which may have a substituent, or a C2-C5 monovalent complex which may have a substituent. Indicates ventilation.)

In addition, the present invention relates to the carbazole-containing amine compound, wherein Ar ⁵ is represented by the following formula (9).

(Wherein, R ³³ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a phenyl group which may have a substituent.)

In addition, the present invention relates to the carbazole-containing amine compound, wherein Ar ⁵ is represented by the following general formula (10).

(Wherein, R ²³ represents the same as R ²³ in the formula 8, R ²⁴ ~R ²⁷ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a substituent Represents a phenyl group which may have

In addition, the present invention relates to the carbazole-containing amine compound, wherein Ar ⁵ is represented by the following formula (11).

(In formula, R <^28> -R <^32> respectively independently represents a hydrogen atom, a halogen atom, a cyano group, a C1-C4 alkyl group which may have a substituent, or a phenyl group which may have a substituent.)

The present invention also relates to the carbazole-containing amine compound having a glass transition temperature (Tg) of 130 ° C or higher.

Moreover, this invention relates to the material for organic electroluminescent elements containing the said carbazole containing amine compound.

In addition, the present invention provides an organic electroluminescent 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 layer of the organic layer comprises the organic electroluminescent device material. Related to the device.

The present invention also relates to an organic electroluminescent device having a hole injection layer and / or a hole transporting layer, wherein the hole injection layer and / or the hole transporting layer comprises the organic electroluminescent device material.

In addition, the present invention relates to a carbazole derivative represented by the following formula (12) which is a raw material for preparing a carbazole-containing amine compound represented by the formula (1).

(Wherein, Ar ⁵ are as defined above by Ar ⁵ in the general formula (4), and, R ¹⁶ ~R ²² is as defined above in R ¹⁶ ~R ²² of the chemical formula 4 and, X is chlorine, bromine or iodine A halogen atom selected from atoms.)

As a preferable compound represented by General formula (12) of this invention, Ar <^5> is a 1-naphthyl group or 2-naphthyl group in Formula (12), R <^16> -R <^22> is a hydrogen atom, X is a chlorine atom, a bromine atom, or an iodine atom Carbazole derivatives which are halogen atoms selected from;

[Effects of the Invention]

The organic EL device using the carbazole-containing amine compound of the present invention as a material for an organic EL device has a very high stability of a thin film, emits light at a low driving voltage, and has a long life, which is used as a flat panel display or a flat light emitter for a wall-mounted television. It can be used suitably, and can be applied to light sources, such as a copy machine and a printer, light sources, such as a liquid crystal display and instruments, a display board, a cover, etc.

Best Mode for Carrying Out the Invention

Hereinafter, the present invention will be described in detail. First, the carbazole-containing amine compound represented by the formula (1) will be described.

In the carbazole-containing amine compound represented by the formula (1), A represents a phenylene group represented by the formula (2) or a biphenylene group represented by the formula (3).

In Formula (2), one of R ¹ to R ⁵ forms a phenylene group with a bond. In formula (3), one of R ⁶ to R ¹⁰ and one of R ¹¹ to R ¹⁵ form a bond to form a biphenylene group.

There is no restriction | limiting in particular about the position of a bond, When it becomes a phenylene bond of general formula (2), it may be o-phenylene, m-phenylene, p-phenylene, and when it becomes a biphenylene bond of general formula (3), , 2'-biphenylene, 3,3'-biphenylene, 4,4'-biphenylene, 2,3'-biphenylene, 2,4'-biphenylene, 3,4'-bi Phenylene and the like.

Preferred among these bonds include p-phenylene, in which R ⁵ is a bond, and 4,4'-biphenylene, in which R ⁶ and R ¹¹ are bonds. This is because the symmetry of the molecules is high, high heat resistance and high Tg can be expected, and it is also easy to synthesize a compound.

Such phenylene groups and biphenylene groups may each independently have a hydrogen atom, a halogen atom or a monovalent organic residue on the carbon which is not a bonding position.

As a halogen atom here, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

Although there is no restriction | limiting in particular as monovalent organic residue, Monovalent aliphatic hydrocarbon group which may have a substituent, Monovalent aromatic hydrocarbon group which may have a substituent, Monovalent aliphatic heterocyclic group which may have a substituent, Monovalent which may have a substituent Aromatic heterocyclic group, cyano group, alkoxy group, aryloxy group, alkylthio group, arylthio group, substituted amino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, etc. are mentioned.

Here, the monovalent aliphatic hydrocarbon group refers to a C1-C18 monovalent aliphatic hydrocarbon group, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl group.

Examples of the alkyl group include 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, decyl group and dode And an alkyl group having 1 to 18 carbon atoms such as a real group, a pentadecyl group, and an octadecyl group.

As the alkenyl group, a 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- C2-C18 alkenyl group like an octadecenyl group is mentioned.

Moreover, as an alkynyl group, such as an ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group, 1-octadecynyl group, C2-C18 alkynyl group is mentioned.

Moreover, as a cycloalkyl group, C3-C18 cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctadecyl group, are mentioned.

Moreover, as a monovalent aromatic hydrocarbon group, a C6-C18 monovalent monocyclic, condensed ring, ring aggregate hydrocarbon group is mentioned. Here, as the C6-C18 monovalent monocyclic aromatic hydrocarbon group, carbon number, such as a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2, 4- xylyl group, p- cumenyl group, and mesityl group, etc. 6-18 monovalent monocyclic aromatic hydrocarbon group is mentioned.

As the monovalent condensed cyclic hydrocarbon group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1 -C10-C18 monovalent condensed cyclic hydrocarbon groups, such as an acenaphthyl group, 2-azurenyl group, 1-pyrenyl group, and 2-triphenyrel group, are mentioned.

Moreover, as a monovalent ring aggregate hydrocarbon group, C12-C18 monovalent ring aggregate hydrocarbon groups, such as o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group, are mentioned.

As the monovalent aliphatic heterocyclic group, 3 having 1 to 3 nitrogen atoms, oxygen atoms and / or sulfur atoms as hetero atoms, such as 2-pyrazolino group, piperidino group, morpholino group and 2-morpholinyl group 8-membered, preferably 5- to 7-membered C3-C18 monovalent aliphatic heterocyclic group is mentioned.

As the monovalent aromatic heterocyclic group, 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 Heterogeneous, such as -quinolyl group, 1-isoquinolyl group, 2-quinoxalinyl group, 2-benzofuryl group, 2-benzothienyl group, N-indolyl group, N-carbazolyl group, and N-acridinyl group Examples of the atom include a 3-8 membered, preferably 5-7 membered monovalent aromatic heterocyclic group having 1 to 3 nitrogen atoms, oxygen atoms and / or sulfur atoms.

Examples of the alkoxy group include alkoxyl groups having 1 to 8 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group, octyloxy group and tert-octyloxy group.

Moreover, as an aryloxy group, C6-C14 aryloxy groups, such as a phenoxy group, 4-tert- butylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, and 9- anthryloxy group, are mentioned.

Examples of the alkylthio group include alkylthio groups having 1 to 8 carbon atoms such as methylthio group, ethylthio group, tert-butylthio group, hexylthio group, and octylthio group.

Moreover, as an arylthio group, C6-C14 arylthio groups, such as a phenylthio group, 2-methylphenylthio group, and 4-tert- butylphenylthio group, are mentioned.

As the substituted amino group, N-methylamino group, N-ethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N-benzylamino group, N, N-di Benzylamino 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-bifetylyl) amino group, bis [4- (4-methyl) bipetylyl] amino group, N-α-naphthyl-N-phenylamino group, N-β-naphthyl-N-phenylamino group, etc. And a substituted C2-C16 amino group.

Moreover, as an acyl group, C2-C14 acyl groups, such as an acetyl group, a propionyl group, a pivaloyl group, a cyclohexyl carbonyl group, a benzoyl group, a toluoyl group, an anisoyl group, and a cinnamoyl group, are mentioned.

Moreover, as an alkoxycarbonyl group, C2-C14 alkoxycarbonyl groups, such as a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group, are mentioned.

Moreover, as an aryloxycarbonyl group, C7-14 aryloxycarbonyl groups, such as a phenoxycarbonyl group and a naphthyloxycarbonyl group, are mentioned.

Moreover, as an alkyl sulfonyl group, C2-C14 alkyl sulfonyl groups, such as a mesyl group, an ethyl sulfonyl group, and a propyl sulfonyl group, are mentioned.

Moreover, as an arylsulfonyl group, C6-C14 arylsulfonyl groups, such as a benzenesulfonyl group and p-toluenesulfonyl group, are mentioned.

The monovalent aliphatic hydrocarbon group, aromatic hydrocarbon group, aliphatic heterocyclic group, and aromatic heterocyclic group described above may also be substituted by other substituents. In addition, these substituents may be bonded to each other to form a ring together with an adjacent atom. Examples of such a substituent include a halogen atom, cyano group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, substituted amino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group and the like. Examples of such a substituent include those mentioned above.

As a preferable monovalent organic residue, C1-C18 alkyl group which may be substituted by other substituent; A cycloalkyl group having 3 to 18 carbon atoms which may be substituted by another substituent; C6-C18 monocyclic, condensed cyclic or polycyclic aromatic hydrocarbon group which may be substituted by other substituent; An alkoxyl group having 1 to 8 carbon atoms which may be substituted by another substituent; C6-C14 aryloxy group which may be substituted by other substituent; And a substituted amino group substituted with a hydrocarbon group having 2 to 16 carbon atoms which may be substituted by other substituents. Examples of the other substituent include alkyl group, halogen atom, cyano group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, substituted amino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group and arylsulfonyl group. And substituents selected from the group given.

More preferred examples among all R ¹ ~R ¹⁵ non-bonding hands in the above examples, may be mentioned a hydrogen atom, an alkyl group of 1 to 3 carbons, a phenyl group, a tolyl group or the like. In the case where such a group is used as a substituent, the molecular weight is also relatively small, which is easy to sublimate the compound (material) by vapor deposition or the like, and is also preferable in terms of stability.

Preferred A in the general formula (1) of the present invention is a biphenylene group represented by the formula (3), more preferably a 4-biphenylene group represented by the formula (6), more preferably a 4,4'-biphenylene group represented by the following formula (13) Can be mentioned. More specifically. For example, a biphenylene group which may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom, a phenyl group and a tolyl group, preferably a 4,4'-biphenylene group Can be mentioned.

(In formula, R <^7> -R <^10> and R <^12> -R <^15> respectively independently represent a hydrogen atom, a halogen atom, or monovalent organic residue.)

Next, Ar ^{1 to} Ar ⁴ in the formula (1) will be described. Ar ^{1 to} Ar ⁴ each independently represent a C6-C18 monovalent aromatic hydrocarbon group which may have a substituent, a C2-C18 monovalent heterocyclic group which may have a substituent, or a carbazolyl group represented by the formula (4).

As the monovalent aromatic hydrocarbon group having a carbon number of 6-18 are the same as those described in the case of a monovalent organic residue of R ¹ ~R ^15. Moreover, as a substituent which can couple | bond these, the above-mentioned halogen atom and the above-mentioned monovalent organic residue are mentioned.

Further, it is the same as the monovalent aliphatic heterocyclic group or a monovalent aromatic heterocyclic group described above in the case of a monovalent organic residue of R ¹ ~R ¹⁵ As the monovalent heterocyclic group having a carbon number of 2 to 18. Moreover, as a substituent which can couple | bond these, the above-mentioned halogen atom and the above-mentioned monovalent organic residue are mentioned.

At least one of Ar ^{1 to} Ar ⁴ in the general formula (1) of the present invention, preferably two, more preferably ^two of Ar ¹ and Ar ² are carbazolyl groups represented by the general formula (4), and the remaining Ar ^{1 to} Ar ⁴ Are each independently a C6-C18 monovalent aromatic hydrocarbon group which may have a substituent, or a C2-C18 monovalent heterocyclic group which may have a substituent. Preferred remaining Ar ^{1 to} Ar ⁴ are 6 to 18 carbon atoms which may be substituted by one or two or more substituents, preferably 6 to 14 monocyclic, polycyclic or condensed cyclic aromatic hydrocarbon groups, or one or two As a hetero atom which can be substituted by the above substituent, the 3-8 membered, 1-5 membered aromatic heterocyclic group which has 1-3 nitrogen atoms, an oxygen atom, and / or a sulfur atom is preferable. As a substituent of such a group, a C1-C6 linear or branched alkyl group, a C1-C6 linear or branched alkyl group substituted by 1-6 halogen atoms, a C1-C6 linear or branched alkoxy group, And substituents selected from the group consisting of halogen atoms and cyano groups. As a preferable aromatic hydrocarbon group, a phenyl group, a naphthyl group, anthranyl group, a biphenylyl group, etc. are mentioned. Moreover, a pyridyl group, furanyl group, thienyl group, etc. are mentioned as a preferable aromatic heterocyclic group.

At least one of Ar ^{1 to} Ar ⁴ in the general formula (1) of the present invention, preferably two, more preferably ^two of Ar ¹ and Ar ² is a carbazolyl group represented by the general formula (4), and R ¹⁶ of the general formula (4) Examples of the monovalent organic residue in ˜R ²² include the same ones as the monovalent organic residues of R ¹ to R ¹⁵ described in the above formulas (2) and (3). In preferable R <^16> -R <^22> , as monovalent organic residue, a C1-C6 linear or branched alkyl group, a C1-C6 linear or branched alkyl group substituted by 1-6 halogen atoms, C1-C6 And a substituent selected from the group consisting of a linear or branched alkoxy group and a cyano group. Preferred R ¹⁶ to R ²² in the general formula (4) include a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, but a hydrogen atom is preferable in terms of production convenience and cost.

Therefore, as a preferable example of the carbazolyl group represented by General formula (4) of this invention, the carbazolyl group represented by said Formula (7) is mentioned.

Ar <^5> in General formula (4) and (7) represents the C6-C18 monovalent aromatic hydrocarbon group which may have a substituent, or the C2-C18 monovalent aromatic heterocyclic group which may have a substituent.

The monovalent aromatic hydrocarbon group and monovalent aromatic heterocyclic group here are the same as what was demonstrated in the case of the monovalent organic residue of R <^1> -R <^15> . Moreover, as a substituent which can couple | bond these, the above-mentioned halogen atom and monovalent organic residue are mentioned.

In addition, R <^16> -R <^22> in General formula (4) represents a hydrogen atom, a halogen atom, or monovalent organic residue each independently. A halogen atom, a monovalent organic residue as the same as those described in the case of a monovalent organic residue of R ¹ ~R ^15.

Here, it is more preferable that the 3-carbazoyl group of General formula (4) is General formula (7). The carbazoyl group of the formula (7) is a case where R ¹⁶ to R ²² of the carbazoyl group of the formula (4) are hydrogen atoms. It is because when it has such a structure, molecular weight is also comparatively small, it is easy at the time of forming a thin film by sublimating a compound (material) by vapor deposition etc., and it is excellent also in stability.

In addition, Ar ⁵ in Formula 4 or 7 preferably has a structure of Formula 8 or 10 or 11. R ²³ in formula (8) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, 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 Indicates. Examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms and the monovalent heterocyclic group having 2 to 5 carbon atoms in R ²³ in the formula (8) include those having the corresponding carbon atoms among those described in the case of the monovalent organic residue of R ¹ to R ¹⁵ . Can be mentioned. Moreover, as a substituent which can have, the above-mentioned halogen atom and monovalent organic residue are mentioned. Particularly preferred examples of R ²³ include a hydrogen atom, a phenyl group, a biphenyl group, a tolyl group, a xylyl group, a methyl group, an ethyl group, a fluorine atom, and the like.

More preferable Ar ⁵ in the general formula (4) or (7) of the present invention includes the case where R ²³ in the general formula (8) is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and the structure of the formulas (10) and (11). In the formula (8), when R ²³ is a C6-C18 monovalent aromatic hydrocarbon group which may have a substituent, for example, a phenyl group in which R ²³ may have a substituent may be mentioned. In this case, Ar ⁵ is a biphenyl group which may have a substituent. As a preferable biphenyl group, the 4 'substituted or unsubstituted 4-biphenyl group like the said Formula (9) is mentioned.

The following reason is considered as a reason why it is preferable that Ar <^5> in Formula (4) or (7) of this invention is a structure like Formula (9), (10) or (11).

As compared with the chemical structural formula shown below, carbazole compounds generally have a strong structure and high thermal stability as compared to diphenylamino compounds having no bonds.

In carbazole compounds, N-alkyl compounds in which an alkyl group is disposed at another bonding position on nitrogen are well known, but in the compound of the present invention, the substituent (= Ar ⁵ ) bonded at this position is an aromatic group or a heteroaromatic compound. One of the characteristics of the group is that it is a relatively large aromatic group such as a biphenyl group or a naphthyl group. Such an aromatic group and a heteroaromatic group also have a large effect of increasing stability, and among them, an effect of improving stability is expected in the case where Ar ⁵ is a phenyl group having the formula 8, that is, a phenyl group having a R ²³ on a nitrogen atom, and more preferable. The case where R ²³ in the formula (8) is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and the structure of formulas (10) and (11).

On the other hand, the carbazole-containing amine compound of the general formula (1) described above is at least one of Ar ^{1 to} Ar ⁴ is a carbazolyl group bonded to the 3-position represented by the general formula (4) or (7). The number of carbazolyl groups may be any one of 1 to 4, but preferred is a carbazolyl group in which Ar ¹ and Ar ² are represented by the formula (7), and Ar ³ and Ar ⁴ are each independently a monovalent aromatic having 6 to 18 carbon atoms. The case of a hydrocarbon group is mentioned.

Here, the group is a monovalent aromatic hydrocarbon having a carbon number of 6-18 same as described in R ¹ ~R ^15, however, especially it preferred there may be mentioned a phenyl group, a tolyl group, a naphthyl group, a biphenyl group and the other phenyl group.

Here, the effect of the carbazolyl group bonded to the 3 position is mentioned. The amino group usually works as an electron donor, but the nitrogen atom of the carbazole does not have most of the donor for substituents bonded on the nitrogen atom. This is considered to be due to the fact that the carbazole ring has a planarity and is a considerably bulky substituent, and therefore it is difficult to take a planar structure with a substituent on a nitrogen atom. Conversely, the carbazole ring bonded at the 3-position can be electron donating to the benzene ring portion due to the planarity of the ring, as shown in the following chemical structure.

Therefore, in the carbazole-containing amine compound of the present invention, both the amino group bonded to the carbazole ring and the nitrogen atom of the carbazole ring become electron donors to the benzene ring of the carbazole ring, and as shown in the following chemical structure, phenylenediamine It is thought to exert an electron donating effect equivalent to or higher than the structure.

For this reason, the carbazole-containing amine compound of the present invention tends to be a compound having a small ionization potential (a compound having a higher level of organic molecules in the ground state), and when preparing an organic EL device, a compound having high hole injection transportability is used. It is possible.

In addition, the carbazole ring bonded at the 3-position has a lower molecular symmetry than the carbazole ring bonded to a nitrogen atom, and thus, the crystallinity of the molecule is lowered and the amorphousness is increased, which can greatly contribute to the improvement of stability when forming a thin film. .

On the other hand, when the carbazole-containing amine compound of the present invention is used as a material for an organic EL device, generally, the higher the Tg, the better.

Preferable examples of the carbazole-containing amine compound of the present invention include those having a Tg of 130 ° C or higher. This high Tg is achieved only when the substituent Ar ⁵ on the nitrogen atom of the carbazole is an aromatic group or a heteroaromatic group.

As mentioned above, although the carbazole containing amine compound represented by General formula (1) used for this invention was demonstrated, When using this carbazole containing amine compound as a material for organic electroluminescent elements, the molecular weight of a compound is preferably 1500 or less, and 1300 or less More preferably, 1200 or less are more preferable, and 1100 or less are especially preferable. The reason for this is that if the molecular weight is large, the vapor deposition property may deteriorate when the device is manufactured by vapor deposition.

Representative examples of the compounds of the present invention are shown in Tables 1 to 17 below, but the present invention is not limited only to these representative examples.

When describing the compound represented by General formula (1) of this invention in this specification, the compound number described in the left side of each table | surface of Table 1-Table 17 is used.

As a manufacturing method of the carbazole containing amine compound represented by General formula (1) of this invention, manufacturing method A-manufacturing method D shown below are mentioned as a typical manufacturing method (wherein X is a chlorine atom, a bromine atom, and iodine). A halogen atom selected from atoms).

Manufacturing Method A

Manufacturing Method B

Manufacturing Method C

Manufacturing Method D

In the preparation method shown above, Schemes A-1, A-2, A-3, A-4, B-1, B-2, B-3, B-4, C-1, C-3, C- The reaction of 4, D-1, D-2, D-3, and D-4 is a reaction for synthesizing secondary and tertiary amine compounds, commonly known as the Uulman reaction, for example, copper powder and anhydrous potassium carbonate, etc. The industry-known method described in Unexamined-Japanese-Patent No. 7-126226 etc. which made the base react at high temperature about 100-180 degreeC in high boiling solvents, such as nitrobenzene, can be used. In addition, a method of using a palladium compound and a phosphorus compound in the presence of a base in place of a copper powder and a base is also known. In this case, triflate instead of the halogen compound represented by Ar ¹ -X, Ar ² -X, XAX, etc. Or sulfonate. Such methods are described, for example, in Japanese Patent Laid-Open Nos. 10-81667, 10-139742, 10-310561, John F. Hartwig, Angew. Chem. Int. Ed., Vol. 37, pp. 2046-2067 (1998); Bryant H. Yang, Stephen L Buchwald, J. Organomet. Chem., 576, pp. 125-146 (1999); John P. Wolfe, Stephen L Buchwald, J. Org. Chem., Vol. 65, pp. 1144-1157 (2000); John P. Wolfe, Stephen L Buchwald, J. Org. Chem., Vol. 62, pp. 1264-1267 (1997); Janis Louie, Michael S. Driver, Blake C. Hamann, John F. Hartwig, J. Org. Industry known methods described in Chem., Vol. 62, pp. 1268-1273 (1997) and the like can be used. As another manufacturing method, the method of Unexamined-Japanese-Patent No. 63-35548, Unexamined-Japanese-Patent No. 6-100503, 2001-515879, and Republished patent WO2002 / 076922 can also be used, for example.

In the above production method, when Ar ¹ and Ar ² , Ar ³ and Ar ⁴ are the same group, Scheme A-3, Scheme A-4, Scheme B-1, Scheme B-2, Scheme B-3, and Scheme B -4 can be manufactured in one-pot. Also in this case, it can manufacture using the industry-known method shown above.

In the production method C, the reaction of Scheme C-2 is a reduction reaction of nitro group, which has been known for a long time, and is reduced by zinc or tin (II) chloride under acidic conditions, hydrogen in the presence of a catalyst such as palladium black or Raney nickel. By a reduction using a reducing agent such as lithium aluminum hydride or the like, a considerable amount of the amine compound can be obtained in good yield from the nitro compound. This reduction reaction is, for example, by Calvin A. Buehler, by Donald E. Pearson, SURVEY OF ORGANIC SYNTHESES, pp. 413-417, Wiley-Interscience (1970), Japanese Chemical Society, New Experimental Chemistry Course 14, 1333- The industry-known method described in p. 1335, U.S. Pat. (1978) etc. can be used.

In addition, the 3-halo-9-arylcarbazole derivative represented by Ar ¹ -X or Ar ² -X in the above production method is, for example, the method described in Industrial Chemical Magazine, Vol. 70, p. 63 (1967), and the like. It can be synthesized using.

Among them, the carbazole derivative represented by the formula (12) can be preferably used as a raw material for producing the carbazole-containing amine compound of the present invention. In particular, by using a carbazole derivative wherein Ar ⁵ of Formula 12 is a 1-naphthyl group or 2-naphthyl group, R ¹⁶ to R ²² are hydrogen atoms, and X is a halogen atom selected from chlorine atom, bromine atom or iodine atom The prepared carbazole-containing amine compound of the present invention can be suitably used for various uses shown below.

The carbazole-containing amine compound represented by the formula (1) of the present invention can be used for various purposes. As a material expressing functions such as a sensitizing effect, a heating effect, a coloring effect, a fading effect, a photoluminescent effect, a phase change effect, a photoelectric conversion effect, a magneto-optical effect, a photocatalytic effect, a light modulation effect, a light recording effect, and a radical generating effect Alternatively, or vice versa, it can be used as a material having a light emitting function. 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, and base generating Materials, photoluminescent materials, nonlinear optical materials, second harmonic generating materials, third harmonic generating materials, photosensitive materials, light absorbing materials, near infrared absorbing materials, photochemical hole-burning materials, light sensing materials, light A display material, a sensitizing material for photochemical treatment, an image change recording material, an optical sintered recording material, a magneto-optical recording material, a dye for photodynamic therapy, and the like.

Particularly preferred among the various uses of these examples are those used as organic EL materials (materials for organic EL and materials for organic EL elements).

In the case of using as an organic EL device material, a material of high purity is particularly required. In such a case, the carbazole-containing amine compound 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 these methods can be combined and implemented. Among these purification methods, those by the recrystallization method are preferable. In the compound which has sublimation, it is preferable by the sublimation purification method. In sublimation refining, it is preferable to employ | adopt the method which removes the sublimation impurity beforehand by maintaining a sublimation board at low temperature rather than the temperature which a target compound sublimes. In addition, it is preferable to perform a temperature gradient on the part where the sublimate is collected so that the sublimate is dispersed in impurities and targets. Sublimation purification as described above is a purification to separate impurities, it is applicable to the present invention. In addition, sublimation purification also helps to predict the difficulty of vapor deposition of the material.

Here, the organic EL device which can be produced using the carbazole-containing amine compound of the present invention will be described in detail.

The organic EL device is composed of a device in which a single layer or a multi-layered organic layer is formed between an anode and a cathode, wherein the one-layer type organic EL device refers to a device having only a light emitting layer between the anode and the cathode. On the other hand, the multilayer organic EL device is intended to facilitate the injection of holes or electrons into the light emitting layer in addition to the light emitting layer, or to facilitate recombination of holes and electrons in the light emitting layer, and includes a hole injection layer, a hole transport layer, and a hole blocking layer. , An electron injection layer or the like is laminated. Therefore, typical device configurations of the multilayer organic EL device include (1) anode / hole injection layer / light emitting layer / cathode, (2) anode / hole injection layer / hole transporting layer / light emitting layer / cathode, and (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 / 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) anode / light emitting layer / hole blocking layer / electron injection layer / cathode, (8) anode / light emitting layer / electron injection Considering a device configuration laminated in a multilayer configuration such as a layer / cathode.

In addition, each of the above-mentioned organic layers may be formed by a layer structure of two or more layers, respectively, and several layers may be repeatedly stacked. As such an example, the element structure called "multi-photon emission" which multiplies a part of the above-mentioned multilayer type organic electroluminescent element for the purpose of taking out light and improving efficiency is proposed. This is, for example, in an organic EL element composed of a glass substrate, an anode, a hole transporting layer, an electron transporting light emitting layer, an electron injection layer, a charge generating layer, a light emitting unit, and a cathode, in which a plurality of layers of a charge generating layer and a light emitting unit are laminated. A method is mentioned.

Although the carbazole containing amine compound (material for organic electroluminescent elements) of this invention may be used for any of the layers mentioned above, it can use suitably especially for a hole injection layer, a hole transport layer, and a light emitting layer. In addition, the material for an organic electroluminescent device of the present invention can be used not only as a single compound but also as a combination of two or more kinds of compounds, that is, mixing, co-deposition, lamination, and the like. Further, the above-described hole injection layer, hole transport layer, and light emitting layer may be used together with other materials.

As the hole injection layer, a hole injection material which exhibits a hole injection effect superior to that of the light emitting layer and which can form a hole injection layer excellent in adhesion to the anode interface and thin film formability is used. In addition, when such a material is laminated in multiple layers and a material having a high hole injection effect and a material having a high hole transport effect is laminated in multiple layers, the materials used for each may be referred to as a hole injection material or a hole transport material. The material for an organic electroluminescent element of the present invention can be suitably used for both a hole injection material and a hole transport material. These hole injection materials and hole transport materials need to have a high hole mobility and a small ionization energy of 5.5 eV or less. As such a hole injection layer, a material for transporting holes to the light emitting layer with a lower electric field strength is preferable, and the mobility of holes is at least 10 ⁻⁶ cm 2 / when applying an electric field of 10 ⁴ to 10 ⁶ V / cm, for example. It is preferable that it is V * second. Other hole injection materials and hole transport materials that can be mixed with the organic electroluminescent device material of the present invention are not particularly limited as long as they have the above desirable properties, and are conventionally used as charge transport materials for holes in conventional photoconductive materials. Any of those known and used in the hole injection layer of the organic EL device can be selected and used.

As such a hole injecting material or a hole transporting material, for example, a triazole derivative (see US Patent No. 3,112,197, etc.), an oxadiazole derivative (see US Patent No. 3,189,447, etc.), an imidazole derivative ( (See Japanese Patent Application Laid-Open No. 37-16096, etc.), polyarylalkane derivative (US Patent No. 3,615,402 Specification, US Patent No. 3,820,989 Specification, US Patent No. 3,542,544 Specification, Japanese Patent Application Publication No. 45-555, Japanese Patent Application Publication No. 51-10983 JP-A 51-93224, JP-A 55-17105, JP-A 56-4148, JP-A 55-108667, JP-A 55-156953, JP-A 56-36656 Etc.), pyrazoline derivatives and pyrazolone derivatives (US Pat. No. 3,180,729, US Pat. No. 4,278,746, Japanese Patent Laid-Open No. 55-88064, Japanese Patent Laid-Open No. 55-88065, Japanese Patent Laid-Open No. 49-105537, Japanese Patent Application Laid-Open No. 55-51086, Japanese Patent Application Laid-Open No. 56-80051, Japanese Patent Publication No. 56-88141 JP-A No. 57-45545, JP-A 54-112637, JP-A 55-74546, etc.), phenylenediamine derivatives (US Pat. No. 3,615,404, JP-A 51-10105, JP-A 46-3712, JP-A 47-25336, JP-A 54-53435, JP-A 54-110536, JP-A 54-119925, etc., arylamine derivatives (US Patent No. US Pat. No. 3,567,450, US Pat. No. 3,180,703, US Pat. No. 3,240,597, US Pat. No. 3,658,520, US Pat. No. 4,232,103, US Pat. No. 4,175,961, US Pat. No. 4,012,376, 35702, Japanese Patent Application Laid-Open No. 39-27577, Japanese Patent Application Laid-Open No. 55-144250, Japanese Patent Application Laid-Open No. 56-119132, Japanese Patent Application Laid-Open No. 56-22437, German Patent No. 1,110,518, etc.) (See US Pat. No. 3,526,501, etc.), Oxazole Derivatives (US Pat. No. 3,257,2 03, etc.), styryl anthracene derivatives (see Japanese Patent Application Laid-Open No. 56-46234, etc.), fluorenone derivatives (see Japanese Patent Application Laid-Open No. 54-110837, etc.), hydrazone derivatives (US Pat. No. 3,717,462) JP-A-54-59143, JP-A 55-52063, JP-55-52064, JP-55-46760, JP-55-85495, JP-57-57350 (See Japanese Patent Application Laid-Open No. 57-148749, Japanese Patent Laid-Open No. 2-311591, etc.), Stilbene derivatives (Japanese Patent Application Laid-Open No. 61-210363, Japanese Patent Application Laid-Open No. 61-228451, Japanese Patent Application Laid-Open No. 61-14642 72255, JP 62-47646, JP 62-36674, JP 62-10652, JP 62-30255, JP 60-93455, JP 60-94462 Publication, Japanese Patent Application Laid-Open No. 60-174749, Japanese Patent Application Laid-Open No. 60-175052, etc.), Silazane Derivatives (US Pat. No. 4,950,950), Polysilane (JP-A 2-204996), Aniline Aerial And a conductive polymer oligomer (particularly a thiophene oligomer) disclosed in the combination (JP-A-2-282263) and Japanese Patent Laid-Open No. 1-211399.

As the hole injecting material or the hole transporting material, the above-mentioned ones can be used, and porphyrin compounds (Japanese Patent Application Laid-Open No. 63-2956965), aromatic tertiary amine compounds and styrylamine compounds (US Patent No. 4,127,412, Japanese Patent Application Laid-Open No. 53-27033) Publication No. 54-58445, Publication No. 54-149634, Publication 54-64299, Publication 55-79450, Publication 55-144250, Publication 56-119132 (See Japanese Patent Application Laid-Open No. 61-295558, Japanese Patent Laid-Open No. 61-98353, Japanese Patent Laid-Open No. 63-295695, etc.). For example, 4,4'-bis (N- (1-naphthyl) -N-phenylamino) biphenyl etc. which have two condensed aromatic rings described in US Pat. No. 5,061,569 in a molecule, and the like 4,4 ', 4' '-tris (N- (3-methylphenyl) -N-phenylamino) triphenylamine, etc. in which the triphenylamine units described in Japanese Patent Application No. 4-308688 are connected in three starburst forms Can be mentioned. In addition, phthalocyanine derivatives, such as copper phthalocyanine and hydrogen phthalocyanine, are also mentioned as a hole injection material. In addition, inorganic compounds such as aromatic dimethylidene compounds, p-type Si, and p-type SiC can also be used as the material for the hole injection material and the hole transport material.

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-phenylcyclohexane, N, N'- Bis (4'-diphenylamino-4-biphenylyl) -N, N'-diphenylbenzidine, N, N'-bis (4'-diphenylamino-4-phenyl) -N, N'-di Phenylbenzidine, 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, and these can be used for both the hole injection material and the hole transport material.

As the hole injecting material and the hole transporting material used together with the compound of the present invention (material for organic EL device), those similar to the following formulas (14) to (19) can also be used.

(In formula, R <^a11> -R <^a14> represents a hydrogen atom, an alkoxyl group, or a cyano group each independently, and all do not become a hydrogen atom simultaneously.)

Here, as an alkoxyl group, a methoxy group, an ethoxy group, a propoxy group, butoxy group, tert-butoxy group, octyloxy group, tert-octyloxy group, 2-bornyloxy group, 2-isobornyloxy group, 1-a C1-C18 alkoxyl groups, such as a danyloxy group, are mentioned. In particular, a preferred combination of R ^{a11 a14} ~R is preferably of R ^{a11 a14} ~R case are both a methoxy group, an ethoxy group or a cyano group.

(Wherein, Z ²¹ is a linking group and represents any of a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, an oxygen atom, and a sulfur atom.) R ^a21 to R ^a26 each independently represent a monovalent aromatic hydrocarbon group. Indicates.)

Examples of the linking group for Z ²¹ include 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, 9,10- anthylene group is preferable, and a single bond, a vinylene group, a p-phenylene group, and 1, 4- naphthylene group are more preferable. As R ^a21 to R ^a26 , monovalent aromatic hydrocarbon groups selected from phenyl group, 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m-biphenylyl group and p-biphenylyl group are preferable.

(In the formula, Z ³¹ is linking group, a single bond, a divalent aliphatic hydrocarbon group, a divalent represents any one of aromatic hydrocarbon groups, an oxygen atom, a sulfur atom. R ^a31 ~R ^a36 are each independently a monovalent aromatic hydrocarbon Group.)

Examples of the linking group for Z ³¹ include 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, 9,10- anthylene group is preferable, and a single bond, a vinylene group, a p-phenylene group, and a 1, 4- naphthylene group are also preferable. In addition, R ^{a31 a36} ~R as phenyl, 1-naphthyl, 2-naphthyl group, o- biphenyl group, a phenyl group and a monovalent group m- non-aromatic hydrocarbons selected from the group-p- biphenyl are preferred.

(In formula, R <^a41> -R <^a48> represents a monovalent aromatic hydrocarbon group each independently.)

As R <^a41> -R <^a48> , the monovalent aromatic hydrocarbon group chosen from a phenyl group, 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group is preferable.

(In formula, R ^{< a51>} -R ^{< a56>} represents a monovalent aromatic hydrocarbon group each independently.)

As R ^{< a51>} -R ^{< a56>} , a monovalent aromatic hydrocarbon group chosen from a phenyl group, 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group is preferable.

(In formula, R <^a61> -R ^{< a64>} represents a monovalent aromatic hydrocarbon group each independently, and p represents the integer of 1-4.)

As R <^a61> -R ^{< a64>} , the monovalent aromatic hydrocarbon group chosen from a phenyl group, 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group is preferable.

The compounds represented by the above formulas (14) to (19) are particularly suitably used as hole injection materials. Especially preferable examples are shown to the following Tables 18-21.

In this specification, when describing the compound represented by General formula 14-19 of this invention, the number of the compound described in the column of the left of each table | surface of Table 18-21 is used.

In addition, as the hole transporting material which can be used together with the compound of the present invention (material for organic EL device), known compounds shown in the following Tables 22 to 28 are also mentioned.

In this specification, when describing the compound of Table 22-28, the number of the compound described in the column of the left side of each table of Table 22-28 is used.

In forming the hole injection layer, the compound is thinned by a known method such as, for example, vacuum deposition, spin coating, casting, or LB. The thickness of the hole injection layer is not particularly limited, but is usually 5 nm-5 micrometers.

On the other hand, the electron injection material which uses the electron injection layer which shows the outstanding electron injection effect with respect to a light emitting layer, and is excellent in adhesiveness with a cathode interface, and thin film formation property is used. Examples of such electron injecting materials include metal complex compounds, nitrogen-containing five-membered ring derivatives, fluorenone derivatives, anthraquinodimethane derivatives, diphenoquinone derivatives, thiopyrandioxide derivatives, perylenetetracarboxylic acid derivatives, pleorenylidenemethane derivatives, and Tron derivatives, sirol derivatives, triarylphosphine oxide derivatives, calcium acetylacetonate, sodium acetate and the like. In addition, lectures on inorganic / organic composite materials doped with metals such as cesium to vasophenanthroline (Preparation of Polymer Society, Vol. 50, No. 4, page 660, published in 2001) or the 50th Association of Applied Physics BCP, TPP, T5MPyTZ, etc., described in the preliminary publication No. 3, p. 1402, issued in 2003, are also mentioned as examples of electron injecting materials, but a thin film required for device creation can be formed, and electrons from the cathode can be injected, If it is a material that can transport, it is not limited to these in particular.

Particularly effective electron injecting materials among the above electron injecting materials include metal complex compounds, nitrogen-containing five-membered ring derivatives, sirol derivatives, and triarylphosphine oxide derivatives. As a preferable metal complex compound which can be used for this invention, the metal complex of 8-hydroxyquinoline or its derivative (s) is preferable. Specific examples of metal complexes of 8-hydroxyquinoline or derivatives thereof include tris (8-hydroxyquinolinate) aluminum, tris (2-methyl-8-hydroxyquinolinatealuminum, tris (4-methyl-8-hydride) Hydroxyquinolinate) aluminum, tris (5-methyl-8-hydroxyquinolinate) aluminum, tris (5-phenyl-8-hydroxyquinolinate) aluminum, bis (8-hydroxyquinolinate) ( 1-naphtholate) aluminum, bis (8-hydroxyquinolinate) (2-naphtholate) aluminum, bis (8-hydroxyquinolinate) (phenolate) aluminum, bis (8-hydroxyquinolinate (4-Cyano-1-naphthorate aluminum, bis (4-methyl-8-hydroxyquinolinate) (1-naphtholate) aluminum, bis (5-methyl-8-hydroxyquinolinate) (2-naphtholate) aluminum, bis (5-phenyl-8-hydroxyquinolinate) (phenolate) aluminum, bis (5-cyano-8-hydrate Aluminum complexes such as cyquinolinate) (4-cyano-1-naphtholate aluminum, bis (8-hydroxyquinolinate) chloroaluminum, bis (8-hydroxyquinolinate) (o-cresolate) aluminum Compound, tris (8-hydroxyquinolinate) gallium, tris (2-methyl-8-hydroxyquinolinate) gallium, tris (4-methyl-8-hydroxyquinolinate) gallium, tris (5- Methyl-8-hydroxyquinolinate) gallium, tris (2-methyl-5-phenyl-8-hydroxyquinolinate) gallium, bis (2-methyl-8-hydroxyquinolinate) (1-naphthol Gallium, bis (2-methyl-8-hydroxyquinolinate) (2-naphtholate) gallium, bis (2-methyl-8-hydroxyquinolinate) (phenolate) gallium, bis (2- Methyl-8-hydroxyquinolinate) (4-cyano-1-naphtholate) gallium, bis (2,4-dimethyl-8-hydroxyquinolinate) (1-naphtholate) gallium, bis (2 , 5-dimethyl-8-hydroxyquinoline Yit) (2-naphtholate) gallium, bis (2-methyl-5-phenyl-8-hydroxyquinolinate) (phenolate) gallium, bis (2-methyl-5-cyano-8-hydroxyqui Nolinate) (4-cyano-1-naphtholate) gallium, bis (2-methyl-8-hydroxyquinolinate) chlorogallium, bis (2-methyl-8-hydroxyquinolinate) (o- Lithium 8-hydroxyquinolinate lithium, bis (8-hydroxyquinolinate) copper, bis (8-hydroxyquinolinate) manganese, bis (10-hydroxy) other than gallium complex compounds, such as cresolate) gallium And metal complex compounds such as benzo [h] quinolinate) beryllium, bis (8-hydroxyquinolinate) zinc and bis (10-hydroxybenzo [h] quinolinate) zinc.

Preferred nitrogen-containing five-membered ring derivatives among the electron injecting materials usable in the present invention include oxazole derivatives, thiazole derivatives, oxadiazole derivatives, thiadiazole derivatives and triazole derivatives. Specifically, 2,5- 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 -Butylbenzene], 2- (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, etc. Can be mentioned.

In addition, as an especially preferable oxadiazole conductor among the electron injection materials which can be used for this invention, the oxadiazole derivative represented by following General formula (20) can be shown.

(In formula, Ar ^r1 and Ar ^r2 each independently represent a monovalent aromatic hydrocarbon group or monovalent nitrogen-containing aromatic heterocyclic group which may have a substituent.)

As the monovalent nitrogen-containing aromatic heterocyclic group in the formula (20), 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 3-pyridyl group, 4-pyridazyl group, 2-pyrimidyl group, 4-pyrimidyl group, Monovalent nitrogen-containing monocyclic aromatic heterocyclic groups, such as 5-pyrimidyl group, 2-pyrazyl group, and 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, Monovalent nitrogen-containing condensed cyclic aromatic heterocyclic groups such as 6-quinoxalyl group, 1-indolyl group, 9-carbazolyl group, 2,2'-bipyridyl-3-yl group, 2,2'-bipyridyl- 4-yl, 3,3'-bipyridyl-2-yl, 3,3'-bipyridyl-4-yl, 4,4'-bipyridyl-2-yl, 4,4'-bipyri Monovalent nitrogen-containing ring-containing aromatic heterocyclic groups such as a di-3-yl group, and the hydrogen atom on these monovalent nitrogen-containing aromatic heterocyclic groups may be a monovalent aliphatic hydrocarbon group or a monovalent aliphatic hydrocarbon group. It may be substituted with an aromatic hydrocarbon group.

Moreover, as a monovalent aromatic hydrocarbon group preferable as Ar ^r1 and Ar ^r2 , 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m which can be substituted by monovalent aliphatic hydrocarbon group or monovalent nitrogen-containing aromatic heterocyclic group, m Biphenylyl group and p-biphenylyl group, and further preferred monovalent nitrogen-containing aromatic heterocyclic groups include 2-pyridyl group, 3-pyridyl group, which may be substituted with monovalent aliphatic hydrocarbon group or monovalent aromatic hydrocarbon group, 4-pyridyl group, 2,2'-bipyridyl-3-yl group, and 2,2'-bipyridyl-4-yl group are mentioned.

Tables 29 to 32 below show specific examples of oxadiazole derivatives usable in the present invention.

In this specification, when describing the oxadiazole derivative which can be used for this invention, the number of the compound described in the column of the left side of each table of Tables 29-32 is used.

Moreover, the triazole derivative represented by following formula (21) is mentioned as an especially preferable triazole derivative among the electron injection materials which can be used for this invention.

(In the formula, Ar ^{t1 to} Ar ^t3 each independently represent a monovalent aromatic hydrocarbon group or monovalent nitrogen-containing aromatic heterocyclic group which may have a substituent.)

Here, as the monovalent aromatic hydrocarbon group preferable as Ar ^t1 and Ar ^t2 , a phenyl group, 1-naphthyl group, 2-naphthyl group, o-ratio which may be substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group The phenylyl group, m-biphenylyl group, and p-biphenylyl group are mentioned, Preferable monovalent nitrogen-containing aromatic heterocyclic group is the 2-pyridyl group which can be substituted by monovalent aliphatic hydrocarbon group or monovalent aromatic hydrocarbon group, 3 -Pyridyl group, 4-pyridyl group, 2,2'-bipyridyl-3-yl group, and 2,2'-bipyridyl-4-yl group. Moreover, as a monovalent aromatic hydrocarbon group which is preferable as Ar ^t3 , the phenyl group, 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m- which may be substituted by monovalent aliphatic hydrocarbon group or monovalent nitrogen-containing aromatic heterocyclic group The biphenylyl group and p-biphenylyl group can also be mentioned, Moreover, as a preferable monovalent nitrogen-containing aromatic heterocyclic group, 2-pyridyl group, 3-pyridyl group, and 4 which can be substituted by monovalent aliphatic hydrocarbon group or monovalent aromatic hydrocarbon group -A pyridyl group.

Hereinafter, the specific example of the triazole derivative which can be used for this invention in Table 33-37 is shown.

In this specification, when describing the triazole derivative which can be used for this invention, the number of the compound described in the column of the left side of each table of Table 33-37 is used.

Among the electron injection materials usable in the present invention, particularly preferred sirol derivatives include sirol derivatives represented by the following general formula (22).

^Wherein R ^p1 and R ^p2 each independently represent a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group which may have a substituent. Ar ^{p1 to} Ar ^p4 each independently represent a substituent. Or a monovalent aromatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group which may have R. The adjacent groups of R ^p1 , R ^p2 and Ar ^{p1 to} Ar ^p4 may be connected to each other to form a ring.)

Here, the monovalent aliphatic hydrocarbon group preferable as R ^p1 and R ^p2 includes a methyl group, an ethyl group, a propyl group and a butyl group which may be substituted with a monovalent aromatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group. Examples of the valent aromatic hydrocarbon group include a phenyl group, m-biphenylyl group, and p-biphenylyl group which may be substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group, and as the preferable monovalent nitrogen-containing aromatic heterocyclic group To be substituted with a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group 2-pyridyl group, 3-pyridyl group, 4-pyridyl group which can be mentioned. Moreover, as a monovalent aromatic hydrocarbon group preferable as Ar ^p1 -Ar ^p4 , the phenyl group, 1-naphthyl group, 2-naphthyl group, o-biphenylyl group which can be substituted by monovalent aliphatic hydrocarbon group or monovalent nitrogen-containing aromatic heterocyclic group , m-biphenylyl group and p-biphenylyl group, and as the preferable monovalent nitrogen-containing aromatic heterocyclic group, 2-pyridyl group and 3-pyridine which may be substituted with monovalent aliphatic hydrocarbon group or monovalent aromatic hydrocarbon group And dialkyl, 4-pyridyl, 2,2'-bipyridyl-3-yl and 2,2'-bipyridyl-4-yl.

Hereinafter, Table 38-42 shows the specific example of the sirol derivative which can be used for this invention.

In this specification, when describing the sirol derivative which can be used for this invention, the number of the compound described in the column of the left side of each table of Table 38-42 is used.

Moreover, among the electron injection materials which can be used for this invention, as a preferable sirol derivative, the sirol derivative shown below is mentioned, for example.

Moreover, as a preferable triaryl phosphine oxide derivative among the electron injection materials which can be used for this invention, the tree of Unexamined-Japanese-Patent No. 2002-63989, 2004-95221, 2004-203828, 2004-204140 is disclosed. An aryl phosphine oxide derivative and the triaryl phosphine oxide derivative represented by following General formula (23) are mentioned.

(In the formula, Ar ^{q1 to} Ar ^q3 each independently represents a monovalent aromatic hydrocarbon group which may have a substituent.)

Here, as the monovalent aromatic hydrocarbon group preferable as Ar ^{q1 to} Ar ^q3 , a phenyl group, 1-naphthyl group, 2-naphthyl group, o-biphenyl which can be substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group A aryl group, m-biphenylyl group, and p-biphenylyl group are mentioned.

Hereinafter, the specific example of the triaryl phosphine oxide derivative which can be used for this invention in Table 43-Table 47 is shown.

In this specification, when describing the triaryl phosphine oxide derivative which can be used for this invention, the number of the compound described in the column of the left of each table | surface of Table 43-Table 47 is used.

As a preferable triaryl phosphine oxide derivative, the triaryl phosphine oxide derivative shown below is mentioned, for example.

As the hole blocking layer, a hole blocking material capable of preventing the holes passing through the light emitting layer from reaching the electron injection layer and forming a layer excellent in thin film formability is used. 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-phenylphenol Nitrogen-containing condensed aromatic compounds, such as a gallium complex compound, such as the rate) gallium, and 2, 9- dimethyl- 4, 7- diphenyl- 1, 10- phenanthroline (BCP), are mentioned.

As a light emitting layer of the organic electroluminescent element of this invention, it is preferable to have the following functions.

Injection function; A function capable of injecting holes from an anode or a hole injection layer when an electric field is applied, and injecting electrons from a cathode or an electron injection layer.

Transport function; The function of moving injected charges (electrons and holes) by the force of an electric field.

Light emitting function; Provides a place for recombination of electrons and holes, and associates it with light emission.

However, there may be a difference between being easy to inject holes and easily injecting electrons, and there may be a difference in the transport capacity expressed by the mobility of holes and electrons. desirable.

The light emitting material of the organic EL device is mainly an organic compound, and specifically, the following compounds are used depending on the desired color tone.

For example, when obtaining violet light emission from an ultraviolet region, the compound represented by following formula (24) is used preferably.

(Wherein, X1 represents a group represented by the following formula (25), and X2 represents any one of a phenyl group, 1-naphthyl group, 2-naphthyl group.)

(In formula, m represents the integer of 2-5.)

The phenyl group, 1-naphthyl group, 2-naphthyl group, phenylene group represented by X 1 and X 2 of the general formula (24) is a single or plural C1-4 alkyl group, C1-4 alkoxyl group, hydroxyl group, sulfonyl group, carbonyl group It may be substituted with a substituent such as an amino group, a dimethylamino group or a diphenylamino group. In addition, when there exist a plurality of these substituents, they may combine with each other to form a ring. In addition, the phenylene group represented by X1 is preferably bonded to the para position so that the bondability is good and a smooth vapor deposition film is easily formed. Specific examples of the compound represented by Formula 24 are as follows (wherein Ph represents a phenyl group).

Among these compounds, p-quaterphenyl derivatives and p-shankphenyl derivatives are particularly preferable.

In addition, in order to obtain light emission from the visible region, in particular, blue to green, fluorescent brighteners such as benzothiazole series, benzoimidazole series, and benzoxazole series, metal chelation oxynoid compounds, and styrylbenzene series compounds can be used. Can be. As a specific example of these compounds, the compound disclosed by Unexamined-Japanese-Patent No. 59-194393 is mentioned, for example. Further useful compounds are exemplified in chemistry of synthetic dies (1971) on pages 628-637 and 640.

As said metal chelation oxynoid compound, the compound disclosed by Unexamined-Japanese-Patent No. 63-295695 can be used, for example. Representative examples thereof include 8-hydroxyquinoline-based metal complexes such as tris (8-quinolinol) aluminum, dilithium epitridione and the like as preferred compounds.

As the styrylbenzene-based compound, for example, those disclosed in European Patent No. 0319881 or European Patent No. 0373582 can be used. The distyrylpyrazine derivative disclosed in Japanese Patent Laid-Open No. 2-252793 can also be used as a material for the light emitting layer. In addition, the polyphenyl-based compound disclosed in European Patent No. 0387715 can also be used as a material of the light emitting layer.

In addition to the above-described fluorescent brighteners, metal chelated oxynoid compounds, styrylbenzene-based compounds 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 (above Appl. Phys. Lett., Vol. 56, L799 (1990)), Naphthalimide derivatives (Japanese Patent Laid-Open No. 2-305886), perylene derivatives (Japanese Patent Laid-Open No. 2-189890), oxadiazole derivatives (Japanese Patent Laid-Open No. 2-216791 or the 38th Association of Applied Physics) Oxadiazole derivatives disclosed by Suda et al., Aldazine derivatives (JP-A-2-220393), pyrazilin derivatives (JP-A-2-220394), cyclopentadiene derivatives (JP-A-2-289675), Pyropyrrole derivatives (JP-A-2-296891), styrylamine derivatives (Appl. Phys. Lett., Vol. 56, L799 (1990)), coumarin-based compounds (JP-A-2-191694), international Patent publication WO90 / 13148 B) high molecular compounds, such as those described in Appl. Phys. Lett., Vol 58, 18, P1982 (1991), 9,9 ', 10,10'-tetraphenyl-2,2'-bianthracene, PPV (poly Paraphenylenevinylene) derivatives, polyfluorene derivatives, copolymers thereof, and the like, for example, those having the structures represented by the following formulas (26) to (28), and 9,10-bis (N- (4- (2-phenylvinyl)). -1-yl) phenyl) -N-phenylamino) anthracene can also be used as a material for the light emitting layer, and furthermore, the phenylanthracene derivative represented by the following formula (29) as disclosed in Japanese Patent Application Laid-Open No. 8-12600 can also emit light. It can be used as a material.

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

( ^Wherein , 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.)

( ^Wherein , R ^X5 and R ^X6 each independently represent a monovalent aliphatic hydrocarbon group, and n4 and n5 each independently represent an integer of 3 to 100. Ph represents a phenyl group.)

A1-L-A2

(Wherein A 1 and A 2 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, as the divalent linking group represented by L, a divalent monocyclic or condensed aromatic hydrocarbon group which may have a substituent is preferable. In particular, the phenylanthracene derivative represented by the following general formula (30) or general formula (31) is preferable.

(Wherein, 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, a monovalent aliphatic heterocyclic group, or a monovalent aromatic group. Heterocyclic groups, which may be the same or different, r1 to r4 each independently represent an integer of 0 or 1 to 5. When r1 to r4 each independently represent an integer of 2 or more, between R ^Z1, between R ^Z2 , and R ^{Z 3} and R ^{Z 4} may be the same or different, and R ^{Z 1} , R ^{Z 2} , R ^{Z 3} , and R ^{Z 4} may be bonded to each other to form a ring. A divalent monocyclic or condensed aromatic hydrocarbon group, which may have a substituent, is an alkylene group, -O-, -S- or -NR-, where R represents an alkyl group or an aryl group May be intervened.)

(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 aliphatic heterocyclic group, or a monovalent aromatic group. Heterocyclic groups, which may be the same or different, r5 and r6 each independently represent an integer of 0 or 1 to 5. When r5 and r6 each independently represent an integer of 2 or more, between R ^Z5 and R ^Z6 are each May be the same or different, and may be bonded to each other to form a ring between R ^Z5 and R ^Z6 L2 represents a divalent monocyclic or condensed aromatic hydrocarbon group which may have a single bond or a substituent, and 2 which may have a substituent The monovalent or condensed cyclic aromatic hydrocarbon group may be interrupted by an alkylene group, -O-, -S- or -NR- (where R represents an alkyl group or an aryl group).

Of the above formula (30), the phenylanthracene derivative represented by the following formula (32) or formula (33) is more preferable.

(Wherein, R ^Z11 to R ^Z30 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 aliphatic heterocyclic group, or a monovalent aromatic group. Heterocyclic groups may be the same or different, and R ^Z11 to R ^Z30 may be linked to each other to form a ring. K1 represents an integer of 0 to 3.)

(In formula, R <^Z31> -R <^Z50> is respectively 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 aliphatic heterocyclic group, and a monovalent aromatic. Heterocyclic groups may be the same or different, and R ^Z31 to R ^Z50 may be linked to each other to form a ring. K2 represents an integer of 0 to 3.)

Further, in the above formula (31), the phenylanthracene derivative represented by the following formula (34) is more preferable.

( ^Wherein , R ^Z51 to R ^Z60 each independently represents 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 aliphatic heterocyclic group, or a monovalent aromatic group. ^Heterocyclic groups may be the same or different, and R ^Z51 to R ^Z60 may be linked to each other to form a ring. K3 represents an integer of 0 to 3.)

As a specific example of said Formula (32)-Formula (34), the following compounds etc. are mentioned, for example.

Furthermore, the following compounds are also mentioned as a specific example.

The amine compound represented by the following formula (35) is also useful as a light emitting material.

(Wherein h represents an integer of 1 to 6 in valence. E ¹ represents an n-valent aromatic hydrocarbon group, E ² represents an amino group selected from a dialkylamino group, a diarylamino group, and an alkylarylamino group.)

Here, as the parent structure of the n-valent aromatic hydrocarbon group represented by E ¹ , naphthalene, anthracene, 9-phenylanthracene, 9,10-diphenylanthracene, naphthacene, pyrene, perylene, biphenyl, vinaphthyl, biantryl This is preferable and a diarylamino group is preferable as an amino group represented by E <^1> . Moreover, 1-4 are preferable and, as for n, it is most preferable that it is 2 especially. In the formula (35), an amine compound represented by the following formulas (36) to (45) is particularly preferable.

Wherein 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, a monovalent aromatic heterocyclic group or a dialkylamino group, or a diaryl. An amino group selected from an amino group or an alkylarylamino group, and at least one of R ^y1 to R ^y8 represents an amino group selected from a dialkylamino group, a diarylamino group or an alkylarylamino group, ^wherein R ^y1 to R ^y8 may be the same or different, Neighboring groups may be connected to each other to form a ring.)

(Wherein, R ^y11 to R ^y20 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group or a dialkylamino group, or a diarylamino group. Or an amino group selected from an alkylarylamino group, and at least one of R ^y11 to R ^y20 represents an amino group selected from a dialkylamino group, a diarylamino group, or an alkylarylamino group, wherein R ^y11 to R ^y20 may be the same or different, and each other. Adjacent groups may be connected to form a ring.)

( ^Wherein , R ^y21 to R ^y34 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, a monovalent aromatic heterocyclic group or a dialkylamino group, or a diarylamino group. Or an amino group selected from an alkylarylamino group, and at least one of R ^y21 to R ^y34 represents an amino group selected from a dialkylamino group, a diarylamino group, or an alkylarylamino group, wherein R ^y21 to R ^y34 may be the same or different and mutually Adjacent groups may be connected to form a ring.)

(Wherein, R ^y35 ~R ^y52 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group or dialkylamino group, diarylamino group or represents a group selected from an alkylaryl group, R ^y35 ~R least one of ^y52 represents an amino group selected from a dialkylamino group, diarylamino group, or an alkyl aryl group. R ^{y35 y52} ~R may be the same or different and each Adjacent groups may be connected to form a ring.)

(Wherein, R ^y53 ~R ^y64 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group or dialkylamino group, diarylamino group Or an amino group selected from alkylarylamino groups, R ^y53 to R ^y64 At least one represents an amino group selected from a dialkylamino group, a diarylamino group or an alkylarylamino group. R ^{y53 y64} ~R may be the same or different, it is a group between the adjacent connection may form a ring.)

(Wherein, R ^y65 ~R ^y74 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group or dialkylamino group, diarylamino group Or an amino group selected from alkylarylamino groups, R ^y65 to R ^y74 At least one represents an amino group selected from a dialkylamino group, a diarylamino group or an alkylarylamino group. R ^{y65 y74} ~R may be the same or different, it is a group between the adjacent connection may form a ring.)

(Wherein, R ^y75 ~R ^y86 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group or dialkylamino group, diarylamino group Or an amino group selected from alkylarylamino groups, R ^y75 to R ^y86 At least one represents an amino group selected from a dialkylamino group, a diarylamino group or an alkylarylamino group. R ^{y75 y86} ~R may be the same or different, it is a group between the adjacent connection may form a ring.)

(Wherein, R ^y87 ~R ^y96 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group or dialkylamino group, diarylamino group Or an amino group selected from alkylarylamino groups, R ^y87 to R ^y96 At least one represents an amino group selected from a dialkylamino group, a diarylamino group or an alkylarylamino group. R ^{y87 y96} ~R may be the same or different, it is a group between the adjacent connection may form a ring.)

(Wherein, R ^{y97 y110} ~R 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, a monovalent aromatic heterocyclic group or dialkylamino group, diarylamino group or it represents a group selected from an alkylaryl group, R ^y97 ~R least one of ^y110 represents a group selected from a dialkylamino group, diarylamino group, or an alkyl aryl group. R ^{y97 y110} ~R may be the same or different from, one another Adjacent groups may be connected to form a ring.)

(Wherein, R ^y111 ~R ^y128 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group or dialkylamino group, diarylamino group or it represents a group selected from an alkylaryl group, R ^y111 ~R least one of ^y128 represents a group selected from a dialkylamino group, diarylamino group, or an alkyl aryl group. R ^y111 ~R ^y128 may be the same or different from, one another Adjacent groups may be connected to form a ring.)

The amine compounds of the above-mentioned formulas (40) and (42) can be preferably used when yellow to red light emission is obtained. Specific examples of the amine compound represented by the formulas (35) to (45) include compounds having the following structures (wherein Ph represents a phenyl group).

In addition, in Chemical Formulas 35 to 45, a compound containing at least one styryl group represented by Chemical Formula 46 or Chemical Formula 47 as an alternative to an amino group (for example, European Patent No. 0388768, JP-A 3-231970). And the ones disclosed in Japanese Patent Application Laid-Open No. 1, etc.) can also be preferably used as the light emitting material.

(In formula, ^{Ry129- Ry131} represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent aromatic hydrocarbon group each independently. ^{Ry129- Ry131} may connect between adjacent groups, and may form a ring.)

(Wherein, R ^y132 ~R ^y138 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or a monovalent aromatic hydrocarbon group. R ^y134 ~R ^y138 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic hydrocarbon group or represents a group selected from a dialkylamino group, a diaryl amino group or alkyl aryl group, at least one of R ^y134 ~R ^y138 is a group selected from a dialkylamino group, diarylamino group, or an alkyl aryl group. R ^y132 ~R ^y138 May be connected between adjacent groups to form a ring.)

Specific examples of the compound including at least one styryl group represented by the above-mentioned general formula (46) or general formula (47) include compounds having the following structure (wherein Ph represents a phenyl group).

In addition, the chemical formula described in Japanese Patent Application Laid-Open No. 5-258862,

(Rs-Q) ₂ -Al-O-L3

(Wherein L3 is a hydrocarbon having 6 to 24 carbon atoms containing a phenyl moiety, O-L3 is a phenolate ligand, Q represents a substituted 8-quinolinolate ligand, and Rs is substituted to an aluminum atom 8-) Also shown are compounds represented by the 8-quinolinolate ring substituents selected to steric hindrance that the quinolinolate ligands are more than two bound. Nolinoleate) (paraphenyl phenolate) aluminum (III), bis (2-methyl-8-quinolinolate) (1-naphtholate) aluminum (III), etc. are mentioned.

In addition, the method of obtaining high efficiency blue and green mixed light emission using doping by Unexamined-Japanese-Patent No. 6-9953 is mentioned. In this case, as a host, the above-mentioned luminescent material and an impurity fluorescent dye which is strong from blue to green, for example, coumarin type or the same fluorescent dye used as said host, can be mentioned. Specifically, a light emitting material having a distyryl arylene skeleton as a host, particularly preferably 4,4'-bis (2,2-diphenylvinyl) biphenyl, as an impurity is diphenylaminovinyl arylene, and particularly preferably For example, N, N- diphenylamino vinyl benzene is mentioned.

Although there is no restriction | limiting in particular as a light emitting layer which acquires white light emission, The following can be used.

The energy level of each layer of an organic EL laminated structure is prescribed | regulated, and light-emitted using tunnel injection (European patent 0390551). Similarly, a device using tunnel injection, in which a white light emitting device is described (see Japanese Patent Application Laid-Open No. 3-230584).

A light emitting layer having a two-layer structure is described (Japanese Patent Application Laid-Open No. 2-220390 and Japanese Patent Laid-Open No. 2-216790). A light emitting layer is divided into a plurality and composed of materials having different light emission wavelengths (Japanese Patent Application Laid-Open No. 4-51491). A blue luminescent body (fluorescence peak 380-480 nm) and a green luminescent body (480-580 nm) are laminated | stacked, and the thing of the structure which contained the red fluorescent substance (JP-A-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 has a green fluorescent substance (JP-A-7-142169).

In these, the thing of the said structure is especially preferable.

In addition, as a light emitting material, the well-known compound shown below is used preferably, for example, Ph represents a phenyl group.

In addition, a phosphorescent material can be used as the organic electroluminescent device of the present invention. Examples of the phosphorescent material or the doping material which can be used as the organic electroluminescent device of the present invention include organometallic complexes, wherein the metal atoms are usually transition metals, preferably cycles 5 or 6 As the cycle and the group, elements of the group 6 to 11 and more preferably the group 8 to 10 are targeted. Specifically, it is iridium or platinum. Examples of the ligand include 2-phenylpyridine, 2- (2'-benzothienyl) pyridine, and the like, and the carbon atoms on the ligand are directly bonded to the metal. As another example, porphyrin or tetraaza porphyrin ring complex etc. are mentioned, and a platinum etc. are mentioned as a center metal. For example, the following well-known compound is used suitably as a phosphorescence emitting material (however, Ph represents a phenyl group).

The material used for the anode of the organic EL device of the present invention is preferably one having a large work function (4 eV or more) of a metal, an alloy, an electrically conductive compound, or a mixture thereof as an electrode material. Specific examples of such electrode materials include metals such as Au and conductive materials such as CuI, ITO, SnO ₂ , and ZnO. In order to form an anode, such an electrode material can be formed into a thin film by a method such as a vapor deposition method or a sputtering method. Such an anode preferably has characteristics such that the light transmittance of the light emitting layer from the anode is such that the transmittance of the anode is greater than 10%. In addition, the sheet resistance of the anode is preferably set to several hundred Ω / cm 2 or less. In addition, the film thickness of the anode is. Depending on the material, it is usually selected in the range of 10 nm to 1 m, preferably 10 to 200 nm.

As the material used for the cathode of the organic EL device of the present invention, one having a small work function (4 eV or less) of a metal, an alloy, an electrically conductive compound, or a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloys, magnesium, lithium, magnesium-silver alloys, aluminum / aluminum oxides, aluminum-lithium alloys, indium, rare earth metals, and the like. The cathode can be produced by forming a thin film of such an electrode material by a method such as vapor deposition or sputtering. Here, in the case where the light emission in the light emitting layer is taken out from the cathode, the transmittance of the cathode from light emission is preferably greater than 10%. In addition, the sheet resistance of the cathode is preferably several hundred Ω / cm 2 or less, and the film thickness is usually 10 nm to 1 m, preferably 50 to 200 nm.

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

This organic EL element is produced on a light-transmissive substrate. The light-transmissive substrate is a substrate for supporting an organic EL element, and in light transmittance, a transmittance of visible light of 400 to 700 nm is preferably 50% or more, preferably 90% or more, and it is preferable to use a smooth substrate. desirable.

These substrates are not particularly limited as long as they have mechanical and thermal strength and are transparent. For example, glass plates, synthetic resin plates and the like are preferably used. As a glass plate, the board especially shape | molded with sodium carbonate lime glass, barium strontium containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, etc. are mentioned. Moreover, as a synthetic resin board, plates, such as a polycarbonate resin, an acrylic resin, a polyethylene terephthalate resin, a polyether sulfide resin, a polysulfone resin, are mentioned.

As a method for forming each layer of the organic EL device of the present invention, any one of dry film formation methods such as vacuum deposition, electron beam beam irradiation, sputtering, plasma, ion plating, or wet film formation methods such as spin coating, dipping and flow coating can be used. The method can be applied. In particular, the organic layer is preferably a molecular deposit film. Here, the molecular deposited film is a thin film formed by depositing from a material compound in a gaseous state, or a film formed by solidifying from a material compound in a solution state or a liquid state. The molecular deposited film is a thin film formed by an LB method (molecular). Cumulative film) can be distinguished by a difference in agglomeration structure, a high dimensional structure, or a functional difference resulting therefrom. Further, as disclosed in Japanese Patent Application Laid-Open No. 57-51781, an organic layer can also be formed by dissolving a binder such as a resin and a material compound in a solvent to form a solution and then thinning it by spin coating or the like. 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. On the contrary, if the film thickness is too thin, a pinhole or the like is generated. Even if it is applied, it becomes difficult to obtain sufficient light emission luminance. Therefore, the range of 1 nm-1 micrometer is suitable for the film thickness of each layer, and the range of 10 nm-0.2 micrometer is more preferable.

Moreover, in order to improve stability with respect to temperature, humidity, atmosphere, etc. of an organic electroluminescent element, a protective layer can be provided in the surface of an element, or the whole element can be coat | covered or sealed by resin etc. In particular, when covering or sealing the whole element, the photocurable resin hardened | cured by light is used suitably.

The current applied to the organic EL element of the present invention is usually a direct current, but pulse current or alternating current can also be used. The current value and the voltage value are not particularly limited as long as they do not destroy the device, but it is desirable to emit light efficiently with as little electric energy as possible in consideration of the power consumption and the lifetime of the device.

The drive method of the organic EL element of the present invention can be driven not only by the passive matrix method but also by the active matrix method. In addition, the method of extracting light from the organic EL device of the present invention is not only a bottom emission method of emitting light from the anode side, but also a top emission method of emitting light from the cathode side. It is also applicable to the method. Such methods and techniques are described in the book, [All of Organic EL], and Japan Industrial Publishing Co., Ltd. (issued in 2003).

In addition, the organic EL element of this invention may employ | adopt a micro cavity structure. This is because the organic EL device has a structure in which a light emitting layer is sandwiched between an anode and a cathode, and the emitted light has multiple interferences between the anode and the cathode, but the optical characteristics such as reflectance and transmittance of the anode and cathode are interposed therebetween. It is a technique of controlling the light emission wavelength taken out from an element by actively using the multiple interference effect by suitably selecting the film thickness of the organic layer clamped on the inside. This also makes it possible to improve the emission chromaticity. The mechanism of such multiple interference effects is described in AM-LCD Digest of Technical Papers, OD-2, p. 77-80 (2002) by J. Yamada et al.

As described above, the organic EL device using the carbazole-containing amine compound of the present invention can obtain light emission for a long time with low driving voltage. Therefore, the present organic EL element can be considered as a flat panel display such as a wall-mounted television or various flat light emitters, and further, applications such as light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display panels, signs, and the like.

1 is a mass spectral chart of compound (2).

2 is a ¹ H-NMR chart of Compound (2) (in THF-d ₈ ).

3 is a ¹³ C-NMR chart of Compound (2) (of THF-d ₈ ).

4 is a mass spectral chart of Compound (22).

5 is a ¹ HNMR chart of Compound (22). (In THF-d ₈ )

6 is a ¹³ CNMR chart of Compound (22) (of THF-d ₈ ).

7 is a mass spectral chart of Compound (39).

8 is a ¹ HNMR chart of compound (39). (In THF-d ₈ )

9 is a mass spectral chart of Compound (45).

10 is a ¹ HNMR chart of Compound (45). (Of THF-d ₈ )

11 is a mass spectral chart of 9- (1-naphthyl) -3-bromocarbazole.

12 is a ¹ HNMR chart of 9- (1-naphthyl) -3-bromocarbazole (in chloroform-d).

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

In the Examples, unless otherwise stated, mass spectra (Autoflex II, manufactured by Vulkadaltonics Co., Ltd.), ¹ H-NMR, and ¹³ C-NMR (manufactured by Nippon Electronics Co., Ltd., GSX-270W) were used. . In addition, the glass transition temperature (Tg) of the compound was measured using the DSC6200 differential scanning calorimeter by Seiko Instruments.

In addition, unless otherwise indicated in the following Example, a mixture ratio shows a weight ratio all. Vapor deposition (vacuum vapor deposition) was performed under conditions without temperature control such as substrate heating and cooling in a vacuum of 10 ⁻⁶ Torr. In evaluating the light emission characteristics of the device, the characteristics of the organic EL device having an electrode area of 2 mm × 2 mm were measured.

Example  One

Synthesis method of Compound (2)

Compound (2) ((iii) in the scheme) was prepared by the scheme shown below.

3.9 g (15 mmol) of N, N'-diphenyl-phenylenediamine (i) under nitrogen atmosphere, 10.5 g (33 mmol) of 3-bromo-9-phenylcarbazole (ii), 0.1 g of palladium acetate, 0.15 g of tri-tert-butylphosphine and 3.4 g of potassium carbonate were placed in a 300 ml four-necked flask, and 200 ml of dehydrated xylene was added and heated to reflux for 1.5 hours. The reaction solution was poured into 1 L of methyl alcohol, and the precipitated solid was collected by filtration and dried in vacuo. 10.4 g (yield 95%) of (vi) (= compound (2)) were obtained as a crude product. The obtained crude product was purified by silica gel column chromatography, and further sublimed purification. The glass transition temperature of this compound (2) was 135 degreeC (differential scanning calorimeter, the product of Seiko Instruments).

The mass spectrum of the compound (Autoflex II, manufactured by Vulkadaltonics Co., Ltd.) is shown in FIG. 1.

Calculation: 742.31 (M ⁺ ),

Found: 742.313

¹ H-NMR and ¹³ C-NMR (manufactured by Nippon Electronics Co., Ltd., GSX-270W) are shown in Figs.

Example  2

Synthesis Method of Compound (22)

Compound (22) ((v) in scheme) was prepared by the scheme shown below.

Compound (2) except that 4,4'-diphenylbenzidine was used instead of N, N'-diphenyl-phenylenediamine (i) in Synthesis Example of Compound (2) above (V) (= Compound (22)) was obtained as a crude product in the same manner as the synthesis method (yield 97% of crude product). The obtained crude product was purified by silica gel column chromatography, and further sublimed purification was performed. The glass transition temperature of this compound is 148 degreeC (differential scanning calorimeter, the Seiko instrument company make).

The mass spectrum of the compound (Autoflex II, manufactured by Vulkadaletonics Co., Ltd.) is shown in FIG. 4.

Calculation: 818.34 (M ⁺ ),

Found: 818.305

^{1 H-NMR, 13 C-} NMR also the (Japan Electronic claim, GSX-270W) are shown in 5-6.

In addition, 3-bromo-9-phenylcarbazole (ii) used for the synthesis of the compounds (2) and (22) has been described by reference to the Journal of Industrial Chemistry, 1967, Vol. 70, p. 63. The site was brominated and subsequently synthesized by reacting iodine benzene with the Woolman method using a copper catalyst.

Example  3

Preparation of Compound (39) (Preparation of Compound (39) by Production Method A)

(1) Preparation of 9-biphenylylcarbazole

16.7 g of carbazole, 36.4 g of 4-iodobiphenyl, 1.9 g of first copper iodide, 138 g of anhydrous potassium carbonate, 0.53 g of 18-crown-6 and 1,3-dimethyl-3,4,5,6-tetrahydro ( 500 ml of 1H) -pyrimidinone was mixed and reacted at 170 ° C for 8 hours under a nitrogen atmosphere. The reaction product was filtered, 10 ml of concentrated ammonia water was added to the filtrate, followed by extraction with 300 ml of diethyl ether and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate) to obtain 27.5 g of 9-biphenylylcarbazole.

(2) Preparation of 9-biphenylyl-3-iodocarbazole

After adding 500 mL of 80% acetic acid aqueous solution to 16.0 g of obtained 9-biphenylylcarbazole, 6.79 g of iodine and 1.67 g of ortho periodic acid were added, and the mixture was reacted at 80 ° C. for 2 hours under a nitrogen atmosphere. The reaction product was extracted with 250 ml of diethyl ether and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate) to obtain 18.5 g of 9-biphenylyl-3-iodocarbazole.

(3) Preparation of 9-biphenylyl-3- (N-phenyl) aminocarbazole

13.3 g of 9-biphenylyl-3-iodocarbazole, 3.08 g of aniline, 4.56 g of anhydrous potassium carbonate, 0.381 g of copper powder, and 50 ml of nitrobenzene were mixed and reacted at 190 to 200 ° C. under a nitrogen atmosphere for 8 hours. The reaction product was extracted with 200 ml of toluene, the insolubles were separated by filtration and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate) to obtain 8.33 g of 9-biphenylyl-3- (N-phenyl) aminocarbazole.

(4) Preparation of Compound (39)

Nitrogen atmosphere was mixed with 8.21 g of 9-biphenylyl-3- (N-phenyl) aminocarbazole, 4.06 g of 4,4'-diiodobiphenyl, 1.52 g of anhydrous potassium carbonate, 0.127 g of copper powder, and 30 ml of nitrobenzene. It was made to react at 190-200 degreeC under 16 hours. The reaction product was extracted with 100 ml of toluene, the insolubles were separated by filtration and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: toluene) to obtain 4.95 g of compound (39). The structure of the compound (39) was confirmed by mass spectrum, ¹ H-NMR, ¹³ C-NMR. The mass spectrum of this compound (39) showed m / z = 970.400 (theoretical value = 970.404) and the glass transition temperature was 168 ° C. A mass spectral chart is shown in FIG. 7 and a ¹ H-NMR spectrum chart is shown in FIG. 8.

Example  4

Preparation of Compound (39) (Preparation of Compound (39) by Production Method B)

8.91 g of 9-biphenylyl-3-iodocarbazole, 3.36 g of N, N'-diphenylbenzidine, 1.52 g of anhydrous potassium carbonate, 0.127 g of copper powder, nitro prepared by the method described in (2) of Example 3 30 mL of benzene was mixed and reacted at 190-200 degreeC for 16 hours in nitrogen atmosphere. The reaction product was extracted with 100 ml of toluene, the insolubles were separated by filtration and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: toluene) to obtain 4.52 g of compound (39). The structure of the compound (39) obtained here was confirmed to be the same as the compound (39) prepared in Example 3 by mass spectrum ¹ H-NMR and ¹³ C-NMR.

Example  5

Preparation of Compound (46) (Preparation of Compound (46) by Manufacturing Method A)

(1) Preparation of 9- (2-naphthyl) carbazole

16.7 g of carbazole, 25.4 g of 2-iodonaphthalene, 1.9 g of first copper iodide, 138 g of anhydrous potassium carbonate, 18-crown-6'0.53 g, 1,3-dimethyl-3,4,5,6-tetrahydro ( 500 mL of 1H) -pyrimidinone was mixed and reacted at 170 ° C. for 10 hours under a nitrogen atmosphere. The reaction product was filtered and 10 ml of concentrated ammonia water was added to the filtrate, followed by extraction with 300 ml of diethyl ether and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate) to obtain 25.5 g of 9- (2-naphthyl) carbazole.

(2) Preparation of 9- (2-naphthyl) -3-iodocarbazole

After adding 500 ml of 80% acetic acid aqueous solution to 14.7 g of 9- (2-naphthyl) carbazole, 6.79 g of iodine and 1.67 g of ortho periodic acid were added, and the mixture was reacted at 80 ° C. for 2 hours under a nitrogen atmosphere. The reaction product was extracted with 250 ml of diethyl ether and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate) to obtain 16.4 g of 9- (2-naphthyl) -3-iodocarbazole.

(3) Preparation of 9- (2-naphthyl) -3- (N-phenyl) aminocarbazole

12.6 g of 9- (2-naphthyl) -3-iodocarbazole, 3.08 g of aniline, 4.56 g of anhydrous potassium carbonate, 0.381 g of copper powder, and 50 ml of nitrobenzene were mixed and reacted at 190 to 200 ° C. under a nitrogen atmosphere for 10 hours. I was. The reaction product was extracted with 200 ml of toluene, the insolubles were separated by filtration and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate) to obtain 7.85 g of 9- (2-naphthyl) -3- (N-phenyl) aminocarbazole.

(4) Preparation of Compound (46)

7.69 g of 9- (2-naphthyl) -3- (N-phenyl) aminocarbazole and 4.06 g of 4,4'-diiodobiphenyl, 1.52 g of anhydrous potassium carbonate, 0.127 g of copper powder, and 30 ml of nitrobenzene are mixed The reaction was carried out at 190 to 200 ° C. for 20 hours under a nitrogen atmosphere. The reaction product was extracted with 100 mL of toluene and the insolubles were filtered off and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: toluene) to obtain 4.82 g of compound (46). The structure of the compound (46) was confirmed by mass spectrum, ¹ H-NMR and ¹³ C-NMR. The mass spectrum of this compound (46) shows m / z = 918.369 (theoretical value = 918.372), and the glass transition temperature is 172 ° C.

Example  6

Preparation of Compound (46) (Preparation of Compound (46) by Production Method B)

8.39 g of 9- (2-naphthyl) -3-iodocarbazole, 3.36 g of N, N'-diphenylbenzidine, 1.52 g of anhydrous potassium carbonate, copper powder 0.127, prepared by the method described in (2) of Example 5. g and nitrobenzene 30 ml were mixed and reacted at 190 to 200 캜 for 20 hours under a nitrogen atmosphere. The reaction product was extracted with 100 ml of toluene, the insolubles were separated by filtration and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: toluene) to obtain 4.31 g of compound (46). The structure of the compound (46) obtained here was confirmed to be the same as the compound (46) produced in Example 5 by mass spectrum, ¹ H-NMR and ¹³ C-NMR.

Example  7

Preparation of Compound (40)

According to the method described in Example 5 or Example 6, compound (40) was prepared according to the method of Preparation Method D described above.

Mass Spectrum of Compound (40):

Calculation: 820.331,

Found: 820.334 (M ⁺ )

Example  8

Preparation of Compound (45)

According to the method described in Example 5 or Example 6, the compound (45) was prepared according to the method of preparation method B.

Mass Spectrum of Compound (45):

Calculated: 918.372,

Found: 918.370 (M ⁺ )

The mass spectrum chart of the compound (45) is shown in FIG. 9, and the ¹ H-NMR spectrum chart of the compound (45) is shown in FIG.

Example  9-39

Compounds (47) to (77) were prepared according to the method described in Example 5 or Example 6. Each compound was confirmed by mass spectrum, ¹ H-NMR, and ¹³ C-NMR. In Table 48, the manufacturing method of each compound and the actually measured value of the mass spectrum of the compound manufactured by this are shown.

Example  40 ~ Example  70

Compounds (78) to (108) were prepared according to the above production method. Each compound was confirmed by mass spectrum, ¹ H-NMR, and ¹³ C-NMR. In Table 49, the manufacturing method of each compound and the actual value of the mass spectrum of the compound which were produced by this are shown.

Example  71- Example  126

Compounds (109) to (164) were prepared according to the above-described production method. Each compound was confirmed by mass spectrum, ¹ H-NMR, and ¹³ C-NMR. In Tables 50-51, the manufacturing method of each compound and the actually measured value of the mass spectrum of the compound manufactured by this are shown.

Hereinafter, the synthesis | combining method of the carbazole derivative which is a raw material for manufacturing the carbazole containing amine compound of this invention is demonstrated. For the identification of carbazole derivatives, unless otherwise stated, mass spectra (Autoflex II, manufactured by Vulkadaltonics Co., Ltd.), ¹ H-NMR, and ¹³ C-NMR (manufactured by Nippon Electronics Co., Ltd., GSX-270W) were used.

Example  127

Preparation of 9- (2-naphthyl) -3-bromocarbazole represented by the following formula

600 ml of glacial acetic acid was added to 14.7 g of 9- (2-naphthyl) carbazole prepared by the method described in Example 5 (1) to completely dissolve it, and then 8.90 g of N-bromohobacterimide was added to room temperature. The reaction was stirred for 16 hours at. The reaction product was poured into 1 liter of water, and the precipitated product was extracted with 250 ml of diethyl ether and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: hexane / ethyl acetate) to obtain 16.4 g of 9- (2-naphthyl) -3-bromocarbazole. Mass spectrum found: M ⁺ = 371.029 (Theoretical value: M ⁺ = 371.031).

Example  128

Preparation of 9- (2-naphthyl) -3-chlorocarbazole represented by the following formula

600 ml of glacial acetic acid was added to 14.7 g of 9- (2-naphthyl) carbazole synthesized by the method described in Example 5 (1) to completely dissolve it, and then 6.68 g of N-chloro-hobamic acid imide was added thereto at room temperature. The reaction was stirred for 16 hours. The reaction product was poured into 1 liter of water, and the precipitated product was extracted with 250 ml of diethyl ether and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: hexane / ethyl acetate) to obtain 13.9 g of 9- (2-naphthyl) -3-chlorocarbazole. Mass spectrum found: M ⁺ = 327.079 (Theoretical value: M ⁺ = 327.081).

Example  129

Preparation of 9- (1-naphthyl) -3-iodocarbazole represented by the following formula

T. Ahn, H. K. Shim, Macromol. Chem. 9- (1-naphthyl) carbazole was first synthesized with reference to the method described in Phys., Vol. 202, 3180 (2001). 16.7 g of carbazole, 22.4 g of 1-bromonaphthalene, 1.02 g of copper powder, 13.9 g of anhydrous potassium carbonate, and 250 ml of nitrobenzene were mixed and reacted under reflux for 10 hours under a nitrogen atmosphere. Steam distillation removed the nitrobenzene and unreacted 1-bromonaphthalene and dried the residue. This was purified using column chromatography (carrier: silica gel, eluent: hexane / ethyl acetate) to give 22.3 g of 9- (1-naphthyl) carbazole. Melting point: 124-125 degreeC.

Subsequently, 500 ml of 80% acetic acid aqueous solution was added to 14.7 g of 9- (1-naphthyl) carbazole, 6.79 g of iodine and 1.67 g of orthoguaioic acid were added, and the mixture was reacted at 80 ° C. for 2 hours under a nitrogen atmosphere. The reaction product was extracted with 250 ml of diethyl ether and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: hexane / ethyl acetate) to obtain 15.7 g of 9- (1-naphthyl) -3-iodocarbazole. Mass spectrum found: M ⁺ = 419.012 (Theoretical value: M ⁺ = 419.017).

Example  130

Preparation of 9- (1-naphthyl) -3-bromocarbazole represented by the following formula

600 ml of glacial acetic acid was added to 14.7 g of 9- (2-naphthyl) carbazole synthesized in the same manner as in Example 129, and completely dissolved. 8.90 g of N-bromohobacteramide was added thereto, followed by stirring at room temperature for 16 hours. Reacted. The reaction product was poured into 1 liter of water, and the precipitated product was extracted with 250 ml of diethyl ether and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: hexane / ethyl acetate) to obtain 16.4 g of 9- (1-naphthyl) -3-bromocarbazole. 11 shows mass spectra measured by Agilent Technologies Corporation's 5973N Mass Selective Detector (actual values: M ⁺ = 371, theoretical values: M ⁺ = 371). 12 shows the ¹ H-NMR spectrum measured in chloroform-d.

Example  131

Preparation of 9- (1-naphthyl) -3-chlorocarbazole represented by the following formula

600 ml of glacial acetic acid was added to 14.7 g of 9- (2-naphthyl) carbazole synthesized by the method described in Example 129, and completely dissolved. I was. The reaction product was poured into 1 liter of water, and the precipitated product was extracted with 250 ml of diethyl ether and concentrated to dryness. This was purified using column chromatography (carrier: silica gel, eluent: hexane / ethyl acetate) to obtain 13.9 g of 9- (1-naphthyl) -3-bromocarbazole. Mass spectrum found: M ⁺ = 327.079 (Theoretical value: M ⁺ = 327.081).

Example  132

Compound (1) was vacuum-deposited on the glass plate with a washed ITO electrode, and the hole injection layer with a film thickness of 60 nm was obtained. Subsequently, 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, a tris (8-hydroxyquinoline) aluminum complex was vacuum deposited to form an electron injection light emitting layer having a film thickness of 60 nm, and thereafter, lithium fluoride was deposited at 1 nm, then aluminum at 200 nm, and an electrode was formed to form an electrode. An EL device was obtained.

Example  133

An organic EL device similar to Example 132 was prepared except that Compound (22) was used instead of Compound (1).

Example  134

An organic EL device similar to Example 132 was produced except that Compound (28) was used instead of Compound (1).

Example  135

Copper phthalocyanine was deposited on the glass plate to which the ITO electrode was attached, and the hole injection layer with a film thickness of 25 nm was formed. Next, Compound (39) and Compound (A) shown below were co-deposited at a composition ratio of 100: 8 to form a light emitting layer having a thickness of 45 nm. Subsequently, the compound (B) shown below was deposited to form an electron injection layer having a film thickness of 20 nm. 1 nm of lithium oxide (Li ₂ O) and 100 nm of aluminum (Al) were deposited thereon to form a cathode to obtain an organic electroluminescent device. The device has an external quantum efficiency of 6.2% at a DC voltage of 10V. In addition, the half life when driving a constant current at a light emission luminance of 200 (cd / m 2) was 5000 hours or more.

Example  136

Compound (C) shown below was deposited on a glass plate with an ITO electrode to form a hole injection layer having a film thickness of 60 nm, and then compound (33) was deposited to form a hole transport layer having a film thickness of 20 nm. Next, Alq3 was deposited to form an electron injecting light emitting layer having a thickness of 60 nm, and lithium fluoride was deposited thereon at 1 nm and aluminum was deposited at 200 nm for vacuum to form an electrode, thereby obtaining an organic electroluminescent device. The luminous efficiency of this device at a DC voltage of 5 V was 1.8 (lm / W). In addition, the half life when driving a constant current at room temperature with a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  137

NPD was vacuum-deposited on the glass plate with an ITO electrode, and the hole injection layer with a film thickness of 40 nm was obtained. Subsequently, Compound (17) and Compound (D) shown below were co-deposited at a ratio of 98: 3 to form a light emitting layer having a film thickness of 40 nm, and then Alq3 was vacuum deposited to form an electron injection layer having a film thickness of 30 nm. Created. Lithium fluoride was deposited thereon at 0.7 nm, and then aluminum was vacuum deposited at 200 nm to form electrodes to obtain an organic phosphorescent device. The device can obtain light emission of emission luminance 360 (cd / m 2) and maximum emission luminance 87600 (cd / m 2) at a DC voltage of 5V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 4500 hours.

Comparative example  One

An organic EL device similar to Example 132 was produced except that the following compound (E) was used instead of the compound (1) for the hole injection layer.

Comparative example  2

An organic EL device similar to Example 132 was created except that the following compound (F) was used instead of the compound (1) for the hole injection layer.

The devices of Examples 132 to 134 and Comparative Examples 1 and 2 were allowed to emit light continuously for a predetermined time at a current density of 10 mA / cm 2 at room temperature and 100 ° C., and the luminance was measured. The results are shown in Table 52.

Initial voltage (V) Initial luminance (cd / ㎡) Room temperature, luminance after 1000 hours (cd / m²) Luminance after 100 hours at 100 ° C (cd / m²) Tg (° C) of each compound Example 132 5.1 400 381 368 135 Example 133 4.8 500 490 479 148 Example 134 4.6 480 465 460 155 Comparative Example 1 6.7 350 210 Breakdown 113 Comparative Example 2 6.5 280 195 80 117

As can be seen from Table 52, both of the compounds of the present invention are higher than the Tg of the two compounds (E) and (F), and the devices produced using them also have lower initial voltages than the comparative examples, and have high luminance with a long lifetime. It was obvious.

Example  138

Compound (46) of the present invention was vacuum deposited on a glass plate with a washed ITO electrode to obtain a hole injection layer having a film thickness of 60 nm. Subsequently, HTM9 in Table 24 was vacuum deposited to obtain a 20 nm hole transport layer. Further, a tris (8-hydroxyquinoline) aluminum complex was vacuum deposited to form an electron injection type light emitting layer having a film thickness of 60 nm, firstly depositing 1 nm of lithium fluoride, followed by 200 nm of aluminum, and forming an electrode. An EL device was obtained. The half life when the device was driven at a constant current at room temperature with a light emission luminance of 500 (cd / m 2) was measured. In addition, light emission was performed continuously for 100 hours at a current density of 10 mA / cm 2 in an environment of 150 ° C, and luminance was measured. The results are shown in Table 53.

Example  139- Example  259

An element similar to Example 138 was created except that the hole injection layer was formed using the compound shown in Tables 53 to 59 instead of Compound (46). The half life when the device was driven at a constant current at room temperature with a light emission luminance of 500 (cd / m 2) was measured. In addition, light emission was performed continuously for 100 hours at a current density of 10 mA / cm 2 in an environment of 150 ° C, and luminance was measured. The results are shown in Tables 53 to 59 together with Example 138 and Comparative Examples 3 and 4 described later.

Comparative example  3 and Comparative example  4

A device similar to Example 138 was produced except that the hole injection layer was formed using the above-mentioned known compound (E) (Comparative Example 3) or compound (F) (Comparative Example 4) instead of compound (46). The half life when the device was driven at a constant current at room temperature with a light emission luminance of 500 (cd / m 2) was measured. In addition, light emission was performed continuously for 100 hours at a current density of 10 mA / cm 2 in an environment of 150 ° C, and luminance was measured. These results are collectively shown in Tables 53-59.

As is clear from the results shown in Tables 53 to 59, all of the compounds of the present invention are higher than the Tg of the compound (E) and the compound (F), and the device made using them has a longer half-life and higher than the comparative example. Luminance was obtained.

Example  260

Copper phthalocyanine was deposited on the glass plate to which the ITO electrode was attached, and the hole injection layer with a film thickness of 25 nm was formed. Next, Compound (47) and Compound (A) were co-deposited at a composition ratio of 100: 8 to form an emission layer having a film thickness of 45 nm. Further, the compound (B) was deposited to form an electron injection layer having a film thickness of 20 nm. 1 nm of lithium oxide (Li ₂ O) and 100 nm of aluminum (Al) were deposited thereon to form a cathode to obtain an organic EL device. The device has an external quantum efficiency of 8.0% at a DC voltage of 10V. In addition, the half life when driving a constant current at a light emission luminance of 240 (cd / m 2) was 5000 hours or more.

Example  261- Example  284

Instead of compound (47) in Example 260, compound (48), compound (49), compound (50), compound (52), compound (54), compound (57) and compound (61) in Tables 1 to 17. ), Compound (62), Compound (64), Compound (65), Compound (69), Compound (76), Compound (81), Compound (84), Compound (88), Compound (91), Compound (94 ), Compound (95), Compound (96), Compound (101), Compound (109), Compound (112), Compound (117), and Compound (119), except that the respective elements were used in the same manner as in Example 260. Was written. The external quantum efficiency of the device at a DC voltage of 10 V was all 8% or more, and the half life of the constant current driving at the light emission luminance of 240 (cd / m 2) was 5000 hours or more.

Example  285

Copper phthalocyanine was deposited on the glass plate to which the ITO electrode was attached, and the hole injection layer with a film thickness of 25 nm was formed. Next, Compound (122) and Compound (A) were co-deposited at a composition ratio of 100: 8 to form a light emitting layer having a film thickness of 45 nm. Further, the compound (B) was deposited to form an electron injection layer having a film thickness of 20 nm. 1 nm of lithium oxide (Li ₂ O) and 100 nm of aluminum (Al) were deposited thereon to form a cathode to obtain an organic EL device. The device has an external quantum efficiency of 7.8% at 10V DC. In addition, the half life when driving a constant current at a light emission luminance of 200 (cd / m 2) was 5000 hours or more.

Example  286-296

Instead of compound (122) in Example 285, compound (123), compound (124), compound (125), compound (127), compound (129), compound (132), and compound (136) shown in Tables 1-17. ), Compound (137), Compound (139), Compound (145) and Compound (152) were used in the same manner as in Example 285 except that the respective elements were prepared. The external quantum efficiency of the device at a DC voltage of 10 V was 7% or more, and the half life of the constant current driving at the light emission luminance of 220 (cd / m 2) was 5000 hours or more.

Example  297

Compound HIM16 in Table 21 was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 60 nm, and then compound (54) was deposited to form a hole transport layer having a thickness of 20 nm. Next, Alq3 was deposited to form an electron injecting light emitting layer having a thickness of 60 nm, and lithium fluoride was formed thereon by 1 nm and aluminum was 200 nm deposited thereon, thereby forming an electrode to obtain an organic EL device. The luminous efficiency of this device at a DC voltage of 5 V was 2.4 (lm / W). In addition, the half life when driving a constant current at room temperature with a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  298-302

An element was created in the same manner as in Example 297 except that HIM2, HIM3, HIM4, HIM5, and HIM9 in Tables 18 to 19 were used instead of HIM16. The half-life of the device when the constant current was driven at room temperature with a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  303-328

Instead of compound (54) in Example 297, compound (45), compound (46), compound (48), compound (49), compound (50), compound (56) and compound (58) in Tables 1-17. ), Compound (59), Compound (60), Compound (62), Compound (63), Compound (67), Compound (70), Compound (72), Compound (74), Compound (78), Compound (80 ), Compound (82), Compound (85), Compound (89), Compound (92), Compound (93), Compound (97), Compound (102), Compound (104) and Compound (107), respectively. In the same manner as in Example 297, an element was created. The half-life of these devices when driven at a room temperature with a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  329

After depositing the compound HIM16 in Table 21 to form a hole injection layer having a film thickness of 60 nm on the glass plate with an ITO electrode, the compound (129) in Tables 1 to 17 was deposited to deposit a hole transport layer having a film thickness of 20 nm. Formed. Next, Alq3 was deposited to form an electron injecting light emitting layer having a thickness of 60 nm, and lithium fluoride was formed thereon by 1 nm and aluminum was 200 nm deposited thereon, thereby forming an electrode to obtain an organic EL device. The luminous efficiency of this device at a DC voltage of 5 V was 2.2 (lm / W). In addition, the half life when driving a constant current at room temperature with a light emission luminance of 450 (cd / m 2) was 5000 hours or more.

Example  330-334

An element was created in the same manner as in Example 329 except that HIM2, HIM3, HIM4, HIM5, and HIM9 in Tables 18 to 19 were used instead of HIM16. The half-life of the device when the constant current was driven at room temperature with a light emission luminance of 450 (cd / m 2) was 5000 hours or more.

Example  335-344

Instead of compound (129) in Example 329, compound (39), compound (123), compound (124), compound (125), compound (131), compound (133), and compound (134) in Tables 1 to 17. ), A compound (135), a compound (137), and a compound (138) were used, and an element was created in the same manner as in Example 329. The half-life of these devices when driven at a room temperature with a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  345

HIM4 was vacuum-deposited on the glass plate with an ITO electrode, and the hole injection layer with a film thickness of 40 nm was obtained. Subsequently, the compound (51) and the compound (D) described above were co-deposited at a ratio of 98: 2 to form a light emitting layer having a film thickness of 40 nm, and then Alq3 was vacuum deposited to prepare an electron injection layer having a film thickness of 40 nm. It was. Lithium fluoride was deposited thereon at 0.5 nm, followed by aluminum at 200 nm for vacuum deposition to form an electrode. This device can obtain light emission of emission luminance 500 (cd / m 2) and maximum emission luminance 96500 (cd / m 2) at a DC voltage of 5V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  346-367

Instead of compound (51) in Example 345, compound (45), compound (46), compound (53), compound (55), compound (65), compound (66), and compound (67) in Tables 1-17. ), Compound (68), Compound (70), Compound (71), Compound (73), Compound (90), Compound (98), Compound (100), Compound (103), Compound (110), Compound (111 ), Compound (113), Compound (114), Compound (118), Compound (120), and Compound (121) were used in the same manner as in Example 345 except for using the compounds. The half-life of the device when the constant current was driven at room temperature with a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  368

HIM4 was vacuum-deposited on the glass plate with an ITO electrode, and the hole injection layer with a film thickness of 40 nm was obtained. Subsequently, Compound (126) and Compound (D) were co-deposited at a ratio of 98: 2 to form a light emitting layer having a film thickness of 40 nm, and then Alq3 was vacuum deposited to prepare an electron injection layer having a film thickness of 40 nm. . Lithium fluoride was deposited thereon at 0.5 nm, followed by aluminum at 200 nm under vacuum to form an electrode to obtain an element. This device can obtain light emission of emission luminance 480 (cd / m 2) and maximum emission luminance 92100 (cd / m 2) at a DC voltage of 5V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  369-378

Compound (39), Compound (128), Compound (130), Compound (140), Compound (141), Compound (142) and Compound (143) shown in Tables 1 to 17 instead of Compound (126) in Example 368. The device was constructed in the same manner as in Example 368 except that Compound (144), Compound (146), and Compound (147) were used. The half-life of the device when the constant current was driven at room temperature with a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  379

After depositing HIM9 on the glass plate with ITO electrode to form a hole injection layer having a film thickness of 50 nm, compound (46) was deposited by 20 nm to form a hole transport layer. Further, Alq3 was deposited to form a light emitting layer having a film thickness of 20 nm. Compound EX3 was also deposited to form an electron injection layer having a film thickness of 30 nm. 1 nm of lithium oxide and 100 nm of aluminum were vapor-deposited on it, the cathode was formed, and the organic electroluminescent element was obtained. This element exhibited a light emission luminance of 850 (cd / m 2) at a direct current voltage of 5.0 V. In addition, the half-life of the device when the constant current was driven at room temperature with a light emission luminance of 500 (cd / m 2) was 5000 hours or more with respect to the device immediately after the device creation and after 1 hour storage in an oven at 150 ° C.

Example  380-392

Instead of compound EX3 in Example 379, using the compound EX4, the compound EX5, the compound EX7, the compound EX9, the compound EX10, the compound EX12 to the compound EX15, the compound EX17 to the compound EX20 as the electron injection layer, under the same conditions as in Example 379 The device was created. The characteristic of the element was measured about the element immediately after element preparation and after 1 hour storage in 150 degreeC oven. As a result, the device characteristics when any device is driven at a current density of 10 (mA / cm 2) have a voltage of 4.0 (V) or less, a luminance of 500 (cd / m 2) or more, and an emission luminance of 500 (cd / m 2) at room temperature. The half life of the constant current drive was 5000 hours or more.

Example  393-408

Instead of compound (46) in Example 379, compound (40), compound (45), compound (72), compound (73), compound (74), compound (75) and compound (77) of Tables 1 to 17 ), Compound (78), Compound (79), Compound (80), Compound (81), Compound (82), Compound (99), Compound (108), Compound (115) and Compound (116), respectively. The device was fabricated under the same conditions as in Example 379. The characteristic of the element was measured about the element immediately after element preparation and after 1 hour storage in 150 degreeC oven. As a result, the device characteristics when any device was driven at a current density of 10 (mA / cm 2) were at a voltage of 4.0 (V) or lower, at a luminance of 500 (cd / m 2) or higher, and at a room temperature at a luminance of 500 (cd / m 2). The half life of the constant current drive was 5000 hours or more.

Example  409

After depositing HIM9 on the glass plate with ITO electrode to form a hole injection layer having a film thickness of 50 nm, compound (39) was deposited by 20 nm to form a hole transport layer. Further, Alq3 was deposited to form a light emitting layer having a film thickness of 20 nm. Compound EX3 was also deposited to form an electron injection layer having a film thickness of 30 nm. A cathode was formed by vapor deposition of 1 nm of lithium oxide and 100 nm of aluminum thereon to obtain an organic EL device. The device exhibited a luminance of 750 (cd / m 2) at a direct current voltage of 5.0 V. In addition, the half-life of the device when the constant current was driven at room temperature with a light emission luminance of 500 (cd / m 2) for the device immediately after the device creation and after 1 hour storage in an oven at 150 ° C. was 5000 hours or more.

Example  410-422

Instead of compound EX3 in Example 409, using the compound EX4, the compound EX5, the compound EX7, the compound EX9, the compound EX10, the compound EX12 to the compound EX15, the compound EX17 to the compound EX20 as the electron injection layer, under the same conditions as in Example 409 The device was created. The characteristic of the element was measured about the element immediately after element preparation and after 1 hour storage in 150 degreeC oven. As a result, the device characteristics when driving any device at a current density of 10 (mA / cm 2) were below voltage 4.0 (V) and at brightness 400 (cd / m 2) or higher, and the luminance was 500 (cd / m 2) at room temperature. The half life of the constant current drive was 5000 hours or more.

Example  423 ~ 433

Instead of compound (39) in Example 409, compound (148), compound (214), compound (150), compound (151), compound (153), compound (154), and compound (155) in Tables 1-17. ), Compound (156), Compound (157), Compound (158), and Compound (163) were used, except that the device was prepared under the same conditions as in Example 409. The characteristic of the element was measured about the element immediately after element preparation and after 1 hour storage in 150 degreeC oven. As a result, the device characteristics when driving any device at a current density of 10 (mA / cm 2) were below 4.0 (V) and at least 400 (cd / m 2) of luminance. The half life of the constant current drive was 5000 hours or more.

Example  434

Compound HIM10 was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 55 nm, and then Compound (83) was deposited at 20 nm to form a hole transport layer. Further, Alq3 was deposited to form a light emitting layer having a film thickness of 20 nm. Compound ET3 was also deposited to form an electron injection layer with a thickness of 30 nm. The cathode was formed by depositing 1 nm of lithium oxide and 100 nm of aluminum thereon to obtain an organic EL device. The device exhibited a light emission luminance of 850 (cd / m 2) at a DC voltage of 5V. In addition, the half-life of the device when the constant current was driven at room temperature at a light emission luminance of 500 (cd / m 2) for the device immediately after the device creation and after 1 hour storage in an oven at 150 ° C. was 5000 hours or more.

Example  435- Example  447

In Example 434, the compound ET4, the compound ET5, the compound ET7, the compound ET9, the compound ET10, the compound ET12 to the compound ET14, and the compound ET16 to the compound ET20 were used as the electron injection layer in the same manner as in Example 434. Was written. The characteristic of the element was measured about the element immediately after element preparation and after 1 hour storage in 150 degreeC oven. As a result, the device characteristics when any device is driven at a current density of 10 (mA / cm 2) are at a voltage of 4.0 (V) or less, at a luminance of 500 (cd / m 2) or more, and at a room temperature with a light emission luminance of 500 (cd / m 2). The half life of the constant current drive was 5000 hours or more.

Example  448

Compound HIM10 was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 55 nm, and then Compound 159 was deposited by 20 nm to form a hole transport layer. Alq 3 was deposited to form a light emitting layer having a thickness of 20 nm. Compound ET3 was also deposited to form an electron injection layer with a film thickness of 30 nm. The cathode was formed by depositing 1 nm of lithium oxide and 100 nm of aluminum thereon to obtain an organic EL device. The device exhibited a luminance of 770 (cd / m 2) at a DC voltage of 5V. In addition, the half-life of the device when the constant current was driven at room temperature at a light emission luminance of 500 (cd / m 2) was 5000 hours or more for the device immediately after the device creation and after 1 hour storage in an oven at 150 ° C.

Example  449 ~ 461

In Example 448, instead of the compound ET3, using the compound ET4, the compound ET5, the compound ET7, the compound ET9, the compound ET10, the compound ET12 to the compound ET14, the compound ET16 to the compound ET20 as the electron injection layer under the same conditions as in Example 448 The device was created. The characteristic of the element was measured about the element immediately after element preparation and after 1 hour storage in 150 degreeC oven. As a result, the device characteristics when any device is driven at a current density of 10 (mA / cm 2) have a voltage of 4.0 (V) or less, a luminance of 400 (cd / m 2) or more, and an emission luminance of 500 (cd / m 2) at room temperature. The half life for constant current driving at was over 5000 hours.

Example  462

Compound HIM11 was deposited on a glass plate with an ITO electrode to form a hole injection layer having a film thickness of 60 nm, and then compound (84) was deposited by 15 nm to form a hole transport layer. Alq 3 was deposited to form a light emitting layer having a thickness of 20 nm. Compound ES5 was also deposited to form an electron injection layer with a thickness of 30 nm. The cathode was formed by depositing 1 nm of lithium oxide and 100 nm of aluminum thereon to obtain an organic EL device. This device had a light emission efficiency of 3.5 (lm / W) at a direct current voltage of 5.0 V. In addition, the half-life of the device when the constant current was driven at room temperature at a light emission luminance of 500 (cd / m 2) for the device immediately after the device creation and after 1 hour storage in an oven at 150 ° C. was 5000 hours or more.

Example  463

Compound HIM11 was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 60 nm, and then Compound 160 was deposited by 15 nm to form a hole transport layer. Alq 3 was deposited to form a light emitting layer having a thickness of 20 nm. Compound ES5 was also deposited to form an electron injection layer with a thickness of 30 nm. The cathode was formed by depositing 1 nm of lithium oxide and 100 nm of aluminum thereon to obtain an organic EL device. The device exhibited a light emission efficiency of 3.0 (lm / W) at a direct current voltage of 5.0 V. In addition, the half-life of the device when the constant current was driven at room temperature at a light emission luminance of 500 (cd / m 2) for the device immediately after the device creation and after 1 hour storage in an oven at 150 ° C. was 5000 hours or more.

Example  464

Compound (73) was dissolved in 1,2-dichloroethane on a glass plate with ITO electrode attachment, and a hole injection layer having a film thickness of 50 nm was formed by spin coating. Next, Alq3 was deposited to form an electron injection light emitting layer having a thickness of 30 nm, and an electrode having a thickness of 100 nm was formed from an alloy of magnesium and silver mixed 10: 1 thereon to obtain an element. The luminous efficiency of the device at a DC voltage of 8.0 V was 3.0 (lm / W). In addition, the half life when driving a constant current at room temperature with a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  465

Compound (149) was dissolved in 1,2-dichloroethane on a glass plate with an ITO electrode and a hole injection layer having a film thickness of 50 nm was formed by spin coating. Next, Alq3 was deposited to form an electron injection light emitting layer having a thickness of 30 nm, and an electrode having a thickness of 100 nm was formed from an alloy of magnesium and silver mixed 10: 1 thereon to obtain an element. The luminous efficiency of this device at a DC voltage of 8.0 V was 2.5 (lm / W). In addition, the half life when driving a constant current at room temperature with a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  466

Compound (40) was deposited on a glass plate to which the ITO electrode was attached to form a hole injection layer having a thickness of 35 nm. Subsequently, the compound (G) and Alq3 shown next were co-deposited at the composition ratio of 1:50, and the light emitting layer with a film thickness of 40 nm was formed. Further, Alq3 was deposited to form an electron injection layer having a film thickness of 30 nm. The electrode was formed on 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) by vacuum vapor deposition, and the element was obtained. The device exhibited a light emission efficiency of 0.75 (lm / W) at a direct current voltage of 5.0 V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  467

Compound (161) was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 35 nm. Next, the compound (G) and Alq3 were co-deposited at a composition ratio of 1:50 to form a light emitting layer having a film thickness of 40 nm. Further, Alq3 was deposited to form an electron injection layer having a film thickness of 30 nm. The electrode was formed on 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) by vacuum vapor deposition, and the element was obtained. The device exhibited a light emission efficiency of 0.65 (lm / W) at a direct current voltage of 5.0 V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  468

Compound (85) and compound (86) were co-deposited at a composition ratio of 1: 1 on the glass plate with an ITO electrode to form a hole injection layer having a film thickness of 60 nm. Subsequently, the compound (H) shown below was deposited to form a light emitting layer having a film thickness of 20 nm. Further, Alq3 was deposited to form an electron injection layer having a film thickness of 20 nm. The electrode was formed on 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) by vacuum vapor deposition, and the element was obtained. The device exhibited a light emission efficiency of 3.0 (lm / W) at a direct current voltage of 5.0 V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  469

Compound (162) and compound (163) were co-deposited at a composition ratio of 1: 1 on the glass plate with an ITO electrode to form a hole injection layer having a film thickness of 60 nm. Next, the compound (H) was deposited to form a light emitting layer having a film thickness of 20 nm. Further, Alq3 was deposited to form an electron injection layer having a film thickness of 20 nm. The electrode was formed on 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) by vacuum vapor deposition, and the element was obtained. This device had a light emission efficiency of 2.5 (lm / W) at a direct current voltage of 5.2 V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  470

Compound (87) was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 60 nm. Subsequently, Compound (I) and Compound (J) shown below were co-deposited at a composition ratio of 20: 1 to form a light emitting layer having a film thickness of 20 nm. Further, Alq3 was deposited to form an electron injection layer having a film thickness of 20 nm. The electrode was formed on 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) by vacuum vapor deposition, and the element was obtained. The device exhibited a light emission efficiency of 6.0 (lm / W) at a direct current voltage of 5.0 V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  471

Compound (164) was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 60 nm. Subsequently, the compound (I) and the compound (J) were co-deposited at a composition ratio of 20: 1 to form a light emitting layer having a film thickness of 20 nm. Further, Alq3 was deposited to form an electron injection layer having a film thickness of 20 nm. The electrode was formed on 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) by vacuum vapor deposition, and the element was obtained. The device exhibited a light emission efficiency of 5.8 (lm / W) at a direct current voltage of 6.0 V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  472

Compound (61) was deposited on a glass plate with an ITO electrode to form a hole injection layer having a film thickness of 45 nm. Subsequently, the compound (K) and the compound (L) shown next were co-deposited at a composition ratio of 20: 1 to form a light emitting layer having a film thickness of 40 nm. Further, Alq3 was deposited to form an electron injection layer having a film thickness of 30 nm. The electrode was formed on 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) by vacuum vapor deposition, and the element was obtained. The device exhibited a luminous efficiency of 3.5 (lm / W) at a direct current voltage of 4.0 V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  473

Compound (136) was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 45 nm. Next, the compound (K) and the compound (L) were co-deposited at a composition ratio of 20: 1 to form a light emitting layer having a film thickness of 40 nm. Further, Alq3 was deposited to form an electron injection layer having a film thickness of 30 nm. The electrode was formed on 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) by vacuum vapor deposition, and the element was obtained. This device had a light emission efficiency of 3.0 (lm / W) at a direct current voltage of 4.0V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  474

Compound (54) of the present invention was deposited on a glass plate with an ITO electrode to form a hole injection layer having a film thickness of 70 nm. Subsequently, Compound (M) and Alq3 shown below were co-deposited at a composition ratio of 1: 1 to form an electron transporting light emitting layer having a thickness of 45 nm. Furthermore, an electrode having a film thickness of 200 nm was formed from an alloy in which magnesium and silver were mixed 1: 3 thereon to obtain an element. The luminous efficiency of this device at a DC voltage of 7.0 V was 2.0 (lm / W). In addition, the half life when driving a constant current at room temperature with a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  475

Compound (129) of the present invention was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 70 nm. Next, the compound (M) and Alq3 were co-deposited at a composition ratio of 1: 1 to form an electron transporting light emitting layer having a thickness of 45 nm. Furthermore, an electrode having a film thickness of 200 nm was formed from an alloy in which magnesium and silver were mixed 1: 3 thereon to obtain an element. The luminous efficiency of this device at a DC voltage of 7.5 V was 1.5 (lm / W). In addition, the half life when driving a constant current at room temperature with an emission luminance of 400 (cd / m 2) was 5000 hours or more.

Example  476

Compound (19) was deposited on a glass plate with an ITO electrode to form a hole injection layer having a film thickness of 50 nm. Next, Compound (K) and Compound (N) shown below were co-deposited at a composition ratio of 100: 1 to form a light emitting layer having a film thickness of 25 nm. Further, BCP was deposited to form an electron injection layer having a film thickness of 25 nm. 0.5 nm of lithium (Li) and 150 nm of silver were vapor-deposited on it, and the element was obtained. The device exhibited a light emission efficiency of 1.5 (lm / W) at a DC voltage of 8.0 V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  477

Compound (139) was deposited on a glass plate to which the ITO electrode was attached to form a hole injection layer having a film thickness of 50 nm. Next, the compound (K) and the compound (N) were co-deposited at a composition ratio of 100: 1 to form a light emitting layer having a film thickness of 25 nm. Further, BCP was deposited to form an electron injection layer having a film thickness of 25 nm. 0.5 nm of lithium (Li) and 150 nm of silver were vapor-deposited on it, and the element was obtained. This device had a light emission efficiency of 1.2 (lm / W) at a direct current voltage of 9.0 V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  478

Compound (76) of the present invention was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 40 nm. Subsequently, compound (O) shown next was deposited by 10 nm to form a hole transport layer. Next, Compound (P) and Compound (VII) shown below were co-deposited at a composition ratio of 1: 9 to form a light emitting layer having a film thickness of 25 nm. In addition, BCP was deposited to form a hole blocking layer of 15 nm. Alq 3 was deposited to form an electron injection layer having a thickness of 25 nm. A cathode was formed thereon by depositing 1 nm of lithium fluoride (LiF) and 100 nm of aluminum (Al) to obtain an element. The device has an external quantum efficiency of 8.0% at a DC voltage of 8V. In addition, the half life when driving a constant current at a light emission luminance of 200 (cd / m 2) was 5000 hours or more.

Example  479

Compound (152) of the present invention was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 40 nm. Next, 10 nm of the compound (O) was deposited to form a hole transport layer. Compound (P) and Compound (IX) were co-deposited at a composition ratio of 1: 9 to form a light emitting layer having a thickness of 25 nm. In addition, BCP was deposited to form a hole blocking layer of 15 nm. Alq 3 was deposited to form an electron injection layer having a thickness of 25 nm. A cathode was formed thereon by depositing 1 nm of lithium fluoride (LiF) and 100 nm of aluminum (Al) to obtain an element. The device showed an external quantum efficiency of 7.5% at a DC voltage of 10V. In addition, the half life when driving a constant current at a light emission luminance of 100 (cd / m 2) was 5000 hours or more.

Example  480

60 nm of the compound (55) of this invention was deposited on the glass plate with an ITO electrode, and the hole injection layer was formed. Further, Alq3 was deposited to form a light emitting layer having a film thickness of 20 nm. Compound (R) shown below was deposited to form an electron injection layer having a film thickness of 30 nm. A cathode was formed thereon by depositing 1 nm of lithium oxide (Li ₂ O) and 100 nm of aluminum (Al) to obtain an element. The device exhibited a luminous efficiency of 3.3 (lm / W) at a direct current voltage of 4.0 V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  481-486

In Example 480, an experiment was carried out under the same conditions as in Example 480 except that ES11, EP2 to 4, EP10, and EP22 were used instead of the compound (R) as the electron injection layer. The characteristics of the device were measured in the same manner as in Example 480 for the device immediately after the device creation and after storage for 1 hour in an oven at 150 ° C. As a result, the device characteristics when any device is driven at a current density of 10 (mA / cm 2) are at a voltage of 4.0 (V) or less, at a luminance of 500 (cd / m 2) or more, and at a room temperature with a light emission luminance of 500 (cd / m 2). The half life of the constant current drive was 5000 hours or more.

Example  487

60 nm of the compound (130) of this invention was deposited on the glass plate with an ITO electrode, and the hole injection layer was formed. Further, Alq3 was deposited to form a light emitting layer having a film thickness of 20 nm. The compound (R) was deposited to form an electron injection layer having a film thickness of 30 nm. A cathode was formed thereon by depositing 1 nm of lithium oxide (Li ₂ O) and 100 nm of aluminum (Al) to obtain an element. The device exhibited a light emission efficiency of 2.7 (lm / W) at a direct current voltage of 4.0 V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  488-493

In Example 487, an experiment was carried out under the same conditions as in Example 487 except for using ES11, EP2 to 4, EP10, and EP22 as the electron injection layer. The characteristics of the device were measured in the same manner as in Example 487 with respect to the device immediately after the device creation and after 1 hour storage in an oven at 150 ° C. As a result, the device characteristics when any device is driven at a current density of 10 (mA / cm 2) are at a voltage of 4.0 (V) or lower, at a luminance of 400 (cd / m 2) or higher, and at a room temperature with a light emission luminance of 500 (cd / m 2). The half life of the constant current drive was 5000 hours or more.

Example  494

Compound (46) of the present invention was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 35 nm. HTM9 was also deposited to form a hole transport layer with a film thickness of 20 nm. Subsequently, Compound (S) and Compound (T) shown below were co-deposited at a composition ratio of 50: 1 to form a light emitting layer having a thickness of 35 nm. Further, the compound (U) shown below was deposited to form an electron injection layer having a film thickness of 30 nm. The electrode was formed on 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) by vacuum vapor deposition, and the element was obtained. This device had a light emission efficiency of 5.0 (lm / W) at a DC voltage of 3.5V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  495-511

Compound (50), Compound (54), Compound (58), Compound (61), Compound (64), Compound (76), Compound (80), Compound (84) instead of Compound (49) in Example 494, Examples except for using Compound (88), Compound (91), Compound (95), Compound (97), Compound (101), Compound (104), Compound (109), Compound (114) and Compound (119), respectively The device was created under the same conditions as 494. As a result, the device characteristics when any device is driven at a current density of 10 (mA / cm 2) are at a voltage of 4.0 (V) or lower, at a luminance of 500 (cd / m 2) or higher, and at a room temperature with a light emission luminance of 500 (cd / m 2). The half life of the constant current drive was 5000 hours or more.

Example  512

Compound (39) of the present invention was deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 35 nm. HTM9 was also deposited to form a hole transport layer with a film thickness of 20 nm. Compound (S) and Compound (T) were co-deposited at a composition ratio of 50: 1 to form a light emitting layer having a thickness of 35 nm. In addition, the compound (iii) was deposited to form an electron injection layer having a thickness of 30 nm. The electrode was formed on 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) by vacuum vapor deposition, and the element was obtained. The device exhibited a light emission efficiency of 4.5 (lm / W) at a DC voltage of 3.5V. In addition, the half life when driving a constant current at a light emission luminance of 500 (cd / m 2) was 5000 hours or more.

Example  513-519

Example 512 except for using Compound (125), Compound (129), Compound (133), Compound (136), Compound (139), Compound (152), and Compound (156) in Example 512, respectively. The device was created under the same conditions as. As a result, the device characteristics when any device was driven at a current density of 10 (mA / cm 2) were at a voltage of 4.0 (V) or lower, at a luminance of 450 (cd / m 2) or higher, and at a room temperature with a light emission luminance of 500 (cd / m 2). The half life of the constant current drive was 5000 hours or more.

As mentioned above, the EL element of high performance can be created by using the compound shown by this invention. It is clear that a markedly high performance is exhibited compared with a comparative compound, and low driving voltage and long life of an organic EL element can be achieved.

The present invention provides a novel carbazole-containing amine compound useful as a material for an organic electroluminescent device, an aspect of the present invention is as follows.

(1) Formula 1

[Formula 1]

(Wherein A is

[Formula 2]

(In formula, one of R <^1> -R <^5> represents a bond, and the other represents a hydrogen atom, a halogen atom, or monovalent organic residue each independently.)

A phenylene group represented by the following Formula 3

[Formula 3]

(In formula, one of R <^6> -R <^10> and one of R <^11> -R <^15> represent a bond, and the remainder each independently represents a hydrogen atom, a halogen atom, or monovalent organic residue.)

Represents a biphenylene group represented by: Ar ^{1 to} Ar ⁴ each independently represent a C 6-18 monovalent aromatic hydrocarbon group which may have a substituent, a C 2-18 monovalent heterocyclic group which may have a substituent, or Formula 4

[Formula 4]

Wherein Ar ⁵ represents a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a monovalent aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent, and each of R ¹⁶ to R ²² is independent Represents a hydrogen atom, a halogen atom or a monovalent organic residue.)

The carbazolyl group represented by this is shown. Provided that at least one of Ar ^{1 to} Ar ⁴ is a carbazolyl group represented by the formula (4).

Carbazole-containing amine compound represented by.

(2) In Formula 1, A is represented by Formula 5,

[Formula 5]

(In formula, R <^1> -R <^4> represents a hydrogen atom, a halogen atom, or monovalent organic residue each independently.)

Or, the formula

[Formula 6]

(In formula, one of R <^6> -R <^10> represents a bond, the remainder each independently represents a hydrogen atom, a halogen atom, or monovalent organic residue, and R <^12> -R <^15> is each independently a hydrogen atom, a halogen atom, or Monovalent organic residue.)

The carbazole-containing amine compound according to the above (1), which is a divalent group represented by.

(3) In Formula 1, A is represented by Formula 13,

[Formula 13]

(In formula, R <^7> -R <^10> and R <^12> -R <^15> respectively independently represent a hydrogen atom, a halogen atom, or monovalent organic residue.)

The carbazole-containing amine compound according to the above (1) or (2), which is a 4,4'-biphenylene group represented by.

(4) In Formula 1, two or more of Ar ^{1 to} Ar ⁴ may be represented by Formula 4 below:

[Formula 4]

(In formula, Ar <^5> represents the C6-C18 monovalent aromatic hydrocarbon group which may have a substituent, or C2-C18 monovalent aromatic heterocyclic group which may have a substituent, R <^16> -R <^22> is respectively independently Hydrogen atom, halogen atom or monovalent organic residue.)

The carbazole-containing amine compound according to any one of (1) to (3), which is a carbazolyl group represented by.

(5) The carbazole-containing amine compound according to the above (4), wherein Ar ¹ and Ar ² in Ar ^{1 to} Ar ⁴ in the general formula (1) are carbazolyl groups represented by the general formula (4).

(6) Ar ¹ and Ar ² in Ar ^{1 to} Ar ⁴ in the general formula (1) are carbazolyl groups represented by the general formula (4), and Ar ³ and Ar ⁴ each independently have a monovalent aromatic carbon atom having 6 to 18 carbon atoms. The carbazole-containing amine compound according to the above (5), which is a hydrocarbon group.

(7) At least one of the carbazolyl group represented by the formula (4) is

[Formula 7]

(In formula, Ar <^5> represents the C6-C18 monovalent aromatic hydrocarbon group which may have a substituent, or a C2-C18 monovalent aromatic heterocyclic group which may have a substituent.)

The carbazole-containing amine compound according to any one of (1) to (6), which is a carbazolyl group represented by.

(8) The carbazole-containing amine compound according to any one of (1) to (7), wherein Ar ⁵ in Formula 4 or Formula 7 is a C6-C18 monovalent aromatic hydrocarbon group which may have a substituent.

(9) Ar ⁵ in Formula 4 or Formula 7 is represented by Formula 8,

[Formula 8]

(In formula, R <^23> is a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a C6-C12 monovalent aromatic hydrocarbon group which may have a substituent, or a C2-C5 monovalent complex which may have a substituent. Indicates ventilation.)

The carbazole-containing amine compound according to (8), which is a group represented by the above.

(10) The carbazole-containing amine compound according to the above (9), wherein in formula (8), R ²³ is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent.

(11) Ar ⁵ in Formula 4 or Formula 7 is represented by Formula 9,

[Formula 9]

(Wherein, R ³³ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms which may have a substituent or a phenyl group which may have a substituent.)

The carbazole-containing amine compound according to the above (10), which is a biphenyl group which may have a substituent represented by.

(12) The carbazole-containing amine compound according to any one of (1) to (7), wherein Ar ⁵ in formula (4) or (7) is a naphthyl group which may have a substituent.

(13) Ar ⁵ in Formula 4 or Formula 7 is represented by Formula 10,

[Formula 10]

(Wherein, R ²³ represents the same as R ²³ in the formula 8, R ²⁴ ~R ²⁷ is an alkyl group or an alkyl group having 1 to 4 carbon atoms which may have a hydrogen atom, a halogen atom, a cyano group, the substituents are each independently A phenyl group which may have.)

The carbazole-containing amine compound according to the above (12), which is a naphthyl group which may have a substituent represented by.

(14) Ar ⁵ in Formula 4 or Formula 7 is represented by Formula 11,

[Formula 11]

(In formula, R <^28> -R <^32> respectively independently represents a hydrogen atom, a halogen atom, a cyano group, a C1-C4 alkyl group which may have a substituent, or a phenyl group which may have a substituent.)

The carbazole-containing amine compound according to the above (12), which is a naphthyl group which may have a substituent represented by.

(15) In formula (4) or (7), Ar ⁵ may have a 1-anthryl group which may have a substituent, a 2-anthryl group which may have a substituent, a 9-anthryl group which may have a substituent, or may have a substituent The carbazole-containing amine compound according to any one of (1) to (7), which is a 9-phenanthryl group.

(16) The carbazole-containing amine compound according to any one of (1) to (15), wherein the glass transition temperature (Tg) is 130 ° C or higher.

(17) The material for organic electroluminescent elements containing the carbazole containing amine compound in any one of said (1)-(15).

(18) An organic electroluminescent 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 layer of the organic layer comprises the material for an organic electroluminescent device according to (17) above. Organic electroluminescent device.

(19) An organic electroluminescent device having a hole injection layer and / or a hole transport layer, wherein the hole injection layer and / or the hole transport layer comprises an organic electroluminescent device material according to (17) above. .

(20) Formula 12,

[Formula 12]

(In formula, Ar <^5> represents the C6-C18 monovalent aromatic hydrocarbon group which may have a substituent, or C2-C18 monovalent aromatic heterocyclic group which may have a substituent, R <^16> -R <^22> is respectively independently Represents a hydrogen atom, a halogen atom or a monovalent organic residue, and X represents a halogen atom selected from a chlorine atom, bromine atom or iodine atom.)

Carbazole derivatives represented by.

(21) In formula (12), Ar ⁵ is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and R ¹⁶ to R ²² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, and 3 carbon atoms. Substitution substituted with a cycloalkyl group of 18 to 6, a monocyclic, condensed cyclic or polycyclic aromatic hydrocarbon group having 6 to 18 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an aryloxy group having 6 to 14 carbon atoms or a hydrocarbon group having 2 to 16 carbon atoms The carbazole derivative according to the above (20), which is an amino group.

(22) The carbazole derivative according to the above (20) or (21), wherein Ar ⁵ in Formula 12 is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.

(23) The carbazole derivative according to any one of (20) to (22), wherein R ¹⁶ to R ²² in the formula (12) are hydrogen atoms.

The present invention provides a novel carbazole-containing amine compound useful as a material for an organic electroluminescent (organic EL) device, an organic electroluminescent device material using the carbazole-containing amine compound, an organic electroluminescent device, and the like. In addition, it is useful in the electric industry, daily necessities industry, etc., and has industrial applicability.

Claims (23)

Formula 1 [Formula 1]

(Wherein A is [Formula 2]

(In formula, one of R <^1> -R <^5> represents a bond, and the other represents a hydrogen atom, a halogen atom, or monovalent organic residue each independently.) A phenylene group represented by the following Formula 3 [Formula 3]

(In formula, one of R <^6> -R <^10> and one of R <^11> -R <^15> represent a bond, and the remainder each independently represents a hydrogen atom, a halogen atom, or monovalent organic residue.) Represents a biphenylene group represented by: Ar ^{1 to} Ar ⁴ each independently represent a C 6-18 monovalent aromatic hydrocarbon group which may have a substituent, a C 2-18 monovalent heterocyclic group which may have a substituent, or Formula 4 [Formula 4]

Wherein Ar ⁵ represents a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a monovalent aromatic heterocyclic group having 2 to 18 carbon atoms which may have a substituent, and each of R ¹⁶ to R ²² is independent Represents a hydrogen atom, a halogen atom or a monovalent organic residue.) The carbazolyl group represented by this is shown. Provided that at least one of Ar ^{1 to} Ar ⁴ is a carbazolyl group represented by the formula (4). Carbazole-containing amine compound represented by. The method of claim 1, wherein in Formula 1, A is represented by the following Formula 5, [Formula 5]

(In formula, R <^1> -R <^4> represents a hydrogen atom, a halogen atom, or monovalent organic residue each independently.) Or, the formula [Formula 6]

(In formula, one of R <^6> -R <^10> represents a bond, the remainder each independently represents a hydrogen atom, a halogen atom, or monovalent organic residue, and R <^12> -R <^15> is each independently a hydrogen atom, a halogen atom, or Monovalent organic residue.) Carbazole-containing amine compound represented by bivalent group. The compound of claim 1 or 2, wherein in Formula 1, [Formula 13]

(In formula, R <^7> -R <^10> and R <^12> -R <^15> respectively independently represent a hydrogen atom, a halogen atom, or monovalent organic residue.) A carbazole-containing amine compound which is a 4,4'-biphenylene group represented by. The compound according to any one of claims 1 to 3, wherein at least two of Ar ^{1 to} Ar ⁴ in formula (1) are represented by the following formula (4): [Formula 4]

(In formula, Ar <^5> represents the C6-C18 monovalent aromatic hydrocarbon group which may have a substituent, or C2-C18 monovalent aromatic heterocyclic group which may have a substituent, R <^16> -R <^22> is respectively independently Hydrogen atom, halogen atom or monovalent organic residue.) A carbazole-containing amine compound which is a carbazolyl group represented by. The carbazole-containing amine compound according to claim 4, wherein Ar ¹ and Ar ² in Ar ^{1 to} Ar ⁴ in Formula 1 are carbazolyl groups represented by Formula 4. The C6-C18 compound according to claim 5, wherein Ar ¹ and Ar ² in Ar ^{1 to} Ar ⁴ in Formula 1 are carbazolyl groups represented by Formula 4, and Ar ³ and Ar ⁴ may each independently have a substituent. Carbazole-containing amine compound which is a monovalent aromatic hydrocarbon group. The method according to any one of claims 1 to 6, wherein at least one of the carbazolyl group represented by the formula (4) is [Formula 7]

(In formula, Ar <^5> represents the C6-C18 monovalent aromatic hydrocarbon group which may have a substituent, or a C2-C18 monovalent aromatic heterocyclic group which may have a substituent.) A carbazole-containing amine compound which is a carbazolyl group represented by. 8. The carbazole-containing amine compound according to any one of claims 1 to 7, wherein Ar ⁵ is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent in formula (4) or (7). According to claim 8, Ar ⁵ in Formula 4 or Formula 7 is represented by the following formula 8, [Formula 8]

(In formula, R <^23> is a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a C6-C12 monovalent aromatic hydrocarbon group which may have a substituent, or a C2-C5 monovalent complex which may have a substituent. Indicates ventilation.) Carbazole-containing amine compound which is a group represented by. The carbazole-containing amine compound according to claim 9, wherein in formula (8), R ²³ is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. The method of claim 10, wherein in Formula 4 or Formula 7 Ar ⁵ is represented by the following formula 9, [Formula 9]

(Wherein, R ³³ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms which may have a substituent or a phenyl group which may have a substituent.) A carbazole-containing amine compound which is a biphenyl group which may have a substituent represented by. 8. The carbazole-containing amine compound according to any one of claims 1 to 7, wherein Ar ⁵ in formula (4) or (7) is a naphthyl group which may have a substituent. The method of claim 12, wherein in Formula 4 or Formula 7 Ar ⁵ is represented by the following formula 10, [Formula 10]

(Wherein, R ²³ represents the same as R ²³ in the formula 8, R ²⁴ ~R ²⁷ is an alkyl group or an alkyl group having 1 to 4 carbon atoms which may have a hydrogen atom, a halogen atom, a cyano group, the substituents are each independently A phenyl group which may have.) A carbazole-containing amine compound which is a naphthyl group which may have a substituent represented by. The method of claim 12, wherein in Formula 4 or Formula 7 Ar ⁵ is represented by the following formula 11, [Formula 11]

(In formula, R <^28> -R <^32> respectively independently represents a hydrogen atom, a halogen atom, a cyano group, a C1-C4 alkyl group which may have a substituent, or a phenyl group which may have a substituent.) A carbazole-containing amine compound which is a naphthyl group which may have a substituent represented by. The compound according to any one of claims 1 to 7, wherein in Formula 4 or Formula 7, Ar ⁵ may have a substituent, 1-anthryl group may have a substituent, 2-anthryl group may have a substituent, and 9 may have a substituent. A carbazole-containing amine compound which is a 9-phenanthryl group which may have an anthryl group or a substituent. The carbazole-containing amine compound according to any one of claims 1 to 15, wherein the glass transition temperature (Tg) is 130 ° C or higher. An organic electroluminescent device material comprising the carbazole-containing amine compound according to any one of claims 1 to 15. In an organic electroluminescent device formed by forming a plurality of organic layers including an organic layer or a light emitting layer between a pair of electrodes, at least one layer of the organic layer comprises an organic electroluminescent device material according to claim 17 EL device. An organic electroluminescent device having a hole injection layer and / or a hole transport layer, wherein the hole injection layer and / or the hole transport layer comprises the organic electroluminescent device material according to claim 17. Formula 12, [Formula 12]

(In formula, Ar <^5> represents the C6-C18 monovalent aromatic hydrocarbon group which may have a substituent, or C2-C18 monovalent aromatic heterocyclic group which may have a substituent, R <^16> -R <^22> is respectively independently Represents a hydrogen atom, a halogen atom or a monovalent organic residue, and X represents a halogen atom selected from a chlorine atom, bromine atom or iodine atom.) Carbazole derivatives represented by. 21. The compound of claim 20, wherein Ar ⁵ in Formula 12 is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and R ¹⁶ to R ²² are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 18 carbon atoms. A cycloalkyl group having 3 to 18 carbon atoms, a monocyclic, condensed or polycyclic aromatic hydrocarbon group having 6 to 18 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an aryloxy group having 6 to 14 carbon atoms or a hydrocarbon group having 2 to 16 carbon atoms Carbazole derivatives that are substituted substituted amino groups. 22. The carbazole derivative according to claim 20 or 21, wherein Ar ⁵ in Formula 12 is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. The carbazole derivative according to any one of claims 20 to 22, wherein R ¹⁶ to R ²² in Formula 12 are hydrogen atoms.

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