JP2009194042A - Charge transporting material for use of organic electroluminescence element containing carbazolyl group and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a charge transporting material for use in an organic EL element whose molecules are hardly crystallized even with high Tg and which has excellent characteristics such as low voltage drive and a long service life when used as a material for the organic EL element. <P>SOLUTION: The charge transporting material for use in an organic electroluminescence element has a carbazolyl group expressed by a general formula [1], where X refers to a linking group having a fluorene group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel material for a carbazolyl-containing organic electroluminescence device, and more specifically, when used in an organic electroluminescence device (hereinafter abbreviated as an organic EL device), the molecular crystallinity is low and the glass transition temperature (Tg ) Is high, the present invention relates to a carbazolyl-containing charge transport material for organic electroluminescence devices having excellent performance (low voltage driving, long life, high stability).

  Conventionally, application of carbazole derivatives to various functional materials and electronic materials has been studied. Utilizing the fact that the carbazole skeleton has a hole transporting property and a structure having high heat resistance, it can be applied to, for example, a charge transport material for an electrophotographic photosensitive member or a material for an organic EL device. It is being considered. As typical examples, polyvinyl carbazole (PVK) and N, N′-dicarbazolyl-4,4′-biphenyl (CBP) have been widely studied as materials for organic EL devices (Non-patent Document 1). , 2). When an organic EL element is driven or stored under a normal high temperature environment, adverse effects such as a change in emission color, a decrease in emission efficiency, an increase in drive voltage, and a shortened emission lifetime occur. In order to prevent this, it is necessary to increase the glass transition temperature (Tg) of the material. Although carbazoles such as PVK and CBP have a relatively high Tg and heat resistance, they have a highly symmetrical structure, so that when a thin film is formed by vacuum deposition or spin coating, etc. The stability of the device is low, the crystallized easily, and the lifetime of the device is extremely short.

  Under such circumstances, amine compounds in which the 3-position of N-ethylcarbazole is substituted with an amino group have been disclosed (see Non-patent Documents 3 and 4, Patent Document 1). These diamine compounds have high film stability because they have an appropriate Ip as a hole injection material and a hole transport material and are non-crystalline due to the asymmetry of the carbazole ring. However, on the other hand, Tg was not so high, and the heat resistance was inferior, and sufficient life characteristics as an EL element could not be obtained.

  Moreover, as derivatives having a low-molecular carbazolyl group, thiophene derivatives, naphthalene derivatives, fluorene derivatives, and spiro derivatives linked by a divalent linking group have been reported (see Patent Documents 2 to 3). However, organic EL devices prepared using these derivatives have problems that the light emission life is short and the color purity is not excellent.

Applied Physics Letters, 2001, 78, 278 Journal of the American Chemical Society 2001, 123, 4304 European Polymer Journal 2005, 41, 1821 Environmental and Chemical Physics 2002, 24, 30 Special table 2004-536134 gazette WO03 / 090502 JP-T-2004-217557

  The problem of the present invention is that, while having a high Tg, the molecule is difficult to crystallize, and when used as a material for an organic EL device, it is low voltage driven, has a long life, and is purified by a sublimation method or the like. An object of the present invention is to provide a charge transport material for an organic EL device having excellent characteristics such as less damage to an organic material and easy purification.

As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention.
That is, the present invention relates to a charge transport material for an organic EL device having a carbazolyl group represented by the following general formula [1].

General formula [1]

(In the formula, X represents a linking group represented by the general formula [2] or [3].
Ar ¹ and Ar ² each independently represent a substituted or unsubstituted monovalent aromatic hydrocarbon group or a substituted or unsubstituted monovalent aromatic heterocyclic group.
R ^{1 to} R ¹⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted Monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio Group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted It represents an alkylsulfonyl group or a substituted or unsubstituted arylsulfonyl group. )

General formula [2]

Wherein R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, substituted or unsubstituted. A monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, a cyano group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted Alkylthio group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted An alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group,
R ^{17 to} R ²² are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted Monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio Group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted It represents an alkylsulfonyl group or a substituted or unsubstituted arylsulfonyl group. )

General formula [3]

Wherein R ^{23 to} R ³⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted Or an unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, a cyano group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, substituted or Unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted Or an unsubstituted alkylsulfonyl group or a substituted or unsubstituted arylsulfonyl group.)

The present invention also relates to a charge transport material for an organic electroluminescence device, wherein Ar ¹ and Ar ² are each independently a substituted or unsubstituted phenyl group represented by the following general formula [4].

General formula [4]

Wherein R ^{37 to} R ⁴¹ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted Or an unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, a cyano group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, substituted or Unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl oxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group, or ants substituted or unsubstituted -. represents a Rusuruhoniru group also, R ³⁷ to R ⁴¹ are, Substituents together in contact may be bonded to form a new ring.)

The present invention also relates to a charge transport material for an organic EL device having the above carbazolyl group in which R ^{37 to} R ⁴¹ are hydrogen atoms.

  The present invention also relates to a charge transport material for an organic EL device having the carbazolyl group, which is a hole injection material or a hole transport material.

 Further, the present invention provides an organic electroluminescence device having a hole injection layer and / or a hole transport layer between a pair of electrodes, wherein the hole injection layer and / or the hole transport layer is the above organic EL device. It relates to being a material.

  An organic EL element using the organic EL element material of the present invention as an organic EL element material has extremely high thin film stability, emits light at a low driving voltage, and has a long lifetime. It can be suitably used as a flat panel display or a flat light emitter, and can be applied to light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display plates, and indicator lights.

  Hereinafter, the present invention will be described in detail.

R ^{1 to} R ¹⁴ in the general formula [1] are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, or a substituted or unsubstituted monovalent aromatic hydrocarbon group. Substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, Substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group Represents a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group.

  Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Here, the monovalent aliphatic hydrocarbon group refers to a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group. Is mentioned.

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, C1-C18 alkyl groups, such as a decyl group, a dodecyl group, a pentadecyl group, and an octadecyl group, are mentioned.

  Examples of the alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1-decenyl group, 1 -C2-C18 alkenyl groups, such as an octadecenyl group, are mentioned.

  Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group and 1-octadecynyl group. Examples include alkynyl groups having 2 to 18 carbon atoms.

  Examples of the cycloalkyl group include cycloalkyl groups having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctadecyl group.

  Furthermore, examples of the monovalent aromatic hydrocarbon group include a monovalent monocyclic ring, a condensed ring, and a ring assembly hydrocarbon group. Here, examples of the monovalent monocyclic aromatic hydrocarbon group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,4-xylyl group, a p-cumenyl group, and a mesityl group. Examples thereof include monovalent monocyclic aromatic hydrocarbon groups having 6 to 18 carbon atoms.

  Examples of the monovalent condensed ring hydrocarbon group include 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1- Examples thereof include monovalent condensed ring hydrocarbon groups having 10 to 18 carbon atoms such as acenaphthyl group, 2-azurenyl group, 1-pyrenyl group and 2-triphenylyl group.

  Examples of the monovalent ring assembly hydrocarbon group include monovalent ring assembly hydrocarbon groups having 12 to 18 carbon atoms such as o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group.

  Examples of the monovalent aliphatic heterocyclic group include monovalent aliphatic heterocyclic groups having 3 to 18 carbon atoms such as a 2-pyrazolino group, a piperidino group, a morpholino group, and a 2-morpholinyl group.

  Examples of the monovalent aromatic heterocyclic group include triazolyl group, 3-oxadiazolyl group, 2-furanyl group, 3-furanyl group, 2-furyl group, 3-furyl group, 2-thienyl group and 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 Group, 8-quinolyl group, 1-isoquinolyl group, 2-quinoxalinyl group, 2-benzofuryl group, 2-benzothienyl group, N-indolyl group, N-carbazolyl group, N-acridinyl group, 2- Ofeniru group, 3-thiophenyl group, bipyridyl group, and monovalent aromatic heterocyclic group having 2 to 18 carbon atoms such phenanthrolyl group.

  Moreover, as an alkoxyl group, C1-C8 alkoxyl groups, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, an octyloxy group, a tert-octyloxy group, are mentioned.

  The aryloxy group includes aryloxy groups having 6 to 14 carbon atoms such as phenoxy group, 4-tert-butylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, and 9-anthryloxy group. Can be mentioned.

  Moreover, as an alkylthio group, a C1-C8 alkylthio group, such as a methylthio group, an ethylthio group, a tert- butylthio group, a hexylthio group, and an octylthio group, is mentioned.

  Examples of the arylthio group include arylthio groups having 6 to 14 carbon atoms such as a phenylthio group, a 2-methylphenylthio group, and a 4-tert-butylphenylthio group.

  The substituted amino group includes N-methylamino group, N-ethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N-benzylamino group, N , N-dibenzylamino group, N-phenylamino group, N-phenyl-N-methylamino group, N, N-diphenylamino group, N, N-bis (m-tolyl) amino group, N, N-bis (P-tolyl) amino group, N, N-bis (p-biphenylyl) amino group, bis [4- (4-methyl) biphenylyl] amino group, N-α-naphthyl-N-phenylamino group, N-β -Substituted amino groups having 2 to 26 carbon atoms such as naphthyl-N-phenylamino 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, a cinnamoyl group, are mentioned.

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

  Moreover, as an aryloxycarbonyl group, C2-C14 aryloxycarbonyl groups, such as a phenoxycarbonyl group and a naphthyloxycarbonyl group, are mentioned.

  Moreover, as an alkylsulfonyl group, C2-C14 alkylsulfonyl groups, such as a mesyl group, an ethylsulfonyl group, a propylsulfonyl group, are mentioned.

  Moreover, as an arylsulfonyl group, C2-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 in R ^{1 to} R ¹⁴ may be further substituted with other substituents. Such substituents include halogen atoms, cyano groups, alkoxyl groups, aryloxy groups, alkylthio groups, arylthio groups, substituted amino groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, alkylsulfonyls. Group, arylsulfonyl group and the like. Examples of these substituent groups include those described above.

In the general formula [1], Ar ¹ and Ar ² each independently represent a substituted or unsubstituted monovalent aromatic hydrocarbon group or a substituted or unsubstituted monovalent aromatic heterocyclic group. Here, the monovalent aromatic hydrocarbon group and the monovalent aromatic heterocyclic group are the monovalent aromatic hydrocarbon group and monovalent aromatic heterocyclic group in R ^{1 to} R ¹⁴ described above. It is synonymous with.

Preferred examples of Ar ¹ include a substituted or unsubstituted monovalent aromatic hydrocarbon group having 10 to 18 carbon atoms and a substituted or unsubstituted phenyl group represented by the general formula [4].

Here, the monovalent aromatic hydrocarbon group having 10 to 18 carbon atoms, the same meaning as the number of carbon atoms which corresponds among those described in the monovalent aromatic hydrocarbon group for R ¹ to R ^14.

R ¹⁵ and R ¹⁶ in the general formula [2] are each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted Or an unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, a cyano group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, substituted or Unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted Or an unsubstituted alkylsulfonyl group or a substituted or unsubstituted arylsulfonyl group, R ^{17 to} R ²² each independently represents a hydrogen atom, halo Gen atom, substituted or unsubstituted monovalent aliphatic hydrocarbon group, substituted or unsubstituted monovalent aromatic hydrocarbon group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted Monovalent aromatic heterocyclic group, cyano group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or Unsubstituted substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylsulfonyl group, or substituted or unsubstituted Represents a substituted arylsulfonyl group.

Here, in R ^{15 to} R ²² , a halogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group, a cyano group , Alkoxyl group, aryloxy group, alkylthio group, arylthio group, substituted amino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, R ¹ to R ¹⁴ is a halogen atom, substituted or unsubstituted monovalent aliphatic hydrocarbon group, substituted or unsubstituted monovalent aromatic hydrocarbon group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted Or an unsubstituted monovalent aromatic heterocyclic group, cyano group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, substituted amino group, acyl group, alkoxycarbonyl group, It is synonymous with an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group.

Moreover, as a substituent which R < ¹⁵ > -R < ²² > may have, the substituent which the above-mentioned R < ¹ > -R < ¹⁴ > may have is mentioned.

Preferred examples of R ¹⁵ and R ¹⁶ in the general formula [2] include a substituted or unsubstituted monovalent aliphatic hydrocarbon group and a substituted or unsubstituted monovalent aromatic hydrocarbon group. More preferred is a substituted or unsubstituted monovalent aromatic hydrocarbon group.

R ^{17 to} R ²² in the general formula [2] are preferably a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group. More preferable examples include a hydrogen atom and a substituted or unsubstituted monovalent aromatic hydrocarbon group, and particularly preferable examples include a hydrogen atom.

R ^{23 to} R ³⁶ in the general formula [3] are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon. Group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group Substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl Represents a group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group.

Here, in R ^{23 to} R ³⁶ , a halogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group, cyano Group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, substituted amino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group include R ¹ To R ¹⁴ , a halogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group, a cyano group, an alkoxyl group, Synonymous with aryloxy group, alkylthio group, arylthio group, substituted amino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group. is there.

Examples of the substituent that may be possessed by R ²³ to R ^36, include the substituents may be R ¹ to R ¹⁴ has the above.

R ^{23 to} R ³⁶ in the general formula [3] are preferably a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, or a substituted or unsubstituted monovalent aromatic hydrocarbon group. More preferable examples include a hydrogen atom and a substituted or unsubstituted monovalent aromatic hydrocarbon group, and particularly preferable examples include a hydrogen atom.

R ^{37 to} R ⁴¹ in the general formula [4] are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon. Group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group Substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl Represents a group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group.

And a halogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group, or a cyano group in R ^{37 to} R ⁴¹ . , Alkoxyl group, aryloxy group, alkylthio group, arylthio group, substituted amino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, or arylsulfonyl group is R ^1. To R ¹⁴ , a halogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group, a cyano group, an alkoxyl group, Aryloxy group, alkylthio group, arylthio group, substituted amino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, or arylsulfonyl group It is synonymous with.

As the substituent that may be possessed by R ³⁷ to R ^41, include the substituent which may be possessed by R ¹ to R ¹⁴ described above.

In addition, R ^{37 to} R ⁴¹ may form a new ring by bonding adjacent substituents. Examples of the new ring to be formed include a 1-naphthyl group, a 2-naphthyl group, a quinolyl group, and the like.

  Next, the superiority of the carbazolyl group will be described.

  In general, a carbazole compound has a stronger structure and a higher thermal stability than a diphenylamino compound having no bond (see Chemical Formula 5).

In the carbazole compound, an N-alkyl compound in which an alkyl group is arranged at another bonding position on nitrogen is well known, but the compound of the present invention has a substituent ( One feature is that = Ar ¹ ) is an aromatic group or a heteroaromatic group. Aromatic groups and heteroaromatic groups have a greater effect of increasing stability, and among them, the effect of increasing stability can be expected when Ar ¹ is the general formula [4], that is, a phenyl group It is.

  By the way, the effect of the carbazolyl group bonded at the 3-position will be mentioned. Usually, the amino group acts as an electron donor, but the nitrogen atom of the carbazole has little donor property with respect to the substituent bonded on the nitrogen atom. This is because the carbazole ring has planarity and is a very bulky substituent, and it is difficult to form a planar structure with the substituent on the nitrogen atom. It is thought that there is. On the contrary, since the carbazole ring bonded at the 3-position has the planarity of the ring, it can be an electron donor for the benzene ring portion (see Chemical formula 6).

  For these reasons, the organic EL device material having a carbazolyl group of the present invention tends to be a compound having a small ionization potential (a compound in which the ground state of the organic molecule is at a higher level). Can be a compound having a high hole injecting and transporting property.

  Furthermore, since the carbazole ring bonded at the 3-position has a lower molecular symmetry than the carbazole ring bonded on the nitrogen atom, the crystallinity of the molecule is lowered and the amorphous property is increased. It is also possible to greatly contribute to the improvement of stability when a thin film is formed.

  In particular, the material for an organic EL element of the present invention has a high amorphous property, and as a result, crystallization hardly occurs. When this property is used as a material for an organic EL element, the stability of the thin film is improved and the life of the organic EL element is prolonged.

  Moreover, when producing an organic EL element by vapor deposition, if the molecular weight is large, there is a concern that the vapor deposition property in the case of producing an element by vapor deposition is deteriorated. There is little damage to these organic compounds, and devices can be easily fabricated. Even when an organic EL element is produced by a coating method, it can be used in a wide range of solvents because of its high solubility in a general-purpose organic solvent.

  Specific examples of the compound of the present invention are shown in Table 1 below, but the present invention is not limited to this example.

Table 1

  Although the element material for organic EL elements of the present invention can be used for various applications, it is particularly preferably used as an organic EL material (hole injection / transport material for organic EL).

  Here, the organic EL element that can be produced using the hole injection / transport material for the organic EL element of the present invention will be described in detail.

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

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

  The hole injection / transport material for organic EL devices of the present invention can be used not only as a single compound but also as a combination of two or more compounds, that is, mixed, co-evaporated, laminated, etc. Is possible.

  Specific examples of the hole injection material and the hole transport material that can be combined with the organic EL device material of the present invention include triazole derivatives (see, for example, US Pat. No. 3,112,197), oxadiazo -Derivatives (see U.S. Pat. No. 3,189,447, etc.), imidazole derivatives (see JP-B-37-16096, etc.), polyarylalkane derivatives (U.S. Pat. No. 3,615,402, 3,820,989, 3,542,544, JP-B-45-555, 51-10983, JP-A-51-93224, 55-17105 No. 56-4148, No. 55-108667, No. 55-156953, No. 56-36656, etc.), pyrazoline derivatives and pyrazo Derivatives (US Pat. Nos. 3,180,729, 4,278,746, JP-A-55-88064, JP-A-55-88065, JP-A-49-105537, No. 55-51086, No. 56-80051, No. 56-88141, No. 57-45545, No. 54-112737, No. 55-74546, etc.), phenylenediamine derivatives (US patents) No. 3,615,404, Japanese Patent Publication Nos. 51-10105, 46-3712, 47-25336, Japanese Patent Laid-Open Nos. 54-53435, 54-11536, 54 -1192525), arylamine derivatives (US Pat. Nos. 3,567,450, 3,180,703, , 240,597, 3,658,520, 4,232,103, 4,175,961, 4,012,376 , JP-B-49-35702, JP-A-39-27577, JP-A-55-144250, JP-A-56-119132, JP-A-56-22437, West German Patent No. 1,110,518 Amino-substituted chalcone derivatives (see US Pat. No. 3,526,501 etc.), oxazole derivatives (disclosed in US Pat. No. 3,257,203 etc.), styrylanthracene, etc. Derivatives (see JP 56-46234 A, etc.), fluorenone derivatives (see JP 54-110837 A, etc.), hydrazone derivatives (US Pat. No. 3,717,462) , JP-A-54-59143, 55-52063, 55-52064, 55-46760, 55-85495, 57-11350, 57-1448749 And stilbene derivatives (Japanese Patent Laid-Open Nos. 61-210363, 61-228451, 61-14642, 61-72255, 62). -47646, 62-36674, 62-10652, 62-30255, 60-93455, 60-94462, 60-174749, 60- No. 175052), silazane derivatives (US Pat. No. 4,950,950), polysilanes (Japanese Patent Laid-Open No. 2-20 / 1990) 996), aniline copolymers (JP-A-2-282263), and conductive polymer oligomers (especially thiophene oligomers) disclosed in JP-A-1-211399. .

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

  As the hole injection material and hole transport material used together with the compound of the present invention (charge transport material for organic EL device), the following general formulas [5] to [10] can be used.

General formula [5]

(In the formula, R ^{a11 to} R ^a14 each independently represent a hydrogen atom, an alkoxyl group, or a cyano group, but they are not all hydrogen atoms at the same time.)

Here, as an alkoxyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, an octyloxy group, a tert-octyloxy group, a 2-bornyloxy group, a 2-isobornyloxy group, 1- Examples thereof include an alkoxyl group having 1 to 18 carbon atoms such as an adamantyloxy group. Particularly preferred combinations of ^{R a11 ~R a14, R a11 ~R} a14 are all methoxy group, or a case of an ethoxy group or cyano group.

General formula [6]

(In the formula, Z ²¹ represents a linking group, and represents a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, an oxygen atom or a sulfur atom. R ^{a21 to} R ^a26 are And each independently represents a monovalent aromatic hydrocarbon group.)

As the linking group for Z ²¹ , a single bond, vinylene group, o-phenylene group, m-phenylene group, p-phenylene group, 1,4-naphthylene group, 2,6-naphthylene group, 9,10-phenanthrylene group, A 9,10-anthrylene group is preferable, and a single bond, vinylene group, p-phenylene group, and 1,4-naphthylene group are more preferable. R ^{a21 to} R ^a26 include a monovalent aromatic hydrocarbon group selected from a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group. preferable.

General formula [7]

(In the formula, Z ³¹ represents a linking group, and represents a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, an oxygen atom, or a sulfur atom. R ^{a31 to} R ^a36 represent And each independently represents a monovalent aromatic hydrocarbon group.)

As the linking group for Z ³¹ , a single bond, vinylene group, o-phenylene group, m-phenylene group, p-phenylene group, 1,4-naphthylene group, 2,6-naphthylene group, 9,10-phenanthrylene group, A 9,10-anthrylene group is preferable, and a single bond, vinylene group, p-phenylene group, and 1,4-naphthylene group are more preferable. R ^{a31 to} R ^a36 include a monovalent aromatic hydrocarbon group selected from a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group. preferable.

  General formula [8]

(In the formula, R ^{a41 to} R ^a48 each independently represents a monovalent aromatic hydrocarbon group.)

R ^{a41 to} R ^a48 are preferably monovalent aromatic hydrocarbon groups selected from a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group.

General formula [9]

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

R ^{a51 to} R ^a56 are preferably monovalent aromatic hydrocarbon groups selected from a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group.

Formula [10]

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

R ^{a61 to} R ^a64 are preferably monovalent aromatic hydrocarbon groups selected from a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group.

  The compounds represented by the general formulas [5] to [10] described above are preferably used in combination with the organic EL device material of the present invention, particularly as a hole injection material. Table 2 below shows particularly preferred examples.

Table 2

  Moreover, as a hole transport material which can be used with the organic EL element material of this invention, the well-known compound shown in following Table 3 is mention | raise | lifted.

Table 3

  In order to form this hole injection layer, the above compound is thinned by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. Although there is no restriction | limiting in particular, Usually, they are 5 nm-5 micrometers.

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

  Among the electron injection materials, particularly effective electron injection materials include metal complex compounds, nitrogen-containing five-membered ring derivatives, silole derivatives, and triarylphosphine oxide derivatives. As a preferable metal complex compound that can be used in the present invention, a metal complex of 8-hydroxyquinoline or a derivative thereof is suitable. Specific examples of the metal complex of 8-hydroxyquinoline or its derivatives include tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (4-methyl- 8-hydroxyquinolinato) aluminum, tris (5-methyl-8-hydroxyquinolinato) aluminum, tris (5-phenyl-8-hydroxyquinolinato) aluminum, bis (8-hydroxyquinolinato) G) (1-naphtholato) aluminum, bis (8-hydroxyquinolinato) (2-naphtholato) aluminum, bis (8-hydroxyquinolinato) (phenolate) aluminum, bis (8 -Hydroxyquinolinato) (4-cyano-1-naphtholato) aluminum, bis (4-methyl-8) Hydroxyquinolinato) (1-naphtholato) aluminum, bis (5-methyl-8-hydroxyquinolinato) (2-naphtholato) aluminum, bis (5-phenyl-8-hydroxyquinolina) G) (phenolate) aluminum, bis (5-cyano-8-hydroxyquinolinato) (4-cyano-1-naphtholato) aluminum, bis (8-hydroxyquinolinato) chloroaluminum, bis Aluminum complex compounds such as (8-hydroxyquinolinato) (o-cresolato) aluminum, tris (8-hydroxyquinolinato) gallium, tris (2-methyl-8-hydroxyquinolinato) gallium , Tris (4-methyl-8-hydroxyquinolinato) gallium, tris (5-methyl-8-hydroxyquinolinato) Gallium, tris (2-methyl-5-phenyl-8-hydroxyquinolinato) gallium, bis (2-methyl-8-hydroxyquinolinato) (1-naphtholato) gallium, bis (2-methyl) -8-hydroxyquinolinato) (2-naphtholato) gallium, bis (2-methyl-8-hydroxyquinolinato) (phenolate) gallium, bis (2-methyl-8-hydroxyquinolina) -To) (4-cyano-1-naphtholato) gallium, bis (2,4-dimethyl-8-hydroxyquinolinato) (1-naphtholato) gallium, bis (2,5-dimethyl-8) -Hydroxyquinolinato) (2-naphtholato) gallium, bis (2-methyl-5-phenyl-8-hydroxyquinolinato) (phenolate) gallium, bis (2-methyl-5- Cyano-8-hydroxyquinolinato) (4-cyano-1-naphtholato) gallium, bis (2-methyl-8-hydroxyquinolinato) chlorogallium, bis (2-methyl-8-hydroxyquino) In addition to gallium complex compounds such as linato) (o-cresolato) gallium, 8-hydroxyquinolinatolithium, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) Metal complex compounds such as manganese, bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (8-hydroxyquinolinato) zinc, bis (10-hydroxybenzo [h] quinolinato) zinc It is done.

  Among the electron injection materials that can be used in the present invention, preferred nitrogen-containing five-membered ring derivatives include oxazole derivatives, thiazol derivatives, oxadiazol derivatives, thiadiazol derivatives, and triazole derivatives. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazol, 2 , 5-bis (1-phenyl) -1,3,4-oxadiazol, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazol, 2,5-bis (1-naphthyl) -1,3,4-oxadiazol, 1,4-bis [2- (5-phenyloxadiazolyl).) Benzene, 1,4-bis [2- ( 5-Phenyloxadiazolyl) -4-tert-butyl Nzene], 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-thiadiazol, 2,5-bis (1-naphthyl) -1,3,4 -Thiadiazol, 1,4-bis [2- (5-phenylthiadiazolyl). ) Benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4 -Triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like.

  Among the electron injection materials that can be used in the present invention, particularly preferred oxadiazole derivatives include oxadiazole derivatives represented by the following general formula [11].

General formula [11]

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

  Examples of the monovalent nitrogen-containing aromatic heterocyclic group include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 3-pyridyl group, 4-pyridazyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5- Monovalent nitrogen-containing monocyclic aromatic heterocyclic group such as pyrimidyl group, 2-pyrazyl group, 1-imidazolyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl Group, 7-quinolyl group, 8-quinolyl group, 2-quinazolyl group, 4-quinazolyl group, 5-quinazolyl group, 2-quinoxalyl group, 5-quinoxalyl group, 6-quinoxalyl group, 1-indolyl group, 9-caribazolyl Monovalent nitrogen-containing fused ring aromatic heterocyclic group such as a group, 2,2′-bipyridyl-3-yl group, 2,2′-bipyridyl-4-yl group, 3,3′-bipyridyl-2-yl Group, 3,3′-bipyridyl And monovalent nitrogen-containing ring-assembled aromatic heterocyclic groups such as 4-yl group, 4,4′-bipyridyl-2-yl group, and 4,4′-bipyridyl-3-yl group. The hydrogen atom on the valent nitrogen-containing aromatic heterocyclic group may be substituted with a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group.

A preferred monovalent aromatic hydrocarbon group as Ar ^r1 and Ar ^r2 is a 1-naphthyl group optionally substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group. , 2-naphthyl group, o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group, and a preferable monovalent nitrogen-containing aromatic heterocyclic group is a monovalent aliphatic hydrocarbon group or 1 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2,2′-bipyridyl-3-yl group, and 2,2′-bipyridyl-, which may be substituted with a valent aromatic hydrocarbon group 4-yl group is mentioned.

  Table 4 shows specific examples of oxadiazole derivatives that can be used in the present invention.

Table 4

  Among the electron injection materials that can be used in the present invention, a particularly preferred triazole derivative is a triazole derivative represented by the following general formula [12].

Formula [12]

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

Here, as Ar ^t1 and Ar ^t2 , preferred monovalent aromatic hydrocarbon group is phenyl which may be substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group. Group, 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group. Preferred monovalent nitrogen-containing aromatic heterocyclic groups include monovalent aliphatic groups. 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2,2′-bipyridyl-3-yl group, and 2 which may be substituted with an aromatic hydrocarbon group or a monovalent aromatic hydrocarbon group , 2'-bipyridyl-4-yl group. As Ar ^t3 , preferred monovalent aromatic hydrocarbon groups include a phenyl group, which may be substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group, Examples thereof include a naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group. Preferred monovalent nitrogen-containing aromatic heterocyclic groups are monovalent aliphatic hydrocarbon groups. Or the 2-pyridyl group, 3-pyridyl group, and 4-pyridyl group which may be substituted by the monovalent | monohydric aromatic hydrocarbon group are mention | raise | lifted.

  Table 5 shows specific examples of triazole derivatives that can be used in the present invention.

Table 5

  Further, among the electron injecting materials that can be used in the present invention, particularly preferred silole derivatives include silole derivatives represented by the following general formula [13].

Formula [13]

(In the formula, R ^p1 and R ^p2 are each independently a monovalent aliphatic hydrocarbon group, monovalent aromatic hydrocarbon group, or monovalent nitrogen-containing aromatic complex which may have a substituent. Ar ^{p1 to} Ar ^p4 each independently represents a monovalent aromatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group which may have a substituent, R ^p1 , The adjacent groups of R ^p2 and Ar ^{p1 to} Ar ^p4 may be linked to each other to form a ring.

Here, as R ^p1 and R ^p2 , preferred monovalent aliphatic hydrocarbon group is methyl which may be substituted with a monovalent aromatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group. Group, ethyl group, propyl group, and butyl group. Preferred monovalent aromatic hydrocarbon groups are substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group. And a phenyl group, an m-biphenylyl group, and a p-biphenylyl group. Preferred monovalent nitrogen-containing aromatic heterocyclic groups include a monovalent aliphatic hydrocarbon group or a monovalent aromatic carbon group. Examples thereof include a 2-pyridyl group, a 3-pyridyl group and a 4-pyridyl group, which may be substituted with a hydrogen group. In addition, as Ar ^{p1 to} Ar ^p4 , a preferable monovalent aromatic hydrocarbon group is a phenyl group which may be substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group. , 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group, and preferable monovalent nitrogen-containing aromatic heterocyclic groups are monovalent aliphatic A 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2,2′-bipyridyl-3-yl group, which may be substituted with a hydrocarbon group or a monovalent aromatic hydrocarbon group, and 2, A 2'-bipyridyl-4-yl group is mentioned.

  Table 6 shows specific examples of silole derivatives that can be used in the present invention.

Table 6

  Of the electron injecting materials that can be used in the present invention, preferred triarylphosphine oxide derivatives include those disclosed in JP-A-2002-63989, JP-A-2004-95221, JP-A-2004-203828, and JP-A-2004. -204140 and the triarylphosphine oxide derivative represented by the following general formula [14] can be shown.

General formula [14]

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

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

  Table 7 shows specific examples of triarylphosphine oxide derivatives that can be used in the present invention.

Table 7

  Furthermore, a hole blocking material that can prevent holes from passing through the light emitting layer from reaching the electron injection layer and form a layer having excellent thin film formability is used for the hole blocking layer. Examples of such hole blocking materials include aluminum complex compounds such as bis (8-hydroxyquinolinato) (4-phenylphenolato) aluminum, and bis (2-methyl-8-hydroxyquinolina). -To) (4-phenylphenolato) gallium complex compounds such as gallium, and nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP). .

The light emitting layer of the organic EL device of the present invention preferably has the following functions.
Injection function; function transport function that can inject holes from the anode or hole injection layer when an electric field is applied, and electrons from the cathode or electron injection layer; electric field of injected charges (electrons and holes) Light emitting function: A function that provides a field for recombination of electrons and holes and connects it to light emission. However, there is a difference between the ease of hole injection and the ease of electron injection. In addition, the transport ability represented by the mobility of holes and electrons may be large or small, but it is preferable to move one of the charges.

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

  For example, when obtaining violet emission from the ultraviolet region, a compound represented by the following general formula [15] is preferably used.

General formula [15]

(Wherein X1 represents a group represented by the following general formula [16], and X2 represents any one of a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.)

Formula [16]

(In the formula, m represents an integer of 2 to 5)

  The phenyl group, 1-naphthyl group, 2-naphthyl group, and phenylene group represented by X1 and X2 in the general formula [15] are one or more alkyl groups having 1 to 4 carbon atoms and 1 to 4 carbon atoms. It may be substituted with a substituent such as an alkoxyl group, a hydroxyl group, a sulfonyl group, a carbonyl group, an amino group, a dimethylamino group or a diphenylamino group. Moreover, when there are a plurality of these substituents, they may be bonded to each other to form a ring. Furthermore, the phenylene group represented by X1 is preferably bonded at the para position because it has good bonding properties and can easily form a smooth deposited film. Specific examples of the compound represented by the general formula [15] are as follows (where Ph represents a phenyl group).

  Among these compounds, p-quarter-phenyl derivatives and p-quinkphenyl derivatives are particularly preferable.

  Further, in order to obtain light emission in the visible region, particularly blue to green, for example, fluorescent whitening agents such as benzothiazole, benzimidazole, benzoxazole, metal chelated oxinoid compounds, styrylbenzene System compounds can be used. Specific examples of these compounds include, for example, compounds disclosed in JP-A-59-194393. Still other useful compounds are listed in Chemistry of Synthetic Soybean (1971) pages 628-637 and 640.

  As the metal chelated oxinoid compound, for example, compounds disclosed in JP-A-63-295695 can be used. As typical examples, 8-hydroxyquinoline-based metal complexes such as tris (8-quinolinol) aluminum, dilithium epinetridione and the like can be mentioned as suitable compounds.

  As the styrylbenzene compound, for example, those disclosed in European Patent No. 0319881 and European Patent No. 0373582 can be used. And the distyrylpyrazine derivative currently disclosed by Unexamined-Japanese-Patent No. 2-252793 can also be used as a material of a light emitting layer. In addition, polyphenyl compounds disclosed in EP 0387715 can also be used as a material for the light emitting layer.

  Further, in addition to the above-described optical brightener, metal chelated oxinoid compound, styrylbenzene compound, etc., 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., 56, L799 (1990)), naphthalimide derivatives ( Disclosed in JP-A-2-305886), perylene derivatives (JP-A-2-189890), oxadiazol derivatives (JP-A-2-21691, or the 38th Applied Physics Related Conference) by Hamada et al. Oxadiazol derivatives), aldazine derivatives (JP-A-2-220393), pyrazirine Conductors (JP-A-2-220394), cyclopentadiene derivatives (JP-A-2-289675), pyrrolopyrrole derivatives (JP-A-2-29691), styrylamine derivatives (Appl. Phys. Lett., No. 2). 56, L799 (1990), coumarin compounds (Japanese Patent Laid-Open No. 2-191694), international patent publications WO90 / 13148 and Appl. Phys. Lett., Vol 58, 18, P1982 (1991). Polymer compounds, 9,9 ′, 10,10′-tetraphenyl-2,2′-bianthracene, PPV (polyparaphenylene vinylene) derivatives, polyfluorene derivatives and copolymers thereof, for example, the following general formula [17] to those having the structure of the general formula [19],

General formula [17]

(In the formula, R ^x1 and R ^X2 each independently represent a monovalent aliphatic hydrocarbon group, and n1 represents an integer of 3 to 100.)

General formula [18]

(In the formula, R ^x3 and R ^X4 each independently represent a monovalent aliphatic hydrocarbon group, and n2 and n3 each independently represent an integer of 3 to 100.)

General formula [19]

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

  9,10-bis (N- (4- (2-phenylvinyl-1-yl) phenyl) -N-phenylamino) anthracene or the like can also be used as a material for the light emitting layer. Furthermore, a phenylanthracene derivative represented by the following general formula [20] as disclosed in JP-A-8-12600 can also be used as a light emitting material.

General formula [20]

(In the formula, A1 and A2 each independently represent a monophenylanthryl group or a diphenylanthryl group, which may be the same or different. L represents a single bond or a divalent linking group. )
Here, the divalent linking group represented by L is preferably a divalent monocyclic or condensed ring aromatic hydrocarbon group which may have a substituent. In particular, phenylanthracene derivatives represented by the following general formulas [21] to [22] are preferable.

Formula [21]

(In the formula, R ^{Z1 to} R ^Z4 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a monovalent aromatic hydrocarbon group, an alkoxyl group, an aryloxy group, a diarylamino group, A monovalent aliphatic heterocyclic group and a monovalent aromatic heterocyclic group, which may be the same or different, r1 to r4 each independently represents an integer of 0 or 1 to 5; When r1 to r4 are each independently an integer of 2 or more, R ^Z1 , R ^Z2 , R ^Z3 , R ^Z4 may be the same or different, and R ^Z1 , ^{Z2 to} each other, ^{RZ3 to} each other, and ^{RZ4 to} each other may form a ring, and L1 represents a single bond or a divalent monocyclic or condensed ring aromatic hydrocarbon group which may have a substituent. The divalent monocyclic or condensed ring aromatic hydrocarbon group which may have a substituent is An alkylene group, —O—, —S—, or —NR— (wherein R represents an alkyl group or an aryl group) may be interposed.

General formula [22]

(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 and a monovalent aromatic heterocyclic group, which may be the same or different, and r5 and r6 each independently represents 0 or an integer of 1 to 5. When r5 and r6 are each independently an integer of 2 or more, R ^Z5 and R ^Z6 may be the same or different, and R ^Z5 and R ^Z6 are bonded to form a ring. L2 represents a divalent monocyclic or condensed aromatic hydrocarbon group which may have a single bond or a substituent, and may represent a divalent monocyclic or condensed which may have a substituent. The ring aromatic hydrocarbon group is an alkylene group, -O-, -S- or -NR- (wherein R is an alkyl group or ants - represents Le group) or may be mediated).

  Of the general formula [22], phenylanthracene derivatives represented by the following general formula [23] to general formula [24] are more preferable.

General formula [23]

(Wherein R ^{Z11 to} R ^Z30 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, Represents a monovalent aliphatic heterocyclic group and a monovalent aromatic heterocyclic group, which may be the same or different, and R ^{Z11 to} R ^Z30 are formed by connecting adjacent groups to each other; (K1 represents an integer of 0 to 3).

General formula [24]

(In the formula, R ^{Z31 to} R ^Z50 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, Represents a monovalent aliphatic heterocyclic group and a monovalent aromatic heterocyclic group, which may be the same or different, and R ^{Z31 to} R ^Z50 are formed by connecting adjacent groups to each other; (K2 represents an integer of 0 to 3).

  Of the general formula [24], a phenylanthracene derivative represented by the following general formula [25] is more preferable.

Formula [25]

(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, Represents a monovalent aliphatic heterocyclic group and a monovalent aromatic heterocyclic group, which may be the same or different, and R ^{Z51 to} R ^Z60 are formed by connecting adjacent groups to each other; (K3 represents an integer of 0 to 3).

  Specific examples of the general formulas [21] to [25] include the following compounds.

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

  An amine compound represented by the following general formula [26] is also useful as a light emitting material.

General formula [26]

(In the formula, h is a valence and represents an integer of ^{1 to} 6. E ¹ is an n-valent aromatic hydrocarbon group, E ² is a dialkylamino group, a diallylamino group, or an alkylarylamino group. Represents an amino group selected from

Here, the base structure of the N-valent aromatic hydrocarbon group represented by E ¹ includes naphthalene, anthracene, 9-phenylanthracene, 9,10-diphenylanthracene, naphthacene, pyrene, perylene, biphenyl, binaphthyl, and bianthryl. Preferably, the amino group represented by E ¹ is preferably a diarylamino group. N is preferably 1 to 4, and most preferably 2. Of the general formula [26], amine compounds represented by the following general formula [27] to general formula [36] are particularly preferable.

General formula [27]

(Wherein R ^{y1 to} R ^y8 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic group. heterocyclic group or a dialkylamino group, diaryl - arylamino group, alkylaryl - represents an amino group selected from arylamino groups, of R ^y1 to R ^y8, at least one, dialkylamino group, diaryl - arylamino group And R ^{y1 to} R ^y8 may be the same or different, and adjacent groups may be linked to form a ring.)

General formula [28]

( ^Wherein R ^{y11 to} R ^y20 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic group. heterocyclic group or a dialkylamino group, diaryl - arylamino group, alkylaryl - represents an amino group selected from arylamino groups, of R ^y11 to R ^y20, at least one, dialkylamino group, diaryl - arylamino group And R ^{y11 to} R ^y20 may be the same or different, and adjacent groups may be linked to form a ring.)

General formula [29]

( ^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, or a monovalent aromatic group. heterocyclic group or a dialkylamino group, diaryl - arylamino group, alkylaryl - represents an amino group selected from arylamino groups, of R ^y21 to R ^Y34, at least one, dialkylamino group, diaryl - arylamino group ^{And Ry21 to Ry34} may be the same or different, and adjacent groups may be linked to form a ring.)

General formula [30]

( ^Wherein R ^{y35 to} R ^y52 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic group. heterocyclic group or a dialkylamino group, diaryl - arylamino group, alkylaryl - represents an amino group selected from arylamino groups, of R ^y35 to R ^y52, at least one, dialkylamino group, diaryl - arylamino group And R ^{y35 to} R ^y52 may be the same or different, and adjacent groups may be linked to form a ring.)

Formula [31]

( ^Wherein R ^{y53 to} R ^y64 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic group. heterocyclic group or a dialkylamino group, diaryl - arylamino group, alkylaryl - represents an amino group selected from arylamino groups, of R ^y53 to R ^Y64, at least one, dialkylamino group, diaryl - arylamino group And R ^{y53 to} R ^y64 may be the same or different, and adjacent groups may be linked to form a ring.)

General formula [32]

( ^Wherein R ^{y65 to} R ^y74 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic group. heterocyclic group or a dialkylamino group, diaryl - arylamino group, alkylaryl - represents an amino group selected from arylamino groups, of R ^Y65 to R ^Y74, at least one, dialkylamino group, diaryl - arylamino group ^{And Ry65 to Ry74} may be the same or different, and adjacent groups may be linked to form a ring.)

Formula [33]

( ^Wherein R ^{y75 to} R ^y86 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic group. heterocyclic group or a dialkylamino group, diaryl - arylamino group, alkylaryl - represents an amino group selected from arylamino groups, of R ^Y75 to R ^Y86, at least one, dialkylamino group, diaryl - arylamino group ^{And Ry75 to Ry86} may be the same or different, and adjacent groups may be linked to form a ring.)

General formula [34]

( ^Wherein R ^{y87 to} R ^y96 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic group. heterocyclic group or a dialkylamino group, diaryl - arylamino group, alkylaryl - represents an amino group selected from arylamino groups, of ^R y87 ~R y96, at least one, dialkylamino group, diaryl - arylamino group ^{And Ry87 to Ry96} may be the same or different, and adjacent groups may be linked to form a ring.)

General formula [35]

( ^Wherein R ^{y97 to} R ^y110 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic group. heterocyclic group or a dialkylamino group, diaryl - arylamino group, alkylaryl - represents an amino group selected from arylamino groups, of R ^Y97 to R ^y110, at least one, dialkylamino group, diaryl - arylamino group ^{And Ry97 to Ry110} may be the same or different, and adjacent groups may be linked to form a ring.)

General formula [36]

( ^Wherein R ^{y111 to} R ^y128 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, a monovalent aliphatic heterocyclic group, or a monovalent aromatic group. heterocyclic group or a dialkylamino group, diaryl - arylamino group, alkylaryl - represents an amino group selected from arylamino groups, of ^R y111 ~R y128, at least one, dialkylamino group, diaryl - arylamino group And R ^{y111 to} R ^y128 may be the same or different, and adjacent groups may be linked to form a ring.)

  The amine compounds of the general formulas [27] to [36] described above can be suitably used when yellow to red light emission is obtained. Specific examples of the amine compounds represented by the general formulas [27] to [36] described above include compounds having the following structure (where Ph represents a phenyl group).

  In addition, in the above general formula [27] to general formula [36], a compound containing at least one styryl group represented by the following general formula [37] to general formula [38] instead of an amino group (for example, EP 0388768, JP-A-3-231970, etc.) can also be suitably used as the light emitting material.

General formula [37]

( ^Wherein R ^{y129 to} R ^y131 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent aromatic hydrocarbon group. R ^{y129 to} R ^y131 are formed by connecting adjacent groups to each other. And may form a ring.)

General formula [38]

( ^Wherein R ^{y132 to} R ^y138 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or a monovalent aromatic hydrocarbon group. R ^{y134 to} R ^y138 each independently represents a hydrogen atom, alkyl group, a cycloalkyl group, a monovalent aromatic hydrocarbon group, or a dialkylamino group, diaryl - arylamino group, alkylaryl - represents an amino group selected from arylamino groups, of ^R y134 ~R y138, at least one is a dialkylamino group, diaryl - arylamino group, alkylaryl - arylamino amino group selected from the group ^.R y132 ~R y138 is between adjacent groups are connected, may form a ring. )

  Specific examples of the compound containing at least one styryl group represented by the general formula [37] to general formula [38] described above can include compounds having the following structure (where Ph represents a phenyl group): .

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

  In addition, there is a method for obtaining a high-efficiency blue and green mixed emission using doping according to Japanese Patent Laid-Open No. 6-9953. In this case, examples of the host include the above-mentioned light emitting material, and examples of the dopant include strong fluorescent dyes from blue to green, for example, coumarins or fluorescent dyes similar to those used as the above-mentioned host. Specifically, a luminescent material having a distyryl arylene skeleton as a host, particularly preferably 4,4′-bis (2,2-diphenylvinyl) biphenyl, and diphenylaminovinylarylene as a dopant, particularly preferably, for example, N , N-diphenylaminovinylbenzene.

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

  Furthermore, for example, the following known compounds are preferably used as the light emitting material (where Ph represents a phenyl group).

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

Furthermore, the material used for the anode of the organic EL device of the present invention is preferably a material having a work function (4 eV or more) metal, alloy, electrically conductive compound or a mixture thereof as an electrode substance. Specific examples of such an electrode substance include metals such as Au, and conductive materials such as CuI, ITO, SNO ₂ , and ZNO. In order to form this anode, a thin film can be formed from these electrode materials by a method such as vapor deposition or sputtering. The anode desirably has such a characteristic that when light emitted from the light emitting layer is extracted from the anode, the transmittance of the anode for light emission is greater than 10%. The sheet resistance of the anode is preferably several hundred Ω / □ or less. Further, although the film thickness of the anode depends on the material, it is usually selected in the range of 10 Nm to 1 μm, preferably 10 to 200 nm.

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

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

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

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

  Examples of the method for forming the organic EL device of the present invention include dry film formation methods such as vacuum deposition, electron beam irradiation, sputtering, plasma, ion plating, spin coating, dipping, flow coating, and ink jet. A wet film-forming method such as a method, a method of vapor-depositing a light emitter on a donor film, and also described in JP-T-2002-534882 and STLee, et al., Proceedings of SID'02, p.784 (2002). It is possible to apply any of the laser thermal transfer methods (also referred to as laser induced thermal imaging (LITI)), and the organic layer is particularly preferably a molecular deposited film. A thin film formed by deposition from a material compound in a gas phase state or a film formed by solidification from a material compound in a solution state or a liquid phase state. The thin film (molecular accumulation film) formed by the LB method can be classified by the difference in aggregated structure and higher order structure, and the functional difference resulting therefrom, which is disclosed in JP-A-57-51781. As described above, 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 reducing the thickness by a spin coating method or the like. The film thickness is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Conversely, if the film thickness is too thin, pinholes, etc. Therefore, it is difficult to obtain sufficient light emission luminance even when an electric field is applied, and thus the thickness of each layer is preferably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.

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

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

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

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

  As described above, the organic EL element using the organic EL element material of the present invention can emit light for a long time with a low driving voltage. Therefore, this organic EL element is used as a flat panel display such as a wall-mounted television and various flat light emitters, as well as a light source such as a copying machine and a printer, a light source such as a liquid crystal display and instruments, a display board, a marker lamp, etc. Application to is considered.

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

  First, a synthesis example of the material of the present invention is shown. Moreover,% represents weight% in description.

Synthesis example 1
Synthesis Method of Compound (1) A synthesis scheme is shown in Reaction 1. (N-C ₆ H ₁₃ represents an n-hexyl group.)

Reaction 1

Hereinafter, the synthesis method will be described with reference to Reaction 1. Under a nitrogen atmosphere, 5.0 g (0.01 mol) of (I), 8.0 g (0.025 mol) of 3-bromo-9-phenylcarbazole (II), 0.96 g of tetrakis (triphenylphosphine) palladium, potassium carbonate (2M aqueous solution) 100 g and tetrahydrofuran 100 g were placed in a four-necked flask and heated to reflux for 5 hours. Thereafter, the reaction solution was poured into 400 ml of methanol, and the precipitated solid was collected by filtration and dried in a hot vacuum to obtain 8.76 g of Compound (1) as a crude product. The obtained crude product was purified by silica gel column chromatography, and further sublimation purification was performed. The compound was identified by mass spectrum (manufactured by Bruker Daltonics, Autoflex II), ¹ H-NMR, and ¹³ C-NMR (manufactured by JEOL Ltd., ECX-400P). ¹ H-NMR, ¹³ C-NMR, UV spectrum, and fluorescence (PL) spectrum of the compound (1) are shown in FIGS. The UV spectrum was measured with a Hitachi spectrophotometer (U-3500), and the fluorescence (PL) spectrum was measured with a fluorescence spectrophotometer (FP-6500) manufactured by JASCO Corporation.

  In addition, (I) used for the synthesis | combination of a compound (1) used the commercially available reagent. As 3-bromo-9-phenylcarbazole (II), one synthesized according to the method described in WO2007 / 43484 was used.

Synthesis Examples 2 to 40
In the synthesis method, the compounds shown in Table 1 were synthesized by combining the following reactions 2 to 7.

Reaction 2

R ^{37 to} R ⁴¹ are substituents necessary for synthesizing the compound of the present invention, and are a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent group. Aromatic hydrocarbon group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted Aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted Alternatively, it represents an unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group.

As a synthesis method, Li-lithium produced by reacting 3-bromo-9-phenylcarbazole derivative (III) with n-butyllithium (n-BuLi) at −76 ° C. under a nitrogen stream in accordance with a conventional method to produce Li The derivative was reacted with B (OMe) ₃ to synthesize the desired boronic acid derivative (IV) form.

Reaction 3

R ¹⁵ and R ¹⁶ are substituents necessary for synthesizing the compound of the present invention, and each independently represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent group. Aromatic hydrocarbon group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted Aryloxy groups, substituted or unsubstituted alkylthio groups, substituted or unsubstituted arylthio groups, substituted or unsubstituted substituted amino groups, substituted or unsubstituted acyl groups, substituted or unsubstituted alkoxycarbonyl groups, Represents a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group . R ^{37 to} R ⁴¹ are as defined above.

  As a synthesis method, the target compound was obtained by the same operation as in Synthesis Example 1 except that the carbazole derivative (IV) was reacted with 3 equivalents of the 2,7-dibromofluorene derivative (V).

Reaction 4

Here, R ^{1 to} R ⁷ are substituents necessary for synthesizing the compound of the present invention, and each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted group. Or an unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, a cyano group, a substituted or unsubstituted alkoxyl Group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted A substituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted aryl It represents a Rusuruhoniru group. Ar ¹ represents a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, or a substituted or unsubstituted monovalent aromatic heterocyclic group. To express.

As a synthesis method, under a nitrogen stream at −78 ° C., 3-bromocarbazole derivative (VII) is reacted with n-butyllithium to lithiate, and the resulting Li derivative is reacted with B (OMe) ₃ . The desired boronic acid derivative (VIII) was synthesized.

Reaction 5

R ^{17 to} R ²² are substituents necessary for synthesizing the compound of the present invention, and each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted group. A substituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, a cyano group, a substituted or unsubstituted alkoxyl group, Substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted An alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted aryls Represents a sulfonyl group. Ar ¹ and R ^{1 to} R ⁷ have the same meanings as described above.

  The synthesis method is the same as in Synthesis Example 1 except that the fluorene derivative (X) corresponding to (I) in Synthesis Example 1 is reacted with 3 equivalents of the carbazole derivative (VIII) corresponding to (II). The target compound (XI) was obtained by performing the operations described above.

Reaction 6

R ^{17 to} R ²² are substituents necessary for synthesizing the compound of the present invention, and each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted group. A substituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, a cyano group, a substituted or unsubstituted alkoxyl group, Substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted An alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted aryls Represents a sulfonyl group.

  As a synthesis method, (X) was obtained by reacting fluorene derivative (XII) with an equal amount of bromine or N-bromosuccinimide in toluene according to a conventional method.

Reaction 7

R ^{15 to} R ²² and R ^{1 to} R ⁷ are substituents necessary for synthesizing the compound of the present invention and have the same meanings as described above. As the synthesis method, the target compound was easily obtained by the same operation as in Synthesis Example 1.

  The structure of the compound of the present invention obtained by combining the above reactions 2 to 7 was identified by mass spectrum (manufactured by Bruker Daltonics, Autoflex II). The results are shown in Table 8. The compound numbers are the same as those in Table 1.

Table 8

  Next, the synthesis method of the compounds (41) to (65) in Table 1 is shown below.

Synthesis Example 41
Method for synthesizing compound (41)

Reaction 8

Hereinafter, the synthesis method will be described with reference to Reaction 8. Under nitrogen atmosphere, (XIV) 2.73 g (0.0058 mol), (II) 5.0 g (0.0174 mol), tetrakis (triphenylphosphine) palladium 0.5 g, potassium carbonate (2M aqueous solution) 50 g, tetrahydrofuran 50 g Was added to a four-necked flask and heated to reflux for 5 hours. Thereafter, the reaction solution was poured into 400 ml of methanol, and the precipitated solid was collected by filtration and dried in a heat vacuum to obtain 3.12 g of Compound (41) as a crude product. The obtained crude product was purified by silica gel column chromatography, and further sublimation purification was performed. The compound was identified by mass spectrum (manufactured by Bruker Daltonics, Autoflex II), ¹ H-NMR, and ¹³ C-NMR (manufactured by JEOL, ECX-400P). ¹ H-NMR, ¹³ C-NMR, UV spectrum, and fluorescence (PL) spectrum of the compound (41) are shown in FIGS. The UV spectrum was measured with a Hitachi spectrophotometer (U-3500), and the fluorescence (PL) spectrum was measured with a fluorescence spectrophotometer (FP-6500) manufactured by JASCO Corporation.

Synthesis Examples 42 to 65
The synthesis method synthesized the compounds in Table 2 by combining the reactions described above and reactions 9 to 11 shown below.

Reaction 9

R ^{23 to} R ³⁶ are substituents necessary for synthesizing the compound used in the present invention, and are a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent group. Aromatic hydrocarbon group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted Aryloxy groups, substituted or unsubstituted alkylthio groups, substituted or unsubstituted arylthio groups, substituted or unsubstituted substituted amino groups, substituted or unsubstituted acyl groups, substituted or unsubstituted alkoxycarbonyl groups, A substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group; The R ^{23 to} R ³⁶ are as defined above.

  As a synthesis method, the target compound is obtained by the same operation as in Synthesis Example 1 except that 3 equivalents of the carbazole derivative (IV) are reacted with the dibromospirobifluorenone derivative (XIV).

Reaction 10

R ^{23 to} R ³⁶ are as defined above. As a synthesis method, at -78 ° C. under a nitrogen stream, n-butyllithium was reacted with dibromonaphthalene derivative (XV) to lithiate, and the resulting Li derivative was reacted with B (OMe) ₃ to obtain the target. A boronic acid derivative (XVI) was synthesized.

Reaction 11

R ^{1 to} R ⁷ and Ar ¹ have the same meanings as described above. As a synthesis method, the target compound (XVII) was prepared by the same procedure as described above except that 3 equivalents of the corresponding spirobifluorenone derivative (XVI) was reacted with the carbazole derivative (VII) instead of (XIII) in Reaction 7. )was gotten.

  The structure of the compound of the present invention obtained by combining the above reactions 8 to 11 was identified by mass spectrum (manufactured by Bruker Daltonics, Autoflex II). The results are shown in Table 9. The compound numbers are the same as those in Table 1.

Table 9

  Hereinafter, although the example of creation of the organic EL element using the material of the present invention is shown as an example, the present invention is not limited to the following example. In this example, all mixing ratios are weight ratios unless otherwise specified.

Vapor deposition (vacuum deposition) was performed in a vacuum of 10 ⁻⁶ Torr and under conditions without temperature control such as substrate heating and cooling. In the evaluation of the light emission characteristics of the element, the characteristics of an organic EL element having a light emission area of 2 mm × 2 mm were measured.

Example 1
On the washed glass plate with an ITO electrode, the compound (21) was vacuum-deposited to obtain a hole injection layer having a thickness of 60 nm. Subsequently, HTM9 of Table 3 was vacuum-deposited and the 20-nm hole transport layer was obtained. Furthermore, a tris (8-hydroxyquinoline) aluminum complex is vacuum-deposited to form an electron-injection type light-emitting layer having a thickness of 60 nm, and then an electrode is formed by first depositing 1 nm of lithium fluoride and then 200 nm of aluminum. Thus, an organic EL element was obtained.

Examples 2-7
An organic EL device was prepared in the same manner as in Example 1 except that the compound in Table 1 was used instead of the compound (1) for the hole injection layer.

In addition, the devices of Examples 1 to 7 were allowed to emit light continuously for a certain time at a current density of 10 mA / cm ^{2 in} a room temperature environment, and the luminance was measured. The results are shown in Table 10.

Table 10

Example 8
On the washed glass plate with an ITO electrode, HIM2 in Table 2 was vacuum-deposited to obtain a hole injection layer having a thickness of 50 nm. Subsequently, the compound (1) of Table 1 was vacuum-deposited and the 30-nm hole transport layer was obtained. Furthermore, a tris (8-hydroxyquinoline) aluminum complex is vacuum-deposited to form an electron-injection type light-emitting layer having a thickness of 60 nm, and then an electrode is formed by first depositing 1 nm of lithium fluoride and then 200 nm of aluminum. Thus, an organic EL element was obtained.

Examples 9-34
An organic EL device was prepared in the same manner as in Example 8 except that the compound in Table 1 was used instead of the compound (1) for the hole injection layer.

In addition, the devices of Examples 8 to 34 were allowed to emit light continuously at a current density of 10 mA / cm ² for a certain period of time in a room temperature environment, and the luminance was measured. The results are shown in Table 11.

Table 11

Example 35
On the glass plate with an ITO electrode, HIM4 of Table 2 was vacuum-deposited to obtain a 50 nm-thick hole injection layer. Subsequently, the compound (2) of Table 1 was vacuum-deposited to obtain a 30 nm hole transport layer. Next, the compound (A) shown below was vapor-deposited to form a light-emitting layer having a thickness of 20 nm. Further, Alq3 was deposited to form an electron injection layer having a thickness of 20 nm. On top of this, an electrode was formed by vacuum deposition of 1 nm of lithium fluoride and 200 nm of aluminum, and an element was obtained. This device showed a light emission efficiency of 3.0 (lm / W) at a DC voltage of 5.0V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 1000 hours or more.

Example 36
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid) was formed into a film thickness of 60 nm on a glass plate with an ITO electrode by a spin coating method. Furthermore, the compound (5) shown in Table 1 was dissolved in a toluene solvent and applied by a spin coating method to prepare a hole transport layer having a thickness of 50 nm. (A) was further deposited on this coated substrate by a vacuum deposition method to form a light emitting layer having a thickness of 30 nm. A 30 nm-thick electron injection layer was formed thereon by further vapor-depositing (B) by a vacuum evaporation method. Finally, a cathode was formed by vapor deposition of 1 nm of lithium oxide and 100 nm of aluminum to obtain an organic electroluminescence element. This device showed an external quantum efficiency of 5.3% at a DC voltage of 10V. Further, the half-life when driven at a constant current at an emission luminance of 100 (cd / m ² ) was 5000 hours or more.

Example 37
On the glass plate with an ITO electrode, HIM7 of Table 2 was vacuum-deposited to obtain a 50 nm-thick hole injection layer. Subsequently, the compound (3) of Table 1 was vacuum-deposited to obtain a 30 nm hole transport layer. Next, the following compound (C) was deposited to form a light emitting layer having a thickness of 30 nm. Further, Alq3 was deposited to form an electron injection layer having a thickness of 20 nm. On top of this, an electrode was formed by vacuum deposition of 1 nm of lithium fluoride and 200 nm of aluminum, and an element was obtained. This device showed a luminous efficiency of 3.5 (lm / W) at a DC voltage of 5.0V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 1000 hours or more.

Example 38
Copper phthalocyanine was vapor-deposited on a glass plate with an ITO electrode to form a hole injection layer having a thickness of 50 nm. Next, the compound (10) in Table 1 was deposited to form a 30 nm-thick hole transport layer. Further, 1.3.5-tri (9H-carbazolyl-9-yl) benzene and compound (D) were co-evaporated at a composition ratio of 100: 8 to form a light emitting layer having a thickness of 45 nm. Further, (E) was deposited to form a blocking layer having a thickness of 5 nm, and further, Alq3 was deposited to form an electron injection layer having a thickness of 20 nm. On top of that, a cathode was formed by vapor deposition of 1 nm of lithium oxide and 100 nm of aluminum to obtain an organic electroluminescence element. This device showed an external quantum efficiency of 6.5% at a DC voltage of 10V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 1000 hours or more.

Example 39
On the glass plate with an ITO electrode, HIM9 in Table 2 was vapor-deposited to form a 40 nm-thick hole injection layer, and the compound (44) of the present invention was vapor-deposited to form a 35-nm-thick hole transport layer. Formed. Further, a compound (F) shown below and a compound (G) shown below were co-evaporated at a composition ratio of 50: 1 to form a light emitting layer having a thickness of 35 nm. Further, the following compound (H) was deposited to form an electron injection layer having a thickness of 30 nm. On top of that, an electrode was formed by vacuum deposition of 1 nm of lithium fluoride (LiF) and 200 nm of aluminum (Al) to obtain an element. This device showed a luminous efficiency of 5.0 (lm / W) at a DC voltage of 3.5V. Further, the half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 1000 hours or more.

Example 40
On the glass plate with an ITO electrode, HIM8 of Table 2 was vacuum-deposited to obtain a hole injection layer having a thickness of 60 nm. Next, the compound (1) in Table 1 and the HTM25 in Table 3 were co-deposited at a ratio of 1: 1 to form a 40 nm-thick hole transport layer. Further, Alq3 was deposited to form an electron injecting light emitting layer having a thickness of 30 nm. On top of this, lithium fluoride was evaporated to form an electron injection layer having a thickness of 20 nm. Furthermore, a cathode was formed by vapor deposition of aluminum at 100 nm to obtain an organic EL device. This element showed an external quantum efficiency of 2.5% at a DC voltage of 10V. Further, the luminance half-life when driven at a constant current at an emission luminance of 500 (cd / m ² ) was 1000 hours or more.

Comparative Example 1
A device was prepared in the same manner as in Example 8 except that Compound (I) was used instead of Compound (1). The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was measured. Further, the luminance was measured after initial luminance, and 100 hours to continuously driven at 100 ° C. environment when driven at a current density of 10 mA / cm ^2. The results are shown in Table 12.

Comparative Example 2
A device was prepared in the same manner as in Example 40 except that the compound (J) was used instead of the compound (1). The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m ² ) was measured. Further, the luminance was measured after initial luminance, and 100 hours to continuously driven at 100 ° C. environment when driven at a current density of 10 mA / cm ^2. The results are shown in Table 12.

Table 12

  As is clear from Table 12, all of the compounds of the present invention had a longer lifetime and higher luminance than the devices prepared using the compounds (I) and (J) of Comparative Examples.

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

FIG. 1 is a ¹ H-NMR spectrum of compound (1). (In heavy THF solvent)

FIG. 2 is a ¹³ C-NMR spectrum of compound (1). (In heavy THF solvent)

FIG. 3 is a UV spectrum of the compound (1). (In toluene solvent)

FIG. 4 is a PL spectrum of the compound (1). (In toluene solvent)

FIG. 5 is a ¹ H-NMR spectrum of compound (41). (In heavy THF solvent)

FIG. 6 is a ¹³ C-NMR spectrum of compound (41). (In heavy THF solvent)

FIG. 7 is the UV spectrum of compound (41). (In toluene solvent)

FIG. 8 is a PL spectrum of the compound (41). (In toluene solvent)

Claims (5)

A charge transport material for an organic electroluminescence device having a carbazolyl group represented by the following general formula [1].
General formula [1]

(In the formula, X represents a linking group represented by the general formula [2] or [3].
Ar ¹ and Ar ² each independently represent a substituted or unsubstituted monovalent aromatic hydrocarbon group or a substituted or unsubstituted monovalent aromatic heterocyclic group.
R ^{1 to} R ¹⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted Monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio Group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted It represents an alkylsulfonyl group or a substituted or unsubstituted arylsulfonyl group. )
General formula [2]

Wherein R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, substituted or unsubstituted. A monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, a cyano group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted Alkylthio group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted An alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group,
R ^{17 to} R ²² are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted Monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio Group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted It represents an alkylsulfonyl group or a substituted or unsubstituted arylsulfonyl group. )
General formula [3]

Wherein R ^{23 to} R ³⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted Or an unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, a cyano group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, substituted or Unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted Or an unsubstituted alkylsulfonyl group or a substituted or unsubstituted arylsulfonyl group.) The charge transport material for an organic electroluminescence device according to claim 1, wherein Ar ¹ and Ar ² are each independently a substituted or unsubstituted phenyl group represented by the following general formula [4].
General formula [4]

Wherein R ^{37 to} R ⁴¹ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted Or an unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted monovalent aromatic heterocyclic group, a cyano group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, substituted or Unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted amino group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylsulfonyl group or a substituted or unsubstituted ants -. represents a Rusuruhoniru group also, R ³⁷ to R ⁴¹ are substituents each other adjacent Combined may form a new ring.) The charge transport material for an organic electroluminescence device having a carbazolyl group according to claim 1, wherein R ^{37 to} R ⁴¹ are hydrogen atoms.   The charge transport material for organic electroluminescent elements having a carbazolyl group according to any one of claims 1 to 3, which is a hole injection material or a hole transport material.   The organic electroluminescent element which has a positive hole injection layer and / or a positive hole transport layer between a pair of electrodes, The said positive hole injection layer and / or a positive hole transport layer is an electric charge for organic electroluminescent elements of Claim 4 An organic electroluminescence device comprising a transport material.

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