JP2008174468A - Material for organic electroluminescence device and organic electroluminescence device - Google Patents

Abstract

Provided is an organic electroluminescent element material that exhibits red light emission with high light emission luminance and long life.
A specific diketopyrrolo in which N and N ′ are each independently substituted with a hydrogen atom, a substituted or unsubstituted alkyl group, or the like, and a ring carbon is substituted with a phenyl group substituted with an amino group or the like. A pyrrole compound is used and used as a material for an organic electroluminescence device.
[Selection] Figure 1

Description

  The present invention relates to an organic electroluminescence element used for a planar light source and display. More specifically, the present invention relates to an organic electroluminescent element for red light emission and a material for an organic electroluminescent element that exhibit high color purity and luminance at a low driving voltage.

  An organic electroluminescence (EL) element that emits light when an electron injected from a cathode and a hole injected from an anode are recombined in an organic phosphor sandwiched between these two electrodes is a solid light emitting display element. In recent years, research and development has been actively conducted.

This study was conducted by Eastman Kodak's C.I. W. Tang et al., Appl. Phys. Lett. 51, 913, published in 1987, which originated from an EL element with an organic thin film laminated. In this report, a metal chelate complex is used for the light emitting layer and an amine compound is used for the hole injection layer. Thus, green light emission having a luminance of several thousand (cd / m ² ) at a DC voltage of 6 to 10 V and a maximum luminous efficiency of 1.5 (lm / W) is obtained. It can be said that the organic EL elements currently being developed by various research institutes basically follow the configuration of Eastman Kodak Company.

  Among organic EL elements, organic EL elements that emit red light have been researched for elements using various materials because of their usefulness, but a method such as co-evaporation of a small amount of dopant in the host material. A method of forming a light-emitting layer by mixing them to obtain light emission from a dopant has been studied as an effective method. As such an example, C.I. H. Chen et al., Macromol. Symp. 125, 34-36 and 49-58, published in 1997, tris (8-hydroxyquinolinate) aluminum as a host material and 4H such as DCM, DCJ, DCJT, DCJTB -An organic EL device capable of emitting orange to red light using a pyran derivative as a dopant has been reported.

  In addition, as for organic EL elements using a compound having a 1,4-diketopyrrolo (3,4-c) pyrrole structure known as a red pigment, for example, JP-A-2-296891 and JP-A-5-320633 are disclosed. JP 2001-139940 A, WO 03/048268 pamphlet, and JP 2003-155286 A are known.

Appl. Phys. Lett. 51, 913, 1987 Macromol. Symp. 125, 34-36 and 49-58, 1997 Japanese Patent Laid-Open No. 2-29691 JP-A-5-320633 JP 2001-139940 A WO03 / 048268 pamphlet JP 2003-155286 A

  In the organic EL device for obtaining red high-intensity light emission described in the prior art, the organic EL device using a 4H-pyran derivative as a dopant has insufficient light emission color, high driving voltage and low light emission luminance. There was a problem. In addition, in an organic EL device using a compound having a 1,4-diketopyrrolo (3,4-c) pyrrole structure as a dopant, an element with high color purity can be produced, but the concentration is high due to high molecular cohesion. Quenching is likely to occur and control of the doping concentration is an important issue. Therefore, there has been a demand for an organic EL element material capable of obtaining red light emission having high light emission luminance and a long lifetime without causing problems such as concentration quenching.

  As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention. That is, this invention relates to the material for organic electroluminescent elements containing the diketopyrrolopyrrole compound represented by following General formula [1].

General formula [1]

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ^{3 to} R ¹² each independently represent a hydrogen atom or a substituent, At least one of R ^{3 to} R ¹² is an amino group represented by the general formula [2]. Further, among R ^{3 to} R ¹² , adjacent substituents other than the amino group may be bonded to each other to form a ring. ]

General formula [2]

[Wherein, R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent. Further, at least one of R ¹³ and R ^14, or a carbazolyl group represented by the general formula [3], R ¹³ and R ¹⁴ may be bonded to each other to form a ring. ]

General formula [3]

[Wherein Ar ¹ is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or a monovalent heterocyclic ring having 2 to 18 carbon atoms which may have a substituent. Represents a C 1-6 monovalent aliphatic hydrocarbon group which may have a group or a substituent, and R ^{15 to} R ²¹ each independently represents a hydrogen atom, a halogen atom, or a substituent. To express. R ^{15 to} R ²¹ may form a ring by bonding adjacent substituents to each other. ]
Moreover, this invention relates to the said organic electroluminescent element material whose diketopyrrolopyrrole compound represented by General formula [1] is a diketopyrrolopyrrole compound represented by following General formula [4].

General formula [4]

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ^{3 to} R ¹⁰ each independently represent a hydrogen atom or a substituent. R ^{22 to} R ²⁵ each independently represents a hydrogen atom or a substituent, and at least one of R ^{22 to} R ²⁵ is a carbazolyl group represented by the general formula [3]. R ^{3 to} R ¹⁰ may form a ring by bonding adjacent substituents to each other. ]

  Moreover, this invention relates to the said organic electroluminescent element material whose diketopyrrolopyrrole compound represented by General formula [4] is a diketopyrrolopyrrole compound represented by the following general formula [5].

General formula [5]

[Wherein, R ¹ and R ² each independently represent a hydrogen atom and a substituted or unsubstituted alkyl group, and R ^{3 to} R ¹⁰ and R ^{15 to} R ⁵² each independently represent a hydrogen atom. Or represents a substituent. Moreover, R < ³ > -R < ¹⁰ > and R < ¹⁵ > -R < ⁵² > may combine adjacent substituents mutually and may form a ring. ]

  Moreover, this invention relates to the said organic electroluminescent element material which comprises the said organic electroluminescent element material and the amine compound represented by General formula [6].

General formula [6]

[In the formula, Ar ² represents a substituted or unsubstituted perylenyl group, R ⁵³ and R ⁵⁴ each independently represents a substituted or unsubstituted monovalent aromatic hydrocarbon group, or a substituted or unsubstituted monovalent group. An aromatic heterocyclic group. Ar ² and R ⁵³ , Ar ² and R ⁵⁴ , and R ⁵³ and R ⁵⁴ may combine with each other to form a ring. ]

  In addition, the present invention provides an organic electroluminescence device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes composed of an anode and a cathode. The present invention relates to an organic electroluminescence element including an element material.

  In addition, the present invention provides an organic electroluminescence device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes composed of an anode and a cathode, wherein the light emitting layer is the above organic electroluminescence. The present invention relates to an organic electroluminescence element including an element material.

  The organic EL device material containing the diketopyrrolopyrrole compound of the present invention is particularly excellent in red light emission due to the specific structure of the diketopyrrolopyrrole compound, and is difficult to cause concentration quenching, achieving both high emission luminance and long life. It is characterized by being able to do it. Organic EL devices created using this material can be used suitably as flat panel displays and flat light emitters, such as light sources for copiers and printers, light sources for liquid crystal displays and instruments, display boards, indicator lights, etc. Application to is possible.

Hereinafter, the present invention will be described in detail. In the diketopyrrolopyrrole compound represented by the general formula [1], R ¹ and R ² represent a substituted or unsubstituted alkyl group. R ^{3 to} R ¹² represent a hydrogen atom or a substituent, and at least one of R ^{3 to} R ¹² is an amino group represented by the general formula [2]. Further, among R ^{3 to} R ¹² , adjacent substituents other than the amino group may be bonded to each other to form a ring.

Examples of the unsubstituted alkyl group represented by R ¹ and R ^{2 in} the present invention include a linear alkyl group and a cyclic alkyl group. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, C 1-18 straight chain such as butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, octadecyl group Examples thereof include a chain alkyl group.

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

  The substituted alkyl group includes a fluoromethyl group, a chloromethyl group, a bromomethyl group, a benzyl group, a 4-biphenylylmethyl group, a 4- (p-terphenylyl) methyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group. , 9-phenanthrylmethyl group, 9-anthrylmethyl group, 2-phenethyl group, 2- (4-biphenylyl) ethyl group, 2- {4- (p-terphenylyl)} ethyl group, 2- (1- Naphthyl) ethyl group, 2- (2-naphthyl) ethyl group, 2- (9-phenanthryl) ethyl group, 2- (9-anthryl) ethyl group, 3-phenylpropyl group, 3- (4-biphenylyl) propyl group , 3- {4- (p-terphenylyl)} propyl group, 3- (1-naphthyl) propyl group, 3- (2-naphthyl) propyl group, 3- (9-phenanthri ) Propyl group, 3- (9-anthryl) propyl group, 2-thienylmethyl group, 2-benzo [b] thienylmethyl group, 2-naphtho [2,3-b] thienylmethyl group, 2-furylmethyl group, (2H-pyran-3-yl) methyl group, 1-isobenzofuranylmethyl group, 1-methyl-2-pyrrolylmethyl group, 1-methyl-2-imidazolylmethyl group, 2-pyrazinylmethyl group, 2-pyridylmethyl group 2-pyrimidinylmethyl group, 3-pyridazinylmethyl group, 3-methylcyclohexyl group, 3.5-dimethylcyclohexyl group and the like.

In the present invention, the substituents R ^{3 to} R ¹² include a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, and a monovalent aromatic heterocyclic group. , Halogen atom, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, trialkylsilyl group, cyano group, amino group, etc. It is done.

  The monovalent aliphatic hydrocarbon group referred to in the present invention refers to a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and examples thereof include an alkyl group, an alkenyl group, and an alkynyl group. It is done.

The alkyl group has the same meaning as those described for R ¹ and R ² in the general formula [1],
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 and 1-octadecenyl group. And an alkenyl group having 2 to 18 carbon atoms such as a group.

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

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

  Examples of the monovalent condensed ring aromatic hydrocarbon group include 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1-acenaphthyl group, 2-azurenyl group, 1-pyrenyl group, 2-triphenylyl group, 2-pyrenyl group, 1-perylenyl group, 2-perylenyl group, 3-perylenyl group, 2-trephenylenyl group, 2-indenyl group, Examples thereof include monovalent condensed ring aromatic hydrocarbon groups having 10 to 30 carbon atoms such as 1-acenaphthylenyl group, 2-naphthacenyl group, and 2-pentacenyl group.

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

  The monovalent aliphatic heterocyclic group referred to in the present invention includes 1,3-dioxolanyl group, 1,3-dioxanyl group, 1,4-dioxanyl group, 2-tetrahydrofuryl group, 2-morpholino group, 4 -C3-C18 monovalent | monohydric aliphatic heterocyclic groups, such as a morpholino group and a piperidino group, are mention | raise | lifted.

  The monovalent aromatic heterocyclic group referred to in the present invention includes 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, N-pyrrolyl group, 2-benzofuryl group, 2-benzoyl group. Examples thereof include monovalent aromatic heterocyclic groups having 3 to 30 carbon atoms such as thienyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-quinolyl, and 5-isoquinolyl group.

  In addition, examples of the halogen atom in the present invention include a fluorine atom, a chlorine atom, and a bromine atom.

  In addition, as the alkoxyl group in the present invention, methoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group, octyloxy group, tert-octyloxy group, 2-bornyloxy group, 2-isobornyloxy group And an alkoxyl group having 1 to 18 carbon atoms such as 1-adamantyloxy group.

  The aryloxy group referred to in the present invention is an aryloxy group having 6 to 30 carbon atoms such as a phenoxy group, 4-tert-butylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy group. Group.

  In addition, examples of the alkylthio group in the present invention include an alkylthio group having 1 to 18 carbon atoms such as a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, and an octylthio group.

  Examples of the arylthio group in the present invention include arylthio groups having 6 to 30 carbon atoms such as a phenylthio group, a 2-methylphenylthio group, and a 4-tert-butylphenylthio group.

  Examples of the acyl group in the present invention include C2-C18 acyl groups such as acetyl group, propionyl group, pivaloyl group, cyclohexylcarbonyl group, benzoyl group, toluoyl group, anisoyl group, and cinnamoyl group.

  Examples of the alkoxycarbonyl group in the present invention include C2-C18 alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, and benzyloxycarbonyl group.

  In addition, examples of the aryloxycarbonyl group referred to in the present invention include aryloxycarbonyl groups having 7 to 30 carbon atoms such as a phenoxycarbonyl group and a naphthyloxycarbonyl group.

  Moreover, as an alkylsulfonyl group as used in the field of this invention, C1-C18 alkylsulfonyl groups, such as a mesyl group, an ethylsulfonyl group, a propylsulfonyl group, are mention | raise | lifted.

  Examples of the arylsulfonyl group include arylsulfonyl groups having 6 to 30 carbon atoms such as a benzenesulfonyl group and a p-toluenesulfonyl group.

  Examples of the trialkylsilyl group in the present invention include trialkylsilyl groups having 6 to 18 carbon atoms such as a trimethylsilyl group, a triethylsilyl group, a dimethylethylsilyl group, a triisopropylsilyl group, and a tributylsilyl group.

  Examples of the amino group in the present invention include amino groups having 6 to 30 carbon atoms such as diethylamino group, dibutylamino group, diphenylamino group, ditolylamino group, and ethylphenylamino group.

  The monovalent aliphatic hydrocarbon group, aromatic hydrocarbon group, aliphatic heterocyclic group and aromatic heterocyclic group described above are further substituted with the substituent described in the general formula [1]. Also good. These substituents may be bonded to each other to form a ring.

Further, among R ^{3 to} R ¹² , adjacent substituents other than the amino group may be bonded to each other to form a ring. Specific examples thereof include a benzene ring, a cyclohexyl ring, a pyridine ring, a pyrrole ring, and a thiophene. For example, forming a ring.

Next, in the general formula [2], R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent. Further, at least one of R ¹³ and R ^14, or a carbazolyl group represented by the general formula [3], R ¹³ and R ¹⁴ may be bonded to each other to form a ring.

Here, the substituents of R ¹³ and R ^{14 have} the same meanings as those described for R ^{3 to} R ¹² in the general formula [1], preferably a monovalent aromatic hydrocarbon group, particularly preferably. Includes a phenyl group, a tolyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl group, and a terphenyl group. Moreover, the C1-C6 monovalent aliphatic hydrocarbon group which may have a substituent is also synonymous with what was mentioned above.

R ¹³ and R ¹⁴ may be bonded to each other to form a ring. Specific examples thereof include R ¹³ and R ¹⁴ forming a benzene ring, a cyclohexyl ring, a pyridine ring, a pyrrole ring, and a thiophene ring. And so on.

Next, in General Formula [3], Ar ¹ is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and 2 to 18 carbon atoms which may have a substituent. A monovalent heterocyclic group or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and R ^{15 to} R ²¹ each independently represent a hydrogen atom, a halogen atom, Represents an atom or a substituent. R ^{15 to} R ²¹ may form a ring by bonding adjacent substituents to each other.

C1-C18 monovalent aromatic hydrocarbon group which may have a substituent shown here, C2-C18 monovalent heterocyclic group which may have a substituent, or The monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent has the same meaning as described for R ^{3 to} R ¹² in the general formula [1], preferably monovalent And particularly preferred are a phenyl group, a tolyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl group, and a terphenyl group.

In addition, R ^{15 to} R ²¹ may form a ring by bonding adjacent substituents to each other. Specific examples thereof include a benzene ring, a cyclohexyl ring, a pyridine ring, a pyrrole ring, and a thiophene ring. Etc.

Next, in the general formula [4], R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, or Represents a substituent. R ^{22 to} R ²⁵ each independently represents a hydrogen atom or a substituent, and at least one of R ^{22 to} R ²⁵ is a carbazolyl group represented by the general formula [3]. R ^{3 to} R ¹⁰ may form a ring by bonding adjacent substituents to each other.

  As an alkyl group shown here, it is synonymous with what was described by General formula [1].

In addition, the substituents of R ^{3 to} R ¹⁰ and R ^{22 to} R ²⁵ are a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent aliphatic group. Aromatic heterocyclic group, halogen atom, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, trialkylsilyl group, cyano group, An amino group etc. are mention | raise | lifted and it is synonymous with what was described by General formula [1].

Further, at least one of R ^{22 to} R ²⁵ is a carbazolyl group represented by the general formula [3], and in particular, either one of R ²² and R ²³ and one of R ²⁴ and R ^25. More preferably, a carbazolyl group is bonded to. This is because the amino group-substituted benzene ring bonded to the diketopyrrolopyrrole ring behaves as an electron-donating substituent, and as an electronic effect based on this, the absorption wavelength of the molecule is increased. . A carbazolyl group is effective as a substituent that further enhances this effect.

Further, the number of substitution by the carbazolyl group can be the longest wavelength (deep red) by replacing all positions of R ^{22 to} R ^{25 with} the carbazolyl group. However, the molecular weight of these diketopyrrolopyrrole compounds is preferably 2000 or less, and more preferably 1500 or less. This is because, when the molecular weight is large, there is a concern that the vapor deposition property in the case of producing an element by vapor deposition is deteriorated. For these reasons, the case where a rubazolyl group is bonded to one of R ²² and R ²³ and one of R ²⁴ and R ²⁵ is most preferable.

Further, R ^{3 to} R ¹⁰ may form a ring by bonding adjacent substituents to each other. Specific examples thereof include a benzene ring, a cyclohexyl ring, a pyridine ring, a pyrrole ring, and a thiophene ring. And so on.

Next, in the general formula [5], R ¹ and R ² each independently represent a hydrogen atom and a substituted or unsubstituted alkyl group, and R ^{3 to} R ¹⁰ and R ^{15 to} R ⁵² are Each independently represents a hydrogen atom or a substituent. Moreover, R < ³ > -R < ¹⁰ > and R < ¹⁵ > -R < ⁵² > may combine adjacent substituents mutually and may form a ring.
The substituted or unsubstituted alkyl shown here is as defined in the general formula [1], preferably a substituted or unsubstituted alkyl group, particularly preferably a methyl group, an ethyl group, Examples thereof include a propyl group and a benzyl group.

The substituents R ^{3 to} R ¹⁰ and R ^{15 to} R ⁵² are a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent group. Aromatic heterocyclic group, halogen atom, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, trialkylsilyl group, cyano group And amino groups, etc., which are synonymous with those described in the general formula [1].
In addition, R ^{3 to} R ¹⁰ and R ^{15 to} R ⁵² are examples in which adjacent substituents are bonded to each other to form a ring, such as a benzene ring, a cyclohexyl ring, a pyridine ring, a pyrrole ring, and a thiophene ring. For example, R ⁴⁶ and R ⁴⁷ form a ring to form naphthalene.

  By the way, the effect of the carbazolyl group bonded at the 3-position will be mentioned. Usually, the amino group acts as an electron donor, but the nitrogen atom of carbazole has almost no donor property with respect to the substituent bonded on the nitrogen atom. This is because the carbazole ring has planarity and is a very bulky substituent, and it is caused by difficulty in taking a planar structure with the substituent on the nitrogen atom. Conceivable. On the other hand, since the carbazole ring has ring planarity, it can be electron donor to the benzene ring portion (see Chemical Formula 7).

  Therefore, in the diaminoarylene compound having a carbazolyl group bonded at the 3-position of the present invention, both the amino group bonded to the carbazole ring and the nitrogen atom of the carbazole ring serve as electron donors to the benzene ring of the carbazole ring. Therefore, it is considered that an electron donor effect equivalent to or higher than that of the phenylenediamine structure can be exhibited (see Chemical Formula 8).

  For these reasons, the diketopyrrolopyrrole compound having a carbazolyl group of the present invention can have a longer wavelength.

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

  Hereinafter, typical examples of the amine compound represented by the general formula [1] that can be used as the material for the organic EL element of the present invention are shown in Table 1, but the present invention is not limited thereto.

Table 1

Next, the amine compound represented by the general formula [6] used in the present invention will be described.
Ar ² in the general formula [6] represents a substituted or unsubstituted perylenyl group, and R ⁵³ and R ⁵⁴ each independently represents a substituted or unsubstituted monovalent aromatic hydrocarbon group, or a substituted or unsubstituted group. A substituted monovalent aromatic heterocyclic group. Ar ² and R ⁵³ , Ar ² and R ⁵⁴ , and R ⁵³ and R ⁵⁴ may combine with each other to form a ring.

Here, examples of the unsubstituted perylenyl group include a 1-perylenyl group, a 2-perylenyl group, and a 3-perylenyl group. These perylenyl groups may be further substituted with other substituents. As the substituent for Ar ^1, a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group, a halogen atom, an alkoxyl group, Aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, trialkylsilyl group, cyano group and the like can be mentioned.

R ⁵³ and R ⁵⁴ are monovalent organic residues selected from a substituted or unsubstituted monovalent aromatic hydrocarbon group, or a substituted or unsubstituted monovalent aromatic heterocyclic group. The substituent for R ⁵³ and R ⁵⁴ has the same meaning as the substituent described for the substituent for Ar ¹ .

  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. Can be given.

  Examples of the alkyl group, alkenyl group, alkynyl group, and cycloalkyl group mentioned here are the same as those in the general formula [1].

Furthermore, examples of the monovalent aromatic hydrocarbon group include monovalent monocyclic, condensed ring, and ring-aggregated aromatic hydrocarbon groups having 6 to 30 carbon atoms.
Here, the monovalent monocyclic aromatic hydrocarbon group having 6 to 30 carbon atoms, the monovalent condensed ring aromatic hydrocarbon group, and the monovalent ring assembly aromatic hydrocarbon group may be represented by the general formula [1] to This is synonymous with that described in [5].

  Also, monovalent aliphatic heterocyclic group, monovalent aromatic heterocyclic group, halogen atom, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl Examples of the group, arylsulfonyl group and trialkylsilyl group include those described in the general formulas [1] to [5].

  These substituents may be further substituted by the substituents described in the general formulas [1] to [5], and these substituents may be bonded to each other to form a ring.

Ar ² in the general formula [6] described above includes a substituted or unsubstituted 1-perylenyl group, a substituted or unsubstituted 2-perylenyl group, and a substituted or unsubstituted 3-perylenyl group. Of these, a substituted or unsubstituted 3-perylenyl group is preferable, and an unsubstituted 3-perylenyl group is particularly preferable.

Moreover, as carbon number in the substituent of Ar < ² >, R ^<53> , R ^<54 > mentioned above, 1-18 are preferable and 1-12 are more preferable. The reason for this is that if the carbon number of these substituents increases, there is a concern that the vapor deposition property when an element is formed by vapor deposition is deteriorated.

  The amine compound represented by the general formula [6] used in the present invention has been described above. The molecular weight of these amine compounds is preferably 2000 or less, more preferably 1500 or less, and particularly preferably 1000 or less. This is because, when the molecular weight is large, there is a concern that the vapor deposition property in the case of producing an element by vapor deposition is deteriorated.

  Table 2 below shows typical examples of amine compounds represented by the general formula [6] that can be used as the material for the organic EL device of the present invention, but the present invention is not limited to these ( In the table, t-Bu represents a tert-butyl group, Ph represents a phenyl group, and Tol represents a p-tolyl group).

Table 2

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

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

For the hole injection layer, a hole injection material that exhibits an excellent hole injection effect with respect to the light emitting layer and that can form a hole injection layer excellent in adhesion to the anode interface and thin film formability is used. In addition, when such materials are laminated in multiple layers and a material having a high hole injection effect and a material having a high hole transport effect are laminated, the materials used for each are called a hole injection material and a hole transport material. Sometimes. The organic electroluminescent element material of the present invention can be suitably used for both hole injection materials and hole transport materials. These hole injection materials and hole transport materials need to have high hole mobility and low ionization energy, usually 5.5 eV or less. Such a hole injection layer is preferably a material that transports holes to the light emitting layer with a lower electric field strength, and further has a hole mobility of at least when an electric field of 10 ⁴ to 10 ⁶ V / cm is applied. What is 10 ^<-6 > cm ^{< 2} > / V * second is preferable. Other hole injection materials and hole transport materials that can be used by mixing with the organic electroluminescence device material of the present invention are not particularly limited as long as they have the above-mentioned preferable properties. An arbitrary material can be selected and used from those commonly used as a charge transport material for holes in an optical transmission material and known materials used for a hole injection layer of an organic EL element.

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

  As the hole injecting material and the hole transporting material, those described above can be used. Porphyrin compounds (Japanese Patent Laid-Open No. 63-295965), aromatic tertiary amine compounds and styrylamine compounds (US Pat. No. 4,127,412, JP-A-53-27033, 54-58445, 54-149634, 54-64299, 55-79450, 55-144250 No. 56-119132, No. 61-295558, No. 61-98353, No. 63-295695, etc.) can also be used. For example, 4,4′-bis (N- (1-naphthyl) -N-phenylamino) biphenyl having two condensed aromatic rings in the molecule described in US Pat. No. 5,061,569, etc. And 4,4 ′, 4 ″ -tris (N- (3-methylphenyl)-, 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 (material for organic EL device), the following general formulas [7] to [12] can be used.

General formula [7]

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

Here, as an alkoxyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, an octyloxy group, a tert-octyloxy group, a 2-bornyloxy group, a 2-isobornyloxy group, 1- Examples thereof include an alkoxyl group having 1 to 18 carbon atoms such as an adamantyloxy group. In particular, as a preferable combination of R ^{a11 to} R ^a14 of the general formula [15], it is preferable that all of R ^{a11 to} R ^a14 are a methoxy group, an ethoxy group, or a cyano group.

General formula [8]

(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.)

In the general formula [13], as a 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, A 9,10-phenanthrylene group and a 9,10-anthrylene group are preferred, and a single bond, vinylene group, p-phenylene group, and 1,4-naphthylene group are more preferred. R ^{a21 to} R ^a26 include a monovalent aromatic hydrocarbon group selected from a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group. preferable.

General formula [9]

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

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

Formula [10]

(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 [11]

(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 [12]

(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 [7] to [12] described above are particularly preferably used as hole injection materials. Table 3 below shows particularly preferred examples.

Table 3

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

Table 4

  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 [13].

Formula [13]

(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.

In general formula [13], as Ar ^r1 and Ar ^r2 , preferred monovalent aromatic hydrocarbon groups are substituted with a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group. 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group are preferable, and preferable monovalent nitrogen-containing aromatic heterocyclic groups are monovalent A 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2,2′-bipyridyl-3-yl group, which may be substituted with an aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group, and A 2,2′-bipyridyl-4-yl group can be mentioned.

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

Table 5

  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 [14].

General formula [14]

(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 6 shows specific examples of triazole derivatives that can be used in the present invention.

Table 6

  Among the electron injection materials that can be used in the present invention, particularly preferred silole derivatives include silole derivatives represented by the following general formula [15].

General formula [15]

(In the formula, R ^p1 and R ^p2 are each independently a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or a 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 7 shows specific examples of silole derivatives that can be used in the present invention.

Table 7

  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. The triaryl phosphine oxide derivative described in Japanese Patent No. -204140 and the triaryl phosphine oxide derivative represented by the following general formula [16] can be shown.

Formula [16]

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

Table 8

  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). .

  Moreover, when using the organic EL element material of this invention for a light emitting layer, you may contain another host material and a dopant. In this case, the dopant concentration is preferably contained in the range of 0.001 to 30% by weight with respect to the host material, more preferably in the range of 0.01 to 10% by weight, More preferably, it is contained in the range of ˜5% by weight.

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.

As a method for forming each layer of the organic EL device of the present invention, a dry film forming method such as vacuum deposition, electron beam irradiation, sputtering, plasma, ion plating, or spin coating, dipping, flow coating, etc. , A wet film forming method such as an ink jet method, a method of depositing a light emitter on a donor film, and Japanese Patent Application Laid-Open No. 2002-534782 and S.A. T.A. Lee, et al. Proceedings of SID'02, p. LITI (Laser Induced Thermal Imaging) method described in 784 (2002), printing (offset printing, flexographic printing, gravure printing, screen printing), inkjet, and the like can also be applied.
The organic layer is particularly preferably a molecular deposited film. Here, the molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidifying from a material compound in a solution state or a liquid phase state. Can be classified from a thin film (accumulated film) formed by the LB method according to a difference in an agglomerated structure and a higher-order structure and a functional difference resulting therefrom. Also, as disclosed in JP-A-57-51781, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, and then this is thinned by a spin coat method or the like. Also, an organic layer can be formed. The film thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Conversely, if the film thickness is too thin, the pinhole is used. Or the like, and even when an electric field is applied, it is difficult to obtain sufficient light emission luminance. Accordingly, the thickness of each layer is suitably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.

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

  The current applied to the organic EL element of the present invention is usually a direct current, but a pulse current or an alternating current may be used. The current value and 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).

  The main methods of the full color method of the organic EL element of the present invention include a three-color coating method, a color conversion method, and a color filter method. In the three-color coating method, there are a vapor deposition method using a shadow mask, an ink jet method and a printing method. In addition, Special Tables 2002-534882 and S.A. T.A. Lee, et al. , Proceedings of SID'02, p. 784 (2002) can also be used. The laser thermal transfer method (also referred to as Laser Induced Thermal Imaging, LITI method) can also be used. In the color conversion method, a blue light emitting layer is used to convert green and red having a longer wavelength than blue through a color conversion (CCM) layer in which fluorescent dyes are dispersed. The color filter method uses a white light emitting organic EL element to extract light of three primary colors through a color filter for liquid crystal. In addition to these three primary colors, a part of white light is directly extracted and used for light emission. Thus, the luminous efficiency of the entire device can be increased.

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 technique for controlling the emission wavelength extracted from the element by actively utilizing the multiple interference effect 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 can obtain red light emission exhibiting high color purity and luminance at a low driving voltage. Therefore, this organic EL device can be applied to flat panel displays and flat light emitters such as wall-mounted TVs, light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display boards, and indicator lights. Can be considered.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following Example.

Synthesis method of the compound of the present invention Each compound was synthesized by combining the following reaction formulas 1 to 6.
[In the reaction formulas 1 to 6, Ar ³ is synonymous with Ar ¹ described in the general formula [3], Ar ⁴ is synonymous with R ¹³ and R ¹⁴ described in the general formula [2], R and R ^′ are synonymous with R ¹ and R ² described in the general formula [1], and Pr represents a propyl group. ]

Reaction formula 1

Reaction formula 2

Reaction formula 3

Reaction formula 4

Reaction formula 5

Reaction formula 6

  3BrCz in reaction formula 2 is brominated at the 3-position of the carbazole derivative with reference to the Industrial Chemical Journal, published 1967, volume 70, page 63, and then reacted with the iodobenzene derivative by the Ullmann method using a copper catalyst. Was synthesized.

  The Ullman method is a coupling reaction of aryl iodide and arylamine, in which a copper powder and a base such as anhydrous potassium carbonate are reacted at a temperature of about 100 to 180 ° C. in a high boiling point solvent such as nitrobenzene. The method known in the industry described in 7-126226 etc. was referred.

The synthesis of arylamine by the Ullmann method could also be used for the synthesis in Reaction Scheme 6.
In the reaction of aryl bromide and arylamine in the reaction formulas 1, 3 and 6, a method in which a palladium compound and a phosphorus compound are used as a catalyst in the presence of a base instead of the copper powder and base used in the Ullman method. I used. Regarding this method, JP-A-10-81667, JP-A-10-139742, JP-A-10-310561, John F. et al. By Hartwig, Angew. Chem. Int. Ed. 37, 2046-2067 (1998), Bryant H., et al. Yang, Stephen L Buchwald, J.A. Organomet. Chem. 576, 125-146 (1999), John P. et al. Wolfe, Stephen L Buchwald, J.A. Org. Chem. 65, 1144-1157 (2000), John P. Wolfe, Stephen L Buchwald, J.A. Org. Chem. 62, 1264-1267 (1997), Janis Louie, Michael S., et al. Driver, Blake C .; Hammann, John F. By Hartwig, J.H. Org. Chem. 62, pp. 1268 to 1273 (1997), JP-A 63-35548, JP-A 6-100503, JP 2001-515879, and re-published patent WO 2002/076922.
In addition, the synthesis method of 1,4-diketopyrrolo (3,4-C) pyrrole in Reaction Scheme 4 was referred to the method described in Journal of Coatings Technology, 60 , 37 (1988).

  Further, the synthesis method of 1,4-diketopyrrolo (3,4-C) pyrrole substituted with N-alkyl in the reaction formula 5 was referred to the method described in JP-A-7-188234.

Example 1
Synthesis Method of Compound (7) in Table 1 Under a nitrogen stream, 5.2 g of 3-bromo-9-ethylcarbazole and aniline in 10 g of 1,3-dimethyl-2-imidazolidinone in a four-necked flask 2.3 g, 2.0 g of anhydrous potassium carbonate, and 0.2 g of copper powder were heated and stirred at 200 ° C. for 10 hours. After completion of the reaction, extraction was performed with 100 g of toluene, and the toluene layer was concentrated. Purification by column chromatography using silica gel yielded 4.2 g of a white solid. It was confirmed by molecular weight analysis by FD-MS that it was 3-aminophenyl-9-ethylcarbazole.
Under a nitrogen stream, 11.2 g (100 mmol) of tert-butoxypotassium and 18.2 g (1000 mmol) of 4-bromophenyl-1-carbonitrile were added at room temperature in 53 ml of tert-pentyl alcohol in a four-necked flask. To do. Thereafter, the temperature was raised to 97-99 ° C., and 6.7 g (33 mmol) of diisopropyl succinate was added dropwise at this temperature. During the addition, the temperature of the reaction was maintained at 97-99 ° C. After completion of the dropping, stirring was performed for 3 hours at the same temperature while removing isopropyl alcohol as a by-product from the system. Thereafter, the mixture was cooled to 60 ° C., and at this temperature, a mixed solution of 12.0 g of acetic acid and 240 g of methanol was added dropwise. After completion of the addition, reflux heating was performed for 3 hours. Next, after cooling to room temperature, the precipitated crystals were filtered, washed with methanol, and dried at 70 ° C. Further, the mixture was heated in DMF at 100 ° C. for 30 minutes and then filtered while hot, and washed with DMF and methanol. By drying at 70 ° C., 13.8 g of dark red powder was obtained. It was confirmed from the results of mass spectrometry, infrared spectroscopy, and elemental analysis on carbon, hydrogen, and nitrogen that this substance was the compound (I) represented by the above reaction formula 4.

13.2 g (30 mmol) of the compound (I) represented by the reaction formula 4 obtained by the above method is suspended in 216 g of dimethylacetamide and heated to 50 ° C. with stirring. At this temperature, 8.7 g (90 mmol) of tert-butoxy sodium are added and stirred at 50 ° C. for 30 minutes. Next, 14.1 g (90 mmol) of ethyl iodide is added dropwise, and after completion of the addition, stirring is performed at 50 ° C. for 2 hours. When the reaction solution is cooled to room temperature and gradually poured into a mixed solution of 300 g of water and 90 g of methanol, red crystals are precipitated and become a suspended state. The mixture was stirred at room temperature for 1 hour, filtered, washed with water, washed with methanol and dried to obtain 8.5 g of a red powder. Results of mass spectrometry, nuclear magnetic resonance spectroscopy, infrared spectroscopy, and elemental analysis on carbon, hydrogen, and nitrogen that this substance is a compound represented by reaction formula 5 (II; R = C ₂ H ₅ ) Confirmed from.

Under a nitrogen stream, 7.15 g (2.5 mmol) of 3-aminophenyl-9-ethylcarbazole and 5.00 g (1.0 mmol) of acetic acid in the above compound (II; R = C ₂ H ₅ ) in a four-necked flask 0.012 g of palladium, 0.040 g of tri-tert-butylphosphine, and 1.12 g of potassium carbonate were placed in a 50 ml four-necked flask, 20 ml of dehydrated xylene was added, and the mixture was heated to reflux for 2 hours. The reaction solution was poured into 200 ml of methanol, and the precipitated solid was collected by filtration and dried in a hot vacuum. As a crude product, 7.2 g of Compound (7) was obtained. The resulting crude product was purified by silica gel column chromatography. The ionization potential of this compound (7) was 5.3 eV (AC-1 manufactured by Riken Keiki). The compound was confirmed by mass spectrum. The results are shown in Table 9. (Made by Bruker Daltonics, Autoflex II) Moreover, it identified by < ¹ > H-NMR and < ¹³ > C-NMR.

Example 2
Synthesis Method of Compound (8) in Table 1 6.4 g of 3-bromo-9-phenylcarbazole in 10 g of 1,3-dimethyl-2-imidazolidinone in a four-necked flask under a nitrogen stream Then, 2.3 g of aniline, 2.0 g of anhydrous potassium carbonate, and 0.2 g of copper powder were heated and stirred at 200 ° C. for 10 hours. After completion of the reaction, extraction was performed with 100 g of toluene, and the toluene layer was concentrated. Purification was performed by column chromatography using silica gel to obtain 5 g of a white solid. It was confirmed by molecular weight analysis by FD-MS that it was 3-phenyl-9-phenylcarbazole.

Under a nitrogen stream, in a four-necked flask, 8.35 g (2.5 mmol) of 3-aminophenyl-9-phenylcarbazole and 5.00 g (1.0 mmol) of palladium acetate 0.012 g of the above compound (II), 0.040 g of tri-tert-butylphosphine and 1.12 g of potassium carbonate were placed in a 50 ml four-necked flask, 20 ml of dehydrated xylene was added, and the mixture was heated to reflux for 2 hours. The reaction solution was poured into 200 ml of methanol, and the precipitated solid was collected by filtration and dried in a hot vacuum. 9.5 g of compound (8) was obtained as a crude product. The resulting crude product was purified by silica gel column chromatography. The ionization potential of this compound (8) was 5.3 eV (AC-1 manufactured by Riken Keiki). The compound was confirmed by mass spectrum. The results are shown in Table 9. (Made by Bruker Daltonics, Autoflex II) Moreover, it identified by < ¹ > H-NMR and < ¹³ > C-NMR. A ¹ H-NMR spectrum of the compound (8) (manufactured by JEOL Ltd., GSX-270W) is shown in FIG.

Examples 3-48
The compounds of the present invention described in Table 1 could be synthesized by combining reaction formulas 1 to 6 or a similar reaction. The structure of the obtained compound was confirmed by mass spectrum (manufactured by Bruker Daltonics, Autoflex II). The results are shown in Table 9. The compound numbers are the same as those in Table 1.

Table 9

Examples of Organic EL Device The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In the examples, all mixing ratios are weight ratios unless otherwise specified. The vacuum deposition method was performed in a vacuum of 10 ⁻⁶ Torr and without temperature control such as substrate heating and cooling. In the evaluation of the light emission characteristics of the element, the characteristics of an organic EL element having an electrode area of 2 mm × 2 mm were measured. Compound (A) and compound (B) were synthesized according to the method described in the literature (Journal of the Chemical Society of Japan, 11, 1540 (1991)). Compound (C) and compound (D) were synthesized using Reaction Schemes 1-6.

Example 49
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid, BAYTRON P VP CH8000 manufactured by Bayer) manufactured by a spin coat method on the cleaned glass plate with an ITO electrode A hole injection layer having a thickness of 40 nm was obtained. Next, 60% PVK (polyvinylcarbazole) and 3% of the compound (7) in Table 1 as a diketopyrrolopyrrole compound and 37% of the electron transport material (compound (A)) were dissolved in toluene at a concentration of 2.0 wt%. Then, a light emitting layer having a thickness of 70 nm was obtained by a spin coating method. Furthermore, after depositing 20 nm of Ca thereon, 200 nm of Al was deposited to form an electrode to obtain an organic EL device. When an energization test was performed on this device, red light emission with a maximum light emission luminance of 300 cd / m ² was obtained.

Compound (A)

Example 50
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid, BAYTRON P VP CH8000 manufactured by Bayer) manufactured by a spin coat method on the cleaned glass plate with an ITO electrode A hole injection layer having a thickness of 40 nm was obtained. Next, 60% of PVK (polyvinylcarbazole) and 3% of the compound (8) in Table 1 as a diketopyrrolopyrrole compound and 37% of the electron transport material (compound (B)) were dissolved in toluene at a concentration of 2.0 wt%. Then, a light emitting layer having a thickness of 70 nm was obtained by a spin coating method. Furthermore, after depositing Ca to 20 nm thereon, Al was deposited to 200 nm to form an electrode to obtain an organic EL device (50). When an energization test was performed on this device, red light emission with a maximum light emission luminance of 380 cd / m ² was obtained. The EL emission spectrum of this organic EL element (50) is shown in FIG.

Compound (B)

Example 51
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid, BAYTRON P VP CH8000 manufactured by Bayer) manufactured by a spin coat method on the cleaned glass plate with an ITO electrode A film was formed by spin coating to obtain a hole injection layer having a thickness of 40 nm. Next, 30% PVK (polyvinylcarbazole) and 1.5% of the compound (7) in Table 1 as a diketopyrrolopyrrole compound, 48.5% of the compound (78) in Table 2, and an electron transport material (compound (A )) 20% was dissolved in toluene at a concentration of 2.0 wt%, and a light emitting layer having a thickness of 70 nm was obtained by a spin coating method. Furthermore, after depositing 20 nm of Ca thereon, 200 nm of Al was deposited to form an electrode to obtain an organic EL device. When an energization test was performed on this device, red light emission with a maximum light emission luminance of 8000 cd / m ² was obtained.

Example 52
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid, BAYTRON P VP CH8000 manufactured by Bayer) manufactured by a spin coat method on the cleaned glass plate with an ITO electrode A hole injection layer having a thickness of 40 nm was obtained. Subsequently, 30% of PVK (polyvinylcarbazole) and 1.5% of the compound (8) in Table 1 and 48.5% of the compound (51) in Table 2 as a diketopyrrolopyrrole compound, 48.5% of an electron transport material (compound (A )) 20% was dissolved in toluene at a concentration of 2.0 wt%, and a light emitting layer having a thickness of 70 nm was obtained by a spin coating method. Furthermore, after depositing Ca to 20 nm thereon, Al was deposited to 200 nm to form an electrode to obtain an organic EL device (52). When an energization test was performed on this device, red light emission with a maximum light emission luminance of 12000 cd / m ² was obtained. The EL emission spectrum of this organic EL element (52) is shown in FIG.

Example 53
Α-NPD was vacuum-deposited on the washed glass plate with an ITO electrode to obtain a 20 nm-thick hole transport layer. Subsequently, the compound (7) of Table 1 was vacuum-deposited as a diketopyrrolopyrrole compound, and the light emitting layer with a film thickness of 40 nm was obtained. Next, tris (8-hydroxyquinolinate) aluminum (Alq3) was deposited to obtain an electron injection layer having a thickness of 30 nm. Further thereon, LiF was deposited to a thickness of 0.2 nm, and then Al was deposited to form an electrode having a thickness of 150 nm to obtain an organic EL device. When an energization test was performed on this device, red light emission with a maximum light emission luminance of 5000 cd / m ² was obtained. The half life when driven at a constant current of 500 cd / m ² was 1000 hours.

Examples 54-70
An organic EL device was produced in the same manner as in Example 53 except that the diketopyrrolopyrrole compound shown in Table 3 was used instead of the compound (7). Table 10 shows the maximum light emission luminance and the half life when these elements are driven at a constant current of 500 cd / m ² .

Comparative Example 1 and Comparative Example 2
An organic EL device was produced in the same manner as in Example 53 except that the following comparative compounds (C) and (D) were used in place of the compound (7). All of these devices emitted orange light. Table 10 shows the maximum luminance and the half-life when driven at a constant current of 500 cd / m ² .

化合物（Ｄ） Compound (C)

Compound (D)

Table 10

  As is clear by comparing Examples 53 to 70 and Comparative Examples 1 and 2, by using the compound represented by the general formula [1], deeper red light emission, high maximum light emission luminance, and long half life are obtained. I was able to achieve both.

Example 71
NPD was vacuum-deposited on the washed glass plate with the ITO electrode to obtain a 20 nm-thick hole transport layer. Next, the compound (7) in Table 1 as the diketopyrrolopyrrole compound and the compound (51) in Table 2 as the amine compound were co-evaporated at a composition ratio of 3:95 (weight ratio) to form a light emitting layer having a thickness of 40 nm. Got. Next, tris (8-hydroxyquinolinate) aluminum (Alq3) was deposited to obtain an electron injection layer having a thickness of 30 nm. Further thereon, LiF was deposited to a thickness of 0.2 nm, and then Al was deposited to form an electrode having a thickness of 150 nm to obtain an organic EL device. When this device was subjected to an energization test, red light emission with a maximum light emission luminance of 35000 cd / m ² was obtained. Further, the half-life when driven at a constant current at 500 cd / m ² was 2500 hours.

Example 72 to Example 108
Except that the compound shown in Table 4 was used instead of the compound (7) in Table 1 as the diketopyrrolopyrrole compound, and the compound shown in Table 4 was used instead of the compound (51) in Table 2 as the amine compound, all of Example 71 and An organic EL element was produced in the same manner. Table 11 shows the maximum light emission luminance and half life when these elements are driven at a constant current of 500 cd / m ² .

Comparative Examples 3-4
An organic EL device was produced in the same manner as in Example 71 except that tris (8-hydroxyquinolinato) aluminum (Alq3) was used instead of the compound (51) in Table 2. Table 11 shows the maximum light emission luminance at this time and the half life when driven at a constant current of 500 cd / m ² .

Table 11

  As is clear by comparing Examples 71 to 108 and Comparative Examples 3 to 4, the compound represented by the general formula [1] and the amine compound represented by the general formula [6] were particularly excellent. Performance.

FIG. 1 is a ¹ H-NMR spectrum of compound (8). (In chloroform-d) FIG. 2 is a fluorescence spectrum of the compound (8). (In toluene solvent) FIG. 3 is an EL emission spectrum of the device (50). FIG. 4 is an EL emission spectrum of the device (52).

Claims (6)

The diketopyrrolopyrrole compound represented by the following general formula [1], and a material for an organic electroluminescence element.
General formula [1]

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ^{3 to} R ¹² each independently represent a hydrogen atom or a substituent, At least one of R ^{3 to} R ¹² is an amino group represented by the general formula [2]. Further, among R ^{3 to} R ¹² , adjacent substituents other than the amino group may be bonded to each other to form a ring. ]

General formula [2]

[Wherein, R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent. Further, at least one of R ¹³ and R ^14, or a carbazolyl group represented by the general formula [3], R ¹³ and R ¹⁴ may be bonded to each other to form a ring. ]

General formula [3]

[Wherein Ar ¹ is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or a monovalent heterocyclic ring having 2 to 18 carbon atoms which may have a substituent. Represents a C 1-6 monovalent aliphatic hydrocarbon group which may have a group or a substituent, and R ^{15 to} R ²¹ each independently represents a hydrogen atom, a halogen atom, or a substituent. To express. R ^{15 to} R ²¹ may form a ring by bonding adjacent substituents to each other. ] The material for organic electroluminescent elements according to claim 1, wherein the diketopyrrolopyrrole compound represented by the general formula [1] is a diketopyrrolopyrrole compound represented by the following general formula [4].
General formula [4]

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ^{3 to} R ¹⁰ each independently represent a hydrogen atom or a substituent. R ^{22 to} R ²⁵ each independently represents a hydrogen atom or a substituent, and at least one of R ^{22 to} R ²⁵ is a carbazolyl group represented by the general formula [3]. R ^{3 to} R ¹⁰ may form a ring by bonding adjacent substituents to each other. ] The diketopyrrolopyrrole compound represented by the general formula [4] is a diketopyrrolopyrrole compound represented by the following general formula [5].
General formula [5]

[Wherein, R ¹ and R ² each independently represent a hydrogen atom and a substituted or unsubstituted alkyl group, and R ^{3 to} R ¹⁰ and R ^{15 to} R ⁵² each independently represent a hydrogen atom. Or represents a substituent. Moreover, R < ³ > -R < ¹⁰ > and R < ¹⁵ > -R < ⁵² > may combine adjacent substituents mutually and may form a ring. ] The organic electroluminescent element material which contains the organic electroluminescent element material in any one of Claim 1 thru | or 3, and the amine compound represented by General formula [6].


General formula [6]

[In the formula, Ar ² represents a substituted or unsubstituted perylenyl group, R ⁵³ and R ⁵⁴ each independently represents a substituted or unsubstituted monovalent aromatic hydrocarbon group, or a substituted or unsubstituted monovalent group. An aromatic heterocyclic group. Ar ² and R ⁵³ , Ar ² and R ⁵⁴ , and R ⁵³ and R ⁵⁴ may combine with each other to form a ring. ] 5. The organic electroluminescence device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes composed of an anode and a cathode, wherein at least one layer is according to claim 1. An organic electroluminescence device comprising a material for an organic electroluminescence device. 5. The organic electroluminescent device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes composed of an anode and a cathode, wherein the light emitting layer is according to claim 1. An organic electroluminescence device comprising a material for an organic electroluminescence device.

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