JP5907233B1 - Material for organic electroluminescence device and use thereof - Google Patents

Abstract

When used in an organic EL device, it can be formed by vapor deposition or spin coating, and has excellent performance ((high glass transition temperature, high luminous efficiency, low voltage drive, high color purity, long life, deep The present invention provides a material for an organic EL device that exhibits red (long wavelength), and can be suitably used particularly for a red light emitting material. The thiophene ring further has a substituent having a specific structure. [Selection] None

Description

The present invention relates to a material for a novel organic electroluminescence element (hereinafter abbreviated as an organic EL element) used for a planar light source and display and its use. More specifically, when used in an organic EL device, it can be formed by vapor deposition or spin coating, and has excellent performance (high glass transition temperature, high luminous efficiency, low voltage drive, high color purity, long life, deep The present invention relates to a material for an organic EL element that exhibits red (long wavelength light emission) and can be suitably used particularly for a red light emitting material.

In recent years, organic EL elements have been required to have a long lifetime. There are various factors that can affect the lifetime of the device. One of the factors is considered to be that the glass transition temperature (Tg) of the material constituting the device has a significant effect on the lifetime of the device. . That is, it is pointed out that when the temperature of the element exceeds the Tg of the constituent material due to the use environment of the element or the heat generated during driving, the constituent material is crystallized and a non-light emitting region called a dark spot is generated. ing. Therefore, a material having a higher Tg has been demanded (Non-Patent Document 1).

Among these organic EL elements, organic EL elements that emit red light have been researched on elements using various materials because of their usefulness. However, a small amount of dopant is co-deposited in the host material. A method of forming a light emitting layer by mixing by a method and obtaining light emission from a dopant has been studied as an effective method (Non-Patent Document 2). In this method, Tris (8-
Hydroxyquinolinato) Aluminum as host material, DCM, DCJ, DCJT, D
An organic EL device that emits orange to red light using a 4H-pyran derivative such as CJTB as a dopant has been reported.

Moreover, several patents are reported about the organic EL element using the compound which has a 1, 4- diketopyrrolo (3,4-c) pyrrole structure known as a red pigment (patent documents 1-6). However, all of them have 1,4-diketopyrrolo (3,4) having a benzene ring.
-C) A pyrrole structure.

On the other hand, 1,4-having a hetero ring called a pyrrole ring, a furan ring or a thiophene ring
Diketopyrrolo (3,4-c) pyrrole derivatives have been reported to have longer absorption wavelengths (Patent Document 7). However, since the crystallinity is high, there is a disadvantage that the lifetime of the element is short and it is difficult to be a practical material.

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 JP 2010-235870 A Japanese Patent Application Laid-Open No. 2006-117591

The subject of the present invention is an organic EL device for obtaining red high-luminance emission described in the prior art,
An organic EL device using a 4H-pyran derivative as a dopant has a problem that the emission color is insufficient, the driving voltage is high, and the emission luminance is low. In addition, 1,4-diketopyrrolo (3
, 4-c) Although an organic EL device using a compound having a pyrrole structure as a dopant can produce a device with high color purity, concentration quenching easily occurs due to high molecular cohesion, and doping concentration control Has become an important issue. Therefore, there has been a demand for a material for an organic EL element capable of obtaining deep red light emission of high color purity showing high light emission luminance and long life 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 organic electroluminescent element material represented by the following general formula [ 5 ] and / or the following general formula [ 6 ].
General formula [ 5 ]


(Wherein R ²⁶ and R ²⁷ each independently represents an unsubstituted alkyl group,
R ^{28 to} R ³¹ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted silyl group, or a substituted amino group. Represent. )
General formula [ 6 ]



(Wherein R ³² and R ³³ each independently represents an unsubstituted alkyl group,
R ^{34 to} R ³⁷ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted silyl group, or a substituted amino group. Represent. )

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 present invention also relates to the above organic electroluminescent device, wherein the light emitting layer contains a perylene derivative as a host material.

Moreover, this invention relates to the organic electroluminescent element whose light emitting layer is the coating film formed material of the said organic electroluminescent element material .

Moreover, this invention relates to the ink composition for organic electroluminescent elements which consists of the said organic electroluminescent element material and an organic solvent.

The organic EL device material containing the compound of the present invention has a high color purity and deep (long wavelength) red light emission due to the specific structure of the material, hardly causes concentration quenching, has high light emission luminance and long life. It is characterized by being compatible. Furthermore, the organic EL element created using this material is
It can be suitably used as a flat panel display such as a wall-mounted television 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 boards, and indicator lights. . In particular, it is suitable for applications that are difficult in the prior art, such as agricultural light sources adapted to the absorption band of chlorophyll due to the deep red color, and medical sensors that utilize the difference between red and near infrared absorption characteristics depending on the presence or absence of oxygen in hemoglobin. I can do it.

  Hereinafter, embodiments of the present invention will be described in detail.

In the organic EL element material represented by the general formula [5], R ²⁶ and R ²⁷ each independently represents an unsubstituted alkyl group, R ²⁸ to R ³¹ are independently a hydrogen atom, a substituted or unsubstituted alkyl group, substitution or unsubstituted alkoxyl group, a substituted or unsubstituted Ari - aryloxy group, substitution silyl group, or a substituted amino group.

Examples of the unsubstituted alkyl group represented by R ²⁶ and R ^{27 in} the present invention include a linear alkyl group, a cyclic alkyl group, and an aliphatic heterocyclic group. The linear alkyl group includes a methyl group, an ethyl group, and the like. Propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, octadecyl group, etc. Examples thereof include a linear alkyl group having 1 to 18 carbon atoms.

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.

Examples of the substituted alkyl group include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a benzyl group, a 4-biphenylylmethyl group, a 4- (p-terphenylyl) methyl group, 1-
Naphthylmethyl group, 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-phenanthryl) 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-iso Benzofuranylmethyl 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.

Examples of the aliphatic heterocyclic group include 1,3-dioxolanyl group, 1,3-dioxanyl group, 1,4-dioxanyl group, 2-tetrahydrofuryl group, 2-morpholino group, 4-morpholino group, piperidino group and the like. And a monovalent aliphatic heterocyclic group having 3 to 18 carbon atoms.

The unsubstituted alkyl group for R ^{28 to} R ^{31 in} the present invention has the same meaning as the unsubstituted alkyl group for R ²⁶ and R ²⁷ .

As the unsubstituted alkoxyl group of R ^{28 to} R ^{31 in} the present invention, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, an octyloxy group, a tert-octyloxy group, and the like. Of the alkoxyl group.

Examples of the unsubstituted aryloxy group for R ^{28 to} R ^{31 in} the present invention include a phenoxy group, a 4-tert-butylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a 9-anthryloxy group. Examples include aryloxy groups having 6 to 14 carbon atoms.

In the present invention, the substituted silyl group of R ^{28 to} R ³¹ is a substituted or unsubstituted alkyl group, or a silyl group substituted by a substituted or unsubstituted aryl group, and includes a monoalkylsilyl group and a monoarylsilyl group. And substituted silyl groups such as a group, a dialkylsilyl group, a diarylsilyl group, a trialkylsilyl group, and a triarylsilyl group.

Here, as the monoalkylsilyl group, a monomethylsilyl group, a monoethylsilyl group,
Examples thereof include monoalkylsilyl groups such as a monobutylsilyl group, a monoisopropylsilyl group, a monodecanesilyl group, a monoicosanesilyl group, and a monotriacontanesilyl group.

As the monoarylsilyl group, a monophenylsilyl group, a monotolylsilyl group,
Examples thereof include monoarylsilyl such as mononaphthylsilyl group and monoanthrylsilyl group.

Examples of the dialkylsilyl group include dialkylsilyl groups such as dimethylsilyl group, diethylsilyl group, dimethylethylsilyl group, diisopropylsilyl group, dibutylsilyl group, dioctylsilyl group, and didecanesilyl group.

Examples of the diarylsilyl group include diarylsilyl such as diphenylsilyl group and ditolylsilyl group.

Examples of the trialkylsilyl group include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, dimethylethylsilyl group, triisopropylsilyl group, tributylsilyl group, and trioctylsilyl group.

Examples of the triarylsilyl group include triarylsilyl groups such as a triphenylsilyl group and a tolylsilylsilyl group.

As the substituted amino group of R ^{28 to} R ^{31 in} the present invention, examples of the substituted amino group include 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 Examples thereof include substituted amino groups having 2 to 26 carbon atoms such as -α-naphthyl-N-phenylamino group and N-β-naphthyl-N-phenylamino group.

In the organic EL element material represented by one general formula [6], it is a unsubstituted alkyl group for R ³² and R ^33, the same meaning as the alkyl group unsubstituted in R ²⁶ and R ^27.

In the organic EL element material represented by one general formula [6], unsubstituted alkyl groups R ³⁴ to R ^37, unsubstituted alkoxyl group, unsubstituted ant - aryloxy group, substitution silyl group, or, the substituted amino group, an alkyl group unsubstituted in R ²⁸ to R ^31, unsubstituted alkoxyl group, unsubstituted ant - aryloxy group, substitution silyl group or, the same meanings as substituted amino group.

Mentioned above, an alkyl group, A Rukokishiru group, ant - aryloxy group, silyl group, or an amino group additionally the general formula [5] may be substituted by a substituent described in. These substituents may be bonded to each other to form a ring.

Table 1 below shows typical examples of the organic EL element material represented by the general formula [5] and the general formula [6] that can be used as the organic EL element material of the present invention. It is not limited to these.

  Next, the perylene derivative used in the present invention will be described.

Table 2 below shows typical examples of perylene derivatives that can be used as the organic EL device material of the present invention, but the present invention is not limited to these.

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 / hole injection layer / light emission layer / hole blocking layer / electron injection layer / cathode, (6) anode / hole injection layer / hole transport layer / light emitting layer / Hole blocking layer / electron injection layer / cathode, (7) anode / light emitting layer / hole blocking layer / electron injection layer / cathode, (8) anode / light emitting layer / electron injection layer / cathode, etc. An element configuration can be 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. As such a hole injection layer, a material that transports holes to the light emitting layer with a lower electric field strength is preferable, and the mobility of holes is, for example, when an electric field of 10 ⁴ to 10 ^6-6 V / cm is applied. , At least 10 ^-6 cm
Those having ² / V · sec are preferred. 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). No. 447, etc.), imidazol derivatives (Japanese Patent Publication No. 37-16096)
No. 3,615,402), polyarylalkane derivatives (US Pat. No. 3,615,402,
3,820,989, 3,542,544, JP-B-45-55
No. 5, No. 51-10983, JP-A No. 51-93224, No. 55-171
No. 05, No. 56-4148, No. 55-108667, No. 55-1569
53, 56-35656, etc.), pyrazoline derivatives and pyrazolone derivatives (US Pat. Nos. 3,180,729, 4,278,746, JP-A-55-88064). Gazette, 55-88065 gazette, 49-105537 gazette,
No. 55-51086, No. 56-80051, No. 56-88141, No. 57-45545, No. 54-112737, No. 55-74546, etc.), phenylenediamine derivatives (US) Japanese Patent No. 3,615,404, Japanese Patent Publication No. 51
-10105, 46-3712, 47-25336, JP 54
No. 53435, 54-110536, 54-1119925, etc.), arylamine derivatives (US Pat. No. 3,567,450, 3,180,
No. 703, No. 3,240,597, No. 3,658,520,
4,232,103, 4,175,961, 4,012,
376, JP-B-49-35702, JP-A-39-27577, JP-A-5
5-144250, 56-119132, 56-22437, West German Patent 1,110,518, etc.), amino-substituted chalcone derivatives (US Pat. No. 3,526,501) Oxazole derivatives (US Pat. No. 3,257,2).
03 and the like, and styrylanthracene derivatives (Japanese Patent Laid-Open No. 56-46234).
Fluorenone derivatives (see JP 54-110837 A), hydrazone derivatives (US Pat. No. 3,717,462, JP 54-59143 A, 55-52063). Gazette, 55-52064 gazette, 55-46760 gazette,
55-85495, 57-11350, 57-148799,
JP-A-2-315991), stilbene derivatives (JP-A-61-210363)
Gazette, 61-228451 gazette, 61-14642 gazette, 61-7225 gazette.
No. 5, No. 62-47646, No. 62-36674, No. 62-10652.
No. 6, No. 62-30255, No. 60-93455, No. 60-94462, No. 60-174749, No. 60-175052, etc.), silazane derivatives (US Pat. No. 4,950) , 950 specification), polysilane (Japanese Patent Laid-Open No. 2-20499).
6), aniline-based copolymers (JP-A-2-282263), JP-A-1-211.
Examples thereof include conductive polymer oligomers (particularly thiophene oligomers) disclosed in Japanese Patent No. 399.

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
Gazette, 54-58445 gazette, 54-149634 gazette, 54-64299 gazette.
Publication No. 55-79450 Publication No. 55-144250 Publication No. 56-11913
No. 2, No. 61-295558, No. 61-98353, No. 63-2956
No. 95 publication 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. Or 4,4 ', 4 "in which three triphenylamine units described in JP-A-4-308688 are connected in a starburst type.
-Tris (N- (3-methylphenyl) -N-phenylamino) triphenylamine and the like can be mentioned. Examples of the hole injection material include phthalocyanine derivatives such as copper phthalocyanine and hydrogen phthalocyanine. Furthermore, inorganic compounds such as aromatic dimethylidene compounds, p-type Si, and p-type SiC can also be used as the material for the hole injection material and the hole transport material.

Specific examples of the aromatic tertiary amine derivative include, for example, N, N′-diphenyl-N, N ′.
-(3-methylphenyl) -1,1'-biphenyl-4,4'-diamine, N, N, N '
, N ′-(4-methylphenyl) -1,1′-phenyl-4,4′-diamine, N, N,
N ′, N ′-(4-methylphenyl) -1,1′-biphenyl-4,4′-diamine, N
, N′-diphenyl-N, N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine, N, N ′-(methylphenyl) -N, N ′-(4-N-butylphenyl) -Phenanthrene-9,10-diamine, N, N-bis (4-di-4-tolylaminophenyl) -4
-Phenyl-cyclohexane, N, N'-bis (4'-diphenylamino-4-biphenylyl) -N, N'-diphenylbenzidine, 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.

  Table 3 shows examples particularly preferable as the hole injection material.

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. 3, 14
Examples of electron injection materials include BCP, TPP, T5MPyTZ, etc., published on page 02, 2003. Materials that can transport electrons by forming a thin film necessary for device fabrication and injecting electrons from the cathode. If there is, it is not limited 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 a derivative thereof 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) (1-naphtholato) aluminum, bis (8-hydroxyquinolinato) (2-naphtholato) aluminum, bis (8-hydroxyquinolinato) (phenola) -To) 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-hydroxyquinolinato) (phenolate) aluminum, bis (5-cyano-8-hydroxyquinolina)
G) (4-Cyano-1-naphtholato) aluminum, bis (8-hydroxyquinolina)
G) Aluminum complex compounds such as chloroaluminum, bis (8-hydroxyquinolinato) (o-cresolato) aluminum, tris (8-hydroxyquinolinato) gallium, tris (2-methyl-8-hydroxy) Quinolinato) gallium, tris (4-methyl-8-hydroxyquinolinato) gallium, tris (5-methyl-8-hydroxyquinolinato) gallium, tris (2-methyl-5-phenyl-8) -Hydroxyquinolinate)
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-hydroxyquinolinato) (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-hydroxyquinolinate) (o-cresolate)
In addition to gallium complex compounds such as gallium, 8-hydroxyquinolinatotrithium, bis (8
-Hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, bis (
Examples thereof include metal complex compounds such as 10-hydroxybenzo [h] quinolinato) beryllium, bis (8-hydroxyquinolinato) zinc, and bis (10-hydroxybenzo [h] quinolinato) zinc.

Among the electron injection materials that can be used in the present invention, preferred nitrogen-containing five-membered ring derivatives include
Examples thereof include oxazole derivatives, thiazole 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-butylbenzene], 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-triazol, 2,5-bis (1-naphthyl) -1,3,4-triazo
And 1,4-bis [2- (5-phenyltriazolyl)] benzene.

As a nitrogen-containing aromatic heterocyclic group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group,
Monovalent nitrogen-containing monocyclic aromatic heterocyclic groups such as 3-pyridazyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-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 group, etc. A monovalent nitrogen-containing fused ring aromatic heterocyclic group, 2,2′-bipyridyl-3-yl group, 2,2′-bipyridyl-4-yl group, 3,3′-bipyridyl-2-yl group, 3,3′-bipyridyl-4-yl group, 4,4′-bipyridyl-2-yl group, 4,4′-
And monovalent nitrogen-containing ring-assembled aromatic heterocyclic groups such as bipyridyl-3-yl groups.

  Table 5 shows specific examples of oxadiazole derivatives.

Table 5

  Table 6 shows specific examples of triazole derivatives.

Table 6

  Table 7 shows specific examples of silole derivatives.

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). -G)
Gallium complex compounds such as (4-phenylphenolato) gallium, 2,9-dimethyl-4
, 7-diphenyl-1,10-phenanthroline (BCP), and the like.

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 0. 0 with respect to the host material.
It is preferably contained in the range of 001 to 30% by weight, more preferably contained in the range of 0.01 to 10% by weight, and further preferably contained in the range of 0.1 to 5% by weight. .

Furthermore, the material used for the anode of the organic EL device of the present invention has a large work function (4 eV).
As described above, those using metals, alloys, electrically conductive compounds or mixtures thereof as electrode materials are preferably used. Specific examples of such electrode materials include metals such as Au, CuI, and ITO.
, SNO2, and ZNO. In order to form this anode, a thin film can be formed from these electrode materials by a method such as vapor deposition or sputtering. This anode has a transmittance for light emission of the anode of 10 when light emitted from the light emitting layer is taken out from the anode.
It is desirable to have characteristics that are greater than%. The sheet resistance of the anode is
What is several hundred ohms / square or less is preferable. 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 alloys,
Examples include 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 20
0 Nm.

About 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 may be formed, and finally a cathode may be formed. 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. As a glass plate,
Examples include plates formed of da-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. T. et al. Lee
, Et al. Proceedings of SID'02, p. 784 (2
LI) (Laser Induced Thermal I)
A method such as a printing method, a laser thermal transfer method, a printing method (offset printing, flexographic printing, gravure printing, screen printing), an inkjet method, or 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 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. Also, Special Table 2002-53
4782 and S.C. T. T. et al. Lee, et al. , Proceedings of SID
'02, p. 784 (2002). Laser thermal transfer method (Laser I
nduced Thermal Imaging (also called LITI method) can also be used. The color conversion method uses a blue light-emitting layer to disperse fluorescent dyes (
This is a method of converting to green and red having a longer wavelength than blue through a CCM) layer. 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 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. Regarding the mechanism of this multiple interference effect,
J. et al. AM-LCD Digest of Technical P by Yamada et al.
apers, OD-2, p. 77-80 (2002).
As described above, the organic EL element can obtain deep 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 such as wall-mounted televisions and flat light emitters, as well as 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.

  Method for synthesizing organic EL device material of the present invention

The synthesis method of 1,4-diketopyrrolo (3,4-C) pyrrole is described in Journal of
The method described in Coatings Technology, 60, 37 (1988) was referred to.

The synthesis method of N-alkyl substituted 1,4-diketopyrrolo (3,4-C) pyrrole is
Reference was made to the method described in JP-A-7-188234.

First, synthesis examples of the present invention will be described, but the present invention is not limited to these synthesis examples.

Synthesis example 2
Synthesis Method of Organic EL Device Material (2) Compound (2) was synthesized according to Reaction Formula 1 to Reaction Formula 4.

Reaction formula 1

Hereinafter, the synthesis method will be described with reference to Reaction Scheme 1.
Under nitrogen atmosphere, 9.6 g (0.24 mol) of sodium hydride (60%) and 25 g of 2-cyanothiophene (0.2 g) were added in 200 ml of tert-pentyl alcohol.
5 mol) is added at room temperature. Thereafter, the temperature was raised to 100 ° C., and 16 g (0.08 mol) of diisopropyl succinate was added dropwise at this temperature. During the addition, the temperature of the reaction product was maintained at 100 ° C. After completion of the dropwise addition, stirring was performed for 3 hours at the same temperature while removing by-produced isopropyl alcohol out of the system. Thereafter, the mixture was cooled to 60 ° C., and at this temperature, a mixed solution of 21 g of acetic acid and 300 g of methanol was added dropwise. It was then filtered, washed with methanol and dried at 60 ° C. Further, the mixture was heated in methanol at 60 ° C. for 30 minutes, filtered while hot, and washed with methanol. 19g of (III) was obtained as dark red powder by drying at 60 degreeC.

Reaction formula 2

Hereinafter, the synthesis method will be described with reference to Reaction Scheme 2.
Under a nitrogen atmosphere, the compound (9 g) represented by (III) obtained by the above method is suspended in 230 g of dimethylacetamide and heated to 50 ° C. with stirring. At this temperature, 8.64 g of sodium tert-butoxy are added and stirred at 50 ° C. for 30 minutes. Next, 25 g of 1-bromo-2-ethylhexane was added dropwise, and after completion of the addition, 50 ° C.
For 2 hours. The reaction solution was cooled to room temperature, 1000 g of water and 80 of methanol.
When gradually poured into 0 g of the mixed solution, a dark red solid precipitates and becomes suspended. 1 at room temperature
The mixture was stirred for a period of time, filtered, washed with water, washed with methanol and then dried to obtain 13.5 g of (V) as a dark red powder.

Reaction formula 3

Hereinafter, the synthesis method will be described with reference to Reaction Scheme 3.
Under a nitrogen atmosphere, the compound (5 g) represented by (V) obtained by the above method is suspended in 100 g of chloroform and cooled to 0 ° C. with stirring. At this temperature, 3.74 g of N-bromosuccinimide (NBS) is added, and the mixture is returned to room temperature and stirred for 12 hours. When the reaction solution is cooled to room temperature and gradually poured into a mixed solution of 1000 g of water and 800 g of methanol, a dark red-purple solid is precipitated and becomes a suspended state. The mixture was stirred at room temperature for 1 hour, filtered, washed with water, washed with methanol, and dried to obtain 3.5 g of (VI) as a dark red-purple powder.

Reaction formula 4

Hereinafter, the synthesis method will be described with reference to Reaction Scheme 4.
Under a nitrogen atmosphere, 1.6 g of the compound represented by (VI) 2 obtained by the above method (2.
4 mmol), 1.014 g (5.7 mmo) of benzo [b] thiophen-2-ylboronic acid
l), ethanol 10 ml, tetrakis (triphenylphosphine) palladium 0.1 g
4 g of potassium carbonate (2M aqueous solution) 10 g, ethylene glycol dimethyl ether 30 g
It added to the necked flask and heated and refluxed for 6 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 0.5% of compound (2) as a blue powder.
7 g was obtained. The obtained crude product was further purified by silica gel column chromatography. Compound (2) is a mass spectrum (manufactured by Bruker Daltonics, Autoflex II).
), ¹ H-NMR, and ¹³ C-NMR (manufactured by JEOL, ECX-400P).

A commercially available reagent was used for benzo [b] thiophen-2-ylboronic acid used for the synthesis of compound (3).

Synthesis Examples 3, 4, 11, 18, 19
The compounds in Table 1 were synthesized by combining the following reaction formulas 5 to 13.

Reaction formula 5

In Reaction Scheme 5, R ^{3 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryl group, Represents a ruoxy group, a substituted or unsubstituted thioalkoxyl group, a substituted or unsubstituted thioaryloxy group, a substituted silyl group, or a substituted amino group; However, any of R ^{3 to} R ⁸ represents a substituent represented by the general formula [3] or the general formula [4].

Reaction formula 6

In Reaction Scheme 6, R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryl group. Represents a ruoxycarbonyl group,
R ^{3 to} R ⁸ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted It represents an unsubstituted thioalkoxyl group, a substituted or unsubstituted thioaryloxy group, a substituted silyl group, or a substituted amino group. However, any of R ^{3 to} R ⁸ represents a substituent represented by the general formula [3] or the general formula [4].

Reaction formula 7

In Reaction Scheme 7, R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryl group. Represents a ruoxycarbonyl group,
R ^{3 to} R ⁸ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted It represents an unsubstituted thioalkoxyl group, a substituted or unsubstituted thioaryloxy group, a substituted silyl group, or a substituted amino group. However, any of R ^{3 to} R ⁸ represents a substituent represented by the general formula [3] or the general formula [4].

Reaction formula 8

In Reaction Scheme 8, R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryl group. Represents a ruoxycarbonyl group,
R ^{3 to} R ⁸ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted It represents an unsubstituted thioalkoxyl group, a substituted or unsubstituted thioaryloxy group, a substituted silyl group, or a substituted amino group. However, any of R ^{3 to} R ⁸ represents a substituent represented by the general formula [3] or the general formula [4].

Reaction formula 9

In Reaction Scheme 9, R ^{11 to} R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryl group. Represents a ruoxy group, a substituted or unsubstituted thioalkoxyl group, a substituted or unsubstituted thioaryloxy group, a substituted silyl group, or a substituted amino group; However, any of R ^{11 to} R ¹⁶ represents a substituent represented by the general formula [3] or the general formula [4].

Reaction formula 10

In Reaction Scheme 10, R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryl group. Represents a ruoxycarbonyl group,
R ^{11 to} R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted It represents an unsubstituted thioalkoxyl group, a substituted or unsubstituted thioaryloxy group, a substituted silyl group, or a substituted amino group. However, R ^{11 to} R ¹⁶
Represents a substituent represented by the general formula [3] or the general formula [4].

Reaction formula 11

In Reaction Scheme 11, R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryl group. Represents a ruoxycarbonyl group,
R ^{11 to} R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted It represents an unsubstituted thioalkoxyl group, a substituted or unsubstituted thioaryloxy group, a substituted silyl group, or a substituted amino group. However, R ^{11 to} R ¹⁶
Represents a substituent represented by the general formula [3] or the general formula [4].

Reaction formula 12

In Reaction Scheme 12, R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryl group. Represents a ruoxycarbonyl group,
R ^{11 to} R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted It represents an unsubstituted thioalkoxyl group, a substituted or unsubstituted thioaryloxy group, a substituted silyl group, or a substituted amino group. However, R ^{11 to} R ¹⁶
Represents a substituent represented by the general formula [3] or the general formula [4].

The structure of the compound of the present invention obtained by combining the above reaction formulas (5) to (12) was identified by mass spectrum, ¹ H-NMR, and ¹³ C-NMR as in Synthesis Example 2 . Table 8 shows the measurement results of the mass spectrum of the synthesized compound. The compound numbers are the same as those described in Table 1 in this specification.

Table 8

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 under conditions without temperature control such as substrate heating and cooling. In the evaluation of the light emission characteristics of the element, the characteristics of an organic EL element having an electrode area of 2 mm × 2 mm were measured.

Example 44
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 ( 2 ) of Table 1 was vacuum-deposited 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 this device was subjected to an energization test, deep red EL light emission with high color purity was obtained.

Examples 45, 46, 53, 60, 61
An organic EL device was produced in the same manner as in Example 44 , except that the compound shown in Table 1 was used instead of the compound ( 2 ). Table 9 shows the half lives when these elements were driven at a constant current at a current density of 12.5 mA / cm ² .

Comparative Example 1
An organic EL device was produced in the same manner as in Example 44 , except that the following comparative compound (A) was used instead of the compound ( 2 ). This device emitted orange light. Table 9 shows the half-life when driven at a constant current at a current density of 12.5 mA / cm ² .

Compound (A)

Table 9

As is clear from Table 9, when Examples 44 to 46 , 53 , 60 , 61 and Comparative Example 1 were compared, by using the organic EL materials represented by the general formula [ 5 ] and the general formula [ 6 ], It was possible to achieve both deep red light emission with high color purity, high maximum light emission brightness and long half-life.

Example 80
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 ( 2 ) in Table 1 as a diketopyrrolopyrrole compound and the compound (H-1) in Table 2 as a perylene derivative were co-evaporated at a composition ratio of 3:97 (weight ratio) to form a film having a thickness of 40 nm. A light emitting layer 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 this device was subjected to an energization test, deep red light emission with high color purity was obtained. In addition, Table 10 shows the half-life when driven at a constant current at a current density of 12.5 mA / cm ² .

Examples 81 and 82
The compounds of Table 1 were used in the same manner as in Example 80 except that the compounds of Table 1 were used instead of the compounds ( 2 ) of Table 1 and the compounds shown in Table 2 were used as perylene derivatives instead of the compounds (H-1) of Table 2. An organic EL element was produced. Table 10 shows the half lives when these elements were driven at a constant current at a current density of 12.5 mA / cm ² .

Comparative Example 2
An organic EL device was produced in the same manner as in Example 80 except that the compound (A) was used instead of the compound ( 2 ) in Table 1. This device emitted orange light. Table 10 shows the half-life when driven at a constant current at a current density of 12.5 mA / cm ² .

Table 10

As is apparent from Table 10, all the elements using the organic EL element material of the present invention had a longer life and higher luminance than the element prepared in Comparative Example 2.

Example 99
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid, Bayer BAYTR) on the cleaned glass plate with ITO electrode
ON P VP CH8000) was formed by a spin coating method to obtain a hole injection layer having a thickness of 40 nm. Subsequently, the compound (2) in Table 1 was dissolved in toluene at a concentration of 2.0 wt%, and a light emitting layer having a thickness of 60 nm was obtained by a spin coating method. 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, deep red light emission with high color purity was obtained.

Example 100
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid, Bayer BAYTR) on the cleaned glass plate with ITO electrode
ON P VP CH8000) was formed by a spin coating method to obtain a hole injection layer having a thickness of 40 nm. Next, the compound (2) in Table 1 and the compound (H-10) in Table 2 were mixed at a ratio of 2:98, dissolved in toluene at a concentration of 2.0 wt%, and 60 n by spin coating.
A light emitting layer having a thickness of m was obtained. Then tris (8-hydroxyquinolinate) aluminum (
Alq3) was deposited to obtain an electron injection layer having a thickness of 30 nm. In addition, LiF
After vapor deposition of 2 nm, Al was vapor-deposited to form an electrode having a film thickness of 150 nm to obtain an organic EL element. When this device was subjected to an energization test, deep red light emission with high color purity was obtained.

As described above, by using the organic EL element material of 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 the organic EL device can achieve high luminous efficiency, low driving voltage, long life, high color purity and deep red light emission.

Claims (5)

The organic electroluminescent element material represented by the following general formula [ 5 ] and / or the following general formula [ 6 ].
General formula [ 5 ]


(Wherein R ²⁶ and R ²⁷ each independently represents an unsubstituted alkyl group,
R ^{28 to} R ³¹ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted silyl group, or a substituted amino group. Represent. )
General formula [ 6 ]


(Wherein R ³² and R ³³ each independently represents an unsubstituted alkyl group,
R ^{34 to} R ³⁷ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted silyl group, or a substituted amino group. Represent. ) Between a pair of electrodes including an anode and a cathode in the organic electroluminescent device obtained by forming an organic compound thin film of multiple layers including a light emitting layer or a light emitting layer, light emitting layer, for an organic electroluminescence device according to claim 1, wherein An organic electroluminescence device including a material. The organic electroluminescence device according to claim 2, wherein the light emitting layer contains a perylene derivative as a host material. The organic electroluminescent element whose light emitting layer is the coating film-forming thing of the material for organic electroluminescent elements of Claim 1 . An ink composition for an organic electroluminescence device comprising the organic electroluminescence device material according to claim 1 and an organic solvent.