JP2009221442A - Material for organic electroluminescent element and organic electroluminescent element - Google Patents

Material for organic electroluminescent element and organic electroluminescent element Download PDF

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JP2009221442A
JP2009221442A JP2008070526A JP2008070526A JP2009221442A JP 2009221442 A JP2009221442 A JP 2009221442A JP 2008070526 A JP2008070526 A JP 2008070526A JP 2008070526 A JP2008070526 A JP 2008070526A JP 2009221442 A JP2009221442 A JP 2009221442A
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Kan Iwata
Yasuyuki Takada
貫 岩田
泰行 高田
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Toyo Ink Mfg Co Ltd
東洋インキ製造株式会社
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Abstract

An organic EL element material exhibiting excellent characteristics such as high luminance, high efficiency, low voltage driving, long life, and heat resistance, and an organic EL element using the material.
An organic EL element material represented by the following general formula [1]. General formula [1]

(In the formula, R 1 represents a substituted or unsubstituted aromatic group or a heterocyclic group. R 2 represents a substituted or unsubstituted condensed polycyclic group or a heterocyclic group. R 3 and R 4 represent Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aromatic group.) The organic EL device material is used as a light-emitting material or a host material of a light-emitting layer of the EL device.
[Selection figure] None

Description

  The present invention relates to a material for an organic electroluminescence element used for a planar light source and display, and an organic electroluminescence element using the same.

  An organic electroluminescence (hereinafter referred to as “organic EL”) element that emits light when electrons injected from the cathode and holes injected from the anode are recombined in the organic phosphor sandwiched between the two electrodes is a solid light emitting type. In recent years, research and development has been actively conducted in recent years.

This study was conducted by Eastman Kodak's C.I. W. Tang et al. Originated from an EL device in which organic thin films are laminated. In this report, by using a metal chelate complex as a light emitting layer and an amine compound as a hole injection layer, a direct current voltage of 6 to 10 V is used. Has a luminance of several thousand (cd / m 2 ) and a maximum light emission efficiency of 1.5 (lm / W), thus obtaining green light emission (Non-patent Document 1). Currently, various research institutes are working on high-efficiency and high-durability organic EL elements for the practical application of full-color displays, and materials with various structures are being considered as materials for organic EL elements. Yes.

  In particular, with respect to blue light emitting elements, there are few blue light emitting materials that provide elements with excellent durability. As an example, a technique using an anthracene compound for a blue light emitting element is disclosed. Blue light emitting devices using various anthracene compounds (Patent Documents 1 to 4) have been reported, but all have insufficient durability against heat and oxygen.

  In addition, organic EL devices have been studied for devices using various materials so far, but a small amount of dopant material is mixed into the host material by a method such as co-evaporation to form a light emitting layer, A method of obtaining light emission from a dopant has been studied as an effective method, and a method using a phenanthrene derivative has also been studied (Patent Documents 5 to 10).

Appl. Phys. Lett. 51, 913, 1987 JP 2003-306454 A JP 2004-002351 A WO2005 / 113531 pamphlet JP 2007-63501 A Japanese Patent Laid-Open No. 1991-037991 WO2002 / 052905 pamphlet JP 2007-109988 A WO2007 / 017995 pamphlet JP 2000-012229 A JP-A-6-346049

  The subject of this invention is providing the organic electroluminescent element material which shows the outstanding characteristics, such as high brightness | luminance, high efficiency, low voltage drive, long life, and heat resistance, and an organic electroluminescent element using the same. .

  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 characterized by being a compound represented by the following general formula [1].

General formula [1]

(In the formula, R 1 represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group.
R 2 represents a substituted or unsubstituted condensed polycyclic group or a substituted or unsubstituted heterocyclic group.
R 3 and R 4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group. )

  Moreover, this invention relates to the light emitting layer material for organic electroluminescent elements which comprises said organic electroluminescent element material.

  Further, the present invention is an organic electroluminescence device in which a single layer or a multilayer organic layer is formed between a pair of electrodes composed of an anode and a cathode, and at least one layer is a layer containing the above-mentioned organic electroluminescence device material. It is related with said organic electroluminescent element.

  Moreover, this invention relates to said organic electroluminescent element whose layer containing said light emitting layer material for organic electroluminescent elements is a light emitting layer.

  Moreover, this invention relates to said organic electroluminescent element in which a light emitting layer contains a condensed polycyclic aromatic compound further.

  Moreover, this invention relates to said organic electroluminescent element in which a light emitting layer contains a phosphorescence-emitting material further.

  Since the compound represented by the general formula [1] of the present invention exhibits strong light emission, it is useful as a light-emitting material to be contained in the light-emitting layer of the organic electroluminescence device, and of course, the light-emitting layer host in organic electroluminescence. It is also useful as a material, a light emitting layer dopant material, and an electron injection material, and can also be used as a fluorescent indicator for detecting trace components by utilizing its light emission characteristics. Organic electroluminescent elements using these organic electroluminescent element materials can be suitably used as flat panel displays such as wall-mounted televisions and flat light emitters because they are driven at a low voltage and have a long lifetime. It 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.

  Hereinafter, the present invention will be described in detail.

R 1 in the general formula [1] in the present invention is represented by a substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group.

In R 1 , the substituted or unsubstituted aromatic group is preferably a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 6 to 40 carbon atoms, more preferably 6 to 18 carbon atoms. A substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having, for example, a phenyl group, 1-naphthyl group, 2-naphthyl group, p-biphenyl group, m-biphenyl group, 2-anthryl group, 9- Anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluorenyl group, 3-fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perylenyl group, o- Tolyl group, m-tolyl group, p-tolyl group, 4-methylbiphenyl group, terphenyl group, 4-methyl-1-naphthyl group, 4-tert-butyl-1-na Examples include a til group, 2-trifluoromethyl-1-naphthyl group, 4-naphthyl-1-naphthyl group, 6-phenyl-2-naphthyl group, 10-phenyl-9-anthryl group, and spirofluorenyl group. .

In R 1 , the substituted or unsubstituted heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group containing O, N, or S as a hetero atom, or a condensed polycyclic heterocyclic group. . The heterocyclic group is preferably a heterocyclic group having 4 to 40 carbon atoms, more preferably a heterocyclic group having 4 to 20 carbon atoms, such as a thienyl group, a furyl group, a pyridyl group, a pyridinyl group. , Pyrazinyl group, pyrimidinyl group, pyridazinyl group, triazinyl group, indolinyl group, quinolyl group, quinoxalyl group, acridinyl group, pyrrolyl group, pyranyl group, thiopyranyl group, dioxanyl group, piperidinyl group, morpholinyl group, piperazinyl group, carbazolyl group, oxazolyl Group, oxadiazolyl group, benzoxazolyl group, thiazolyl group, thiadiazolyl group, benzothiazolyl group, triazolyl group, imidazolyl group, imidazolpyridyl group, benzoimidazolyl group, pranyl group, morpholyl group, piperidyl group, piperazinyl group, benzofuryl Group, 2-benzothienyl group, indolyl group, acridinyl group, phenanthrolyl group, and the like.

In the present invention, R 2 in the general formula [1] is represented by a substituted or unsubstituted condensed polycyclic group or a substituted or unsubstituted heterocyclic group.

In R 2 , the substituted or unsubstituted condensed polycyclic group is preferably a substituted or unsubstituted condensed polycyclic group having 9 to 40 carbon atoms, more preferably a substituted or unsubstituted group having 9 to 18 carbon atoms. Substituted condensed polycyclic groups, such as 1-naphthyl group, 2-naphthyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluorenyl group 3-fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perylenyl group, 4-methyl-1-naphthyl group, 4-tert-butyl-1-naphthyl group, 2-trifluoro Methyl-1-naphthyl group, 4-naphthyl-1-naphthyl group, 6-phenyl-2-naphthyl group, 10-phenyl-9-anthryl group, spirofluoreni Such as a group, and the like.

In R 2 , the substituted or unsubstituted heterocyclic group has the same meaning as the substituted or unsubstituted heterocyclic group represented by R 1 described above.

In the general formula [1] in the present invention, R 3 and R 4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group.

In R 3 and R 4 , the substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 40 carbon atoms, more preferably a substituted alkyl group having 1 to 20 carbon atoms, for example, methyl An unsubstituted linear group such as a group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, etc. In addition to branched alkyl group, ethoxyethyl group, ethoxymethyl group, methoxymethyl group, methoxyethyl group, 2-phenylisopropyl group, trichloromethyl group, trifluoromethyl group, benzyl group, α-phenoxybenzyl group, α, α-dimethylbenzyl group, α, α-methylphenylbenzyl group, α, α-ditrifluoromethylbenzyl group, tri Enirumechiru group, such as α- benzyloxybenzyl group.

In R 3 and R 4 , the substituted or unsubstituted aromatic group has the same meaning as the substituted or unsubstituted aromatic group represented by R 1 described above.

  As mentioned above, although the compound represented by General formula [1] which is a material for organic electroluminescent elements of this invention was demonstrated, as a molecular weight of these compounds, 2000 or less is preferable, 1500 or less is further more preferable, and 1000 or less is especially preferable. preferable. 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.

  Typical examples of the compound represented by the general formula [1], which is the material for an organic electroluminescence element of the present invention, are shown in the following Table 1. However, the present invention is not limited to these representative examples.

Table 1

  The compound group represented by the general formula [1] can be obtained by a known method. For example, as shown in the following reaction formula 1, a 2,7-diiodophenanthrene derivative is used as a starting material and a boronic acid derivative and 1 or 2 It can be obtained through a staged reaction. (See Synthesis Communication, 1981, Vol. 11, 513)

Reaction formula 1

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

  Here, the organic electroluminescent element which can be produced using the organic electroluminescent element material of the present invention will be described in detail.

  An organic electroluminescent 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, a single layer type organic electroluminescent element is composed of only a light emitting layer between an anode and a cathode. The element which becomes. On the other hand, a multi-layer organic electroluminescent element is one that facilitates the 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 example, a layer in which a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, and the like are stacked is used. Therefore, typical device configurations of the multilayer organic electroluminescence device 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 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 configuration in which a multilayer structure such as () anode / light emitting layer / hole blocking layer / electron injection layer / cathode, (8) anode / light emitting layer / electron injection layer / cathode 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, in recent years, for the purpose of improving the light extraction efficiency, an element configuration called “multi-photon emission” in which some layers of the above-described multilayer organic electroluminescence element are multilayered has been proposed. . For example, in an organic electroluminescence 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, a charge generating layer and a light emitting unit The method of laminating | stacking two or more layers of this part is mentioned.

  The organic EL device material of the present invention may be used for any of the above-described layers, but can be particularly suitably used for a light emitting layer.

  If necessary, in addition to the organic electroluminescence device material of the present invention, further known light emitting materials, doping materials, hole injection materials and electron injection materials can be used for the light emitting layer. Depending on the type and composition of the material used, it is possible to improve emission luminance and emission efficiency, and to obtain various emission colors such as red, blue, and green. In addition, white light emission can be obtained by combining a plurality of light emitting materials.

  Examples of the light emitting material or doping material that can be used in the light emitting layer together with the organic electroluminescent device material of the present invention include anthracene derivatives, naphthalene derivatives, phenanthrene derivatives, pyrene derivatives, tetracene derivatives, coronene derivatives, chrysene derivatives, fluorescein derivatives, perylene derivatives, Phthaloperylene derivatives, naphthaloperylene derivatives, perinone derivatives, phthaloperinone derivatives, naphthaloperinone derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, coumarin derivatives, oxadiazole derivatives, aldazine derivatives, bisbenzoxazoline derivatives, bisstyryl derivatives, diketopyrrolopyrrole derivatives, Pyrazine derivatives, cyclopentadiene derivatives, quinoline metal complex derivatives, diphenylethylene derivatives, biphenyl Luanthracene derivatives, carbazole derivatives, pyran derivatives, thiopyran derivatives, polymethine derivatives, merocyanine derivatives, imidazole chelating oxinoid compounds, quinacridone derivatives, rubrene derivatives, fluorescent dyes for dye lasers and whitening, etc. Is not to be done.

  Among the above materials, the light emitting layer constituting material that can be suitably used includes naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, tetracene derivatives, perylene derivatives, carbazole derivatives, benzothiophene derivatives, benzofuran derivatives, benzoxazole derivatives, Examples thereof include benzothiazole derivatives, biphenyl derivatives, diketopyrrolopyrrole derivatives, and quinoline metal complexes.

  In addition, the light-emitting layer includes insulating resins such as polystyrene, polycarbonate, polyacrylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and copolymers thereof, poly-N-vinylcarbazole. To the polymer such as photoconductive resin such as polysilane, conductive resin such as polythiophene and polypyrrole, the material of the present invention and the above light emitting layer constituting material, film formation improvement, film pinhole prevention, etc. What mixed antioxidant, a ultraviolet absorber, a plasticizer, etc. can also be used.

  Any of the organic electroluminescence device material of the present invention and the above-mentioned compound that can be used in the light emitting layer in the light emitting layer may be the main component. That is, depending on the combination of the above compound and the material for an organic electroluminescence device of the present invention, the compound of the present invention can be a main material for forming a light emitting layer or a dopink material in another main material.

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 a high hole mobility and a small ionization energy of 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. Any one of those commonly used as hole charge transport materials in photoconductive materials and known materials used in hole injection layers of organic electroluminescent elements can be selected and used.

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

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

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

  Particularly preferred examples of the hole injection material are shown in Table 2.

Table 2


  Moreover, as a hole transport material which can be used with the organic electroluminescent element material of this invention, the compound shown in following Table 3 is also mentioned.

Table 3


  In order to form the hole injection layer described above, the above-mentioned compound is thinned by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. The thickness of the hole injection layer is not particularly limited, but is usually 5 nm to 5 μm.

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

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

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

  Specific examples of particularly preferred oxadiazole derivatives among the electron injection materials that can be used in the present invention are shown in Table 4.

Table 4


  Specific examples of particularly preferred triazole derivatives among the electron injection materials that can be used in the present invention are shown in Table 5. In Table 5, Ph represents a phenyl group.

Table 5


  Specific examples of particularly preferred silole derivatives among the electron injection materials that can be used in the present invention are shown in Table 6.

Table 6


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

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

  The material for an organic electroluminescence element of the present invention can be suitably used as a light emitting layer. The organic electroluminescence device material of the present invention can be used as a host material or a dopant material in a light emitting layer, and can be combined with other compounds to form a light emitting layer. In particular, a dopant material for producing a blue light emitting device. Can be suitably used.

  Fluorescent brighteners such as benzothiazole, benzimidazole, and benzoxazole, metal chelated oxinoid compounds, styrylbenzene, in order to obtain blue to green light emission by using the organic electroluminescent device material of the present invention Compounds can be used. Specific examples of these compounds include compounds disclosed in, for example, JP-A-59-194393. Still other useful compounds are listed in Chemistry of Synthetic Soybean (1971) pages 628-637 and 640.

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

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

  Further, in addition to the above-described fluorescent brightener, metal chelated oxinoid compound, styrylbenzene compound and the like, for example, 12-phthaloperinone (J. Appl. Phys., Vol. 27, L713 (1988)), 1,4- Diphenyl-1,3-butadiene, 1,1,4,4-tetraphenyl-1,3-butadiene (Appl. Phys. Lett., Vol. 56, L799 (1990)), naphthalimide derivatives No. 2-305886), perylene derivatives (Japanese Patent Laid-Open No. 2-189890), oxadiazole derivatives (Japanese Patent Laid-Open No. Hei 2-216791, or the 38th Applied Physics Related Conference) were disclosed by Hamada et al. Oxadiazole derivatives), aldazine derivatives (JP-A-2-220393), pyrazirine Conductor (JP-A-2-220394), cyclopentadiene derivative (JP-A-2-289675), pyrrolopyrrole derivative (JP-A-2-29691), styrylamine derivative (Appl. Phys. Lett., 56th) Vol. L799 (1990), coumarin compounds (Japanese Patent Laid-Open No. 2-191694), International Patent Publications WO 90/13148 and Appl. Phys. Lett., Vol 58, 18, P1982 (1991). Polymer compounds, 9,9 ′, 10,10′-tetraphenyl-2,2′-bianthracene, PPV (polyparaphenylene vinylene) derivatives, polyfluorene derivatives and copolymers thereof, for example, the following general formula [ 2] to those having the structure of the general formula [4].

General formula [2]

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

General formula [3]

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

General formula [4]

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

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

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

  In the organic electroluminescence device of the present invention, a light emitting layer may be formed using the compound of the present invention. At this time, the light emitting layer is a single light emitting layer using one compound of the present invention or the present invention. It can be set as the mixed light emitting layer using 2 or more of these compounds.

  Further, a mixed layer of the compound of the present invention and the condensed polycyclic aromatic compound can be used as a light emitting layer. In this case, the compound of the present invention can be used as both a dopant material and a host material. Moreover, when forming a mixed layer, you may use multiple types of compound of this invention or multiple types of condensed polycyclic aromatic compounds. Examples of the condensed polycyclic aromatic compound include naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, perylene derivatives, fluorene derivatives, carbazole derivatives, and condensed aromatic heterocyclic derivatives. For example, the following known compounds are preferably used, but the present invention is not limited to these representative examples.

  Moreover, in the organic electroluminescent element of this invention, the mixed layer of the compound of this invention and a phosphorescence-emitting material can be used as a light emitting layer. In this case, the compound of the present invention can be used as a host material in the light emitting layer. Moreover, when forming a mixed layer, you may use multiple types of phosphorescence-emitting material. The phosphorescent light-emitting material here means a compound that emits light when transitioning from an excited triplet state to a ground state. Examples of phosphorescent materials that can be used in the organic electroluminescence device of the present invention include organometallic complexes, where the metal atom is usually a transition metal, preferably in the fifth or sixth period, Group 6 to 11 elements, more preferably group 8 to 10 elements are targeted. Specific examples include iridium and platinum. Examples of the ligand include 2-phenylpyridine and 2- (2'-benzothienyl) pyridine, and the carbon atom on these ligands is directly bonded to the metal. Another example is a porphyrin or tetraazaporphyrin ring complex, and the central metal includes platinum. For example, the following known compounds are preferably used as the phosphorescent material, but the present invention is not limited to these representative examples. (In the figure, Ph represents a phenyl group).

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

  Regarding the method for producing the organic electroluminescence 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. What is necessary is just to form. Moreover, an organic electroluminescent element can also be produced from the cathode to the anode in the reverse order.

  This organic electroluminescence element is manufactured on a translucent substrate. This light-transmitting substrate is a substrate that supports the organic electroluminescence element. Regarding the light-transmitting property, it is desirable that the light transmittance in the visible region of 400 to 700 nm is 50% or more, preferably 90% or more. Further, it is preferable to use a smoother substrate.

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

  As a method for forming each layer of the organic electroluminescence device of the present invention, a dry film forming method such as vacuum deposition, electron beam irradiation, sputtering, plasma, ion plating, or a wet film forming method such as spin coating, dipping, or flow coating is used. Any method of law can be applied. In addition, Special Table 2002-53482, S.I. 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. Further, as disclosed in JP-A-57-51781, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, which is then thinned by a spin coat method or the like. An organic layer can be formed. The film thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Conversely, if the film thickness is too thin, pinholes, etc. And it becomes difficult to obtain sufficient light emission luminance even when an electric field is applied. Accordingly, the thickness of each layer is suitably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.

  Further, in order to improve the stability of the organic electroluminescence element against temperature, humidity, atmosphere, etc., 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 electroluminescence element of the present invention is usually a direct current, but a pulse current or an alternating current may be used. The current value and the voltage value are not particularly limited as long as the element is within a range not destroying the element. However, considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electrical energy as possible.

  The organic electroluminescence element driving method of the present invention can be driven not only by the passive matrix method but also by the active matrix method. The method for extracting light from the organic electroluminescence 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 Keiji Kido, “All about organic electroluminescence”, published by Nihon Jitsugyo Shuppansha (published in 2003).

  Examples of the main method of full colorization of the organic electroluminescence 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, an evaporation method using a shadow mask, an ink jet method, and a printing method can be used. In addition, Special Table 2002-53482, S.I. 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 electroluminescence element to extract light of the three primary colors through the color filter for liquid crystal. In addition to these three primary colors, some white light is extracted as it is and used for light emission. As a result, the luminous efficiency of the entire device can be increased.

  Furthermore, the organic electroluminescence element of the present invention may adopt a microcavity structure. This is an organic electroluminescence element having a structure in which a light emitting layer is sandwiched between an anode and a cathode, and the emitted light causes multiple interference between the anode and the cathode, but the reflectance of the anode and the cathode, A technology that actively utilizes the multiple interference effect and controls the emission wavelength extracted from the device by appropriately selecting the optical characteristics such as transmittance and the film thickness of the organic layer sandwiched between them. is there. 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 electroluminescence element of the present invention can emit light for a long time with a low driving voltage. Therefore, the organic electroluminescence element of the present invention is used as a flat panel display such as a wall-mounted television or various flat light emitters, and further as a light source such as a copying machine or a printer, a light source such as a liquid crystal display or an instrument, a display board, a sign. It can be applied to lamps.

  Prior to Examples, the synthesis of compounds used as the material for an organic electroluminescence device of the present invention will be described.

Synthesis example 1
Method for synthesizing compound 1 In a 300 ml flask, 2,7-diiodophenanthrene (4.02 g), 1-naphthaleneboronic acid (3.70 g), tetrakis (triphenylphosphine) palladium (0) (0.8 g), THF ( 140 mL), 2M aqueous potassium carbonate solution (100 ml) was added, and the mixture was stirred at 64 ° C. for 6 hours under a nitrogen atmosphere. After cooling the reaction solution, the organic layer was separated, and the aqueous layer was extracted with toluene (3 × 50 mL). This was combined with the previous organic layer and dried over magnesium sulfate. After the desiccant was filtered off, activated carbon (3.6 g) was added to the filtrate and stirred for 1 hour. After the activated carbon was filtered off, the filtrate was concentrated under reduced pressure, and the concentrated solution was placed in hexane (600 ml) and stirred for 1 hour. The precipitated solid was collected and purified by column chromatography to obtain Compound 1 (2.34 g). EI-MS (PolarisQ manufactured by Thermo Electron) m / z = 431 (molecular weight: 431).

Synthesis Examples 2-19
In the above synthesis example 1, the boronic acid derivative used is changed to a boronic acid derivative corresponding to each compound, and 2,7-diiodophenanthrene (starting material 1), 2,7-diiodo- 9-tert-butylphenanthrene (starting material 2), 2,7-diiodo-9-phenylphenanthrene (starting material 3), 2,7-diiodo-9,10-bis (1-naphthyl) phenanthrene (starting material 4) The compounds shown in Table 1 were synthesized using any of the above.

  About the structure of the compound which is the organic electroluminescent element material of this invention obtained by the above synthesis examples 1-19, it identified by EI-MS spectrum. Table 7 shows the synthesized compounds, starting materials used, boronic acid derivatives used, and mass spectrum measurement results of the compounds. The compound numbers are the same as those described in Table 1 in this specification.

Table 7

Synthesis Example 20
Synthesis Method of Compound 117 In a 300 ml flask, 2,7-diiodophenanthrene (5.00 g), 4-biphenylboronic acid (2.31 g), tetrakis (triphenylphosphine) palladium (0) (0.87 g), THF ( 140 mL), 2M aqueous potassium carbonate solution (100 ml) was added, and the mixture was stirred at 30 ° C. for 3 days under a nitrogen atmosphere. After cooling the reaction solution, the organic layer was separated, and the aqueous layer was extracted with toluene (3 × 50 mL). This was combined with the previous organic layer and dried over magnesium sulfate. After the desiccant was filtered off, the filtrate was concentrated under reduced pressure, and the resulting solid was purified by column chromatography to obtain 2-biphenyl-7-iodophenanthrene (intermediate 1) (2.21 g). EI-MS m / z = 454 456 458 (molecular weight: 456).

  Intermediate 1 (2.00 g), 2-naphthaleneboronic acid (0.87 g), tetrakis (triphenylphosphine) palladium (0) (0.5 g), THF (80 mL), 2M potassium carbonate obtained in a 300 ml flask An aqueous solution (70 ml) was added and stirred at 64 ° C. for 5 hours under a nitrogen atmosphere. After cooling the reaction solution, the organic layer was separated, and the aqueous layer was extracted with toluene (3 × 50 mL). This was combined with the previous organic layer and dried over magnesium sulfate. After the desiccant was filtered off, the filtrate was concentrated under reduced pressure, and the resulting solid was purified by column chromatography to give compound 117 (1.50 g). EI-MS m / z = 457 (molecular weight: 457).

Synthesis Examples 21 to 43
In the above synthesis example 20, the boronic acid used is changed to a boronic acid derivative corresponding to each compound, and 2,7-diiodophenanthrene (starting material 1), 2,7-diiodo-9 is used as a starting material. The compounds shown in Table 1 were synthesized by using either -tert-butylphenanthrene (starting material 2) or 2,7-diiodo-9-phenylphenanthrene (starting material 3).
About the structure of the compound which is the organic electroluminescent element material of this invention obtained by the above synthesis examples 20-43, it identified by EI-MS spectrum. Table 8 shows the synthesized compounds, the starting materials used, the boronic acid derivatives used, and the mass spectrum measurement results of the compounds. The compound numbers are the same as those described in Table 1 in this specification.

Table 8

Synthesis Example 44
Method for synthesizing compound 90 In a 200 ml flask, 2,7-diiodo-9-phenylphenanthrene (5.00 g), carbazole (3.46 g), sodium tri-tert-butoxy (2.00 g), palladium acetate (0.2 g) Bis (2- (diphenylphosphino) phenyl) ether (hereinafter DPEphos) (0.46 g) and xylene (80 ml) were added, and the mixture was stirred at 134 ° C. for 4 hours under a nitrogen atmosphere. After the reaction solution was cooled, activated carbon (2.00 g) was added and stirred for 1 hour, and a filtrate was obtained by suction filtration. After concentration, the residue was purified by column chromatography to obtain Compound 90 (4.52 g). EI-MS m / z = 585 (molecular weight: 585).

Synthesis example 45
Synthesis Method of Compound 128 In a 300 ml flask, 2,7-diiodophenanthrene (5.00 g), 4-biphenylboronic acid (2.31 g), tetrakis (triphenylphosphine) palladium (0) (0.87 g), THF ( 140 mL), 2M aqueous potassium carbonate solution (100 ml) was added, and the mixture was stirred at 30 ° C. for 3 days under a nitrogen atmosphere. After cooling the reaction solution, the organic layer was separated, and the aqueous layer was extracted with toluene (3 × 50 mL). This was combined with the previous organic layer and dried over magnesium sulfate. After the desiccant was filtered off, the filtrate was concentrated under reduced pressure, and the resulting solid was purified by column chromatography to obtain 2-biphenyl-7-iodophenanthrene (Intermediate 1) (2.21 g). EI-MS m / z = 454 456 458 (molecular weight: 456).
Intermediate 1 (3.00 g), carbazole (1.21 g), sodium tri-tert-butoxy (0.7 g), palladium acetate (0.1 g), DPEphos (0.23 g), xylene (50 ml) in a 100 ml flask And stirred at 134 ° C. for 3 hours under a nitrogen atmosphere. After the reaction solution was cooled, activated carbon (1.00 g) was added and stirred for 1 hour, and a filtrate was obtained by suction filtration. After concentration, the residue was purified by column chromatography to obtain Compound 128 (2.91 g). EI-MS m / z = 496 (molecular weight: 496).

Synthesis Examples 46-50
In the synthesis example 45 described above, the compounds shown in Table 1 were synthesized by changing the boronic acid derivatives used to boronic acid derivatives corresponding to the respective compounds.

  About the structure of the compound which is the organic electroluminescent element material of this invention obtained by the above synthesis examples 45-50, it identified by EI-MS spectrum. Table 9 shows the synthesized compounds, starting materials used, boronic acid derivatives used, and mass spectrum measurement results of the compounds. The compound numbers are the same as those described in Table 1 in this specification.

Table 9

Examples of Organic EL Device Hereinafter, the organic EL device using the organic EL device material of the present invention will be described with reference to the following examples, but the present invention is not limited to the following examples. In the examples, all mixing ratios are weight ratios unless otherwise specified. Vapor deposition (vacuum deposition) was performed in a vacuum of 10 −6 Torr under conditions where temperature control such as heating and cooling of the substrate was not performed. The light emission characteristics of the element were measured using an organic EL element having a light emitting element area of 2 mm × 2 mm.

Example 1
On the cleaned glass plate with an ITO electrode, α-NPD (HIM1 described in Table 2) was vacuum-deposited to obtain a hole injection layer having a thickness of 75 nm. Subsequently, the compound 1 of this invention was vacuum-deposited and the light emitting layer with a film thickness of 40 nm was obtained. Further, TPBI (the following compound A) is vacuum-deposited to form an electron-injecting layer having a thickness of 20 nm, on which first 1 nm of lithium fluoride and then 150 nm of aluminum (Al) are evaporated to form an electrode, An organic EL device was obtained. When this element is driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), the chromaticity is blue emission of CIE (x, y) = (0.15, 0.06), and the luminous efficiency is It was 3.4 cd / A. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 100 ° C. were measured. The results are shown in Table 10.

Examples 2-50
A device was prepared in the same manner as in Example 1 except that a light emitting layer was prepared using the compounds shown in Table 10 instead of Compound 1. The efficiency was measured when this device was driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ). Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 100 ° C. were measured. The results are shown in Table 10.

Comparative Example 1
A device was prepared in the same manner as in Example 1 except that a light emitting layer was prepared using Compound B shown below. The efficiency was measured when this device was driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ). Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 100 ° C. were measured. The results are shown in Table 10.

Table 10

  As is clear from Table 10, all of the compounds of the present invention had a longer life and higher efficiency than the device prepared in Comparative Example 1.

Example 51
The following compound C was vacuum-deposited on a glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 70 nm. Next, Compound 1 in Table 1 and the following Compound D were co-evaporated at a composition ratio of 5: 100 to form a light-emitting layer having a thickness of 40 nm. Further, TPBI (Compound A) was deposited to form an electron injection layer having a thickness of 20 nm. On top of that, a cathode was formed by vapor deposition of 1 nm of lithium fluoride and 100 nm of Al to obtain an organic EL device. When this element is driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), the chromaticity is blue emission of CIE (x, y) = (0.15, 0.10), and the emission efficiency is It was 6.0 cd / A. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 100 ° C. were measured. The results are shown in Table 11.

Examples 52-100
A device was prepared in the same manner as in Example 51 except that the compounds in Table 11 were used instead of Compound 1. When these devices were driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), the emission color was blue and the emission efficiency was 4 cd / A or more. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 100 ° C. were measured. The results are shown in Table 11.

Comparative Examples 2-3
A device was prepared in the same manner as in Example 51 except that compounds B and E were used in place of compound 1. Luminous efficiency was measured when these devices were driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ). Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 100 ° C. were measured. The results are shown in Table 11.

Table 11

  As is clear from Table 11, all of the compounds of the present invention had a longer life and higher efficiency than the devices prepared in Comparative Examples 2 and 3.

Example 101
On the glass plate with an ITO electrode, HTM8 described in Table 3 was vacuum-deposited to obtain a hole injection layer having a thickness of 80 nm. Next, Compound 1 and Compound D were co-evaporated at a weight composition ratio of 3: 100 to form a light emitting layer having a thickness of 30 nm. Further, TPBI (Compound A) was deposited to form an electron injection layer having a thickness of 30 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide (Li 2 O) and 100 nm of Al to obtain an organic EL device. When this device was driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), the luminous efficiency was 5.6 cd / A. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 100 ° C. were measured. The results are shown in Table 12.

Examples 102-150
A device was prepared in the same manner as in Example 101 except that the compound in Table 12 was used instead of Compound 1. When these elements are driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), the luminous efficiency is 4 cd / A or more, and when driven at a current density of 12.5 mA / cm 2. , And the luminance after 100 hours of continuous driving in an environment of 100 ° C. were measured. The results are shown in Table 12.

Comparative Example 4
A device was prepared in the same manner as in Example 101 except that Compound B was used instead of Compound 1. Luminous efficiency was measured when this device was driven at a constant current at room temperature with a luminous luminance of 300 (cd / m 2 ). Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 100 ° C. were measured. The results are shown in Table 12.

Table 12


  As is clear from Table 12, all the compounds of the present invention had a longer life and higher efficiency than the device prepared in Comparative Example 4.

Example 151
Compound C was vacuum deposited on a glass plate with an ITO electrode to obtain a 65 nm-thick hole injection layer. Next, the following compound F and compound 1 were co-evaporated at a composition ratio of 3: 100 to form a light emitting layer having a thickness of 30 nm. Further, TPBI (Compound A) was deposited to form an electron injection layer having a thickness of 30 nm. On top of that, a cathode was formed by vapor deposition of 1 nm of lithium fluoride and 100 nm of Al to obtain an organic EL device. When this element is driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), the chromaticity is blue emission of CIE (x, y) = (0.16, 0.11), and the emission efficiency is It showed 5.7 cd / A. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 100 ° C. were measured. The results are shown in Table 13.

Examples 152-200
A device was prepared in the same manner as in Example 151 except that the compounds in Table 13 were used instead of Compound 1. When these devices were driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), the light emission efficiency was 4 cd / A or more. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 100 ° C. were measured. The results are shown in Table 13.

Comparative Example 5
A device was prepared in the same manner as in Example 151 except that Compound E was used instead of Compound 1. Luminous efficiency was measured when this device was driven at a constant current at room temperature with a luminous luminance of 300 (cd / m 2 ). Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 100 ° C. were measured. The results are shown in Table 13.

Table 13


  As is apparent from Table 13, all the compounds of the present invention had a longer life and higher efficiency than the device prepared in Comparative Example 5.

Example 201
On the glass plate with an ITO electrode, HTM8 described in Table 3 was vacuum deposited to obtain a hole injection layer having a thickness of 60 nm. Next, the following compound G and compound 1 were co-evaporated at a composition ratio of 2: 100 to form a light emitting layer having a thickness of 40 nm. Further, TPBI was deposited to form an electron injection layer having a thickness of 40 nm. On top of that, a cathode was formed by vapor deposition of 1 nm of lithium fluoride and 100 nm of Al to obtain an organic EL device. When this element is driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), the chromaticity is blue emission of CIE (x, y) = (0.14, 0.11), and the luminous efficiency. Showed 6.2 cd / A. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 100 ° C. were measured. The results are shown in Table 14.

Examples 202-213
A device was prepared in the same manner as in Example 201 except that the compound in Table 14 was used instead of Compound 1. When these elements are driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), the light emission efficiency is 4 cd / A or more, and when the elements are driven at a current density of 12.5 mA / cm 2 . The initial luminance and the luminance after 100 hours of continuous driving in an environment of 100 ° C. were measured. The results are shown in Table 14.

Table 14

Example 214
On the glass plate with an ITO electrode, HTM8 described in Table 3 was vacuum-deposited to obtain a hole injection layer having a thickness of 80 nm. Next, Compound 1 and Compound 117 were co-evaporated at a weight composition ratio of 3: 100 to form a light emitting layer having a thickness of 30 nm. Further, TPBI (Compound A) was deposited to form an electron injection layer having a thickness of 30 nm. A cathode was formed thereon by vapor deposition of 1 nm of lithium oxide (Li 2 O) and 100 nm of Al to obtain an organic EL device. When this element is driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), the chromaticity is blue emission of CIE (x, y) = (0.15, 0.11), and the luminous efficiency. Showed 6.0 cd / A. The results are shown in Table 15.

Examples 215-223
A device was prepared in the same manner as in Example 214 except that the compounds in the combinations shown in Table 15 were used in place of Compound 1 and Compound 117. When these devices were driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), they emitted blue light, and their luminous efficiencies showed 5 cd / A or more. The results are shown in Table 15.

Table 15

Example 224
On the glass plate with an ITO electrode, HIM4 described in Table 3 was deposited to form a hole injection layer having a thickness of 60 nm. Next, the compound 1 of Table 1 and the following compound H were co-evaporated with the composition ratio of 100: 5, and the light emitting layer with a film thickness of 40 nm was formed. Furthermore, Balq (compound I below) is vapor-deposited to form a 10 nm-thick hole blocking layer, and then Alq3 is vacuum-deposited thereon to form a 30-nm-thick electron injection layer. First, lithium fluoride was deposited to 1 nm, and then Al was deposited to 200 nm to form an electrode to obtain an organic EL device. When this device was driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), it emitted blue light, and its luminous efficiency was 9.0 cd / A.

Examples 225-228
A device was prepared in the same manner as in Example 224, except that the compound in Table 16 was used instead of Compound 1. When these devices were driven at a constant current at room temperature with an emission luminance of 300 (cd / m 2 ), the luminous efficiency was 9 cd / A or more. The results are shown in Table 16.

Table 16

Example 229
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 50 nm was obtained. Next, 60% of PVK (polyvinylcarbazole), 4% of compound 1 and 36% of electron transport material (EIMO1 described in Table 4) were dissolved in toluene at a concentration of 2.0 wt%, and the film thickness was 60 nm by spin coating. The light emitting layer was obtained. 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 this device was subjected to an energization test, blue light emission with a maximum light emission luminance of 490 cd / m 2 was obtained.

Example 230
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 50 nm was obtained. Next, 60% of PVK (polyvinylcarbazole), 5% of compound 117 and 35% of electron transport material (EIMS1) were dissolved in toluene at a concentration of 2.0 wt%, and a light emitting layer having a thickness of 70 nm was formed by spin coating. Got. 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 this device was subjected to an energization test, blue light emission with a maximum light emission luminance of 550 cd / m 2 was obtained.

Example 231
On the washed glass plate with an ITO electrode, the compound 46 of the present invention was vacuum-deposited to obtain a hole injection layer having a thickness of 50 nm. Next, α-NPD (HIM1 described in Table 2) was vacuum-deposited to obtain a 30 nm hole transport layer. Further, Alq3 is vacuum-deposited to form an electron-injection-type light emitting layer having a thickness of 50 nm, and then an electrode is formed by first depositing 1 nm of lithium fluoride and then 200 nm of Al to form an organic EL device. It was. When this device was subjected to an energization test, yellow light emission with a maximum light emission luminance of 1530 cd / m 2 was obtained.

Example 232
On the glass plate with an ITO electrode, HTM8 described in Table 3 was vapor-deposited to form a 50 nm-thick hole injection layer, and then compound 90 was vapor-deposited to form a 30-nm-thick hole transport layer. Next, Alq3 was deposited to form an electron injecting light emitting layer having a thickness of 50 nm, and an electrode was formed thereon by vacuum deposition of 1 nm of lithium fluoride and 200 nm of Al, thereby obtaining an organic EL device. When this device was subjected to an energization test, yellow light emission with a maximum light emission luminance of 1890 cd / m 2 was obtained.

Example 233
On the glass plate with an ITO electrode, HTM8 described in Table 3 was vacuum deposited to obtain a hole injection layer having a thickness of 50 nm. Next, Alq3 was deposited to form a light-emitting layer having a thickness of 40 nm. Further, a compound 90 was deposited to form an electron injection layer having a thickness of 30 nm. On top of that, a cathode was formed by vapor deposition of 1 nm of lithium fluoride and 100 nm of Al to obtain an organic EL device. When this device was subjected to a current test, yellow light emission with a maximum light emission luminance of 1680 cd / m 2 was obtained.

  As is clear from the examples described above, the organic EL device of the present invention can achieve improvement in luminous efficiency and long life.

Claims (6)

  1. A material for an organic electroluminescence device represented by the following general formula [1].
    General formula [1]


    (In the formula, R 1 represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group.
    R 2 represents a substituted or unsubstituted condensed polycyclic group or a substituted or unsubstituted heterocyclic group.
    R 3 and R 4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group. )
  2.   The light emitting layer material for organic electroluminescent elements which comprises the material for organic electroluminescent elements of Claim 1.
  3.   2. An organic electroluminescence device comprising a single layer or a plurality of organic layers formed between a pair of electrodes comprising an anode and a cathode, wherein at least one layer is a layer containing the organic electroluminescence device material according to claim 1. Luminescence element.
  4.   The organic electroluminescent element of Claim 3 whose layer containing the light emitting layer material for organic electroluminescent elements of Claim 2 is a light emitting layer.
  5.   The organic electroluminescent device according to claim 4, wherein the light emitting layer further contains a condensed polycyclic aromatic compound.
  6. The organic electroluminescent element according to claim 4, wherein the light emitting layer further contains a phosphorescent light emitting material.

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