JP5699581B2 - Fused pyrrole polycyclic compound, material for light emitting layer, and organic electroluminescent device using the same - Google Patents

Description

  The present invention relates to a condensed pyrrole polycyclic compound, a luminescent material containing the compound, an organic electroluminescent device using the luminescent material (hereinafter sometimes abbreviated as an organic EL device), and the like.

  The organic EL element is a self-luminous light emitting element and is expected as a light emitting element for display or illumination. 2. Description of the Related Art Conventionally, display devices using light emitting elements that emit electroluminescence have been studied variously because they can save power and can be thinned. Furthermore, organic EL elements made of organic materials can be easily reduced in weight and size. Therefore, it has been actively studied.

  The organic EL element has a structure composed of a pair of electrodes composed of an anode and a cathode, and a single layer or a plurality of layers disposed between the pair of electrodes and containing an organic compound. The layer containing an organic compound includes a light-emitting layer and a charge transport / injection layer that transports or injects charges such as holes and electrons. Various organic materials have been developed as the organic compound. In particular, research and development of organic materials for the light emitting layer are actively conducted.

  The light emitting material of the organic EL element is classified into a fluorescent material using singlet excitons and a phosphorescent material using triplet states depending on the light emission mechanism. It is known that the theoretical luminous efficiency is improved about 4 times by using a phosphorescent material as the light emitting material of the organic EL element (see Non-Patent Document 1).

  In a phosphorescent organic EL element, for example, phosphorescence emission is extracted by doping a host material with a metal complex light emitting material containing a heavy metal such as platinum or iridium as a phosphorescent emitting dopant (hereinafter abbreviated as a phosphorescent dopant) (non-phosphorescent). (See Patent Document 1). The light emission efficiency and the light emission lifetime of the phosphorescent dopant are dependent on the host material. The basic performance required for the host material of the phosphorescent organic EL device is that it has a hole transporting property and an electron transporting property, and the triplet state energy level (T1) of the host material is the triplet state energy level of the phosphorescent dopant. It is higher than (T1). In order to put phosphorescent organic EL elements into practical use, green phosphorescent host materials have been actively developed so far (see, for example, Patent Document 1, Patent Document 2, and Non-Patent Document 2). Many of these green phosphorescent host materials are characterized by using a material containing a carbazolyl group. For example, it is well known to use 4,4-N, N′-dicarbazole-biphenyl (hereinafter abbreviated as CBP) (see, for example, Patent Document 3 and Non-Patent Document 1). However, since CBP has a symmetric molecular structure and has a property of being easily crystallized, there is a concern that the stability of the light emitting layer containing the compound is poor. For these reasons, the phosphorescent organic EL element has a serious problem in driving stability of the element for practical use.

JP 2005-174917 A JP 2008-311528 A JP 2001-313178 A

Apllied Physics Letters, 75, 4 (1999) Thin Solid Films, 436, 264 (2003)

  As described above, at present, an organic EL element having sufficient performance with respect to heat resistance, driving voltage, light emission efficiency, current efficiency, element lifetime, external quantum efficiency, and the like has not yet been obtained. Under such circumstances, it is desired to develop an organic EL element that is further excellent in these characteristics, particularly a phosphorescent organic EL element. Therefore, a compound capable of obtaining an organic EL device having such excellent characteristics, that is, a green phosphorescent host that can form a stable light-emitting layer that is difficult to crystallize and realizes high efficiency and high driving stability. Development of materials is desired.

  Also, in order to cope with the mass production of full-color flat panel displays, it is necessary to develop a host material that has high performance and can be used simultaneously with fluorescence and phosphorescence.

  As a result of intensive studies to solve the above problems, the present inventors have succeeded in producing a condensed pyrrole polycyclic compound represented by the following formula (1), and using a layer containing this condensed pyrrole polycyclic compound. By making the organic electroluminescent element configured, an organic EL element having improved characteristics such as driving voltage, luminous efficiency, current efficiency, element lifetime, and external quantum efficiency, in particular, a phosphorescent organic EL element having excellent green emission characteristics It was found that it was obtained.

  That is, the present invention provides the following condensed pyrrole polycyclic compound that is optimal as a material for the light emitting layer and an organic electroluminescent device using the same.

[1] A compound represented by the following formula (1).

In formula (1), Ar ¹ is a fluorene ring fused to a pyrrole ring;
The optional site “—CH═” in the condensed ring formed by the indole ring and the fluorene ring may be the site “—N═”,
Arbitrary hydrogen in the condensed ring formed by the indole ring and the fluorene ring is alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 30 carbon atoms, or 1 to 30 carbon atoms. May be substituted with heteroaryl, and when two hydrogens at the 9-position of the fluorene ring are substituted, these substituents may be bonded to each other to form a spiro ring;
Ar ² is aryl having 10 to 30 carbon atoms. However, when biphenylyl is selected from aryl having 10 to 30 carbon atoms, it is biphenylyl represented by the following formula (BP).

In Formula (BP), Ar ³ is heteroaryl having 1 to 30 carbons which may be substituted with at least one group selected from aryl having 6 to 30 carbons and heteroaryl having 1 to 30 carbons .

[2] The compound according to [1], which is represented by any one of the following formulas (1-1) to (1-6).

In the formulas (1-1) to (1-6), any site “—CH═” in the condensed ring formed by the indole ring and the fluorene ring may be the site “—N═”;
R ¹ and R ² are each independently aryl having 6 to 18 carbon atoms or heteroaryl having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other to form a spiro ring. Often;
Ar ² is aryl having 10 to 30 carbon atoms. However, when biphenylyl is selected from aryl having 10 to 30 carbon atoms, it is biphenylyl represented by the following formula (BP).

In Formula (BP), Ar ³ is heteroaryl having 1 to 30 carbons which may be substituted with at least one group selected from aryl having 6 to 30 carbons and heteroaryl having 1 to 30 carbons .

[3] R ¹ and R ² are phenyl, biphenylyl, naphthyl, phenanthryl, pyridyl, or imidazolyl, which may be bonded to each other to form a spiro ring;
Ar ² is naphthyl, phenanthryl or biphenylyl represented by the following formula (BP),

In the formula (BP), Ar ³ is a heteroaryl having 1 to 20 carbons which may be substituted with at least one group selected from aryl having 6 to 20 carbons and heteroaryl having 1 to 20 carbons The compound according to [2] above.

[4] R ¹ and R ² are phenyl or pyridyl, which may be bonded to each other to form a spiro ring;
Ar ² is naphthyl, phenanthryl or biphenylyl represented by the following formula (BP),

In the formula (BP), Ar ³ is pyridyl, carbazolyl, indenocarbazolyl, which may be substituted with at least one group selected from aryl having 6 to 10 carbon atoms and heteroaryl having 1 to 10 carbon atoms , Pyrrolyl, indolyl, isoindolyl, or isoxazolyl, and the optional site “—CH═” in these rings may be the site “—N═”, according to [2] or [3] above.

[5] R ¹ and R ² are phenyl, which may be bonded to each other to form a spiro ring;
Ar ² is biphenylyl represented by the following formula (BP),

In the formula (BP), Ar ³ is carbazolyl, carbolinyl, indenocarbazolyl, indenocarbolinyl, or benzoimidazolyl, which may be substituted with phenyl, any of the above [2] to [4] A compound according to claim 1.

[6] The compound according to any one of [2] to [5], which is represented by the following formula (1-1-28) or formula (1-222).

[7] A light emitting layer material for an organic electroluminescence device, comprising the compound according to any one of [1] to [6].

[8] Further, it contains at least one compound selected from the group consisting of an amine having a stilbene structure, an amine having a benzofluorene structure, an aromatic amine, a coumarin derivative, a pyran derivative, an iridium complex, a rhenium complex, and a platinum complex. The light emitting layer material according to [7] above.

[9] An organic electroluminescence device comprising a pair of electrodes composed of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes and containing the light emitting layer material according to [7] or [8] .

[10] Furthermore, it has an electron transport layer and / or an electron injection layer arranged between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer is a quinolinol-based metal complex, The organic electroluminescence device according to [9] above, which contains at least one selected from the group consisting of pyridine derivatives, phenanthroline derivatives, borane derivatives, and benzimidazole derivatives.

[11] At least one of the electron transport layer and the electron injection layer may further include an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, At least one selected from the group consisting of alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes The organic electroluminescent element according to [10], which is contained.

[12] A display device comprising the organic electroluminescent element according to any one of [9] to [11].

[13] An illumination device including the organic electroluminescent element according to any one of [9] to [11].

  Since the compound represented by the above formula (1) has an asymmetric molecular structure, it is easy to form an amorphous state at the time of preparing an organic EL device, exhibits a stable glass state, and forms a stable amorphous film by vapor deposition or the like. Can be formed. Therefore, the compound is excellent in heat resistance and stable even when an electric field is applied. In addition, the compound represented by the above formula (1) has high solubility in an organic solvent, and is not only easily purified by recrystallization or column chromatography, but also has a free layer forming means when forming a layer of an organic EL device. Can be adopted. For example, in general, in the layer formation by the vapor deposition method, there is a risk of decomposition of the compound or non-uniformity in the crystal structure of the formed layer, but the compound represented by the above formula (1) has various Since a spin coating method can be easily employed using a solvent, it is possible to form a layer that eliminates these fears.

  The compound represented by the above formula (1) is effective as a host light-emitting material. The compound represented by the above formula (1) has a short emission wavelength and can be used as a fluorescent blue host light-emitting material, but particularly as a green phosphorescent host material because of its high triplet state energy level (T1). It is valid. When used as a host material for a green phosphorescent organic EL device, energy transfer to the green dopant is efficiently performed, and a phosphorescent organic EL device with high efficiency and long life can be obtained.

It is a schematic sectional drawing which shows the organic electroluminescent element which concerns on this embodiment.

1. The condensed pyrrole polycyclic compound represented by the formula (1) First, the condensed pyrrole polycyclic compound represented by the following formula (1) will be described in detail.

In the formula (1), examples of the condensed ring formed by the indole ring and the fluorene ring (Ar ¹ ) include the following six types from (1-1) type to (1-6) type. The following structural formulas show only the basic skeleton, and the substituents are omitted. Among these, preferred types are (1-1) type, (1-2) type and (1-5) type.

  Further, the optional site “—CH═” in the condensed ring formed by the indole ring and the fluorene ring may be the site “—N═”. For example, the optional site “—CH═” in the indole ring may be Examples include the case where the moiety is “—N═”, and more specifically, a case where the carbon atom at the 4-position or 6-position of the indole ring is substituted with a nitrogen atom. Examples of the number of positions where the moiety “—CH═” is substituted by the moiety “—N═” include three, two, and one place in the entire condensed ring.

  As a C1-C20 alkyl substituted by the condensed ring formed by an indole ring and a fluorene ring, any of a straight chain and a branched chain may be sufficient, a C1-C20 linear alkyl or C3-C3 There are 20 branched chain alkyls. Preferred is alkyl having 1 to 10 carbons (branched alkyl having 3 to 10 carbons), more preferred is alkyl having 1 to 6 carbons (branched alkyl having 3 to 6 carbons), and Preferred is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl and the like are mentioned, and methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl is preferable. More preferably, isopropyl or tert-butyl.

  Preferred examples of the cycloalkyl having 3 to 20 carbon atoms substituted on the condensed ring formed by the indole ring and the fluorene ring include cycloalkyl having 1 to 10 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl and dimethylcyclohexyl.

  The aryl having 6 to 30 carbon atoms substituted on the condensed ring formed by the indole ring and the fluorene ring is preferably an aryl having 6 to 18 carbon atoms, more preferably an aryl having 6 to 14 carbon atoms, More preferred is aryl having 6 to 12 carbon atoms.

  Specific aryls include monocyclic aryl phenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, condensed bicyclic aryl (1-, 2-) naphthyl, three Ring system aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-tel Phenyl-4′-yl, p-terphenyl-2′-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2 -Yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), condensation Acenaphthyl, a tricyclic aryl -(1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1- , 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl which is a tetracyclic aryl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl- 3-yl, 5′-phenyl-m-terphenyl-4-yl, m-quaterphenyl), condensed tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-, 2) -, 4-) yl, naphthacene- (1-, 2-, 5-) yl, fused pentacyclic aryl perylene- (1-, 2-, 3-) yl, pentacene- (1-, 2- , 5-, 6-) yl and the like.

  Among these, aryl is preferably phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, chrysenyl or triphenylenyl, more preferably phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-biphenyl. Naphthyl, 2-naphthyl or phenanthryl is exemplified, and phenyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl or 9-phenanthryl is particularly preferred.

  The heteroaryl having 1 to 30 carbon atoms substituted on the condensed ring formed by the indole ring and the fluorene ring is preferably a heteroaryl having 2 to 20 carbon atoms, more preferably a heteroaryl having 2 to 15 carbon atoms, particularly Preferably, a C2-C10 heteroaryl is mentioned. Further, examples thereof include a heterocyclic group containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon.

  Examples of heteroaryl include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl , Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl Benzofuranyl, isobenzofuranyl Benzo [b] thienyl, phenoxathiinyl, thianthrenyl, and the like. Among these, pyridyl, quinolinyl, isoquinolinyl and the like are preferable.

If two hydrogen at position 9 of the fluorene ring (Ar ¹⁾ in the formula (1) are substituted, these substituents together may form a spiro ring bonded, a structure shown in, for example, the following Can be mentioned. In the following structural formulas, the fluorene ring is indicated by a broken line, and the substituents are omitted.

Examples of the compound represented by the above formula (1) include compounds represented by any of the following formulas (1-1) to (1-6).

In the above formulas (1-1) to (1-6), any site “—CH═” in the condensed ring formed by the indole ring and the fluorene ring may be the site “—N═”, and R ^{As 1} and R ² , the description of the substituents substituted on the condensed ring formed by the indole ring and the fluorene ring can be cited.

Ar ² in the above formula (1) or the above formulas (1-1) to (1-6) is aryl having 10 to 30 carbon atoms, such as 4-biphenylyl which is a bicyclic aryl, or a condensed bicyclic ring. (1-, 2-) naphthyl which is an aryl group, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, which is a condensed tricyclic aryl group 4-, 9-) yl, phenalen- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, condensed tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3) which is a fused pentacyclic aryl -) Yl, pentacene- (1-, 2-, 5-, 6-) yl and the like. Among these, 4-biphenylyl, (1-, 2-) naphthyl and (1-, 2-, 3-, 4-, 9-) phenanthryl are preferable.

However, when biphenylyl is selected from aryl having 10 to 30 carbon atoms, it is 4-biphenylyl substituted with Ar ³ represented by the following formula (BP).

In the above formula (BP), Ar ³ is a heteroaryl having 1 to 30 carbon atoms which may be substituted with at least one group selected from aryl having 6 to 30 carbon atoms and heteroaryl having 1 to 30 carbon atoms. However, for these specific explanations, the explanations of aryl and heteroaryl described above can be cited.

Further, constituting the compound represented by formula (1), a hydrogen atom in the fused ring formed by the indole ring and a fluorene ring, a hydrogen atom in the substituent to the condensed ring, also a hydrogen atom in the substituent Ar ² All or part of may be deuterium.

<Specific examples of compounds>
Specific examples of the compounds of the present invention are shown by the formulas listed below, but the present invention is not limited by the disclosure of these specific structures.

  Examples of the compound represented by the above formula (1-1) include compounds represented by the following formulas (1-1-1) to (1-1127). Among these, preferred compounds are compounds represented by formulas (1-1-28) to (1-1-31) and formulas (1-1-37) to (1-1-52), and more preferred. The compound is a compound represented by Formulas (1-1-28) to (1-1-31).

  In the compound represented by the formula (1-1), specific examples in which an arbitrary site “—CH═” of the condensed ring is substituted with a site “—N═” include the following formulas (1-1-128) to It is a compound represented by (1-1-269). Among these, preferred compounds are formulas (1-1136) to (1-1-143), formulas (1-1-156) to (1-1-163), formulas (1-1-177) to (1-1-184), Formulas (1-1-198) to (1-1-205), Formulas (1-1-210) to (1-1-217), Formula (1-1-220) To (1-1-227), formula (1-1-230) to (1-1-237), formula (1-1-240) to (1-1-247), formula (1-1-260) ) To (1-1-267), and more preferable compounds are the formula (1-1136), the formula (1-1-156), the formula (1-1-177), the formula (1-1-198), formula (1-1-210), formula (1-1-220), formula (1-1-230), formula (1-1-240), formula (1-1- 260) .

Specific examples in which the portion corresponding to fluorene condensed in the compound represented by formula (1-1) forms a spiro ring include the following formulas (1-1-270) to (1-1-718). ), And specific examples in which an arbitrary part “—CH═” of the condensed ring is replaced with a part “—N═” are also included. Among these, preferred compounds are those represented by formulas (1-1-274) to (1-1-278), formulas (1-1-303) to (1-1-307), and formulas (1-1-334) to (1-1-338), formulas (1-1-364) to (1-1-368), formulas (1-1-393) to (1-1-397), formula (1-1-422) To (1-1 to 426), Formulas (1-1 to 452) to (1-1 to 457), Formulas (1-1 to 482) to (1-1 to 486), Formula (1-1 to 511). ) To (1-1-515), formulas (1-1-540) to (1-1-544), formulas (1-1-569) to (1-1-573), formula (1-1-1) 598) to (1-1-602), formulas (1-1-627) to (1-1-631), formulas (1-1-656) to (1-1-660), formula (1- 1-685) to (1-1-689) Is a compound,
More preferred compounds are formula (1-1-274), formula (1-1-307), formula (1-1-334), formula (1-1-364), formula (1-1-393), formula (1-1-422), formula (1-1-452), formula (1-1-482), formula (1-1-511), formula (1-1-540), formula (1-1- 569), formulas (1-1-598), (1-1-627), formulas (1-1-656), and formulas (1-1-685).

  In the compound represented by the formula (1-1), 5,12-dihydroindeno [1,2-c] carbazole or any part “—CH═” of this structure is substituted with the part “—N═”. Specific examples of having two condensed rings as partial structures include compounds represented by the following formulas (1-1-719) to (1-1-735), and these include sites corresponding to fluorene. Specific examples in which forms a spiro ring are also included. Among these, preferred compounds are compounds represented by formula (1-1-719), formula (1-1-721), formula (1-1-722) to formula (1-1-726), More preferred compounds are compounds represented by formula (1-1-719) and formula (1-1-721).

  Examples of the compound represented by the formula (1-2) include compounds represented by the following formulas (1-2-1) to (1-2103). Among these, preferred compounds are compounds represented by formulas (1-222) to (1-2-24) and formulas (1-229) to (1-2-40), and more preferred. The compound is a compound represented by the formula (1-2-22).

  Specific examples of the compound represented by the formula (1-2) in which an arbitrary site “—CH═” of the condensed ring is substituted with the site “—N═” include the following formulas (1-2125) to ( The compound represented by 1-2289) is mentioned. Among these, preferable compounds are represented by formulas (1-2134) to (1-2139), formulas (1-2154) to (1-2157), and formulas (1-2169) to (1-287), formulas (1-299-199) to (1-2202), formulas (1-214) to (1-2217), formula (1-229) To (1-2232), formulas (1-2244) to (1-2247), compounds represented by formulas (1-259) to (1-2262), More preferable compounds are represented by the formula (1-2134), formula (1-2154), formula (1-2169), formula (1-299), (1-2214), formula (1-2) 1-2-229), formula (1-2-244), formula (1-2-259), and a compound represented by formula (1-2-274).

  Specific examples in which the portion corresponding to fluorene condensed in the compound represented by formula (1-2) forms a spiro ring include the following formulas (1-290) to (1-2554). ), And specific examples in which any —CH═ of the condensed ring is replaced by —N═ are also included. Among these, preferred compounds are those represented by formulas (1-290) to (1-2294), formulas (1-2306) to (1-2310), and formulas (1-232) to (1-226), Formulas (1-2-338) to (1-2342), Formulas (1-2-354) to (1-2-358), Formula (1-2-370) -(1-2-374), Formulas (1-2386)-(1-2-390), Formulas (1-2402)-(1-2406), Formula (1-2-418) ) To (1-2422), formulas (1-2434) to (1-2438), formulas (1-2450) to (1-2454), formula (1-2) 466) to (1-2470), formulas (1-2482) to (1-2486), formulas (1-2498) to (1-2502), formula (1-2) -514) to (1-2-518), the formula (1- -530) to (1-2-534), and more preferable compounds are the formula (1-2-290), the formula (1-2306), the formula (1-2-322), Formula (1-2-338), Formula (1-2-354), Formula (1-2-370), Formula (1-2-386), Formula (1-2-402), Formula (1-2) -418), formula (1-2-434), formula (1-2-450), formula (1-2-466), formula (1-2-482), formula (1-2-498), formula (1-2-514), a compound represented by formula (1-2-530).

  In the compound represented by the formula (1-2), 5,7-dihydroindeno [2,1-b] carbazole or any part “—CH═” of this structure is substituted with the part “—N═”. Specific examples having two condensed rings as partial structures include compounds represented by the following formulas (1-2-555) to (1-2-580), and these include a site corresponding to fluorene. Specific examples of forming a spiro ring are also included. Among these, preferable compounds are compounds represented by formulas (1-2555) to (1-2564) and formulas (1-2569) to (1-2576), and more preferable. The compound is a compound represented by Formula (1-2555) or Formula (1-2556).

  Specific examples of the compound represented by the formula (1-3) include compounds represented by the following formulas (1-3-1) to (1-3-84). Among these, preferred compounds are compounds represented by formulas (1-3-10) to (1-3-24), and more preferred compounds are compounds represented by formula (1-3-10). .

  Specific examples in which an arbitrary site “—CH═” of the condensed ring in the compound represented by formula (1-3) is substituted with a site “—N═” include the following formulas (1-3-85) to ( 1-3-295). Among these, preferable compounds are represented by formulas (1-3-88) to (1-3-94), formulas (1-3-109) to (1-3-115), and formulas (1-3-130) to (1-136), Formulas (1-3-151) to (1-3-157), Formulas (1-3-172) to (1-3-178), Formula (1-3-193) To (1-3-199), Formulas (1-3-214) to (1-3-220), Formulas (1-3-235) to (1-3-241), Formulas (1-3 to 256) ) To (1-3-262) and formulas (1-3-277) to (1-3-283), and more preferable compounds are formulas (1-3-88) and (1). -3-109), formula (1-3-130), formula (1-3-151), formula (1-3-172), formula (1-3-193), formula (1-3-214) , Formula (1-3-235), Formula (1 3-256), a compound represented by the formula (1-3-277).

  Specific examples of the portion corresponding to fluorene condensed in the compound represented by formula (1-3) forming a spiro ring include the following formulas (1-3-296) to (1-3-539). ), And specific examples in which an arbitrary part “—CH═” of the condensed ring is substituted with a part “—N═” are also included. Among these, preferred compounds are those represented by formulas (1-3-296) to (1-3-300), formulas (1-3-3-111) to (1-3-315), and formulas (1-3-326) to (1-3-330), Formulas (1-3-341) to (1-3-345), Formulas (1-3-356) to (1-3-360), Formula (1-3-371) To (1-3-375), formulas (1-3-386) to (1-3-390), formulas (1-3-401) to (1-3-405), formulas (1-3 to 416) ) To (1-3-420), formulas (1-3-431) to (1-3-445), formulas (1-3-446) to (1-3-450), formula (1-3- 461) to (1-3-465), formulas (1-3 to 476) to (1-3-480), formulas (1-3-501) to (1-3-505), formula (1-3) -516) to (1-3-520) More preferable compounds are compounds of formula (1-3-296), formula (1-3-311), formula (1-3-326), formula (1-3-341), formula (1-3). -356), formula (1-3-371), formula (1-3-386), formula (1-3-401), formula (1-3-416), formula (1-3-431), formula It is a compound represented by (1-3-446), formula (1-3-461), formula (1-3-476), formula (1-3-501), formula (1-3-516). .

  In the compound represented by the formula (1-3), 5,8-dihydroindeno [2,1-c] carbazole or any part “—CH═” of this structure is substituted with the part “—N═”. Specific examples having two condensed rings as partial structures include compounds represented by the following formulas (1-3-540) to (1-3-565), and these include a site corresponding to fluorene. Specific examples of forming a spiro ring are also included. Among these, preferred compounds are compounds represented by formulas (1-3-540) to (1-3-550), and more preferred compounds are formulas (1-3-540) and formulas (1-3- 541).

  Specific examples of the compound represented by the formula (1-4) include compounds represented by the following formulas (1-4-1) to (1-4-89). Among these, preferred compounds are compounds represented by formulas (1-4-13) to (1-4-29), and more preferred compounds are compounds represented by formula (1-4-13).

  Specific examples of the compound represented by the formula (1-4) in which any site “—CH═” of the condensed ring is substituted with the site “—N═” include the following formulas (1-4-90) to (1 -4-280). Among these, preferred compounds are those represented by formulas (1-4-90) to (1-4-97), formulas (1-4-109) to (1-4-116), and formulas (1-4-128) to (1-4-135), formulas (1-4-147) to (1-4-154), formulas (1-4-166) to (1-4-173), formulas (1-4-185) To (1-4-192), formulas (1-4-204) to (14-211), formulas (1-223) to (1-4-230), formulas (1-4-242) ) To (1-4-249) and (1-4-261) to (1-4-268), and more preferable compounds are the formula (1-4-90) and the formula (1- 4-109), formula (1-4-128), formula (1-4-147), formula (1-4-166), formula (1-4-185), formula (1-4-204), Formula (1-4-223), Formula ( -4-242) is a compound represented by the formula (1-4-261).

  Specific examples in which the site corresponding to the fluorene condensed in the compound represented by the formula (1-4) forms a spiro ring include the following formulas (1-4-281) to (1-4-529) These include a specific example in which an arbitrary part “—CH═” of the condensed ring is substituted with a part “—N═”. Among these, preferred compounds are those represented by formulas (1-4-281) to (1-4-285), formulas (1-4-297) to (1-4-301), formulas (1-4-313) to (1-4-317), Formulas (1-4-329) to (1-4-3-333), Formulas (1-4-345) to (1-4-349), Formula (1-4-361) To (1-4-365), formulas (1-4-377) to (1-4-381), formulas (1-4-393) to (1-4-397), formulas (1-4-409) ) To (1-4-413), formulas (1-4-425) to (1-4-429), formulas (1-4-441) to (1-4-445), formula (1-4- 457) to (1-4-461), formulas (1-4-473) to (1-4-477), formulas (1-4-489) to (1-4-493), formula (1-4) -505) to (1-4-509) More preferable compounds are the compounds of formula (1-4-281), formula (1-4-297), formula (1-4-313), formula (1-4-329), formula (1-4-). 345), formula (1-4-361), formula (1-4-377, formula (1-4-393), formula (1-4-409), formula (1-4-425), formula (1) -4-441), Formula (1-4-457), Formula (1-4-473), Formula (1-4-489), and Formula (1-4-505).

  In the compound represented by the formula (1-4), 7,12-dihydroindeno [1,2-a] carbazole or any part “—CH═” of this structure is substituted with the part “—N═” Specific examples having two condensed rings as partial structures include compounds represented by the following formulas (1-4-530) to (1-4-555), in which a portion corresponding to fluorene is a spiro ring. The specific example which forms is also included. Among these, preferred compounds are compounds represented by formulas (1-4-530) to (1-4-539) and formulas (1-4-544) to formulas (1-4-551), and more preferred. The compound is a compound represented by formula (1-4-530) or formula (1-4-531).

  Specific examples of the compound represented by the formula (1-5) include compounds represented by the following formulas (1-5-1) to (1-5-60). Among these, preferred compounds are compounds represented by formulas (1-5-7) to (1-5-21), and more preferred compounds are compounds represented by formula (1-5-7).

  Specific examples of the compound represented by the formula (1-5) in which any site “—CH═” of the condensed ring is substituted with the site “—N═” include the following formulas (1-5-61) to (1 The compound represented by -5-243) is mentioned. Among these, preferred compounds are those represented by formulas (1-5-61) to (1-5-67), formulas (1-5-79) to (1-5-85), formulas (1-5-97) to (1-5-103), formulas (1-5-115) to (1-5-121), formulas (1-5-133) to (1-5-139), formulas (1-5-151) To (1-5-157), formula (1-5-169) to (1-5-175), formula (1-5-187) to (1-5-193), formula (1-5-205) ) To (1-5-211), and more preferable compounds are those represented by formula (1-5-61), formula (1-5-79), formula (1-5-97), formula (1). -5-115), formula (1-5-133), formula (1-5-151), formula (1-5-169), formula (1-5-187), formula (1-5-205) It is a compound represented by these.

  Specific examples in which the portion corresponding to the condensed fluorene in the compound represented by the formula (1-5) forms a spiro ring include the following formulas (1-5-244) to (1-5-477). These include a specific example in which an arbitrary part “—CH═” of the condensed ring is substituted with a part “—N═”. Among these, preferred compounds are those represented by formulas (1-5-244) to (1-5-248), formulas (1-5-259) to (1-5-263), formulas (1-5-274) to (1-5-278), formulas (1-5-289) to (1-5-293), formulas (1-5-304) to (1-5-308), formulas (1-5-319) To (1-5-323), Formula (1-5-334) to (1-5-338), Formula (1-5-349) to (1-5-353), Formula (1-5-364) ) To (1-5-368), formulas (1-5-379) to (1-5-383), formulas (1-5-394) to (1-5-398), formula (1-5 409) to (1-5-413), formulas (1-5-424) to (1-5-428), formulas (1-5-439) to (1-5-443), formula (1-5) -454) to (1-5-458) More preferred compounds are the compounds of formula (1-5-244), formula (1-5-259), formula (1-5-274), formula (1-5-289), formula (1-5 304), formula (1-5-319), formula (1-5-334), formula (1-5-349), formula (1-5-364), formula (1-5-379), formula ( 1-5-394), formula (1-5-409), formula (1-5-424), formula (1-5-439), and compound represented by formula (1-5-454).

  In the compound represented by the formula (1-5), 5,11-dihydroindeno [1,2-b] carbazole or any part “—CH═” of this structure is substituted with the part “—N═” Specific examples having two condensed rings as partial structures include compounds represented by the following formulas (1-5-478) to (1-5-504), in which the site corresponding to fluorene is a spiro ring. The specific example which forms is also included. Among these, preferred compounds are compounds represented by formulas (1-5-478) to (1-5-488) and formulas (1-5-493) to formulas (1-5-500), and more preferred. The compound is a compound represented by formula (1-5-478) or formula (1-5-480).

  Specific examples of the compound represented by the formula (1-6) include compounds represented by the following formulas (1-6-1) to (1-6-24). Among these, preferred compounds are compounds represented by formula (1-6-1) to (1-6-12), and more preferred compounds are compounds represented by formula (1-6-1).

  Specific examples of the compound represented by the formula (1-6) in which any site “—CH═” of the condensed ring is substituted with the site “—N═” include the following formulas (1-6-25) to (1 -6-104). Among these, preferred compounds are those represented by formulas (1-6-25) to (1-6-29), formulas (1-6-33) to (1-6-37), formulas (1-6-41) to (1-6-45), formulas (1-6-49) to (1-6-53), formulas (1-6-57) to (1-6-61), formula (1-6-65) To (1-6-69), formulas (1-6-73) to (1-6-77), formulas (1-6-81) to (1-6-85), formulas (1-6-89) ) To (1-6-93) and compounds represented by formulas (1-6-97) to (1-6-101), and more preferred compounds are those represented by formulas (1-6-25) and (1- 6-33), formula (1-6-41), formula (1-6-49), formula (1-6-57), formula (1-6-65), formula (1-6-73), Formulas represented by formula (1-6-81), formula (1-6-89), and formula (1-6-97) Thing is.

  Specific examples in which the portion corresponding to the condensed fluorene in the compound represented by the formula (1-6) forms a spiro ring include the following formulas (1-6-105) to (1-6-360). These include specific examples in which an arbitrary part “—CH═” of the condensed ring is replaced with a part “—N═”. Among these, preferred compounds are those represented by formulas (1-6-105) to (1-6-109), formulas (1-6-121) to (1-6-125), formulas (1-6-137) to (1-6-141), formulas (1-6-153) to (1-6-157), formulas (1-6-169) to (1-6-173), formulas (1-6-185) To (1-6-189), formulas (1-6-201) to (1-6-205), formulas (1-6-217) to (1-6-221), formulas (1-6-233) ) To (1-6-237), formulas (1-6-249) to (1-6-253), formulas (1-6-265) to (1-6-269), formulas (1-6 281) to (1-6-285), formulas (1-6-297) to (1-6-301), formulas (1-6-313) to (1-6-317), formula (1-6) -329) to (1-6-333) More preferable compounds are the compounds of formula (1-6-105), formula (1-6-121), formula (1-6-137), formula (1-6-153), formula (1-6-6). 169), formula (1-6-185), formula (1-6-201), formula (1-6-217), formula (1-6-233), formula (1-6-249), formula ( 1-6-265), formula (1-6-281), formula (1-6-297), formula (1-6-313), and a compound represented by formula (1-6-329).

  Examples of the compound according to the present invention include compounds represented by the above formulas (1-1) to (1-6) in a compound in which two condensed rings formed of carbazole and indene are connected to the 4,4′-position of biphenyl. In addition to those listed in the specific examples, compounds having two different condensed ring structures are also included. In this application, such a group of compounds is classified into compounds represented by the formula (1-7). Specific examples of the compound represented by the formula (1-7) include compounds represented by the following formulas (1-7-1) to (1-7-14), and these include any compound of this structure. Specific examples having two condensed rings in which the moiety “—CH═” is substituted with the moiety “—N═” as a partial structure and specific examples in which the moiety corresponding to fluorene forms a spiro ring are also included. Among these, preferred compounds are compounds represented by formulas (1-7-1) to (1-7-4) and formulas (1-7-7) to (1-7-10).

2. Method for producing compounds represented by formulas (1-1) to (1-6) The compounds represented by formulas (1-1) to (1-6) should be produced using known synthesis methods. Can do. For example, it can be synthesized according to the routes shown in the following reactions 1 to 5. Moreover, it can also synthesize | combine according to the route shown to following reaction 6-9.

First, the route of reaction 1-5 is demonstrated as a synthesis example of the compound represented by Formula (1-1) and (1-2).

In Reaction 1, using a palladium catalyst or a copper catalyst, 3-carbazolyl halide or triflate is reacted with a bromide or iodide of Ar ² in the presence of a base and a reaction accelerator, and the 9-position is replaced with Ar ² . To do. Here Ar ² is the same as Ar ² in the formula (1).

In Reaction 2, carbazolyl boron having Ar ² was reacted with carbazolyl halide or triflate having Ar ² obtained in Reaction 1 using bis (pinacolato) diboron in the presence of a base using a palladium catalyst. Synthesize acid ester derivatives.

In Reaction 3, using a palladium catalyst in the presence of a base, the carbazolylboronic acid ester derivative having Ar ² obtained in Reaction 2 was subjected to Suzuki coupling reaction with methyl o-bromobenzoate to produce Ar ² . An ortho-carbazolyl methyl benzoate derivative is synthesized.

In Reaction 4, a tertiary alcohol derivative is synthesized by reacting the ortho-carbazolyl methyl benzoate derivative having Ar ² obtained in Reaction 3 with 2 moles of an organometallic reagent. Here, R ¹ and R ² are the same as R ¹ and R ² in the formula (1), respectively, and an organometallic reagent corresponding to R ¹ or R ² is selected.

In Reaction 5, the compounds represented by formulas (1-1) and (1-2) are produced by cyclization of the inside of the molecule in the presence of an acid catalyst. A mixture comprising these compounds can be separated by a column purification method, a recrystallization method, a sublimation purification method, or the like.

  In the routes of the above reactions 1 to 5, if 4-carbazolyl halide or triflate is used in reaction 1, the compound represented by the formula (1-3) can be produced. If ril halide or triflate is used, a compound represented by formula (1-4) can be produced. If 2-carbazolyl halide or triflate is used, formula (1-5) and formula (1) The compound represented by -6) can be produced.

  Next, pathways of reactions 6 to 9 will be described as synthesis examples of the compounds represented by formulas (1-5) and (formula 1-6).

In Reaction 6, a fluorene derivative having a nitrophenyl group is synthesized by subjecting 2-fluoreneboronic acid to 2-halogen nitrobenzene or 2-triflate nitrobenzene by Suzuki coupling reaction using a palladium catalyst in the presence of a base. Here, R ¹ and R ² are the same as R ¹ and R ² in the formula (1), respectively.

In Reaction 7, the fluorene derivative having a nitrophenyl group obtained in Reaction 6 is reductively cyclized using PPh ₃ or P (OEt) ₃ to obtain the compounds of formulas (1-5 ′) and (1-6 ′). ) Is synthesized.

In Reaction 8, an indenecarbazole derivative represented by the formulas (1-5 ′) and (1-6 ′) obtained in Reaction 7 was used in the presence of a base and a reaction accelerator using a palladium catalyst or a copper catalyst. The compounds represented by the formulas (1-5) and (1-6) are produced by reacting each with a bromide or iodide of Ar ² . Here Ar ² is the same as Ar ² in the formula (1).

In Reaction 9, an indenecarbazole derivative represented by the formulas (1-5 ′) and (1-6 ′) obtained in Reaction 7 was used in the presence of a base and a reaction accelerator using a palladium catalyst or a copper catalyst. Bimer bromide or iodide is reacted with each other to produce a dimer contained in the compounds represented by formulas (1-5) and (1-6).

  In the route of the above reactions 6 to 9, if 1-fluoreneboronic acid is used in reaction 6, the compound represented by the formula (1-1) can be produced, and 3-fluoreneboronic acid can be used. For example, a compound represented by formula (1-2) and formula (1-4) can be produced. If 4-fluoreneboronic acid is used, a compound represented by formula (1-3) is produced. Can do.

  When a copper catalyst is used in Reaction 1, Reaction 8 or Reaction 9, copper powder, copper oxide, copper halide or the like is used. The base used is potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydride and the like, and the reaction accelerator is crown ether (for example, 18-crown-6-ether), polyethylene glycol (PEG), polyethylene glycol dialkyl ether. (PEGDM). As the reaction solvent, N, N-dimethylformamide, nitrobenzene, dimethyl sulfoxide, dichlorobenzene, quinoline and the like are used. The reaction temperature is 160 to 250 ° C., but if the substrate has low reactivity, a higher temperature reaction may be performed using an autoclave or the like.

  When a palladium catalyst is used in Reaction 1, Reaction 8 or Reaction 9, palladium acetate, palladium chloride, palladium bromide, tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium chloroform complex ( 0), tetrakis (triphenylphosphine) palladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichlorolithodichloromethane complex (1: 1) and the like are used. The base used is lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydride, alkoxy potassium (for example, methoxy potassium, ethoxy potassium, normal propoxy potassium, isopropoxy potassium, n-butoxy Potassium and tert-butoxypotassium) alkoxy sodium (such as sodium methoxy, sodium ethoxy, normal propoxy sodium, isopropoxy sodium, n-butoxy sodium and tert-butoxy sodium). The reaction accelerator is 2,2 ′-(diphenylphosphino) -1,1′-binaphthyl, 1,1 ′-(diphenylphosphino) ferrocene, dicyclohexylphosphinobiphenyl, di-tert-butylphosphinobiphenyl, tri ( tert-butyl) phosphine, 1- (N, N-dimethylaminomethyl) -2- (di-tert-butylphosphino) ferrocene, 1- (N, N-dibutylaminomethyl) -2- (di-tert- Butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-tert-butylphosphino) ferrocene, 1,1′-bis (di-tert-butylphosphino) ferrocene, 2,2′-bis ( Di-tert-butylphosphino) -1,1′-binaphthyl, 2-methoxy-2 ′-(di-tert-butylphosphino) Such as 1,1'-binaphthyl is used. An aromatic hydrocarbon solvent such as benzene, toluene, xylene, mesitylene is used as the reaction solvent. A solvent may be used independently and may be used as a mixed solvent. The reaction temperature is usually 50 to 200 ° C., more preferably 80 to 140 ° C.

Examples of the palladium catalyst used in Reaction 2, Reaction 3 or Reaction 6 include Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0), tris (Dibenzylideneacetone) dipalladium chloroform complex (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichlorolithodichloromethane complex (1: 1) and the like. In order to accelerate the reaction, a phosphine compound may be added to these palladium compounds. Examples of the phosphine compounds are tri (tert-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (ditert-butylphosphino) ferrocene, 1- (N, N- Dibutylaminomethyl) -2- (ditert-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (ditert-butylphosphino) ferrocene, 1,1′-bis (ditert-butylphosphino) Ferrocene, 2,2′-bis (ditert-butylphosphino) -1,1′-binaphthyl, 2-methoxy-2 ′-(ditert-butylphosphino) -1,1′-binaphthyl and the like. Examples of bases used in this reaction are sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium tert-butoxide, sodium acetate, potassium acetate, Tripotassium phosphate, potassium fluoride and the like. Furthermore, examples of the solvent used in this reaction are benzene, toluene, xylene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, tert-butylmethyl ether, 1,4-dioxane, methanol, ethanol, isopropyl alcohol, cyclopentyl. Such as methyl ether. These solvents may be used alone or as a mixed solvent. The reaction temperature is usually 50 to 180 ° C, more preferably 70 to 130 ° C.

  In Reaction 4, tetrahydrofuran, diethyl ether, dimethyl ether, 1,2-dimethoxyethane, cyclopentylmethyl ether, tert-butylmethyl ether, 1,4-dioxane and the like are used as the reaction solvent. A solvent may be used independently and may be used as a mixed solvent. The reaction temperature is usually in the range of -90 ° C to 150 ° C. The reaction temperature varies depending on the metal reagent used. When a lithium reagent is used, the reaction temperature is preferably -70 to -40 ° C. When a Grignard reagent is used, the reaction temperature is preferably 0 to 80 ° C.

Examples of the acid catalyst used in the reaction 5 include inorganic acids such as sulfuric acid, hydrochloric acid and polyphosphoric acid, organic acids such as methanesulfonic acid and trifluoromethanesulfonic acid, silica gel, alumina, BF ₃ · OEt ₂ , AlCl ₃ and AlBr. ₃ , Lewis acids such as EtAlCl ₂ and Et ₂ AlCl. Examples of the reaction solvent include acetic acid, CH ₂ Cl ₂ , CHCl ₃ , nitrobenzene, CS _{2 and the} like. The reaction temperature is usually in the range of −70 ° C. to 150 ° C., more preferably −10 to 100 ° C.

  In Reaction 7, toluene, xylene, chlorobenzene, o-dichlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, or the like is used as a reaction solvent. A solvent may be used independently and may be used as a mixed solvent. The reaction temperature is usually in the range of 100 ° C to 220 ° C. More preferably, it is 130-190 degreeC.

3. Organic Electroluminescent Device The condensed pyrrole polycyclic compound according to the present invention can be used, for example, as a material for an organic electroluminescent device. Below, the organic electroluminescent element which concerns on this embodiment is demonstrated in detail based on drawing. FIG. 1 is a schematic cross-sectional view showing an organic electroluminescent element according to this embodiment.

<Structure of organic electroluminescence device>
An organic electroluminescent device 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole injection layer 103. A hole transport layer 104 provided on the light emitting layer 105, a light emitting layer 105 provided on the hole transport layer 104, an electron transport layer 106 provided on the light emitting layer 105, and an electron transport layer 106. And the cathode 108 provided on the electron injection layer 107.

  The organic electroluminescent element 100 is manufactured in the reverse order, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer. An electron transport layer 106 provided on 107, a light-emitting layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light-emitting layer 105, and a hole transport layer 104 A structure including the hole injection layer 103 provided above and the anode 102 provided on the hole injection layer 103 may be employed.

  Not all of the above layers are necessary, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection. The layer 107 is an arbitrarily provided layer. Moreover, each said layer may consist of a single layer, respectively, and may consist of multiple layers. Further, a hole blocking layer may be provided between the light emitting layer 105 and the electronic layer (106 or 107).

  As an aspect of the layer constituting the organic electroluminescence device, in addition to the above-described configuration aspect of “substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode”, "Substrate / anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode", "substrate / Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode ”,“ substrate ” / Anode / light emitting layer / electron transport layer / electron injection layer / cathode ”,“ substrate / anode / hole transport layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole transport layer / light emitting layer / “Electron transport layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron injection layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron transport” Layer / cathode "," substrate / anode / light emitting layer / electron transporting layer / cathode "may be configured aspect of the" substrate / anode / light emitting layer / electron injection layer / cathode ". In addition, there is a configuration in which a hole blocking layer is provided between the light emitting layer and the electron layer.

<Substrate in organic electroluminescence device>
The substrate 101 serves as a support for the organic electroluminescent device 100, and usually quartz, glass, metal, plastic, or the like is used. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape according to the purpose. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Of these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable. In the case of a glass substrate, soda lime glass, non-alkali glass, or the like is used, and the thickness only needs to be sufficient to maintain the mechanical strength. The upper limit value of the thickness is, for example, 2 mm or less, preferably 1 mm or less. The glass material is preferably alkali-free glass because it is better to have less ions eluted from the glass. However, soda lime glass with a barrier coat such as SiO ₂ is also commercially available, so it can be used. it can. Further, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one surface in order to improve the gas barrier property, and a synthetic resin plate, film or sheet having a low gas barrier property is used as the substrate 101. When used, it is preferable to provide a gas barrier film.

<Anode in organic electroluminescence device>
The anode 102 serves to inject holes into the light emitting layer 105. When the hole injection layer 103 and / or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. .

  As materials for forming the anode 102, examples of the anode material include inorganic compounds and organic compounds having a work function larger than 4 eV. Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide). Products (IZO), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, and the like. Examples of the organic compound include polythiophene such as poly (3-methylthiophene), conductive polymer such as polypyrrole and polyaniline, and the like. In addition, it can select suitably from the substances currently used as an anode of an organic electroluminescent element, and can use it.

  The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but is preferably low resistance from the viewpoint of power consumption of the light emitting element. For example, an ITO substrate of 300Ω / □ or less functions as an element electrode. However, since it is now possible to supply a substrate of about 10Ω / □, for example, 100-5Ω / □, preferably 50-5Ω. It is particularly desirable to use a low resistance product of / □. The thickness of ITO can be arbitrarily selected according to the resistance value, but is usually used in a range of 50 to 300 nm.

<Hole injection layer and hole transport layer in organic electroluminescence device>
The hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104. The hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are each formed by laminating and mixing one kind or two or more kinds of hole injection / transport materials or a mixture of the hole injection / transport material and the polymer binder. Is done. In addition, an inorganic salt such as iron (III) chloride may be added to the hole injection / transport material to form a layer.

  As a hole injection / transport material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes to which an electric field is applied. The hole injection efficiency is high, and the injected holes are transported efficiently. It is desirable to do. For this purpose, it is preferable to use a substance that has a low ionization potential, a high hole mobility, excellent stability, and is less likely to generate trapping impurities during production and use.

As a material for forming the hole injection layer 103 and the hole transport layer 104, in a photoconductive material, a compound conventionally used as a charge transport material for holes, a p-type semiconductor, and a hole injection of an organic electroluminescent element are used. Any known material used for the layer and the hole transport layer can be selected and used. Specific examples thereof include carbazole derivatives (eg, N ⁴ , N ^{4 ′} -diphenyl) such as carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), bis (N-allylcarbazole), or bis (N-alkylcarbazole). -N ⁴ , N ^{4 ′} -bis (9-phenyl-9H-carbazolyl-3-yl)-[1,1′-biphenyl] -4,4′-diamine, etc.), triarylamine derivatives (aromatic third Polymer having primary amino group in main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4'-diaminobiphenyl, N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminobiphenyl (NPD), N, N'-diphe Nyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine, N, N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl- 1,1′-diamine, 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine and other triphenylamine derivatives, starburst amine derivatives and the like, stilbene derivatives, Phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, heterocyclic compounds such as oxadiazole derivatives, porphyrin derivatives, and polysilanes. Polycarbonate, styrene derivatives, polyvinyl carbazole, polysilane, etc. in the side chain are preferred. Bur, forming a thin film necessary for manufacturing a light-emitting element, and can inject holes from the anode, and is not particularly limited as long as it is a further compound capable of transporting holes.

  It is also known that the conductivity of organic semiconductors is strongly influenced by the doping. Such an organic semiconductor matrix material is composed of a compound having a good electron donating property or a compound having a good electron accepting property. Strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known for doping of electron donor materials. (For example, the document “M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 (1998)”) and the document “J. Blochwitz, M Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998)). These generate so-called holes by an electron transfer process in an electron donating base material (hole transport material). Depending on the number and mobility of holes, the conductivity of the base material varies considerably. Known matrix substances having hole transporting properties include, for example, benzidine derivatives (TPD and the like), starburst amine derivatives (TDATA and the like), and specific metal phthalocyanines (particularly zinc phthalocyanine ZnPc and the like). 2005-167175).

<Light emitting layer in organic electroluminescent element>
The light emitting layer 105 emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state It is preferable that the compound exhibits a high emission (fluorescence and / or phosphorescence) efficiency.

  The light emitting layer may be either a single layer or a plurality of layers, and each is formed of a light emitting layer material (host material, dopant material). Each of the host material and the dopant material may be one kind or a plurality of combinations. The dopant material may be included in the host material as a whole, or may be included partially. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited.

  The amount of the host material used varies depending on the type of the host material, and may be determined according to the characteristics of the host material. The amount of the host material used is preferably 50 to 99.999% by weight, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight of the entire light emitting layer material. It is.

  The amount of dopant material used depends on the type of dopant material, and may be determined according to the characteristics of the dopant material. The standard of the amount of dopant used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and further preferably 0.1 to 10% by weight of the entire material for the light emitting layer. is there. The above range is preferable in that, for example, the concentration quenching phenomenon can be prevented.

  Since the compound represented by the above formula (1) of the present invention has high emission quantum efficiency, hole injection property, hole transport property, electron injection property and electron transport property, it is effectively used as a light emitting material in a light emitting layer. it can. The organic EL device of the present invention can form a light emitting layer only with the compound of the present invention. The organic EL device of the present invention can improve light emission luminance and light emission efficiency or obtain blue, green, red and white light emission by combining the light emitting material of the present invention and another light emitting material. In this case, the compound of the present invention is preferably used as a host material.

  The light emitting material of the light emitting element according to the present embodiment may be either fluorescent or phosphorescent.

  As a host material that can be used in combination with the compound represented by the above formula (1) according to the present invention, Asahi High Speed Printing Co., Ltd., Toray Research Center Research Division Luminescent materials as described in Publication (2002) P125-132, “Organic EL materials and displays” supervised by Junji Kido, Luminescent materials as described in CMC Publishing (2001) P153-156, and P170 Triplet materials as described in ˜172.

  Moreover, as a host material that can be used in combination, a polycyclic aromatic compound, a heteroaromatic compound, an organometallic complex, a dye, a polymer-based light emitting material, a styryl derivative, a coumarin derivative, a borane derivative, an oxazine derivative, a compound having a spiro ring, Also included are oxadiazole derivatives and fluorene derivatives. Examples of the polycyclic aromatic compound are anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, pyrene derivatives, chrysene derivatives, perylene derivatives, coronene derivatives, rubrene derivatives, and the like. Examples of heteroaromatic compounds are oxadiazole derivatives having a dialkylamino group or diarylamino group, pyrazoloquinoline derivatives, pyridine derivatives, pyran derivatives, phenanthroline derivatives, silole derivatives, thiophene derivatives having a triphenylamino group, quinacridone derivatives Etc. Examples of organometallic complexes are zinc, aluminum, beryllium, europium, terbium, dysprosium, iridium, platinum, rhenium, osmium, silver, gold and the like, quinolinol derivatives, benzoxazole derivatives, benzothiazole derivatives, oxadiazole derivatives, A complex with a thiadiazole derivative, a phenylpyridine derivative, a phenylbenzimidazole derivative, a pyrrole derivative, a pyridine derivative, a phenanthroline derivative, or the like. Examples of dyes are xanthene derivatives, polymethine derivatives, porphyrin derivatives, coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, oxobenzanthracene derivatives, carbostyril derivatives, perylene derivatives, benzoxazole derivatives, benzothiazole derivatives, benzimidazoles And pigments such as derivatives. Examples of the polymer light-emitting material include polyparaphenylvinylene derivatives, polythiophene derivatives, polyvinylcarbazole derivatives, polysilane derivatives, polyfluorene derivatives, polyparaphenylene derivatives, and the like. Examples of styryl derivatives are amine-containing styryl derivatives, styrylarylene derivatives, and the like.

  In addition, as a host material, it can select and use suitably from the compound etc. which were described in the chemical industry June, 2004 issue page 13, and the reference cited up.

  In addition, the light-emitting dopant material when using the compound of the present invention as a host is not particularly limited, and a known compound can be used, and various materials can be used depending on the desired emission color. You can choose. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene, rubrene and chrysene, benzoxazole derivatives, benzthiazole derivatives, benzimidazole derivatives, benztriazole derivatives, oxazoles Derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, distyrylbenzene derivatives, etc. (Japanese Patent Laid-Open No. 1-245087), bisstyrylarylene derivatives (Japanese Patent Laid-Open No. 2-24727) Gazette), diazaindacene derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, dimesitylisobenzofuran, di (2-methylphenyl) isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, phenylisobenzofuran, etc. Isobenzofuran derivatives, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzthiazolylcoumarin derivatives, 3 -Coumarin derivatives such as benzimidazolyl coumarin derivatives and 3-benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, Nin derivatives, oxobenzanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyril derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1, Examples include 2,5-thiadiazolopyrene derivatives, pyromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives, and benzofluorene derivatives.

  Illustrated for each color light, blue to blue-green dopant materials include naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, chrysene and other aromatic hydrocarbon compounds and derivatives thereof, furan, pyrrole, thiophene, Aromatic heterocycles such as silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene Ring compounds and their derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazoles, thiazoles, thiadiazos Azole derivatives such as sulfazole, carbazole, oxazole, oxadiazole, triazole and metal complexes thereof and N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1 Examples include aromatic amine derivatives represented by '-diamine.

  Examples of the green to yellow dopant material include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, and naphthacene derivatives such as rubrene, and the above blue A compound in which a substituent capable of increasing the wavelength such as an aryl group, a heteroaryl group, an arylvinyl group, an amino group, or a cyano group is introduced into the compound exemplified as the blue-green dopant material is also a suitable example.

  Further, examples of the orange to red dopant material include naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic imide, perinone derivatives, rare earth complexes such as Eu complexes having acetylacetone, benzoylacetone and phenanthroline as ligands, 4 -(Dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinacridone Derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrrolopyridine derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, phenoxazones Conductors and thiadiazolopyrene derivatives, etc., and further increase the wavelength of aryl, heteroaryl, arylvinyl, amino, and cyano groups to the compounds exemplified above as blue to blue-green and green to yellow dopant materials A compound into which a substituent is introduced is also a suitable example. Furthermore, a phosphorescent metal complex having iridium represented by tris (2-phenylpyridine) iridium (III) or platinum as a central metal is also a suitable example.

  In addition, as a dopant, it can select and use suitably from the compound etc. which were described in the chemical industry June, 2004 issue page 13, and the reference cited up.

  Among the dopant materials described above, amines having a stilbene structure, perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives, pyrene derivatives, iridium complexes, platinum complexes, or rhenium complexes are particularly preferable. Among these, a green phosphorescent dopant material of an iridium complex, a platinum complex or a rhenium complex is preferable.

The amine having a stilbene structure is represented by the following formula, for example.

In the formula, Ar ¹ is an m-valent group derived from aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ are each independently aryl having 6 to 30 carbon atoms, Ar ^{1 to} Ar ^At least one of ³ has a stilbene structure, Ar ^{1 to} Ar ³ may be substituted, and m is an integer of 1 to 4.

The amine having a stilbene structure is more preferably a diaminostilbene represented by the following formula.

In the formula, Ar ² and Ar ³ are each independently aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ may be substituted.

  Specific examples of the aryl having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, stilbene, distyrylbenzene, distyrylbiphenyl, and distyryl. Examples include fluorene.

Specific examples of amines having a stilbene structure include N, N, N ′, N′-tetra (4-biphenylyl) -4,4′-diaminostilbene, N, N, N ′, N′-tetra (1-naphthyl) ) -4,4′-diaminostilbene, N, N, N ′, N′-tetra (2-naphthyl) -4,4′-diaminostilbene, N, N′-di (2-naphthyl) -N, N '-Diphenyl-4,4'-diaminostilbene, N, N'-di (9-phenanthryl) -N, N'-diphenyl-4,4'-diaminostilbene, 4,4'-bis [4 "-bis (Diphenylamino) styryl] -biphenyl, 1,4-bis [4′-bis (diphenylamino) styryl] -benzene, 2,7-bis [4′-bis (diphenylamino) styryl] -9,9-dimethyl Fluorene, 4,4′-bis (9-ethyl-3-cal And bazovinylene) -biphenyl and 4,4′-bis (9-phenyl-3-carbazovinylene) -biphenyl.
Moreover, you may use the amine which has a stilbene structure described in Unexamined-Japanese-Patent No. 2003-347056, Unexamined-Japanese-Patent No. 2001-307884, etc.

Examples of perylene derivatives include 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene, 3,10-diphenylperylene, 3,4- Diphenylperylene, 2,5,8,11-tetra-tert-butylperylene, 3,4,9,10-tetraphenylperylene, 3- (1′-pyrenyl) -8,11-di (tert-butyl) perylene 3- (9′-anthryl) -8,11-di (tert-butyl) perylene, 3,3′-bis (8,11-di (tert-butyl) perylenyl), and the like.
JP-A-11-97178, JP-A-2000-133457, JP-A-2000-26324, JP-A-2001-267079, JP-A-2001-267078, JP-A-2001-267076, Perylene derivatives described in JP-A No. 2000-34234, JP-A No. 2001-267075, JP-A No. 2001-217077 and the like may be used.

Examples of the borane derivative include 1,8-diphenyl-10- (dimesitylboryl) anthracene, 9-phenyl-10- (dimesitylboryl) anthracene, 4- (9′-anthryl) dimesitylborylnaphthalene, 4- (10 ′). -Phenyl-9'-anthryl) dimesitylborylnaphthalene, 9- (dimesitylboryl) anthracene, 9- (4'-biphenylyl) -10- (dimesitylboryl) anthracene, 9- (4 '-(N-carbazolyl) phenyl) -10- (Dimesitylboryl) anthracene and the like.
Moreover, you may use the borane derivative described in the international publication 2000/40586 pamphlet.

The aromatic amine derivative is represented by the following formula, for example.

In the formula, Ar ⁴ is an n-valent group derived from aryl having 6 to 30 carbon atoms, Ar ⁵ and Ar ⁶ are each independently aryl having 6 to 30 carbon atoms, and Ar ^{4 to} Ar ⁶ are It may be substituted and n is an integer from 1 to 4.

In particular, Ar ⁴ is a divalent group derived from anthracene, chrysene or pyrene, Ar ⁵ and Ar ⁶ are each independently an aryl having 6 to 30 carbon atoms, and Ar ^{4 to} Ar ⁶ are substituted. An aromatic amine derivative in which n is 2 and n is 2 is more preferable.

  Specific examples of the aryl having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorenephenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, and pentacene.

  Examples of the aromatic amine derivative include chrysene-based compounds such as N, N, N ′, N′-tetraphenylchrysene-6,12-diamine, N, N, N ′, N′-tetra (p-tolyl). Chrysene-6,12-diamine, N, N, N ′, N′-tetra (m-tolyl) chrysene-6,12-diamine, N, N, N ′, N′-tetrakis (4-isopropylphenyl) chrysene -6,12-diamine, N, N, N ', N'-tetra (naphthalen-2-yl) chrysene-6,12-diamine, N, N'-diphenyl-N, N'-di (p-tolyl) ) Chrysene-6,12-diamine, N, N′-diphenyl-N, N′-bis (4-ethylphenyl) chrysene-6,12-diamine, N, N′-diphenyl-N, N′-bis ( 4-ethylphenyl) chrysene-6 2-diamine, N, N′-diphenyl-N, N′-bis (4-isopropylphenyl) chrysene-6,12-diamine, N, N′-diphenyl-N, N′-bis (4-t-butyl) Phenyl) chrysene-6,12-diamine, N, N′-bis (4-isopropylphenyl) -N, N′-di (p-tolyl) chrysene-6,12-diamine, and the like.

  Examples of the pyrene-based compound include N, N, N ′, N′-tetraphenylpyrene-1,6-diamine, N, N, N ′, N′-tetra (p-tolyl) pyrene-1,6. -Diamine, N, N, N ', N'-tetra (m-tolyl) pyrene-1,6-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) pyrene-1,6- Diamine, N, N, N ′, N′-tetrakis (3,4-dimethylphenyl) pyrene-1,6-diamine, N, N′-diphenyl-N, N′-di (p-tolyl) pyrene-1 , 6-diamine, N, N′-diphenyl-N, N′-bis (4-ethylphenyl) pyrene-1,6-diamine, N, N′-diphenyl-N, N′-bis (4-ethylphenyl) ) Pyrene-1,6-diamine, N, N'-diphenyl-N, N'- Su (4-isopropylphenyl) pyrene-1,6-diamine, N, N′-diphenyl-N, N′-bis (4-t-butylphenyl) pyrene-1,6-diamine, N, N′-bis (4-Isopropylphenyl) -N, N′-di (p-tolyl) pyrene-1,6-diamine, N, N, N ′, N′-tetrakis (3,4-dimethylphenyl) -3,8- And diphenylpyrene-1,6-diamine.

  Examples of the anthracene system include N, N, N, N-tetraphenylanthracene-9,10-diamine, N, N, N ′, N′-tetra (p-tolyl) anthracene-9,10-diamine. N, N, N ′, N′-tetra (m-tolyl) anthracene-9,10-diamine, N, N, N ′, N′-tetrakis (4-isopropylphenyl) anthracene-9,10-diamine, N, N′-diphenyl-N, N′-di (p-tolyl) anthracene-9,10-diamine, N, N′-diphenyl-N, N′-di (m-tolyl) anthracene-9,10- Diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) anthrace -9,10-diamine, N, N'-diphenyl-N, N'-bis (4-isopropylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-bis (4- t-butylphenyl) anthracene-9,10-diamine, N, N′-bis (4-isopropylphenyl) -N, N′-di (p-tolyl) anthracene-9,10-diamine, 2,6-di -T-butyl-N, N, N ', N'-tetra (p-tolyl) anthracene-9,10-diamine, 2,6-di-t-butyl-N, N'-diphenyl-N, N' -Bis (4-isopropylphenyl) anthracene-9,10-diamine, 2,6-di-t-butyl-N, N'-bis (4-isopropylphenyl) -N, N'-di (p-tolyl) Anthracene-9,10-diamy 2,6-dicyclohexyl-N, N′-bis (4-isopropylphenyl) -N, N′-di (p-tolyl) anthracene-9,10-diamine, 2,6-dicyclohexyl-N, N′- Bis (4-isopropylphenyl) -N, N′-bis (4-t-butylphenyl) anthracene-9,10-diamine, 9,10-bis (4-diphenylamino-phenyl) anthracene, 9,10-bis (4-Di (1-naphthylamino) phenyl) anthracene, 9,10-bis (4-di (2-naphthylamino) phenyl) anthracene, 10-di-p-tolylamino-9- (4-di-p- Tolylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (4-diphenylamino-1-naphthyl) anthracene, 10-diphenylamino- And 9- (6-diphenylamino-2-naphthyl) anthracene.

Examples of pyrene-based compounds include N, N, N, N-tetraphenyl-1,8-pyrene-1,6-diamine and N-biphenyl-4-yl-N-biphenyl-1,8-pyrene-1. , ^6-diamine, N 1, ^{N 6} - diphenyl ^-N 1, ^{N 6} - bis - (4-trimethylsilanyl - phenyl)-1H, such 8H- 1,6-diamine.

In addition, [4- (4-diphenylamino-phenyl) naphthalen-1-yl] -diphenylamine, [4- (4-diphenylamino-phenyl) naphthalen-1-yl] -diphenylamine, [6- ( 4-diphenylamino-phenyl) naphthalen-2-yl] -diphenylamine, 4,4′-bis [4-diphenylaminonaphthalen-1-yl] biphenyl, 4,4′-bis [6-diphenylaminonaphthalene-2- Yl] biphenyl, 4,4 "-bis [4-diphenylaminonaphthalen-1-yl] -p-terphenyl, 4,4" -bis [6-diphenylaminonaphthalen-2-yl] -p-terphenyl, etc. Can be given.
Moreover, you may use the aromatic amine derivative described in Unexamined-Japanese-Patent No. 2006-156888.

Examples of the coumarin derivative include coumarin-6 and coumarin-334.
Moreover, you may use the coumarin derivative described in Unexamined-Japanese-Patent No. 2004-43646, Unexamined-Japanese-Patent No. 2001-76876, and Unexamined-Japanese-Patent No. 6-298758.

Examples of the pyran derivative include the following DCM and DCJTB.

Also, JP 2005-126399, JP 2005-097283, JP 2002-234892, JP 2001-220577, JP 2001-081090, and JP 2001-052869. Alternatively, pyran derivatives described in the above may be used.

Examples of the iridium complex include the following tris (2-phenylpyridine) iridium (III) :( Ir (ppy) ₃ ), tris (2- (4-tolyl) pyridine) iridium (III) :( Ir (mppy) ₃ ). Bis (2-phenylpyridine) acetylacetonatoiridium (III) :( Ir (ppy) ₂ (acac)), bis (2-phenylpyridine) (1-phenylpyrazole) iridium (III) :( Ir (ppy) ₂ (ppz)).

Further, the iridium complexes described in JP-A-2006-089398, JP-A-2006-080419, JP-A-2005-298483, JP-A-2005-097263, JP-A-2004-111379, etc. It may be used.

As the platinum complex, the following PtOEP, 3,3 ′-(6,6 ′-(propane-2,2-diyl) bis (pyridine-6,2-diyl)) dibenzonitrile platinum: (Pt-1), Bis (2- (3-tert-butylpyrazol-5-yl) pyridine) platinum: (Pt-2), bis (2- (3-tert-butyl-1,2,4-triazol-5-yl) pyridine ) Platinum: (Pt-3).

Further, the platinum complexes described in JP-A-2006-190718, JP-A-2006-128634, JP-A-2006-093542, JP-A-2004-335122, JP-A-2004-331508, etc. It may be used.

Examples of the rhenium complex include the following Re-1.

<Hole blocking layer>
The hole blocking layer serves to confine holes and electrons in the light emitting layer and improve the light emission efficiency. The hole blocking layer is preferably a substance that prevents holes moving from the anode from reaching the cathode and efficiently transports electrons injected from the cathode toward the light emitting layer. That is, the material for forming the hole blocking layer is required to have a property of high electron mobility and low hole mobility in order to improve luminous efficiency. In addition, high driving stability is also required from the demand for extending the life of organic electroluminescent elements.

  Specifically, organometallic complexes (mixed ligand complexes, binuclear metal complexes, etc.), styryl compounds (distyryl biphenyl derivatives, etc.), triazole derivatives, phenanthroline derivatives, borane derivatives, and anthracene derivatives (for example, JP-A 2006- No. 049570) and the like. These materials can be used alone or in combination with different materials. Among these, organometallic complexes (such as mixed ligand complexes and binuclear metal complexes), phenanthroline derivatives, and borane derivatives are preferable.

  Specific examples of organometallic complexes (such as mixed ligand complexes and binuclear metal complexes) include bis (2-methyl-8-quinolinolato) (phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2- Methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (4-methylphenolate) aluminum, bis (2-methyl- 8-quinolinolato) (2-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (Hereinafter abbreviated as Balq), bis (2-methyl-8-quinolyl) Lat) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethyl) Phenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-di-tert-butylphenolate) aluminum Bis (2-methyl-8-quinolinolato) (2,4-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,5-diphenylphenolato) aluminum, bis (2-methyl-8) -Quinolinolate) (2,6-diphenylphenolate) aluminum, bis 2-methyl-8-quinolinolato) (2,4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-trimethylphenolato) aluminum, bis (2-methyl) -8-quinolinolato) (2,4,5,6-tetramethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2 -Naphtholate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3-phenylphenolato) aluminum, bis (2 , 4-Dimethyl-8-quinolinolate) (4-phenylphenolate) aluminum Ni, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-di-tert-butylphenolate) Aluminum, bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis ( 2,4-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-4-ethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-ethyl-8-quinolinolato) aluminum, bis ( 2-methyl-4-methoxy-8-quinolinolate) aluminum-μ-oxo-bis ( -Methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, and And bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum.

  Specific examples of phenanthroline derivatives include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (hereinafter abbreviated as BCP), 2, 4,9,7-tetraphenyl-1,10-phenanthroline, 9,10-di (1,10-phenanthroline-2-yl) anthracene, 2,6-di (1,10-phenanthroline-5-yl) pyridine 1,3,5-tri (1,10-phenanthroline-5-yl) benzene, 1,3-bis (2-phenyl-1,10-phenanthroline-9-yl) benzene, and the like.

  Specific examples of the borane derivative include 9- (4′-dimesitylborylbiphenyl-4-yl) -9H-carbazole, 9- (4- (4-dimesitylborylnaphthalen-1-yl) phenyl. ) -9H-carbazole, 9- (4- (4-dimesitylborylphenyl) naphthalen-1-yl) -9H-carbazole, 9- (4- (6-dimesitylborylnaphthalen-2-yl) phenyl ) -9H-carbazole, 9- (6- (4-Dimesitylborylphenyl) naphthalen-2-yl) -9H-carbazole, 9- (7-Dimesitylboryl-9,9-dimethyl-9H-fluorene-2- Yl) -9H-carbazole, 9- (7-dimesitylboryl-9,9-diphenyl-9H-fluoren-2-yl) -9H-carbazole, 4,4′-bis (dimethyl) Tilboryl) biphenyl, 1-dimesitylboryl-4- (4-dimesitylborylphenyl) naphthalene, 2-dimesitylboryl-6- (4-dimesitylborylphenyl) naphthalene, 2,7-bis (dimesitylboryl) -9,9 -Dimethyl-9H-fluorene, 2,7-bis (dimesitylboryl) -9,9-diphenyl-9H-fluorene, and the like. Further, a borane derivative described in Japanese Patent Application No. 2005-210638 may be used.

<Electron injection layer and electron transport layer in organic electroluminescence device>
The electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106. The electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport / injection materials or a mixture of the electron transport / injection material and the polymer binder.

  The electron injection / transport layer is a layer that is responsible for injecting electrons from the cathode and further transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. For this purpose, it is preferable to use a substance that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate trapping impurities during production and use. However, considering the transport balance between holes and electrons, if the role of effectively preventing the holes from the anode from flowing to the cathode side without recombination is mainly played, the electron transport capability is much higher. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material having a high electron transport capability. Therefore, the electron injection / transport layer in this embodiment may include a function of a layer that can efficiently block the movement of holes.

  As a material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107, a compound conventionally used as an electron transport compound in a photoconductive material, an electron injection layer and an electron transport layer of an organic electroluminescent element can be used. It can be arbitrarily selected from known compounds used.

  Materials used for the electron transport layer or the electron injection layer include compounds composed of aromatic rings or heteroaromatic rings composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, and pyrrole derivatives. And at least one selected from the condensed ring derivatives thereof and metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4′-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinones And quinone derivatives such as diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials can be used alone or in combination with different materials. Among them, anthracene derivatives such as 9,10-bis (2-naphthyl) anthracene, styryl aromatic ring derivatives such as 4,4′-bis (diphenylethenyl) biphenyl, 4,4′-bis (N-carbazolyl) biphenyl A carbazole derivative such as 1,3,5-tris (N-carbazolyl) benzene is preferably used from the viewpoint of durability.

  Specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazoles. Derivatives (1,3-bis [(4-tert-butylphenyl) 1,3,4-oxadiazolyl] phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4- Triazole, etc.), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluoro Phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis (benzo [h] quinolin-2-yl) -9,9'-spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benz Imidazole derivatives (such as tris (N-phenylbenzimidazol-2-yl) benzene), benzoxazole derivatives, benzthiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis (4 '-(2,2': 6'2 "-terpyridinyl)) benzene), naphthyridine derivatives (bis (1-naphthyl) -4- (1,8-naphthyridin-2-yl) phenylphosphine oxide), aldazine Derivatives, carbazole derivatives, Ndoru derivatives, phosphorus oxide derivatives, such as bis-styryl derivatives.

  In addition, metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. can give.

  Although the above-mentioned materials are used alone, they may be mixed with different materials.

  Among the materials described above, quinolinol-based metal complexes, bipyridine derivatives, phenanthroline derivatives, or borane derivatives are preferable.

The quinolinol-based metal complex is a compound represented by the following general formula (E-1).

In the formula, R ^{1 to} R ⁶ are hydrogen or a substituent, M is Li, Al, Ga, Be, or Zn, and n is an integer of 1 to 3.

  Specific examples of the quinolinol-based metal complex include 8-quinolinol lithium, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl-8-quinolinolato) aluminum, tris (3 , 4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) ( Phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolato) aluminum, bis (2-methyl-8- Quinolinolato) (4-me Ruphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2-methyl-8- Quinolinolato) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-dimethylphenolate) ) Aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2-methyl) -8-quinolinolate) (3,5-di-ter -Butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenolate) Aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5,6-tetramethylphenolate) aluminum Bis (2-methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2- Phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolino) Rato) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethyl Phenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-di-tert-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-bis ( 2-methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-4- Ethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4) Ethyl-8-quinolinolato) aluminum, bis (2-methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl- 5-cyano-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum-μ- Examples thereof include oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum and bis (10-hydroxybenzo [h] quinoline) beryllium.

A bipyridine derivative is a compound represented by the following general formula (E-2).

In the formula, G represents a simple bond or an n-valent linking group, and n is an integer of 2 to 8. Carbon atoms that are not used for bonding of pyridine-pyridine or pyridine-G may be substituted.

Examples of G in the general formula (E-2) include the following structural formulas. In addition, R in the following structural formula is each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, or terphenylyl.

  Specific examples of the pyridine derivative include 2,5-bis (2,2′-bipyridyl-6-yl) -1,1-dimethyl-3,4-diphenylsilole, 2,5-bis (2,2′- Bipyridyl-6-yl) -1,1-dimethyl-3,4-dimesitylsilole, 2,5-bis (2,2′-bipyridyl-5-yl) -1,1-dimethyl-3,4 Diphenylsilole, 2,5-bis (2,2′-bipyridyl-5-yl) -1,1-dimethyl-3,4-dimesitylsilole, 9,10-di (2,2′-bipyridyl-6) -Yl) anthracene, 9,10-di (2,2'-bipyridyl-5-yl) anthracene, 9,10-di (2,3'-bipyridyl-6-yl) anthracene, 9,10-di (2 , 3′-bipyridyl-5-yl) anthracene, 9,10-di (2, '-Bipyridyl-6-yl) -2-phenylanthracene, 9,10-di (2,3'-bipyridyl-5-yl) -2-phenylanthracene, 9,10-di (2,2'-bipyridyl- 6-yl) -2-phenylanthracene, 9,10-di (2,2′-bipyridyl-5-yl) -2-phenylanthracene, 9,10-di (2,4′-bipyridyl-6-yl) 2-phenylanthracene, 9,10-di (2,4′-bipyridyl-5-yl) -2-phenylanthracene, 9,10-di (3,4′-bipyridyl-6-yl) -2-phenyl Anthracene, 9,10-di (3,4'-bipyridyl-5-yl) -2-phenylanthracene, 3,4-diphenyl-2,5-di (2,2'-bipyridyl-6-yl) thiophene, 3,4-dipheni -2,5-di (2,3'-bipyridyl-5-yl) thiophene, 6'6 "-di (2-pyridyl) 2,2 ': 4', 4": 2 ", 2" '-qua Examples include terpyridine.

A phenanthroline derivative is a compound represented by the following general formula (E-3-1) or (E-3-2).

In the formula, R ^{1 to} R ⁸ are hydrogen or a substituent, adjacent groups may be bonded to each other to form a condensed ring, G represents a simple bond or an n-valent linking group, and n represents 2 It is an integer of ~ 8. Moreover, as G of general formula (E-3-2), the same thing as what was demonstrated in the column of the bipyridine derivative is mention | raise | lifted, for example.

  Specific examples of the phenanthroline derivative include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di (1,10-phenanthroline- 2-yl) anthracene, 2,6-di (1,10-phenanthroline-5-yl) pyridine, 1,3,5-tri (1,10-phenanthroline-5-yl) benzene, 9,9′-difluor -Bis (1,10-phenanthroline-5-yl), bathocuproin, 1,3-bis (2-phenyl-1,10-phenanthroline-9-yl) benzene and the like.

  In particular, the case where a phenanthroline derivative is used for an electron transport layer and an electron injection layer will be described. In order to obtain stable light emission over a long period of time, a material excellent in thermal stability and thin film formation is desired, and among phenanthroline derivatives, the substituent itself has a three-dimensional structure, or a phenanthroline skeleton or Those having a three-dimensional structure by steric repulsion with an adjacent substituent or those having a plurality of phenanthroline skeletons linked to each other are preferred. Furthermore, when linking a plurality of phenanthroline skeletons, a compound containing a conjugated bond, a substituted or unsubstituted aromatic hydrocarbon, or a substituted or unsubstituted aromatic heterocycle in the linking unit is more preferable.

The borane derivative is a compound represented by the following general formula (E-4), and is disclosed in detail in JP-A-2007-27587.

In the formula, each of R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group. At least one, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and X is an optionally substituted arylene group And Y is an optionally substituted aryl group having 16 or less carbon atoms, a substituted boryl group, or an optionally substituted carbazole group, and n is each independently an integer of 0 to 3 is there.

Among the compounds represented by the general formula (E-4), the compounds represented by the following general formula (E-4-1), and further the following general formulas (E-4-1-1) to (E-4) The compound represented by -1-4) is preferable. Specific examples include 9- [4- (4-Dimesitylborylnaphthalen-1-yl) phenyl] carbazole, 9- [4- (4-Dimesitylborylnaphthalen-1-yl) naphthalen-1-yl. Carbazole and the like.

In the formula, each of R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group. At least one, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and R ²¹ and R ²² are each independently Each independently is a hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group, and X ¹ is , An optionally substituted arylene group having 20 or less carbon atoms, n is each independently an integer of 0 to 3, and m is each independently an integer of 0 to 4.

In each formula, R ^{31 to} R ³⁴ are each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl. It is.

Among the compounds represented by the general formula (E-4), a compound represented by the following general formula (E-4-2), and a compound represented by the following general formula (E-4-2-1) Is preferred.

In the formula, each of R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group. At least one, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and X ¹ is an optionally substituted carbon. An arylene group having a number of 20 or less, and each n is independently an integer of 0 to 3.

In the formula, R ^{31 to} R ³⁴ are each independently any of methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently any of hydrogen, methyl, isopropyl or phenyl It is.

Among the compounds represented by the general formula (E-4), a compound represented by the following general formula (E-4-3-3), and further, the following general formula (E-4-3-1) or (E-4) The compound represented by -3-2) is preferable.

In the formula, each of R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group. At least one, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and X ¹ is an optionally substituted carbon. It is an arylene group having several tens or less, Y ¹ is an optionally substituted aryl group having 14 or less carbon atoms, and n is each independently an integer of 0 to 3.

In each formula, R ^{31 to} R ³⁴ are each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl. It is.

The benzimidazole derivative is a compound represented by the following general formula (E-5).

In the formula, Ar ^{1 to} Ar ³ are each independently hydrogen or aryl having 6 to 30 carbon atoms which may be substituted. In particular, a benzimidazole derivative which is anthryl optionally substituted with Ar ¹ is preferable.

  Specific examples of the aryl having 6 to 30 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, acenaphthylene-1-yl, acenaphthylene-3-yl, acenaphthylene-4-yl, acenaphthylene-5-yl, and fluorene-1- Yl, fluoren-2-yl, fluoren-3-yl, fluoren-4-yl, fluoren-9-yl, phenalen-1-yl, phenalen-2-yl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, fluoranthen-1-yl, fluoranthen-2-yl, fluoranthen-3-yl, fluoranthen-7-yl, fluoranthen-8-yl, Triphenylene-1-yl, triphenylene-2-yl, pyreth -1-yl, pyren-2-yl, pyren-4-yl, chrysen-1-yl, chrysen-2-yl, chrysen-3-yl, chrysen-4-yl, chrysen-5-yl, chrysene-6 -Yl, naphthacene-1-yl, naphthacene-2-yl, naphthacene-5-yl, perylene-1-yl, perylene-2-yl, perylene-3-yl, pentacene-1-yl, pentasen-2-yl , Pentacene-5-yl and pentacene-6-yl.

  Specific examples of benzimidazole derivatives include 1,3,5-tris (1-phenyl-1H-benzo [d] imidazol-2-yl) benzene (TPBi), 1-phenyl-2- (4- (10-phenyl). Anthracen-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [d ] Imidazole, 2- (3- (10- (Naphthalen-2-yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 5- (10- (naphthalen-2-yl) ) Anthracen-9-yl) -1,2-diphenyl-1H-benzo [d] imidazole, 1- (4- (10- (naphthalen-2-yl) anthracen-9-yl) ) Phenyl) -2-phenyl-1H-benzo [d] imidazole, 2- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [D] imidazole, 1- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 5- (9,10 -Di (naphthalen-2-yl) anthracen-2-yl) -1,2-diphenyl-1H-benzo [d] imidazole.

  The electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As this reducing substance, various substances can be used as long as they have a certain reducing ability. For example, alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkali From the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes At least one selected can be suitably used.

  Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2. 9eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and alkaline earth metals such as those having a work function of 2.9 eV or less are particularly preferable. Among these, a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of two or more alkali metals is also preferable. Particularly, a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by adding to the material for forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended.

<Cathode in organic electroluminescence device>
The cathode 108 serves to inject electrons into the light emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.

  The material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer. However, the cathode material is made of a metal, an alloy, an electrically conductive compound, and a mixture thereof having a work function smaller than 4 eV. Can be used. Examples thereof include aluminum, calcium, magnesium, lithium, magnesium alloy, aluminum alloy and the like. Examples of the alloy include aluminum / lithium fluoride, aluminum / lithium, magnesium / silver, and magnesium / indium. In order to efficiently extract light emitted from the organic EL element, it is desirable that at least one of the electrodes has a light transmittance of 10% or more. The sheet resistance as the electrode is preferably several hundred Ω / □ or less. Although the film thickness depends on the properties of the electrode material, it is usually set in the range of 10 nm to 1 μm, preferably 10 to 400 nm. Such an electrode can be produced by forming a thin film by a method such as vapor deposition or sputtering using the electrode material described above.

  Furthermore, for electrode protection, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride Lamination of hydrocarbon polymer compounds and the like is a preferred example. The method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam, sputtering, ion plating, and coating.

<Binder that may be used in each layer>
The materials used for the hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can form each layer alone, but as a polymer binder, polyvinyl chloride, polycarbonate, Polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polysulfone, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin , Dispersed in solvent-soluble resins such as polyurethane resin, curable resins such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, etc. To be possible.

<Method for producing organic electroluminescent element>
Each layer constituting the organic electroluminescent element is formed by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method or cast method, coating method, etc. It can be formed by using a thin film. The thickness of each layer formed in this way is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like. When a thin film is formed using a vapor deposition method, the vapor deposition conditions vary depending on the type of material, the target crystal structure and association structure of the film, and the like. Deposition conditions generally include boat heating temperature +50 to + 400 ° C., vacuum degree 10 ⁻⁶ to 10 ⁻³ Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature −150 to + 300 ° C., film thickness 2 nm to 5 μm. It is preferable to set appropriately within the range.

  Next, as an example of a method for producing an organic electroluminescent element, an organic electric field composed of an anode / hole injection layer / hole transport layer / a light emitting layer composed of a host material and a dopant material / electron transport layer / electron injection layer / cathode. A method for manufacturing a light-emitting element will be described. A thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-evaporated to form a thin film to form a light emitting layer. An electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by vapor deposition. By forming it as a cathode, a desired organic electroluminescent element can be obtained. In the preparation of the above-described organic electroluminescence device, the order of preparation may be reversed, and the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode may be fabricated in this order. Is possible.

  When a DC voltage is applied to the organic electroluminescent device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. When a voltage of about 2 to 40 V is applied, the organic electroluminescent device is transparent or translucent. Luminescence can be observed from the electrode side (anode or cathode, and both). The organic electroluminescent element emits light when an alternating current is applied. The alternating current waveform to be applied may be arbitrary.

<Application examples of organic electroluminescent devices>
The present invention can also be applied to a display device provided with an organic electroluminescent element or a lighting device provided with an organic electroluminescent element.
A display device or an illuminating device including an organic electroluminescent element can be manufactured by a known method such as connecting the organic electroluminescent element according to the present embodiment and a known driving device, such as direct current driving, pulse driving, or alternating current. It can be driven by appropriately using a known driving method such as driving.

  Examples of the display device include a panel display such as a color flat panel display, and a flexible display such as a flexible color organic electroluminescence (EL) display (for example, JP-A-10-335066 and JP-A-2003-321546). Gazette, JP-A-2004-281086, etc.). Examples of the display method of the display include a matrix and / or segment method. Note that the matrix display and the segment display may coexist in the same panel.

  A matrix means a pixel in which pixels for display are two-dimensionally arranged such as a lattice or a mosaic, and displays a character or an image with a set of pixels. The shape and size of the pixel are determined by the application. For example, a square pixel with a side of 300 μm or less is usually used for displaying images and characters on a personal computer, monitor, TV, and a pixel with a side of mm order for a large display such as a display panel. become. In monochrome display, pixels of the same color may be arranged. However, in color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type. The matrix driving method may be either a line sequential driving method or an active matrix. The line-sequential driving has the advantage of a simple structure. However, the active matrix may be superior in consideration of the operating characteristics, so it is necessary to use it depending on the application.

  In the segment system (type), a pattern is formed so as to display predetermined information, and a predetermined region is caused to emit light. For example, the time and temperature display in a digital clock or a thermometer, the operation state display of an audio device or an electromagnetic cooker, the panel display of an automobile, and the like can be mentioned.

  Examples of the illuminating device include an illuminating device such as indoor lighting, a backlight of a liquid crystal display device, and the like (for example, JP 2003-257621 A, JP 2003-277741 A, JP 2004-119211 A). Etc.) The backlight is used mainly for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, a sign, and the like. In particular, as a backlight for liquid crystal display devices, especially personal computers for which thinning is an issue, considering that conventional methods are made of fluorescent lamps and light guide plates, it is difficult to reduce the thickness. The backlight using the light emitting element according to the embodiment is thin and lightweight.

  The present invention will be described in more detail based on examples. First, synthesis examples of the condensed pyrrole polycyclic compound used in the examples are described below.

<Synthesis Example of Compound Represented by Formula (1-1-28) or Formula (1-222)>

<Synthesis of 9- (4 ′-(9H-carbazol-9-yl)-[1,1′-biphenyl] -4-yl) -3-bromo-9H-carbazole>

  Under a nitrogen atmosphere, 4.1 g of 3-bromo-9H-carbazole, 2.27 g of 9- (4′-iodo- [1,1′-biphenyl] -4-yl) -9H-carbazole, 1.17 g of copper powder, A flask was charged with 5.09 g of potassium carbonate, 0.12 g of 18-crown-6 (18-C-6), and 46 ml of o-dichlorobenzene, and the mixture was refluxed at 180 ° C. for 15 hours. After cooling the reaction liquid and filtering to remove the solid, the filtrate was concentrated under reduced pressure, and the resulting crude product was subjected to column purification with silica gel (solvent: heptane / toluene = 4/1 (volume ratio)). Intermediate compound (1-1a): 9- (4 ′-(9H-carbazol-9-yl)-[1,1′-biphenyl] -4-yl) -3-bromo-9H-carbazole 2 Obtained .65 g (yield: 51%).

<9- (4 ′-(9H-carbazol-9-yl)-[1,1′-biphenyl] -4-yl) -3- (4,4,5,5-tetramethyl-1,3,2) -Synthesis of Dioxaborolan-2-yl) -9H-carbazole>

  Under a nitrogen atmosphere, 2.65 g of the intermediate compound (1-1a), 1.43 g of bis (pinacolato) diboron, [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichlorochloride dichloromethane complex ( 1: 1) 0.12 g, 1.38 g of potassium acetate and 25 ml of cyclopentyl methyl ether were placed in a flask and stirred for 5 minutes. Thereafter, the mixture was refluxed for 5 hours. After completion of the heating, the reaction solution is cooled and filtered to remove the solid, and then the filtrate is concentrated under reduced pressure. 1b): 9- (4 ′-(9H-carbazol-9-yl)-[1,1′-biphenyl] -4-yl) -3- (4,4,5,5-tetramethyl-1,3 , 2-Dioxaborolan-2-yl) -9H-carbazole was obtained (yield: 89%).

<Synthesis of methyl 2- (9- (4 ′-(9H-carbazol-9-yl)-[1,1′-biphenyl] -4-yl) 9H-carbazol-3-yl) benzoate>

Under nitrogen atmosphere, intermediate compound (1-1b) 2.54 g, o-benzoic acid methyl 1.07 g, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 0.24 g, sodium carbonate 0 .88 g and 20 ml of a mixed solvent of toluene and ethanol (toluene / ethanol = 4/1 (volume ratio)) were placed in a flask and stirred for 5 minutes. Thereafter, 4 ml of water was added and refluxed for 14 hours. After completion of the heating, the reaction solution was cooled, the organic layer was separated, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solid obtained by removing the desiccant and evaporating the solvent under reduced pressure was subjected to column purification with silica gel (solvent: heptane / toluene = 3/1 (volume ratio)) to obtain an intermediate compound (1-1c ): 2.37 g of methyl 2- (9- (4 ′-(9H-carbazol-9-yl)-[1,1′-biphenyl] -4-yl) 9H-carbazol-3-yl) benzoate Rate: 92%).

<Synthesis of (2- (9- (4 ′-(9H-carbazol-9-yl)-[1,1′-biphenyl] -4-yl) 9H-carbazol-3-yl) phenyl) diphenylmethanol>

  Under a nitrogen atmosphere, a solution of 2.37 g of the intermediate compound (1-1c) in THF (40 ml) was cooled to -70 ° C. To this solution, 6 ml of 1.9M phenyl lithium dibutyl ether was added dropwise from a syringe. After dropping, the solution was stirred at the same temperature for 1 hour. Then, it returned to room temperature all night. Next, water was added to the reaction mixture, the target component was extracted with ethyl acetate, and the organic layer was concentrated under reduced pressure. The intermediate compound (1-1d) :( 2- (9- (4 ′-(9H-carbazol-9-yl)-[1,1′-biphenyl] -4-yl) 9H There was obtained 2.65 g (yield: 93%) of -carbazol-3-yl) phenyl) diphenylmethanol.

<Synthesis of final target compound>

  Under a nitrogen atmosphere, a solution of 2.4 g of the intermediate compound (1-1d) in dichloromethane (35 ml) was cooled to 0 ° C. To this solution, 0.69 g of boron trifluoride ether was added dropwise. After dropping, the solution was stirred at the same temperature for 1 hour. Then, while cooling ice water, water was added to the reaction mixture, the target component was extracted with chloroform, and the solid obtained by concentrating the organic layer under reduced pressure was subjected to column purification with silica gel (solvent: heptane / toluene = 3 / 1 (volume ratio)), and a crude product of the compound represented by the formula (1-1-28) and the compound represented by the formula (1-2-22) was obtained. Further, the crude products of these compounds were recrystallized (solvent: toluene) and then purified by sublimation to obtain the target compound: 5- (4 ′-(9H-carbazol-9-yl)-[1,1′- Biphenyl] -4-yl) -12,12-diphenyl-5,12-dihydroindeno [1,2-c] carbazole (compound represented by formula (1-1-28)) 0.57 g (yield) : 25%), and the target compound: 5- (4 ′-(9H-carbazol-9-yl)-[1,1′-biphenyl] -4-yl) -7,7-diphenyl-5,7-dihydro 0.55 g (yield: 24%) of indeno [2,1-b] carbazole (a compound represented by the formula (1-2-22)) was obtained.

The structures of these compounds were confirmed by MS spectrum and NMR measurement.
<Compound represented by formula (1-1-28)>
¹ H-NMR (CDCl ₃ ): σ = 8.18 (d, 2H), 7.95 to 7.92 (m, 5H), 7.77 to 7.71 (m, 5H), 7.56 to 7.43 (m, 11H), 7.34-7.17 (m, 13H).
<Compound represented by Formula (1-2-22)>
¹ H-NMR (CDCl ₃ ): σ = 8.51 (s, 1H), 8.23 to 8.16 (m, 3H), 7.92 to 7.85 (m, 5H), 7.70 to 7.60 (m, 4H), 7.51 to 7.19 (m, 23H).

Other physical properties of these compounds were as follows. [Measuring instrument: Diamond DSC (manufactured by PERKIN-ELMER), measurement conditions: cooling rate 200 ° C / Min., Heating rate 10 ° C / Min.]
<Compound represented by formula (1-1-28)>
Glass transition temperature (Tg): 184.8 ° C
<Compound represented by Formula (1-2-22)>
Glass transition temperature (Tg): 179.6 ° C

  By appropriately selecting the starting compounds, other compounds of the present invention can be synthesized by a method according to the above synthesis example.

<Physical properties of the target compound>
Table 1 below summarizes the physical property values of the compound represented by the formula (1-1-28) and the formula (1-2-22) and the compound “CBP” of Comparative Example (manufactured by Dojindo Laboratories). It was shown to. The compound “CBP” has the following structure.

Melting point (Tm), glass transition temperature (Tg) and crystallization temperature (Tc) were measured using a Diamond DSC manufactured by Perkin-Elmer (measuring conditions: cooling rate 200 ° C./min, heating rate 10 ° C./min). Min).
Moreover, the thin film fluorescence maximum wavelength (λmax) was measured by using a V-560 type spectrophotometer manufactured by JASCO Corporation with an excitation wavelength of 360 nm.
Further, the triplet state energy level (T1) was calculated from the rising position of the spectrum by measuring the phosphorescence spectrum. The phosphorescence spectrum was measured by attaching a low temperature measurement accessory to the fluorescence spectrophotometer F-7000 manufactured by Hitachi High-Technologies Corporation. A sample obtained by dissolving a measurement compound in ethanol is used as a sample. After freeze-deaeration, the sample is emitted at a liquid nitrogen temperature (77 K) by applying excitation light having a wavelength of 360 nm to the sample in a pulsed manner (40 Hz) with a chopper. Data was acquired after the component was quenched, and only the phosphorescent component was extracted.

  From this measurement result, it can be expected that the compound represented by the formula (1) of the present invention has a stable glass state and forms a stable amorphous film by vapor deposition or the like. Further, when the measurement results of the triplet state energy level (T1) and the thin film fluorescence maximum wavelength (λmax) are examined, the compound represented by the formula (1) of the present invention is effective as a green phosphorescent host material, and at the same time, fluorescence It can also be seen that it can be used as a blue host luminescent material.

Next, the compound represented by the formula (1-1-28) and the formula (1-2-22) and the compound “CBP” of the comparative example are used as a phosphorescent host material, and Ir (ppy) ₃ is used as a phosphorescent green dopant material. The phosphorescence quantum yield was measured. The measurement was performed according to the description in Japanese Journal of Applied Physics Vol. 43, No. 11A, 2004, pp. 7729-7730.

First, a sample for measuring the quantum yield of light emission was produced as follows. A synthetic quartz substrate (10 mm × 10 mm × 0.7 t) was used as the substrate. This substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus. A metal mask was also attached to the substrate holder at the same time so that the vapor deposition area had a diameter of 5 mmφ. A molybdenum vapor deposition boat containing a host material and a molybdenum vapor deposition boat containing a dopant material were mounted on the vapor deposition apparatus. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and the molybdenum vapor deposition boat containing the host material and the molybdenum vapor deposition boat containing the dopant material are heated at the same time. A sample for measurement was prepared by vapor deposition. At this time, the dopant concentration of the dopant material was about 5% by weight. The deposition rate was 0.01-1 nm / second.

According to Japanese Journal of Applied Physics Vol. 43, No. 11A, 2004, pp. 7729-7730., The emission quantum yield η _PL is given by the following equation.
N _emission is the number of photons emitted from the material, N _Absorption is the number of photons absorbed by the material, and the emission quantum yield is obtained as the ratio. Where α is the correction coefficient of the measurement system, λ is the wavelength, h is the Planck constant, c is the speed of light, I _em (λ) is the emission intensity of the sample, and I _ex (λ) is the intensity of the excitation light before the sample is installed. , I ′ _ex (λ) is the excitation light intensity observed when the sample is irradiated with the excitation light. By performing two spectrum observations of I _em and I ′ _ex + I _em , the emission quantum yield can be measured.

  The measuring device is composed of an excitation light source, an excitation light guide unit, an integrating sphere, and a multichannel spectrometer. Excitation light output from the excitation light source is introduced into the integrating sphere via an excitation light guide unit including a condenser lens, an ND filter, and an optical fiber. Excitation light and sample emission are uniformly scattered within the integrating sphere and detected by a multi-channel spectrometer via an optical fiber probe. The measurement was performed under a nitrogen gas flow.

  Excitation light source is HeCd laser Kinmon IK5352R-D (wavelength: 325 nm, output 10 mW), emission spectrum is observed by Hamamatsu Photoelectronics multi-channel spectrometer PMA-11 (C7473-36), integrating sphere is Labsphere IS- 080-SF was used.

A quartz substrate similar to the sample for measuring luminescence quantum yield was used as a blank substrate. The blank substrate was set in a substrate holder for measuring the emission quantum yield, and the excitation light spectrum I _ex (λ) was measured. The blank substrate was removed, a sample for measuring the emission quantum yield was set, and the excitation light spectrum and the emission spectrum I ′ _ex (λ) + I _em (λ) were observed. The multichannel spectrometer was set to an exposure time of 200 ms and an averaging count of 20 times.

  The quantum yield of the sample using the compound represented by Formula (1-1-28) and Formula (1-2-22) or the compound “CBP” of Comparative Example was measured in the same manner as described above. Further, the quantum yield (relative value) was calculated using the light emission quantum yield value of the sample using CBP as a standard value. The measurement results are shown in Table 2 below.

<Organic EL device using target compound>
Next, as described below, the organic EL elements according to Examples 1 and 2 were manufactured, and voltage (V) and current density (mA / cm ² ), which are characteristics at the time of light emission of 1000 cd / m ² , respectively. The emission efficiency (Lm / W), current efficiency (cd / A), emission wavelength (nm), and chromaticity (x, y) were measured.

Table 3 below shows the material configuration of each layer in the manufactured organic EL elements according to Examples 1 and 2.

In Table 1, “HI-1” represents N ⁴ , N ^{4 ′} -diphenyl-N ⁴ , N ^{4 ′} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl]- 4,4′-diamine, “NPD” is N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, “BD-1” is 7,7, N ⁵ , N ⁹ -tetra Phenyl-7H-benzo [c] fluorene-5,9-diamine, “TPBi” is 1,3,5-tris (1-phenyl-1H-benzo [d] imidazol-2-yl) benzene, It has the chemical structure shown below.

<Example 1>
A glass substrate of 26 mm × 28 mm × 0.7 mm on which ITO was deposited to a thickness of 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus, a molybdenum vapor deposition boat containing HI-1, a molybdenum vapor deposition boat containing NPD, and represented by the formula (1-1-28). Molybdenum deposition boat containing compound, molybdenum deposition boat containing Ir (ppy) ₃ , molybdenum deposition boat containing TPBi, molybdenum deposition boat containing lithium fluoride, and aluminum A tungsten evaporation boat was attached.

The vacuum chamber is depressurized to 1 × 10 ⁻³ Pa, the vapor deposition boat containing HT-1 is heated, HT-1 is vapor-deposited to a film thickness of 40 nm, and a hole injection layer is formed. The evaporation boat containing NPD was heated, and NPD was evaporated to a film thickness of 25 nm to form a hole transport layer. Next, the molybdenum evaporation boat containing the compound represented by the formula (1-1-28) and the molybdenum evaporation boat containing Ir (ppy) ₃ are heated so that the film thickness becomes 25 nm. Both compounds were co-evaporated to form a light emitting layer. At this time, the doping concentration of Ir (ppy) ₃ was about 5% by weight. Next, the evaporation boat containing TPBi was heated to deposit TPBi to a film thickness of 30 nm to form an electron transport layer. The above deposition rate was 0.1 to 1 nm / second.

  Thereafter, the vapor deposition boat containing lithium fluoride is heated to deposit lithium fluoride at a vapor deposition rate of 0.005 to 0.01 nm / second so as to have a film thickness of 1 nm, and then vapor deposition containing aluminum. An organic EL element was produced by heating the boat and depositing aluminum at a deposition rate of 0.1 to 1 nm / second so as to have a film thickness of 100 nm.

Using the ITO electrode as the anode and the lithium fluoride / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The voltage was 6.1 V, the current density was 5.73 mA / cm ² , the emission efficiency was 9.1 Lm / W, the current The efficiency was 17.5 cd / A, the emission wavelength was 511 nm, and the chromaticity (0.287, 0.618).

<Example 2>
An organic EL device was produced by the method according to Example 1 except that Ir (ppy) ₃ used as the green phosphorescent dopant in Example 1 was replaced with the fluorescent blue dopant BD-1. Using the ITO electrode as the anode and the lithium fluoride / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The voltage was 6.95 V, the current density was 32.5 mA / cm ² , the light emission efficiency was 1.4 Lm / W, the current The efficiency was 3.1 cd / A, the emission wavelength was 460 nm, and the chromaticity (0.140, 0.139).

The above results are summarized in Table 4.

  According to a preferred embodiment of the present invention, since the condensed pyrrole polycyclic compound of the present invention has a high Tg, a stable thin film can be formed. In addition, when an organic EL device is produced using the condensed pyrrole polycyclic compound of the present invention, an organic material having better performance in at least one of heat resistance, light emission efficiency, current efficiency, device lifetime, external quantum efficiency, and the like. An EL element, a display device including the EL element, a lighting device including the EL device, and the like can be provided.

DESCRIPTION OF SYMBOLS 100 Organic electroluminescent element 101 Substrate 102 Anode 103 Hole injection layer 104 Hole transport layer 105 Light emitting layer 106 Electron transport layer 107 Electron injection layer 108 Cathode

Claims (12)

The compound represented by either the following formula (1-1), formula (1-2), or formula (1-6) .
In the formula (1-1), formula (1-2) or formula (1-6) , any site “—CH═” in the condensed ring formed by the indole ring and the fluorene ring is the site “—N═”. May be;
Arbitrary hydrogen in the condensed ring formed by the indole ring and the fluorene ring is alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 30 carbon atoms, or 1 to 30 carbon atoms. Optionally substituted with heteroaryl;
R ¹ and R ² are each independently aryl having 6 to 18 carbon atoms or heteroaryl having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other to form a spiro ring. Often;
Ar ² is aryl having 10 to 30 carbon atoms. However, when biphenylyl is selected from aryl having 10 to 30 carbon atoms, it is biphenylyl represented by the following formula (BP).
In Formula (BP), Ar ³ is heteroaryl having 1 to 30 carbons which may be substituted with at least one group selected from aryl having 6 to 30 carbons and heteroaryl having 1 to 30 carbons . R ¹ and R ² are phenyl, biphenylyl, naphthyl, phenanthryl, pyridyl, or imidazolyl, which may be bonded to each other to form a spiro ring;
Ar ² is naphthyl, phenanthryl or biphenylyl represented by the following formula (BP),
In the formula (BP), Ar ³ is a heteroaryl having 1 to 20 carbons which may be substituted with at least one group selected from aryl having 6 to 20 carbons and heteroaryl having 1 to 20 carbons The compound according to claim 1 . R ¹ and R ² are phenyl or pyridyl, which may be bonded to each other to form a spiro ring;
Ar ² is naphthyl, phenanthryl or biphenylyl represented by the following formula (BP),
In the formula (BP), Ar ³ is pyridyl, carbazolyl, indenocarbazolyl, which may be substituted with at least one group selected from aryl having 6 to 10 carbon atoms and heteroaryl having 1 to 10 carbon atoms , pyrrolyl, indolyl, an isoindolyl or isoxazolyl, any site "-CH =" in these rings may be site "-N = 'a compound according to claim 1 or 2. R ¹ and R ² are phenyl, which may be bonded to each other to form a spiro ring;
Ar ² is biphenylyl represented by the following formula (BP),
In the formula (BP), Ar ³ may be substituted by phenyl, carbazolyl, carbolinyl, indeno carbazolyl a indeno carbonitrile Li cycloalkenyl or benzimidazolyl,, according to any of claims 1 to 3 Compound. The compound in any one of Claims 1-4 represented by a following formula (1-1-28) or a formula (1-2-22).
The light emitting layer material for organic electroluminescent elements containing the compound in any one of Claims 1-5 . Further, containing amines, amines having a benzo fluorene structure, an aromatic amine, coumarin derivatives, pyran derivatives, iridium complexes, at least one compound selected from the group consisting of rhenium complexes, and platinum complexes having a stilbene structure, wherein Item 7. The light emitting layer material according to Item 6 . An organic electroluminescence device comprising a pair of electrodes composed of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes and containing the light emitting layer material according to claim 6 or 7 . Furthermore, it has an electron transport layer and / or an electron injection layer disposed between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer includes a quinolinol-based metal complex, a pyridine derivative, The organic electroluminescent element according to claim 8 , comprising at least one selected from the group consisting of a phenanthroline derivative, a borane derivative and a benzimidazole derivative. At least one of the electron transport layer and the electron injection layer may further include an alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, alkaline earth Containing at least one selected from the group consisting of metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes, The organic electroluminescent element according to claim 9 . The display apparatus provided with the organic electroluminescent element in any one of Claims 8-10 . The illuminating device provided with the organic electroluminescent element in any one of Claims 8-10 .