TWI491602B - Benzo(c)carbazole compound having substituent including pyridine and organic electroluminescent device - Google Patents

Description

Benzo[c]carbazole compound having pyridine substituent and organic electroluminescent device

The present invention relates to a benzo[c]carbazole compound having a pyridine substituent and an electron transporting material, an organic electroluminescent device, a display device, and a lighting device using the benzo[c]carbazole compound.

In the prior art, a display device using an electroluminescence light-emitting element has been subjected to various studies because of its low power and thinness, and the organic electroluminescence element formed of an organic material is easily lightened or enlarged. I was actively researched. In particular, the development of an organic material having a light-emitting property including blue, which is one of the three primary colors of light, and the development of an organic material having a charge transporting ability of a hole or an electron (having the possibility of becoming a semiconductor or a superconductor), Polymer compounds and low molecular compounds have been actively studied to date.

For example, an organic electroluminescent device using a compound in which an aryl group or a heteroaryl group such as a pyridyl group is substituted on a central skeleton of a ruthenium has been reported (Japanese Patent Laid-Open Publication No. 2003-146951: Patent Japanese Patent Laid-Open Publication No. 2005-170911: Patent Document 2, International Publication No. 2007/086552: Patent Document 3).

Further, a compound having a central skeleton of hydrazine, binaphthyl or a combination of naphthalene and fluorene has been reported as a material for an organic electroluminescent device (for example, a material for an electron transport layer or an electron injection layer; an electron transport material) (Japanese Patent Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

Further, a compound containing a carbazole ring and a pyridine ring or a pyrimidine ring has been reported as a charge transport (hole transporting and electron transporting) material (Japanese Patent Laid-Open No. 2006-199679: Patent Document 7, Japanese Patent) Japanese Patent Publication No. 2005-268199: Patent Document 8).

As described above, a compound having an aryl group or a heteroaryl group substituted on the central skeleton of the fluorene or a compound using hydrazine, binaphthyl or a combination of naphthalene and anthracene as a central skeleton or containing a carbazole ring and a pyridine ring or a pyrimidine ring There are several known compounds, but these known materials do not sufficiently and well balance the characteristics of the extended element life required for an electron transporting material, and the driving voltage of the light-emitting element. Under such circumstances, it has been desired to develop an electron transporting material having excellent lifetime and driving voltage of a light-emitting element. In particular, a blue light-emitting element cannot obtain an electron transport material having excellent characteristics as compared with a red or green light-emitting element, and it is desired to develop an electron transport material suitable for improving the characteristics of the blue light-emitting element.

The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, found that an organic electroluminescent device having an organic layer containing an electron represented by the following formula (1) as an electron transporting material can be produced. The present invention has been completed in order to obtain an organic electroluminescence device which is excellent in terms of device life and excellent in balance with driving voltage.

[1] A benzo[c]carbazole compound represented by the following formula (1):

[化22]

In the above formula (1), R is an aryl group having 6 to 24 carbon atoms or a heteroaryl group having 2 to 24 carbon atoms, and A and A' are each independently selected from the group consisting of hydrogen and the above formula (A-1). a group represented by the group represented by the above formula (A-2), the group represented by the above formula (A-3), and the group represented by the formula (A-4), but A And A' cannot be both hydrogen, and the ring contained in the structures of R, A and A' may be substituted by an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group or a phenyl group, and constitutes the formula (1). The benzoxazole skeleton of the compound represented, and any of R, A and A' substituted there may be substituted by hydrazine.

[2] The benzo[c]carbazole compound according to the above [1], wherein R is a group selected from the group consisting of the following formula (R-1) to formula (R-20); In the above, each of A and A' is independently selected from the group consisting of hydrogen, a group represented by the following formula (A-1-1) to formula (A-1-3), and the following formula (A-2-1). The group represented by (A-2-18), the group represented by the following formula (A-3-1) to formula (A-3-6), and the following formula (A-4-1) to formula (A). A-4-6) A group consisting of the groups represented by the group, but A and A' cannot both be hydrogen, and the benzoxazole skeleton constituting the compound represented by the formula (1) is subjected to Any hydrogen in the substituted R, A and A' may also be replaced by deuterium.

[Chem. 24]

[3] The benzo[c]carbazole compound according to the above [1], wherein R is a group selected from the group consisting of the groups represented by the above formulas (R-1) to (R-14) In the above, each of A and A' is independently selected from the group represented by the above formula (A-1-1) to formula (A-1-3), and the above formula (A-2-1) to formula (A-2- 18) the base represented by the formula (A-3-1) to the formula (A-3-6) and the formula (A-4-1) to the formula (A-4-6) One of the groups formed by the base.

[B] The benzo[c]carbazole compound according to the above [1], wherein R is a group selected from the group consisting of the groups represented by the above formulas (R-1) to (R-11). In the above, each of A and A' is independently selected from the group represented by the above formula (A-1-1) to formula (A-1-3), and the above formula (A-2-1) to formula (A-2- 18) the base represented by the formula (A-3-1) to the formula (A-3-6) and the formula (A-4-1) to the formula (A-4-3) One of the groups formed by the base.

[5] The benzo[c]carbazole compound according to the above [1], wherein R is a group represented by the above formula (R-1), formula (R-10) or formula (R-11), A and A' are each independently selected from the group represented by the above formula (A-1-1) to formula (A-1-3), and the above formula (A-2-1) to formula (A-2-4). The group represented by the above formula (A-2-7) to formula (A-2-9), the group represented by the above formula (A-2-12), and the above formula (A-2-15) The group represented by the formula (A-3-1) to the formula (A-3-6) and the formula (A-4-1) to the formula (A-4-3) A group of groups formed by the base.

[6] The benzo[c]carbazole compound according to the above [1], wherein R is a group represented by the above formula (R-1) or formula (R-11), and A and A' are each independently The group represented by the above formula (A-1-1) to formula (A-1-3), the group represented by the above formula (A-2-1), and the formula (A-2-2) are selected. The group represented by the above formula (A-2-8), the group represented by the above formula (A-2-12), and the formula (A-3-1) to the formula (A-3-6) One of the groups represented by the base represented by the above formula (A-4-1) to the formula (A-4-3).

[7] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-10):

[8] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-4):

[9] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-744):

[化27]

[10] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-5):

[11] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-634):

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[12] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-20):

[13] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-24):

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[14] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-743):

[15] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-8710):

[化33]

[16] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-8711):

[17] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-8712): [Chem. 35]

[18] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-1):

[19] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-2): [Chem. 37]

[20] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-541):

[21] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-564):

[39]

[22] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-575):

[23] The benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-599):

[化41]

[24] A benzo[c]carbazole compound according to the above [1], which is represented by the following formula (1-742):

[25] An electron transporting material comprising the compound according to any one of [1] to [24] above.

[26] An organic electroluminescence device comprising: a pair of electrodes formed of an anode and a cathode: a light-emitting layer disposed between the pair of electrodes: disposed between the cathode and the light-emitting layer, and containing the above [25] An electron transport layer and/or an electron injection layer of the electron transport material.

[27] The organic electroluminescent device according to the above [26], wherein at least one of the electron transport layer and the electron injecting layer further contains a metal complex selected from a quinolinol group, a pyridine derivative, and a bipyridine. At least one of the group consisting of a derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative.

[28] The organic electroluminescent device according to the above [27], wherein at least one of the electron transport layer and the electron injecting layer further contains an oxide selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal, and an alkali metal. Alkali metal halide, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal oxide, rare earth metal halide, alkali metal organic complex, alkaline earth metal organic complex and rare earth metal organic At least one of the group consisting of the complexes.

[29] A display device comprising the organic electroluminescent device according to any one of [26] to [28] above.

[30] An illuminating device comprising the organic electroluminescent device according to any one of [26] to [28] above.

[Effects of the Invention]

According to a preferred aspect of the present invention, an organic electroluminescent device which is excellent in the life of a light-emitting element can be obtained. Further, according to another preferred aspect of the present invention, an organic electroluminescence device which is excellent not only in achieving excellent element life but also in balance with a driving voltage can be obtained. Further, the preferred electron transporting material of the present invention is particularly suitable for a blue light-emitting element, by which a blue light-emitting element having an element life comparable to that of a red or green light-emitting element can be manufactured. Further, by using the organic electroluminescent device, a high-performance display device such as a full-color display can be obtained.

1. A benzo[c]carbazole compound represented by the formula (1)

The benzo[c]carbazole compound having a pyridine-containing substituent of the present invention will be described in detail. The benzo[c]carbazole compound of the present invention is a compound represented by the following formula (1). Further, the benzoxazole skeleton constituting the compound represented by the formula (1) and any hydrogen of R, A and A' substituted there may be substituted by hydrazine.

R in the formula (1) is an aryl group having 6 to 24 carbon atoms or a heteroaryl group having 2 to 24 carbon atoms.

Further, in the formula (1), A and A' are each independently selected from the group represented by hydrogen, the group represented by the above formula (A-1), the group represented by the above formula (A-2), and the above formula (A-3). The group represented by the group represented by the above formula (A-4) and the group of the aryl group having 6 to 18 carbon atoms, but either one of A or A' is selected from the above formula (A-). 1) One of the groups consisting of the groups represented by the formula (A-2), the formula (A-3), and the formula (A-4). That is, A and A' are not the above-mentioned "aryl group having 6 to 18 carbon atoms" which will be described later in detail.

Among these bases, it is particularly preferable in the present invention that the conditions satisfying the following conditions: A and A' are each independently selected from the group consisting of hydrogen, the formula (A-1), and the above formula (A-2). The group represented by the group represented by the above formula (A-3) and the group represented by the above formula (A-4), and both A and A' are not hydrogen. That is, in this aspect, any of A and A' is not "aryl group having 6 to 18 carbon atoms".

Further, in the group represented by the above formula (A-1) to formula (A-4), the bond attached to the ring is bonded to any carbon atom constituting the ring, but not two of the same carbon atom are bonded. key. In the group represented by the formula (A-4), the two rings in which the bond between the pyridine ring and the naphthalene ring and the naphthalene ring are bonded to each other means that the bond and the naphthalene ring are bonded to the benzo[c]carbazole. Any carbon atom other than the carbon atom is bonded.

Further, the ring contained in the structures of R, A and A' may be substituted by an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group or a phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, n-pentyl group and isoprene. Base, neopentyl, third amyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl or 2-ethylbutyl. Among the alkyl groups, as the substituent on the ring contained in the structures of R, A and A', a methyl group, an isopropyl group or a tert-butyl group is preferred, and a third butyl group is particularly preferred. . The number of the substituents is, for example, the maximum number of substitutables, preferably one to three, more preferably one to two, and still more preferably one.

The "aryl group having 6 to 24 carbon atoms" in R is preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms.

Specific examples of the "aryl group" include a phenyl group as a monocyclic aryl group and a (2-, 3-, 4-) biphenyl group as a bicyclic aryl group as a condensed bicyclic aryl group (1). -, 2-) naphthyl, as a tricyclic aryl group of triphenyl (m-triphenyl-2'-yl, m-triphenyl-4'-yl, m-triphenyl-5'-yl, O-triphenyl-3'-yl, ortho-triphenyl-4'-yl, p-triphenyl-2'-yl, m-triphenyl-2-yl, m-triphenyl-3-yl, inter-three Phen-4-yl, o-triphenyl-2-yl, o-triphenyl-3-yl, o-triphenyl-4-yl, p-triphenyl-2-yl, p-triphenyl-3-yl, couplet Triphenyl-4-yl), as a condensed tricyclic aryl group -(1-,3-,4-,5-)yl, 茀-(1-,2-,3-,4-,9- ), fluorenyl-(1-,2-)yl, (1-,2-,3-,4-,9-)phenanthryl, as a tetracyclic aryl phenylene (5'-phenyl- Cross-linked triphenyl-2-yl, 5'-phenyl-m-triphenyl-3-yl, 5'-phenyl-m-triphenyl-4-yl, meta-tetraphenyl) as a condensed tetracyclic ring a triphenyl-(1-,2-)yl, anthracene-(1-,2-,4-)yl, fused tetraphenyl-(1-,2-,5-)yl group as an aryl group苝-(1-, 2-, 3-)-based, fused penta-(1-, 2-, 5-, 6-)yl and the like of the ring aryl group. Further, a group in which a condensed ring-based aryl group is substituted with a phenyl group or the like is also exemplified. The number of the substituents is, for example, the maximum number of substitutables, preferably one to three, more preferably one to two, and still more preferably one. Preferred among these groups are a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a naphthyl group substituted by a phenyl group, and the like.

The "heteroaryl group having 2 to 24 carbon atoms" in R is preferably a heteroaryl group having 2 to 20 carbon atoms, more preferably a heteroaryl group having 2 to 15 carbon atoms, particularly preferably It is a heteroaryl group having a carbon number of 2 to 10. In addition, examples of the "heteroaryl group" include a heterocyclic group containing one to five hetero atoms selected from the group consisting of oxygen, sulfur, and nitrogen as atoms constituting the ring.

For example, a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, an oxadiazolyl group, a thiadiazolyl group, a triazolyl group, a tetrazolyl group, Pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, fluorenyl, isodecyl, 1H-carbazolyl, benzimidazolyl, benzoxazolyl, benzo Thiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolinyl, porphyrinyl, quinazolinyl, quinoxalinyl, pyridazinyl, naphthyridinyl, indolyl, acridinyl, Carbazolyl, acridinyl, phenoxazinyl, phenothiazine, cyanoazinyl, pyridazinyl, furazinyl, benzofuranyl, isobenzofuranyl, benzo[b]thienyl, Phenylthio, thiophene and the like. Preferred among these groups are a pyridyl group, a quinolyl group, an isoquinolyl group and the like.

R is particularly preferably a group represented by the following formula (R-1) to formula (R-20). Further, among these groups, those represented by the following formulas (R-1) to (R-14) are preferred, and those of the following formulas (R-1) to (R-11) are more preferred. Further, it is more preferably a group represented by the following formula (R-1), formula (R-10) and formula (R-11).

[化44]

The group represented by the above formula (A-1) selected as A or A' may, for example, be a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group.

The group represented by the above formula (A-2) selected as A or A' may be exemplified by 2,2'-bipyridyl-(3-,4-,5-,6-)yl, 2,3'- Bipyridyl-(3-,4-,5-,6-)yl, 2,4'-bipyridyl-(3-,4-,5-,6-yl), 3,2'-bipyridine-( 2-,4-,5-,6-)yl, 3,3'-bipyridyl-(2-,4-,5-,6-yl), 3,4'-bipyridine-(2-,4 -,5-,6-)yl, 4,2'-bipyridyl-(2-,3-,5-,6-yl), 4,3'-bipyridine-(2-,3-,5- , 6-), 4,4'-bipyridyl-(2-,3-,5-,6-)yl.

The group represented by the above formula (A-3) selected as A or A' may, for example, be (pyridin-2-yl)phenyl-2-yl or (pyridin-3-yl)phenyl-2-yl. (pyridin-4-yl)phenyl-2-yl, (pyridin-2-yl)phenyl-3-yl, (pyridin-3-yl)phenyl-3-yl, (pyridin-4-yl)benzene 3-yl, (pyridin-2-yl)phenyl-4-yl, (pyridin-3-yl)phenyl-4-yl, (pyridin-4-yl)phenyl-4-yl.

The group represented by the above formula (A-4) selected as A or A' may be exemplified by 1-(2-pyridyl)naphthalene-(2-, 3-, 4-, 5-, 6-, 7-, 8-), 1-(3-pyridyl)naphthalene-(2-,3-,4-,5-,6-,7-,8-yl), 1-(4-pyridyl)naphthalene-(2- ,3-,4-,5-,6-,7-,8-)yl, 2-(2-pyridyl)naphthalene-(1-,3-,4-,5-,6-,7-,8 -), 2-(3-pyridyl)naphthalene-(1-,3-,4-,5-,6-,7-,8-)yl, 2-(4-pyridyl)naphthalene-(1-, 3-, 4-, 5-, 6-, 7-, 8-).

The "aryl group having 6 to 18 carbon atoms" selected as A or A' is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. For example, the group exemplified in the description of the "aryl group having 6 to 24 carbon atoms" in the above R (only for a group having a carbon number of 18 or less).

In the above, A or A' is preferably hydrogen, a group represented by the following formula (A-1-1) to formula (A-1-3), and the following formula (A-2-1). a group represented by the formula (A-2-18), a group represented by the following formula (A-3-1) to the formula (A-3-6), and a formula (A-4-1) to the following formula: The group represented by (A-4-6) and the group represented by the following formula (A-5-1) to formula (A-5-11).

[化45]

The group which is more preferably A or A' is a group represented by the above formula (A-1-1) to formula (A-1-3), and the above formula (A-2-1) to formula (A-2-18). The group represented by the above formula (A-3-1) to the formula (A-3-6) and the formula (A-4-1) to the formula (A-4-6) base.

Further preferred as A or A' is a group represented by the above formula (A-1-1) to formula (A-1-3), and the above formula (A-2-1) to formula (A-2- 18) the base represented by the formula (A-3-1) to the formula (A-3-6), and the formula (A-4-1) to the formula (A-4-3) The basis.

The group which is more preferably A or A' is a group represented by the above formula (A-1-1) to formula (A-1-3), and the above formula (A-2-1) to formula (A-2-4). a group represented by the above formula (A-2-7) to formula (A-2-9), a group represented by the above formula (A-2-12), and the above formula (A-2-) 15) the base represented by the formula (A-3-1) to the formula (A-3-6), and the formula (A-4-1) to the formula (A-4-3) The basis.

The group which is particularly preferable as A or A' is a group represented by the above formula (A-1-1) to formula (A-1-3), a group represented by the above formula (A-2-1), and the above formula ( A group represented by A-2-2), a group represented by the above formula (A-2-8), a group represented by the above formula (A-2-12), and a formula (A-3-1) to The group represented by (A-3-6) and the group represented by the above formula (A-4-1) to formula (A-4-3).

The group which is optimal as A or A' is a group represented by the above formula (A-1-3), a group represented by the above formula (A-2-1), and a group represented by the above formula (A-2-2). The group represented by the above formula (A-2-8), the group represented by the above formula (A-2-12), and the formula (A-3-1) to the formula (A-3-3) The group represented by the above formula (A-3-5), the group represented by the above formula (A-3-6), and the group represented by the above formula (A-4-3).

The above-mentioned preferred examples of A or A' are preferably most suitable when R is particularly a phenyl or naphthyl group. Moreover, A and A' may be the same structure or may be a basis of different structures.

Specific examples of the compound represented by the above formula (1) include a compound represented by the following formula (1-1) to formula (1-30), and a formula (1-531) to formula (1- a compound represented by the following formula (1-7831) to the formula (1-7860), a compound represented by the following formula (1-8361) to the formula (1-8585), and the following formula; (1-8701) - a compound represented by the formula (1-8730), and a compound represented by the following formula (1-9231) to formula (1-9455).

[Chem. 46]

[化47]

[48]

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[化50]

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[化53]

[54]

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[化59]

[60]

[化61]

[化62]

[化63]

[化64]

[化65]

[化66]

[67]

[化68]

[化69]

[化70]

[71]

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[化73]

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[化78]

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[化90]

With respect to the compound represented by the above formula (1-1) to formula (1-864), among these compounds, the above formula (1-1) to formula (1-6) and formula (1-10) are particularly preferable. Formula (1-15), Formula (1-19) - Formula (1-21), Formula (1-24), Formula (1-531) - Formula (1-634), Formula (1-645) - Formula (1-650), formula (1-664) to formula (1-669), formula (1-676) to formula (1-681), formula (1-688) to formula (1-693), formula ( 1-700) to (1-705), (1-712) to (1-717), (1-724) to (1-729), and (1-736) to (1) -741), formula (1-744), formula (1-748) to formula (1-753), formula (1-760) to formula (1-765), formula (1-772) to formula (1- 777), a compound represented by the formula (1-784) to the formula (1-789), and the formula (1-793) to the formula (1-864).

2. A method for producing a benzo[c]carbazole compound represented by the formula (1)

Next, a method for producing the compound of the present invention will be described.

As the compound of the present invention, a known compound can be used, and a known synthesis method such as Suzuki coupling reaction or root-shore coupling reaction (for example, "Metal-Catalyzed Cross-Coupling Reactions-Second, Completely Revised and Enlarged Edition" can be used. Recorded) and synthesized. Further, the two reactions may be combined to carry out the synthesis. The procedure for synthesizing the compound represented by the formula (1) by a Suzuki coupling reaction or a root-shore coupling reaction is exemplified as follows.

<Method for Producing Compound represented by Formula (1) (Part 1)>

<Synthesis of pyridine bonded with a phenyl group or a naphthyl group having a reactive substituent>

First, a zinc chloride complex of pyridine is synthesized by the following reaction formula (1), and then a zinc chloride complex of pyridine and 1,4-dibromobenzene are obtained by the following reaction formula (2). Reaction of 1,4-dibromonaphthalene whereby 2-(4-bromophenyl)pyridine or 2-(4-bromonaphthalen-1-yl)pyridine can be synthesized.

[化91]

Further, "ZnCl ₂ ‧ TMEDA" in the reaction formula (1) is a tetramethylethylenediamine complex of zinc chloride. In the "RLi" or "RMgX" in the above reaction formula (1), R represents a linear or branched alkyl group, preferably a linear alkyl group having a carbon number of 1 to 4 or a carbon number of 3 to 3. a branched alkyl group of 4, and X is a halogen.

Here, a method of synthesizing 2-(4-bromophenyl)pyridine and 2-(4-bromonaphthalen-1-yl)pyridine using 2-bromopyridine as a raw material is exemplified, and 3-bromopyridine or 4- can also be used. Bromopyridine is used as a raw material, and iodide is used instead of bromide, thereby obtaining corresponding targets, namely 3-(4-bromophenyl)pyridine, 4-(4-bromophenyl)pyridine, 3- (4-Butonaphthalen-1-yl)pyridine and 4-(4-bromonaphthalen-1-yl)pyridine.

Moreover, the synthesis of 2-(4-bromophenyl)pyridine and 2-(4-bromonaphthalen-1-yl)pyridine using 1,4-dibromobenzene or 1,4-dibromonaphthalene as raw materials is exemplified herein. The method may also use 1,3-dibromobenzene, 2,6-dibromonaphthalene or 2,7-dibromonaphthalene as a raw material, and additionally use dichloro, diiodide, bis(trifluoromethanesulfonic acid). Ester) or such a mixture (for example, 1-bromo-4-iodobenzene, etc.) instead of using a dibromide, thereby obtaining a corresponding target, 2-(3-bromophenyl)pyridine, 2-(6-bromonaphthalen-2-yl)pyridine, 2-(7-bromonaphthalen-2-yl)pyridine and the like.

Further, instead of reacting 1,4-dibromobenzene or the like with a zinc chloride complex of pyridine, a coupling reaction of 1,4-dibromobenzene or the like with pyridylboronic acid or pyridyl boronic acid ester may be used instead. The coupling reaction is carried out to obtain the above target.

Further, by appropriately selecting a raw material, a raw material for synthesis of the compound of the present invention represented by the formula (1), that is, a pyridine having a phenyl group or a naphthyl group having various reactive substituents bonded thereto can be obtained.

<Synthesis of pyridyl-substituted phenyl/naphthylboronic acid and boric acid ester>

Next, as shown in the following reaction formula (3), 2-(4-bromophenyl)pyridine or 2-(4-bromonaphthalen-1-yl)pyridine can be lithiated using an organolithium reagent, or magnesium can be used. Or organomagnesium reagent is reacted with trimethyl borate, triethyl borate or triisopropyl borate as a Grignard reagent, thereby synthesizing 4-(pyridin-2-yl)phenyl borate and 4-( Pyridin-2-yl)naphthalen-1-ylborate. Further, the boronic acid ester can be hydrolyzed by the following reaction formula (4), thereby synthesizing 4-(2-pyridyl)phenylboronic acid and 4-(pyridin-2-yl)naphthalene-1- Boronic acid.

[化92]

In the "RLi" or "RMgX" in the above reaction formula (3), R represents a linear or branched alkyl group, preferably a linear alkyl group having a carbon number of 1 to 4 or a carbon number of 3 to 3. a branched alkyl group of 4, and X is a halogen.

Further, lithium (2-bromophenyl)pyridine or 2-(4-bromonaphthalen-1-yl)pyridine can be lithiated using an organolithium reagent as shown in the following reaction formula (5), or magnesium can be used. Or organomagnesium reagent as a Grignard reagent to react with bis(pinacolato)diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborane Thus, other 4-(pyridin-2-yl)phenylborate or 4-(pyridin-2-yl)naphthalen-1-ylborate was synthesized. Further, as shown in the following reaction formula (6), 2-(4-bromophenyl)pyridine or 2-(4-bromonaphthalen-1-yl)pyridine and diboronic acid can be used using a palladium catalyst and a base. The alcoholic ester or 4,4,5,5-tetramethyl-1,3,2-dioxaborane is subjected to a coupling reaction, whereby the same 4-(pyridin-2-yl)phenylborate is synthesized Or 4-(pyridin-2-yl)naphthalen-1-ylborate.

In the "RLi" or "RMgX" in the above reaction formula (5), R represents a linear or branched alkyl group, preferably a linear alkyl group having a carbon number of 1 to 4 or a carbon number of 3~ a branched alkyl group of 4, and X is a halogen.

Further, in the above reaction formula (3), reaction formula (5) or reaction formula (6), the corresponding positional isomer may be used to synthesize the corresponding boric acid/borate ester: 3-(4) -Bromophenyl)pyridine, 4-(4-bromophenyl)pyridine, 2-(3-bromophenyl)pyridine, 3-(3-bromophenyl)pyridine, 4-(3-bromophenyl)pyridine , 3-(4-bromophthalen-1-yl)pyridine, 4-(4-bromophthalen-1-yl)pyridine, 2-(4-bromonaphthalene) -1-yl)pyridine, 2-(6-bromonaphthalen-2-yl)pyridine, 3-(6-bromonaphthalen-2-yl)pyridine, 4-(6-bromonaphthalen-2-yl)pyridine, 2 -(7-bromonaphthalen-2-yl)pyridine, 3-(7-bromonaphthalen-2-yl)pyridine, 4-(7-bromonaphthalen-2-yl)pyridine.

Further, in the above reaction formula (3), reaction formula (5) or reaction formula (6), a chloride, an iodide or a trifluoromethanesulfonate may be used instead of, for example, 2-(4-bromophenyl)pyridine. And a bromide such as 3-(4-bromonaphthalen-1-yl)pyridine, which was synthesized in the same manner.

<Synthesis of bipyridine having a reactive substituent>

First, a zinc chloride complex of pyridine is synthesized by the following reaction formula (7), and then a zinc chloride complex of pyridine and 2,5-dibromopyridine are obtained by the following reaction formula (8). Reaction, whereby 5-bromo-2,2'-bipyridine can be synthesized.

Further, "ZnCl ₂ ‧ TMEDA" in the reaction formula (7) is a tetramethylethylenediamine complex of zinc chloride. In the "RLi" or "RMgX" in the above reaction formula (7), R represents a linear or branched alkyl group, preferably a linear alkyl group having a carbon number of 1 to 4 or a carbon number of 3~ a branched alkyl group of 4, and X is a halogen.

Here, a method of synthesizing 5-bromo-2,2'-bipyridine using 2-bromopyridine as a raw material is exemplified, but 3-bromopyridine or 4-bromopyridine may also be used as a raw material, and iodide may be used instead of using Bromide, whereby the corresponding target is obtained, namely 5-bromo-2,3'-bipyridine or 5-bromo-2,4'-bipyridine.

Further, a method of synthesizing 5-bromo-2,2'-bipyridine using 2,5-dibromobenzene as a raw material is exemplified here, but 2,4-dibromopyridine or 2,6-dibromo can also be used. Pyridine or 3,5-dibromopyridine as a raw material, and additionally using dichloro, diiodide, bis(trifluoromethanesulfonate) or such a mixture (for example, 2-bromo-6-iodopyridine, etc.) Instead of using a dibromide, the corresponding target is obtained, namely 6-bromo-2,2'-bipyridine, 4-bromo-2,2'-bipyridine, and the like.

Further, instead of coupling the 2,5-dibromopyridine to the zinc chloride complex of pyridine, a coupling reaction of 2,5-dibromopyridine with pyridylboronic acid or pyridyl boronate can be used instead. The reaction is carried out to obtain the above target.

Further, by appropriately selecting a raw material, a raw material for synthesis of the compound of the present invention represented by the formula (1), that is, bipyridine having various reactive substituents can be obtained.

<Synthesis of bipyridyl boric acid/borate ester>

Next, as shown in the following reaction formula (9), 5-bromo-2,2'-bipyridine may be lithiated using an organolithium reagent, or magnesium or organomagnesium reagent may be used as a Grignard reagent with trimethyl borate. The 2,2'-bipyridyl borate is synthesized by reacting an ester, triethyl borate or triisopropyl borate. Further, the 2,2'-bipyridyl borate can be hydrolyzed by the following reaction formula (10) to synthesize 2,2'-bipyridylboronic acid.

In the "RLi" or "RMgX" in the above reaction formula (9), R represents a linear or branched alkyl group, preferably a linear alkyl group having a carbon number of 1 to 4 or a carbon number of 3 to 3. a branched alkyl group of 4, and X is a halogen.

Further, as shown in the following reaction formula (11), 5-bromo-2,2'-bipyridine may be lithiated using an organolithium reagent, or magnesium or organomagnesium reagent may be used as a Grignard reagent with boronic acid. The alcohol ester or 4,4,5,5-tetramethyl-1,3,2-dioxaborane is reacted to synthesize other 2,2'-bipyridyl borate. Further, as shown in the following reaction formula (12), 5-bromo-2,2'-bipyridine and boronic acid pinacol ester or 4,4,5,5-tetramethyl can be obtained by using a palladium catalyst and a base. The keto-1,3,2-dioxaborane is subjected to a coupling reaction, whereby the same 2,2'-bipyridyl borate is synthesized.

[化96]

In the "RLi" or "RMgX" in the above reaction formula (11), R represents a linear or branched alkyl group, preferably a linear alkyl group having a carbon number of 1 to 4 or a carbon number of 3 to 3. a branched alkyl group of 4, and X is a halogen.

Further, in the above reaction formula (9), reaction formula (11) or reaction formula (12), 5-bromo-2,3'-bipyridine, 5-bromo-2,4-bipyridine, 5 may also be used. a positional isomer such as bromine _- 3,4'-bipyridyl or 4-bromo-2,2'-bipyridine to synthesize the corresponding boric acid/borate.

Further, in the above reaction formula (9), reaction formula (11) or reaction formula (12), a chloride, an iodide or a trifluoromethanesulfonate may be used instead of, for example, 5-bromo-2,2'-linkage. A bromide such as pyridine is synthesized in the same manner.

<Synthesis of an aryl group having a reactive substituent and its boronic acid/boronic acid ester>

When selecting "aryl group having 6 to 18 carbon atoms" (for example, a group represented by formula (A-5-1) to formula (A-5-11)) as A or A', A compound having a reactive substituent bonded thereto or a boronic acid/boronic acid ester thereof may be used as a commercially available compound, or may be synthesized by referring to the above-mentioned synthesis method.

<Synthesis of the central skeleton part

First, 1-methoxy-4-(4-methoxy-2-nitrophenyl)naphthalene is synthesized by a coupling reaction as shown in the following reaction formula (13). Here, Suzuki coupling using boric acid is exemplified in the reaction formula (13), but root-shore coupling using a zinc complex may also be employed. Next, a cyclization reaction is carried out using triethyl phosphite or triphenylphosphine to obtain a benzo[c]carbazole derivative (BCz-A). The BCz-A is formed into BCz-B by a coupling reaction using a palladium catalyst or a Ullmann reaction, and then demethylated by boron tribromide or pyridine hydrochloride. Into BCz-C. Thereafter, it is reacted with trifluoromethanesulfonic anhydride to obtain a central skeleton portion of the compound of the present invention: bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diyl ester.

[化97]

The above-mentioned third-stage reaction is a reaction in which a moiety corresponding to R in the compound represented by the formula (1) is bonded, in which a corresponding aryl or heteroaryl bromide or iodide is used. Instead of bromobenzene or iodobenzene, an intermediate having different substituents on N can be synthesized.

<Synthesis of the central skeleton part

Moreover, the central skeleton portion can also be synthesized in the following manner. First, 4,4'-(2-nitro-1,4-phenylene)bis(1-methoxynaphthalene) was synthesized by a coupling reaction as shown in the following reaction formula (13'). Here, Suzuki coupling using boric acid is exemplified in the reaction formula (13'), and root-shore coupling using a zinc complex compound may also be employed. Next, a cyclization reaction is carried out using triethyl phosphite or triphenylphosphine to obtain a benzo[c]carbazole derivative (BCz-A'). Thereafter, N-phenylation (BCz-B') is carried out by the above method, followed by demethylation (BCz-C'), and finally reacted with trifluoromethanesulfonic anhydride to obtain a central skeleton of the compound of the present invention. Part: 4-(7-Phenyl-5(((trifluoromethyl))sulfonyl)oxy)-7H-benzo[c]indazol-9-yl)naphthalene-1-trifluoromethanesulfonate Base ester.

<Synthesis of diborate ester in the central skeleton portion

The bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5 obtained by the reaction of the formula (13) can be obtained by using a palladium catalyst and a base as shown in the following reaction formula (14). , 9-di-ester ester is coupled with pinacol borate or 4,4,5,5-tetramethyl-1,3,2-dioxaborane to synthesize 7-phenyl- 7H-Benzo[c]carbazole-5,9-diborate.

[化99]

<Synthesis of diborate ester in the central skeleton portion

The 4-(7-phenyl-5((trifluoromethyl)) trifluoromethanesulfonate obtained by the reaction formula (13') can be obtained by using a palladium catalyst and a base as shown in the following reaction formula (14'). Sulfomethyl)oxy)-7H-benzo[c]indazol-9-yl)naphthalen-1-yl ester with pinacol borate or 4,4,5,5-tetramethyl-1, Synthesis of 7-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2 by coupling reaction with 3,2-dioxaborane -yl)-9-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-1-yl)-7H-benzo[ c] carbazole.

<Synthesis of a benzo[c]carbazole compound of the present invention using a Suzuki coupling reaction>

The above bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9 can be obtained in the presence of a palladium catalyst and a base as shown in the following reaction formula (15). -di-diester is reacted with 2 times molar pyridine boric acid or borate ester, pyridyl-substituted phenyl/naphthyl boric acid or borate or bipyridine boric acid or borate The benzo[c]carbazole compound of the present invention. Here, the use of 4-pyridylboronic acid/borate, 4-(pyridin-2-yl)phenylboronic acid/borate, 4-(pyridin-2-yl)naphthalen-1-ylboronic acid/boron is exemplified. The acid salt and the 2,2'-bipyridin-5-ylboronic acid/boronic acid ester are synthesized, but they can also be synthesized in the same manner using the respective positional isomers. Further, 4-(7-phenyl-5(((trifluoromethyl)sulfonyl)oxy)-7H-benzo[c]indazol-9-yl)naphthalene trifluoromethanesulfonate can also be used. The benzo[c]carbazole compound of the present invention is synthesized by substituting -1-yl ester for bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diyl ester.

In the above reaction formula (15), R represents a linear or branched alkyl group, preferably a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms.

Further, 7-phenyl-7H-benzo[c]carbazole-5,9-diborate can be made 2 times in the presence of a palladium catalyst and a base as shown in the following reaction formula (16). a pyridine having a reactive substituent, a pyridine having a phenyl/naphthyl group having a reactive substituent or a bipyridyl reaction having a reactive substituent, thereby synthesizing the benzo[c] of the present invention Carbazole compound. The use of 4-reactive substituted pyridine, 2-(4-reactive substituted phenyl)pyridine, 2-(4-reactive substituted naphthalen-1-yl)pyridine or 5-reactive substituted-2,2 is exemplified herein. '-Bipyridine synthesis method, but it is also possible to synthesize in the same manner using the respective positional isomers. Moreover, 7-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9-(4-(4, 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-1-yl)-7H-benzo[c]carbazole instead of 7-phenyl-7H- The benzo[c]carbazole compound of the present invention is synthesized from benzo[c]carbazole-5,9-diborate.

Further, as described in the following reaction formula (17), the above bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole can be obtained in the presence of a palladium catalyst and a base. 5,9-di-ester ester is synthesized by reacting 1 or 2 moles of pyridine boric acid or borate ester, pyridyl-substituted phenyl/naphthyl boric acid or boric acid ester or bipyridyl boric acid or boric acid ester (first stage), further with 1 mole of pyridine boric acid or borate, pyridyl substituted phenyl/naphthyl boric acid or borate or bipyridine in the presence of a palladium catalyst and a base The boronic acid or borate ester is reacted (second stage) to synthesize the benzo[c]carbazole compound of the present invention. Further, 4-(7-phenyl-5(((trifluoromethyl)sulfonyl)oxy)-7H-benzo[c]indazol-9-yl)naphthalene trifluoromethanesulfonate can also be used. The benzo[c]carbazole compound of the present invention is synthesized by substituting -1-yl ester for bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diyl ester.

[化103]

In the reaction of the reaction formula (17), after the end of the first stage reaction, the purification operation may be carried out as needed. Furthermore, it is also possible to use 1 mol of a boronic acid or a boric acid ester of a pyridine different from the first stage, a boronic acid or a boronic acid ester of a phenyl/naphthyl group substituted with a pyridyl group or a boric acid or a boric acid ester of a bipyridine. A benzo[c]carbazole compound different in the substitution of the 5-position and the 9-position is synthesized.

In addition, an aryl boronic acid such as phenylboronic acid or naphthylboronic acid may be used in the first stage or the second stage, whereby a benzo group substituted with an aryl group at the 5- or 9-position of the benzoxazolyl group is synthesized. c] carbazole compound. This compound corresponds to A or A' in the compound represented by the formula (1), and "an aryl group having 6 to 18 carbon atoms" is selected (for example, the formula (A-5-1) to the formula (A-5-11). The compound represented by the group).

Similarly, 7-phenyl-7H-benzo[c]carbazole-5,9-diborate is reacted with a palladium catalyst and a base as shown in the above reaction formula (16). In the case of a pyridine in which a substituent is bonded or a phenyl group in which a phenyl/naphthyl group having a reactive substituent is bonded, a phenyl group having a phenyl/naphthyl group having a reactive substituent or, for example, The aryl halide such as bromobenzene or bromine is reacted in two stages, whereby the benzo[c]carbazole compound of the present invention can be synthesized.

Specific examples of the palladium catalyst used in the Suzuki coupling reaction include Pd(PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd(OAc) ₂ , and tris(dibenzylideneacetone) dipalladium (0). , tris(dibenzylideneacetone)dipalladium(0)chloroform complex, or bis(dibenzylideneacetone)palladium(0).

Further, in order to promote the reaction, a phosphine compound may be added to the palladium compounds as the case may be. Specific examples of the phosphine compound include tris(t-butyl)phosphine, tricyclohexylphosphine, and 1-(N,N-dimethylaminomethyl)-2-(di-t-butylphosphino)dilenate. Iron, 1-(N,N-dibutylaminomethyl)-2-(di-t-butylphosphino)ferrocene, 1-(methoxymethyl)-2-(di-tertiary) Ferrocenyl)ferrocene, 1,1'-bis(di-t-butylphosphino)ferrocene, 2,2'-bis(di-t-butylphosphino)-1,1'-binaphthyl 2-methoxy-2'-(di-t-butylphosphino)-1,1'-binaphthyl or 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl.

Specific examples of the base to be used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium butoxide, sodium acetate, and phosphoric acid. Potassium, or potassium fluoride.

Further, specific examples of the solvent used in the reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N,N-dimethylformamide, tetrahydrofuran, diethyl ether, and third. Butyl methyl ether, 1,4-dioxane, methanol, ethanol, cyclopentyl methyl ether or isopropanol. These solvents may be appropriately selected and may be used singly or as a mixed solvent.

<Method for Producing Compound represented by Formula (1) (Part 2)>

The synthesis method of the benzo[c]carbazole compound of the present invention using Suzuki coupling has been described above, and root-shore coupling can also be utilized.

First, as shown in the following reaction formula (18), an organolithium reagent is used for 4-bromopyridine, 4-(2-pyridyl)-1-bromobenzene, 4-(2-pyridyl)-1-bromonaphthalene. Or 5-bromo-2,2'-bipyridine for lithiation, or use magnesium or organomagnesium reagent as a Grignard reagent with zinc chloride or zinc chloride tetramethylethylenediamine complex (ZnCl ₂ ‧TMEDA) The reaction, whereby the respective zinc complexes are synthesized.

Further, "ZnCl ₂ ‧ TMEDA" in the reaction formula (18) is a tetramethylethylenediamine complex of zinc chloride. In the "RLi" or "RMgX" in the above reaction formula (18), R represents a linear or branched alkyl group, preferably a linear alkyl group having a carbon number of 1 to 4 or a carbon number of 3 to 3. a branched alkyl group of 4.

Alternatively, the iodide may be used in the same manner as the bromide. Moreover, the use of 4-bromopyridine, 4-(2-pyridyl)-1-bromobenzene, 4-(2-pyridyl)-1-bromonaphthalene and 5-bromo-2,2'-linkage is exemplified herein. As an example of the raw material of pyridine, the respective positional isomers can be synthesized in the same manner.

<Synthesis of a benzo[c]carbazole compound of the present invention using a root-shore coupling reaction>

Finally, bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-di can be obtained in the presence of a palladium catalyst as shown in the following reaction formula (19). a 4-pyridyl zinc complex, 4-(pyridin-2-yl)phenyl/naphthalen-1-yl zinc complex or 2,2'- synthesized as described above with 2 moles of a molar. The bipyridyl-5-yl zinc complex is reacted, whereby the benzo[c]carbazole compound of the present invention is synthesized. Further, as shown in the following reaction formula (20), the zinc complex of 1 mol of the zinc or the zinc complex of an aryl group such as a phenyl group or a naphthyl group may be the same as the above reaction formula (17). The reaction is carried out in two stages to synthesize the benzo[c]carbazole compound of the present invention. Further, 4-(7-phenyl-5(((trifluoromethyl)sulfonyl)oxy)-7H-benzo[c]indazol-9-yl)naphthalene trifluoromethanesulfonate can also be used. Synthesis of the benzo[c]carbazole compound of the present invention by substituting -1-yl ester for bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diyl ester .

[化105]

Specific examples of the palladium catalyst used in the root-shore coupling reaction include Pd(PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd(OAc) ₂ , and tris(dibenzylideneacetone) dipalladium (0). , tris(dibenzylideneacetone)dipalladium(0)chloroform complex, bis(dibenzylideneacetone)palladium(0), bis(tri-t-butylphosphino)palladium(0), or (1 , 1'-bis(diphenylphosphino)ferrocene)palladium(II) chloride.

Further, specific examples of the solvent used in the reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N,N-dimethylformamide, tetrahydrofuran, diethyl ether, and third. Butyl methyl ether, cyclopentyl methyl ether or 1,4-dioxane. These solvents may be appropriately selected and may be used singly or as a mixed solvent.

<5 or 9 benzo[c]carbazole compounds of hydrogen>

The compound in which the 5- or 9-position of the benzo[c]carbazole compound of the present invention is hydrogen can be synthesized by using a compound having no methoxy group as one of the starting materials of the above reaction formula (13). The synthesis is carried out in the coupling reaction in the latter stage.

That is, 1-naphthylboronic acid can be used in place of 4-methoxy-1-naphthylboronic acid to react with 4-chloro-3-nitroanisole, and then the reaction is carried out in accordance with the reaction formula (13), thereby synthesizing The 5-position of benzo[c]carbazole is hydrogen and the 9-position is a compound of triflate. This monotrifluoromethanesulfonate is supplied to the coupling reaction in the latter stage, whereby a benzo[c]carbazole compound which is hydrogen at the 5-position can be obtained.

Further, 2-chloronitrobenzene can be used instead of 4-chloro-3-nitroanisole to react with 4-methoxy-1-naphthaleneboronic acid, and then the reaction can be carried out in accordance with the reaction formula (13). The compound at the 9 position of the benzo[c]carbazole is hydrogen and the 5-position is a triflate. The monotrifluoromethanesulfonate is supplied to the coupling reaction in the subsequent stage, whereby a benzo[c]carbazole compound having a hydrogen position at the 9 position can be obtained.

3. Organic electroluminescent components

The benzo[c]carbazole compound having a pyridine-containing substituent of the present invention can be used, for example, as a material for an organic electroluminescent device. Hereinafter, the organic electroluminescent device of the present embodiment will be described in detail based on the drawings. Fig. 1 is a schematic cross-sectional view showing an organic electroluminescent device of the embodiment.

<Structure of Organic Electroluminescence Element>

The organic electroluminescent device 100 shown in FIG. 1 has a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole transport layer provided on the hole injection layer 103. The light emitting layer 105 disposed on the hole transport layer 104, the electron transport layer 106 disposed on the light emitting layer 105, the electron injection layer 107 disposed on the electron transport layer 106, and the cathode 108 disposed on the electron injection layer 107 .

In addition, the organic electroluminescent device 100 may be reversed in the order of fabrication, for example, having the following components: a substrate 101, a cathode 108 disposed on the substrate 101, an electron injection layer 107 disposed on the cathode 108, and an electron injection layer. An electron transport layer 106 on the layer 107, a light-emitting layer 105 disposed on the electron transport layer 106, a hole transport layer 104 disposed on the light-emitting layer 105, and a hole injection layer 103 disposed on the hole transport layer 104. The anode 102 is implanted on the hole injection layer 103.

It is not necessary to be the above-mentioned respective layers, and the smallest constituent unit is composed of the anode 102, the light-emitting layer 105, the electron transport layer 106, and/or the electron injection layer 107, and the cathode 108. The hole injection layer 103 and the hole transport layer 104 are arbitrarily set. Layer. Further, each of the above layers may be composed of a single layer or may be composed of a plurality of layers.

As a configuration of the layer constituting the organic electroluminescence element, in addition to the above-described configuration of the "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode", It can also be: "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" / luminescent layer / electron transport layer / cathode", "substrate / anode / hole injection layer / luminescent layer / electron injection layer / cathode", "substrate / anode / hole injection layer / luminescent layer / electron transport layer / cathode" , "substrate / anode / luminescent layer / electron transport layer / cathode", "substrate / anode / luminescent layer / electronic note Constituting layer / cathode "like the state.

<Substrate of Organic Electroluminescence Element>

The substrate 101 serves as a support for the organic electroluminescent device 100, and generally, quartz, glass, metal, plastic, or the like is used. The substrate 101 may be formed into a plate shape, a film shape, or a sheet shape as needed. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like can be used. Among them, a glass plate, and a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate or polyfluorene is preferred. In the case of a glass substrate, soda lime glass, alkali-free glass, or the like is used, and if the thickness is also a thickness sufficient to maintain mechanical strength, it is preferably 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. Regarding the material of the glass, it is preferable that the eluted ions from the glass are small, so that alkali-free glass is preferable, but since soda lime glass which is subjected to a barrier coat such as SiO _{2 is} commercially available, Can be used. Further, in order to improve gas barrier properties on the substrate 101, a gas barrier film such as a dense ruthenium oxide film may be provided on at least the surface of the substrate, and in particular, a plate, a film or a sheet made of a synthetic resin having low gas barrier properties may be used. In the case of the substrate 101, it is preferred to provide a gas barrier film.

<Anode of Organic Electroluminescence Element>

The anode 102 functions to inject a hole into the light-emitting layer 105. Further, 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, the hole injection layer 103 and/or the hole transport layer 104 are formed via the hole injection layer 103 and/or the hole transport layer 104. The light emitting layer 105 is injected into the hole.

Examples of the material forming the anode 102 include an inorganic compound and an organic compound. Examples of the inorganic compound include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxides, tin oxides, indium-tin oxides (ITO), indium-zinc oxides). (IZO), etc., a metal halide (such as copper iodide), copper sulfide, carbon black, ITO glass, or Nesa glass. Examples of the organic compound include conductive polymers such as polythiophene such as poly(3-methylthiophene), polypyrrole, and polyaniline. Further, it can be suitably selected from the materials used as the anode of the organic electroluminescence element.

The electric resistance of the transparent electrode is not particularly limited as long as it can supply a sufficient current to the light-emitting element, and it is preferable that the electric resistance of the light-emitting element is low resistance. For example, an ITO substrate of 300 Ω/□ or less functions as an element electrode, and a substrate of about 10 Ω/□ is now available. Therefore, for example, it is particularly preferable to use 100 Ω/□ to 5 Ω/□, preferably Low resistance product of 50Ω/□~5Ω/□. The thickness of ITO can be arbitrarily selected according to the resistance value, and is usually used between 100 nm and 300 nm. many.

<Curtain injection layer and hole transport layer of organic electroluminescence element>

The hole injection layer 103 serves to inject the holes moved from the anode 102 into the light-emitting layer 105 or the hole transport layer 104 efficiently. The hole transport layer 104 functions to efficiently transfer the holes injected from the anode 102 or the 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 may be formed by laminating and mixing one or more types of holes and transport materials, or by injecting and transporting materials and a polymer binder. Formed by a mixture of ). Further, an inorganic salt such as iron (III) chloride may be added to the hole injection and transport material to form a layer.

As a hole injection and a transporting substance, it is necessary to efficiently inject and transport a hole from the positive electrode between the electrodes for applying an electric field. Therefore, it is preferable that the hole injection efficiency is high, and the injected hole can be efficiently transmitted. . Therefore, it is preferable that the ionization potential is small, the hole mobility is large, and the stability is excellent, and it is difficult to generate impurities which are traps during production and use.

The material for forming the hole injection layer 103 and the hole transport layer 104 can be selected from any of the following compounds: a compound which has been conventionally used as a charge transport material for a hole in a photoconductive material, in p-type A well-known compound used in a hole injection layer and a hole transport layer of a semiconductor, an organic electroluminescence element. Specific examples of such compounds are preferably: carbazole derivatives (N-phenylcarbazole, polyvinyl carbazole, etc.), double (N-aryl) A biscarbazole derivative such as carbazole or bis(N-alkylcarbazole), a triarylamine derivative (a polymer having an aromatic tertiary amino group in a main chain or a side chain, 1,1-double ( 4-di-p-tolylaminophenyl)cyclohexane, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diaminobiphenyl , N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-bis(3-methyl Phenyl)-4,4'-diphenyl-1,1'-diamine, N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl-1, Triphenylamine derivatives such as 1'-diamine, 4,4',4"-tris(3-methylphenyl(phenyl)amino)triphenylamine, derived from starburst amine Et, derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrroline derivatives, lanthanide compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, porphyrin derivatives a heterocyclic compound, polydecane, etc. Preferred in the polymer system is a polycarbonate or a styrene derivative having a monomer in a side chain, a polyvinyl carbazole, a polydecane, or the like. The film necessary for the fabrication of the component, from the anode to the hole, and the transmission of the hole The compound is not particularly limited.

Moreover, it is also known that the conductivity of an organic semiconductor is strongly affected by the doping. Such an organic semiconductor host material is composed of a compound having good electron supply properties or a compound having good electron acceptability. In order to dope electron-donating substances, tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinodimethane (F4TCNQ) is known to be strong. Electron acceptors (for example, the reference "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 compounds generate so-called holes due to electron transfer processes in the electron supply type base material (hole transport material). The conductivity of the base material varies considerably due to the number of holes and the mobility. Examples of the host material having the hole transporting property include a benzidine derivative (TPD or the like) or a starburst amine derivative (TDATA, etc.), or a specific metal phthalocyanine (particularly zinc phthalocyanine ZnPc, etc.) (Japan) Patent Laid-Open Publication No. 2005-167175).

<Light-emitting layer of organic electroluminescence element>

The light-emitting layer 105 is a layer that emits light between the electrodes that are applied to the electric field by recombining the holes injected from the anode 102 with the electrons injected from the cathode 108. The material forming the light-emitting layer 105 may be a compound (light-emitting compound) that excites light by recombination of a hole and electrons, and preferably forms a stable film shape and exhibits a strong state in a solid state. A compound that emits (fluorescent and/or phosphorescent) efficiencies.

The light-emitting layer may be formed of a single layer or a plurality of layers, and may be formed of a light-emitting material (host material, dopant material). The main material and the doping material may be one type or a combination of any one of them, and any one of them may be used. The doping material may be included in the entirety of the host material, or may be partially included, in either case. The doping method can be formed by a co-evaporation method with a host material, or can be simultaneously vapor-deposited after being mixed with a host material in advance.

The amount of the host material used varies depending on the type of the host material, and can be determined according to the characteristics of the host material. The standard of the amount of the host material used is preferably from 50% by weight to 99.999% by weight, more preferably from 80% by weight to 99.95% by weight, still more preferably from 90% by weight to 99.9% by weight.

The amount of the doping material used varies depending on the type of the doping material, and can be determined according to the characteristics of the doping material. The standard of the amount of the dopant to be used is preferably from 0.001% by weight to 50% by weight based on the total amount of the luminescent material, more preferably from 0.05% by weight to 20% by weight, still more preferably from 0.1% by weight to 10% by weight. If it is the above range, it is preferable in terms of, for example, a concentration quenching phenomenon.

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

The host material is not particularly limited, and can be suitably used: a condensed ring derivative such as ruthenium or osmium which has been known as an illuminant, and a metal chelate such as tris(8-hydroxyquinoline)aluminum. a bisstyryl derivative such as an oxinoid compound, a bisstyryl fluorene derivative or a distyrylbenzene derivative, a tetraphenylbutadiene derivative, a coumarin derivative, or the like Oxadiazole derivative, pyrrole pyridine derivative, benzalkonone derivative, cyclopentadiene derivative, oxadiazole derivative, thiadiazolidine derivative, pyrrole pyrrole derivative, anthracene derivative, benzene And an anthracene derivative, and a polyphenylacetylene derivative, a polyparaphenylene derivative, and a polythiophene derivative in a polymer system.

In addition, as the host material, it can be suitably selected and used from the compounds described in the Chemical Industry, June, 2004, page 13, and the references cited therein.

Further, the doping material is not particularly limited, and known compounds can be used, and can be selected from various materials depending on the desired luminescent color. Specific examples thereof include condensed ring derivatives such as phenanthrene, anthracene, anthracene, fused tetraphenyl, fused pentabenzene, anthracene, naphthoquinone, dibenzofluorene, erythroprene, and 1,2-benzophenanthrene. , benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives , triazole derivative, pyrroline derivative, anthracene derivative, thiophene derivative, tetraphenylbutadiene derivative, cyclopentadiene derivative, bisstyrylfluorene derivative or stilbene benzene derivative A bisstyryl derivative (Japanese Patent Laid-Open No. Hei 1-245087), a bisstyryl aromatic derivative (Japanese Patent Laid-Open No. Hei 2-247278), and a diazaindacene derivative. , furan derivative, benzofuran derivative, phenyl isobenzofuran, 6(2,4,6-trimethylphenyl)isobenzofuran, bis(2-methylphenyl)isobenzofuran, An isobenzofuran derivative such as 6(2-trifluoromethylphenyl)isobenzofuran or phenylisobenzofuran, a dibenzofuran derivative or a 7-dialkylamine Coumarin derivative, 7-piperidine coumarin derivative, 7-hydroxycoumarin derivative, 7-methoxycoumarin derivative, 7-acetoxycoumarin derivative, 3 a coumarin derivative such as a benzothiazolyl coumarin derivative, a 3-benzimidazolyl coumarin derivative, a 3-benzoxazolyl coumarin derivative, or a dicyanomethylenepyran Derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives, pendant oxybenzoxanthene derivatives, dibenzopyran derivatives, rose red derivatives, luciferin Derivatives, pyran derivatives, carbostyril derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrrole Anthracene pyridine derivative, furopyridinium pyridine derivative, 1,2,5-thiadiazolidine derivative, pyrromethene derivative, piconone derivative, pyrrole pyrrole derivative, squaraine (squarylium) derivatives, purpurin derivatives, naphthazine derivatives, acridone derivatives, deazaflavin derivatives, anthracene derivatives, and benzofluorene derivatives.

When exemplified by the color light, the blue to blue-green doping material may be exemplified by an aromatic hydrocarbon compound such as naphthalene, anthracene, phenanthrene, anthracene, a terphenyl, anthracene, anthracene, anthracene or a 1,2-benzophenanthrene. Or a derivative thereof, furan, pyrrole, thiophene, fluorene heterocyclopentadiene, 9-fluorene, 9,9'-spirobifluorene, benzothiophene, benzofuran, anthracene, dibenzothiophene, Aromatic heterocyclic compound such as benzofuran, imidazolium pyridinium, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolizidine pyridine, thioxanthene or a derivative thereof, distyrylbenzene derivative, tetraphenyl butyl Diene derivatives, anthracene derivatives, aldehyde nitrogen derivatives, coumarin derivatives, imidazoles, thiazoles, thiadiazoles, oxazoles, oxazoles, oxadiazoles, triazoles and the like, and their metal mismatches And an aromatic amine represented by N,N'-diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine Derivatives, etc.

Further, the green to yellow doping material may, for example, be a coumarin derivative, a phthalimide derivative, a naphthoquinone imine derivative, a purpurin derivative, a pyrrole pyrrole derivative, or the like. Examples of the cyclopentadiene derivative, the acridone derivative, the quinacridone derivative, and the thick tetraphenyl derivative such as erythritol, and the following compounds are also exemplified as the above-mentioned blue color. The compound exemplified as the cyan-doped material is introduced with a compound having a long-wavelength substituent such as an aryl group, a heteroaryl group, an arylvinyl group, an amine group or a cyano group.

Further, the orange to red doping material may, for example, be a naphthoquinone imine derivative such as bis(diisopropylphenyl)phosphonium tetracarboxylate, a purple ring ketone derivative, or an acetoacetone or a benzamidine. A rare earth complex such as Eu complex which is a ligand such as acetone and phenanthroline, 4-(dicyanomethylidene)-2-methyl-6-(p-dimethylaminostyryl) a metal phthalocyanine derivative such as -4H-pyran or its analog, magnesium phthalocyanine or chloroaluminum phthalocyanine, rosin compound, deazaflavin derivative, coumarin derivative, quinacridone derivative, a phenoxazine derivative, an oxazine derivative, a quinazoline derivative, a pyrrolizidine derivative, a squaraine derivative, a purpurinone derivative, a phenazine derivative, a phenoxazinone derivative, and a thiazide The azole derivative or the like may be exemplified by the following compounds: an aryl group, a heteroaryl group, and an aromatic group are introduced into the compound exemplified as the blue to cyan and green to yellow doping materials. A compound having a long-wavelength substituent such as a vinyl group, an amine group or a cyano group. Further, as a suitable example, a phosphorescent metal complex represented by tris(2-phenylpyridine)iridium (III) and having a rhodium or a platinum as a central metal may be mentioned.

In addition, as a dopant, it can also be suitably selected and used from the compound described in the Chemical Industry, June, 2004, page 13, and the references cited therein.

Among the above doped materials, particularly preferred are anthracene derivatives, borane derivatives, amine-containing styryl derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives, and ruthenium complexes. Or platinum complex.

Examples of the anthracene derivative include 3,10-bis(2,6-dimethylphenyl)anthracene, 3,10-bis(2,4,6-trimethylphenyl)anthracene, and 3,10-di. Phenylhydrazine, 3,4-diphenylfluorene, 2,5,8,11-tetra-t-butylphosphonium, 3,4,9,10-tetraphenylphosphonium, 3-(1'-fluorenyl) )-8,11-di(t-butyl)anthracene, 3-(9'-fluorenyl)-8,11-di(t-butyl)anthracene, 3,3'-bis(8,11-di (Third butyl) fluorenyl) and the like.

In addition, Japanese Patent Laid-Open No. Hei 11-97178, Japanese Patent Laid-Open No. 2000-133457, Japanese Patent Laid-Open Publication No. 2000-26324, Japanese Patent Laid-Open No. 2001-267079, and Japanese Patent Laid-Open No. 2001 Japanese Laid-Open Patent Publication No. 2001-267076, Japanese Patent Laid-Open Publication No. JP-A No. 2000-34234, Japanese Patent Laid-Open No. Publication No. 2001-267075, and Japanese Patent Laid-Open No. 2001-217077 Anthraquinone derivatives.

Examples of the borane derivative include 1,8-diphenyl-10-(bis(2,4,6-trimethylphenyl)boryl)phosphonium, 9-phenyl-10-(di(2,4, 6-trimethylphenyl)boronium, 4-(9'-fluorenyl)bis(2,4,6-trimethylphenyl)boranyl, 4-(10'-phenyl-9'-fluorenyl) Bis(2,4,6-trimethylphenyl)borane, 9-(di(2,4,6-trimethylphenyl)boranium, 9-(4'-biphenyl)-10- (bis(2,4,6-trimethylphenyl)boryl)phosphonium, 9-(4'-(N-carbazolyl)phenyl)-10-(bis(2,4,6-trimethylphenyl)) Boron based).

Further, a borane derivative described in the specification of International Publication No. 2000/40586 or the like can also be used.

Examples of the amine-containing styryl derivative include N, N, N', N'-tetrakis(4-biphenyl)-4,4'-diaminostilbene, N, N, N', N'-tetrakis(1-naphthyl)-4,4'-diaminostilbene, N,N,N',N'-tetrakis(2-naphthyl)-4,4'-diaminodi Styrene, N,N'-bis(2-naphthyl)-N,N'-diphenyl-4,4'-diaminostilbene, N,N'-bis(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 Bismuth, 4,4'-bis(9-ethyl-3-carbazolevinylidene)-biphenyl, 4,4'-bis(9-phenyl-3-carbazolevinylidene)-biphenyl, etc. Further, an amine-containing styryl derivative described in JP-A-2003-347056, and JP-A-2001-307884, etc., may be used.

Examples of the aromatic amine derivative include N,N,N,N-tetraphenylphosphonium-9,10-diamine, 9,10-bis(4-diphenylamino-phenyl)fluorene, 9, 10-bis(4-bis(1-naphthylamino)phenyl)anthracene, 9,10-bis(4-di(2-naphthylamino)phenyl)anthracene, 10-di-p-tolylamine 9-(4-di-p-tolylamino-1-naphthyl)anthracene, 10-diphenylamino-9-(4-diphenylamino-1-naphthyl)anthracene, 10- Diphenylamino-9-(6-diphenylamino-2-naphthyl)anthracene, [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-diphenylnaphthyl-1-yl]biphenyl, 4,4'-bis[6-diphenylnaphthylamine-2-yl]biphenyl, 4 4"-bis[4-diphenylnaphthylamine-1-yl]-para-triphenyl, 4,4"-bis[6-diphenylnaphthylamine-2-yl]-para-triphenyl or the like.

Further, an aromatic amine derivative described in JP-A-2006-156888 or the like can also be used.

The coumarin derivative may, for example, be coumarin-6 or coumarin-334.

Further, the coumarin derivative described in JP-A-2004-43646, JP-A-2001-76876, and JP-A-H06-298758, and the like can be used.

Examples of the pyran derivative include DCM, DCJTB, and the like described below.

[化106]

In addition, Japanese Patent Laid-Open Publication No. 2005-126399, Japanese Patent Laid-Open No. Hei. No. 2005-097283, Japanese Patent Laid-Open No. Publication No. 2002-234892, Japanese Patent Laid-Open No. 2001-220577, and Japanese Patent Laid-Open No. 2001 A pyran derivative described in Japanese Laid-Open Patent Publication No. 2001-052869, and the like.

Examples of the ruthenium complex include Ir(ppy) ₃ and the like described below.

In addition, Japanese Patent Laid-Open No. 2006-089398, Japanese Patent Laid-Open No. Hei. No. 2006-080419, Japanese Patent Laid-Open No. Hei. No. 2005-298483, Japanese Patent Laid-Open No. 2005-097263, and Japanese Patent Laid-Open The ruthenium complex described in JP-A-2004-111379.

Examples of the platinum complex compound include PtOEP and the like described below.

In addition, Japanese Patent Laid-Open No. Hei. No. 2006-190718, Japanese Patent Laid-Open No. Hei. No. 2006-128634, Japanese Patent Laid-Open No. Hei. No. Hei. No. 2006-093542, No. 2004-335122, and Japanese Patent Laid-Open A platinum complex as described in JP-A-2004-331508.

<Electron injection layer and electron transport layer of organic electroluminescence element>

The electron injection layer 107 functions to inject electrons moving from the cathode 108 into the light-emitting layer 105 or the electron transport layer 106 efficiently. The electron transport layer 106 functions to efficiently transfer electrons injected from the cathode 108 or electrons injected from the cathode 108 via the electron injection layer 107 to the light-emitting layer 105. The electron transport layer 106 and the electron injection layer 107 may be formed by laminating or mixing one or more of electron transporting and injecting materials, or by electron transport, a mixture of an injecting material and a polymer binder.

The electron injection and transport layer is a layer that is responsible for injecting electrons from the cathode and further transporting electrons. It is desirable that the electron injection efficiency is high and the injected electrons are efficiently transmitted. Therefore, it is preferable that the electron affinity is large, the electron mobility is large, the stability is excellent, and it is difficult to generate impurities which are trapping impurities during production and use. However, when considering the case where the transmission balance between the hole and the electron is mainly in the case of efficiently blocking the hole from the anode and no longer combining and flowing to the cathode side, even if the electron transport capability is not so The ground height is still equivalent to the material having high electron transport capability, and has an effect of improving luminous efficiency. Therefore, the electron injecting and transporting layer of the present embodiment may also include a function of efficiently preventing the layer from moving the hole.

The material (electron transport material) forming the electron transport layer 106 or the electron injection layer 107 can use the compound represented by the above formula (1).

The content of the compound represented by the above formula (1) in the electron transport layer 106 or the electron injection layer 107 varies depending on the kind of the compound, and can be determined depending on the characteristics of the compound. The standard of the content of the compound represented by the formula (1) is preferably from 1 wt% to 100 wt%, more preferably from 10 wt% to 100 wt%, based on the total amount of the material for the electron transport layer (or the material for the electron injection layer). Further, more preferably 50 wt% to 100 wt%, particularly preferably 80 wt% to 100 wt%. In the case where the compound represented by the formula (1) is not used alone (100 wt%), other materials as described in detail below may be mixed.

Other materials for forming the electron transport layer or the electron injecting layer may be used arbitrarily from the following compounds: a compound conventionally used as an electron transporting compound in a photoconductive material, an electron injecting layer in an organic electroluminescent device, and A well-known compound used in an electron transport layer.

The material used in the electron transport layer or the electron injecting layer preferably contains at least one selected from the group consisting of an aromatic ring composed of one or more atoms selected from the group consisting of carbon, hydrogen, oxygen, sulfur, antimony and phosphorus. Or a heteroaromatic ring compound, a pyrrole derivative and a fused ring derivative thereof, and a metal complex having electron accepting nitrogen. Specific examples thereof include a condensed ring-based aromatic ring derivative such as naphthalene or an anthracene, a styrene-based aromatic ring derivative represented by 4,4′-bis(diphenylvinyl)biphenyl, and a purple ring ketone derivative. a coumarin derivative, a naphthoquinone imine derivative, an anthracene derivative such as hydrazine or a dip-benzoquinone, a phosphorus oxide derivative, a carbazole derivative, and an anthracene derivative. Examples of the metal complex compound having electron-accepting nitrogen include a hydroxyzole complex such as a hydroxyphenyl oxazole complex, a azomethine complex, and a tropolone metal complex. , flavonol metal complex, and benzoquinoline metal complex, and the like. These materials can be used alone or in combination with different materials. Among them, from the viewpoint of durability, an anthracene derivative such as 9,10-bis(2-naphthyl)anthracene or a styryl group such as 4,4'-bis(diphenylvinyl)biphenyl can be preferably used. An oxazole derivative such as an aromatic ring derivative, 4,4'-bis(N-carbazolyl)biphenyl or 1,3,5-tris(N-carbazolyl)benzene.

Further, specific examples of the other electron-transporting compound include a pyridine derivative other than the compound represented by the above formula (1), a naphthalene derivative represented by the formula (1), an anthracene derivative, a phenanthroline derivative, and a purple ring. Ketone derivatives, coumarin derivatives, naphthoquinone imine derivatives, anthracene derivatives, terephthalamide derivatives, biphenyl hydrazine derivatives, anthracene derivatives, oxadiazole derivatives (1, 3) - bis[(4-t-butylphenyl) 1,3,4-oxadiazolyl]benzene, etc., thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl- 1,3,4-triazole, etc.), thiadiazole derivative, metal complex of 8-oxoquinoline (oxine) derivative, hydroxyquinoline metal complex, quinoxaline derivative, quinoxaline a polymer of a porphyrin derivative, a quinone compound, a gallium complex, a pyrazole derivative, a perfluorinated phenyl derivative, a triazine derivative, a pyrazine derivative, a benzoquinoline derivative (2, 2'-bis(benzo[h]quinolin-2-yl)-9,9'-spirobifluorene, etc.), imidazolium pyridine derivative, borane derivative, benzimidazole derivative (three (N- Phenylbenzimidazol-2-yl)benzene, benzoxazole derivatives, benzothiazole derivatives Oligopyridine derivatives such as biological, quinoline derivatives, and terpyridines, bipyridine derivatives, and terpyridine derivatives (1,3-bis(4'-(2,2':6'2"-tripyridyl) Benzene or the like, a naphthyridine derivative (bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide, etc.), an aldehyde nitrogen derivative, the above formula (1) An oxazole derivative, an anthracene derivative, a phosphorus oxide derivative, a bisstyryl derivative or the like other than the compound represented by the compound.

Further, a metal complex having electron-accepting nitrogen may be used, and examples thereof include a hydroxyquinoline metal complex or a hydroxyzole complex compound such as a hydroxyzole complex or a methine azo complex. Compound, tropolone metal complex, flavonol metal complex, and benzoquinoline metal complex, and the like.

The above materials may be used singly or in combination with different materials.

Preferred among the above materials are a quinolinol metal complex, a bipyridine derivative, a phenanthroline derivative, a borane derivative or a benzimidazole derivative.

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

In the formula, R ¹ to R ⁶ are hydrogen or a substituent, M is Li, Al, G _a , B _e or Zn, and n is an integer of from 1 to 3.

Specific examples of the hydroxyquinoline-based metal complex include lithium 8-hydroxyquinolate, aluminum tris(8-hydroxyquinoline), aluminum tris(4-methyl-8-hydroxyquinoline), and tris(5- Methyl-8-hydroxyquinoline)aluminum, tris(3,4-dimethyl-8-hydroxyquinoline)aluminum, tris(4,5-dimethyl-8-hydroxyquinoline)aluminum, tris(4) ,6-Dimethyl-8-hydroxyquinoline) aluminum, bis(2-methyl-8-hydroxyquinoline) (phenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (2-A Phenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (3-methylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (4-methylphenol) aluminum, double (2-methyl-8-hydroxyquinoline) (2-phenylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (3-phenylphenol) aluminum, bis(2-methyl- 8-hydroxyquinoline (4-phenylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (2,3-dimethylphenol) aluminum, bis(2-methyl-8-hydroxyl Quinoline) (2,6-dimethylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (3,4-dimethylphenol) aluminum, bis(2-methyl-8-hydroxyl Quinoline) (3,5-dimethylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (3,5-di-tert-butylphenol) aluminum, bis(2-methyl- 8-hydroxyquinoline) (2,6-diphenylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (2,4,6- Phenylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (2,4,6-trimethylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (2,4 ,5,6-tetramethylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (1-naphthol) aluminum, bis(2-methyl-8-hydroxyquinoline) (2-naphthalene) Phenol) aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(2-phenylphenol)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline) (3-phenyl Phenol) aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(4-phenylphenol)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline) (3,5- Dimethylphenol) aluminum, bis(2,4-dimethyl-8-hydroxyquinoline) (3,5-di-tert-butylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) Aluminum-μ-sideoxy-bis(2-methyl-8-hydroxyquinoline)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)aluminum-μ-sideoxy-double ( 2,4-Dimethyl-8-hydroxyquinoline)aluminum, bis(2-methyl-4-ethyl-8-hydroxyquinoline)aluminum-μ-sideoxy-bis(2-methyl-4) -ethyl-8-hydroxyquinoline)aluminum, bis(2-methyl-4-methoxy-8-hydroxyquinoline)aluminum-μ-sideoxy-bis(2-methyl-4-methoxy Alkyl-8-hydroxyquinoline)aluminum, bis(2-methyl-5-cyano-8-hydroxyquinoline)aluminum-μ-sideoxy-bis(2-methyl-5-cyano-8- Hydroxyquinoline) aluminum, bis(2-methyl-5-three Methyl-8-hydroxyquinoline)aluminum-μ-sideoxy-bis(2-methyl-5-trifluoromethyl-8-hydroxyquinoline)aluminum, bis(10-hydroxybenzo[h]quina Porphyrin), etc.

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

In the formula, G represents a simple bond or a n-valent linking group, and n is an integer of 2-8. Moreover, carbon which is not used for the bonding of pyridine-pyridine or pyridine-G may also be substituted.

G of the general formula (E-2) is, for example, a group represented by the following structural formula. Further, R in the following structural formula is each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenyl or terphenyl.

[111]

Specific examples of the pyridine derivative include 2,5-bis(2,2'-bipyridyl-6-yl)-1,1-dimethyl-3,4-diphenylfluorene, 2,5-bis(2,2'-bipyridyl-6-yl)-1,1-dimethyl-3,4-di(2,4,6-trimethylphenyl)fluorene, 2,5-bis(2,2'-bipyridin-5-yl)-1,1-dimethyl-3,4-diphenylfluorene, 2,5-bis (2,2 '-Bipyridin-5-yl)-1,1-dimethyl-3,4-bis(2,4,6-trimethylphenyl)fluorene, 9,10-di (2,2 '-Bipyridyl-6-yl)anthracene, 9,10-bis(2,2'-bipyridin-5-yl)anthracene, 9,10-di(2,3'-bipyridin-6-yl)anthracene 9,10-bis(2,3'-bipyridin-5-yl)anthracene, 9,10-bis(2,3'-bipyridin-6-yl)-2-phenylindole, 9,10- Bis(2,3'-bipyridin-5-yl)-2-phenylindole, 9,10-bis(2,2'-bipyridin-6-yl)-2-phenylindole, 9,10- Bis(2,2'-bipyridin-5-yl)-2-phenylindole, 9,10-bis(2,4'-bipyridin-6-yl)-2-phenylindole, 9,10- Bis(2,4'-bipyridin-5-yl)-2-phenylindole, 9,10-bis(3,4'-bipyridin-6-yl)-2-phenylindole, 9,10- Bis(3,4'-bipyridin-5-yl)-2-phenylindole, 3,4-diphenyl-2,5-di(2,2'-bipyridin-6-yl)thiophene, 3 ,4-diphenyl-2,5-bis(2,3'-bipyridin-5-yl)thiophene, 6'6"-di(2- Piperidinyl) 2,2 ': 4', 4 ': 2', 2 '' '- bipyridine four.

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

In the formula, R ¹ to R ⁸ are hydrogen or a substituent, and adjacent groups may be bonded to each other to form a condensed ring, G represents a simple bond or a n-valent linking group, and n is an integer of 2 to 8. Further, G of the formula (E-3-2) is, for example, the same as those described in the column of the bipyridine derivative.

Specific examples of the phenanthroline derivative include 4,7-diphenyl-1,10-morpholine, 2,9-dimethyl-4,7-diphenyl-1,10-morpholine, 9, 10-bis(1,10-morpholin-2-yl)indole, 2,6-bis(1,10-morpholin-5-yl)pyridine, 1,3,5-tris(1,10-morpholine -5-yl)benzene, 9,9'-difluoro-bis(1,10-morpholin-5-yl), 2,9-dimethyl-4,7-biphenyl-1,10-morpholine (bathocuproine) or 1,3-bis(2-phenyl-1,10-morpholin-9-yl)benzene.

In particular, a case where a phenanthroline derivative is used for an electron transport layer or an electron injection layer will be described. In order to obtain stable luminescence over a long period of time, a material excellent in thermal stability or film formability is desired. In the phenanthroline derivative, it is preferred that the substituent itself has a three-dimensional structure or due to a phenanthroline skeleton or a contiguous substituent. A compound having a three-dimensional structure by steric repulsion or a compound having a plurality of morpholine skeletons. Further, in the case where a plurality of morpholine skeletons are bonded, a compound containing a conjugated bond, a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring in a linking unit is more preferable. .

The borane derivative is a compound represented by the following formula (E-4), which is disclosed in detail in Japanese Patent Laid-Open Publication No. 2007-27587.

Wherein R ¹¹ and R ¹² are each independently hydrogen, an alkyl group, a substituted aryl group, a substituted decyl group, a substituted nitrogen-containing hetero ring, or at least one of cyano groups, R ¹³ ~ R ^{16 is} independently an optionally substituted alkyl group or a substituted aryl group, X is a substituted aryl group, and Y is an aryl group which may be substituted with a carbon number of 16 or less and substituted. The boron group or the carbazole which may also be substituted, and n is independently an integer of 0 to 3.

Among the compounds represented by the above formula (E-4), preferred are compounds represented by the following formula (E-4-1), more preferably the following formula (E-4-1-1). )~ A compound represented by the formula (E-4-1-4). Specific examples include 9-[4-(4-bis(2,4,6-trimethylphenyl)borylnaphthalen-1-yl)phenyl]carbazole, 9-[4-(4-di(2) , 4,6-Trimethylphenyl)borylnaphthalen-1-yl)naphthalen-1-yl]carbazole and the like.

Wherein R ¹¹ and R ¹² are each independently hydrogen, an alkyl group, a substituted aryl group, a substituted decyl group, a substituted nitrogen-containing hetero ring, or at least one of cyano groups, R ¹³ ~ R ^{16 is} independently an optionally substituted alkyl group or a substituted aryl group, and R ²¹ and R ²² are each independently hydrogen, an alkyl group, a substituted aryl group, a substituted decyl group, or And at least one of the substituted nitrogen-containing heterocyclic ring or the cyano group, X ¹ is an extended aryl group having a carbon number of 20 or less, and n is independently an integer of 0 to 3, and m is independently 0 to 0. An integer of 4.

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

Among the compounds represented by the above formula (E-4), preferred are compounds represented by the following formula (E-4-2), more preferably the following formula (E-4-2-1) ) the compound represented.

[116]

Wherein R ¹¹ and R ¹² are each independently hydrogen, an alkyl group, a substituted aryl group, a substituted decyl group, a substituted nitrogen-containing hetero ring, or at least one of cyano groups, R ¹³ ~ R ^{16 is} independently an alkyl group which may be substituted or an aryl group which may be substituted, and X ¹ is an optionally substituted aryl group having a carbon number of 20 or less, and n is independently an integer of 0 to 3 .

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

Among the compounds represented by the above formula (E-4), preferred are compounds represented by the following formula (E-4-3), more preferably the following formula (E-4-3-1) Or a compound represented by the formula (E-4-3-2).

In the formula, R ¹¹ and R ¹² are each independently hydrogen, an alkyl group, a substituted aryl group, a substituted decyl group, a substituted nitrogen-containing hetero ring, or at least one of cyano groups, R ¹³ ～ R ^{16 is} independently an alkyl group which may be substituted or an aryl group which may be substituted, and X ¹ is an optionally substituted aryl group having a carbon number of 10 or less, and Y ¹ is a carbon number which may be substituted It is an aryl group of 14 or less, and n is independently an integer of 0-3.

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

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

In the formula, each of Ar ¹ to Ar ^{3 is} independently hydrogen or an aryl group having 6 to 30 carbon atoms which may be substituted. Particularly preferred is a benzimidazole derivative in which Ar ¹ is a thiol group which may also be substituted.

Specific examples of the aryl group having 6 to 30 carbon atoms are: phenyl, 1-naphthyl, 2-naphthyl, indol-1-yl, indol-3-yl, indol-4-yl, indol-5-yl. , indol-1-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-9-yl, indol-1-yl, indol-2-yl, 1-phenanthryl, 2- Phenylidene, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-indolyl, 2-indolyl, 9-fluorenyl, fluoren-1-yl, fluoran-2-yl, fluorene- 3-yl, fluorescein-7-yl, fluoren-8-yl, tert-triphenyl-1-yl, tert-triphenyl-2-yl, indol-1-yl, ind-2-yl, indole-4- 1,1,2-benzophenan-1-yl, 1,2-benzophenan-2-yl, 1,2-benzophenan-3-yl, 1,2-benzophen-4-yl, 1,2-benzophenan-5-yl, 1,2-benzophenan-6-yl, fused tetraphenyl-1-yl, fused tetraphenyl-2-yl, fused tetraphenyl-5-yl, hydrazine- 1-yl, indol-2-yl, indol-3-yl, fused pentaphenyl-1-yl, fused pentaphenyl-2-yl, fused pentaphenyl-5-yl, fused pentaphenyl-6-yl.

Specific examples of benzimidazole derivatives are: 1-phenyl-2-(4-(10-phenylfluoren-9-yl)phenyl)-1H-benzo[d]imidazole, 2-(4-( 10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 2-(3-(10-(naphthalen-2-yl)anthracene- 9-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 5-(10-(naphthalen-2-yl)indol-9-yl)-1,2-diphenyl-1H -Benzo[d]imidazole, 1-(4-(10-(naphthalen-2-yl)indol-9-yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 2-( 4-(9,10-bis(naphthalen-2-yl)indol-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 1-(4-(9,10-di) (naphthalen-2-yl)indol-2-yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 5-(9,10-di(naphthalen-2-yl)indole-2- -1,2-diphenyl-1H-benzo[d]imidazole.

Further, a substance capable of reducing a material forming the electron transport layer or the electron injection layer may be further contained in the electron transport layer or the electron injection layer. When the reducing substance has a certain degree of reductive property, various substances can be used. For example, at least one selected from the group consisting of alkali metal, alkaline earth metal, rare earth metal, and alkali metal can be suitably used. , alkali metal halide, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal oxide, rare earth metal halide, alkali metal organic complex, alkaline earth metal organic complex, and rare earth An organic complex of metals.

Preferred reducing substances include alkali metals such as Na (work function is 2.36 eV), K (work function is 2.28 eV), Rb (work function is 2.16 eV), or Cs (work function is 1.95 eV), or Ca ( An alkaline earth metal such as a work function of 2.9 eV), Sr (work function of 2.0 eV to 2.5 eV) or Ba (work function of 2.52 eV), particularly preferably a material having a work function of 2.9 eV or less. Among these, a more preferable reducing substance is an alkali metal of K, Rb or Cs, still more preferably Rb or Cs, and most preferably Cs. In particular, the alkali metal has a high reducing ability and is added to a material forming the electron transport layer or the electron injecting layer in a small amount, whereby the luminance of the organic EL element can be improved or the life can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of two or more kinds of alkali metals is also preferable, and particularly preferably a combination of Cs, such as Cs and Na, Cs and K, Cs and Rb, Or Cs combined with Na and K. By including Cs, the reducing ability can be efficiently exhibited, and by adding to the material forming the electron transport layer or the electron injecting layer, the luminance of the organic EL element can be improved or the life can be extended.

<Cathode of Organic Electroluminescence Element>

The cathode 108 functions to inject electrons into the light-emitting layer 105 via the electron injection layer 107 and the electron transport layer 106.

The material forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, and the same material as the material forming the anode 102 can be used. Preferred among these are metals such as tin, magnesium, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, rubidium, and magnesium, or alloys thereof. (magnesium-silver alloy, magnesium-indium alloy, aluminum-lithium alloy such as lithium fluoride/aluminum, etc.). In order to improve the electron injection efficiency and improve the element characteristics, lithium, sodium, potassium, barium, calcium, magnesium, or an alloy containing the low work function metals is effective. However, these low work function metals are often unstable in the atmosphere in most cases. In order to improve this aspect, for example, a method of using a highly stable electrode by doping a trace amount of lithium, lanthanum or magnesium in an organic layer is known. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cerium oxide can also be used. However, it is not limited to these substances.

Further, a preferred method is as follows: a metal such as platinum, gold, silver, copper, iron, tin, aluminum, or indium is deposited for protecting the electrode, or an alloy containing the metal, and ruthenium dioxide, An inorganic substance such as titanium dioxide or cerium nitride, polyvinyl alcohol, polyvinyl chloride or a hydrocarbon-based polymer compound. The electrodes may be produced by resistance heating, electron beam, sputtering, ion plating, coating, etc., and there is no particular limitation if conduction is obtained.

<Binders that can also be used in each layer>

The materials used in the above hole injection layer, hole transport layer, light-emitting layer, electron transport layer, and electron injecting layer may be separately formed into layers, or may be dispersed in the following polymer binder: polychlorinated Ethylene, polycarbonate, polystyrene, poly(N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polyfluorene, polyphenylene ether, polybutadiene, hydrocarbon Solvent-soluble resin such as resin, ketone resin, phenoxy resin, polyamine, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin or phenol resin, xylene resin, petroleum resin, urea A curable resin such as a resin, a melamine resin, an unsaturated polyester resin, an alkyd resin, an epoxy resin, or a silicone resin.

<Method for Producing Organic Electroluminescence Element>

The layers constituting the organic electroluminescent device can be formed by a vapor deposition method, a resistance heating vapor deposition method, an electron beam evaporation method, a sputtering method, a molecular layering method, a printing method, a spin coating method, a casting method, or a coating method. The material constituting each layer is formed into a film. The film thickness of each layer formed in this manner is not particularly limited, and may be appropriately set depending on the nature of the material, and is usually in the range of 2 nm to 5000 nm. The film thickness can be usually measured by a quartz oscillation type film thickness measuring device or the like. In the case of thin film formation by a vapor deposition method, the vapor deposition conditions vary depending on the kind of the material, the target crystal structure of the film, and the association structure. Preferably, the evaporation condition is usually at a boat heating temperature of 50 ° C to 400 ° C, a vacuum of 10 ^-6 Pa to 10 ^-3 Pa, a vapor deposition rate of 0.01 nm / sec to 50 nm / sec, and a substrate temperature of -150 ° C. It is suitably set within a range of +300 ° C and a film thickness of 2 nm to 5 μm.

Next, as an example of a method of producing an organic electroluminescence device, a method of fabricating an organic electroluminescence device having the following structure will be described: an anode/hole injection layer/hole transport layer/by a host material and a dopant material A light-emitting layer/electron transport layer/electron injection layer/cathode. After forming an anode on a suitable substrate by forming a thin film of an anode material by a vapor deposition method or the like, a film of a hole injection layer and a hole transport layer is formed on the anode. Forming a thin film on the co-evaporation host material and the doping material to form an emission layer, forming an electron transport layer and an electron injection layer on the light-emitting layer, and forming a thin film made of a cathode material by a vapor deposition method or the like. A cathode is formed, whereby a target organic electroluminescent element is obtained. Further, in the production of the above-described organic electroluminescent device, the order of fabrication may be reversed, and the cathode, the electron injecting layer, the electron transporting layer, the light emitting layer, the hole transporting layer, the hole injecting layer, and the anode may be sequentially formed.

When a DC voltage is applied to the organic electroluminescence device thus obtained, the anode may be set to a polarity of + and the cathode may be set to a polarity of -, and the applied voltage may be about 2 V to 40 V. Luminescence was observed from the transparent or translucent electrode side (anode or cathode, and two poles). Further, the organic electroluminescence element can emit light even when a pulse current or an alternating current is applied. In addition, the waveform of the applied alternating current may be an arbitrary waveform.

<Application Example of Organic Electroluminescence Element>

Moreover, the present invention can also be applied to a display device having an organic electroluminescence element or an illumination device having an organic electroluminescence element or the like.

A display device or an illumination device having an organic electroluminescence device can be manufactured by a known method such as connecting an organic electroluminescence device of the present embodiment to a known driving device, and DC driving, pulse driving, and alternating current can be suitably used. Driving is performed by a known driving method such as driving.

For example, a panel display such as a color flat panel display, a flexible display such as a flexible color organic electroluminescence (EL) display, or the like can be used (for example, see Japanese Patent Laid-Open No. Hei 10-335066, Japanese Patent Laid-Open No. 2003-321546 Japanese Patent Laid-Open Publication No. 2004-281086, etc.). Further, examples of the display mode of the display include a matrix and/or a segment method. In addition, the matrix display and the segment display can coexist in the same panel.

The matrix means that the pixels to be displayed are two-dimensionally arranged in a lattice shape or a mosaic shape, and characters or images are displayed by a collection of pixels. The shape or size of the pixels is determined by the purpose. For example, in a video display and a character display of a personal computer, a monitor, a television, a quadrilateral pixel having a side of 300 μm or less is usually used, and in the case of a large display such as a display panel, a pixel of one millimeter is used. In the case of monochrome display, the pixels of the same color can be arranged; in the case of color display, the pixels of red, green and blue are arranged and displayed. In this case, a typical delta type and a stripe type are typical. Moreover, the driving method of the matrix may be any of a line sequential driving method or an active matrix. The line sequence drive has the advantage of a simple structure, but when the action characteristics are considered, there is a case where the active matrix is excellent, and therefore it must be flexibly used according to the use.

In the segment type (type), a pattern is formed so as to display predetermined information, and the determined region is illuminated. For example, a digital clock or a thermometer, a temperature display, an operation state display of an audio device or an induction cooker, and a panel display of a car can be cited.

For example, Japanese Patent Laid-Open No. 2003-257621, Japanese Patent Laid-Open No. 2003-277741, and Japanese Patent Laid-Open No. 2004-119211 Wait). The backlight is mainly used for improving the visibility of a display device that does not emit light by itself, and is used in a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, and a logo. In particular, in consideration of the following aspects, the backlight using the light-emitting element of the present embodiment is characterized by being thin and lightweight: as a liquid crystal display device, and particularly a backlight for personal computer applications in which thinness is a problem The device of the prior art is constituted by a fluorescent lamp or a light guide plate and is difficult to be thinned.

[Example]

<Synthesis Example of Compound represented by Formula (1-10)>

First, a solution of 2-(4-bromophenyl)pyridine (15 g) and boranoic acid pinacol ester (19.5 g) was added to cyclopentyl methyl ether (CPME) (64 ml) under nitrogen. Palladium acetate (Pd(OAc) ₂ ) (0.4 g), triphenylphosphine (PPh ₃ ) (1.5 g), and potassium acetate (AcOK) (18.9 g) were added while stirring at room temperature. After stirring at reflux temperature for 2 hours, the reaction liquid was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) (35 ml) and toluene (500 ml) were added. The organic matter from which the salt was removed by a water washing operation was purified by activated carbon column chromatography (toluene). Thus, 2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridine (11.2 g) was obtained.

Next, 2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridine (6.9 g) obtained as above was obtained. , bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diyl ester (6.6 g) in THF/isopropanol (IPA) solution (volume ratio 3 :1) (37 ml) Palladium acetate (0.1 g), triphenylphosphine (0.3 g) and potassium phosphate (K ₃ PO ₄ ) (9.4 g) were added while stirring under a nitrogen atmosphere at room temperature. After stirring at reflux temperature for 5 hours, the reaction liquid was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) (50 ml) and toluene (500 ml) were added. The organic substance which removed the salt by a water washing operation was purified by activated carbon column chromatography (toluene/ethyl acetate = 10/1 (volume ratio)) to obtain a compound represented by the formula (1-10): 7 -Phenyl-5,9-bis(4-(pyridin-2-yl)phenyl)-7H-benzo[c]carbazole (1.2 g).

[化121]

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): δ=8.97 (d, 1H), 8.74 (m, 3H), 8.11 (m, 5H), 7.76 (m, 9H), 7.54 (m, 6H), 7.47 (m, 2H), 7.45 (m, 1H), 7.35-7.23 (m, 2H).

<Synthesis Example of Compound represented by Formula (1-4)>

First, bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diester (5.9 g) was added to cyclopentyl methyl ether (50 ml). And a solution of boranoic acid pinacol ester (6.1 g), adding (1,1'-bis(diphenylphosphino)ferrocene) dichloropalladium (II) while stirring at room temperature under nitrogen atmosphere ) (0.41 g) and potassium acetate (5.9 g). Thereafter, the mixture was stirred at reflux temperature for 4 hours, and then the reaction liquid was cooled to room temperature, and water and ethyl acetate were added to carry out a water washing operation. Next, methanol was added, and the mixture was heated and refluxed to carry out washing. Thus, 7-phenyl-7H-benzo[c]carbazole-5,9-diborate (5.3 g) was obtained.

Next, 7-phenyl-7H-benzo[c]carbazole-5,9-diboron obtained as above was added to pseudocumene (1,2,4-trimethylbenzene) (50 ml). Add bis(dibenzylideneacetone)palladium (0) to a solution of the acid ester (5.3 g) and 5-bromo-2,2'-bipyridine (5.6 g) under a nitrogen atmosphere at room temperature with stirring. (Pd(dba) ₂ ) (0.6 g), tricyclohexylphosphine (PCy ₃ ) (0.6 g) and potassium phosphate (K ₃ PO ₄ ) (9.4 g). Thereafter, the mixture was stirred at 150 ° C for 5 hours, and then the reaction liquid was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added thereto, followed by a water washing operation. The organic matter which removed the salt by a water washing operation was treated by a short-tank column (ethyl acetate), followed by activated alumina column chromatography (toluene/ethyl acetate = 9/1 (volume ratio)) Purification was carried out. Further, heptane is added to the toluene solution to carry out reprecipitation to obtain a compound represented by the formula (1-4): 5,9-di([2,2'-bipyridyl]-5-yl)-7-benzene Base-7H-benzo[c]carbazole (2.5 g).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): 6 = 9.02 (m, 1H), 8.88 (d, 1H), 8.86 (m, 1H), 8.80 (d, 1H), 8.75 (m, 2H), 8.55 (d, 1H), 8.45-8.53 (m, 3H), 8.13 (dd, 1H), 8.00-8.08 (m, 2H), 7.75-7.89 (m, 5H), 7.67 (m, 4H), 7.56 (m) , 2H), 7.51 (t, 1H), 7.30-7.37 (m, 2H).

<Synthesis Example of Compound represented by Formula (1-744)>

Addition of 7-phenyl-7H-benzo[c]carbazole-5,9-diborate (4.9 g) to pseudocumene (1,2,4-trimethylbenzene) (50 ml) And a solution of 4-(3-bromophenyl)pyridine (4.6 g), a triphenylphosphine palladium catalyst (Pd(PPh ₃ ) ₄ ) (0.5 g) was added while stirring at room temperature under a nitrogen atmosphere. And potassium phosphate (K ₃ PO ₄ ) (12 g). Thereafter, the mixture was stirred at 160 ° C for 12 hours, and then the reaction liquid was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added thereto to carry out a water washing operation. The organic matter from which the salt was removed by a water washing operation was purified by activated alumina column chromatography (toluene/ethyl acetate = 4/6 (volume ratio)). Further, it is recrystallized from toluene to obtain a compound represented by the formula (1-744): 7-phenyl-5,9-bis(3-(pyridin-4-yl)phenyl)7H-benzo[c] Carbazole (3.5 g).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): δ=8.89 (d, 1H), 8.77 (d, 1H), 8.69 (m, 4H), 8.1 (d, 1H), 7.92 (m, 1H), 7.80 (m, 2H), 7.69-7.77 (m, 4H), 7.50-7.67 (m, 14H), 7.47 (t, 1H).

<Synthesis Example of Compound represented by Formula (1-5)>

Add 7-phenyl-7H-benzo[c]carbazole-5,9-diborate (5.0 g) to pseudocumene (1,2,4-trimethylbenzene) (50 ml) In a solution of 5-bromo-2,3'-bipyridyl (5.0 g), Pd(PPh ₃ ) ₄ (0.5 g) and potassium phosphate (12 g) were added while stirring at room temperature under a nitrogen atmosphere. Thereafter, after stirring at 150 ° C for 20 hours, the reaction liquid was cooled to room temperature, an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added, and the solid in the liquid was collected by suction filtration. Next, purification was carried out by activated alumina column chromatography (developing solution: toluene/ethyl acetate mixed solvent). In this case, refer to the "Organic Chemistry Experiment Guide (1) - Substance Operation Method and Separation and Purification Method -", published by Chemical Society, and the method described on page 94, so that the ratio of ethyl acetate in the developing solution is gradually increased. The target is dissolved. Further, it is recrystallized from chlorobenzene to obtain a compound represented by the formula (1-5): 5,9-bis([2,3'-bipyridyl]-5-yl)-7-phenyl-7H-benzene And [c]carbazole (1.9 g).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): 6 = 9.26 (m, 2H), 9.07 (m, 1H), 8.99 (d, 1H), 8.91 (m, 1H), 8.80 (d, 1H), 8.69 (m, 2H), 8.40 (m, 2H), 8.10 (dd, 1H), 8.03 (d, 1H), 7.99 (dd, 1H), 7.91 (d, 1H), 7.84 (m, 2H), 7.76 ( m, 2H), 7.66 (m, 4H), 7.50-7.60 (m, 3H), 7, 45 (m, 2H).

<Synthesis Example of Compound represented by Formula (1-20)>

Addition of 7-phenyl-7H-benzo[c]carbazole-5,9-diborate (5.1 g) to pseudocumene (1,2,4-trimethylbenzene) (50 ml) In a solution of 6-bromo-2,3'-bipyridine (4.6 g), Pd(PPh ₃ ) ₄ (0.5 g) and potassium phosphate (12 g) were added while stirring under a nitrogen atmosphere at room temperature. Thereafter, after stirring at 120 ° C for 5 hours, the reaction liquid was cooled to room temperature, methanol was added, and the solid in the liquid was collected by suction filtration. The solid was washed with an aqueous solution of ethylenediaminetetraacetic acid (EDTA), washed with water, and further washed with methanol. Further, it is recrystallized from chlorobenzene to obtain a compound represented by the formula (1-20): 5,9-bis([2,3'-bipyridyl]-6-yl)-7-phenyl-7H-benzene And [c]carbazole (4.5 g).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): δ=9.34 (m, 1H), 9.29 (m, 1H), 9.00 (d, 1H), 8.80 (d, 1H), 8.66 (m, 2H), 8.40 -8.48 (m, 2H), 8.26 (m, 3H), 7.93 (t, 1H), 7.79-7.89 (m, 4H), 7.75 (s, 1H), 7.65-7.72 (m, 5H), 7.61 (d) , 1H), 7.49-7.58 (m, 2H), 7, 37-7.45 (m, 2H)

<Synthesis Example of Compound represented by Formula (1-24)>

Add 7-phenyl-7H-benzo[c]carbazole-5,9-diborate (5.0 g) to pseudocumene (1,2,4-trimethylbenzene) (50 ml) In a solution of 5-bromo-3,4'-bipyridyl (5.0 g), Pd(PPh ₃ ) ₄ (1.2 g) and potassium phosphate (11.7 g) were added while stirring at room temperature under a nitrogen atmosphere. Thereafter, the mixture was stirred at reflux temperature for 16 hours, and then the reaction liquid was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and toluene were added thereto to carry out liquid separation. After distilling off the solvent under reduced pressure, purification was carried out by silica gel column chromatography (developing solvent: toluene/ethyl acetate mixed solvent) to obtain a compound represented by formula (1-24): 5,9-di ([3 , 4'-bipyridyl]-5-yl)-7-phenyl-7H-benzo[c]carbazole (1.0 g). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target.

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): δ=8.99 (m, 3H), 8.86 (m, 2H), 8.82 (d, 1H), 8.75 (m, 4H), 8.16 (m, 1H), 8.09 (m, 1H), 7.95 (d, 1H), 7.85 (t, 1H), 7.75 (dd, 1H), 7.63-7.72 (m, 5H), 7.51-7.60 (m, 7H).

<Synthesis Example of Compound represented by Formula (1-634)>

Stage 1: Implanted with (4-methoxynaphthalen-1-yl)boronic acid (43.1 g), 1,4-dibromo-2-nitrobenzene (25.0 g), potassium phosphate (182 g), A flask of Pd(PPh ₃ ) ₄ (2.5 g), pseudocumene (1,2,4-trimethylbenzene) (1000 ml), third butanol (200 ml) and water (40 ml) in a nitrogen atmosphere Stir at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, and water and toluene were added for liquid separation, and the solvent was evaporated under reduced pressure to give 4,4'-(2-nitro-1,4-phenylene)bis(1-methoxy group. Naphthalene) (32.5 g). This crude product was used directly in the next step without purification.

Stage 2: 4,4'-(2-nitro-1,4-phenylene)bis(1-methoxynaphthalene) (27.7 g) and triethyl phosphite (64 ml) The flask was stirred at 145 ° C for 1 hour. The reaction solution was cooled to room temperature, methanol was added, and the precipitated solid was collected by suction filtration. The solid was further washed with methanol to give 5-methoxy-9-(4-methoxynaphthalen-1-yl)-7H-benzo[c]carbazole (25.0 g).

Stage 3: 5-methoxy-9-(4-methoxynaphthalen-1-yl)-7H-benzo[c]carbazole (25.0 g), bromobenzene (11.7 g), Bis(dibenzylideneacetone)palladium(0)(1.8 g), [1,1'-biphenyl]-2-yldi-tert-butylphosphine (2.2 g), potassium carbonate (25.7 g) and A flask of cumene (1,2,4-trimethylbenzene) (250 ml) was stirred at 155 ° C for 4 hours. The reaction solution was cooled to room temperature, and water and toluene were added to conduct liquid separation, and the solvent was evaporated under reduced pressure. The obtained solid was further washed with methanol to give 5-methoxy-9-(4-methoxynaphthalen-1-yl)-7-phenyl-7H-benzo[c]carbazole (23.0 g).

Stage 4: 5-methoxy-9-(4-methoxynaphthalen-1-yl)-7-phenyl-7H-benzo[c]carbazole (23.0 g) and pyridinium salt The flask of the acid salt (143 g) was stirred at 200 ° C for 1 hour. The reaction solution was cooled to room temperature, and after adding water and stirring, an insoluble solid was collected by suction filtration. The solid was further washed with water to give 9-(4-hydroxynaphthalen-1-yl)-7-phenyl-7H-benzo[c]oxazol-5-ol (22.0 g).

Stage 5: loaded with 9-(4-hydroxynaphthalen-1-yl)-7-phenyl-7H-benzo[c]indazol-5-ol (22.0 g) and pyridine (250 ml) The flask was cooled in an ice bath, and trifluoromethanesulfonic acid anhydride (50.2 g) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour to complete the reaction. Thereafter, toluene and water were added to carry out liquid separation, and the organic layer was washed with 1 N hydrochloric acid, and then washed with sodium hydrogencarbonate. The solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (heptane / toluene = 9 / 1 (volume ratio)). 4-(7-phenyl-5-(((trifluoromethyl)sulfonyl)oxy)-7H-benzo[c]indazol-9-yl)naphthalen-1-yl methanesulfonate ( 23.1 g).

[化127]

Under the nitrogen atmosphere, 4-(7-phenyl-5-(((trifluoromethyl))sulfonyl)oxy)-7H-benzo[c] trifluoromethanesulfonate obtained above was charged. Carbazole-9-yl)naphthalen-1-yl ester (11.5 g), 4-pyridine boronic acid (4.9 g) potassium phosphate (13.7 g), Pd(PPh ₃ ) ₄ (2.8 g), pseudocumene (1, A flask of 2,4-trimethylbenzene (100 ml), tert-butanol (10 ml) and water (10 ml) was stirred at reflux temperature for 4 hours. The reaction solution was cooled to room temperature, and toluene and water were added for liquid separation. The solid obtained by distilling off the solvent under reduced pressure was washed with methanol, followed by heating and dissolving in chlorobenzene, and then filtered while hot. The solvent was distilled off in an appropriate amount under reduced pressure, and then re-precipitated by adding methanol. The obtained solid is recrystallized from nitrobenzene to obtain a compound represented by the formula (1-634): 7-phenyl-5-(pyridin-4-yl)-9-(4-(pyridin-4-yl) Naphthyl-1-yl)-7H-benzo[c]carbazole (2.9 g).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): 6 = 9.03 (d, 1H), 8.80 (d, 1H), 8.76 (m, 4H), 8.10 (m, 1H), 8.00 (d, 1H), 7.92 (m, 1H), 7.82 (t, 1H), 7.60-7.68 (m, 7H), 7.47-7.54 (m, 10H).

<Synthesis Example of Compound represented by Formula (1-743)>

First, 3-(3-bromophenyl)pyridine (6.0 g), pinacol borate (7.8 g), (1,1'-bis(diphenylphosphino)ferrocene) will be charged. A flask of dichloropalladium (II) (0.6 g), potassium acetate (AcOK) (7.6 g) and cyclopentyl methyl ether (CPME) (52 ml) was stirred at reflux temperature for 3 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and toluene were added and washed with water. The solid obtained by distilling off the solvent under reduced pressure by activated carbon column chromatography (toluene) was purified to afford 3-(3-(4,4,5,5-tetramethyl-1,3,2- Dioxaborolan-2-yl)phenyl)pyridine (6.0 g).

Next, 3-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridine (4.1) obtained as above was charged. g), bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diester (3.8 g), potassium phosphate (2.7 g), Pd (PPh ₃ ) A flask of ₄ (0.2 g), pseudocumene (1,2,4-trimethylbenzene) (13 ml), isopropanol (2.6 ml) and water (0.5 ml) was stirred under a nitrogen atmosphere at reflux temperature. 6 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and toluene were added for liquid separation. The solid obtained by distilling off the solvent under reduced pressure was purified by alumina column chromatography (eluent: toluene/ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target. Thereafter, it is recrystallized from chlorobenzene to obtain a compound represented by the formula (1-743): 7-phenyl-5,9-bis(3-(pyridin-3-yl)phenyl)-7H-benzo. [c]carbazole (0.7 g).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): δ=8.98 (d, 1H), 8.92 (d, 2H), 8.76 (d, 1H), 8.62 (m, 2H), 8.05 (d, 1H), 7.93 (m, 2H), 7.87 (m, 1H), 7.45-7.81 (m, 17H), 7.38 (t, 2H).

<Synthesis Example of Compound represented by Formula (1-8710)>

Stage 1: Under a nitrogen atmosphere, 58.6-dimethoxy-7H-benzo[c]carbazole 38.6 g, 1-fluoronaphthalene (38.8 g), cesium carbonate (90.6 g) and A flask of dimethyl hydrazine (DMSO) (460 ml) was stirred with heating at 145 ° C for 4 hours. After cooling the reaction liquid to room temperature, the salt was removed by suction filtration, and DMSO was evaporated under reduced pressure. After the obtained solid was washed with methanol, it was purified by silica gel column chromatography (eluent: heptane / toluene = 1 / 1 (volume ratio)) to obtain 5,9-dimethoxy-7- (naphthalen-1-yl)-7H-benzo[c]carbazole (32.5 g).

Stage 2: Under a nitrogen atmosphere, 5,9-dimethoxy-7-(naphthalen-1-yl)-7H-benzo[c]carbazole (42.5 g), pyridine hydrochloride A flask of (121 g) and N-methylpyrrolidone (NMP) (43 ml) was heated and stirred at 200 ° C for one and a half hours. The reaction solution was cooled to room temperature, and water and ethyl acetate were added to conduct liquid separation. After distilling off the solvent under reduced pressure, purification was carried out by using a short-tane column to obtain 7-(naphthalen-1-yl)-7H-benzo[c]carbazole-5,9-diol (45 g).

Stage 3: Under a nitrogen atmosphere, 7-(naphthalen-1-yl)-7H-benzo[c]oxazole-5,9-diol (45 g) and pyridine (130 ml) were charged. The flask was cooled in an ice bath and trifluoromethanesulfonic acid anhydride (71.1 g) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 16 hours to complete the reaction, water was added, and the solid in the liquid was collected by suction filtration. After the obtained solid was washed with methanol, it was purified by silica gel column chromatography (developing liquid: toluene) to obtain bis(trifluoromethanesulfonic acid) 7-(naphthalen-1-yl)-7H-benzene. [c] carbazole-5,9-diester (63.2 g).

[化130]

Under the nitrogen atmosphere, the 2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl group obtained above was charged. Pyridine (8.4 g), bis(trifluoromethanesulfonic acid) 7-(naphthalen-1-yl)-7H-benzo[c]indazol-5,9-diyl ester (6.4 g), potassium phosphate (8.5 a flask of g), Pd(PPh ₃ ) ₄ (1.1 g), pseudocumene (1,2,4-trimethylbenzene) (75 ml), third butanol (5 ml) and water (1 ml) Stir at reflux temperature for 10 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and toluene were added for liquid separation. The solid obtained by distilling off the solvent under reduced pressure was dissolved in chlorobenzene by heating and filtered while hot. The solid obtained by distilling off the solvent under reduced pressure was recrystallized from chlorobenzene to obtain a compound represented by formula (1-8 710): 7-(naphthalen-1-yl)-5,9-bis(4-(pyridine- 2-yl)phenyl)-7H-benzo[c]carbazole (1.8 g).

[化131]

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500MHz, CDCl} 3): δ = 9.02 (d, 1H), 8.80 (d, 1H), 8.70 (m, 2H), 8.09 (m, 2H), 8.03 (m, 5H), 7.69- 7.83 (m, 10H), 7.55 (m, 3H), 7.48 (t, 1H), 7.39 (m, 1H), 7.30-7.38 (m, 2H), 7.23 (m, 2H), 7.18 (s, 1H) .

<Synthesis Example of Compound represented by Formula (1-8711)>

First, it will be charged with bis(trifluoromethanesulfonic acid) 7-(naphthalen-1-yl)-7H-benzo[c]carbazole-5,9-diester (6.4g), borboric acid Alcohol ester (6.1 g), (1,1'-bis(diphenylphosphino)ferrocene) dichloropalladium (II) (0.32 g), potassium acetate (5.9 g) and cyclopentyl methyl ether ( The flask of CPME) (50 ml) was stirred under a nitrogen atmosphere at reflux temperature for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added, and the mixture was washed with water, and then methanol was added thereto, and the mixture was heated and refluxed and washed. Thus, 7-(naphthalen-1-yl)-7H-benzo[c]carbazole-5,9-diborate (5.7 g) was obtained.

Next, 7-(naphthalen-1-yl)-7H-benzo[c]carbazole-5,9-diborate (5.2 g) and 3-(4-bromobenzene) obtained as above were charged. Pyridine (4.9 g), potassium phosphate (9.2 g), Pd(PPh ₃ ) ₄ (0.50 g), 1,2,4-trimethylbenzene (pseudocumene) (35 ml), third butanol ( A flask of 7 ml) and water (1.4 ml) was stirred under a nitrogen atmosphere at reflux temperature for 4 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added thereto, followed by suction filtration to obtain a solid. Next, after washing with methanol, chlorobenzene was added and heated, and the excess components were filtered off by suction filtration. Thereafter, the solvent was distilled off under reduced pressure, and recrystallized from chlorobenzene to obtain a compound represented by formula (1-8711): 7-(naphthalen-1-yl)-5,9-bis(4-(pyridine-3) -yl)phenyl)-7H-benzo[c]carbazole (4.4 g).

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500MHz, CDCl} 3): δ = 9.03 (d, 1H), 8.87 (m, 2H), 8.81 (d, 1H), 8.09 (t, 2H), 8.03 (d, 1H), 7.67- 7.93 (m, 9H), 7.46-7.65 (m, 9H), 7.27-7.39 (m, 5H), 7.17 (s, 1H).

<Synthesis Example of Compound represented by Formula (1-8712)>

Will be charged with 7-(naphthalen-1-yl)-7H-benzo[c]carbazole-5,9-diborate (4.8 g), 4-(4-bromophenyl)pyridine (4.5 g) ), potassium phosphate (8.5g), Pd(PPh ₃ ) ₄ (0.46g), 1,2,4-trimethylbenzene (pseudocumene) (30ml), third butanol (6ml) and water (1.2 The flask of ml) was stirred under a nitrogen atmosphere at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added thereto, followed by suction filtration to obtain a solid. After washing with methanol, chlorobenzene was added for heating, and the excess components were filtered off by suction filtration. Thereafter, the solvent was distilled off under reduced pressure, and recrystallized from chlorobenzene to obtain a compound represented by formula (1-8712): 7-(naphthalen-1-yl)-5,9-bis(4-(pyridine-4) -yl)phenyl)-7H-benzo[c]carbazole (3.5 g).

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500MHz, CDCl} 3): δ = 9.03 (d, 1H), 8.81 (d, 1H), 8.66 (m, 4H), 8.11 (d, 1H), 8.05 (t, 2H), 7.83 ( t,1H), 7.65-7.80 (m, 9H), 7.49-7.59 (m, 8H), 7.36 (m, 2H), 7.29 (m, 1H), 7.16 (s, 1H).

<Synthesis Example of Compound represented by Formula (1-1)>

Will be charged with bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diyl ester (7.3 g), 2-pyridyl zinc bromide 0.5 M-THF The flask of the solution (50 ml) and Pd(PPh ₃ ) ₄ (0.96 g) was stirred under a nitrogen atmosphere at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added to conduct liquid separation. The organic layer was washed with saturated brine and the solvent was evaporated evaporated. Next, it is purified by silica gel chromatography (developing solution: ethyl acetate/toluene = 1/20 (volume ratio)), and further recrystallized from toluene to obtain a compound represented by the formula (1-1): 7- Phenyl-5,9-bis(pyridin-2-yl)-7H-benzo[c]carbazole (1.2 g).

[化134]

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): δ = 8.97 (d, 1H), 8.79 (m, 1H), 8.76 (d, 1H), 8.70 (m, 1H), 8.15 (m, 2H), 8.08 ( Dd,1H), 7.73-7.84 (m, 4H), 7.58-7.68 (m, 6H), 7.46-7.55 (m, 2H), 7.33 (m, 1H), 7.21 (m, 1H).

<Synthesis Example of Compound represented by Formula (1-2)>

Will be charged with bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diester (5.9 g), 3-pyridineboronic acid (2.5 g), sodium carbonate A flask of (4.0 g), Pd(PPh ₃ ) ₄ (0.5 g), toluene (40 ml), ethanol (12 ml) and water (12 ml) was stirred under a nitrogen atmosphere at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, and brine was added with saturated brine and ethyl acetate. The solid obtained by distilling off the solvent under reduced pressure was purified by silica gel chromatography (developing solvent: toluene/ethyl acetate = 1/1 (volume ratio)), followed by recrystallization from heptane, and further from ethanol. Crystallization gave the compound represented by the formula (1-2): 7-phenyl-5,9-bis(pyridin-3-yl)-7H-benzo[c]carbazole (2.1 g).

[化135]

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500MHz, CDCl} 3): δ = 9.06 (m, 2H), 8.77 (m, 2H), 8.69 (m, 1H), 8.59 (m, 1H), 7.97 (m, 1H), 7.93 ( d,1H), 7.86 (m, 1H), 7.81 (t, 1H), 7.61-7.71 (m, 6H), 7.56 (t, 1H), 7.49 (m, 2H), 7.43 (m, 1H), 7.38 (m, 1H).

<Synthesis Example of Compound represented by Formula (1-541)>

First, bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diyl ester (14.7 g), 2-pyridyl zinc bromide 0.5 M will be charged. A flask of THF solution (50 ml), Pd (PPh ₃ ) ₄ (0.87 g), and THF (50 ml) was stirred under a nitrogen atmosphere at reflux temperature for 3 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added to conduct liquid separation. Further, the organic layer was washed with saturated brine, and the solvent was evaporated evaporated. Subsequently, it was purified by silica gel chromatography (developing solution: ethyl acetate/toluene = 1/100 (volume ratio)), and further recrystallized from ethanol to obtain 7-phenyl-9-(pyridine) trifluoromethanesulfonate. 2-yl)-7H-benzo[c]indazol-5-yl ester (5.1 g).

Next, 7-phenyl-9-(pyridin-2-yl)-7H-benzo[c]oxazol-5-yl trifluoromethanesulfonate (2.8 g) obtained as above was charged. 4-(pyridin-2-yl)phenyl)boronic acid (1.3 g), sodium carbonate (1.2 g), Pd(PPh ₃ ) ₄ (0.31 g), toluene (12 ml), ethanol (4 ml) and water (4 ml) The flask was stirred under a nitrogen atmosphere at reflux temperature for 1.5 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added to conduct liquid separation. Further, the organic layer was washed with saturated brine, and the solvent was evaporated evaporated. The obtained solid was purified by a silica gel column chromatography (developing solvent: toluene/ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target. Then, the solid obtained by distilling off the solvent under reduced pressure with ethyl acetate was washed to obtain a compound represented by formula (1-541): 7-phenyl-9-(pyridin-2-yl)-5-( 4-(Pyridin-2-yl)phenyl)-7H-benzo[c]carbazole (0.4 g).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): δ = 8.97 (d, 1H), 8.80 (m, 1H), 8.75 (d, 1H), 8.72 (m, 1H), 8.15 (d, 1H), 8.10 ( d, 2H), 7.73-7.83 (m, 8H), 7.63-7.70 (m, 5H), 7.61 (d, 1H), 7.53 (m, 1H), 7.49 (t, 1H), 7.33 (m, 1H) , 7.23 (m, 1H).

<Synthesis Example of Compound represented by Formula (1-564)>

Under nitrogen, 4-(7-phenyl-5-(((trifluoromethyl)sulfonyl)oxy)-7H-benzo[c]carbazole-9 is loaded with trifluoromethanesulfonate. -Naphthalen-1-yl ester (6.0 g), 2-pyridylzinc bromide 0.5 mol/l THF solution (50 ml) and Pd(PPh ₃ ) ₄ (0.25 g) flask were stirred at reflux temperature 3 hour. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added to conduct liquid separation. The solvent was distilled off under reduced pressure, and the obtained solid was purified by activated alumina column chromatography (developing solvent: toluene/ethyl acetate mixed solvent), and then by a gel column chromatography (developing solution: toluene / Purification by ethyl acetate mixed solvent to obtain a compound represented by formula (1-564): 7-phenyl-5-(pyridin-2-yl)-9-(4-(pyridin-2-yl)naphthalene- 1-yl)-7H-benzo[c]carbazole (0.4 g). At this time, in any of the chromatographic methods, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target.

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500MHz, CDCl} 3): δ = 9.01 (d, 1H), 8.80 (m, 3H), 8.16 (m, 2H), 8.09 (d, 1H), 7.77-7.86 (d, 3H), 7.72 (s, 1H), 7.57-7.67 (m, 10H), 7.43 - 7.53 (m, 4H), 7.35 (m, 2H).

<Synthesis Example of Compound represented by Formula (1-575)>

First, it will be charged with bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diester) (5.9 g), 3-pyridineboronic acid (1.4 g). A flask of sodium carbonate (2.1 g), Pd(PPh ₃ ) ₄ (0.23 g), toluene (21 ml), ethanol (7 ml) and water (7 ml) was stirred under a nitrogen atmosphere at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added to conduct liquid separation. The solvent was evaporated under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target. Thereafter, the solid obtained by distilling off the solvent under reduced pressure with methanol was washed, and then recrystallized from ethanol to obtain 7-phenyl-9-(pyridin-3-yl)-7H-benzene trifluoromethanesulfonate. [c] carbazole ester (2.5 g).

Next, 7-phenyl-9-(pyridin-3-yl)-7H-benzo[c]carbazole ester (1.3 g) and (4-(pyridine) of trifluoromethanesulfonate obtained above are charged. a flask of 2-yl)phenyl)boronic acid (1.3g), sodium carbonate (1.2g), Pd(PPh ₃ ) ₄ (0.31g), toluene (12ml), ethanol (4ml) and water (4ml) in nitrogen Stir for 1.5 hours under the environment at reflux temperature. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and toluene were added to carry out liquid separation. Further, the organic layer was washed with saturated brine, and the solvent was evaporated evaporated. The obtained solid was washed with methanol, washed with ethyl acetate, and then recrystallized from toluene to give the compound of formula (1-575): 7-phenyl-5-(4-(pyridine-2) -yl)phenyl)-9-(pyridin-3-yl)-7H-benzo[c]carbazole (1.1 g).

[化138]

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): δ=8.98 (d, 1H), 8.79 (m, 1H), 8.71 - 8.76 (m, 2H), 8.69 (m, 1H), 8.10 (d, 2H), 7.93 (d, 1H), 7.87 (dt, 1H), 7.75-7.82 (m, 7H), 7.63-7.69 (m, 4H), 7.55 (m, 1H), 7.49 (m, 2H), 7.43 (m, 1H), 7.23 (m, 1H).

<Synthesis Example of Compound represented by Formula (1-599)>

Under nitrogen, 4-(7-phenyl-5-(((trifluoromethyl)sulfonyl)oxy)-7H-benzo[c]carbazole-9 is loaded with trifluoromethanesulfonate. -yl)naphthalen-1-yl ester (3.0 g), 3-pyridineboronic acid (1.6 g), potassium phosphate (3.6 g), Pd(PPh ₃ ) ₄ (0.25 g), 1,2-dimethoxy B A flask of alkane (18 ml) and water (3.6 ml) was stirred at reflux temperature for 12 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added, and the solid in the liquid was collected by suction filtration. Next, purification is carried out by activated alumina column chromatography (developing solution: toluene/ethyl acetate mixed solvent) to obtain a compound represented by the formula (1-599): 7-phenyl-5-(pyridine-3- 9-(4-(pyridin-3-yl)naphthalen-1-yl)-7H-benzo[c]carbazole (1.0 g). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target.

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): δ=9.03 (d, 1H), 8.80 (m, 3H), 8.70 (m, 2H), 8.10 (m, 1H), 7.96 (d, 1H), 7.89 ( m, 3H), 7.82 (t, 1H), 7.58-7.67 (m, 7H), 7.43-7.54 (m, 8H).

<Synthesis Example of Compound represented by Formula (1-742)>

Adding 7-phenyl-7H-benzo[c]carbazole-5,9-diborate (5.0 g) to pseudocumene (1,2,4-trimethylbenzene) (50 ml) To a solution of 2-(3-bromophenyl)pyridine (4.7 g), Pd(PPh ₃ ) ₄ (3.6 g) and potassium phosphate (11.7 g) were added while stirring under a nitrogen atmosphere at room temperature. Thereafter, the mixture was stirred at reflux temperature for 16 hours, and then the reaction liquid was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and toluene were added thereto to carry out liquid separation. After distilling off the solvent under reduced pressure, purification was carried out by silica gel column chromatography (developing solvent: toluene/ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target. Further, the coloring component is removed by an activated carbon column (developing solution: toluene) to obtain a compound represented by the formula (1-742): 7-phenyl-5,9-bis(3-(pyridin-2-yl) Phenyl)-7H-benzo[c]carbazole (0.5 g).

[化140]

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): δ=8.96 (d, 1H), 8.69-8.77 (m, 3H), 8.29 (m, 1H), 8.12 (m, 1H), 8.08 (m, 1H) , 8.02 (m, 1H), 7.97 (m, 1H), 7.71-7.81 (m, 7H), 7.54-7.66 (m, 7H), 7.50 (m, 1H), 7.45 (t, 1H), 7.25 (m) , 2H).

<Synthesis Example of Compound represented by Formula (1-335)>

Stage 1: will be loaded with 2-naphthalene boronic acid (1.9 g), bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diester (5.9 g ), potassium acetate (0.02 g), triphenylphosphine (0.03 g), potassium phosphate (K ₃ PO ₄ ) (8.5 g) and THF / isopropanol (IPA) solution (3:1 by volume) (30) The flask of ml) was stirred under a nitrogen atmosphere at reflux temperature for 0.5 hour. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added to conduct liquid separation, and the solvent was evaporated under reduced pressure. The obtained solid was washed with methanol to give 9-(naphthalen-2-yl)-7-phenyl-7H-benzo[c]oxazol-5-yl trifluoromethanesulfonate (5.4 g).

Stage 2: 9-(naphthalen-2-yl)-7-phenyl-7H-benzo[c]oxazol-5-yl trifluoromethanesulfonate (5.4 g), bis-borate Alcohol ester (3.0 g), (1,1'-bis(diphenylphosphino)ferrocene) dichloropalladium (II) (0.16 g), potassium acetate (2.9 g) and cyclopentyl methyl ether ( A 30 ml) flask was stirred at reflux temperature for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added to conduct liquid separation, and the solvent was evaporated under reduced pressure. The obtained solid was washed with methanol to obtain 9-(naphthalen-2-yl)-7-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaboron. Alkan-2-yl)-7H-benzo[c]carbazole (4.9 g).

9-(naphthalen-2-yl)-7-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborane as obtained above) 2-yl)-7H-benzo[c]carbazole (4.9 g), 2-(4-bromophenyl)pyridine (2.5 g), Pd(PPh ₃ ) ₄ (0.3 g), potassium phosphate (K ₃ A flask of PO ₄ ) (12.0 g) and 1,2,4-trimethylbenzene (pseudocumene) (50 ml) was stirred at reflux temperature. The reaction solution was cooled to room temperature, water was added, and the precipitated solid was collected by suction filtration. The obtained solid was washed with water, washed with methanol, heated and washed with heptane, and purified by activated alumina column chromatography (developing solvent: toluene/ethyl acetate mixed solvent). In this case, refer to the "Organic Chemistry Experiment Guide (1) - Substance Operation Method and Separation and Purification Method -", published by Chemical Society, Inc., page 94, so that the ratio of ethyl acetate in the developing solution is gradually increased to achieve the target. Dissolve. After distilling off the solvent under reduced pressure, the obtained solid is dissolved in chlorobenzene by heating, and heptane is added to carry out reprecipitation to obtain a compound represented by the formula (1-335): 9-(naphthalen-2-yl)-7- Phenyl-5-(4-(pyridin-2-yl)phenyl)-7H-benzo[c]carbazole (3.3 g).

[化141]

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ): δ = 8.93 (d, 1H), 8.71 (d, 1H), 8.68 (m, 1H), 8.06 (d, 2H), 8.01 (d, 1H), 7.95 (s, 1H), 7.83-7.93 (m, 3H), 7.70-7.80 (m, 7H), 7.58-7.65 (m, 5H), 7.55 (s, 1H), 7.46-7.52 (m, 3H), 7.41 (t, 1H), 7.2 (m, 1H).

Other derivative compounds of the present invention can be synthesized by appropriately changing the starting compounds and using the method based on the above synthesis examples.

Hereinafter, the examples are exemplified to explain the present invention in more detail, but the present invention is not limited to the examples.

<Example 1 to Example 3 and Comparative Example 1 and Comparative Example 2>

The electroluminescent elements of Examples 1 to 3 and Comparative Example 1 and Comparative Example 2 were produced, and the driving start voltage (V) of the constant current driving test and the time (h) of maintaining the brightness of 80% or more of the initial brightness were measured. Hereinafter, examples and comparative examples will be described in detail.

The material compositions of the respective layers of the electroluminescent devices of Examples 1 to 3 and Comparative Examples 1 and 2 produced were as shown in Table 1 below.

In Table 1, "CuPc" is copper phthalocyanine, "NPD" is N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, and the compound (A) Is 9-phenyl-10-[6-(1,1';3,1")bitriphenyl-5'-yl]naphthalen-2-ylindole, and the compound (B) is N ⁵ , N ⁵ , N ⁹ , N ⁹ -7,7-hexaphenyl-7H-benzo[c]indole-5,9-diamine, the compound (C) is 5,5'-(2-phenylindole-9,10- The diyl)di-2,2'-bipyridine and the compound (D) are 2-phenyl-9,10-bis[4-(2-pyridyl)phenyl]anthracene, each having the following chemical structure.

[化142]

<Example 1>

<Components using Compound (1-10) in the electron transport layer>

A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Opto Science, Inc.) obtained by sputtering a film having a thickness of 180 nm by sputtering to 150 nm was used as a transparent supporting substrate. The transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Vacuum Machinery Co., Ltd.), and a molybdenum vapor deposition boat in which CuPc is placed and a molybdenum vapor deposition plated with NPD are placed. A boat for vapor deposition by molybdenum containing the compound (A), a boat for vapor deposition made of molybdenum containing the compound (B), and a compound represented by the formula (1-10); A boat for vapor deposition of molybdenum, a boat for vapor deposition made of molybdenum containing lithium fluoride, and a boat for vapor deposition of tungsten filled with aluminum.

The following layers were sequentially formed on the ITO film of the transparent supporting substrate. The vacuum chamber was depressurized to 5 × 10 ^-4 Pa. First, the vapor deposition boat loaded with CuPc was heated, and the film was deposited to a thickness of 100 nm to form a hole injection layer. Secondly, the steam was charged with NPD. The plating was heated by a boat and vapor-deposited to a film thickness of 30 nm to form a hole transport layer. Next, the vapor deposition boat in which the compound (A) was placed and the vapor deposition boat in which the compound (B) was placed were simultaneously heated and vapor-deposited to have a film thickness of 35 nm to form a light-emitting layer. The vapor deposition rate was adjusted so that the weight ratio of the compound (A) to the compound (B) became about 95 to 5. Next, the vapor deposition boat in which the compound represented by the formula (1-10) was charged was heated and vapor-deposited to a thickness of 15 nm to form an electron transport layer. The vapor deposition rate of each layer is from 0.01 nm/sec to 1 nm/sec.

Thereafter, the boat for vapor deposition in which lithium fluoride was charged was heated, and vapor-deposited at a vapor deposition rate of 0.003 nm/sec to 0.1 nm/sec to a film thickness of 0.5 nm, followed by steaming with aluminum. The plating was heated by a boat, and vapor-deposited at a deposition rate of 0.01 nm/sec to 10 nm/sec to a film thickness of 100 nm to form a cathode, thereby obtaining an organic electroluminescence element.

The ITO electrode was used as an anode, and the lithium fluoride/aluminum electrode was used as a cathode. When a direct current voltage was applied, blue light emission having a wavelength of about 455 nm was obtained. Moreover, a constant current drive test was carried out by using a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 5.78 V, and the time to maintain the brightness of 80% (1600 cd/m ² ) or more of the initial brightness was 166 hours.

<Example 2>

<Components using Compound (1-4) in the electron transport layer>

An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-10) was replaced by the compound represented by the formula (1-4). A constant current driving test was carried out by using an ITO electrode as an anode and a lithium fluoride/aluminum electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 7.75 V, and the time to maintain the brightness of 80% or more of the initial brightness was 393 hours.

<Example 3>

<Components using compound (1-744) in the electron transport layer>

An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-10) was replaced by the compound represented by the formula (1-744). A constant current driving test was carried out by using an ITO electrode as an anode and a lithium fluoride/aluminum electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 5.93 V, and the time to maintain the brightness of 80% or more of the initial brightness was 213 hours.

<Comparative Example 1>

An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-10) was replaced by the compound (C). A constant current driving test was carried out by using an ITO electrode as an anode and a lithium fluoride/aluminum electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 4.78 V, and the time to maintain the brightness of 80% or more of the initial brightness was 39 hours.

<Comparative Example 2>

An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-10) was replaced by the compound (D). A constant current driving test was carried out by using an ITO electrode as an anode and a lithium fluoride/aluminum electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 4.74 V, and the time to maintain the brightness of 80% or more of the initial brightness was 24 hours.

The above results are summarized in Table 2.

<Example 4 to Example 13 and Comparative Example 3, Comparative Example 4>

The electroluminescent elements of Examples 4 to 13 and Comparative Example 3 and Comparative Example 4 were produced, and the driving start voltage (V) of the constant current driving test and the time (h) of maintaining the brightness of the initial brightness of 80% or more were measured. Hereinafter, examples and comparative examples will be described in detail.

The material constitution of each of the electroluminescent devices of Examples 4 to 13 and Comparative Example 3 and Comparative Example 4 produced is shown in Table 3 below.

[table 3]

In Table 3, "HI" is N ⁴ , N ^{4 '} -diphenyl-N ⁴ , N ^{4 '} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1'- Biphenyl]-4,4'-diamine, compound (E) is 9-phenyl-10-(4-phenylnaphthalen-1-yl)anthracene, and compound (F) is 9,10-di ([2 2'-bipyridyl]-5-yl)anthracene, the compound (G) is 2,7-bis([2,4'-bipyridyl]-6-yl)-9-phenyl-9H-carbazole. The chemical structure is expressed as follows with "Liq".

[化143]

<Example 4>

<Components using Compound (1-10) in the electron transport layer>

A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Opto Science, Inc.) obtained by sputtering a film having a thickness of 180 nm by sputtering to 150 nm was used as a transparent supporting substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Showa Vacuum Co., Ltd.), and a boat for vapor deposition made of HI molybdenum and a molybdenum plated with NPD were deposited. A boat for vapor deposition by molybdenum containing the compound (E), a boat for vapor deposition made of molybdenum containing the compound (B), and a compound represented by the formula (1-10); A boat for vapor deposition of molybdenum, a boat for vapor deposition made of molybdenum containing Liq, a boat with molybdenum loaded with magnesium, and a boat for vapor deposition of tungsten filled with silver.

The following layers were sequentially formed on the ITO film of the transparent supporting substrate. The vacuum chamber was depressurized to 5 × 10 ^-4 Pa. First, the boat for vapor deposition in which HI was charged was heated, vapor-deposited to a film thickness of 40 nm to form a hole injection layer, and secondly, an evaporation of NPD was performed. The boat was heated and vapor-deposited to a film thickness of 30 nm to form a hole transport layer. Then, the vapor deposition boat in which the compound (E) was placed and the vapor deposition boat in which the compound (B) was charged were simultaneously heated, and vapor-deposited to a film thickness of 35 nm to form a light-emitting layer. The vapor deposition rate was adjusted so that the weight ratio of the compound (E) to the compound (B) became about 95 to 5. Next, the vapor deposition boat in which the compound represented by the formula (1-10) was charged was heated and vapor-deposited to have a film thickness of 15 nm to form an electron transport layer. The vapor deposition rate of each layer is from 0.01 nm/sec to 1 nm/sec.

Thereafter, the boat for vapor deposition in which Liq was charged was heated, and vapor-deposited at a deposition rate of 0.01 nm/sec to 0.1 nm/sec to a film thickness of 1 nm. Next, the boat loaded with magnesium and the boat loaded with silver were simultaneously heated, and vapor-deposited to a film thickness of 100 nm to form a cathode. In this case, the vapor deposition rate was adjusted so that the atomic ratio of magnesium to silver was 10 to 1, and the cathode was formed so that the vapor deposition rate was 0.1 nm/sec to 10 nm/sec to obtain an organic electroluminescence device.

The ITO electrode was used as an anode, and the magnesium/silver electrode was used as a cathode. When a direct current voltage was applied, blue light emission having a wavelength of about 460 nm was obtained. Moreover, by the time for obtaining the initial luminance of 2000cd / m ² current density constant current driving test of the embodiment, the driving voltage of the test starting 5.09V, holding time 80% of the initial luminance (1600cd / m ²⁾ or more of luminance was 245 hours.

<Example 5>

<Components using compound (1-5) in the electron transport layer>

An organic EL device was obtained by the method of Example 4 except that the compound (1-10) was replaced with the compound (1-5). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 4.13 V, and the time to maintain the brightness of 80% or more of the initial brightness was 246 hours.

<Example 6>

<Components using compound (1-634) in the electron transport layer>

An organic EL device was obtained by the method of Example 4 except that the compound (1-10) was replaced with the compound (1-634). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 5.41 V, and the time for maintaining the brightness of 80% or more of the initial brightness was 400 hours.

<Example 7>

<Components using compound (1-744) in the electron transport layer>

An organic EL device was obtained by the method of Example 4 except that the compound (1-10) was replaced with the compound (1-744). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 4.96 V, and the time for maintaining the brightness of 80% or more of the initial brightness was 231 hours.

<Example 8>

<Components using compound (1-20) in the electron transport layer>

An organic EL device was obtained by the method of Example 4 except that the compound (1-10) was replaced with the compound (1-20). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 3.54 V, and the time to maintain the brightness of 80% or more of the initial brightness was 132 hours.

<Example 9>

<Components using compound (1-24) in the electron transport layer>

An organic EL device was obtained by the method of Example 4 except that the compound (1-10) was replaced with the compound (1-24). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 5.26 V, and the time to maintain the brightness of 80% or more of the initial brightness was 265 hours.

<Example 10>

<Components using compound (1-743) in the electron transport layer>

An organic EL device was obtained by the method of Example 4 except that the compound (1-10) was replaced with the compound (1-743). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 4.61 V, and the time to maintain the brightness of 80% or more of the initial brightness was 315 hours.

<Example 11>

<Components using a compound (1-8710) in an electron transport layer>

An organic EL device was obtained by the method of Example 4 except that the compound (1-10) was replaced with the compound (1-8710). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 4.83 V, and the time to maintain the brightness of 80% or more of the initial brightness was 430 hours.

<Example 12>

<Components using compound (1-8711) in the electron transport layer>

An organic EL device was obtained by the method of Example 4 except that the compound (1-10) was replaced with the compound (1-8711). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 3.85 V, and the time to maintain the brightness of 80% or more of the initial brightness was 229 hours.

<Example 13>

<Components using a compound (1-8712) in an electron transport layer>

An organic EL device was obtained by the method of Example 4 except that the compound (1-10) was replaced with the compound (1-8712). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 4.00 V, and the time for maintaining the brightness of 80% or more of the initial brightness was 240 hours.

<Comparative Example 3>

An organic EL device was obtained by the method of Example 4 except that the compound (1-10) was replaced with the compound (F). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . As a result, the driving test starting voltage was 3.86 V, and the time for maintaining the brightness of 80% or more of the initial luminance was 196 hours.

<Comparative Example 4>

An organic EL device was obtained by the method of Example 4 except that the compound (1-10) was replaced with the compound (G). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . As a result, the driving test starting voltage was 3.87 V, and the time for maintaining the brightness of 80% or more of the initial luminance was 120 hours.

The above results are summarized in Table 4.

<Reference Example 1 and Comparative Example 5>

The electroluminescent elements of Reference Example 1 and Comparative Example 5 were produced, and the driving start voltage (V) of the constant current driving test and the time (h) of maintaining the brightness of the initial brightness of 80% or more were measured. Hereinafter, reference examples and comparative examples will be described in detail.

The material constitution of each layer in the electroluminescent device of Reference Example 1 and Comparative Example 5 produced is as shown in Table 5 below.

In Table 5, "CuPc" is copper phthalocyanine, "NPD" is N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, and the compound (A) Is 9-phenyl-10-[6-(1,1';3,1")bitriphenyl-5'-yl]naphthalen-2-ylindole, and the compound (B) is N ⁵ , N ⁵ , N ⁹ , N ⁹ -7,7-hexaphenyl-7H-benzo[c]indole-5,9-diamine, the compound (C) is 5,5'-(2-phenylindole-9,10- Dikibium)di-2,2'-bipyridine has the following chemical structures, respectively.

[化144]

<Reference Example 1>

<Components using compound (1-335) in the electron transport layer>

A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Opto Science, Inc.) obtained by sputtering a film having a thickness of 180 nm by sputtering to 150 nm was used as a transparent supporting substrate. The transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Vacuum Machinery Co., Ltd.), and a molybdenum vapor deposition boat in which CuPc is placed and a molybdenum vapor deposition plated with NPD are placed. A boat for vapor deposition by molybdenum containing the compound (A), a boat for vapor deposition made of molybdenum containing the compound (B), and a compound represented by the formula (1-335). A boat for vapor deposition of molybdenum, a boat for vapor deposition made of molybdenum containing lithium fluoride, and a boat for vapor deposition of tungsten filled with aluminum.

The following layers were sequentially formed on the ITO film of the transparent supporting substrate. The vacuum chamber was depressurized to 5 × 10 ^-4 Pa. First, the vapor deposition boat loaded with CuPc was heated, and the film was deposited to a thickness of 100 nm to form a hole injection layer, followed by steaming with NPD. The plating was heated by a boat and vapor-deposited to a film thickness of 30 nm to form a hole transport layer. Next, the vapor deposition boat in which the compound (A) was placed and the vapor deposition boat in which the compound (B) was placed were simultaneously heated and vapor-deposited to have a film thickness of 35 nm to form a light-emitting layer. The vapor deposition rate was adjusted so that the weight ratio of the compound (A) to the compound (B) became about 95 to 5. Next, the vapor deposition boat in which the compound represented by the formula (1-335) was charged was heated and vapor-deposited to a thickness of 15 nm to form an electron transport layer. The vapor deposition rate of each layer is from 0.01 nm/sec to 1 nm/sec.

Thereafter, the boat for vapor deposition in which lithium fluoride was charged was heated, and vapor-deposited at a vapor deposition rate of 0.003 nm/sec to 0.1 nm/sec to a film thickness of 0.5 nm, followed by steaming with aluminum. The plating was heated by a boat, and vapor-deposited at a deposition rate of 0.01 nm/sec to 10 nm/sec to a film thickness of 100 nm to form a cathode, thereby obtaining an organic electroluminescence element.

The ITO electrode was used as an anode, and the lithium fluoride/aluminum electrode was used as a cathode. When a direct current voltage was applied, blue light emission having a wavelength of about 455 nm was obtained. Moreover, a constant current drive test was carried out by using a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 6.10 V, and the time to maintain the brightness of 80% (1600 cd/m ² ) or more of the initial brightness was 600 hours.

<Comparative Example 5>

An organic EL device was obtained in the same manner as in Reference Example 1 except that the compound represented by the formula (1-335) was replaced by the compound (C). A constant current driving test was carried out by using an ITO electrode as an anode and a lithium fluoride/aluminum electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 4.78 V, and the time to maintain the brightness of 80% or more of the initial value was 39 hours.

The above results are summarized in Table 6.

[Industrial availability]

According to a preferred embodiment of the present invention, an organic electroluminescence device which can improve the lifetime of the light-emitting element and is excellent in balance with a driving voltage, and a display device having the organic electroluminescence device and the display device can be provided. An illumination device or the like of an organic electroluminescence element.

100‧‧‧Organic electroluminescent components

101‧‧‧Substrate

102‧‧‧Anode

103‧‧‧ hole injection layer

104‧‧‧ hole transport layer

105‧‧‧Lighting layer

106‧‧‧Electronic transport layer

107‧‧‧Electronic injection layer

108‧‧‧ cathode

Fig. 1 is a schematic cross-sectional view showing an organic electroluminescent device of the embodiment.

100‧‧‧Organic electroluminescent components

101‧‧‧Substrate

102‧‧‧Anode

103‧‧‧ hole injection layer

104‧‧‧ hole transport layer

105‧‧‧Lighting layer

106‧‧‧Electronic transport layer

107‧‧‧Electronic injection layer

108‧‧‧ cathode

Claims (29)

A benzo[c]carbazole compound represented by the following formula (1): In the above formula (1), R is a group selected from the group consisting of the groups represented by the following formulas (R-1) to (R-20), and A and A' are each independently selected from hydrogen, a group represented by the following formula (A-1-1) to formula (A-1-3), a group represented by the following formula (A-2-1) to formula (A-2-18), and the following A group represented by the formula (A-3-1) to the formula (A-3-6) and a group represented by the following formula (A-4-1) to formula (A-4-6) One of the groups, but A and A' cannot both be hydrogen, [Chemical 2] [Chemical 3] The benzo[c]carbazole compound according to claim 1, wherein R is a group selected from the group consisting of the groups represented by the above formula (R-1) to formula (R-14). , A and A' are each independently selected from the group represented by the above formula (A-1-1) to formula (A-1-3), and the above formula (A-2-1) to formula (A-2-18) The base represented by the formula (A-3-1) to the formula (A-3-6) and the formula (A-4-1) to the formula (A-4-6) A group of groups formed by the base. Benzo[c]carbazole compound as described in claim 1 And R is a group selected from the group consisting of the groups represented by the above formula (R-1) to formula (R-11), and A and A' are each independently selected from the above formula (A-1- 1) a group represented by the formula (A-1-3), a group represented by the above formula (A-2-1) to the formula (A-2-18), and the above formula (A-3-1). One of the groups represented by (A-3-6) and the group represented by the above formula (A-4-1) to formula (A-4-3). The benzo[c]carbazole compound according to claim 1, wherein R is a group represented by the above formula (R-1), formula (R-10) or formula (R-11), A And A' are each independently selected from the group represented by the above formula (A-1-1) to formula (A-1-3), and the above formula (A-2-1) to formula (A-2-4). a group represented by the above formula (A-2-7) to formula (A-2-9), a group represented by the above formula (A-2-12), and the above formula (A-2-15) The group represented by the above formula (A-3-1) to the formula (A-3-6) and the group represented by the above formula (A-4-1) to formula (A-4-3) One of the groups formed. The benzo[c]carbazole compound according to claim 1, wherein R is a group represented by the above formula (R-1) or formula (R-11), and A and A' are independently selected. The group represented by the above formula (A-1-1) to formula (A-1-3), the group represented by the above formula (A-2-1), and the formula (A-2-2) The group represented by the above formula (A-2-8), the group represented by the above formula (A-2-12), and the formula (A-3-1) to the formula (A-3-6) Base And one of the groups consisting of the groups represented by the above formula (A-4-1) to formula (A-4-3). The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-10): The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-4): The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-744): The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-5): The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-634): [Chemical 8] The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-20): The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-24): [Chemical 10] The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-743): The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-8710): [Chemical 12] The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-8711): The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-8712): [Chem. 14] The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-1): The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-2): [Chem. 16] The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-541): The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-564): [Chem. 18] The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-575): The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-599): [Chem. 20] The benzo[c]carbazole compound according to claim 1, which is represented by the following formula (1-742): An electron transporting material comprising the compound according to any one of claims 1 to 23. An organic electroluminescence device comprising: a pair of electrodes formed by an anode and a cathode; a light-emitting layer disposed between the pair of electrodes; disposed between the cathode and the light-emitting layer, as claimed in the patent application An electron transport layer and/or an electron injection layer of an electron transport material according to item 24. Organic electroluminescent element as described in claim 25 And at least one of the electron transport layer and the electron injecting layer further contains a metal quinolate compound, a pyridine derivative, a bipyridine derivative, a phenanthroline derivative, a borane derivative, and a benzoate. At least one of the group consisting of imidazole derivatives. The organic electroluminescent device according to claim 26, wherein at least one of the electron transport layer and the electron injecting layer further contains an oxide selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal, and a base. Metal halides, alkaline 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 metals At least one of the group consisting of the compounds. A display device having the organic electroluminescent device according to any one of claims 25 to 27. An illuminating device having the organic electroluminescent device according to any one of claims 25 to 27.