TWI586788B - Material for light emitting layer and organic electroluminescent device using the same - Google Patents

Description

Light-emitting layer material and organic electroluminescent element using same

The present invention relates to a material for a light-emitting layer of an antimony compound, and further relates to an organic electroluminescence element suitable for use as a display element of a display device such as a color display. More specifically, the present invention relates to an organic electroluminescence element (hereinafter sometimes referred to simply as an organic EL) which is improved in driving voltage, luminous efficiency, lifetime, and the like by using a specific cerium compound in a light-emitting layer. Luminescence) is simply referred to as a component).

The organic EL element is a self-luminous type light-emitting element, and is expected as a light-emitting element for display or illumination, and has been actively studied in recent years. In order to promote the practical use of the organic EL element, the low power consumption and long life of the element are indispensable elements, and in particular, it is a big problem in terms of the blue light-emitting element.

Therefore, various studies have been conducted on organic light-emitting materials, and in order to improve the luminous efficiency or lifetime of blue light-emitting elements, derivatives in which various substituents are bonded to the basic skeleton of germanium have been improved (for example, patent document) 1 to Patent Document 3). Patent Document 1 discloses a luminescent material which is achieved by bonding two phenyl groups to the 9-position and the 10-position of the fluorene skeleton and allowing the various groups to be meta-substituted on one of the phenyl groups. Long life. Patent Document 2 discloses a blue light-emitting material which is achieved by bonding a substituted/unsubstituted phenyl group and a substituted/unsubstituted naphthyl group to an anthracene skeleton. The same characteristics as those required in this application. Further, Patent Document 3 discloses an attempt to attach an ortho-substituted phenyl group at the 9-position and the 10-position of the anthracene skeleton, and further to bond a substituted amino group or a benzofuran to the phenyl group. A compound such as a base to improve luminous efficiency or component life.

[PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-273056 [Patent Document 2] Japanese Patent Laid-Open No. Hei. No. 2006-045503 (Patent Document 3) Japanese Patent Laid-Open No. 2009-249551 Bulletin

[Problems to be Solved by the Invention] However, even the anthracene derivatives disclosed in the above-mentioned respective patent documents have not been able to obtain sufficient characteristics. Under such circumstances, it has been desired to develop a blue light-emitting element having improved driving voltage, luminous efficiency, and device life, and a display device using the same. [Means for solving the problem]

In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that a ruthenium compound represented by the general formula (X) having a specific structure (that is, the general formula (1) to the general formula (4)) is used. The material for a light-emitting layer used in the light-emitting layer can obtain an organic electric field light-emitting element having improved driving voltage, luminous efficiency, and element lifetime, and the like.

That is, the present invention provides a material for a light-emitting layer, an organic electroluminescence device, and a display device and an illumination device including the organic electroluminescence device.

[1] A material for a light-emitting layer comprising a ruthenium compound represented by the following formula (X): In the formula (X), φ is a phenyl group, a naphthyl group, a phenanthryl group or a triphenylenyl group bonded to a phenyl group and may be substituted with Ar ¹ and R, and Ar is a substitutable aryl group. n is 1 or 2, and in the case where n is 1, Ar is bonded to any of the x and y positions, and in the case where n is 2, Ar is bonded to both the x and y positions and their respective The structure may be the same or different, Ar ¹ is a substitutable aryl group, m is a maximum integer which can be substituted from 0 to φ, and when m is 2 or more, the structures of Ar ¹ may be the same or different, R Each is independently an alkyl group or a cycloalkyl group, a is an integer of 0 to 5, b is an integer of 0 to 3, and b+n is 4 or less, and c is a maximum integer which can be substituted from 0 to φ and c+m d is an integer of 0 to 4, and at least one hydrogen in the hydrazine compound represented by the formula (X) may be substituted with hydrazine.

[2] The material for a light-emitting layer according to the above [1], which comprises a ruthenium compound represented by the following formula (1): In the formula (1), Ar is a substitutable aryl group, n is 1 or 2, and in the case where n is 1, Ar is bonded to any of the x and y positions, and when n is 2 When Ar is bonded to both the x-position and the y-position, and the respective structures may be the same or different, Ar ¹ is a substitutable aryl group, m is an integer of 0 to 5, and when m is 2 or more, Ar The structures of ¹ may be the same or different, R is independently an alkyl group or a cycloalkyl group, a is an integer of 0 to 5, b is an integer of 0 to 3, and b+n is 4 or less, and c is 0 to 5. The integer is c and m is 5 or less, and d is an integer of 0 to 4, and at least one hydrogen in the hydrazine compound represented by the formula (1) may be substituted with hydrazine.

[3] The material for a light-emitting layer according to the above [2], wherein Ar is an aryl group having 6 to 18 carbon atoms and may be substituted with an aryl group having 6 to 18 carbon atoms, and n is 1 or 2, and n is In the case of 1 , Ar is bonded to any of the x and y positions. When n is 2, Ar is bonded to both the x and y positions and the respective structures are the same, and Ar ¹ is a carbon number of 6 The aryl group of ～18 is substituted by an aryl group having 6 to 18 carbon atoms, and m is an integer of 0 to 2. When m is 2, the structures of Ar ¹ are the same, and R is independently a carbon number of 1 to 2 An alkyl group of 4 or a cycloalkyl group having 3 to 6 carbon atoms, a is an integer of 0 to 2, b is 0 or 1, c is an integer of 0 to 2, and d is an integer of 0 to 2, and further, At least one hydrogen in the ruthenium compound represented may be substituted with hydrazine.

[4] The material for a light-emitting layer according to the above [2], wherein Ar is a phenyl group, a naphthyl group, a phenanthryl group or a tribenzophenyl group and may be a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group or Triphenylphenyl substituted, n is 1 or 2. In the case where n is 1, Ar is bonded to either the x and y positions, and in the case where n is 2, Ar is bonded to the x position and y. Both of them are the same in structure, and Ar ¹ is a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group or a tribenzophenyl group, and it may be substituted by a phenyl group, a naphthyl group or a phenanthryl group, and m is 0 to 2 An integer, and R is independently methyl, ethyl, n-propyl, isopropyl, tert-butyl or cyclohexyl, a is 0 or 1, b is 0 or 1, c is 0, and d is 0.

[5] The material for a light-emitting layer according to the above [2], which is a compound represented by the following formula (1-1), formula (1-301) or formula (1-307): .

[6] The material for a light-emitting layer according to the above [2], which is represented by the following formula (1-3), formula (1-23), formula (1-53) or formula (1-83). Compound: .

[7] The material for a light-emitting layer according to the above [2], which is represented by the following formula (1-252), formula (1-255), formula (1-261), formula (1-262), and formula ( 1-283), a compound represented by formula (1-559) or formula (1-560): .

[8] The material for a light-emitting layer according to the above [1], which comprises a ruthenium compound represented by the following formula (2): In the formula (2), the naphthalene ring represented by the formula (2) is a 1-naphthyl group or a 2-naphthyl group bonded to a phenyl group, and Ar is a substitutable aryl group, and n is 1 or 2, When n is 1, Ar is bonded to any of the x and y bits. When n is 2, Ar is bonded to both the x and y positions, and the respective structures may be the same or different. Ar ¹ is a substitutable aryl group, and m is an integer of 0 to 7. When m is 2 or more, the structures of Ar ¹ may be the same or different, and R is independently an alkyl group or a cycloalkyl group, a An integer of 0 to 5, b is an integer of 0 to 3, and b+n is 4 or less, c is an integer of 0 to 7 and c+m is 7 or less, and d is an integer of 0 to 4, and Formula (2) At least one hydrogen in the ruthenium compound represented may be substituted with hydrazine.

[9] The material for a light-emitting layer according to the above [8], wherein the naphthalene ring represented by the formula (2) is a 1-naphthyl group or a 2-naphthyl group bonded to a phenyl group, and Ar is a carbon number of 6 to An aryl group of 18 which may be substituted with an aryl group having 6 to 18 carbon atoms, n being 1 or 2, and in the case where n is 1, Ar is bonded to any of the x and y positions, and n is 2 In the case where Ar is bonded to both the x-position and the y-position and the respective structures are the same, Ar ¹ is an aryl group having 6 to 18 carbon atoms and may be substituted with an aryl group having 6 to 18 carbon atoms, and m is 0 to An integer of 2, when m is 2, the structures of Ar ¹ are the same, and R is independently an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and a is an integer of 0 to 2, b is 0 or 1, c is an integer of 0 to 2, d is an integer of 0 to 2, and at least one hydrogen in the hydrazine compound represented by the formula (2) may be substituted with hydrazine.

[10] The material for a light-emitting layer according to the above [8], wherein the naphthalene ring represented by the formula (2) is a 1-naphthyl group or a 2-naphthyl group bonded to a phenyl group, and Ar is a phenyl group or a naphthalene group. a phenanthrenyl group or a tribenzophenyl group which may be substituted by a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group or a tribenzophenyl group, n being 1 or 2, and Ar bonding in the case where n is 1. In any of the x and y positions, in the case where n is 2, Ar is bonded to both the x and y positions and the respective structures are the same, and Ar ¹ is a phenyl group, a naphthyl group, a biphenyl group, Fenyl or tribenzophenyl and which may be substituted by phenyl, naphthyl or phenanthryl, m is an integer from 0 to 2, and R is independently methyl, ethyl, n-propyl or isopropyl , tert-butyl or cyclohexyl, a is 0 or 1, b is 0 or 1, c is 0, and d is 0.

[11] The material for a light-emitting layer according to the above [8], which is a compound represented by the following formula (2-1): .

[12] The material for a light-emitting layer according to the above [1], which comprises a ruthenium compound represented by the following formula (3): In the formula (3), the phenanthrene ring represented by the formula (3) is a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group or a 9-phenanthryl group bonded to a phenyl group, Ar Is a substituted aryl group, n is 1 or 2, and in the case where n is 1, Ar is bonded to either the x-position and the y-position, and in the case where n is 2, Ar is bonded to the x-position and The structure of the y position may be the same or different, and Ar ¹ is a substitutable aryl group, and m is an integer of 0 to 9. When m is 2 or more, the structures of Ar ¹ may be the same. R is independently an alkyl group or a cycloalkyl group, a is an integer of 0 to 5, b is an integer of 0 to 3, and b+n is 4 or less, c is an integer of 0 to 9 and c+m is 9 Hereinafter, d is an integer of 0 to 4, and at least one hydrogen in the hydrazine compound represented by the formula (3) may be substituted with hydrazine.

[13] The material for a light-emitting layer according to the above [12], wherein the phenanthrene ring represented by the formula (3) is a 2-phenanthryl group, a 3-phenanthryl group or a 9-phenanthryl group bonded to a phenyl group, Ar It is an aryl group having 6 to 18 carbon atoms and which may be substituted with an aryl group having 6 to 18 carbon atoms, n is 1 or 2, and in the case where n is 1, Ar is bonded to any of the x-position and the y-position. In the case where n is 2, Ar is bonded to both the x-position and the y-position and the respective structures are the same, and Ar ¹ is an aryl group having 6 to 18 carbon atoms and can be substituted with an aryl group having 6 to 18 carbon atoms. m is an integer of 0 to 2, and when m is 2, the structures of Ar ¹ are the same, and R is independently an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and a is 0. An integer of ～2, b is 0 or 1, c is an integer of 0 to 2, and d is an integer of 0 to 2, and at least one hydrogen in the hydrazine compound represented by the formula (3) may be substituted with hydrazine.

[14] The material for a light-emitting layer according to [12], wherein the phenanthrene ring represented by the formula (3) is a 9-phenanthryl group bonded to a phenyl group, and Ar is a phenyl group, a naphthyl group, a phenanthryl group or Triphenylphenyl and which may be substituted by phenyl, naphthyl, biphenyl, phenanthryl or tribenzophenyl, n is 1 or 2, in the case where n is 1, Ar is bonded to the x position and y In any of the positions, in the case where n is 2, Ar is bonded to both the x and y positions and the respective structures are the same, and Ar ¹ is a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group or a triphenyl group. And a phenyl group which may be substituted by a phenyl group, a naphthyl group or a phenanthryl group, m is an integer of 0 to 2, and R is independently a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a t-butyl group. Or cyclohexyl, a is 0 or 1, b is 0 or 1, c is 0, and d is 0.

[15] The material for a light-emitting layer according to the above [1], which comprises a ruthenium compound represented by the following formula (4): In the formula (4), the tribenzophenone ring represented by the formula (4) is a 1-triphenylphenyl group or a 2-triphenylphenyl group bonded to a phenyl group, and Ar is a substitutable aromatic group. Base, n is 1 or 2. In the case where n is 1, Ar is bonded to either the x and y bits, and in the case where n is 2, Ar is bonded to both the x and y positions. The respective structures may be the same or different, Ar ¹ is a substitutable aryl group, m is an integer of 0 to 11, and when m is 2 or more, the structures of Ar ¹ may be the same or different, and R is independently In the case of an alkyl group or a cycloalkyl group, a is an integer of 0 to 5, b is an integer of 0 to 3, and b+n is 4 or less, c is an integer of 0 to 11 and c+m is 11 or less, and d is 0 to An integer of 4, and at least one hydrogen in the hydrazine compound represented by the formula (4) may be substituted with hydrazine.

[16] The material for a light-emitting layer according to [15], wherein the tribenzophenone ring represented by the formula (4) is a 1-triphenylphenyl group or a 2-triphenyl group bonded to a phenyl group. Phenyl group, Ar is an aryl group having 6 to 18 carbon atoms and may be substituted with an aryl group having 6 to 18 carbon atoms, n is 1 or 2, and in the case where n is 1, Ar is bonded to the x-position and the y-position. In either case, in the case where n is 2, Ar is bonded to both the x-position and the y-position and the respective structures are the same, and Ar ¹ is an aryl group having 6 to 18 carbon atoms and may have a carbon number of 6 to 18 The aryl group is substituted, m is an integer of 0 to 2. When m is 2, the structures of Ar ¹ are the same, and R is independently an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. a is an integer of 0 to 2, b is 0 or 1, c is an integer of 0 to 2, d is an integer of 0 to 2, and at least one hydrogen in the ruthenium compound represented by the formula (4) can be passed through Replace.

[17] The material for a light-emitting layer according to the above [15], wherein the tribenzophenone ring represented by the formula (4) is a 2-tribenzophenyl group bonded to a phenyl group, and Ar is a phenyl group. Naphthyl, phenanthryl or tribenzophenyl and which may be substituted by phenyl, naphthyl, biphenyl, phenanthryl or tribenzophenyl, n is 1 or 2, in the case where n is 1, Ar bond In the case of any of the x and y positions, in the case where n is 2, Ar is bonded to both the x and y positions and the respective structures are the same, and Ar ¹ is a phenyl group, a naphthyl group, a biphenyl group. , phenanthryl or tribenzophenyl and which may be substituted by phenyl, naphthyl or phenanthryl, m is an integer from 0 to 2, and R is independently methyl, ethyl, n-propyl or isopropyl Base, tert-butyl or cyclohexyl, a is 0 or 1, b is 0 or 1, c is 0, and d is 0.

[18] An organic electroluminescence device comprising: a pair of electrodes including an anode and a cathode; and a light-emitting layer according to any one of the above [1] to [17] The luminescent layer of the material.

[19] The organic electroluminescent device according to [18], wherein the light-emitting layer contains a group selected from the group consisting of an amine having a stilbene structure, an aromatic amine derivative, and a coumarin derivative. At least one of them.

[20] The organic electroluminescence device according to [18] or [19], further comprising an electron transport layer and/or an electron injection layer disposed between the cathode and the light-emitting layer, the electron transport layer and the electron At least one of the injection layers contains at least one selected from the group consisting of a hydroxyquinoline metal complex, a pyridine derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative.

[21] The organic electroluminescence device according to the above [20], wherein at least one of the electron transport layer and the electron injection layer further contains an oxide selected from an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal, or an alkali 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 organic complexes of rare earth metals At least one of the group consisting of objects.

[22] A display device comprising the organic electroluminescence device according to any one of [18] to [21] above.

[23] An illuminating device comprising the organic electroluminescent device according to any one of [18] to [21] above. [Effects of the Invention]

According to a preferred embodiment of the present invention, an organic electroluminescence element having a low driving voltage, high luminous efficiency, and long device life can be provided. Further, a display device, an illumination device, and the like including the effective organic electroluminescence device can be provided.

1. An oxime compound represented by the formula (X) The oxime compound represented by the formula (X) is classified into a compound represented by the formula (1) (φ = phenyl) and a compound represented by the formula (2) ( φ = naphthyl), a compound represented by the formula (3) (φ = phenanthryl), and a compound represented by the formula (4) (φ = tribenzophenyl).

The compound of the present invention is substantially in the oxime compound in which two phenyl groups are bonded to the 9-position and the 10-position, and the specific aryl group is substituted at the 2-position of one of the phenyl groups (bonded to the oxime at the 1-position) And a compound which is formed by a material for the light-emitting layer by selecting such a substitution site and an aryl structure by selecting a compound having a position of 5, 3, and 4 or 2 and 4 and 5, and selecting a substitution site and an aryl structure. Compounds with luminous efficiency and component lifetime.

1.1 Anthracene compound represented by the formula (1) First, the anthracene compound represented by the above formula (1) will be described in detail. The general formula (1) is classified into the structure represented by the following formula (1a), the structure represented by the formula (1b), and the structure represented by the formula (1c).

The "aryl group" of the "substitutable aryl group" of Ar of the formula (1) is, for example, an aryl group having 6 to 30 carbon atoms. The preferred "aryl group" is an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still 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, a (1-, 2-)naphthyl group as a condensed bicyclic aryl group, and a fluorene-(1- as a condensed tricyclic aryl group. , 3-, 4-, 5-), 茀-(1-, 2-, 3-, 4-, 9-), 萉-(1-, 2-), (1-, 2-, 3-, 4-, 9-) phenanthryl, tribenzobenzo-(1-, 2-)yl, fluorenyl-(1-, 2-, 4-)yl, condensed four as a condensed tetracyclic aryl Benzene-(1-, 2-, 5-)yl, 苝-(1-, 2-, 3-)yl as a condensed pentacyclic aryl, fused pentabenzene-(1-, 2-, 5-, 6-) base and so on.

Preferred examples of the "aryl group" include a phenyl group, a naphthyl group, and a phenanthryl group. Further, a phenyl group, a 1-naphthyl group, a 2-naphthyl group or a phenanthryl group may be mentioned, and a phenyl group, a 1-naphthyl group or a 2-naphthyl group is particularly preferable.

The substituent on the "aryl group" is not particularly limited as long as the desired properties are obtained, and preferably an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a aryl group having 6 to 18 carbon atoms is preferred. Base.

The "alkyl group having 1 to 12 carbon atoms" as the substituent may be either a straight chain or a branched chain. That is, it is a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 6 carbon atoms (branched alkyl group having 3 to 6 carbon atoms), and more preferably an alkyl group having 1 to 4 carbon atoms (branched alkyl group having 3 to 4 carbon atoms). Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, and Tripentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl or 2-ethylbutyl, etc., preferably methyl or ethyl , n-propyl, isopropyl, n-butyl, isobutyl, t-butyl or t-butyl, more preferably methyl, isopropyl or tert-butyl.

In addition, specific examples of the "cycloalkyl group having 3 to 12 carbon atoms" as the substituent include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclopentyl group, and a cycloheptyl group. Methylcyclohexyl, cyclooctyl or dimethylcyclohexyl, and the like. Among these, a cyclopentyl group or a cyclohexyl group is preferred.

In addition, the "aryl group having 6 to 18 carbon atoms" as the substituent is preferably an aryl group having 6 to 14 carbon atoms, particularly preferably an aryl group having 6 to 10 carbon atoms. Specific examples are phenyl, (2-, 3-, 4-)biphenyl, (1-, 2-)naphthyl, (1-, 2-, 3-, 4-, 9-)phenanthryl, ( 1-, 2-) tribenzophenyl and the like.

The substituent on the "aryl group" is preferably unsubstituted, and in the case where a substituent is present, the number thereof is, for example, the maximum number of substitutions, preferably from 1 to 3, more preferably 1 One to two, and then one is better.

The "aryl group" of the "substitutable aryl group" of Ar ¹ of the formula (1) is, for example, an aryl group having 6 to 30 carbon atoms. The preferred "aryl group" is an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still 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, a (2-, 3-, 4-) biphenyl group as a bicyclic aryl group, and a condensed bicyclic aryl group (1). -, 2-) naphthyl, as a condensed tricyclic aryl group of fluorene-(1-, 3-, 4-, 5-), 茀-(1-, 2-, 3-, 4-, 9- ), fluorenyl-(1-, 2-)yl, (1-, 2-, 3-, 4-, 9-)phenanthryl, triphenylbenzene-(1-, condensed tetracyclic aryl 2-), 芘-(1-, 2-, 4-)-based, fused tetraphenyl-(1-, 2-, 5-)yl, as condensed pentacyclic aryl 苝-(1-, 2 -, 3-) group, fused pentabenzene-(1-, 2-, 5-, 6-) group and the like.

Preferred examples of the "aryl group" include a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group. Or a tribenzophenyl group, etc., and further preferably a phenyl group, a 3-biphenyl group, a 4-biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenanthryl group or a tribenzophenyl group. Phenyl, 1-naphthyl or 2-naphthyl are listed.

The substituent on the "aryl group" is not particularly limited as long as the desired properties are obtained, and preferably an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a aryl group having 6 to 18 carbon atoms is preferred. Base.

The "alkyl group having 1 to 12 carbon atoms" or the "cycloalkyl group having 3 to 12 carbon atoms" as the substituent may be the same as those described in the column of Ar described above.

In addition, the "aryl group having 6 to 18 carbon atoms" as the substituent is preferably an aryl group having 6 to 14 carbon atoms, particularly preferably an aryl group having 6 to 10 carbon atoms. Specific examples are phenyl, (1-, 2-)naphthyl, (1-, 2-, 3-, 4-, 9-)phenanthryl and the like.

The substituent on the "aryl group" is preferably unsubstituted, and in the case where a substituent is present, the number thereof is, for example, the maximum number of substitutions, preferably from 1 to 3, more preferably 1 One to two, and then one is better.

The number of substituents m of Ar ¹ is an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1.

The "alkyl group" of R in the general formula (1) is, for example, an alkyl group having 1 to 12 carbon atoms, and the description of the column in which the above Ar can be referred to is specifically described.

The "cycloalkyl group" of R in the general formula (1) is, for example, a cycloalkyl group having 3 to 12 carbon atoms, and the description of the column in which the above Ar can be referred to is specifically described.

With respect to the number of substituents (a to d) of R, a is preferably an integer of 0 to 5, b is an integer of 0 to 3 (b+n is 4 or less), and c is an integer of 0 to 5 (c+m is 5 or less), and d is an integer of 0 to 4. More preferably, a is an integer of 0 to 2, b is 0 or 1, c is an integer of 0 to 2, and d is an integer of 0 to 2. Further, it is preferable that a to d are 0.

Further, a hydrogen atom in the anthracene skeleton constituting the compound represented by the formula (1), a hydrogen atom in the phenyl group substituted at the 9-position or the 10-position of the anthracene, and hydrogen in the Ar group, the Ar ¹ group or the R group All or part of an atom may also be 氘.

Specific examples of the compound represented by the above formula (1) include the following formula (1-1) to formula (1-244) and formula (1-251) which are the structures represented by the above formula (1a). The compound represented by the formula (1-294) belongs to the following formula (1-301) to formula (1-544) and formula (1-552) to formula (1-562) of the structure represented by the above formula (1b). The compound represented by the formula (1-601) to the formula (1-612) represented by the above formula (1c).

Among the following compounds, the following formula (1-1) to formula (1-10), formula (1-22) to formula (1-36), and formula (1-52) to formula (1-66) are preferred. ), Formula (1-82) to Formula (1-96), Formula (1-112) to Formula (1-120), Formula (1-142) to Formula (1-150), Formula (1-154) -Formula (1-156), Formula (1-221) - Formula (1-244), Formula (1-251), Formula (1-252), Formula (1-255), Formula (1-261), Formula (1-262), Formula (1-283), Formula (1-301) to Formula (1-313), Formula (1-320) to Formula (1-333), Formula (1-352) to Formula (1-360), Formula (1-382) to Formula (1-396), Formula (1-412) to Formula (1-423), Formula (1-442) to Formula (1-453), Formula ( 1-521) to formula (1-532), formula (1-534) to formula (1-542), formula (1-559), formula (1-560) to formula (1-562), formula (1) Further, the compound represented by the formula (1-1) to the formula (1-1) to the formula (1-10), the formula (1-21) to the formula (1-30), and the formula (1). 1-35), Formula (1-52) to Formula (1-60), Formula (1-221) to Formula (1-229), Formula (1-251), Formula (1-252), Formula (1) -255), formula (1 -261), Formula (1-262), Formula (1-283), Formula (1-301) - Formula (1-310), Formula (1-322) - Formula (1-330), Formula (1- 352) to formula (1-360), formula (1-382) to formula (1-390), formula (1-412) to formula (1-420), formula (1-442) to formula (1-450) ), formula (1-521) to formula (1-530), formula (1-534) to formula (1-542), formula (1-559), formula (1-560) to formula (1-562) A compound represented by the formula (1-601) to the formula (1-606).

1.2 Anthracene compound represented by the formula (2) Next, the anthracene compound represented by the above formula (2) will be described in detail. The general formula (2) is classified into the structure represented by the following formula (2a), the structure represented by the formula (2b), and the structure represented by the formula (2c). In each structure, the naphthalene ring is 1-naphthyl or 2-naphthyl.

Ar, Ar ¹ and R of the formula (2) are as illustrated in the formula (1). Further, the number of substituents m of Ar ¹ is an integer of 0 to 7, preferably an integer of 0 to 2, more preferably 0 or 1. The number of substituents (a to d) of R is preferably an integer of 0 to 5, b is an integer of 0 to 3 (b+n is 4 or less), and c is an integer of 0 to 7 (c+m is 7 or less), and d is an integer of 0-4. More preferably, a is an integer of 0 to 2, b is 0 or 1, c is an integer of 0 to 2, and d is an integer of 0 to 2. Further, it is preferable that a to d are 0.

Further, a hydrogen atom in the anthracene skeleton constituting the compound represented by the formula (2), a hydrogen atom in the phenyl group substituted at the 9-position or the 10-position of the anthracene, a hydrogen atom in the naphthalene ring, and an Ar group, Ar ¹ All or a portion of the hydrogen atoms in the group or R group may also be deuterium.

Specific examples of the compound represented by the above formula (2) include the following formula (2-1) to formula (2-12) and formula (2-51) which are the structures represented by the above formula (2a). The compound represented by the formula (2-62) belongs to the following formula (2-101) to formula (2-112) and formula (2-151) to formula (2-162) of the structure represented by the above formula (2b). ) the compound represented.

Among the following compounds, the following formula (2-1) to formula (2-3), formula (2-5), formula (2-9) to formula (2-12), and formula (2-51) are preferred. ) - formula (2-53), formula (2-55), formula (2-59) - formula (2-62), formula (2-101) - formula (2-103), formula (2-105) Equations (2-109) to (2-112), (2-151) to (2-153), (2-155), and (2-159) to (2-162) The compound represented.

1.3 Anthracene compound represented by the formula (3) Next, the anthracene compound represented by the above formula (3) will be described in detail. The general formula (3) is classified into the structure represented by the following formula (3a), the structure represented by the formula (3b), and the structure represented by the formula (3c). In each structure, the phenanthrene ring is 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl.

Ar, Ar ¹ and R of the formula (3) are as illustrated in the formula (1). Further, the number m of substituents of Ar ¹ is an integer of 0 to 9, preferably an integer of 0 to 2, more preferably 0 or 1. The number of substituents (a to d) of R is preferably an integer of 0 to 5, b is an integer of 0 to 3 (b+n is 4 or less), and c is an integer of 0 to 9 (c+m is 9 or less), and d is an integer of 0 to 4. More preferably, a is an integer of 0 to 2, b is 0 or 1, c is an integer of 0 to 2, and d is an integer of 0 to 2. Further, it is preferable that a to d are 0.

Further, a hydrogen atom in the anthracene skeleton constituting the compound represented by the formula (3), a hydrogen atom in the phenyl group substituted at the 9-position or the 10-position of the anthracene, a hydrogen atom in the phenanthrene ring, and an Ar group, Ar ¹ All or a portion of the hydrogen atoms in the group or R group may also be deuterium.

Specific examples of the compound represented by the above formula (3) include compounds represented by the following formula (3-1) to formula (3-12) which belong to the structure represented by the above formula (3a), and belong to the above formula. (3b) The compound represented by the following formula (3-51) to formula (3-62).

Among the following compounds, the following formula (3-1) to formula (3-3), formula (3-5), formula (3-9) to formula (3-12), and formula (3-51) are preferred. - a compound represented by the formula (3-53), the formula (3-55), and the formula (3-59) to the formula (3-62).

1.4 Anthracene compound represented by the formula (4) Next, the anthracene compound represented by the above formula (4) will be described in detail. The general formula (4) is classified into a structure represented by the following formula (4a), a structure represented by the formula (4b), and a structure represented by the formula (4c). In each structure, the tribenzophenone ring is 1-triphenylphenyl or 2-triphenylphenyl.

Ar, Ar ¹ and R of the formula (4) include those described in the formula (1). Further, the number of substituents m of Ar ¹ is an integer of 0 to 11, preferably an integer of 0 to 2, more preferably 0 or 1. With respect to the number of substituents (a to d) of R, a is preferably an integer of 0 to 5, b is an integer of 0 to 3 (b+n is 4 or less), and c is an integer of 0 to 11 (c+m is 11 or less), and d is an integer of 0 to 4. More preferably, a is an integer of 0 to 2, b is 0 or 1, c is an integer of 0 to 2, and d is an integer of 0 to 2. Further, it is preferable that a to d are 0.

Further, a hydrogen atom in the anthracene skeleton constituting the compound represented by the formula (4), a hydrogen atom in the phenyl group substituted at the 9-position or the 10-position of the anthracene, a hydrogen atom in the tribenzobenzene ring, and an Ar group are also included. All or a part of the hydrogen atoms in the Ar ¹ group or the R group may be ruthenium.

Specific examples of the compound represented by the above formula (4) include compounds represented by the following formulas (4-1) to (4-12) which belong to the structure represented by the above formula (4a), and belong to the above formula. (4b) The compound represented by the following formula (4-51) to formula (4-62).

Among the following compounds, the following formula (4-1) to formula (4-3), formula (4-5), formula (4-9) to formula (4-12), and formula (4-51) are preferred. - a compound represented by the formula (4-53), the formula (4-55), and the formula (4-59) to the formula (4-62).

2. Process for producing an anthracene compound represented by the formula (X) The anthracene compound represented by the formula (X) is classified into a compound represented by the formula (1) (φ = phenyl group) and represented by the formula (2). The compound (φ = naphthyl), the compound represented by the formula (3) (φ = phenanthryl), and the compound represented by the formula (4) (φ = tribenzophenyl).

The hydrazine compound represented by the formula (1) can be produced by a known synthesis method. First, the synthesis method will be described by taking the hydrazine compound represented by the formula (1a) as an example. The hydrazine compound represented by the formula (1a) can be synthesized, for example, via a route represented by the following reaction formula (1).

First, in the first-stage reaction, the sulfonium bromide derivative (1a-2) and the compound (1a-1) are subjected to Suzuki coupling reaction using a palladium catalyst in the presence of a base to synthesize the intermediate compound (1a-3). . Next, in the second stage, an intermediate compound (1a-5) is synthesized by using a palladium catalyst and subjecting the boric acid derivative (1a-4) to the intermediate compound (1a-3) obtained above in the presence of a base. Further, the boric acid derivative (1a-6) is subjected to a Suzuki coupling reaction, whereby the anthracene compound represented by the formula (1a) of the present invention can be synthesized. Ar, Ar ¹ , R, n, m and a to d in the formula are the same as those used in the formula (1).

In the reaction formula (1), a boronic acid derivative (1a-4) having a different structure and a boronic acid derivative can be obtained by differentiating the reactivity of the reactive group Y ¹ and the reactive group Y ² in the compound (1a-1). The compound (1a-6) is reacted in order to synthesize the hydrazine compound represented by the formula (1a). When the boronic acid derivative (1a-4) and the boronic acid derivative (1a-6) have the same structure (for example, the compound represented by the formula (1-1)), the reactivity of the reactive group Y ¹ and the reactive group Y ² It can be the same.

Further, by changing the position of the reactive group Y ² in the compound (1a-1) or further adding the reactive group Y ³ in the reaction formula (1), the hydrazine compound represented by the formula (1b) or the formula (1c) can be synthesized. ) the bismuth compound represented.

Next, the reaction formula (2) which is another reaction path will be described. In the reaction formula (2), a suzuki coupling reaction is carried out using a palladium catalyst and a bismuth borate derivative (1a-2) in the presence of a base with a compound (1a-7) obtained in advance or as a commercially available product. Thereby, the hydrazine compound represented by the formula (1a) of the present invention can be synthesized.

In the reaction formula (2), the hydrazine compound represented by the formula (1b) or the hydrazine compound represented by the formula (1c) can be synthesized by selecting the compound (1a-7) prepared in advance.

Next, the reaction formula (3) which is another reaction path will be described. In the reaction formula (3), a boronic acid derivative or a boronic acid ester derivative (1a-9) and a compound (1a-8) which are obtained in advance or synthesized as a commercial product in the presence of a base using a palladium catalyst are used. The Suzuki coupling reaction is carried out, whereby the hydrazine compound represented by the formula (1a) of the present invention can be synthesized.

In the reaction formula (3), the hydrazine compound represented by the formula (1b) or the hydrazine compound represented by the formula (1c) can be synthesized by selecting the compound (1a-9) prepared in advance.

Specific examples of the palladium catalyst used in the Suzuki coupling reaction can be used: tetrakis(triphenylphosphine)palladium(0):Pd(PPh ₃ ) ₄ , bis(triphenylphosphine)dichloropalladium(II):PdCl ₂ (PPh ₃ ) ₂ , palladium (II) acetate: Pd(OAc) ₂ , tris(dibenzylideneacetone) dipalladium (0): Pd ₂ (dba) ₃ , tris(dibenzylideneacetone) dipalladium ( 0) Chloroform complex: Pd ₂ (dba) ₃ · CHCl ₃ , bis (dibenzylideneacetone) palladium (0): Pd (dba) ₂ , bis (tri-tert-butylphosphino) palladium (0) :Pd(P(t-Bu) ₃ ) ₂ , or [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane complex (1:1) : PdCl ₂ (dppf)·CH ₂ Cl ₂ and the like.

Further, in order to promote the reaction, a phosphine compound may be added to the palladium compounds as the case may be. Examples of the phosphine compound include tris(t-butyl)phosphine: t-Bu ₃ P, tricyclohexylphosphine: PCy ₃ , 1-(N,N-dimethylaminomethyl)-2-(di Tributylphosphino)ferrocene, 1-(N,N-dibutylaminomethyl)-2-(di-t-butylphosphino)ferrocene, 1-(methoxymethyl) -2-(di-tert-butylphosphino)ferrocene, 1,1'-bis(di-tert-butylphosphino)ferrocene, 2,2'-bis(di-third -phosphonyl)-1,1'-binaphthyl, 2-methoxy-2'-(di-tert-butylphosphino)-1,1'-binaphthyl or 2-dicyclohexylphosphino-2 ',6'-dimethoxybiphenyl and the like.

Further, specific examples of the base used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium tributoxide, and sodium acetate. , tripotassium phosphate: K ₃ PO ₄ or potassium fluoride.

Further, examples of the solvent used in the above reaction formula (1) to reaction formula (3) include benzene, toluene, xylene, 1,2,4-trimethylbenzene, and N,N-dimethylformamide. , N,N-dimethylacetamide, tetrahydrofuran, diethyl ether, tert-butyl methyl ether, 1,4-dioxane, methanol, ethanol, isopropanol, tert-butanol, cyclopentyl methyl ether, etc. . These solvents may be used singly or in the form of a mixed solvent. The reaction is usually carried out at a temperature ranging from 50 ° C to 180 ° C, more preferably from 70 ° C to 130 ° C.

Further, the compound of the present invention also contains at least a part of hydrogen atoms which are substituted by hydrazine, and such a compound can be synthesized in the same manner as described above by using a raw material obtained by deuteration of a desired site.

In the above, a method for producing a compound (a ruthenium compound represented by the formula (1)) in which a phenyl group is selected as φ in the formula (X) has been described, but the formula (2) to the formula (4) are represented. The ruthenium compound can also be produced by the above production method. In other words, in the above production method, the raw material compound selected so that φ becomes a phenyl group is changed to a raw material compound in which φ is a naphthyl group, a phenanthryl group or a tribenzophenyl group.

3. Organic Electric Field Light-Emitting Element The germanium compound of the present invention can be used, for example, as a material of an organic electric field light-emitting element. 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 electroluminescence device of the embodiment.

<Configuration of Organic Electric Field Light-Emitting Element> The organic electro-optic light-emitting element 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 injection layer 103. The upper hole transport layer 104, 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 electron injection layer Cathode 108 on layer 107.

Further, the organic electroluminescent device 100 may be configured to have a substrate 101, a cathode 108 provided on the substrate 101, an electron injection layer 107 provided on the cathode 108, and an electron injection layer. An electron transport layer 106 on 107, a light-emitting layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light-emitting layer 105, a hole injection layer 103 provided on the hole transport layer 104, and The hole is injected into the anode 102 on the layer 103.

Not all of the above layers are necessary, and the minimum constituent unit is configured to include the anode 102, the light-emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection layer 107 are arbitrarily provided. Floor. In addition, each of the above layers may include a single layer or a plurality of layers.

The embodiment of the layer constituting the organic electroluminescent device may be a substrate other than the above-described configuration of "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode". /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 / luminescent layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole transport layer / luminescent layer / electron injection layer / cathode", "substrate / anode / hole transport layer / luminescent layer / electron transport Layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron injection layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron transport layer/cathode", "substrate/anode" Light-emitting layer/electron transport layer/cathode", "substrate/anode/light-emitting layer/electron injection layer/yin The way the pole is constructed.

<Substrate in Organic Electric Field Light-Emitting Element> The substrate 101 serves as a support for the organic electro-optic light-emitting element 100, and generally, quartz, glass, metal, plastic, or the like can be used. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape depending on the purpose. 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 transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polyfluorene are preferable. In the case of a glass substrate, soda lime glass or alkali-free glass may be used, and the thickness may be sufficient to ensure mechanical strength. For example, the thickness may be 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. The material of the glass is preferably an alkali-free glass because the eluted ions in the glass are less preferred, but a soda lime glass having a barrier coat such as SiO _{2 is} also 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 tantalum oxide film may be provided on at least one surface, and in particular, a synthetic resin plate, film or sheet having low gas barrier properties may be used as the substrate 101. In the case of the case, it is preferred to provide a gas barrier film.

<Anode in Organic Electric Field Light-Emitting 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, holes are injected into the light-emitting layer 105 through the layers.

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.) and metal oxides (indium oxide, tin oxide, indium tin oxide (ITO), indium). - zinc oxide (Indium Zinc Oxide, 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 may be appropriately selected from those used as the anode of the organic electroluminescence element.

The electric resistance of the transparent electrode is not limited as long as a sufficient current can be supplied to the light emission of the light-emitting element, and from the viewpoint of power consumption of the light-emitting element, it is preferable to have a low electric resistance. For example, an ITO substrate of 300 Ω/□ or less functions as a device electrode. However, since a substrate of about 10 Ω/□ is currently available, it is particularly preferable to use 100 Ω/□ to 5 Ω/□, for example. Good low resistance products from 50 Ω/□ to 5 Ω/□. The thickness of ITO can be arbitrarily selected according to the resistance value, and is usually used mostly between 50 nm and 300 nm.

<Pore Injection Layer and Hole Transport Layer in Organic Electric Field Light-Emitting Element> The hole injection layer 103 functions to efficiently inject a hole moved from the anode 102 into the light-emitting layer 105 or the hole transport layer 104. Inside. The hole transport layer 104 serves to efficiently transfer holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light-emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are formed by laminating and mixing one or two or more holes injecting/transporting materials, respectively, or by injecting/transporting a mixture of a material and a polymer binder. And formed. Further, an inorganic salt such as iron (III) chloride may be added to the hole injection/transport material to form a layer.

The hole injection/transporting substance must efficiently inject/transmit a hole from the positive electrode between the electrodes to which the electric field is applied, and it is desirable that the hole injection efficiency is high and the injected hole is efficiently transported. Therefore, it is preferable that the ionization potential is small, the hole mobility is large, and the stability is excellent, and impurities which are traps are hard to be generated at the time of production and use.

As a material for forming the hole injection layer 103 and the hole transport layer 104, any one of the following compounds may be selected from the following compounds: a compound which has been conventionally used as a charge transport material for a hole in a photoconductive material, p-type semiconductor, organic A known compound used in the hole injection layer and the hole transport layer of the electric field light-emitting element. Specific examples of these are carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), bis(N-arylcarbazole) or bis(N-alkylcarbazole) and the like. , a triarylamine derivative (a polymer having an aromatic tertiary amino group in a main chain or a side chain, 1,1-bis(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-methylphenyl)-4,4'-diphenyl-1,1'-di Amine, N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl-1,1'-diamine, 4,4',4"-tris(3-A Triphenylamine derivatives such as phenyl(phenyl)amino)triphenylamine, starburst amine derivatives, etc., anthracene derivatives, phthalocyanine derivatives (metal-free phthalocyanine, copper) a phthalocyanine derivative, a pyrazine derivative, an anthraquinone compound, a benzofuran derivative or a thiophene derivative, an oxadiazole derivative, a porphyrin derivative, a heterocyclic compound, a polydecane, etc. a polymer system. Preferably, the polycarbonate or styrene derivative having the above monomer in the side chain, polyethylene B The alkenyl carbazole, the polydecane, and the like are not particularly limited as long as they are a film necessary for forming a light-emitting element, a compound capable of injecting a hole from the anode, and further capable of transporting a hole.

In addition, it is also known that the conductivity of an organic semiconductor is strongly influenced by its dopant. Such an organic semiconductor host material contains a compound having good electron donating 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 (2,3,5 is known). , 6-tetrafluorotetracyano-1,4-benzo quinodimethane, F4TCNQ) and other strong electron acceptors (for example, reference "M.Pfeiffer, A.Beyer, T.Fritz, K.Leo, Applied Physics (Appl.Phys.Lett) .), 73(22), 3202-3204 (1998) and the literature "J. Blochwitz, M. Pheiffer, T. Fritz, K. Leo, Applied Physics (Appl. Phys. Lett.), 73(6) , 729-731 (1998)"). These generate so-called holes by an electron transfer process in an electron-donating matrix substance (hole transport material). The conductivity of the matrix material varies considerably depending on the number and mobility of the holes. A matrix substance having a hole transporting property is known, for example, as a benzidine derivative (N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)benzidine (N,N'- Bis(3-methylphenyl)-N, N'-bis(phenyl)benzidine, TPD), or a starburst amine derivative (4,4',4"-tris(N,N-benzidine)triphenylamine (4,4',4"-tris(N,N-benzidylamino)triphenylamine, TDATA), or a specific metal phthalocyanine (especially zinc phthalocyanine ZnPc, etc.) (Japanese Patent Laid-Open Publication No. 2005-167175) .

<Light Emitting Layer in Organic Electric Field Light Emitting Element> The light emitting layer 105 emits light by recombining a hole injected from the anode 102 with electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material forming the light-emitting layer 105 may be a compound (light-emitting compound) that emits light by being excited by recombination of a hole and electrons, and preferably forms a stable film shape and exhibits strong light emission in a solid state. (fluorescent) efficiency compound. In the present invention, a compound represented by the above formula (X) (i.e., the formula (1) to the formula (4)) can be used as a material for the light-emitting layer.

The light-emitting layer may be a single layer or a plurality of layers, and is formed by a material for a light-emitting layer (host material, doping material). The host material and the dopant material may each be one kind or a combination of a plurality of types. The doping material may be contained in the entire host material or partially contained in the host material. The doping method may be formed by a co-evaporation method with a host material, or may be simultaneously vapor-deposited while being mixed with the host material.

The amount of use of the host material varies depending on the type of the host material, and may 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, even more preferably from 90% by weight to 99.9% by weight, based on the total amount of the material for the light-emitting layer. The compound represented by the above formula (X) (i.e., the formula (1) to the formula (4)) of the present invention is particularly preferably used as a host material.

The amount of the dopant used varies depending on the type of the dopant, and may be determined according to the characteristics of the dopant. The standard of the amount of the dopant used is preferably from 0.001% by weight to 50% by weight, more preferably from 0.05% by weight to 20% by weight, even more preferably from 0.1% by weight to 10% by weight, based on the total amount of the material for the light-emitting layer. If it is the above range, it is preferable, for example, in that it can prevent the concentration extinction phenomenon.

The host material which can be used in combination with the compound represented by the above formula (X) (i.e., the formula (1) to the formula (4)) of the present invention may be a condensed ring of ruthenium or osmium which has been known as an illuminant. a bisstyryl derivative such as a derivative, a bisstyrylhydrazine derivative or a distyrylbenzene derivative, a tetraphenylbutadiene derivative, a cyclopentadiene derivative, an anthracene derivative, or a benzindene derivative Things and so on.

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 phenanthrene, anthracene, anthracene, fused tetraphenyl, pentacene, anthracene, naphthoquinone, dibenzopyrene, rubrene, and (chrysene) condensed ring derivative; benzoxazole derivative, benzothiazole derivative, benzimidazole derivative, benzotriazole derivative, oxazole derivative, oxadiazole derivative, thiazole derivative, Imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, anthracene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyryl fluorene a bisstyryl derivative such as a derivative or a distyrylbenzene derivative (Japanese Patent Laid-Open No. Hei 1-245087), a bisstyryl aryl derivative (Japanese Patent Laid-Open No. Hei 2-247278), Diazaindacene derivative, furan derivative, benzofuran derivative, phenylisobenzofuran, bis(2,4,6-trimethylphenyl)isobenzofuran, di(2- Isobenzofuran derivatives such as methylphenyl)isobenzofuran, bis(2-trifluoromethylphenyl)isobenzofuran, phenylisobenzofuran, dibenzofuran derivatives, 7-di Alkylamine coumarin derivative, 7-piperidinyl coumarin derivative, 7-hydroxycoumarin derivative, 7-methoxycoumarin Derivative, 7-acetoxycoumarin derivative, 3-benzothiazolylcoumarin derivative, 3-benzimidazolyl coumarin derivative, 3-benzoxazolylcoumarin a coumarin derivative such as a derivative, a dicyanomethylenepyran derivative, a dicyanomethylenethiopyran derivative, a polymethine derivative, a cyanine derivative, an oxabenzopyrene derivative ( Oxabenzanthracene derivative), xanthene derivative, rhodamine derivative, fluorescein derivative, pyrylium derivative, carbon styryl Derivatives, acridine derivatives, oxazine derivatives, phenyl ether derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2,5-thiadi An oxazolopurine derivative, a pyrromethene derivative, a perinone derivative, a pyrrolopyrrole derivative, a squaraine derivative, a violanthrone derivative, Phenazine derivative, acridone derivative , deazaflavin derivative, anthracene derivative and benzindene derivative, and the like.

The examples of the blue to blue-green doping materials include naphthalene, anthracene, phenanthrene, anthracene, tribenzobenzene, anthracene, anthracene, anthracene (indene), respectively. An aromatic hydrocarbon compound or a derivative thereof, furan, pyrrole, thiophene, silole, 9-silafluorene, 9,9'-spirobifluorene, benzothiophene, benzofuran, An aromatic heterocyclic compound such as hydrazine, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene or a derivative thereof, a distyrylbenzene derivative, a tetraphenylbutadiene derivative, an anthracene derivative, an aldazine derivative, a coumarin derivative, an imidazole, a thiazole, a thiadiazole, an oxazole, an oxazole , oxadiazole, triazole and other azole derivatives and metal complexes thereof and N,N'-diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diphenyl An aromatic amine derivative represented by a -1,1'-diamine or the like.

In addition, examples of the green to yellow doping materials include coumarin derivatives, phthalimide derivatives, naphthoquinone derivatives, piperidone derivatives, pyrrolopyrrole derivatives, and cyclopentadiene. a condensed tetraphenyl derivative such as a derivative, an acridone derivative, a quinacridone derivative, or a red fluorene, and further, an aryl group is introduced into a compound exemplified as the blue to blue-green doping material, A compound in which a substituent having a long wavelength can be obtained, such as a heteroaryl group, an arylvinyl group, an amine group or a cyano group, is also preferably exemplified.

Further, examples of the orange to red doping material include naphthyl imine derivatives such as bis(diisopropylphenyl)phosphonium tetracarboxylate, and piperidone derivatives, which are acetonitrile or benzamidine acetone. A rare earth complex such as Eu complex which is a ligand such as phenanthroline, 4-(dicyanomethylidene)-2-methyl-6-(p-dimethylaminostyryl)-4H -pyran or its analogue, metal phthalocyanine derivative such as magnesium phthalocyanine, aluminum chlorophthalocyanine, rhodamine compound, flazafusine derivative, coumarin derivative, quinacridone derivative, brown Oxazine derivative, oxazine derivative, quinazoline derivative, pyrrolopyridine derivative, squarylium guanidine derivative, purpurinone derivative, phenazine derivative, phenoxazinone derivative and thiadiazole Further, an aryl group, a heteroaryl group, an aryl vinyl group, an amine group, a cyano group or the like can be introduced into the compound exemplified as the blue to cyan and green to yellow doping materials. A compound having a long wavelength of a substituent may also be mentioned as a preferred example.

In addition, the dopants can be appropriately selected and used from the compounds described in the Chemical Industry, June 2004, No. 13, page, and the references cited therein.

Among the above dopant materials, an amine having an anthracene structure, an anthracene derivative, a borane derivative, an aromatic amine derivative, a coumarin derivative, a pyran derivative or an anthracene derivative is particularly preferred.

The amine having a fluorene structure is represented, for example, by the following formula. In the formula, Ar ¹ is an m-valent group derived from an aryl group having 6 to 30 carbon atoms, and Ar ² and Ar ³ are each independently an aryl group having 6 to 30 carbon atoms and at least one of Ar ¹ to Ar ³ . It has a fluorene structure, and Ar ¹ to Ar ³ may be substituted, and m is an integer of 1-4.

The amine having a fluorene structure is more preferably a diamine hydrazine represented by the following formula. In the formula, Ar ² and Ar ³ are each independently an aryl group having 6 to 30 carbon atoms, and Ar ² and Ar ³ may be substituted.

Specific examples of the aryl group having 6 to 30 carbon atoms include benzene, naphthalene, anthracene, anthracene, anthracene, phenanthrene, anthracene, fluoranthene, tribenzobenzene, anthracene, , fused tetraphenyl, anthracene, anthracene, distyrylbenzene, distyrylbiphenyl, distyrylfluorene, and the like.

Specific examples of the amine having a fluorene structure include N, N, N', N'-tetrakis (4-biphenyl)-4,4'-diamino fluorene, N, N, N', N'- Tetrakis(1-naphthyl)-4,4'-diaminopurine, N,N,N',N'-tetrakis(2-naphthyl)-4,4'-diaminopurine, N,N' -bis(2-naphthyl)-N,N'-diphenyl-4,4'-diaminopurine, N,N'-bis(9-phenanthryl)-N,N'-diphenyl- 4,4'-diaminopurine, 4,4'-bis[4"-bis(diphenylamino)styryl]-biphenyl, 1,4-bis[4'-bis(diphenyl Amino)styryl]-benzene, 2,7-bis[4'-bis(diphenylamino)styryl]-9,9-dimethylindole, 4,4'-bis (9- Ethyl-3-carbazole vinyl)-biphenyl (4,4'-bis(9-ethyl-3-carbazovinylene) biphenyl), 4,4'-bis(9-phenyl-3-carbazole vinyl) In addition, an amine having a fluorene structure described in JP-A-2003-347884, and JP-A-2001-307884 can also be used.

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 No. 2000-26324, Japanese Patent Laid-Open No. 2001-267079, and Japanese Patent Laid-Open No. 2001 Deuterium derivative described in Japanese Laid-Open Patent Publication No. 2001-267076, Japanese Patent Laid-Open No. Hei. No. 2000-34234, Japanese Patent Laid-Open No. 2001-267075, and Japanese Patent Laid-Open Publication No. 2001-217077 Things.

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-(bis(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) and the like. Further, a borane derivative described in International Publication No. 2000/40586, and the like can also be used.

The aromatic amine derivative is represented, for example, by the following formula. In the formula, Ar ⁴ is an n-valent group derived from an aryl group having 6 to 30 carbon atoms, and Ar ⁵ and Ar ⁶ are each independently an aryl group having 6 to 30 carbon atoms, and Ar ⁴ to Ar ⁶ may be substituted. Further, n is an integer of 1 to 4.

More preferably, it is an aromatic amine derivative in which Ar ⁴ is derived from hydrazine, Or a divalent group of ruthenium, Ar ⁵ and Ar ⁶ are each independently an aryl group having 6 to 30 carbon atoms, Ar ⁴ to Ar ⁶ may be substituted, and n is 2.

Specific examples of the aryl group having 6 to 30 carbon atoms include benzene, naphthalene, anthracene, anthracene, anthracene, phenanthrene, anthracene, fluoranthene, tribenzobenzene, anthracene, , thick tetraphenyl, anthracene, thick pentene and the like.

As an aromatic amine derivative, For example, N, N, N', N'-tetraphenyl -6,12-diamine, N,N,N',N'-tetra(p-tolyl) -6,12-diamine, N,N,N',N'-tetra(m-tolyl) -6,12-diamine, N,N,N',N'-tetrakis(4-isopropylphenyl) -6,12-diamine, N,N,N',N'-tetra(naphthalen-2-yl) -6,12-diamine, N,N'-diphenyl-N,N'-bis(p-tolyl) -6,12-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl) -6,12-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl) -6,12-diamine, N,N'-diphenyl-N,N'-bis(4-isopropylphenyl) -6,12-diamine, N,N'-diphenyl-N,N'-bis(4-tert-butylphenyl) -6,12-diamine, N,N'-bis(4-isopropylphenyl)-N,N'-di(p-tolyl) -6,12-diamine, etc.

Further, examples of the lanthanide series include N, N, N', N'-tetraphenylphosphonium-1,6-diamine, N,N,N',N'-tetrakis(p-tolyl)fluorene-1, 6-Diamine, N,N,N',N'-tetrakis(m-tolyl)indole-1,6-diamine, N,N,N',N'-tetrakis(4-isopropylphenyl) Indole-1,6-diamine, N,N,N',N'-tetrakis(3,4-dimethylphenyl)indole-1,6-diamine, N,N'-diphenyl-N , N'-bis(p-tolyl)indole-1,6-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl)indole-1,6-diamine , N,N'-diphenyl-N,N'-bis(4-ethylphenyl)indole-1,6-diamine, N,N'-diphenyl-N,N'-double (4 -isopropylphenyl)indole-1,6-diamine, N,N'-diphenyl-N,N'-bis(4-t-butylphenyl)phosphonium-1,6-diamine, N,N'-bis(4-isopropylphenyl)-N,N'-bis(p-tolyl)indole-1,6-diamine, N,N,N',N'-tetra (3, 4-Dimethylphenyl)-3,8-diphenylfluorene-1,6-diamine, and the like.

Further, examples of the lanthanide series include N, N, N, N-tetraphenylphosphonium-9,10-diamine, N,N,N',N'-tetrakis(p-tolyl)fluorene-9,10- Diamine, N,N,N',N'-tetrakis(m-tolyl)indole-9,10-diamine, N,N,N',N'-tetrakis(4-isopropylphenyl)anthracene- 9,10-Diamine, N,N'-diphenyl-N,N'-di(p-tolyl)fluorene-9,10-diamine, N,N'-diphenyl-N,N'- Di(m-tolyl)fluorene-9,10-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl)fluorene-9,10-diamine, N,N '-Diphenyl-N,N'-bis(4-ethylphenyl)fluorene-9,10-diamine, N,N'-diphenyl-N,N'-bis(4-isopropyl Phenyl) fluorene-9,10-diamine, N,N'-diphenyl-N,N'-bis(4-t-butylphenyl)fluorene-9,10-diamine, N,N' - bis(4-isopropylphenyl)-N,N'-bis(p-tolyl)oxime-9,10-diamine, 2,6-di-t-butyl-N,N,N', N'-tetrakis(p-tolyl)fluorene-9,10-diamine, 2,6-di-t-butyl-N,N'-diphenyl-N,N'-bis(4-isopropyl Phenyl)phosphonium-9,10-diamine, 2,6-di-t-butyl-N,N'-bis(4-isopropylphenyl)-N,N'-bis(p-tolyl)蒽-9,10-diamine, 2,6-dicyclohexyl-N,N'-bis(4-isopropylphenyl)-N,N'-bis(p-tolyl)fluorene-9,10- Diamine, 2,6-dicyclohexyl-N,N'-bis(4-isopropylphenyl)-N,N'-bis (4- Tert-butylphenyl)phosphonium-9,10-diamine, 9,10-bis(4-diphenylamino-phenyl)anthracene, 9,10-bis(4-di(1-naphthylamine) Phenyl) fluorene, 9,10-bis(4-bis(2-naphthylamino)phenyl)anthracene, 10-di-p-tolylamino-9-(4-di-p-tolylamine -1--1-naphthyl)anthracene, 10-diphenylamino-9-(4-diphenylamino-1-naphthyl)anthracene, 10-diphenylamino-9-(6-diphenyl Aminoamino-2-naphthyl)anthracene and the like.

Further, examples of the lanthanide series include N, N, N, N-tetraphenyl-1,8-fluorene-1,6-diamine, N-biphenyl-4-yl-N-biphenyl-1,8 -芘-1,6-diamine, N ¹ ,N ⁶ -diphenyl-N ¹ ,N ⁶ -bis-(4-trimethyldecyl-phenyl)-1H,8H-芘-1,6 - Diamine and the like.

Further, in addition to the above, [4-(4-diphenylamino-phenyl)naphthalen-1-yl]-diphenylamine, [6-(4-diphenylamino-phenyl) Naphthalen-2-yl]-diphenylamine, 4,4'-bis[4-diphenylaminonaphthalen-1-yl]biphenyl, 4,4'-bis[6-diphenylaminonaphthalene -2-yl]biphenyl, 4,4"-bis[4-diphenylaminonaphthalen-1-yl]-para-triphenyl, 4,4"-bis[6-diphenylaminonaphthalene-2 -Based]-Phed triphenyl and the like. Further, an aromatic amine derivative described in JP-A-2006-156888 or the like can also be used.

Examples of the coumarin derivative include coumarin-6, coumarin-334, and the like. In addition, the coumarin derivative described in JP-A-2004-43646, JP-A-2001-76876, and JP-A-H06-298758 can also be used.

The pyran derivative may, for example, be 4-dicyanomethylene-2-methyl-6-p-dimethylaminostyryl-4H-pyran (4-(dicyanomethylene)-2-methyl-6-). [p-(dimethylamino)-styryl]-4H-pyran, DCM), 4-(dicyanomethylidene)-2-tert-butyl-6-(1,1,7,7-tetramethyl for a long time 4-(Dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidin-4-vinyl)-4H-pyran, DCJTB )Wait. In addition, Japanese Patent Laid-Open Publication No. 2005-126399, Japanese Patent Laid-Open No. Hei. No. 2005-097283, Japanese Patent Laid-Open No. Hei 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.

<Electron Injection Layer and Electron Transport Layer in Organic Electric Field Light-Emitting Element> The electron injection layer 107 functions to efficiently inject electrons moved from the cathode 108 into the light-emitting layer 105 or the electron transport layer 106. The electron transport layer 106 serves 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 are formed by laminating and mixing one or two or more electron transport/injection materials, respectively, or by a mixture of an electron transport/injection material and a polymer binder.

The electron injection/transport layer refers to a layer that functions to inject electrons from the cathode and further transport electrons. It is desirable that the electron injection efficiency is high and the injected electrons are efficiently transported. Therefore, it is preferable that the electron affinity is large, the electron mobility is large, and the stability is excellent, and it is difficult to generate impurities which are traps at the time of production and use. However, in consideration of the case where the transmission balance between the hole and the electron is mainly performed in the case where the hole from the anode can be efficiently prevented from flowing to the cathode side without being combined, even if the electron transporting ability is not so high. It also has the same effect of improving luminous efficiency as a material with high electron transport capability. Therefore, the electron injecting/transporting layer in the present embodiment may also include a function of a layer that can efficiently prevent the movement of the hole.

The material (electron transport material) forming the electron transport layer 106 or the electron injection layer 107 can be arbitrarily selected from the following compounds: a compound conventionally used as an electron transport compound in a photoconductive material, and electron injection of an organic electric field light-emitting element. Well-known compounds used in layers and electron transport layers.

The material used in the electron transport layer or the electron injecting layer preferably contains at least one selected from the group consisting of a compound containing an aromatic ring or a heteroaromatic ring (the above aromatic ring or heteroaromatic ring contains a carbon, hydrogen, oxygen, or the like). One or more atoms of sulfur, antimony and phosphorus), a pyrrole derivative and a condensed ring derivative thereof, and a metal complex having an 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, a piperidone derivative, and a fragrance. Bean derivatives, naphthoquinone derivatives, anthracene derivatives such as hydrazine or diphenyl hydrazine, phosphorus oxide derivatives, carbazole derivatives, anthracene derivatives, and the like. Examples of the metal complex having an electron-accepting nitrogen include a hydroxyzole complex such as a hydroxyphenyl oxazole complex, an azomethine complex, a tropolone metal complex, and a flavonoid. A flavonol metal complex, a benzoquinoline metal complex, and the like. These materials can be used alone or in combination with different materials.

Further, specific examples of the other electron transporting compound include a pyridine derivative, a naphthalene derivative, an anthracene derivative, a phenanthroline derivative, a piperidone derivative, a coumarin derivative, a naphthoquinone derivative, and an anthracene. Derivatives, diphenyl hydrazine derivatives, diphenyl hydrazine derivatives, anthracene derivatives, oxadiazole derivatives (1,3-bis[(4-tert-butylphenyl) 1,3,4-oxadiazole Benzene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4-triazole, etc.), thiadiazole derivatives, 8-hydroxyquinoline a metal complex of an oxine derivative, a hydroxyquinoline metal complex, a quinoxaline derivative, a polymer of a quinoxaline derivative, a benzazole compound, a gallium complex, Pyrazole derivatives, perfluorinated benzene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis(benzo[h]quinolin-2-yl)-9 , 9'-spirobiguanidine, etc., imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris(N-phenylbenzimidazol-2-yl)benzene, etc.), benzoxazole derivatives , benzothiazole derivatives, quinoline derivatives, triplet Oligopyridine derivative, bipyridine derivative, terpyridine derivative (1,3-bis(4'-(2,2':6'2"-tripyridyl))benzene, etc.), naphthalene a pyridine derivative (bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide, etc.), an aldehyde nitrogen derivative, a carbazole derivative, an anthracene derivative, Phosphorus oxide derivatives, bisstyryl derivatives, and the like.

Further, a metal complex having an electron-accepting nitrogen may be used, and examples thereof include a hydroxyquinoline compound such as a hydroxyquinoline metal complex or a hydroxyphenyl oxazole complex, and an azomethine group. 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.

Among the above materials, a hydroxyquinoline metal complex, a bipyridine derivative, a phenanthroline derivative or a borane derivative is preferred.

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, Ga, Be or Zn, and n is an integer of 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-triphenyl) Phenol) 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-naphthol) Aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(2-phenylphenol)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(3-phenylphenol) Aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(4-phenylphenol)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline) (3,5-dimethyl Phenol) aluminum, bis(2,4-dimethyl-8-hydroxyquinoline) (3,5-di-tert-butylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) aluminum -μ-oxo-bis(2-methyl-8-hydroxyquinoline)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)aluminum-μ-oxo-bis(2,4- Dimethyl-8-hydroxyquinoline)aluminum, bis(2-methyl-4-ethyl-8-hydroxyquinoline)aluminum-μ-oxo-bis(2-methyl-4-ethyl-8 -hydroxyquinoline)aluminum, bis(2-methyl-4-methoxy-8-hydroxyquinoline)aluminum-μ-oxo-bis(2-methyl-4-methoxy-8-hydroxyquine Porphyrin) aluminum, bis(2-methyl-5-cyano-8-hydroxyquinoline)aluminum-μ-oxo-bis(2-methyl-5-cyano-8-hydroxyquinoline) aluminum, double (2-methyl-5-trifluoromethyl-8-hydroxyquine ) Aluminum -μ- oxo - bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum, bis (10-hydroxybenzo [h] quinoline) beryllium.

The bipyridine derivative is a compound represented by the following formula (E-2). In the formula, G represents a single bond or an n-valent linking group, and n is an integer of 2 to 8. In addition, carbon atoms which are not used for the bonding of pyridine-pyridine or pyridine-G may be substituted.

G of the general formula (E-2) is exemplified by the following structural formula. Further, R in the following structural formula is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenyl or triphenylene. (terphenyl).

Specific examples of the pyridine derivative include 2,5-bis(2,2'-pyridin-6-yl)-1,1-dimethyl-3,4-diphenylsulfol, 2,5-double (2,2'-Pyridin-6-yl)-1,1-dimethyl-3,4-di(2,4,6-trimethylphenyl)thiazole, 2,5-bis (2,2' -pyridin-5-yl)-1,1-dimethyl-3,4-diphenylthiazole, 2,5-bis(2,2'-pyridin-5-yl)-1,1-dimethyl Base-3,4-bis(2,4,6-trimethylphenyl)thiazole, 9,10-bis(2,2'-pyridin-6-yl)anthracene, 9,10-di(2,2' -pyridin-5-yl)anthracene, 9,10-bis(2,3'-pyridin-6-yl)anthracene, 9,10-di(2,3'-pyridin-5-yl)anthracene, 9,10 - bis(2,3'-pyridin-6-yl)-2-phenylindole, 9,10-bis(2,3'-pyridin-5-yl)-2-phenylindole, 9,10-di (2,2'-Pyridin-6-yl)-2-phenylindole, 9,10-bis(2,2'-pyridin-5-yl)-2-phenylindole, 9,10-di(2) , 4'-pyridyl-6-yl)-2-phenylindole, 9,10-bis(2,4'-pyridin-5-yl)-2-phenylindole, 9,10-di(3,4 '-Pyridin-6-yl)-2-phenylindole, 9,10-bis(3,4'-pyridin-5-yl)-2-phenylindole, 3,4-diphenyl-2,5 - bis(2,2'-pyridin-6-yl)thiophene, 3,4-diphenyl-2,5-di(2,3'-pyridin-5-yl)thiophene, 6'6"-di ( 2-pyridyl) 2,2':4',4":2",2"'-tetrapyridine, and the like.

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 single bond or an 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 morpholine 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-bi(1,10-morpholin-5-yl), 2,9-dimethyl-4,7-biphenyl-1,10-o-di Bathocuproin or 1,3-bis(2-phenyl-1,10-morpholin-9-yl)benzene.

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

The borane derivative is a compound represented by the following formula (E-4), and is disclosed in detail in Japanese Laid-Open Patent Publication No. 2007-27587. Wherein R ¹¹ and R ¹² are each independently at least one of a hydrogen atom, an alkyl group, a substituted aryl group, a substituted fluorenyl group, a substituted nitrogen-containing heterocyclic group or a cyano group, R ¹³ ～ R ^{16 is} each independently a substitutable alkyl group or a substitutable aryl group, X is a substitutable extended aryl group, and Y is a substitutable aryl group having 16 or less carbon atoms, a substituted boron group or The carbazolyl group which may be substituted, and each of n is independently an integer of 0 to 3.

Among the compounds represented by the above formula (E-4), a compound represented by the following formula (E-4-1) is preferred, and a compound of the following formula (E-4-1-1) is further preferably used. 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 at least one of a hydrogen atom, an alkyl group, a substituted aryl group, a substituted fluorenyl group, a substituted nitrogen-containing heterocyclic group or a cyano group, R ¹³ ～ R ^{16 is} each independently a substitutable alkyl group or a substitutable aryl group, and R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group, a substituted aryl group, a substituted decyl group, or the like. At least one of the substituted nitrogen-containing heterocyclic group or the cyano group, X ¹ is a substitutable aryl group having 20 or less carbon atoms, and n is independently an integer of 0 to 3, and m is independently 0 to 4, respectively. Integer.

In each formula, R ³¹ to R ³⁴ are each independently a methyl group, an isopropyl group or a phenyl group, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl. Either.

Among the compounds represented by the above formula (E-4), a compound represented by the following formula (E-4-2) is preferred, and further preferably a compound of the following formula (E-4-2-1) The compound represented. Wherein R ¹¹ and R ¹² are each independently at least one of a hydrogen atom, an alkyl group, a substituted aryl group, a substituted fluorenyl group, a substituted nitrogen-containing heterocyclic group or a cyano group, R ¹³ ～ R ^{16 is} independently a substitutable alkyl group or a substitutable aryl group, and X ¹ is a substitutable aryl group having 20 or less carbon atoms, 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 R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl. One.

Among the compounds represented by the above formula (E-4), a compound represented by the following formula (E-4-3) is preferred, and more preferably a compound of the following formula (E-4-3-1) or A compound represented by the formula (E-4-3-2). Wherein R ¹¹ and R ¹² are each independently at least one of a hydrogen atom, an alkyl group, a substituted aryl group, a substituted fluorenyl group, a substituted nitrogen-containing heterocyclic group or a cyano group, R ¹³ ～ R ^{16 is} independently a substitutable alkyl group or a substitutable aryl group, X ¹ is a substitutable aryl group having 10 or less carbon atoms, and Y ¹ is a substitutable aryl group having 14 or less carbon atoms. Further, n is independently an integer of 0 to 3, respectively.

In each formula, R ³¹ to R ³⁴ are each independently a methyl group, an isopropyl group or a phenyl group, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl. Either.

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 a substituted aryl group having 6 to 30 carbon atoms. Particularly preferred is a benzimidazole derivative in which Ar ¹ is a fluorenyl group which may 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, fluorene -1-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-9-yl, indol-1-yl, indol-2-yl, 1-phenanthryl, 2-phenanthryl , 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-indenyl, 2-indenyl, 9-fluorenyl, fluoren-1-yl, fluoran-2-yl, fluorene-3- Base, fluorescein-7-yl, fluoren-8-yl, tribenzoacyl-1-yl, tribenzoacyl-2-yl, indol-1-yl, indol-2-yl, fluorene-4- base, -1-base, -2-base, -3-based, -4-base, -5-based, -6-yl, fused tetraphenyl-1-yl, fused tetraphenyl-2-yl, fused tetraphenyl-5-yl, indol-1-yl, indol-2-yl, ind-3-yl, fused pentabenzene -1-yl, fused penta-2-yl, fused pentaphenyl-5-yl, fused pentaphenyl-6-yl.

A specific example of a benzimidazole derivative is 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)fluorene-9 -yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 5-(10-(naphthalen-2-yl)fluoren-9-yl)-1,2-diphenyl-1H- Benzo[d]imidazole, 1-(4-(10-(naphthalen-2-yl)fluoren-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)indol-2-yl )-1,2-diphenyl-1H-benzo[d]imidazole.

The electron transport layer or the electron injecting layer may further contain a substance which can reduce a material forming the electron transport layer or the electron injecting layer. The reducing substance may have various kinds of materials as long as it has a certain reducing property. For example, oxidation of an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, or an alkaline earth metal can be preferably used. In a group consisting of a halide of an alkaline earth metal, an oxide of a rare earth metal, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal At least one.

Preferred reducing materials 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. Alkaline earth metals (work function 2.9 eV), Sr (work function 2.0 eV to 2.5 eV) or Ba (work function 2.52 eV), especially those with 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, and further preferably Rb or Cs, and most preferably Cs. The alkali metal has a particularly high reducing ability, and can be added to a material forming the electron transport layer or the electron injecting layer in a relatively small amount to improve the luminance of the light emitted from the organic EL element or to extend the life thereof. Further, a reducing substance having a work function of 2.9 eV or less is preferably a combination of two or more of these alkali metals, and particularly preferably a combination containing Cs such as Cs and Na, Cs and K, Cs and Rb, or Cs. Combined with Na and K. By containing Cs, the reducing ability can be effectively 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 in Organic Electric Field Light-Emitting 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 that of the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, barium, 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 characteristics of the element, 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 mostly unstable in the atmosphere. In order to improve this aspect, for example, there is known a method in which a small amount of lithium, barium or magnesium is doped into an organic layer, and an electrode having high stability is used. As the other dopant, an inorganic salt such as lithium fluoride, cesium fluoride, lithium oxide or cerium oxide can also be used. However, it is not limited to these.

Further, a preferred example is as follows: in order to protect the electrode, a metal such as platinum, gold, silver, copper, iron, tin, aluminum, or indium or an alloy using these metals, and ceria, titania, and nitridation are laminated. An inorganic substance such as hydrazine, polyvinyl alcohol, vinyl chloride, or a hydrocarbon-based polymer compound. The method for producing the electrodes is not particularly limited as long as it can be electrically connected, such as resistance heating, electron beam, sputtering, ion plating, and coating.

<Coating Agent Usable in Each Layer> The materials used in the above hole injection layer, hole transport layer, light-emitting layer, electron transport layer, and electron injection layer may be used alone to form respective layers, or may be dispersed as a polymer bond. Used in the following resins: polyvinyl chloride, polycarbonate, polystyrene, poly(N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polyfluorene, Polyphenylene ether, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamine, ethyl cellulose, vinyl acetate resin, acrylonitrile-butadiene-Styrene (ABS) a solvent-soluble resin such as a resin or a polyurethane resin, or a phenol resin, a xylene resin, a petroleum resin, a urea resin, a melamine resin, an unsaturated polyester resin, an alkyd resin, an epoxy resin, an anthrone resin, or the like. Curable resin, etc.

<Method for Producing Organic Electric Field Light-Emitting Element> Each layer constituting the organic electro-field light-emitting element can be formed by vapor deposition method, resistance heating vapor deposition, electron beam evaporation, sputtering, molecular layering method, printing method, or spin A material such as a coating method, a casting method, a coating method, or the like 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 properties 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. When the film is formed by vapor deposition, the vapor deposition conditions differ depending on the type of the material, the crystal structure for forming the film, and the association structure. The evaporation condition is usually preferably at a heating temperature of the boat of +50 ° C to +400 ° C, a vacuum of 10 ^-6 Pa to 10 ^-3 Pa, an evaporation rate of 0.01 nm / s to 50 nm / s, a substrate temperature - It is set as appropriate within the range of 150 ° C to +300 ° C and a film thickness of 2 nm to 5 μm.

Then, as an example of a method of fabricating an organic electric field light-emitting element, an organic electric field including an anode/hole injection layer/hole transport layer/a light-emitting layer/electron transport layer/electron injection layer/cathode containing a host material and a dopant material The method of producing the light-emitting element will be described. A thin film of an anode material is formed on a suitable substrate by a vapor deposition method or the like to form an anode, and then a film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-deposited to form a thin film as a light-emitting layer, an electron transport layer and an electron injection layer are formed on the light-emitting layer, and a film containing a cathode material is formed as a cathode by a vapor deposition method or the like. Thereby, the target organic electric field light-emitting element can be obtained. Further, in the production of the 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 element obtained in this way, a DC voltage may be applied to the anode in a positive (+) polarity and a cathode in a negative (-) polarity, and a voltage of about 2 V to 40 V may be applied. At the voltage, luminescence is observed from the transparent or translucent electrode side (anode or cathode and both). Further, the organic electroluminescent element emits light when a pulse current or an alternating current is applied. Furthermore, the applied AC waveform can be arbitrary.

<Application Example of Organic Electric Field Light-Emitting Element> The present invention can also be applied to a display device including an organic electric field light-emitting element or an illumination device including an organic electric field light-emitting element. A display device or an illumination device including 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 drive device, and DC drive, pulse wave drive, AC drive, etc. can be suitably used. The driving method to drive.

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

The matrix means that the pixels for display are two-dimensionally arranged in a lattice shape or a mosaic shape, and characters or images are displayed in a set of pixels. The shape or size of the pixels is determined according to the purpose. For example, in a video display and a character display of a personal computer, a monitor, and a television, a quadrangular 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. Use a pixel whose side is an order of mm. In the case of monochrome display, it is only necessary to arrange pixels of the same color, and in the case of color display, red, green, and blue pixels are arranged and displayed. In this case, there are typically a delta type and a stripe type. Moreover, the driving method of the matrix may be any one of a line sequential driving method or an active matrix. In the case of the line sequential driving, there is an advantage that the structure is simple, but in the case of considering the operational characteristics, the active matrix may be more excellent in the case of the active matrix, and therefore the driving method must also be used depending on the use.

In the segment mode (type), a pattern is formed so as to display predetermined information, and the determined region is illuminated. For example, the time or temperature display of a digital timepiece or a thermometer, the operation state display of an audio equipment, an induction cooker, etc., and the panel display of an automatic vehicle, etc. are mentioned.

For example, a lighting device such as an indoor lighting device, a backlight of a liquid crystal display device, or the like can be used. 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 the purpose of improving the visibility of a display device that does not emit light, and can be used in a liquid crystal display device, a timepiece, an audio device, an automatic car panel, a display panel, a logo, and the like. In particular, as a liquid crystal display device and a backlight for a personal computer which is a problem of thinning, the backlight of the related art is difficult to be thinned by including a fluorescent lamp or a light guide plate, and in consideration of this, the backlight of the light-emitting element of the present embodiment is used. The thin shape and light weight are characteristic.

[Examples] First, a synthesis example of the ruthenium compound used in the examples will be described below.

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

Synthesis of <9-(2,5-dichlorophenyl)-10-phenylindole> 2-bromo-1,4-dichlorobenzene 15 g, (10-phenylindole-9) under a nitrogen atmosphere -base) 19.8 g of boric acid, 1.53 g of tetrakis(triphenylphosphine)palladium(0)(Pd(PPh ₃ ) ₄ ), 28.19 g of potassium phosphate and 260 ml of a mixed solvent of toluene and ethanol (toluene/ethanol = 4/1 (Volume ratio)) was added to the flask and stirred for 5 minutes. Thereafter, 26 ml of water was added and refluxed for 15 hours. After the completion of the heating, the reaction solution was cooled, and 50 ml of water was added. Thereafter, the reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, and then the desiccant was removed, and the solvent was distilled off under reduced pressure, and the obtained crude product was subjected to short column purification (solvent: toluene) by silica gel. . Further, reprecipitation was carried out with methanol to obtain 18-(2,5-dichlorophenyl)-10-phenylindole as an intermediate compound (yield: 68%).

Synthesis of <9-([1,1':4',1"-bitriphenyl]-2'-yl)-10-phenylindole> 9-(2) as an intermediate compound under nitrogen atmosphere , 5-dichlorophenyl)-10-phenylindole 5 g, phenylboronic acid 4.55 g, bis(dibenzylideneacetone)palladium(0)(Pd(dba) ₂ )0.719 g, tricyclohexylphosphine ( PCy ₃ ) 0.526 g, potassium phosphate 10.61 g and toluene 50 ml were added to the flask and stirred for 5 minutes. Thereafter, 10 ml of water was added and refluxed for 15 hours. After the completion of the heating, the reaction solution was cooled, water was added, and filtration was carried out. The solid portion was used as the crude product 1. The organic layer of the filtrate portion was separated, dried over anhydrous sodium sulfate, and then the desiccant was removed, and the solvent was distilled off under reduced pressure to obtain the obtained solid as crude product 2. Then, the crude product 1 was The crude product 2 was combined and purified by a short column (solvent: toluene), followed by washing with methanol, recrystallization from toluene, and sublimation purification to obtain the target compound represented by the formula (1-1). 9-([1,1':4',1"-bitriphenyl]-2'-yl)-10-phenylindole 2.63 g (yield: 44%).

The structure of the compound (1-1) was confirmed by Mass Spectrometry (MS) spectrum and Nuclear Magnetic Resonance (NMR) measurement. ¹ H-NMR (CDCl ₃ ) : δ = 7.90 to 7.88 (dd, 1H), 7.77 to 7.70 (m, 6H), 7.62 to 7.51 (m, 5H), 7.45 to 7.40 (m, 4H), 7.36 to 7.24 (m, 5H), 7.06~7.04 (m, 2H), 6.92~6.87 (m, 3H).

Further, the glass transition temperature (Tg) of the compound (1-1) was 97.3 °C. [Measurement equipment: Diamond Differential Scanning Calorimetry (DSC) (manufactured by PERKIN-ELMER); measurement conditions: cooling rate 200 ° C / min., temperature increase rate 10 °C/Min.] Further, the measurement of the glass transition temperature of the following compounds was carried out under the same conditions.

<Synthesis Example of Compound represented by Formula (1-301)>

Synthesis of <9-(3,4-dichlorophenyl)-10-phenylindole> 4-Bromo-1,2-dichlorobenzene 15.8 g, (10-phenylindole-9) under nitrogen atmosphere -base) 20.9 g of boric acid, 1.66 g of tetrakis(triphenylphosphine)palladium(0)(Pd(PPh ₃ ) ₄ ), 29.7 g of potassium phosphate and 280 ml of a mixed solvent of toluene and ethanol (toluene/ethanol = 9/1 (Volume ratio)) was added to the flask and stirred for 5 minutes. Thereafter, 28 ml of water was added and refluxed for 5 hours. After the completion of the heating, the reaction solution was cooled, and 100 ml of water was added. Thereafter, the reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, and then the desiccant was removed, and the solvent was distilled off under reduced pressure, and the obtained crude product was subjected to short column purification (solvent: toluene). Further, reprecipitation was carried out with methanol to obtain 9-(3,4-dichlorophenyl)-10-phenylindole 12 g as an intermediate compound (yield: 43%).

Synthesis of <9-([1,1':2',1"-bitriphenyl]-4'-yl)-10-phenylindole> 9-(3) as an intermediate compound under nitrogen atmosphere , 4-dichlorophenyl)-10-phenylindole 5 g, phenylboronic acid 4.55 g, bis(dibenzylideneacetone)palladium(0)(Pd(dba) ₂ )0.719 g, tricyclohexylphosphine ( PCy ₃ ) 0.526 g, potassium phosphate 10.61 g and toluene 50 ml were added to the flask and stirred for 5 minutes. Thereafter, 5 ml of water was added and refluxed for 5 hours. After the completion of the heating, the reaction solution was cooled, and 50 ml of methanol was added to precipitate. The precipitate is washed with methanol and water to obtain a crude product of the target compound represented by the formula (1-301). The crude product is subjected to short column purification (solvent: toluene), and then recrystallized with toluene. Further, sublimation purification is carried out to obtain 9-([1,1':2',1"-bitriphenyl]-4'-yl)-10-phenylindole as a target compound represented by the formula (1-301). 4.59 g (yield: 76%).

The structure of the compound (1-301) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 7.91 to 7.89 (m, 2H), 7.72 to 7.70 (m, 2H), 7.66 (d, 1H), 7.63 to 7.47 (m, 7H), 7.40 to 7.18 (m , 14H).

Further, the glass transition temperature (Tg) of the compound (1-301) was 110.1 °C.

<Synthesis Example of Compound represented by Formula (1-307)>

Synthesis of <9-(4,4"-bis(naphthalen-1-yl)-[1,1':2',1"-bitriphenyl]-4'-yl)-10-phenylindole > 9-(3,4-dichlorophenyl)-10-phenylindole 3.99 g, 4-(naphthalen-1-yl)phenylboronic acid 5.46 g as an intermediate compound, double (secondary) Benzylacetone) palladium (0) (Pd(dba) ₂ ) 0.575 g, tricyclohexylphosphine (PCy ₃ ) 0.421 g, potassium phosphate 8.49 g, and toluene 50 ml were added to the flask, and stirred for 5 minutes. Thereafter, 5 ml of water was added and refluxed for 5 hours. After the completion of the heating, the reaction solution was cooled, 50 ml of methanol was added, and the precipitate was filtered. Further, the precipitate was washed with methanol and water to obtain a crude product of the target compound represented by formula (1-307). This crude product was subjected to short column purification (solvent: toluene) with hydrazine, and then recrystallized from toluene, followed by sublimation purification to obtain 9-(4, 4" as a target compound represented by formula (1-307). -Bis(naphthalen-1-yl)-[1,1':2',1"-bitriphenyl]-4'-yl)-10-phenylindole 5.1 g (yield: 69.4%).

The structure of the compound (1-307) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 7.99 to 7.97 (m, 3H), 7.92 (d, 1H), 7.88 (d, 3H), 7.84 (d, 2H), 7.75 to 7.73 (m, 3H), 7.64~7.61 (m, 3H), 7.58~7.32 (m, 23H).

Further, the glass transition temperature (Tg) of the compound (1-307) was 147.6 °C.

<Synthesis Example of Compound represented by Formula (1-3)>

<9-([1,1':3',1":4",1'":3'",1""-pentaphenyl]-2"-yl)-10-phenylindole (9- Synthesis of ([1,1':3',1":4",1'":3'",1""-quinquephenyl]-2"-yl)-10-phenyl anthracene) > Under nitrogen atmosphere, 9-(2,5-dichlorophenyl)-10-phenylindole 2 g as an intermediate compound, 2.98 g of 3-biphenylboronic acid, and 0.11 g of palladium(II) acetate (Pd(OAc) ₂ ), 0.31 g of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 4.25 g of tripotassium phosphate and a mixed solvent of 1,2,4-trimethylbenzene and tert-butanol 23 ml ( 1,2,4-Trimethylbenzene/tert-butanol = 10/1 (volume ratio) was added to the flask and stirred for 5 minutes. Thereafter, 3 ml of water was added and refluxed for 8 hours. After the completion of the heating, the reaction liquid was cooled, water was added, and the organic layer was separated, and the organic layer was subjected to short column purification (solvent: toluene). Thereafter, the mixture was washed with methanol, recrystallized from ethyl acetate, and purified by column chromatography (solvent: toluene / heptane = 1/3 (volume ratio)). Finally, sublimation purification is carried out to obtain 9-([1,1':3',1":4",1'":3'",1""- as the target compound represented by the formula (1-3). Pentaphenyl]-2"-yl)-10-phenylindole 1.83 g (yield: 57.5%).

The structure of the compound (1-3) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 7.98 (dd, 1H), 7.94 (d, 1H), 7.87 (d, 1H), 7.83 to 7.79 (m, 3H), 7.73 to 7.72 (m, 1H), 7.66~7.42 (m, 12H), 7.36~7.23 (m, 7H), 7.16~7.08 (m, 6H), 6.68~6.65 (m, 2H).

Further, the glass transition temperature (Tg) of the compound (1-3) was 104.1 °C.

<Synthesis Example of Compound represented by Formula (1-23)>

Synthesis of <9-(5-chloro-2-methoxyphenyl)-10-phenylindole> (5-chloro-2-methoxyphenyl)boronic acid 12.59 g, 9- under nitrogen atmosphere Bromo-10-phenylindole 15 g, tetrakis(triphenylphosphine)palladium(0)(Pd(PPh ₃ ) ₄ )1.56 g, tripotassium phosphate 19.11 g and 1,2,4-trimethylbenzene and 182 ml of a mixed solvent of tributanol (1,2,4-trimethylbenzene/tert-butanol = 10/1 (volume ratio)) was added to the flask and stirred for 5 minutes. Thereafter, 17 ml of water was added and refluxed for 15 hours. After the completion of the heating, the reaction solution was cooled, and 100 ml of water was added. Thereafter, filtration was carried out to obtain a solid portion as the crude product 1. The organic layer of the filtrate fraction was separated, dried over anhydrous sodium sulfate, and then the desiccant was removed, and the solvent was distilled off under reduced pressure to give the obtained solid as crude product 2. Thereafter, the crude product 1 was combined with the crude product 2, and subjected to short column purification with a silicone resin (solvent: toluene). Further, reprecipitation was carried out with heptane to obtain the intermediate compound 9-(5-chloro-2-methoxyphenyl)-10-phenylindole 16.5 g (yield: 93%).

Synthesis of <9-(4-methoxy-[1,1':3',1"-bitriphenyl]-3-yl)-10-phenylindole > Intermediate compound 9 under nitrogen atmosphere -(5-chloro-2-methoxyphenyl)-10-phenylindole 5 g, 3-biphenylboronic acid 3.01 g, bis(dibenzylideneacetone)palladium(0)(Pd(dba) ₂ ) 0.36 g, 0.37 g of tricyclohexylphosphine (PCy ₃ ), 5.38 g of tripotassium phosphate and 50 ml of o-xylene were added to the flask and stirred for 5 minutes. Thereafter, 5 ml of water was added and refluxed for 8 hours. The reaction solution was cooled, water was added, and the organic layer was separated, dried over anhydrous sodium sulfate, and then the desiccant was removed, and the solvent was distilled off under reduced pressure, and the obtained solid was subjected to column purification with a silica gel (solvent: heptane / toluene = 2/1 (capacity ratio)), the intermediate compound 9-(4-methoxy-[1,1':3',1"-bitriphenyl]-3-yl)-10-phenylindole 6.3 was obtained. g (yield: 97%).

Synthesis of <3-(10-phenylfluoren-9-yl)-[1,1':3',1"-bitriphenyl]-4-ol > Intermediate compound 9-( under nitrogen atmosphere) 4-methoxy-[1,1':3',1"-bitriphenyl]-3-yl)-10-phenylindole 6.3 g, pyridine hydrochloride 7.1 g and 1-methyl-2- 6 ml of pyrrolidone was added to the flask and heated at 175 ° C for 4 hours. After the completion of the heating, the reaction solution was cooled, and 100 ml of water was added thereto, and the precipitate was filtered. Further, the precipitate was washed with water, and the obtained crude product was subjected to short column purification (solvent: toluene/ethyl acetate = 2/1 (volume ratio)) to obtain the intermediate compound 3-(10-phenylindole-9). -Base)-[1,1':3',1"-bitriphenyl]-4-ol 6.1 g (yield: 99%).

<Synthesis of 3-(10-phenylfluoren-9-yl)-[1,1':3',1"-biphenyl]-4-yl trifluoromethanesulfonate> Under nitrogen atmosphere, Adding the intermediate compound 3-(10-phenylfluoren-9-yl)-[1,1':3',1"-bitriphenyl]-4-ol 6.1 g and pyridine 33 ml to the flask, cooling After the temperature reached 0 ° C, 6.9 g of trifluoromethanesulfonic anhydride was slowly added dropwise. Thereafter, the reaction solution was stirred at 0 ° C for 30 minutes and at room temperature for 2 hours. Then, water was added to the reaction liquid, and the precipitate was filtered. The obtained crude product was subjected to short column purification (solvent: toluene) with oxime, and then washed with heptane to obtain the intermediate compound 3-(10-phenylfluoren-9-yl)-trifluoromethanesulfonate-[ 1,1': 3',1"-bitriphenyl]-4-yl ester 7.67 g (yield: 99%).

Synthesis of <9-([1,1':3',1":4",1'"-biphenylene]-3"-yl)-10-phenylindole > Intermediates under nitrogen atmosphere Compound trifluoromethanesulfonate-3-(10-phenylfluoren-9-yl)-[1,1':3',1"-biphenyl]-4-yl ester 1.4 g, phenylboronic acid 0.41 g Palladium(II) acetate (Pd(OAc) ₂ ) 0.05 g, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl 0.14 g, tripotassium phosphate 0.94 g, potassium bromide 0.53 g And a mixed solvent of 1,2,4-trimethylbenzene and tert-butanol, 14 ml (1,2,4-trimethylbenzene / tert-butanol = 10/1 (volume ratio)) was added to the flask. After stirring for 5 minutes, 2 ml of water was added and refluxed for 6 hours. After the completion of the heating, the reaction liquid was cooled, water was added, and the organic layer was separated, and the organic layer was subjected to a short column purification (solvent: toluene). Thereafter, the mixture was washed with methanol, recrystallized from ethyl acetate, and purified by column chromatography (solvent: toluene / heptane = 1/3 (volume ratio)). Finally, sublimation purification was carried out to obtain the formula (1). -23) 9-([1,1':3',1":4",1'"-biphenyl]-3"-yl)-10-phenylindole 0.57 g of the target compound represented ( Yield: 46%).

The structure of the compound (1-23) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 7.96 (dd, 1H), 7.91 (t, 1H), 7.78 to 7.74 (m, 4H), 7.71 to 7.69 (m, 1H), 7.64 to 7.50 (m, 9H) ), 7.45~7.40 (m, 4H), 7.36~7.25 (m, 5H), 7.07~7.05 (m, 2H), 6.95~6.88 (m, 3H).

Further, the glass transition temperature (Tg) of the compound (1-23) was 102.9 °C.

<Synthesis Example of Compound represented by Formula (1-53)>

Synthesis of <9-((4-naphthalen-1-yl)-[1,1':3',1"-bitriphenyl]-3-yl)-10-phenylindole > under nitrogen atmosphere, Intermediate compound 3-(10-phenylfluoren-9-yl)-[1,1':3',1"-biphenyl]-4-yl trifluoromethanesulfonate 3.2 g, 1-naphthalene 1.31 g of boric acid, 0.11 g of palladium(II) acetate (Pd(OAc) ₂ ), 0.31 g of 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, 2.15 g of tripotassium phosphate, bromination Potassium 1.21 g and a mixed solvent of 1,2,4-trimethylbenzene and tert-butanol 24 ml (1,2,4-trimethylbenzene / tert-butanol = 5 / 1 (capacity ratio)) Stir into the flask for 5 minutes. Thereafter, 4 ml of water was added and refluxed for 8 hours. After the completion of the heating, the reaction liquid was cooled, water was added, and the organic layer was separated, and the organic layer was subjected to short column purification (solvent: toluene). Thereafter, the mixture was washed with methanol, recrystallized from ethyl acetate, and purified by column chromatography (solvent: toluene / heptane = 1 / 5 (volume ratio)). Finally, sublimation purification was carried out to obtain 9-((4-naphthalen-1-yl)-[1,1':3',1"-biphenyl]- as the target compound represented by the formula (1-53). 3-yl)-10-phenylindole 1.42 g (yield: 46%).

The structure of the compound (1-53) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 8.13 (d, 1H), 8.02 to 7.97 (m, 3H), 7.92 (d, 1H), 7.78 to 7.75 (m, 3H), 7.66 to 7.27 (m, 20H) ), 7.03~6.93 (m, 3H), 6.87~6.84 (t, 1H).

Further, the glass transition temperature (Tg) of the compound (1-53) was 122.8 °C.

<Synthesis Example of Compound represented by Formula (1-83)>

Synthesis of <9-((4-naphthalen-2-yl)-[1,1':3',1"-bitriphenyl]-3-yl)-10-phenylindole > under nitrogen atmosphere, Intermediate compound 3-(10-phenylfluoren-9-yl)-[1,1':3',1"-biphenyl]-4-yl trifluoromethanesulfonate 1.4 g, 2-naphthalene Boric acid 0.57 g, palladium(II) acetate (Pd(OAc) ₂ ) 0.05 g, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl 0.14 g, tripotassium phosphate 0.94 g, bromination Potassium 0.53 g and a mixed solvent of 1,2,4-trimethylbenzene and tert-butanol 14 ml (1,2,4-trimethylbenzene / tert-butanol = 10/1 (capacity ratio)) Stir into the flask for 5 minutes. Thereafter, 2 ml of water was added and refluxed for 6 hours. After the completion of the heating, the reaction liquid was cooled, water was added, and the organic layer was separated, and the organic layer was subjected to short column purification (solvent: toluene). Thereafter, the mixture was washed with methanol, recrystallized from ethyl acetate, and purified by column chromatography (solvent: toluene / heptane = 1 / 5 (volume ratio)). Finally, sublimation purification was carried out to obtain 9-((4-naphthalen-2-yl)-[1,1':3',1"-biphenyl]- as the target compound represented by the formula (1-83). 3-yl)-10-phenylindole 0.67 g (yield: 50%).

The structure of the compound (1-83) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 7.99 (dd, 1H), 7.94 (t, 1H), 7.85 to 7.82 (m, 4H), 7.73 (tt, 1H), 7.65 to 7.50 (m, 11H), 7.46~7.43 (m, 4H), 7.37~7.23 (m, 9H), 7.15 (dd, 1H).

Further, the glass transition temperature (Tg) of the compound (1-83) was 110.2 °C.

<Synthesis Example of Compound represented by Formula (1-252)>

Synthesis of <9-(4-methoxy-[1,1'-biphenyl]-3-yl)-10-phenylindole > Intermediate compound 9-(5-chloro-2) under nitrogen atmosphere -methoxyphenyl)-10-phenylindole 36.7 g, phenylboronic acid 17 g, bis(dibenzylideneacetone)palladium(0)(Pd(dba) ₂ )1.6 g, tricyclohexylphosphine (PCy ₃ ) 1.2 g, 39.5 g of tripotassium phosphate and 400 ml of o-xylene were added to the flask and refluxed for 10 hours. After the completion of the heating, the reaction liquid was cooled, water was added, the organic layer was separated, dried over anhydrous sodium sulfate, and then the desiccant was removed, and the solvent was distilled off under reduced pressure, and the obtained solid was subjected to column purification with a silica gel (solvent: heptane) /toluene = 1/1 (volume ratio)), the intermediate compound 9-(4-methoxy-[1,1'-biphenyl]-3-yl)-10-phenylindole 40.5 g was obtained (yield :100%).

Synthesis of <3-(10-phenylfluoren-9-yl)-[1,1'-biphenyl]-4-ol > Intermediate compound 9-(4-methoxy-[ under nitrogen atmosphere] 1,1'-biphenyl]-3-yl)-10-phenylindole 40.5 g, pyridine hydrochloride 53.6 g and 1-methyl-2-pyrrolidone 40 ml were added to the flask at 175 ° C Heat for 3 hours. After the completion of the heating, the reaction solution was cooled, and 500 ml of water was added thereto, and the precipitate was filtered. Further, the precipitate was washed with water, and the obtained crude product was subjected to short column purification (solvent: toluene/ethyl acetate = 2/1 (volume ratio)) to obtain the intermediate compound 3-(10-phenylindole-9). -yl)-[1,1'-biphenyl]-4-ol 40 g (yield: 100%).

<Synthesis of 3-(10-phenylfluoren-9-yl)-[1,1'-biphenyl]-4-yl trifluoromethanesulfonate> Intermediate compound 3-( under nitrogen atmosphere) 40 g of 10-phenylindole-9-yl)-[1,1'-biphenyl]-4-ol and 450 ml of pyridine were added to the flask, and after cooling to 0 ° C, trifluoromethane was slowly added dropwise. Anhydride 54 g. Thereafter, the reaction solution was stirred at 0 ° C for 30 minutes and at room temperature for 2 hours. Then, water was added to the reaction liquid, and the precipitate was filtered. The obtained crude product was subjected to short column purification (solvent: toluene/heptane = 3/1 (capacity ratio)), and then washed with heptane to obtain an intermediate compound of trifluoromethanesulfonic acid-3-(10). -Phenylfluoren-9-yl)-[1,1'-biphenyl]-4-yl ester 50 g (yield: 93%).

Synthesis of <9-(4-(naphthalen-2-yl)-[1,1'-biphenyl]-3-yl)-10-phenylindole > Intermediate compound trifluoromethanesulfonate under nitrogen atmosphere Acid-3-(10-phenylfluoren-9-yl)-[1,1'-biphenyl]-4-yl ester 3 g, 2-naphthalene boronic acid 1.4 g, palladium(II) acetate (Pd(OAc) ₂ ) 0.12 g, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl 0.33 g, tripotassium phosphate 2.3 g, potassium bromide 1.29 g and 1,2,4-trimethylbenzene 26 ml of a mixed solvent of terp-butanol (1,2,4-trimethylbenzene/t-butanol = 10/1 (volume ratio)) was added to the flask and stirred for 5 minutes. Thereafter, 2 ml of water was added and refluxed for 5 hours. After the completion of the heating, the reaction liquid was cooled, water was added, and the organic layer was separated, and the organic layer was subjected to short column purification (solvent: toluene). Thereafter, the mixture was washed with methanol, recrystallized from ethyl acetate, and purified by column chromatography (solvent: toluene / heptane = 1/3 (volume ratio)). Finally, sublimation purification was carried out to obtain 9-(4-(naphthalen-2-yl)-[1,1'-biphenyl]-3-yl)-10- which is the target compound represented by formula (1-252). Phenylhydrazine 1.25 g (yield: 44%).

The structure of the compound (1-252) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 7.92 (dd, 1H), 7.83 to 7.81 (m, 3H), 7.76 to 7.72 (m, 3H), 7.61 to 7.49 (m, 7H), 7.46 to 7.42 (m , 4H), 7.37~7.22 (m, 9H), 7.14 (dd, 1H).

Further, the glass transition temperature (Tg) of the compound (1-252) was 107.8 °C.

<Synthesis Example of Compound represented by Formula (1-255)>

Synthesis of <9-(4-([1,2'-binaphthyl]-4-yl)-[1,1'-biphenyl]-3-yl)-10-phenylindole > under nitrogen atmosphere, The intermediate compound 3-(10-phenylfluoren-9-yl)-[1,1'-biphenyl]-4-yl trifluoromethanesulfonate 3 g, 2-([1,2'- Biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane 2.5 g, palladium(II) acetate (Pd(OAc) ₂ ) 0.04 g, 0.10 g of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 2.3 g of tripotassium phosphate, 1.3 g of potassium bromide and 1,2,4-trimethylbenzene and tert-butanol 33 ml of a mixed solvent (1,2,4-trimethylbenzene/tert-butanol = 10/1 (volume ratio)) was added to the flask and stirred for 5 minutes. Thereafter, 3 ml of water was added and refluxed for 15 hours. After the completion of the heating, the reaction liquid was cooled, water was added, and the organic layer was separated, and the organic layer was subjected to short column purification (solvent: toluene). Then, it was washed with methanol, recrystallized from ethyl acetate, and further subjected to sublimation purification to obtain 9-(4-([1,2'-binaphthyl]-) as the target compound represented by formula (1-255). 4-yl)-[1,1'-biphenyl]-3-yl)-10-phenylindole 0.1 g (yield: 3%).

The structure of the compound (1-255) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 8.20 (d, 1H), 8.03 (d, 1H), 7.95 (dd, 1H), 7.88 (d, 1H), 7.86 to 7.72 (m, 9H), 7.64 ( d, 1H), 7.56~7.27 (m, 16H), 7.11~7.01 (m, 3H), 6.91 (d, 1H).

Further, the glass transition temperature (Tg) of the compound (1-255) was 150.3 °C.

<Synthesis Example of Compound represented by Formula (1-261)>

Synthesis of <9-(4-(phenanthr-9-yl)-[1,1'-biphenyl]-3-yl)-10-phenylindole > The intermediate compound trifluoromethanesulfonate under nitrogen atmosphere Acid-3-(10-phenylfluoren-9-yl)-[1,1'-biphenyl]-4-yl ester 3 g, 9-phenanthroic boric acid 1.8 g, palladium(II) acetate (Pd(OAc) ₂ ) 0.12 g, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl 0.33 g, tripotassium phosphate 2.3 g, potassium bromide 1.3 g and 1,2,4-trimethylbenzene 26 ml of a mixed solvent of terp-butanol (1,2,4-trimethylbenzene/t-butanol = 10/1 (volume ratio)) was added to the flask and stirred for 5 minutes. Thereafter, 2 ml of water was added and refluxed for 6 hours. After the completion of the heating, the reaction liquid was cooled, water was added, and the organic layer was separated, and the organic layer was subjected to short column purification (solvent: toluene). Thereafter, the mixture was washed with methanol, recrystallized from ethyl acetate, and purified by column chromatography (solvent: toluene / heptane = 1/3 (volume ratio)). Finally, sublimation purification was carried out to obtain 9-(4-(phenanthrene-9-yl)-[1,1'-biphenyl]-3-yl)-10- which is the target compound represented by formula (1-261). Phenylhydrazine 0.57 g (yield: 18%).

The structure of the compound (1-261) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 8.49 (d, 1H), 8.43 (d, 1H), 8.16 (d, 1H), 8.07 (d, 1H), 7.95 (dd, 1H), 7.90 (d, 1H), 7.83 to 7.77 (m, 4H), 7.58 (d, 1H), 7.51 to 7.29 (m, 15H), 7.18 to 7.12 (m, 2H), 7.03 to 7.00 (m, 2H).

Further, the glass transition temperature (Tg) of the compound (1-261) was 136.0 °C.

<Synthesis Example of Compound represented by Formula (1-262)>

Synthesis of <9-(4-(tribenzoacyl-2-yl)-[1,1'-biphenyl]-3-yl)-10-phenylindole > Intermediate compound III under nitrogen atmosphere 3-(10-phenylfluoren-9-yl)-[1,1'-biphenyl]-4-yl fluoromethanesulfonate 3 g, 2-tribenzobenzene boronic acid 1.8 g, palladium acetate (II (Pd(OAc) ₂ ) 0.04 g, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl 0.10 g, tripotassium phosphate 2.3 g, potassium bromide 1.3 g and 1,2, 33 ml of a mixed solvent of 4-trimethylbenzene and tert-butanol (1,2,4-trimethylbenzene/t-butanol = 10/1 (volume ratio)) was added to the flask and stirred for 5 minutes. Thereafter, 3 ml of water was added and refluxed for 28 hours. After the completion of the heating, the reaction liquid was cooled, water was added, and the organic layer was separated, and the organic layer was subjected to short column purification (solvent: toluene). Thereafter, it was washed with methanol, recrystallized from ethyl acetate, and further subjected to sublimation purification to obtain 9-(4-(tribenzobenzo-2-yl)- which is a target compound represented by formula (1-262). [1,1'-Biphenyl]-3-yl)-10-phenylindole 0.75 g (yield: 22%).

The structure of the compound (1-262) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 8.49 to 8.40 (m, 3H), 8.30 (d, 1H), 8.08 (d, 1H), 8.00 to 7.88 (m, 5H), 7.78 (d, 2H), 7.60~7.27 (m, 17H), 7.20 (t, 1H), 6.98 (d, 1H), 6.80 (d, 1H).

Further, the glass transition temperature (Tg) of the compound (1-262) was 148.4 °C.

<Synthesis Example of Compound represented by Formula (1-283)>

<9-(5',5'"-diphenyl-[1,1':3',1":4",1'":3'",1""-pentaphenyl]-2"- Synthesis of benzylphenyl hydrazine> 9-(2,5-dichlorophenyl)-10-phenylindole 2 g, [1,1':3 as an intermediate compound under nitrogen atmosphere ',1"-bitriphenyl]-5'-ylboronic acid 4.12 g, palladium (II) acetate (Pd(OAc) ₂ ) 0.11 g, 2-dicyclohexylphosphino-2', 6'-dimethyl 0.31 g of oxybiphenyl, 4.25 g of tripotassium phosphate and a mixed solvent of 1,2,4-trimethylbenzene and tert-butanol 23 ml (1,2,4-trimethylbenzene/t-butanol = 10/1 (capacity ratio)) was added to the flask and stirred for 5 minutes. Thereafter, 3 ml of water was added and refluxed for 12 hours. After the completion of the heating, the reaction solution was cooled, water was added, and the organic layer was separated to obtain an organic layer. Purification by short column (solvent: toluene), followed by reprecipitation with methanol, and further purification by column chromatography (solvent: toluene / heptane = 1/4 (capacity ratio)). Finally, sublimation purification was carried out. 9-(5',5'"-diphenyl-[1,1':3',1":4",1'":3'" as the target compound represented by the formula (1-283) , 1""-pentaphenyl]-2"-yl)-10-phenylindole 1.90 g (yield: 48%).

The structure of the compound (1-283) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 8.08 (dd, 1H), 7.99 (d, 1H), 7.95 (d, 2H), 7.93 (d, 1H), 7.85 (d, 2H), 7.82 (t, 1H), 7.73~7.67 (m, 6H), 7.61~7.59 (m, 1H), 7.55~7.46 (m, 7H), 7.40~7.25 (m, 16H), 7.02~7.01 (m, 4H).

Further, the glass transition temperature (Tg) of the compound (1-283) was 145.3 °C.

<Synthesis Example of Compound represented by Formula (1-559)>

Synthesis of <2-chloro-4-(10-phenylfluoren-9-yl)phenol> 9 g of 4-bromo-2-chlorophenol and (10-phenylfluoren-9-yl) under nitrogen atmosphere 12.93 g of boric acid, 0.75 g of bis(dibenzylideneacetone)palladium(0)(Pd(dba) ₂ ), 0.55 g of tricyclohexylphosphine (PCy ₃ ), 18.42 g of tripotassium phosphate and a mixed solvent of toluene and ethanol 180 Mol (toluene/ethanol = 4/1 (capacity ratio)) was added to the flask and stirred for 5 minutes. Thereafter, 18 ml of water was added and refluxed for 15 hours. After the completion of the heating, the reaction solution was cooled, and 100 ml of water was added. Thereafter, the reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, and then the desiccant was removed, and the solvent was distilled off under reduced pressure, and the obtained crude product was purified by column chromatography (solvent: heptane / toluene = 1 / 2 (volume ratio)), an intermediate compound 2-chloro-4-(10-phenylfluoren-9-yl)phenol 8.3 g (yield: 50%) was obtained.

Synthesis of <5-(10-phenylfluoren-9-yl)-[1,1'-biphenyl]-2-ol > Intermediate compound 2-chloro-4-(10-benzene) under nitrogen atmosphere 7.9-9-yl)phenol 7.9 g, phenylboronic acid 3.79 g, bis(dibenzylideneacetone)palladium(0)(Pd(dba) ₂ )0.6 g, tricyclohexylphosphine (PCy ₃ )0.44 g, 0.81 g of tripotassium phosphate and 80 ml of o-xylene were added to the flask and stirred for 5 minutes. Thereafter, 8 ml of water was added and refluxed for 5 hours. After the completion of the heating, the reaction liquid was cooled, and water was added. Thereafter, filtration was carried out to obtain a solid portion as the crude product 1. The organic layer of the filtrate fraction was separated, dried over anhydrous sodium sulfate, and then the desiccant was removed, and the solvent was distilled off under reduced pressure, and the obtained solid was used as crude product 2. Thereafter, the crude product 1 was combined with the crude product 2, and subjected to short column purification with a silicone resin (solvent: toluene). Further, reprecipitation was carried out with heptane to obtain 8.4 g of an intermediate compound 5-(10-phenylfluoren-9-yl)-[1,1'-biphenyl]-2-ol (yield: 95.9%).

<Synthesis of 5-(10-phenylfluoren-9-yl)-[1,1'-biphenyl]-2-yl trifluoromethanesulfonate> Intermediate compound 5-( under nitrogen atmosphere) 8.4 g of 10-phenylindole-9-yl)-[1,1'-biphenyl]-2-ol and 80 ml of pyridine were added to the flask, and after cooling to 0 ° C, trifluoromethane was slowly added dropwise. The anhydride was 11.2 g. Thereafter, the reaction solution was stirred at 0 ° C for 30 minutes and at room temperature for 2 hours. Then, water was added to the reaction liquid, and the precipitate was filtered. The obtained crude product was subjected to short column purification (solvent: toluene) with hydrazine, and then washed with heptane to obtain an intermediate compound of trifluoromethanesulfonic acid-5-(10-phenylfluoren-9-yl)-[ 1,1'-biphenyl]-2-yl ester 11 g (yield: 100%).

Synthesis of <9-(6-(naphthalen-1-yl)-[1,1'-biphenyl]-3-yl)-10-phenylindole > Intermediate compound trifluoromethanesulfonate under nitrogen atmosphere Acid-5-(10-phenylfluoren-9-yl)-[1,1'-biphenyl]-2-yl ester 2.6 g, 1-naphthalene boronic acid 1.21 g, palladium(II) acetate (Pd(OAc) ₂ ) 0.11 g, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl 0.29 g, tripotassium phosphate 1.99 g, potassium bromide 1.12 g and 1,2,4-trimethylbenzene 20 ml of a mixed solvent of t-butanol (1,2,4-trimethylbenzene/tert-butanol = 10/1 (volume ratio)) was added to the flask and stirred for 5 minutes. Thereafter, 2 ml of water was added and refluxed for 6 hours. After the completion of the heating, the reaction liquid was cooled, water was added, and the organic layer was separated, and the organic layer was subjected to short column purification (solvent: toluene). Thereafter, the mixture was washed with methanol, recrystallized from ethyl acetate, and purified by column chromatography (solvent: toluene / heptane = 1/3 (volume ratio)). Finally, sublimation purification was carried out to obtain 9-(6-(naphthalen-1-yl)-[1,1'-biphenyl]-3-yl)-10- which is the target compound represented by formula (1-559). Phenylhydrazine 1.2 g (yield: 48%).

The structure of the compound (1-559) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 7.97 (q, 2H), 7.94 to 7.92 (m, 1H), 7.89 to 7.87 (m, 1H), 7.81 (d, 1H), 7.73 (d, 2H), 7.71 (d, 1H), 7.67 (d, 1H), 7.64 to 7.55 (m, 4H), 7.52 to 7.35 (m, 10H), 7.16 to 7.14 (m, 2H), 7.03 to 7.01 (m, 3H).

Further, the glass transition temperature (Tg) of the compound (1-559) was 126.6 °C.

<Synthesis Example of Compound represented by Formula (1-560)>

Synthesis of <9-(6-(naphthalen-2-yl)-[1,1'-biphenyl]-3-yl)-10-phenylindole > Intermediate compound trifluoromethanesulfonate under nitrogen atmosphere Acid-5-(10-phenylfluoren-9-yl)-[1,1'-biphenyl]-2-yl ester 2.6 g, 2-naphthalene boronic acid 1.21 g, palladium(II) acetate (Pd(OAc) ₂ ) 0.11 g, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl 0.29 g, tripotassium phosphate 1.99 g, potassium bromide 1.12 g and 1,2,4-trimethylbenzene 20 ml of a mixed solvent of t-butanol (1,2,4-trimethylbenzene/tert-butanol = 10/1 (volume ratio)) was added to the flask and stirred for 5 minutes. Thereafter, 2 ml of water was added and refluxed for 6 hours. After the completion of the heating, the reaction liquid was cooled, water was added, and the organic layer was separated, and the organic layer was subjected to short column purification (solvent: toluene). Thereafter, the mixture was washed with methanol, recrystallized from ethyl acetate, and purified by column chromatography (solvent: toluene / heptane = 1/3 (volume ratio)). Finally, sublimation purification was carried out to obtain 9-(6-(naphthalen-2-yl)-[1,1'-biphenyl]-3-yl)-10- which is the target compound represented by formula (1-560). Phenylhydrazine 1.4 g (yield: 56%).

The structure of the compound (1-560) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 7.96 (s, 1H), 7.92 (d, 2H), 7.85 to 7.81 (m, 2H), 7.78 (d, 1H), 7.73 to 7.68 (m, 3H), 7.63 to 7.54 (m, 5H), 7.51 to 7.47 (m, 4H), 7.42 to 7.28 (m, 7H), 7.18 to 7.16 (m, 3H).

Further, the glass transition temperature (Tg) of the compound (1-560) was 116.6 °C.

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

Synthesis of <9-(2-methoxy-5(naphthalen-1-yl)phenyl)-10-phenylindole> Intermediate compound 9-(5-chloro-2-methoxy) under nitrogen atmosphere Phenylphenyl)-10-phenylindole 6 g, 1-naphthalene boronic acid 3.14 g, bis(dibenzylideneacetone)palladium(0)(Pd(dba) ₂ )0.26 g, tricyclohexylphosphine (PCy ₃ ) 0.19 g, 3.55 g of tripotassium phosphate and 50 ml of xylene were added to the flask and stirred for 5 minutes. Thereafter, 5 ml of water was added and refluxed for 14 hours. After the completion of the heating, the reaction liquid was cooled, water was added, the organic layer was separated, dried over anhydrous sodium sulfate, and then the desiccant was removed, and the solvent was distilled off under reduced pressure, and the obtained solid was subjected to column purification by solvent (solvent: g Alkane/toluene=2/1 (volume ratio)), the intermediate compound 9-(2-methoxy-5(naphthalen-1-yl)phenyl)-10-phenylindole 5.3 g was obtained (yield: 71.7) %).

Synthesis of <4-(naphthalen-1-yl)-2-(10-phenylfluoren-9-yl)phenol> The intermediate compound 9-(2-methoxy-5(naphthalene)- under nitrogen atmosphere 5.3 g of 1-yl)phenyl)-10-phenylindole, 6.3 g of pyridine hydrochloride and 5 ml of 1-methyl-2-pyrrolidone were placed in a flask and heated at 175 ° C for 4 hours. After the completion of the heating, the reaction solution was cooled, and 100 ml of water was added thereto, and the precipitate was filtered. Further, the precipitate was washed with water, and the obtained crude product was subjected to short column purification with a silica gel (solvent: toluene/ethyl acetate = 2/1 (capacity ratio)) to obtain an intermediate compound 4-(naphthalen-1-yl)- 2-(10-Phenylfluoren-9-yl)phenol 4.6 g (yield: 89%).

Synthesis of <Trifluoromethanesulfonic acid-4-(naphthalen-1-yl)-2-(10-phenylfluoren-9-yl)phenyl ester> Intermediate compound 4-(naphthalene-1) under nitrogen atmosphere 4.6 g of 2-(10-phenylfluoren-9-yl)phenol and 25 ml of pyridine were placed in a flask, and after cooling to 0 ° C, 5.5 g of trifluoromethanesulfonic anhydride was gradually added dropwise. Thereafter, the reaction solution was stirred at 0 ° C for 30 minutes and at room temperature for 2 hours. Then, water was added to the reaction liquid, and the precipitate was filtered. The obtained crude product was subjected to short column purification (solvent: toluene) with oxime, and then washed with heptane to obtain an intermediate compound of trifluoromethanesulfonic acid-4-(naphthalen-1-yl)-2-(10- Phenylfluoren-9-yl)phenyl ester 5.95 g (yield: 100%).

[化139]

Synthesis of <9-(4-(naphthalen-1-yl)-([1,1'-biphenyl]-2-yl))-10-phenylindole > Intermediate compound trifluoride under nitrogen atmosphere 4.7 g of 4-(naphthalen-1-yl)-2-(10-phenylfluoren-9-yl)phenyl sulfonate, 1.42 g of phenylboronic acid, palladium(II) acetate (Pd(OAc) ₂ ) 0.09 g, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl 0.27 g, tripotassium phosphate 1.65 g, sodium bromide 0.80 g and 1,2,4-trimethylbenzene 33 ml Add to the flask and stir for 5 minutes. Thereafter, 3 ml of water was added and refluxed for 8 hours. After the completion of the heating, the reaction liquid was cooled, water was added, and the organic layer was separated, and the organic layer was subjected to short column purification (solvent: toluene). Thereafter, it was reprecipitated with methanol, and further purified by column chromatography using a silicone resin (solvent: toluene/heptane = 1/6 (capacity ratio)). Finally, sublimation purification is carried out to obtain 9-(4-(naphthalen-1-yl)-([1,1'-biphenyl]-2-yl))- as the target compound represented by the formula (2-1). 10-phenylindole 1.68 g (yield: 40.5%).

[化140]

The structure of the compound (2-1) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 8.21 to 8.19 (m, 1H), 7.91 to 7.84 (m, 4H), 7.79 (q, 2H), 7.62 to 7.46 (m, 10H), 7.41 to 7.38 (m , 2H), 7.35~7.32 (m, 2H), 7.27~7.24 (m, 2H), 7.11 (dd, 2H), 6.95~6.93 (m, 3H).

Further, the glass transition temperature (Tg) of the compound (2-1) was 106.4 °C.

<Synthesis Example of Comparative Example Compound (A)> Compound (A)

Synthesis of <9-([1,1':3',1"-bitriphenyl]-5'-yl)-10-phenylindole> 3,5-diphenylbromobenzene under nitrogen atmosphere 3.87 g, (10-phenylfluoren-9-yl)boronic acid 4.1 g, tetrakis(triphenylphosphine)palladium(0)(Pd(PPh ₃ ) ₄ )0.29 g, potassium phosphate 5.31 g and a mixture of toluene and ethanol 50 ml of a solvent (toluene/ethanol = 3/1 (capacity ratio)) was added to the flask, and the mixture was stirred for 5 minutes. Thereafter, 5 ml of water was added and refluxed for 7 hours. After the completion of the heating, the reaction solution was cooled, and 50 ml of water was added. Then, the reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, and then the desiccant was removed, and the solvent was distilled off under reduced pressure, and the obtained crude product was subjected to short column purification (solvent: toluene) with toluene. Recrystallization was carried out, followed by sublimation purification to obtain 9-([1,1':3',1"-biphenyl]-5'-yl)-10-phenyl as a comparative compound (A).蒽 3.3 g (yield: 54.7%). In addition, the compound of the comparative example (A) is a compound E87 of the synthesis example described in the above-mentioned Patent Document 1 (Japanese Patent Laid-Open Publication No. 2000-273056).

The structure of the comparative example compound (A) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 8.03 (t, 1H), 7.88 to 7.86 (m, 2H), 7.77 to 7.71 (m, 8H), 7.63 to 7.55 (m, 3H), 7.51 to 7.45 (m , 6H), 7.39~7.33 (m, 6H).

Further, the glass transition temperature (Tg) of the comparative example compound (A) was 104.9 °C.

<Synthesis Example of Comparative Compound (B)> Compound (B)

Synthesis of <9-([1,1'-biphenyl]-2-yl)-10-phenylindole> 9-bromo-10-蒽3 g, 2-biphenylboronic acid 2.14 g under nitrogen atmosphere , bis(dibenzylideneacetone)palladium(0)(Pd(dba) ₂ ) 0.16 g, tricyclohexylphosphine (PCy ₃ ) 0.11 g, tripotassium phosphate 3.82 g and 1,2,4-trimethylbenzene 36 ml of a mixed solvent of terp-butanol (1,2,4-trimethylbenzene/t-butanol = 10/1 (volume ratio)) was added to the flask and stirred for 5 minutes. Thereafter, 3 ml of water was added and refluxed for 8 hours. After the completion of the heating, the reaction liquid was cooled, water was added, and the organic layer was separated, and the organic layer was subjected to short column purification (solvent: toluene). Thereafter, reprecipitation was carried out with methanol, followed by recrystallization from ethyl acetate. Finally, sublimation purification was carried out to obtain 9-([1,1'-biphenyl]-2-yl)-10-phenylindole 1.99 g (yield: 54%) as the compound (B).

The structure of the comparative example compound (B) was confirmed by MS spectrum and NMR measurement. ¹ H-NMR (CDCl ₃ ) : δ = 7.68 (dd, 2H), 7.63 (d, 2H), 7.60 to 7.50 (m, 6H), 7.44 to 7.38 (m, 3H), 7.30 to 7.23 (m, 4H) ), 7.01~6.99 (m, 2H), 6.90~6.84 (m, 3H).

Further, the glass transition temperature (Tg) of the comparative example compound (B) was 65.1 °C.

<Evaluation of Organic EL Element> Hereinafter, an embodiment of the organic EL element using the compound of the present invention will be described in order to explain the present invention in more detail, but the present invention is not limited to the examples.

The organic EL devices of Example 1, Example 2, and Comparative Example 1 were produced, and the voltage (V), the EL emission wavelength (nm), and the external quantum efficiency (%) which are characteristics at 1000 cd/m ^{2 of} light emission were measured, respectively. The following time (hours) was measured: the time (hour) at which the luminance of 90% (1800 cd/m ² ) or more of the initial luminance was maintained at a constant current driving at a current density at a luminance of 2000 cd/m ² . Hereinafter, examples and comparative examples will be described in detail.

Further, among the quantum efficiencies of the light-emitting elements, there are internal quantum efficiency and external quantum efficiency, and the following ratios are internal quantum efficiencies: external energy injected as electrons (or holes) in the light-emitting layer of the light-emitting element is purely The proportion of turns into photons. On the other hand, the external quantum efficiency is calculated based on the amount by which the photon is released to the outside of the light-emitting element, and a part of the photons generated in the light-emitting layer are continuously absorbed or reflected inside the light-emitting element without being released to the light-emitting element. External, so the external quantum efficiency is lower than the internal quantum efficiency.

The method of measuring the external quantum efficiency is as follows. The voltage of the element was applied to a voltage of 1000 cd/m ² using a voltage/current generator R6144 manufactured by Advantest, Inc., to cause the element to emit light. The spectral radiance of the visible light region was measured from the vertical direction on the light-emitting surface using a spectroradiometer SR-3AR manufactured by TOPCON. Assuming that the light-emitting surface is a complete diffusion surface, the value of the measured spectral radiance of each wavelength component divided by the wavelength energy and multiplied by π is the number of photons at each wavelength. Then, the number of photons is accumulated over the entire wavelength range of the observation as the total number of photons emitted from the element. The value obtained by dividing the applied current value by the basic charge is taken as the number of carriers to be injected into the element, and the total number of photons emitted from the element divided by the number of carriers injected into the element is the external quantum efficiency.

The material compositions of the respective layers in the produced organic EL devices of Example 1, Example 2, and Comparative Example 1 are shown in Table 1 below. [Table 1]

In Table 1, "HI" is N ⁴ , N ^{4 '} -diphenyl-N ⁴ , N ^{4 '} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1'- Biphenyl]-4,4'-diamine, "NPD" is N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, "BD1" is 7 ,7-Dimethyl-N ⁵ ,N ⁹ -diphenyl-N ⁵ ,N ⁹ -bis(4-(trimethyldecyl)phenyl)-7H-benzo[c]indole-5,9 - Diamine, "ET1" is 4,4'-((2-phenylfluorene-9,10-diyl)bis(4,1-phenylene))dipyridine. Further, "Liq" is lithium quinolate. The chemical structure is shown below.

<Example 1> <Element for using the compound (1-1) for the host material of the light-emitting layer> The ITO which was formed into a film having a thickness of 180 nm by sputtering was polished to 150 nm, and 26 mm × 28 A glass substrate (manufactured by Optoscience Co., Ltd.) of mm × 0.7 mm was used as a transparent support 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 molybdenum vapor deposition boat in which HI was placed and a molybdenum vapor deposition in which NPD was placed were attached. A boat for vapor deposition made of molybdenum containing the compound (1-1) of the present invention, a boat for vapor deposition made of molybdenum containing BD1, and a boat for vapor deposition of molybdenum containing ET1. A boat for vapor deposition of molybdenum containing Liq, a boat for vapor deposition made of molybdenum containing magnesium, and a boat for vapor deposition of molybdenum containing silver.

The following layers were sequentially formed on the ITO film of the transparent support substrate. When the vacuum chamber was depressurized to 5 × 10 ^-4 Pa, the boat for vapor deposition in which HI was placed was first heated, and vapor deposition was performed so as to have a film thickness of 40 nm to form a hole injection layer, and then, The vapor deposition boat in which NPD was placed was heated, and vapor deposition was performed so that the film thickness became 30 nm to form a hole transport layer. Then, the vapor deposition boat in which the compound (1-1) was placed and the vapor deposition boat in which the BD1 was placed were simultaneously heated, and vapor deposition was performed so that the film thickness became 35 nm, and the light-emitting layer was formed. The vapor deposition rate was adjusted so that the weight ratio of the compound (1-1) to the BD1 was approximately 95 to 5. Then, the vapor deposition boat in which ET1 was placed was heated, and vapor deposition was performed so that the film thickness became 15 nm, and an electron transport layer was formed. The vapor deposition rate of each layer is from 0.01 nm/s to 1 nm/s.

Thereafter, the vapor deposition boat in which Liq was placed was heated, and vapor deposition was performed at a deposition rate of 0.01 nm/s to 0.1 nm/s so that the film thickness became 1 nm. Then, the boat in which magnesium was placed and the boat in which silver was placed were simultaneously heated, and vapor deposition was performed so that the film thickness became 100 nm, and the cathode was formed. In this case, the vapor deposition rate was adjusted so that the atomic ratio of magnesium to silver was 10 to 1, and the organic EL device was obtained so that the vapor deposition rate was 0.01 nm/s to 2 nm/s.

When the ITO electrode was used as the anode and the Liq/magnesium + silver electrode was used as the cathode to measure the characteristics at the time of 1000 cd/m ² luminescence, the driving voltage was 5.87 V, and the external quantum efficiency was 5.85% (blue luminescence having a wavelength of about 459 nm). ). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 50 hours.

<Example 2><Element of the host material of the light-emitting layer of the compound (1-301)> In addition to the compound (1-1) which is a host material of the light-emitting layer, the compound (1-301) is used. The organic EL device was obtained by the method of Example 1. When the ITO electrode was used as the anode and the Liq/magnesium + silver electrode was used as the cathode to measure the characteristics at 1000 cd/m ² , the driving voltage was 5.78 V, and the external quantum efficiency was 5.70% (the wavelength was about 459 nm blue). Glowing). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 85 hours.

<Comparative Example 1> An organic EL device was obtained by the method according to Example 1 except that the compound (1-1) which is a host material of the light-emitting layer was replaced with the compound (A). When the ITO electrode was used as an anode and the Liq/magnesium + silver electrode was used as a cathode to measure the characteristics at 1000 cd/m ² light emission, the driving voltage was 6.35 V, and the external quantum efficiency was 5.02% (wavelength was about 464 nm blue). Glowing). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 10 hours.

The above results are summarized in Table 2. [Table 2]

The material compositions of the respective layers in the produced organic EL devices of Examples 3 to 10, Comparative Example 2, and Comparative Example 3 are shown in Table 3 below. [table 3]

In Table 3, "HI2" is 1,4,5,8,9,12-hexaazatribenzobenzene-2,3,6,7,10,11-hexacarbonitrile. The chemical structure is shown below.

<Example 3> <Element for using the compound (1-1) for the host material of the light-emitting layer> The ITO which was formed into a film having a thickness of 180 nm by sputtering was polished to 150 nm, and 26 mm × 28 A glass substrate (manufactured by Optoscience Co., Ltd.) of mm × 0.7 mm was used as a transparent support 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 molybdenum vapor deposition boat in which HI was placed and a molybdenum vapor deposition in which HI2 was placed were attached. A boat for vapor deposition of molybdenum in which NPD is placed, a boat for vapor deposition made of molybdenum containing the compound (1-1) of the present invention, and a boat for vapor deposition of molybdenum in which BD1 is placed. , a molybdenum vapor deposition boat with ET1, a molybdenum vapor deposition boat in which Liq is placed, a molybdenum vapor deposition boat in which magnesium is placed, and a molybdenum vapor deposition plate in which silver is placed. Boat.

The following layers were sequentially formed on the ITO film of the transparent support substrate. When the vacuum chamber is depressurized to 5 × 10 ^-4 Pa, the vapor deposition boat in which HI is placed is heated, and vapor deposition is performed so as to have a film thickness of 40 nm to form a first layer hole injection layer. Furthermore, the boat for vapor deposition in which HI2 was placed was heated, and vapor deposition was performed so that the film thickness became 5 nm, and the second layer hole injection layer was formed, and then the vapor deposition boat in which NPD was placed was placed. Heating was carried out to carry out vapor deposition so that the film thickness became 20 nm, and a hole transport layer was formed. Then, the vapor deposition boat in which the compound (1-1) was placed and the vapor deposition boat in which the BD1 was placed were simultaneously heated, and vapor deposition was performed so as to have a film thickness of 25 nm to form a light-emitting layer. The vapor deposition rate was adjusted so that the weight ratio of the compound (1-1) to the BD1 was approximately 95 to 5. Then, the vapor deposition boat in which ET1 was placed was heated, and vapor deposition was performed so that the film thickness became 15 nm, and an electron transport layer was formed. The vapor deposition rate of each layer is from 0.01 nm/s to 1 nm/s.

Thereafter, the vapor deposition boat in which Liq was placed was heated, and vapor deposition was performed at a deposition rate of 0.01 nm/s to 0.1 nm/s so that the film thickness became 1 nm. Then, the boat in which magnesium was placed and the boat in which silver was placed were simultaneously heated, and vapor deposition was performed so that the film thickness became 100 nm, and the cathode was formed. In this case, the vapor deposition rate was adjusted so that the atomic ratio of magnesium to silver was 10 to 1, and the organic EL device was obtained so that the vapor deposition rate was 0.01 nm/s to 2 nm/s.

When the ITO electrode was used as an anode and the Liq/magnesium + silver electrode was used as a cathode to measure the characteristics at 1000 cd/m ² light emission, the driving voltage was 4.34 V, and the external quantum efficiency was 5.08% (wavelength was about 457 nm blue). Glowing). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 198 hours.

<Example 4><Element of the host material of the light-emitting layer of the compound (1-3)> In addition to the compound (1-1) which is a host material of the light-emitting layer, the compound (1-3) is used. The organic EL device was obtained by the method of Example 3. When the ITO electrode was used as an anode and the Liq/magnesium + silver electrode was used as a cathode to measure the characteristics at 1000 cd/m ² , the driving voltage was 4.39 V, and the external quantum efficiency was 4.85% (wavelength was about 457 nm). Glowing). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 140 hours.

<Example 5> Element for using the compound (1-23) for the host material of the light-emitting layer> In addition to the compound (1-1) which is a host material of the light-emitting layer, the compound (1-23) is used. The organic EL device was obtained by the method of Example 3. When the ITO electrode was used as an anode and the Liq/magnesium + silver electrode was used as a cathode to measure the characteristics at 1000 cd/m ² light emission, the driving voltage was 4.31 V, and the external quantum efficiency was 4.57% (wavelength was about 455 nm blue). Glowing). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 135 hours.

<Example 6><Element of the host material of the light-emitting layer of the compound (1-53)> In addition to the compound (1-1) which is a host material of the light-emitting layer, the compound (1-53) is used. The organic EL device was obtained by the method of Example 3. When the ITO electrode was used as the anode and the Liq/magnesium + silver electrode was used as the cathode to measure the characteristics at the time of 1000 cd/m ² light emission, the driving voltage was 4.52 V, and the external quantum efficiency was 4.80% (the wavelength was about 457 nm blue). Glowing). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 70 hours.

<Example 7><Element of the host material of the light-emitting layer of the compound (1-83)> In addition to the compound (1-1) which is a host material of the light-emitting layer, the compound (1-1) is used. The organic EL device was obtained by the method of Example 3. When the ITO electrode was used as the anode and the Liq/magnesium + silver electrode was used as the cathode to measure the characteristics at the time of 1000 cd/m ² light emission, the driving voltage was 4.16 V, and the external quantum efficiency was 4.62% (the wavelength was about 456 nm blue). Glowing). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 97 hours.

<Example 8><Element of the host material of the light-emitting layer of the compound (1-261)> In addition to the compound (1-1) which is a host material of the light-emitting layer, the compound (1-261) is used. The organic EL device was obtained by the method of Example 3. When the ITO electrode was used as the anode and the Liq/magnesium + silver electrode was used as the cathode to measure the characteristics at the time of 1000 cd/m ² luminescence, the driving voltage was 4.43 V, and the external quantum efficiency was 4.91% (the wavelength was about 457 nm blue). Glowing). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 83 hours.

<Example 9><Element of the host material of the light-emitting layer of the compound (1-262)> In addition to the compound (1-1) which is a host material of the light-emitting layer, the compound (1-262) is used. The organic EL device was obtained by the method of Example 3. When the ITO electrode was used as the anode and the Liq/magnesium + silver electrode was used as the cathode to measure the characteristics at the time of 1000 cd/m ² luminescence, the driving voltage was 3.82 V, and the external quantum efficiency was 4.94% (the wavelength was about 459 nm blue). Glowing). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 68 hours.

<Example 10><Element of the host material of the light-emitting layer of the compound (2-1)> In addition to the compound (1-1) which is a host material of the light-emitting layer, the compound (2-1) is used. The organic EL device was obtained by the method of Example 3. When the ITO electrode was used as an anode and the Liq/magnesium + silver electrode was used as a cathode to measure the characteristics at 1000 cd/m ² light emission, the driving voltage was 4.24 V, and the external quantum efficiency was 4.92% (wavelength was about 456 nm blue). Glowing). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 171 hours.

<Comparative Example 2> An organic EL device was obtained by the method according to Example 3, except that the compound (1-1) which is a host material of the light-emitting layer was replaced with the compound (A). When the ITO electrode was used as the anode and the Liq/magnesium + silver electrode was used as the cathode to measure the characteristics at the time of 1000 cd/m ² luminescence, the driving voltage was 4.55 V, and the external quantum efficiency was 4.14% (the wavelength was about 456 nm blue). Glowing). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 6 hours.

<Comparative Example 3> An organic EL device was obtained by the method according to Example 3, except that the compound (1-1) which is a host material of the light-emitting layer was replaced by the compound (B). When the ITO electrode was used as an anode and the Liq/magnesium + silver electrode was used as a cathode to measure the characteristics at 1000 cd/m ² light emission, the driving voltage was 4.56 V, and the external quantum efficiency was 4.74% (wavelength was about 455 nm blue). Glowing). Further, by performing a constant current driving test with a current density of an initial luminance of 2000 cd/m ² , the time for maintaining the luminance of 90% (1800 cd/m ² ) or more of the initial value was 28 hours.

The above results are summarized in Table 4. [Table 4] [Industrial availability]

According to a preferred embodiment of the present invention, an organic electroluminescence device having excellent driving voltage, luminous efficiency, and device life can be provided, and a display device including the same, an illumination device including the same, and the like can be provided.

100‧‧‧Organic electric field light-emitting elements
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 electroluminescence device of the embodiment.

100‧‧‧Organic electric field light-emitting elements

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 (10)

A material for a light-emitting layer comprising a ruthenium compound represented by the following formula (1): In the formula (1), Ar is a naphthyl group, a phenanthryl group or a tribenzophenyl group and may be substituted by a phenyl group, a naphthyl group or a biphenyl group, and Ar ¹ is a substitutable aryl group, and m is 0 to 5 In the case where m is 2 or more, the structure of Ar ¹ may be the same or different, and R is independently an alkyl group or a cycloalkyl group, and a is an integer of 0 to 2, and is represented by the formula (1). At least one hydrogen in the hydrazine compound may be substituted with hydrazine. The material for a light-emitting layer according to claim 1, wherein Ar is a naphthyl group, a phenanthryl group or a tribenzophenyl group and may be substituted by a phenyl group, a naphthyl group or a biphenyl group, and Ar ¹ is a carbon number of 6 The aryl group of ～18 is substituted by an aryl group having 6 to 18 carbon atoms, and m is an integer of 0 to 2. When m is 2, the structures of Ar ¹ are the same, and R is independently a carbon number of 1 to 2 The alkyl group of 4 or a cycloalkyl group having 3 to 6 carbon atoms, a is an integer of 0 to 2, and at least one hydrogen in the hydrazine compound represented by the formula (1) may be substituted with hydrazine. The material for a light-emitting layer according to claim 1, wherein Ar is a naphthyl group, a phenanthryl group or a tribenzophenyl group and may be substituted by a phenyl group, a naphthyl group or a biphenyl group, and Ar ¹ is a phenyl group or a naphthalene group. a group, a biphenyl group, a phenanthryl group or a tribenzophenyl group which may be substituted by a phenyl group, a naphthyl group or a phenanthryl group, m is an integer of 0 to 2, and R is independently a methyl group, an ethyl group, a positive group A propyl, isopropyl, tert-butyl or cyclohexyl group, a being 0 or 1. The material for a light-emitting layer according to claim 1, which is represented by the following formula (1-53), formula (1-83), formula (1-252), formula (1-255), and formula (1- 261) or a compound represented by formula (1-262): . An organic electroluminescent device comprising: a pair of electrodes including an anode and a cathode; and a material for the light-emitting layer according to any one of the first to fourth aspects of the invention, Light-emitting layer. The organic electroluminescent device according to claim 5, wherein the light-emitting layer contains at least one selected from the group consisting of an amine having an anthracene structure, an aromatic amine derivative, and a coumarin derivative. . The organic electroluminescence device according to claim 5, further comprising an electron transport layer and/or an electron injection layer disposed between the cathode and the light-emitting layer, at least one of the electron transport layer and the electron injection layer At least one selected from the group consisting of a hydroxyquinoline metal complex, a pyridine derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative is contained. The organic electroluminescent device according to claim 7, 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 an alkali 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 metal organic complexes At least one of the group consisting of. A display device comprising the organic electroluminescence device according to any one of claims 5 to 8. An illuminating device comprising the organic electroluminescent device according to any one of claims 5 to 8.