Triazine compound, material for organic electroluminescent element, and organic electroluminescent element

Abstract

Provided are a triazine compound having a high glass transition temperature that contributes to the formation of an organic electroluminescent element that exhibits high luminous efficiency and long life, a material for an organic electroluminescent element containing the triazine compound, and an organic electroluminescent element. A triazine compound having a specific structure represented by formula (1). #imgabs0#

Description

Technical Field

[0001] The present application relates to a triazine compound, a material for an organic electroluminescent element, and an organic electroluminescent element. Background Art

[0002] Organic electroluminescent elements have begun to be put into practical use, mainly for small mobile applications. However, in order to further expand their applications, performance must be improved, and materials with high luminous efficiency and long life characteristics are required. In addition, organic electroluminescent elements need to be used at high temperatures when used in areas with high temperatures or for vehicle-mounted applications. Therefore, materials for organic electroluminescent elements are required to have a high glass transition temperature.

[0003] Patent Document 1 discloses a triazine compound as a material for an organic electroluminescent element capable of reducing a driving voltage with high efficiency.

[0004] Patent Document 2 discloses a triazine compound as a material for an organic electroluminescent element having high heat resistance and capable of reducing a driving voltage.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2017-178931

[0008] Patent Document 2: Japanese Patent Application Publication No. 2011-63584 Summary of the invention

[0009] Problem that the invention aims to solve

[0010] However, the market has a strong demand for the expansion of applications and the expansion of usable environments. Regarding the three characteristics of high glass transition temperature, high luminous efficiency and long life, the triazine compounds described in Patent Documents 1 and 2 cannot be said to fully meet these characteristics, and it is sought to achieve the above three characteristics at a higher level.

[0011] Therefore, one embodiment of the present application aims to provide a triazine compound having a high glass transition temperature that contributes to the formation of an organic electroluminescent element that exhibits high luminous efficiency and long life characteristics.

[0012] Another aspect of the present application is to provide an organic electroluminescent device material comprising the triazine compound.

[0013] Furthermore, another aspect of the present application aims to provide an organic electroluminescent element that exhibits high luminous efficiency and long life characteristics and can be used in various applications or in various environments.

[0014] Solutions for solving problems

[0015] The triazine compound of one embodiment of the present application is a triazine compound represented by formula (1):

[0016]

[0017] In formula (1),

[0018] Ar 1 and Ar 2 each independently represents a phenyl group, a biphenyl group or a naphthyl group;

[0019] Ar 3 express:

[0020] Aromatic hydrocarbon group belonging to a tricyclic condensed ring or a tetracyclic condensed ring,

[0021] A nitrogen-containing aromatic group consisting of only six-membered rings belonging to a tricyclic condensed ring or a tetracyclic condensed ring, or

[0022] A heteroaromatic group in which the heteroatom belonging to the tricyclic condensed ring or the tetracyclic condensed ring is a Group VI A element;

[0023] Ar 4 represents phenyl, azaphenyl, diazaphenyl, naphthyl, azanaphthyl or diazanaphthyl;

[0024] Ar 1 ,Ar 2 ,Ar 3 and Ar 4 each independently optionally substituted by one or more groups selected from the group consisting of a fluorine atom, a methyl group, a phenyl group, a naphthyl group, an azaphenyl group, a diazaphenyl group, an azanaphthyl group and a diazanaphthyl group;

[0025] X represents phenylene, naphthylene, azaphenylene, diazaphenylene, azanaphthylene or diazanaphthylene;

[0026] p represents 0, 1 or 2;

[0027] When p is 2, two Xs may be the same as or different from each other.

[0028] A material for an organic electroluminescent device according to another embodiment of the present application contains the above-mentioned triazine compound.

[0029] An organic electroluminescent device according to another embodiment of the present application contains the above-mentioned triazine compound.

[0030] Effects of the Invention

[0031] According to one embodiment of the present application, a triazine compound having a high glass transition temperature and contributing to the formation of an organic electroluminescent element that exhibits high luminous efficiency and long life characteristics can be provided. In addition, according to another embodiment of the present application, a material for an organic electroluminescent element comprising the above triazine compound can be provided. Furthermore, according to another embodiment of the present application, an organic electroluminescent element that exhibits high luminous efficiency and long life characteristics and can be used for various purposes can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a schematic cross-sectional view showing an example of a stacked structure of an organic electroluminescent element according to one embodiment of the present application.

[0033] Figure 2 It is a schematic cross-sectional view showing an example of another stacked structure of the organic electroluminescent element according to one embodiment of the present application (structure of element example-1). DETAILED DESCRIPTION

[0034] Hereinafter, the triazine compound according to one embodiment of the present application will be described in detail.

[0035] <Triazine compounds>

[0036] The triazine compound of one embodiment of the present application is a triazine compound represented by formula (1):

[0037]

[0038] In formula (1),

[0039] Ar 1 and Ar 2 each independently represents a phenyl group, a biphenyl group or a naphthyl group;

[0040] Ar 3 express:

[0041] Aromatic hydrocarbon group belonging to a tricyclic condensed ring or a tetracyclic condensed ring,

[0042] A nitrogen-containing aromatic group consisting of only six-membered rings belonging to a tricyclic condensed ring or a tetracyclic condensed ring, or

[0043] A heteroaromatic group in which the heteroatom belonging to the tricyclic condensed ring or the tetracyclic condensed ring is a Group VI A element;

[0044] Ar 4 represents phenyl, azaphenyl, diazaphenyl, naphthyl, azanaphthyl or diazanaphthyl;

[0045] Ar 1 ,Ar 2 ,Ar 3 and Ar 4each independently optionally substituted by one or more groups selected from the group consisting of a fluorine atom, a methyl group, a phenyl group, a naphthyl group, an azaphenyl group, a diazaphenyl group, an azanaphthyl group and a diazanaphthyl group;

[0046] X represents phenylene, naphthylene, azaphenylene, diazaphenylene, azanaphthylene or diazanaphthylene;

[0047] p represents 0, 1 or 2;

[0048] When p is 2, two Xs may be the same as or different from each other.

[0049] Hereinafter, the triazine compound represented by the formula (1) may also be referred to as a triazine compound (1). Definitions and preferred specific examples of the substituents in the triazine compound (1) are as follows.

[0050] [About Ar 1 and Ar 2 ]

[0051] Ar 1 and Ar 2 Each independently represents a phenyl group, a biphenyl group or a naphthyl group. 1 and Ar 2 Each independently may be substituted by one or more groups selected from the group consisting of a fluorine atom, a methyl group, a phenyl group, a naphthyl group, an azaphenyl group, a diazaphenyl group, an azanaphthylidene group and a diazanaphthylidene group.

[0052] Ar 1 and Ar 2 Preferably they are the same groups. 1 with Ar 2 When they are the same group, the triazine compound (1) can be easily synthesized.

[0053] The triazine compound (1) preferably has Ar 1 and Ar 2 Each is independently an unsubstituted phenyl group, an unsubstituted biphenyl group or an unsubstituted naphthyl group.

[0054] As Ar 1 and Ar 2, each independently thereof includes, for example, phenyl, p-tolyl, m-tolyl, o-tolyl, p-fluorophenyl, m-fluorophenyl, o-fluorophenyl, 3,5-difluorophenyl, 2,4,6-trifluorophenyl, pentafluorophenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, mesityl, 1-naphthyl, 2-naphthyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, 3-methylbiphenyl-4-yl, 2'-methylbiphenyl-4-yl, 4'-methylbiphenyl-4-yl, 2,2'-dimethylbiphenyl-4-yl, 6-methylbiphenyl-3-yl, 5-methylbiphenyl-3-yl, 2'-methylbiphenyl-3-yl, 4'-methylbiphenyl-3-yl, 6,2'-diphenyl methylbiphenyl-3-yl, 5-methylbiphenyl-2-yl, 6-methylbiphenyl-2-yl, 2'-methylbiphenyl-2-yl, 4'-methylbiphenyl-2-yl, 6,2'-dimethylbiphenyl-2-yl, 2-(2-pyridyl)phenyl, 3-(2-pyridyl)phenyl, 4-(2-pyridyl)phenyl, 2-(3-pyridyl)phenyl, 3-(3-pyridyl)phenyl, 4-(3-pyridyl)phenyl, 2-(4-pyridyl)phenyl, 3-(4-pyridyl)phenyl, 4-(4-pyridyl)phenyl, 2-(3-methylpyridin-2-yl)phenyl, 3-(3-methylpyridin-2-yl)phenyl, 4-(3-methylpyridin-2-yl)phenyl, 2 phenyl, 3-(4-methylpyridin-2-yl)phenyl, 4-(4-methylpyridin-2-yl)phenyl, 2-(5-methylpyridin-2-yl)phenyl, 3-(5-methylpyridin-2-yl)phenyl, 4-(5-methylpyridin-2-yl)phenyl, 2-(6-methylpyridin-2-yl)phenyl, 3-(6-methylpyridin-2-yl)phenyl, 4-(6-methylpyridin-2-yl)phenyl, 2-(2-methylpyridin-3-yl)phenyl, 3-(2-methylpyridin-3-yl)phenyl, 4-(2-methylpyridin-3-yl)phenyl, 2-(4-methylpyridin-3-yl)phenyl, 3-(4-methylpyridin-2-yl)phenyl, phenyl, 3-(2-methylpyridin-4-yl)phenyl, 4-(2-methylpyridin-4-yl)phenyl, 2-(3-methylpyridin-4-yl)phenyl, 3-(3-methylpyridin-4-yl)phenyl, 4-(3-methylpyridin-4-yl)phenyl, and the like.

[0055] [About Ar 3 ]

[0056] In formula (1), Ar3 express:

[0057] Aromatic hydrocarbon group belonging to a tricyclic condensed ring or a tetracyclic condensed ring,

[0058] A nitrogen-containing aromatic group consisting of only six-membered rings belonging to a tricyclic condensed ring or a tetracyclic condensed ring, or

[0059] The heteroatom belonging to the tricyclic condensed ring or the tetracyclic condensed ring is a heteroaromatic group of which the heteroatom is a Group VI A element.

[0060] Ar 3 The group consisting of a fluorine atom, a methyl group, a phenyl group, a naphthyl group, an azaphenyl group, a diazaphenyl group, an azanaphthylidene group and a naphthylidene group may be substituted by one or more groups selected from the group consisting of a fluorine atom, a methyl group, a phenyl group, a naphthylidene group and a naphthylidene group.

[0061] Examples of the aromatic hydrocarbon group belonging to the tricyclic condensed ring or the tetracyclic condensed ring include phenanthryl, anthracenyl, pyrenyl, fluorenyl, benzofluorenyl, triphenanthrenyl or fluoranthenyl, etc. These groups may be substituted with one or more groups selected from the group consisting of a fluorine atom, a methyl group, a phenyl group, an azaphenyl group, a diazaphenyl group, a naphthyl group, azanaphthylidene group and a diazanaphthylidene group.

[0062] The triazine compound (1) is preferably Ar from the viewpoint of contributing to the formation of a high-performance organic electroluminescent device. 3 It is a tricyclic or tetracyclic condensed aromatic hydrocarbon group which is optionally substituted by one or more groups selected from the group consisting of a fluorine atom, a methyl group, a phenyl group, an azaphenyl group, a diazaphenyl group, a naphthyl group, an azaphthalene group and a diazaphthalene group.

[0063] In addition, from the viewpoint of easy synthesis of the triazine compound (1), Ar 3 An unsubstituted condensed-ring aromatic hydrocarbon group is preferred.

[0064] Examples of the nitrogen-containing aromatic group consisting of only a six-membered ring belonging to a tricyclic condensed ring or a tetracyclic condensed ring include benzo[b]quinolyl, benzo[c]quinolyl, benzo[f]quinolyl, benzo[g]quinolyl, benzo[h]quinolyl, phenazinyl, azapyrenyl, diazapyrenyl, azatriphenylenyl, diazatriphenylenyl, etc. These groups may be substituted with one or more groups selected from the group consisting of a fluorine atom, a methyl group, a phenyl group, a naphthyl group, azaphenylenyl, diazaphenylenyl, and diazaphenylenyl.

[0065] The triazine compound (1) is preferably Ar from the viewpoint of contributing to the formation of a high-performance organic electroluminescent device. 3 It is unsubstituted benzo[b]quinolyl, benzo[c]quinolyl, benzo[f]quinolyl, benzo[g]quinolyl, benzo[h]quinolyl, azapyrenyl, diazapyrenyl, azatriphenylenyl, diazatriphenylenyl.

[0066] Examples of the heteroaromatic group in which the heteroatom belonging to the tricyclic condensed ring or the tetracyclic condensed ring is a Group VI A element include dibenzothiophenyl, dibenzofuranyl, benzonaphthofuranyl, benzonaphthothiophenyl, etc. These groups may be substituted with one or more groups selected from the group consisting of a fluorine atom, a methyl group, a phenyl group, a naphthyl group, an azaphenyl group, a diazaphenyl group, a diazanaphthylidene group, and a diazanaphthylidene group.

[0067] The triazine compound (1) is preferably Ar from the viewpoint of contributing to the formation of a high-performance organic electroluminescent device. 3 It is an unsubstituted dibenzofuranyl group or an unsubstituted dibenzothiophenyl group.

[0068] [About Ar 4 ]

[0069] Ar 4 represents phenyl, azaphenyl, diazaphenyl, naphthyl, naphthazinyl or naphthazinyl. These groups may be substituted by one or more groups selected from the group consisting of fluorine atoms, methyl groups, phenyl, azaphenyl, diazaphenyl, naphthyl, naphthazinyl and naphthazinyl.

[0070] As Ar 4 , for example, phenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, quinolyl, isoquinolyl, naphthyridinyl, quinoxalinyl, quinazolinyl, etc. These groups may be substituted by one or more groups selected from the group consisting of fluorine atoms, methyl, phenyl, azaphenyl, diazaphenyl, naphthyl, azanaphthyl and diazanaphthyl.

[0071] The triazine compound (1) is preferably Ar from the viewpoint of contributing to the formation of a high-performance organic electroluminescent device. 4 is phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, naphthyl, pyridyl, methylpyridyl, dimethylpyridyl, phenylpyridyl, diphenylpyridyl, pyrimidinyl, methylpyrimidinyl, dimethylpyrimidinyl, phenylpyrimidinyl, diphenylpyrimidinyl, pyrazinyl, methylpyrazinyl or phenylpyrazinyl.

[0072] [About X]

[0073] X represents a phenylene group, an azaphenylene group, a diazaphenylene group, a naphthylene group, an azanaphthylene group or a diazanaphthylene group.

[0074] Examples of X include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,3-pyridylene, 2,4-pyridylene, 2,5-pyridylene, 2,6-pyridylene, 2,4-pyrimidylene, 2,5-pyrimidylene, 2,5-pyrazinylene, 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,6-naphthylene, 1,7-naphthylene, 1,8-naphthylene, 2,3-naphthylene, 2,4-naphthylene, 2,5-naphthylene, 2,6-naphthylene, 2,7-naphthylene, 2,8-naphthylene, 2,9-naphthylene, 3-naphthylene, 4-naphthylene, 5-naphthylene, 6-naphthylene, 7-naphthylene, 8-naphthylene, 2,9-naphthylene, 1,10-naphthylene, 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,6-naphthylene, 1,7-naphthylene, 1,8-naphthylene, 2,3-naphthylene, 2,4-naphthylene, 2,5-naphthylene, 2,6-naphthylene, 2,7-naphthylene, 2,8-naphthylene, 2,9-naphthylene, 3-naphthylene, 2 3-quinolylene, 2,4-quinolylene, 2,5-quinolylene, 2,6-quinolylene, 2,7-quinolylene, 2,8-quinolylene, 3,4-quinolylene, 3,5-quinolylene, 3,6-quinolylene, 3,7-quinolylene, 3,8-quinolylene, 4,5-quinolylene, 4,6-quinolylene, 4,7-quinolylene, 4,8-quinolylene, 5,8-quinolylene, 2,3-quinoxalylene, 2,5-quinoxalylene, 2,6-quinoxalylene, 2,4-quinazolinylene, 2,5-quinazolinylene, 2,6-quinazolinylene and the like.

[0075] Regarding the triazine compound (1), from the viewpoint of contributing to the formation of a high-performance organic electroluminescent device, X is preferably a phenylene group or an azaphenylene group, and more preferably a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 2,3-pyridylene group, a 2,4-pyridylene group, a 2,5-pyridylene group, or a 2,6-pyridylene group.

[0076] [About p]

[0077] p represents 0, 1 or 2. When p is 2, two Xs may be the same as or different from each other.

[0078] Regarding the triazine compound (1), p is more preferably 0 or 1 from the viewpoint of further contributing to formation of a high-performance organic electroluminescent device.

[0079] [Specific examples of triazine compounds (1)]

[0080] As specific examples of the triazine compound (1), the following (A-1) to (A-285) can be illustrated, but the present application is not limited thereto. From the perspective of good performance as an electron transport material in an organic electroluminescent element, the triazine compound (1) is preferably a compound represented by (A-3), (A-39), (A-49), (A-53), (A-54), (A-58), (A-62), (A-98), (A-106), (A-122), (A-129), (A-130), (A-182), (A-254), and (A-269).

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] Next, the method for producing the triazine compound (1) is described.

[0100] The triazine compound (1) can be produced by the methods shown in the following synthesis routes (i) to (vi).

[0101] Synthesis route (i)

[0102]

[0103] Synthetic route (ii)

[0104]

[0105] Synthesis route (iii)

[0106]

[0107] Synthesis route (iv)

[0108]

[0109] Synthetic route (v)

[0110]

[0111] Synthetic route (vi)

[0112]

[0113] In formulas (2) to (12),

[0114] Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 The definitions of X and p are the same as those of Ar in formula (1). 1 ,Ar 2 ,Ar 3 ,Ar 4 , X and p have the same definition;

[0115] Y 1 , Y 2 , Y 3 and Y 4 each independently represents a halogen atom;

[0116] R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group;

[0117] B(OR 1 )2's two R's 1 Optional: same or different;

[0118] Two R's 1 Optionally, it forms a ring with an oxygen atom and a boron atom.

[0119] As Y 1 , Y 2 , Y 3 and Y 4 The halogen atom shown may be, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a chlorine atom or a bromine atom is preferred from the viewpoint of a good yield of the triazine compound (1).

[0120] As B(OR 1 )2, for example, B(OH)2, B(OMe)2, B(O i Pr)2, B(OBu)2, B(OPh)2, etc. It should be noted that Me represents a methyl group. iPr represents isopropyl, Bu represents butyl, and Ph represents phenyl.

[0121] As two R 1 When forming a ring with oxygen and boron atoms, B(OR 1 As examples of )2, for example, the groups represented by the following (I) to (VI) can be illustrated, and the group represented by (II) is preferred from the viewpoint of good yield.

[0122]

[0123] The coupling reaction in the synthetic routes (i) to (vi) is a method of reacting an aryl halide represented by formula (2), (3), (4), (11) or (12) with a boron compound represented by formula (5), (6), (7), (8), (9) or (10) in the presence of a palladium catalyst and a base, and the reaction conditions of the conventional Suzuki-Miyaura reaction can be applied.

[0124] The boron compound can be produced according to the method disclosed in, for example, The Journal of Organic Chemistry, Vol. 60, p. 7508, 1995 or The Journal of Organic Chemistry, Vol. 65, p. 164, 2000.

[0125] The aryl halide can be prepared according to, for example, Journal of the American Chemical Society, Vol. 74, p. 6289, 1952 or Synlett, p. 808, 2002. Alternatively, commercially available products may be used. From the perspective of a good reaction yield, the aryl halide is preferably used in an amount of 0.5 to 3.0 molar equivalents relative to the boron compound.

[0126] The borylation reaction in the synthetic routes (iii) to (vi) is a method for producing a boron compound represented by formula (5), (6), (7) or (8) by reacting an aryl halide represented by formula (2), (3) or (4) with a boron raw material (e.g., pinacol borane, bis-pinacol diboron, etc.) in the presence of a palladium catalyst and a base. These boron compounds can be produced according to the method disclosed in, for example, The Journal of Organic Chemistry, Vol. 60, p. 7508, 1995 or Tetrahedron Letters, Vol. 38, p. 3447, 1997.

[0127] As palladium catalysts used in the above-mentioned coupling reaction and borylation reaction, palladium salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate can be listed. Furthermore, coordination compounds such as π-allyl palladium chloride dimer, palladium acetylacetonate, tris(dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloropalladium, and bis(benzonitrile)dichloropalladium can be listed; and palladium complexes having tertiary phosphine as ligands such as bis(triphenylphosphine)dichloropalladium, tetrakis(triphenylphosphine)palladium, (1,1'-bis(diphenylphosphine)ferrocene)dichloropalladium, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, and bis(tricyclohexylphosphine)dichloropalladium can be listed. Tertiary phosphine can also be added to these palladium salts or coordination compounds and prepared in the reaction system.

[0128] Examples of the tertiary phosphine include triphenylphosphine, trimethylphosphine, tributylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(diphenylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)xanthene, and 1,2-bis(diphenylphosphino)methane. (Diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, tri(2-furyl)phosphine, tri(o-tolyl)phosphine, tri(2,5-xylyl)phosphine, (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, etc.

[0129] Among them, a palladium complex having a tertiary phosphine as a ligand is preferred from the viewpoint of good yield, and a palladium complex having 2-dicyclohexylphosphine-2′,4′,6′-triisopropylbiphenyl or tricyclohexylphosphine as a ligand is more preferred.

[0130] The molar ratio of the tertiary phosphine to the palladium salt or coordination compound is preferably in the range of 1:10 to 10:1, and is more preferably in the range of 1:2 to 3:1 from the perspective of good yield. The amount of the palladium catalyst used in the coupling reaction and the borylation reaction is not limited, and the molar equivalent of the palladium catalyst relative to the boron compound is preferably in the range of 0.005 to 0.5 molar equivalents from the perspective of good yield.

[0131] As the base used in the above-mentioned coupling reaction and borylation reaction, for example, metal hydroxide salts such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, metal carbonates such as metal acetate, sodium acetate, metal acetate, potassium phosphate, sodium phosphate, metal phosphates such as sodium fluoride, potassium fluoride, cesium fluoride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium isopropoxide, potassium tert-butoxide, etc. can be listed. Among them, from the aspect of good reaction yield, metal carbonate or metal phosphate is preferred, and potassium carbonate or potassium phosphate is further preferred. The amount of the base used is not particularly limited. From the aspect of good reaction yield, the molar ratio of the base to the boron compound is preferably in the range of 1:2 to 10:1, and more preferably in the range of 1:1 to 4:1.

[0132] When used in the aforementioned coupling reaction and borylation reaction, it can be carried out in a solvent.

[0133] Examples of the solvent include water, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, dimethoxyethane and other ethers; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin and other aromatic hydrocarbons; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-fluoroethylene carbonate and other carbonates; ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyric acid and other aromatic hydrocarbons. Esters such as methyl esters and γ-lactones; amides such as N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP); ureas such as N,N,N',N'-tetramethylurea (TMU) and N,N'-dimethylpropyleneurea (DMPU); alcohols such as dimethyl sulfoxide (DMSO), methanol, ethanol, isopropanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol. They can be used alone or in any proportion. The amount of solvent used is not particularly limited. Among them, water, ethers, amides, alcohols, and mixed solvents thereof are preferred from the perspective of good reaction yield, and a mixed solvent of THF and water, or a mixed solvent of toluene and 1-butanol is further preferred.

[0134] The coupling reaction and borylation reaction can be carried out at a temperature appropriately selected from 0°C to 200°C, and are preferably carried out at a temperature appropriately selected from 60°C to 160°C from the viewpoint of good reaction yield.

[0135] The coupling reaction and borylation reaction can be carried out by appropriately combining, as necessary, conventional purification treatments such as recrystallization, column chromatography, sublimation purification, and preparative HPLC after completion of the reaction to obtain the target product.

[0136] The triazine compound (1) can be used for organic electronic devices such as organic electroluminescent devices and photoelectric devices.

[0137] <Materials for organic electroluminescent devices>

[0138] An organic electroluminescent device material according to one embodiment of the present application contains the triazine compound (1).

[0139] The triazine compound (1) can be used as an electron transport material for an organic electroluminescent device. The organic electroluminescent device material containing the triazine compound (1) contributes to the production of an organic electroluminescent device that exhibits high luminous efficiency and long life and can be used in various applications or environments.

[0140] <Organic electroluminescent element>

[0141] The organic electroluminescent device (hereinafter sometimes simply referred to as an organic electroluminescent device) containing the triazine compound (1) is described below.

[0142] An organic electroluminescent device according to one embodiment of the present application contains a triazine compound (1).

[0143] The structure of the organic electroluminescent element is not particularly limited, and examples thereof include the structures (i) to (v) shown below.

[0144] (i): Anode / light-emitting layer / cathode

[0145] (ii): Anode / hole transport layer / light-emitting layer / cathode

[0146] (iii): Anode / light-emitting layer / electron transport layer / cathode

[0147] (iv): anode / hole transport layer / light-emitting layer / electron transport layer / cathode

[0148] (v): anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode

[0149] The triazine compound (1) may be contained in any of the above layers, but is preferably contained in one or more layers selected from the group consisting of a light-emitting layer and a layer between the light-emitting layer and a cathode, from the viewpoint of excellent light-emitting properties of the organic electroluminescent element. Therefore, in the case of the above-mentioned structures (i) to (v), the triazine compound (1) is preferably contained in one or more layers selected from the group consisting of a light-emitting layer, an electron transport layer, and an electron injection layer.

[0150] Hereinafter, the above-mentioned structure (v) is cited as an example, referring to Figure 1 An organic electroluminescent element according to one embodiment of the present application will be described in more detail.

[0151] It should be noted that Figure 1 The organic electroluminescent element shown has a so-called bottom emission element structure, but the organic electroluminescent element of one embodiment of the present application is not limited to the bottom emission element structure. That is, the organic electroluminescent element of one embodiment of the present application may be a top emission element or other known element structure.

[0152] Figure 1 This is a schematic cross-sectional view showing an example of a laminated structure of an organic electroluminescent element including a triazine compound according to one embodiment of the present application.

[0153] The organic electroluminescent element 100 sequentially comprises a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a cathode 8. Among them, some of the layers may be omitted, and conversely, other layers may be added. For example, a hole blocking layer may be provided between the light-emitting layer 5 and the electron transport layer 6, or the hole injection layer 3 may be omitted and the hole transport layer 4 may be provided directly on the anode 2. In addition, a single layer having the functions of multiple layers, such as an electron injection / transport layer having the functions of an electron injection layer and an electron transport layer in a single layer, may be used to replace the multiple layers. Furthermore, for example, a single-layer hole transport layer 4 and a single-layer electron transport layer 6 may be formed by multiple layers, respectively.

[0154] <<Layer containing triazine compound (1)>>

[0155] Figure 1 In the illustrated configuration example, the organic electroluminescent element 100 contains the triazine compound (1) in at least one layer selected from the group consisting of the light-emitting layer 5, the electron transport layer 6, and the electron injection layer 7. It is particularly preferred that the electron transport layer 6 contains the triazine compound (1). It should be noted that the triazine compound (1) may be contained in a plurality of layers included in the organic electroluminescent element.

[0156] In addition, the organic electroluminescent element 100 in which the electron transport layer 6 contains the triazine compound (1) is described below.

[0157] [Substrate 1]

[0158] The substrate 1 is not particularly limited, and examples thereof include a glass plate, a quartz plate, and a plastic plate.

[0159] Examples of the substrate 1 include a glass plate, a quartz plate, a plastic plate, and a plastic film. Among them, a glass plate, a quartz plate, and a light-transmitting plastic film are preferred.

[0160] Examples of light-transmitting plastic films include films formed from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), triacetyl cellulose (TAC), cellulose acetate propionate (CAP), and the like.

[0161] In addition, in the case of a configuration in which light emission is extracted from the substrate 1 side, the substrate 1 is transparent to the wavelength of light.

[0162] [Anode 2]

[0163] An anode 2 is provided on the substrate 1 (on the hole injection layer 3 side).

[0164] The material of the anode includes metals, alloys, conductive compounds and mixtures thereof with a large work function (e.g., 4 eV or more). Specific examples of the material of the anode include metals such as Au; conductive transparent materials such as CuI, indium tin oxide (ITO), SnO2, and ZnO.

[0165] In the case of an organic electroluminescent element having a structure in which light emission is extracted through an anode, the anode is formed of a conductive transparent material that allows the light emission to pass or substantially pass.

[0166] [Hole injection layer 3, hole transport layer 4]

[0167] Between the anode 2 and a light-emitting layer 5 described later, a hole injection layer 3 and a hole transport layer 4 are provided in this order from the anode 2 side.

[0168] The hole injection layer and the hole transport layer have the function of transporting holes injected from the anode to the light-emitting layer. By sandwiching the hole injection layer and the hole transport layer between the anode and the light-emitting layer, more holes can be injected into the light-emitting layer under a lower electric field.

[0169] In addition, the hole injection layer and the hole transport layer also function as the layer of electron barrier. That is, the potential barrier of the electrons existing at the interface of the luminescent layer and the hole injection layer and / or the hole transport layer is utilized to suppress the leakage of the electrons injected from the cathode and transported to the luminescent layer by the electron injection layer and / or the electron transport layer to the hole injection layer and / or the hole transport layer. As a result, the electrons are accumulated at the interface in the luminescent layer, bringing the effects such as improving the luminous efficiency, and obtaining the organic electroluminescent element with excellent luminescent performance.

[0170] The material of the hole injection layer and the hole transport layer has at least any one of hole injection property, hole transport property and electron barrier property. The material of the hole injection layer and the hole transport layer may be any of organic and inorganic substances.

[0171] Specific examples of materials for the hole injection layer and the hole transport layer include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyaryl alkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, aromatic amine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers (especially thiophene oligomers), porphyrin compounds, aromatic tertiary amine compounds, styrylamine compounds, etc. Among them, porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds are preferred from the perspective of good performance of the organic electroluminescent element, and aromatic tertiary amine compounds are particularly preferred.

[0172] Specific examples of the aromatic tertiary amine compound and the styrylamine compound include N,N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N'-bis(m-tolyl)-[1,1'-biphenyl]-4,4'-diamine (TPD), 2,2-bis(4-di-p-tolylaminophenyl)propane, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis(4-di-p-tolylaminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenylmethane, N,N'-diphenyl-N ,N'-bis(4-methoxyphenyl)-4,4'-diaminobiphenyl, N,N,N',N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis(diphenylamino)tetraphenyl, N,N,N-tri(p-tolyl)amine, 4-(di-p-tolylamino)-4'-〔4-(di-p-tolylamino)phenylvinyl〕stilbene, 4-N,N-diphenylamino-(2-diphenylvinyl)benzene, 3-methoxy-4'-N,N-diphenylaminophenylvinylbenzene, N-phenylcarbazole, 4,4'-bis〔N-(1-naphthyl)-N-phenylamino〕biphenyl (NPD), 4,4',4"-tri〔N-(m-tolyl)-N-phenylamino〕triphenylamine (MTDATA), etc.

[0173] Inorganic compounds such as p-type-Si and p-type-SiC can also be given as examples of the material of the hole injection layer and the material of the hole transport layer.

[0174] The hole injection layer and the hole transport layer may have a single structure formed of one or two or more materials, or may have a stacked structure formed of a plurality of layers of the same composition or different compositions.

[0175] [Luminous layer 5]

[0176] The light emitting layer 5 is provided between the hole transport layer 4 and the electron transport layer 6 described later.

[0177] Examples of the material of the light-emitting layer include phosphorescent materials, fluorescent materials, and thermally activated delayed fluorescent materials. In the light-emitting layer, electron / hole pairs recombine, resulting in emission of light.

[0178] The light-emitting layer can be formed of a single low-molecular material or a single polymer material, and more generally, is formed of a host material obtained by doping with a guest compound. The light emission is mainly generated by the dopant and can have any color.

[0179] Examples of the host material include compounds having biphenyl, fluorenyl, triphenylsilyl, carbazole, pyrenyl, and anthracene groups. More specifically, DPVBi (4,4'-bis(2,2-diphenylvinyl)-1,1'-biphenyl), BCzVBi (4,4'-bis(9-ethyl-3-carbazolylidene)-1,1'-biphenyl), TBADN (2-tert-butyl-9,10-di(2-naphthyl)anthracene), ADN (9,10-di(2-naphthyl)anthracene), CBP (4,4'-bis(carbazole-9-yl)biphenyl), CDBP (4,4'-bis(carbazole-9-yl)-2,2'-dimethylbiphenyl), 2-(9-phenylcarbazole-3-yl)-9-[4-(4-phenylphenylquinazolin-2-yl)carbazole, and 9,10-bis(biphenyl)anthracene.

[0180] As fluorescent dopants, for example, anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylene pyran compounds, thiopyran compounds, polymethine compounds, pyrylium, thiopyranium compounds, fluorene derivatives, diindenopyrene derivatives, indenoperylene derivatives, bis(azinyl)amine boron compounds, bis(azinyl)methane compounds, quinolone compounds, etc. The fluorescent dopant may be combined with two or more selected from them.

[0181] Examples of the phosphorescent dopant include organic metal complexes of transition metals such as iridium, platinum, palladium, and osmium.

[0182] Specific examples of fluorescent dopants and phosphorescent dopants include Alq3 (tris(8-hydroxyquinoline)aluminum), DPAVBi (4,4'-bis[4-(di-p-tolylamino)phenylvinyl]biphenyl), perylene, bis[2-(4-n-hexylphenyl)quinoline](acetylacetonate)iridium(III), Ir(PPy)3 (tris(2-phenylpyridine)iridium(III)) and FIrPic (bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(III))).

[0183] In addition, the luminescent material is not limited to being contained only in the luminescent layer. For example, the layer adjacent to the luminescent layer (hole transport layer 4 or electron transport layer 6) may also contain the luminescent material. This can further improve the current efficiency of the organic electroluminescent element.

[0184] The light-emitting layer may have a single-layer structure formed of one or two or more materials, or may have a stacked structure formed of a plurality of layers having the same composition or different compositions.

[0185] [Electron transport layer 6]

[0186] An electron transport layer 6 is provided between the light emitting layer 5 and an electron injection layer 7 described later.

[0187] The electron transport layer has the function of transporting electrons injected from the cathode to the light-emitting layer. By sandwiching the electron transport layer between the cathode and the light-emitting layer, electrons are injected into the light-emitting layer under a lower electric field.

[0188] The electron transport layer preferably contains the triazine compound (1) as described above. In addition, the electron transport layer may further contain one or more selected from conventionally known electron transport materials in addition to the triazine compound (1).

[0189] When the triazine compound (1) is contained in another layer instead of the electron transport layer, one or more selected from conventionally known electron transport materials can be used as the electron transport material constituting the electron transport layer.

[0190] Examples of conventionally known electron transporting materials include alkali metal complexes, alkaline earth metal complexes, and earth metal complexes. Examples of alkali metal complexes, alkaline earth metal complexes, and earth metal complexes include, for example, 8-hydroxyquinoline lithium (Liq), bis(8-hydroxyquinoline) zinc, bis(8-hydroxyquinoline) copper, bis(8-hydroxyquinoline) manganese, tris(8-hydroxyquinoline) aluminum, tris(2-methyl-8-hydroxyquinoline) aluminum, tris(8-hydroxyquinoline) gallium, bis(10-hydroxybenzo[h]quinoline) beryllium, bis(10-hydroxybenzo[h]quinoline) zinc, bis(2-methyl-8-quinoline) chlorogallium, bis(2-methyl-8-quinoline)(o-cresol) gallium, bis(2-methyl-8-quinoline)-1-naphthoaluminum, and bis(2-methyl-8-quinoline)-2-naphthoaluminum.

[0191] The electron transport layer may have a single layer structure formed of one or two or more materials, or may have a stacked structure formed of a plurality of layers having the same composition or different compositions.

[0192] In the organic electroluminescent element of this embodiment, an electron injection layer may be provided in order to enhance electron injection properties and improve element characteristics (for example, luminous efficiency, constant voltage driving, or high durability).

[0193] [Electron injection layer 7]

[0194] An electron injection layer 7 is provided between the electron transport layer 6 and a cathode 8 described later.

[0195] The electron injection layer has the function of transferring electrons injected from the cathode to the light-emitting layer. By sandwiching the electron injection layer between the cathode and the light-emitting layer, electrons are injected into the light-emitting layer under a lower electric field.

[0196] As the material of the electron injection layer, there can be listed organic compounds such as fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenyl methane, anthraquinone dimethane, anthrone, etc. In addition, as the material of the electron injection layer, there can also be listed inorganic compounds such as various oxides, nitrides, and oxynitrides such as SiO2, AlO, SiN, SiON, AlON, GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, and C.

[0197] [Cathode 8]

[0198] A cathode 8 is provided on the electron injection layer 7 .

[0199] In the case of an organic electroluminescent element having a configuration in which only light emitted through the anode is extracted, the cathode may be formed of any conductive material.

[0200] Examples of the cathode material include metals with a small work function (hereinafter also referred to as electron-injecting metals), alloys, conductive compounds, and mixtures thereof. Here, the metal with a small work function refers to, for example, a metal with a work function of 4 eV or less.

[0201] Specific examples of cathode materials include sodium, sodium-potassium alloys, magnesium, lithium, magnesium / copper mixtures, magnesium / silver mixtures, magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al2O3) mixtures, indium, lithium / aluminum mixtures, and rare earth metals.

[0202] Among them, from the aspects of electron injectability and durability against oxidation, etc., preferred are mixtures of an electron injectable metal and a second metal, such as a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al2O3) mixture, a lithium / aluminum mixture, etc., wherein the second metal is a metal having a work function value larger than that of the above-mentioned electron injectable metal and being stable.

[0203] [Method for forming each layer]

[0204] Each layer other than the electrode (anode, cathode) described above can be formed by thin filming by known methods such as vacuum evaporation, spin coating, casting, LB (Langmuir-Blodgett method), etc. The material of each layer can be used alone or together with a material such as a binder resin or a solvent as needed.

[0205] The film thickness of each layer formed in this way is not particularly limited and can be appropriately selected depending on the situation, but is usually in the range of 5 nm to 5 μm.

[0206] The anode and cathode can be formed by thinning the electrode material by vapor deposition, sputtering, etc. The pattern can be formed through a mask of a desired shape during vapor deposition or sputtering, or after forming a thin film by vapor deposition, sputtering, etc., the pattern of the desired shape can be formed by photolithography.

[0207] The film thickness of the anode and the cathode is preferably 1 μm or less, more preferably 10 nm or more and 200 nm or less.

[0208] It should be noted that when forming a layer containing the triazine compound (1), it can be used in combination with the above-mentioned conventionally known electron transporting material. Therefore, for example, the triazine compound (1) and the conventionally known electron transporting material can be co-evaporated, or a layer of a conventionally known electron transporting material can be stacked on the layer of the triazine compound (1).

[0209] Organic electroluminescent elements can be used as a kind of lamp such as a light source for lighting or exposure, and can also be used as a projection device of the type that projects images onto a screen, or a display device (display) of the type that directly views static images or dynamic images. When using organic electroluminescent elements as a display device for video playback, the driving method can be a simple matrix (passive matrix) method or an active matrix method. In addition, by using two or more organic electroluminescent elements with different luminescent colors, a full-color display device can be produced.

[0210] When the triazine compound (1) is used as an electron transport layer, it is possible to provide an organic electroluminescent element with significantly superior luminous efficiency and long life characteristics compared to the conventionally known triazine compounds. Furthermore, the triazine compound (1) has high film stability due to its sterically hindered skeleton and high amorphous property. Therefore, it is expected to improve the driving stability of the organic electroluminescent element, improve the luminous efficiency, and other effects. In addition, the triazine compound (1) has high chemical stability due to its characteristic skeleton, which can contribute to the long life of the organic electroluminescent element.

[0211] By using the triazine compound (1) as the electron transport layer of an organic electroluminescent element, a triazine compound that can simultaneously achieve low voltage drive, high efficiency and long life of the element at a high level can be provided. Furthermore, an organic electroluminescent element that can achieve low voltage drive, high efficiency and long life using the triazine compound (1) can be provided.

[0212] The various aspects of the present application include the following [1] to

[10] .

[0213] [1]: A triazine compound represented by formula (1):

[0214]

[0215] In formula (1),

[0216] Ar 1 and Ar 2 each independently represents a phenyl group, a biphenyl group or a naphthyl group;

[0217] Ar 3 express:

[0218] Aromatic hydrocarbon group belonging to a tricyclic condensed ring or a tetracyclic condensed ring,

[0219] A nitrogen-containing aromatic group consisting of only six-membered rings belonging to a tricyclic condensed ring or a tetracyclic condensed ring, or

[0220] A heteroaromatic group in which the heteroatom belonging to the tricyclic condensed ring or the tetracyclic condensed ring is a Group VI A element;

[0221] Ar 4 represents phenyl, azaphenyl, diazaphenyl, naphthyl, azanaphthyl or diazanaphthyl;

[0222] Ar 1 ,Ar 2 ,Ar 3 and Ar 4 each independently optionally substituted by one or more groups selected from the group consisting of a fluorine atom, a methyl group, a phenyl group, a naphthyl group, an azaphenyl group, a diazaphenyl group, an azanaphthyl group and a diazanaphthyl group;

[0223] X represents phenylene, naphthylene, azaphenylene, diazaphenylene, azanaphthylene or diazanaphthylene;

[0224] p represents 0, 1 or 2;

[0225] When p is 2, two Xs may be the same as or different from each other.

[0226] [2]: The triazine compound according to [1], wherein Ar 1 and Ar 2are the same group.

[0227] [3]: The triazine compound according to [1] or [2], wherein Ar 1 and Ar 2 Each is independently an unsubstituted phenyl group, an unsubstituted biphenyl group or an unsubstituted naphthyl group.

[0228] [4]: The triazine compound according to any one of [1] to [3], wherein Ar 3 It is a tricyclic or tetracyclic condensed aromatic hydrocarbon group which is optionally substituted by one or more groups selected from the group consisting of a fluorine atom, a methyl group, a phenyl group, a naphthyl group, an azaphenyl group, a diazaphenyl group, an azaphthalene group and a diazaphthalene group.

[0229] [5]: The triazine compound according to any one of [1] to [4], wherein Ar 3 It is an unsubstituted tricyclic or tetracyclic condensed-ring aromatic hydrocarbon group.

[0230] [6]: The triazine compound according to any one of [1] to [5], wherein Ar 4 is phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, naphthyl, pyridyl, methylpyridyl, dimethylpyridyl, phenylpyridyl, diphenylpyridyl, pyrimidinyl, methylpyrimidinyl, dimethylpyrimidinyl, phenylpyrimidinyl, diphenylpyrimidinyl, pyrazinyl, methylpyrazinyl or phenylpyrazinyl.

[0231] [7]: The triazine compound according to any one of [1] to [6], wherein X is a phenylene group or an azaphenylene group.

[0232] [8]: The triazine compound according to any one of [1] to [7], wherein p is 0 or 1.

[0233] [9]: A material for an organic electroluminescent device, comprising the triazine compound according to any one of [1] to [8].

[0234]

[10] : An organic electroluminescent device comprising the triazine compound according to any one of [1] to [9].

[0235] Example

[0236] Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not to be construed as being limitative of these Examples.

[0237] [ 1 H-NMR measurement]

[0238] 1Bruker ASCEND 400 (400 MHz; manufactured by BRUKER) was used for H-NMR measurement. 1 H-NMR was measured using deuterated chloroform (CDCl3) as a measurement solvent and tetramethylsilane (TMS) as an internal standard substance. In addition, commercially available reagents were used.

[0239] [DSC measurement (glass transition temperature, crystallization temperature, melting point)]

[0240] The glass transition temperature, crystallization temperature and melting point were measured using a DSC (Differential Scanning Calorimetry) apparatus DSC7020 (product name, manufactured by Hitachi High-Tech Science Corporation.) Alumina (Al2O3) was used as a reference in the DSC measurement, and the measurement was performed using a 10 mg sample.

[0241] As a pretreatment for the measurement, the sample was heated from 30°C to a temperature above the melting point at a rate of 15°C / min to melt it, and then quenched with liquid nitrogen. Next, the pretreated sample was heated from 30°C at a rate of 5°C / min to measure the glass transition temperature, crystallization temperature, and melting point.

[0242] [FDMS measurement]

[0243] The FDMS measurement was performed using M-80B manufactured by Hitachi, Ltd.

[0244] [Luminescence characteristics measurement]

[0245] The light emission characteristics of the organic electroluminescent element were evaluated by applying a direct current to the element prepared in each Example (described later) under an environment of 25° C. using a luminance meter BM-9 (product name, manufactured by TOPCON TECHNOHOUSE CORPORATION).

[0246] Synthesis Example-1

[0247]

[0248] Thionyl chloride (295 g, 2.5 mol) was added to 4-bromo-3-chlorobenzoic acid (152 g, 650 mmol) and DMF (2 mL), and the mixture was heated under reflux for 20 hours. After cooling to room temperature, the low boiling fraction was distilled off under reduced pressure to obtain 4-bromo-3-chlorobenzoyl chloride. The substance was used in the next step without purification.

[0249] Under an argon atmosphere, 4-bromo-3-chlorobenzoyl chloride (164 g, 650 mmol) and benzonitrile (146 g, 1.4 mol) were suspended in monochlorobenzene (1.3 L). Antimony chloride (82 mL, 650 mmol) was added dropwise while cooling the suspension with an ice bath, and stirred at 0°C for 15 minutes, and then stirred at 70°C for 12 hours. After the reaction, the reaction mixture was added dropwise to 30%-ammonia water (2 L) while cooling with an ice bath, and stirred at room temperature for 8 hours. The generated solid was filtered and washed with water. The obtained solid was suspended in toluene (5 L) and heated and stirred at 110°C for 30 minutes. The suspension was filtered, and the low-boiling components were distilled off from the filtrate under reduced pressure. The obtained solid was washed with methanol and hexane, and the obtained crude purified product was repeatedly recrystallized from toluene to obtain 2-(4-bromo-3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (150 g, 55%) as a white solid.

[0250] 1 H-NMR (CDCl3): δ7.58-7.66 (m, 6H), 7.82 (d, J=8.4Hz, 1H), 8.52 (dd, J=8.4, 2.0Hz, 1H), 8.76 (brd, J=6.7Hz, 4H), 8.84 (d, J=2.0Hz, 1H).

[0251] Synthesis Example-1

[0252]

[0253] Under an argon atmosphere, 2-(4-bromo-3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (10.1 g, 24 mmol), bis-pinacolato diboron (7.25 g, 29 mmol), bis(triphenylphosphine) palladium dichloride (842 mg, 1.2 mmol) and potassium acetate (8.50 g, 86 mmol) were suspended in THF (48 mL) and stirred at 80 ° C for 21 hours. After cooling to room temperature, chloroform was added to the reaction mixture to extract the organic layer, and the organic layer was washed with water, saturated sodium bicarbonate aqueous solution, and saturated saline. Sodium sulfate and activated carbon were added to the organic layer and stirred, and then the solid content was removed by diatomaceous earth filtration, and the solvent was distilled off. The crude purified product was further suspended in hexane and collected by filtration to obtain 2-[3-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (6.5 g, 52%) as a yellow solid.

[0254] 1H-NMR (CDCl3): δ1.43 (s, 12H), 7.57-7.65 (m, 6H), 7.88 (d, J=7.8Hz, 1H), 8.61 (dd, J=7.8Hz, 1.4Hz, 1H), 8.75 (d, J=1.4Hz, 1H), 8.78 (brd, J=6.6Hz, 4H).

[0255] Synthesis Example-2

[0256]

[0257] Under an argon atmosphere, 2-[3-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (6.40 g, 14 mmol), 3-bromo-2,6-dimethylpyridine (2.1 mL, 16 mmol) and bis(triphenylphosphine)palladium dichloride (295 mg, 0.42 mmol) were suspended in THF (28 mL). A 2.0 M potassium phosphate aqueous solution (25 mL) was added to the suspension and stirred at 80°C for about 16 hours. After cooling to room temperature, water and methanol were added to the reaction mixture, and the precipitated solid was filtered out and washed with water and methanol. The obtained solid was dissolved in chloroform (600 mL), and after filtering the insoluble portion with filter paper, activated carbon was added to the filtrate and stirred for a while. After stirring, celite filtration was performed, and low-boiling components were distilled off from the filtrate to obtain a crude purified product. The crude purified product was repeatedly recrystallized from toluene to obtain the target product 2-[3-chloro-4-(2,6-dimethylpyridin-3-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (2.8 g, 45%).

[0258] 1 H-NMR (CDCl3): δ2.40 (s, 3H), 2.63 (s, 3H), 7.12 (d, J=7.8Hz, 1H), 7.43 (d, J=8.0Hz, 1H), 7.44 (d, J=7.8H z, 1H), 7.57-7.67 (m, 6H), 8.73 (dd, J=8.0Hz, 1.6Hz, 1H), 8.80 (brd, J=6.6Hz, 4H), 8.88 (d, J=1.6Hz, 1H).

[0259] Synthesis Example-3

[0260]

[0261] Under an argon atmosphere, 2-[3-chloro-4-(2,6-dimethylpyridin-3-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (2.53 g, 5.6 mmol) and 9-phenanthrene boronic acid (1.88 g, 8.45 mmol) were suspended in a mixed solvent of 1-butanol (56 mL) and toluene (51 mL). A toluene solution (5 mL) of palladium acetate (126 mg, 0.56 mmol) and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (476 mg, 1.1 mmol) and a 5M-sodium hydroxide aqueous solution (5 mL) were added to the suspension and stirred at 120°C for 41 hours. After cooling to room temperature, ethyl acetate and chloroform were added to the reaction mixture to extract the organic layer, and the organic layer was washed with water and then with saturated saline. Sodium sulfate and activated carbon were added to the organic layer and stirred, and then filtered through diatomaceous earth to remove low-boiling components. The obtained crude product was purified by recrystallization from toluene and silica gel column chromatography (chloroform: ethyl acetate = 2: 1) to obtain the target 2-[3-(phenanthrene-9-yl)-4-(2,6-dimethylpyridin-3-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-39) (1.6 g, 48%).

[0262] 1 H-NMR (CDCl3): δ2.44 (s, 3H), 2.83 (brs, 3H), 6.56 (brs, 1H), 7.52-7.71 (m, 14H), 7.82 (brs, 1H), 8.67 ( d, J=8.0Hz, 1H), 8.70 (brs, 1H), 8.76 (brd, J=6.8Hz, 4H), 8.88 (brs, 1H) 8.94 (dd, J=8.0Hz, 1.8Hz, 1H).

[0263] The obtained compound A-39 had a glass transition temperature of 135°C, a melting point of 292°C, and no crystallization temperature was detected.

[0264] Synthesis Example-4

[0265]

[0266] Under an argon atmosphere, 2-(4-bromo-3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (8.03 g, 19 mmol), 2-biphenylboronic acid (4.52 g, 23 mmol), bis(triphenylphosphine)palladium dichloride (667 mg, 1.0 mmol) and 2M-potassium phosphate aqueous solution (34 mL, 68 mmol) were suspended in THF (190 mL) and stirred at 80 ° C for 21 hours. After cooling to room temperature, ethyl acetate and water were added to the reaction mixture to extract the organic layer, and the organic layer was then washed with water and then saturated brine. Sodium sulfate and activated carbon were added to the organic layer and stirred. Chloroform was then added to suspend it, and the solid component was removed by diatomaceous earth filtration, and the low boiling point component was distilled off under reduced pressure from the resulting solution. Furthermore, the crude purified product was recrystallized using toluene to obtain 2-[2-chloro-1,1′:2′,1″-terphenyl-4-yl]-4,6-diphenyl-1,3,5-triazine as a white solid (amount: 6.70 g, yield: 71%).

[0267] 1 H-NMR (CDCl3) δ (ppm): 7.16-7.21 (m, 5H), 7.31 (d, J=8.0Hz, 1H), 7.43 (d, J=7.3Hz, 1H), 7. 45-7.53 (m, 3H), 7.55-7.64 (m, 6H), 8.54 (dd, J=8.0, 1.6Hz, 1H), 8.76 (brd, J=7.4Hz, 5H).

[0268] Synthesis Example-5

[0269]

[0270] Under an argon atmosphere, the obtained 2-[2-chloro-1,1':2',1"-terphenyl-4-yl]-4,6-diphenyl-1,3,5-triazine (3.37 g, 6.8 mmol), 9-phenanthreneboric acid (1.96 g, 8.8 mmol), palladium acetate (76 mg, 0.36 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (324 mg, 0.68 mmol) and 5M-sodium hydroxide aqueous solution (5.4 mL, 27 mmol) were suspended in THF (68 mL) and stirred at 80° C. for 20 min. hours. After cooling to room temperature, chloroform and water were added, the organic layer was extracted, and the organic layer was washed with water and then with saturated brine. Sodium sulfate and activated carbon were added to the organic layer and stirred. The solid component was removed by diatomaceous earth filtration, and the low-boiling components were distilled off from the solution under reduced pressure. The crude purified product was then recrystallized using toluene to obtain 4,6-diphenyl-2-[2-(9-phenanthrenyl)-1,1':2',1"-triphenyl-4-yl]-1,3,5-triazine (Compound A-3) as a white solid (yield 3.30 g, yield 75%).

[0271] 1 H-NMR (CDCl3) δ (ppm): 6.44-7.25 (m, 9H), 7.38-7.94 (m, 13H), 8.60-8.65 (m, 3H), 8.74 (d, J=7.3Hz, 4H), 8.94 (brd, J=7.3Hz, 1H).

[0272] Synthesis Example-6

[0273]

[0274] Under an argon atmosphere, 2-[3"-chloro-1,1':2',1"-terphenyl-5"-yl]-4,6-diphenyl-1,3,5-triazine (3.34 g, 6.7 mmol), 9,9-dimethyl-2-fluoreneboric acid (2.40 g, 10 mmol), palladium acetate (76 mg, 0.34 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (286 mg, 0.67 mmol) were suspended in 1,4-dioxane (67 mL). 2M-sodium hydroxide aqueous solution (6.1 mL) was added to the suspended solution, and the mixture was stirred at 110° C. for 40 hours. The mixture was cooled to 40° C. After room temperature, water and chloroform were added to the reaction mixture, the organic layer was extracted, activated carbon and sodium sulfate were added to the extract and stirred for a while. After stirring, diatomaceous earth filtration was performed, and low-boiling components were distilled off from the filtrate. The crude purified product was recrystallized from toluene (115°C, 5 mL), and the precipitated solid was filtered. The obtained solid was further purified by column chromatography (hexane: chloroform = 3: 1) to obtain 2-[2-(9,9-dimethyl-9H-fluoren-2-yl)-1,1':2',1"-terphenyl-4-yl]-4,6-diphenyl-1,3,5-triazine (Compound A-98) (2.3 g, 52%) as a white solid.

[0275] 1 H-NMR (CDCl3) δ (ppm): 8.81 (dd, J=8.0Hz, 1.8Hz, 1H), 8.78 (ddd, J=6.6Hz, 1.6Hz, 1.4Hz, 4H), 8.68 (d, J=1.8Hz, 1H), 7.54-7.63 (m, 7H) 7.43-7.48 (m, 2H), 7.29-7.41 (m, 4H), 7.15 ( J=7.6Hz, 1.2Hz, 1H), 7.07 (t, J=7.4Hz, 4H), 6.79 (t, J=7.8Hz, 2H), 6.79 (d, J=1.2Hz, 1H) , 6.72 (dd, J=7.8Hz, 1.6Hz, 1H), 6.64 (dd, J=8.4Hz, 1.4Hz, 1H), 1.28 (s, 3H), 1.19 (s, 3H).

[0276] Synthesis Example-7

[0277] 4,6-diphenyl-2-[2-(phenanthrene-9-yl)-3'-(2,6-phenylpyridin-4-yl)biphenyl-4-yl]-1,3,5-triazine (Compound A-49) was synthesized according to the following synthetic route. The synthetic conditions were the same as those of Synthesis Examples 1 to 6. The obtained Compound A-49 had a FDMS of 791.

[0278]

[0279] Synthesis Example-8

[0280] 4,6-diphenyl-2-[2-(phenanthrene-9-yl)-4'-(2-pyridyl)biphenyl-4-yl]-1,3,5-triazine (Compound A-53) was synthesized according to the following synthetic route. The synthetic conditions were the same as those of Synthesis Examples 1 to 6. The obtained Compound A-53 had a FDMS of 791.

[0281]

[0282] Synthesis Example-9

[0283] 4,6-diphenyl-2-[2-(phenanthrene-9-yl)-4'-(3-pyridyl)biphenyl-4-yl]-1,3,5-triazine (Compound A-54) was synthesized according to the following synthetic route. The synthetic conditions were the same as those of Synthesis Examples 1 to 6. The obtained Compound A-54 had a FDMS of 639.

[0284]

[0285] Synthesis Example-10

[0286] 4,6-diphenyl-2-[2-(phenanthrene-9-yl)-3'-(3-pyridyl)biphenyl-4-yl]-1,3,5-triazine (Compound A-58) was synthesized according to the following synthesis route. The synthesis conditions were the same as those of Synthesis Examples 1 to 6. The obtained Compound A-58 had a FDMS of 639.

[0287]

[0288] Synthesis Example-11

[0289] 4,6-diphenyl-2-[2-(phenanthrene-9-yl)-2'-(3-pyridyl)biphenyl-4-yl]-1,3,5-triazine (Compound A-62) was synthesized according to the following synthetic route. The synthetic conditions were the same as those of Synthesis Examples 1 to 6. The obtained Compound A-62 had a FDMS of 639.

[0290]

[0291] Synthesis Example-12

[0292] 4,6-diphenyl-2-[2-(anthracen-9-yl)-biphenyl-4-yl]-1,3,5-triazine (Compound A-129) was synthesized according to the following synthetic route. The synthetic conditions were the same as those of Synthesis Examples 1 to 6. The obtained Compound A-129 had a FDMS of 639.

[0293]

[0294] Synthesis Example-13

[0295] 4,6-Diphenyl-2-[2-(anthracen-9-yl)-1,1':2',1"-terphenyl-4-yl]-1,3,5-triazine (Compound A-130) was synthesized according to the following synthetic route. The synthesis conditions were the same as those of Synthesis Examples 1 to 6. The obtained Compound A-130 had a FDMS of 638.

[0296]

[0297] Synthesis Example-14

[0298] 4,6-diphenyl-2-[2-(dibenzofuran-4-yl)-4'-(3-pyridyl)biphenyl-4-yl]-1,3,5-triazine (Compound A-269) was synthesized according to the following synthetic route. The synthetic conditions were the same as those of Synthesis Examples 1 to 6. The obtained Compound A-54 had a FDMS of 629.

[0299]

[0300] Reference Example-1

[0301] The compound described in Synthesis Example 2 of Japanese Patent Publication No. 2017-178931, namely 2-[3-(4-methyl-3-pyridyl)-5-(9-phenanthrenyl)phenyl]-4,6-diphenyl-1,3,5-triazine (hereinafter referred to as ETL-1) was synthesized, and its DSC measurement was performed. The glass transition temperature of this compound is 113°C, the crystallization temperature is 197°C, and the melting point is 240°C. It should be noted that this compound was synthesized by the method described in Japanese Patent Publication No. 2017-178931, and the DSC measurement was performed under the same conditions as Synthesis Example-1 in this specification (conditions described in paragraph

[0090] ).

[0302]

[0303] Reference Example-2

[0304]

[0305] Under nitrogen atmosphere, 2-[3-chloro-5-(phenanthrene-9-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (1.00 g, 1.9 mmol), phenylboric acid (282 mg, 2.3 mmol), palladium acetate (13.0 mg, 0.06 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (55.0 mg, 0.12 mmol), 1,4-dioxane (50 mL) and 2M-tripotassium phosphate aqueous solution (2.9 mL, 5.8 mmol) were added to a 300 mL four-necked flask and stirred at 95° C. for 6 hours. After the obtained reaction solution was cooled to room temperature, water (100 mL) was added to the reaction mixture, and the precipitate was filtered out and washed with water, methanol, and then hexane to obtain a gray powder. The obtained gray powder was purified by recrystallization with toluene to obtain the target gray powder of 4,6-diphenyl-2-[5-(phenanthrene-9-yl)-biphenyl-3-yl]-1,3,5-triazine (Compound ETL-2) (amount: 700 mg, yield: 65%).

[0306] 1 H-NMR (CDCl3): δ7.45 (t, J=7.3Hz, 1H), 7.52-7.63 (m, 9H), 7.67 (t, J=7.2Hz, 1H), 7.73 (t, J=7.8Hz, 1.3Hz, 2H), 7.84 (dd, J=8.1Hz, 1.0Hz, 2H), 7.8 8(s, 1H), 7.98(dd, J=7.8Hz, 1.4Hz, 1H), 8.01-8.04(m, 2H), 8.77-8.80(m , 5H), 8.85 (d, J=8.3Hz, 1H), 8.93 (t, J=1.7Hz, 1H), 9.12 (t, J=1.7Hz, 1H).

[0307] Reference Example-3

[0308]

[0309] 4,6-diphenyl-2-[6-(triphenylene-1-yl)-biphenyl-3-yl]-1,3,5-triazine (ETL-3) was synthesized by the method described in Example 7 of International Publication No. 2018 / 095390.

[0310] FDMS: 611

[0311] The obtained compound ETL-2 had a glass transition temperature of 108° C., a crystallization temperature of 207° C., and a melting point of 260° C. It should be noted that the DSC measurement was performed under the same conditions as those of Synthesis Example-1 of the present application.

[0312] According to the above results, the triazine compound obtained in Synthesis Example 3 has a higher glass transition temperature than the conventionally known triazine compounds obtained in Reference Example 1 and Reference Example 2. It can be further known that the triazine compound obtained in Synthesis Example 3 has low crystallinity due to the characteristics of its skeleton, and no crystallization temperature is detected or it has a high crystallization temperature. Therefore, the triazine compound (1) can be expected to have high amorphous properties when forming a thin film, and it is speculated that when the triazine compound (1) is used to make an organic electroluminescent element, it has high driving stability and high luminous efficiency.

[0313] Next, device evaluation was carried out using the obtained compound.

[0314] [Evaluation as Electron Transport Layer 6]

[0315] Element Example-1 (refer to Figure 2 )

[0316] (Preparation of substrate 1 and anode 2)

[0317] As the substrate 1 having the anode 2 on its surface, a glass substrate with an ITO transparent electrode obtained by patterning a 2 mm wide indium tin oxide (ITO) film (thickness 110 nm) into stripes was prepared. Next, the substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning.

[0318] (Preparation for vacuum deposition)

[0319] On the cleaned and surface-treated substrate, each layer is vacuum-deposited by vacuum deposition to form each layer in a stacked manner.

[0320] First, the glass substrate is placed in a vacuum deposition tank and the pressure is reduced to 1.0×10 -4 Pa. Then, the film formation conditions of each layer were respectively prepared in the following order. It should be noted that each organic material was formed into a film by resistance heating.

[0321] (Preparation of Hole Injection Layer 3)

[0322] The sublimation-purified N-[1,1'-biphenyl]-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluoren-2-amine and 1,2,3-tris[(4-cyano-2,3,5,6-tetrafluorophenyl)methylene]cyclopropane were formed into a 10 nm film at a ratio of 99:1 (mass ratio) to prepare the hole injection layer 3. The film formation rate was 0.1 nm / sec.

[0323] (Fabrication of First Hole Transport Layer 41)

[0324] The sublimation-purified N-[1,1′-biphenyl]-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluoren-2-amine was deposited into a film of 85 nm at a rate of 0.2 nm / sec to form the first hole transport layer 41 .

[0325] (Fabrication of Second Hole Transport Layer 42)

[0326] The sublimation-purified N-phenyl-N-(9,9-diphenylfluoren-2-yl)-N-(1,1′-biphenyl-4-yl)amine was deposited into a 5 nm thick film at a rate of 0.15 nm / sec to form the second hole transport layer 42 .

[0327] (Production of Light Emitting Layer 5)

[0328] Sublimation-purified 3-(10-phenyl-9-anthryl)dibenzofuran and 2,7-bis[N,N-di(4-tert-butylphenyl)]amino-bisbenzofuranyl-9,9'-spirofluorene were formed into a 20 nm film at a ratio of 95:5 (mass ratio) to prepare the light-emitting layer 5. The film formation speed was 0.1 nm / sec.

[0329] (Production of Hole Blocking Layer 9)

[0330] The sublimation-purified 2-[3′-(9,9-dimethyl-9H-fluoren-2-yl)[1,1′-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine was deposited into a film with a thickness of 6 nm at a rate of 0.05 nm / sec to form the hole blocking layer 9 .

[0331] (Fabrication of Electron Transport Layer 6)

[0332] 2-[3-(phenanthrene-9-yl)-(2,6-dimethylpyridin-3-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-39) synthesized in Synthesis Example-3 and 8-hydroxyquinoline lithium (hereinafter referred to as Liq) were formed into a 25 nm film at a ratio of 50:50 (mass ratio) to prepare an electron transport layer 6. The film formation rate was 0.15 nm / sec.

[0333] (Fabrication of Electron Injection Layer 7)

[0334] Liq was deposited into a film of 1 nm at a rate of 0.02 nm / sec to form the electron injection layer 7 .

[0335] (Manufacturing of cathode 8)

[0336] Finally, a metal mask was arranged to be orthogonal to the ITO stripes (anode 2) on the substrate 1, and a cathode 8 was formed. The cathode was formed into a two-layer structure by forming silver / magnesium (mass ratio of 1 / 10) and silver in 80 nm and 20 nm, respectively. The film forming speed of silver / magnesium was 0.5 nm / sec, and the film forming speed of silver was 0.2 nm / sec.

[0337] Through the above operations, Figure 2 The light emitting area shown is 4mm 2 The organic electroluminescent element 100. The film thickness of each film was measured using a stylus film thickness meter (DEKTAK, manufactured by Bruker).

[0338] Furthermore, the device was sealed in a nitrogen atmosphere glove box with an oxygen and water concentration of 1 ppm or less. A glass sealing cover and a film-forming substrate (device) were sealed using bisphenol F epoxy resin (manufactured by Nagase Chemical Co., Ltd.).

[0339] Component Example-2

[0340] In Element Example-1, for the electron transport layer 6, instead of forming a 25 nm film (film formation rate of 0.15 nm / sec) with 2-[3-(phenanthrene-9-yl)-(2,6-dimethylpyridin-3-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-39) and Liq in a ratio of 50:50 (mass ratio), a 25 nm film (film formation rate of 0.15 nm / sec) is formed with Compound A-49 and Liq in a ratio of 50:50 (mass ratio). Except for this, an organic electroluminescent element is prepared by the same method as Element Example-1.

[0341] Component Example-3

[0342] In Element Example-1, for the electron transport layer 6, instead of forming a 25 nm film (film formation rate of 0.15 nm / sec) with 2-[3-(phenanthrene-9-yl)-(2,6-dimethylpyridin-3-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-39) and Liq in a ratio of 50:50 (mass ratio), a 25 nm film (film formation rate of 0.15 nm / sec) is formed with Compound A-53 and Liq in a ratio of 50:50 (mass ratio). The organic electroluminescent element is prepared by the same method as Element Example-1 except that the ratio is 50:50 (mass ratio).

[0343] Component Example-4

[0344] In Element Example-1, for the electron transport layer 6, instead of forming a 25 nm film (film formation rate of 0.15 nm / sec) with 2-[3-(phenanthrene-9-yl)-(2,6-dimethylpyridin-3-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-39) and Liq in a ratio of 50:50 (mass ratio), a 25 nm film (film formation rate of 0.15 nm / sec) is formed with Compound A-54 and Liq in a ratio of 50:50 (mass ratio). The organic electroluminescent element is prepared by the same method as Element Example-1 except that the ratio is 50:50 (mass ratio).

[0345] Component Example-5

[0346] In Element Example-1, for the electron transport layer 6, instead of forming a 25 nm film (film formation rate of 0.15 nm / sec) with 2-[3-(phenanthrene-9-yl)-(2,6-dimethylpyridin-3-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-39) and Liq in a ratio of 50:50 (mass ratio), a 25 nm film (film formation rate of 0.15 nm / sec) is formed with Compound A-58 and Liq in a ratio of 50:50 (mass ratio). The organic electroluminescent element is prepared by the same method as Element Example-1.

[0347] Component Example-6

[0348] In Element Example-1, for the electron transport layer 6, instead of forming a 25 nm film (film formation rate of 0.15 nm / sec) with 2-[3-(phenanthrene-9-yl)-(2,6-dimethylpyridin-3-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-39) and Liq in a ratio of 50:50 (mass ratio), a 25 nm film (film formation rate of 0.15 nm / sec) is formed with Compound A-62 and Liq in a ratio of 50:50 (mass ratio). Except for this, an organic electroluminescent element is prepared by the same method as Element Example-1.

[0349] Component Example-7

[0350] In Element Example-1, for the electron transport layer 6, instead of forming a 25 nm film (film formation rate of 0.15 nm / sec) with 2-[3-(phenanthrene-9-yl)-(2,6-dimethylpyridin-3-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-39) and Liq in a ratio of 50:50 (mass ratio), a 25 nm film (film formation rate of 0.15 nm / sec) is formed with Compound A-182 and Liq in a ratio of 50:50 (mass ratio). The organic electroluminescent element is prepared by the same method as Element Example-1 except that the ratio is 50:50 (mass ratio).

[0351] Component Example-8

[0352] In Element Example-1, for the electron transport layer 6, instead of forming a 25 nm film (film formation rate of 0.15 nm / sec) with 2-[3-(phenanthrene-9-yl)-(2,6-dimethylpyridin-3-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-39) and Liq in a ratio of 50:50 (mass ratio), a 25 nm film (film formation rate of 0.15 nm / sec) is formed with Compound A-269 and Liq in a ratio of 50:50 (mass ratio). Except for this, an organic electroluminescent element is prepared by the same method as Element Example-1.

[0353] Component Reference Example-1

[0354] In Element Example-1, for the electron transport layer 6, instead of forming a 25 nm film (film formation rate of 0.15 nm / sec) with 2-[3-(phenanthrene-9-yl)-(2,6-dimethylpyridin-3-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (Compound A-39) and Liq in a ratio of 50:50 (mass ratio), ETL-1 and Liq in a ratio of 50:50 (mass ratio) are formed into a 25 nm film (film formation rate of 0.15 nm / sec). Except for this, an organic electroluminescent element is prepared by the same method as Element Example-1.

[0355] A direct current was applied to the produced organic electroluminescent element, and the light emission characteristics were evaluated according to the method described in the above-mentioned measurement of light emission characteristics.

[0356] As the luminescence characteristics, the current density was measured at 10 mA / cm 2 The voltage (V) and current efficiency (cd / A) at the time of continuous lighting were measured. The device life was measured at an initial brightness of 1000 cd / m 2 The brightness decay time when the continuous lighting is driven, and the brightness (cd / m 2 ) is reduced to 3%. It should be noted that the values ​​of voltage (V), current efficiency (cd / A) and life are expressed as relative values ​​when the element reference example-1 is set to 100. The results are shown in Table 1.

[0357] [Table 1]

[0358] Compound Voltage Current efficiency Component life Component Example-1 A-39 98 110 124 Component Example-2 A-49 99 104 120 Component Example-3 A-53 97 104 127 Component Example-4 A-54 98 102 135 Component Example-5 A-58 98 104 116 Component Example-6 A-62 97 114 104 Component Example-7 A-182 98 105 112 Component Example-8 A-269 98 110 102 Component Reference Example-1 ETL-1 100 100 100

[0359] [Evaluation as Hole Blocking Layer 9]

[0360] Component Example-9

[0361] In Element Example-1, for the hole blocking layer 9, instead of forming a 6 nm film of 2-[3'-(9,9-dimethyl-9H-fluorene-2-yl)[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine (film formation rate is 0.05 nm / sec), a 6 nm film of compound A-3 (film formation rate is 0.05 nm / sec) is formed. Except for this, an organic electroluminescent element is prepared by the same method as Element Example-1.

[0362] Component Example-10

[0363] In Element Example-1, for the hole blocking layer 9, instead of forming a 6 nm film of 2-[3'-(9,9-dimethyl-9H-fluorene-2-yl)[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine (film formation rate is 0.05 nm / sec), compound A-98 is formed into a 6 nm film (film formation rate is 0.05 nm / sec). Except for this, an organic electroluminescent element is prepared by the same method as Element Example-1.

[0364] Component Example-11

[0365] In Element Example-1, for the hole blocking layer 9, instead of forming a 6 nm film of 2-[3'-(9,9-dimethyl-9H-fluorene-2-yl)[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine (film formation rate is 0.05 nm / sec), compound A-129 is formed into a 6 nm film (film formation rate is 0.05 nm / sec). Except for this, an organic electroluminescent element is prepared by the same method as Element Example-1.

[0366] Component Example-12

[0367] In Element Example-1, for the hole blocking layer 9, instead of forming a 6 nm film of 2-[3'-(9,9-dimethyl-9H-fluorene-2-yl)[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine (film formation rate is 0.05 nm / sec), a 6 nm film of compound A-130 (film formation rate is 0.05 nm / sec) is formed. Except for this, an organic electroluminescent element is prepared by the same method as Element Example-1.

[0368] Component Reference Example-2

[0369] In Element Example-1, for the hole blocking layer 9, instead of forming a 6 nm film of 2-[3'-(9,9-dimethyl-9H-fluorene-2-yl)[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine (film formation rate is 0.05 nm / sec), the compound ETL-3 is formed into a 6 nm film (film formation rate is 0.05 nm / sec). Except for this, an organic electroluminescent element is prepared by the same method as Element Example-1.

[0370] A direct current was applied to the produced organic electroluminescent element, and the light emission characteristics were evaluated according to the method described in the above-mentioned measurement of light emission characteristics.

[0371] As the luminescence characteristics, the current density was measured at 10 mA / cm 2 The voltage (V) and current efficiency (cd / A) at the time of continuous lighting were measured. The device life was measured at an initial brightness of 1000 cd / m 2 The brightness decay time when the continuous lighting is driven, and the brightness (cd / m 2 ) is reduced to 3%. It should be noted that the values ​​of voltage (V), current efficiency (cd / A) and life are expressed as relative values ​​when the element reference example-2 is set to 100. The results are shown in Table 2.

[0372] [Table 2]

[0373] Compound Voltage Current efficiency Component life Component Example-9 A-3 95 112 130 Component Example-10 A-98 98 102 145 Component Example-11 A-129 93 104 112 Component Example-12 A-130 94 109 108 Component Reference Example-2 ETL-3 100 100 100

[0374] From Tables 1 and 2, it was found that the voltage, luminous efficiency and device life of the organic electroluminescent device using the triazine compound (1) were all excellent at high levels compared with those of the reference example.

[0375] It should be noted that the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-225358 filed on November 30, 2018, and the specification, claims, drawings, and abstract of Japanese Patent Application No. 2019-211421 filed on November 22, 2019 are incorporated herein as the disclosed contents of the specification of the present invention.

[0376] Description of Reference Numerals

[0377] 1.Substrate

[0378] 2. Anode

[0379] 3. Hole injection layer

[0380] 4. Hole transport layer

[0381] 5. Luminous layer

[0382] 6. Electron transport layer

[0383] 7. Electron injection layer

[0384] 8. Cathode

[0385] 9. Hole blocking layer

[0386] 51.First hole transport layer

[0387] 52. Second hole transport layer

[0388] 100. Organic electroluminescent elements

Claims

1. A triazine compound represented by formula (1): In formula (1), Ar 1 and Ar 2 each independently represents an unsubstituted phenyl group or an unsubstituted biphenyl group; Ar 3 express: A tricyclic condensed ring aromatic hydrocarbon group, dibenzothiophenyl group, dibenzofuranyl group, benzonaphthofuranyl group or benzonaphthothiophenyl group; Ar 4 represents a phenyl or pyridyl group; Ar 3 and Ar 4 Each independently may be substituted with one or more groups selected from the group consisting of a fluorine atom, a methyl group and a phenyl group; X represents a phenylene group or a pyridylene group; p represents 0 or 1.

2. The triazine compound according to claim 1, wherein Ar 1 and Ar 2 are the same group.

3. The triazine compound according to claim 1 or 2, wherein Ar 3 It is a tricyclic condensed-ring aromatic hydrocarbon group which is optionally substituted by one or more groups selected from the group consisting of a fluorine atom, a methyl group and a phenyl group.

4. The triazine compound according to claim 1 or 2, wherein Ar 3 It is an unsubstituted tricyclic condensed-ring aromatic hydrocarbon group.

5. The triazine compound according to claim 1 or 2, wherein Ar 4 is phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, pyridyl, methylpyridyl, dimethylpyridyl, phenylpyridyl or diphenylpyridyl. 6 . A material for an organic electroluminescent device, comprising the triazine compound according to claim 1 . 7 . An organic electroluminescent device comprising the triazine compound according to claim 1 .

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