WO2021079915A1 - Composé de triazine ayant un groupe pyridyle et un composé de pyridine - Google Patents

Composé de triazine ayant un groupe pyridyle et un composé de pyridine Download PDF

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WO2021079915A1
WO2021079915A1 PCT/JP2020/039606 JP2020039606W WO2021079915A1 WO 2021079915 A1 WO2021079915 A1 WO 2021079915A1 JP 2020039606 W JP2020039606 W JP 2020039606W WO 2021079915 A1 WO2021079915 A1 WO 2021079915A1
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group
carbon atoms
aromatic hydrocarbon
compound according
biphenylyl
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信道 新井
宏和 新屋
弘之 川島
智宏 荘野
史成 上原
雅也 平野
桂甫 野村
田中　剛
宏亮 佐藤
尚斗 濱口
秀典 相原
拓也 山縣
洋平 小野
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東ソー株式会社
公益財団法人相模中央化学研究所
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers

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  • the present invention relates to triazine compounds and pyridine compounds having a pyridyl group, materials for organic electroluminescent elements, electron transport materials for organic electroluminescent elements, and organic electroluminescent elements.
  • Organic electroluminescent devices have begun to be put into practical use mainly for small mobile applications. However, performance improvement is indispensable for further expansion of applications, and materials having low driving voltage, high luminous efficiency characteristics, and long life characteristics are required. Further, as a material used for an organic electroluminescent device, crystallization when the material is made into a thin film often becomes a problem, and a material having a high crystallization temperature is required.
  • Patent Document 1 discloses a pyridine compound having 1,3,5-triazine as a partial structure, which is a material for an organic electroluminescent element having a long life and excellent light emitting characteristics.
  • one aspect of the present invention is a pyridine compound having a high crystallization temperature, which contributes to the formation of an organic electroluminescent element that exhibits driving voltage characteristics, long life characteristics, and light emission efficiency characteristics at a high level, and the pyridine compound. It is directed to provide a material for an organic electroluminescent element including, and an electron transport material for an organic electroluminescent element.
  • Still another aspect of the present invention is to provide an organic electroluminescent device that has a low drive voltage, high luminous efficiency, exhibits long life characteristics, and can be used in various applications or in various environments. Is aimed at.
  • the triazine compound having a pyridyl group according to one aspect of the present invention is a triazine compound represented by the formula (1).
  • Ar 1 is Aromatic hydrocarbon groups with 6 to 18 carbon atoms, A complex aromatic group having 4 to 17 carbon atoms, which is formed of only a 6-membered ring and consists of only C, H, and N, or Represents a complex aromatic group with 8 to 16 carbon atoms with Group 16 elements
  • Ar 2 is Aromatic hydrocarbon groups with 6 to 18 carbon atoms, or It represents a complex aromatic group having 4 to 17 carbon atoms, which is formed only by a 6-membered ring and consists of only C, H, and N;
  • the substituents are each independently one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a cyano group and a methyl group;
  • L 1 , L 2 and L 3 are independent of each other.
  • One of X 1 and X 2 represents a nitrogen atom and the other represents CH;
  • n represents 1, 2 or 3; when n is 2 or more, a plurality of L 2 is may be the same or different; a represents 0, 1 or 2; When a is 2, the plurality of Ar 1 may be different from each other;
  • the pyridine compound according to one aspect of the present invention is a pyridine having a partial structure represented by the formula (Q-1), (Q-2) or (Q-3) and a 1,3,5-triazyl group.
  • Aromatic hydrocarbon groups with 6 to 18 carbon atoms A complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or Represents a complex aromatic group consisting of C, H and Group 16 elements with 8 to 16 carbon atoms;
  • Ar 3 is an aromatic hydrocarbon group with 6 to 18 carbon atoms;
  • L 5 is a single bond, Ar 4 is an aromatic hydrocarbon group with 6 to 18 carbon atoms;
  • One of X 3 , X 4 and X 5 is a nitrogen atom and the other is CH;
  • One of X 6 , X 7 and X 8 is a nitrogen atom and the other is CH;
  • One of X 9 , X 10 and X 11 is a nitrogen atom and the other is CH;
  • One of X 6 and X 7 is a nitrogen atom and the other is CH;
  • L 4 , L 5 , Ar 3 , Ar 4 are each independently substituted with one or more groups selected from
  • the pyridine compound according to one aspect of the present invention is a pyridine compound represented by the formula (13).
  • Ar 5 is Aromatic hydrocarbon groups with 6 to 18 carbon atoms, A complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or Represents a complex aromatic group consisting of C, H and Group 16 elements with 8 to 16 carbon atoms
  • Ar 6 is Hydrogen atom, Aromatic hydrocarbon groups with 6 to 18 carbon atoms, A complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or Represents a complex aromatic group consisting of C, H and Group 16 elements with 8 to 16 carbon atoms
  • L 6 is Single bond, Divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms, A divalent complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or Represents a divalent complex aromatic group consisting of C, H and Group 16 elements with 8 to 16 carbon atoms
  • L 7 represents a trivalent
  • Aromatic hydrocarbon groups with 6 to 18 carbon atoms A complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or Represents a complex aromatic group consisting of C, H and Group 16 elements with 8 to 16 carbon atoms;
  • Ar 3 is an aromatic hydrocarbon group with 6 to 18 carbon atoms;
  • L 5 is a single bond, Ar 4 is an aromatic hydrocarbon group with 6 to 18 carbon atoms;
  • One of X 3 , X 4 and X 5 is a nitrogen atom and the other is CH;
  • One of X 6 , X 7 and X 8 is a nitrogen atom and the other is CH;
  • One of X 9 , X 10 and X 11 is a nitrogen atom and the other is CH;
  • L 4 , L 5 , L 6 , L 7 , Ar 3 , Ar 4 , Ar 5 and Ar 6 each independently consist of a group consisting of a phenyl group, a
  • the material for an organic electroluminescent device contains at least one selected from the above-mentioned triazine compound having a pyridyl group and a pyridine compound.
  • the organic electroluminescent device contains at least one selected from the above-mentioned triazine compound having a pyridyl group and a pyridine compound.
  • a pyridine compound having a high crystallization temperature which contributes to the formation of an organic electroluminescent element that exhibits driving voltage characteristics, luminous efficiency characteristics and long life characteristics at a high level.
  • an organic electroluminescent device containing the above-mentioned pyridine compound and an electron transport material for an organic electroluminescent device. Further, according to still another aspect of the present invention, it is possible to provide an organic electroluminescent device that exhibits low drive voltage, high luminous efficiency, and long life characteristics, and can be used for various purposes.
  • triazine compound having a pyridyl group hereinafter, also simply referred to as a triazine compound
  • a pyridine compound according to each aspect of the present invention will be described in detail.
  • the triazine compound according to one aspect of the present invention is a triazine compound represented by the formula (1).
  • Ar 1 is Aromatic hydrocarbon groups with 6 to 18 carbon atoms, A complex aromatic group having 4 to 17 carbon atoms, which is formed of only a 6-membered ring and consists of only C, H, and N, or Represents a complex aromatic group with 8 to 16 carbon atoms with Group 16 elements
  • Ar 2 is Aromatic hydrocarbon groups with 6 to 18 carbon atoms, or It represents a complex aromatic group having 4 to 17 carbon atoms, which is formed only by a 6-membered ring and consists of only C, H, and N;
  • the substituents are each independently one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a cyano group and a methyl group;
  • L 1 , L 2 and L 3 are independent of each other.
  • One of X 1 and X 2 represents a nitrogen atom and the other represents CH;
  • triazine compound represented by the formula (1) may be referred to as a triazine compound (1).
  • substituents in the triazine compound (1) and preferred specific examples thereof are as follows.
  • Ar 1 is Aromatic hydrocarbon groups with 6 to 18 carbon atoms, A complex aromatic group having 4 to 17 carbon atoms, which is formed of only a 6-membered ring and consists of only C, H, and N, or It represents a complex aromatic group having 8 to 16 carbon atoms and having a group 16 element.
  • the substituent is one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a cyano group and a methyl group.
  • Ar 1 examples include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 2-pyrazyl group, and 6-methylpyridine-2-yl.
  • Ar 1 is substituted with one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a cyano group and a methyl group in that the triazine compound (1) has excellent electron transporting material properties. It is also preferable that it is an aromatic hydrocarbon group having 6 to 18 carbon atoms.
  • It is preferably an unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms because it is easy to adapt to the vapor deposition process, and it is a phenyl group, a naphthyl group, or a biphenylyl group because it is easy to synthesize. Is more preferable.
  • Ar 2 is Aromatic hydrocarbon groups with 6 to 18 carbon atoms, or It represents a complex aromatic group having 4 to 17 carbon atoms, which is formed of only a 6-membered ring and consists of only C, H, and N.
  • the substituent is one group selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a cyano group and a methyl group.
  • Ar 2 examples include, for example, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 2-pyrazyl group, and 6-methylpyridine-2.
  • Ar 2 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms because the triazine compound (1) has excellent electron-transporting material properties, and a phenyl group, a biphenylyl group, or a biphenylyl group because it is easy to synthesize. It is more preferably a naphthyl group.
  • L 1 , L 2 and L 3 are independent of each other.
  • Single bond A divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or It represents a divalent complex aromatic group having 4 to 17 carbon atoms, which is formed of only a 6-membered ring and consists of only C, H, and N.
  • L 1 , L 2 or L 3 examples include a single bond, a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 2,3-pyridylene group and a 2,4-pyridylene group.
  • L 1 , L 2 and L 3 are preferably single bonds or divalent aromatic hydrocarbon groups having 6 to 18 carbon atoms, respectively. , Single bond or
  • one of X 1 and X 2 independently represents a nitrogen atom and the other represents CH. It is more preferable that X 1 is a nitrogen atom and X 2 is CH in that the triazine compound (1) contributes to the formation of a higher performance organic electroluminescent device.
  • L 1 is a 1,4-phenylene group
  • L 2 is not a 1,3-phenylene group. It is more preferable that a is 2 and b is 1 in that the triazine compound (1) contributes to the formation of a higher-performance organic electroluminescent device.
  • triazine compound (1) Specific examples of the triazine compound (1) include the following (A-1) to (A-252), but the present invention is not limited thereto.
  • the triazine compound (1) is preferably a compound represented by A-53, A-56, A-87, A-205, or A-220 in that it has good performance as an electron transport material in an organic electroluminescent device.
  • the triazine compound (1) can be produced by the methods shown in the following synthetic routes (i) to (v).
  • X 1 , X 2 , n, a and b; Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 each independently represent a halogen atom;
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group;
  • B (OR 1) 2 one of R 1 of 2, may be different from each be the same;
  • Examples of the halogen atom represented by Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • a chlorine atom or a bromine atom is preferable in terms of good yield.
  • the B (OR 1) for example, can be exemplified B (OH) 2, B ( OMe) 2, B (O i Pr) 2, B (OBu) 2, B (OPh) 2 or the like.
  • Me is a methyl group
  • i Pr is an isopropyl group
  • Bu is a butyl group
  • Ph is a phenyl group.
  • B (OR 1 ) 2 in the case where two OR 1 groups and a boron atom are integrally formed to form a ring, for example, the groups represented by the following (I) to (VI) are shown.
  • the group represented by (II) is preferable in that the yield is good.
  • the coupling reaction in the synthetic pathways (i) to (v) is the same as the aryl halide compound represented by the formulas (2), (4), (5), (7), (8) or (10).
  • This is a method of reacting a boron compound represented by (3), (6), (9), (11) or (12) with a palladium catalyst and the presence of a base, and is a general reaction condition of Suzuki-Miyaura reaction. Can be applied.
  • Boron compounds can be produced, for example, according to the method disclosed in The Journal of Organic Chemistry, Vol. 60, p. 7508, 1995 or The Journal of Organic Chemistry, Vol. 65, p. 164, 2000.
  • Aryl halide compounds (2), (4), (5), (7), (8) or (10) are, for example, Journal of the American Chemical Society, Vol. 74, p. 6289, 1952 or Synlett, p. 808. , Can be manufactured according to 2002. Moreover, you may use a commercially available product. It is preferable to use 0.5 to 3.0 molar equivalents of the aryl halide compound with respect to the boron compound in terms of good reaction yield.
  • the boring reaction in the synthetic pathways (i) to (v) involves the presence of an aryl halide compound represented by the formulas (2), (5), (7), (8) or (10) in a palladium catalyst and a base.
  • a boron reagent eg, pinacholate borane, bispinacolato diboron, etc.
  • boron compounds can be produced, for example, according to the method disclosed in The Journal of Organic Chemistry, Vol. 60, p. 7508, 1995 or Tetrahedron Letters, Vol. 38, p. 3447, 1997.
  • Examples of the palladium catalyst used in the above-mentioned coupling reaction and boration reaction include palladium salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate. Further, complex compounds such as ⁇ -allyl palladium chloride dimer, palladium acetylacetonato, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, dichlorobis (acetritale) palladium, dichlorobis (benzonitrile) palladium; Dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichloro (1,1'-bis (diphenylphosphino) ferrocene) palladium, bis (tri-tert-butylphosphine) palladium, bis (tricyclohexylphosphin
  • tertiary phosphine examples 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) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (1
  • a palladium complex having a tertiary phosphine as a ligand is preferable in terms of good yield, and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl or tricyclohexylphosphine is a ligand.
  • the palladium complex having as is more preferable.
  • the molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably in the range of 1:10 to 10: 1, and further preferably in the range of 1: 2 to 3: 1 in terms of good yield. preferable.
  • the amount of the palladium catalyst used in the above-mentioned coupling reaction and boration reaction is not limited, but the molar equivalent of the palladium catalyst is in the range of 0.005 to 0.5 molar equivalent with respect to the boron compound in terms of good yield. It is preferable to be in.
  • Examples of the base used for the above-mentioned coupling reaction and alkoxide reaction include metal hydroxide salts such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and metals such as sodium carbonate, potassium carbonate, lithium carbonate and cesium carbonate.
  • Metal acetates such as carbonates, potassium acetate and sodium acetate
  • metal phosphates such as potassium phosphate and sodium phosphate
  • metal fluoride salts such as sodium fluoride, potassium fluoride and cesium fluoride, sodium methoxide
  • Examples thereof include metal alkoxides such as potassium methoxide, sodium methoxide, potassium isopropyl oxide, and potassium tert-butoxide.
  • metal carbonate or metal phosphate is preferable, and potassium carbonate or potassium phosphate is more preferable in terms of good reaction yield.
  • the amount of base used is preferably in the range of 1: 2 to 10: 1, and more preferably in the range of 1: 1 to 4: 1.
  • Solvents include water, diisopropyl ether, dibutyl ether, cyclopentylmethyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahexyl, 1,4-dioxane, dimethoxyethane and other ethers; benzene, toluene, xylene, mesitylene, tetraline.
  • Aromatic hydrocarbons such as; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-fluoroethylene carbonate; ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, etc.
  • Esters such as ⁇ -lactone; amides such as N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP); N, N, N', N'-tetramethylurea (TMU) , N, N'-dimethylpropylene urea (DMPU) and other ureas; dimethyl sulfoxide (DMSO), methanol, ethanol, isopropyl alcohol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 2, Alcohols such as 2,2-trifluoroethanol; and the like. These may be used alone or may be mixed and used at an arbitrary ratio.
  • amides such as N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP); N, N, N', N'-tetramethylurea
  • solvent used there is no particular limitation on the amount of solvent used. Of these, water, ether, amide, alcohol, and a mixed solvent thereof are preferable from the viewpoint of good reaction yield, and a mixed solvent of THF and water or a mixed solvent of toluene and butanol is more preferable.
  • the above-mentioned coupling reaction and boration reaction can be carried out at a temperature appropriately selected from 0 ° C. to 200 ° C., and at a temperature appropriately selected from 60 ° C. to 160 ° C. in terms of good reaction yield. It is preferable to carry out.
  • the triazine compound (1) can be used, for example, in organic electronic device applications such as organic electroluminescent devices and photoelectric devices.
  • the pyridine compound according to one aspect of the present invention is a pyridine having a partial structure represented by the formula (Q-1), (Q-2) or (Q-3) and a 1,3,5-triazyl group. It is a compound.
  • Aromatic hydrocarbon groups with 6 to 18 carbon atoms A complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or Represents a complex aromatic group consisting of C, H and Group 16 elements with 8 to 16 carbon atoms;
  • Ar 3 is an aromatic hydrocarbon group with 6 to 18 carbon atoms;
  • L 5 is a single bond, Ar 4 is an aromatic hydrocarbon group with 6 to 18 carbon atoms;
  • One of X 3 , X 4 and X 5 is a nitrogen atom and the other is CH;
  • One of X 6 , X 7 and X 8 is a nitrogen atom and the other is CH;
  • One of X 9 , X 10 and X 11 is a nitrogen atom and the other is CH;
  • L 4 , L 5 , Ar 3 , Ar 4 are each independently substituted with one or more groups selected from the group consisting of a phenyl group, a biphenylyl group,
  • the pyridine compound according to another aspect of the present invention is a pyridine compound represented by the formula (13).
  • Ar 5 is Aromatic hydrocarbon groups with 6 to 18 carbon atoms, A complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or Represents a complex aromatic group consisting of C, H and Group 16 elements with 8 to 16 carbon atoms
  • Ar 6 is Hydrogen atom, Aromatic hydrocarbon groups with 6 to 18 carbon atoms, A complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or Represents a complex aromatic group consisting of C, H and Group 16 elements with 8 to 16 carbon atoms
  • L 6 is Single bond, Divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms, A divalent complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or Represents a divalent complex aromatic group consisting of C, H and Group 16 elements with 8 to 16 carbon atoms
  • L 7 represents a trivalent
  • Aromatic hydrocarbon groups with 6 to 18 carbon atoms A complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or Represents a complex aromatic group consisting of C, H and Group 16 elements with 8 to 16 carbon atoms;
  • Ar 3 is an aromatic hydrocarbon group with 6 to 18 carbon atoms;
  • L 5 is a single bond, Ar 4 is an aromatic hydrocarbon group with 6 to 18 carbon atoms;
  • One of X 3 , X 4 and X 5 is a nitrogen atom and the other is CH;
  • One of X 6 , X 7 and X 8 is a nitrogen atom and the other is CH;
  • One of X 9 , X 10 and X 11 is a nitrogen atom and the other is CH;
  • L 4 , L 5 , L 6 , L 7 , Ar 3 , Ar 4 , Ar 5 and Ar 6 each independently consist of a group consisting of a phenyl group, a
  • substituents in formulas (13), (Q-1), (Q-2) and (Q-3), and preferable specific examples thereof are as follows.
  • the pyridine compound represented by 13) may be generically referred to as a pyridine compound (Q).
  • Ar 3 and Ar 4 are independent of each other.
  • Aromatic hydrocarbon groups with 6 to 18 carbon atoms A complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or Represents a complex aromatic group consisting of C, H and Group 16 elements with 8 to 16 carbon atoms;
  • Ar 3 and Ar 4 may be substituted with one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a pyridyl group, a cyano group and a methyl group.
  • Ar 3 is an aromatic hydrocarbon group having 6 to 18 carbon atoms.
  • Ar 4 is an aromatic hydrocarbon group having 6 to 18 carbon atoms.
  • Ar 3 and Ar 4 are independently selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a pyridyl group, a cyano group and a methyl group in that the pyridine compound (Q) has excellent electron transporting material properties. It is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms which may be substituted with one or more groups. A phenyl group, a biphenylyl group, a naphthyl group or a pyridylphenyl group is more preferable because it is easy to synthesize.
  • Ar 3 and Ar 4 examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl-2-yl group, a biphenyl-3-yl group, a biphenyl-4-yl group, and a 2-methylphenyl group.
  • Ar 5 is Aromatic hydrocarbon groups with 6 to 18 carbon atoms, A complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or It represents a complex aromatic group consisting of C, H and Group 16 elements and having 8 to 16 carbon atoms.
  • Ar 5 may be substituted with one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a pyridyl group, a cyano group and a methyl group.
  • Ar 5 is replaced with one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a pyridyl group, a cyano group and a methyl group in that the pyridine compound (Q) has excellent electron transporting material properties. It is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms which may be used. A phenyl group or a biphenylyl group is more preferable because it is easy to synthesize.
  • Ar 5 examples include phenyl group, 1-naphthyl group, 2-naphthyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, 2-methylphenyl group and 3-methyl.
  • Ar 6 is Hydrogen atom, Aromatic hydrocarbon groups with 6 to 18 carbon atoms, A complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or It represents a complex aromatic group consisting of C, H and Group 16 elements and having 8 to 16 carbon atoms.
  • Ar 6 may be substituted with one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a pyridyl group, a cyano group and a methyl group.
  • Ar 6 is one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a pyridyl group, a cyano group and a methyl group in that the pyridine compound (Q) has excellent electron transporting material properties. It is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms which may be substituted. A hydrogen atom, a phenyl group, a biphenylyl group, a naphthyl group, a phenanthryl group, an anthryl group, a fluoranthenyl group, a pyrenyl group, or a triphenylenyl group is more preferable in terms of ease of synthesis. It is particularly preferable that Ar 6 is a hydrogen atom.
  • Ar 6 examples include a hydrogen atom, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl-2-yl group, a biphenyl-3-yl group, a biphenyl-4-yl group, and a 2-methylphenyl group.
  • L 4 and L 5 each independently Single bond, A divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or Represents a divalent complex aromatic group consisting of C, H and Group 16 elements and having 8 to 16 carbon atoms.
  • L 4 and L 5 may each be independently substituted with one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a pyridyl group, a cyano group and a methyl group.
  • L 4 and L 5 are each independently Single bond or A divalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may be substituted with one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a pyridyl group, a cyano group and a methyl group. Is preferable.
  • a single bond, a phenylene group, a naphthylene group, a phenanthrylene group, an anthrylene group, a triphenylene group, a fluoranthenylene group, or a pyrenylene group is more preferable because it is easy to synthesize.
  • L 4 and L 5 include a single bond, a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,2-naphthylene group, a 1,3-naphthylene group, 1, 4-naphthylene group, 1,5-naphthylene group, 1,2-phenanthrylene group, 1,3-phenanthrylene group, 1,4-phenanthrylene group, 1,5-phenanthrylene group, 1,6-phenanthrylene group, 1,7 -Phenanthrylene group, 1,8-Phenitylene group, 1,9-Phenitrylene group, 1,10-Phenitrylene group, 2,3-Phenitrylene group, 2,4-Fenantrylene group, 2,5-Fenantrylene group, 2,6- Phenanthrylene group, 2,7-phenanthrylene group, 2,8-phenanthrylene group, 2,9-phenanthrylene group, 2,10-pheny
  • These groups may be substituted with one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a pyridyl group, a cyano group and a methyl group.
  • L 6 is Single bond, Divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms, A divalent complex aromatic group having 4 to 17 carbon atoms consisting of C, H and N formed only by a 6-membered ring, or Represents a divalent complex aromatic group consisting of C, H and Group 16 elements and having 8 to 16 carbon atoms.
  • L 6 may be substituted with one or more groups selected from the group consisting of a phenyl group, a biphenylyl group, a naphthyl group, a pyridyl group, a cyano group and a methyl group.
  • L 6 is preferably a phenylene group because the pyridine compound (Q) is excellent in electron transporting material properties.
  • L 6 examples include a single bond, a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,2-naphthylene group, a 1,3-naphthylene group, and a 1,4-naphthylene.
  • L 7 represents a trivalent or tetravalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
  • L 7 examples include a benzenetriyl group, a naphthalenetriyl group, a phenanthrenetriyl group, an anthracene triyl group, a triphenylene triyl group, a fluoranthentryl group, a pyrentryyl group, a benzenetetrayl group, and a naphthalenetetrayl group. , Phenanthrene tetrayl group, anthracene tetrayl group, triphenylene tetrayl group, fluorentene tetrayl group, pyrene tetrayl group and the like. L 7 is preferably a benzenetriyl group because the pyridine compound (Q) is excellent in electron transporting material properties.
  • d represents 0, 1 or 2.
  • e represents 1, 2 or 3.
  • d + e is 3.
  • the two Ar 5 may be the different from each other.
  • e is 2 or more, a plurality of L 6 , L 7 , Ar 6 , Q, r, and q may be different from each other.
  • D is preferably 2 in that the pyridine compound (Q) can be easily synthesized.
  • [About q] q represents 1 or 2.
  • the two L 7 and Ar 6 may be different from each other.
  • Q is preferably 1 in that the pyridine compound (Q) can be easily synthesized.
  • [About r] r represents 1 or 2; When r is 2, the two Qs may be different from each other; R is preferably 1 in that the pyridine compound (Q) can be easily synthesized.
  • Q is a substituent represented by the formula (Q-1), (Q-2) or (Q-3).
  • the pyridine compound (Q) is a pyridine compound having a partial structure represented by the formula (Q-1), (Q-2) or (Q-3) and a 1,3,5-triazyl group.
  • Examples of the partial structure represented by the formulas (Q-1), (Q-2) or (Q-3) include the following (B-1) to (B-207). It is not limited.
  • Examples of the 1,3,5-triazyl group to which the pyridine skeleton exemplified in (B-1) to (B-207) is bound include the following (T-1) to (T-122).
  • the present invention is not limited thereto.
  • the Q described in the following (T-1) to (T-122) is any one of the above formulas (Q-1), (Q-2) or (Q-3).
  • pyridine compound (Q) examples include the following (AA-1) to (AA-117), but the present invention is not limited thereto.
  • the pyridine compound (Q) includes AA-57, AA-58, AA-60, AA-66, AA-67, AA-69, and AA-76 in that it has good performance as an electron transport material in an organic electroluminescent element. , AA-84, AA-85, AA-90, AA-117 are preferred.
  • the pyridine compound (Q) can be produced by the methods shown in the following synthetic routes (vi) to (x).
  • Y 7 , Y 8 , Y 9 , Y 10 , Y 11 and Y 12 each independently represent a halogen atom;
  • R 2 represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms;
  • B (OR 2) 2 two R 2 of 2, may be different from each be the same;
  • Examples of the halogen atom represented by Y 7 , Y 8 , Y 9 , Y 10 , Y 11 and Y 12 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and of the pyridine compound (Q).
  • a chlorine atom or a bromine atom is preferable in terms of good yield.
  • the B (OR 2) 2 for example, can be exemplified B (OH) 2, B ( OMe) 2, B (O i Pr) 2, B (OBu) 2, B (OPh) 2 or the like.
  • Me is a methyl group
  • i Pr is an isopropyl group
  • Bu is a butyl group
  • Ph is a phenyl group.
  • B (OR 2 ) 2 in the case where two OR 2 groups and a boron atom are integrally formed to form a ring, for example, the groups shown by the following (I) to (VI) are shown.
  • the group represented by (II) is preferable in that the yield is good.
  • the coupling reaction in the synthetic pathways (vi) to (x) is the same as the aryl halide compound represented by the formulas (14), (16), (17), (19), (20) or (22).
  • This is a method of reacting a boron compound represented by (15), (18), (21), (23) or (24) with a palladium catalyst and the presence of a base, and is a general reaction condition of the Suzuki-Miyaura reaction. Can be applied.
  • Boron compounds can be produced, for example, according to the method disclosed in The Journal of Organic Chemistry, Vol. 60, p. 7508, 1995 or The Journal of Organic Chemistry, Vol. 65, p. 164, 2000.
  • Aryl halide compounds (14), (16), (17), (19), (20) or (22) are, for example, Journal of the American Chemical Society, Vol. 74, p. 6289, 1952 or Synlett, p. 808. , Can be manufactured according to 2002. Moreover, you may use a commercially available product. It is preferable to use 0.5 to 3.0 molar equivalents of the aryl halide compound with respect to the boron compound in terms of good reaction yield.
  • the boring reaction in the synthetic pathways (vi) to (x) involves the presence of an aryl halide compound represented by the formulas (14), (17), (19), (20) or (22) in a palladium catalyst and a base.
  • the boron compound represented by the formulas (15), (18), (21), (23) or (24) is produced by reacting with a boron reagent (for example, pinacholate borane, bispinacolato diboron, etc.) below.
  • a boron reagent for example, pinacholate borane, bispinacolato diboron, etc.
  • Examples of the palladium catalyst used in the above-mentioned coupling reaction and boration reaction include palladium salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate. Further, complex compounds such as ⁇ -allyl palladium chloride dimer, palladium acetylacetonato, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, dichlorobis (acetritale) palladium, dichlorobis (benzonitrile) palladium; Dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichloro (1,1'-bis (diphenylphosphino) ferrocene) palladium, bis (tri-tert-butylphosphine) palladium, bis (tricyclohexylphosphin
  • tertiary phosphine examples 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) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (1
  • a palladium complex having a tertiary phosphine as a ligand is preferable in terms of good yield, and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl or tricyclohexylphosphine is a ligand.
  • the palladium complex having as is more preferable.
  • the molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably in the range of 1:10 to 10: 1, and further preferably in the range of 1: 2 to 3: 1 in terms of good yield. preferable.
  • the amount of the palladium catalyst used in the above-mentioned coupling reaction and boration reaction is not limited, but the molar equivalent of the palladium catalyst is in the range of 0.005 to 0.5 molar equivalent with respect to the boron compound in terms of good yield. It is preferable to be in.
  • Examples of the base used for the above-mentioned coupling reaction and alkoxide reaction include metal hydroxide salts such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and metals such as sodium carbonate, potassium carbonate, lithium carbonate and cesium carbonate.
  • Metal acetates such as carbonates, potassium acetate and sodium acetate
  • metal phosphates such as potassium phosphate and sodium phosphate
  • metal fluoride salts such as sodium fluoride, potassium fluoride and cesium fluoride, sodium methoxide
  • Examples thereof include metal alkoxides such as potassium methoxide, sodium methoxide, potassium isopropyl oxide, and potassium tert-butoxide.
  • metal carbonate or metal phosphate is preferable, and potassium carbonate or potassium phosphate is more preferable in terms of good reaction yield.
  • the amount of base used is preferably in the range of 1: 2 to 10: 1, and more preferably in the range of 1: 1 to 4: 1.
  • Solvents include water, diisopropyl ether, dibutyl ether, cyclopentylmethyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahexyl, 1,4-dioxane, dimethoxyethane and other ethers; benzene, toluene, xylene, mesitylene, tetraline.
  • Aromatic hydrocarbons such as; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-fluoroethylene carbonate; ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, etc.
  • Esters such as ⁇ -lactone; amides such as N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP); N, N, N', N'-tetramethylurea (TMU) , N, N'-dimethylpropylene urea (DMPU) and other ureas; dimethyl sulfoxide (DMSO), methanol, ethanol, isopropyl alcohol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 2, Alcohols such as 2,2-trifluoroethanol; and the like.
  • amides such as N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP); N, N, N', N'-tetramethylurea (TMU) , N, N'-dimethylpropylene
  • solvents may be used alone or may be mixed and used at an arbitrary ratio.
  • amount of solvent used There is no particular limitation on the amount of solvent used. Of these, water, ether, amide, alcohol, and a mixed solvent thereof are preferable from the viewpoint of good reaction yield, and a mixed solvent of THF and water or a mixed solvent of toluene and butanol is more preferable.
  • the above-mentioned coupling reaction and boration reaction can be carried out at a temperature appropriately selected from 0 ° C. to 200 ° C., and at a temperature appropriately selected from 60 ° C. to 160 ° C. in terms of good reaction yield. It is preferable to carry out.
  • the above-mentioned coupling reaction and boring reaction obtain the desired product by appropriately combining general purification treatments such as recrystallization, column chromatography, sublimation purification, and preparative HPLC as necessary. Can be done.
  • the pyridine compound can be used, for example, in organic electronic device applications such as organic electroluminescent devices and photoelectric devices.
  • the material for an organic electroluminescent device contains a triazine compound (1) and a pyridine compound (Q).
  • the triazine compound (1) and the pyridine compound (Q) can be used, for example, as an electron transport material for an organic electroluminescent device.
  • Materials for organic electroluminescent devices containing the triazine compound (1) or pyridine compound (Q) have a long life, exhibit high luminous efficiency and low voltage characteristics, and are organic that can be used in various applications or in various environments. It contributes to the production of electroluminescent elements.
  • organic electroluminescent device containing a triazine compound and a pyridine compound according to one aspect of the present invention (hereinafter, may be simply referred to as an organic electroluminescent device) will be described.
  • the organic electroluminescent device contains a triazine compound (1) and a pyridine compound (Q).
  • the configuration of the organic electroluminescent device is not particularly limited, and examples thereof include the configurations (i) to (v) shown below.
  • the triazine compound (1) and the pyridine compound (Q) may be contained in any of the above layers, but the light emitting layer and the space between the light emitting layer and the cathode are excellent in the light emitting characteristics of the organic electroluminescent element. It is preferable that it is contained in one or more layers selected from the group consisting of the above layers. Therefore, in the case of the configurations shown in (i) to (v) above, one layer in which the triazine compound (1) and the pyridine compound (Q) are selected from the group consisting of a light emitting layer, an electron transport layer, and an electron injection layer. It is preferable to be included in the above.
  • the organic electroluminescent device shown in FIG. 1 has a so-called bottom emission type element configuration, but the organic electroluminescent device according to one aspect of the present invention is not limited to the bottom emission type element configuration. Absent. That is, the organic electroluminescent device according to one aspect of the present invention may have another known device configuration such as a top emission type.
  • FIG. 1 is a schematic cross-sectional view showing an example of a laminated configuration of organic electroluminescent devices according to one aspect of the present invention.
  • the organic electroluminescent device 100 includes 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 in this order.
  • some of these layers may be omitted, and conversely, other layers may be added.
  • a hole blocking layer may be provided between the light emitting layer 5 and the electron transporting layer 6, the hole injection layer 3 is omitted, and the hole transporting layer 4 is directly provided on the anode 2. May be good.
  • a single layer having a function of a plurality of layers such as an electron injection / transport layer having a function of an electron injection layer and a function of an electron transport layer in a single layer, is formed into the plurality of layers. It may be a configuration provided instead of. Further, for example, the single-layer hole transport layer 4 and the single-layer electron transport layer 6 may each be composed of a plurality of layers.
  • the organic electroluminescent device 100 has one or more layers selected from the group consisting of the light emitting layer 5, the electron transport layer 6, and the electron injection layer 7, and the triazine compound (1) and the pyridine compound (Q). including.
  • the electron transport layer 6 contains a triazine compound (1) and a pyridine compound (Q).
  • the triazine compound (1) and the pyridine compound (Q) may be contained in a plurality of layers included in the organic electroluminescent device. Further, in one aspect of the present invention, both may be contained in the same layer.
  • the organic electroluminescent device 100 in which the electron transport layer 6 contains the triazine compound (1) or the pyridine compound (Q) will be described.
  • the substrate 1 is not particularly limited, and examples thereof include a glass plate, a quartz plate, and a plastic plate.
  • the substrate 1 include a glass plate, a quartz plate, a plastic plate, a plastic film, and the like. Among these, a glass plate, a quartz plate, and a light-transmitting plastic film are preferable.
  • the light-transmitting plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, and polycarbonate (PC). ), Cellulose triacetate (TAC), cellulose acetate propionate (CAP) and the like.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PES polyethersulfone
  • PA polyetherimide
  • polyetheretherketone polyphenylene sulfide
  • PC polycarbonate
  • PC
  • An anode 2 is provided on the substrate 1 (on the hole injection layer 3 side).
  • the material of the anode include metals, alloys, electrically conductive compounds and mixtures thereof having a large work function (for example, 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), SnO 2, and ZnO.
  • the anode is formed of a conductive transparent material that allows or substantially passes the light emission.
  • a hole injection layer 3 and a hole transport layer 4 are provided in this order between the anode 2 and the light emitting layer 5 described later from the anode 2 side.
  • the hole injection layer and the hole transport layer have a function of transmitting holes injected from the anode to the light emitting layer, and the hole injection layer and the hole transport layer are interposed between the anode and the light emitting layer. Injects more holes into the light emitting layer with a lower electric field.
  • the hole injection layer and the hole transport layer also function as electron barrier layers.
  • the electrons injected from the cathode and transported from the electron injection layer and / or the electron transport layer to the light emitting layer are generated by the electron barrier existing at the interface between the light emitting layer and the hole injection layer and / or the hole transport layer. , Leakage into the hole injection layer and / or the hole transport layer is suppressed. As a result, the electrons are accumulated at the interface in the light emitting layer to bring about effects such as improvement of luminous efficiency, and an organic electroluminescent device having excellent light emitting performance can be obtained.
  • the material of the hole injection layer and the hole transport layer has at least 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 either an organic substance or an inorganic substance.
  • the materials for the hole injection layer and the hole transport layer include triazole derivative, oxadiazole derivative, imidazole derivative, polyarylalkane derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, arylamine derivative, and amino-substituted chalcone.
  • aromatic tertiary amine compound and the styrylamine compound include N, N, N', N'-tetraphenyl-4,4'-diaminophenyl, N, N'-diphenyl-N, N'-.
  • Inorganic compounds such as p-type-Si and p-type-SiC can also be mentioned as examples of the material of the hole injection layer and the material of the hole transport layer.
  • the hole injection layer and the hole transport layer may have a single structure made of one or more kinds of materials, or may have a laminated structure made of a plurality of layers having the same composition or different compositions.
  • a light emitting layer 5 is provided between the hole transport layer 4 and the electron transport layer 6 described later.
  • Examples of the material of the light emitting layer include a phosphorescent light emitting material, a fluorescent light emitting material, and a thermal activated delayed fluorescent light emitting material. In the light emitting layer, electron-hole pairs are recombined, resulting in light emission.
  • the light emitting layer may consist of a single low molecular weight material or a single polymer material, but more generally it consists of a host material doped with a guest compound. The luminescence comes primarily from the dopant and can have any color.
  • Examples of the host material include compounds having a biphenylyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, and an anthryl group. More specifically, DPVBi (4,4'-bis (2,2-diphenylvinyl) -1,1'-biphenyl), BCzVBi (4,4'-bis (9-ethyl-3-carbazobinylene) 1, 1'-biphenyl), TBADN (2-tertiary 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-phenylcarba
  • Examples of the fluorescent dopant include anthracene, pyrene, tetracene, xanthene, perylene, lubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyrane compound, thiopyran compound, polymethine compound, pyrylium, thiapyrylium compound, fluorene derivative, periversene derivative and indenoperylene. Examples thereof include derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, carbostyryl compounds, boron compounds, cyclic amine compounds and the like.
  • the fluorescent dopant may be a combination of two or more selected from these.
  • Examples of the phosphorescent dopant include organometallic complexes of transition metals such as iridium, platinum, palladium, and osmium.
  • fluorescent dopant and phosphorescent dopant include Alq 3 (tris (8-hydroxyquinoline) aluminum), DPAVBi (4,4'-bis [4- (di-p-tolylamino) styryl] biphenyl), perylene, and bis.
  • the light emitting material is not limited to being contained only in the light emitting layer.
  • the light emitting material may contain a layer (hole transport layer 4 or electron transport layer 6) adjacent to the light emitting layer. This makes it possible to further increase the luminous efficiency of the organic electroluminescent device.
  • the light emitting layer may have a single layer structure made of one or more kinds of materials, or may have a laminated structure made of a plurality of layers having the same composition or different compositions.
  • Electrode transport layer 6 An electron transport layer 6 is provided between the light emitting layer 5 and the electron injection layer 7 described later.
  • the electron transport layer has a function of transferring electrons injected from the cathode to the light emitting layer. By interposing the electron transport layer between the cathode and the light emitting layer, electrons are injected into the light emitting layer with a lower electric field.
  • the electron transport layer preferably contains a triazine compound (1) and a pyridine compound (Q). Further, the electron transport layer may contain one or more selected from conventionally known electron transport materials in addition to the triazine compound (1) and the pyridine compound (Q).
  • the triazine compound (1) and the pyridine compound (Q) are not contained in the electron transport layer but are contained in another layer, one or more selected from conventionally known electron transport materials constitute the electron transport layer. It can be used as an electron transport material.
  • Examples of conventionally known electron-transporting materials include alkali metal complexes, alkaline earth metal complexes, and earth metal complexes.
  • Examples of the alkali metal complex, alkaline earth metal complex, and earth metal complex include 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinate) zinc, and bis (8-hydroxyquinolinate) copper.
  • the electron transport layer may have a single-layer structure composed of one or more kinds of materials, or may have a laminated structure composed of a plurality of layers having the same composition or a different composition.
  • an electron injection layer may be provided for the purpose of improving the electron injection property and the device characteristics (for example, luminous efficiency, low voltage drive, or high durability).
  • An electron injection layer 7 is provided between the electron transport layer 6 and the cathode 8 described later.
  • the electron injection layer has a function of transferring electrons injected from the cathode to the light emitting layer. By interposing the electron injection layer between the cathode and the light emitting layer, electrons are injected into the light emitting layer with a lower electric field.
  • Materials for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fleolenilidenemethane, anthraquinodimethane, and antron. Examples include organic compounds.
  • the material of the electron injection layer includes various oxides and fluorides such as SiO 2 , AlO, SiN, SiON, AlON, GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, LiF, C and Yb. , Nitride, oxide nitride and other inorganic compounds are also mentioned.
  • a cathode 8 is provided on the electron injection layer 7.
  • the cathode can be formed from any conductive material.
  • the material of the cathode include metals having a small work function (hereinafter, also referred to as electron-injectable metals), alloys, electrically conductive compounds, and mixtures thereof.
  • the metal having a small work function is, for example, a metal having a work function of 4 eV or less.
  • cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ).
  • examples include mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this for example, magnesium / silver mixture, magnesium / Aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) mixture, lithium / aluminum mixture and the like are preferable.
  • Each layer excluding the electrodes (anode, cathode) described above is formed by thinning by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB (Langmuir-Blodgett method) method. be able to.
  • the material of each layer may be used alone, or may be used together with a material such as a binder resin and a solvent, if necessary.
  • the film thickness of each layer thus formed is not particularly limited and may be appropriately selected depending on the situation, but is usually in the range of 5 nm to 5 ⁇ m.
  • the anode and cathode can be formed by thinning the electrode material by a method such as thin film deposition or sputtering.
  • a pattern may be formed through a mask having a desired shape during vapor deposition or sputtering, or a thin film may be formed by vapor deposition or sputtering, and then a pattern having a desired shape may be formed by photolithography.
  • the film thickness of the anode and the cathode is preferably 1 ⁇ m or less, and more preferably 10 nm or more and 200 nm or less.
  • the layer containing the triazine compound (1) and the pyridine compound (Q) it may be used in combination with the above-mentioned conventionally known electron-transporting material. Therefore, for example, the triazine compound (1) and the pyridine compound (Q) may be co-deposited with the conventionally known electron transporting material, and the conventionally known electrons may be formed in the layer of the triazine compound (1) and the pyridine compound (Q). Layers of transportable material may be laminated.
  • the organic electroluminescent element may be used as a kind of lamp such as an illumination or an exposure light source, a projection device of a type that projects an image on a screen or the like, or a display of a type that directly visually recognizes a still image or a moving image. It may be used as a device (display).
  • the drive method may be a simple matrix (passive matrix) method or an active matrix method.
  • a full-color display device can be manufactured by using two or more kinds of organic electroluminescent elements having different emission colors.
  • the triazine compound and the pyridine compound according to one aspect of the present invention provide an organic electroluminescent element which is remarkably superior in light emission efficiency and low voltage characteristics as compared with conventionally known triazine compounds and pyridine compounds when used as an electron transport layer. can do. Further, the triazine compound and the pyridine compound according to one aspect of the present invention are highly amorphous due to their steric hindrance skeleton and have high film quality stability. Therefore, effects such as improvement of driving stability of the organic electroluminescent element and improvement of luminous efficiency are expected. Moreover, the triazine compound and the pyridine compound according to one aspect of the present invention have high chemical stability due to their characteristic skeleton, and can contribute to extending the life of the organic electroluminescent element.
  • the triazine compound and the pyridine compound according to one aspect of the present invention can be used as an electron transport layer of an organic electroluminescent element to achieve a high level of low voltage drive, high efficiency, and long life of the element.
  • pyridine compounds can be provided. Further, it is possible to provide an organic electroluminescent device capable of exhibiting low voltage drive, high efficiency and long life by using the pyridine compound according to one aspect of the present invention.
  • DSC measurement glass transition temperature, crystallization temperature
  • the glass transition temperature, crystallization temperature, and melting point were measured using a DSC (Differential scanning calorimetry) device DSC7020 (manufactured by Hitachi High-Tech Science Co., Ltd.).
  • Aluminum oxide (Al 2 O 3 ) was used as a reference in the DSC measurement, and the sample was measured at 10 mg.
  • the temperature was raised from 30 ° C. to a temperature above the melting point at a rate of 10 ° C./min to melt the sample, and then the sample was brought into contact with dry ice to quench it. Subsequently, the temperature of the pretreated sample was raised at a rate of 30 ° C. to 10 ° C./min, and the glass transition temperature and the crystallization temperature were measured.
  • 3-bromo-4'-chloro-1,1'-biphenyl (25.1 g, 94.0 mmol), bis (pinacolato) diboron (35.8 g, 141 mmol), tetrakis (triphenylphosphine) palladium ( 0) (1.09 g, 0.94 mmol) and potassium acetate (27.7 g, 282 mmol) were suspended in tetrahydrofuran (310 mL) and stirred at 70 ° C. for 17 hours. After cooling to room temperature, the aqueous layer and the organic layer were separated, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure.
  • the compounds A-53, A-56, AA-66 and AA-57 obtained in this synthesis example are higher than the conventionally known compounds obtained in Reference Example-1. It was found to have a crystallization temperature.
  • device Example-1T (T is an element made of a triazine compound) and 1P (P is an element made of a pyridine compound) were formed as follows. Except for the electron transport layer 6, the device Examples-1T and 1P are common.
  • a glass substrate with an ITO transparent electrode in which a 2 mm wide indium tin oxide (ITO) film (thickness 110 nm) was patterned in a stripe shape was prepared. Then, after cleaning this substrate with isopropyl alcohol, surface treatment was performed by ozone ultraviolet cleaning.
  • ITO indium tin oxide
  • Each layer was vacuum-deposited by a vacuum-film deposition method on the surface-treated substrate after cleaning, and each layer was laminated and formed.
  • the glass substrate was introduced into a vacuum vapor deposition tank, and the pressure was reduced to 1.0 ⁇ 10 -4 Pa. Then, it was produced in the following order according to the film forming conditions of each layer.
  • Each organic material was formed by a resistance heating method.
  • Second hole transport layer 42 Sublimated and purified N-phenyl-N- (9,9-diphenylfluorene-2-yl) -N- (1,1'-biphenyl-4-yl) amine was formed into a 5 nm film at a rate of 0.15 nm / sec. , The second hole transport layer 42 was prepared.
  • Example-1P Device Example-1P> Synthesis Example-4,6-bis (biphenyl) -2- [3'-(2,3-diphenyl) -pyridyl-5-yl-] biphenyl-3-yl-1,3,5-synthesized in Example-7 Triazine (Compound AA-84) and 8-hydroxyquinolinolate lithium (hereinafter, Liq) were formed into a film at a ratio of 50:50 (mass ratio) at 25 nm to prepare an electron transport layer 6. The film forming rate was 0.15 nm / sec.
  • cathode 8 (Preparation of cathode 8) Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe (anode 2) on the substrate 1, and the cathode 8 was formed into a film.
  • silver / magnesium (mass ratio 1/10) and silver were formed in this order at 80 nm and 20 nm, respectively, to form a two-layer structure.
  • the film formation rate of silver / magnesium was 0.5 nm / sec, and the film formation rate of silver was 0.2 nm / sec.
  • the 2 organic electroluminescent device 100 having a light emitting area of 4 mm as shown in FIG. 2 was manufactured.
  • Each film thickness was measured with a stylus type film thickness measuring meter (DEKTAK, manufactured by Bruker).
  • this element was sealed in a nitrogen atmosphere glove box having an oxygen and water concentration of 1 ppm or less. Sealing was performed by using a glass sealing cap and a film-forming substrate (element) with a bisphenol F type epoxy resin (manufactured by Nagase ChemteX Corporation).
  • Element Example-2T In the device Example-1T, 2,4-bis (4-biphenylyl) -6- [4'-(2-phenylpyridine-3-yl) biphenyl-3-yl] -1,3 was formed on the electron transport layer 6. , 5-Triazine (Compound A-56) and Liq were synthesized in Synthesis Example-2 instead of forming a 25 nm film (forming rate 0.15 nm / sec) at a ratio of 50:50 (mass ratio).
  • Element Example-2P In Element Example-1P, 4,6-bis (biphenyl) -2- [3'-(2,3-diphenyl) -pyridyl-5-yl-] biphenyl-3-yl-1 was added to the electron transport layer 6. , 3,5-Triazine (Compound AA-84) and Liq were synthesized in Synthesis Example-4 instead of forming a 25 nm film (forming rate 0.15 nm / sec) at a ratio of 50:50 (mass ratio).
  • Element Example-3P In Element Example-1P, 4,6-bis (biphenyl) -2- [3'-(2,3-diphenyl) -pyridyl-5-yl-] biphenyl-3-yl-1 was added to the electron transport layer 6. , 3,5-Triazine (Compound AA-84) and Liq were synthesized in Synthesis Example-6 instead of forming a 25 nm film (forming rate 0.15 nm / sec) at a ratio of 50:50 (mass ratio).
  • Element Example-4P In Element Example-1P, 4,6-bis (biphenyl) -2- [3'-(2,3-diphenyl) -pyridyl-5-yl-] biphenyl-3-yl-1 was added to the electron transport layer 6. , 3,5-Triazine (Compound AA-84) and Liq were synthesized in Synthesis Example-7 instead of forming a 25 nm film (forming rate 0.15 nm / sec) at a ratio of 50:50 (mass ratio).
  • Element Example-5P In Element Example-1P, 4,6-bis (biphenyl) -2- [3'-(2,3-diphenyl) -pyridyl-5-yl-] biphenyl-3-yl-1 was added to the electron transport layer 6. , 3,5-Triazine (Compound AA-84) and Liq were synthesized in Synthesis Example-12 instead of forming a 25 nm film (forming rate 0.15 nm / sec) at a ratio of 50:50 (mass ratio).
  • Element Example-6P In Element Example-1P, 4,6-bis (biphenyl) -2- [3'-(2,3-diphenyl) -pyridyl-5-yl-] biphenyl-3-yl-1 was added to the electron transport layer 6. , 3,5-Triazine (Compound AA-84) and Liq were synthesized in Synthesis Example-18 instead of forming a 25 nm film (forming rate 0.15 nm / sec) at a ratio of 50:50 (mass ratio).
  • Element Example-7P In Element Example-1P, 4,6-bis (biphenyl) -2- [3'-(2,3-diphenyl) -pyridyl-5-yl-] biphenyl-3-yl-1 was added to the electron transport layer 6. , 3,5-Triazine (Compound AA-84) and Liq were synthesized in Synthesis Example-20 instead of forming a 25 nm film (forming rate 0.15 nm / sec) at a ratio of 50:50 (mass ratio).
  • Element Example-8P In Element Example-1P, 4,6-bis (biphenyl) -2- [3'-(2,3-diphenyl) -pyridyl-5-yl-] biphenyl-3-yl-1 was added to the electron transport layer 6. , 3,5-Triazine (Compound AA-84) and Liq were synthesized in Synthesis Example-13 instead of forming a 25 nm film (forming rate 0.15 nm / sec) at a ratio of 50:50 (mass ratio).
  • Element Example-9P In Element Example-1P, 4,6-bis (biphenyl) -2- [3'-(2,3-diphenyl) -pyridyl-5-yl-] biphenyl-3-yl-1 was added to the electron transport layer 6. , 3,5-Triazine (Compound AA-84) and Liq were synthesized in Synthesis Example-19 instead of forming a 25 nm film (forming rate 0.15 nm / sec) at a ratio of 50:50 (mass ratio).
  • Element Example-10P In Element Example-1P, 4,6-bis (biphenyl) -2- [3'-(2,3-diphenyl) -pyridyl-5-yl-] biphenyl-3-yl-1 was added to the electron transport layer 6. , 3,5-Triazine (Compound AA-84) and Liq were synthesized in Synthesis Example-26 instead of forming a 25 nm film (forming rate 0.15 nm / sec) at a ratio of 50:50 (mass ratio).
  • Element reference example-1 In Device Examples-1T and 1P, ETL-1 and Liq synthesized in Reference Example-1 were used in a ratio of 50:50 (mass ratio) instead of Compound A-2 and Compound AA-84 in the electron transport layer 6.
  • An organic electroluminescent device was produced in the same manner as in Device Examples-1T and 1P except that a 25 nm film was formed (deposition rate 0.15 nm / sec).
  • a direct current was applied to the produced organic electroluminescent device, and the light emission characteristics were evaluated according to the method described in the above light emission characteristic measurement.
  • the voltage (V) and the power efficiency (lm / A) when a current density of 10 mA / cm 2 was passed were measured, and the element life during continuous lighting was measured.
  • the device lifetime was measured luminance decay time at the time of continuous lighting when driving the initial luminance 1000 cd / m 2, to measure the time required until the luminance (cd / m 2) is reduced 5%.
  • the values of voltage (V), power efficiency (lm / A), and life are expressed as relative values when the device reference example-1 is set to 100. The results are shown in Tables 1 and 2.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Le but de la présente invention est de fournir : un composé de triazine ayant une température de cristallisation élevée qui est utile pour former des éléments électroluminescents organiques ayant une faible tension de fonctionnement, un rendement luminescent élevé et une longue durée de vie ; un matériau pour des éléments électroluminescents organiques qui comprend le composé de triazine ; un matériau de transport d'électrons pour des éléments électroluminescents organiques ; et un élément électroluminescent organique.　L'objectif a été atteint avec un composé de triazine ayant une structure spécifique représentée par la formule (1) et un composé de pyridine ayant à la fois une structure partielle représentée par la formule (Q-1), (Q-2) ou (Q-3) et un groupe 1,3,5-triazyle.
PCT/JP2020/039606 2019-10-24 2020-10-21 Composé de triazine ayant un groupe pyridyle et un composé de pyridine WO2021079915A1 (fr)

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Cited By (1)

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JP7450432B2 (ja) 2020-03-30 2024-03-15 東ソー株式会社 トリアジン化合物

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KR20140094408A (ko) * 2013-01-22 2014-07-30 덕산하이메탈(주) 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
CN105294663A (zh) * 2015-11-11 2016-02-03 上海道亦化工科技有限公司 一种含吡啶化合物及其有机电致发光器件
WO2016024745A2 (fr) * 2014-08-12 2016-02-18 삼성에스디아이 주식회사 Composé, diode optoélectronique organique comprenant ledit composé et dispositif d'affichage
US20160260901A1 (en) * 2015-03-06 2016-09-08 Samsung Display Co., Ltd. Organic light-emitting device
WO2020009381A1 (fr) * 2018-07-06 2020-01-09 주식회사 두산 Composé organique et dispositif électroluminescent organique le comprenant
WO2020085319A1 (fr) * 2018-10-22 2020-04-30 東ソー株式会社 Composé d'azine cyclique, matériau pour éléments électroluminescents organiques, matériau de transport d'électrons pour éléments électroluminescents organiques, et élément électroluminescent organique

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KR20140094408A (ko) * 2013-01-22 2014-07-30 덕산하이메탈(주) 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
WO2016024745A2 (fr) * 2014-08-12 2016-02-18 삼성에스디아이 주식회사 Composé, diode optoélectronique organique comprenant ledit composé et dispositif d'affichage
US20160260901A1 (en) * 2015-03-06 2016-09-08 Samsung Display Co., Ltd. Organic light-emitting device
CN105294663A (zh) * 2015-11-11 2016-02-03 上海道亦化工科技有限公司 一种含吡啶化合物及其有机电致发光器件
WO2020009381A1 (fr) * 2018-07-06 2020-01-09 주식회사 두산 Composé organique et dispositif électroluminescent organique le comprenant
WO2020085319A1 (fr) * 2018-10-22 2020-04-30 東ソー株式会社 Composé d'azine cyclique, matériau pour éléments électroluminescents organiques, matériau de transport d'électrons pour éléments électroluminescents organiques, et élément électroluminescent organique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7450432B2 (ja) 2020-03-30 2024-03-15 東ソー株式会社 トリアジン化合物

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