WO2020096001A1 - Composé et élément électroluminescent organique faisant appel à celui-ci - Google Patents

Composé et élément électroluminescent organique faisant appel à celui-ci Download PDF

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WO2020096001A1
WO2020096001A1 PCT/JP2019/043701 JP2019043701W WO2020096001A1 WO 2020096001 A1 WO2020096001 A1 WO 2020096001A1 JP 2019043701 W JP2019043701 W JP 2019043701W WO 2020096001 A1 WO2020096001 A1 WO 2020096001A1
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group
substituted
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carbon atoms
ring
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匡 羽毛田
裕 工藤
裕勝 伊藤
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出光興産株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/58—Naphthylamines; N-substituted derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • 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
    • H10K50/15—Hole transporting layers

Definitions

  • the present invention relates to a compound and an organic electroluminescence device using the compound.
  • an organic electroluminescence element (“organic EL element”) is composed of an anode, a cathode, and an organic layer sandwiched between the anode and the cathode.
  • organic EL element When a voltage is applied between both electrodes, electrons are injected from the cathode side and holes are injected from the anode side into the light emitting region, and the injected electrons and holes are recombined in the light emitting region to generate an excited state, and excited. It emits light when the state returns to the ground state. Therefore, development of a device structure that transports electrons or holes to the light emitting region and promotes recombination of electrons and holes is important for obtaining a high-performance organic EL device.
  • Patent Document 1 describes an amine compound in which a central nitrogen atom has two structures selected from a direct fluorene structure and a non-fused aromatic ring structure and a non-fused aromatic heterocyclic structure.
  • an amine compound having a central nitrogen atom having a direct fluorene structure and two groups selected from a biphenylyl group and a terphenylyl group is a hole injection layer 1 / hole transport layer / hole injection layer 2 / electron block layer. It is used for an electron blocking layer of an organic EL device having a layer structure of / light emitting layer / electron transporting layer.
  • Patent Document 1 exemplifies an amine compound in which the central nitrogen atom has a direct fluorene structure, a linear quaterphenyl group, and a biphenylyl group or a terphenylyl group, but its EL performance has not been measured.
  • Patent Document 2 describes an organic EL device having a first hole transport layer and a second hole transport layer composed of a single layer or a plurality of layers formed between the first hole transport layer and the light emitting layer.
  • the first hole transport layer contains an amine compound in which a 3-carbazolyl group bonded to a central nitrogen atom directly or via a linker is essential.
  • the material of the second hole transport layer is selected from the amine compounds represented by the formulas (2) to (4).
  • the example of Patent Document 2 has a first hole-transporting layer containing an amine compound HTM3 or the like in which a 3-carbazolyl group is bonded to a central nitrogen atom via a linker, and three aryl groups bonded to the central nitrogen atom.
  • Patent Document 2 discloses, as an amine compound of formula (2) (second hole transport layer material), a central nitrogen atom has a 3 ′, 5′-diphenyl-4-biphenylyl group, a direct-bonded fluorene structure, and a biphenylyl group. The compounds are exemplified. However, the performance of devices using this compound has not been measured.
  • Patent Document 3 discloses amine compounds 1-3, 1-4, and 1-20 in which a central nitrogen atom has a 3 ′, 5′-diphenyl-4-biphenylyl group, a direct fluorene structure, and a biphenylyl group or a fluorene structure. It has been described. These compounds are used as a cohost of a light emitting layer together with a compound in which a carbazole structure is condensed with an indole ring, a benzothiophene ring, a benzofuran ring, an indene ring and the like.
  • the central nitrogen atom is selected from a 3 ′, 5′-diphenyl-4-biphenylyl group, a group containing an aromatic heterocycle, and a group containing an aromatic heterocycle and an aryl group.
  • Amine compounds H1 to H32 having groups are described.
  • the amine compound is used for a single-layer hole transport layer.
  • the hole transport layer has a multilayer structure in order to improve the performance of the organic EL device.
  • an organic EL having a multilayer hole transport layer is known. There is still a demand for further improvement in device performance.
  • the present invention has been made to solve the above problems, and provides an organic EL device having improved device performance and a compound capable of realizing the same.
  • an amine compound having a 3 ′, 5′-diphenyl-4-biphenylyl group, a 3 ′, 5′-diphenyl-4-biphenylyl group, a phenyl group or a naphthyl group on the central nitrogen atom It has been found that an amine compound having a condensed aryl group such as, and a 9,9-diphenylfluorenyl group has high performance as a hole transport layer material.
  • the present invention may refer to a compound represented by the following formula (1) (hereinafter, a compound represented by the formula (1) and a formula of a preferred embodiment thereof is referred to as "invention compound (1)”. )I will provide a.
  • R 1 to R 4 is a single bond bonded to * a, R 5 to R 8 , R 10 to R 19 , and R 1 to R 4 which are not a single bond bonded to * a are: Each independently a hydrogen atom or a substituent, The substituent is Halogen atom, cyano group, nitro group, A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 ring-forming carbon atoms, A substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, A substituted or unsubstituted aralkyl group having 7 to 36 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 ring-forming carbon atoms
  • R 5 to R 8 two adjacent ones selected from R 10 to R 19 and two adjacent ones selected from R 1 to R 4 which is not a single bond to * a.
  • R 30 to R 46 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
  • two adjacent groups selected from R 30 and R 33 , R 31 and R 32 , R 37 to R 41 , and two adjacent groups selected from R 42 to R 46 are each independently a hydrogen atom or They represent a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or they are bonded to each other to form a substituted or unsubstituted ring structure.
  • Ar is A substituted or unsubstituted phenyl group, A substituted or unsubstituted condensed aryl group having 10 to 26 ring-forming carbon atoms and composed only of 6-membered rings, A substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, Arbitrary substituent of the above “substituted or unsubstituted” for Ar is An unsubstituted alkyl group having 1 to 30 carbon atoms, A mono-, di- or tri-substituted silyl group having a substituent selected from unsubstituted alkyl groups having 1 to 30 carbon atoms, L is a single bond or a substituted or unsubstituted arylene group having 6 to 20 ring carbon atoms. )
  • the present invention provides a material for an organic EL device, which comprises the invention compound (1).
  • the present invention is an organic electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode,
  • the organic layer comprises a light emitting layer and a hole transport zone disposed between the anode and the light emitting layer,
  • the hole transport zone includes a first hole transport layer on the anode side and a second hole transport layer on the cathode side,
  • One of the first hole transport layer and the second hole transport layer contains a compound represented by the formula (1), and the other contains a compound represented by the following formula (2) (hereinafter, formula (2) and A compound represented by the formula of a preferred embodiment thereof may be referred to as "invention compound (2)”), and an organic electroluminescence device is provided.
  • X 1 is an oxygen atom, a sulfur atom, CRaRb, or a nitrogen atom bonded to * c
  • R 50 to R 53 is a single bond bonded to * c
  • R 50 ⁇ R 53 is not a single bond to bond to R 54 ⁇
  • * c are each independently a hydrogen atom or a substituent, the substituent is a halogen atom, a cyano group, a nitro group, a substituted Or an unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring forming carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring forming carbon atoms, substituted or unsubstituted An aralkyl group having 7 to 36 carbon atoms,
  • two adjacent groups selected from R 50 to R 53 and two adjacent groups selected from R 54 to R 57 which are not a single bond bonded to * c are each independently a hydrogen atom or the above substituent. Represented or bonded to each other to form a substituted or unsubstituted ring structure.
  • Ra and Rb each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or Combine to form a substituted or unsubstituted ring structure
  • L 1 , L 2 and L 3 are each independently a single bond or a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.
  • R 54 to R 57 , R 50 to R 53 which is not a single bond bonded to * c, the ring structure, and any of “substituted or unsubstituted” represented by “substituted or unsubstituted” of L 1 to L 3 , Ar 1 and Ar 2 .
  • the substituents are each independently a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted group Or an unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 36 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted ring formation
  • the present invention provides an electronic device including the organic EL element.
  • the “carbon number XX to YY” in the expression “substituted or unsubstituted ZZ group having XX to YY carbon atoms” means the number of carbon atoms when the ZZ group is unsubstituted. If present, the carbon number of the substituent is not included.
  • atom number XX to YY in the expression “substituted or unsubstituted ZZ group having XX to YY atoms” means the number of atoms when the ZZ group is unsubstituted. The number of atoms of the substituent when it is included is not included.
  • the “unsubstituted ZZ group” in the case of “substituted or unsubstituted ZZ group” means that the hydrogen atom of the ZZ group is not substituted with a substituent.
  • the “hydrogen atom” includes isotopes having different neutron numbers, that is, light hydrogen (protium), deuterium (deuterium), and tritium (tritium).
  • aryl group and arylene group are aromatic hydrocarbon residues, and are distinguished from heteroaryl groups and heteroarylene groups containing a ring-forming heteroatom.
  • the “number of carbon atoms forming a ring” refers to the ring itself of a compound having a structure in which atoms are bonded in a ring (for example, a monocyclic compound, a condensed ring compound, a bridging compound, a carbocyclic compound, a heterocyclic compound). It represents the number of carbon atoms among the constituent atoms.
  • the carbon included in the substituent is not included in the ring-forming carbon. The same applies to the “ring carbon number” described below unless otherwise specified.
  • a benzene ring has 6 ring carbon atoms
  • a naphthalene ring has 10 ring carbon atoms
  • a pyridine ring has 5 ring carbon atoms
  • a furan ring has 4 ring carbon atoms.
  • the carbon number of the alkyl group is not included in the number of ring-forming carbon atoms.
  • the carbon number of the fluorene ring as a substituent is not included in the ring-forming carbon number.
  • the “number of ring-forming atoms” refers to a compound having a structure in which atoms are bonded in a ring (for example, a monocyclic ring, a condensed ring, a ring assembly) (for example, a monocyclic compound, a condensed ring compound, a bridge compound, a carbocyclic compound) , Heterocyclic compound) represents the number of atoms constituting the ring itself.
  • An atom that does not form a ring for example, a hydrogen atom that terminates a bond of an atom that forms a ring
  • an atom included in a substituent when the ring is substituted with a substituent is not included in the number of ring-forming atoms.
  • the pyridine ring has 6 ring-forming atoms
  • the quinazoline ring has 10 ring-forming atoms
  • the furan ring has 5 ring-forming atoms.
  • Hydrogen atoms bonded to the ring-forming carbon atoms of the pyridine ring or quinazoline ring or atoms constituting the substituent are not included in the number of ring-forming atoms.
  • a fluorene ring is bonded to the fluorene ring as a substituent (including a spirobifluorene ring)
  • the number of atoms of the fluorene ring as a substituent is not included in the number of ring-forming atoms.
  • Inventive compound (1) is represented by the following formula (1).
  • R 1 to R 4 is a single bond bonded to * a.
  • R 2 is preferably a single bond that binds to * a
  • R 4 is preferably a single bond that binds to * a.
  • the invention compound (1) includes a compound represented by the following formula (1-a) or (1-b).
  • R 5 to R 8 , R 10 to R 19 , and R 1 to R 4 which are not a single bond bonded to * a are each independently a hydrogen atom or a substituent.
  • two adjacent ones selected from R 5 to R 8, two adjacent ones selected from R 10 to R 19 and two adjacent ones selected from R 1 to R 4 which is not a single bond to * a are each independently represent a hydrogen atom or the above-mentioned substituent, or are bonded to each other to form a substituted or unsubstituted ring structure.
  • At least one pair of adjacent two form a substituted or unsubstituted ring structure, and in another aspect, the adjacent two form a substituted or unsubstituted ring structure.
  • R 5 to R 8 , R 10 to R 19 , and R 1 to R 4 which are not a single bond bonding to * a are all hydrogen atoms.
  • the substituent is a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted alkyl group having 1 to 30, preferably 1 to 18 and more preferably 1 to 8 carbon atoms; a substituted or unsubstituted ring forming carbon number 3 to 30, preferably 3 to 10, more preferably 3 to 8, more preferably 5 or 6 cycloalkyl group; substituted or unsubstituted 6 to 30 ring-forming carbon atoms, preferably 6 to 25, more preferably 6-18 aryl group; substituted or unsubstituted C7-36, preferably 7-26, more preferably 7-20 aralkyl group; substituted or unsubstituted C1-30, preferably 1-18 , More preferably 1-8 alkoxy group; substituted or unsubstituted 6-30 ring-forming carbon atoms, preferably 6-25, more preferably 6-18 aryloxy group; substituted or A substituted alkyl group having 1 to 30,
  • a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms a substituted or unsubstituted cycloalkyl group having 3 to 30 ring forming carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring forming carbon atoms
  • aryl groups Selected from the group consisting of aryl groups; More preferably, it is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms is particularly preferable.
  • the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a fluorine atom is preferable.
  • the alkyl group having 1 to 30 carbon atoms is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group.
  • S-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, or dodecyl group Preferably, it is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, or a pentyl group, More preferably, it is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, or a t-butyl group, More preferably, it is a methyl group or a t-butyl group.
  • the cycloalkyl group having 3 to 30 ring carbon atoms is, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a cycloalkyl group. It is a heptyl group, and preferably a cyclopentyl group or a cyclohexyl group.
  • the substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms includes an isomer group when present.
  • the aryl group having 6 to 30 ring carbon atoms is, for example, phenyl group, biphenylyl group, terphenylyl group, biphenylenyl group, naphthyl group, anthryl group.
  • a phenyl group, a biphenylyl group, a terphenylyl group, or a naphthyl group More preferably, a phenyl group, 2-, 3-, or 4-biphenylyl group, 2-, 3-, or 4-o-terphenylyl group, 2-, 3-, or 4-m-terphenylyl group, 2-, A 3- or 4-p-terphenylyl group, or a 1- or 2-naphthyl group, More preferably, it is a phenyl group, a 2-, 3-, or 4-biphenylyl group, or a 1- or 2-naphthyl group, Particularly preferred is a phenyl group.
  • the substituted aryl group having 6 to 30 ring carbon atoms is, for example, tolyl group, t-butylphenyl group, 9,9-dimethylfluorenyl group, 9,9-diphenylfluorenyl group, or 9, It is a 9'-spirobifluorenyl group.
  • the substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms includes an isomer group when present.
  • the aryl moiety of the aralkyl group having 7 to 36 carbon atoms has 6 to 30 ring-forming carbon atoms, preferably 6 to 25, more preferably 6 to It is selected from 18 aryl groups and the alkyl moiety is selected from the above substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, preferably 1 to 18 carbon atoms, and more preferably 1 to 8 carbon atoms.
  • the aralkyl group having 7 to 36 carbon atoms is, for example, a benzyl group, a phenethyl group or a phenylpropyl group, and a benzyl group is preferable.
  • the substituted or unsubstituted aralkyl group having 7 to 36 carbon atoms includes an isomer group when present.
  • the alkyl moiety of the alkoxy group having 1 to 30 carbon atoms is the substituted or unsubstituted 1 to 30 carbon atom, preferably 1 to 18 carbon atoms, more preferably It is selected from 1 to 8 alkyl groups.
  • the alkoxy group having 1 to 30 carbon atoms is, for example, a t-butoxy group, a propoxy group, an ethoxy group or a methoxy group, preferably an ethoxy group or a methoxy group, and more preferably a methoxy group.
  • the substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms includes an isomer group when present.
  • the aryl moiety of the aryloxy group having 6 to 30 ring carbon atoms is the above substituted or unsubstituted 6 to 30 ring carbon atoms, preferably It is selected from 6 to 25, more preferably 6 to 18 aryl groups.
  • the aryloxy group having 6 to 30 ring carbon atoms is, for example, a terphenyloxy group, a biphenyloxy group, or a phenoxy group, preferably a biphenyloxy group or a phenoxy group, and more preferably a phenoxy group. is there.
  • the substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms includes an isomer group when present.
  • the substituent of the mono-, di- or tri-substituted silyl group is the above-mentioned substituted or unsubstituted alkyl group having 1 to 30, preferably 1 to 18, more preferably 1 to 8 carbon atoms, and the substituted or unsubstituted Is selected from aryl groups having 6 to 30, preferably 6 to 25, and more preferably 6 to 18 ring carbon atoms.
  • a tri-substituted silyl group is preferable, and examples thereof include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a propyldimethylsilyl group, an isopropyldimethylsilyl group, a triphenylsilyl group, a phenyldimethylsilyl group, a t-butyldiphenylsilyl group, Or a tritolylsilyl group is more preferable.
  • the mono-, di-, or tri-substituted silyl groups, if present, include isomeric groups.
  • the haloalkyl group having 1 to 30 carbon atoms is the same as the above alkyl group having 1 to 30 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms. It is a group obtained by substituting at least one hydrogen atom, preferably 1 to 7 hydrogen atoms, or all hydrogen atoms with halogen atoms.
  • the halogen atom is selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and is preferably a fluorine atom.
  • the haloalkyl group is preferably a fluoroalkyl group having 1 to 30, preferably 1 to 18, more preferably 1 to 8 carbon atoms, such as a heptafluoropropyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, Alternatively, a trifluoromethyl group is more preferable, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, or a trifluoromethyl group is further preferable, and a trifluoromethyl group is particularly preferable.
  • the substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms includes an isomer group when present.
  • the haloalkyl moiety of the haloalkoxy group having 1 to 30 carbon atoms has 1 to 30 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms.
  • Selected from haloalkyl groups of The haloalkoxy group is preferably a fluoroalkoxy group having 1 to 30, preferably 1 to 18, more preferably 1 to 8 carbon atoms, and a heptafluoropropoxy group, a pentafluoroethoxy group, a 2,2,2-trifluoroethoxy group.
  • a trifluoromethoxy group is more preferable, a pentafluoroethoxy group, a 2,2,2-trifluoroethoxy group, or a trifluoromethoxy group is further preferable, and a trifluoromethoxy group is particularly preferable.
  • the substituted or unsubstituted haloalkoxy group having 1 to 30 carbon atoms includes an isomer group when present.
  • the heteroaryl group having 5 to 30 ring atoms is 1 to 5, preferably 1 to 3, and more preferably 1 to 2.
  • the ring-forming heteroatom is selected from, for example, a nitrogen atom, a sulfur atom and an oxygen atom.
  • the free valency of the heteroaryl group is on the ring-forming carbon atom or, where possible, on the ring-forming nitrogen atom.
  • the heteroaryl group having 5 to 30 ring atoms is, for example, pyrrolyl group, furyl group, thienyl group, pyridyl group, imidazopyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, oxazolyl group, Thiazolyl group, pyrazolyl group, isoxazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, indolyl group, isoindolyl group, indolizinyl group, quinolidinyl group, quinolyl group, isoquinolyl group, cinnolyl group, phthalazinyl group, quinazolinyl group , Quinoxalinyl group, benzimidazolyl group, be
  • a benzofuranyl group an isobenzofuranyl group, a naphthobenzofuranyl group, a dibenzofuranyl group, a benzothiophenyl group, an isobenzothiophenyl group, a naphthobenzothiophenyl group, a dibenzothiophenyl group, a carbazolyl group (9- A carbazolyl group, or a 1-, 2-, 3- or 4-carbazolyl group).
  • the substituted heteroaryl group having 5 to 30 ring atoms is, for example, 9-phenylcarbazolyl group, 9-biphenylylcarbazolyl group, 9-phenylphenylcarbazolyl group, 9-naphthylcarbazolyl group.
  • the substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms includes an isomer group when present.
  • the ring structure to be formed is, for example, a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 18 ring forming carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon ring having 5 to 18 ring forming carbon atoms, a substituted or unsubstituted ring structure. It is an aromatic heterocycle having 5 to 18 substituted ring-forming atoms, or a substituted or unsubstituted aliphatic heterocycle having 5 to 18 ring-forming atoms.
  • aromatic hydrocarbon ring having 6 to 18 ring carbon atoms examples include benzene ring, biphenylene ring, naphthalene ring, anthracene ring, benzoanthracene ring, phenanthrene ring, benzophenanthrene ring, phenalene ring, pyrene ring, chrysene ring, Or it is a triphenylene ring, preferably a benzene ring or a naphthalene ring.
  • the aliphatic hydrocarbon ring having 5 to 18 ring carbon atoms is, for example, a cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a cyclohexadiene ring, or a partial aromatic hydrocarbon ring having 6 to 18 ring carbon atoms. It is an aliphatic ring obtained by hydrogenation.
  • aromatic heterocycle having 5 to 18 ring atoms examples include pyrrole ring, furan ring, thiophene ring, pyridine ring, imidazole ring, pyrazole ring, indole ring, isoindole ring, benzofuran ring, isobenzofuran ring, benzo ring.
  • a thiophene ring a benzimidazole ring, an indazole ring, a dibenzofuran ring, a naphthobenzofuran ring, a dibenzothiophene ring, a naphthobenzothiophene ring, a carbazole ring, or a benzocarbazole ring.
  • the aliphatic heterocycle having 5 to 18 ring atoms is, for example, an aliphatic heterocycle obtained by partially hydrogenating the aromatic heterocycle having 5 to 18 ring atoms. Two or more of the above ring structures may be formed on the same ring.
  • Ar is a substituted or unsubstituted phenyl group, a substituted or unsubstituted condensed aryl group having 10 to 26 ring-forming carbon atoms and composed only of a 6-membered ring, a substituted or unsubstituted dibenzofuranyl group, or a substituted Alternatively, it is an unsubstituted dibenzothiophenyl group, and the arbitrary substituent in the above-mentioned “substituted or unsubstituted” of Ar is an unsubstituted alkyl group having 1 to 30 carbon atoms or an unsubstituted alkyl group having 1 to 30 carbon atoms.
  • the arbitrary substituent when the above-mentioned “substituted or unsubstituted” of Ar is an unsubstituted alkyl group having 1 to 30, preferably 1 to 18 and more preferably 1 to 8 carbon atoms, It is a mono-, di- or tri-substituted silyl group having an unsubstituted alkyl group having 1 to 30, preferably 1 to 18, more preferably 1 to 8 alkyl group as a substituent.
  • the alkyl group having 1 to 30 carbon atoms is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s -Butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, or dodecyl group, Preferably, it is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, or a pentyl group, More preferably, it is a methyl group, an ethyl group, an methyl group, an ethyl group, an methyl group, an eth
  • the substituted or unsubstituted alkyl group having 1 to 30 carbon atoms includes an isomer group when present.
  • the details of the alkyl group are the same as the details of the alkyl group described above for the unsubstituted alkyl group having 1 to 30 carbon atoms.
  • the above-mentioned fused or unsubstituted aryl group having 10 to 26 ring-forming carbon atoms and composed only of 6-membered ring, and the condensed aryl group consisting only of 6-membered ring having 10 to 26 ring-forming carbon atoms are, for example, naphthyl group, anthryl group, benzoanthryl group, phenanthryl group, benzophenanthryl group, phenalenyl group, picenyl group, pyrenyl group, chrysenyl group, benzochrysenyl group, perylenyl group, or triphenylenyl group, Of these, a naphthyl group and a phenanthryl group are preferable.
  • Ar contains a phenyl group represented by the following formula (3-1).
  • One of R 71 to R 76 represents a single bond that binds to * h, and details of R 71 to R 76 other than the single bond that binds to * h are independent of each other and are any substituents of Ar described above. Is the same as the details.
  • R 71 to R 76 which are not a single bond bonding to * h are all hydrogen atoms.
  • Ar is particularly preferably a substituted or unsubstituted phenyl group.
  • Ar contains a naphthyl group represented by the following formula (3-2).
  • One of R 71 , R 72 , R 75 , R 76 , and R 82 to R 85 represents a single bond bonded to * h, and R 71 , R 72 , R 75 other than the single bond bonded to * h. , R 76 , and R 82 to R 85 are the same as the details of the optional substituents of Ar described above, independently of each other.
  • R 72 , R 75 , R 82 , or R 85 bonded to the naphthalene skeleton is a single bond bonded to a nitrogen atom through * h.
  • R 71 , R 72 , R 75 , R 76 , and R 82 to R 85 which are not a single bond bonding to * h are all hydrogen atoms.
  • R 72 , R 75 , R 82 , or R 85 bonded to the naphthalene skeleton is a single bond bonded to the nitrogen atom via * h, and other R 71 , R which is not a single bond. It is preferred that 72 , R 75 , R 76 , and R 82 to R 85 are all hydrogen atoms.
  • Ar contains a phenanthryl group represented by the following formula (3-3).
  • One of R 71 , R 72 , R 73 , R 76 , and R 90 to R 95 represents a single bond bonded to * h, and R 71 , R 72 , R 73 other than the single bond bonded to * h. , R 76 , and R 90 to R 95 are the same as the details of the arbitrary substituents of Ar described above, independently of each other.
  • R 95 , R 76 , R 71 , or R 72 bonded to the phenanthrene skeleton is a single bond bonded to a nitrogen atom through * h.
  • R 71 , R 72 , R 73 , R 76 , and R 90 to R 95 which are not a single bond bonding to * h are all hydrogen atoms.
  • R 95 , R 76 , R 71 or R 72 bonded to the phenanthrene skeleton is a single bond bonded to the nitrogen atom through * h, and other R 71 , R which is not a single bond.
  • 72 , R 73 , R 76 , and R 90 to R 95 are all hydrogen atoms.
  • Ar is preferably a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothiophenyl group.
  • Ar contains a dibenzofuranyl group represented by the following formula (3-4).
  • One of R 101 to R 108 represents a single bond that binds to * h, and details of R 101 to R 108 other than the single bond that binds to * h are independent of each other and are any substituents of Ar described above. Is the same as the details.
  • R 101 , R 102 , R 103 or R 104 bonded to the dibenzofuran skeleton is a single bond bonded to the nitrogen atom via * h.
  • R 101 to R 108 which are not a single bond bonding to * h are all hydrogen atoms.
  • R 101 , R 102 , R 103 or R 104 bonded to the dibenzofuran skeleton is a single bond bonded to the nitrogen atom via * h, and other R 101 to R 108 which are not a single bond.
  • Ar contains a dibenzothiophenyl group represented by the following formula (3-5).
  • formula (3-5) One of R 111 to R 118 represents a single bond bonded to * h, and details of R 111 to R 118 other than the single bond bonded to * h are independently the arbitrary substitution of Ar described above. It is the same as the details of the group.
  • R 111 , R 112 , R 113, or R 114 bonded to the dibenzothiophene skeleton is a single bond bonded to a nitrogen atom through * h.
  • all R 111 to R 118 which are not a single bond bonding to * h are hydrogen atoms.
  • R 111 , R 112 , R 113 or R 114 bonded to the dibenzothiophene skeleton is a single bond bonded to the nitrogen atom through * h, and other R 111 to R It is preferable that all 118 are hydrogen atoms.
  • R 30 to R 46 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30, preferably 1 to 18, and more preferably 1 to 8 carbon atoms.
  • adjacent R 30 and R 33 , adjacent R 31 and R 32 , adjacent two selected from R 37 to R 41 , and adjacent two selected from R 42 to R 46 are each independently Represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or is bonded to each other to form a substituted or unsubstituted ring structure.
  • At least one pair of adjacent two form a substituted or unsubstituted ring structure, and in another aspect, the adjacent two form a substituted or unsubstituted ring structure. Not preferably.
  • R 30 to R 46 are all hydrogen atoms.
  • the details of the alkyl group are the same as the details of the alkyl group described above with respect to R 5 to R 8 , R 10 to R 19 , and R 1 to R 4 which is not a single bond bonded to * a.
  • R 30 and R 33 which are adjacent to each other, two R 31 and R 32 which are adjacent to each other, two adjacent ones selected from R 37 to R 41 and two adjacent ones selected from R 42 to R 46 are optionally formed.
  • the details are the same as the details of the ring structure described above for R 5 to R 8 , R 10 to R 19 , and R 1 to R 4 which are not a single bond bonded to * a. Two or more of the above ring structures may be formed on the same ring.
  • L is a single bond or a substituted or unsubstituted arylene group having 6 to 20, preferably 6 to 18, and more preferably 6 to 14 ring-forming carbon atoms. In one aspect of the present invention, L is preferably a single bond. Therefore, in a preferred embodiment of the present invention, the compound of formula (1) includes a compound represented by the following formula (1-c).
  • R 1 to R 8 , R 10 to R 19 , R 30 to R 46 , * a are as defined in the formula (1).
  • L is a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms. It is preferably 6 to 20, more preferably 6 to 18, and still more preferably 6 to 14 arylene groups.
  • the arylene group having 6 to 30 ring carbon atoms is, for example, a phenylene group, a biphenylene group, a terphenylene group, a biphenylenylene group or a naphthylene group.
  • a phenylene group, a biphenylene group, or a naphthylene group More preferably a phenylene group or a biphenylene group, More preferably, it is a phenylene group.
  • the phenylene group is an o-phenylene group, an m-phenylene group, or a p-phenylene group, and a p-phenylene group is particularly preferable.
  • the biphenylene group is preferably a 4,2′-biphenylene group, a 4,3′-biphenylene group, a 4,4′-biphenylene group, or a 3,3′-biphenylene group, more preferably a 4,3′- It is a biphenylene group, a 4,4′-biphenylene group, or a 3,3′-biphenylene group, and a 4,4′-biphenylene group is more preferable.
  • the naphthylene group is preferably a 1,4-naphthylene group or a 2,6-naphthylene group, more preferably a 1,4-naphthylene group. Therefore, in a preferred embodiment of the present invention, the compound of formula (1) includes a compound represented by the following formula (1-d).
  • R 1 to R 8 , R 10 to R 19 , R 30 to R 46 , and * a are as defined in formula (1),
  • One selected from R 51 to R 56 is a single bond bonded to * b1;
  • One selected from R 51 to R 56 other than the single bond bonded to b1 is a single bond bonded to b2,
  • R 51 to R 56 which are neither a single bond bound to * b1 nor a single bond bound to * b2 are bound to R 5 to R 8 , R 10 to R 19 and * a of the formula (1). Is not a single bond but is defined similarly to R 1 to R 4 .
  • the compound of formula (1) includes a compound represented by the following formula (1-e).
  • R 1 to R 8 , R 10 to R 19 , R 30 to R 46 , and * a are as defined in formula (1),
  • One selected from R 51 to R 54 and R 56 is a single bond bonded to * b3
  • One selected from R 57 to R 61 is a single bond bonded to * b4
  • R 51 to R 54 and R 56 to R 61 which are neither a single bond bound to * b3 nor a single bond bound to * b4 are R 5 to R 8 and R 10 to R 19 of the formula (1).
  • * 1 as well as R 1 to R 4 which are not a single bond.
  • the compound of formula (1) includes the compound represented by the following formula (1-f).
  • R 1 to R 8 , R 10 to R 19 , R 30 to R 46 , and * a are as defined in formula (1),
  • One selected from R 51 , R 52 , R 55 , R 56 , and R 62 to R 65 is a single bond bonded to * b5, * One selected from R 51 , R 52 , R 55 , R 56 , and R 62 to R 65 which is not a single bond bonded to * b5 is a single bond bonded to * b6, R 51 , R 52 , R 55 , R 56 , and R 62 to R 65 which are neither a single bond bound to * b5 nor a single bond bound to * b6 are R 5 to R in the formula (1). 8 , R 10 to R 19 and R 1 to R 4 which are not single bonds bonded to * a are similarly defined. )
  • the "hydrogen atom" used in the present specification includes a light hydrogen atom, a deuterium atom, and a tritium atom. Therefore, the compound (1) of the invention may contain a deuterium atom derived from nature. Further, a deuterium atom may be intentionally introduced into the invention compound (1) by using a deuterated compound as a part or all of the raw material compounds. Therefore, in one aspect of the present invention, the compound (1) of the invention contains at least one deuterium atom. That is, the invention compound (1) may be a compound represented by the formula (1) or a formula of a preferred embodiment thereof, in which at least one hydrogen atom contained in the compound is a deuterium atom. .
  • At least one hydrogen atom selected from the hydrogen atom of the group, the condensed aryl group, the dibenzofuranyl group, or the dibenzothiophenyl group, and the hydrogen atom of the arylene group represented by L may be a deuterium atom.
  • the deuteration rate of the invention compound (1) (the ratio of the number of deuterium atoms to the total number of hydrogen atoms in the invention compound (1)) depends on the deuteration rate of the raw material compound used. Since it is usually difficult to set the deuteration ratio of all the starting compounds used to 100%, the deuteration ratio of the invention compound (1) is less than 100%, preferably 95% or less, more preferably 90%. Or less, more preferably 80% or less.
  • the deuteration rate (the ratio of the number of deuterium atoms to the total number of hydrogen atoms in the invention compound (1)) is 1% or more, preferably 3% or more, and It is preferably at least 5%, more preferably at least 10%.
  • Invention compound (1) may be a mixture containing a deuterated compound and a non-deuterated compound, or a mixture of two or more compounds having different deuteration rates.
  • the deuteration rate of such a mixture (the ratio of the number of deuterium atoms to the total number of hydrogen atoms in the invention compound (1) contained in the mixture) is 1% or more, preferably 3% or more, more preferably 5%.
  • the above is more preferably 10% or more and less than 100%, preferably 95% or less, and more preferably 90% or less.
  • At least one hydrogen atom selected from the hydrogen atoms represented by R 1 to R 4 , R 5 to R 8 and R 10 to R 19 may be a deuterium atom.
  • the deuteration ratio ratio of the number of deuterium atoms to the total number of hydrogen atoms represented by R 1 to R 4 , R 5 to R 8 , and R 10 to R 19 ) is 1% or more, preferably 3% or more, It is preferably 5% or more, more preferably 10% or more and less than 100%, preferably 95% or less, more preferably 90% or less.
  • At least one hydrogen atom selected from the hydrogen atoms represented by R 30 to R 46 may be a deuterium atom.
  • Deuteration ratio ratio of the number of deuterium atoms to the total number of hydrogen atoms represented by R 30 to R 46 ) is 1% or more, preferably 3% or more, more preferably 5% or more, further preferably 10% or more, and , Less than 100%, preferably 95% or less, more preferably 90% or less.
  • compound (1) at least one hydrogen atom selected from the phenyl group represented by Ar, the condensed aryl group, the dibenzofuranyl group, or the dibenzothiophenyl group has a deuterium atom.
  • the deuteration rate (the ratio of the number of deuterium atoms to the total number of hydrogen atoms in the phenyl group, condensed aryl group, dibenzofuranyl group, or dibenzothiophenyl group) is 1% or more, preferably 3% or more, more preferably Is 5% or more, more preferably 10% or more and less than 100%, preferably 95% or less, more preferably 90% or less.
  • At least one hydrogen atom selected from the hydrogen atoms contained in the arylene group represented by L may be a deuterium atom.
  • Deuteration ratio ratio of the number of deuterium atoms to the total number of hydrogen atoms contained in the arylene group
  • % Preferably 95% or less, more preferably 90% or less.
  • Invention compound (2) is represented by the following formula (2).
  • X 1 is an oxygen atom, a sulfur atom, CRaRb, or a nitrogen atom bonded to * c.
  • X 1 is an oxygen atom, a sulfur atom, or CRaRb
  • one of R 50 to R 53 is a single bond bonded to * c.
  • R 51 or R 53 is preferably a single bond that binds to * c.
  • X 1 is preferably an oxygen atom, a sulfur atom, or CRaRb, and in another aspect, X 1 is preferably a nitrogen atom bonded to * c.
  • R 50 ⁇ R 53 is not a single bond to bond to R 54 ⁇ R 57 and * c are each independently hydrogen atom or a substituent.
  • two adjacent groups selected from R 50 to R 53 and two adjacent groups selected from R 54 to R 57 which are not a single bond bonded to * c are each independently a hydrogen atom or the above substituent.
  • R 54 to R 57 and R 50 to R 53 which are not a single bond bonding to * c are all hydrogen atoms.
  • the substituent is a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted alkyl group having 1 to 30, preferably 1 to 18 and more preferably 1 to 8 carbon atoms; a substituted or unsubstituted ring forming carbon number 3 to 30, preferably 3 to 10, more preferably 3 to 8, more preferably 5 or 6 cycloalkyl group; substituted or unsubstituted 6 to 30 ring-forming carbon atoms, preferably 6 to 25, more preferably 6-18 aryl group; substituted or unsubstituted C7-36, preferably 7-26, more preferably 7-20 aralkyl group; substituted or unsubstituted C1-30, preferably 1-18 , More preferably 1-8 alkoxy group; substituted or unsubstituted 6-30 ring-forming carbon atoms, preferably 6-25, more preferably 6-18 aryloxy group; substituted or A substituted alkyl group having 1 to 30,
  • the substituent is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring forming carbon atoms, a substituted or unsubstituted 6 to 6 ring forming carbon atom.
  • aryl groups Selected from the group consisting of aryl groups; More preferably, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms is particularly preferable.
  • the details of the substituents are the same as the details of the corresponding substituents described above for R 5 to R 8 , R 10 to R 19 of Formula (1) and R 1 to R 4 which is not a single bond bonded to * a. Is.
  • Ra and Rb are each independently a hydrogen atom, a substituted or unsubstituted carbon group having 1 to 30, preferably 1 to 18, more preferably 1 to 8 alkyl group, or a substituted or unsubstituted ring-forming carbon number. 6 to 30, preferably 6 to 25, more preferably 6 to 18 aryl groups, or are joined together to form a substituted or unsubstituted ring structure.
  • R 5 to R 8 , R 10 to R 19 of the formula (1) and R 1 to R 4 which is not a single bond bonded to * a. Same as the details.
  • Ra and Rb are each independently a substituted or unsubstituted methyl group or a substituted or unsubstituted phenyl group, or a ring bonded to each other to complete a spiro ring structure,
  • a substituted or unsubstituted cyclopentane ring, a substituted or unsubstituted cyclohexane ring, or a substituted or unsubstituted fluorene ring is formed.
  • each of Ra and Rb is a methyl group or a phenyl group or is bonded to each other to form a fluorene ring which completes a 9,9'-spirobifluorene structure.
  • L 1 , L 2 and L 3 are each independently a single bond or a substituted or unsubstituted arylene group having 6 to 30, preferably 6 to 25, and more preferably 6 to 20 ring-forming carbon atoms.
  • the details of the arylene group are the same as the details of the arylene group described above for L in the formula (1).
  • L 3 is preferably a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms, and a phenylene group (p-phenylene group, o-phenylene group).
  • L 3 is preferably a single bond or a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms, and a single bond or a phenylene group (p-phenylene group) Is more preferable.
  • L 3 is a single bond, and a group represented by the following formula: A 2-, 3-, or 4-dibenzofuranyl group, or a 2-, 3-, or 4-dibenzothiophenyl group, or L 3 is a p-phenylene group, and is represented by the following formula:
  • the base is A 1-, 2-, 3-, or 4-dibenzofuranyl group, or a 1-, 2-, 3-, or 4-dibenzothiophenyl group.
  • L 3 is a p-phenylene group, and a group represented by the following formula is Is a 9,9-dimethylfluoren-1-yl group, or L 3 is a single bond, and a group represented by the following formula is 9,9-dimethylfluoren-1-yl group, 9,9-dimethylfluoren-2-yl group, 9,9-dimethylfluoren-4-yl group, 9,9-diphenylfluoren-2-yl group, 9, It is preferably a 9-diphenylfluoren-4-yl group, a 9,9′-spirobifluoren-2-yl group, or a 9,9′-spirobifluoren-4-yl group.
  • Ar 1 and Ar 2 are each independently an aryl group having 6 to 30, preferably 6 to 25, more preferably 6 to 18, a substituted or unsubstituted ring-forming carbon atom or a substituted or unsubstituted ring-forming atom number. 5 to 30, preferably 5 to 24, more preferably 5 to 13 heteroaryl groups.
  • the details of the aryl group and the heteroaryl group, the heteroaryl group is 1, 2, 3, or except that it does not contain a 4-carbazolyl group, R 5 ⁇ R 8 of formula (1), R It is the same as the details of the aryl group and heteroaryl group described above with respect to 10 to R 19 and R 1 to R 4 which are not a single bond bonded to * a.
  • the invention compound (1) and the invention compound (2) are different, and in another embodiment of the present invention, when Ar 1 and / or Ar 2 is a substituted or unsubstituted aryl group, the aryl group It is preferred that the group is not a 3 ', 5'-diphenyl-4-biphenylyl group.
  • Ar 1 and Ar 2 are each independently a phenyl group, a biphenylyl group (4-biphenylyl group, 3-biphenylyl group, or 2-biphenylyl group), a terphenylyl group (preferably 1, 1 ': 4', 1 "-terphenyl-4-yl group, 1,1 ': 4', 1" -terphenyl-2-yl group), 1-naphthyl group, 2-naphthyl group, dibenzofuranyl Group (1-, 2-, 3- or 4-dibenzofuranyl group), dibenzothiophenyl group (1-, 2-, 3- or 4-dibenzothiophenyl group), 9,9-dimethylfluorenyl group (Preferably 9,9-dimethylfluoren-1-yl group, 9,9-dimethylfluoren-2-yl group, or 9,9-dimethylfluoren-4-yl group), 9,9-dip
  • L 1 is a single bond
  • Ar 1 is a phenyl group, 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, 1,1 ′: 4 ′, 1 ′′ -terphenyl -4-yl group, 1,1 ′: 4 ′, 1 ′′ -terphenyl-2-yl group, 9,9-dimethylfluoren-1-yl group, 9,9-dimethylfluoren-2-yl group, 9 , 9-diphenylfluoren-2-yl group, 9,9-diphenylfluoren-4-yl group, 9,9'-spirobifluoren-2-yl group, 9,9'-spirobifluoren-4-yl group
  • a 2-, 3-, or 4-dibenzofuranyl group, or a 2-, 3-, or 4-dibenzothiophenyl group, or L 1 is a p-phenylene group or a 4,4′-biphenyl
  • L 2 is a single bond
  • Ar 2 is 4-biphenylyl group, 2-biphenylyl group, 1,1 ′: 4 ′, 1 ′′ -terphenyl-4-yl group, 1, 1 ': 4', 1 "-terphenyl-2-yl group, 9,9-dimethylfluoren-2-yl group, 9,9-diphenylfluoren-2-yl group, 9,9-diphenylfluoren-4- An yl group, a 9,9'-spirobifluoren-2-yl group, or a 9,9'-spirobifluoren-4-yl group, or L 2 is a p-phenylene group or 4,4'- A biphenylene group, especially a p-phenylene group, and Ar 2 is a 1-naphthyl group, a 2-naphthyl group, a 2- or 4-dibenzofuranyl group, or a 2- or 4-dibenzothi
  • the compound (2) of the invention is represented by the following formula (2a).
  • X 1 , R 50 to R 57 , * c, L 1 to L 3 , and Ar 2 are as defined in formula (2).
  • X 2 is an oxygen atom, a sulfur atom, CRcRd, or a nitrogen atom bonded to * d, preferably an oxygen atom, a sulfur atom, or CRcRd.
  • R 60 to R 63 is a single bond bonded to * d.
  • R 64 to R 67 and R 60 to R 63 which are not a single bond bound to * d are each independently R 50 to R 57 which are not a single bond bonded to R 54 to R 57 and * c in the formula (2).
  • R 53 It is defined similarly to R 53 .
  • R 54 to R 57 , R 50 to R 53 which is not a single bond bound to * c, R 64 to R 67 , and R 60 to R 63 which is not a single bond bound to * d. Are preferably all hydrogen atoms.
  • Rc and Rd are each independently defined similarly to Ra and Rb in the formula (2).
  • X 1 is a nitrogen atom bonded to * c
  • X 2 is an oxygen atom, a sulfur atom, or CRcRd
  • X 1 is an oxygen atom
  • X 2 is preferably an oxygen atom, a sulfur atom or CRcRd.
  • the compound (2) of the invention is represented by the following formula (2b).
  • X 1 , X 2 , R 50 to R 57 , R 60 to R 67 , * c, * d, and L 1 to L 3 are as defined in formulas (2) and (2a).
  • X 3 is an oxygen atom, a sulfur atom, CReRf, or a nitrogen atom bonded to * e, preferably an oxygen atom, a sulfur atom, or CReRf, and more preferably CReRf.
  • X 3 is an oxygen atom, a sulfur atom, or CReRf
  • one of R 70 to R 73 is a single bond bonded to * e.
  • R 70 - R 73 is not a single bond to bond to R 74 ⁇ R 77 and * e are each independently, R 50 is not a single bond to bond to R 54 ⁇ R 57 and * c of the formula (2) to It is defined similarly to R 53 .
  • Re and Rf are each independently defined similarly to Ra and Rb in the formula (2).
  • the compound of formula (2) preferably has only one 9-carbazolyl group bonded to the central nitrogen atom directly or via a linker.
  • Group A is a group selected from Formulas A1 to A27
  • Ar 1 -L 1 is a group selected from Formulas B1 to B29 of Group B below
  • -L 2 -Ar 2 is a formula C1 of Group C below. Examples thereof include compounds that are groups selected from to C15, but are not limited thereto.
  • Inventive compound (2) may contain a deuterium atom of natural origin, or is a compound represented by formula (2) or a formula of a preferred embodiment thereof, wherein at least one of hydrogen atoms contained in the compound is It may be a compound that is a deuterium atom.
  • the invented compound (2) can be obtained by a person skilled in the art by reacting a starting material compound corresponding to the target compound with a known synthetic reaction and a synthetic reaction in which the known synthetic reaction is modified.
  • an arbitrary substituent when referred to as “substituted or unsubstituted” is a halogen atom; a cyano group; a nitro group; a carbon number of 1 to 30, preferably 1 to 18, and more preferably 1 unless otherwise specified.
  • the optional substituent is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring forming carbon atoms, or a substituted or unsubstituted 6 ring forming carbon atom.
  • the details of the optional substituents are the details of the corresponding substituents described above for R 5 to R 8 , R 10 to R 19 of Formula (1) and R 1 to R 4 which is not a single bond bonded to * a. Is the same as.
  • the organic EL device includes a cathode, an anode, and an organic layer between the cathode and the anode.
  • the organic layer includes a light emitting layer and a hole transport zone disposed between the anode and the light emitting layer.
  • the hole transport zone includes a first hole transport layer on the anode side and a second hole transport layer on the cathode side, one of the first hole transport layer and the second hole transport layer having the formula (1) ), And the other includes the compound represented by the formula (2).
  • the light-emitting unit may be of a laminated type having a plurality of phosphorescent-emitting layers or fluorescent-emitting layers. In that case, a phosphorescent-emitting layer is formed between the respective light-emitting layers.
  • a space layer may be provided for the purpose of preventing the excitons from diffusing into the fluorescence emitting layer.
  • a typical layer structure of the simple type light emitting unit is shown below. Layers in parentheses are optional.
  • A (hole injection layer /) first hole transport layer / second hole transport layer / fluorescent light emitting layer (/ electron transport layer / electron injection layer)
  • B (hole injection layer /) first hole transport layer / second hole transport layer / phosphorescent emitting layer (/ electron transport layer / electron injection layer)
  • C (hole injection layer /) first hole transport layer / second hole transport layer / first fluorescent light emitting layer / second fluorescent light emitting layer (/ electron transport layer / electron injection layer)
  • D (hole injection layer /) first hole transport layer / second hole transport layer / first phosphorescent light emitting layer / second phosphorescent light emitting layer (/ electron transport layer / electron injection layer)
  • E (hole injecting layer /) first hole transporting layer / second hole transporting layer / phosphorescent emitting layer / space layer / fluorescent emitting layer (/ electron transporting layer / electron injecting layer)
  • F (hole injection layer /) first hole transport layer / second hole transport layer / fluorescent
  • Each of the phosphorescent or fluorescent light emitting layers may have a different emission color.
  • An electron blocking layer may be appropriately provided between each light emitting layer and the second hole transport layer or the space layer.
  • a hole blocking layer may be appropriately provided between each light emitting layer and the electron transport layer.
  • the following element configurations can be given as typical element configurations of the tandem type organic EL element.
  • the first light emitting unit and the second light emitting unit can be independently selected from the above light emitting units, for example. ..
  • the intermediate layer is also generally called an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, and an intermediate insulating layer, and it supplies electrons to the first light emitting unit and holes to the second light emitting unit.
  • Known material configurations for feeding can be used.
  • FIG. 1 is a schematic diagram showing an example of the configuration of the organic EL element of the present invention.
  • the organic EL element 1 has a substrate 2, an anode 3, a cathode 4, and a light emitting unit 10 arranged between the anode 3 and the cathode 4.
  • the light emitting unit 10 has a light emitting layer 5.
  • a hole transport zone 6 (hole injection layer, hole transport layer, etc.) between the light emitting layer 5 and the anode 3, and an electron transport zone 7 (electron injection layer, electron transport layer) between the light emitting layer 5 and the cathode 4. Etc.).
  • the hole transport zone 6 includes a first hole transport layer on the anode side and a second hole transport layer on the light emitting layer side.
  • an electron blocking layer (not shown) may be provided on the anode 3 side of the light emitting layer 5, and a hole blocking layer (not shown) may be provided on the cathode 4 side of the light emitting layer 5. This makes it possible to confine electrons and holes in the light emitting layer 5 and further facilitate the generation of excitons in the light emitting layer 5.
  • FIG. 2 is a schematic diagram showing another configuration of the organic EL element of the present invention.
  • the organic EL element 11 has a substrate 2, an anode 3, a cathode 4, and a light emitting unit 20 arranged between the anode 3 and the cathode 4.
  • the light emitting unit 20 has a light emitting layer 5.
  • the hole transport zone arranged between the anode 3 and the light emitting layer 5 is formed of the first hole transport layer 6a and the second hole transport layer 6b.
  • the electron transporting zone disposed between the light emitting layer 5 and the cathode 4 is formed by the first electron transporting layer 7a and the second electron transporting layer 7b.
  • a host combined with a fluorescent dopant is called a fluorescent host
  • a host combined with a phosphorescent dopant is called a phosphorescent host
  • the fluorescent host and the phosphorescent host are not distinguished from each other only by the molecular structure. That is, the phosphorescent host means a material forming a phosphorescent emitting layer containing a phosphorescent dopant, and does not mean that it cannot be used as a material forming a fluorescent emitting layer. The same applies to the fluorescent host.
  • the substrate is used as a support for the organic EL device.
  • a plate made of glass, quartz, plastic, or the like can be used.
  • a flexible substrate may be used.
  • the flexible substrate include plastic substrates made of polycarbonate, polyarylate, polyether sulfone, polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, and the like.
  • an inorganic vapor deposition film can be used.
  • Anode It is preferable to use, for the anode formed on the substrate, a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a high work function (specifically, 4.0 eV or more).
  • a metal an alloy, an electrically conductive compound, a mixture thereof, or the like having a high work function (specifically, 4.0 eV or more).
  • ITO indium oxide-tin oxide
  • ITO indium tin oxide
  • indium oxide-tin oxide containing silicon or silicon oxide indium oxide-zinc oxide
  • indium oxide containing tungsten oxide and zinc oxide Examples include graphene and the like.
  • gold Au
  • platinum Pt
  • nickel Ni
  • tungsten W
  • Cr chromium
  • Mo molybdenum
  • iron Fe
  • Co cobalt
  • Cu copper
  • palladium examples thereof include Pd), titanium (Ti), and nitrides of the above metals (for example, titanium nitride).
  • indium oxide-zinc oxide is a target obtained by adding 1 to 10 wt% zinc oxide to indium oxide, and indium oxide containing tungsten oxide and zinc oxide is 0.5 to 5 wt% tungsten oxide to indium oxide.
  • Zinc oxide can be formed by a sputtering method by using a target containing 0.1 to 1 wt% of zinc oxide. Alternatively, it may be formed by a vacuum vapor deposition method, a coating method, an inkjet method, a spin coating method, or the like.
  • the hole injection layer formed in contact with the anode is formed of a material that facilitates hole injection regardless of the work function of the anode, and thus is generally used as an electrode material (for example, metal). , Alloys, electrically conductive compounds, and mixtures thereof, and elements belonging to Group 1 or 2 of the periodic table of elements.
  • An element belonging to Group 1 or 2 of the periodic table of elements which is a material having a small work function, that is, an alkali metal such as lithium (Li) or cesium (Cs), and magnesium (Mg), calcium (Ca), or strontium
  • alkaline earth metals such as (Sr) and alloys containing these (for example, MgAg, AlLi), rare earth metals such as europium (Eu) and ytterbium (Yb), and alloys containing these.
  • a vacuum evaporation method or a sputtering method can be used.
  • silver paste or the like a coating method, an inkjet method, or the like can be used.
  • the hole injection layer is a layer containing a material having a high hole injection property (hole injection material), and is formed between the anode and the first hole transport layer as needed.
  • Examples of the hole injecting material include molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, and tungsten oxide. Materials, manganese oxide and the like can be used.
  • TDATA N-diphenylamino triphenylamine
  • MTDATA 4,4 ′, 4 ′′ -tris [N- (3- Methylphenyl) -N-phenylamino] triphenylamine
  • DPAB 4,4′-bis [N- (4-diphenylaminophenyl) -N-phenylamino] biphenyl
  • DNTPD 1,3,5-tris [N -(4-Diphenylaminophenyl) -N-phenylamino] benzene
  • High molecular compounds (oligomers, dendrimers, polymers, etc.) can also be used.
  • poly (N-vinylcarbazole) (abbreviation: PVK)
  • poly (4-vinyltriphenylamine) (abbreviation: PVTPA)
  • PVTPA poly (4-vinyltriphenylamine)
  • PTPDMA poly [N- (4- ⁇ N '-[4- (4-diphenylamino)) Phenyl] phenyl-N'-phenylamino ⁇ phenyl) methacrylamide]
  • PTPDMA poly [N, N'-bis (4-butylphenyl) -N, N'-bis (phenyl) benzidine]
  • Polymer compounds such as Poly-TPD
  • a polymer compound to which an acid such as poly (3,4-ethylenedioxythiophene) / poly (styrenesulfonic acid) (PEDOT / PSS) or polyaniline / poly (styrenesulfonic acid) (PAni / PSS) is added is used.
  • an acceptor material such as a hexaazatriphenylene (HAT) compound represented by the following formula (K) is also preferable as the hole injection layer material.
  • HAT hexaazatriphenylene
  • R 21 to R 26 are each independently a cyano group, —CONH 2 , a carboxyl group, or —COOR 27 (R 27 is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms) Represents).
  • R 21 and R 22 , R 23 and R 24 , or R 25 and R 26 may be bonded to each other to form a group represented by —CO—O—CO—.
  • R 27 examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a cyclopentyl group and a cyclohexyl group.
  • the hole transport layer is a layer containing a material having a high hole transport property (hole transport material), and in the case where a hole injection layer is formed between the anode and the light emitting layer, hole injection is performed. It is formed between the layer and the light emitting layer.
  • the hole transport layer of the organic EL device of the present invention has a multilayer structure including a first hole transport layer on the anode side and a second hole transport layer on the cathode side (light emitting layer side).
  • One of the layer and the second hole transport layer contains the invention compound (1), and the other contains the invention compound (2).
  • the invention compound (1) and the invention compound (2) are different compounds.
  • the second hole transport layer may be adjacent to the light emitting layer, or a blocking layer described below may be interposed between the second hole transport layer and the light emitting layer.
  • the first hole transport layer contains the invention compound (1) and the second hole transport layer contains the invention compound (2).
  • the first hole transport layer contains the invention compound (2) and the second hole transport layer contains the invention compound (1).
  • the invented compound (1) contained in one of the first hole transport layer and the second hole transport layer is a hydrogen hydride (1) from the viewpoint of production cost.
  • the invention compound (2) contained in the other is preferably a deuterium compound (2).
  • the light hydrogen body (1) is an invention compound (1) in which all the hydrogen atoms in the formula (1) are light hydrogen atoms, and the light hydrogen body (2) is the formula (2).
  • the invention compound (2) is a compound in which all hydrogen atoms are light hydrogen atoms. Therefore, in the present invention, one of the first hole transport layer and the second hole transport layer contains the invented compound (1) consisting essentially of the light hydrogen hydride (1), and the other is substantially light. It includes an organic EL device containing the invention compound (2) consisting only of the hydrogen body (2).
  • invention compound (1) substantially consisting of the light hydrogen body (1) means that the content ratio of the light hydrogen body (1) to the total amount of the compounds represented by the formula (1) is 90 mol% or more, It means preferably 95 mol% or more, more preferably 99 mol% or more (including 100% each).
  • invention compound (2) consisting essentially of the light hydrogen compound (2) means that the content ratio of the light hydrogen compound (2) to the total amount of the compounds represented by the formula (2) is 90 mol% or more, It means preferably 95 mol% or more, more preferably 99 mol% or more (including 100% each).
  • an aromatic amine compound for example, an aromatic amine compound, a carbazole derivative, an anthracene derivative or the like may be used.
  • the aromatic amine compound include 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviation: NPB) and N, N′-bis (3-methylphenyl) -N , N′-diphenyl- [1,1′-biphenyl] -4,4′-diamine (abbreviation: TPD), 4-phenyl-4 ′-(9-phenylfluoren-9-yl) triphenylamine (abbreviation: BAFLP), 4,4'-bis [N- (9,9-dimethylfluoren-2-yl) -N-phenylamino] biphenyl (abbreviation: DFLDPBi), 4,4 ', 4 "-tris (N- (1-naphthyl) -N-phen
  • carbazole derivative examples include 4,4′-di (9-carbazolyl) biphenyl (abbreviation: CBP), 9- [4- (9-carbazolyl) phenyl] -10-phenylanthracene (abbreviation: CzPA), and 9-phenyl-3- [4- (10-phenyl-9-anthryl) phenyl] -9H-carbazole (abbreviation: PCzPA) can be given.
  • CBP 4,4′-di (9-carbazolyl) biphenyl
  • CzPA 9- [4- (9-carbazolyl) phenyl] -10-phenylanthracene
  • PCzPA 9-phenyl-3- [4- (10-phenyl-9-anthryl) phenyl] -9H-carbazole
  • anthracene derivative examples include 2-t-butyl-9,10-di (2-naphthyl) anthracene (abbreviation: t-BuDNA), 9,10-di (2-naphthyl) anthracene (abbreviation: DNA), and , 9,10-diphenylanthracene (abbreviation: DPAnth).
  • a high molecular compound such as poly (N-vinylcarbazole) (abbreviation: PVK) or poly (4-vinyltriphenylamine) (abbreviation: PVTPA) can also be used.
  • PVK N-vinylcarbazole
  • PVTPA poly (4-vinyltriphenylamine
  • the light-emitting layer is a layer containing a material having a high light-emitting property (dopant material), and various materials can be used.
  • a fluorescent light emitting material or a phosphorescent light emitting material can be used as a dopant material.
  • a fluorescent material is a compound that emits light from a singlet excited state
  • a phosphorescent material is a compound that emits light from a triplet excited state.
  • a pyrene derivative, a styrylamine derivative, a chrysene derivative, a fluoranthene derivative, a fluorene derivative, a diamine derivative, a triarylamine derivative, or the like can be used as a blue-based fluorescent light emitting material that can be used in the light emitting layer.
  • N, N′-bis [4- (9H-carbazol-9-yl) phenyl] -N, N′-diphenylstilbene-4,4′-diamine (abbreviation: YGA2S)
  • 4- (9H -Carbazol-9-yl) -4 '-(10-phenyl-9-anthryl) triphenylamine (abbreviation: YGAPA)
  • 4- (10-phenyl-9-anthryl) -4'-(9-phenyl-9H -Carbazol-3-yl) triphenylamine abbreviation: PCBAPA
  • An aromatic amine derivative or the like can be used as a green fluorescent material that can be used for the light emitting layer.
  • a tetracene derivative, a diamine derivative, or the like can be used as a red fluorescent light emitting material that can be used in the light emitting layer.
  • N, N, N ′, N′-tetrakis (4-methylphenyl) tetracene-5,11-diamine (abbreviation: p-mPhTD), 7,14-diphenyl-N, N, N ′
  • Examples thereof include N'-tetrakis (4-methylphenyl) acenaphtho [1,2-a] fluoranthene-3,10-diamine (abbreviation: p-mPhAFD).
  • a metal complex such as an iridium complex, an osmium complex or a platinum complex is used as a blue phosphorescent light emitting material that can be used in the light emitting layer.
  • An iridium complex or the like is used as a green phosphorescent material that can be used in the light emitting layer.
  • a metal complex such as an iridium complex, a platinum complex, a terbium complex, or a europium complex is used as a red phosphorescent light emitting material that can be used in the light emitting layer.
  • iridium complex bis [2- (2′-benzo [4,5- ⁇ ] thienyl) pyridinato-N, C3 ′] iridium (III) acetylacetonate (abbreviation: Ir (btp) 2 (acac)), Bis (1-phenylisoquinolinato-N, C2 ′) iridium (III) acetylacetonate (abbreviation: Ir (piq) 2 (acac)), (acetylacetonato) bis [2,3-bis (4-fluoro) Phenyl) quinoxalinato] iridium (III) (abbreviation: Ir (Fdpq) 2 (acac)), 2,3,7,8,12,
  • tris (acetylacetonato) (monophenanthroline) terbium (III) (abbreviation: Tb (acac) 3 (Phen)
  • tris (1,3-diphenyl-1,3-propanedionate) (monophenanthroline) europium (III) (abbreviation: Eu (DBM) 3 (Phen)
  • tris [1- (2-thenoyl) -3,3,3-trifluoroacetonato] (monophenanthroline) europium (III) (abbreviation: Eu ( A rare earth metal complex such as TTA) 3 (Phen)) emits light from a rare earth metal ion (electron transition between different multiplicities) and thus can be used as a phosphorescent material.
  • the light-emitting layer may have a structure in which the above-mentioned dopant material is dispersed in another material (host material). It is preferable to use a material having a higher lowest unoccupied orbital level (LUMO level) and a lower highest occupied orbital level (HOMO level) than the dopant material.
  • LUMO level lowest unoccupied orbital level
  • HOMO level lowest occupied orbital level
  • a metal complex such as an aluminum complex, a beryllium complex, or a zinc complex
  • a heterocyclic compound such as an oxadiazole derivative, a benzimidazole derivative, or a phenanthroline derivative
  • a condensed aromatic compound such as a carbazole derivative, anthracene derivative, phenanthrene derivative, pyrene derivative, or chrysene derivative
  • An aromatic amine compound such as a triarylamine derivative or a condensed polycyclic aromatic amine derivative is used.
  • tris (8-quinolinolato) aluminum (III) (abbreviation: Alq)
  • tris (4-methyl-8-quinolinolato) aluminum (III) abbreviation: Almq3)
  • bis (10-hydroxybenzo [h] quinolinato) beryllium (II) (abbreviation: BeBq2)
  • bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (III) abbreviation: BAlq
  • bis (8-quinolinolato) zinc (II) (abbreviation: Znq)
  • Bis [2- (2-benzoxazolyl) phenolato] zinc (II) abbreviation: ZnPBO
  • bis [2- (2-benzothiazolyl) phenolato] zinc (II) abbreviation: ZnBTZ
  • anthracene compound in the case of a blue fluorescent element, it is preferable to use the following anthracene compound as a host material.
  • the electron transport layer is a layer containing a material having a high electron transport property (electron transport material).
  • a material having a high electron transport property for example, (1) Metal complexes such as aluminum complex, beryllium complex and zinc complex, (2) Heteroaromatic compounds such as imidazole derivative, benzimidazole derivative, azine derivative, carbazole derivative and phenanthroline derivative, (3) A polymer compound can be used.
  • metal complex examples include tris (8-quinolinolato) aluminum (III) (abbreviation: Alq), tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq3), bis (10-hydroxybenzo [h] quinolinato.
  • Beryllium abbreviation: BeBq 2
  • bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (III) abbreviation: BAlq
  • bis (8-quinolinolato) zinc II)
  • Znq bis [2- (2-benzoxazolyl) phenolato] zinc
  • ZnPBO bis [2- (2-benzothiazolyl) phenolato] zinc
  • heteroaromatic compound examples include 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD) and 1,3-bis [5 -(Ptert-butylphenyl) -1,3,4-oxadiazol-2-yl] benzene (abbreviation: OXD-7), 3- (4-tert-butylphenyl) -4-phenyl-5- (4 -Biphenylyl) -1,2,4-triazole (abbreviation: TAZ), 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenylyl) -1,2,4 -Triazole (abbreviation: p-EtTAZ), bathophenanthroline (abbreviation: BPhen), bathocuproine (abbreviation: BCP), 4,4'-bis (5-methylbenz
  • polymer compound examples include poly [(9,9-dihexylfluorene-2,7-diyl) -co- (pyridine-3,5-diyl)] (abbreviation: PF-Py), poly [(9, 9-dioctylfluorene-2,7-diyl) -co- (2,2′-bipyridine-6,6′-diyl)] (abbreviation: PF-BPy).
  • the above material is a material having an electron mobility of 10 ⁇ 6 cm 2 / Vs or more. Note that a material other than the above may be used for the electron-transporting layer as long as the material has a higher electron-transporting property than a hole-transporting property.
  • the electron transport layer may be a single layer or a multilayer including two or more layers.
  • the electron transport layer may be a layer including a first electron transport layer (anode side) and a second electron transport layer (cathode side).
  • the two or more electron transport layers are each formed of the electron transport material.
  • the electron injection layer is a layer containing a material having a high electron injection property.
  • the electron injection layer includes lithium (Li), cesium (Cs), calcium (Ca), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF2), lithium oxide (LiOx), and the like.
  • Alkali metals, alkaline earth metals, or compounds thereof can be used.
  • a material having an electron-transporting property containing an alkali metal, an alkaline earth metal, or a compound thereof, specifically, a material containing Alq containing magnesium (Mg) or the like may be used. In this case, electron injection from the cathode can be performed more efficiently.
  • a composite material obtained by mixing an organic compound and an electron donor (donor) may be used for the electron injection layer.
  • a composite material has an excellent electron injecting property and an electron transporting property because the organic compound receives an electron from the electron donor.
  • the organic compound is preferably a material excellent in transporting received electrons, and specifically, for example, the above-mentioned material constituting the electron transport layer (metal complex, heteroaromatic compound, etc.) is used. be able to.
  • the electron donor any material having an electron donating property with respect to the organic compound may be used.
  • alkali metals, alkaline earth metals and rare earth metals are preferable, and examples thereof include lithium, cesium, magnesium, calcium, erbium and ytterbium.
  • alkali metal oxides and alkaline earth metal oxides are preferable, and lithium oxide, calcium oxide, barium oxide and the like can be mentioned.
  • a Lewis base such as magnesium oxide.
  • an organic compound such as tetrathiafulvalene (abbreviation: TTF) can be used.
  • Cathode It is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a low work function (specifically, 3.8 eV or less) for the cathode.
  • a cathode material include elements belonging to Group 1 or Group 2 of the periodic table of the elements, that is, alkali metals such as lithium (Li) and cesium (Cs), and magnesium (Mg), calcium (Ca). ), Strontium (Sr) and other alkaline earth metals, and alloys containing these (eg MgAg, AlLi), europium (Eu), ytterbium (Yb) and other rare earth metals and alloys containing these.
  • a vacuum evaporation method or a sputtering method can be used.
  • a coating method, an inkjet method, or the like can be used.
  • a cathode is formed using various conductive materials such as Al, Ag, ITO, graphene, silicon, or indium oxide-tin oxide containing silicon oxide regardless of the magnitude of the work function. can do.
  • These conductive materials can be formed by a sputtering method, an inkjet method, a spin coating method, or the like.
  • Insulating layer The organic EL element is likely to cause pixel defects due to leakage or short circuit because an electric field is applied to the ultrathin film.
  • an insulating layer formed of an insulating thin film layer may be inserted between the pair of electrodes.
  • the material used for the insulating layer include aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, silicon oxide. , Germanium oxide, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, vanadium oxide and the like. In addition, you may use these mixtures and laminated bodies.
  • the space layer for example, when laminating a fluorescent light emitting layer and a phosphorescent light emitting layer, do not diffuse excitons generated in the phosphorescent light emitting layer into the fluorescent light emitting layer, or for the purpose of adjusting the carrier balance, It is a layer provided between the fluorescent light emitting layer and the phosphorescent light emitting layer. Further, the space layer may be provided between the plurality of phosphorescent emitting layers. Since the space layer is provided between the light emitting layers, it is preferably a material having both electron transporting property and hole transporting property. Further, the triplet energy is preferably 2.6 eV or more in order to prevent the diffusion of triplet energy in the adjacent phosphorescent emitting layer. Examples of the material used for the space layer include the same materials as those used for the hole transport layer described above.
  • a blocking layer such as an electron blocking layer, a hole blocking layer or an exciton blocking layer may be provided adjacent to the light emitting layer.
  • the electron blocking layer is a layer that prevents electrons from leaking from the light emitting layer to the hole transport layer
  • the hole blocking layer is a layer that prevents holes from leaking from the light emitting layer to the electron transport layer.
  • the exciton blocking layer has a function of preventing excitons generated in the light emitting layer from diffusing into an adjacent layer and confining the excitons in the light emitting layer.
  • Each layer of the organic EL element can be formed by a conventionally known vapor deposition method, coating method, or the like.
  • a vapor deposition method such as a vacuum vapor deposition method and a molecular beam vapor deposition method (MBE method), or a dipping method, a spin coating method, a casting method, a bar coating method, a roll coating method, etc. using a solution of a compound forming a layer. It can be formed by a known method according to the above coating method.
  • each layer is not particularly limited, but generally, if the thickness is too thin, defects such as pinholes are likely to occur, and conversely, if it is too thick, a high driving voltage is required and efficiency deteriorates. Therefore, it is preferably 5 nm to 10 ⁇ m. 10 nm to 0.2 ⁇ m is more preferable.
  • the organic EL element can be used for display parts such as organic EL panel modules, display devices such as televisions, mobile phones and personal computers, and electronic devices such as lighting and light emitting devices for vehicle lighting.
  • a compound was obtained by performing the same operation in the synthesis of Compound 1 except that Intermediate IM was used instead of Intermediate IC.
  • Example 1 Manufacture of Organic EL Device A 25 mm ⁇ 75 mm ⁇ 1.1 mm glass substrate with an ITO transparent electrode (manufactured by Geomatec Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning for 30 minutes. The thickness of the ITO transparent electrode was 130 nm. The glass substrate with the ITO transparent electrode after washing was mounted on a substrate holder of a vacuum vapor deposition device, and first, the compound HI-1 was vapor-deposited so as to cover the ITO transparent electrode to form a hole injection layer having a film thickness of 5 nm.
  • the compound 2s was vapor-deposited on the hole injection layer to form a first hole transport layer having a film thickness of 80 nm.
  • Compound 1 (second hole transport layer material) obtained in Synthesis Example 1 was vapor-deposited on the first hole transport layer to form a second hole transport layer having a film thickness of 10 nm.
  • the compound BH-1 (host material) and the compound BD-1 (dopant material) were co-evaporated to form a light emitting layer having a thickness of 25 nm.
  • the concentration of the compound BD-1 in the light emitting layer was 4.0% by mass.
  • the compound ET-1 was vapor-deposited on the light emitting layer to form a first electron transporting layer having a film thickness of 10 nm.
  • the following compound ET-2 was vapor-deposited on the first electron transport layer to form a second electron transport layer having a film thickness of 20 nm.
  • LiF was vapor-deposited on the second electron transport layer to form an electron injecting electrode (cathode) having a film thickness of 1 nm.
  • metal Al was vapor-deposited on the electron injecting electrode to form a metal Al cathode having a film thickness of 80 nm.
  • the structure of the organic EL device of Example 1 is shown below.
  • Examples 2-3 Organic EL device in the same manner as in Example 1 except that the compound 2 (Example 2) or the compound 22 (Example 3) was used in place of the compound 1 used in the second hole transport layer of Example 1. Was produced.
  • Comparative Examples 1-2 Organic compound was prepared in the same manner as in Example 1 except that Comparative Compound 1 (Comparative Example 1) or Comparative Compound 2 (Comparative Example 2) was used in place of Compound 1 used in the second hole transport layer of Example 1. An EL device was produced.
  • Example 4 Manufacture of Organic EL Device A 25 mm ⁇ 75 mm ⁇ 1.1 mm glass substrate with an ITO transparent electrode (manufactured by Geomatec Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning for 30 minutes. The thickness of the ITO transparent electrode was 130 nm. The glass substrate with the ITO transparent electrode after washing was mounted on the substrate holder of the vacuum vapor deposition apparatus, and the compound 2t and the compound HI-2 were co-evaporated so as to cover the ITO transparent electrode to form a hole injection layer with a thickness of 10 nm. Formed. The concentration of the compound HI-2 in the hole injection layer was 3.0% by mass.
  • the compound 2t (first hole transport layer material) was vapor-deposited on the hole injection layer to form a first hole transport layer having a film thickness of 110 nm.
  • Compound 1 (second hole transport layer material) was vapor-deposited on the first hole transport layer to form a second hole transport layer having a film thickness of 35 nm.
  • the compound H-1 (host material 1), the compound H-2 (host material 2), and the compound D-1 (dopant material) were co-evaporated on the second hole transport layer to give a film thickness of 40 nm.
  • the light emitting layer of was formed.
  • the concentration of compound H-2 (host material 2) in the light emitting layer was 31.7% by mass, and the concentration of compound D-1 in the light emitting layer was 5.0% by mass.
  • the compound ET-3 was vapor-deposited on the light emitting layer to form a first electron transporting layer having a film thickness of 5 nm.
  • the following compound ET-4 and Liq were co-evaporated on this first electron transport layer to form a second electron transport layer having a film thickness of 20 nm.
  • the concentration of Liq in the second electron transport layer was 50% by mass.
  • Liq was vapor-deposited on the second electron transport layer to form an electron injecting electrode (cathode) having a film thickness of 1 nm.
  • metal Al was vapor-deposited on the electron injecting electrode to form a metal Al cathode having a film thickness of 50 nm.
  • the structure of the organic EL device of Example 4 is shown below.
  • Examples 5-6 An organic EL device was manufactured in the same manner as in Example 4 except that the compound 2 (Example 5) or the compound 7 (Example 6) was used in place of the compound 1 used in the second hole transport layer of Example 4. Was produced.
  • Comparative Examples 3-4 Organic compound was prepared in the same manner as in Example 4 except that Comparative Compound 1 (Comparative Example 3) or Comparative Compound 3 (Comparative Example 4) was used in place of Compound 1 used in the second hole transport layer of Example 4. An EL device was produced.
  • the invention compounds (1) and (2) having a specific structure were used as materials for the hole transport layer of the organic EL device for green phosphorescence, and thus the compounds of Comparative compounds 1 and 3 were realized. It can be seen that an organic EL device having a high external quantum efficiency can be obtained.
  • Example 7 Manufacture of Organic EL Device A 25 mm ⁇ 75 mm ⁇ 1.1 mm glass substrate with an ITO transparent electrode (manufactured by Geomatec Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning for 30 minutes. The thickness of the ITO transparent electrode was 130 nm. The glass substrate with the ITO transparent electrode after cleaning was mounted on the substrate holder of the vacuum vapor deposition apparatus, and first, the compound 1 and the compound HI-2 were co-evaporated so as to cover the ITO transparent electrode to form a hole injection layer with a thickness of 10 nm. Formed. The concentration of the compound HI-2 in the hole injection layer was 5.0% by mass.
  • Compound 1 (first hole transport layer material) was vapor-deposited on the hole injection layer to form a first hole transport layer having a film thickness of 80 nm.
  • the compound 2u (second hole transport layer material) was vapor-deposited on the first hole transport layer to form a second hole transport layer having a film thickness of 10 nm.
  • the compound BH-1 (host material) and the compound BD-2 (dopant material) were co-evaporated on the second hole transport layer to form a light emitting layer having a film thickness of 25 nm.
  • the concentration of the compound BD-2 in the light emitting layer was 4.0% by mass.
  • compound ET-2 and compound ET-5 were co-evaporated to form an electron transport layer having a film thickness of 20 nm.
  • the concentration of the compound ET-5 in the electron transport layer was 50% by mass.
  • LiF was vapor-deposited on the electron transport layer to form an electron injecting electrode (cathode) having a film thickness of 1 nm.
  • metal Al was vapor-deposited on the electron injecting electrode to form a metal Al cathode having a film thickness of 50 nm.
  • the structure of the organic EL device of Example 7 is shown below.
  • Example 8 An organic EL device was produced in the same manner as in Example 7, except that Compound 3 was used instead of Compound 1 used in the first hole transport layer of Example 7.
  • Comparative Examples 5-6 Organic compound was prepared in the same manner as in Example 7 except that Comparative Compound 1 (Comparative Example 5) or Comparative Compound 2 (Comparative Example 6) was used in place of Compound 1 used in the first hole transport layer of Example 7. An EL device was produced.

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Abstract

L'invention concerne un composé représenté par la formule (1) (dans laquelle R1 à R8, R10 à R19, R30 à R46, Ar, L et *a sont tels que définis dans la description), qui est utile pour fournir un élément électroluminescent organique offrant des performances améliorées.
PCT/JP2019/043701 2018-11-07 2019-11-07 Composé et élément électroluminescent organique faisant appel à celui-ci WO2020096001A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Publication number Priority date Publication date Assignee Title
US11618740B2 (en) 2019-03-15 2023-04-04 Idemitsu Kosan Co., Ltd. Compound, material for organic electroluminescence devices, organic electroluminescence device, and electronic device
WO2022055092A1 (fr) * 2020-09-08 2022-03-17 주식회사 엘지화학 Nouveau composé et dispositif électroluminescent organique le comprenant
WO2022071424A1 (fr) * 2020-09-30 2022-04-07 出光興産株式会社 Composé, matériau pour élément électroluminescent organique, élément électroluminescent organique et appareil électronique
KR20240004351A (ko) 2021-04-28 2024-01-11 이데미쓰 고산 가부시키가이샤 화합물, 유기 전기발광 소자용 재료, 유기 전기발광 소자 및 전자 기기

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