WO2020096001A1 - Compound and organic electroluminescent element employing same - Google Patents

Compound and organic electroluminescent element employing same Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituted
unsubstituted
carbon atoms
ring
Prior art date
Application number
PCT/JP2019/043701
Other languages
French (fr)
Japanese (ja)
Inventor
匡 羽毛田
裕 工藤
裕勝 伊藤
Original Assignee
出光興産株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Publication of WO2020096001A1 publication Critical patent/WO2020096001A1/en

Links

Images

Classifications

    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Furan Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A compound represented by formula (1) (wherein R1 to R8, R10 to R19, R30 to R46, Ar, L, and *a are as defined in the description) is useful in providing an organic EL element having improved element performance.

Description

化合物及びそれを用いた有機エレクトロルミネッセンス素子Compound and organic electroluminescence device using the same
　本発明は、化合物及びそれを用いた有機エレクトロルミネッセンス素子に関する。 The present invention relates to a compound and an organic electroluminescence device using the compound.
　一般に有機エレクトロルミネッセンス素子（“有機ＥＬ素子”）は陽極、陰極、及び陽極と陰極に挟まれた有機層から構成されている。両電極間に電圧が印加されると、陰極側から電子、陽極側から正孔が発光領域に注入され、注入された電子と正孔は発光領域において再結合して励起状態を生成し、励起状態が基底状態に戻る際に光を放出する。従って、電子又は正孔を発光領域に輸送し、電子と正孔との再結合を促進する素子構造の開発は高性能有機ＥＬ素子を得る上で重要である。 Generally, 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. 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.
　特許文献１は、中心窒素原子が、直結フルオレン構造、及び非縮合芳香族環構造及び非縮合芳香族複素環構造から選ばれる２つの構造を有するアミン化合物を記載している。
　実施例では、中心窒素原子が、直結フルオレン構造、及びビフェニリル基とターフェニリル基から選ばれる２つの基を有するアミン化合物が正孔注入層１／正孔輸送層／正孔注入層２／電子ブロック層／発光層／電子輸送層の層構造を有する有機ＥＬ素子の電子ブロック層に使用されている。
　特許文献１は、中心窒素原子が、直結フルオレン構造、直鎖状クォーターフェニル基、及びビフェニリル基又はターフェニリル基を有するアミン化合物を例示しているが、そのＥＬ性能は測定されていない。 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.
In the examples, 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.
　特許文献２は、第１正孔輸送層及び該第１正孔輸送層と発光層の間に形成された単層又は複数層からなる第２正孔輸送層を有する有機ＥＬ素子を記載している。第１正孔輸送層は中心窒素原子に直接又はリンカーを介して結合した３－カルバゾリル基が必須であるアミン化合物を含む。第２正孔輸送層の材料は式（２）～（４）のアミン化合物から選ばれる。
　特許文献２の実施例には、３－カルバゾリル基が中心窒素原子にリンカーを介して結合したアミン化合物ＨＴＭ３などを含む第１正孔輸送層及び中心窒素原子に結合した３個のアリール基を有するアミン化合物ＨＴＭ６などを含む第２正孔輸送層を有する有機ＥＬ素子が記載されている。
　特許文献２は、式（２）のアミン化合物（第２正孔輸送層材料）として、中心窒素原子が、３’、５’－ジフェニル－４－ビフェニリル基、直結フルオレン構造、及びビフェニリル基を有する化合物が例示している。しかし、この化合物を使用した素子の性能は測定されていない。 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. There is. 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. An organic EL device having a second hole transport layer containing an amine compound HTM6 and the like is described.
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.
　特許文献３は、中心窒素原子が、３’、５’－ジフェニル－４－ビフェニリル基、直結フルオレン構造、及びビフェニリル基又はフルオレン構造を有するアミン化合物１－３、１－４、及び１－２０を記載している。これらの化合物は、カルバゾール構造にインドール環、ベンゾチオフェン環、ベンゾフラン環、インデン環などが縮合した化合物と共に発光層のコホストとして使用されている。 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.
　特許文献４の実施例には、中心窒素原子が、３’、５’－ジフェニル－４－ビフェニリル基、芳香族複素環を含む基、及び、芳香族複素環を含む基及びアリール基から選ばれる基を有するアミン化合物Ｈ１～Ｈ３２が記載されている。該アミン化合物は、単層の正孔輸送層に使用されている。 In the examples of Patent Document 4, 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.
特表第２０１５－５３０７３５号公報Japanese Patent Publication No. 2015-530735 韓国公開１０－２０１７－０１３４１６３号公報Korean publication 10-2017-0134163 韓国公開１０－２０１８－００２２３２５号公報Korean publication 10-2018-0022325 国際公開ＷＯ２０１１／０５９０９９号公報International publication WO2011 / 059099
　特許文献１及び２に記載されているように、有機ＥＬ素子の性能を改善するために、正孔輸送層を多層構造にすることが知られているが、多層正孔輸送層を有する有機ＥＬ素子の性能をより改善することが依然として求められている。 As described in Patent Documents 1 and 2, it is known that the hole transport layer has a multilayer structure in order to improve the performance of the organic EL device. However, an organic EL having a multilayer hole transport layer is known. There is still a demand for further improvement in device performance.
　本発明は、前記の課題を解決するためになされたもので、素子性能が改善された有機ＥＬ素子及びこれを実現することができる化合物を提供する。 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.
　本発明者らが、３’、５’－ジフェニル－４－ビフェニリル基を有するアミン化合物について研究した結果、中心窒素原子上に３’、５’－ジフェニル－４－ビフェニリル基、フェニル基もしくはナフチル基等の縮合アリール基、及び９，９－ジフェニルフルオレニル基を有するアミン化合物が正孔輸送層材料として高性能であることが分かった。
　また、本発明者らは、これらの知見に基づいて鋭意研究を重ねた結果、陽極側の第１正孔輸送層と陰極側（発光層側）の第２正孔輸送層の一方が、中心窒素原子に結合した３’、５’－ジフェニル－４－ビフェニリル基を含む下記式（１）で表されるモノアミンを含み、他方が、中心窒素原子に直接又はリンカーを介して結合したフルオレニル基、ジベンゾフラニル基、ジベンゾチオフェニル基、及びカルバゾリル基から選ばれる基を含むモノアミン（後述する式（２）で表される化合物）を含む有機ＥＬ素子が、改善された寿命を示すことを見出し、本発明を完成した。 As a result of the present inventors' research on 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.
In addition, as a result of intensive studies based on these findings, the present inventors have found that one of the first hole transport layer on the anode side and the second hole transport layer on the cathode side (light emitting layer side) is centered. A monoamine represented by the following formula (1) containing a 3 ′, 5′-diphenyl-4-biphenylyl group bonded to a nitrogen atom, and the other one is a fluorenyl group bonded to a central nitrogen atom directly or via a linker, It has been found that an organic EL device containing a monoamine containing a group selected from a dibenzofuranyl group, a dibenzothiophenyl group, and a carbazolyl group (a compound represented by the formula (2) described below) exhibits an improved lifetime, The present invention has been completed.
　すなわち、一態様において、本発明は下記式（１）で表される化合物（以下、式（１）及びその好ましい態様の式で表される化合物を「発明化合物（１）」と称することもある）を提供する。 That is, in one aspect, 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.
　下記式（１）で表される化合物。
Figure JPOXMLDOC01-appb-C000010
（式（１）において、
　Ｒ１～Ｒ４から選ばれる1つは＊ａに結合する単結合であり、
　Ｒ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４は、
それぞれ独立して、水素原子又は置換基であり、
該置換基は、
ハロゲン原子、シアノ基、ニトロ基、
置換もしくは無置換の炭素数１～３０のアルキル基、
置換もしくは無置換の環形成炭素数３～３０のシクロアルキル基、
置換もしくは無置換の環形成炭素数６～３０のアリール基、
置換もしくは無置換の炭素数７～３６のアラルキル基、
置換もしくは無置換の炭素数１～３０のアルコキシ基、
置換もしくは無置換の環形成炭素数６～３０のアリールオキシ基、
置換もしくは無置換の炭素数１～３０のアルキル基及び置換もしくは無置換の環形成炭素数６～３０のアリール基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基、
置換もしくは無置換の炭素数１～３０ハロアルキル基、
置換もしくは無置換の炭素数１～３０のハロアルコキシ基、及び、
置換もしくは無置換の環形成原子数５～３０のヘテロアリール基からなる群から選ばれる。
　ただし、Ｒ５～Ｒ８から選ばれる隣接する２つ、Ｒ１０～Ｒ１９から選ばれる隣接する２つ、及び＊ａに結合する単結合ではないＲ１～Ｒ４から選ばれる隣接する２つは、それぞれ独立して、水素原子又は前記置換基を表すか、又は、互いに結合して置換もしくは無置換の環構造を形成する。
　Ｒ３０～Ｒ４６は、それぞれ独立して、水素原子、又は置換もしくは無置換の炭素数１～３０のアルキル基である。ただし、Ｒ３０とＲ３３、Ｒ３１とＲ３２、Ｒ３７～Ｒ４１から選ばれる隣接する２つ、及びＲ４２～Ｒ４６から選ばれる隣接する２つは、それぞれ独立して、水素原子又は置換もしくは無置換の炭素数１～３０のアルキル基を表すか、又は、互いに結合して置換もしくは無置換の環構造を形成する。
　Ａｒは、
置換もしくは無置換のフェニル基、
置換もしくは無置換の環形成炭素数１０～２６の、６員環からのみで構成される縮合アリール基、
置換もしくは無置換のジベンゾフラニル基、又は置換もしくは無置換のジベンゾチオフェニル基であり、
Ａｒの前記「置換もしくは無置換」というときの任意の置換基が、
無置換の炭素数１～３０のアルキル基、
無置換の炭素数１～３０のアルキル基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基であり、
　Ｌは単結合、又は置換もしくは無置換の環形成炭素数６～２０のアリーレン基である。） A compound represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000010
(In formula (1),
One selected from 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,
A mono-, di- or tri-substituted silyl group having a substituent selected from a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms,
A substituted or unsubstituted haloalkoxy group having 1 to 30 carbon atoms, and
It is selected from the group consisting of a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.
However, 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. 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.
R 30 to R 46 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. However, 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. )
　他の態様において、本発明は前記発明化合物（１）からなる有機ＥＬ素子用材料を提供する。 In another aspect, the present invention provides a material for an organic EL device, which comprises the invention compound (1).
　さらに他の態様において、本発明は、陽極、陰極、及び該陽極と該陰極との間に配置された有機層を含む有機エレクトロルミネッセンス素子であって、
　該有機層が発光層及び該陽極と該発光層の間に配置された正孔輸送帯域を含み、
　該正孔輸送帯域が陽極側の第１正孔輸送層と陰極側の第２正孔輸送層を含み、
　該第１正孔輸送層及び該第２正孔輸送層の一方が式（１）で表される化合物を含み、他方が下記式（２）で表される化合物（以下、式（２）及びその好ましい態様の式で表される化合物を「発明化合物（２）」と称することもある）を含む、有機エレクトロルミネッセンス素子を提供する。
Figure JPOXMLDOC01-appb-C000011
（式中、
　Ｘ１は酸素原子、硫黄原子、ＣＲａＲｂ、又は＊ｃに結合する窒素原子であり、
　Ｘ１が酸素原子、硫黄原子、又はＣＲａＲｂである場合、Ｒ５０～Ｒ５３の１つが＊ｃに結合する単結合であり、
　Ｒ５４～Ｒ５７及び＊ｃに結合する単結合ではないＲ５０～Ｒ５３は、それぞれ独立して、水素原子又は置換基であり、該置換基は、ハロゲン原子、シアノ基、ニトロ基、置換もしくは無置換の炭素数１～３０のアルキル基、置換もしくは無置換の環形成炭素数３～３０のシクロアルキル基、置換もしくは無置換の環形成炭素数６～３０のアリール基、置換もしくは無置換の炭素数７～３６のアラルキル基、置換もしくは無置換の炭素数１～３０のアルコキシ基、置換もしくは無置換の環形成炭素数６～３０のアリールオキシ基、置換もしくは無置換の炭素数１～３０のアルキル基及び置換もしくは無置換の環形成炭素数６～３０のアリール基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基、置換もしくは無置換の炭素数１～３０ハロアルキル基、置換もしくは無置換の炭素数１～３０のハロアルコキシ基、及び、置換もしくは無置換の環形成原子数５～３０のヘテロアリール基からなる群から選ばれる。
　ただし、＊ｃに結合する単結合ではないＲ５０～Ｒ５３から選ばれる隣接する２つ及びＲ５４～Ｒ５７から選ばれる隣接する２つは、それぞれ独立して、水素原子又は前記置換基を表すか、又は、互いに結合して置換もしくは無置換の環構造を形成する。
　Ｒａ及びＲｂは、それぞれ独立して、水素原子、置換もしくは無置換の炭素数１～３０のアルキル基、又は置換もしくは無置換の環形成炭素数６～３０のアリール基であるか、又は、互いに結合して置換もしくは無置換の環構造を形成し、
　Ｌ１、Ｌ２、及びＬ３は、それぞれ独立して、単結合又は置換もしくは無置換の環形成炭素数６～３０のアリーレン基であり、
　Ａｒ１及びＡｒ２は、それぞれ独立して、置換もしくは無置換の環形成炭素数６～３０のアリール基又は置換もしくは無置換の環形成原子数５～３０のヘテロアリール基である。
　Ｒ５４～Ｒ５７、＊ｃに結合する単結合ではないＲ５０～Ｒ５３、前記環構造、Ｌ１～Ｌ３、Ａｒ１、及びＡｒ２の「置換もしくは無置換」で表される任意の置換基は、それぞれ独立して、ハロゲン原子、シアノ基、ニトロ基、置換もしくは無置換の炭素数１～３０のアルキル基、置換もしくは無置換の環形成炭素数３～３０のシクロアルキル基、置換もしくは無置換の環形成炭素数６～３０のアリール基、置換もしくは無置換の炭素数７～３６のアラルキル基、置換もしくは無置換の炭素数１～３０のアルコキシ基、置換もしくは無置換の環形成炭素数６～３０のアリールオキシ基、置換もしくは無置換の炭素数１～３０のアルキル基及び置換もしくは無置換の環形成炭素数６～３０のアリール基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基、置換もしくは無置換の炭素数１～３０ハロアルキル基、置換もしくは無置換の炭素数１～３０のハロアルコキシ基、及び、置換もしくは無置換の環形成原子数５～３０のヘテロアリール基からなる群から選ばれる。） In yet another aspect, 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.
Figure JPOXMLDOC01-appb-C000011
(In the formula,
X 1 is an oxygen atom, a sulfur atom, CRaRb, or a nitrogen atom bonded to * c,
When 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 50 ~ R 53 is not a single bond to bond to R 54 ~ R 57 and * 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, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted ring forming aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted 1 to 3 carbon atom A mono-, di- or tri-substituted silyl group having a substituent selected from 30 alkyl groups and a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, a substituted or unsubstituted C 1 group 30 haloalkyl group, a substituted or unsubstituted haloalkoxy group having 1 to 30 carbon atoms, and is selected from the group consisting of heteroaryl groups substituted or unsubstituted ring atoms 5-30.
However, 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 A model having a substituent selected from an aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms. A di- or tri-substituted silyl group, a substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted haloalkoxy group having 1 to 30 carbon atoms, and a substituted or unsubstituted ring forming atom number 5 to 30 Selected from the group consisting of heteroaryl groups of )
　さらにまた他の態様において、本発明は前記有機ＥＬ素子を備えた電子機器を提供する。 In still another aspect, the present invention provides an electronic device including the organic EL element.
　素子性能が改善された有機ＥＬ素子及びこれを実現することができる化合物を提供することができる。 It is possible to provide an organic EL device having improved device performance and a compound capable of realizing the same.
本発明の一態様に係る有機ＥＬ素子の層構成の一例を示す概略図である。It is a schematic diagram showing an example of layer composition of an organic EL element concerning one mode of the present invention. 本発明の一態様に係る有機ＥＬ素子の層構成の他の例を示す概略図である。It is a schematic diagram showing other examples of layer composition of an organic EL element concerning one mode of the present invention.
　本明細書において、「置換もしくは無置換の炭素数ＸＸ～ＹＹのＺＺ基」という表現における「炭素数ＸＸ～ＹＹ」は、ＺＺ基が無置換である場合の炭素数を表すものであり、置換されている場合の置換基の炭素数は含めない。 In the present specification, 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.
　本明細書において、「置換もしくは無置換の原子数ＸＸ～ＹＹのＺＺ基」という表現における「原子数ＸＸ～ＹＹ」は、ＺＺ基が無置換である場合の原子数を表すものであり、置換されている場合の置換基の原子数は含めない。 In the present specification, “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.
　本明細書において、「置換もしくは無置換のＺＺ基」という場合における「無置換ＺＺ基」とは、ＺＺ基の水素原子が置換基で置換されていないことを意味する。 In the present specification, 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.
　本明細書において、「水素原子」とは、中性子数が異なる同位体、すなわち、軽水素（ｐｒｏｔｉｕｍ）、重水素（ｄｅｕｔｅｒｉｕｍ）、及び三重水素（ｔｒｉｔｉｕｍ）を包含する。 In the present specification, the “hydrogen atom” includes isotopes having different neutron numbers, that is, light hydrogen (protium), deuterium (deuterium), and tritium (tritium).
　本明細書において、「アリール基」及び「アリーレン基」とは、芳香族炭化水素の残基であり、環形成ヘテロ原子を含むヘテロアリール基及びヘテロアリーレン基とは区別される。 In the present specification, the “aryl group” and “arylene group” are aromatic hydrocarbon residues, and are distinguished from heteroaryl groups and heteroarylene groups containing a ring-forming heteroatom.
　本明細書において、「環形成炭素数」とは、原子が環状に結合した構造の化合物（例えば、単環化合物、縮合環化合物、架橋化合物、炭素環化合物、複素環化合物）の当該環自体を構成する原子のうちの炭素原子の数を表す。当該環が置換基によって置換される場合、置換基に含まれる炭素は環形成炭素には含まない。以下で記される「環形成炭素数」については、特筆しない限り同様とする。例えば、ベンゼン環は環形成炭素数が６であり、ナフタレン環は環形成炭素数が１０であり、ピリジン環は環形成炭素数５であり、フラン環は環形成炭素数４である。また、ベンゼン環やナフタレン環に置換基として例えばアルキル基が置換している場合、当該アルキル基の炭素数は、環形成炭素数の数に含めない。また、フルオレン環に置換基として例えばフルオレン環が結合している場合（スピロフルオレン環を含む）、置換基としてのフルオレン環の炭素数は環形成炭素数に含めない。 In the present specification, 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. When the ring is substituted with a substituent, 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. For example, a benzene ring has 6 ring carbon atoms, a naphthalene ring has 10 ring carbon atoms, a pyridine ring has 5 ring carbon atoms, and a furan ring has 4 ring carbon atoms. When the benzene ring or naphthalene ring is substituted with, for example, an alkyl group, the carbon number of the alkyl group is not included in the number of ring-forming carbon atoms. When a fluorene ring is bonded to the fluorene ring as a substituent (including a spirofluorene ring), the carbon number of the fluorene ring as a substituent is not included in the ring-forming carbon number.
　本明細書において、「環形成原子数」とは、原子が環状に結合した構造（例えば単環、縮合環、環集合）の化合物（例えば単環化合物、縮合環化合物、架橋化合物、炭素環化合物、複素環化合物）の当該環自体を構成する原子の数を表す。環を構成しない原子（例えば環を構成する原子の結合手を終端する水素原子）や、当該環が置換基によって置換される場合の置換基に含まれる原子は環形成原子数には含まない。以下で記される「環形成原子数」については、特筆しない限り同様とする。例えば、ピリジン環は環形成原子数は６であり、キナゾリン環は環形成原子数が１０であり、フラン環の環形成原子数は５である。ピリジン環やキナゾリン環の環形成炭素原子にそれぞれ結合している水素原子や置換基を構成する原子は、環形成原子数の数に含めない。また、フルオレン環に置換基として例えばフルオレン環が結合している場合（スピロビフルオレン環を含む）、置換基としてのフルオレン環の原子数は環形成原子数の数に含めない。 In the present specification, 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) or 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 same applies to the “number of ring-forming atoms” described below unless otherwise specified. For example, the pyridine ring has 6 ring-forming atoms, the quinazoline ring has 10 ring-forming atoms, and 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. When 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.
発明化合物（１）
　発明化合物（１）は下記式（１）で表される。
Figure JPOXMLDOC01-appb-C000012
 Invention Compound (1)
Inventive compound (1) is represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000012
　Ｒ１～Ｒ４から選ばれる１つ、好ましくは、Ｒ２又はＲ４は、＊ａに結合する単結合である。本発明の一態様においては、Ｒ２が＊ａに結合する単結合であることが好ましく、他の態様においてはＲ４が＊ａに結合する単結合であることが好ましい。 One selected from R 1 to R 4 , preferably R 2 or R 4 is a single bond bonded to * a. In one aspect of the present invention, R 2 is preferably a single bond that binds to * a, and in another aspect, R 4 is preferably a single bond that binds to * a.
　従って、本発明の好ましい態様において、発明化合物（１）は下記式（１-ａ）又は（１-ｂ）で表される化合物を含む。
Figure JPOXMLDOC01-appb-C000013
 Therefore, in a preferred embodiment of the present invention, the invention compound (1) includes a compound represented by the following formula (1-a) or (1-b).
Figure JPOXMLDOC01-appb-C000013
　Ｒ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４は、それぞれ独立して、水素原子又は置換基である。ただし、Ｒ５～Ｒ８から選ばれる隣接する２つ、Ｒ１０～Ｒ１９から選ばれる隣接する２つ、及び＊ａに結合する単結合ではないＲ１～Ｒ４から選ばれる隣接する２つは、それぞれ独立して、水素原子又は前記置換基を表すか、又は、互いに結合して置換もしくは無置換の環構造を形成する。本発明の一態様においては、少なくとも一組の隣接する２つが置換もしくは無置換の環構造を形成することが好ましく、他の態様においては、前記隣接する２つが置換もしくは無置換の環構造を形成しないことが好ましい。
　本発明の一態様において、Ｒ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４はすべて水素原子であることが好ましい。 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. However, 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. 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. In one aspect of the present invention, it is preferable that 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.
In one embodiment of the present invention, it is preferable that 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.
　前記置換基は、ハロゲン原子；シアノ基；ニトロ基；置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基；置換もしくは無置換の環形成炭素数３～３０、好ましくは３～１０、より好ましくは３～８、さらに好ましくは５又は６のシクロアルキル基；置換もしくは無置換の環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリール基；置換もしくは無置換の炭素数７～３６、好ましくは７～２６、より好ましくは７～２０のアラルキル基；置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルコキシ基；置換もしくは無置換の環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリールオキシ基；置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基及び置換もしくは無置換の環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリール基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基；置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８ハロアルキル基；置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のハロアルコキシ基；及び、置換もしくは無置換の環形成原子数５～３０、好ましくは５～２４、より好ましくは５～１３のヘテロアリール基からなる群から選ばれる。
　前記置換基の中で、
　好ましくは、置換もしくは無置換の炭素数１～３０のアルキル基、置換もしくは無置換の環形成炭素数３～３０のシクロアルキル基、置換もしくは無置換の環形成炭素数６～３０のアリール基、置換もしくは無置換の炭素数１～３０のアルキル基及び置換もしくは無置換の環形成炭素数６～３０のアリール基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基、及び、置換もしくは無置換の環形成原子数５～３０のヘテロアリール基からなる群から選ばれ；
　より好ましくは、置換もしくは無置換の炭素数１～３０のアルキル基、置換もしくは無置換の環形成炭素数６～３０のアリール基、及び、置換もしくは無置換の環形成原子数５～３０のヘテロアリール基からなる群から選ばれ；
　更に好ましくは置換もしくは無置換の炭素数１～３０のアルキル基又は置換もしくは無置換の環形成炭素数６～３０のアリール基であり、
　特に好ましくは置換もしくは無置換の炭素数１～３０のアルキル基である。 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, preferably 1 to 18, more preferably 1 to 8 and a substituted or unsubstituted ring-forming carbon number of 6 to 30, preferably 6 to 25, more preferably 6 to 18 A mono-, di- or tri-substituted silyl group having a substituent selected from an aryl group; a substituted or unsubstituted C1-30, preferably 1-18, more preferably 1-8 haloalkyl group; a substituted or unsubstituted carbon A haloalkoxy group having a number of 1 to 30, preferably 1 to 18, more preferably 1 to 8; and a substituted or unsubstituted number of ring-forming atoms of 5 to 30, preferably 5 to 24, more preferably 5 to 13 It is selected from the group consisting of heteroaryl groups.
Among the above substituents,
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 aryl group having 6 to 30 ring forming carbon atoms, A mono-, di- or tri-substituted silyl group having a substituent selected from a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and substituted or unsubstituted Selected from the group consisting of substituted heteroaryl groups having 5 to 30 ring-forming atoms;
More preferably, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring forming carbon atoms, and a substituted or unsubstituted hetero group having 5 to 30 ring forming atoms. 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.
　前記ハロゲン原子はフッ素原子、塩素原子、臭素原子、又はヨウ素原子であり、フッ素原子が好ましい。 The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a fluorine atom is preferable.
　前記置換もしくは無置換の炭素数１～３０のアルキル基において、該炭素数１～３０のアルキル基は、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、又はドデシル基であり、
　好ましくは、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、又はペンチル基であり、
　より好ましくは、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、又はｔ－ブチル基であり、
　更に好ましくは、メチル基又はｔ－ブチル基である。
　前記置換もしくは無置換の炭素数１～３０のアルキル基は、存在する場合には異性体基を含む。 In the substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, 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 substituted or unsubstituted alkyl group having 1 to 30 carbon atoms includes an isomer group when present.
　前記置換もしくは無置換の環形成炭素数３～３０のシクロアルキル基において、該環形成炭素数３～３０のシクロアルキル基は、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、又はシクロヘプチル基であり、好ましくは、シクロペンチル基又はシクロヘキシル基である。
　前記置換もしくは無置換の環形成炭素数３～３０のシクロアルキル基は、存在する場合には異性体基を含む。 In the substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, 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.
　前記置換もしくは無置換の環形成炭素数６～３０のアリール基において、該環形成炭素数６～３０のアリール基は、例えば、フェニル基、ビフェニリル基、ターフェニリル基、ビフェニレニル基、ナフチル基、アントリル基、ベンゾアントリル基、フェナントリル基、ベンゾフェナントリル基、フェナレニル基、ピセニル基、ペンタフェニル基、ピレニル基、クリセニル基、ベンゾクリセニル基、フルオレニル基、フルオランテニル基、ペリレニル基、又はトリフェニレニル基であり、
　好ましくは、フェニル基、ビフェニリル基、ターフェニリル基、又は、ナフチル基であり、
　より好ましくは、フェニル基、２－、３－、又は４－ビフェニリル基、２－、３－、又は４－ｏ－ターフェニリル基、２－、３－、又は４－ｍ－ターフェニリル基、２－、３－、又は４－ｐ－ターフェニリル基、又は、１－又は２－ナフチル基であり、
　更に好ましくは、フェニル基、２－、３－、又は４－ビフェニリル基、又は、１－又は２－ナフチル基であり、
　特に好ましくは、フェニル基である。
　置換された環形成炭素数６～３０のアリール基は、例えば、トリル基、ｔ－ブチルフェニル基、９，９－ジメチルフルオレニル基、９，９－ジフェニルフルオレニル基、又は、９，９’－スピロビフルオレニル基である。
　前記置換もしくは無置換の環形成炭素数６～３０のアリール基は、存在する場合には異性体基を含む。 In the substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, 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 benzoanthryl group, a phenanthryl group, a benzophenanthryl group, a phenalenyl group, a picenyl group, a pentaphenyl group, a pyrenyl group, a chrysenyl group, a benzochrysenyl group, a fluorenyl group, a fluoranthenyl group, a perylenyl group, or a triphenylenyl group. ,
Preferably, 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.
　前記置換もしくは無置換の炭素数７～３６のアラルキル基において、該炭素数７～３６のアラルキル基のアリール部位は上記の環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリール基から選択され、アルキル部位は上記の置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基から選択される。該炭素数７～３６のアラルキル基は、例えば、ベンジル基、フェネチル基、又は、フェニルプロピル基であり、ベンジル基が好ましい。
　前記置換もしくは無置換の炭素数７～３６のアラルキル基は、存在する場合には異性体基を含む。 In the substituted or unsubstituted aralkyl group having 7 to 36 carbon atoms, 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.
　前記置換もしくは無置換の炭素数１～３０のアルコキシ基において、該炭素数１～３０のアルコキシ基のアルキル部位は上記置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基から選択される。該炭素数１～３０のアルコキシ基は、例えば、ｔ－ブトキシ基、プロポキシ基、エトキシ基、又はメトキシ基であり、好ましくは、エトキシ基又はメトキシ基であり、より好ましくは、メトキシ基である。
　前記置換もしくは無置換の炭素数１～３０のアルコキシ基は、存在する場合には異性体基を含む。 In the substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, 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.
　前記置換もしくは無置換の環形成炭素数６～３０のアリールオキシ基において、該環形成炭素数６～３０アリールオキシ基のアリール部位は上記置換もしくは無置換の環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリール基から選択される。該環形成炭素数６～３０のアリールオキシ基は、例えば、ターフェニルオキシ基、ビフェニルオキシ基、又はフェノキシ基であり、好ましくは、ビフェニルオキシ基又はフェノキシ基であり、より好ましくは、フェノキシ基である。
　前記置換もしくは無置換の環形成炭素数６～３０のアリールオキシ基は、存在する場合には異性体基を含む。 In the substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, 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.
　前記モノ、ジ又はトリ置換シリル基が有する置換基は、上記置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基、及び、上記置換もしくは無置換の環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリール基から選択される。トリ置換シリル基が好ましく、例えば、トリメチルシリル基、トリエチルシリル基、ｔ－ブチルジメチルシリル基、プロピルジメチルシリル基、イソプロピルジメチルシリル基、トリフェニルシリル基、フェニルジメチルシリル基、ｔ－ブチルジフェニルシリル基、又はトリトリルシリル基がより好ましい。
　前記モノ、ジ又はトリ置換シリル基は、存在する場合には異性体基を含む。 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.
　前記置換もしくは無置換の炭素数１～３０のハロアルキル基において、該炭素数１～３０のハロアルキル基は、上記炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基の少なくとも１個の水素原子、好ましくは１～７個の水素原子、又は全ての水素原子をハロゲン原子で置換して得られる基である。該ハロゲン原子は、フッ素原子、塩素原子、臭素原子、及びヨウ素原子から選ばれ、好ましくはフッ素原子である。該ハロアルキル基は炭素数１～３０、好ましくは１～１８、より好ましくは１～８のフルオロアルキル基が好ましく、ヘプタフルオロプロピル基、ペンタフルオロエチル基、２,２,２－トリフルオロエチル基、又はトリフルオロメチル基がより好ましく、ペンタフルオロエチル基、２,２,２－トリフルオロエチル基、又はトリフルオロメチル基がさらに好ましく、トリフルオロメチル基が特に好ましい。
　前記置換もしくは無置換の炭素数１～３０のハロアルキル基は、存在する場合には異性体基を含む。 In the substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms, 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.
　前記置換もしくは無置換の炭素数１～３０のハロアルコキシ基において、該炭素数１～３０のハロアルコキシ基のハロアルキル部位は上記炭素数１～３０、好ましくは１～１８、より好ましくは１～８のハロアルキル基から選択される。該ハロアルコキシ基は炭素数１～３０、好ましくは１～１８、より好ましくは１～８のフルオロアルコキシ基が好ましく、ヘプタフルオロプロポキシ基、ペンタフルオロエトキシ基、２,２,２－トリフルオロエトキシ基、又はトリフルオロメトキシ基がより好ましく、ペンタフルオロエトキシ基、２,２,２－トリフルオロエトキシ基、又はトリフルオロメトキシ基がさらに好ましく、トリフルオロメトキシ基が特に好ましい。
　前記置換もしくは無置換の炭素数１～３０のハロアルコキシ基は、存在する場合には異性体基を含む。 In the substituted or unsubstituted haloalkoxy group having 1 to 30 carbon atoms, 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. , Or 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.
　前記置換もしくは無置換の環形成原子数５～３０のヘテロアリール基において、該環形成原子数５～３０のヘテロアリール基は１～５個、好ましくは１～３個、より好ましくは１～２個の環形成ヘテロ原子を含む。該環形成ヘテロ原子は、例えば、窒素原子、硫黄原子及び酸素原子から選択される。該ヘテロアリール基の遊離原子価は環形成炭素原子上に存在するか、又は、可能な場合には、環形成窒素原子上に存在する。
　該環形成原子数５～３０のヘテロアリール基は、例えば、ピロリル基、フリル基、チエニル基、ピリジル基、イミダゾピリジル基、ピリダジニル基、ピリミジニル基、ピラジニル基、トリアジニル基、イミダゾリル基、オキサゾリル基、チアゾリル基、ピラゾリル基、イソオキサゾリル基、イソチアゾリル基、オキサジアゾリル基、チアジアゾリル基、トリアゾリル基、テトラゾリル基、インドリル基、イソインドリル基、インドリジニル基、キノリジニル基、キノリル基、イソキノリル基、シンノリル基、フタラジニル基、キナゾリニル基、キノキサリニル基、ベンゾイミダゾリル基、ベンゾオキサゾリル基、ベンゾチアゾリル基、インダゾリル基、ベンゾイソキサゾリル基、ベンゾイソチアゾリル基、フェナントリジニル基、アクリジニル基、フェナントロリニル基、フェナジニル基、フェノチアジニル基、フェノキサジニル基、キサンテニル基、ベンゾフラニル基、イソベンゾフラニル基、ナフトベンゾフラニル基、ジベンゾフラニル基、ベンゾチオフェニル基（ベンゾチエニル基、以下同様）、イソベンゾチオフェニル基（イソベンゾチエニル基、以下同様）、ナフトベンゾチオフェニル基（ナフトベンゾチエニル基、以下同様）、ジベンゾチオフェニル基（ジベンゾチエニル基、以下同様）、又はカルバゾリル基である。
　好ましくは、ベンゾフラニル基、イソベンゾフラニル基、ナフトベンゾフラニル基、ジベンゾフラニル基、ベンゾチオフェニル基、イソベンゾチオフェニル基、ナフトベンゾチオフェニル基、ジベンゾチオフェニル基、カルバゾリル基（９－カルバゾリル基、又は、１－、２－、３－又は４－カルバゾリル基）である。
　置換された環形成原子数５～３０のヘテロアリール基は、例えば、９－フェニルカルバゾリル基、９－ビフェニリルカルバゾリル基、９－フェニルフェニルカルバゾリル基、９－ナフチルカルバゾリル基、フェニルジベンゾフラニル基、又はフェニルジベンゾチオフェニル基（フェニルジベンゾチエニル基、以下同様）である。
　前記置換もしくは無置換の環形成原子数５～３０のヘテロアリール基は、存在する場合には異性体基を含む。 In the substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, the heteroaryl group having 5 to 30 ring atoms is 1 to 5, preferably 1 to 3, and more preferably 1 to 2. Includes 4 ring-forming heteroatoms. 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, benzoxazolyl group, benzothiazolyl group, indazolyl group, benzisoxazolyl group, benzisothiazolyl group, phenanthridinyl group, acridinini Group, phenanthrolinyl group, phenazinyl group, phenothiazinyl group, phenoxazinyl group, xanthenyl group, benzofuranyl group, isobenzofuranyl group, naphthobenzofuranyl group, dibenzofuranyl group, benzothiophenyl group (benzothienyl group, Hereinafter the same), isobenzothiophenyl group (isobenzothienyl group, the same below), naphthobenzothiophenyl group (naphthobenzothienyl group, the same below), dibenzothiophenyl group (dibenzothienyl group, the same below), or carbazolyl group Is.
Preferably, 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. Group, a phenyldibenzofuranyl group, or a phenyldibenzothiophenyl group (phenyldibenzothienyl group, the same applies hereinafter).
The substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms includes an isomer group when present.
　Ｒ５～Ｒ８から選ばれる隣接する２つ、Ｒ１０～Ｒ１９から選ばれる隣接する２つ、及び＊ａに結合する単結合ではないＲ１～Ｒ４から選ばれる隣接する２つが任意に形成する前記環構造は、例えば、置換もしくは無置換の環形成炭素数６～１８の芳香族炭化水素環、置換もしくは無置換の環形成炭素数５～１８の脂肪族炭化水素環、置換もしくは無置換の環形成原子数５～１８の芳香族複素環、又は置換もしくは無置換の環形成原子数５～１８の脂肪族複素環である。
　前記環形成炭素数６～１８の芳香族炭化水素環は、例えば、ベンゼン環、ビフェニレン環、ナフタレン環、アントラセン環、ベンゾアントラセン環、フェナントレン環、ベンゾフェナントレン環、フェナレン環、ピレン環、クリセン環、又はトリフェニレン環であり、好ましくはベンゼン環又はナフタレン環である。
　前記環形成炭素数５～１８の脂肪族炭化水素環は、例えば、シクロペンテン環、シクロペンタジエン環、シクロヘキセン環、シクロヘキサジエン環、又は、前記環形成炭素数６～１８の芳香族炭化水素環を部分的に水素化して得られる脂肪族環である。
　前記環形成原子数５～１８の芳香族複素環は、例えば、ピロール環、フラン環、チオフェン環、ピリジン環、イミダゾール環、ピラゾール環、インドール環、イソインドール環、ベンゾフラン環、イソベンゾフラン環、ベンゾチオフェン環、ベンゾイミダゾール環、インダゾール環、ジベンゾフラン環、ナフトベンゾフラン環、ジベンゾチオフェン環、ナフトベンゾチオフェン環、カルバゾール環、又はベンゾカルバゾール環である。
　前記環形成原子数５～１８の脂肪族複素環は、例えば、上記環形成原子数５～１８の芳香族複素環を部分的に水素化して得られる脂肪族複素環である。
　２個以上の前記環構造が同一の環上に形成されてもよい。 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 arbitrarily selected. 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.
Examples of the aromatic hydrocarbon ring having 6 to 18 ring carbon atoms 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.
Examples of the aromatic heterocycle having 5 to 18 ring atoms include pyrrole ring, furan ring, thiophene ring, pyridine ring, imidazole ring, pyrazole ring, indole ring, isoindole ring, benzofuran ring, isobenzofuran ring, benzo ring. It is 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は、置換もしくは無置換のフェニル基、置換もしくは無置換の環形成炭素数１０～２６の、６員環からのみで構成される縮合アリール基、置換もしくは無置換のジベンゾフラニル基、又は置換もしくは無置換のジベンゾチオフェニル基であり、Ａｒの前記「置換もしくは無置換」というときの任意の置換基が、無置換の炭素数１～３０のアルキル基、無置換の炭素数１～３０のアルキル基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基である。 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. A mono-, di- or tri-substituted silyl group having a substituent selected from an alkyl group.
　Ａｒの前記「置換もしくは無置換」というときの任意の置換基は、無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基であり、
無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基を置換基に有するモノ、ジ又はトリ置換シリル基である。
　前記無置換の炭素数１～３０のアルキル基において、該炭素数１～３０のアルキル基は、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、又はドデシル基であり、
　好ましくは、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、又はペンチル基であり、
　より好ましくは、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、又はｔ－ブチル基であり、
　更に好ましくは、メチル基又はｔ－ブチル基である。
　前記置換もしくは無置換の炭素数１～３０のアルキル基は、存在する場合には異性体基を含む。
　また、無置換の炭素数１～３０のアルキル基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基の、該モノ、ジ又はトリ置換シリル基が有する無置換の炭素数１～３０のアルキル基の詳細は、無置換の炭素数１～３０のアルキル基に関して上記したアルキル基の詳細と同じである。 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.
In the unsubstituted alkyl group having 1 to 30 carbon atoms, 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 substituted or unsubstituted alkyl group having 1 to 30 carbon atoms includes an isomer group when present.
In addition, a mono-, di- or tri-substituted silyl group having a substituent selected from an unsubstituted alkyl group having 1 to 30 carbon atoms, which has an unsubstituted carbon number of 1 to 30 contained in the mono-, di- or tri-substituted silyl group 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.
　前記置換もしくは無置換の環形成炭素数１０～２６の、６員環からのみで構成される縮合アリール基において、該環形成炭素数１０～２６の６員環からのみで構成される縮合アリール基は、例えば、ナフチル基、アントリル基、ベンゾアントリル基、フェナントリル基、ベンゾフェナントリル基、フェナレニル基、ピセニル基、ピレニル基、クリセニル基、ベンゾクリセニル基、ペリレニル基、又はトリフェニレニル基であり、
　好ましくは、ナフチル基、フェナントリル基である。 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.
　本発明の好ましい態様において、Ａｒは下記式（３－１）で表されるフェニル基を含む。
Figure JPOXMLDOC01-appb-C000014
　式（３－１）において、
　Ｒ７１～Ｒ７６の１つは、*ｈに結合する単結合を表し、*ｈに結合する単結合以外のＲ７１～Ｒ７６の詳細は、それぞれ独立に、上記したＡｒの任意の置換基の詳細と同じである。 In a preferred embodiment of the present invention, Ar contains a phenyl group represented by the following formula (3-1).
Figure JPOXMLDOC01-appb-C000014
In equation (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.
　本発明の他の一態様においては、＊ｈに結合する単結合ではないＲ７１～Ｒ７６はすべて水素原子であることが好ましい。
　本発明の一態様において、Ａｒは、置換もしくは無置換のフェニル基が特に好ましい。 In another aspect of the present invention, it is preferable that R 71 to R 76 which are not a single bond bonding to * h are all hydrogen atoms.
In one aspect of the present invention, Ar is particularly preferably a substituted or unsubstituted phenyl group.
　本発明の好ましい態様において、Ａｒは下記式（３－２）で表されるナフチル基を含む。
Figure JPOXMLDOC01-appb-C000015
　（式（３－２）において、
　Ｒ７１、Ｒ７２、Ｒ７５、Ｒ７６、及びＲ８２～Ｒ８５の１つは、*ｈに結合する単結合を表し、*ｈに結合する単結合以外のＲ７１、Ｒ７２、Ｒ７５、Ｒ７６、及びＲ８２～Ｒ８５の詳細は、それぞれ独立に、上記したＡｒの任意の置換基の詳細と同じである。 In a preferred embodiment of the present invention, Ar contains a naphthyl group represented by the following formula (3-2).
Figure JPOXMLDOC01-appb-C000015
(In 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.
　本発明の一態様において、ナフタレン骨格に結合するＲ７２、Ｒ７５、Ｒ８２、又はＲ８５が＊ｈを介して窒素原子に結合する単結合であることが好ましい。
　本発明の一態様においては、＊ｈに結合する単結合ではないＲ７１、Ｒ７２、Ｒ７５、Ｒ７６、及びＲ８２～Ｒ８５はすべて水素原子であることが好ましい。
　本発明の他の態様において、ナフタレン骨格に結合するＲ７２、Ｒ７５、Ｒ８２、又はＲ８５が＊ｈを介して窒素原子に結合する単結合であり、単結合でない他のＲ７１、Ｒ７２、Ｒ７５、Ｒ７６、及びＲ８２～Ｒ８５がすべて水素原子であることが好ましい。 In one embodiment of the present invention, it is preferable that 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.
In one aspect of the present invention, it is preferable that 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.
In another embodiment of the present invention, 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.
　本発明の好ましい態様において、Ａｒは下記式（３－３）で表されるフェナントリル基を含む。
Figure JPOXMLDOC01-appb-C000016
　（式（３－３）において、
　Ｒ７１、Ｒ７２、Ｒ７３、Ｒ７６、及びＲ９０～Ｒ９５の１つは、*ｈに結合する単結合を表し、*ｈに結合する単結合以外のＲ７１、Ｒ７２、Ｒ７３、Ｒ７６、及びＲ９０～Ｒ９５の詳細は、それぞれ独立に、上記したＡｒの任意の置換基の詳細と同じである。 In a preferred embodiment of the present invention, Ar contains a phenanthryl group represented by the following formula (3-3).
Figure JPOXMLDOC01-appb-C000016
(In 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.
　本発明の一態様において、フェナントレン骨格に結合するＲ９５、Ｒ７６、Ｒ７１、又はＲ７２が＊ｈを介して窒素原子に結合する単結合であることが好ましい。
　本発明の一態様においては、＊ｈに結合する単結合ではないＲ７１、Ｒ７２、Ｒ７３、Ｒ７６、及びＲ９０～Ｒ９５はすべて水素原子であることが好ましい。
　本発明の他の態様において、フェナントレン骨格に結合するＲ９５、Ｒ７６、Ｒ７１、又はＲ７２が＊ｈを介して窒素原子に結合する単結合であり、単結合でない他のＲ７１、Ｒ７２、Ｒ７３、Ｒ７６、及びＲ９０～Ｒ９５がすべて水素原子であることが好ましい。 In one embodiment of the present invention, it is preferable that 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.
In one aspect of the present invention, it is preferable that 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.
In another embodiment of the present invention, 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. It is preferable that 72 , R 73 , R 76 , and R 90 to R 95 are all hydrogen atoms.
　本発明の他の態様において、Ａｒは、置換もしくは無置換のジベンゾフラニル基、又は置換もしくは無置換のジベンゾチオフェニル基であることが好ましい In another aspect of the present invention, Ar is preferably a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothiophenyl group.
　従って、本発明の好ましい態様において、Ａｒは下記式（３－４）で表されるジベンゾフラニル基を含む。
Figure JPOXMLDOC01-appb-C000017
　式（３－４）において、
　Ｒ１０１～Ｒ１０８の１つは、*ｈに結合する単結合を表し、*ｈに結合する単結合以外のＲ１０１～Ｒ１０８の詳細は、それぞれ独立に、上記したＡｒの任意の置換基の詳細と同じである。 Therefore, in a preferred embodiment of the present invention, Ar contains a dibenzofuranyl group represented by the following formula (3-4).
Figure JPOXMLDOC01-appb-C000017
In 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.
　本発明の一態様において、ジベンゾフラン骨格に結合するＲ１０１、Ｒ１０２、Ｒ１０３又はＲ１０４が＊ｈを介して窒素原子に結合する単結合であることが好ましい。
　本発明の一態様においては、＊ｈに結合する単結合ではないＲ１０１～Ｒ１０８はすべて水素原子であることが好ましい。
　本発明の他の態様において、ジベンゾフラン骨格に結合するＲ１０１、Ｒ１０２、Ｒ１０３又はＲ１０４が＊ｈを介して窒素原子に結合する単結合であり、単結合でない他のＲ１０１～Ｒ１０８がすべて水素原子であることが好ましい。 In one embodiment of the present invention, it is preferable that 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.
In one aspect of the present invention, it is preferable that R 101 to R 108 which are not a single bond bonding to * h are all hydrogen atoms.
In another embodiment of the present invention, 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. Are preferably all hydrogen atoms.
　本発明の好ましい態様において、Ａｒは下記式（３－５）で表されるジベンゾチオフェニル基を含む。
Figure JPOXMLDOC01-appb-C000018
　式（３－５）において、
　Ｒ１１１～Ｒ１１８の１つは、*ｈに結合する単結合を表し、*ｈに結合する単結合以外の、Ｒ１１１～Ｒ１１８の詳細は、それぞれ独立に、上記したＡｒの任意の置換基の詳細と同じである。 In a preferred embodiment of the present invention, Ar contains a dibenzothiophenyl group represented by the following formula (3-5).
Figure JPOXMLDOC01-appb-C000018
In 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.
　本発明の一態様において、ジベンゾチオフェン骨格に結合するＲ１１１、Ｒ１１２、Ｒ１１３又はＲ１１４が＊ｈを介して窒素原子に結合する単結合であることが好ましい。
　本発明の一態様においては、＊ｈに結合する単結合ではないＲ１１１～Ｒ１１８はすべて水素原子であることが好ましい。
　本発明の他の態様において、ジベンゾチオフェン骨格に結合するＲ１１１、Ｒ１１２、Ｒ１１３又はＲ１１４が＊ｈを介して窒素原子に結合する単結合であり、単結合でない他のＲ１１１～Ｒ１１８がすべて水素原子であることが好ましい。 In one embodiment of the present invention, it is preferable that 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.
In one aspect of the present invention, it is preferable that all R 111 to R 118 which are not a single bond bonding to * h are hydrogen atoms.
In another embodiment of the present invention, 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.
　Ｒ３０～Ｒ４６は、それぞれ独立して、水素原子又は置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基である。ただし、隣接するＲ３０とＲ３３、隣接するＲ３１とＲ３２、Ｒ３７～Ｒ４１から選ばれる隣接する２つ、及びＲ４２～Ｒ４６から選ばれる隣接する２つは、それぞれ独立して、水素原子又は置換もしくは無置換の炭素数１～３０のアルキル基を表すか、又は、互いに結合して置換もしくは無置換の環構造を形成する。本発明の一態様においては、少なくとも一組の隣接する２つが置換もしくは無置換の環構造を形成することが好ましく、他の態様においては、前記隣接する２つが置換もしくは無置換の環構造を形成しないことが好ましい。
　本発明の一態様において、Ｒ３０～Ｒ４６はすべて水素原子であることが好ましい。 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. However, 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. In one aspect of the present invention, it is preferable that 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.
In one aspect of the present invention, it is preferable that R 30 to R 46 are all hydrogen atoms.
　該アルキル基の詳細は、Ｒ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４に関して上記したアルキル基の詳細と同じである。
　隣接するＲ３０とＲ３３、隣接するＲ３１とＲ３２、Ｒ３７～Ｒ４１から選ばれる隣接する２つ、及Ｒ４２～Ｒ４６から選ばれる隣接する２つが任意に形成する前記環構造の詳細は、Ｒ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４に関して上記した環構造の詳細と同じである。２個以上の前記環構造が同一の環上に形成されてもよい。 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は単結合又は置換もしくは無置換の環形成炭素数６～２０、好ましくは６～１８、より好ましくは６～１４のアリーレン基である。
　本発明の一態様においては、Ｌは単結合であることが好ましい。従って、本発明の好ましい態様において、式（１）の化合物は下記式（１－ｃ）で表される化合物を含む。
Figure JPOXMLDOC01-appb-C000019
 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).
Figure JPOXMLDOC01-appb-C000019
（式中、Ｒ１～Ｒ８、Ｒ１０～Ｒ１９、Ｒ３０～Ｒ４６、＊ａは式（１）において定義したとおりである。） (In the formula, R 1 to R 8 , R 10 to R 19 , R 30 to R 46 , * a are as defined in the formula (1).)
　本発明の他の態様においては、Ｌは置換もしくは無置換の環形成炭素数６～３０のアリーレン基である。好ましくは６～２０、より好ましくは６～１８、さらに好ましくは６～１４のアリーレン基である。
　前記置換もしくは無置換の環形成炭素数６～３０のアリーレン基において、該環形成炭素数６～３０のアリーレン基は、例えば、フェニレン基、ビフェニレン基、ターフェニレン基、ビフェニレニレン基、ナフチレン基、アントリレン基、ベンゾアントリレン基、フェナントリレン基、ベンゾフェナントリレン基、フェナレニレン基、ピセニレン基、ペンタフェニレン基、ピレニレン基、クリセニレン基、ベンゾクリセニレン基、フルオレニレン基、フルオランテニレン基、ペリレニレン基、又はトリフェニレニレン基であり、
　好ましくは、フェニレン基、ビフェニレン基、又はナフチレン基であり、
　より好ましくは、フェニレン基又はビフェニレン基であり、
　更に好ましくは、フェニレン基である。
　前記フェニレン基は、ｏ－フェニレン基、ｍ－フェニレン基、又はｐ－フェニレン基であり、ｐ－フェニレン基が特に好ましい。
　前記ビフェニレン基は、好ましくは４，２’－ビフェニレン基、４，３’－ビフェニレン基、４，４’－ビフェニレン基、又は３，３’－ビフェニレン基であり、より好ましくは４，３’－ビフェニレン基、４，４’－ビフェニレン基、又は３，３’－ビフェニレン基であり、４，４’－ビフェニレン基がさらに好ましい。
　前記ナフチレン基は、好ましくは１，４－ナフチレン基又は２，６－ナフチレン基、より好ましくは１，４－ナフチレン基である。
　従って、本発明の好ましい態様において、式（１）の化合物は下記式（１－ｄ）で表される化合物を含む。
Figure JPOXMLDOC01-appb-C000020
 In another embodiment of the present invention, 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.
In the substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms, 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. , Anthrylene group, benzoanthrylene group, phenanthrylene group, benzophenanthrylene group, phenalenylene group, picenylene group, pentaphenylene group, pyrenylene group, chrysenylene group, benzochrysenylene group, fluorenylene group, fluoranthenylene group, perenylene group Or a triphenylenylene group,
Preferably, 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).
Figure JPOXMLDOC01-appb-C000020
（式中、
　Ｒ１～Ｒ８、Ｒ１０～Ｒ１９、Ｒ３０～Ｒ４６、及び＊ａは式（１）において定義したとおりであり、
　Ｒ５１～Ｒ５６から選ばれる１つは＊ｂ１に結合する単結合であり、
　＊ｂ１に結合する単結合以外のＲ５１～Ｒ５６から選ばれる１つはｂ２に結合する単結合であり、
　＊ｂ１に結合する単結合ではなく、かつ、＊ｂ２に結合する単結合でもないＲ５１～Ｒ５６は、式（１）のＲ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４と同様に定義される。） (In the formula,
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 . )
　本発明の他の好ましい態様において、式（１）の化合物は下記式（１－ｅ）で表される化合物を含む。
Figure JPOXMLDOC01-appb-C000021
 In another preferred embodiment of the present invention, the compound of formula (1) includes a compound represented by the following formula (1-e).
Figure JPOXMLDOC01-appb-C000021
（式中、
　Ｒ１～Ｒ８、Ｒ１０～Ｒ１９、Ｒ３０～Ｒ４６、及び＊ａは式（１）において定義したとおりであり、
　Ｒ５１～Ｒ５４及びＲ５６から選ばれる１つは＊ｂ３に結合する単結合であり、
　Ｒ５７～Ｒ６１から選ばれる１つは＊ｂ４に結合する単結合であり、
　＊ｂ３に結合する単結合ではなく、かつ、＊ｂ４に結合する単結合でもないＲ５１～Ｒ５４及びＲ５６～Ｒ６１は、式（１）のＲ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４と同様に定義される。） (In the formula,
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). , And * 1 as well as R 1 to R 4 which are not a single bond. )
　本発明の好ましい態様において、式（１）の化合物は下記式（１－ｆ）で表される化合物を含む。
Figure JPOXMLDOC01-appb-C000022
 In a preferred embodiment of the present invention, the compound of formula (1) includes the compound represented by the following formula (1-f).
Figure JPOXMLDOC01-appb-C000022
（式中、
　Ｒ１～Ｒ８、Ｒ１０～Ｒ１９、Ｒ３０～Ｒ４６、及び＊ａは式（１）において定義したとおりであり、
　Ｒ５１、Ｒ５２、Ｒ５５、Ｒ５６、及びＲ６２～Ｒ６５から選ばれる１つは＊ｂ５に結合する単結合であり、
　＊ｂ５に結合する単結合ではないＲ５１、Ｒ５２、Ｒ５５、Ｒ５６、及びＲ６２～Ｒ６５から選ばれる１つは＊ｂ６に結合する単結合であり、
　＊ｂ５に結合する単結合ではなく、かつ、＊ｂ６に結合する単結合でもないＲ５１、Ｒ５２、Ｒ５５、Ｒ５６、及びＲ６２～Ｒ６５は、式（１）のＲ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４と同様に定義される。） (In the formula,
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. )
　上記したように、本明細書において使用する「水素原子」は軽水素原子、重水素原子、及び三重水素原子を包含する。従って、発明化合物（１）は天然由来の重水素原子を含んでいてもよい。
　又、原料化合物の一部又は全てに重水素化した化合物を使用することにより、発明化合物（１）に重水素原子を意図的に導入してもよい。従って、本発明の一態様において、発明化合物（１）は少なくとも１個の重水素原子を含む。すなわち、発明化合物（１）は、式（１）又はその好ましい態様の式で表される化合物であって、該化合物に含まれる水素原子の少なくとも一つが重水素原子である化合物であってもよい。
　さらに、式（１）において、＊ａに結合する単結合ではないＲ１～Ｒ４、Ｒ５～Ｒ８、Ｒ１０～Ｒ１９、及びＲ３０～Ｒ４６が表す水素原子、Ａｒが表すフェニル基、縮合アリール基、ジベンゾフラニル基、又はジベンゾチオフェニル基が有する水素原子、及びＬが表すアリーレン基が有する水素原子から選ばれる少なくとも一つの水素原子が重水素原子であってもよい。 As mentioned above, 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. .
Further, in the formula (1), hydrogen atom represented by R 1 to R 4 , R 5 to R 8 , R 10 to R 19 , and R 30 to R 46 which is not a single bond bonded to * a, and phenyl represented by Ar. 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.
　発明化合物（１）の重水素化率（発明化合物（１）中の全水素原子数に対する重水素原子数の割合）は使用する原料化合物の重水素化率に依存する。使用する全ての原料化合物の重水素化率を１００％にすることは通常困難であるので、発明化合物（１）の重水素化率は１００％未満、好ましくは９５％以下、より好ましくは９０％以下、さらに好ましくは８０％以下である。 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.
　発明化合物（１）が重水素を包含する場合の重水素化率（発明化合物（１）中の全水素原子数に対する重水素原子数の割合）は、１％以上、好ましくは３％以上、より好ましくは５％以上、さらに好ましくは１０％以上である。 When the invented compound (1) includes deuterium, 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%.
　発明化合物（１）は、重水素化された化合物と重水素化されていない化合物を含む混合物、異なる重水素化率を有する２以上の化合物の混合物であってもよい。このような混合物の重水素化率（混合物に含まれる発明化合物（１）中の全水素原子数に対する重水素原子数の割合）は、１％以上、好ましくは３％以上、より好ましくは５％以上、さらに好ましくは１０％以上、かつ、１００％未満、好ましくは９５％以下、より好ましくは９０％以下である。 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.
　発明化合物（１）において、Ｒ１～Ｒ４、Ｒ５～Ｒ８、及びＲ１０～Ｒ１９が表す水素原子から選ばれる少なくとも一つの水素原子が重水素原子であってもよい。重水素化率（Ｒ１～Ｒ４、Ｒ５～Ｒ８、及びＲ１０～Ｒ１９が表す全水素原子数に対する重水素原子数の割合）は、１％以上、好ましくは３％以上、より好ましくは５％以上、さらに好ましくは１０％以上、かつ、１００％未満、好ましくは９５％以下、より好ましくは９０％以下である。 In the compound (1) of the invention, 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.
　発明化合物（１）において、Ｒ３０～Ｒ４６が表す水素原子から選ばれる少なくとも一つの水素原子が重水素原子であってもよい。重水素化率（Ｒ３０～Ｒ４６表す全水素原子数に対する重水素原子数の割合）は、１％以上、好ましくは３％以上、より好ましくは５％以上、さらに好ましくは１０％以上、かつ、１００％未満、好ましくは９５％以下、より好ましくは９０％以下である。 In the invention compound (1), 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.
　発明化合物（１）において、Ａｒが表すフェニル基、縮合アリール基、ジベンゾフラニル基、又はジベンゾチオフェニル基が有する水素原子から選ばれる少なくとも一つの水素原子が重水素原子であってもよい。重水素化率（フェニル基、縮合アリール基、ジベンゾフラニル基、又はジベンゾチオフェニル基が有する全水素原子数に対する重水素原子数の割合）は、１％以上、好ましくは３％以上、より好ましくは５％以上、さらに好ましくは１０％以上、かつ、１００％未満、好ましくは９５％以下、より好ましくは９０％以下である。 In the invention 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.
　発明化合物（１）において、Ｌが表すアリーレン基が有する水素原子から選ばれる少なくとも一つの水素原子が重水素原子であってもよい。重水素化率（アリーレン基が有する全水素原子数に対する重水素原子数の割合）は、１％以上、好ましくは３％以上、より好ましくは５％以上、さらに好ましくは１０％以上、かつ、１００％未満、好ましくは９５％以下、より好ましくは９０％以下である。 In the invention compound (1), 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) is 1% or more, preferably 3% or more, more preferably 5% or more, further preferably 10% or more, and 100. %, Preferably 95% or less, more preferably 90% or less.
　以下に発明化合物（１）の具体例を示すが、これらに限定されるものではない。 Specific examples of the invention compound (1) are shown below, but the invention compound (1) is not limited thereto.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
発明化合物（２）
　発明化合物（２）は下記式（２）で表される。
Figure JPOXMLDOC01-appb-C000051
 Invention compound (2)
Inventive compound (2) is represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000051
　Ｘ１は酸素原子、硫黄原子、ＣＲａＲｂ、又は＊ｃに結合する窒素原子である。
　Ｘ１が酸素原子、硫黄原子、又はＣＲａＲｂである場合、Ｒ５０～Ｒ５３の１つが＊ｃに結合する単結合である。Ｘ１がＣＲａＲｂである場合、Ｒ５１又はＲ５３が＊ｃに結合する単結合であることが好ましい。
　本発明の一態様においては、Ｘ１は酸素原子、硫黄原子、又はＣＲａＲｂであることが好ましく、他の態様においては、Ｘ１は＊ｃに結合する窒素原子であることが好ましい。 X 1 is an oxygen atom, a sulfur atom, CRaRb, or a nitrogen atom bonded to * c.
When 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. When X 1 is CRaRb, R 51 or R 53 is preferably a single bond that binds to * c.
In one aspect of the present invention, 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.
　Ｒ５４～Ｒ５７及び＊ｃに結合する単結合ではないＲ５０～Ｒ５３は、それぞれ独立して、水素原子又は置換基である。ただし、＊ｃに結合する単結合ではないＲ５０～Ｒ５３から選ばれる隣接する２つ及びＲ５４～Ｒ５７から選ばれる隣接する２つは、それぞれ独立して、水素原子又は前記置換基を表すか、又は、互いに結合して置換もしくは無置換の環構造を形成する。本発明の一態様においては、少なくとも一組の前記隣接する２つが置換もしくは無置換の環構造を形成することが好ましく、他の態様においては、前記隣接する２つが置換もしくは無置換の環構造を形成しないことが好ましい。
　本発明の一態様において、Ｒ５４～Ｒ５７及び＊ｃに結合する単結合ではないＲ５０～Ｒ５３がすべて水素原子であることが好ましい。 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. However, 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. In one aspect of the present invention, it is preferable that 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. It is preferably not formed.
In one aspect of the present invention, it is preferable that R 54 to R 57 and R 50 to R 53 which are not a single bond bonding to * c are all hydrogen atoms.
　前記置換基は、ハロゲン原子；シアノ基；ニトロ基；置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基；置換もしくは無置換の環形成炭素数３～３０、好ましくは３～１０、より好ましくは３～８、さらに好ましくは５又は６のシクロアルキル基；置換もしくは無置換の環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリール基；置換もしくは無置換の炭素数７～３６、好ましくは７～２６、より好ましくは７～２０のアラルキル基；置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルコキシ基；置換もしくは無置換の環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリールオキシ基；置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基及び置換もしくは無置換の環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリール基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基；置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８ハロアルキル基；置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のハロアルコキシ基；及び、置換もしくは無置換の環形成原子数５～３０、好ましくは５～２４、より好ましくは５～１３のヘテロアリール基からなる群から選ばれる。
　前記置換基は、好ましくは、置換もしくは無置換の炭素数１～３０のアルキル基、置換もしくは無置換の環形成炭素数３～３０のシクロアルキル基、置換もしくは無置換の環形成炭素数６～３０のアリール基、置換もしくは無置換の炭素数１～３０のアルキル基及び置換もしくは無置換の環形成炭素数６～３０のアリール基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基、及び、置換もしくは無置換の環形成原子数５～３０のヘテロアリール基からなる群から選ばれ；
　より好ましくは、置換もしくは無置換の炭素数１～３０のアルキル基、置換もしくは無置換の環形成炭素数６～３０のアリール基、及び、置換もしくは無置換の環形成原子数５～３０のヘテロアリール基からなる群から選ばれ；
　更に好ましくは、置換もしくは無置換の炭素数１～３０のアルキル基又は置換もしくは無置換の環形成炭素数６～３０のアリール基であり、
　特に好ましくは置換もしくは無置換の炭素数１～３０のアルキル基である。
　前記置換基の詳細は、式（１）のＲ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４に関して上記した対応する置換基の詳細と同じである。 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, preferably 1 to 18, more preferably 1 to 8 and a substituted or unsubstituted ring-forming carbon number of 6 to 30, preferably 6 to 25, more preferably 6 to 18 A mono-, di- or tri-substituted silyl group having a substituent selected from an aryl group; a substituted or unsubstituted C1-30, preferably 1-18, more preferably 1-8 haloalkyl group; a substituted or unsubstituted carbon A haloalkoxy group having a number of 1 to 30, preferably 1 to 18, more preferably 1 to 8; and a substituted or unsubstituted number of ring-forming atoms of 5 to 30, preferably 5 to 24, more preferably 5 to 13 It is selected from the group consisting of heteroaryl groups.
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. A mono-, di- or tri-substituted silyl group having a substituent selected from an aryl group having 30 aryl groups, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, And a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms;
More preferably, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring forming carbon atoms, and a substituted or unsubstituted hetero group having 5 to 30 ring forming atoms. 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.
　＊ｃに結合する単結合ではないＲ５０～Ｒ５３から選ばれる隣接する２つ及びＲ５４～Ｒ５７から選ばれる隣接する２つが任意に形成する前記環構造の詳細は、式（１）のＲ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４に関して上記した環構造の詳細と同じである。２個以上の前記環構造が同一の環上に形成されてもよい。 * The details of the ring structure which is not a single bond and is adjacent to two selected from R 50 to R 53 and two adjacent to each other selected from R 54 to R 57 which are not a single bond bonded to * c are described in Formula (1). The details of the ring structure are the same as those 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.
　Ｒａ及びＲｂは、それぞれ独立して、水素原子、置換もしくは無置換の炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基、又は置換もしくは無置換の環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリール基であるか、又は、互いに結合して置換もしくは無置換の環構造を形成する。
　前記アルキル基及びアリール基の詳細は、式（１）のＲ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４に関して上記した対応する置換基の詳細と同じである。
　本発明の好ましい態様において、Ｒａ及びＲｂは、それぞれ独立して、置換もしくは無置換のメチル基又は置換もしくは無置換のフェニル基であるか、又は、互いに結合してスピロ環構造を完成する環、例えば、置換もしくは無置換のシクロペンタン環、置換もしくは無置換のシクロヘキサン環、又は置換もしくは無置換のフルオレン環を形成する。
　本発明の他の好ましい態様において、Ｒａ及びＲｂのそれぞれは、メチル基又はフェニル基であるか、又は、互いに結合して９，９’－スピロビフルオレン構造を完成するフルオレン環を形成する。 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.
For details of the alkyl group and the aryl group, refer to 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.
In a preferred embodiment of the present invention, 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, For example, a substituted or unsubstituted cyclopentane ring, a substituted or unsubstituted cyclohexane ring, or a substituted or unsubstituted fluorene ring is formed.
In another preferred embodiment of the present invention, 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.
　Ｌ１、Ｌ２、及びＬ３は、それぞれ独立して、単結合又は置換もしくは無置換の環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～２０のアリーレン基である。該アリーレン基の詳細は、式（１）のＬに関して前記したアリーレン基の詳細と同じである。
　Ｘ１が＊ｃに結合する窒素原子である場合、Ｌ３は置換もしくは無置換の環形成炭素数６～３０のアリーレン基であることが好ましく、フェニレン基（ｐ－フェニレン基、ｏ－フェニレン基、又はｍ－フェニレン基）又はビフェニレン基（４，４’－ビフェニレン基、４，３’－ビフェニレン基、又は４，２’－ビフェニレン基）であることがより好ましい。
　Ｘ１が酸素原子又は硫黄原子である場合、Ｌ３は単結合又は置換もしくは無置換の環形成炭素数６～３０のアリーレン基であることが好ましく、単結合又はフェニレン基（ｐ－フェニレン基）であることがより好ましい。さらに好ましくは、Ｌ３が単結合であり、かつ、下記式で表される基が、
Figure JPOXMLDOC01-appb-C000052
２－、３－、もしくは４－ジベンゾフラニル基、又は２－、３－、もしくは４－ジベンゾチオフェニル基であるか、又は、Ｌ３がｐ－フェニレン基であり、かつ、下記式で表される基が、
Figure JPOXMLDOC01-appb-C000053
１－、２－、３－、もしくは４－ジベンゾフラニル基、又は１－、２－、３－、もしくは４－ジベンゾチオフェニル基である。
　Ｘ１がＣＲａＲｂである場合、Ｌ３がｐ－フェニレン基であり、かつ、下記式で表される基が、
Figure JPOXMLDOC01-appb-C000054
９，９－ジメチルフルオレン－１－イル基であるか、又は、Ｌ３が単結合であり、かつ、下記式で表される基が、
Figure JPOXMLDOC01-appb-C000055
９，９－ジメチルフルオレン－１－イル基、９，９－ジメチルフルオレン－２－イル基、９，９－ジメチルフルオレン－４－イル基、９，９－ジフェニルフルオレン－２－イル基、９，９－ジフェニルフルオレン－４－イル基、９，９’－スピロビフルオレン－２－イル基、又は９，９’－スピロビフルオレン－４－イル基であることが好ましい。 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).
When X 1 is a nitrogen atom bonded to * c, 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). , Or m-phenylene group) or a biphenylene group (4,4′-biphenylene group, 4,3′-biphenylene group, or 4,2′-biphenylene group).
When X 1 is an oxygen atom or a sulfur atom, 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. More preferably, L 3 is a single bond, and a group represented by the following formula:
Figure JPOXMLDOC01-appb-C000052
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
Figure JPOXMLDOC01-appb-C000053
A 1-, 2-, 3-, or 4-dibenzofuranyl group, or a 1-, 2-, 3-, or 4-dibenzothiophenyl group.
When X 1 is CRaRb, L 3 is a p-phenylene group, and a group represented by the following formula is
Figure JPOXMLDOC01-appb-C000054
Is a 9,9-dimethylfluoren-1-yl group, or L 3 is a single bond, and a group represented by the following formula is
Figure JPOXMLDOC01-appb-C000055
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.
　Ａｒ１及びＡｒ２は、それぞれ独立して、置換もしくは無置換の環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリール基又は置換もしくは無置換の環形成原子数５～３０、好ましくは５～２４、より好ましくは５～１３ヘテロアリール基である。
　前記アリール基及び前記ヘテロアリール基の詳細は、ヘテロアリール基が１－、２－、３－、又は４－カルバゾリル基を含まないことを除いて、式（１）のＲ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４に関して上記したアリール基及びヘテロアリール基の詳細と同じである。
　本発明の一態様において、発明化合物（１）と発明化合物（２）は異なり、本発明の他の態様において、Ａｒ１及び／又はＡｒ２が置換もしくは無置換のアリール基である場合、該アリール基は３’、５’－ジフェニル－４－ビフェニリル基ではないことが好ましい。 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.
In one embodiment of the present invention, 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.
　本発明の好ましい態様において、Ａｒ１及びＡｒ２は、それぞれ独立して、フェニル基、ビフェニリル基（４－ビフェニリル基、３－ビフェニリル基、又は２－ビフェニリル基）、ターフェニリル基（好ましくは、１，１’：４’，１”－ターフェニル－４－イル基、１，１’：４’，１”－ターフェニル－２－イル基）、１－ナフチル基、２－ナフチル基、ジベンゾフラニル基（１－、２－、３－又は４－ジベンゾフラニル基）、ジベンゾチオフェニル基（１－、２－、３－又は４－ジベンゾチオフェニル基）、９，９－ジメチルフルオレニル基（好ましくは、９，９－ジメチルフルオレン－１－イル基、９，９－ジメチルフルオレン－２－イル基、又は９，９－ジメチルフルオレン－４－イル基）、９，９－ジフェニルフルオレニル基（好ましくは、９，９－ジフェニルフルオレン－２－イル基又は９，９－ジフェニルフルオレン－４－イル基）、又は９，９’－スピロビフルオレニル基（好ましくは、９，９’－スピロビフルオレン－２－イル基又は９，９’－スピロビフルオレン－４－イル基）である。 In a preferred embodiment of the present invention, 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-diphenylfluorenyl Group (preferably Or 9,9-diphenylfluoren-2-yl group or 9,9-diphenylfluoren-4-yl group) or 9,9'-spirobifluorenyl group (preferably 9,9'-spiro group) Bifluoren-2-yl group or 9,9′-spirobifluoren-4-yl group).
　式（２）において、Ｌ１は単結合であり、かつ、Ａｒ１はフェニル基、４－ビフェニリル基、３－ビフェニリル基、２－ビフェニリル基、１，１’：４’，１”－ターフェニル－４－イル基、１，１’：４’，１”－ターフェニル－２－イル基、９，９－ジメチルフルオレン－１－イル基、９，９－ジメチルフルオレン－２－イル基、９，９－ジフェニルフルオレン－２－イル基、９，９－ジフェニルフルオレン－４－イル基、９，９’－スピロビフルオレン－２－イル基、９，９’－スピロビフルオレン－４－イル基、２－、３－、もしくは４－ジベンゾフラニル基、又は２－、３－、もしくは４－ジベンゾチオフェニル基であるか、又は、Ｌ１はｐ－フェニレン基又は４，４’－ビフェニレン基、特に、ｐ－フェニレン基であり、かつ、Ａｒ１は１－ナフチル基、２－ナフチル基、９，９－ジメチルフルオレン－１－イル基、１－、２－、３－、もしくは４－ジベンゾフラニル基、又は、１－、２－、３－、もしくは４－ジベンゾチオフェニル基であることが好ましい。 In the formula (2), L 1 is a single bond, and 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′-biphenylene group , in particular, a p- phenylene group, and, Ar 1 1-naphthyl group, 2-naphthyl group, 9,9-dimethylfluoren-1-yl group, 1-, 2-, 3-, or 4-dibenzofuranyl group, or 1-, 2-, 3-, Alternatively, it is preferably a 4-dibenzothiophenyl group.
　式（２）において、Ｌ２は単結合であり、かつ、Ａｒ２は４－ビフェニリル基、２－ビフェニリル基、１，１’：４’，１”－ターフェニル－４－イル基、１，１’：４’，１”－ターフェニル－２－イル基、９，９－ジメチルフルオレン－２－イル基、９，９－ジフェニルフルオレン－２－イル基、９，９－ジフェニルフルオレン－４－イル基、９，９’－スピロビフルオレン－２－イル基、又は９，９’－スピロビフルオレン－４－イル基であるか、又は、Ｌ２はｐ－フェニレン基又は４，４’－ビフェニレン基、特に、ｐ－フェニレン基であり、Ａｒ２は１－ナフチル基、２－ナフチル基、２－もしくは４－ジベンゾフラニル基、又は、２－もしくは４－ジベンゾチオフェニル基であることが好ましい。 In the formula (2), L 2 is a single bond, and 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-dibenzothiophenyl group preferable.
　本発明の一態様において、発明化合物（２）は下記式（２ａ）で表される。
Figure JPOXMLDOC01-appb-C000056
 In one aspect of the present invention, the compound (2) of the invention is represented by the following formula (2a).
Figure JPOXMLDOC01-appb-C000056
　Ｘ１、Ｒ５０～Ｒ５７、＊ｃ、Ｌ１～Ｌ３、及びＡｒ２は式（２）において定義したとおりである。
　Ｘ２は酸素原子、硫黄原子、ＣＲｃＲｄ、又は＊ｄに結合する窒素原子、好ましくは酸素原子、硫黄原子、又はＣＲｃＲｄである。Ｘ２が酸素原子、硫黄原子、又はＣＲｃＲｄである場合、Ｒ６０～Ｒ６３の１つが＊ｄに結合する単結合である。
　Ｒ６４～Ｒ６７及び＊ｄに結合する単結合ではないＲ６０～Ｒ６３は、それぞれ独立して、式（２）のＲ５４～Ｒ５７及び＊ｃに結合する単結合ではないＲ５０～Ｒ５３と同様に定義される。
　本発明の一態様においては、Ｒ５４～Ｒ５７、＊ｃに結合する単結合ではないＲ５０～Ｒ５３、Ｒ６４～Ｒ６７、及び＊ｄに結合する単結合ではないＲ６０～Ｒ６３はすべて水素原子であることが好ましい。
　Ｒｃ及びＲｄは、それぞれ独立して、式（２）のＲａ及びＲｂと同様に定義される。 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. When X 2 is an oxygen atom, a sulfur atom, or CRcRd, one of 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). It is defined similarly to R 53 .
In one embodiment of the present invention, 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).
　本発明の一態様において、Ｘ１が＊ｃに結合する窒素原子であり、かつ、Ｘ２が酸素原子、硫黄原子、又はＣＲｃＲｄであることが好ましく、他の態様においては、Ｘ１が酸素原子、硫黄原子、又はＣＲｃＲｄであり、かつ、Ｘ２が酸素原子、硫黄原子、又はＣＲｃＲｄであることが好ましい。 In one aspect of the present invention, it is preferable that X 1 is a nitrogen atom bonded to * c, and X 2 is an oxygen atom, a sulfur atom, or CRcRd, and in another aspect, X 1 is an oxygen atom. , Sulfur atom or CRcRd, and X 2 is preferably an oxygen atom, a sulfur atom or CRcRd.
　本発明の一態様において、発明化合物（２）は下記式（２ｂ）で表される。
Figure JPOXMLDOC01-appb-C000057
 In one aspect of the present invention, the compound (2) of the invention is represented by the following formula (2b).
Figure JPOXMLDOC01-appb-C000057
　Ｘ１、Ｘ２、Ｒ５０～Ｒ５７、Ｒ６０～Ｒ６７、＊ｃ、＊ｄ、及びＬ１～Ｌ３は式（２）及び（２ａ）で定義したとおりである。
　Ｘ３は酸素原子、硫黄原子、ＣＲｅＲｆ、又は＊ｅに結合する窒素原子、好ましくは酸素原子、硫黄原子、又はＣＲｅＲｆ、更に好ましくはＣＲｅＲｆである。Ｘ３が酸素原子、硫黄原子、又はＣＲｅＲｆである場合、Ｒ７０～Ｒ７３の１つが＊ｅに結合する単結合である。
　Ｒ７４～Ｒ７７及び＊ｅに結合する単結合ではないＲ７０～Ｒ７３は、それぞれ独立して、式（２）のＲ５４～Ｒ５７及び＊ｃに結合する単結合ではないＲ５０～Ｒ５３と同様に定義される。本発明の一態様においては、Ｒ５４～Ｒ５７、＊ｃに結合する単結合ではないＲ５０～Ｒ５３、Ｒ６４～Ｒ６７、＊ｄに結合する単結合ではないＲ６０～Ｒ６３、Ｒ７４～Ｒ７７、及び＊ｅに結合する単結合ではないＲ７０～Ｒ７３はすべて水素原子であることが好ましい。
　Ｒｅ及びＲｆは、それぞれ独立して、式（２）のＲａ及びＲｂと同様に定義される。 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. When 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 . In one embodiment of the present invention, R 54 to R 57 , R 50 to R 53 which is not a single bond bound to * c, R 64 to R 67 , R 60 to R 63 which is not a single bond bound to * d, It is preferable that R 74 to R 77 and R 70 to R 73 which are not a single bond bonding to * e are all hydrogen atoms.
Re and Rf are each independently defined similarly to Ra and Rb in the formula (2).
　本発明の一態様において、式（２）の化合物は、中心窒素原子に直接又はリンカーを介して結合する９－カルバゾリル基を１個だけ有することが好ましい。 In one aspect of the present invention, the compound of formula (2) preferably has only one 9-carbazolyl group bonded to the central nitrogen atom directly or via a linker.
　発明化合物（２）の具体例としては、例えば、式（２）において、下記式で表される基が、
Figure JPOXMLDOC01-appb-C000058
 Specific examples of the invention compound (2) include, for example, a group represented by the following formula in the formula (2):
Figure JPOXMLDOC01-appb-C000058
下記グループＡの式Ａ１～Ａ２７から選ばれる基であり、Ａｒ１－Ｌ１－が下記グループＢの式Ｂ１～Ｂ２９から選ばれる基であり、－Ｌ２－Ａｒ２が下記グループＣの式Ｃ１～Ｃ１５から選ばれる基である化合物が挙げられるが、これらに限定されるものではない。 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, and -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.
グループＡ
Figure JPOXMLDOC01-appb-C000059
 Group A
Figure JPOXMLDOC01-appb-C000059
グループＢ
Figure JPOXMLDOC01-appb-C000060
 Group B
Figure JPOXMLDOC01-appb-C000060
グループＣ
Figure JPOXMLDOC01-appb-C000061
 Group C
Figure JPOXMLDOC01-appb-C000061
　上記各基において、“＊”は中心窒素原子への結合位置を表す。 ”In each of the above groups,“ * ”represents the bonding position to the central nitrogen atom.
　発明化合物（２）は天然由来の重水素原子を含んでいてもよいし、式（２）又はその好ましい態様の式で表される化合物であって、該化合物に含まれる水素原子の少なくとも一つが重水素原子である化合物であってもよい。 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.
　発明化合物（２）は、当業者であれば、目的物に対応する原料化合物を既知の合成反応及びそれを変更した合成反応を用いて反応させることにより得ることができる。 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.
　本明細書において、「置換もしくは無置換」というときの任意の置換基は、特に断らない限り、ハロゲン原子；シアノ基；ニトロ基；炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基；環形成炭素数３～３０、好ましくは３～１０、より好ましくは３～８、さらに好ましくは５又は６のシクロアルキル基；環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリール基；炭素数７～３６、好ましくは７～２６、より好ましくは７～２０のアラルキル基；炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルコキシ基；環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリールオキシ基；炭素数１～３０、好ましくは１～１８、より好ましくは１～８のアルキル基及び環形成炭素数６～３０、好ましくは６～２５、より好ましくは６～１８のアリール基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基；炭素数１～３０、好ましくは１～１８、より好ましくは１～８ハロアルキル基；炭素数１～３０、好ましくは１～１８、より好ましくは１～８のハロアルコキシ基；及び、環形成原子数５～３０、好ましくは５～２４、より好ましくは５～１３のヘテロアリール基からなる群より選ばれる。
　上記任意の置換基は、好ましくは置換もしくは無置換の炭素数１～３０のアルキル基、置換もしくは無置換の環形成炭素数３～３０のシクロアルキル基、置換もしくは無置換の環形成炭素数６～３０のアリール基、置換もしくは無置換の炭素数１～３０のアルキル基及び置換もしくは無置換の環形成炭素数６～３０のアリール基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基、及び、置換もしくは無置換の環形成原子数５～３０のヘテロアリール基からなる群から選ばれ；より好ましくは置換もしくは無置換の炭素数１～３０のアルキル基、置換もしくは無置換の環形成炭素数６～３０のアリール基、及び、置換もしくは無置換の環形成原子数５～３０のヘテロアリール基からなる群から選ばれ；更に好ましくは置換もしくは無置換の炭素数１～３０のアルキル基又は置換もしくは無置換の環形成炭素数６～３０のアリール基であり、特に好ましくは置換もしくは無置換の炭素数１～３０のアルキル基である。
　上記任意の置換基の詳細は、式（１）のＲ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４に関して上記した対応する置換基の詳細と同じである。 In the present specification, 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. -8 alkyl group; 3-30 ring-forming carbon atoms, preferably 3-10, more preferably 3-8, more preferably 5 or 6 cycloalkyl group; 6-30 ring-forming carbon atoms, preferably 6- 25, more preferably 6-18 aryl group; 7-36 carbon atoms, preferably 7-26 carbon atoms, more preferably 7-20 aralkyl group; 1-30 carbon atoms, preferably 1-18 carbon atoms, more preferably 1 An alkoxy group having 8 to 8 carbon atoms; an aryloxy group having 6 to 30 ring-forming carbon atoms, preferably 6 to 25 carbon atoms, more preferably 6 to 18 carbon atoms; 1 to 30 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms. A A mono-, di-, or tri-substituted silyl group having a substituent selected from an aryl group having 6 to 30, preferably 6 to 25, and more preferably 6 to 18 ring-forming carbon atoms, and 1 to 30, preferably 1 to 30 carbon atoms. 1-18, more preferably 1-8 haloalkyl group; 1-30 carbon atoms, preferably 1-18, more preferably 1-8 haloalkoxy group; and 5-30 ring-forming atoms, preferably 5- 24, more preferably 5 to 13 heteroaryl groups.
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. Mono-, di-, or tri-substituted silyl group having a substituent selected from an aryl group having 30 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms And a substituted or unsubstituted heteroaryl group having 5 to 30 ring-forming atoms; more preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted ring formation It is selected from the group consisting of aryl groups having 6 to 30 carbon atoms and substituted or unsubstituted heteroaryl groups having 5 to 30 ring atoms; more preferably substituted or unsubstituted. A conversion aryl alkyl group or a substituted or unsubstituted ring carbon atoms 6 to 30 of 1 to 30 carbon atoms, particularly preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
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.
　以下、有機ＥＬ素子構成について説明する。
　有機ＥＬ素子は、陰極、陽極、及び、陰極と陽極の間に有機層を含む。該有機層は発光層及び該陽極と該発光層の間に配置された正孔輸送帯域を含む。該正孔輸送帯域は陽極側の第１正孔輸送層と陰極側の第２正孔輸送層を含み、該第１正孔輸送層及び該第２正孔輸送層の一方が前記式（１）で表される化合物を含み、他方が前記式（２）で表される化合物を含む。 The configuration of the organic EL element will be described below.
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).
　例えば、シンプル型有機ＥＬ素子の代表的な素子構成としては、以下の素子構成を挙げることができる。
（１）陽極／発光ユニット／陰極
　また、上記発光ユニットは、燐光発光層や蛍光発光層を複数有する積層型であってもよく、その場合、各発光層の間に、燐光発光層で生成された励起子が蛍光発光層に拡散することを防ぐ目的で、スペース層を有していてもよい。シンプル型発光ユニットの代表的な層構成を以下に示す。括弧内の層は任意である。
（ａ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／蛍光発光層（／電子輸送層／電子注入層）
（ｂ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／燐光発光層（／電子輸送層／電子注入層）
（ｃ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／第１蛍光発光層／第２蛍光発光層（／電子輸送層／電子注入層）
（ｄ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／第１燐光発光層／第２燐光発光層（／電子輸送層／電子注入層）
（ｅ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／燐光発光層／スペース層／蛍光発光層（／電子輸送層／電子注入層）
（ｆ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／第１燐光発光層／第２燐光発光層／スペース層／蛍光発光層（／電子輸送層／電子注入層）
（ｇ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層層／第１燐光発光層／スペース層／第２燐光発光層／スペース層／蛍光発光層（／電子輸送層／電子注入層）
（ｈ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／燐光発光層／スペース層／第１蛍光発光層／第２蛍光発光層（／電子輸送層／電子注入層）
（ｉ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／電子阻止層／蛍光発光層（／電子輸送層／電子注入層）
（ｊ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／電子阻止層／燐光発光層（／電子輸送層／電子注入層）
（ｋ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／励起子阻止層／蛍光発光層（／電子輸送層／電子注入層）
（ｌ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／励起子阻止層／燐光発光層（／電子輸送層／電子注入層）
（ｍ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／蛍光発光層／第１電子輸送層／第２電子輸送層（／電子注入層）
（ｎ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／燐光発光層／第１電子輸送層／第２電子輸送層（／電子注入層）
（ｏ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／蛍光発光層／正孔阻止層（／電子輸送層／電子注入層）
（ｐ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／燐光発光層／正孔阻止層（／電子輸送層／電子注入層）
（ｑ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／蛍光発光層／励起子阻止層（／電子輸送層／電子注入層）
（ｒ）（正孔注入層／）第１正孔輸送層／第２正孔輸送層／燐光発光層／励起子阻止層（／電子輸送層／電子注入層） For example, the following element configuration can be given as a typical element configuration of a simple organic EL element.
(1) Anode / Light-Emitting Unit / Cathode 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 / first phosphorescent light emitting layer / second phosphorescent light emitting layer / space layer / fluorescent light emitting layer (/ electron transport layer / electron injection) layer)
(G) (hole injecting layer /) first hole transporting layer / second hole transporting layer / first phosphorescent emitting layer / space layer / second phosphorescent emitting layer / space layer / fluorescent emitting layer (/ electron transporting) Layer / electron injection layer)
(H) (hole injecting layer /) first hole transporting layer / second hole transporting layer / phosphorescent emitting layer / space layer / first fluorescent emitting layer / second fluorescent emitting layer (/ electron transporting layer / electron injecting layer) layer)
(I) (hole injection layer /) first hole transport layer / second hole transport layer / electron blocking layer / fluorescent light emitting layer (/ electron transport layer / electron injection layer)
(J) (hole injection layer /) first hole transport layer / second hole transport layer / electron blocking layer / phosphorescent emitting layer (/ electron transport layer / electron injection layer)
(K) (hole injection layer /) first hole transport layer / second hole transport layer / exciton blocking layer / fluorescent emission layer (/ electron transport layer / electron injection layer)
(L) (hole injecting layer /) first hole transporting layer / second hole transporting layer / exciton blocking layer / phosphorescent emitting layer (/ electron transporting layer / electron injecting layer)
(M) (hole injection layer /) first hole transport layer / second hole transport layer / fluorescent light emitting layer / first electron transport layer / second electron transport layer (/ electron injection layer)
(N) (hole injection layer /) first hole transport layer / second hole transport layer / phosphorescent light emitting layer / first electron transport layer / second electron transport layer (/ electron injection layer)
(O) (hole injection layer /) first hole transport layer / second hole transport layer / fluorescent emission layer / hole blocking layer (/ electron transport layer / electron injection layer)
(P) (hole injecting layer /) first hole transporting layer / second hole transporting layer / phosphorescent emitting layer / hole blocking layer (/ electron transporting layer / electron injecting layer)
(Q) (hole injection layer /) first hole transport layer / second hole transport layer / fluorescent emission layer / exciton blocking layer (/ electron transport layer / electron injection layer)
(R) (hole injection layer /) first hole transport layer / second hole transport layer / phosphorescence emitting layer / exciton blocking layer (/ electron transport layer / electron injection layer)
　上記各燐光又は蛍光発光層は、それぞれ互いに異なる発光色を示すものとすることができる。具体的には、上記積層発光ユニット（ｆ）において、（正孔注入層／）第１正孔輸送層／第２正孔輸送層／第１燐光発光層（赤色発光）／第２燐光発光層（緑色発光）／スペース層／蛍光発光層（青色発光）／電子輸送層といった層構成等が挙げられる。
　なお、各発光層と第２正孔輸送層あるいはスペース層との間には、適宜、電子阻止層を設けてもよい。また、各発光層と電子輸送層との間には、適宜、正孔阻止層を設けてもよい。電子阻止層や正孔阻止層を設けることで、電子又は正孔を発光層内に閉じ込めて、発光層における正孔と電子の再結合を容易にし、発光効率を向上させることができる。 Each of the phosphorescent or fluorescent light emitting layers may have a different emission color. Specifically, in the laminated light emitting unit (f), (hole injection layer /) first hole transport layer / second hole transport layer / first phosphorescent light emitting layer (red light emitting) / second phosphorescent light emitting layer (Green emission) / space layer / fluorescent emission layer (blue emission) / electron transport layer.
An electron blocking layer may be appropriately provided between each light emitting layer and the second hole transport layer or the space layer. Further, a hole blocking layer may be appropriately provided between each light emitting layer and the electron transport layer. By providing the electron blocking layer or the hole blocking layer, it is possible to confine electrons or holes in the light emitting layer, facilitate recombination of holes and electrons in the light emitting layer, and improve light emission efficiency.
　タンデム型有機ＥＬ素子の代表的な素子構成としては、以下の素子構成を挙げることができる。
（２）陽極／第１発光ユニット／中間層／第２発光ユニット／陰極
　ここで、上記第１発光ユニット及び第２発光ユニットとしては、例えば、それぞれ独立に上述の発光ユニットから選択することができる。
　上記中間層は、一般的に、中間電極、中間導電層、電荷発生層、電子引抜層、接続層、中間絶縁層とも呼ばれ、第１発光ユニットに電子を、第２発光ユニットに正孔を供給する、公知の材料構成を用いることができる。 The following element configurations can be given as typical element configurations of the tandem type organic EL element.
(2) Anode / first light emitting unit / intermediate layer / second light emitting unit / cathode Here, 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.
　図１に、本発明の有機ＥＬ素子の構成の一例を示す概略図である。有機ＥＬ素子１は、基板２、陽極３、陰極４、及び該陽極３と陰極４との間に配置された発光ユニット１０とを有する。発光ユニット１０は、発光層５を有する。発光層５と陽極３との間に正孔輸送帯域６（正孔注入層、正孔輸送層等）、発光層５と陰極４との間に電子輸送帯域７（電子注入層、電子輸送層等）を有する。前記正孔輸送帯域６は、陽極側の第１正孔輸送層と発光層側の第２正孔輸送層を含む。また、発光層５の陽極３側に電子阻止層（図示せず）を、発光層５の陰極４側に正孔阻止層（図示せず）を、それぞれ設けてもよい。これにより、電子や正孔を発光層５に閉じ込めて、発光層５における励起子の生成をさらに容易にすることができる。 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. Further, 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.
　図２は、本発明の有機ＥＬ素子の他の構成を示す概略図である。有機ＥＬ素子１１は、基板２、陽極３、陰極４、及び該陽極３と陰極４との間に配置された発光ユニット２０とを有する。発光ユニット２０は、発光層５を有する。陽極３と発光層５の間に配置された正孔輸送帯域は、第１正孔輸送層６ａ及び第２正孔輸送層６ｂから形成されている。また、発光層５と陰極４の間に配置された電子輸送帯域は、第１電子輸送層７ａ及び第２電子輸送層７ｂから形成されている。 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. Further, 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.
　なお、本発明において、蛍光ドーパント（蛍光発光材料）と組み合わされたホストを蛍光ホストと称し、燐光ドーパントと組み合わされたホストを燐光ホストと称する。蛍光ホストと燐光ホストは分子構造のみにより区分されるものではない。すなわち、燐光ホストとは、燐光ドーパントを含有する燐光発光層を形成する材料を意味し、蛍光発光層を形成する材料として利用できないことを意味しているわけではない。蛍光ホストについても同様である。 In the present invention, a host combined with a fluorescent dopant (fluorescent material) is called a fluorescent host, and 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.
基板
　基板は、有機ＥＬ素子の支持体として用いられる。基板としては、例えば、ガラス、石英、プラスチックなどの板を用いることができる。また、可撓性基板を用いてもよい。可撓性基板としては、例えば、ポリカーボネート、ポリアリレート、ポリエーテルスルフォン、ポリプロピレン、ポリエステル、ポリフッ化ビニル、ポリ塩化ビニルからなるプラスチック基板等が挙げられる。また、無機蒸着フィルムを用いることもできる。 Substrate The substrate is used as a support for the organic EL device. As the substrate, for example, a plate made of glass, quartz, plastic, or the like can be used. Alternatively, a flexible substrate may be used. Examples of the flexible substrate include plastic substrates made of polycarbonate, polyarylate, polyether sulfone, polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, and the like. Also, an inorganic vapor deposition film can be used.
陽極
　基板上に形成される陽極には、仕事関数の大きい（具体的には４．０ｅＶ以上）金属、合金、電気伝導性化合物、およびこれらの混合物などを用いることが好ましい。具体的には、例えば、酸化インジウム－酸化スズ（ＩＴＯ：Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ）、珪素若しくは酸化珪素を含有した酸化インジウム－酸化スズ、酸化インジウム－酸化亜鉛、酸化タングステンおよび酸化亜鉛を含有した酸化インジウム、グラフェン等が挙げられる。この他、金（Ａｕ）、白金（Ｐｔ）、ニッケル（Ｎｉ）、タングステン（Ｗ）、クロム（Ｃｒ）、モリブデン（Ｍｏ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、銅（Ｃｕ）、パラジウム（Ｐｄ）、チタン（Ｔｉ）、または前記金属の窒化物（例えば、窒化チタン）等が挙げられる。 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). Specifically, for example, 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. In addition, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium ( Examples thereof include Pd), titanium (Ti), and nitrides of the above metals (for example, titanium nitride).
　これらの材料は、通常、スパッタリング法により成膜される。例えば、酸化インジウム－酸化亜鉛は、酸化インジウムに対し１～１０ｗｔ％の酸化亜鉛を加えたターゲットを、酸化タングステンおよび酸化亜鉛を含有した酸化インジウムは、酸化インジウムに対し酸化タングステンを０．５～５ｗｔ％、酸化亜鉛を０．１～１ｗｔ％含有したターゲットを用いることにより、スパッタリング法で形成することができる。その他、真空蒸着法、塗布法、インクジェット法、スピンコート法などにより作製してもよい。 -These materials are usually formed by a sputtering method. For example, 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.
　陽極に接して形成される正孔注入層は、陽極の仕事関数に関係なく正孔注入が容易である材料を用いて形成されるため、電極材料として一般的に使用される材料（例えば、金属、合金、電気伝導性化合物、およびこれらの混合物、元素周期表の第１族または第２族に属する元素）を用いることができる。
　仕事関数の小さい材料である、元素周期表の第１族または第２族に属する元素、すなわちリチウム（Ｌｉ）やセシウム（Ｃｓ）等のアルカリ金属、およびマグネシウム（Ｍｇ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）等のアルカリ土類金属、およびこれらを含む合金（例えば、ＭｇＡｇ、ＡｌＬｉ）、ユーロピウム（Ｅｕ）、イッテルビウム（Ｙｂ）等の希土類金属およびこれらを含む合金等を用いることもできる。なお、アルカリ金属、アルカリ土類金属、およびこれらを含む合金を用いて陽極を形成する場合には、真空蒸着法やスパッタリング法を用いることができる。さらに、銀ペーストなどを用いる場合には、塗布法やインクジェット法などを用いることができる。 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 It is also possible to use 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. Note that when the anode is formed using an alkali metal, an alkaline earth metal, or an alloy containing these, a vacuum evaporation method or a sputtering method can be used. Furthermore, when silver paste or the like is used, a coating method, an inkjet method, or the like can be used.
正孔注入層
　正孔注入層は、正孔注入性の高い材料（正孔注入性材料）を含む層であり、陽極と第１正孔輸送層の間に必要に応じて形成される。 Hole Injection Layer 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.
　正孔注入性材料としては、モリブデン酸化物、チタン酸化物、バナジウム酸化物、レニウム酸化物、ルテニウム酸化物、クロム酸化物、ジルコニウム酸化物、ハフニウム酸化物、タンタル酸化物、銀酸化物、タングステン酸化物、マンガン酸化物等を用いることができる。 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.
　低分子の有機化合物である４，４’，４’’－トリス（Ｎ，Ｎ－ジフェニルアミノ）トリフェニルアミン（略称：ＴＤＡＴＡ）、４，４’，４’’－トリス［Ｎ－（３－メチルフェニル）－Ｎ－フェニルアミノ］トリフェニルアミン（略称：ＭＴＤＡＴＡ）、４，４’－ビス［Ｎ－（４－ジフェニルアミノフェニル）－Ｎ－フェニルアミノ］ビフェニル（略称：ＤＰＡＢ）、４，４’－ビス（Ｎ－｛４－［Ｎ’－（３－メチルフェニル）－Ｎ’－フェニルアミノ］フェニル｝－Ｎ－フェニルアミノ）ビフェニル（略称：ＤＮＴＰＤ）、１，３，５－トリス［Ｎ－（４－ジフェニルアミノフェニル）－Ｎ－フェニルアミノ］ベンゼン（略称：ＤＰＡ３Ｂ）、３－［Ｎ－（９－フェニルカルバゾール－３－イル）－Ｎ－フェニルアミノ］－９－フェニルカルバゾール（略称：ＰＣｚＰＣＡ１）、３，６－ビス［Ｎ－（９－フェニルカルバゾール－３－イル）－Ｎ－フェニルアミノ］－９－フェニルカルバゾール（略称：ＰＣｚＰＣＡ２）、３－［Ｎ－（１－ナフチル）－Ｎ－（９－フェニルカルバゾール－３－イル）アミノ］－９－フェニルカルバゾール（略称：ＰＣｚＰＣＮ１）等の芳香族アミン化合物等も正孔注入層材料として挙げられる。 4,4 ′, 4 ″ -tris (N, N-diphenylamino) triphenylamine (abbreviation: TDATA), which is a low molecular weight organic compound, 4,4 ′, 4 ″ -tris [N- (3- Methylphenyl) -N-phenylamino] triphenylamine (abbreviation: MTDATA), 4,4′-bis [N- (4-diphenylaminophenyl) -N-phenylamino] biphenyl (abbreviation: DPAB), 4,4 '-Bis (N- {4- [N'-(3-methylphenyl) -N'-phenylamino] phenyl} -N-phenylamino) biphenyl (abbreviation: DNTPD), 1,3,5-tris [N -(4-Diphenylaminophenyl) -N-phenylamino] benzene (abbreviation: DPA3B), 3- [N- (9-phenylcarbazol-3-yl) -N-phenylamino] -9- Phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis [N- (9-phenylcarbazol-3-yl) -N-phenylamino] -9-phenylcarbazole (abbreviation: PCzPCA2), 3- [N- (1 Aromatic amine compounds such as -naphthyl) -N- (9-phenylcarbazol-3-yl) amino] -9-phenylcarbazole (abbreviation: PCzPCN1) and the like can also be used as the hole injection layer material.
　高分子化合物（オリゴマー、デンドリマー、ポリマー等）を用いることもできる。例えば、ポリ（Ｎ－ビニルカルバゾール）（略称：ＰＶＫ）、ポリ（４－ビニルトリフェニルアミン）（略称：ＰＶＴＰＡ）、ポリ［Ｎ－（４－｛Ｎ’－［４－（４－ジフェニルアミノ）フェニル］フェニル－Ｎ’－フェニルアミノ｝フェニル）メタクリルアミド］（略称：ＰＴＰＤＭＡ）、ポリ［Ｎ，Ｎ’－ビス（４－ブチルフェニル）－Ｎ，Ｎ’－ビス（フェニル）ベンジジン］（略称：Ｐｏｌｙ－ＴＰＤ）などの高分子化合物が挙げられる。また、ポリ（３，４－エチレンジオキシチオフェン）／ポリ（スチレンスルホン酸）（ＰＥＤＯＴ／ＰＳＳ）、ポリアニリン／ポリ（スチレンスルホン酸）（ＰＡｎｉ／ＰＳＳ）等の酸を添加した高分子化合物を用いることもできる。 High molecular compounds (oligomers, dendrimers, polymers, etc.) can also be used. For example, poly (N-vinylcarbazole) (abbreviation: PVK), poly (4-vinyltriphenylamine) (abbreviation: PVTPA), poly [N- (4- {N '-[4- (4-diphenylamino)) Phenyl] phenyl-N'-phenylamino} phenyl) methacrylamide] (abbreviation: PTPDMA), poly [N, N'-bis (4-butylphenyl) -N, N'-bis (phenyl) benzidine] (abbreviation: Polymer compounds such as Poly-TPD) are included. Further, 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. You can also
　さらに、下記式（Ｋ）で表されるヘキサアザトリフェニレン（ＨＡＴ）化合物などのアクセプター材料も正孔注入層材料として好ましい。
Figure JPOXMLDOC01-appb-C000062
 Further, an acceptor material such as a hexaazatriphenylene (HAT) compound represented by the following formula (K) is also preferable as the hole injection layer material.
Figure JPOXMLDOC01-appb-C000062
　上記式中、Ｒ２１～Ｒ２６は、それぞれ独立にシアノ基、－ＣＯＮＨ２、カルボキシル基、又は－ＣＯＯＲ２７（Ｒ２７は炭素数１～２０のアルキル基又は炭素数３～２０のシクロアルキル基を表す）を表す。ただし、Ｒ２１及びＲ２２、Ｒ２３及びＲ２４、又はＲ２５及びＲ２６は互いに結合して－ＣＯ－Ｏ－ＣＯ－で示される基を形成してもよい。
　Ｒ２７としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。 In the above formula, 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). However, 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—.
Examples of R 27 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.
正孔輸送層
　正孔輸送層は、正孔輸送性の高い材料（正孔輸送性材料）を含む層であり、陽極と発光層の間、正孔注入層を形成した場合は、正孔注入層と発光層の間に形成される。
　本発明の有機ＥＬ素子の正孔輸送層は、陽極側の第１正孔輸送層と陰極側（発光層側）の第２正孔輸送層を含む多層構造であり、該第１正孔輸送層と該第２正孔輸送層の一方が発明化合物（１）、他方が発明化合物（２）を含む。ただし、発明化合物（１）と発明化合物（２）は異なる化合物である。
　第２正孔輸送層は発光層に隣接していてもよく、又、第２正孔輸送層と発光層の間に後述する阻止層などを介在させてもよい。
　本発明の一態様においては、第１正孔輸送層が発明化合物（１）を含み、第２正孔輸送層が発明化合物（２）を含む。他の態様においては、第１正孔輸送層が発明化合物（２）を含み、第２正孔輸送層が発明化合物（１）を含む。 Hole Transport Layer 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). However, 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.
In one aspect of the present invention, the first hole transport layer contains the invention compound (1) and the second hole transport layer contains the invention compound (2). In another embodiment, the first hole transport layer contains the invention compound (2) and the second hole transport layer contains the invention compound (1).
　本発明の一態様において、前記第１正孔輸送層と前記第２正孔輸送層の一方に含まれる発明化合物（１）は、製造コストの観点から、軽水素体（１）であることが好ましく、他方に含まれる発明化合物（２）は軽水素体（２）であることが好ましい。
　前記軽水素体（１）とは、式（１）中の全ての水素原子が軽水素原子である発明化合物（１）のことであり、前記軽水素体（２）とは、式（２）中の全ての水素原子が軽水素原子である発明化合物（２）のことである。
　従って、本発明は、前記第１正孔輸送層と前記第２正孔輸送層の一方が実質的に軽水素体（１）のみからなる発明化合物（１）を含み、他方が実質的に軽水素体（２）のみからなる発明化合物（２）を含む有機ＥＬ素子を含む。「実質的に軽水素体（１）のみからなる発明化合物（１）」とは、式（１）で表される化合物の総量に対する軽水素体（１）の含有割合が、９０モル％以上、好ましくは９５モル％以上、より好ましくは９９モル％以上（それぞれ１００％を含む）であることを意味する。「実質的に軽水素体（２）のみからなる発明化合物（２）」とは、式（２）で表される化合物の総量に対する軽水素体（２）の含有割合が、９０モル％以上、好ましくは９５モル％以上、より好ましくは９９モル％以上（それぞれ１００％を含む）であることを意味する。 In one aspect of the present invention, 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). The "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). The "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).
　発明化合物（１）及び（２）以外の第１正孔輸送層材料又は第２正孔輸送層材料として、例えば、芳香族アミン化合物、カルバゾール誘導体、アントラセン誘導体等を使用してもよい。
　芳香族アミン化合物としては、例えば、４，４’－ビス［Ｎ－（１－ナフチル）－Ｎ－フェニルアミノ］ビフェニル（略称：ＮＰＢ）やＮ，Ｎ’－ビス（３－メチルフェニル）－Ｎ，Ｎ’－ジフェニル－［１，１’－ビフェニル］－４，４’－ジアミン（略称：ＴＰＤ）、４－フェニル－４’－（９－フェニルフルオレン－９－イル）トリフェニルアミン（略称：ＢＡＦＬＰ）、４，４’－ビス［Ｎ－（９，９－ジメチルフルオレン－２－イル）－Ｎ－フェニルアミノ］ビフェニル（略称：ＤＦＬＤＰＢｉ）、４，４’，４”－トリス（Ｎ，Ｎ－ジフェニルアミノ）トリフェニルアミン（略称：ＴＤＡＴＡ）、４，４’，４”－トリス［Ｎ－（３－メチルフェニル）－Ｎ－フェニルアミノ］トリフェニルアミン（略称：ＭＴＤＡＴＡ）、及び、４，４’－ビス［Ｎ－（スピロ－９，９’－ビフルオレン－２－イル）－Ｎ―フェニルアミノ］ビフェニル（略称：ＢＳＰＢ）が挙げられる。上記化合物は、１０－６ｃｍ２／Ｖｓ以上の正孔移動度を有する。 As the first hole transport layer material or the second hole transport layer material other than the invention compounds (1) and (2), for example, an aromatic amine compound, a carbazole derivative, an anthracene derivative or the like may be used.
Examples of 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, N -Diphenylamino) triphenylamine (abbreviation: TDATA), 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (abbreviation: MTDATA), and 4, 4'-bi And spu [N- (spiro-9,9′-bifluoren-2-yl) -N-phenylamino] biphenyl (abbreviation: BSPB). The above compound has a hole mobility of 10 −6 cm 2 / Vs or higher.
　カルバゾール誘導体としては、例えば、４，４’－ジ（９－カルバゾリル）ビフェニル（略称：ＣＢＰ）、９－［４－（９－カルバゾリル）フェニル］－１０－フェニルアントラセン（略称：ＣｚＰＡ）、及び、９－フェニル－３－［４－（１０－フェニル－９－アントリル）フェニル］－９Ｈ－カルバゾール（略称：ＰＣｚＰＡ）が挙げられる。
　アントラセン誘導体としては、例えば、２－ｔ－ブチル－９，１０－ジ（２－ナフチル）アントラセン（略称：ｔ－ＢｕＤＮＡ）、９，１０－ジ（２－ナフチル）アントラセン（略称：ＤＮＡ）、及び、９，１０－ジフェニルアントラセン（略称：ＤＰＡｎｔｈ）が挙げられる。
　ポリ（Ｎ－ビニルカルバゾール）（略称：ＰＶＫ）やポリ（４－ビニルトリフェニルアミン）（略称：ＰＶＴＰＡ）等の高分子化合物を用いることもできる。
　但し、電子輸送性よりも正孔輸送性の方が高い化合物であれば、上記以外の化合物を用いてもよい。 Examples of the carbazole derivative 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.
Examples of the anthracene derivative 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.
However, compounds other than the above may be used as long as the compounds have a hole transporting property higher than an electron transporting property.
発光層のドーパント材料
　発光層は、発光性の高い材料（ドーパント材料）を含む層であり、種々の材料を用いることができる。例えば、蛍光発光材料や燐光発光材料をドーパント材料として用いることができる。蛍光発光材料は一重項励起状態から発光する化合物であり、燐光発光材料は三重項励起状態から発光する化合物である。 Dopant Material for Light-Emitting Layer The light-emitting layer is a layer containing a material having a high light-emitting property (dopant material), and various materials can be used. For example, 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, and a phosphorescent material is a compound that emits light from a triplet excited state.
　発光層に用いることができる青色系の蛍光発光材料として、ピレン誘導体、スチリルアミン誘導体、クリセン誘導体、フルオランテン誘導体、フルオレン誘導体、ジアミン誘導体、トリアリールアミン誘導体等が使用できる。具体的には、Ｎ，Ｎ’－ビス［４－（９Ｈ－カルバゾール－９－イル）フェニル］－Ｎ，Ｎ’－ジフェニルスチルベン－４，４’－ジアミン（略称：ＹＧＡ２Ｓ）、４－（９Ｈ－カルバゾール－９－イル）－４’－（１０－フェニル－９－アントリル）トリフェニルアミン（略称：ＹＧＡＰＡ）、４－（１０－フェニル－９－アントリル）－４’－（９－フェニル－９Ｈ－カルバゾール－３－イル）トリフェニルアミン（略称：ＰＣＢＡＰＡ）などが挙げられる。 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. Specifically, 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) and the like.
　発光層に用いることができる緑色系の蛍光発光材料として、芳香族アミン誘導体等を使用できる。具体的には、Ｎ－（９，１０－ジフェニル－２－アントリル）－Ｎ，９－ジフェニル－９Ｈ－カルバゾール－３－アミン（略称：２ＰＣＡＰＡ）、Ｎ－［９，１０－ビス（１，１’－ビフェニル－２－イル）－２－アントリル］－Ｎ，９－ジフェニル－９Ｈ－カルバゾール－３－アミン（略称：２ＰＣＡＢＰｈＡ）、Ｎ－（９，１０－ジフェニル－２－アントリル）－Ｎ，Ｎ’，Ｎ’－トリフェニル－１，４－フェニレンジアミン（略称：２ＤＰＡＰＡ）、Ｎ－［９，１０－ビス（１，１’－ビフェニル－２－イル）－２－アントリル］－Ｎ，Ｎ’，Ｎ’－トリフェニル－１，４－フェニレンジアミン（略称：２ＤＰＡＢＰｈＡ）、Ｎ－［９，１０－ビス（１，１’－ビフェニル－２－イル）］－Ｎ－［４－（９Ｈ－カルバゾール－９－イル）フェニル］－Ｎ－フェニルアントラセン－２－アミン（略称：２ＹＧＡＢＰｈＡ）、Ｎ，Ｎ，９－トリフェニルアントラセン－９－アミン（略称：ＤＰｈＡＰｈＡ）などが挙げられる。 An aromatic amine derivative or the like can be used as a green fluorescent material that can be used for the light emitting layer. Specifically, N- (9,10-diphenyl-2-anthryl) -N, 9-diphenyl-9H-carbazol-3-amine (abbreviation: 2PCAPA), N- [9,10-bis (1,1) '-Biphenyl-2-yl) -2-anthryl] -N, 9-diphenyl-9H-carbazol-3-amine (abbreviation: 2PCABPhA), N- (9,10-diphenyl-2-anthryl) -N, N ', N'-Triphenyl-1,4-phenylenediamine (abbreviation: 2DPAPA), N- [9,10-bis (1,1'-biphenyl-2-yl) -2-anthryl] -N, N' , N'-triphenyl-1,4-phenylenediamine (abbreviation: 2DPABPhA), N- [9,10-bis (1,1'-biphenyl-2-yl)]-N- [4- (9H-carbazole -9-yl Phenyl] -N- phenyl-anthracene-2-amine (abbreviation: 2YGABPhA), N, N, 9- triphenylamine anthracene-9-amine (abbreviation: DPhAPhA), and the like.
　発光層に用いることができる赤色系の蛍光発光材料として、テトラセン誘導体、ジアミン誘導体等が使用できる。具体的には、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラキス（４－メチルフェニル）テトラセン－５，１１－ジアミン（略称：ｐ－ｍＰｈＴＤ）、７，１４－ジフェニル－Ｎ，Ｎ，Ｎ’，Ｎ’－テトラキス（４－メチルフェニル）アセナフト［１，２－ａ］フルオランテン－３，１０－ジアミン（略称：ｐ－ｍＰｈＡＦＤ）などが挙げられる。 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. Specifically, 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).
　発光層に用いることができる青色系の燐光発光材料として、イリジウム錯体、オスミウム錯体、白金錯体等の金属錯体が使用される。具体的には、ビス［２－（４’，６’－ジフルオロフェニル）ピリジナト－Ｎ，Ｃ２’］イリジウム（ＩＩＩ）テトラキス（１－ピラゾリル）ボラート（略称：ＦＩｒ６）、ビス［２－（４’，６’－ジフルオロフェニル）ピリジナト－Ｎ，Ｃ２’］イリジウム（ＩＩＩ）ピコリナート（略称：ＦＩｒｐｉｃ）、ビス［２－（３’，５’ビストリフルオロメチルフェニル）ピリジナト－Ｎ，Ｃ２’］イリジウム（ＩＩＩ）ピコリナート（略称：Ｉｒ（ＣＦ３ｐｐｙ）２（ｐｉｃ））、ビス［２－（４’，６’－ジフルオロフェニル）ピリジナト－Ｎ，Ｃ２’］イリジウム（ＩＩＩ）アセチルアセトナート（略称：ＦＩｒａｃａｃ）などが挙げられる。 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. Specifically, bis [2- (4 ′, 6′-difluorophenyl) pyridinato-N, C2 ′] iridium (III) tetrakis (1-pyrazolyl) borate (abbreviation: FIr6), bis [2- (4 ′ , 6′-Difluorophenyl) pyridinato-N, C2 ′] iridium (III) picolinate (abbreviation: FIrpic), bis [2- (3 ′, 5′bistrifluoromethylphenyl) pyridinato-N, C2 ′] iridium (III) ) Picolinate (abbreviation: Ir (CF3ppy) 2 (pic)), bis [2- (4 ′, 6′-difluorophenyl) pyridinato-N, C2 ′] iridium (III) acetylacetonate (abbreviation: FIracac), etc. Can be mentioned.
　発光層に用いることができる緑色系の燐光発光材料として、イリジウム錯体等が使用される。トリス（２－フェニルピリジナト－Ｎ，Ｃ２’）イリジウム（ＩＩＩ）（略称：Ｉｒ（ｐｐｙ）３）、ビス（２－フェニルピリジナト－Ｎ，Ｃ２’）イリジウム（ＩＩＩ）アセチルアセトナート（略称：Ｉｒ（ｐｐｙ）２（ａｃａｃ））、ビス（１，２－ジフェニル－１Ｈ－ベンゾイミダゾラト）イリジウム（ＩＩＩ）アセチルアセトナート（略称：Ｉｒ（ｐｂｉ）２（ａｃａｃ））、ビス（ベンゾ［ｈ］キノリナト）イリジウム（ＩＩＩ）アセチルアセトナート（略称：Ｉｒ（ｂｚｑ）２（ａｃａｃ））などが挙げられる。 An iridium complex or the like is used as a green phosphorescent material that can be used in the light emitting layer. Tris (2-phenylpyridinato-N, C2 ′) iridium (III) (abbreviation: Ir (ppy) 3), bis (2-phenylpyridinato-N, C2 ′) iridium (III) acetylacetonate ( Abbreviation: Ir (ppy) 2 (acac)), bis (1,2-diphenyl-1H-benzimidazolato) iridium (III) acetylacetonate (abbreviation: Ir (pbi) 2 (acac)), bis (benzo [ h] quinolinato) iridium (III) acetylacetonate (abbreviation: Ir (bzq) 2 (acac)) and the like.
　発光層に用いることができる赤色系の燐光発光材料として、イリジウム錯体、白金錯体、テルビウム錯体、ユーロピウム錯体等の金属錯体が使用される。具体的には、ビス［２－（２’－ベンゾ［４，５－α］チエニル）ピリジナト－Ｎ，Ｃ３’］イリジウム（ＩＩＩ）アセチルアセトナート（略称：Ｉｒ（ｂｔｐ）２（ａｃａｃ））、ビス（１－フェニルイソキノリナト－Ｎ，Ｃ２’）イリジウム（ＩＩＩ）アセチルアセトナート（略称：Ｉｒ（ｐｉｑ）２（ａｃａｃ））、（アセチルアセトナート）ビス［２，３－ビス（４－フルオロフェニル）キノキサリナト］イリジウム（ＩＩＩ）（略称：Ｉｒ（Ｆｄｐｑ）２（ａｃａｃ））、２，３，７，８，１２，１３，１７，１８－オクタエチル－２１Ｈ，２３Ｈ－ポルフィリン白金（ＩＩ）（略称：ＰｔＯＥＰ）等の有機金属錯体が挙げられる。 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. Specifically, bis [2- (2′-benzo [4,5-α] 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)), 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin platinum (II) (abbreviation) : PtOEP) and the like.
　また、トリス（アセチルアセトナート）（モノフェナントロリン）テルビウム（ＩＩＩ）（略称：Ｔｂ（ａｃａｃ）３（Ｐｈｅｎ））、トリス（１，３－ジフェニル－１，３－プロパンジオナト）（モノフェナントロリン）ユーロピウム（ＩＩＩ）（略称：Ｅｕ（ＤＢＭ）３（Ｐｈｅｎ））、トリス［１－（２－テノイル）－３，３，３－トリフルオロアセトナト］（モノフェナントロリン）ユーロピウム（ＩＩＩ）（略称：Ｅｕ（ＴＴＡ）３（Ｐｈｅｎ））等の希土類金属錯体は、希土類金属イオンからの発光（異なる多重度間の電子遷移）であるため、燐光発光材料として用いることができる。 In addition, 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.
発光層のホスト材料
　発光層は、上述したドーパント材料を他の材料（ホスト材料）に分散させた構成としてもよい。ドーパント材料よりも最低空軌道準位（ＬＵＭＯ準位）が高く、最高占有軌道準位（ＨＯＭＯ準位）が低い材料を用いることが好ましい。 Host Material of Light-Emitting Layer 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.
　ホスト材料としては、例えば
（１）アルミニウム錯体、ベリリウム錯体、又は亜鉛錯体等の金属錯体、
（２）オキサジアゾール誘導体、ベンゾイミダゾール誘導体、又はフェナントロリン誘導体等の複素環化合物、
（３）カルバゾール誘導体、アントラセン誘導体、フェナントレン誘導体、ピレン誘導体、又はクリセン誘導体等の縮合芳香族化合物、
（４）トリアリールアミン誘導体又は縮合多環芳香族アミン誘導体等の芳香族アミン化合物が使用される。 As the host material, for example, (1) a metal complex such as an aluminum complex, a beryllium complex, or a zinc complex,
(2) a heterocyclic compound such as an oxadiazole derivative, a benzimidazole derivative, or a phenanthroline derivative,
(3) a condensed aromatic compound such as a carbazole derivative, anthracene derivative, phenanthrene derivative, pyrene derivative, or chrysene derivative;
(4) An aromatic amine compound such as a triarylamine derivative or a condensed polycyclic aromatic amine derivative is used.
　例えば、トリス（８－キノリノラト）アルミニウム（ＩＩＩ）（略称：Ａｌｑ）、トリス（４－メチル－８－キノリノラト）アルミニウム（ＩＩＩ）（略称：Ａｌｍｑ３）、ビス（１０－ヒドロキシベンゾ［ｈ］キノリナト）ベリリウム（ＩＩ）（略称：ＢｅＢｑ２）、ビス（２－メチル－８－キノリノラト）（４－フェニルフェノラト）アルミニウム（ＩＩＩ）（略称：ＢＡｌｑ）、ビス（８－キノリノラト）亜鉛（ＩＩ）（略称：Ｚｎｑ）、ビス［２－（２－ベンゾオキサゾリル）フェノラト］亜鉛（ＩＩ）（略称：ＺｎＰＢＯ）、ビス［２－（２－ベンゾチアゾリル）フェノラト］亜鉛（ＩＩ）（略称：ＺｎＢＴＺ）などの金属錯体；
　２－（４－ビフェニリル）－５－（４－ｔｅｒｔ－ブチルフェニル）－１，３，４－オキサジアゾール（略称：ＰＢＤ）、１，３－ビス［５－（ｐ－ｔｅｒｔ－ブチルフェニル）－１，３，４－オキサジアゾール－２－イル］ベンゼン（略称：ＯＸＤ－７）、３－（４－ビフェニリル）－４－フェニル－５－（４－ｔｅｒｔ－ブチルフェニル）－１，２，４－トリアゾール（略称：ＴＡＺ）、２，２’，２’’－（１，３，５－ベンゼントリイル）トリス（１－フェニル－１Ｈ－ベンゾイミダゾール）（略称：ＴＰＢＩ）、バソフェナントロリン（略称：ＢＰｈｅｎ）、バソキュプロイン（略称：ＢＣＰ）などの複素環化合物；
　９－［４－（１０－フェニル－９－アントリル）フェニル］－９Ｈ－カルバゾール（略称：ＣｚＰＡ）、３，６－ジフェニル－９－［４－（１０－フェニル－９－アントリル）フェニル］－９Ｈ－カルバゾール（略称：ＤＰＣｚＰＡ）、９，１０－ビス（３，５－ジフェニルフェニル）アントラセン（略称：ＤＰＰＡ）、９，１０－ジ（２－ナフチル）アントラセン（略称：ＤＮＡ）、２－ｔｅｒｔ－ブチル－９，１０－ジ（２－ナフチル）アントラセン（略称：ｔ－ＢｕＤＮＡ）、９，９’－ビアントリル（略称：ＢＡＮＴ）、９，９’－（スチルベン－３，３’－ジイル）ジフェナントレン（略称：ＤＰＮＳ）、９，９’－（スチルベン－４，４’－ジイル）ジフェナントレン（略称：ＤＰＮＳ２）、３，３’，３’’－（ベンゼン－１，３，５－トリイル）トリピレン（略称：ＴＰＢ３）、９，１０－ジフェニルアントラセン（略称：ＤＰＡｎｔｈ）、６，１２－ジメトキシ－５，１１－ジフェニルクリセンなどの縮合芳香族化合物；及び
　Ｎ，Ｎ－ジフェニル－９－［４－（１０－フェニル－９－アントリル）フェニル］－９Ｈ－カルバゾール－３－アミン（略称：ＣｚＡ１ＰＡ）、４－（１０－フェニル－９－アントリル）トリフェニルアミン（略称：ＤＰｈＰＡ）、Ｎ，９－ジフェニル－Ｎ－［４－（１０－フェニル－９－アントリル）フェニル］－９Ｈ－カルバゾール－３－アミン（略称：ＰＣＡＰＡ）、Ｎ，９－ジフェニル－Ｎ－｛４－［４－（１０－フェニル－９－アントリル）フェニル］フェニル｝－９Ｈ－カルバゾール－３－アミン（略称：ＰＣＡＰＢＡ）、Ｎ－（９，１０－ジフェニル－２－アントリル）－Ｎ，９－ジフェニル－９Ｈ－カルバゾール－３－アミン（略称：２ＰＣＡＰＡ）、４，４’－ビス［Ｎ－（１－ナフチル）－Ｎ－フェニルアミノ］ビフェニル（略称：ＮＰＢまたはα－ＮＰＤ）、Ｎ，Ｎ’－ビス（３－メチルフェニル）－Ｎ，Ｎ’－ジフェニル－［１，１’－ビフェニル］－４，４’－ジアミン（略称：ＴＰＤ）、４，４’－ビス［Ｎ－（９，９－ジメチルフルオレン－２－イル）－Ｎ－フェニルアミノ］ビフェニル（略称：ＤＦＬＤＰＢｉ）、４，４’－ビス［Ｎ－（スピロ－９，９’－ビフルオレン－２－イル）－Ｎ―フェニルアミノ］ビフェニル（略称：ＢＳＰＢ）などの芳香族アミン化合物を用いることができる。ホスト材料は複数種用いてもよい。 For example, 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), and other metal complexes. ;
2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis [5- (p-tert-butylphenyl) -1,3,4-oxadiazol-2-yl] benzene (abbreviation: OXD-7), 3- (4-biphenylyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2 , 4-triazole (abbreviation: TAZ), 2,2 ′, 2 ″-(1,3,5-benzenetriyl) tris (1-phenyl-1H-benzimidazole) (abbreviation: TPBI), bathophenanthroline ( Abbreviation: BPhen), heterocyclic compounds such as bathocuproine (abbreviation: BCP);
9- [4- (10-phenyl-9-anthryl) phenyl] -9H-carbazole (abbreviation: CzPA), 3,6-diphenyl-9- [4- (10-phenyl-9-anthryl) phenyl] -9H -Carbazole (abbreviation: DPCzPA), 9,10-bis (3,5-diphenylphenyl) anthracene (abbreviation: DPPA), 9,10-di (2-naphthyl) anthracene (abbreviation: DNA), 2-tert-butyl -9,10-Di (2-naphthyl) anthracene (abbreviation: t-BuDNA), 9,9'-bianthryl (abbreviation: BANT), 9,9 '-(stilbene-3,3'-diyl) diphenanthrene ( Abbreviation: DPNS), 9,9 '-(Stilbene-4,4'-diyl) diphenanthrene (abbreviation: DPNS2), 3,3', 3 "-(benzene-1,3,5- Condensed aromatic compounds such as (lyl) tripyrene (abbreviation: TPB3), 9,10-diphenylanthracene (abbreviation: DPAnth), 6,12-dimethoxy-5,11-diphenylchrysene; and N, N-diphenyl-9- [ 4- (10-phenyl-9-anthryl) phenyl] -9H-carbazol-3-amine (abbreviation: CzA1PA), 4- (10-phenyl-9-anthryl) triphenylamine (abbreviation: DPhPA), N, 9 -Diphenyl-N- [4- (10-phenyl-9-anthryl) phenyl] -9H-carbazol-3-amine (abbreviation: PCAPA), N, 9-diphenyl-N- {4- [4- (10- Phenyl-9-anthryl) phenyl] phenyl} -9H-carbazol-3-amine (abbreviation: PCAPBA), N- (9, 0-diphenyl-2-anthryl) -N, 9-diphenyl-9H-carbazol-3-amine (abbreviation: 2PCAPA), 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl ( Abbreviation: NPB or α-NPD), N, N′-bis (3-methylphenyl) -N, N′-diphenyl- [1,1′-biphenyl] -4,4′-diamine (abbreviation: TPD), 4,4'-bis [N- (9,9-dimethylfluoren-2-yl) -N-phenylamino] biphenyl (abbreviation: DFLDPBi), 4,4'-bis [N- (spiro-9,9 ' An aromatic amine compound such as -bifluoren-2-yl) -N-phenylamino] biphenyl (abbreviation: BSPB) can be used. Plural kinds of host materials may be used.
　特に、青色蛍光素子の場合には、下記のアントラセン化合物をホスト材料として用いることが好ましい。 In particular, in the case of a blue fluorescent element, it is preferable to use the following anthracene compound as a host material.
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
電子輸送層
　電子輸送層は電子輸送性の高い材料（電子輸送性材料）を含む層である。電子輸送層には、例えば、
（１）アルミニウム錯体、ベリリウム錯体、亜鉛錯体等の金属錯体、
（２）イミダゾール誘導体、ベンゾイミダゾール誘導体、アジン誘導体、カルバゾール誘導体、フェナントロリン誘導体等の複素芳香族化合物、
（３）高分子化合物を使用することができる。 Electron Transport Layer The electron transport layer is a layer containing a material having a high electron transport property (electron transport material). In the electron transport layer, 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.
　金属錯体としては、例えば、トリス（８－キノリノラト）アルミニウム（ＩＩＩ）（略称：Ａｌｑ）、トリス（４－メチル－８－キノリノラト）アルミニウム（略称：Ａｌｍｑ３）、ビス（１０－ヒドロキシベンゾ［ｈ］キノリナト）ベリリウム（略称：ＢｅＢｑ2）、ビス（２－メチル－８－キノリノラト）（４－フェニルフェノラト）アルミニウム（ＩＩＩ）（略称：ＢＡｌｑ）、ビス（８－キノリノラト）亜鉛（ＩＩ）（略称：Ｚｎｑ）、ビス［２－（２－ベンゾオキサゾリル）フェノラト］亜鉛（ＩＩ）（略称：ＺｎＰＢＯ）、ビス［２－（２－ベンゾチアゾリル）フェノラト］亜鉛（ＩＩ）（略称：ＺｎＢＴＺ）が挙げられる。 Examples of the metal complex 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) (abbreviation: Znq) ), Bis [2- (2-benzoxazolyl) phenolato] zinc (II) (abbreviation: ZnPBO), and bis [2- (2-benzothiazolyl) phenolato] zinc (II) (abbreviation: ZnBTZ).
　複素芳香族化合物としては、例えば、２－（４－ビフェニリル）－５－（４－ｔｅｒｔ－ブチルフェニル）－１，３，４－オキサジアゾール（略称：ＰＢＤ）、１，３－ビス［５－（ｐｔｅｒｔ－ブチルフェニル）－１，３，４－オキサジアゾール－２－イル］ベンゼン（略称：ＯＸＤ－７）、３－（４－ｔｅｒｔ－ブチルフェニル）－４－フェニル－５－（４－ビフェニリル）－１，２，４－トリアゾール（略称：ＴＡＺ）、３－（４－ｔｅｒｔ－ブチルフェニル）－４－（４－エチルフェニル）－５－（４－ビフェニリル）－１，２，４－トリアゾール（略称：ｐ－ＥｔＴＡＺ）、バソフェナントロリン（略称：ＢＰｈｅｎ）、バソキュプロイン（略称：ＢＣＰ）、４，４’－ビス（５－メチルベンゾオキサゾール－２－イル）スチルベン（略称：ＢｚＯｓ）が挙げられる。 Examples of the heteroaromatic compound 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-methylbenzoxazol-2-yl) stille Emissions (abbreviation: BzOs), and the like.
　高分子化合物としては、例えば、ポリ［（９，９－ジヘキシルフルオレン－２，７－ジイル）－ｃｏ－（ピリジン－３，５－ジイル）］（略称：ＰＦ－Ｐｙ）、ポリ［（９，９－ジオクチルフルオレン－２，７－ジイル）－ｃｏ－（２，２’－ビピリジン－６，６’－ジイル）］（略称：ＰＦ－ＢＰｙ）が挙げられる。 Examples of the polymer compound 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).
　上記材料は、１０－６ｃｍ２／Ｖｓ以上の電子移動度を有する材料である。なお、正孔輸送性よりも電子輸送性の高い材料であれば、上記以外の材料を電子輸送層に用いてもよい。 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.
　電子輸送層は、単層でもよく、２以上の層を含む多層でもよい。例えば、電子輸送層は第１電子輸送層（陽極側）と第２電子輸送層（陰極側）を含む層であってもよい。２以上の電子輸送層は、それぞれ前記電子輸送性材料により形成される。 The electron transport layer may be a single layer or a multilayer including two or more layers. For example, 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.
電子注入層
　電子注入層は、電子注入性の高い材料を含む層である。電子注入層には、リチウム（Ｌｉ）、セシウム（Ｃｓ）、カルシウム（Ｃａ）、フッ化リチウム（ＬｉＦ）、フッ化セシウム（ＣｓＦ）、フッ化カルシウム（ＣａＦ２）、リチウム酸化物（ＬｉＯｘ）等のアルカリ金属、アルカリ土類金属、またはそれらの化合物を用いることができる。その他、電子輸送性を有する材料にアルカリ金属、アルカリ土類金属、またはそれらの化合物を含有させたもの、具体的にはＡｌｑ中にマグネシウム（Ｍｇ）を含有させたもの等を用いてもよい。なお、この場合には、陰極からの電子注入をより効率良く行うことができる。
　あるいは、電子注入層に、有機化合物と電子供与体（ドナー）とを混合してなる複合材料を用いてもよい。このような複合材料は、有機化合物が電子供与体から電子を受け取るため、電子注入性および電子輸送性に優れている。この場合、有機化合物としては、受け取った電子の輸送に優れた材料であることが好ましく、具体的には、例えば上述した電子輸送層を構成する材料（金属錯体や複素芳香族化合物等）を用いることができる。電子供与体としては、有機化合物に対し電子供与性を示す材料であればよい。具体的には、アルカリ金属、アルカリ土類金属及び希土類金属が好ましく、リチウム、セシウム、マグネシウム、カルシウム、エルビウム、イッテルビウム等が挙げられる。また、アルカリ金属酸化物やアルカリ土類金属酸化物が好ましく、リチウム酸化物、カルシウム酸化物、バリウム酸化物等が挙げられる。また、酸化マグネシウムのようなルイス塩基を用いることもできる。また、テトラチアフルバレン（略称：ＴＴＦ）等の有機化合物を用いることもできる。 Electron injection layer 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. Alternatively, 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.
Alternatively, a composite material obtained by mixing an organic compound and an electron donor (donor) may be used for the electron injection layer. Such 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. In this case, 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. As the electron donor, any material having an electron donating property with respect to the organic compound may be used. Specifically, alkali metals, alkaline earth metals and rare earth metals are preferable, and examples thereof include lithium, cesium, magnesium, calcium, erbium and ytterbium. Further, alkali metal oxides and alkaline earth metal oxides are preferable, and lithium oxide, calcium oxide, barium oxide and the like can be mentioned. It is also possible to use a Lewis base such as magnesium oxide. Alternatively, an organic compound such as tetrathiafulvalene (abbreviation: TTF) can be used.
陰極
　陰極には、仕事関数の小さい（具体的には３．８ｅＶ以下）金属、合金、電気伝導性化合物、およびこれらの混合物などを用いることが好ましい。このような陰極材料の具体例としては、元素周期表の第１族または第２族に属する元素、すなわちリチウム（Ｌｉ）やセシウム（Ｃｓ）等のアルカリ金属、およびマグネシウム（Ｍｇ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）等のアルカリ土類金属、およびこれらを含む合金（例えば、ＭｇＡｇ、ＡｌＬｉ）、ユーロピウム（Ｅｕ）、イッテルビウム（Ｙｂ）等の希土類金属およびこれらを含む合金等が挙げられる。
　なお、アルカリ金属、アルカリ土類金属、これらを含む合金を用いて陰極を形成する場合には、真空蒸着法やスパッタリング法を用いることができる。また、銀ペーストなどを用いる場合には、塗布法やインクジェット法などを用いることができる。
　なお、電子注入層を設けることにより、仕事関数の大小に関わらず、Ａｌ、Ａｇ、ＩＴＯ、グラフェン、珪素若しくは酸化珪素を含有した酸化インジウム－酸化スズ等様々な導電性材料を用いて陰極を形成することができる。これらの導電性材料は、スパッタリング法やインクジェット法、スピンコート法等を用いて成膜することができる。 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. Specific examples of such 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.
Note that when the cathode is formed using an alkali metal, an alkaline earth metal, or an alloy containing these, a vacuum evaporation method or a sputtering method can be used. When using silver paste or the like, a coating method, an inkjet method, or the like can be used.
By providing the electron injecting layer, 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.
絶縁層
　有機ＥＬ素子は、超薄膜に電界を印加するために、リークやショートによる画素欠陥が生じやすい。これを防止するために、一対の電極間に絶縁性の薄膜層からなる絶縁層を挿入してもよい。
　絶縁層に用いられる材料としては、例えば、酸化アルミニウム、弗化リチウム、酸化リチウム、弗化セシウム、酸化セシウム、酸化マグネシウム、弗化マグネシウム、酸化カルシウム、弗化カルシウム、窒化アルミニウム、酸化チタン、酸化珪素、酸化ゲルマニウム、窒化珪素、窒化ホウ素、酸化モリブデン、酸化ルテニウム、酸化バナジウム等が挙げられる。なお、これらの混合物や積層物を用いてもよい。 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. In order to prevent this, an insulating layer formed of an insulating thin film layer may be inserted between the pair of electrodes.
Examples of 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.
スペース層
　上記スペース層とは、例えば、蛍光発光層と燐光発光層とを積層する場合に、燐光発光層で生成する励起子を蛍光発光層に拡散させない、あるいは、キャリアバランスを調整する目的で、蛍光発光層と燐光発光層との間に設けられる層である。また、スペース層は、複数の燐光発光層の間に設けることもできる。
　スペース層は発光層間に設けられるため、電子輸送性と正孔輸送性を兼ね備える材料であることが好ましい。また、隣接する燐光発光層内の三重項エネルギーの拡散を防ぐため、三重項エネルギーが２．６ｅＶ以上であることが好ましい。スペース層に用いられる材料としては、上述の正孔輸送層に用いられるものと同様のものが挙げられる。 Space layer 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.
阻止層
　電子阻止層、正孔阻止層、励起子阻止層などの阻止層を発光層に隣接して設けてもいい。電子阻止層とは発光層から正孔輸送層へ電子が漏れることを防ぐ層であり、正孔阻止層とは発光層から電子輸送層へ正孔が漏れることを防ぐ層である。励起子阻止層は発光層で生成した励起子が隣接する層へ拡散することを防止し、励起子を発光層内に閉じ込める機能を有する。 Blocking Layer 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, and 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.
　前記有機ＥＬ素子の各層は従来公知の蒸着法、塗布法等により形成することができる。例えば、真空蒸着法、分子線蒸着法（ＭＢＥ法）などの蒸着法、あるいは、層を形成する化合物の溶液を用いた、ディッピング法、スピンコーティング法、キャスティング法、バーコート法、ロールコート法等の塗布法による公知の方法で形成することができる。 Each layer of the organic EL element can be formed by a conventionally known vapor deposition method, coating method, or the like. For example, 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.
　各層の膜厚は特に制限されないが、一般に膜厚が薄すぎるとピンホール等の欠陥が生じやすく、逆に厚すぎると高い駆動電圧が必要となり効率が悪くなるため、好ましくは５ｎｍ～１０μｍであり、１０ｎｍ～０．２μｍがより好ましい。 The thickness of 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 μm. 10 nm to 0.2 μm is more preferable.
　前記有機ＥＬ素子は、有機ＥＬパネルモジュール等の表示部品、テレビ、携帯電話、パーソナルコンピュータ等の表示装置、及び、照明、車両用灯具の発光装置等の電子機器に使用できる。 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.
　以下、本発明を実施例により具体的に説明するが、本発明はこれらにより何ら限定されるものではない。
　本発明の一態様に係る発明化合物（１）の合成実施例を以下に示す。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these.
A synthesis example of the invented compound (1) according to one aspect of the present invention is shown below.
中間体Ｉ－Ｃの合成
Figure JPOXMLDOC01-appb-C000066
 Synthesis of Intermediate IC
Figure JPOXMLDOC01-appb-C000066
　アルゴン雰囲気下、９，９－ジフェニルフルオレン－２－アミン　Ｉ－Ａ　６．６７ｇ（２０．０ｍｍｏｌ）、クロロ体　Ｉ－Ｂ　６．８２ｇ（２０．０ｍｍｏｌ）、トリス（ジベンリジリデンアセトン）パラジウム（０）３６６ｍｇ（０．４ｍｍｏｌ）、ＢＩＮＡＰ　４９８ｍｇ（０．８ｍｍｏｌ）、及びナトリウム－ｔ－ブトキシド２．６９ｇ（２８．０ｍｍｏｌ）のキシレン（１００ｍｌ）溶液を１１０°Ｃにて６時間加熱攪拌した。反応液を室温に冷却し、トルエンを加え、不溶物を濾別した。ろ液から溶媒を除去し、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、中間体Ｉ－Ｃ　４．０７ｇを得た。収率は３２％であった。 Under an argon atmosphere, 9,9-diphenylfluoren-2-amine IA 6.67 g (20.0 mmol), chloro compound IB 6.82 g (20.0 mmol), tris (dibenzylidylideneacetone) palladium ( 0) 366 mg (0.4 mmol), BINAP 498 mg (0.8 mmol), and sodium-t-butoxide 2.69 g (28.0 mmol) in xylene (100 ml) were heated and stirred at 110 ° C. for 6 hours. The reaction solution was cooled to room temperature, toluene was added, and the insoluble material was filtered off. The solvent was removed from the filtrate, and the obtained residue was purified by silica gel column chromatography to obtain 4.07 g of intermediate IC. The yield was 32%.
中間体Ｉ－Ｅの合成
Figure JPOXMLDOC01-appb-C000067
 Synthesis of Intermediate IE
Figure JPOXMLDOC01-appb-C000067
　中間体Ｉ－Ｃの合成法において、Ｉ－Ａの代わりにＩ－Ｄを用いて同様な方法にて中間体Ｉ－Ｅを得た。収率は４４％であった。 Intermediate IE was obtained in the same manner as in the method for synthesizing intermediate IC, using ID instead of IA. The yield was 44%.
中間体Ｉ－Ｇの合成
Figure JPOXMLDOC01-appb-C000068
 Synthesis of Intermediate IG
Figure JPOXMLDOC01-appb-C000068
　中間体Ｉ－Ｃの合成法において、Ｉ－Ａの代わりにＩ－Ｆを用いて同様な方法にて中間体Ｉ－Ｇを得た。収率は４７％であった。 Intermediate IF was obtained by a similar method using IF in place of IA in the method for synthesizing intermediate IC. The yield was 47%.
中間体Ｉ－Ｉの合成
Figure JPOXMLDOC01-appb-C000069
 Synthesis of Intermediate II
Figure JPOXMLDOC01-appb-C000069
　中間体Ｉ－Ｃの合成法において、Ｉ－Ａの代わりにＩ－Ｈを用いて同様な方法にて中間体Ｉ－Ｉを得た。収率は５１％であった。 Intermediate I-I was obtained in the same manner as in the method of synthesizing intermediate I-C by using I-H instead of IA. The yield was 51%.
中間体Ｉ－Ｋの合成
Figure JPOXMLDOC01-appb-C000070
 Synthesis of Intermediate IK
Figure JPOXMLDOC01-appb-C000070
　中間体Ｉ－Ｃの合成法において、Ｉ－Ａの代わりにＩ－Ｊを用いて同様な方法にて中間体Ｉ－Ｋを得た。収率は２９％であった。 Intermediate IK was obtained in the same manner as in the method of synthesizing intermediate IC, using IJ instead of IA. The yield was 29%.
中間体Ｉ－Ｍの合成
Figure JPOXMLDOC01-appb-C000071
 Synthesis of Intermediate IM
Figure JPOXMLDOC01-appb-C000071
　中間体Ｉ－Ｃの合成法において、Ｉ－Ａの代わりにＩ－Ｌを用いて同様な方法にて中間体Ｉ－Ｍを得た。収率は３０％であった。 Intermediate IL was obtained in a similar manner by using IL in place of IA in the method for synthesizing intermediate IC. The yield was 30%.
合成実施例１：化合物１の合成
Figure JPOXMLDOC01-appb-C000072
 Synthesis Example 1: Synthesis of compound 1
Figure JPOXMLDOC01-appb-C000072
　アルゴン雰囲気下、中間体Ｉ―Ｃ　３．８３ｇ（６．０ｍｍｏｌ）、ブロモベンゼン　９４２ｍｇ（６．０ｍｍｏｌ）、トリス（ジベンリジリデンアセトン）パラジウム（０）　１１０ｍｇ（０．１２ｍｍｏｌ）、トリーｔ－ブチルホスホニウムテトラフルオロボレート１３９ｍｇ（０．４８ｍｍｏｌ）およびナトリウム－ｔ－ブトキシド１．７３ｇ（１８ｍｍｏｌ）のトルエン６０ｍＬ溶液を１１０℃にて６時間攪拌した。室温に冷却したのち、析出した固体を濾取した。得られた固体をシリカゲルカラムクロマトグラフィーおよび再結晶にて精製し、化合物（３．９８ｇ）を得た。収率は９３％であった。得られた化合物は、マススペクトル分析の結果、化合物１であり、分子量７１３．９２に対しｍ／ｅ＝７１３であった。 Under an argon atmosphere, intermediate IC 3.83 g (6.0 mmol), bromobenzene 942 mg (6.0 mmol), tris (dibenzylidylideneacetone) palladium (0) 110 mg (0.12 mmol), tri-t-butyl A solution of 139 mg (0.48 mmol) of phosphonium tetrafluoroborate and 1.73 g (18 mmol) of sodium-t-butoxide in 60 mL of toluene was stirred at 110 ° C for 6 hours. After cooling to room temperature, the precipitated solid was collected by filtration. The obtained solid was purified by silica gel column chromatography and recrystallization to obtain a compound (3.98g). The yield was 93%. As a result of mass spectrum analysis, the obtained compound was compound 1, which had a molecular weight of 713.92 and m / e = 713.
合成実施例２：化合物２の合成
Figure JPOXMLDOC01-appb-C000073
 Synthesis Example 2: Synthesis of compound 2
Figure JPOXMLDOC01-appb-C000073
　化合物１の合成において、ブロモベンゼンのかわりに３－ブロモジベンゾフランを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物２であり、分子量８０４．００に対しｍ／ｅ＝８０４であった。 In the synthesis of compound 1, the same operation was performed except that 3-bromodibenzofuran was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 2, which was m / e = 804 for a molecular weight of 804.00.
合成実施例３：化合物３の合成
Figure JPOXMLDOC01-appb-C000074
 Synthesis Example 3: Synthesis of compound 3
Figure JPOXMLDOC01-appb-C000074
　化合物１の合成において、ブロモベンゼンのかわりに１－ブロモナフタレンを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物３であり、分子量７６３．９８に対しｍ／ｅ＝７６３であった。 In the synthesis of compound 1, the same operation was performed except that 1-bromonaphthalene was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 3, which had a molecular weight of 763.98 and m / e = 763.
合成実施例４：化合物４の合成
Figure JPOXMLDOC01-appb-C000075
 Synthesis Example 4: Synthesis of compound 4
Figure JPOXMLDOC01-appb-C000075
　化合物１の合成において、ブロモベンゼンのかわりに９―ブロモフェナントレンを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物４であり、分子量８１４．０４に対しｍ／ｅ＝８１４であった。 In the synthesis of compound 1, the same operation was performed except that 9-bromophenanthrene was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 4, which had a molecular weight of 814.04 and m / e = 814.
合成実施例５：化合物５の合成
Figure JPOXMLDOC01-appb-C000076
 Synthesis Example 5: Synthesis of compound 5
Figure JPOXMLDOC01-appb-C000076
　化合物１の合成において、ブロモベンゼンのかわりに２－ブロモジベンゾチオフェンを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物５であり、分子量８２０．０７に対しｍ／ｅ＝８２０であった。 In the synthesis of compound 1, the same operation was performed except that 2-bromodibenzothiophene was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 5, which had a molecular weight of 820.07 and m / e = 820.
合成実施例６：化合物６の合成
Figure JPOXMLDOC01-appb-C000077
 Synthesis Example 6: Synthesis of compound 6
Figure JPOXMLDOC01-appb-C000077
　化合物１の合成において、ブロモベンゼンのかわりに１－ブロモジベンゾフランを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物６であり、分子量８０４．０１に対しｍ／ｅ＝８０４であった。 In the synthesis of compound 1, the same operation was performed except that 1-bromodibenzofuran was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 6, which was m / e = 804 with respect to a molecular weight of 804.01.
合成実施例７：化合物７の合成
Figure JPOXMLDOC01-appb-C000078
 Synthesis Example 7: Synthesis of Compound 7
Figure JPOXMLDOC01-appb-C000078
　化合物１の合成において、中間体Ｉ－Ｃのかわりに中間体Ｉ－Ｅを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物７であり、分子量７１３．９２に対しｍ／ｅ＝７１３であった。 In the synthesis of compound 1, the same operation was performed except that intermediate IE was used instead of intermediate IC to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 7, which was m / e = 713 with respect to the molecular weight of 713.92.
合成実施例８：化合物８の合成
Figure JPOXMLDOC01-appb-C000079
 Synthesis Example 8: Synthesis of compound 8
Figure JPOXMLDOC01-appb-C000079
　化合物７の合成において、ブロモベンゼンのかわりに２－ブロモナフチレンを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物８であり、分子量７６３．９８に対しｍ／ｅ＝７６３であった。 In the synthesis of compound 7, the same operation was performed except that 2-bromonaphthylene was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 8, which was m / e = 763 with respect to the molecular weight of 763.98.
合成実施例９：化合物９の合成
Figure JPOXMLDOC01-appb-C000080
 Synthesis Example 9: Synthesis of Compound 9
Figure JPOXMLDOC01-appb-C000080
　化合物７の合成において、ブロモベンゼンのかわりに２－ブロモジベンゾフランを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物９であり、分子量８０４．０１に対しｍ／ｅ＝８０４であった。 In the synthesis of compound 7, the same operation was performed except that 2-bromodibenzofuran was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 9, which had a molecular weight of 804.01 and m / e = 804.
合成実施例１０：化合物１０の合成
Figure JPOXMLDOC01-appb-C000081
 Synthesis Example 10: Synthesis of Compound 10
Figure JPOXMLDOC01-appb-C000081
　化合物１の合成において、中間体Ｉ－Ｃのかわりに中間体Ｉ－Ｇを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物１０であり、分子量７９０．０２に対しｍ／ｅ＝７９０であった。 A compound was obtained by performing the same operation in the synthesis of Compound 1, except that Intermediate IG was used instead of Intermediate IC.
As a result of mass spectrum analysis, the obtained compound was compound 10, which was m / e = 790 for a molecular weight of 790.02.
合成実施例１１：化合物１１の合成
Figure JPOXMLDOC01-appb-C000082
 Synthesis Example 11: Synthesis of compound 11
Figure JPOXMLDOC01-appb-C000082
　化合物１０の合成において、ブロモベンゼンのかわりに１―ブロモナフタレンを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物１１であり、分子量８４０．０８に対しｍ／ｅ＝８４０であった。 In the synthesis of compound 10, the same operation was performed except that 1-bromonaphthalene was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 11, which had a molecular weight of 840.08 and m / e = 840.
合成実施例１２：化合物１２の合成
Figure JPOXMLDOC01-appb-C000083
 Synthesis Example 12: Synthesis of compound 12
Figure JPOXMLDOC01-appb-C000083
　化合物１０の合成において、ブロモベンゼンのかわりに４―ブロモジベンゾチオフェンを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物１２であり、分子量８９６．１６に対しｍ／ｅ＝８９６であった。 In the synthesis of compound 10, the same operation was performed except that 4-bromodibenzothiophene was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 12, which had a molecular weight of 896.16 and m / e = 896.
合成実施例１３：化合物１３の合成
Figure JPOXMLDOC01-appb-C000084
 Synthesis Example 13: Synthesis of compound 13
Figure JPOXMLDOC01-appb-C000084
　化合物１の合成において、中間体Ｉ－Ｃのかわりに中間体Ｉ－Ｉを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物１３であり、分子量７９０．０２に対しｍ／ｅ＝７９０であった。 A compound was obtained by performing the same operation in the synthesis of compound 1, except that intermediate II was used instead of intermediate IC.
As a result of mass spectrum analysis, the obtained compound was compound 13, which was m / e = 790 for a molecular weight of 790.02.
合成実施例１４：化合物１４の合成
Figure JPOXMLDOC01-appb-C000085
 Synthesis Example 14: Synthesis of compound 14
Figure JPOXMLDOC01-appb-C000085
　化合物１３の合成において、ブロモベンゼンのかわりに２－ブロモジベンゾフランを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物１４であり、分子量８８０．１０に対しｍ／ｅ＝８８０であった。 In the synthesis of compound 13, the same operation was performed except that 2-bromodibenzofuran was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 14, which had a molecular weight of 880.10 and m / e = 880.
合成実施例１５：化合物１５の合成
Figure JPOXMLDOC01-appb-C000086
 Synthesis Example 15: Synthesis of compound 15
Figure JPOXMLDOC01-appb-C000086
　化合物１の合成において、中間体Ｉ－Ｃのかわりに中間体Ｉ－Ｋを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物１５であり、分子量７９０．０２に対しｍ／ｅ＝７９０であった。 A compound was obtained by performing the same operation in the synthesis of Compound 1, except that Intermediate IK was used instead of Intermediate IC.
As a result of mass spectrum analysis, the obtained compound was compound 15, which had a molecular weight of 790.02 and m / e = 790.
合成実施例１６：化合物１６の合成
Figure JPOXMLDOC01-appb-C000087
 Synthesis Example 16: Synthesis of compound 16
Figure JPOXMLDOC01-appb-C000087
　化合物１５の合成において、ブロモベンゼンのかわりに１－ブロモナフタレンを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物１６であり、分子量８４０．０８に対しｍ／ｅ＝８４０であった。 In the synthesis of compound 15, the same operation was performed except that 1-bromonaphthalene was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 16, which was m / e = 840 for a molecular weight of 840.08.
合成実施例１７：化合物１７の合成
Figure JPOXMLDOC01-appb-C000088
 Synthesis Example 17: Synthesis of compound 17
Figure JPOXMLDOC01-appb-C000088
　化合物１５の合成において、ブロモベンゼンのかわりに１－ブロモジベンゾフランを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物１７であり、分子量８８０．１０に対しｍ／ｅ＝８８０であった。 In the synthesis of compound 15, the same operation was performed except that 1-bromodibenzofuran was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 17, which had a molecular weight of 880.10 and m / e = 880.
合成実施例１８：化合物１８の合成
Figure JPOXMLDOC01-appb-C000089
 Synthesis Example 18: Synthesis of Compound 18
Figure JPOXMLDOC01-appb-C000089
　化合物１の合成において、中間体Ｉ－Ｃのかわりに中間体Ｉ－Ｍを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物１８であり、分子量７９０．０２に対しｍ／ｅ＝７９０であった。 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.
As a result of mass spectrum analysis, the obtained compound was compound 18, which was m / e = 790 for a molecular weight of 790.02.
合成実施例１９：化合物１９の合成
Figure JPOXMLDOC01-appb-C000090
 Synthesis Example 19: Synthesis of compound 19
Figure JPOXMLDOC01-appb-C000090
　化合物１８の合成において、ブロモベンゼンのかわりに３－ブロモジベンゾフランを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物１９であり、分子量８８０．１０に対しｍ／ｅ＝８８０であった。 In the synthesis of compound 18, the same operation was performed except that 3-bromodibenzofuran was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 19, which had a molecular weight of 880.10 and m / e = 880.
合成実施例２０：化合物２０の合成
Figure JPOXMLDOC01-appb-C000091
 Synthesis Example 20: Synthesis of Compound 20
Figure JPOXMLDOC01-appb-C000091
　化合物１８の合成において、ブロモベンゼンのかわりに２－ブロモジベンゾチオフェンを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物２０であり、分子量８９６．１６に対しｍ／ｅ＝８９６であった。 In the synthesis of compound 18, the same operation was performed except that 2-bromodibenzothiophene was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 20, which was m / e = 896 for a molecular weight of 896.16.
合成実施例２１：化合物２１の合成
Figure JPOXMLDOC01-appb-C000092
 Synthesis Example 21: Synthesis of Compound 21
Figure JPOXMLDOC01-appb-C000092
　化合物１８の合成において、ブロモベンゼンのかわりに２－ブロモフェナントレンを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果、化合物２１であり、分子量８９０．１４に対しｍ／ｅ＝８９０であった。 In the synthesis of compound 18, the same operation was performed except that 2-bromophenanthrene was used instead of bromobenzene to obtain a compound.
As a result of mass spectrum analysis, the obtained compound was compound 21, which was m / e = 890 with respect to a molecular weight of 890.14.
合成実施例２２：化合物２２の合成
Figure JPOXMLDOC01-appb-C000093
 Synthesis Example 22: Synthesis of compound 22
Figure JPOXMLDOC01-appb-C000093
　化合物１の合成において、ブロモベンゼンのかわりにd5-ブロモベンゼンを用いたほかは同様の操作を行い、化合物を得た。
　得られた化合物は、マススペクトル分析の結果化合物２２であり、分子量７１８．３４に対しｍ／ｅ＝７１８であった。 In the synthesis of compound 1, the same operation was performed except that d5-bromobenzene was used instead of bromobenzene to obtain a compound.
The obtained compound was the compound 22 as a result of the mass spectrum analysis, and was m / e = 718 with respect to the molecular weight of 718.34.
下記実施例１～３の第２正孔輸送層に用いた発明化合物 Inventive compounds used in the second hole transport layer of Examples 1 to 3 below
Figure JPOXMLDOC01-appb-C000094
Figure JPOXMLDOC01-appb-C000094
下記比較例１～２の第２正孔輸送層に用いた比較化合物 Comparative compounds used in the second hole transport layer of Comparative Examples 1 and 2 below
Figure JPOXMLDOC01-appb-C000095
Figure JPOXMLDOC01-appb-C000095
下記実施例１～３及び下記比較例１～２の有機ＥＬ素子の製造に用いた他の化合物 Other compounds used in the production of organic EL devices of Examples 1 to 3 and Comparative Examples 1 and 2 below
Figure JPOXMLDOC01-appb-C000096
Figure JPOXMLDOC01-appb-C000096
Figure JPOXMLDOC01-appb-C000097
Figure JPOXMLDOC01-appb-C000097
実施例１
有機ＥＬ素子の製造
　２５ｍｍ×７５ｍｍ×１．１ｍｍのＩＴＯ透明電極付きガラス基板（ジオマテック株式会社製）をイソプロピルアルコール中で超音波洗浄を５分間行なった後、ＵＶオゾン洗浄を３０分間行った。ＩＴＯ透明電極の厚さは１３０ｎｍとした。
　洗浄後のＩＴＯ透明電極付きガラス基板を真空蒸着装置の基板ホルダーに装着し、まずＩＴＯ透明電極を覆うようにして化合物ＨＩ－１を蒸着して膜厚５ｎｍの正孔注入層を形成した。
　次に、この正孔注入層上に、化合物２ｓ（第１正孔輸送層材料）を蒸着して膜厚８０ｎｍの第１正孔輸送層を形成した。
　次に、この第１正孔輸送層上に、合成実施例1で得られた化合物１（第２正孔輸送層材料）を蒸着して膜厚１０ｎｍの第２正孔輸送層を形成した。
　次に、この第２正孔輸送層上に、化合物ＢＨ－１（ホスト材料）と化合物ＢＤ－１（ドーパント材料）を共蒸着し、膜厚２５ｎｍの発光層を形成した。化合物ＢＤ－１の発光層中の濃度は４．０質量％であった。
　次に、この発光層の上に、化合物ＥＴ－１を蒸着して膜厚１０ｎｍの第１電子輸送層を形成した。
　次に、この第１電子輸送層の上に、下記化合物ＥＴ－２を蒸着して膜厚２０ｎｍの第２電子輸送層を形成した。
　次に、この第２電子輸送層上に、ＬｉＦを蒸着して膜厚１ｎｍの電子注入性電極（陰極）を形成した。
　そして、この電子注入性電極上に金属Ａｌを蒸着して膜厚８０ｎｍの金属Ａｌ陰極を形成した。
　実施例１の有機ＥＬ素子の構成を以下に示す。
ＩＴＯ（１３０）／ＨＩ－１（５）／化合物２ｓ（８０）／化合物１（１０）／
ＢＨ－１：ＢＤ－１＝９６．０：４．０（２５）／ＥＴ－１（１０）／ＥＴ－２（２０）／ＬｉＦ（１）／Ａｌ（８０）
　なお、括弧内の数字は、膜厚（単位：ｎｍ）を示す。 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.
Next, the compound 2s (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.
Next, 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.
Next, on this second hole transport layer, 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.
Next, 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.
Next, 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.
Next, LiF was vapor-deposited on the second electron transport layer to form an electron injecting electrode (cathode) having a film thickness of 1 nm.
Then, 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.
ITO (130) / HI-1 (5) / Compound 2s (80) / Compound 1 (10) /
BH-1: BD-1 = 96.0: 4.0 (25) / ET-1 (10) / ET-2 (20) / LiF (1) / Al (80)
The number in parentheses indicates the film thickness (unit: nm).
実施例２～３
　実施例１の第２正孔輸送層に用いた化合物１に代えて、化合物２（実施例２）又は化合物２２（実施例３）を用いたこと以外は実施例１と同様にして有機ＥＬ素子を作製した。 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.
比較例１～２
　実施例１の第２正孔輸送層に用いた化合物１に代えて、比較化合物１（比較例１）又は比較化合物２（比較例２）を用いたこと以外は実施例１と同様にして有機ＥＬ素子を作製した。 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.
外部量子効率（ＥＱＥ）の測定
　実施例１～３及び比較例１～２で得られた各有機ＥＬ素子を室温下、電流密度１０ｍＡ／ｃｍ２で直流定電流駆動し、輝度計（ミノルタ社製分光輝度放射計ＣＳ－１０００）を用いて輝度を測定した。測定結果から外部量子効率（％）を求めた。結果を表１に示す。 Measurement of External Quantum Efficiency (EQE) Each of the organic EL devices obtained in Examples 1 to 3 and Comparative Examples 1 to 2 was driven at a constant current with a current density of 10 mA / cm 2 at room temperature to obtain a luminance meter (Minolta Co. The luminance was measured using a spectral luminance radiometer CS-1000). The external quantum efficiency (%) was calculated from the measurement results. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000098
Figure JPOXMLDOC01-appb-T000098
　表１から明らかなように、特定の構造を有する発明化合物（１）及び発明化合物（２）を青色用の有機ＥＬ素子の正孔輸送層材料として用いることにより、比較化合物１及び２では実現されない、高い外部量子効率を有する有機ＥＬ素子が得られることがわかる。 As is clear from Table 1, by using the invention compound (1) and the invention compound (2) having a specific structure as the hole transport layer material of the organic EL device for blue color, it is not realized by the comparative compounds 1 and 2. It can be seen that an organic EL device having a high external quantum efficiency can be obtained.
下記実施例４～６の第２正孔輸送層に用いた発明化合物 Invention compounds used in the second hole transport layer of Examples 4 to 6 below
Figure JPOXMLDOC01-appb-C000099
Figure JPOXMLDOC01-appb-C000099
下記比較例３～４の第２正孔輸送層に用いた比較化合物 Comparative compounds used in the second hole transport layer of Comparative Examples 3 to 4 below
Figure JPOXMLDOC01-appb-C000100
Figure JPOXMLDOC01-appb-C000100
下記実施例４～６及び下記比較例３～４の有機ＥＬ素子の製造に用いた他の化合物 Other compounds used in the production of organic EL devices of Examples 4 to 6 and Comparative Examples 3 to 4 below
Figure JPOXMLDOC01-appb-C000101
Figure JPOXMLDOC01-appb-C000101
Figure JPOXMLDOC01-appb-C000102
Figure JPOXMLDOC01-appb-C000102
実施例４
有機ＥＬ素子の製造
　２５ｍｍ×７５ｍｍ×１．１ｍｍのＩＴＯ透明電極付きガラス基板（ジオマテック株式会社製）をイソプロピルアルコール中で超音波洗浄を５分間行なった後、ＵＶオゾン洗浄を３０分間行った。ＩＴＯ透明電極の厚さは１３０ｎｍとした。
　洗浄後のＩＴＯ透明電極付きガラス基板を真空蒸着装置の基板ホルダーに装着し、まずＩＴＯ透明電極を覆うようにして化合物２ｔと化合物ＨＩ－２を共蒸着して膜厚１０ｎｍの正孔注入層を形成した。化合物ＨＩ－２の正孔注入層中の濃度は３．０質量％、であった。
　次に、この正孔注入層上に、化合物２ｔ（第１正孔輸送層材料）を蒸着して膜厚１１０ｎｍの第１正孔輸送層を形成した。
　次に、この第１正孔輸送層上に、化合物１（第２正孔輸送層材料）を蒸着して膜厚３５ｎｍの第２正孔輸送層を形成した。
　次に、この第２正孔輸送層上に、化合物Ｈ－１（ホスト材料１）と化合物Ｈ－２（ホスト材料２）、及び化合物Ｄ－１（ドーパント材料）を共蒸着し、膜厚４０ｎｍの発光層を形成した。化合物Ｈ－２（ホスト材料２）の発光層中の濃度は３１．７質量％、また、化合物Ｄ－１の発光層中の濃度は５．０質量％であった。
　次に、この発光層の上に、化合物ＥＴ－３を蒸着して膜厚５ｎｍの第１電子輸送層を形成した。
　次に、この第１電子輸送層の上に、下記化合物ＥＴ－４とＬｉｑを共蒸着して膜厚２０ｎｍの第２電子輸送層を形成した。Ｌｉｑの第２電子輸送層中の濃度は５０質量％であった。
　次に、この第２電子輸送層上に、Ｌｉｑを蒸着して膜厚１ｎｍの電子注入性電極（陰極）を形成した。
　そして、この電子注入性電極上に金属Ａｌを蒸着して膜厚５０ｎｍの金属Ａｌ陰極を形成した。
　実施例４の有機ＥＬ素子の構成を以下に示す。
ＩＴＯ（１３０）／化合物２ｔ：ＨＩ－２＝９７．０：３．０（１０）／化合物２ｔ（１１０）／化合物１（３５）／Ｈ－１：Ｈ－２：Ｄ－１＝６３．３：３１．７：５．０
（４０）／ＥＴ－３（５）／ＥＴ－４：Ｌｉｑ＝５０：５０（２０）／Ｌｉｑ（１）／
Ａｌ（５０）
　なお、括弧内の数字は、膜厚（単位：ｎｍ）を示す。 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.
Next, 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.
Next, 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.
Then, 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.
Next, 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.
Next, 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.
Next, Liq was vapor-deposited on the second electron transport layer to form an electron injecting electrode (cathode) having a film thickness of 1 nm.
Then, 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.
ITO (130) / Compound 2t: HI-2 = 97.0: 3.0 (10) / Compound 2t (110) / Compound 1 (35) /H-1:H-2:D-1=63.3 : 31.7: 5.0
(40) / ET-3 (5) / ET-4: Liq = 50: 50 (20) / Liq (1) /
Al (50)
The number in parentheses indicates the film thickness (unit: nm).
実施例５～６
　実施例４の第２正孔輸送層に用いた化合物１に代えて、化合物２（実施例５）又は化合物７（実施例６）を用いたこと以外は実施例４と同様にして有機ＥＬ素子を作製した。 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.
比較例３～４
　実施例４の第２正孔輸送層に用いた化合物１に代えて、比較化合物１（比較例３）又は比較化合物３（比較例４）を用いたこと以外は実施例４と同様にして有機ＥＬ素子を作製した。 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.
外部量子効率（ＥＱＥ）の測定
　実施例４～６及び比較例３～４で得られた各有機ＥＬ素子の外部量子効率（％）を上記と同じ方法で求めた。結果を表２に示す。 Measurement of External Quantum Efficiency (EQE) The external quantum efficiency (%) of each organic EL device obtained in Examples 4 to 6 and Comparative Examples 3 to 4 was determined by the same method as above. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000103
Figure JPOXMLDOC01-appb-T000103
　表２から明らかなように、特定の構造を有する発明化合物（１）及び発明化合物（２）を緑燐光用の有機ＥＬ素子の正孔輸送層材料として用いることにより、比較化合物１及び３では実現されない、高い外部量子効率を有する有機ＥＬ素子が得られることがわかる。 As is clear from Table 2, 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.
下記実施例７～８の第１正孔輸送層に用いた発明化合物 Inventive compounds used in the first hole transport layer of Examples 7 to 8 below
Figure JPOXMLDOC01-appb-C000104
Figure JPOXMLDOC01-appb-C000104
下記比較例５～６の第１正孔輸送層に用いた比較化合物 Comparative compounds used in the first hole transport layer of Comparative Examples 5 to 6 below
Figure JPOXMLDOC01-appb-C000105
Figure JPOXMLDOC01-appb-C000105
下記実施例７～８及び下記比較例５～６の有機ＥＬ素子の製造に用いた他の化合物 Other compounds used in the production of organic EL devices of Examples 7 to 8 below and Comparative Examples 5 to 6 below
Figure JPOXMLDOC01-appb-C000106
Figure JPOXMLDOC01-appb-C000106
Figure JPOXMLDOC01-appb-C000107
Figure JPOXMLDOC01-appb-C000107
実施例７
有機ＥＬ素子の製造
　２５ｍｍ×７５ｍｍ×１．１ｍｍのＩＴＯ透明電極付きガラス基板（ジオマテック株式会社製）をイソプロピルアルコール中で超音波洗浄を５分間行なった後、ＵＶオゾン洗浄を３０分間行った。ＩＴＯ透明電極の厚さは１３０ｎｍとした。
　洗浄後のＩＴＯ透明電極付きガラス基板を真空蒸着装置の基板ホルダーに装着し、まずＩＴＯ透明電極を覆うようにして化合物１と化合物ＨＩ－２を共蒸着して膜厚１０ｎｍの正孔注入層を形成した。化合物ＨＩ－２の正孔注入層中の濃度は５．０質量％であった。
　次に、この正孔注入層上に、化合物１（第１正孔輸送層材料）を蒸着して膜厚８０ｎｍの第１正孔輸送層を形成した。
　次に、この第１正孔輸送層上に、化合物２ｕ（第２正孔輸送層材料）を蒸着して膜厚１０ｎｍの第２正孔輸送層を形成した。
　次に、この第２正孔輸送層上に、化合物ＢＨ－１（ホスト材料）と化合物ＢＤ－２（ドーパント材料）を共蒸着し、膜厚２５ｎｍの発光層を形成した。化合物ＢＤ－２の発光層中の濃度は４．０質量％であった。
　次に、この発光層の上に、化合物ＥＴ－２と化合物ＥＴ－５を共蒸着して膜厚２０ｎｍの電子輸送層を形成した。化合物ＥＴ―５の電子輸送層中の濃度は５０質量％であった。
　次に、この電子輸送層上に、ＬｉＦを蒸着して膜厚１ｎｍの電子注入性電極（陰極）を形成した。
　そして、この電子注入性電極上に金属Ａｌを蒸着して膜厚５０ｎｍの金属Ａｌ陰極を形成した。
　実施例７の有機ＥＬ素子の構成を以下に示す。
ＩＴＯ（１３０）／化合物１：ＨＩ－２＝９５．０：５．０（１０）／化合物１（８０）／化合物２ｕ（１０）／ＢＨ－１：ＢＤ－２＝９６．０：４．０（２５）／
ＥＴ－２：ＥＴ－５＝５０：５０（２０）／ＬｉＦ（１）／Ａｌ（５０）
　なお、括弧内の数字は、膜厚（単位：ｎｍ）を示す。 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.
Next, 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.
Next, 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.
Next, 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.
Next, on this light emitting layer, 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.
Next, LiF was vapor-deposited on the electron transport layer to form an electron injecting electrode (cathode) having a film thickness of 1 nm.
Then, 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.
ITO (130) / Compound 1: HI-2 = 95.0: 5.0 (10) / Compound 1 (80) / Compound 2u (10) /BH-1:BD-2=96.0:4.0 (25) /
ET-2: ET-5 = 50: 50 (20) / LiF (1) / Al (50)
The number in parentheses indicates the film thickness (unit: nm).
実施例８
　実施例７の第１正孔輸送層に用いた化合物１に代えて、化合物３を用いたこと以外は実施例７と同様にして有機ＥＬ素子を作製した。 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.
比較例５～６
　実施例７の第１正孔輸送層に用いた化合物１に代えて、比較化合物１（比較例５）又は比較化合物２（比較例６）を用いたこと以外は実施例７と同様にして有機ＥＬ素子を作製した。 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.
素子寿命の測定
　実施例７～８及び比較例５～６で得られた各有機ＥＬ素子を、電流密度５０ｍＡ／ｃｍ２で直流駆動し、輝度が初期輝度の９５％に減少するまでの時間を測定し、これを９５％寿命（ＬＴ９５）とした。結果を表３に示す。 Measurement of Device Life Time Each organic EL device obtained in Examples 7 to 8 and Comparative Examples 5 to 6 was driven by direct current at a current density of 50 mA / cm 2 , and the time required for the brightness to decrease to 95% of the initial brightness was measured. The measurement was performed and this was defined as 95% life (LT95). The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000108
Figure JPOXMLDOC01-appb-T000108
　表３から明らかなように、特定の構造を有する発明化合物（１）及び発明化合物（２）を青色有機ＥＬ素子の正孔輸送層材料として用いることにより、比較化合物１及び２では実現されない、素子寿命が改善された有機ＥＬ素子が得られることがわかる。 As is clear from Table 3, by using the invented compound (1) and the invented compound (2) having a specific structure as the hole transport layer material of the blue organic EL device, the device which cannot be realized by the comparative compounds 1 and 2 is obtained. It can be seen that an organic EL device having an improved life can be obtained.
　１、１１　有機ＥＬ素子
　２　基板
　３　陽極
　４　陰極
　５　発光層
　６　正孔輸送帯域
　６ａ　第１正孔輸送層
　６ｂ　第２正孔輸送層
　７　電子輸送帯域
　７ａ　第１電子輸送層
　７ｂ　第２電子輸送層
　１０、２０　発光ユニット

  1, 11 Organic EL element 2 Substrate 3 Anode 4 Cathode 5 Light emitting layer 6 Hole transporting zone 6a First hole transporting layer 6b Second hole transporting layer 7 Electron transporting zone 7a First electron transporting layer 7b Second electron transporting layer 10, 20 light emitting unit

Claims (23)

  1. 　下記式（１）で表される化合物。
    Figure JPOXMLDOC01-appb-C000001
    （式（１）において、
    　Ｒ１～Ｒ４から選ばれる1つは＊ａに結合する単結合であり、
    　Ｒ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４は、
    それぞれ独立して、水素原子又は置換基であり、
    該置換基は、
    ハロゲン原子、シアノ基、ニトロ基、
    置換もしくは無置換の炭素数１～３０のアルキル基、
    置換もしくは無置換の環形成炭素数３～３０のシクロアルキル基、
    置換もしくは無置換の環形成炭素数６～３０のアリール基、
    置換もしくは無置換の炭素数７～３６のアラルキル基、
    置換もしくは無置換の炭素数１～３０のアルコキシ基、
    置換もしくは無置換の環形成炭素数６～３０のアリールオキシ基、
    置換もしくは無置換の炭素数１～３０のアルキル基及び置換もしくは無置換の環形成炭素数６～３０のアリール基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基、
    置換もしくは無置換の炭素数１～３０ハロアルキル基、
    置換もしくは無置換の炭素数１～３０のハロアルコキシ基、及び、
    置換もしくは無置換の環形成原子数５～３０のヘテロアリール基からなる群から選ばれる。
    　ただし、Ｒ５～Ｒ８から選ばれる隣接する２つ、Ｒ１０～Ｒ１９から選ばれる隣接する２つ、及び＊ａに結合する単結合ではないＲ１～Ｒ４から選ばれる隣接する２つは、それぞれ独立して、水素原子又は前記置換基を表すか、又は、互いに結合して置換もしくは無置換の環構造を形成する。
    　Ｒ３０～Ｒ４６は、それぞれ独立して、水素原子、又は置換もしくは無置換の炭素数１～３０のアルキル基である。ただし、Ｒ３０とＲ３３、Ｒ３１とＲ３２、Ｒ３７～Ｒ４１から選ばれる隣接する２つ、及びＲ４２～Ｒ４６から選ばれる隣接する２つは、それぞれ独立して、水素原子又は置換もしくは無置換の炭素数１～３０のアルキル基を表すか、又は、互いに結合して置換もしくは無置換の環構造を形成する。
    　Ａｒは、
    置換もしくは無置換のフェニル基、
    置換もしくは無置換の環形成炭素数１０～２６の、６員環からのみで構成される縮合アリール基、
    置換もしくは無置換のジベンゾフラニル基、又は置換もしくは無置換のジベンゾチオフェニル基であり、
    Ａｒの前記「置換もしくは無置換」というときの任意の置換基が、
    無置換の炭素数１～３０のアルキル基、
    無置換の炭素数１～３０のアルキル基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基であり、
    　Ｌは単結合、又は置換もしくは無置換の環形成炭素数６～２０のアリーレン基である。）     A compound represented by the following formula (1).
    Figure JPOXMLDOC01-appb-C000001
    (In formula (1),
    One selected from 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,
    A mono-, di- or tri-substituted silyl group having a substituent selected from a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms,
    A substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms,
    A substituted or unsubstituted haloalkoxy group having 1 to 30 carbon atoms, and
    It is selected from the group consisting of a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.
    However, 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. 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.
    R 30 to R 46 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. However, 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. )
  2. 　前記式（１）で表される化合物が少なくとも１個の重水素原子を含む請求項１に記載の化合物。 The compound according to claim 1, wherein the compound represented by the formula (1) contains at least one deuterium atom.
  3. 　前記式（１）で表される化合物が、下記式（１－ａ）又は（１－ｂ）で表される、請求項１又は２に記載の化合物。
    Figure JPOXMLDOC01-appb-C000002
    （式（１－ａ）及び（１－ｂ）において、Ｒ１～Ｒ８、Ｒ１０～Ｒ１９、Ｒ３０～Ｒ４６、Ｌ、及びＡｒは式（１）において定義したとおりである。）     The compound according to claim 1 or 2, wherein the compound represented by the formula (1) is represented by the following formula (1-a) or (1-b).
    Figure JPOXMLDOC01-appb-C000002
    (In the formulas (1-a) and (1-b), R 1 to R 8 , R 10 to R 19 , R 30 to R 46 , L, and Ar are as defined in the formula (1).)
  4. 　前記式（１）で表される化合物が、下記式（１－ａ）で表される、請求項１～３のいずれか１項に記載の化合物。
    Figure JPOXMLDOC01-appb-C000003
    （式（１－ａ）において、Ｒ１～Ｒ８、Ｒ１０～Ｒ１９、Ｒ３０～Ｒ４６、Ｌ、及びＡｒは式（１）において定義したとおりである。）     The compound according to any one of claims 1 to 3, wherein the compound represented by the formula (1) is represented by the following formula (1-a).
    Figure JPOXMLDOC01-appb-C000003
    (In the formula (1-a), R 1 to R 8 , R 10 to R 19 , R 30 to R 46 , L, and Ar are as defined in the formula (1).)
  5. 　前記式（１）で表される化合物が、下記式（１－ｂ）で表される、請求項１～３のいずれか１項に記載の化合物。
    Figure JPOXMLDOC01-appb-C000004
    （式（１－ｂ）において、Ｒ１～Ｒ８、Ｒ１０～Ｒ１９、Ｒ３０～Ｒ４６、Ｌ、及びＡｒは式（１）において定義したとおりである。）     The compound according to any one of claims 1 to 3, wherein the compound represented by the formula (1) is represented by the following formula (1-b).
    Figure JPOXMLDOC01-appb-C000004
    (In the formula (1-b), R 1 to R 8 , R 10 to R 19 , R 30 to R 46 , L, and Ar are as defined in the formula (1).)
  6. 　前記式（１）で表される化合物が、下記式（１－ｃ）で表される、請求項１又は２に記載の化合物。
    Figure JPOXMLDOC01-appb-C000005
    （式（１－ｃ）において、Ｒ１～Ｒ８、Ｒ１０～Ｒ１９、Ｒ３０～Ｒ４６、Ａｒ、及び＊ａは式（１）において定義したとおりである。）     The compound according to claim 1 or 2, wherein the compound represented by the formula (1) is represented by the following formula (1-c).
    Figure JPOXMLDOC01-appb-C000005
    (In the formula (1-c), R 1 to R 8 , R 10 to R 19 , R 30 to R 46 , Ar, and * a are as defined in the formula (1).)
  7. 　前記式（１）のＬが置換もしくは無置換のフェニレン基、置換もしくは無置換のナフチレン基、又は置換もしくは無置換のビフェニレン基である請求項１～５のいずれか１項に記載の化合物。 The compound according to any one of claims 1 to 5, wherein L in the formula (1) is a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted biphenylene group.
  8. 　前記式（１）で表される化合物が、下記式（１－ｄ）で表される請求項１～５及び７のいずれか１項に記載の化合物。
    Figure JPOXMLDOC01-appb-C000006
    （式（１－ｄ）において、
    　Ｒ１～Ｒ８、Ｒ１０～Ｒ１９、Ｒ３０～Ｒ４６、Ａｒ、及び＊ａは式（１）において定義したとおりであり、
    　Ｒ５１～Ｒ５６から選ばれる１つは＊ｂ１に結合する単結合であり、
    　＊ｂ１に結合する単結合以外のＲ５１～Ｒ５６から選ばれる１つは＊ｂ２に結合する単結合であり、
    　＊ｂ１に結合する単結合ではなく、かつ、＊ｂ２に結合する単結合でもないＲ５１～Ｒ５６は、式（１）のＲ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４と同様に定義される。）     The compound according to any one of claims 1 to 5 and 7, wherein the compound represented by the formula (1) is represented by the following formula (1-d).
    Figure JPOXMLDOC01-appb-C000006
    (In formula (1-d),
    R 1 to R 8 , R 10 to R 19 , R 30 to R 46 , Ar, 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 . )
  9. 　前記式（１）で表される化合物が、下記式（１－ｅ）で表される請求項１～５及び７のいずれか１項に記載の化合物。
    Figure JPOXMLDOC01-appb-C000007
    （式（１－ｅ）において、
    　Ｒ１～Ｒ８、Ｒ１０～Ｒ１９、Ｒ３０～Ｒ４６、Ａｒ、及び＊ａは式（１）において定義したとおりであり、
    　Ｒ５１～Ｒ５４及びＲ５６から選ばれる１つは＊ｂ３に結合する単結合であり、
    　Ｒ５７～Ｒ６１から選ばれる１つは＊ｂ４に結合する単結合であり、
    　＊ｂ３に結合する単結合ではなく、かつ、＊ｂ４に結合する単結合でもないＲ５１～Ｒ５４及びＲ５６～Ｒ６１は、式（１）のＲ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４と同様に定義される。）     The compound according to any one of claims 1 to 5 and 7, wherein the compound represented by the formula (1) is represented by the following formula (1-e).
    Figure JPOXMLDOC01-appb-C000007
    (In the formula (1-e),
    R 1 to R 8 , R 10 to R 19 , R 30 to R 46 , Ar, 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). , And * 1 as well as R 1 to R 4 which are not a single bond. )
  10. 　前記式（１）で表される化合物が、下記式（１－ｆ）で表される請求項１～５及び７のいずれか１項に記載の化合物。
    Figure JPOXMLDOC01-appb-C000008
    （式中、
    　Ｒ１～Ｒ８、Ｒ１０～Ｒ１９、Ｒ３０～Ｒ４６、Ａｒ、及び＊ａは式（１）において定義したとおりであり、
    　Ｒ５１、Ｒ５２、Ｒ５５、Ｒ５６、及びＲ６２～Ｒ６５から選ばれる１つは＊ｂ５に結合する単結合であり、
    　＊ｂ５に結合する単結合ではないＲ５１、Ｒ５２、Ｒ５５、Ｒ５６、及びＲ６２～Ｒ６５から選ばれる１つは＊ｂ６に結合する単結合であり、
    　＊ｂ５に結合する単結合ではなく、かつ、＊ｂ６に結合する単結合でもないＲ５１、Ｒ５２、Ｒ５５、Ｒ５６、及びＲ６２～Ｒ６５は、式（１）のＲ５～Ｒ８、Ｒ１０～Ｒ１９、及び＊ａに結合する単結合ではないＲ１～Ｒ４と同様に定義される。）     The compound according to any one of claims 1 to 5 and 7, wherein the compound represented by the formula (1) is represented by the following formula (1-f).
    Figure JPOXMLDOC01-appb-C000008
    (In the formula,
    R 1 to R 8 , R 10 to R 19 , R 30 to R 46 , Ar, 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. )
  11. 　Ａｒが置換もしくは無置換のフェニル基である、請求項１～１０のいずれか１項に記載の化合物。 The compound according to any one of claims 1 to 10, wherein Ar is a substituted or unsubstituted phenyl group.
  12. 　Ａｒが置換もしくは無置換の環形成炭素数１０～２６の、６員環からのみで構成される縮合アリール基である、請求項１～１０のいずれか１項に記載の化合物。 The compound according to any one of claims 1 to 10, wherein Ar is a substituted or unsubstituted fused aryl group having 10 to 26 ring-forming carbon atoms and composed only of a 6-membered ring.
  13. 　Ａｒが置換もしくは無置換のナフチル基、又は置換もしくは無置換のフェナントリル基である、請求項１～１０及び１２のいずれか１項に記載の有機エレクトロルミネッセンス素子。 The organic electroluminescent device according to any one of claims 1 to 10 and 12, wherein Ar is a substituted or unsubstituted naphthyl group or a substituted or unsubstituted phenanthryl group.
  14. 　Ａｒが置換もしくは無置換のジベンゾフラニル基、又は置換もしくは無置換のジベンゾチオフェニル基である、請求項１～１０のいずれか１項に記載の有機エレクトロルミネッセンス素子。 The organic electroluminescent device according to any one of claims 1 to 10, wherein Ar is a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothiophenyl group.
  15. 　請求項１～１４のいずれか１項に記載の化合物からなる、有機エレクトロルミネッセンス素子用材料。 A material for an organic electroluminescence device, which comprises the compound according to any one of claims 1 to 14.
  16. 　陽極、陰極、及び該陽極と該陰極との間に配置された有機層を含む有機エレクトロルミネッセンス素子であって、
    　該有機層が発光層及び該陽極と該発光層の間に配置された正孔輸送帯域を含み、
    　該正孔輸送帯域が陽極側の第１正孔輸送層と陰極側の第２正孔輸送層を含み、
    　該第１正孔輸送層及び該第２正孔輸送層の一方が請求項１～１４のいずれか１項に記載の式（１）で表される化合物を含み、他方が下記式（２）で表される化合物を含む、有機エレクトロルミネッセンス素子。
    Figure JPOXMLDOC01-appb-C000009
    （式中、
    　Ｘ１は酸素原子、硫黄原子、ＣＲａＲｂ、又は＊ｃに結合する窒素原子であり、
    　Ｘ１が酸素原子、硫黄原子、又はＣＲａＲｂである場合、Ｒ５０～Ｒ５３の１つが＊ｃに結合する単結合であり、
    　Ｒ５４～Ｒ５７及び＊ｃに結合する単結合ではないＲ５０～Ｒ５３は、それぞれ独立して、水素原子又は置換基であり、該置換基は、ハロゲン原子、シアノ基、ニトロ基、置換もしくは無置換の炭素数１～３０のアルキル基、置換もしくは無置換の環形成炭素数３～３０のシクロアルキル基、置換もしくは無置換の環形成炭素数６～３０のアリール基、置換もしくは無置換の炭素数７～３６のアラルキル基、置換もしくは無置換の炭素数１～３０のアルコキシ基、置換もしくは無置換の環形成炭素数６～３０のアリールオキシ基、置換もしくは無置換の炭素数１～３０のアルキル基及び置換もしくは無置換の環形成炭素数６～３０のアリール基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基、置換もしくは無置換の炭素数１～３０ハロアルキル基、置換もしくは無置換の炭素数１～３０のハロアルコキシ基、及び、置換もしくは無置換の環形成原子数５～３０のヘテロアリール基からなる群から選ばれる。
    　ただし、＊ｃに結合する単結合ではないＲ５０～Ｒ５３から選ばれる隣接する２つ及びＲ５４～Ｒ５７から選ばれる隣接する２つは、それぞれ独立して、水素原子又は前記置換基を表すか、又は、互いに結合して置換もしくは無置換の環構造を形成する。
    　Ｒａ及びＲｂは、それぞれ独立して、水素原子、置換もしくは無置換の炭素数１～３０のアルキル基、又は置換もしくは無置換の環形成炭素数６～３０のアリール基であるか、又は、互いに結合して置換もしくは無置換の環構造を形成し、
    　Ｌ１、Ｌ２、及びＬ３は、それぞれ独立して、単結合又は置換もしくは無置換の環形成炭素数６～３０のアリーレン基であり、
    　Ａｒ１及びＡｒ２は、それぞれ独立して、置換もしくは無置換の環形成炭素数６～３０のアリール基又は置換もしくは無置換の環形成原子数５～３０のヘテロアリール基である。
    　Ｒ５４～Ｒ５７、＊ｃに結合する単結合ではないＲ５０～Ｒ５３、前記環構造、Ｌ１～Ｌ３、Ａｒ１、及びＡｒ２の「置換もしくは無置換」で表される任意の置換基は、それぞれ独立して、ハロゲン原子、シアノ基、ニトロ基、置換もしくは無置換の炭素数１～３０のアルキル基、置換もしくは無置換の環形成炭素数３～３０のシクロアルキル基、置換もしくは無置換の環形成炭素数６～３０のアリール基、置換もしくは無置換の炭素数７～３６のアラルキル基、置換もしくは無置換の炭素数１～３０のアルコキシ基、置換もしくは無置換の環形成炭素数６～３０のアリールオキシ基、置換もしくは無置換の炭素数１～３０のアルキル基及び置換もしくは無置換の環形成炭素数６～３０のアリール基から選ばれる置換基を有するモノ、ジ又はトリ置換シリル基、置換もしくは無置換の炭素数１～３０ハロアルキル基、置換もしくは無置換の炭素数１～３０のハロアルコキシ基、及び、置換もしくは無置換の環形成原子数５～３０のヘテロアリール基からなる群から選ばれる。）     An organic electroluminescent device comprising an anode, a cathode, and an organic layer arranged 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) according to any one of claims 1 to 14, and the other one of the following formula (2): An organic electroluminescence device containing a compound represented by.
    Figure JPOXMLDOC01-appb-C000009
    (In the formula,
    X 1 is an oxygen atom, a sulfur atom, CRaRb, or a nitrogen atom bonded to * c,
    When 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 50 ~ R 53 is not a single bond to bond to R 54 ~ R 57 and * 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, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted ring forming aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted 1 to 3 carbon atom A mono-, di- or tri-substituted silyl group having a substituent selected from 30 alkyl groups and a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, a substituted or unsubstituted C 1 group 30 haloalkyl group, a substituted or unsubstituted haloalkoxy group having 1 to 30 carbon atoms, and is selected from the group consisting of heteroaryl groups substituted or unsubstituted ring atoms 5-30.
    However, 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 A model having a substituent selected from an aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms. A di- or tri-substituted silyl group, a substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted haloalkoxy group having 1 to 30 carbon atoms, and a substituted or unsubstituted ring forming atom number 5 to 30 Selected from the group consisting of heteroaryl groups of )
  17. 　前記式（１）で表される化合物が少なくとも１個の重水素原子を含む請求項１６に記載の有機エレクトロルミネッセンス素子。 The organic electroluminescent device according to claim 16, wherein the compound represented by the formula (1) contains at least one deuterium atom.
  18. 　前記第１正孔輸送層が前記式（１）で表される化合物を含み、前記第２正孔輸送層が前記式（２）で表される化合物を含む、請求項１６又は１７に記載の有機エレクトロルミネッセンス素子。 The said 1st positive hole transport layer contains the compound represented by the said Formula (1), The said 2nd positive hole transport layer contains the compound represented by the said Formula (2), The method of Claim 16 or 17. Organic electroluminescent device.
  19. 　前記第１正孔輸送層が前記式（２）で表される化合物を含み、前記第２正孔輸送層が前記式（１）で表される化合物を含む、請求項１６又は１７に記載の有機エレクトロルミネッセンス素子。 The first hole transport layer comprises a compound represented by the formula (2), and the second hole transport layer comprises a compound represented by the formula (1). Organic electroluminescent device.
  20. 　前記第２正孔輸送層が前記発光層に隣接する、請求項１６～１９のいずれか１項に記載の有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to any one of claims 16 to 19, wherein the second hole transport layer is adjacent to the light emitting layer.
  21. 　前記発光層が蛍光ドーパントを含む、請求項１６～２０のいずれか１項に記載の有機エレクトロルミネッセンス素子。 The organic electroluminescent element according to any one of claims 16 to 20, wherein the light emitting layer contains a fluorescent dopant.
  22. 　前記発光層が燐光ドーパントを含む、請求項１６～２０のいずれか１項に記載の有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to any one of claims 16 to 20, wherein the light emitting layer contains a phosphorescent dopant.
  23. 　請求項１６～２２のいずれか１項に記載の有機エレクトロルミネッセンス素子を備えた、電子機器。

          An electronic device comprising the organic electroluminescent element according to any one of claims 16 to 22.

PCT/JP2019/043701 2018-11-07 2019-11-07 Compound and organic electroluminescent element employing same WO2020096001A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018210093A JP2022037253A (en) 2018-11-07 2018-11-07 Compound and organic electroluminescent element employing the same
JP2018-210093 2018-11-07

Publications (1)

Publication Number Publication Date
WO2020096001A1 true WO2020096001A1 (en) 2020-05-14

Family

ID=70610930

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/043701 WO2020096001A1 (en) 2018-11-07 2019-11-07 Compound and organic electroluminescent element employing same

Country Status (2)

Country Link
JP (1) JP2022037253A (en)
WO (1) WO2020096001A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022055092A1 (en) * 2020-09-08 2022-03-17 주식회사 엘지화학 Novel compound and organic light emitting device comprising same
WO2022071424A1 (en) * 2020-09-30 2022-04-07 出光興産株式会社 Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic appliance
US11618740B2 (en) 2019-03-15 2023-04-04 Idemitsu Kosan Co., Ltd. Compound, material for organic electroluminescence devices, organic electroluminescence device, and electronic device
KR20240004351A (en) 2021-04-28 2024-01-11 이데미쓰 고산 가부시키가이샤 Compounds, materials for organic electroluminescent devices, organic electroluminescent devices and electronic devices

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010114017A1 (en) * 2009-04-01 2010-10-07 出光興産株式会社 Organic electroluminescent element
KR20150089427A (en) * 2014-01-28 2015-08-05 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR20160087755A (en) * 2015-01-14 2016-07-22 주식회사 엘지화학 Amine-based compound and organic light emitting device comprising the same
KR20180053121A (en) * 2016-11-11 2018-05-21 주식회사 엘지화학 Organic light emitting device
KR20180116740A (en) * 2017-04-17 2018-10-25 주식회사 동진쎄미켐 Novel compound and organic electroluminescent divice including the same
KR20180131091A (en) * 2017-05-31 2018-12-10 주식회사 동진쎄미켐 Novel compound and organic electroluminescent divice including the same
KR20190103991A (en) * 2018-02-28 2019-09-05 주식회사 엘지화학 Organic light emitting device

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010114017A1 (en) * 2009-04-01 2010-10-07 出光興産株式会社 Organic electroluminescent element
KR20150089427A (en) * 2014-01-28 2015-08-05 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR20160087755A (en) * 2015-01-14 2016-07-22 주식회사 엘지화학 Amine-based compound and organic light emitting device comprising the same
KR20180053121A (en) * 2016-11-11 2018-05-21 주식회사 엘지화학 Organic light emitting device
KR20180116740A (en) * 2017-04-17 2018-10-25 주식회사 동진쎄미켐 Novel compound and organic electroluminescent divice including the same
KR20180131091A (en) * 2017-05-31 2018-12-10 주식회사 동진쎄미켐 Novel compound and organic electroluminescent divice including the same
KR20190103991A (en) * 2018-02-28 2019-09-05 주식회사 엘지화학 Organic light emitting device

Cited By (4)

* Cited by examiner, † Cited by third party
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 (en) * 2020-09-08 2022-03-17 주식회사 엘지화학 Novel compound and organic light emitting device comprising same
WO2022071424A1 (en) * 2020-09-30 2022-04-07 出光興産株式会社 Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic appliance
KR20240004351A (en) 2021-04-28 2024-01-11 이데미쓰 고산 가부시키가이샤 Compounds, materials for organic electroluminescent devices, organic electroluminescent devices and electronic devices

Also Published As

Publication number Publication date
JP2022037253A (en) 2022-03-09

Similar Documents

Publication Publication Date Title
JP7155249B2 (en) Compounds, materials for organic electroluminescence devices, organic electroluminescence devices, and electronic devices
JP6454226B2 (en) COMPOUND, MATERIAL FOR ORGANIC ELECTROLUMINESCENT ELEMENT, ORGANIC ELECTROLUMINESCENT ELEMENT, AND ELECTRONIC DEVICE
JPWO2019027040A1 (en) Compound, material for organic electroluminescence device, organic electroluminescence device, and electronic device
WO2018164201A1 (en) Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic device
WO2018164265A1 (en) Compound, organic electroluminescent element material, organic electroluminescent element, and electronic device
WO2017022730A1 (en) Compound, material for organic electroluminescence elements, organic electroluminescence element, and electronic device
JP6819964B2 (en) Compounds, materials for organic electroluminescence devices, organic electroluminescence devices, and electronic devices
JP6696091B2 (en) Compound, material for organic electroluminescence device, organic electroluminescence device, and electronic device
WO2020111253A1 (en) Compound, material for organic electroluminescent elements, organic electroluminescent element and electronic device
WO2018164239A1 (en) Compound, material for organic electroluminescence element, organic electroluminescence element, and electronic device
WO2020096001A1 (en) Compound and organic electroluminescent element employing same
WO2019216411A1 (en) Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic device
WO2020095998A1 (en) Organic electroluminescent element and electronic device
WO2017022727A1 (en) Compound, material for organic electroluminescence elements, organic electroluminescence element, and electronic device
JP2018108939A (en) Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic apparatus
WO2020116418A1 (en) Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device
WO2021033730A1 (en) Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device
WO2016204151A1 (en) Compound, material for organic electroluminescence element, organic electroluminescence element, and electronic device
WO2016056640A1 (en) Compound, organic electroluminescent element material, organic electroluminescent element, and electronic apparatus
WO2020050217A1 (en) Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic device
JP2019199442A (en) Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic device
JP2020043182A (en) Organic electroluminescence element and electronic equipment
JP7249470B2 (en) Compounds, materials for organic electroluminescence devices, organic electroluminescence devices and electronic devices
WO2022210821A1 (en) Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic device
WO2022163735A1 (en) Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19881156

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19881156

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP