WO2022185897A1 - Composé aromatique polynucléaire - Google Patents

Composé aromatique polynucléaire Download PDF

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WO2022185897A1
WO2022185897A1 PCT/JP2022/005815 JP2022005815W WO2022185897A1 WO 2022185897 A1 WO2022185897 A1 WO 2022185897A1 JP 2022005815 W JP2022005815 W JP 2022005815W WO 2022185897 A1 WO2022185897 A1 WO 2022185897A1
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ring
aryl
formula
carbon atoms
alkyl
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琢次 畠山
康平 諌山
亮介 川角
靖宏 近藤
敬太 田端
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学校法人関西学院
エスケーマテリアルズジェイエヌシー株式会社
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Priority to CN202280017455.7A priority Critical patent/CN116888132A/zh
Priority to JP2023503689A priority patent/JPWO2022185897A1/ja
Priority to KR1020237030556A priority patent/KR20230154308A/ko
Publication of WO2022185897A1 publication Critical patent/WO2022185897A1/fr

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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/658—Organoboranes
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to polycyclic aromatic compounds.
  • the present invention also relates to an organic device material, an organic electroluminescence device, a display device and a lighting device containing the polycyclic aromatic compound.
  • An organic EL element has a structure consisting of a pair of electrodes consisting of an anode and a cathode, and one or more layers disposed between the pair of electrodes and containing an organic compound.
  • a layer containing an organic compound (sometimes referred to as an "organic layer” in this specification) includes a light-emitting layer, a charge transport/injection layer that transports or injects charges such as holes and electrons, and the like.
  • organic materials have been developed that are suitable for the layer.
  • Patent Document 1 discloses that polycyclic aromatic compounds in which aromatic rings are linked by heteroatoms such as boron, phosphorus, oxygen, nitrogen, and sulfur are useful as materials for organic electroluminescent devices and the like. It is This polycyclic aromatic compound has a large HOMO-LUMO gap, a high lowest excited triplet energy level (E T ), and exhibits thermally activated delayed fluorescence, and is therefore particularly useful as a fluorescent material for organic electroluminescent devices. It is reported that there is
  • An object of the present invention is to provide a novel material useful as an organic device material such as an organic EL element.
  • the present inventors have made intensive studies to solve the above problems, and have succeeded in producing new compounds as polycyclic aromatic compounds in which aromatic rings are linked by heteroatoms such as boron, phosphorus, oxygen, nitrogen, and sulfur. . Further, the present inventors have found that an excellent organic EL device can be obtained by arranging a layer containing this polycyclic aromatic compound between a pair of electrodes to form an organic EL device, and completed the present invention. That is, the present invention provides the following polycyclic aromatic compounds, organic device materials, etc. containing the following polycyclic aromatic compounds.
  • each Y is B.
  • ⁇ 4> The polycyclic aromatic according to any one of ⁇ 1> to ⁇ 3>, wherein the A ring, B ring, D ring, C ring and E ring are all optionally substituted benzene rings. family compound.
  • ⁇ 5> The polycyclic aromatic compound according to any one of ⁇ 1> to ⁇ 4>, wherein all n are 1.
  • Me is methyl and tBu is t-butyl.
  • ⁇ 7> An organic device material containing the polycyclic aromatic compound according to any one of ⁇ 1> to ⁇ 6>.
  • ⁇ 8> The organic device material according to ⁇ 7>, wherein the organic device material is an organic electroluminescence element material, an organic field effect transistor material, or an organic thin film solar cell material.
  • the organic electroluminescent element material is a light-emitting layer material.
  • An organic layer comprising a pair of electrodes consisting of an anode and a cathode, and an organic layer disposed between the pair of electrodes and containing the polycyclic aromatic compound according to any one of ⁇ 1> to ⁇ 6> Electroluminescence device.
  • the organic electroluminescence device according to ⁇ 10>, wherein the organic layer is a light-emitting layer.
  • the host material is a compound having a lowest excited triplet energy level higher than the lowest excited triplet energy level of the polycyclic aromatic compound by at least 0.01 eV. element.
  • a display device or lighting device comprising the organic electroluminescence device according to any one of ⁇ 10> to ⁇ 13>.
  • the present invention provides a novel polycyclic aromatic compound.
  • the polycyclic aromatic compound of the present invention is useful as an organic device material, particularly as a light-emitting layer material for forming a light-emitting layer of an organic electroluminescence device.
  • FIG. 3 is an energy level diagram showing the energy relationship between a host, an assisting dopant and an emitting dopant in a TAF device using a general fluorescent dopant.
  • FIG. 2 is an energy level diagram showing an example of the energy relationship among a host, an assisting dopant, and an emitting dopant in an organic electroluminescence device of one embodiment of the present invention. It is a figure explaining the method of manufacturing an organic EL element using the inkjet method on the board
  • substituted with substituent A means that “substituent B having Y carbon atoms” is substituted with “substituent A (with no carbon number limitation)”.
  • the carbon number Y is not the total carbon number of the substituents A and B.
  • polycyclic aromatic compounds 1-1 Polycyclic Aromatic Compound
  • the polycyclic aromatic compound of the present invention is a polycyclic aromatic compound represented by formula (4).
  • the polycyclic aromatic compound represented by formula (4) is useful as a compound for forming highly efficient and long-life organic EL devices.
  • polycyclic aromatic compounds represented by formula (4) have high TADF properties.
  • the polycyclic aromatic compound represented by formula (4) adopting a steric structure that increases the spin angular momentum, introducing heavy atoms into the molecule, or combining them can be achieved by
  • the polycyclic aromatic compound represented by formula (4) is less likely to decompose during vapor deposition than analogous compounds having approximately the same molecular weight.
  • n is 0 or 1 each independently. When n is 1 in —(X) n — that connects the A ring and the D ring, it indicates that the A ring and the D ring are connected by a connecting group X, and when n is 0, A Indicates that the ring and the D ring are bonded with a single bond.
  • Ring A, ring B, ring C, ring D and ring E are each independently an optionally substituted aryl ring or an optionally substituted heteroaryl ring.
  • Each of the A ring, B ring, C ring, D ring and E ring is preferably bonded to Y in the 5- or 6-membered ring. It is also preferably bonded to N or -(X) n - through the same 5- or 6-membered ring.
  • "bonded in a 5- or 6-membered ring” means that the ring is formed only by the 5- or 6-membered ring, or the 5- or 6-membered ring is included.
  • Y and N or -(X) n - that are bonded to the same ring may be bonded to adjacent ring-constituting atoms.
  • the "aryl ring" in the A ring, B ring, C ring, D ring and E ring includes, for example, an aryl ring having 6 to 30 carbon atoms, preferably an aryl ring having 6 to 16 carbon atoms, and 6 carbon atoms.
  • An aryl ring with ⁇ 12 carbon atoms is more preferred, and an aryl ring with 6 to 10 carbon atoms is particularly preferred.
  • aryl rings include monocyclic benzene ring, bicyclic biphenyl ring, condensed bicyclic naphthalene ring and indene ring, tricyclic terphenyl ring (m-ter phenyl, o-terphenyl, p-terphenyl), condensed tricyclic acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, anthracene ring, condensed tetracyclic triphenylene ring, pyrene ring, naphthacene ring, Examples include a chrysene ring, a condensed pentacyclic perylene ring, and a pentacene ring.
  • the fluorene ring, benzofluorene ring, and indene ring also include structures in which fluorene rings, benzofluorene rings, cyclopentane rings, and the like are spiro-bonded, respectively.
  • fluorene ring, the benzofluorene ring and the indene ring two of the two hydrogen atoms of methylene are respectively substituted with alkyl such as methyl as the first substituent described later to form a dimethylfluorene ring and a dimethylbenzofluorene ring. and those with a dimethylindene ring and the like are also included.
  • the "heteroaryl ring" in the A ring, B ring, C ring, D ring and E ring includes, for example, a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms, A heteroaryl ring having 2 to 20 carbon atoms is more preferable, a heteroaryl ring having 2 to 15 carbon atoms is more preferable, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferable.
  • Examples of the "heteroaryl ring” include heterocyclic rings containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.
  • heteroaryl rings include, for example, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring , cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine
  • dihydroacridine ring, xanthene ring, and thioxanthene ring two of the two hydrogens in methylene are respectively substituted with alkyl such as methyl as the first substituent described below, resulting in a dimethyldihydroacridine ring, dimethyl Those having a xanthene ring, a dimethylthioxanthene ring, or the like are also preferable.
  • Bipyridine ring phenylpyridine ring and pyridylphenyl ring which are bicyclic ring systems, and terpyridyl ring, bispyridylphenyl ring and pyridylbiphenyl ring which are tricyclic systems are also mentioned as “heteroaryl ring”.
  • a pyran ring shall also be contained in a "heteroaryl ring.”
  • the substituent is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino , substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino (amino having aryl and heteroaryl), substituted or unsubstituted diarylboryl (two aryls are connected via a single bond or a linking group optionally bonded), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted silyl, or -L-Ak are preferred.
  • the substituents include aryl, heteroaryl, alky
  • At least one hydrogen in the above “aryl ring” or “heteroaryl ring” is the first substituent, substituted or unsubstituted “aryl”, substituted or unsubstituted “heteroaryl”, substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino”, substituted or unsubstituted "diarylboryl (two aryls are may be bonded)”, substituted or unsubstituted “alkyl”, substituted or unsubstituted “cycloalkyl”, substituted or unsubstituted “alkoxy”, substituted or unsubstituted “aryloxy”, substituted “ silyl” or —L—Ak.
  • Aryl of and aryl of "aryloxy” include the above-mentioned monovalent groups of "aryl ring” or “heteroaryl ring".
  • aryl include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, and aryl having 6 to 16 carbon atoms. is more preferred, aryl having 6 to 12 carbon atoms is particularly preferred, and aryl having 6 to 10 carbon atoms is most preferred.
  • aryls include, for example, monocyclic aryl phenyl, bicyclic aryl (2-,3-,4-)biphenylyl, condensed bicyclic aryl (1-,2-)naphthyl , (2-,3-,4-,5-,6-,7-)indenyl, tricyclic aryl terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o-terphenyl-4′-yl, p-terphenyl-2′-yl, m-terphenyl-2-yl, m -terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-
  • heteroaryl includes, for example, heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, more preferably heteroaryl having 2 to 20 carbon atoms, and 2 to 2 carbon atoms. Heteroaryl of 15 is more preferred, and heteroaryl of 2 to 10 carbon atoms is particularly preferred. Heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.
  • heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, benzo[b]thienyl, dibenzothienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinox
  • Alkyl as the first substituent may be either straight-chain or branched-chain, for example, straight-chain alkyl having 1 to 24 carbon atoms or branched-chain alkyl having 3 to 24 carbon atoms.
  • Alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms) is preferable, alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms) is more preferable, and alkyl having 1 to 8 carbon atoms (Branched chain alkyl having 3 to 8 carbon atoms) is more preferable, alkyl having 1 to 6 carbon atoms (branched chain alkyl having 3 to 6 carbon atoms) is particularly preferable, and alkyl having 1 to 5 carbon atoms (branched chain alkyl having 3 to 5 carbon atoms) is more preferable. branched chain alkyl) are most preferred.
  • alkyls include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl), n- hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl (1,1,3,3 -tetramethylbutyl), 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-dec
  • tertiary-alkyl represented by the following formula (tR) is substituted when at least one hydrogen in the above aryl ring or heteroaryl ring is substituted with a substituent It is one of the particularly preferred groups. This is because such a bulky substituent increases the intermolecular distance, thereby improving the light emission quantum yield (PLQY). Further, a substituent in which a tertiary-alkyl represented by formula (tR) substitutes another substituent as a second substituent is also preferable.
  • tertiary-alkyl-substituted diarylamino represented by (tR) tertiary-alkyl-substituted carbazolyl (preferably N-carbazolyl) represented by (tR) or (tR) and benzocarbazolyl (preferably N-benzocarbazolyl) substituted with tertiary-alkyl represented.
  • “Diarylamino” includes the groups described as the "first substituent” below.
  • Substitution forms of the group of formula (tR) on diarylamino, carbazolyl and benzocarbazolyl include substitution of a group of formula (tR) for some or all hydrogens of the aryl ring or benzene ring in these groups.
  • substitution forms of the group of formula (tR) on diarylamino, carbazolyl and benzocarbazolyl include substitution of a group of formula (tR) for some or all hydrogens of the aryl ring or benzene ring in these
  • R a , R b , and R c are each independently alkyl having 1 to 24 carbon atoms, and any —CH 2 — in the alkyl may be substituted with —O—.
  • * is the binding position.
  • C1-C24 alkyl of R a , R b and R c may be either linear or branched chain, for example, C 1-24 linear alkyl or C 3-24 branched Chain Alkyl, C1-C18 Alkyl (C3-C18 Branched Alkyl), C1-C12 Alkyl (C3-C12 Branched Alkyl), C1-C6 Alkyl (Cb branched chain alkyl having 3 to 6 carbon atoms) and alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms).
  • the total number of carbon atoms of R a , R b and R c in formula (tR) is preferably 3-20 carbon atoms, particularly preferably 3-10 carbon atoms.
  • R a , R b , and R c include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t -pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1- methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl,
  • Examples of groups represented by formula (tR) include t-butyl, t-amyl, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-ethyl-1- methylbutyl, 1,1,3,3-tetramethylbutyl, 1,1,4-trimethylpentyl, 1,1,2-trimethylpropyl, 1,1-dimethyloctyl, 1,1-dimethylpentyl, 1,1- dimethylheptyl, 1,1,5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl-1,3-dimethylbutyl, 1,1,2,2-tetramethylpropyl, 1-butyl-1- methylpentyl, 1,1-diethylbutyl, 1-ethyl-1-methylpentyl, 1,1,3-trimethylbutyl, 1-propyl-1-methylpentyl, 1,1,2-trimethylprop
  • Cycloalkyl as the first substituent includes cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, Examples include cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, and cycloalkyl having 5 carbon atoms.
  • cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, alkyl (especially methyl)-substituted products thereof having 1 to 5 carbon atoms, norbornyl (bicyclo[2 .2.1]heptyl), bicyclo[1.1.0]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.1.0]pentyl, bicyclo[2.1.1]hexyl, bicyclo[ 3.1.0]hexyl, bicyclo[2.2.2]octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.
  • Alkoxy as the first substituent includes, for example, straight chain alkoxy having 1 to 24 carbon atoms or branched chain alkoxy having 3 to 24 carbon atoms. Alkoxy having 1 to 18 carbon atoms (branched alkoxy having 3 to 18 carbon atoms) is preferable, alkoxy having 1 to 12 carbon atoms (branched alkoxy having 3 to 12 carbon atoms) is more preferable, and 1 to 6 carbon atoms. (branched alkoxy having 3 to 6 carbon atoms) is more preferred, and alkoxy having 1 to 5 carbon atoms (branched alkoxy having 3 to 5 carbon atoms) is particularly preferred.
  • alkoxy examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, t-amyloxy, pentyloxy, hexyloxy, heptyloxy, and octyloxy.
  • Substituted silyl as the first substituent includes, for example, silyl substituted with three substituents selected from the group consisting of alkyl, cycloalkyl and aryl. Examples include trialkylsilyls, tricycloalkylsilyls, dialkylcycloalkylsilyls, alkyldicycloalkylsilyls, triarylsilyls, dialkylarylsilyls, and alkyldiarylsilyls.
  • Trialkylsilyl includes a group in which three hydrogen atoms in a silyl group are each independently substituted with alkyl, and this alkyl refers to the group described as "alkyl" in the first substituent above be able to.
  • Preferred alkyl for substitution is alkyl having 1 to 5 carbon atoms, and specific examples include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, t-amyl and the like.
  • trialkylsilyls include trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, trisec-butylsilyl, tri-t-butylsilyl, tri-t-amylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, t-amyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethyl silyl, t-butyldiethylsilyl, t-amyldiethylsilyl,
  • tricycloalkylsilyl include groups in which three hydrogen atoms in a silyl group are each independently substituted with cycloalkyl, and this cycloalkyl is described as the "cycloalkyl" in the first substituent described above. groups can be cited.
  • Preferred cycloalkyls for substitution are cycloalkyls having 5 to 10 carbon atoms, specifically cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo[1.1.1]pentyl, bicyclo[ 2.1.0]pentyl, bicyclo[2.1.1]hexyl, bicyclo[3.1.0]hexyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, adamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.
  • tricycloalkylsilyls include tricyclopentylsilyl and tricyclohexylsilyl.
  • dialkylcycloalkylsilyl substituted by 2 alkyl and 1 cycloalkyl and alkyldicycloalkylsilyl substituted by 1 alkyl and 2 cycloalkyl are selected from the above specific alkyl and cycloalkyl and silyl substituted with a group such as
  • dialkylarylsilyl substituted by 2 alkyl and 1 aryl alkyldiarylsilyl substituted by 1 alkyl and 2 aryl
  • triarylsilyl substituted by 3 aryl include the specific alkyl and silyl substituted with a group selected from aryl.
  • triarylsilyls include, in particular, triphenylsilyl.
  • aryl in the "diarylboryl” of the first substituent, the above description of aryl can be cited.
  • the two aryls may also be linked via a single bond or a linking group (eg >C(--R) 2 , >O, >S or >NR).
  • R in >C(--R) 2 and >N--R is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy (the above are the first substituents);
  • the substituent may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl (these are the second substituents), and specific examples of these groups include the above-mentioned aryl as the first substituent, hetero References may be made to aryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy.
  • L is >N-R, >O or >S
  • R in >N-R is optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted cycloalkyl.
  • R in the above >NR may be bonded to Ak via a linking group or a single bond.
  • Ak is hydrogen, optionally substituted alkyl or optionally substituted cycloalkyl, wherein at least one hydrogen in said alkyl and cycloalkyl may be substituted, and at least one in said alkyl and cycloalkyl —CH 2 — may be substituted with —O— and —S—.
  • L is >NR.
  • R when L is >N--R is preferably alkyl or aryl optionally substituted with cycloalkyl, heteroaryl optionally substituted with alkyl or cycloalkyl, alkyl or cycloalkyl, and alkyl aryl optionally substituted with, heteroaryl optionally substituted with alkyl, more preferably alkyl or cycloalkyl, more preferably aryl optionally substituted with alkyl, substituted with methyl phenyl, which may be optionally substituted, is particularly preferred.
  • Ak is preferably alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, preferably alkyl having 1 to 4 carbon atoms or cycloalkyl having 3 to 8 carbon atoms, and It is more preferably 4 alkyl, even more preferably methyl.
  • R when L is >NR may be attached to Ak through a linking group or a single bond.
  • the linking group at this time include >O, >S, and >Si(-R) 2 .
  • >Si(-R) 2 R is hydrogen, aryl having 6 to 12 carbon atoms, alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms. Examples of structures in which R in >NR is bound to Ak via a linking group or a single bond are as follows.
  • Me is methyl, and is bonded at the * position to a ring-constituting atom of the aryl ring or heteroaryl ring in the A ring, B ring, C ring, D ring, or E ring.
  • At least one hydrogen in may be substituted with a second substituent.
  • the second substituent include aryl, heteroaryl, alkyl, or cycloalkyl, and specific examples thereof include the above-described monovalent groups of "aryl ring” or “heteroaryl ring", Reference can be made to the description of "alkyl” or "cycloalkyl” as the first substituent.
  • at least one hydrogen in them is aryl such as phenyl (specific examples are the groups described above), methyl, alkyl such as t-butyl (specific examples are the groups described above).
  • a structure substituted with cycloalkyl such as cyclohexyl is also included in the aryl or heteroaryl as the second substituent.
  • the second substituent is carbazolyl
  • carbazolyl in which at least one hydrogen at the 9-position is substituted with an aryl such as phenyl, an alkyl such as methyl, or a cycloalkyl such as cyclohexyl is also a second substituent.
  • heteroaryl as a substituent.
  • the emission wavelength can be adjusted by the steric hindrance, electron donating and electron withdrawing properties of the structure of the first substituent.
  • Groups represented by the following structural formulas are preferable, and more preferably methyl, t-butyl, t-amyl, t-octyl, neopentyl, adamantyl, phenyl, o-tolyl, p-tolyl, 2,4- xylyl, 2,5-xylyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis(p-(t-butyl)phenyl)amino, carbazolyl (especially N- carbazolyl), 3,6-dimethylcarbazolyl, 3,6-di-t-butylcarbazolyl and phenoxy, more preferably methyl, t-butyl, t-amyl, t-octyl
  • t-butyl t-amyl, t-octyl, adamantyl, o-tolyl, p-tolyl , 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 2,4,6-mesityl, di-p-tolylamino, bis(p-(t-butyl)phenyl)amino, 3,6- Dimethylcarbazolyl and 3,6-di-t-butylcarbazolyl are preferred.
  • the substituent when two or three hydrogen atoms bonded to consecutive (adjacent) carbon atoms are substituted may be a group represented by formula (A20).
  • L S is >N—R, >O, >Si(—R) 2 or >S
  • R in >N—R is optionally substituted aryl, substituted optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted cycloalkyl
  • R in >Si(—R) 2 is hydrogen, optionally substituted aryl, substituted optionally substituted alkyl or optionally substituted cycloalkyl, which may be bonded to each other to form a ring, and at least R of the above >NR and the above >Si(-R) 2 one may be bonded to at least one selected from the group consisting of A ring, B ring, C ring, D ring, E ring and RS via a linking group or a single bond; r is an integer from 1 to 4, Each R S is independently hydrogen, optionally substituted alkyl or optionally substituted cycloalkyl, and any R S is bonded to any other R S through a linking group or
  • the number thereof is preferably one or two.
  • the group represented by formula (A20) may be a substituent in any of the A, B, C, D and E rings.
  • the group represented by formula (A20) is bound by two * to two adjacent atoms on the ring of the aryl or heteroaryl ring.
  • the group represented by formula (A20) is bound with two *'s, respectively, to two adjacent atoms on the aryl or heteroaryl ring.
  • both of the two adjacent atoms on the ring are preferably carbon atoms.
  • a condensed ring structure is formed by bonding the group represented by formula (A20) to the aryl ring or heteroaryl ring.
  • the compound represented by formula (4) having this condensed ring structure has a more rigid structure. If it becomes rigid, it is expected that the vibration of the molecule will be suppressed, the EQE will be improved, the stability of the molecule will be increased, and the life of the device will be extended.
  • L S is >NR, >O, >Si(-R) 2 or >S. It is possible to control the HOMO and LUMO of the compound of the present invention by selecting the type of L s in the group represented by formula (A20).
  • L S is NR, >O or >S
  • the HOMO and LUMO are shallow, and when it is Si, the HOMO and LUMO are deep. If the HOMO and LUMO become shallow, it is expected that the TTF element using this will have a long life, high efficiency, and low driving voltage.
  • the dopant will lose its hole-trapping property, and it is expected that the drive voltage will be significantly lowered.
  • L S >N—R is optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted cyclo is alkyl.
  • R of >Si(—R) 2 for L S in formula (A20) is hydrogen, optionally substituted aryl, optionally substituted alkyl or optionally substituted cycloalkyl; Also, two R's may combine with each other to form a ring.
  • at least one of the >N—R and the R of the >Si(—R) 2 is selected from the group consisting of A ring, B ring, C ring, D ring, E ring and R 2 by a linking group or a single bond. It may be combined with at least one selected.
  • L is preferably >NR, >O or >S, more preferably >NR or >O, even more preferably >NR.
  • R when L S is >N—R is aryl optionally substituted by alkyl or cycloalkyl, heteroaryl optionally substituted by alkyl or cycloalkyl, alkyl or cycloalkyl, It is more preferably aryl optionally substituted with alkyl or cycloalkyl, or heteroaryl optionally substituted with alkyl or cycloalkyl, and aryl optionally substituted with alkyl or cycloalkyl. Phenyl optionally substituted with alkyl or cycloalkyl is particularly preferred.
  • r is an integer of 1 to 4, preferably 2 or 3, more preferably 2.
  • each R S is independently hydrogen, optionally substituted alkyl or optionally substituted cycloalkyl, and any R S is any other R S and a linking group or They may be linked to each other by a single bond.
  • R s are preferably bonded to each other via a linking group or a single bond.
  • the linking group include >O and >S.
  • the divalent group formed by bonding with each other includes alkylene. At least one hydrogen in the alkylene may be substituted with alkyl or cycloalkyl, and at least one (preferably one) —CH 2 — in the alkylene is substituted with —O— and —S— good too.
  • the divalent group formed by bonding to each other is preferably a straight-chain alkylene having 2 to 5 carbon atoms, more preferably a straight-chain alkylene having 3 or 4 carbon atoms, and a straight-chain alkylene having 4 carbon atoms (-( CH 2 ) 4 -) is more preferred. It is particularly preferred that the linear alkylene having 4 carbon atoms (--(CH 2 ) 4 --) is unsubstituted.
  • R s respectively bonded to adjacent carbon atoms are bonded to each other by a linking group or a single bond
  • the remaining R s not participating in this bond are each independently hydrogen or substituted. or is bound to R of >N--R or >Si(--R) 2 which is L 2 S.
  • the optionally substituted alkyl as the remaining R s not participating in this bond is is more preferably optionally substituted alkyl having 1 to 6 carbon atoms, more preferably unsubstituted alkyl having 1 to 6 carbon atoms, and most preferably methyl. That is, a preferable example of the group represented by formula (A20) is the group represented by formula (A20-a).
  • Me is methyl
  • At least one of R of >N—R and >Si(—R) 2 of L S is selected from the group consisting of A ring, B ring, C ring, D ring, E ring and R S by a linking group or a single bond. It may be combined with at least one selected.
  • Examples of when L s is >N—R include groups represented by any of the following formulas, and groups represented by formula (A20-b-1) are preferred.
  • Me is methyl.
  • two or three consecutive (adjacent) rings on any of the aryl, heteroaryl or cycloalkane rings in the A, B, C, D and E rings each bond to one atom.
  • Two Y's in the polycyclic aromatic compound of the present invention may be the same or different, but are preferably the same.
  • Each X in formula (4) is independently >C(-R) 2, >NR, >O, >Si(-R) 2 , >S or >Se, and the >NR is hydrogen, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted cycloalkyl, and the above >C(-R) 2 and >Si(-R) 2 , each R is independently hydrogen, optionally substituted aryl, optionally substituted alkyl or optionally substituted cycloalkyl, and >C(- Two Rs in each of R) 2 and >Si(-R) 2 may be bonded to each other to form a ring, and the >NR, the >C(-R) 2 and the > At least one R in Si(--R) 2 may be bonded to at least one of the A, B, C, D, or E rings via a linking group or a single bond.
  • Plural X's in the polycyclic aromatic compound of the present invention may be the same
  • R of >Si(—R) 2 in X of formula (4) is optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted cyclo It is alkyl, and the substituent includes the second substituent described above.
  • the aryl, heteroaryl, alkyl or cycloalkyl includes the groups mentioned above. In particular, aryl having 6 to 10 carbon atoms (eg phenyl, naphthyl etc.), heteroaryl having 2 to 15 carbon atoms (eg carbazolyl etc.), alkyl having 1 to 5 carbon atoms (eg methyl, ethyl etc.) or 5 to 10 carbon atoms.
  • cycloalkyl preferably cyclohexyl or adamantyl is preferred.
  • R of >C(-R) 2 in X of formula (4) is hydrogen, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted It is a good cycloalkyl, and the substituent includes the second substituent described above.
  • the aryl, heteroaryl, alkyl or cycloalkyl includes the groups mentioned above. In particular, aryl having 6 to 10 carbon atoms (eg phenyl, naphthyl etc.), heteroaryl having 2 to 15 carbon atoms (eg carbazolyl etc.), alkyl having 1 to 5 carbon atoms (eg methyl, ethyl etc.) or 5 to 10 carbon atoms.
  • cycloalkyl preferably cyclohexyl or adamantyl is preferred.
  • two Rs in each of >C(-R) 2 and >Si(-R) 2 which are X may be bonded to each other to form a ring.
  • Two R's may be bonded via a single bond or a linking group (collectively referred to as a linking group).
  • the position where the two R are bonded by the bonding group is not particularly limited as long as it is a bondable position, but it is preferable to bond at the most adjacent position.
  • the position where the two R are phenyl "C” in phenyl It is preferable to bond at the ortho (2-position) positions with respect to the bonding position (1-position) of or "Si" (see the structural formula above).
  • At least one of X in formula (4) is the above-described >NR, and the other Xs are each independently preferably >O, >NR or >S, and any one more preferably >N-R, any one or more >N-R and any one or more >O, and >N-R, >O and >S, respectively It is even more preferable to include one or more.
  • High efficiency or long life devices can be formed with compounds of the invention containing >S as X.
  • aryl, heteroaryl, alkyl, cycloalkyl in R of >NR in X reference can be made to their description as the first substituent above.
  • >N—R in X is preferably optionally substituted aryl, optionally substituted heteroaryl or optionally substituted cycloalkyl, and optionally substituted aryl is more preferred.
  • aryl is preferably phenyl, biphenylyl (especially 2-biphenylyl) and terphenylyl (especially terphenyl-2'-yl), more preferably phenyl and biphenylyl.
  • the substituent is preferably methyl or tertiary-alkyl represented by the above formula (tR).
  • the number of substituents in aryl is preferably 0 to 3, more preferably 1 to 2.
  • R of >NR in X unsubstituted phenyl, phenyl having methyl bonded to the ortho or para position, and phenyl having methyl bonded to one or two ortho positions are particularly preferred.
  • R of >NR in X may have the structure shown below. Having an o-phenylene structure in R of >NR can prevent intermolecular stacking and suppress concentration quenching. >When R of NR has a p-phenylene structure, it is possible to impart horizontal orientation to the molecule and improve light extraction efficiency. >When R of NR has a heteroaryl structure or a heteroarylene structure, the emission wavelength and hole or electron acceptability can be adjusted. In the following, the wavy line indicates the bonding site with N.
  • R of >N-R in X unsubstituted phenyl, phenyl (3,5-dimethylphenyl) with methyl attached to two meta positions, phenyl with methyl attached to ortho or para position, one or two Phenyl having methyl attached to one ortho position, and 2-biphenylyl optionally substituted with tertiary-alkyl are further preferred, and 3,5-dimethylphenyl and 2-biphenylyl optionally substituted with tertiary-alkyl are particularly preferred. preferable.
  • R is a linking group or a single bond to ring A, B, C, D or E. may be bonded to at least one ring in
  • the linking group is preferably -O-, -S- or -C(-R) 2 -.
  • R in the above "-C(-R) 2 -" is hydrogen, alkyl or cycloalkyl.
  • the alkyl or cycloalkyl includes the groups described above.
  • alkyl having 1 to 5 carbon atoms eg, methyl, ethyl, etc.
  • cycloalkyl having 5 to 10 carbon atoms preferably cyclohexyl and adamantyl
  • This description refers to the linking group "—C ( -R) 2 -”.
  • R is a linking group or a single bond to ring A, B, C, D or E.
  • Specific examples of the structure in which are bonded to at least one ring include structures represented by formula (A10) described below.
  • the formed condensed ring D' (or condensed ring A') is, for example, a carbazole ring, a phenoxazine ring, or a phenothiazine ring.
  • At least one of X connecting the ring structures is >NR, and this R is optionally substituted alkyl or optionally substituted It is also preferred that it is a good cycloalkyl and has a structure in which it is linked to at least one aryl ring or heteroaryl ring of the A ring, B ring, C ring, D ring, or E ring via a linking group or a single bond. .
  • partial structure (A10) may be formed by the above linkage.
  • R A1 to R A4 are each independently hydrogen, optionally substituted alkyl or optionally substituted cycloalkyl, and any 2 to 4 of R A1 to R A4 may be bonded to each other by a linking group or a single bond, and two * positions are bonded to one of the two rings to which X is bonded, and ** is bonded to the other ring. That is, N in formula (A10) is N of >NR when X is >NR.
  • the atoms on the ring that are bonded at the two * positions may be adjacent atoms (preferably carbon atoms).
  • the partial structure represented by the formula (A10) contains an NC bond with a weak bond dissociation energy (BDE), but due to the presence of another bond forming a ring, a reverse reaction ( recombination reaction) is promoted, resulting in a more stable structure. Therefore, an organic EL device manufactured using the polycyclic aromatic compound of the present invention having such a structure is expected to have a long device life.
  • the polycyclic aromatic compound of the present invention includes a structure represented by formula (A10), the number thereof is from 1 to “the number of X”, preferably 1 or 2.
  • any 2 to 4 of R A1 to R A4 may be linked to each other through a linking group.
  • R A1 to R A4 are any two (R A1 and R A4 , R A1 and R A4 and R A1 and R A4 , R A1 and R A2 , R A3 and R A4 , R A1 and R A4 and R A1 and R A4 ) are preferably bonded to each other via a linking group or a single bond, and more preferably R A1 and R A4 are bonded to each other via a linking group or a single bond.
  • the divalent group formed by bonding with each other includes alkylene.
  • At least one hydrogen in the alkylene may be substituted with alkyl or cycloalkyl, and at least one (preferably one) —CH 2 — in the alkylene is substituted with —O— and —S— good too.
  • the divalent group formed by bonding to each other is preferably a straight-chain alkylene having 2 to 5 carbon atoms, more preferably a straight-chain alkylene having 3 or 4 carbon atoms, and a straight-chain alkylene having 4 carbon atoms (-( CH 2 ) 4 -) is more preferred. It is particularly preferred that the linear alkylene having 4 carbon atoms (--(CH 2 ) 4 --) is unsubstituted.
  • R A1 to R A4 not participating in the linking by the linking group are each independently preferably hydrogen or optionally substituted alkyl, optionally substituted C 1-6 It is more preferably alkyl, more preferably unsubstituted alkyl having 1 to 6 carbon atoms, and most preferably methyl. That is, the structure represented by the following formula (A11) is preferable as the partial structure represented by the formula (A10).
  • Me is methyl, and is bonded at two * positions to one of the two rings to which X is bonded, and at ** positions to the other ring.
  • examples of when both n are 1 are compounds represented by formula (4-1), one n is 0 and the other is 1 Some examples include compounds represented by formula (4-11), formula (4-12), formula (4-13) or formula (4-14).
  • Each X is independently >C(-R) 2, >NR, >O, >Si(-R) 2 , >S or >Se, and R in >NR is substituted optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted cycloalkyl, and the above >C(-R) 2 and >Si(-R) R of 2 is hydrogen, optionally substituted aryl, optionally substituted alkyl or optionally substituted cycloalkyl, and >C(--R) 2 and >Si(--R) 2 respectively may be bonded to each other to form a ring, and at least one of the Rs of the >N—
  • the ring formed may be substituted, from the group consisting of an aryl ring and a heteroaryl ring in the structure represented by formula (4-1), formula (4-11), formula (4-12), formula (4-13) or formula (4-14)
  • At least one selected may be fused with at least one cycloalkane, at least one hydrogen in the cycloalkane may be substituted, and at least one —CH 2 — in the cycloalkane may be — optionally substituted with O—
  • At least one hydrogen in the structure represented by formula (4-1), formula (4-11), formula (4-12), formula (4-13) or formula (4-14) is deuterium, cyano Alternatively, it may be substituted with halogen.
  • a ring, B ring, C ring, and D The ring has the same meaning as ring A, ring B, ring C and ring D in formula (4), and preferred ranges are also the same.
  • Y has the same definition as Y in Formula (4), and the preferred range is also the same.
  • X has the same definition as X in formula (4), and the preferred range is also the same.
  • Each R Z is independently hydrogen or a substituent. More specifically, each R Z is independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls are optionally bonded), alkyl, cycloalkyl, alkoxy, aryloxy, substituted silyl or -L-Ak, wherein at least one hydrogen in each of the above groups other than -L-Ak is aryl, heteroaryl, alkyl or may be substituted with cycloalkyl.
  • adjacent groups of R 2 may be bonded to form an aryl ring or heteroaryl ring together with the ring to which the R 2 is bonded, and at least one hydrogen in the formed ring is substituted.
  • substituents include substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (two aryls may be linked via a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted Examples include unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted silyl or -L-Ak. Substituent
  • a structure in which two adjacent Z's are replaced with -C(-R Z ) 2 -, -Si(-R Z ) 2 -, -N(-R Z )-, -O-, or -S- includes cyclopentadiene ring, pyrrole ring, furan ring, thiophene ring, thiazole ring, oxazole ring and the like. provided that two adjacent Zs are replaced with -C(-R Z ) 2 -, -Si(-R Z ) 2 -, -N(-R Z )-, -O-, or -S- preferably not.
  • a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, or a 1,3,5-triazine ring is preferable, and a pyridine ring, a pyrazine ring, or a pyrimidine A ring is more preferred.
  • R 1 Z at any given time is independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diarylboryl (wherein Aryl is an aryl having 6 to 12 carbon atoms, and two aryl may be bonded via a single bond or a linking group), alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, tria It is preferably arylsilyl (where aryl is aryl having 6 to 12 carbon atoms) or trialkylsilyl (where alkyl is alkyl having 1 to 6 carbon atoms), which may have a substituent, provided that , adjacent R Z may be bonded to form an aryl ring having 9 to 16 carbon atoms or
  • Each R Z is independently hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 20 carbon atoms, diarylamino (where aryl is aryl having 6 to 10 carbon atoms), alkyl having 1 to 12 carbon atoms. or more preferably cycloalkyl having 3 to 16 carbon atoms (each of which may have a substituent), each independently hydrogen, aryl having 6 to 16 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms), alkyl having 1 to 12 carbon atoms or cycloalkyl having 3 to 16 carbon atoms (each of which may have a substituent).
  • R Z is preferably substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, or substituted or unsubstituted alkyl, and aryl or alkyl optionally substituted with alkyl.
  • Optionally substituted diarylamino or alkyl are preferred.
  • R Z are substituents and the others are preferably hydrogen.
  • the substituent R Z is preferably at the para-position of Y. It is also preferred that R Z which is methyl is in one or two of the meta positions of Y.
  • R Z is more specifically alkyl or diarylamino. is preferred.
  • a diarylamino as R Z is at the para-position of Y from the viewpoint of obtaining high TADF properties and high oscillator strength.
  • R Z is preferably alkyl, cycloalkyl, aryl having alkyl as a substituent, heteroaryl having alkyl as a substituent, or diarylamino having alkyl as a substituent from the viewpoint of preventing an increase in sublimation temperature.
  • R Z in each ring in formula (4-1), formula (4-11), formula (4-12), formula (4-13) and formula (4-14) is a ring structure (A ring, B It is preferable that 0 to 1 substituents other than hydrogen and the others are hydrogen for each aryl ring or heteroaryl ring (ring, C ring, D ring, and E ring).
  • R Z may bond together to form an aryl ring or heteroaryl ring together with the ring containing the C (carbon atom).
  • Structural examples of rings containing Z in each of formulas (4-1), (4-11), (4-12), (4-13) and (4-14) are Examples of structures containing one and bound to X and Y are shown below.
  • R has the same meaning as R 2 Z , but does not mean that the R's are bonded together.
  • n is an integer of 0 to 4
  • R N and R c are hydrogen, alkyl or aryl optionally substituted with cycloalkyl, heteroaryl optionally substituted with alkyl or cycloalkyl, cycloalkyl or cycloalkyl optionally substituted with alkyl, and two Rc 's may combine with each other to form a ring.
  • X >C(-R) 2 and >Si(-R) 2 combine with each other to form a ring.
  • the polycyclic aromatic compound represented by formula (4-1) preferably contains X >NR.
  • R in >NR is preferably unsubstituted cycloalkyl or optionally substituted aryl, unsubstituted cyclohexyl, optionally substituted phenyl or optionally substituted biphenylyl Preferably. It is also preferred that R in >NR has a structure in which Z adjacent to any carbon atom to which N is directly bonded is bonded via a linking group or a single bond.
  • the linking group is preferably -O-, -S- or -C(-R) 2 -.
  • R in "-C(-R) 2 -" is hydrogen, alkyl or cycloalkyl.
  • alkyl or cycloalkyl includes the groups described above.
  • alkyl having 1 to 5 carbon atoms eg, methyl, ethyl, etc.
  • cycloalkyl having 5 to 10 carbon atoms preferably cyclohexyl and adamantyl are preferred.
  • Ring C in formula (4-11) and ring D in formula (4-13) are preferably condensed heteroaryl rings (which may have substituents), and have substituents.
  • It is preferable that the above C ring and D ring are bonded to Y at the carbon atom constituting the heteroaryl ring, and bonded to the carbon atom constituting the ring containing Z at the nitrogen atom.
  • a 6-membered ring containing this nitrogen atom and Y is formed.
  • a 6-membered ring containing this nitrogen atom and Y is formed.
  • each of the following includes Y at the * position and Z at the # position. It is preferably bonded to a carbon atom that constitutes the ring.
  • Each ring may have a substituent.
  • the compound represented by formula (4-11) or formula (4-13) having these rings as C ring or D ring is the predetermined X in formula (4-1)>NR is also a compound represented by formula (4-1) in which R is bonded to Z adjacent to any carbon atom directly bonded to N via a linking group or a single bond.
  • the dibenzazepine ring is phenyl>R in NR is attached to the carbon atom in Z by alkenylene
  • the iminodibenzyl ring is phenyl>R in NR is attached to the carbon atom in Z by alkylene Bonded structure
  • tribenzazepine ring is biphenylyl>R in NR is bonded to a carbon atom in Z by a single bond
  • carbazole ring is phenyl>R in NR is a carbon atom in Z can be considered as a structure in which a single bond is attached to
  • Ring B in formula (4-12) and ring A in formula (4-14) are preferably condensed heteroaryl rings (which may have substituents), and have substituents.
  • a 6-membered ring containing this nitrogen atom and Y is formed.
  • the indole ring, the benzimidazole ring, the dibenzazepine ring, the iminodibenzyl ring, the tribenzazepine ring, or the carbazole ring are bonded to Y, Y is at the position of * and X is at the position of **, respectively.
  • # are preferably bonded to the carbon atoms constituting the ring containing Z.
  • Each ring may have a substituent.
  • the compound represented by formula (4-12) or formula (4-14) having these rings as B ring or A ring is a predetermined X in formula (4-1)>NR is also a compound represented by formula (4-1) in which R is bonded to Z adjacent to any carbon atom directly bonded to N via a linking group or a single bond.
  • At least one selected from the group consisting of an aryl ring and a heteroaryl ring in the compound represented by formula (4) may be fused with at least one cycloalkane, and at least one hydrogen in the cycloalkane is It may be substituted, and at least one —CH 2 — in the cycloalkane may be replaced with —O—.
  • This description also applies to compounds represented by formulas (4-1), (4-11), (4-12), (4-13) and (4-14). applies to
  • Cycloalkane includes cycloalkanes having 3 to 24 carbon atoms, cycloalkanes having 3 to 20 carbon atoms, cycloalkanes having 3 to 16 carbon atoms, cycloalkanes having 3 to 14 carbon atoms, cycloalkanes having 5 to 10 carbon atoms, Examples include alkanes, cycloalkanes having 5 to 8 carbon atoms, cycloalkanes having 5 to 6 carbon atoms, cycloalkanes having 5 carbon atoms, and the like.
  • cycloalkanes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, norbornane (bicyclo[2.2.1]heptane), bicyclo[1.1.0]butane , bicyclo[1.1.1]pentane, bicyclo[2.1.0]pentane, bicyclo[2.1.1]hexane, bicyclo[3.1.0]hexane, bicyclo[2.2.1]heptane , bicyclo[2.2.2]octane, adamantane, diamantane, decahydronaphthalene and decahydroazulene, and alkyl (especially methyl)-substituted, halogen (especially fluorine)-substituted and heavy Examples thereof include hydrogen-substituted products.
  • a structure in which at least one hydrogen at the ⁇ -position carbon of the cycloalkane (the carbon at the position adjacent to the carbon of the condensation site in the cycloalkyl condensed to the aryl ring or heteroaryl ring) is substituted is preferable.
  • a structure in which two hydrogens at the carbons are substituted is more preferable, and a structure in which a total of four hydrogens at the two ⁇ -position carbons are substituted is even more preferable.
  • this substituent include alkyl (especially methyl)-substituted ones having 1 to 5 carbon atoms, halogen (especially fluorine)-substituted ones and deuterium-substituted ones.
  • a structure in which a partial structure represented by the following formula (B10) is bonded to adjacent carbon atoms in an aryl ring or heteroaryl ring is preferable.
  • Me represents methyl and * represents the binding position.
  • All or part of hydrogen in the chemical structure of the polycyclic aromatic compound represented by formula (4) may be replaced with deuterium, cyano, or halogen.
  • R alkyl, cycloalkyl, aryl
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine, even more preferably fluorine. From the viewpoint of durability, it is also preferable that all or part of hydrogen in the chemical structure of the polycyclic aromatic compound represented by formula (4) is deuterated. This description also applies to compounds represented by formulas (4-1), (4-11), (4-12), (4-13) and (4-14). applies to
  • formula (4-1) Of the polycyclic aromatic compounds represented by formula (4-1), formula (4-11), formula (4-12), formula (4-13) or formula (4-14), formula (4- Polycyclic aromatic compounds represented by 1) are preferred.
  • a compound represented by formula (4-1-A) is preferable.
  • Xd is >O, >N—R Xd , or >S
  • R Xd is optionally substituted aryl or optionally substituted heteroaryl
  • Xd including R Xd is may be bonded to the carbon adjacent to any carbon atom to which it is directly bonded through a linking group or a single bond
  • R dn is optionally substituted aryl or optionally substituted heteroaryl
  • R d each independently represents hydrogen, unsubstituted alkyl, aryl optionally substituted with alkyl, heteroaryl optionally substituted with alkyl, or diarylamino optionally substituted with alkyl.
  • R Xd is aryl optionally substituted with alkyl, aryl, diarylamino, or arylheteroarylamino, or heteroaryl optionally substituted with alkyl, aryl, diarylamino, or arylheteroarylamino is preferred.
  • R dn is aryl optionally substituted with alkyl, aryl, diarylamino or arylheteroarylamino or heteroaryl optionally substituted with alkyl, aryl, diarylamino or arylheteroarylamino is preferred.
  • polycyclic aromatic compounds represented by formula (4-1), formula (4-11), formula (4-12), formula (4-13) or formula (4-14) include any of the following An example represented by the following formula is given. 0 to 2 hydrogen atoms in each benzene ring in each formula below may be substituted with the above substituent (first substituent).
  • polycyclic aromatic compounds represented by formula (4-1), formula (4-11), formula (4-12), formula (4-13) or formula (4-14) includes compounds represented by the following structural formulas.
  • “Me” is methyl and “tBu” is t-butyl.
  • Reactive compounds, polymer compounds, crosslinked polymers, pendant polymer compounds, and pendant polymer crosslinked polycyclic aromatic compounds represented by the formula (4) are respectively substituted with reactive substituents.
  • polymer compound (the monomer for obtaining this polymer compound has a polymerizable substituent), or a polymer crosslinked product obtained by further cross-linking the polymer compound (this high
  • the polymer compound for obtaining a molecular crosslinked body has a crosslinkable substituent), or a pendant polymer compound obtained by reacting a main chain polymer with the reactive compound (this pendant polymer compound is The reactive compound for obtaining the reactive compound has a reactive substituent), or the pendant-type polymer crosslinked body obtained by further crosslinking the pendant-type polymer compound (the pendant-type high molecular crosslinked body for obtaining the pendant-type polymer crosslinked body).
  • the molecular compound has a crosslinkable substituent) can also be used for organic device materials such as organic electroluminescence element materials, organic field effect transistor materials, or organic thin
  • polymer compound means a compound having a molecular weight distribution and a polystyrene-equivalent number-average molecular weight of 1 ⁇ 10 3 to 1 ⁇ 10 8 (1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 8 ) means a polymer that is
  • Mn polystyrene-equivalent number-average molecular weight
  • SEC size exclusion chromatography
  • the polymer compound to be measured is dissolved in tetrahydrofuran at a concentration of about 0.05% by mass, and 10 ⁇ L of the solution is injected into the SEC.
  • the flow rate of the mobile phase is 1.0 mL/min, and PLgelMIXED_B (manufactured by Polymer Laboratories) is used as the column.
  • a UV_VIS detector manufactured by Toso Ichi, trade name: UV-8320GPC
  • the polymer compound of the present invention preferably has a number average molecular weight of 2000 to 1 ⁇ 10 8 , more preferably 5000 to 1 ⁇ 10 8 .
  • reactive substituent including the polymerizable substituent, the crosslinkable substituent, and a reactive substituent for obtaining a pendant polymer, hereinafter also simply referred to as a "reactive substituent"
  • a substituent capable of increasing the molecular weight of the above polycyclic aromatic compound a substituent capable of further cross-linking the polymer compound thus obtained, and a substituent capable of pendent reaction with the main chain type polymer.
  • alkenyl, alkynyl, unsaturated cycloalkyl eg, cyclobutenyl
  • unsaturated cycloalkyl eg, cyclobutenyl
  • a group in which at least one —CH 2 — in cycloalkyl is substituted with —O— eg, epoxy
  • unsaturated fused cycloalkane eg, alkenyl, alkynyl, unsaturated cycloalkyl (eg, cyclobutenyl), a group in which at least one —CH 2 — in cycloalkyl is substituted with —O— (eg, epoxy), unsaturated fused cycloalkane.
  • Saturated compounds for example, condensed cyclobutene
  • substituents having the following structures are preferred. * in each structural formula indicates a binding position.
  • substituents represented by formula (XLS-1), formula (XLS-2), formula (XLS-3), formula (XLS-9), formula (XLS-10) or formula (XLS-17) is preferred, and a group represented by formula (XLS-1), formula (XLS-3) or formula (XLS-17) is more preferred.
  • polymer compounds and polymer crosslinked bodies The details of the uses of such polymer compounds, polymer crosslinked bodies, pendant polymer compounds, and pendant polymer crosslinked bodies (hereinafter also simply referred to as "polymer compounds and polymer crosslinked bodies") will be described later.
  • a polycyclic aromatic compound represented by the formula (4) is basically prepared by first bonding the A ring, the B ring, the C ring), the D ring, and the E ring to a bonding group (X or N-containing group) to prepare an intermediate (first reaction), then A-ring, B-ring, C-ring, D-ring, and E-ring are linked by a linking group (group containing Y) can produce the final product (second reaction).
  • first reaction for example, general reactions such as nucleophilic substitution reaction and Ullmann reaction can be used for the etherification reaction, and general reactions such as the Buchwald-Hartwig reaction can be used for the amination reaction.
  • tandem hetero Friedel-Crafts reaction continuous aromatic electrophilic substitution reaction, hereinafter the same
  • Organic Device The polycyclic aromatic compound according to the present invention can be used as a material for organic devices.
  • Organic devices include, for example, organic electroluminescence devices, organic field effect transistors, organic thin film solar cells, and the like.
  • FIG. 1 is a schematic cross-sectional view showing an organic EL element according to this embodiment.
  • An organic EL device 100 shown in FIG. A hole-transporting layer 104 provided on the injection layer 103, a light-emitting layer 105 provided on the hole-transporting layer 104, an electron-transporting layer 106 provided on the light-emitting layer 105, and an electron-transporting layer It has an electron injection layer 107 provided on 106 and a cathode 108 provided on the electron injection layer 107 .
  • the organic EL element 100 is fabricated in reverse order, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer 107 an electron transport layer 106 provided on the electron transport layer 106; a light emitting layer 105 provided on the electron transport layer 106; a hole transport layer 104 provided on the light emitting layer 105; A structure having a hole-injection layer 103 provided at the bottom and an anode 102 provided on the hole-injection layer 103 may be employed.
  • All of the above layers are not indispensable, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection Layer 107 is an optional layer.
  • each of the above layers may be composed of a single layer, or may be composed of a plurality of layers.
  • the layers constituting the organic EL element may include " substrate/anode/hole-transporting layer/luminescent layer/electron-transporting layer/electron-injecting layer/cathode”, “substrate/anode/hole-injecting layer/luminescent layer/electron-transporting layer/electron-injecting layer/cathode”, “substrate/ Anode/Hole Injection Layer/Hole Transport Layer/Light Emitting Layer/Electron Injection Layer/Cathode", "Substrate/Anode/Hole Injection Layer/Hole Transport Layer/Light Emitting Layer/Electron Transport Layer/Cathode", "Substrate/ Anode/light emitting layer/electron transport layer/electron injection layer/electron injection layer/
  • the substrate substrate 101 in the organic electroluminescence element is a support for the organic EL element 100, and is usually made of quartz, glass, metal, plastic, or the like.
  • the substrate 101 is formed in a plate shape, a film shape, or a sheet shape depending on the purpose, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used.
  • glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate and polysulfone are preferred. If it is a glass substrate, soda-lime glass, alkali-free glass, or the like is used, and the thickness should be sufficient to maintain the mechanical strength.
  • the upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less.
  • the material of the glass it is preferable to use non-alkali glass because the fewer ions eluted from the glass, the better.
  • soda-lime glass with a barrier coating such as SiO 2 is also available on the market and can be used. can.
  • the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side thereof in order to enhance gas barrier properties. When used, it is preferable to provide a gas barrier film.
  • the anode 102 in the organic electroluminescent device plays a role of injecting holes into the light-emitting layer 105 .
  • the hole injection layer 103 and/or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. .
  • Materials for forming the anode 102 include inorganic compounds and organic compounds.
  • inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide metal (IZO), etc.), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, and the like.
  • Examples of organic compounds include polythiophenes such as poly(3-methylthiophene), and conductive polymers such as polypyrrole and polyaniline. In addition, it can be used by appropriately selecting from materials used as anodes of organic EL elements.
  • the resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but a low resistance is desirable from the viewpoint of power consumption of the light emitting element.
  • an ITO substrate of 300 ⁇ / ⁇ or less functions as an element electrode, but it is now possible to supply a substrate of about 10 ⁇ / ⁇ . It is particularly desirable to use a low resistance product of / ⁇ .
  • the thickness of ITO can be arbitrarily selected according to the resistance value, it is usually used in the range of 50 to 300 nm.
  • the hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104. Fulfill.
  • the hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105 .
  • the hole injection layer 103 and the hole transport layer 104 are each formed by stacking and mixing one or more kinds of hole injection/transport materials, or by a mixture of a hole injection/transport material and a polymer binder. be done. Also, an inorganic salt such as iron (III) chloride may be added to the hole injection/transport material to form the layer.
  • the ionization potential is low, the hole mobility is high, the stability is excellent, and impurities that become traps are less likely to occur during manufacture and use.
  • Materials for forming the hole injection layer 103 and the hole transport layer 104 include compounds conventionally used as charge transport materials for holes in photoconductive materials, p-type semiconductors, and hole injection layers of organic EL devices. Any compound can be selected and used from known compounds used for the hole transport layer.
  • carbazole derivatives N-phenylcarbazole, polyvinylcarbazole, etc.
  • biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole)
  • triarylamine derivatives aromatic tertiary Polymers with amino in the main or side chain, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N'-diphenyl-N,N'-di(3-methylphenyl)-4 ,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-di(3-methylphenyl)-4 ,4′-diphenyl-1,1′-diamine, N,N′-dinaphthyl-N,N
  • Polycarbonate, styrene derivatives, polyvinylcarbazole, polysilane and the like having the above-mentioned monomers in side chains are preferable for polymer systems. is not particularly limited as long as it is a compound capable of transporting
  • the organic semiconductor matrix material is composed of a compound with good electron-donating property or a compound with good electron-accepting property.
  • Strong electron acceptors such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinonedimethane (F4TCNQ) are known for doping electron donors.
  • TCNQ tetracyanoquinonedimethane
  • F4TCNQ 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinonedimethane
  • the hole injection layer material and the hole transport layer material described above are polymer compounds obtained by polymerizing a reactive compound having a reactive substituent substituted thereon as a monomer, or a polymer crosslinked product thereof, or A pendant-type polymer compound obtained by reacting a main chain-type polymer with the reactive compound or a pendant-type polymer crosslinked product thereof can also be used as a hole layer material.
  • the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (4) can be cited. The details of the uses of such polymer compounds and crosslinked polymers will be described later.
  • Emissive layer Emissive layer 105 in the organic electroluminescent device emits light by recombination of holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. .
  • any compound (light-emitting compound) that emits light when excited by recombination of holes and electrons can be used. Compounds that exhibit strong luminescence (fluorescence) efficiency at .
  • the light-emitting layer may be a single layer or a plurality of layers, each of which is formed of a light-emitting layer material (host material, dopant material).
  • the host material and the dopant material may be of one kind, or may be a combination of a plurality of them.
  • emitting dopants and assisting dopants may be used as dopant materials.
  • the dopant material may be included entirely or partially in the host material.
  • As a doping method it can be formed by a co-evaporation method with a host material, but it may be mixed with the host material in advance and then vapor-deposited simultaneously.
  • the light-emitting layer can also be formed by a wet film-forming method using a light-emitting layer-forming composition prepared by dissolving materials in an organic solvent.
  • the polycyclic aromatic compound of the present invention can be preferably used as a material for forming a luminescent layer of an organic electroluminescent device.
  • the polycyclic aromatic compound of the present invention is more preferably used as an emitting dopant or assisting dopant in the light-emitting layer, more preferably as an emitting dopant.
  • the polycyclic aromatic compound represented by the formula (4) is an organic EL element (hereinafter sometimes referred to as a "TADF element") that exhibits thermally activated delayed fluorescence (TADF) as a “thermally activated delayed phosphor". may be used as an emitting dopant for By reducing the energy difference between the lowest excited singlet state and the lowest excited triplet state in the "thermally activated delayed phosphor", the transition probability from the lowest excited triplet state to the lowest excited singlet state is normally low. Reverse intersystem cross-transfer occurs with high efficiency, and luminescence from singlet (thermally activated delayed fluorescence, TADF) is expressed.
  • TADF element organic EL element
  • the polycyclic aromatic compound represented by formula (4) is an emitting dopant of the "TADF element", an emitting dopant of the TADF element using two types of hosts, and another thermally activated delayed phosphor as an assisting dopant.
  • Emitting dopant of the organic electroluminescent device used TADF-assisted fluorescent device, TAF device
  • organic electroluminescent device using phosphorescent material as assisting dopant phosphor-sensitized fluorescent) element
  • PSF element organic electroluminescent device using phosphorescent material as assisting dopant
  • the emitting dopant of the TADF element and the emitting dopant of the TADF element using two kinds of hosts are preferable, and the emitting dopant of the TADF element is more preferable.
  • the emitting dopant of the TAF element and the emitting dopant of the phosphorescent assist element are preferable, and the emitting dopant of the TAF element is more preferable.
  • ⁇ E S1T1 is the energy difference between the lowest excited singlet energy level (E S1 ) and the lowest excited triplet energy level (E T1 ). Specifically, the value of ⁇ E S1T1 is preferably 0.20 eV or less, more preferably 0.15 eV or less.
  • the light-emitting layer containing the polycyclic aromatic compound of the present invention may contain a host compound.
  • the host compound may be of one type or two or more types.
  • the light-emitting layer may be either a single layer or a plurality of layers.
  • the host compound, the emitting dopant material, and the assisting dopant material may be contained in the same layer, or at least one component each may be contained in multiple layers.
  • the host compound and dopant material (emitting dopant or assisting dopant) contained in the light-emitting layer may be of one type or a combination of a plurality of them. Assisting dopants and emitting dopants may be wholly or partially contained in the host compound as the matrix.
  • the amount of host material used varies depending on the type of host material, and should be determined according to the properties of the host material.
  • a guideline for the amount of the host material used is preferably 50 to 99.999% by mass, more preferably 80 to 99.95% by mass, and still more preferably 90 to 99.9% by mass of the total material for the light-emitting layer. is.
  • the amount of dopant material used varies depending on the type of dopant material, and should be determined according to the characteristics of the dopant material.
  • a guideline for the amount of the dopant used is preferably 0.001 to 50% by mass, more preferably 0.05 to 20% by mass, and still more preferably 0.1 to 10% by mass of the total light-emitting layer material. be.
  • the above range is preferable in that, for example, the phenomenon of concentration quenching can be prevented.
  • an organic electroluminescence device using a TADF material as a dopant material a low concentration of the dopant material is preferable in that concentration quenching phenomenon can be prevented.
  • One is preferable from the viewpoint of the efficiency of the thermally activated delayed fluorescence mechanism.
  • the amount of the emitting dopant used is lower than that of the assisting dopant. It is preferred that the amount is low.
  • the amounts of the host material, the assisting dopant and the emitting dopant are 40 to 99 wt%, 59 to 1 wt% and 20 to 99 wt%, respectively, based on the total light-emitting layer material. 0.001% by weight, preferably 60 to 95% by weight, 39 to 5% by weight and 10 to 0.01% by weight, more preferably 70 to 90% by weight and 29 to 10% by weight, respectively and 5 to 0.05% by mass. If an assisting dopant material is used, it may form an exciplex with either the host material or the emitting dopant material.
  • the lowest excited triplet energy level (E T1 ) of the host material (sometimes referred to as “T1 energy”) is from the viewpoint of promoting the generation of TADF in the light-emitting layer without inhibiting it. is preferably higher than the T1 energy of the dopant or assisting dopant having the highest T1 energy in the T1 energy.
  • the T1 energy of the host is preferably 0.01 eV or more, more preferably 0.03 eV or more, and 0 0.1 eV or more is more preferable.
  • a high T1 compound having a T1 energy at least 0.01 eV higher than the T1 energy of the polycyclic aromatic compound represented by formula (4) is preferred. It is also preferable that the high T1 compound is contained in the organic layer adjacent to the light-emitting layer.
  • a TADF-active compound may also be used as the host material.
  • the light-emitting layer may contain one host material, or two or more host materials. When two or more types are contained, it is preferable to contain a hole-transporting host material and an electron-transporting host material that satisfy the following relationship.
  • the HOMO (Highest Occupied Molecular Orbital) of the hole-transporting host material (HH) is shallower than the HOMO of the electron-transporting host material (EH),
  • the LUMO (Lowest Unoccupied Molecular Orbital) of the electron-transporting host material (EH) is deeper than that of the hole-transporting host material (HH).
  • the host material has at least one partial structure selected from partial structure group A, or has at least two partial structures selected from partial structure group A and partial structure group B, Furthermore, a compound optionally having at least one partial structure selected from partial structure group C as a linking group or substituent is preferred.
  • at least one * binds to a partial structure other than hydrogen, and the other * binds to hydrogen.
  • the carbon-carbon bond connecting the benzene rings in each partial structure and the bond connecting the partial structures are at the o-position or the m-position. At this time, high T1 and high charge mobility are obtained. From the viewpoint of high T1, binding at the o-position is preferred, and from the viewpoint of high charge mobility, binding at the m-position is preferred.
  • the partial structure group A is preferably the partial structure group Aa
  • the partial structure group B is preferably the partial structure group Bb
  • the partial structure group C is preferably the partial structure group Cc.
  • Examples of the host material include a compound represented by the following formula (H1), a compound represented by the following formula (H3), a compound containing a structure represented by the following formula (H4), and a compound represented by the following formula (H5). and compounds represented by the following formulas (H6) and (H8).
  • L 1 is arylene having 6 to 24 carbon atoms or heteroarylene having 5 to 23 carbon atoms, preferably arylene having 6 to 16 carbon atoms and heteroarylene having 5 to 15 carbon atoms, and 6 carbon atoms.
  • Arylene having up to 12 carbon atoms and/or heteroarylene having 5 to 11 carbon atoms are more preferable, and arylene having 6 to 10 carbon atoms or heteroarylene having 5 to 9 carbon atoms are particularly preferable.
  • Bivalent or trivalent groups such as phenyl ring, fluorene ring, spirofluorene ring, phenalene ring, triphenylene ring, pyridine ring, pyrimidine ring, triazine ring, biphenylpyridine ring, biphenylpyrimidine ring and biphenyltriazine ring.
  • At least one hydrogen in the compound represented by formula (H1) may be substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, cyano, halogen or deuterium.
  • Each MU is independently a divalent aromatic group
  • each EC is independently a monovalent aromatic group
  • k is an integer of 2-50,000.
  • k is an integer from 2 to 50,000. k is preferably an integer of 20 to 50,000, more preferably an integer of 100 to 50,000.
  • At least one hydrogen in MU and EC in formula (H3) may be substituted with alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, halogen or deuterium; Any —CH 2 — may be substituted with —O— or —Si(CH 3 ) 2 —, and any —CH 2 — excluding —CH 2 — directly linked to EC in formula (H3) in said alkyl —CH 2 — may be substituted with arylene having 6 to 24 carbon atoms, and any hydrogen in the alkyl may be substituted with fluorine.
  • a divalent derivative of the following structure for example, a divalent group represented by removing any two hydrogen atoms from any compound of the following structure, any compound of the following structure A divalent group composed of a combination of two or more divalent groups represented by excluding any two hydrogen atoms from, a divalent group in which at least one of the hydrogens in those groups is substituted with alkyl etc. base, etc.).
  • MUs join other MUs or ECs at *.
  • examples of EC include groups represented by the following formulas. In these, EC binds to MU at *.
  • 10 to 100% of the total number of MUs (k) in the molecule preferably has an alkyl having 1 to 24 carbon atoms, from the viewpoint of solubility and coating film properties.
  • 10 to 100% of the total number of MUs in the molecule (k) have alkyls with 1 to 18 carbon atoms (branched alkyls with 3 to 18 carbon atoms), and the total number of MUs in the molecule (k)
  • 50-100% of the MU have C1-C12 alkyl (C3-C12 branched chain alkyl).
  • the total number of MUs in the molecule (k) have alkyl groups of 7 to 24 carbon atoms, and the total number of MUs in the molecule (k ) have C7-C24 alkyl (C7-C24 branched chain alkyl).
  • Compound containing a structure represented by formula (H4) has a plurality of structures represented by formula (H4), preferably 1 to 5, more preferably 1 It contains up to 3, more preferably 1 to 2, and most preferably 1, and when it contains more than one, the structures are directly bonded with a single bond or bonded with a specific linking group.
  • aryl examples include phenyl, tolyl, xylyl, triphenylenyl, fluorenyl, 9,9-dimethylfluorenyl, benzofluorenyl, dibenzofluorenyl, biphenylyl, terphenylyl and quaterphenylyl. and the like, preferably phenyl, biphenylyl, terphenylyl and fluorenyl.
  • substituted aryl examples include tolyl, xylyl and 9,9-dimethylfluorenyl.
  • aryl includes both fused and non-fused aryl.
  • heteroaryl examples include pyrrolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridyl, triazinyl, indolyl, isoindolyl, imidazolyl, benzimidazolyl, indazolyl, imidazo[1,2-a]pyridinyl, furyl, Benzofuranyl, isobenzofuranyl, dibenzofuranyl, azadibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, azadibenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, naphthyridinyl, carbazolyl, azacarbazolyl, phenanthridinyl, acridinyl, phenazinyl , phenothiazin
  • substituted silyl is preferably a group selected from the group consisting of substituted or unsubstituted trialkylsilyl, substituted or unsubstituted arylalkylsilyl, and substituted or unsubstituted triarylsilyl. .
  • substituted or unsubstituted trialkylsilyl include trimethylsilyl and triethylsilyl.
  • substituted or unsubstituted arylalkylsilyl include diphenylmethylsilyl, ditolylmethylsilyl and phenyldimethylsilyl.
  • substituted or unsubstituted triarylsilyl include triphenylsilyl and tritolylsilyl.
  • substituted phosphine oxide group which is a substituent is also preferably a substituted or unsubstituted diarylphosphine oxide group.
  • substituted or unsubstituted diarylphosphine oxide groups include diphenylphosphine oxide and ditolylphosphine oxide.
  • Substituted carboxy which is a substituent, includes, for example, benzoyloxy and the like.
  • Examples of the linking group that connects multiple structures represented by formula (H4) include divalent to tetravalent, divalent to trivalent, or divalent derivatives of the above-described aryl or heteroaryl.
  • R 1 to R 11 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, wherein at least one hydrogen is It may further be substituted with aryl, heteroaryl or diarylamino.
  • At least one hydrogen in the compound represented by formula (H5) may be substituted with alkyl having 1 to 24 carbon atoms, and any —CH 2 — in the alkyl may be —O— or — Any —CH 2 — excluding —CH 2 — which may be substituted with Si(CH 3 ) 2 — and which is directly linked to the compound represented by formula (H5) in the above alkyl has 6 to 24 carbon atoms. and any hydrogen in said alkyl may be substituted with fluorine. At least one hydrogen in the compound represented by formula (H5) may be substituted with halogen or deuterium.
  • R 1 to R 16 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, wherein at least one hydrogen is It may further be substituted with aryl, heteroaryl or diarylamino.
  • At least one hydrogen in the compound represented by formula (H-6) may be substituted with alkyl having 1 to 24 carbon atoms, and any —CH 2 — in the alkyl may be —O— or —Si(CH 3 ) 2 —, and any —CH 2 — excluding —CH 2 — directly linked to the compound represented by formula (H6) in the above alkyl has 6 carbon atoms ⁇ 24 arylene and any hydrogen in said alkyl may be replaced by fluorine.
  • At least one hydrogen in the compound represented by formula (H6) may be substituted with halogen or deuterium.
  • R 1 to R 11 in Formula (H5) and “R 1 to R 16 in Formula (H6) ” “R 1 to R 11 in formula (H5)” and “R 1 to R 16 in formula (H6)” are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroaryl amino or aryloxy, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (amino having two aryl having 6 to 30 carbon atoms), diheteroarylamino (two carbon atoms amino having 2 to 30 heteroaryl), arylheteroarylamino (amino having aryl having 6 to 30 carbon atoms and heteroaryl having 2 to 30 carbon atoms) or aryloxy having 6 to 30 carbon atoms are preferred.
  • aryl examples include monocyclic benzene ring, bicyclic biphenyl ring, condensed Bicyclic naphthalene ring, tricyclic terphenyl ring (m-terphenyl, o-terphenyl, p-terphenyl), condensed tricyclic acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, condensed tetracyclic ring system such as triphenylene ring, pyrene ring and naphthacene ring, and condensed pentacyclic ring system such as perylene ring and pentacene ring.
  • these aryls substituted with heteroaryls defined below are also defined as aryls in formulas (H5) and
  • Heteroaryl of "heteraryl”, “diheteroarylamino”, and heteroaryl of “arylheteroarylamino” include, for example, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring , oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzo oxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, qui
  • the aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy described as R 1 to R 11 in formula (H5) and R 1 to R 16 in formula (H6) are At least one hydrogen in may be further substituted with aryl, heteroaryl or diarylamino.
  • the aryl, heteroaryl or diarylamino substituted in this way includes the same as those described in the columns of R 1 to R 11 and R 1 to R 16 .
  • R 1 to R 11 and R 1 to R 16 include groups represented by the following formulas (RG-1) to (RG-10).
  • the groups represented by formulas (RG-1) to (RG-10) below are bonded to rings a to d in formulas (H5) and (H6) at *.
  • (RG-7) is aryl
  • formula (RG-2) is heteroaryl
  • formula (RG-9) is heteroaryl substituted heteroaryl
  • Formula (RG-10) is heteroaryl-substituted aryl.
  • the formula (RG-5) is aryl (phenyl) substituted with diarylamino (diphenylamino)
  • the formula (RG-8) is diarylamino (diphenylamino).
  • first reaction for example, general reactions such as nucleophilic substitution reaction and Ullmann reaction can be used for the etherification reaction, and general reactions such as the Buchwald-Hartwig reaction can be used for the amination reaction.
  • second reaction a tandem hetero Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, hereinafter the same) can be used.
  • the second reaction is a reaction of introducing B (boron) that bonds the rings a, b and c, for example in the case of the compound represented by the formula (H5) are shown below.
  • a hydrogen atom between two Os is ortho-metallated with n-butyllithium, sec-butyllithium, t-butyllithium or the like.
  • boron trichloride, boron tribromide, or the like is added to perform metal-metal exchange of lithium-boron, and then a Bronsted base such as N,N-diisopropylethylamine is added to cause a tandem bolus Friedel-Crafts reaction. , you can get the object.
  • a Lewis acid such as aluminum trichloride may be added to promote the reaction.
  • lithium is introduced to the desired position by ortho-metalation, but as in scheme (2) below, a bromine atom or the like is introduced to the position where lithium is desired to be introduced, and halogen-metal exchange is also performed to the desired position. Lithium can be introduced.
  • the first reaction and the second reaction in the above-described method for producing the compound represented by formula (H5) can also be applied to the method for producing the compound represented by formula (H6).
  • the second reaction is a reaction to introduce B (boron) that bonds NH with c-ring and d-ring.
  • B boron
  • boron tribromide, or the like is added to carry out metal exchange of lithium-boron, and a Bronsted base such as N,N-diisopropylethylamine is added to cause a tandem bolus Friedel-Crafts reaction, you can get the target.
  • a Lewis acid such as aluminum trichloride may be added to promote the reaction.
  • Compound containing a structure represented by formula (H8) has a plurality of structures represented by formula (H8), preferably 1 to 5, more preferably 1 It contains up to 3, more preferably 1 to 2, and most preferably 1, and when it contains more than one, the structures are directly bonded with a single bond or bonded with a specific linking group.
  • aryl examples include phenyl, tolyl, xylyl, triphenylenyl, fluorenyl, 9,9-dimethylfluorenyl, benzofluorenyl, dibenzofluorenyl, biphenylyl, terphenylyl and quaterphenylyl. and the like, preferably phenyl, biphenylyl, terphenylyl and fluorenyl.
  • substituted aryl examples include tolyl, xylyl and 9,9-dimethylfluorenyl.
  • aryl includes both fused and non-fused aryl.
  • heteroaryl examples include pyrrolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridyl, triazinyl, indolyl, isoindolyl, imidazolyl, benzimidazolyl, indazolyl, imidazo[1,2-a]pyridinyl, furyl, Benzofuranyl, isobenzofuranyl, dibenzofuranyl, azadibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, azadibenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, naphthyridinyl, carbazolyl, azacarbazolyl, phenanthridinyl, acridinyl, phenazinyl , phenothiazin
  • substituted silyl is preferably a group selected from the group consisting of substituted or unsubstituted trialkylsilyl, substituted or unsubstituted arylalkylsilyl, and substituted or unsubstituted triarylsilyl. .
  • substituted or unsubstituted trialkylsilyl include trimethylsilyl and triethylsilyl.
  • substituted or unsubstituted arylalkylsilyl include diphenylmethylsilyl, ditolylmethylsilyl and phenyldimethylsilyl.
  • substituted or unsubstituted triarylsilyl include triphenylsilyl and tritolylsilyl.
  • substituted phosphine oxide group which is a substituent is also preferably a substituted or unsubstituted diarylphosphine oxide group.
  • substituted or unsubstituted diarylphosphine oxide groups include diphenylphosphine oxide and ditolylphosphine oxide.
  • Substituted carboxy which is a substituent, includes, for example, benzoyloxy and the like.
  • Examples of the linking group that connects multiple structures represented by formula (H8) include divalent to tetravalent, divalent to trivalent, or divalent derivatives of the above-described aryl or heteroaryl.
  • TADF Materials High T1 compounds may be TADF materials.
  • a TADF material means a material that is a "thermally activated delayed phosphor". In thermally activated delayed phosphors, by reducing the energy difference between the excited singlet state and the excited triplet state, the reverse energy transfer from the excited triplet state, which normally has a low transition probability, to the excited singlet state is enhanced. Efficiency is generated, and luminescence from the singlet (thermally activated delayed fluorescence, TADF) is expressed.
  • TADF materials use electron-donating substituents called donors and electron-accepting substituents called acceptors to localize HOMOs and LUMOs in the molecule for efficient reverse intersystem crossing.
  • DA type TADF compound is preferably a donor-acceptor type TADF compound.
  • the term "electron-donating substituent” means a substituent and partial structure in which the HOMO orbital is localized in the TADF compound molecule
  • an “electron-accepting substituent” means a substituent and a partial structure in which a LUMO orbital is localized in a TADF compound molecule.
  • a TADF compound using a donor or acceptor has a large spin orbit coupling (SOC: Spin Orbit Coupling) due to its structure, and a small exchange interaction between HOMO and LUMO and a small ⁇ EST . Very fast inverse intersystem crossing velocities are obtained.
  • SOC Spin Orbit Coupling
  • TADF compounds using donors and acceptors exhibit greater structural relaxation in the excited state (for some molecules, the stable structure differs between the ground state and the excited state, so external stimuli can cause conversion from the ground state to the excited state). , then the structure changes to a stable structure in the excited state), giving a broad emission spectrum, which may reduce color purity when used as a light-emitting material.
  • the polycyclic aromatic compound represented by formula (4) functions as an emitting dopant and the TADF material functions as an assisting dopant.
  • the TADF material may be a compound whose emission spectrum at least partially overlaps with the absorption spectrum of the polycyclic aromatic compound represented by formula (4).
  • Both the polycyclic aromatic compound represented by formula (4) and the TADF material may be contained in the same layer or may be contained in adjacent layers.
  • TADF materials that can be used for such purposes include compounds represented by the following formula (H7) and compounds having the following formula (H7) as a partial structure.
  • ED is an electron-donating group
  • Ln is a linking group
  • EA is an electron-accepting group
  • the lowest excited singlet energy level (E S1 ) and the lowest excited triplet energy level (E T1 ) is less than 0.2 eV (Hiroki Uoyama, Kenichi Goushi, Katsuyuki Shizu, Hiroko Nomura, Chihaya Adachi, Nature, 492, 234- 238 (2012)).
  • the energy difference ( ⁇ E ST ) is preferably 0.15 eV or less, more preferably 0.10 eV or less, and still more preferably 0.08 eV or less.
  • ED includes, for example, functional groups containing sp 3 nitrogen, more specifically carbazole, dimethylcarbazole, di-tert-butylcarbazole, dimethoxycarbazole, tetramethylcarbazole, benzofluorocarbazole, benzothienocarbazole.
  • phenyldihydroindolocarbazole phenylbicarbazole, bicarbazole, tercarbazole
  • diphenylcarbazolylamine tetraphenylcarbazolyldiamine
  • phenoxazine dihydrophenazine, phenothiazine, dimethyldihydroacridine, diphenylamine, bis(tert-butylphenyl) amines such as N1-(4-(diphenylamino)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, dimethyltetraphenyldihydroacridinediamine, tetramethyl-dihydro-indenoacridine and diphenyl-dihydrodibenzazacillin;
  • a group derived from is exemplified.
  • EA examples include sp2 nitrogen - containing aromatic rings, CN-substituted aromatic rings, rings with ketones and cyano, more specifically sulfonyldibenzene, benzophenone, phenylenebis(phenylmethanone), benzo Nitrile, isonicotinonitrile, phthalonitrile, isophthalonitrile, paraphthalonitrile, triazole, oxazole, thiadiazole, benzothiazole, benzobis(thiazole), benzoxazole, benzobis(oxazole), quinoline, benzimidazole, dibenzoquinoxaline, heptaaza phenalene, thioxanthone dioxide, dimethylanthracenone, anthracenedione, pyridine, 5H-cyclopenta[1,2-b:5,4-b']dipyridine, benzenetricarbonitrile, fluorenedicarbonitrile, pyrazinedi
  • Ln examples include a single bond and arylene, more specifically phenylene, biphenylene, naphthylene and the like.
  • hydrogen in any structure may be substituted with alkyl, cycloalkyl and aryl.
  • at least one partial structure selected from carbazole, phenoxazine, acridine, triazine, pyrimidine, pyrazine, thioxanthene, benzonitrile, phthalonitrile, isophthalonitrile, diphenylsulfone, triazole, oxadiazole, thiadiazole and benzophenone It is preferably a compound having one.
  • the linking group Ln functions as a spacer structure separating the donor partial structure and the acceptor partial structure.
  • the compound represented by formula (H7) may be a compound represented by formula (H7-1), formula (H7-2) or formula (H7-3).
  • Each M is independently a single bond, —O—, >N—Ar or >C(—Ar) 2 , and the depth of the HOMO and the lowest excited singlet energy level and the lowest excited From the viewpoint of the height of the triplet energy level, preferably a single bond, -O- or >N-Ar, J is a linking group corresponding to Ln in formula (H7), each independently an arylene having 6 to 18 carbon atoms, and the magnitude of conjugation oozing out from the donor partial structure and the acceptor partial structure.
  • arylene having 6 to 12 carbon atoms is preferable, more specifically, phenylene, methylphenylene and dimethylphenylene
  • Each Ar is independently hydrogen, aryl having 6 to 24 carbon atoms, heteroaryl having 2 to 24 carbon atoms, alkyl having 1 to 12 carbon atoms or cycloalkyl having 3 to 18 carbon atoms, and forming a partial structure From the viewpoint of the HOMO depth and the height of the lowest excited singlet energy level and the lowest excited triplet energy level, preferably hydrogen, aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 14 carbon atoms, alkyl having 1 to 4 carbon atoms or cycloalkyl having 6 to 10 carbon atoms, more preferably hydrogen,
  • Examples of compounds represented by formula (H7) include compounds represented by the following structures.
  • * indicates a bonding position
  • "Me” indicates methyl
  • "tBu” indicates t-butyl.
  • the polycyclic aromatic compound of the present invention is preferably used as a dopant material.
  • the dopant material that can be used other than the polycyclic aromatic compound of the present invention is not particularly limited, and known compounds can be used, and can be selected from various materials depending on the desired emission color. can.
  • phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene and chrysene condensed ring derivatives benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives (JP-A-1-245087), bisstyrylarylene derivatives (JP-A-2-247278),
  • blue to blue-green dopant materials for each colored light include aromatic hydrocarbon compounds such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, and chrysene, derivatives thereof, furan, pyrrole, thiophene, Heteroaromatic compounds such as silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene, etc.
  • aromatic hydrocarbon compounds such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene
  • Cyclic compounds and their derivatives distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, azole derivatives such as imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, triazole and their metal complexes and N , N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine and the like.
  • green to yellow dopant materials include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, and naphthacene derivatives such as rubrene.
  • Suitable examples include compounds obtained by introducing substituents such as aryl, heteroaryl, arylvinyl, amino, and cyano into the compounds exemplified as blue-green dopant materials, which enable wavelength lengthening.
  • naphthalimide derivatives such as bis(diisopropylphenyl)perylenetetracarboxylic acid imide, perinone derivatives, rare earth complexes such as Eu complexes having acetylacetone, benzoylacetone, and phenanthroline as ligands; -(Dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran and its analogues, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinacridone derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrrolopyridine derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, phenoxazone derivatives and thiadia
  • amines having a stilbene structure perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives or pyrene derivatives are particularly preferred.
  • An amine having a stilbene structure is represented by, for example, the following formula.
  • Ar 1 is an m-valent group derived from aryl having 6 to 30 carbon atoms
  • Ar 2 and Ar 3 are each independently aryl having 6 to 30 carbon atoms
  • Ar 1 to Ar 3 has a stilbene structure
  • Ar 1 to Ar 3 are aryl, heteroaryl, alkyl, cycloalkyl, trisubstituted silyl (silyl trisubstituted with aryl, alkyl and/or cycloalkyl) or cyano and m is an integer from 1 to 4.
  • the amine having a stilbene structure is more preferably diaminostilbene represented by the following formula.
  • Ar 2 and Ar 3 are each independently aryl having 6 to 30 carbon atoms, and Ar 2 and Ar 3 are aryl, heteroaryl, alkyl, cycloalkyl, trisubstituted silyl (aryl, alkyl and /or silyl trisubstituted with cycloalkyl) or cyano.
  • aryl having 6 to 30 carbon atoms are phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, perylenyl, stilbenyl, distyrylphenyl and distyrylbiphenylyl. , distyrylfluorenyl, and the like.
  • amines having a stilbene structure include N,N,N',N'-tetra(4-biphenylyl)-4,4'-diaminostilbene, N,N,N',N'-tetra(1-naphthyl )-4,4′-diaminostilbene, N,N,N′,N′-tetra(2-naphthyl)-4,4′-diaminostilbene, N,N′-di(2-naphthyl)-N,N '-diphenyl-4,4'-diaminostilbene, N,N'-di(9-phenanthryl)-N,N'-diphenyl-4,4'-diaminostilbene, 4,4'-bis[4''-bis (diphenylamino)styryl]-biphenyl, 1,4-bis[4′-bis(diphenylamino)styryl]-benzene,
  • Perylene derivatives include, for example, 3,10-bis(2,6-dimethylphenyl)perylene, 3,10-bis(2,4,6-trimethylphenyl)perylene, 3,10-diphenylperylene, 3,4- Diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3-(1'-pyrenyl)-8,11-di(t-butyl)perylene , 3-(9′-anthryl)-8,11-di(t-butyl)perylene, 3,3′-bis(8,11-di(t-butyl)perylenyl) and the like.
  • JP-A-11-97178, JP-A-2000-133457, JP-A-2000-26324, JP-A-2001-267079, JP-A-2001-267078, JP-A-2001-267076, Perylene derivatives described in JP-A-2000-34234, JP-A-2001-267075, and JP-A-2001-217077 may also be used.
  • Borane derivatives include, for example, 1,8-diphenyl-10-(dimesitylboryl)anthracene, 9-phenyl-10-(dimesitylboryl)anthracene, 4-(9'-anthryl)dimesitylborylnaphthalene, 4-(10'-phenyl-9'-anthryl)dimesitylborylnaphthalene, 9-(dimesitylboryl)anthracene, 9-(4'-biphenylyl)-10-(dimesitylboryl)anthracene, 9-(4'-(N-carbazolyl)phenyl) -10-(dimesitylboryl)anthracene and the like. Borane derivatives described in International Publication No. 2000/40586 and the like may also be used.
  • Ar 4 is an n-valent group derived from aryl having 6 to 30 carbon atoms
  • Ar 5 and Ar 6 are each independently aryl having 6 to 30 carbon atoms
  • Ar 4 to Ar 6 are , aryl, heteroaryl, alkyl, cycloalkyl, trisubstituted silyl (silyl trisubstituted with aryl, alkyl and/or cycloalkyl) or cyano
  • n is an integer from 1 to 4 be.
  • Ar 4 is a divalent group derived from anthracene, chrysene, fluorene, benzofluorene or pyrene
  • Ar 5 and Ar 6 are each independently aryl having 6 to 30 carbon atoms
  • Ar 4 to Ar 6 is optionally substituted with aryl, heteroaryl, alkyl, cycloalkyl, trisubstituted silyl (silyl trisubstituted with aryl, alkyl and/or cycloalkyl) or cyano
  • n is 2, aromatic Group amine derivatives are more preferred.
  • aryl having 6 to 30 carbon atoms include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, perylenyl, and pentacenyl.
  • aromatic amine derivatives include chrysene derivatives such as N,N,N',N'-tetraphenylchrysene-6,12-diamine, N,N,N',N'-tetra(p-tolyl) chrysene-6,12-diamine, N,N,N',N'-tetra(m-tolyl)chrysene-6,12-diamine, N,N,N',N'-tetrakis(4-isopropylphenyl)chrysene -6,12-diamine, N,N,N',N'-tetra(naphthalen-2-yl)chrysene-6,12-diamine, N,N'-diphenyl-N,N'-di(p-tolyl ) chrysene-6,12-diamine, N,N′-diphenyl-N,N′-bis(4-ethylpheny
  • pyrene compounds include N,N,N',N'-tetraphenylpyrene-1,6-diamine, N,N,N',N'-tetra(p-tolyl)pyrene-1,6 -diamine, N,N,N',N'-tetra(m-tolyl)pyrene-1,6-diamine, N,N,N',N'-tetrakis(4-isopropylphenyl)pyrene-1,6- Diamine, N,N,N',N'-tetrakis(3,4-dimethylphenyl)pyrene-1,6-diamine, N,N'-diphenyl-N,N'-di(p-tolyl)pyrene-1 ,6-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl)pyrene-1,6-diamine, N,N'-diphenyl-
  • anthracene-based compounds include N,N,N,N-tetraphenylanthracene-9,10-diamine and N,N,N',N'-tetra(p-tolyl)anthracene-9,10-diamine.
  • N,N,N′,N′-tetra(m-tolyl)anthracene-9,10-diamine N,N,N′,N′-tetrakis(4-isopropylphenyl)anthracene-9,10-diamine
  • N,N'-diphenyl-N,N'-di(p-tolyl)anthracene-9,10-diamine N,N'-diphenyl-N,N'-di(m-tolyl)anthracene-9,10- Diamine
  • N,N'-diphenyl-N,N'-bis(4-ethylphenyl)anthracene-9,10-diamine N,N'-diphenyl-N,N'-bis(4-isopropylphenyl)anthracene- 9,10-diamine, N,N'-diphenyl-N,N'-bis(4-t-butylpheny
  • Coumarin derivatives include coumarin-6 and coumarin-334. Coumarin derivatives described in JP-A-2004-43646, JP-A-2001-76876, and JP-A-6-298758 may also be used.
  • Examples of pyran derivatives include the following DCM and DCJTB.
  • JP-A-2005-126399, JP-A-2005-097283, JP-A-2002-234892, JP-A-2001-220577, JP-A-2001-081090, and JP-A-2001-052869 A pyran derivative described in, for example, may be used.
  • Thermally activated delayed phosphor (assisting dopant)
  • the light-emitting layer may contain a thermally activated delayed phosphor as an assisting dopant.
  • Thermally activated delayed phosphor absorbs thermal energy to cause reverse intersystem crossing from the lowest excited triplet state to the lowest excited singlet state, and radiatively deactivates from the lowest excited singlet state to delay It means a compound capable of emitting fluorescence.
  • thermalally activated delayed fluorescence also includes those that pass through a higher triplet in the excitation process from the lowest excited triplet state to the lowest excited singlet state.
  • the target compound when the fluorescence lifetime is measured at 300 K for a sample containing the target compound, the target compound is determined to be a "thermally activated delayed phosphor" based on the fact that a slow fluorescent component is observed.
  • the term "slow fluorescence component” refers to a component having a fluorescence lifetime of 0.1 ⁇ sec or longer.
  • the fluorescence lifetime can be measured using, for example, a fluorescence lifetime measurement device (C11367-01, manufactured by Hamamatsu Photonics K.K.).
  • the polycyclic aromatic compound represented by formula (4) can function as an emitting dopant, and the "thermally activated delayed phosphor” is the emission of the polycyclic aromatic compound represented by formula (4). can function as an assisting dopant that assists the
  • an organic electroluminescence device using a thermally activated delayed phosphor as an assisting dopant may be referred to as a "TAF device” (TADF Assisting Fluorescence device).
  • TAF device TADF Assisting Fluorescence device
  • the “host compound” in the TAF element means that the lowest excited singlet energy level obtained from the shoulder on the short wavelength side of the peak of the fluorescence spectrum is lower than the thermally activated delayed phosphor as an assisting dopant and the emitting dopant. Means high compounds.
  • FIG. 2 shows an energy level diagram of the light-emitting layer of a TAF element using a general fluorescent dopant as the emitting dopant (ED).
  • E (1, G) is the ground state energy level of the host
  • E (1, S, Sh) is the lowest excited singlet energy level obtained from the shoulder on the short wavelength side of the host fluorescence spectrum
  • E (1, S, Sh) is the host
  • the assisting E (2, S, Sh) is the lowest excited singlet energy level obtained from the short-wavelength shoulder of the dopant fluorescence spectrum
  • the energy level is E (2, T, Sh)
  • the energy level of the ground state of the emitting dopant is E (3, G)
  • E (3, S, Sh) is the energy level
  • E (3, T, Sh) is the lowest excited triplet energy level obtained from the shoulder on the short wavelength side of the phosphorescent spectrum of the emitting dopant
  • h is the hole.
  • an electron is e ⁇
  • fluorescence resonance energy transfer is FRET (Fluorescence Resonance Energy Transfer).
  • ED Fluorescence Resonance Energy Transfer
  • the energy transferred from the assisting dopant to the emitting dopant can be efficiently used for light emission, thereby realizing high light emission efficiency. This is presumed to be due to the following light emission mechanism.
  • FIG. 3 shows a preferable energy relationship in the organic electroluminescence device of this embodiment.
  • the compound having a boron atom as the emitting dopant has a high lowest excited triplet energy level E(3, T, Sh).
  • known host compounds can be used, for example, compounds having at least one of a carbazole ring and a furan ring. It is preferable to use a compound in which at least one of is bound. Specific examples include mCP and mCBP.
  • the lowest excited triplet energy level E(1, T, Sh) obtained from the shoulder on the short wavelength side of the peak of the phosphorescence spectrum of the host compound is from the viewpoint of promoting the generation of TADF in the light-emitting layer without hindering it.
  • the lowest excited triplet energy level E(2,T,Sh) of the emitting or assisting dopant having the highest lowest triplet energy level in the layer, higher than E(3,T,Sh) Specifically, the lowest excited triplet energy level E(1, T, Sh) of the host compound is 0 compared to E(2, T, Sh) and E(3, T, Sh). It is preferably 0.01 eV or more, more preferably 0.03 eV or more, and even more preferably 0.1 eV or more.
  • a TADF-active compound may also be used as the host compound.
  • the thermally activated delayed phosphor (TADF compound) used in the TAF element is an intramolecular HOMO (Highest Occupied Molecular Orbital) and LUMO using an electron-donating substituent called a donor and an electron-accepting substituent called an acceptor. (Lowest Unoccupied Molecular Orbital), designed to cause efficient reverse intersystem crossing, donor-acceptor thermally activated delayed phosphor (DA type TADF compound ) is preferred.
  • electron-donating substituent means a substituent and a partial structure in which a HOMO orbital is localized in a thermally activated delayed phosphor molecule.
  • acceptable substituent means a substituent and a partial structure in which a LUMO orbital is localized in a thermally activated delayed phosphor molecule.
  • thermally activated delayed phosphor using a donor or acceptor has a large spin orbit coupling (SOC) due to its structure, and a small exchange interaction between HOMO and LUMO . Its small size results in very fast reverse intersystem crossing velocities.
  • thermally activated delayed fluorophores using donors and acceptors exhibit greater structural relaxation in the excited state (for some molecules, the stable structure differs between the ground state and the excited state, so external stimuli can cause excitation from the ground state). When the conversion occurs, the structure then changes to the stable structure in the excited state), giving a broad emission spectrum, which can reduce color purity when used as a light-emitting material.
  • thermally activated delayed phosphor in the TAF element for example, a compound in which a donor and an acceptor are bound directly or via a spacer can be used.
  • electron-donating group (donor structure) and electron-accepting group (acceptor structure) used in the thermally activated delayed phosphor of the present invention for example, Chemistry of Materials, 2017, 29, 1946-1963 The structures described can be used.
  • Donor structures include carbazole, dimethylcarbazole, di-tert-butylcarbazole, dimethoxycarbazole, tetramethylcarbazole, benzofluorocarbazole, benzothienocarbazole, phenyldihydroindolocarbazole, phenylbicarbazole, bicarbazole, tercarbazole, diphenylcarbazolylamine, tetraphenylcarbazolyldiamine, phenoxazine, dihydrophenazine, phenothiazine, dimethyldihydroacridine, diphenylamine, bis(tert-butylphenyl)amine, N1-(4-(diphenylamino)phenyl)-N4, N4 -diphenylbenzene-1,4-diamine, dimethyltetraphenyldihydroacridinediamine, tetramethyl-dihydro-
  • Acceptor structures include sulfonyldibenzene, benzophenone, phenylenebis(phenylmethanone), benzonitrile, isonicotinonitrile, phthalonitrile, isophthalonitrile, paraphthalonitrile, benzenetricarbonitrile, triazole, oxazole, and thiadiazole.
  • the compound having thermally activated delayed fluorescence in the TAF element has, as a partial structure, carbazole, phenoxazine, acridine, triazine, pyrimidine, pyrazine, thioxanthene, benzonitrile, phthalonitrile, isophthalonitrile, diphenylsulfone, triazole,
  • a compound containing at least one selected from oxadiazole, thiadiazole and benzophenone is preferred.
  • the compound used as the assisting dopant in the light-emitting layer of the TAF element is preferably a thermally activated delayed phosphor whose emission spectrum at least partially overlaps with the absorption peak of the emitting dopant.
  • Phosphorescent material (assisting dopant)
  • a phosphorescent material may be used as an assisting dopant in the light-emitting layer.
  • Phosphorescent materials utilize intramolecular spin-orbital interactions (heavy atom effect) by metal atoms to obtain emission from triplets.
  • a luminescent metal complex can be used as such a phosphorescent material.
  • Examples of the luminescent metal complex include compounds represented by the following formulas (B-1) and (B-2).
  • M is at least one selected from the group consisting of Ir, Pt, Au, Eu, Ru, Re, Ag and Cu; n is an integer of 1 to 3; XY" is each independently a bidentate ligand.
  • M is at least one selected from the group consisting of Pt, Re and Cu, and "WXYZ” is a tetradentate ligand.
  • M is preferably Ir and n is preferably 3 from the viewpoint of efficiency and life.
  • M is preferably Pt from the viewpoint of efficiency and life.
  • the ligand (XY) in formula (B-1) has at least one ligand selected from the group consisting of:
  • the ligand (WXYZ) in formula (B-2) has as a part thereof at least one ligand selected from the group consisting of the following.
  • Y is each independently BR e , NR e , P e , O, S, Se, C ⁇ O, S ⁇ O, SO2, CR e R f , SiRe R f , or GeRe R f each aromatic carbon C-H in the ring may be independently substituted with N, R e and R f may optionally be fused or joined to form a ring; R a , R b , R c , and R d are each independently unsubstituted or optionally substituted from 1 to the maximum possible number of substitutions; R a , R b , R c , R d , R e , and R f are each independently hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl,
  • Examples of compounds represented by formula (B-1) include Ir(ppy) 3 , Ir(ppy) 2 (acac), Ir(mppy) 3 , Ir(PPy) 2 (m-bppy), BtpIr ( acac), Ir(btp) 2 (acac), Ir(2-phq) 3 , Hex-Ir(phq) 3 , Ir(fbi) 2 (acac), fac-Tris(2-(3-p-xylyl) phenyl)pyridine iridium (III), Eu(dbm) 3 (Phen), Ir(piq) 3 , Ir(piq) 2 (acac), Ir(Fliq) 2 (acac), Ir(FIq) 2 (acac), Ru(dtb-bpy) 3 2(PF 6 ), Ir(2-phq) 3 , Ir(BT) 2 (acac), Ir(DMP) 3 , Ir(
  • JP 2006-089398, JP 2006-080419, JP 2005-298483, JP 2005-097263, and JP 2004-111379 US Patent Application Publication No. 2019/ 0051845, etc., or Advanced Materials, 26: 7116-7121, NPG Asia Materials 13, 53 (2021), Applied Physics Letters, 117, 253301 (2020), Light-Emitting Diode - An Platinum complexes described in Outlook On the Empirical Features and Its Recent Technological Advancements, Chapter 5 may also be used.
  • the electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106 .
  • the electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105 .
  • the electron transport layer 106 and the electron injection layer 107 are formed by stacking and mixing one or more electron transport/injection materials, or by a mixture of an electron transport/injection material and a polymer binder.
  • the electron injection/transport layer is a layer in which electrons are injected from the cathode and is responsible for transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are efficiently transported. For this purpose, it is preferable to use a substance that has high electron affinity, high electron mobility, excellent stability, and does not easily generate trapping impurities during production and use. However, when considering the transport balance of holes and electrons, if the function mainly plays the role of efficiently preventing holes from the anode from flowing to the cathode side without recombination, the electron transport capacity is not so high. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material with a high electron transport ability. Therefore, the electron injection/transport layer in this embodiment may also have the function of a layer capable of efficiently blocking the movement of holes.
  • Materials (electron transport materials) forming the electron transport layer 106 or the electron injection layer 107 include compounds conventionally used as electron transport compounds in photoconductive materials, and those used in the electron injection layer and electron transport layer of organic EL elements. It can be used by arbitrarily selecting from among the known compounds that are known.
  • Materials used for the electron transport layer or electron injection layer include compounds composed of aromatic rings or heteroaromatic rings composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus, It preferably contains at least one selected from pyrrole derivatives, condensed ring derivatives thereof, and metal complexes having electron-accepting nitrogen.
  • condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives typified by 4,4'-bis(diphenylethenyl)biphenyl, perinone derivatives, coumarin derivatives, and naphthalimide derivatives.
  • quinone derivatives such as anthraquinone and diphenoquinone
  • phosphine oxide derivatives arylnitrile derivatives
  • indole derivatives examples include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes and benzoquinoline metal complexes. These materials may be used alone, but may be used in combination with different materials.
  • electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, benzofluorene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, and perylene derivatives.
  • oxadiazole derivatives (1,3-bis[(4-t-butylphenyl)1,3,4-oxadiazolyl]phenylene, etc.)
  • thiophene derivatives triazole derivatives (N-naphthyl-2,5-diphenyl-1, 3,4-triazole, etc.)
  • thiadiazole derivatives metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis(benzo[h]quinolin-2-yl)-9,9'-spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris(N- phen
  • Metal complexes having electron-accepting nitrogen can also be used, for example, quinolinol-based metal complexes, hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, benzoquinoline metal complexes, and the like. can give.
  • the above materials can be used alone, but they can be used by mixing with different materials.
  • the borane derivative is, for example, a compound represented by the following formula (ETM-1), which is disclosed in detail in JP-A-2007-27587.
  • R 11 and R 12 are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, optionally substituted silyl, optionally substituted nitrogen-containing hetero ring or at least one of cyano
  • R 13 to R 16 are each independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl
  • X is optionally substituted arylene
  • Y is optionally substituted aryl having up to 16 carbon atoms
  • optionally substituted boryl optionally substituted carbazolyl
  • n are each independently an integer of 0 to 3.
  • substituents in the case of "optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, cycloalkyl and the like.
  • R 11 and R 12 are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, optionally substituted silyl, optionally substituted nitrogen containing heterocyclic ring or at least one of cyano
  • R 13 to R 16 are each independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl
  • R 21 and R 22 are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano is at least one
  • X 1 is an optionally substituted arylene having 20 or less carbon atoms
  • each n is independently an integer of 0 to 3
  • each m is independently an integer of 0 to 4 is an integer of
  • substituents in the case of "optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, cycloalkyl and the like.
  • R 11 and R 12 are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, optionally substituted silyl, optionally substituted nitrogen containing heterocyclic ring or at least one of cyano
  • R 13 to R 16 are each independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl
  • X 1 is an optionally substituted arylene having 20 or less carbon atoms
  • each n is independently an integer of 0 to 3.
  • substituents in the case of "optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, cycloalkyl and the like.
  • X 1 include divalent groups represented by any of the following formulas (X-1) to (X-9). (In each formula, R a is each independently alkyl, cycloalkyl, or optionally substituted phenyl, and * represents a bonding position.)
  • this borane derivative include the following compounds.
  • This borane derivative can be produced using known raw materials and known synthetic methods.
  • the pyridine derivative is, for example, a compound represented by the following formula (ETM-2), preferably a compound represented by formula (ETM-2-1) or (ETM-2-2).
  • ⁇ is an n-valent aryl ring (preferably n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), n is an integer of 1 to 4; be.
  • R 11 to R 18 are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) ) or aryl (preferably aryl having 6 to 30 carbon atoms).
  • R 11 and R 12 are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) ) or aryl (preferably aryl having 6 to 30 carbon atoms), and R 11 and R 12 may combine to form a ring.
  • the "pyridine-based substituent” is any one of the following formulas (Py-1) to (Py-15) (where * represents the bonding position), and the pyridine-based substituent is Each may be independently substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl and the like, with methyl being preferred. Also, the pyridine-based substituent may be bonded to ⁇ , anthracene ring or fluorene ring in each formula via phenylene or naphthylene.
  • the pyridine-based substituent is any one of the formulas (Py-1) to (Py-15) (* in the formula represents the bonding position), but among these, the following formula (Py-21) to formula (Py-44).
  • At least one hydrogen in each pyridine derivative may be replaced with deuterium, and of the two "pyridine-based substituents" in formulas (ETM-2-1) and formula (ETM-2-2), One may be substituted with aryl.
  • the “alkyl” for R 11 to R 18 may be either straight chain or branched chain, and examples thereof include straight chain alkyl having 1 to 24 carbon atoms and branched chain alkyl having 3 to 24 carbon atoms.
  • Preferred “alkyl” are alkyls of 1 to 18 carbon atoms (branched alkyls of 3 to 18 carbon atoms). More preferred “alkyl” is alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms). More preferred “alkyl” is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred “alkyl” is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).
  • alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldec
  • alkyl having 1 to 4 carbon atoms with which the pyridine-based substituent is substituted the description of the above alkyl can be cited.
  • cycloalkyl for R 11 to R 18 include cycloalkyl having 3 to 12 carbon atoms.
  • a preferred “cycloalkyl” is a cycloalkyl having 3 to 10 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 8 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 6 carbon atoms.
  • cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.
  • aryl for R 11 to R 18 , aryl having 6 to 30 carbon atoms is preferable, aryl having 6 to 18 carbon atoms is more preferable, and aryl having 6 to 14 carbon atoms is more preferable. and particularly preferably aryl having 6 to 12 carbon atoms.
  • aryl having 6 to 30 carbon atoms include monocyclic aryl phenyl, condensed bicyclic aryl (1-,2-) naphthyl, condensed tricyclic aryl acenaphthylene-( 1-,3-,4-,5-)yl, fluoren-(1-,2-,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-,2 -,3-,4-,9-)phenanthryl, condensed tetracyclic aryl triphenylene-(1-,2-)yl, pyren-(1-,2-,4-)yl, naphthacene-(1- ,2-,5-)yl, condensed pentacyclic aryl perylene-(1-,2-,3-)yl, pentacene-(1-,2-,5-,6-)yl and the like. .
  • aryl having 6 to 30 carbon atoms includes phenyl, naphthyl, phenanthryl, chrysenyl or triphenylenyl, more preferably phenyl, 1-naphthyl, 2-naphthyl or phenanthryl, particularly preferably phenyl, 1 -naphthyl or 2-naphthyl.
  • R 11 and R 12 in formula (ETM-2-2) may combine to form a ring, and as a result, the 5-membered ring of the fluorene skeleton includes cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane , fluorene or indene may be spiro-bonded.
  • this pyridine derivative include the following compounds.
  • This pyridine derivative can be produced using known raw materials and known synthetic methods.
  • the fluoranthene derivative is, for example, a compound represented by the following formula (ETM-3), which is disclosed in detail in WO2010/134352.
  • X 12 to X 21 are hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted hetero represents aryl.
  • substituents when substituted include aryl, heteroaryl, alkyl, cycloalkyl and the like.
  • this fluoranthene derivative include the following compounds.
  • the BO derivative is, for example, a polycyclic aromatic compound represented by the following formula (ETM-4) or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (ETM-4).
  • R 1 to R 11 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, wherein at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
  • Adjacent groups among R 1 to R 11 may be combined to form an aryl ring or heteroaryl ring together with the a ring, the b ring, or the c ring, and at least one hydrogen atom in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy in which at least one hydrogen is aryl, heteroaryl, alkyl or It may be substituted with cycloalkyl.
  • At least one hydrogen in the compound or structure represented by formula (ETM-4) may be substituted with halogen or deuterium.
  • this BO derivative include the following compounds.
  • This BO-based derivative can be produced using known raw materials and known synthetic methods.
  • a benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6).
  • Ar 1 is each independently an aryl having 6 to 20 carbon atoms, and the same description as “aryl having 6 to 20 carbon atoms” for Ar 2 of formula (ETM-5) can be cited.
  • Aryl having 6 to 16 carbon atoms is preferred, aryl having 6 to 12 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred.
  • Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, and perylenyl.
  • Ar 2 is each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably aryl having 6 to 30 carbon atoms) ) and the two Ar 2 may be combined to form a ring.
  • Alkyl for Ar 2 may be either straight chain or branched chain, and examples thereof include straight chain alkyl having 1 to 24 carbon atoms and branched chain alkyl having 3 to 24 carbon atoms.
  • Preferred “alkyl” are alkyls of 1 to 18 carbon atoms (branched alkyls of 3 to 18 carbon atoms). More preferred “alkyl” is alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms). More preferred “alkyl” is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms).
  • alkyl is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).
  • alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like.
  • Cycloalkyl for Ar 2 includes, for example, cycloalkyl having 3 to 12 carbon atoms.
  • a preferred “cycloalkyl” is a cycloalkyl having 3 to 10 carbon atoms. More preferred "cycloalkyl” is cycloalkyl having 3 to 8 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 6 carbon atoms.
  • cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.
  • the “aryl” for Ar 2 is preferably aryl having 6 to 30 carbon atoms, more preferably aryl having 6 to 18 carbon atoms, more preferably aryl having 6 to 14 carbon atoms, and particularly Aryl having 6 to 12 carbon atoms is preferred.
  • aryl having 6 to 30 carbon atoms include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, naphthacenyl, perylenyl, and pentacenyl.
  • Two Ar2 may be joined to form a ring, so that the 5-membered ring of the fluorene skeleton is spiro-bonded with cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene or indene, etc. may
  • This benzofluorene derivative can be produced using known raw materials and known synthetic methods.
  • a phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1). Details are also described in International Publication No. 2013/079217 and International Publication No. 2013/079678.
  • R 5 is substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms;
  • R 6 is CN, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, 5 to 5 carbon atoms 20 heteroaryl, alkoxy having 1 to 20 carbon atoms or aryloxy having 6 to 20 carbon atoms,
  • R 7 and R 8 are each independently substituted or unsubstituted aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms;
  • R9 is oxygen or sulfur, j is 0 or 1, k is 0 or 1, r is an integer of 0-4, and q is an integer of 1-3.
  • a phosphine oxide derivative may be, for example, a compound represented by the following formula (ETM-7-2).
  • R 1 to R 3 may be the same or different and may be hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, alkylthio, cycloalkylthio, aryl ether (aryl ether group), arylthioether (aryl thioether group), aryl, heterocyclic group, halogen, cyano, aldehyde, carbonyl, carboxyl, amino, nitro, silyl, and condensed rings formed between adjacent substituents.
  • Ar 1 may be the same or different and is arylene or heteroarylene.
  • Ar 2 which may be the same or different, is aryl or heteroaryl. However, at least one of Ar 1 and Ar 2 has a substituent or forms a condensed ring with an adjacent substituent.
  • n is an integer of 0 to 3, and when n is 0, there is no unsaturated structural moiety, and when n is 3, R 1 does not exist.
  • alkyl refers to saturated aliphatic hydrocarbon groups such as methyl, ethyl, propyl and butyl, which may be unsubstituted or substituted.
  • substituents there are no particular restrictions on the substituents in the case of substitution, and examples thereof include alkyl, aryl, heterocyclic groups and the like, and this point is also common to the following description.
  • the number of carbon atoms in the alkyl is not particularly limited, it is usually in the range of 1 to 20 from the standpoint of availability and cost.
  • cycloalkyl indicates, for example, saturated alicyclic hydrocarbon groups such as cyclopropyl, cyclohexyl, norbornyl, and adamantyl, which may be unsubstituted or substituted.
  • the number of carbon atoms in the alkyl moiety is not particularly limited, it is usually in the range of 3-20.
  • Aralkyl means an aromatic hydrocarbon group via an aliphatic hydrocarbon such as benzyl, phenylethyl, etc. Both the aliphatic hydrocarbon and the aromatic hydrocarbon may be unsubstituted or substituted. do not have. Although the number of carbon atoms in the aliphatic portion is not particularly limited, it is usually in the range of 1-20.
  • alkenyl refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as vinyl, allyl, butadienyl, etc., which may be unsubstituted or substituted. Although the number of carbon atoms in alkenyl is not particularly limited, it is usually in the range of 2-20.
  • cycloalkenyl indicates an unsaturated alicyclic hydrocarbon group containing a double bond such as cyclopentenyl, cyclopentadienyl, cyclohexenyl, etc., which may be unsubstituted or substituted.
  • alkynyl refers to an unsaturated aliphatic hydrocarbon group containing a triple bond such as acetylenyl, which may be unsubstituted or substituted. Although the number of carbon atoms in alkynyl is not particularly limited, it is usually in the range of 2-20.
  • alkoxy indicates, for example, an aliphatic hydrocarbon group via an ether bond such as methoxy, and the aliphatic hydrocarbon group may be unsubstituted or substituted.
  • the number of carbon atoms in alkoxy is not particularly limited, it is usually in the range of 1-20.
  • alkylthio is a group in which the oxygen atom of the ether bond of alkoxy is substituted with a sulfur atom.
  • cycloalkylthio is a group in which the oxygen atom of the ether bond of cycloalkoxy is substituted with a sulfur atom.
  • aryl ether refers to, for example, an aromatic hydrocarbon group via an ether bond such as phenoxy, and the aromatic hydrocarbon group may be unsubstituted or substituted.
  • the number of carbon atoms in the aryl ether is not particularly limited, it is usually in the range of 6-40.
  • an arylthioether is a group in which an oxygen atom in an ether bond of an aryl ether is substituted with a sulfur atom.
  • aryl refers to aromatic hydrocarbon groups such as phenyl, naphthyl, biphenylyl, phenanthryl, terphenylyl, and pyrenyl.
  • Aryl may be unsubstituted or substituted. Although the number of carbon atoms in aryl is not particularly limited, it is usually in the range of 6-40.
  • a heterocyclic group is, for example, a cyclic structural group having atoms other than carbon atoms such as furanyl, thienyl, oxazolyl, pyridyl, quinolinyl, carbazolyl, etc., which may be unsubstituted or substituted.
  • the number of carbon atoms in the heterocyclic group is not particularly limited, it is usually in the range of 2-30.
  • Halogen means fluorine, chlorine, bromine, and iodine.
  • Aldehyde, carbonyl, and amino can also include groups substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic rings, and the like.
  • aliphatic hydrocarbons may be unsubstituted or substituted.
  • alicyclic hydrocarbons may be unsubstituted or substituted.
  • aromatic hydrocarbons may be unsubstituted or substituted.
  • heterocycles may be unsubstituted or substituted.
  • Silyl means, for example, a silicon compound group such as trimethylsilyl, which may be unsubstituted or substituted.
  • the number of carbon atoms in silyl is not particularly limited, it is usually in the range of 3-20. Also, the silicon number is usually 1-6.
  • Condensed rings formed between adjacent substituents are, for example, Ar 1 and R 2 , Ar 1 and R 3 , Ar 2 and R 2 , Ar 2 and R 3 , R 2 and R 3 , Ar 1 and Conjugated or non-conjugated fused ring formed between Ar 2 and so on.
  • n 1, two R 1s may form a conjugated or non-conjugated condensed ring.
  • These condensed rings may contain a nitrogen, oxygen or sulfur atom in the ring structure, or may be condensed with another ring.
  • this phosphine oxide derivative include the following compounds.
  • This phosphine oxide derivative can be produced using known raw materials and known synthetic methods.
  • the pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), preferably a compound represented by the following formula (ETM-8-1). Details are also described in International Publication No. 2011/021689.
  • Each Ar is independently optionally substituted aryl or optionally substituted heteroaryl.
  • n is an integer of 1-4, preferably an integer of 1-3, more preferably 2 or 3;
  • aryl of “optionally substituted aryl” includes, for example, aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, Aryl having 6 to 12 carbon atoms is more preferable.
  • aryl includes monocyclic aryl phenyl, bicyclic aryl (2-,3-,4-)biphenylyl, condensed bicyclic aryl (1-,2-)naphthyl , tricyclic aryl terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o -terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, o-terpheny
  • Heteroaryl of “optionally substituted heteroaryl” includes, for example, heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferred, heteroaryl having 2 to 15 carbon atoms is even more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.
  • heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, napthy
  • aryl and heteroaryl may be substituted, and each may be substituted with, for example, the above aryl or heteroaryl.
  • this pyrimidine derivative include the following compounds.
  • This pyrimidine derivative can be produced using known raw materials and known synthetic methods.
  • the arylnitrile derivative is, for example, a compound represented by the following formula (ETM-9) or a multimer in which multiple bonds are formed by single bonds or the like. Details are described in US Publication No. 2014/0197386.
  • Ar ni preferably has a large number of carbon atoms from the viewpoint of fast electron transport, and preferably has a small number of carbon atoms from the viewpoint of high T1.
  • Ar ni preferably has a high T1 specifically for use in a layer adjacent to the light-emitting layer and is aryl having 6 to 20 carbon atoms, preferably aryl having 6 to 14 carbon atoms, more preferably It is an aryl having 6 to 10 carbon atoms.
  • the number n of substituted nitrile groups is preferably large from the viewpoint of high T1, and preferably small from the viewpoint of high S1.
  • the substitution number n of the nitrile group is specifically an integer of 1 to 4, preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and still more preferably 1.
  • Each Ar is independently optionally substituted aryl or optionally substituted heteroaryl. From the viewpoint of high S1 and high T1, donor heteroaryl is preferred, and less donor heteroaryl is preferred for use as an electron-transporting layer. From the viewpoint of charge transportability, aryl or heteroaryl having a large number of carbon atoms is preferable, and it is preferable to have many substituents.
  • the number of substitutions m for Ar is specifically an integer of 1-4, preferably an integer of 1-3, more preferably 1-2.
  • aryl of “optionally substituted aryl” includes, for example, aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, Aryl having 6 to 12 carbon atoms is more preferable.
  • aryl includes monocyclic aryl phenyl, bicyclic aryl (2-,3-,4-)biphenylyl, condensed bicyclic aryl (1-,2-)naphthyl , tricyclic aryl terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o -terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, o-terpheny
  • Heteroaryl of “optionally substituted heteroaryl” includes, for example, heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferred, heteroaryl having 2 to 15 carbon atoms is even more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.
  • heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, napthy
  • aryl and heteroaryl may be substituted, and each may be substituted with, for example, the above aryl or heteroaryl.
  • the arylnitrile derivative may be a multimer in which multiple compounds represented by the formula (ETM-9) are bonded with single bonds or the like. In this case, they may be bonded by an aryl ring (preferably a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring) other than a single bond.
  • an aryl ring preferably a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring
  • this arylnitrile derivative include the following compounds.
  • This arylnitrile derivative can be produced using known raw materials and known synthetic methods.
  • the triazine derivative is, for example, a compound represented by the following formula (ETM-10), preferably a compound represented by the following formula (ETM-10-1). Details are described in US Patent Application Publication No. 2011/0156013.
  • Each Ar is independently optionally substituted aryl or optionally substituted heteroaryl.
  • n is an integer of 1-3, preferably 2 or 3;
  • aryl of “optionally substituted aryl” includes, for example, aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, Aryl having 6 to 12 carbon atoms is more preferable.
  • aryl includes monocyclic aryl phenyl, bicyclic aryl (2-,3-,4-)biphenylyl, condensed bicyclic aryl (1-,2-)naphthyl , tricyclic aryl terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o -terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, o-terpheny
  • Heteroaryl of “optionally substituted heteroaryl” includes, for example, heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferred, heteroaryl having 2 to 15 carbon atoms is even more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.
  • heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, napthy
  • aryl and heteroaryl may be substituted, and each may be substituted with, for example, the above aryl or heteroaryl.
  • this triazine derivative include the following compounds.
  • This triazine derivative can be produced using known raw materials and known synthetic methods.
  • a benzimidazole derivative is, for example, a compound represented by the following formula (ETM-11).
  • ⁇ is an n-valent aryl ring (preferably n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), n is an integer of 1 to 4; and the "benzimidazole-based substituent” is the following benzimidazolyl pyridyl in the "pyridine-based substituent" in formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) (In the formula, * indicates the bonding position.), and at least one hydrogen in the benzimidazole derivative may be replaced with deuterium.
  • R 11 in the benzimidazolyl is hydrogen, alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms or aryl having 6 to 30 carbon atoms, and represented by formula (ETM-2-1) and formula (ETM-2 -2), the description of R 11 can be cited.
  • ⁇ is further preferably an anthracene ring or a fluorene ring, and the structure in this case can refer to the description of formula (ETM-2-1) or formula (ETM-2-2), and each formula For R 11 to R 18 in the formula (ETM-2-1) or (ETM-2-2), the explanation can be cited.
  • this benzimidazole derivative include 1-phenyl-2-(4-(10-phenylanthracen-9-yl)phenyl)-1H-benzo[d]imidazole, 2-(4-(10-( Naphthalen-2-yl)anthracen-9-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 2-(3-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl) -1-phenyl-1H-benzo[d]imidazole, 5-(10-(naphthalen-2-yl)anthracen-9-yl)-1,2-diphenyl-1H-benzo[d]imidazole, 1-(4 -(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 2-(4-(9,10-di(naphthalimid
  • This benzimidazole derivative can be produced using known raw materials and known synthetic methods.
  • a phenanthroline derivative is, for example, a compound represented by the following formula (ETM-12) or formula (ETM-12-1). Details are described in WO2006/021982.
  • ⁇ is an n-valent aryl ring (preferably n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), n is an integer of 1 to 4; be.
  • R 11 to R 18 in each formula are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably carbon aryl of numbers 6 to 30). Further, in formula (ETM-12-1), any one of R 11 to R 18 serves as a bond with ⁇ which is an aryl ring.
  • At least one hydrogen in each phenanthroline derivative may be replaced with deuterium.
  • each R is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl, and * represents a bonding position.
  • this phenanthroline derivative examples include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di(1,10- phenanthrolin-2-yl)anthracene, 2,6-di(1,10-phenanthroline-5-yl)pyridine, 1,3,5-tri(1,10-phenanthroline-5-yl)benzene, 9,9' -Difluoro-bi(1,10-phenanthroline-5-yl), bathocuproine, 1,3-bis(2-phenyl-1,10-phenanthroline-9-yl)benzene, compounds represented by the following structural formulas, etc. can give.
  • This phenanthroline derivative can be produced using known raw materials and known synthetic methods.
  • a quinolinol-based metal complex is, for example, a compound represented by the following formula (ETM-13).
  • R 1 to R 6 are each independently hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy, or aryl
  • M is Li, Al, Ga, Be, or Zn
  • n is an integer from 1 to 3.
  • quinolinol-based metal complexes include 8-quinolinollithium, tris(8-quinolinolato)aluminum, tris(4-methyl-8-quinolinolato)aluminum, tris(5-methyl-8-quinolinolato)aluminum, tris(3 ,4-dimethyl-8-quinolinolato)aluminum, tris(4,5-dimethyl-8-quinolinolato)aluminum, tris(4,6-dimethyl-8-quinolinolato)aluminum, bis(2-methyl-8-quinolinolato) ( phenolate)aluminum, bis(2-methyl-8-quinolinolato)(2-methylphenolate)aluminum, bis(2-methyl-8-quinolinolato)(3-methylphenolate)aluminum, bis(2-methyl-8- quinolinolato)(4-methylphenolate)aluminum, bis(2-methyl-8-quinolin
  • This quinolinol-based metal complex can be produced using known raw materials and known synthesis methods.
  • a thiazole derivative is, for example, a compound represented by the following formula (ETM-14-1).
  • a benzothiazole derivative is, for example, a compound represented by the following formula (ETM-14-2).
  • ⁇ in each formula is an n-valent aryl ring (preferably n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is 1 to 4 is an integer, and the “thiazole-based substituent” and “benzothiazole-based substituent” are the “pyridine-based substituents” in formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) Pyridyl in "group” is a substituent substituted with thiazolyl or benzothiazolyl (* indicates a bonding position) below, and at least one hydrogen in the thiazole derivative and benzothiazole derivative may be substituted with deuterium.
  • ⁇ is further preferably an anthracene ring or a fluorene ring, and the structure in this case can refer to the description of formula (ETM-2-1) or formula (ETM-2-2), and each formula For R 11 to R 18 in the formula (ETM-2-1) or (ETM-2-2), the explanation can be cited.
  • R 11 to R 18 in formula (ETM-2-1) is replaced with a thiazole-based substituent (or a benzothiazole-based substituent), and a “pyridine-based substituent” is represented by R 11 to R 18 . may be replaced.
  • thiazole derivatives or benzothiazole derivatives can be produced using known raw materials and known synthetic methods.
  • a silole derivative is, for example, a compound represented by the following formula (ETM-15). Details are described in JP-A-9-194487.
  • X and Y are each independently alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, aryl, heteroaryl, which are optionally substituted.
  • alkenyloxy and alkynyloxy are groups in which the alkyl portion of alkoxy is replaced with alkenyl or alkynyl, respectively, and details of these alkenyls and alkynyls can be referred to the description of formula (ETM-7-2).
  • X and Y, both of which are alkyl may combine to form a ring.
  • R 1 to R 4 are each independently hydrogen, halogen, alkyl, cycloalkyl, alkoxy, aryloxy, amino, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, azo group, alkylcarbonyloxy, arylcarbonyl oxy, alkoxycarbonyloxy, aryloxycarbonyloxy, sulfinyl, sulfonyl, sulfanyl, silyl, carbamoyl, aryl, heteroaryl, alkenyl, alkynyl, nitro, formyl, nitroso, formyloxy, isocyano, cyanate group, isocyanate group, thiocyanate group, An isothiocyanate group or cyano, which may be substituted with alkyl, cycloalkyl, aryl or halogen, and may form a condensed ring with adjacent substituents.
  • alkyl, aryl and alkoxy in alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy and aryloxycarbonyloxy in R 1 to R 4 are also given in the formula The description in (4) can be cited.
  • Silyl includes a silyl group and a group in which at least one of the three hydrogen atoms in the silyl group is each independently substituted with an aryl, alkyl or cycloalkyl, trisubstituted silyl is preferred, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl and the like.
  • aryl, alkyl and cycloalkyl in these the description in formula (4) can be cited.
  • the condensed ring formed between adjacent substituents is, for example, a conjugated or non-conjugated condensed ring formed between R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , etc. .
  • These condensed rings may contain a nitrogen, oxygen or sulfur atom in the ring structure, or may be condensed with another ring.
  • R 1 and R 4 are phenyl
  • X and Y are not alkyl or phenyl.
  • R 1 and R 4 are thienyl
  • X and Y are alkyl
  • R 2 and R 3 are alkyl, aryl, alkenyl, or cyclo where R 2 and R 3 combine to form a ring. It is a structure that does not satisfy alkyl at the same time.
  • R 1 and R 4 are silyl groups
  • R 2 , R 3 , X and Y are each independently not hydrogen or alkyl having 1 to 6 carbon atoms.
  • X and Y are neither alkyl nor phenyl.
  • silole derivatives can be produced using known raw materials and known synthetic methods.
  • Azoline derivatives are, for example, compounds represented by the following formula (ETM-16). Details are described in WO2017/014226.
  • ⁇ is an m-valent group derived from an aromatic hydrocarbon having 6 to 40 carbon atoms or an m-valent group derived from an aromatic heterocyclic ring having 2 to 40 carbon atoms, and at least one hydrogen of ⁇ has 1 carbon atom ⁇ 6 alkyl, cycloalkyl having 3 to 14 carbon atoms, aryl having 6 to 18 carbon atoms or heteroaryl having 2 to 18 carbon atoms, Y is each independently -O-, -S- or >N-Ar, Ar is aryl having 6 to 12 carbon atoms or heteroaryl having 2 to 12 carbon atoms, and at least one hydrogen of Ar may be substituted with alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, aryl having 6 to 12 carbon atoms or heteroaryl having 2 to 12 carbon atoms, and R 1 to R 5 are each independently is hydrogen, alkyl having 1 to 4 carbon atoms or cycloalkyl
  • at least one hydrogen of L may be substituted with alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, aryl having 6 to 10 carbon atoms or heteroaryl having 2 to 10 carbon atoms; m is
  • a specific azoline derivative is a compound represented by the following formula (ETM-16-1) or formula (ETM-16-2).
  • ⁇ is an m-valent group derived from an aromatic hydrocarbon having 6 to 40 carbon atoms or an m-valent group derived from an aromatic heterocyclic ring having 2 to 40 carbon atoms, and at least one hydrogen of ⁇ has 1 carbon atom ⁇ 6 alkyl, cycloalkyl having 3 to 14 carbon atoms, aryl having 6 to 18 carbon atoms or heteroaryl having 2 to 18 carbon atoms,
  • Y is each independently -O-, -S- or >N-Ar
  • Ar is aryl having 6 to 12 carbon atoms or hetero aryl, and at least one hydrogen of Ar may be substituted with alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, aryl having 6 to 12 carbon atoms or heteroaryl having 2 to 12 carbon atoms;
  • R 1 to R 4 are each independently -O-, -S- or >N-Ar
  • Ar is aryl having 6 to 12 carbon atom
  • at least one hydrogen of L may be substituted with alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, aryl having 6 to 10 carbon atoms or heteroaryl having 2 to 10 carbon atoms; m is
  • ⁇ is a monovalent group represented by the following formulas ( ⁇ 1-1) to ( ⁇ 1-18), and a divalent group represented by the following formulas ( ⁇ 2-1) to ( ⁇ 2-34).
  • group, a trivalent group represented by the following formulas ( ⁇ 3-1) to ( ⁇ 3-3), and a tetravalent group represented by the following formulas ( ⁇ 4-1) to ( ⁇ 4-2) is selected from the group, and at least one hydrogen of ⁇ is substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, aryl having 6 to 18 carbon atoms or heteroaryl having 2 to 18 carbon atoms; good too.
  • Z in the formula is >CR 2 , >N—Ar, >NL, —O— or —S—, and each R in >CR 2 is independently alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, aryl having 6 to 12 carbon atoms or heteroaryl having 2 to 12 carbon atoms, R may be bonded to each other to form a ring, and Ar in >N-Ar is aryl having 6 to 12 carbon atoms or heteroaryl having 2 to 12 carbon atoms, and L in >NL is formula (ETM-16), formula (ETM-16-1) or formula (ETM-16-2) is L in * in the formula represents a binding position.
  • L is a ring divalent group selected from the group consisting of benzene, naphthalene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, and pteridine. and at least one hydrogen of L may be substituted with alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, aryl having 6 to 10 carbon atoms or heteroaryl having 2 to 10 carbon atoms.
  • Ar in >N-Ar as Y or Z is from the group consisting of phenyl, naphthyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, napthyridinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and pteridinyl
  • At least one hydrogen of Ar in selected >N-Ar as Y may be substituted with alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms or aryl having 6 to 10 carbon atoms.
  • R 1 to R 4 are each independently hydrogen, alkyl of 1 to 4 carbon atoms or cycloalkyl of 5 to 10 carbon atoms, provided that R 1 and R 2 are the same, R 3 and R 4 are the same, all of R 1 to R 4 are not hydrogen at the same time, m is 1 or 2, and when m is 2, the group formed by the azoline ring and L are identical.
  • azoline derivatives include the following compounds. "Me” in the structural formula represents methyl.
  • ⁇ is a divalent group represented by the following formula ( ⁇ 2-1), formula ( ⁇ 2-31), formula ( ⁇ 2-32), formula ( ⁇ 2-33) and formula ( ⁇ 2-34) and at least one hydrogen of ⁇ may be substituted with an aryl having 6 to 18 carbon atoms.
  • * in the following formula indicates a binding position.
  • L is a ring divalent group selected from the group consisting of benzene, pyridine, pyrazine, pyrimidine, pyridazine, and triazine, and at least one hydrogen of L is alkyl having 1 to 4 carbon atoms, optionally substituted with 10 cycloalkyl, aryl having 6 to 10 carbon atoms or heteroaryl having 2 to 14 carbon atoms, Ar in >N-Ar as Y is selected from the group consisting of phenyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl, and at least one hydrogen of the Ar is alkyl having 1 to 4 carbon atoms, 5 to 4 carbon atoms, optionally substituted with 10 cycloalkyl or aryl having 6 to 10 carbon atoms, R 1 to R 4 are each independently hydrogen, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon
  • azoline derivative examples include the following compounds.
  • Me in the structural formula represents methyl.
  • This azoline derivative can be produced using known raw materials and known synthetic methods.
  • the electron-transporting layer or electron-injecting layer may further comprise a substance capable of reducing the material forming the electron-transporting layer or electron-injecting layer.
  • a substance capable of reducing the material forming the electron-transporting layer or electron-injecting layer Various substances are used as the reducing substance as long as they have a certain reducing property. from the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes At least one selected can be preferably used.
  • Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2.95 eV). 9 eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and materials with a work function of 2.9 eV or less are particularly preferred.
  • more preferred reducing substances are alkali metals of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs.
  • alkali metals have a particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, it is possible to improve the emission luminance and extend the life of the organic EL device.
  • a combination of two or more of these alkali metals is also preferable, particularly a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred.
  • Cs such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred.
  • the electron injection layer material and the electron transport layer material described above are polymer compounds obtained by polymerizing reactive compounds in which these are substituted with reactive substituents as monomers, or polymer crosslinked products thereof, or main chains.
  • a pendant-type polymer compound obtained by reacting a type polymer with the reactive compound or a pendant-type polymer crosslinked product thereof can also be used as a material for an electronic layer.
  • the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (4) can be cited. The details of the uses of such polymer compounds and crosslinked polymers will be described later.
  • the cathode cathode 108 in the organic electroluminescent device plays a role of injecting electrons into the light emitting layer 105 via the electron injection layer 107 and the electron transport layer 106 .
  • the material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as the material for forming the anode 102 can be used.
  • Metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or their alloys (magnesium-silver alloys, magnesium - indium alloys, aluminum-lithium alloys such as lithium fluoride/aluminum, etc.). Lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective in increasing the electron injection efficiency and improving the device characteristics.
  • these low work function metals are generally unstable in the atmosphere.
  • a method of doping an organic layer with a small amount of lithium, cesium, or magnesium to use a highly stable electrode is known.
  • Other dopants can also be inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide and cesium oxide. However, it is not limited to these.
  • metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, inorganic substances such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride
  • a preferable example is lamination of a hydrocarbon-based polymer compound or the like.
  • the method of manufacturing these electrodes is not particularly limited, either by resistance heating, electron beam deposition, sputtering, ion plating, coating, or the like, as long as it can provide electrical continuity.
  • Adhesives such as polyvinyl chloride, polycarbonate, polystyrene, poly(N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, Solvent-soluble resins such as vinyl acetate resins, ABS resins, polyurethane resins, curable resins such as phenolic resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, etc. It is also possible to use it by dispersing it into.
  • a method for producing an organic electroluminescence device Each layer constituting an organic EL device is formed by applying a material to each layer by vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method or casting method. It can be formed by forming a thin film by a method such as a coating method.
  • the thickness of each layer thus formed is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation film thickness measuring device or the like.
  • the vapor deposition conditions vary depending on the type of material, the desired crystal structure and association structure of the film, and the like.
  • the vapor deposition conditions are generally boat heating temperature +50 to +400° C., degree of vacuum 10 ⁇ 6 to 10 ⁇ 3 Pa, vapor deposition rate 0.01 to 50 nm/sec, substrate temperature ⁇ 150 to +300° C., film thickness 2 nm to 5 ⁇ m. It is preferable to set appropriately within the range.
  • the organic EL device When a DC voltage is applied to the organic EL device thus obtained, it is sufficient to apply the positive polarity to the positive electrode and the negative polarity to the negative electrode. Light emission can be observed from the side (anode or cathode, and both). Further, this organic EL element emits light even when a pulse current or an alternating current is applied. Note that the AC waveform to be applied may be arbitrary.
  • an organic EL device comprising an anode/hole injection layer/hole transport layer/light-emitting layer comprising a host material and a dopant material/electron transport layer/electron injection layer/cathode.
  • the manufacturing method of is explained.
  • a thin film of an anode material is formed on a suitable substrate by a vapor deposition method or the like to prepare an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode.
  • a host material and a dopant material are co-deposited thereon to form a thin film to form a light-emitting layer, an electron-transporting layer and an electron-injecting layer are formed on the light-emitting layer, and a thin film of a cathode material is formed by vapor deposition or the like.
  • a target organic EL element is obtained by forming the material and using it as a cathode.
  • the order of production can be reversed to produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. is.
  • the wet film-forming method is carried out by preparing a low-molecular-weight compound capable of forming each organic layer of an organic EL element as a liquid composition for forming an organic layer, and using this.
  • a reactive compound obtained by substituting a reactive substituent on the low-molecular-weight compound can be used together with other monomers or main-chain polymers that have a solubility function.
  • a composition for forming an organic layer may be prepared from a molecularized polymer compound or the like.
  • a coating film is generally formed through a coating step of applying an organic layer-forming composition to a substrate and a drying step of removing the solvent from the applied organic layer-forming composition.
  • the drying step further crosslinks the polymer to form a crosslinked polymer.
  • the method using a spin coater is called the spin coating method
  • the method using a slit coater is the slit coating method
  • the method using a plate is gravure, offset, reverse offset, flexographic printing
  • the method using an inkjet printer is the inkjet method.
  • the method of spraying in the form of a mist is called the spray method.
  • the bank (200) is provided on the electrode (120) on the substrate (110).
  • ink droplets (310) are dropped between the banks (200) from the inkjet head (300) and dried to form the coating film (130).
  • the next coating film (140) and the light-emitting layer (150) are formed, and the electron-transporting layer, the electron-injecting layer and the electrode are formed using the vacuum evaporation method.
  • An organic EL element can be produced.
  • the drying process includes methods such as air drying, heating, and reduced pressure drying.
  • the drying step may be performed only once, or may be performed multiple times using different methods and conditions. Also, different methods may be used in combination, such as firing under reduced pressure.
  • a wet film-forming method is a film-forming method that uses a solution, such as some printing methods (inkjet methods), spin coating or casting methods, and coating methods. Unlike the vacuum evaporation method, the wet film formation method does not require the use of an expensive vacuum evaporation apparatus and can form a film under atmospheric pressure. In addition, the wet film formation method enables large-area production and continuous production, leading to a reduction in manufacturing costs.
  • the wet film formation method may be difficult to laminate.
  • the wet deposition method is used to fabricate a laminated film, it is necessary to prevent the dissolution of the lower layer by the composition of the upper layer. solvent) is used.
  • solvent is used.
  • wet deposition methods for all film applications.
  • the electron-transporting layer and the electron-injecting layer may also be formed by a wet film-forming method using a layer-forming composition containing an electron-transporting layer material and an electron-injecting layer material, respectively.
  • a means for preventing dissolution of the lower light-emitting layer or a means for forming a film from the cathode side in reverse to the above procedure it is preferable to use a means for preventing dissolution of the lower light-emitting layer or a means for forming a film from the cathode side in reverse to the above procedure.
  • a laser thermal lithography method can be used to form a film from the composition for forming an organic layer.
  • LITI is a method in which a compound adhered to a base material is thermally vapor-deposited with a laser, and an organic layer-forming composition can be used as the material applied to the base material.
  • treatment steps may be appropriately added before and after each step of film formation.
  • treatment steps include exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, cleaning treatment using an appropriate solvent, and heat treatment.
  • a series of steps for fabricating a bank can also be mentioned.
  • Photolithography technology can be used to fabricate the bank.
  • Positive resist materials and negative resist materials can be used as bank materials that can be used in photolithography.
  • patternable printing methods such as ink jet method, gravure offset printing, reverse offset printing, and screen printing can also be used.
  • a permanent resist material can also be used.
  • Materials used for banks include polysaccharides and their derivatives, homopolymers and copolymers of hydroxyl-containing ethylenic monomers, biopolymer compounds, polyacryloyl compounds, polyesters, polystyrenes, polyimides, polyamideimides, and polyetherimides.
  • the composition for forming an organic layer is obtained by dissolving a low-molecular-weight compound capable of forming each organic layer of an organic EL element or a high-molecular-weight compound obtained by polymerizing the low-molecular-weight compound in an organic solvent.
  • the composition for forming a light-emitting layer includes at least one dopant material polycyclic aromatic compound (or polymer compound thereof) as a first component, at least one host material as a second component, and a third It contains at least one organic solvent as a component.
  • the first component functions as a dopant component for the light-emitting layer obtained from the composition
  • the second component functions as a host component for the light-emitting layer.
  • the third component functions as a solvent that dissolves the first and second components in the composition, and provides a smooth and uniform surface profile during application due to the controlled evaporation rate of the third component itself.
  • the composition for forming an organic layer contains at least one kind of organic solvent.
  • By controlling the evaporation rate of the organic solvent during film formation it is possible to control and improve the film formability, the presence or absence of defects in the coating film, the surface roughness, and the smoothness.
  • the stability of the meniscus at the pinhole of the inkjet head can be controlled, and the ejection property can be controlled and improved.
  • the drying rate of the film and the orientation of the derivative molecules the electrical properties, luminescence properties, efficiency and life of the organic EL device having an organic layer obtained from the composition for forming an organic layer are improved. can be done.
  • the boiling point of at least one organic solvent is 130°C to 300°C, more preferably 140°C to 270°C, even more preferably 150°C to 250°C. If the boiling point is higher than 130° C., it is preferable from the viewpoint of ink jetting properties. Moreover, when the boiling point is lower than 300° C., it is preferable from the viewpoint of coating film defects, surface roughness, residual solvent, and smoothness.
  • the organic solvent more preferably contains two or more kinds of organic solvents from the viewpoint of good inkjet ejection properties, film-forming properties, smoothness, and low residual solvent.
  • the composition may be in a solid state by removing the solvent from the organic layer-forming composition in consideration of transportability and the like.
  • the organic solvent comprises a good solvent (GS) and a poor solvent (PS) for at least one of the solutes, wherein the boiling point (BP GS ) of the good solvent (GS) is lower than the boiling point (BP PS ) of the poor solvent (PS) Also low, configurations are particularly preferred.
  • GS good solvent
  • PS poor solvent
  • configurations are particularly preferred.
  • the solubility difference (S GS ⁇ S PS ) is preferably 1% or more, more preferably 3% or more, and even more preferably 5% or more.
  • the boiling point difference (BP PS ⁇ BP GS ) is preferably 10° C. or more, more preferably 30° C. or more, and even more preferably 50° C. or more.
  • the organic solvent is removed from the coating film by a drying process such as vacuum, reduced pressure, or heating.
  • a drying process such as vacuum, reduced pressure, or heating.
  • Tg glass transition temperature
  • drying may be performed multiple times at different temperatures, and multiple drying methods may be used in combination.
  • organic solvents used in the composition for forming an organic layer include alkylbenzene solvents, phenyl ether solvents, alkyl ether solvents, cyclic ketone solvents, aliphatic ketone solvents, and monocyclic solvents. Examples thereof include ketone solvents, solvents having a diester skeleton and fluorine-containing solvents.
  • Specific examples include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexane-2-ol, Heptane-2-ol, octan-2-ol, decan-2-ol, dodecan-2-ol, cyclohexanol, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, terpineol (mixture), ethylene glycol Monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether,
  • composition for forming an organic layer may contain optional components as long as the properties thereof are not impaired.
  • Optional components include binders and surfactants.
  • Binder The composition for forming an organic layer may contain a binder.
  • the binder forms a film during film formation and bonds the obtained film to the substrate. It also plays a role of dissolving, dispersing and binding other components in the composition for forming an organic layer.
  • Binders used in the organic layer-forming composition include, for example, acrylic resins, polyethylene terephthalate, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, acrylonitrile-ethylene-styrene copolymer (AES) resins, Ionomer, chlorinated polyether, diallyl phthalate resin, unsaturated polyester resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, Teflon, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile - Styrene copolymer (AS) resins, phenolic resins, epoxy resins, melamine resins, urea resins, alkyd resins, polyurethanes, and copolymers of the above resins and polymers, including but not limited to.
  • acrylic resins poly
  • the binder used in the composition for forming the organic layer may be of only one type, or may be used by mixing a plurality of types.
  • the organic layer-forming composition contains a surfactant for controlling the film surface uniformity, solvent affinity and liquid repellency of the film surface of the organic layer-forming composition.
  • a surfactant for controlling the film surface uniformity, solvent affinity and liquid repellency of the film surface of the organic layer-forming composition.
  • Surfactants are classified into ionic and nonionic based on the structure of the hydrophilic group, and further classified into alkyl, silicone and fluorine based on the structure of the hydrophobic group. Further, according to the molecular structure, it is classified into a monomolecular system having a relatively small molecular weight and a simple structure and a polymer system having a large molecular weight and having side chains and branches. Also, according to the composition, they are classified into a single system and a mixed system in which two or more kinds of surfactants and a base material are mixed. As the surfactant that can be used in the composition for forming an organic layer, all kinds of surfactants can be used.
  • a surfactant for example, Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbake 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181, Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, BYK-Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF -50-100CS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Futergent 222F,
  • one type of surfactant may be used, or two or more types may be used in combination.
  • composition and physical properties of composition for forming organic layer The content of each component in the organic layer-forming composition is obtained from the good solubility, storage stability, and film-forming properties of each component in the organic layer-forming composition, and the organic layer-forming composition. Good film quality of the coating film, good dischargeability when using the inkjet method, good electrical properties, luminescence properties, efficiency and life of the organic EL element having an organic layer produced using the composition It is determined in consideration of the viewpoint of For example, in the case of a composition for forming a light-emitting layer, the first component is 0.0001% by mass to 2.0% by mass with respect to the total weight of the composition for forming a light-emitting layer, and the second component is for forming a light-emitting layer. 0.0999% by mass to 8.0% by mass with respect to the total mass of the composition, and the third component is 90.0% by mass to 99.9% by mass with respect to the total mass of the composition for forming a light-emitting layer preferable.
  • the first component is 0.005% by mass to 1.0% by mass relative to the total mass of the composition for forming a light-emitting layer
  • the second component is relative to the total mass of the composition for forming a light-emitting layer, 0.095% by mass to 4.0% by mass
  • the third component is 95.0% by mass to 99.9% by mass with respect to the total mass of the light-emitting layer-forming composition.
  • the first component is 0.05% by mass to 0.5% by mass relative to the total mass of the composition for forming a light-emitting layer
  • the second component is relative to the total mass of the composition for forming a light-emitting layer, 0.25% by mass to 2.5% by mass
  • the third component is 97.0% by mass to 99.7% by mass with respect to the total mass of the light-emitting layer-forming composition.
  • the composition for forming an organic layer can be produced by appropriately selecting the above-described components by stirring, mixing, heating, cooling, dissolving, dispersing, etc. by a known method. After preparation, filtration, degassing (also referred to as degassing), ion exchange treatment, inert gas replacement/encapsulation treatment, and the like may be appropriately selected and performed.
  • the viscosity of the composition for forming an organic layer As for the viscosity of the composition for forming an organic layer, a higher viscosity provides better film-forming properties and better ejection properties when using an inkjet method. On the other hand, the lower the viscosity, the easier it is to form a thin film. For this reason, the viscosity of the organic layer-forming composition at 25° C. is preferably 0.3 to 3 mPa ⁇ s, more preferably 1 to 3 mPa ⁇ s. In the present invention, the viscosity is a value measured using a cone-plate rotary viscometer (cone-plate type).
  • the composition for forming an organic layer preferably has a surface tension of 20 to 40 mN/m at 25° C., more preferably 20 to 30 mN/m.
  • surface tension is a value measured using the hanging drop method.
  • ⁇ Crosslinkable Polymer Compound Compound Represented by Formula (XLP-1)>
  • a crosslinkable polymer compound is, for example, a compound represented by the following formula (XLP-1).
  • MUx, ECx and k have the same definitions as MU, EC and k in formula (H3), provided that the compound represented by formula (XLP-1) has at least one crosslinkable substituent (XLS),
  • XLS crosslinkable substituent
  • the content of the monovalent or divalent aromatic group having a crosslinkable substituent is 0.1 to 80% by mass in the molecule.
  • the content of a monovalent or divalent aromatic compound having a crosslinkable substituent is preferably 0.5 to 50% by mass, more preferably 1 to 20% by mass in the molecule.
  • crosslinkable substituent is not particularly limited as long as it is a group that can further crosslink the polymer compound described above, but substituents having the following structures are preferable. * in each structural formula indicates a binding position.
  • substituents represented by formula (XLS-1), formula (XLS-2), formula (XLS-3), formula (XLS-9), formula (XLS-10) or formula (XLS-17) is preferred, and a group represented by formula (XLS-1), formula (XLS-3) or formula (XLS-17) is more preferred.
  • divalent aromatic compounds having a crosslinkable substituent examples include compounds having the following partial structures.
  • a method for producing a polymer compound and a crosslinkable polymer compound will be described using the compound represented by the above formula (H3) and the compound represented by (XLP-1) as examples. These compounds can be synthesized by appropriately combining known production methods.
  • Solvents used in the reaction include aromatic solvents, saturated/unsaturated hydrocarbon solvents, alcohol solvents, ether solvents and the like. -ethoxyethoxy)ethane and the like.
  • reaction may be performed in a two-phase system.
  • a phase transfer catalyst such as a quaternary ammonium salt may be added.
  • the compound of formula (H3) and the compound of (XLP-1) may be produced in one step or in multiple steps.
  • it may be carried out by a batch polymerization method in which the reaction is started after all the raw materials are put into the reaction vessel, or by a dropping polymerization method in which the raw materials are added dropwise to the reaction vessel, and the product may be added as the reaction progresses.
  • a precipitation polymerization method in which precipitation is accompanied by precipitation, and synthesis can be performed by appropriately combining these methods.
  • a monomer having a polymerizable group bonded to the monomer unit (MU) and a monomer having a polymerizable group bonded to the end cap unit (EC) are placed in a reaction vessel.
  • the target product is obtained by reacting in the state of being added to.
  • a monomer having a polymerizable group bonded to the monomer unit (MU) is polymerized to a target molecular weight, and then the end cap unit (EC) is added to the polymerizable group.
  • a desired product is obtained by adding and reacting a monomer to which a group is bonded.
  • a polymer having a concentration gradient in the structure of the monomer unit can be produced by adding a monomer having a polymerizable group bonded to different types of monomer units (MU) in multiple steps and reacting. Also, after preparing the precursor polymer, the target polymer can be obtained by post-reaction.
  • MU monomer units
  • the primary structure of the polymer can be controlled by selecting the polymerizable group of the monomer. For example, as shown in synthetic schemes 1 to 3, it is possible to synthesize polymers with random primary structures (synthetic scheme 1) and regular primary structures (synthetic schemes 2 and 3). and can be used in appropriate combination depending on the object. Furthermore, hyperbranched polymers and dendrimers can be synthesized by using monomers having three or more polymerizable groups.
  • Monomers that can be used in the present invention include JP 2010-189630, WO 2012/086671, WO 2013/191088, WO 2002/045184, WO 2011/049241. , WO 2013/146806, WO 2005/049546, WO 2015/145871, JP 2010-215886, JP 2008-106241, WO 2016/031639, Patent It can be synthesized according to the method described in JP-A-2011-174062.
  • JP 2012-036388, WO 2015/008851, JP 2012-36381, JP 2012-144722, WO 2015/194448 , International Publication No. 2013/146806, International Publication No. 2015/145871, International Publication No. 2016/031639, International Publication No. 2016/125560, International Publication No. 2011/049241. can be done.
  • a display device or a lighting device including an organic EL element can be manufactured by a known method such as connecting the organic EL element according to the present embodiment and a known driving device, and can be manufactured by direct current driving, pulse driving, alternating current driving, or the like. It can be driven by appropriately using a known driving method.
  • display devices include panel displays such as color flat panel displays, and flexible displays such as flexible color organic electroluminescence (EL) displays (for example, JP-A-10-335066 and JP-A-2003-321546). (See Japanese Patent Laid-Open No. 2004-281086, etc.).
  • the display method of the display includes, for example, a matrix and/or a segment method. Note that matrix display and segment display may coexist in the same panel.
  • pixels for display are arranged two-dimensionally, such as in a lattice or mosaic pattern, and characters and images are displayed as a set of pixels.
  • the shape and size of the pixels are determined by the application. For example, in the image and character display of personal computers, monitors, and televisions, square pixels with a side of 300 ⁇ m or less are usually used, and in the case of a large display such as a display panel, a pixel with a side of mm order is used. become.
  • monochrome display pixels of the same color may be arranged, but in the case of color display, pixels of red, green, and blue are displayed side by side. In this case, there are typically delta type and stripe type.
  • a line-sequential driving method or an active matrix method may be used as a method for driving this matrix.
  • the line-sequential drive has the advantage of being simpler in structure, but considering the operating characteristics, the active matrix may be superior.
  • a pattern is formed to display predetermined information, and the determined area is illuminated.
  • Examples include time and temperature displays in digital clocks and thermometers, operating state displays in audio equipment and electromagnetic cookers, and panel displays in automobiles.
  • Examples of the lighting device include lighting devices such as indoor lighting, backlights of liquid crystal display devices, etc. etc.).
  • Backlights are mainly used for the purpose of improving the visibility of display devices that do not emit light by themselves, and are used in liquid crystal display devices, clocks, audio devices, automobile panels, display boards, signs, and the like.
  • a liquid crystal display device especially a backlight for a personal computer, for which thinning is a problem, it is difficult to reduce the thickness of the conventional method because it is made of a fluorescent lamp or a light guide plate.
  • the backlight using the light-emitting element according to 1 is characterized by its thinness and light weight.
  • the polycyclic aromatic compound according to the present invention can be used for the production of organic field effect transistors, organic thin film solar cells, etc., in addition to the organic electroluminescence devices described above.
  • An organic field effect transistor is a transistor that controls current by an electric field generated by voltage input, and has a gate electrode in addition to a source electrode and a drain electrode. It is a transistor that can control current by arbitrarily blocking the flow of electrons (or holes) flowing between a source electrode and a drain electrode by generating an electric field when a voltage is applied to the gate electrode.
  • a field effect transistor is easier to miniaturize than a simple transistor (bipolar transistor), and is often used as an element constituting an integrated circuit or the like.
  • the structure of an organic field effect transistor is generally such that a source electrode and a drain electrode are provided in contact with an organic semiconductor active layer formed using the polycyclic aromatic compound according to the present invention, and furthermore, a source electrode and a drain electrode are provided in contact with the organic semiconductor active layer. It suffices that the gate electrode is provided with an insulating layer (dielectric layer) interposed therebetween. Examples of the device structure include the following structure.
  • Substrate/gate electrode/insulator layer/source electrode/drain electrode/organic semiconductor active layer (2) Substrate/gate electrode/insulator layer/organic semiconductor active layer/source electrode/drain electrode (3) Substrate/organic Semiconductor active layer/source electrode/drain electrode/insulator layer/gate electrode (4) Substrate/source electrode/drain electrode/organic semiconductor active layer/insulator layer/gate electrode It can be applied as a pixel driving switching element of an active matrix driving liquid crystal display or an organic electroluminescence display.
  • An organic thin-film solar cell has a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are laminated on a transparent substrate such as glass.
  • the photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side.
  • the polycyclic aromatic compound according to the present invention can be used as a material for a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, and an electron transport layer depending on its physical properties.
  • the polycyclic aromatic compound according to the present invention can function as a hole-transporting material or an electron-transporting material in an organic thin-film solar cell.
  • the organic thin-film solar cell may appropriately include a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like.
  • a hole blocking layer for the organic thin-film solar cell, known materials used for organic thin-film solar cells can be appropriately selected and used in combination.
  • the polycyclic aromatic compound of the present invention can be used as a wavelength conversion material.
  • Color conversion means wavelength conversion of light emitted from a light-emitting body into light of a longer wavelength, for example, conversion of ultraviolet light or blue light into green light or red light emission.
  • a full-color display can be produced by combining such a white light source, which is a combination of a blue light source and a wavelength conversion film having a color conversion function, as a light source unit, a liquid crystal driving portion, and a color filter. Moreover, if there is no liquid crystal drive part, it can be used as a white light source as it is, and can be applied as a white light source such as LED illumination.
  • a blue organic EL device as a light source in combination with a wavelength conversion film that converts blue light into green light and red light, it is possible to produce a full-color organic EL display without using a metal mask.
  • a blue micro-LED as a light source in combination with a wavelength conversion film that converts blue light into green light and red light, it is possible to fabricate a low-cost full-color micro-LED display.
  • the polycyclic aromatic compound of the present invention can be used as this wavelength conversion material.
  • the wavelength conversion material containing the polycyclic aromatic compound of the present invention light from a light source or light emitting element that generates ultraviolet light or blue light with a shorter wavelength is converted to a display device (a display device using an organic EL device or It can be converted into blue light and green light with high color purity suitable for use in liquid crystal display devices.
  • the color to be converted can be adjusted by appropriately selecting the substituents of the polycyclic aromatic compound of the present invention, the binder resin used in the composition for wavelength conversion described below, and the like.
  • a wavelength converting material can be prepared as a wavelength converting composition containing the polycyclic aromatic compound of the present invention. Moreover, you may form a wavelength conversion film using this composition for wavelength conversion.
  • the wavelength conversion composition may contain a binder resin, other additives, and a solvent in addition to the polycyclic aromatic compound of the present invention.
  • a binder resin for example, those described in paragraphs 0173 to 0176 of WO 2016/190283 can be used.
  • other additives compounds described in paragraphs 0177 to 0181 of WO 2016/190283 can be used.
  • the solvent the description of the solvent contained in the composition for forming the light-emitting layer can be referred to.
  • a wavelength conversion film includes a wavelength conversion layer formed by curing a wavelength conversion composition.
  • a method for producing a wavelength conversion layer from a wavelength conversion composition known film forming methods can be referred to.
  • the wavelength conversion film may consist of only the wavelength conversion layer formed from the composition containing the polycyclic aromatic compound of the present invention, and other wavelength conversion layers (for example, the A wavelength conversion layer, a wavelength conversion layer that converts blue light or green light into red light) may be included.
  • the wavelength conversion film may contain a substrate layer and a barrier layer for preventing deterioration of the color conversion layer due to oxygen, moisture, or heat.
  • Synthesis example (1) Synthesis of compound (v-4001) In a flask containing compound (Int-v-4001) (2.43 g, 3.0 mmol, 1 eq.) and o-dichlorobenzene (400 ml), three Boron bromide (4.52 ml, 48 mmol, 16 eq.) was added. After completion of dropping, the temperature was raised to 180° C. and the mixture was stirred for 20 hours. After that, the mixture was cooled to room temperature again, N,N-diisopropylethylamine (15.40 ml, 90 mmol, 30 eq.) was added, and the mixture was stirred until the heat generation subsided.
  • the PMMA dispersion film was excited at room temperature with an appropriate excitation wavelength (280 nm wavelength) and photoluminescence was measured.
  • the attached cooling unit was used to measure the PMMA-dispersed film in a state of being immersed in liquid nitrogen (temperature 77K).
  • an optical chopper was used to adjust the delay time from irradiation of excitation light to the start of measurement.
  • the width of the spectrum at half the height of the emission peak of the fluorescence spectrum was measured.
  • Fluorescence lifetime was measured at 300K using a PMMA dispersion film and a fluorescence lifetime measurement device (manufactured by Hamamatsu Photonics, C11367-01). Specifically, at the maximum emission wavelength measured at an excitation wavelength of 280 nm, an emission component with a short fluorescence lifetime and an emission component with a slow fluorescence lifetime were observed. In the fluorescence lifetime measurement at room temperature of general organic EL materials that emit fluorescence, it is almost impossible to observe a slow emission component associated with a triplet component derived from phosphorescence due to deactivation of the triplet component by heat. do not have. When a slow emission component is observed in the compound to be evaluated, it indicates that triplet energy with a long excitation life is transferred to singlet energy by thermal activation and observed as delayed fluorescence.
  • Evaluation items and evaluation methods include driving voltage (V), emission wavelength (nm), CIE chromaticity (x, y), external quantum efficiency (%), maximum wavelength (nm) and half width of emission spectrum ( nm) and the like.
  • V driving voltage
  • emission wavelength nm
  • CIE chromaticity x, y
  • external quantum efficiency %
  • maximum wavelength nm
  • half width of emission spectrum nm
  • the quantum efficiency of a light-emitting device includes internal quantum efficiency and external quantum efficiency.
  • the internal quantum efficiency is purely converted from external energy injected as electrons (or holes) into the light-emitting layer of the light-emitting device into photons. indicates the percentage of
  • the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light-emitting device, and some of the photons generated in the light-emitting layer continue to be absorbed or reflected inside the light-emitting device. Therefore, the external quantum efficiency is lower than the internal quantum efficiency because the light is not emitted to the outside of the light emitting device.
  • the methods for measuring spectral radiance (luminescence spectrum) and external quantum efficiency are as follows.
  • a voltage/current generator R6144 manufactured by Advantest Corporation is used to apply a voltage at which the luminance of the device becomes 1000 cd/m 2 to cause the device to emit light.
  • Spectral radiance in the visible light region is measured from a direction perpendicular to the light emitting surface using a spectral radiance meter SR-3AR manufactured by TOPCON. Assuming that the light-emitting surface is a perfect diffusion surface, the number of photons at each wavelength is obtained by dividing the measured spectral radiance of each wavelength component by the wavelength energy and multiplying by ⁇ .
  • the number of photons in the entire observed wavelength region is integrated to obtain the total number of photons emitted from the device.
  • the external quantum efficiency is obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device, with the value obtained by dividing the applied current value by the elementary charge as the number of carriers injected into the device.
  • the half width of the emission spectrum is obtained as the width between the upper and lower wavelengths at which the intensity becomes 50% with respect to the maximum emission wavelength.
  • Table 1 shows the evaluation results of the compounds.
  • the compound (v-4010), compound (v-10054), compound (v-10132) and compound (v-10133) according to the present invention have molecular weights similar to or higher than that of new-DABNA, but the sublimation temperature is It was low and no loss of purity during sublimation was observed.
  • the compound of the present invention has a large molecular strain and low symmetry, and thus has a low sublimation temperature. On the other hand, the decrease in purity during sublimation is very small, indicating the stability of the compound structure.
  • the compound of the present invention gave a preferable emission spectrum from the viewpoint of the emission wavelength (blue) and the half-value width.
  • the ⁇ E S1T1 and Tau (Delay) values of the compounds used in these Examples show that they have high TADF properties.
  • the ⁇ E S1T1 of the compounds of the present invention is larger than that of new- DABNA , but the value of Tau (Delay) is almost the same as that of new- DABNA and almost the same as that of DABNA1. Nevertheless, Tau (Delay) is nearly one order of magnitude faster.
  • the emission wavelength of the compound of the present invention is longer than that of DABNA1 and new-DABNA, but the compound (v-10132) and compound (v-10133) do not differ much in emission wavelength from the device fabricated using DABNA1. . It is expected that this is due to the reduced intermolecular interactions in the device due to the molecular strain and low symmetry of the compounds of the invention.
  • the compound (new-DABNA) (the compound described in International Publication No. 2018/212169) showed very excellent properties in terms of emission wavelength, half width, ⁇ E S1T1 , and Tau (Delay), but the decreased in purity during sublimation. This is probably because the sublimation temperature is high due to the high molecular weight and high symmetry.
  • Example 1 A 26 mm ⁇ 28 mm ⁇ 0.7 mm glass substrate (manufactured by OptoScience Co., Ltd.) was used as a transparent support substrate, on which an ITO film having a thickness of 200 nm was formed by sputtering and polished to 50 nm.
  • This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Shinku Co., Ltd.), and NPD, TcTa, mCP, BH-2, compound (v-4001), 2CzBN and BPy-TP2 were placed therein.
  • a molybdenum vapor deposition boat and a tungsten vapor deposition boat containing LiF and aluminum were installed.
  • the following layers were sequentially formed on the ITO film of the transparent support substrate.
  • the vacuum chamber was evacuated to 5 ⁇ 10 ⁇ 4 Pa, and NPD was first heated and evaporated to a film thickness of 40 nm to form a hole injection layer.
  • TcTa was heated and evaporated to a thickness of 15 nm to form a hole transport layer.
  • mCP was heated and evaporated to a thickness of 15 nm to form an electron blocking layer.
  • BH-2 and the compound (v-4001) were simultaneously heated and evaporated to a thickness of 20 nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of BH-1 to compound (v-4001) was approximately 99:1.
  • 2CzBN was heated and evaporated to a thickness of 10 nm
  • BPy-TP2 was heated and evaporated to a thickness of 20 nm to form an electron transport layer consisting of two layers.
  • the deposition rate of each layer was 0.01-1 nm/sec.
  • LiF is heated and vapor-deposited at a deposition rate of 0.01 to 0.1 nm/sec so that the film thickness becomes 1 nm
  • aluminum is heated and vapor-deposited so that the film thickness becomes 100 nm to form a cathode.
  • an organic EL device was obtained.
  • the deposition rate of aluminum was adjusted to 1 to 10 nm/sec.
  • Example 2 ⁇ Comparative Example 1, Example 2> The dopant compound (v-4001) in Example 1 was changed to each dopant shown in Table 2 to fabricate a device.
  • HAT-CN is 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile and "TcTa” is 4,4',4"-tris(N-carbazolyl)triphenylamine;
  • mCP is 1,3-bis(N-carbazolyl)benzene;
  • 2CzBN is 3,4-dicarbazolylbenzonitrile and
  • BPy-TP2 is 2,7-di([2,2'-bipyridin]-5-yl)triphenylene.
  • Example 3-1 A glass substrate (manufactured by Optoscience Co., Ltd.) of 26 mm ⁇ 28 mm ⁇ 0.7 mm was used as a transparent support substrate. This transparent supporting substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Shinku Co., Ltd.), and a molybdenum vapor deposition boat containing HAT-CN, HTL-1, TcTa, ETL-1, DABNA1 and ET7 was put therein. , LiF and aluminium, respectively.
  • the following layers were sequentially formed on the ITO film of the transparent support substrate.
  • the vacuum chamber was evacuated to 5 ⁇ 10 ⁇ 4 Pa, and HAT-CN was first heated and evaporated to a thickness of 5 nm to form a hole injection layer.
  • HTL-1 is heated and vapor-deposited to a thickness of 90 nm to form a hole-transport layer 1
  • TcTa is heated and vapor-deposited to a thickness of 10 nm to form a hole-transport layer 2. formed.
  • TcTa, ETL-1 and DABNA1 were simultaneously heated and evaporated to a thickness of 20 nm to form a light-emitting layer.
  • the deposition rate was adjusted so that the mass ratio of TcTa to ETL-1 to DABNA1 was approximately 49.5:49.5:1.
  • ETL-1 is heated and evaporated to a thickness of 20 nm to form an electron transport layer 1
  • ET7 is heated and evaporated to a thickness of 10 nm to form an electron transport layer 2.
  • the deposition rate of each layer was 0.01-1 nm/sec.
  • LiF is heated and vapor-deposited at a deposition rate of 0.01 to 0.1 nm/sec so that the film thickness becomes 1 nm
  • aluminum is heated and vapor-deposited so that the film thickness becomes 100 nm to form a cathode.
  • an organic EL device was obtained.
  • the deposition rate of aluminum was adjusted to 1 to 10 nm/sec.
  • Table 4 "Host 1" corresponds to the hole-transporting host material, and "Host 2" corresponds to the electron-transporting host material.
  • the organic EL device using the polycyclic aromatic compound having the structure represented by the formula (4) can obtain blue to sky blue light emission with high efficiency and has a long life. I understand.
  • the polycyclic aromatic compound of the present invention is useful as an organic device material, particularly as a light-emitting layer material for forming the light-emitting layer of an organic electroluminescent device.
  • REFERENCE SIGNS LIST 100 organic electroluminescent element 101 substrate 102 anode 103 hole injection layer 104 hole transport layer 105 light emitting layer 106 electron transport layer 107 electron injection layer 108 cathode 110 substrate 120 electrode 130 coating film 140 coating film 150 light emitting layer 200 bank 300 inkjet head 310 ink droplets

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  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

Selon l'invention, un composé aromatique polynucléaire représenté par la formule (4) est mis en œuvre en tant que composé destiné à former un élément électroluminescent organique hautement efficace et longue durée. Un cycle A, un cycle B, un cycle D, un cycle C et un cycle E représentent un cycle aryle pouvant être substitué ou un cycle hétéroaryle pouvant être substitué. Y représente B. n représente 0 ou 1. X est supérieur à Ｎ－Ｒ, à Ｏ, à Ｓｉ（－Ｒ）２＞Ｓ ou à Ｓｅ. R consiste en un aryle, ou similaire, pouvant être substitué. Au moins un élément choisi dans un groupe constitué du cycle aryle et du cycle hétéroaryle dans le composé aromatique polynucléaire, peut être soumis à une condensation au moyen d'au moins un cycloalcane. Au moins un hydrogène dans ledit composé aromatique polynucléaire peut être substitué par un hydrogène lourd, un cyano ou un halogène.
PCT/JP2022/005815 2021-03-03 2022-02-15 Composé aromatique polynucléaire WO2022185897A1 (fr)

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