WO2020045681A1 - Élément électroluminescent organique utilisant un matériau électroluminescent constitué d'un composé aromatique polycyclique - Google Patents

Élément électroluminescent organique utilisant un matériau électroluminescent constitué d'un composé aromatique polycyclique Download PDF

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WO2020045681A1
WO2020045681A1 PCT/JP2019/034473 JP2019034473W WO2020045681A1 WO 2020045681 A1 WO2020045681 A1 WO 2020045681A1 JP 2019034473 W JP2019034473 W JP 2019034473W WO 2020045681 A1 WO2020045681 A1 WO 2020045681A1
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aryl
ring
carbons
heteroaryl
alkyl
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PCT/JP2019/034473
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Japanese (ja)
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琢次 畠山
靖宏 近藤
田島　晶夫
亮介 川角
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学校法人関西学院
Jnc株式会社
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Priority to KR1020217009580A priority Critical patent/KR20210053945A/ko
Priority to CN201980072016.4A priority patent/CN112997334A/zh
Priority to JP2020539658A priority patent/JPWO2020045681A1/ja
Publication of WO2020045681A1 publication Critical patent/WO2020045681A1/fr

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    • 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
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H10K85/658—Organoboranes
    • 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
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers

Definitions

  • the present invention relates to an organic electroluminescent device using a light emitting material of a polycyclic aromatic compound and a multimer thereof (hereinafter, both are also simply referred to as a polycyclic aromatic compound), and a display device and a lighting device.
  • an organic electroluminescence element made of an organic material (hereinafter, also referred to as an organic EL element) is Because of the ease of weight reduction and enlargement, it has been actively studied. In particular, the development of organic materials having emission characteristics such as blue, which is one of the three primary colors of light, and the development of organic materials having charge transporting ability for holes and electrons (possibility of becoming semiconductors and superconductors) Development has been actively studied so far, regardless of whether it is a high molecular compound or a low molecular compound.
  • the organic EL element has a structure including a pair of electrodes including an anode and a cathode, and one or more layers including an organic compound disposed between the pair of electrodes.
  • the layer containing an organic compound include a light-emitting layer and a charge transport / injection layer that transports or injects charges such as holes and electrons.
  • Various organic materials suitable for these layers have been developed.
  • a benzofluorene-based compound has been developed (WO 2004/061047).
  • a hole transport material for example, a triphenylamine-based compound has been developed (Japanese Patent Application Laid-Open No. 2001-172232).
  • an anthracene-based compound has been developed (Japanese Patent Application Laid-Open No. 2005-170911).
  • the charge transporting property of a NO-linked compound (compound 1 on page 63) is evaluated, but there is no description of a method for producing a material other than the NO-linked compound, and the linking element is If different, the electronic state of the entire compound is different, and thus characteristics obtained from materials other than the NO-linked compound are not yet known.
  • Other examples of such compounds can be found (WO 2011/107186).
  • a compound having a conjugated structure in which the energy (T1) of triplet excitons is large can emit phosphorescence of a shorter wavelength, and thus is useful as a material for a blue light-emitting layer.
  • the host material of the organic EL device is generally a molecule in which a plurality of existing aromatic rings such as benzene and carbazole are connected by a single bond, a phosphorus atom or a silicon atom. This is because a large number of relatively small conjugated aromatic rings are connected to ensure a large HOMO-LUMO gap (band gap Eg in a thin film) required for the host material. Further, a host material of an organic EL device using a phosphorescent material or a thermally activated delayed fluorescent material also needs a high triplet excitation energy (E T ), but the molecule has a donor or acceptor aromatic ring or substitution.
  • E T triplet excitation energy
  • the inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by using a polycyclic aromatic compound in which a plurality of aromatic rings are linked by a boron atom and an oxygen atom as a material for a light emitting layer, an excellent organic EL has been obtained.
  • the inventors have found that an element can be obtained, and have completed the present invention.
  • the chemical structure and the substituent may be represented by the number of carbon atoms.However, when the chemical structure is substituted with a substituent, or when the substituent is further substituted with a substituent, the number of carbon atoms is represented by the chemical structure And the carbon number of each substituent, and does not mean the total carbon number of the chemical structure and the substituent or the total carbon number of the substituent and the substituent.
  • “substituent B having carbon number Y substituted with substituent A having carbon number X” means that “substituent A having carbon number X” is substituted for “substituent B having carbon number Y”. However, the carbon number Y is not the total carbon number of the substituent A and the substituent B.
  • the substituent B having the number of carbon atoms Y substituted with the substituent A means that the “substituent A (there is no limitation on the number of carbon atoms)” replaces the “substituent B having the number of carbon atoms Y”.
  • the carbon number Y is not the total carbon number of the substituent A and the substituent B.
  • Item 1 A pair of electrodes consisting of an anode and a cathode, and an organic electroluminescent element having a light emitting layer disposed between the pair of electrodes, The light emitting layer in the organic electroluminescent device, As a first component, a polycyclic aromatic compound represented by the following general formula (1) is contained as a host, An organic electroluminescent device comprising, as a second component, a boron-containing polycyclic aromatic compound as a dopant.
  • a polycyclic aromatic compound represented by the following general formula (1) is contained as a host
  • An organic electroluminescent device comprising, as a second component, a boron-containing polycyclic aromatic compound as a dopant.
  • R 1 to R 11 each independently represent hydrogen, aryl, heteroaryl, diarylamino, diarylboryl (two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, Alkoxy or aryloxy; At least one hydrogen in the aryl, the heteroaryl, the diarylamino, and the diarylboryl may be substituted with an aryl, heteroaryl, alkyl, or cycloalkyl; At least one hydrogen in the compound represented by the formula (1) may be substituted with cyano, halogen, or deuterium.
  • R 1 to R 11 each independently represent hydrogen, aryl having 6 to 30 carbons, heteroaryl having 2 to 30 carbons, or diarylamino (wherein aryl has 6 to 12 carbons).
  • Aryl diarylboryl (wherein aryl is aryl having 6 to 12 carbons, and two aryls may be linked via a single bond or a linking group), alkyl having 1 to 24 carbons, A cycloalkyl having 3 to 12 carbons, an alkoxy having 1 to 24 carbons or an aryloxy having 6 to 30 carbons,
  • At least one hydrogen atom in the aryl, the heteroaryl, the diarylamino, and the diarylboryl is an aryl having 6 to 30 carbons, a heteroaryl having 2 to 30 carbons, an alkyl having 1 to 24 carbons or 3 to 12 carbons. May be substituted with cycloalkyl, Item 2.
  • R 1 to R 11 each independently represent hydrogen, aryl having 6 to 16 carbons, heteroaryl having 2 to 15 carbons, or diarylamino (wherein aryl has 6 to 10 carbons).
  • Aryl diarylboryl (wherein aryl is aryl having 6 to 10 carbons, and two aryls may be bonded via a single bond or a linking group), alkyl having 1 to 6 carbons, carbon A cycloalkyl having 6 to 10 carbon atoms, an alkoxy having 1 to 6 carbon atoms or an aryloxy having 6 to 16 carbon atoms,
  • At least one hydrogen atom in the aryl, the heteroaryl, the diarylamino, and the diarylboryl is an aryl having 6 to 16 carbons, a heteroaryl having 2 to 15 carbons, an alkyl having 1 to 6 carbons or 6 to 10 carbons. May be substituted with cycloalkyl, Item 2.
  • R 1 to R 11 is a group represented by any of the following formulas (1-a) to (1-s), The organic electroluminescent device according to claim 1.
  • * indicates a bonding position
  • at least one hydrogen atom is an aryl having 6 to 30 carbon atoms or a heteroatom having 2 to 30 carbon atoms.
  • Aryl, alkyl having 1 to 24 carbons or cycloalkyl having 3 to 12 carbons, R in the formula (1-i), the formula (1-j), the formula (1-k) and the formula (1-r) are each independently hydrogen, aryl having 6 to 30 carbon atoms, and 2 to 2 carbon atoms. It represents 30 heteroaryl, alkyl having 1 to 24 carbons or cycloalkyl having 3 to 12 carbons.
  • Item 5 The organic electroluminescent device according to item 4, wherein in the general formula (1), at least one of R 1 to R 11 is a group represented by the above formula (1-d).
  • R 1 to R 11 each independently represent hydrogen, aryl, heteroaryl, diarylamino, diarylboryl (even when two aryls are bonded through a single bond or a linking group). Good), alkyl, cycloalkyl or alkoxy, At least one hydrogen in the aryl, the heteroaryl, the diarylamino, and the diarylboryl may be substituted with an aryl, heteroaryl, alkyl, or cycloalkyl.
  • Item 6. The organic electroluminescent device according to any one of items 1 to 5.
  • Item 7 In the general formula (1), at least one of R 4 to R 11 is heteroaryl, and at least one hydrogen in the heteroaryl may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl.
  • Item 7. The organic electroluminescent device according to any one of items 1 to 6.
  • At least one of R 1 to R 3 is aryl or dibenzofuranyl, and at least one hydrogen in the aryl and dibenzofuranyl is aryl, heteroaryl, alkyl or cycloalkyl.
  • Item 8. The organic electroluminescent device according to any one of items 1 to 7, which may be substituted.
  • At least one of R 1 to R 3 is heteroaryl (at least one hydrogen in the heteroaryl may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl).
  • at least one of R 4 to R 11 is aryl (at least one hydrogen in the aryl may be substituted with aryl, heteroaryl, alkyl or cycloalkyl),
  • Item 10 The organic electroluminescent device according to Item 1, wherein the host of the first component is a polycyclic aromatic compound represented by any of the following formulas.
  • Item 11 The organic electroluminescent device according to any one of Items 1 to 10, wherein the dopant as the second component is a polycyclic aromatic compound represented by the following general formula (2) or a polymer thereof.
  • R 1 to R 11 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls are linked via a single bond or a linking group; ), Alkyl, cycloalkyl, alkoxy, aryloxy, cyano or halogen, wherein at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl; Further, adjacent groups among R 1 to R 11 may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, the b ring or the c ring, and at least one hydrogen atom in the formed ring I
  • R 8 is halogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons, aryl having 6 to 10 carbons or heteroaryl having 2 to 10 carbons, Item 7.
  • R 7 is hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons, aryl having 6 to 10 carbons or heteroaryl having 2 to 10 carbons. element.
  • the dopant as the second component is a dimer compound including two partial structures represented by the general formula (2) and a linking group L1 that connects the two partial structures
  • the linking group L1 is a single bond, arylene having 6 to 12 carbons, heteroarylene having 2 to 15 carbons, alkylene having 1 to 6 carbons, alkenylene having 1 to 6 carbons, alkynylene having 1 to 6 carbons, —O—, —S—,> NR, or a combination thereof, wherein R in> NR is aryl having 6 to 12 carbons, heteroaryl having 2 to 15 carbons, 1 to carbons 6 alkyl or cycloalkyl having 3 to 14 carbon atoms, Item 12.
  • Item 14 The organic electroluminescent device according to any one of items 1 to 11, wherein the dopant as the second component is a polycyclic aromatic compound represented by the following general formula (3).
  • R 3 to R 12 , Z 1 and Z 2 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are a single bond or a linking group) ), Alkyl, cycloalkyl, alkoxy, aryloxy, cyano or halogen, wherein at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
  • adjacent groups among R 5 to R 7 and R 10 to R 12 may be bonded to each other to form an aryl ring or a heteroaryl ring together with at least one of the b ring and the d ring.
  • At least one hydrogen in the ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls may be linked via a single bond or a linking group), alkyl , Cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl;
  • Z 1 may be bonded to ring a by a linking group or a single bond, and Z 2 may be bonded to ring c by a linking group or a single bond;
  • Y is B (boron), X 1 , X 2 , X 3 and X 4 are each independently>
  • Item 15. The organic electroluminescent device according to any one of items 1 to 11, wherein the dopant as the second component is a polycyclic aromatic compound represented by the following general formula (4) or a polymer thereof.
  • R 1 to R 3 and R 5 to R 15 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are a single bond or a linking group) ), Alkyl, cycloalkyl, alkoxy, aryloxy, cyano or halogen, wherein at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
  • adjacent groups among R 1 to R 3 , R 5 to R 7 , R 8 to R 11 and R 12 to R 15 are bonded to each other to form at least one of a ring, b ring, c ring and d ring.
  • aryl ring or a heteroaryl ring together with at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryl May be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these may be aryl, heteroaryl, alkyl or cyclo May be substituted with alkyl, Y 1 is B (boron), X is>O,>NR,>S,> Se or -C (-R) 2- , wherein R of -C (-R) 2- is alkyl having 1 to 6 carbons, A cycloalkyl having 3 to 14 carbons or an aryl having 6 to 12 carbons, wherein R in> NR is an aryl having 6 to 12 carbons, a heteroaryl having 2 to 15 carbons, an alkyl,
  • Item 16 The organic electroluminescent device according to any one of items 1 to 10, wherein the dopant as the second component is a polycyclic aromatic compound represented by the following general formula (5) or a polymer thereof.
  • R 1 to R 9 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls are linked via a single bond or a linking group; ), Alkyl, cycloalkyl, alkoxy, aryloxy, cyano or halogen, wherein at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl; Further, adjacent groups among R 1 to R 9 may be bonded to each other to form an aryl ring or a heteroaryl ring together with at least one of the a ring, the b ring and the c ring.
  • At least one hydrogen is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls may be linked via a single bond or a linking group), alkyl, cycloalkyl , May be substituted with alkoxy or aryloxy, and at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, Y 1 is B (boron), X 1 , X 2 and X 3 are each independently>O,>NR,>S,> Se or —C (—R) 2 — (of X 1 , X 2 and X 3 ) At least two are NR), wherein R of -C (-R) 2- is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons or aryl having 6 to 12 carbons.
  • N—R is aryl having 6 to 12 carbons, heteroaryl having 2 to 15 carbons, alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons.
  • R of —R may be —O—, —S—, —C (—R ′) 2 —, or may be bonded to at least one of the a ring, b ring and c ring by a single bond or a condensate (here, R ′ of the above “—C (—R ′) 2 —” is hydrogen, alkyl having 1 to 5 carbons, or cycloalkyl having 5 to 10 carbons.
  • Loalkyl) and At least one hydrogen in the compound represented by the formula (5) may be substituted with cyano, halogen, or deuterium.
  • Item 17 The organic electroluminescent device according to item 1, wherein the dopant of the second component is a polycyclic aromatic compound represented by any of the following formulas.
  • Item 18 And at least one of an electron transport layer and an electron injection layer disposed between the cathode and the light emitting layer, wherein at least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, or a fluoranthene derivative. Containing at least one selected from the group consisting of a BO derivative, an anthracene derivative, a benzofluorene derivative, a phosphine oxide derivative, a pyrimidine derivative, a carbazole derivative, a triazine derivative, a benzimidazole derivative, a phenanthroline derivative and a quinolinol-based metal complex.
  • Item 18 The organic electroluminescent device according to any one of Items 1 to 17.
  • At least one of the electron transport layer and the electron injection layer further comprises an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, and an alkaline earth metal. Containing at least one selected from the group consisting of halides of rare earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals. 19. The organic electroluminescent device according to 18.
  • R 1 to R 11 each independently represent hydrogen, aryl, heteroaryl, diarylamino, diarylboryl (two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, Alkoxy, aryloxy, At least one hydrogen in the aryl, the heteroaryl, the diarylamino, and the diarylboryl may be substituted with an aryl, heteroaryl, alkyl, or cycloalkyl; At least one of R 1 to R 11 is a group represented by the following formula (1-d), At least one hydrogen in the compound represented by the formula (1) may be substituted with cyano, halogen, or deuterium. ) (In the above formula, * indicates a bonding position, and at least one hydrogen in the formula (1-d) may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl.)
  • R 1 to R 11 each independently represent hydrogen, aryl, heteroaryl, diarylamino, diarylboryl (two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, Alkoxy or aryloxy; At least one hydrogen in the aryl, the heteroaryl, the diarylamino, and the diarylboryl may be substituted with an aryl, heteroaryl, alkyl, or cycloalkyl; At least one hydrogen in the compound represented by the formula (1) may be substituted with cyano, halogen, or deuterium.
  • Item 22 A polymer compound obtained by polymerizing the reactive compound according to Item 21 as a monomer, or a polymer crosslinked product obtained by further crosslinking the polymer compound.
  • Item 23. 21 A pendant polymer compound obtained by substituting the reactive compound according to item 21 into the main chain polymer, or a pendant polymer crosslinked product obtained by further crosslinking the pendant polymer compound.
  • Item 24 As the first component, the reactive compound according to item 21, the polymer compound or crosslinked polymer according to item 22, or the pendant polymer compound or crosslinked pendant polymer according to item 23 is used as a host. Including As a second component, containing a boron-containing polycyclic aromatic compound as a dopant, Including an organic solvent as a third component, A composition for forming a light emitting layer.
  • a polycyclic aromatic compound represented by the following general formula (1) is contained as a host
  • a second component containing a boron-containing polycyclic aromatic compound as a dopant
  • R 1 to R 11 each independently represent hydrogen, aryl, heteroaryl, diarylamino, diarylboryl (two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, Alkoxy or aryloxy; At least one hydrogen in the aryl, the heteroaryl, the diarylamino, and the diarylboryl may be substituted with an aryl, heteroaryl, alkyl, or cycloalkyl; At least one hydrogen in the compound represented by the formula (1) may be substituted with cyano, halogen, or deuterium.
  • Item 26 The composition for forming a light emitting layer according to Item 24 or 25, wherein the at least one organic solvent of the third component has a boiling point of 130 to 350 ° C.
  • the organic solvent of the third component contains a good solvent (GS) and a poor solvent (PS) for at least one of the host of the first component and the dopant of the second component, and the boiling point (BP GS ) of the good solvent ( GS ) There below the boiling point (BP PS) of the poor solvent (PS), light-emitting layer forming composition according to any one of claims 24-26.
  • GS good solvent
  • PS poor solvent
  • the first component is 0.0999% by mass to 8.0% by mass based on the total mass of the composition for forming a light emitting layer;
  • the second component is 0.0001% by mass to 2.0% by mass relative to the total mass of the light emitting layer forming composition;
  • the third component is 90.0% by mass to 99.9% by mass relative to the total mass of the composition for forming a light emitting layer;
  • Item 28 The composition for forming a light emitting layer according to any one of Items 24 to 27.
  • Item 21. A high-molecular-weight composition comprising: a first structural unit derived from the reactive compound according to Item 21; and a second structural unit derived from a reactive compound obtained by replacing a reactive substituent with a boron-containing polycyclic aromatic compound.
  • a composition for forming a light-emitting layer comprising: an organic solvent.
  • Item 30 A pair of electrodes consisting of an anode and a cathode, disposed between the pair of electrodes, Item 30.
  • An organic electroluminescent device having a light emitting layer formed using the light emitting layer forming composition according to any one of items 24 to 29.
  • Item 31 At least one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer is a polymer compound obtained by polymerizing a low molecular compound capable of forming each layer as a monomer, or A polymer crosslinked product obtained by further crosslinking the polymer compound, or a pendant polymer compound obtained by reacting a low molecular compound capable of forming each layer with a main chain polymer, or the pendant polymer compound.
  • Item 32 Item 34. A display device or a lighting device provided with the organic electroluminescent element according to any one of Items 1 to 19, 30, and 31.
  • organic EL characteristics such as light emitting characteristics can be further improved.
  • FIG. 1 is a schematic cross-sectional view illustrating an organic EL device according to an embodiment.
  • Organic EL device The organic EL device of the present invention has a pair of electrodes including an anode and a cathode, and a light emitting layer disposed between the pair of electrodes.
  • the light-emitting layer includes a polycyclic aromatic compound represented by the general formula (1) as a first component, and a boron-containing polycyclic aromatic compound as a second component. I do. Note that, in the light emitting layer, the first component functions as a host, and the second component functions as a dopant.
  • the polycyclic aromatic compound represented by the first component formula (1) has a large HOMO-LUMO gap (band gap Eg in a thin film) and a high triplet excitation energy (E T ). This is because the 6-membered ring containing the hetero element has a low aromatic attribute, so that the reduction of the HOMO-LUMO gap due to the expansion of the conjugated system is suppressed, and the triplet excited state (T1) due to electronic perturbation of the hetero element. Of SOMO1 and SOMO2 are localized.
  • the polycyclic aromatic compound represented by the formula (1) has a high triplet energy, and thus is preferably used as a host of a thermally activated delayed fluorescent material.
  • the excited triplet energy level E (1, T, PT) determined from the peak top of the phosphorescence spectrum of the compound of the first component is a viewpoint that promotes the generation of TADF in the light-emitting layer without inhibiting it. Therefore, it is preferable that the energy is higher than the excited triplet energy level E (2, T, PT) determined from the peak top of the phosphorescence spectrum of the compound of the second component.
  • the triplet energy level E (1, T, PT) is preferably 0.01 eV or more, more preferably 0.03 eV or more, and still more preferably 0.1 eV or more, as compared with E (2, T, PT).
  • a TADF-active compound may be used as the host compound.
  • the first component is a compound used as a host, and generally has a higher content in the light-emitting layer than the dopant as the second component. Therefore, the excited triplet energy is generally obtained in a state close to actual use conditions.
  • the excited triplet energy of the first component is obtained from a single-component deposited film, and the excitation triplet energy of the second component is obtained.
  • the triplet energy can be determined from a film in which the inactive component or the first component is the main component and the low-concentration second component is uniformly dispersed.
  • the first component used in the present invention has a relatively large planar structure formed by a boron atom, an oxygen atom and an a to b ring as represented by the formula (1).
  • the values of the excited singlet energy and the excited triplet energy may be estimated to be lower than those obtained from the above-described single-component vapor-deposited film of the first component. Therefore, in this specification, in order to eliminate the influence of aggregation and interaction between the first components, the excited singlet energy and the excited triplet energy of the first component and the second component are mainly composed of the inactive component. And a film obtained by uniformly dispersing a low concentration of the first component or the second component.
  • the inactive component includes, for example, a polymer that is optically transparent in the range of excitation and emission of the first component or the second component, and specifically, poly (methyl methacrylate), polystyrene, polyolefin and cycloolefin. Olefin polymers are mentioned.
  • the first component preferably has a lower cohesiveness.
  • the molecular structure of the first component is preferably an asymmetric structure, It is preferable to have a large dihedral angle in the molecule, or it is preferable to have a steric hindrance in the molecule.
  • orbits related to charge transport can be close to each other.
  • the glass transition temperature (Tg) of the first component is higher, and it is more preferable that the first component interacts between molecules.
  • the first component and the second component may both use a compound having low cohesiveness, or one of them may use a compound having low cohesiveness.
  • the degree of red shift in the low-concentration uniform dispersion state and the spectrum of the single-component deposited film, or the spectrum of the co-deposited film of the first component and the second component and the spectrum of the second component in the low-concentration uniform dispersion state Can be estimated according to the degree of red shift.
  • R 1 to R 11 are each independently hydrogen, aryl, heteroaryl, diarylamino, diarylboryl (the two aryls may be bonded via a single bond or a linking group. ), Alkyl, cycloalkyl, alkoxy or aryloxy (the above, the first substituent), wherein at least one hydrogen in the aryl, the heteroaryl, the diarylamino and the diarylboryl is aryl, heteroaryl, alkyl or cyclo It may be substituted with alkyl (the above, the second substituent).
  • the “aryl” as the first substituent 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, and 6 to 20 carbon atoms.
  • Aryl having 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.
  • aryl examples include, for example, phenyl which is a monocyclic aryl, (2-, 3-, 4-) biphenylyl which is a bicyclic aryl, and (1-, 2-) naphthyl which is a fused bicyclic aryl Terphenylyl which is a tricyclic aryl (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-ter
  • aryl as the first substituent refers to “aryl” in diarylamino as the first substituent, diarylboryl (two aryls may be bonded via a single bond or a linking group) And “aryl” in aryloxy, and “aryl” as the second substituent.
  • Heteroaryl as the first substituent 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, Heteroaryl having 2 to 15 carbon atoms is more preferable, and heteroaryl having 2 to 10 carbon atoms is particularly preferable.
  • the heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.
  • heteroaryl examples include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanil, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, benzofuranyl, Isobenzofuranyl, dibenzofuranyl, thiophenyl, benzo [b] thienyl, dibenzothiophenyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, is
  • heteroaryl as the first substituent can be similarly quoted for “heteroaryl” as the second substituent.
  • at least one hydrogen in the heteroaryl is an aryl such as phenyl (the specific examples described above) or an alkyl such as methyl (a specific example described later).
  • Substituted groups are also included in the heteroaryl as the second substituent.
  • the second substituent is a carbazolyl group
  • a carbazolyl group in which at least one hydrogen at the 9-position is substituted with an aryl such as phenyl or an alkyl such as methyl is also substituted with a heteroaryl as the second substituent. included.
  • alkyl as the first substituent may be straight-chain or branched, and includes, for example, alkyl having 1 to 24 carbons (branched-chain alkyl having 3 to 24 carbons). Preferred are alkyls having 18 (branched alkyls having 3 to 18 carbon atoms), more preferred are alkyls having 1 to 12 carbons (branched alkyls having 3 to 12 carbons), and alkyls having 1 to 6 carbons (having 3 carbons are preferable). And more preferably an alkyl having 1 to 5 carbons (a branched alkyl having a carbon number of 3 to 5), and more preferably an alkyl having a carbon number of 1 to 4 (a branched chain having 3 to 4 carbons). Alkyl) is particularly preferred, and methyl is most preferred.
  • alkyl includes, for example, 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-trimethyl Hexyl, n-
  • alkyl as the first substituent can be similarly quoted for “alkyl” as the second substituent.
  • the position at which the alkyl as the second substituent substitutes the first substituent is not particularly limited, but based on the bonding position (1 position) of the first substituent to the a ring, b ring and c ring.
  • the 2- or 3-position is preferred, and the 2-position is more preferred.
  • Cycloalkyl as the first substituent includes cycloalkyl having one ring, cycloalkyl having a plurality of rings, cycloalkyl having a double bond not conjugated in a ring, and cycloalkyl having a branch outside the ring.
  • 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, cycloalkyl having 3 to 12 carbon atoms may be used.
  • Examples thereof include alkyl, cycloalkyl having 5 to 10 carbons, cycloalkyl having 5 to 8 carbons, cycloalkyl having 5 to 6 carbons, cycloalkyl having 5 carbons, and cycloalkyl having 6 to 10 carbons.
  • cycloalkyls include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and alkyl (especially methyl) -substituted alkyl having 1 to 5 carbon atoms, norbornenyl, bicyclo [1.0.1] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [3.0.1] hexyl, bicyclo [2.1.2] heptyl, bicyclo [2,2,1] heptyl, bicyclo [2.2.2] octyl, decahydronaphthyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.
  • alkoxy (first substituent) includes, for example, alkoxy having 1 to 24 carbons (alkoxy having a branched chain having 3 to 24 carbons), and alkoxy having 1 to 18 carbons (3 to 18 carbons). Is preferably a C1-C12 alkoxy (C3-C12 branched-chain alkoxy), more preferably a C1-C6 alkoxy (C3-C6 branched-chain alkoxy).
  • an alkoxy having 1 to 5 carbon atoms is even more preferable, and an alkoxy having 1 to 4 carbon atoms (an alkoxy having a branched chain having 3 to 4 carbon atoms) is particularly preferable. preferable.
  • alkoxy examples include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, t-amyloxy, n-pentyloxy, isopentyloxy, neopentyloxy, t-pentyl Oxy, n-hexyloxy, 1-methylpentyloxy, 4-methyl-2-pentyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-heptyloxy, 1-methylhexyloxy, n-octyloxy, t-octyloxy, 1-methylheptyloxy, 2-ethylhexyloxy, 2-propylpentyloxy, n-nonyloxy, 2,2-dimethylheptyloxy, 2,6-dimethyl-4-heptyloxy, 3,5,5 -Trimethylhexyloxy, n-decyloxy
  • aryl in the “diarylboryl” of the first substituent, the above description of aryl can be cited. Further, the two aryls may be linked via a single bond or a linking group (eg,> C (—R) 2 ,>O,> S, or> NR).
  • a linking group eg,> C (—R) 2 ,>O,> S, or> NR.
  • R of> C (—R) 2 and> NR represents aryl, heteroaryl, diarylamino, diarylboryl (two aryls may be bonded via a single bond or a linking group), Alkyl, cycloalkyl, alkoxy or aryloxy (the first substituent), wherein the first substituent is further substituted with aryl, heteroaryl, alkyl or cycloalkyl (the second substituent).
  • the description of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy as the first substituent described above can be cited.
  • the emission wavelength can be adjusted by the steric hindrance, electron donating property and electron withdrawing property of the structure of the first substituent, and is preferably a group represented by the following structural formula, more preferably methyl, t- Butyl, t-amyl, t-octyl, phenyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, diphenyl -P-tolylamino, bis (p- (t-butyl) phenyl) amino, carbazolyl, 3,6-dimethylcarbazolyl, 3,6-di-t-butylcarbazolyl and phenoxy, more preferably Methyl, t-butyl, t-amyl, t-octyl, phenyl, o-tolyl, 2,6-xylyl
  • steric hindrance is large for selective synthesis.
  • Me represents methyl
  • tBu represents t-butyl
  • tAm represents t-amyl
  • tOct represents t-octyl
  • At least one of R 1 to R 11 is preferably a group represented by any of the following formulas (1-a) to (1-s), and a group represented by the following formula (1-d) Is more preferable.
  • At least one hydrogen atom has 6 to 30 carbon atoms as the above-mentioned “second substituent”. May be substituted with a heteroaryl having 2 to 30 carbons, an alkyl having 1 to 24 carbons or a cycloalkyl having 3 to 12 carbons.
  • R in the formula (1-i), the formula (1-j), the formula (1-k) and the formula (1-r) is each independently hydrogen or the above-mentioned “second substituent” Represents aryl having 6 to 30 carbons, heteroaryl having 2 to 30 carbons, alkyl having 1 to 24 carbons or cycloalkyl having 3 to 12 carbons.
  • adjacent groups among R 1 to R 11 may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring.
  • the polycyclic aromatic compound represented by the general formula (1) can have the following formulas (1-L1) and (1-L2) depending on the mutual bonding form of the substituents on the ring a, ring b and ring c.
  • the ring structure constituting the compound changes.
  • the a ′ ring, b ′ ring and c ′ ring in each formula correspond to the above “formed ring (aryl ring or heteroaryl ring)”.
  • each symbol in the formula (1-L1) and the formula (1-L2) is the same as the definition in the formula (1).
  • the compounds represented by the above formulas (1-L1) and (1-L2) include, for example, a benzene ring, an benzene ring, an indole ring, and a pyrrole with respect to a benzene ring which is a ring (and at least one of a b ring and a c ring).
  • Examples of the formed “aryl ring” include an aryl ring having 9 to 30 carbon atoms, an aryl ring having 9 to 24 carbon atoms is preferable, and an aryl ring having 9 to 20 carbon atoms is more preferable.
  • An aryl ring having 9 to 16 carbon atoms is more preferred, an aryl ring having 9 to 12 carbon atoms is particularly preferred, and an aryl ring having 9 to 10 carbon atoms is most preferred.
  • the ring a (ring b or ring c) is already composed of a benzene ring having 6 carbon atoms. Is the number of carbon atoms.
  • ⁇ aryl ring '' include, for example, a fused bicyclic naphthalene ring, a fused tricyclic ring, an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, a fused tetracyclic ring system, a triphenylene ring, and pyrene. Ring, naphthacene ring, condensed pentacyclic perylene ring, pentacene ring and the like.
  • heteroaryl ring examples include a heteroaryl ring having 6 to 30 carbon atoms, preferably a heteroaryl ring having 6 to 25 carbon atoms, and a heteroaryl ring having 6 to 20 carbon atoms. Is more preferable, and a heteroaryl ring having 6 to 15 carbon atoms is further preferable, and a heteroaryl ring having 6 to 10 carbon atoms is particularly preferable.
  • a heteroaryl ring for example, a heterocyclic ring containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms and the like can be mentioned.
  • the total carbon number of the condensed ring obtained by condensing the 5-membered ring with the benzene ring is 6 carbon atoms. It is the lower limit of carbon number.
  • heteroaryl rings include, for example, 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 ring, pteridine ring, carbazole ring, acridine ring, phenoxatiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, indolizine ring, benzofuran ring, isobenzofuran Ring, dibenzofuran ring, benzothiophene ring, dibenzothiophene ring, thianthrene ring and the like.
  • a plurality of R 1 to R 11 may have a first substituent.
  • the substitution positions are selected so that steric hindrance to each other is reduced.
  • Substituents may be present at adjacent positions in the same ring, but in this case, a group having small steric hindrance is preferred.
  • the number of substituents in R 1 to R 11 in the general formula (1) is not particularly limited, but the total number of carbon atoms of the substituents in R 1 to R 11 is preferably 36 or less.
  • R 1 to R 11 have a plurality of first substituents, particularly when a synthesis step of introducing boron at the end is used, from the viewpoint of ease of synthesis, a ring-B bond It is preferable to have a substituent so as to be line-symmetric with respect to. On the other hand, from the viewpoint of reducing crystallinity and cohesion, it is preferable to have a substituent so as to have an asymmetric structure.
  • R 1 to R 11 each independently represent hydrogen, aryl, heteroaryl, diarylamino, diarylboryl (where two aryls are Which may be bonded via a bond or a linking group), alkyl, cycloalkyl or alkoxy (the above is the first substituent), and at least one hydrogen in the aryl, the heteroaryl, and the diarylamino is an aryl. , Heteroaryl, alkyl or cycloalkyl (the second substituent), and a polycyclic aromatic compound. That is, in the polycyclic aromatic compound serving as the host of the first embodiment, a compound having no aryloxy, in which aryloxy such as the group represented by the above formula (1-h) is excluded as the first substituent It is.
  • At least one of R 4 to R 11 is a heteroaryl (the above is a first substituent), and at least one of the heteroaryls is a heteroaryl.
  • One hydrogen includes a polycyclic aromatic compound which may be substituted with an aryl, heteroaryl, alkyl or cycloalkyl (the above is a second substituent).
  • Examples of the polycyclic aromatic compound serving as the host of the second embodiment include a compound (BO2-0431) and a compound (BO2-0520S) described below.
  • R 4 to R 11 is a compound represented by the above formula (1-a), formula (1-b), formula (1-c), or formula (1-c).
  • d a group represented by any one of formulas (1-1), (1-m) and (1-n), and preferably a group represented by the above formulas (1-a) and (1-d) Is more preferable.
  • At least one of R 1 to R 3 is aryl or dibenzofuranyl (the above is a first substituent), and And a polycyclic aromatic compound in which at least one hydrogen in the dibenzofuranyl may be substituted with aryl, heteroaryl, alkyl or cycloalkyl (the above is a second substituent).
  • a polycyclic aromatic compound serving as the host in the third embodiment include a compound (BO2-0264 / 0511S) and a compound (BO2-0231) described below.
  • At least one of R 1 to R 3 is a compound represented by the above formula (1-d), formula (1-f), formula (1-i), or formula (1-i). j) and a group represented by any of formulas (1-k), and more preferably a group represented by any of the above formulas (1-d) and (1-i). preferable.
  • At least one of R 1 to R 3 is a heteroaryl (the above is a first substituent) (at least in the heteroaryl)
  • One hydrogen atom may be substituted with an aryl, heteroaryl, alkyl, or cycloalkyl (or more, a second substituent)
  • at least one of R 4 to R 11 is an aryl (or more, a first substituent)
  • a group) at least one hydrogen in the aryl may be substituted with aryl, heteroaryl, alkyl or cycloalkyl (the above is a second substituent)).
  • Examples of the polycyclic aromatic compound serving as the host of the fourth embodiment include a compound (BO2-0220 / 0510S) and a compound (BO2-0220 / 0511S) described below.
  • at least one of R 1 to R 3 is a compound represented by the above formula (1-a), formula (1-b), formula (1-c) or formula (1-c).
  • d) a group represented by any of formulas (1-1), (1-m) and (1-n), wherein at least one of R 4 to R 11 is a group represented by the above formula (1-f) ), A group represented by any one of formulas (1-i), (1-j) and (1-k).
  • At least one hydrogen in the polycyclic aromatic compound represented by the formula (1) may be substituted with cyano, halogen, or deuterium.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.
  • the polycyclic aromatic compound represented by the general formula (1) is preferably, for example, a compound represented by any one of the following formulas.
  • any hydrogen may be substituted with alkyl having 1 to 5 carbons (eg, methyl or t-butyl) or cycloalkyl having 5 to 10 carbons (eg, cyclopentyl or cyclohexyl).
  • the polycyclic aromatic compound represented by the general formula (1) will be described more specifically.
  • the compound represented by the general formula (1) is associated with the compound number, the compound is also described as a general formula (BO2-1).
  • the symbols of R 1 to R 11 may be omitted for simplification of the expression. Such abbreviations are not used in formulas that represent specific compound structures rather than general formulas.
  • R 1 to R 11 in the general formula (BO2-1) have a substituent other than hydrogen
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 9 , R 10 and R 11 can have any substituent
  • HOMO and LUMO From the viewpoint of control, when deepening the HOMO, it is preferable to introduce an electron-donating substituent into at least one of R 1 , R 3 , R 4 , R 6 , R 9 and R 11 , and conversely When making the HOMO shallow, it is preferable to introduce an electron-withdrawing substituent into at least one of R 1 , R 3 , R 4 , R 6 , R 9 and R 11 .
  • the substituents of R 1 to R 11 having a larger dihedral angle with respect to the aromatic ring formed by rings a to c, a boron atom and an oxygen atom are more likely to have cohesiveness and inter-host or host- Interaction between dopants can be reduced.
  • the compound of the first component used in the present invention and the compounds described below that are suitable as the second component have many compounds having high planarity. Therefore, it is better to reduce the cohesiveness and interaction to reduce the red shift of the emission spectrum and the like. This is preferable from the viewpoint of preventing the width from becoming wide, and achieving emission of deep blue light and high color purity.
  • the dihedral angle of the compound of the first component used in the present invention may use molecular orbital calculation. The calculation does not need to be exact, and for example, MOPAC can be used.
  • polycyclic aromatic compound represented by the general formula (1) which is a host of the first material, include compounds having the following structural formulas. Note that Me represents methyl and tBu represents butyl.
  • the polycyclic aromatic compound represented by the general formula (1) is a polymer compound obtained by polymerizing a reactive compound in which these are substituted with a reactive substituent as a monomer (the above-described monomer for obtaining the polymer compound).
  • a crosslinked pendant polymer crosslinked product (the pendant polymer compound for obtaining the pendant polymer crosslinked product has a crosslinkable substituent) may also be used.
  • Device for material for example, can be used a material for an organic electroluminescence device, an organic field effect transistor materials or organic thin film solar cell material.
  • reactive substituents including the above-mentioned polymerizable substituents, the above-mentioned crosslinkable substituents, and the reactive substituents for obtaining the pendant-type polymer, hereinafter, also simply referred to as “reactive substituents”.
  • substituents having the following structures are preferred. * In each structural formula shows a bonding position.
  • the reactive substituent other than the above may be chlorine, bromine or iodine, or a boron-containing group represented by the following formula (XLS-19). * In the structural formula indicates a bonding position.
  • R 41 and R 42 are each independently an alkyl, and R 41 and R 42 may combine with each other to form a ring. Further, the total carbon number of R 41 and R 42 is preferably 2 to 10.
  • the compound represented by the formula (1) is prepared as an intermediate by first bonding the rings a to c with a bonding group (—O—). Then, the final product can be produced by bonding the rings a to c with a bonding group (group containing B) (second reaction).
  • first reaction for example, a general etherification reaction such as a nucleophilic substitution reaction or an Ullmann reaction can be used.
  • second reaction a tandem hetero Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, the same applies hereinafter) can be used.
  • the details of the first and second reactions can be referred to the description described in WO 2015/102118.
  • the second reaction is a reaction for introducing B (boron) bonding the a ring, the b ring and the c ring as shown in the following scheme (1).
  • a hydrogen atom between two Os is ortho-metallized with n-butyllithium, sec-butyllithium, t-butyllithium, or the like.
  • boron trichloride, boron tribromide, or the like is added, and a metal exchange of lithium-boron is performed.
  • a Brönsted base such as N, N-diisopropylethylamine is added to cause a tandem bola-Friedel-Crafts reaction. You can get things.
  • a Lewis acid such as aluminum trichloride may be added to accelerate the reaction.
  • lithium was introduced to a desired position by orthometalation.
  • a bromine atom or the like was introduced at a position where lithium was to be introduced, and the desired position was also obtained by halogen-metal exchange. Lithium can be introduced.
  • these groups may be introduced into an intermediate in advance, or these groups may be introduced after the second reaction.
  • the compound represented by the formula (1) having a substituent at a desired position and being represented by the formula (1) can be synthesized by appropriately selecting the above synthesis method and appropriately selecting the starting materials to be used.
  • the organic EL device of the present invention contains a boron-containing polycyclic aromatic compound as a dopant in the light emitting layer as a second component.
  • the second component contained in the light emitting layer of the organic EL device of the present invention may be a delayed fluorescent substance or a non-delayed fluorescent substance, a delayed fluorescent substance is preferred, and a thermally activated delayed fluorescent substance is more preferred. preferable.
  • thermally activated delayed phosphor refers to the absorption of thermal energy, which causes an inverse intersystem crossing from an excited triplet state to an excited singlet state, and radiation inactivation from the excited singlet state to cause delayed fluorescence. It means a compound that can emit.
  • thermalally activated delayed fluorescence includes those that undergo higher-order triplets in the process of excitation from the excited triplet state to the excited singlet state. For example, a paper by Monkman et al. Of Durham University (NATURE COMMUNICATIONS, 7: 13680, DOI: 10.1038 / ncomms13680), and a paper by Hosokai et al.
  • the fluorescence lifetime of a sample containing a target compound is measured at 300 K, it is determined that the target compound is a “heat-activated delayed fluorescent substance” when a slow fluorescent component is observed.
  • the slow fluorescent component refers to a component having a fluorescence lifetime of 0.1 ⁇ sec or more.
  • the measurement of the fluorescence lifetime can be performed using, for example, a fluorescence lifetime measuring device (C11367-01, manufactured by Hamamatsu Photonics KK).
  • the compound containing a boron atom which is the second component of the present invention, has an excited triplet energy involved in forward and reverse intersystem crossings from an excited triplet state to an excited singlet state by molecular orbital calculation, It has been pointed out that it may be higher order triplet energy than the excited triplet energy observed by the phosphorescence spectrum (The 98th Annual Meeting of the Chemical Society of Japan, Publication No .: 2I4-15, DABNA Mechanism of high-efficiency light emission in organic EL devices used as light-emitting molecules, presented by Professor Toru Sato of Kyoto University graduate School of Engineering).
  • the inverse intersystem crossing in DABNA2 having a boron atom in the molecule is an FvHT (Fluorescence via Higher Triplet) mechanism using higher triplet orbitals, and the transition from higher triplet orbitals to the ground state is performed. It is suggested that the transition from higher-order triplet orbit to excited singlet orbit occurs because of the suppression.
  • FvHT Fluorescence via Higher Triplet
  • the excitation singlet energy level determined from the short wavelength side peak top of the fluorescence spectrum of the second component is E (2, S, PT), and the excitation triplet energy determined from the short wavelength side peak top of the phosphorescence spectrum of the second component.
  • E (2, T, PT) the energy level
  • ⁇ E (2, ST, PT) the singlet / triplet energy difference ( ⁇ E (2, ST, PT) obtained therefrom has the following relationship.
  • ⁇ E (2, ST, PT) E (2, S, PT) ⁇ E (2, T, PT) ⁇ 0.20 eV That is, in the second component, the magnitude of ⁇ E (ST) is used as an index of TADF activity.
  • ⁇ E (2, ST, PT) is preferably 0.20 eV or less, more preferably 0.15 eV or less, and further preferably 0.10 eV or less.
  • the inverse intersystem crossing speed indicates the speed of the inverse intersystem crossing from the excited triplet to the excited singlet.
  • the inverse intersystem crossing velocity of the second component can be calculated by transient fluorescence spectrometry using the method described in Nat. Commun. 2015, 6, 8476. or Organic Electronics 2013, 14, 2721-2726, Specifically, the inverse intersystem crossing speed of the assisting dopant is preferably 10 5 s ⁇ 1 or more, more preferably 10 6 s ⁇ 1 or more.
  • Luminescence speed indicates the speed of transition from the excited singlet to the ground state via fluorescence emission without going through the TADF process.
  • the emission speed of the second component can be calculated using the method described in Nat. Commun. 2015, 6, 8476. or Organic Electronics 2013, 14, 2721-2726, similarly to the inverse intersystem crossing speed.
  • the inverse intersystem crossing velocity of the second component is preferably 10 7 s ⁇ 1 or more, and more preferably 10 8 s ⁇ 1 or more.
  • any compound other than the compound represented by the formula (1) may be used.
  • suitable polycyclic aromatic compounds will be described in detail.
  • polycyclic aromatic compound represented by the general formula (2) and a multimer thereof as a second component a polycyclic aromatic compound represented by the following general formula (2) or a multimer thereof is used. preferable.
  • R 1 to R 11 each independently represent hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, Diarylboryl (the two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, aryloxy, cyano or halogen (the first substituent), and at least one of these One hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl (the above, the second substituent).
  • adjacent groups among R 1 to R 11 may be bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, the b ring or the c ring, and at least one hydrogen atom in the formed ring Is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls may be linked via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryl It may be substituted by oxy (the first substituent), and at least one hydrogen in these may be substituted by aryl, heteroaryl, alkyl or cycloalkyl (the second substituent).
  • Y 1 is B (boron), and X 1 and X 2 are each independently>O,>NR,>S,> Se or —C (—R) 2 — (provided that X 1 and X 2 are not simultaneously> O), wherein R of —C (—R) 2 — is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons or 6 to 12 carbons R of the formula> NR is an aryl having 6 to 12 carbons, a heteroaryl having 2 to 15 carbons, an alkyl having 1 to 6 carbons or a cycloalkyl having 3 to 6 carbons; Wherein R in the> NR is —O—, —S—, —C (—R ′) 2 —, and may be bonded to at least one of the a ring, b ring and c ring by a single bond or condensation.
  • R ′ of the above “—C (—R ′) 2 —” is hydrogen, alkyl having 1 to 5 carbons or 5 to 5 carbons) 10 cycloalkyl). At least one hydrogen in the compound represented by the general formula (2) may be substituted with cyano, halogen, or deuterium.
  • Aryl “heteroaryl”, “diarylamino”, “diarylboryl (two aryls may be bonded via a single bond or a linking group)” as a first substituent such as R 1
  • R 1 “Alkyl”, “cycloalkyl”, “alkoxy” and “aryloxy”, and “aryl”, “heteroaryl”, “alkyl” and “cycloalkyl” as the second substituent such as R 1 are described above. The description of these groups as the first substituent in the formula (1) can be cited.
  • heteroaryl in diheteroarylamino as the first substituent such as R 1 and “heteroaryl” in arylheteroarylamino are the same as those of heteroaryl as the first substituent in the above formula (1).
  • aryl in the arylheteroarylamino the description of aryl as the first substituent in the above formula (1) can be cited.
  • Halogen which is the first substituent such as R 1 is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.
  • the emission wavelength can be adjusted by the steric hindrance, electron-donating property, and electron-withdrawing property of the structure of R 1 or the like (first substituent), and at least one of R 1 to R 11 is preferably Is a group represented by the following formula, more preferably, methyl, t-butyl, t-amyl, t-octyl, 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, 3,6-dimethylcarbazolyl, , 6-di-t-butylcarbazolyl and phenoxy, more preferably methyl, t-butyl, t-amyl, t-octyl, phenyl,
  • steric hindrance is large for selective synthesis.
  • Me represents methyl
  • tBu represents t-butyl
  • tAm represents t-amyl
  • tOct represents t-octyl
  • Adjacent groups among R 1 to R 11 in the general formula (2) may be bonded to each other to form an aryl ring or a heteroaryl ring together with at least one of a ring, b ring and c ring.
  • the polycyclic aromatic compound represented by the formula (2) has the following general formulas (2-L1) and (2-L2) depending on the mutual bonding form of the substituents on the ring a, ring b and ring c. As shown, the ring structure of the compound changes. The definition of the symbols in each formula is the same as the definition of general formula (2).
  • the a ′ ring, b ′ ring and c ′ ring represent a substituent R 1 to R 3
  • a substituent R 8 to R 11 and a substituent R 4 to R 7 represent an aryl ring or a heteroaryl ring formed together with the a-ring, b-ring and c-ring by bonding adjacent groups (a ring, b-ring or c-ring is condensed with another ring structure) Can also be called a fused ring).
  • R 3 of the a ring and R 4 of the c ring, R 11 of the b ring and R 1 of the a ring are “adjacent” They do not correspond to "groups", and they do not bond. That is, “adjacent groups” means groups that are adjacent on the same ring.
  • R 8 of ring b and R 7 of ring c do not bond to an adjacent group, and do not constitute a part of the formed aryl ring or heteroaryl ring.
  • aryl ring (a ′ ring, b ′ ring or c ′ ring) or “heteroaryl ring” (a ′ ring, b ′ ring or c ′ ring) is an aryl as the first substituent described above. Or a heteroaryl, non-valent ring.
  • the “aryl ring” is The total number of carbon atoms of the condensed ring obtained by condensing a 5-membered ring with the 5-membered ring is the lower limit of the number of carbon atoms. It becomes a number.
  • the compound represented by the formula (2-L1) or the formula (2-L2) is, for example, a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring with respect to a benzene ring which is a ring (or b ring or c ring).
  • a compound having an a ′ ring (or b ′ ring or c ′ ring) formed by condensing a benzothiophene ring, and the formed condensed ring a ′ (or condensed ring b ′ or condensed ring c ′) is They are a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring, respectively.
  • R 1 and the like (the first substituent) described above and aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, and diarylboryl as the first substituent in the formula (1).
  • Two aryls have a single bond or a linking group ), Alkyl, cycloalkyl, alkoxy or aryloxy.
  • X 1 and X 2 in the general formula (2) are each independently>O,>NR,>S,> Se or —C (—R) 2 —, provided that X 1 and X 2 Is different from the polycyclic aromatic compound represented by the general formula (1) in that it is not simultaneously> O.
  • X 1 and X 2 are preferably both>NR,> O and> NR, or> NR and> O, more preferably both> O or both> NR, and both> NR Is more preferred.
  • the R of —C (—R) 2 — is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons or aryl having 6 to 12 carbons, and R of> NR is carbon Aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms, and these substituents are represented by the above-mentioned formula (1). Reference may be made to the description of aryl, heteroaryl, alkyl or cycloalkyl as first substituent.
  • R in the above-mentioned —N—R is —O—, —S—, —C (—R ′) 2 —, and is bonded to at least one of the a ring, b ring and c ring by a single bond or condensation. Is also good.
  • R in the above-mentioned “—C (—R) 2 —” is hydrogen, alkyl having 1 to 5 carbons, or cycloalkyl having 5 to 10 carbons.
  • This rule can be represented by a compound represented by the following formula (2-L3) and having a ring structure in which N is incorporated into a condensed ring b ′ and a condensed ring c ′.
  • a b ′ ring (or c ′ ring) formed by condensing another ring so as to incorporate N into the benzene ring which is the b ring (or c ring) in the general formula (2).
  • the formed condensed ring b ′ (or condensed ring c ′) is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.
  • the above definition can also be represented by a compound represented by the following formula (2-L4) or (2-L5) and having a ring structure in which N is incorporated into a condensed ring a ′.
  • the formed condensed ring a ′ is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.
  • each symbol in the equations (2-L3) to (2-L5) is the same as the definition in the equation (2).
  • a dimer to a hexamer is preferable, a dimer to a trimer is more preferable, and a dimer is more preferable.
  • the multimer may be a form having a plurality of the above-mentioned unit structures in one compound.
  • the above-mentioned unit structure may be a single bond, an alkylene group having 1 to 3 carbon atoms (eg, a methylene group), a phenylene group, a naphthylene.
  • an arbitrary ring (a ring, b ring or c ring) contained in the above unit structure is shared by a plurality of unit structures. It may be in a bonded form (ring-coupling type multimer), or in a form in which arbitrary rings (ring a, ring b or ring c) contained in the above unit structure are fused to each other (ring fused) A multimer), but a ring-sharing multimer and a ring-fused multimer are preferable, and a ring-sharing multimer is more preferable.
  • R 2 is preferably hydrogen.
  • Examples of such multimers include the following general formulas (2-4), (2-4-1), (2-4-2), (2-5-1) to (2-5-1) 5-4) or a multimer represented by the formula (2-6).
  • the multimer represented by the following formula (2-4), as described in the general formula (2) shares a plurality of (two in the following structural formulas) with the benzene ring which is the a ring in common. It is a multimeric compound (ring-sharing multimer) having the unit structure represented by (2) in one compound.
  • the multimer represented by the following formula (2-4-1) may have a plurality (3 in the following structural formula) by sharing the benzene ring which is the a ring, as described in the general formula (2).
  • the multimer represented by the following formula (2-4-2) may have a plurality (6 in the following structural formula) by sharing the benzene ring which is the a ring, as described in the general formula (2).
  • the multimeric compounds represented by the following formulas (2-5-1) to (2-5-4) may share a benzene ring, which is the c-ring, according to the general formula (2).
  • the multimer represented by the following formula (2-6) may be, for example, a benzene ring which is a ring (or a ring or c ring) having a certain unit structure and a certain unit
  • R 2 in each of the following formulas is hydrogen.
  • the multimer includes a multimerized form represented by the formula (2-4), the formula (2-4-1) or the formula (2-4-2), and the formula (2-5-1) to the formula (2-5-1) 5-4) or a multimer in combination with the multimerized form represented by formula (2-6), and may be represented by formulas (2-5-1) to (2-5-4).
  • ) May be combined with the multimeric form represented by formula (2-6) and the multimeric form represented by formula (2-6).
  • the multimer may be a combination of the multimerized form represented by (2-6).
  • At least one hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (2) and a multimer thereof may be substituted with cyano, halogen, or deuterium.
  • ring a, ring b, ring c, substituents on these rings, and X 1 and X 2 are> NR or —C (—R) 2 —.
  • At least one hydrogen at the time R may be replaced by cyano, halogen or deuterium.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.
  • the polycyclic aromatic compound represented by the general formula (2) and a multimer thereof can be produced according to the production method described in International Publication WO 2015/102118. Further, referring to the method for producing the polycyclic aromatic compound represented by the above formula (1), the first reaction is not carried out by an etherification reaction but by a general amination reaction such as a Buchwald-Hartwig reaction. can do.
  • R 8 is halogen, carbon number alkyl of 1-6, cycloalkyl having 3 to 14 carbon atoms, heteroaryl of aryl or C 2 -C 10 6 to 10 carbon atoms
  • R 7 is hydrogen, number alkyl of 1 to 6, carbon atoms carbon atoms
  • Polycyclic aromatic compounds and their multimers which are 3 to 14 cycloalkyl, 6 to 10 carbon aryl or 2 to 10 carbon heteroaryl, are preferred.
  • the halogen of R 8 is fluorine, chlorine, bromine or iodine. From the viewpoint of increasing spin-orbit interaction due to the heavy atom effect, halogen having a large molecular weight is preferable, chlorine, bromine and iodine are preferable, and chlorine and bromine are preferable. Is more preferable, and iodine is still more preferable. From the viewpoint of deepening the HOMO / LUMO orbit by introducing an element having a high electronegativity, an element having a high electronegativity is preferable, fluorine, chlorine and bromine are preferable, fluorine and chlorine are more preferable, and fluorine is further preferable.
  • the alkyl having 1 to 6 carbon atoms for R 8 and R 7 may be linear or branched, and is preferably an alkyl having 1 to 5 carbons (a branched alkyl having 3 to 5 carbons), and preferably 1 to 6 carbons.
  • Alkyl (branched alkyl having 3 to 4 carbon atoms) is more preferable, specifically, 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, etc., and methyl or t-butyl is more preferable. Is more preferred.
  • the cycloalkyl having 3 to 14 carbon atoms of R 8 and R 7 is preferably a cycloalkyl having 3 to 12 carbon atoms, more preferably a cycloalkyl having 5 to 10 carbon atoms, specifically, cyclopentyl, cyclohexyl, norbornenyl or Adamantyl is preferred, and cyclohexyl is more preferred.
  • the aryl having 6 to 10 carbon atoms for R 8 and R 7 is preferably phenyl or naphthyl, and more preferably phenyl.
  • the heteroaryl having 2 to 10 carbon atoms for R 8 and R 7 is the same as the “heteroaryl” of the first substituent in the general formula (1), and includes a 6-membered ring or a 5-membered ring having a partial structure. Groups are preferred.
  • R 8 the following partial structural formulas (m), (e), (v), (t), (h), (p), (q), (q) r), Equation (s), Equation (y), Equation (u), Equation (w), Equation (j), Equation (k), Equation (f), Equation (c), Equation (b), Equation ( i) or groups of formula (n) are preferred, groups of formula (m), formula (t), formula (p), formula (f) or formula (n) are more preferred, and formula (m) or formula (t) ) Are more preferred.
  • R 8 is halogen, alkyl having 1 to 5 (preferably 1 to 4), cycloalkyl or phenyl having 5 to 10 carbons
  • R 7 is It is preferably hydrogen, alkyl having 1 to 5 carbon atoms (preferably 1 to 4), cycloalkyl having 5 to 10 carbon atoms or phenyl, and the sum of the molecular weights of R 8 and R 7 is preferably small. More preferably, R 8 is methyl, t-butyl or phenyl, and R 7 is hydrogen, methyl, t-butyl or phenyl. More preferably, R 8 is methyl or t-butyl, and R 7 is hydrogen or methyl. It is particularly preferred that R 8 is methyl and R 7 is hydrogen or methyl. Most preferably, R 8 is methyl and R 7 is hydrogen.
  • R 10 in the symmetrical position of R 8 is a group other than hydrogen, more preferably R 8 and R 10 are the same group.
  • R 5 at the symmetric position of R 7 is also preferably a group other than hydrogen, and more preferably, R 7 and R 5 are the same group.
  • the R of> NR is aryl, heteroaryl, alkyl or cycloalkyl.
  • the above partial structural formula (m), formula (e), formula (v), formula (t), formula (h), formula (p), formula (q), formula (r), formula (s), formula It is preferably a group represented by formula (y), formula (u), formula (w), formula (j) or formula (k), and formula (p), formula (q), formula (r), formula (s) , Formula (y), Formula (u) or Formula (w), more preferably Formula (p), Formula (q) or Formula (r), and Formula (p) It is particularly preferred that the group is
  • the polycyclic aromatic compound and the multimer thereof of the present embodiment can be produced according to the production method described in WO 2015/102118. Further, referring to the method for producing the polycyclic aromatic compound represented by the above formula (1), the first reaction is not carried out by an etherification reaction but by a general amination reaction such as a Buchwald-Hartwig reaction. can do.
  • the linking group L1 is a single bond, arylene having 6 to 12 carbons, heteroarylene having 2 to 15 carbons, alkylene having 1 to 6 carbons, alkenylene having 1 to 6 carbons, alkynylene having 1 to 6 carbons, —O—, —S—,> NR, or a combination thereof, wherein R in> NR is aryl having 6 to 12 carbons, heteroaryl having 2 to 15 carbons, 1 to carbons 6 alkyl or cycloalkyl having 3 to 14 carbon atoms, and at least one hydrogen in the dimer compound may be substituted with cyano, halogen or deuterium.
  • arylene “heteroarylene” and “alkylene” in the linking group L1
  • the description of the “aryl”, “heteroaryl” and “alkyl” of the first substituent in the above formula (1) is based on these groups. Further, the description can be cited in place of the description as a divalent group represented by excluding any one hydrogen atom.
  • alkynylene is one having two or more —C ⁇ C— groups in alkylene.
  • a group, which can be described by replacing one or more —CH 2 — groups in the above description of “alkylene” with —C C— groups or —C ⁇ C— groups, respectively.
  • the linking group L1 is an arylene having 6 to 12 carbons, a heteroarylene having 2 to 15 carbons, an alkylene having 1 to 6 carbons, an alkenylene having 1 to 6 carbons, an alkynylene having 1 to 6 carbons, —O—, It may be a group formed by combining at least one group selected from the group consisting of -S- and> NR.
  • the connecting point between the connecting group L1 and the partial structure represented by the formula (2) is arbitrary.
  • At least one hydrogen in the dimer compound may be replaced by cyano, halogen or deuterium.
  • at least one hydrogen in R may be substituted, and among these, an embodiment in which all or a part of hydrogen in the aryl or heteroaryl is substituted.
  • the two polycyclic aromatic compounds are bonded by a linking group L1 by a known method.
  • two intermediates for forming a polycyclic aromatic compound are bonded by a linking group L1, and the two intermediate portions linked by the linking group L1 are polyaromaticized. be able to.
  • polycyclic Aromatic Compound Represented by the General Formula (2) is specifically described in Japanese Patent Application No. 2017-199617. And Japanese Patent Application No. 2018-107092, International Application No. PCT / JP2015 / 054426, International Application No. PCT / JP2017 / 001089, and the following compounds are preferred.
  • a polycyclic aromatic compound represented by the following general formula (3) is preferable.
  • the polycyclic aromatic compound represented by the general formula (3) corresponds to a dimer of the polycyclic aromatic compound having two unit structures represented by the general formula (2) described above.
  • R 3 to R 12 , Z 1 and Z 2 each independently represent hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino , Arylheteroarylamino, diarylboryl (the two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, aryloxy, cyano or halogen (the first substituent) And at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl (the above is the second substituent).
  • adjacent groups among R 5 to R 7 and R 10 to R 12 may be bonded to each other to form an aryl ring or a heteroaryl ring together with at least one of the b ring and the d ring.
  • At least one hydrogen in the ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls may be linked via a single bond or a linking group), alkyl , Cycloalkyl, alkoxy or aryloxy (the above, the first substituent), and at least one hydrogen in these is aryl, heteroaryl, alkyl or cycloalkyl (the above, the second substituent) It may be substituted.
  • Z 1 may be linked to ring a by a linking group or a single bond
  • Z 2 may be linked to ring c by a linking group or a single bond
  • Y is B (boron)
  • X 1 , X 2 , X 3 and X 4 are each independently>O,>NR,>S,> Se or -C (-R) 2-
  • the R of —C (—R) 2 — is a carbon atom
  • Alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons, and R of> NR is -O-,
  • R 1 and R 2 are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons, aryl having 6 to 12 carbons, heteroaryl having 2 to 15 carbons, diarylamino (Where aryl is aryl having 6 to 12 carbon atoms) or diarylboryl (where aryl is aryl having 6 to 12 carbon atoms, and the two aryls may be bonded via a single bond or a linking group).
  • at least one hydrogen in the compound represented by the formula (3) may be substituted with cyano, halogen or deuterium.
  • Aryl “heteroaryl”, “diarylamino”, “diarylboryl (two aryls may be bonded via a single bond or a linking group)” as a first substituent such as R 3
  • a first substituent such as R 3
  • R 3 “Alkyl”, “cycloalkyl”, “alkoxy” and “aryloxy”, and “aryl”, “heteroaryl”, “alkyl” and “cycloalkyl” as the second substituent such as R 1 are described above. The description of these groups as the first substituent in the formula (1) can be cited.
  • heteroaryl in diheteroarylamino as the first substituent such as R 3 and “heteroaryl” in arylheteroarylamino are the same as those in the above formula (1).
  • aryl in the arylheteroarylamino, the description of aryl as the first substituent in the above formula (1) can be cited.
  • Halogen which is the first substituent such as R 3 is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.
  • Z 1 and Z 2 in the above formula (3) are each independently aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are a single bond or a linking group. ), Alkyl, cycloalkyl, alkoxy or aryloxy (the above is the first substituent), wherein at least one hydrogen is aryl, heteroaryl, alkyl or cycloalkyl (Above, the second substituent).
  • the polycyclic aromatic compound represented by the general formula (3) can be converted into a compound as shown in the following general formula (3-L1) depending on the mutual bonding form of the substituents on the b-ring and the d-ring.
  • the constituent ring structure changes.
  • the b ′ ring and d ′ ring in the formula (3-L1) correspond to the b ring and d ring in the general formula (3), respectively.
  • the definition of each code in the formula (3-L1) is the same as that in the general formula (3).
  • the b ′ ring and the d ′ ring in the above formula (3-L1) are formed by bonding adjacent groups among the substituents R 5 to R 7 of the b ring and the substituents R 10 to R 12 of the d ring.
  • an aryl ring or a heteroaryl ring formed together with the b-ring and the d-ring, respectively also referred to as a condensed ring formed by condensing another ring structure on the b-ring or d-ring).
  • R 7 of the b-ring and R 12 of the d-ring in the formula (3) do not correspond to “adjacent groups” and are not bonded to each other. . That is, “adjacent groups” means groups that are adjacent on the same ring.
  • Z 1 may be linked to ring a by a linking group or a single bond
  • Z 2 may be linked to ring c by a linking group or a single bond
  • the linking group for linking Z 1 to ring a and the linking group for linking Z 2 to ring c are each independently —O—, —S— or —C (—R ′) 2 — R ′ of the above “—C (—R ′) 2 —” is hydrogen or alkyl having 1 to 6 carbons.
  • the formed “aryl ring” (b ′ ring or d ′ ring) or “heteroaryl ring” (b ′ ring or d ′ ring) may be an unsubstituted aryl or heteroaryl as the first substituent described above. It is a ring. However, since the b-ring or the c-ring constituting a part of the b′-ring or the c′-ring is already a benzene ring having 6 carbon atoms, the “aryl ring” is a condensed ring in which a 5-membered ring is fused to the benzene ring.
  • the lower limit of the carbon number is 6 in the condensed ring obtained by condensing the 5-membered ring with the benzene ring.
  • the compound represented by the formula (3-L1) is obtained by condensing a benzene ring, which is a b-ring or a c-ring, with a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring or a benzothiophene ring, for example.
  • a condensed ring b 'or condensed ring c' is a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring, respectively.
  • R 3 and the like includes the above-described R 3 and the like (first substituent) and aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl as the first substituent in the formula (1).
  • Two aryls have a single bond or a linking group ), Alkyl, cycloalkyl, alkoxy or aryloxy.
  • X 1 , X 2 , X 3 and X 4 in the general formula (3) are each independently>O,>NR,>S,> Se or —C (—R) 2 —, provided that , X 1 and X 2 are not simultaneously> O, and X 3 and X 4 are not simultaneously> O.
  • R of -C (-R) 2- is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons or aryl having 6 to 12 carbons, and R of> NR represents 6 carbons.
  • R in> NR is —O—, —S—, —C (—R ′) 2 —, and is bonded to at least one of the a ring, b ring, c ring, and d ring by a single bond or condensation. It may be.
  • R ′ in the above “—C (—R ′) 2 —” is hydrogen, alkyl having 1 to 5 carbons, or cycloalkyl having 5 to 10 carbons.
  • This rule can be represented by a compound represented by the following formula (3-L2) having a ring structure in which X 1 and X 3 are incorporated into a condensed ring b ′ and a condensed ring d ′.
  • a b ′ ring (or a ring formed by condensing another ring so as to incorporate X 1 (or X 3 ) into a benzene ring which is a ring b (or a ring d) in the general formula (3) d 'ring).
  • the formed condensed ring b ′ (or condensed ring d ′) is, for example, a carbazole ring, a phenoxazine ring, a phenothiazine ring or an acridine ring.
  • the definition of each symbol in the formula (3-L2) is the same as the definition in the general formula (3).
  • R 1 and R 2 in the general formula (3) are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons, aryl having 6 to 12 carbons, 2 to 15 carbons Heteroaryl, diarylamino (wherein aryl is aryl having 6 to 12 carbons) or diarylboryl (where aryl is aryl having 6 to 12 carbons, and the two aryls are linked via a single bond or a linking group.
  • these substituents may be alkyl, cycloalkyl, aryl, heteroaryl, diarylamino, or diarylboryl as the first substituent in the above formula (1) (two aryls are bonded through a single bond or a linking group. May be quoted).
  • At least one hydrogen in the polycyclic aromatic compound represented by the general formula (3) may be substituted with cyano, halogen, or deuterium.
  • ring a, ring b, ring c, ring d, a substituent on these rings, and X 1 to X 4 are> NR or —C (—R) 2 —.
  • At least one hydrogen at the time R may be replaced by cyano, halogen or deuterium.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably chlorine.
  • polycyclic aromatic compound represented by the general formula (3) examples include compounds described in the specification of International Application No. PCT / JP2018 / 018731, and the following compounds are preferred.
  • the polycyclic aromatic compound represented by the general formula (3) is obtained by applying the production method described in WO 2015/102118, and by applying the polycyclic aromatic compound represented by the above formula (1) and It can be produced by referring to the method for producing the multimer.
  • the polycyclic aromatic compound represented by the general formula (3) basically produces an intermediate by bonding the respective ring structures to each other (first reaction), and thereafter, converts the respective ring structures to each other.
  • a final product can be produced by bonding with a boron atom (second reaction).
  • first reaction for example, a general etherification reaction such as a nucleophilic substitution reaction or an Ullmann reaction, or a general amination reaction such as a Buchwald-Hartwig reaction can be used.
  • a tandem hetero Friedel-Crafts reaction (a continuous aromatic electrophilic substitution reaction) can be used.
  • a polycyclic aromatic compound represented by the following general formula (4) or a multimer thereof is preferable.
  • the polycyclic aromatic compound represented by the general formula (4) is one of the compounds having a ring structure in which N is incorporated into a condensed ring c ′ as represented by the above-mentioned formula (2-L3).
  • R 1 to R 3 and R 5 to R 15 each independently represent hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino , Arylheteroarylamino, diarylboryl (the two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, aryloxy, cyano or halogen (the first substituent) And at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl (the above is the second substituent).
  • adjacent groups among R 1 to R 3 , R 5 to R 7 , R 8 to R 11 and R 12 to R 15 are bonded to each other to form at least one of a ring, b ring, c ring and d ring.
  • May form an aryl ring or a heteroaryl ring together with at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryl May be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy (the above is a first substituent), wherein at least one hydrogen atom is an aryl , Heteroaryl, alkyl or cycloalkyl (the above, the second substituent).
  • Y 1 is B (boron), X is>O,>NR,>S,> Se or —C (—R) 2 —, and R of the above —C (—R) 2 — Is an alkyl having 1 to 6 carbons, a cycloalkyl having 3 to 14 carbons or an aryl having 6 to 12 carbons, wherein R in the above-mentioned N—R is an aryl having 6 to 12 carbons and an aryl having 2 to 15 carbons Heteroaryl, alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons, L is a single bond, -C (-R) 2 -,>O,> S or> NR, and R in -C (-R) 2 -and> NR is each independently , Hydrogen, aryl, heteroaryl, diarylamino, diarylboryl (the two aryls may be bonded via a single bond or a linking group), alkyl, cyclo
  • Aryl “heteroaryl”, “diarylamino”, “diarylboryl” as the first substituent such as R 1 in the above formula (4) (the two aryls are bonded via a single bond or a linking group; may also be) ",” alkyl “,” cycloalkyl “,” alkoxy "and” aryloxy ", and” aryl “as a second substituent such as R 1," heteroaryl ",” alkyl “and” cyclo As for “alkyl”, the description of these groups as the first substituent in the formula (1) can be cited.
  • heteroaryl in diheteroarylamino and “heteroaryl” in arylheteroarylamino as the first substituent such as R 1 in the above formula (4) are the same as the first substituent in the above formula (1).
  • aryl in arylheteroarylamino the description of aryl as the first substituent in formula (1) can be cited.
  • Halogen as the first substituent such as R 1 in the above formula (4) is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.
  • the a ′ ring, b ′ ring, c ′ ring and d ′ ring represent substituents R 1 to R 3 , substituents R 5 to R 7 , An aryl ring or a heteroaryl ring formed by bonding adjacent groups among R 8 to R 11 and substituents R 12 to R 15 together with at least one of a ring, b ring, c ring and d ring (Also referred to as a condensed ring formed by condensing another ring structure on ring a, ring b, ring c or ring d).
  • aryl ring (a ′ ring, b ′ ring, c ′ ring or d ′ ring) or “heteroaryl ring” (a ′ ring, b ′ ring, c ′ ring or d ′ ring) is as described above.
  • An aryl or heteroaryl ring as a first substituent.
  • a ring (b ring, c ring or d ring) constituting a part of the a ′ ring (b ′ ring, c ′ ring or d ′ ring) is already a benzene ring having 6 carbon atoms
  • “aryl” For the “ring”, the total number of carbon atoms of the condensed ring in which the 5-membered ring is fused to the benzene ring is 9 as the lower limit, and for the "heteroaryl ring", the total carbon number of the condensed ring in which the 5-membered ring is fused to the benzene ring is Equation 6 is the lower limit of carbon number.
  • the compounds represented by the formulas (4-L1) to (4-L3) are, for example, a benzene ring, an indole ring, a pyrrole ring, a benzene ring which is an a ring (a b ring, a c ring or a d ring).
  • R 1 and the like (the first substituent) described above and aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, and diarylboryl as the first substituent in the formula (1).
  • Two aryls have a single bond or a linking group ), Alkyl, cycloalkyl, alkoxy or aryloxy.
  • Y 1 in the general formula (4) is B (boron), X is>O,>NR,>S,> Se or —C (—R) 2 —, and> O and> N -R is preferred.
  • the R of —C (—R) 2 — is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons or aryl having 6 to 12 carbons. , Aryl having 6 to 12 carbons, heteroaryl having 2 to 15 carbons, alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. ), The description of aryl, heteroaryl, alkyl or cycloalkyl as the first substituent can be cited.
  • L in the general formula (4) is a single bond, —C (—R) 2 —,>O,> S and> NR, preferably a single bond,> O or> NR, and the single bond is More preferred.
  • Aryl, heteroaryl, diarylamino, diarylboryl (two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryl as the first substituent in the formula (1) Oxy's explanation can be quoted.
  • the compound represented by the formula (4) does not include a compound in which X is> NR and L is> O.
  • a dimer to a hexamer is preferable, a dimer to a trimer is more preferable, and a dimer is more preferable.
  • the multimer may be a form having a plurality of the above unit structures in one compound.
  • the above unit structure may be a single bond, an alkylene group having 1 to 3 carbon atoms (eg, a methylene group), a phenylene group, a naphthylene group
  • an arbitrary ring (a ring, b ring, c ring or d ring) contained in the above unit structure may be shared by a plurality of unit structures.
  • Ring-coupling type multimer and any of the rings (a-ring, b-ring, c-ring or d-ring) contained in the above unit structure are bonded together so as to be condensed.
  • the ring-condensed multimer and the ring-condensed multimer are preferable, but the ring-condensed multimer is more preferable.
  • R 2 is hydrogen.
  • Examples of such a multimer include the following general formula (4-4), formula (4-5-1), formula (4-5-2), formula (4-6-1) or formula (4-6-1) And the multimer represented by 6-2).
  • the multimer represented by the following formula (4-4) may have a plurality (two in the following structural formula) of the general formula (4) described in the general formula (4) so as to share the benzene ring which is the a ring. It is a multimeric compound (ring-sharing type multimer) having the unit structure represented by (4) in one compound. Further, the multimers represented by the following formulas (4-5-1) and (4-5-2) can share the benzene ring, which is the b ring, according to the general formula (4).
  • a multimeric compound having a plurality of (two in the following structural formulas) unit structures represented by the general formula (1) in one compound.
  • the multimer represented by the following formula (4-6-1) or (4-6-2) may be, for example, a ring (b ring, c ring) having a certain unit structure as described by the general formula (4).
  • R 2 in each of the following formulas is hydrogen.
  • the multimer is a multimer obtained by combining the multimeric form represented by the formula (4-4) with the multimeric form represented by the formula (4-5-1) or the formula (4-5-2) And a multiplication form represented by the formula (4-4), the formula (4-5-1) or the formula (4-5-2), and the formula (4-6-1) or the formula (4-6-1)
  • the multimer may be a combination of the multimerized form represented by 4-6-2).
  • At least one hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (4) and a multimer thereof may be substituted with cyano, halogen, or deuterium.
  • cyano, halogen, or deuterium when a ring, b ring, c ring, d ring, a substituent to these rings, and X is> NR or —C (—R) 2 —
  • R and L of —C (—R) 2 — or> NR are at least one hydrogen in R may be replaced by cyano, halogen or deuterium.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.
  • one of R 7 and R 8 is halogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons, aryl having 6 to 10 carbons or 2 to 2 carbons.
  • 10 heteroaryl (hereinafter also referred to as “Z substituent”), and the other is hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons, aryl having 6 to 10 carbons or carbon having Preferably, it is 2 to 10 heteroaryls.
  • R 8 of ring b and R 7 of ring c do not bond to an adjacent group, and do not constitute a part of the formed aryl ring or heteroaryl ring.
  • the “one” is R 8 and the “the other” is R 7 .
  • the halogen for R 7 and R 8 is fluorine, chlorine, bromine or iodine.
  • a halogen having a large molecular weight is preferable, chlorine, bromine and iodine are preferable, chlorine and bromine are more preferable, and iodine is further preferable.
  • an element having a high electronegativity is preferable, fluorine, chlorine and bromine are preferable, fluorine and chlorine are more preferable, and fluorine is further preferable.
  • the alkyl having 1 to 6 carbon atoms for R 7 and R 8 may be any of linear or branched, and is preferably an alkyl having 1 to 5 carbons (a branched alkyl having 3 to 5 carbons), and preferably 1 to 6 carbons.
  • Alkyl (branched alkyl having 3 to 4 carbon atoms) is more preferable, specifically, 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, etc., and methyl or t-butyl is more preferable. Is more preferred.
  • the C 3-14 cycloalkyl for R 7 and R 8 is preferably a C 3-12 cycloalkyl, more preferably a C 5-10 cycloalkyl, specifically, cyclopentyl, cyclohexyl, norbornenyl or Adamantyl is preferred, and cyclohexyl is more preferred.
  • the aryl having 6 to 10 carbon atoms for R 7 and R 8 is preferably phenyl or naphthyl, and more preferably phenyl.
  • heteroaryl having 2 to 10 carbon atoms represented by R 7 and R 8 include the same groups as the “heteroaryl” of the first substituent in the general formula (1), and include a 6-membered ring or a 5-membered ring having a partial structure. Groups are preferred.
  • the Z substituent includes the following partial structural formulas (m), (e), (v), (t), (h), (p), (q), and (r) , Expression (s), Expression (y), Expression (u), Expression (w), Expression (j), Expression (k), Expression (f), Expression (c), Expression (b), Expression (i) Or a group of the formula (n) is preferred, a group of the formula (m), the formula (t), the formula (p), the formula (f) or the formula (n) is more preferred, and the formula (m) or the formula (t) Groups are more preferred.
  • both R 7 and R 8 are Z substituents from the viewpoint of shortening the delayed fluorescence lifetime and expressing the TADF mechanism by imparting strain to the molecule. From the viewpoint of obtaining a high PLQY and the stability of the molecule, it is preferable that only one of R 7 and R 8 is a Z substituent. From the viewpoint of ease of synthesis, R 8 is preferably a Z substituent.
  • R 8 when R 8 is a Z substituent, it is preferable that R 10 has a substituent.
  • R 7 when R 5 is a Z substituent, at least one of R 5 and R 13 It is preferable to have a substituent.
  • R 5 when R 5 is a Z substituent, it is more preferable to have a substituent in at least one of R 7 and R 14 .
  • the substituent is preferably small, and the above formulas (m), (e), (v), (t), (h), and (p) ), (Q), (r), (s), (j), (k), (f), (c), (b), (i) and (n) are preferred, and among these, the groups represented by the formulas (m), (e), (v), (t), (p), (f) and (n) are more preferable. Groups of formula (m) and formula (t) are more preferred, and groups of formula (m) are most preferred.
  • R 7 and R 8 among the R 7 and R 8, one of halogen, alkyl having 1-5 carbon atoms (preferably 1-4), cycloalkyl, or phenyl having 5 to 10 carbon atoms
  • the other is preferably hydrogen, alkyl having 1 to 5 carbon atoms (preferably 1 to 4), cycloalkyl having 5 to 10 carbon atoms or phenyl, and the sum of the molecular weights of R 7 and R 8 is small. Is more preferred. More preferably, one is methyl, t-butyl or phenyl and the other is hydrogen, methyl, t-butyl or phenyl. More preferably, one is methyl or t-butyl and the other is hydrogen or methyl. It is particularly preferred that one is methyl and the other is hydrogen or methyl. Most preferably, one is methyl and the other is hydrogen. Further, it is preferable that the “one” is R 8 and the “the other” is R 7 .
  • R 10 in the symmetrical position of R 8 is a group other than hydrogen, more preferably R 8 and R 10 are the same group.
  • R 5 at the symmetric position of R 7 is also preferably a group other than hydrogen, and more preferably, R 7 and R 5 are the same group.
  • polycyclic aromatic compound represented by the general formula (4) and its multimer include compounds described in the specification of Japanese Patent Application No. 2018-110876, and the following compounds are preferred.
  • the polycyclic aromatic compound represented by the formula (4) and a multimer thereof can be produced by applying the production method described in WO 2015/102118. That is, as shown in the following scheme, an intermediate having a Z 1 group is synthesized and cyclized by a tandem hetero Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction) to obtain a desired polycyclic aromatic compound. A group compound and its multimer can be synthesized.
  • Z 1 represents halogen or hydrogen, and the definitions of other symbols are the same as those described above.
  • the intermediate before cyclization in the above scheme can also be synthesized by the method shown in WO 2015/102118 and the like. That is, an intermediate having a desired substituent can be synthesized by appropriately combining a Buchwald-Hartwig reaction, a Suzuki coupling reaction, or an etherification reaction such as a nucleophilic substitution reaction or an Ullmann reaction.
  • a polycyclic aromatic compound represented by the following general formula (5) or a multimer thereof is preferable. .
  • R 1 to R 9 each independently represent hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, Diarylboryl (the two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, aryloxy, cyano or halogen (the first substituent), and at least one of these One hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl (the above, the second substituent).
  • adjacent groups among R 1 to R 9 may be bonded to each other to form an aryl ring or a heteroaryl ring together with at least one of the a ring, the b ring and the c ring.
  • At least one hydrogen is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls may be linked via a single bond or a linking group), alkyl, cycloalkyl , Alkoxy or aryloxy (the first substituent), and at least one hydrogen in these may be substituted with an aryl, heteroaryl, alkyl or cycloalkyl (the second substituent). Is also good.
  • Y 1 is B (boron), and X 1 , X 2 and X 3 are each independently>O,>NR,>S,> Se or —C (—R) 2 —. (At least two of X 1 , X 2 and X 3 are NR), wherein R of —C (—R) 2 — is alkyl having 1 to 6 carbons, cyclo is 3 to 14 carbons.
  • R in the above-mentioned —N—R is aryl having 6 to 12 carbons, heteroaryl having 2 to 15 carbons, alkyl having 1 to 6 carbons or 3 to 6 carbons
  • R in> NR is —O—, —S—, —C (—R ′) 2 —, or at least one of the a ring, b ring and c ring by a single bond or by condensation.
  • optionally one bound (Note that the "-C (-R ') 2 -" of R' is hydrogen or aralkyl of 1 to 5 carbon atoms Cycloalkyl Le carbon atoms or 5-10).
  • At least one hydrogen in the compound represented by the general formula (5) may be substituted with cyano, halogen, or deuterium.
  • Aryl “heteroaryl”, “diarylamino”, “diarylboryl” as the first substituent such as R 1 in the above formula (5) (the two aryls are bonded via a single bond or a linking group; may also be) ",” alkyl “,” cycloalkyl “,” alkoxy "and” aryloxy ", and” aryl “as a second substituent such as R 1," heteroaryl ",” alkyl “and” cyclo As for “alkyl”, the description of these groups as the first substituent in the formula (1) can be cited.
  • heteroaryl in diheteroarylamino and “heteroaryl” in arylheteroarylamino as the first substituent such as R 1 in the above formula (5) are the same as the first substituent in the above formula (1).
  • aryl in arylheteroarylamino the description of aryl as the first substituent in formula (1) can be cited.
  • Halogen as the first substituent such as R 1 in the above formula (5) is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.
  • Adjacent groups among R 1 to R 9 in the general formula (5) may be bonded to each other to form an aryl ring or a heteroaryl ring together with at least one of a ring, b ring and c ring.
  • the polycyclic aromatic compound represented by the formula (5) has the following general formulas (5-L1) and (5-L2) depending on the mutual bonding form of the substituents on the ring a, ring b and ring c. As shown, the ring structure of the compound changes. The definition of the symbols in each formula is the same as the definition of general formula (5).
  • the a ′ ring, b ′ ring and c ′ ring in the formulas (5-L1) and (5-L2) are formed by bonding adjacent groups of the substituents R 1 to R 9 to form a ring a ,
  • An aryl ring or a heteroaryl ring formed together with a ring b and a ring c also referred to as a condensed ring formed by condensing another ring structure on the ring a, ring b or ring c).
  • there are other combinations such as a compound in which all of a ring, b ring and c ring are changed to a ′ ring, b ′ ring and d ′ ring.
  • R 1 of ring a and R 9 of ring b, R 7 of ring b and R 6 of ring c, and ring C of ring c R 4 and R 3 of the a-ring do not correspond to “adjacent groups” and do not bond to each other. That is, “adjacent groups” means groups that are adjacent on the same ring.
  • the formed “aryl ring” (a ′ ring, b ′ ring or c ′ ring) or “heteroaryl ring” (a ′ ring, b ′ ring or c ′ ring) is an aryl as the first substituent described above. Or a heteroaryl, non-valent ring.
  • the a ring (the b ring or the c ring) constituting a part of the a ′ ring (the b ′ ring or the c ′ ring) is already a benzene ring having 6 carbon atoms
  • the “aryl ring” is the benzene ring.
  • the total number of carbon atoms of the condensed ring obtained by condensing a 5-membered ring with the 5-membered ring is the lower limit of the number of carbon atoms.
  • the compound represented by the formula (5-L1) and the formula (5-L2) is, for example, a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring or a benzene ring which is an a ring (a b ring or a c ring).
  • Ring, indole ring, dibenzofuran ring or dibenzothiophene ring is, for example, a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring or
  • R 1 and the like (the first substituent) described above and aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, and diarylboryl as the first substituent in the formula (1).
  • Two aryls have a single bond or a linking group ), Alkyl, cycloalkyl, alkoxy or aryloxy.
  • Y 1 in the general formula (5) is B (boron), and X 1 , X 2 and X 3 are each independently>O,>NR,>S,> Se or -C (- R) 2 - a the proviso that at least two of X 1, X 2 and X 3 is N-R, it is preferable three of X 1, X 2 and X 3 is a N-R.
  • the R of —C (—R) 2 — is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons or aryl having 6 to 12 carbons.
  • Aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms, and these substituents are represented by the above-mentioned formula (1).
  • R in the above-mentioned —N—R is —O—, —S—, —C (—R ′) 2 —, and is bonded to at least one of the a ring, b ring and c ring by a single bond or condensation. Is also good.
  • R ′ in the above “—C (—R ′) 2 —” is hydrogen, alkyl having 1 to 5 carbons, or cycloalkyl having 5 to 10 carbons.
  • This rule specifies a compound represented by the following formula (5-L3) having a ring structure in which N at the position of X 2 or X 1 in the formula (5) is incorporated into a condensed ring b ′ and a condensed ring c ′.
  • b is formed by condensing another ring so as to incorporate N at the position of X 1 (or X 2 ) into the benzene ring which is ring b (or ring c) in the general formula (5). It is a compound having a 'ring (or c' ring).
  • the formed condensed ring b ′ (or condensed ring c ′) is, for example, a phenoxazine ring, a phenothiazine ring, an acridine ring or a phenophosphazine ring.
  • the above definition has a ring structure represented by the following formula (5-L4) or (5-L5) in which N at at least one position of X 1 and X 2 is incorporated into a condensed ring a ′. It can also be expressed as a compound. That is, for example, a ′ is formed by condensing another ring such that N at the position of X 1 (and at least one of X 2 ) is incorporated into the benzene ring which is the a ring in the general formula (5). It is a compound having a ring.
  • the condensed ring A ′ formed is, for example, a phenoxazine ring, a phenothiazine ring, an acridine ring or a phenophosphazine ring. Note that each symbol in the equations (5-L3) to (5-L5) is the same as the definition in the equation (5).
  • N-R a R a X 3 is also included at least one bound forms of b rings and c ring linking group or a single bond.
  • the formed condensed ring b ′ (or condensed ring c ′) is, for example, a phenoxazine ring, a phenothiazine ring, an acridine ring or a phenophosphazine ring.
  • the above definition also includes a form in which X 1 , X 2 or X 3 is incorporated into any one of the condensed rings in a complex form.
  • the polymer of the polycyclic aromatic compound having a plurality of unit structures represented by the general formula (5) is preferably a dimer to a hexamer, more preferably a dimer to a trimer, and further preferably a dimer.
  • the multimer may be a form having a plurality of the above-mentioned unit structures in one compound.
  • the above-mentioned unit structure may be a single bond, an alkylene group having 1 to 3 carbon atoms (eg, a methylene group), a phenylene group, a naphthylene.
  • an arbitrary ring (a ring, b ring or c ring) contained in the above unit structure is shared by a plurality of unit structures. It may be in a bonded form (ring-coupling type multimer), or in a form in which arbitrary rings (ring a, ring b or ring c) contained in the above unit structure are fused to each other (ring fused) A multimer), but a ring-sharing multimer and a ring-fused multimer are preferable, and a ring-sharing multimer is more preferable.
  • R 2 is preferably hydrogen.
  • Such a multimer includes, for example, a multimer represented by the following formula (5-4), formula (5-5) or formula (5-6).
  • the multimer represented by the following formula (5-4) is, as described in the general formula (5), a unit represented by two general formulas (5) so as to share a benzene ring which is a ring. It is a dimer compound having a structure in one compound (ring-sharing multimer).
  • the multimer represented by the following formula (5-5) can be expressed by three general formulas (5) by sharing X 2 with a benzene ring which is an a ring as described in the general formula (5). Is a trimer compound (ring-sharing multimer) having the unit structure represented by the formula in one compound.
  • the multimer represented by the following formula (5-6) is, for example, a benzene ring that is a ring (or a b-ring or a c-ring) of a certain unit structure and a certain unit structure, as described in the general formula (5).
  • a benzene ring which is a ring (or a b ring or a c ring) of a dimer compound having two unit structures represented by the general formula (5) in one compound (ring condensation) Type multimer).
  • each symbol in the following equation is the same as the definition in equation (5).
  • At least one hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (5) and a multimer thereof may be cyano, halogen, or deuterium.
  • a ring, b ring, c ring, substituents on these rings, and X 1 , X 2 and X 3 are> NR or —C (—R) 2
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably chlorine.
  • polycyclic aromatic compound represented by the general formula (5) and its multimer include the compounds described in the specification of Japanese Patent Application No. 2017-171324, and the following compounds are preferred.
  • the polycyclic aromatic compound represented by the formula (5) and a multimer thereof can be produced by applying the production method described in WO 2015/102118. Also, referring to the method for producing the polycyclic aromatic compound represented by the above formula (1) and a multimer thereof, a general amination reaction such as a Buchwald-Hartwig reaction may be used instead of an etherification reaction in the first reaction. Can be manufactured.
  • a general amination reaction such as a Buchwald-Hartwig reaction may be used instead of an etherification reaction in the first reaction. Can be manufactured.
  • the boron-containing polycyclic aromatic compound as the second component is preferably a compound containing any of the following partial structures.
  • at least one hydrogen in the partial structure of the following formula may be substituted with aryl, heteroaryl, alkyl, cycloalkyl, cyano, halogen, or deuterium.
  • a polymer compound obtained by polymerizing the polycyclic aromatic compound of the second component The polycyclic aromatic compound represented by any of the general formulas (2) to (5) is substituted with a reactive substituent.
  • a polymer compound obtained by polymerizing a reactive compound as a monomer, or a crosslinked polymer thereof, or a pendant polymer compound obtained by reacting a main chain polymer with the reactive compound, or a pendant polymer compound thereof It can be used as a light emitting layer material also as a molecular crosslinked product.
  • the reactive substituent in this case the description of the polycyclic aromatic compound represented by the formula (1) can be cited. The details of the use of such a polymer compound and a polymer crosslinked product will be described later.
  • It may be a polymer compound (HD) which is a copolymer having the same.
  • a cross-linked polymer (HD) obtained by further cross-linking the polymer (HD) may be used.
  • the polymer compound (HD) and the crosslinked polymer (HD) have a structure having a first structural unit corresponding to the host and a second structural unit corresponding to the dopant in the same main chain.
  • a pendant polymer compound (HD) in which the reactive compound (H) and the reactive compound (D) are substituted for the main chain polymer may be used, and the pendant polymer compound (HD) is further crosslinked. It may be a pendant type crosslinked polymer (HD).
  • the pendant polymer compound (HD) and the pendant polymer crosslinked product (HD) have a pendant structure in which a side chain corresponding to a host and a dopant is substituted for a main chain.
  • FIG. 1 is a schematic sectional view showing the organic EL device according to the present embodiment.
  • the organic EL element 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, A hole transport layer 104 provided on the injection layer 103; a light emitting layer 105 provided on the hole transport layer 104; an electron transport layer 106 provided on the light emitting layer 105; 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 manufactured by reversing the manufacturing 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, And the anode 102 provided on the hole injection layer 103 may be provided.
  • the minimum constitutional 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, the electron injection layer
  • the layer 107 is an optional layer. Further, each of the above layers may be composed of a single layer or a plurality of layers.
  • the layer constituting the organic EL element in addition to the above-described embodiment of “substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode”, “Substrate / anode / hole transport layer / emission layer / electron transport layer / electron injection layer / cathode”, “substrate / anode / hole injection layer / emission layer / electron transport layer / electron injection layer / cathode”, “substrate / Anode / hole injection layer / hole transport layer / emission layer / electron injection layer / cathode "," substrate / anode / hole injection layer / hole transport layer / emission layer / electron transport layer / cathode "," substrate / Anode / light-emitting layer / electron transport layer / electron injection layer / cathode "," substrate / anode / hole transport layer / emission layer / electron
  • Board substrate 101 in the organic electroluminescent element is a support of the organic EL element 100, typically, quartz, glass, metal, plastic, or the like is used.
  • the substrate 101 is formed in a plate shape, a film shape, or a sheet shape depending on the purpose.
  • a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used.
  • a glass plate and a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable.
  • the thickness only needs to be 0.2 mm or more, as long as it has a thickness sufficient to maintain mechanical strength.
  • the upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less.
  • alkali-free glass is preferable because it is preferable that the amount of ions eluted from the glass is small, but soda lime glass with a barrier coat such as SiO 2 is also commercially available. it can.
  • the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side in order to enhance gas barrier properties.
  • a plate, film, or sheet made of a synthetic resin having low gas barrier properties is used as the substrate 101. 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. Note that when at least one of the hole injection layer 103 and the hole transport layer 104 is provided between the anode 102 and the light-emitting layer 105, holes are injected into the light-emitting layer 105 through these layers. Become.
  • an inorganic compound and an organic compound can be given.
  • the inorganic compound include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide) (IZO), metal halides (eg, copper iodide), copper sulfide, carbon black, ITO glass, Nesa glass, and the like.
  • the organic compound include conductive polymers such as polythiophene such as poly (3-methylthiophene), polypyrrole, and polyaniline. In addition, it can be appropriately selected from the substances used as the anode of the organic EL element.
  • the resistance of the transparent electrode is not limited as long as a current sufficient for light emission of the light emitting element can be supplied, but is preferably low from the viewpoint of power consumption of the light emitting element.
  • an ITO substrate having a resistance of 300 ⁇ / ⁇ or less functions as an element electrode.
  • a substrate of about 10 ⁇ / ⁇ can be supplied at present, for example, 100 to 5 ⁇ / ⁇ , preferably 50 to 5 ⁇ . It is particularly desirable to use a low-resistance product of /.
  • the thickness of ITO can be arbitrarily selected according to the resistance value, but is usually used in a range of 50 to 300 nm.
  • the hole injection layer and the hole transport layer 103 in the organic electroluminescent element serve to inject holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104 efficiently. Fulfill.
  • the hole transport layer 104 plays a role in 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 laminating and mixing one or more of hole injection / transport materials, or by using a mixture of a hole injection / transport material and a polymer binder. It is formed. Further, a layer may be formed by adding an inorganic salt such as iron (III) chloride to the hole injecting / transporting material.
  • a hole injection / transport substance As a hole injection / transport substance, it is necessary to efficiently inject and transport holes from the positive electrode between the electrodes to which an electric field is applied, and the hole injection efficiency is high, and the injected holes are efficiently transported. It is desirable to do. For that purpose, it is preferable that the ionization potential is small, the hole mobility is large, the stability is further improved, and impurities serving as traps are less likely to be generated during production and use.
  • Examples of the material for forming the hole injection layer 103 and the hole transport layer 104 include a compound conventionally used as a hole charge transport material in a photoconductive material, a p-type semiconductor, and a hole injection layer of an organic EL element. Any known compound used in the hole transport layer can be used. Specific examples thereof include a carbazole derivative (N-phenylcarbazole, polyvinylcarbazole, etc.), a biscarbazole derivative such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), and a triarylamine derivative (aromatic tertiary).
  • polycarbonates having the above monomers in the side chain polycarbonates having the above monomers in the side chain, styrene derivatives, polyvinyl carbazole, polysilane, etc. are preferable, but light emission is preferred.
  • the compound is not particularly limited as long as it is a compound capable of forming a thin film necessary for manufacturing an element, injecting holes from the anode, and transporting holes.
  • an organic semiconductor matrix material is composed of a compound having a good electron donating property or a compound having a 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 of electron donors.
  • TCNQ tetracyanoquinonedimethane
  • F4TCNQ 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinonedimethane
  • a matrix material having a hole transporting property for example, a benzidine derivative (such as TPD) or a starburst amine derivative (such as TDATA), or a specific metal phthalocyanine (particularly, zinc phthalocyanine ZnPc or the like) is known (Japanese Unexamined Patent Application, First Publication No. H11-163686). 2005-167175).
  • the above-described material for the hole injection layer and the material for the hole transport layer are a polymer compound obtained by polymerizing a reactive compound in which a reactive substituent is substituted as a monomer, or a cross-linked polymer thereof, or A pendant polymer compound obtained by reacting the main chain polymer with the reactive compound, or a pendant polymer crosslinked product thereof can also be used as a material for the hole layer.
  • a reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited. Details of uses of such a polymer compound and a polymer crosslinked product will be described later.
  • the light emitting layer 105 in the organic electroluminescent element is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied.
  • the material for forming the light-emitting layer 105 may be any compound that emits light when excited by recombination of holes and electrons (light-emitting compound), and can form a stable thin film, and It is preferred that the compound exhibits a strong luminescence (fluorescence) efficiency.
  • 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 each be one kind or a combination of a plurality of kinds.
  • the dopant material may be included in the entire host material, may be partially included, or may be included therein.
  • the light emitting layer included in the organic electroluminescent device of the present invention includes, as a first component, a polycyclic aromatic compound represented by the formula (1) as a host material, and as a second component, a polycyclic aromatic compound containing boron. An aromatic compound is included as a dopant material.
  • the amount of host material used depends on the type of host material, and may be determined according to the characteristics of the host material.
  • the standard of the usage amount of the host material is preferably 50 to 99.999% by weight, more preferably 70 to 99.9% by weight, and still more preferably 80 to 99.9% by weight of the whole light emitting layer material. And particularly preferably 90 to 99.9% by weight.
  • the amount of the dopant material used depends on the type of the dopant material, and may be determined according to the characteristics of the dopant material.
  • the standard of the amount of the dopant to be used is preferably 0.001 to 50% by weight, more preferably 0.1 to 30% by weight, even more preferably 0.1 to 20% by weight of the whole light emitting layer material. And particularly preferably 0.1 to 10% by weight.
  • the above range is preferable, for example, in that the density quenching phenomenon can be prevented.
  • the amount of the dopant is large.
  • the concentration of the dopant is determined not only by the host and the dopant of the light-emitting layer but also by the element configuration because the layer is affected by layers other than the light-emitting layer.
  • Examples of the host material that can be used in combination with the compound represented by the formula (1) include condensed ring derivatives such as anthracene and pyrene, and bisstyryl such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, which have been known as luminescent materials. Derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, benzofluorene derivatives and the like.
  • the dopant material that can be used in combination with the boron-containing polycyclic aromatic compound is not particularly limited, a known compound can be used, and is selected from various materials according to a desired emission color. can do.
  • condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene and chrysene
  • 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,
  • blue-blue-green dopant materials include aromatic hydrocarbon compounds such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, chrysene and derivatives thereof, furan, pyrrole, thiophene, Aromatic complex such as silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene Ring compounds and derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imi
  • Aromatic complex such as silo
  • green to yellow dopant materials examples include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, and naphthacene derivatives such as rubrene.
  • Preferable examples include compounds obtained by introducing a substituent capable of increasing the wavelength, such as aryl, heteroaryl, arylvinyl, amino, and cyano, to the compounds exemplified as the blue-green dopant material.
  • naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic imide, perinone derivatives, rare earth complexes such as Eu complexes having acetylacetone, benzoylacetone and phenanthroline as ligands, and the like.
  • 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, biolanthrone derivatives, phenazine derivatives, phenoxazo Derivatives and thiadiazolopyrene derivatives.
  • 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, biolanthrone derivatives, phenazine derivatives,
  • the compounds exemplified as the blue-cyan-green and green-yellow dopant materials described above may be further substituted with a substituent capable of increasing the wavelength, such as aryl, heteroaryl, arylvinyl, amino, and cyano.
  • a substituent capable of increasing the wavelength such as aryl, heteroaryl, arylvinyl, amino, and cyano.
  • the introduced compound is also a preferred example.
  • the dopant can be appropriately selected and used from the compounds described in Chemical Industry, June 2004, p. 13 and the references cited therein.
  • the amine having a stilbene structure is represented, for example, by the following formula.
  • Ar 1 is an m-valent group represented by removing any m-1 hydrogen atoms from aryl having 6 to 30 carbon atoms, and Ar 2 and Ar 3 are each independently a carbon atom.
  • Ar 1 ⁇ Ar 3 has a stilbene structure may Ar 1 ⁇ Ar 3 is substituted, and, m is an integer of 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 an aryl having 6 to 30 carbon atoms, and Ar 2 and Ar 3 may be substituted.
  • aryl having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, stilbene, distyrylbenzene, distyrylbiphenyl, and distyryl. Fluorene and the like.
  • amine having a stilbene structure examples 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) sty
  • perylene derivatives examples include 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, JP-A-2001-217077 and the like may be used.
  • borane derivative examples include 1,8-diphenyl-10- (dimesitylboryl) anthracene, 9-phenyl-10- (dimesitylboryl) anthracene, 4- (9′-anthryl) dimesitylborylnaphthalene, and 4- (10 ′) -Phenyl-9'-anthryl) dimesitylborylnaphthalene, 9- (dimesitylboryl) anthracene, 9- (4'-biphenylyl) -10- (dimesitylboryl) anthracene, 9- (4 '-(N-carbazolyl) phenyl) And -10- (dimesitylboryl) anthracene.
  • a borane derivative described in WO 2000/40586 pamphlet or the like may be used.
  • the aromatic amine derivative is represented, for example, by the following formula.
  • Ar 4 is an n-valent group represented by removing any n-1 hydrogen atoms from aryl having 6 to 30 carbon atoms
  • Ar 5 and Ar 6 are each independently a carbon atom having 6 to 30 carbon atoms. 6 to 30 aryl, Ar 4 to Ar 6 may be substituted, and n is an integer of 1 to 4.
  • Ar 4 is a divalent group represented by removing any two hydrogen atoms from anthracene, chrysene, fluorene, benzofluorene or pyrene, and Ar 5 and Ar 6 each independently have 6 to 30 carbon atoms.
  • aryl having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorenephenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, pentacene, and the like.
  • aromatic amine derivative examples include, for example, 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'-di (p-tolyl ) Chrys
  • pyrene-based compounds include, for example, N, N, N ', N'-tetraphenylpyrene-1,6-diamine, N, N, N', N'-tetra (p-tolyl) pyrene-1,6.
  • anthracene-based compounds include N, N, N, N-tetraphenylanthracene-9,10-diamine, 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
  • Coumarin derivatives include coumarin-6 and coumarin-334. Further, coumarin derivatives described in JP-A-2004-43646, JP-A-2001-76876, and JP-A-6-298758 may be used.
  • Examples of the pyran derivative include DCM and DCJTB described below. Also, JP 2005-126399, JP 2005-097283, JP 2002-234892, JP 2001-220577, JP 2001-081090, and JP 2001-052869 And the like.
  • the above-mentioned materials for the light emitting layer are a polymer compound obtained by polymerizing a reactive compound in which these are substituted with a reactive substituent as a monomer, or a polymer crosslinked product thereof, or a main chain.
  • Pendant polymer compound obtained by reacting a reactive polymer with the reactive polymer, or a pendant polymer crosslinked product thereof can also be used as a material for the light emitting layer.
  • the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited. Details of uses of such a polymer compound and a polymer crosslinked product will be described later.
  • the electron injection layer and the electron transport layer 107 in the organic electroluminescent element play a role to efficiently inject 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 in 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 transporting layer 106 and the electron injecting layer 107 are each formed by laminating and mixing one or more of the electron transporting / injecting materials or a mixture of the electron transporting / injecting material and the polymer binder.
  • the electron injection / transport layer is a layer that controls the injection of electrons from the cathode and the transport of electrons. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently.
  • the substance be a substance having a high electron affinity, a high electron mobility, excellent stability, and hardly generating impurities serving as traps during production and use.
  • the electron transport capability is not so high. Even if it is not high, the effect of improving the luminous efficiency is equivalent to a material having a high electron transporting ability. Therefore, the electron injecting / transporting layer in the present embodiment may include a function of a layer that can efficiently block the movement of holes.
  • a material (electron transporting material) for forming the electron transporting layer 106 or the electron injecting layer 107 a compound conventionally used as an electron transporting compound in a photoconductive material, and used for an electron injecting layer and an electron transporting layer of an organic EL device. Any of the known compounds can be used.
  • the material used for the electron transporting layer or the electron injecting layer carbon, hydrogen, oxygen, sulfur, a compound comprising an aromatic ring or a heteroaromatic ring composed of one or more atoms selected from silicon and phosphorus, It is preferable to contain at least one selected from a pyrrole derivative, a fused ring derivative thereof, and a metal complex having an electron-accepting nitrogen.
  • condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4'-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, and naphthalimide derivatives
  • quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives and indole derivatives.
  • the metal complex having an electron accepting nitrogen include a hydroxyazole complex such as a hydroxyphenyloxazole complex, an azomethine complex, a tropolone metal complex, a flavonol metal complex, and a benzoquinoline metal complex. These materials may be used alone or in combination with different materials.
  • electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, and oxadiazole.
  • Derivatives such as 1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene), thiophene derivatives, and triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4- Triazole), metal complexes of thiadiazole derivatives, oxine derivatives, quinolinol-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazoles, gallium complexes, pyrazole derivatives, perfluorinated Nylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (such as 2,2'-bis (benzo [h] quinolin-2-yl) -9,9'-spirobifluorene), imidazopyridine derivatives, borane derivatives, benzones Imidazole derivatives (such as tris (N-phenylbenzimidazol
  • a metal complex having an electron-accepting nitrogen can also be used.
  • a metal complex having an electron-accepting nitrogen examples thereof include a hydroxyazole complex such as a quinolinol-based metal complex and a hydroxyphenyloxazole complex, an azomethine complex, a tropolone metal complex, a flavonol metal complex, and a benzoquinoline metal complex.
  • the above-mentioned materials may be used alone, but may be used in combination with different materials.
  • borane derivatives pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol-based metals Complexes are preferred.
  • the borane derivative is, for example, a compound represented by the following general formula (ETM-1), and is disclosed in detail in JP-A-2007-27587.
  • R 11 and R 12 are each independently hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, Or at least one of cyano
  • R 13 to R 16 are each independently an optionally substituted alkyl or an optionally substituted aryl
  • X is an optionally substituted arylene
  • Y is an optionally substituted aryl having 16 or less carbon atoms, a substituted boryl, or an optionally substituted carbazolyl
  • n is each independently an integer of 0-3. is there.
  • substituent when “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl and cycloalkyl.
  • R 11 and R 12 are each independently hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle.
  • R 13 to R 16 are each independently an optionally substituted alkyl or an optionally substituted aryl
  • R 21 and R 22 are each independently And is at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano
  • X 1 is optionally substituted
  • n is each independently an integer of 0 to 3
  • m is each independently an integer of 0 to 4.
  • substituent when “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl and cycloalkyl.
  • R 11 and R 12 are each independently hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle. Or at least one of cyano, and R 13 to R 16 are each independently an optionally substituted alkyl or an optionally substituted aryl, and X 1 is optionally substituted It is a good arylene having 20 or less carbon atoms, and n is each independently an integer of 0 to 3.
  • substituent when “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl and cycloalkyl.
  • X 1 include divalent groups represented by any of the following formulas (X-1) to (X-9).
  • Ra is each independently an alkyl group or an optionally substituted phenyl group.
  • borane derivative examples include the following.
  • This borane derivative can be produced using a known raw material and a known synthesis method.
  • 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 an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. is there.
  • 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) Alkyl) 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) Alkyl) 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 of the following formulas (Py-1) to (Py-15), and the pyridine-based substituents are each independently substituted with alkyl having 1 to 4 carbon atoms. It may be. Further, the pyridine-based substituent may be bonded to ⁇ , an anthracene ring or a fluorene ring in each formula via a phenylene group or a naphthylene group.
  • the pyridine-based substituent is any of the above formulas (Py-1) to (Py-15), and among them, any of the following formulas (Py-21) to (Py-44) Is preferred.
  • At least one hydrogen in each pyridine derivative may be substituted with deuterium, and among the two “pyridine-based substituents” in the above formula (ETM-2-1) and formula (ETM-2-2) May be replaced by an aryl.
  • the “alkyl” for R 11 to R 18 may be linear or branched, and includes, for example, linear alkyl having 1 to 24 carbons or branched alkyl having 3 to 24 carbons.
  • Preferred “alkyl” is alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons). More preferred “alkyl” is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More preferred “alkyl” is alkyl having 1 to 6 carbons (branched alkyl having 3 to 6 carbons). Particularly preferred “alkyl” is alkyl having 1 to 4 carbons (branched alkyl having 3 to 4 carbons).
  • alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, -Propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyl,
  • alkyl having 1 to 4 carbon atoms to be substituted with the pyridine-based substituent the description of the above alkyl can be cited.
  • Cycloalkyl for R 11 to R 18 includes, for example, cycloalkyl having 3 to 12 carbon atoms.
  • Preferred “cycloalkyl” is 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 includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.
  • preferred aryl is aryl having 6 to 30 carbon atoms, more preferred aryl is aryl having 6 to 18 carbon atoms, and still more preferred is aryl having 6 to 14 carbon atoms. And particularly preferably an aryl having 6 to 12 carbon atoms.
  • aryl having 6 to 30 carbon atoms include phenyl which is a monocyclic aryl, (1-, 2-) naphthyl which is a fused bicyclic aryl, and acenaphthylene- (which is a fused tricyclic aryl.
  • Preferred “aryl having 6 to 30 carbon atoms” include phenyl, naphthyl, phenanthryl, chrysenyl or triphenylenyl, more preferably phenyl, 1-naphthyl, 2-naphthyl or phenanthryl, and particularly preferably phenyl, -Naphthyl or 2-naphthyl.
  • R 11 and R 12 in the above formula (ETM-2-2) may combine to form a ring, and as a result, the 5-membered ring of the fluorene skeleton has cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, Cyclohexane, fluorene or indene may be spiro-bonded.
  • pyridine derivative examples include, for example, the following.
  • This pyridine derivative can be produced using a known raw material and a known synthesis method.
  • the fluoranthene derivative is, for example, a compound represented by the following general formula (ETM-3), and is disclosed in detail in WO 2010/134352.
  • X 12 to X 21 represent hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted Represents heteroaryl.
  • the substituent when substituted, includes aryl, heteroaryl, alkyl, cycloalkyl and the like.
  • fluoranthene derivative examples include the following.
  • the BO derivative is, for example, a polycyclic aromatic compound represented by the following formula (ETM-4) or a polymer 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 is May be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
  • adjacent groups among R 1 to R 11 may be bonded to each other to form an aryl ring or a 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, wherein 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 the formula (ETM-4) may be substituted with halogen or deuterium.
  • BO derivative include the following.
  • This BO derivative can be produced using a known raw material and a known synthesis method.
  • One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-1).
  • Ar is each independently divalent benzene or naphthalene;
  • R 1 to R 4 are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons or carbon 6-20 aryls.
  • Ar can be independently selected from divalent benzene or naphthalene as appropriate, and the two Ars may be different or the same, but are the same from the viewpoint of ease of synthesis of the anthracene derivative. It is preferred that Ar is bonded to pyridine to form a “site consisting of Ar and pyridine”, and this site is an anthracene as a group represented by any of the following formulas (Py-1) to (Py-12). Is bound to.
  • a group represented by any of the above formulas (Py-1) to (Py-9) is preferable, and a group represented by any of the above formulas (Py-1) to (Py-6) is preferable.
  • the two “sites composed of Ar and pyridine” bonded to anthracene may have the same or different structures, but preferably have the same structure from the viewpoint of easy synthesis of an anthracene derivative. However, from the viewpoint of device characteristics, it is preferable that the two “sites composed of Ar and pyridine” have the same or different structures.
  • the alkyl having 1 to 6 carbon atoms in R 1 to R 4 may be linear or branched. That is, it is a straight-chain alkyl having 1 to 6 carbons or a branched alkyl having 3 to 6 carbons. More preferably, it is an alkyl having 1 to 4 carbons (a branched alkyl having 3 to 4 carbons).
  • Specific examples 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, or 2-ethylbutyl; and the like, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl , Methyl, ethyl, or t-butyl are more preferred.
  • cycloalkyl having 3 to 6 carbon atoms for R 1 to R 4 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.
  • the aryl having 6 to 20 carbon atoms in R 1 to R 4 is preferably an aryl having 6 to 16 carbon atoms, more preferably an aryl having 6 to 12 carbon atoms, and particularly preferably an aryl having 6 to 10 carbon atoms.
  • aryl having 6 to 20 carbon atoms include phenyl which is a monocyclic aryl, (o-, m-, p-) tolyl, (2,3-, 2,4-, 2,5- , 2,6-, 3,4-, 3,5-) xylyl, mesityl (2,4,6-trimethylphenyl), (o-, m-, p-) cumenyl and 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,
  • Preferred "aryl having 6 to 20 carbon atoms" is phenyl, biphenylyl, terphenylyl or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2-naphthyl or m-terphenyl-5'-yl, More preferably, it is phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, most preferably phenyl.
  • One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-2).
  • Ar 1 is each independently a single bond, divalent benzene, naphthalene, anthracene, fluorene, or phenalene.
  • Ar 2 is independently aryl having 6 to 20 carbon atoms, and the same description as “aryl having 6 to 20 carbon atoms” in the above formula (ETM-5-1) can be referred to.
  • An aryl having 6 to 16 carbon atoms is preferable, an aryl having 6 to 12 carbon atoms is more preferable, and an aryl having 6 to 10 carbon atoms is particularly preferable.
  • phenyl examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl and the like.
  • R 1 to R 4 are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons or aryl having 6 to 20 carbons, and the above formula (ETM-5-1) Can be cited.
  • anthracene derivatives include, for example, the following.
  • anthracene derivatives can be produced using known raw materials and known synthesis methods.
  • the benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6).
  • Ar 1 is independently aryl having 6 to 20 carbon atoms, and the same description as “aryl having 6 to 20 carbon atoms” in the above formula (ETM-5-1) can be cited.
  • An aryl having 6 to 16 carbon atoms is preferable, an aryl having 6 to 12 carbon atoms is more preferable, and an aryl having 6 to 10 carbon atoms is particularly preferable.
  • phenyl examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl and the like.
  • Ar 2 is each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbons), cycloalkyl (preferably cycloalkyl having 3 to 12 carbons) or aryl (preferably aryl having 6 to 30 carbons) ), And the two Ar 2 may combine to form a ring.
  • the “alkyl” in Ar 2 may be either linear or branched, and includes, for example, linear alkyl having 1 to 24 carbons or branched alkyl having 3 to 24 carbons.
  • Preferred “alkyl” is alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons). More preferred “alkyl” is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More preferred “alkyl” is alkyl having 1 to 6 carbons (branched alkyl having 3 to 6 carbons). Particularly preferred “alkyl” is alkyl having 1 to 4 carbons (branched alkyl having 3 to 4 carbons).
  • alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like.
  • the “cycloalkyl” in Ar 2 includes, for example, cycloalkyl having 3 to 12 carbon atoms.
  • Preferred “cycloalkyl” is 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.
  • Specific “cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.
  • a preferred aryl is an aryl having 6 to 30 carbon atoms, a more preferred aryl is an aryl having 6 to 18 carbon atoms, and further preferably an aryl having 6 to 14 carbon atoms. Preferably, it is an aryl having 6 to 12 carbon atoms.
  • aryl having 6 to 30 carbon atoms includes phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, naphthacenyl, perylenyl, pentacenyl and the like.
  • Two Ar 2 may form a ring, as a result, the 5-membered ring of the fluorene skeleton, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene or indene are spiro-linked You may.
  • benzofluorene derivative examples include, for example, the following.
  • This benzofluorene derivative can be produced using a known raw material and a known synthesis method.
  • the phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1). The details are also described in WO2013 / 079217.
  • R 5 is a substituted or unsubstituted alkyl having 1 to 20 carbons, an aryl having 6 to 20 carbons or a heteroaryl having 5 to 20 carbons
  • R 6 is CN, substituted or unsubstituted alkyl having 1 to 20 carbons, heteroalkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, heteroaryl having 5 to 20 carbons, 1 to carbons 20 alkoxy or aryloxy having 6 to 20 carbon atoms
  • R 7 and R 8 are each independently a substituted or unsubstituted aryl having 6 to 20 carbons or a heteroaryl having 5 to 20 carbons
  • R 9 is oxygen or sulfur
  • j is 0 or 1
  • k is 0 or 1
  • r is an integer of 0 to 4
  • q is
  • the 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 include hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an arylether group, and an arylthioether group.
  • Ar 1 may be the same or different and is an arylene group or a heteroarylene group.
  • Ar 2 may be the same or different and is an aryl group or a heteroaryl group. 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. When n is 0, there is no unsaturated structure part, and when n is 3, R 1 does not exist.
  • the alkyl group means a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, and a butyl group, which may be unsubstituted or substituted.
  • the substituent is not particularly limited, and examples thereof include an alkyl group, an aryl group, and a heterocyclic group. This point is also common to the following description.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is usually in the range of 1 to 20 from the viewpoint of availability and cost.
  • cycloalkyl group refers to, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, and adamantyl, which may be unsubstituted or substituted.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is usually in the range of 3 to 20.
  • the aralkyl group refers to, for example, an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group and a phenylethyl group, and both the aliphatic hydrocarbon and the aromatic hydrocarbon are unsubstituted or substituted. It doesn't matter.
  • the carbon number of the aliphatic moiety is not particularly limited, but is usually in the range of 1 to 20.
  • Alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group and a butadienyl group, which may be unsubstituted or substituted.
  • the number of carbon atoms in the alkenyl group is not particularly limited, but is usually in the range of 2 to 20.
  • the cycloalkenyl group refers to, for example, an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, and a cyclohexene group, which may be unsubstituted or substituted. I don't care.
  • Alkynyl group means, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an acetylenyl group, which may be unsubstituted or substituted.
  • the number of carbon atoms in the alkynyl group is not particularly limited, but is usually in the range of 2 to 20.
  • Alkoxy group means, for example, an aliphatic hydrocarbon group via an ether bond such as a methoxy group, and the aliphatic hydrocarbon group may be unsubstituted or substituted.
  • the carbon number of the alkoxy group is not particularly limited, it is usually in the range of 1 to 20.
  • Alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted by a sulfur atom.
  • the aryl ether group refers to, for example, an aromatic hydrocarbon group via an ether bond such as a phenoxy group, and the aromatic hydrocarbon group may be unsubstituted or substituted.
  • the number of carbon atoms in the aryl ether group is not particularly limited, but is usually in the range of 6 to 40.
  • the arylthioether group is a group in which an oxygen atom of an ether bond of the arylether group is substituted with a sulfur atom.
  • the aryl group means, for example, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a terphenyl group, and a pyrenyl group.
  • the aryl group may be unsubstituted or substituted.
  • the carbon number of the aryl group is not particularly limited, but is usually in the range of 6 to 40.
  • heterocyclic group refers to, for example, a cyclic structure group having an atom other than carbon, such as a furanyl group, a thiophenyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group. It doesn't matter.
  • the carbon number of the heterocyclic group is not particularly limited, but is usually in the range of 2 to 30.
  • Halogen refers to fluorine, chlorine, bromine and iodine.
  • the aldehyde group, carbonyl group, and amino group may also include groups substituted with an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic ring, and the like.
  • aliphatic hydrocarbons aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocycles may be unsubstituted or substituted.
  • silyl group means a silicon compound group such as a trimethylsilyl group, which may be unsubstituted or substituted.
  • carbon number of the silyl group is not particularly limited, it is usually in the range of 3 to 20. Further, the number of silicon is usually 1 to 6.
  • the condensed ring formed between adjacent substituents is, 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 It is a conjugated or non-conjugated fused ring formed between Ar 2 and the like.
  • n when n is 1, may be formed conjugated or non-conjugated fused ring with two of R 1 each other.
  • These condensed rings may contain nitrogen, oxygen and sulfur atoms in the ring structure, or may be condensed with another ring.
  • phosphine oxide derivative examples include the following.
  • This phosphine oxide derivative can be produced using a known raw material and a known synthesis method.
  • the pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), and preferably a compound represented by the following formula (ETM-8-1). The details are also described in WO 2011/021689.
  • Ar is each independently an optionally substituted aryl or an optionally substituted heteroaryl.
  • n is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2 or 3.
  • aryl of the “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, More preferably, it is an aryl having 6 to 12 carbon atoms.
  • aryl include phenyl which is a monocyclic aryl, (2-, 3-, 4-) biphenylyl which is a bicyclic aryl, and (1-, 2-) naphthyl which is a fused bicyclic aryl Terphenylyl which is a tricyclic aryl (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-2-
  • heteroaryl of the “optionally substituted heteroaryl” includes, for example, a heteroaryl having 2 to 30 carbon atoms, preferably a heteroaryl having 2 to 25 carbon atoms, and a heteroaryl having 2 to 20 carbon atoms.
  • Aryl is more preferred, heteroaryl having 2 to 15 carbon atoms is still more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred.
  • the heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.
  • heteroaryl examples include, for example, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, prinyl, pteridinyl, carbazolyl, acridinyl, phen
  • At least one hydrogen in the above aryl and heteroaryl may be substituted, for example, each may be substituted with the above aryl and heteroaryl.
  • pyrimidine derivative examples include, for example, the following.
  • This pyrimidine derivative can be produced using a known raw material and a known synthesis method.
  • the carbazole derivative is, for example, a compound represented by the following formula (ETM-9) or a multimer in which a plurality of the carbazole derivatives are bonded by a single bond or the like. The details are described in U.S. Publication No. 2014/0197386.
  • Ar is each independently an optionally substituted aryl or an optionally substituted heteroaryl.
  • n is independently an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably 0 or 1.
  • aryl of the “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, More preferably, it is an aryl having 6 to 12 carbon atoms.
  • aryl include phenyl which is a monocyclic aryl, (2-, 3-, 4-) biphenylyl which is a bicyclic aryl, and (1-, 2-) naphthyl which is a fused bicyclic aryl Terphenylyl which is a tricyclic aryl (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-2-
  • heteroaryl of the “optionally substituted heteroaryl” includes, for example, a heteroaryl having 2 to 30 carbon atoms, preferably a heteroaryl having 2 to 25 carbon atoms, and a heteroaryl having 2 to 20 carbon atoms.
  • Aryl is more preferred, heteroaryl having 2 to 15 carbon atoms is still more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred.
  • the heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.
  • heteroaryl examples include, for example, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, prinyl, pteridinyl, carbazolyl, acridinyl, phen
  • At least one hydrogen in the above aryl and heteroaryl may be substituted, for example, each may be substituted with the above aryl and heteroaryl.
  • the carbazole derivative may be a multimer in which a plurality of compounds represented by the above formula (ETM-9) are bonded by a single bond or the like.
  • ETM-9 a plurality of compounds represented by the above formula
  • 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).
  • carbazole derivative examples include, for example, the following.
  • This carbazole derivative can be produced using a known raw material and a known synthesis method.
  • the triazine derivative is, for example, a compound represented by the following formula (ETM-10), and preferably a compound represented by the following formula (ETM-10-1). Details are described in U.S. Publication No. 2011/0156013.
  • Ar is each independently an optionally substituted aryl or an optionally substituted heteroaryl.
  • n is an integer of 1 to 3, and is preferably 2 or 3.
  • aryl of the “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, More preferably, it is an aryl having 6 to 12 carbon atoms.
  • aryl include phenyl which is a monocyclic aryl, (2-, 3-, 4-) biphenylyl which is a bicyclic aryl, and (1-, 2-) naphthyl which is a fused bicyclic aryl Terphenylyl which is a tricyclic aryl (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-2-
  • heteroaryl of the “optionally substituted heteroaryl” includes, for example, a heteroaryl having 2 to 30 carbon atoms, preferably a heteroaryl having 2 to 25 carbon atoms, and a heteroaryl having 2 to 20 carbon atoms.
  • Aryl is more preferred, heteroaryl having 2 to 15 carbon atoms is still more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred.
  • the heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.
  • heteroaryl examples include, for example, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, prinyl, pteridinyl, carbazolyl, acridinyl, phen
  • At least one hydrogen in the above aryl and heteroaryl may be substituted, for example, each may be substituted with the above aryl and heteroaryl.
  • triazine derivative examples include, for example, the following.
  • This triazine derivative can be produced using a known raw material and a known synthesis method.
  • the benzimidazole derivative is, for example, a compound represented by the following formula (ETM-11).
  • ⁇ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4.
  • the “benzimidazole-based substituent” means that the pyridyl group in the “pyridine-based substituent” in the above formulas (ETM-2), (ETM-2-1) and (ETM-2-2) is benzo. It is a group replaced by an imidazole group, and at least one hydrogen in the benzimidazole derivative may be substituted with deuterium.
  • R 11 in the benzimidazole group is hydrogen, alkyl having 1 to 24 carbons, cycloalkyl having 3 to 12 carbons or aryl having 6 to 30 carbons, and is represented by the above formula (ETM-2-1) or ( It may be cited to the description of R 11 in ETM-2-2).
  • ⁇ is more preferably an anthracene ring or a fluorene ring, and in this case, the structure of the above formula (ETM-2-1) or the formula (ETM-2-2) can be referred to.
  • R 11 to R 18 therein the description of the above formula (ETM-2-1) or (ETM-2-2) can be cited.
  • two pyridine-based substituents are described as being bonded. However, when these are replaced with benzimidazole-based substituents, both are substituted.
  • benzimidazole derivative examples include, for example, 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 (naphthalen-2
  • This benzimidazole derivative can be produced using a known raw material and a known synthesis method.
  • the phenanthroline derivative is, for example, a compound represented by the following formula (ETM-12) or (ETM-12-1). Details are described in WO 2006/021982.
  • ⁇ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. is there.
  • R 11 to R 18 in each formula are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbons), cycloalkyl (preferably cycloalkyl having 3 to 12 carbons) or aryl (preferably carbon Aryl of formulas 6 to 30).
  • alkyl preferably alkyl having 1 to 24 carbons
  • cycloalkyl preferably cycloalkyl having 3 to 12 carbons
  • aryl preferably carbon Aryl of formulas 6 to 30.
  • each phenanthroline derivative may be replaced with deuterium.
  • Alkyl in R 11 ⁇ R 18, cycloalkyl and aryl may be cited to the description of R 11 ⁇ R 18 in the formula (ETM-2).
  • ⁇ is, for example, the following structural formula in addition to the above-mentioned structure.
  • R in the following structural formulas is each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl.
  • phenanthroline derivative examples include, for example, 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di (1,10- Phenanthroline-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 and the like.
  • This phenanthroline derivative can be produced using a known raw material and a known synthesis method.
  • the quinolinol-based metal complex is, for example, a compound represented by the following general formula (ETM-13).
  • R 1 to R 6 are each independently hydrogen, fluorine, alkyl, aralkyl, alkenyl, cyano, alkoxy or aryl
  • M is Li, Al, Ga, Be or Zn
  • n is 1 It is an integer of 33.
  • quinolinol-based metal complexes include 8-quinolinol lithium, tris (8-quinolinolate) aluminum, tris (4-methyl-8-quinolinolate) aluminum, tris (5-methyl-8-quinolinolate) aluminum, tris (3 , 4-Dimethyl-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, tris (4,6-dimethyl-8-quinolinolate) aluminum, bis (2-methyl-8-quinolinolate) ( Phenolate) aluminum, bis (2-methyl-8-quinolinolate) (2-methylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-methylphenolate) aluminum, bis (2-methyl-8- Quinolinolate) (4- Butylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-phenylphenolate) aluminum, bis (2-methyl- 8-quinol lithium
  • This quinolinol-based metal complex can be produced using a known raw material and a known synthesis method.
  • the thiazole derivative is, for example, a compound represented by the following formula (ETM-14-1).
  • the 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 an 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
  • the “thiazole-based substituent” and “benzothiazole-based substituent” The pyridyl group in the “substituent” is a group in which a thiazole group or a benzothiazole group is substituted, and at least one hydrogen in the thiazole derivative and the benzothiazole derivative may be substituted with deuterium.
  • ⁇ is more preferably an anthracene ring or a fluorene ring, and in this case, the structure of the above formula (ETM-2-1) or the formula (ETM-2-2) can be referred to.
  • R 11 to R 18 therein the description of the above formula (ETM-2-1) or (ETM-2-2) can be cited.
  • two pyridine-based substituents are described as being bonded, but these are replaced with thiazole-based substituents (or benzothiazole-based substituents).
  • thiazole derivatives or benzothiazole derivatives can be produced using known raw materials and known synthesis methods.
  • the electron transport layer or the electron injection layer may further contain a substance capable of reducing a material forming the electron transport layer or the electron injection layer.
  • a substance capable of reducing a material forming the electron transport layer or the electron injection layer various substances are used as long as the substance has a certain reducing property, for example, an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, and an alkali metal.
  • 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 suitably used.
  • Preferred reducing substances include alkali metals such as Na (2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2. eV).
  • Alkaline earth metals such as 9 eV), Sr (2.0 to 2.5 eV) and Ba (2.52 eV), and a substance having a work function of 2.9 eV or less is particularly preferable.
  • a more preferable reducing substance is an alkali metal of K, Rb or Cs, further preferably Rb or Cs, and most preferably Cs.
  • alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transporting layer or the electron injecting layer, the emission luminance and the life of the organic EL device can be improved.
  • a reducing substance having a work function of 2.9 eV or less a combination of these two or more kinds of alkali metals is also preferable.
  • a combination containing Cs for example, Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred.
  • Cs for example, Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred.
  • the material for the electron injecting layer and the material for the electron transporting layer described above may be a polymer compound obtained by polymerizing a reactive compound substituted with a reactive substituent as a monomer, or a polymer crosslinked body thereof, or A pendant polymer compound obtained by reacting a chain polymer with the reactive compound, or a pendant polymer crosslinked product thereof can also be used as a material for an electronic layer.
  • a reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited. Details of uses of such a polymer compound and a polymer crosslinked product will be described later.
  • the cathode 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.
  • the material for forming the cathode 108 is not particularly limited as long as it is a substance capable of efficiently injecting 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 alloys thereof (magnesium-silver alloy, magnesium) -An indium alloy, an aluminum-lithium alloy such as lithium fluoride / aluminum, etc.).
  • lithium, sodium, potassium, cesium, calcium, magnesium or an alloy containing these low work function metals is effective.
  • metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic substances such as silica, titania and silicon nitride, polyvinyl alcohol, and vinyl chloride It is preferable to laminate a hydrocarbon polymer compound and the like.
  • the method for producing these electrodes is not particularly limited as long as conduction can be achieved by resistance heating, electron beam, sputtering, ion plating and coating.
  • the materials used for the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer that are higher than the binder that may be used in each layer can be used alone to form each layer.
  • 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 quartz oscillation type film thickness measuring device or the like.
  • the evaporation conditions vary depending on the type of material, the target crystal structure, association structure, and the like of the film.
  • the deposition conditions are as follows: boat heating temperature +50 to + 400 ° C., degree of vacuum 10 ⁇ 6 to 10 ⁇ 3 Pa, 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 anode When a DC voltage is applied to the organic EL device thus obtained, the anode may be applied with a positive polarity and the cathode may be applied with a negative polarity. When a voltage of about 2 to 40 V is applied, a transparent or translucent electrode is applied. Light emission can be observed from the side (anode or cathode, and both).
  • the organic EL element also emits light when a pulse current or an alternating current is applied.
  • the waveform of the applied alternating current may be arbitrary.
  • an organic EL element including an anode / a hole injection layer / a hole transport layer / a light emitting layer composed of a host material and a dopant material / an electron transport layer / an electron injection layer / a cathode The method of manufacturing will be described.
  • a thin film of an anode material is formed on a suitable substrate by an evaporation method or the like to produce 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-evaporated thereon to form a thin film to form a light emitting layer, an electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by a vapor deposition method or the like.
  • a target organic EL device is obtained by forming the cathode.
  • the production order can be reversed, and 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 can be produced in this order. It is.
  • the wet film formation method is carried out by preparing a low molecular weight compound capable of forming each organic layer of an organic EL device as a liquid composition for forming an organic layer, and using this.
  • the low-molecular compound is highly reactive with another monomer or a main-chain type polymer having a solubility function as a reactive compound in which a reactive substituent is substituted.
  • the composition for forming an organic layer may be prepared from a polymerized polymer compound or the like.
  • a coating film is formed through a coating step of applying a composition for forming an organic layer to a substrate and a drying step of removing a solvent from the applied composition for forming an organic layer.
  • the polymer compound has a crosslinkable substituent (this is also referred to as a crosslinkable polymer compound)
  • the polymer is further crosslinked by this drying step to form a crosslinked polymer.
  • the method using a spin coater is a spin coating method
  • the method using a slit coater is a slit coating method
  • the method using a plate is a gravure, offset, reverse offset, flexographic printing method
  • a method using an inkjet printer is an inkjet method.
  • the method of spraying in a mist state is called a spray method.
  • the drying step includes methods such as air drying, heating, and vacuum drying. The drying step may be performed only once, or may be performed a plurality of times using different methods and conditions. Further, for example, different methods such as firing under reduced pressure may be used in combination.
  • the wet film forming method is a film forming method using a solution, and for example, a partial printing method (ink jet method), a spin coating method or a casting method, a coating method, and the like.
  • the wet film formation method does not require an expensive vacuum deposition apparatus unlike the vacuum deposition method, and can form a film under atmospheric pressure.
  • the wet film forming method enables a large area and continuous production, which leads to a reduction in manufacturing cost.
  • the wet film formation method may be difficult to laminate.
  • a multilayer film is formed by a wet film formation method, it is necessary to prevent the dissolution of the lower layer by the composition of the upper layer, a composition having controlled solubility, crosslinking of the lower layer, and an orthogonal solvent (orthogonal solvent, which dissolve each other). No solvent).
  • a method is adopted in which only some of the layers are formed by a wet film forming method, and the remaining layers are formed by a vacuum evaporation method to form an organic EL device.
  • LITI laser heating drawing method
  • an appropriate treatment step, washing step and drying step may be appropriately inserted.
  • the treatment process include an exposure treatment, a plasma surface treatment, an ultrasonic treatment, an ozone treatment, a cleaning treatment using an appropriate solvent, a heat treatment, and the like.
  • a series of steps for manufacturing a bank is also included.
  • Photolithography technology can be used for manufacturing the bank.
  • a bank material that can be used for photolithography any of an inorganic material and an organic material can be used.
  • the inorganic material include SiN x , SiO x and a mixture thereof.
  • examples of the organic material include a positive resist material and a negative resist material.
  • a patternable printing method such as an inkjet method, gravure offset printing, reverse offset printing, and screen printing can also be used. In that case, a permanent resist material can be used.
  • Materials used for the bank include polysaccharides and derivatives thereof, homopolymers and copolymers of ethylenic monomers having hydroxyls, biopolymer compounds, polyacryloyl compounds, polyesters, polystyrene, polyimide, polyamideimide, and polyetherimide.
  • a material exhibiting liquid repellency to the composition for forming an organic layer is applied to the element substrate on which the electrodes are formed, and dried to form an organic layer.
  • a bank can be formed on the element substrate on which the electrodes are formed.
  • a process such as a washing / drying process with a solvent or an ultraviolet treatment may be performed to remove impurities on the surface of the bank.
  • an organic EL element can be manufactured on a substrate having a bank by an ink-jet method.
  • a bank is provided on an element substrate on which electrodes are formed, and an organic head is provided between the banks by an ink-jet head.
  • a film can be formed by dropping a droplet of the layer-forming composition and drying the composition. Then, by repeating this process and sequentially stacking the films and forming the electron transport layer, the electron injection layer, and the electrode by using a vacuum evaporation method, an organic EL element in which light emitting portions are separated by a bank material can be manufactured. it can.
  • the organic EL element manufactured in this manner is preferably covered with a sealing layer in order to protect the element from moisture and oxygen.
  • the sealing layer for example, an inorganic insulating material such as silicon oxynitride (SiON) having low permeability to moisture or oxygen can be used.
  • the organic EL element may be sealed by attaching a sealing substrate such as a transparent glass or an opaque ceramic to an element substrate on which the organic EL element is formed via an adhesive.
  • the organic layer forming composition is a low molecular compound capable of forming each organic layer of an organic EL device, or a polymer obtained by polymerizing the low molecular compound. It is obtained by dissolving a compound in an organic solvent.
  • the composition for forming a light emitting layer includes, as a first component, a polycyclic aromatic compound (or a polymer compound thereof) represented by the above general formula (1), which is a host material, and a dopant as a second component. It is preferable to contain the above-mentioned boron-containing polycyclic aromatic compound (or a polymer compound thereof), which is a material, and at least one organic solvent as the third component.
  • the third component functions as a solvent for dissolving the first component and the second component in the composition, and gives a smooth and uniform surface shape due to the controlled evaporation rate of the third component itself during coating.
  • the polymer compound includes a first structural unit derived from a reactive compound (H) in which a reactive substituent is substituted on the polycyclic aromatic compound represented by the general formula (1),
  • Polymer compound (HD) which is a copolymer having a second structural unit derived therefrom, and a polymer crosslinked body (HD) obtained by further crosslinking the polymer compound (HD); and a main chain polymer.
  • a pendant polymer compound (HD) in which the reactive compound (H) and the reactive compound (D) are substituted, and a pendant polymer crosslinked product (HD) in which the pendant polymer compound (HD) is further crosslinked Is also included. That is, formation of an organic layer containing at least one selected from a polymer compound (HD), a crosslinked polymer (HD), a pendant polymer compound (HD) and a pendant polymer crosslinked product (HD), and an organic solvent. Composition.
  • the polymer compound (HD), the crosslinked polymer (HD), the pendant polymer compound (HD) and the crosslinked pendant polymer (HD) are a host as the first component and a second component. It has a structure in which a dopant is incorporated in the same molecule.
  • the composition for forming an organic layer contains at least one organic solvent.
  • the evaporation rate of the organic solvent at the time of film formation it is possible to control and improve the film formability and the presence / absence of defects in the coating film, surface roughness, and smoothness.
  • the meniscus stability 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 electric characteristics, light-emitting characteristics, efficiency, and lifetime of an organic EL device having an organic layer obtained from the composition for forming an organic layer are improved. Can be.
  • the boiling point of at least one organic solvent is from 130 to 350 ° C., preferably from 140 to 300 ° C., more preferably from 150 to 250 ° C.
  • the organic solvent is more preferably configured to include two or more organic solvents from the viewpoints of good ink jet ejection properties, film formability, smoothness, and low residual solvent.
  • the composition may be in a solid state by removing a solvent from the composition for forming an organic layer in consideration of transportability and the like.
  • the organic solvent contains a good solvent (GS) and a poor solvent (PS) for at least one of the host of the first component and the dopant of the second component, and the boiling point (BP GS ) of the good solvent ( GS ) is poor. It is preferably lower than the boiling point (BP PS ) of ( PS ).
  • the difference in solubility is preferably at least 1%, more preferably at least 3%, even more preferably at least 5%.
  • the difference in boiling points is preferably at least 10 ° C., more preferably at least 30 ° C., even more preferably at least 50 ° C.
  • the organic solvent is removed from the coating film by a drying process such as vacuum, reduced pressure, and heating.
  • a drying process such as vacuum, reduced pressure, and heating.
  • Tg glass transition temperature
  • From the viewpoint of reducing the residual solvent it is preferable to heat the solute at least at least one kind of glass transition point (Tg) of ⁇ 30 ° C. or higher. Even when the heating temperature is lower than the boiling point of the organic solvent, the organic solvent is sufficiently removed because the film is thin. Further, drying may be performed a plurality of times at different temperatures, or a plurality of 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 fluorinated solvents.
  • Specific examples include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexane-2-ol, Heptane-2-ol, octane-2-ol, decane-2-ol, dodecane-2-ol, cyclohexanol, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, terpineol (mixture), ethylene glycol Monomethyle Teracetate, 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,
  • organic solvent one or more selected from an alkylbenzene-based solvent and a phenylether-based solvent is preferable, and a mixed solvent of 3-phenoxytoluene and cyclohexylbenzene is more preferable.
  • composition for forming an organic layer may contain an optional component as long as its properties are not impaired.
  • Optional components include a binder and a surfactant.
  • 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. Further, it plays a role of dissolving, dispersing and binding other components in the composition for forming an organic layer.
  • binder used in the composition for forming an organic layer examples include acrylic resin, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, acrylonitrile-ethylene-styrene copolymer (AES) resin, 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, Re not limited to.
  • AES acrylonitrile-ethylene-s
  • the binder used in the composition for forming an organic layer may be used alone or in combination of two or more.
  • the composition for forming an organic layer contains, for example, a surfactant for controlling the film surface uniformity, the solvent affinity and the liquid repellency of the film surface of the composition for forming an organic layer. Is also good.
  • Surfactants are classified into ionic and nonionic according to the structure of the hydrophilic group, and further classified into alkyl, silicon and fluorine based on the structure of the hydrophobic group. Further, according to the molecular structure, they are classified into a monomolecular system having a relatively small molecular weight and a simple structure and a high molecular system having a large molecular weight and having side chains or branches.
  • the composition is classified into a single system and a mixed system in which two or more surfactants and a base material are mixed from the composition.
  • surfactants that can be used in the composition for forming an organic layer all kinds of surfactants can be used.
  • 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.), Disperbyk 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181, Disperbake Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, manufactured by BYK Japan KK), 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 222
  • the surfactant may be used alone or in combination of two or more.
  • composition and physical properties of the composition for forming an organic layer The content of each component in the composition for forming an organic layer is good solubility of each component in the composition for forming an organic layer, storage stability and film formability, and is obtained from the composition for forming an organic layer. Good film quality of the coating film, good ejection property when using the inkjet method, good electric characteristics, luminous characteristics, efficiency, and life of the organic EL device having the organic layer manufactured using the composition. Is determined in consideration of the viewpoint. For example, in the case of the composition for forming a light emitting layer, the host material of the first component is 0.0999 to 8.0% by mass based on the total mass of the composition for forming the light emitting layer, and the dopant material is the second component.
  • the organic solvent as the third component is 90.0 to 99% by mass with respect to the total mass of the light emitting layer forming composition. It is preferably 0.9% by mass.
  • the host material as the first component is 0.095 to 4.0% by mass based on the total mass of the composition for forming a light emitting layer
  • the second component is based on the total mass of the composition for forming a light emitting layer
  • the organic solvent as the third component is 95.0 to 99.9% by mass based on the total mass of the composition for forming a light emitting layer.
  • the host material as the first component is 0.25 to 2.5% by mass with respect to the total mass of the composition for forming a light emitting layer
  • the dopant material as the second component is a compound of the composition for forming a light emitting layer.
  • the organic solvent as the third component is 0.05 to 0.5% by mass with respect to the total mass, and 97.0 to 99.7% by mass with respect to the total mass of the composition for forming a light emitting layer.
  • the composition for forming an organic layer can be produced by appropriately selecting the above-mentioned components by stirring, mixing, heating, cooling, dissolving, dispersing and the like by a known method. After the preparation, filtration, degassing (also referred to as degassing), ion exchange treatment, inert gas replacement / sealing 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, the higher the viscosity, the better the film formability and the good ejection property when the ink jet method is used. On the other hand, the lower the viscosity, the easier it is to form a thin film. For this reason, the viscosity of the composition for forming an organic layer 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 conical plate type rotary viscometer (cone plate type).
  • the viscosity of the composition for forming an organic layer preferably has a surface tension at 25 ° C. of 20 to 40 mN / m, more preferably 20 to 30 mN / m.
  • the surface tension is a value measured using the hanging drop method.
  • Crosslinkable polymer compound Compound represented by formula (XLP-1) Next, the case where the above-mentioned polymer compound has a crosslinkable substituent will be described.
  • a crosslinkable polymer compound is, for example, a compound represented by the following general formula (XLP-1).
  • MUx, ECx and k have the same definition as MU, EC and k in the above formula (SPH-1), provided that the compound represented by the formula (XLP-1) has at least one crosslinkable substituent (XLS) And preferably the content of the monovalent or divalent aromatic compound having a crosslinkable substituent is 0.1 to 80% by mass in the molecule.
  • the content of the monovalent or divalent aromatic compound having a crosslinkable substituent is preferably from 0.5 to 50% by mass, more preferably from 1 to 20% by mass.
  • crosslinkable substituent is not particularly limited as long as it is a group that can further crosslink the above-described polymer compound, but a substituent having the following structure is preferable. * In each structural formula shows a bonding position.
  • substituents it is represented by the formula (XLS-1), (XLS-2), (XLS-3), (XLS-9), (XLS-10) or (XLS-17).
  • the group represented by the formula (XLS-1), (XLS-3) or (XLS-17) is more preferable.
  • crosslinking substituent other than those described above may be chlorine, bromine or iodine, or a boron-containing group represented by the following formula (XLS-19). * In the structural formula indicates a bonding position.
  • R 41 and R 42 are each independently an alkyl, and R 41 and R 42 may combine with each other to form a ring. Further, the total carbon number of R 41 and R 42 is preferably 2 to 10.
  • Examples of the divalent aromatic compound having a crosslinkable substituent include a compound having the following partial structure. * In each structural formula shows a bonding position.
  • Examples of the solvent used in the reaction include an aromatic solvent, a saturated / unsaturated hydrocarbon solvent, an alcohol solvent, and an ether solvent, and examples thereof include dimethoxyethane, 2- (2-methoxyethoxy) ethane, and 2- (2 -Ethoxyethoxy) ethane and the like.
  • the reaction may be performed in a two-phase system.
  • a phase transfer catalyst such as a quaternary ammonium salt may be added as necessary.
  • the compound When producing the compound of formula (SPH-1) and the compound of (XLP-1), the compound may be produced in one step or may be produced through multiple steps. Further, the reaction 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 may be carried out by a drop polymerization method in which the raw materials are added dropwise to the reaction vessel, or the product may be used in the course of the reaction. It may be carried out by a precipitation polymerization method in which precipitation occurs, and these can be synthesized by appropriately combining them.
  • the desired product is obtained by performing a reaction in a state where a monomer unit (MU) and an end cap unit (EC) are added to a reaction vessel.
  • the monomer unit (MU) is polymerized to a target molecular weight, and then the reaction is performed by adding an end cap unit (EC). Get things.
  • a polymer having a concentration gradient in the structure of the monomer units can be produced.
  • the target polymer can be obtained by post-reaction.
  • the primary structure of the polymer can be controlled by selecting the polymerizable group of the monomer unit (MU). For example, as shown in synthesis schemes 1 to 3, polymers having a random primary structure (synthesis scheme 1), polymers having a regular primary structure (synthesis schemes 2 and 3), and the like can be synthesized. And can be used in an appropriate combination depending on the object. Furthermore, if a monomer unit having three or more polymerizable groups is used, a hyperbranched polymer or dendrimer can be synthesized.
  • a monomer unit having three or more polymerizable groups is used, a hyperbranched polymer or dendrimer can be synthesized.
  • JP 2010-189630 A As the monomer unit that can be used in the present invention, JP 2010-189630 A, International Publication No. 2012/086671, WO 2013/191088, WO 2002/045184, WO 2011/049241 No., WO2013 / 146806, WO2005 / 049546, WO2015 / 145871, JP2010-215886, JP2008-106241, JP2010-215886, International Publication No. 2016/031639, JP 2011-174062, WO 2016/031639, WO 2016/031639, can be synthesized according to the method described in WO 2002/045184. .
  • the present invention can also be applied to a display device including an organic EL element, a lighting device including an organic EL element, and the like.
  • a display device or a lighting device including the organic EL element can be manufactured by a known method such as connecting the organic EL element according to the present embodiment to a known driving device, and includes DC driving, pulse driving, AC driving, and the like. Driving can be performed using a known driving method as appropriate.
  • Examples of the display device include a panel display such as a color flat panel display and a flexible display such as a flexible color organic electroluminescence (EL) display (for example, JP-A-10-335066, JP-A-2003-321546). Gazette, JP-A-2004-281086).
  • Examples of the display method of the display include at least one of a matrix method and a segment method. Note that the matrix display and the segment display may coexist in the same panel.
  • pixels for display are two-dimensionally arranged such as in a grid or mosaic, and a set of pixels displays a character or an image.
  • the shape and size of the pixel depend on the application. For example, a square pixel having a side of 300 ⁇ m or less is normally used for displaying images and characters on a personal computer, a monitor, and a television. In the case of a large display such as a display panel, a pixel having a side of mm order is used. become.
  • pixels of the same color may be arranged, but in the case of color display, red, green and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type.
  • the matrix may be driven by either a line-sequential driving method or an active matrix.
  • the line-sequential driving has an advantage that the structure is simpler.
  • the active matrix may be more excellent. Therefore, it is necessary to use the active matrix properly depending on the application.
  • a pattern is formed so as to display predetermined information, and a predetermined area emits light.
  • a time display and a temperature display on a digital clock or a thermometer an operation state display of an audio device or an electromagnetic cooker, and a panel display of a car.
  • Illumination devices include, for example, illumination devices such as interior lighting, backlights of liquid crystal display devices (for example, JP-A-2003-257621, JP-A-2003-277741, and JP-A-2004-119211). Etc.).
  • a backlight is mainly used for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, a sign, and the like.
  • the backlight using the light emitting element according to the above is characterized by being thin and lightweight.
  • the color conversion is to convert light emitted from a light emitter to light having a longer wavelength (wavelength conversion), for example, to convert blue light to green or red light.
  • wavelength conversion wavelength conversion
  • a full-color display can be manufactured by combining such a blue light source and a film having a wavelength conversion function with a white light source as a light source unit and combining it with a liquid crystal driving portion and a color filter.
  • a liquid crystal driving portion it can be used as it is as a white light source, and can be applied as a white light source such as LED lighting.
  • a blue organic EL element as a light source in combination with a film for converting into green and red
  • a full-color organic EL display without using a metal mask can be manufactured.
  • a blue micro LED as a light source in combination with a film for converting into green and red, a low-cost full-color micro LED display can be manufactured.
  • the polycyclic aromatic compound represented by the general formula (1) is useful as a fluorescent material that emits blue light or green light with high color purity by excitation light, and is also used as a material having such a wavelength conversion function. be able to.
  • the polycyclic aromatic compound of the formula (1) converts light having a wavelength of, for example, 300 nm to 449 nm into blue light emission having a narrow half width (25 nm or less, further 20 nm or less) having a maximum value at 450 nm to 500 nm. It can be used as a wavelength conversion material.
  • the composition having a wavelength conversion function may contain, in addition to the polycyclic aromatic compound of the formula (1), a binder resin, other additives, and a solvent.
  • a binder resin for example, the resins described in paragraphs [0173] to [0176] of WO 2016/190283 can be used.
  • the compounds described in paragraphs [0177] to [0181] of WO 2016/190283 can be used.
  • the wavelength conversion film includes a wavelength conversion layer formed by curing a composition having a wavelength conversion function.
  • a method for producing the wavelength conversion layer from the composition a known film forming method can be referred to.
  • the wavelength conversion film may be composed of only a wavelength conversion layer formed from a composition containing the polycyclic aromatic compound of the formula (1), and may include other wavelength conversion layers (for example, converting blue light into green light or red light). A wavelength conversion layer for converting blue light or green light to red light). Further, the wavelength conversion film may include a base layer and a barrier layer for preventing the color conversion layer from being deteriorated by oxygen, moisture or heat.
  • the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. That is, the configuration of the organic EL device of the present invention is not limited to the configuration shown in the following examples, and the thickness and constituent material of each layer can be appropriately changed according to the basic physical properties of the present invention.
  • the absorption spectrum of the sample was measured using an ultraviolet-visible-near-infrared spectrophotometer (UV-2600, Shimadzu Corporation).
  • the fluorescence spectrum of the sample was measured using a spectrofluorometer (F-7000, manufactured by Hitachi High-Tech Co., Ltd.).
  • photoluminescence was measured by exciting at an appropriate excitation wavelength at room temperature.
  • the sample was immersed in liquid nitrogen (temperature 77 K) using an attached cooling unit. The sample was excited at the appropriate excitation wavelength and photoluminescence was measured.
  • the fluorescence quantum yield (PLQY) is measured using an absolute PL quantum yield measuring device (C9920-02G, manufactured by Hamamatsu Photonics KK).
  • Evaluation items and evaluation methods include driving voltage (V), emission wavelength (nm), CIE chromaticity (x, y), external quantum efficiency (%), maximum wavelength of emission spectrum (nm), and half width ( nm) and roll-off. For these evaluation items, values at appropriate emission luminance can be used.
  • the quantum efficiency of a light-emitting device includes an internal quantum efficiency and an external quantum efficiency.
  • the internal quantum efficiency is such that external energy injected as electrons (or holes) into the light-emitting layer of the light-emitting device is purely converted into photons. Shows the ratio of
  • the external quantum efficiency is calculated based on the amount of this photon emitted to the outside of the light emitting element, and a part of the photon generated in the light emitting layer is continuously absorbed or reflected inside the light emitting element. As a result, the external quantum efficiency is lower than the internal quantum efficiency because the external quantum efficiency is not emitted to the outside of the light emitting element.
  • the method of measuring the spectral radiance (emission spectrum) and external quantum efficiency is as follows.
  • the element was made to emit light by applying a voltage using a voltage / current generator R6144 manufactured by Advantest Corporation.
  • a spectral radiance meter SR-3AR manufactured by TOPCON the spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface. Assuming that the light emitting surface is a perfect diffusion surface, the value obtained by dividing the measured value of the spectral radiance of each wavelength component by the wavelength energy and multiplying by ⁇ is the number of photons at each wavelength.
  • the external quantum efficiency is a value obtained by dividing a value obtained by dividing an applied current value by an elementary charge as the number of carriers injected into the device and dividing the total number of photons emitted from the device by the number of carriers injected into the device.
  • the half width of the emission spectrum is determined as the width between the upper and lower wavelengths at which the intensity becomes 50% with the maximum emission wavelength as the center.
  • Roll-off is a phenomenon in which, when a voltage is applied to an element, the efficiency decreases as the voltage is applied.
  • the TADF element when tau (delay) of the dopant or assist dopant is large, the roll-off is large, and when tau (delay) is small, the roll-off is small.
  • evaluation can be performed by comparing the efficiency at any two points of luminance or current density. Preferably, the efficiency is high and the roll-off is small.
  • the roll-off indicates a degree of reduction in efficiency between any two luminances.
  • a roll-off (RO) between 100 cd / m 2 and 1000 cd / m 2 is obtained by the following equation (XXXX).
  • EQE (100cd / m 2) and EQE (1000cd / m 2) each represent an external quantum efficiency at 100 cd / m 2 and 1000 cd / m 2.
  • RO 1 ⁇ (EQE (100 cd / m 2 ) / EQE (1000 cd / m 2 ))
  • Vapor-deposited organic EL device An organic EL device having a device configuration that can be expected to have high efficiency, which is shown in the literature (Adv. Mater. 2016, 28, 2777-2781) and is suitable for thermally activated delayed fluorescent material Produced.
  • the materials used for forming the layers other than the light emitting layer used are as follows. The forming materials of each layer of the manufactured organic EL device in Table 1 are shown. “HI” as the hole injection layer material is N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, and “HT” as the hole transport layer material is 4,4 ′.
  • the structures of the compounds used as the host and the dopant of the light emitting layer are as follows.
  • a glass substrate (manufactured by OptoScience Corp.) of 26 mm ⁇ 28 mm ⁇ 0.7 mm, which is obtained by polishing ITO formed to a thickness of 200 nm by sputtering to 50 nm, is used as a transparent support substrate.
  • This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Choshu Sangyo Co., Ltd.), and tantalum made of HI, HT, EB, compound (BO2-0220), compound (DABNA2), and ET, respectively.
  • the following layers were sequentially formed on the ITO film of the transparent support substrate.
  • the pressure in the vacuum chamber was reduced to 5 ⁇ 10 ⁇ 4 Pa.
  • HI was heated to deposit a film to a thickness of 40 nm
  • HT was heated to deposit a film to a thickness of 15 nm to form holes.
  • An injection layer and a hole transport layer were formed, respectively.
  • EB was heated to be deposited to a thickness of 15 nm to form an electron blocking layer.
  • the compound (BO2-0220) and the compound (DABNA2) were simultaneously heated and evaporated to a thickness of 20 nm to form a light emitting layer.
  • the deposition rate was adjusted such that the weight ratio of the compound (BO2-0220) to the compound (DABNA2) was 99: 1.
  • ET was heated and vapor-deposited to a thickness of 40 nm to form an electron transport layer.
  • the deposition rate for each layer was 0.01-1 nm / sec.
  • LiF is heated to deposit a film at a deposition rate of 0.01 to 0.1 nm / sec to a thickness of 1 nm
  • aluminum is heated to deposit a film to a thickness of 100 nm to form a cathode.
  • the deposition rate of aluminum was adjusted to be 1 to 10 nm / sec.
  • the light emission spectrum had a peak wavelength of 467 nm, and deep blue light emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 23.7%, and high quantum efficiency was obtained.
  • Example 2 An organic EL device was obtained by the same procedure and configuration as in Example 1 except that the host was changed to the compound (BO2-0511S).
  • the host was changed to the compound (BO2-0511S).
  • the emission spectrum was at a peak wavelength of 465 nm, and deep blue emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 15.4%, and high quantum efficiency was obtained.
  • Example 3 An organic EL device was obtained by the same procedure and configuration as in Example 1 except that the host was changed to the compound (BO2-0264 / 0511S).
  • the host was changed to the compound (BO2-0264 / 0511S).
  • the emission spectrum was at a peak wavelength of 465 nm, and deep blue emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 14.2%, and high quantum efficiency was obtained.
  • Example 4 An organic EL device was obtained in the same procedure and configuration as in Example 1 except that the dopant was changed to the compound (BD1).
  • BD1 the dopant was changed to the compound (BD1).
  • the light emission spectrum had a peak wavelength of 462 nm, and deep blue light emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 28.6%, and high quantum efficiency was obtained.
  • Example 5 An organic EL device was obtained in the same procedure and configuration as in Example 1, except that the host was changed to the compound (BO2-0220 / 0511S) and the dopant was changed to the compound (BD1).
  • the host was changed to the compound (BO2-0220 / 0511S) and the dopant was changed to the compound (BD1).
  • the light emission spectrum had a peak wavelength of 461 nm, and deep blue light emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 22.4%, and high quantum efficiency was obtained.
  • Example 6 An organic EL device was obtained in the same procedure and configuration as in Example 1, except that the host was changed to the compound (BO2-0220) and the dopant was changed to the compound (BD2).
  • the host was changed to the compound (BO2-0220) and the dopant was changed to the compound (BD2).
  • BD2 the dopant was changed to the compound (BD2).
  • the emission spectrum was at a peak wavelength of 473 nm, and deep blue light emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 34.0%, and high quantum efficiency was obtained.
  • Example 7 An organic EL device was obtained in the same procedure and configuration as in Example 1, except that the host was changed to the compound (BO2-0511S) and the dopant was changed to the compound (BD2).
  • the host was changed to the compound (BO2-0511S) and the dopant was changed to the compound (BD2).
  • BD2 the compound
  • the emission spectrum was at a peak wavelength of 473 nm, and deep blue light emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 28.0%, and high quantum efficiency was obtained.
  • Example 8 An organic EL device was obtained in the same procedure and configuration as in Example 1, except that the host was changed to the compound (BO2-0520S) and the dopant was changed to the compound (BD2).
  • the host was changed to the compound (BO2-0520S) and the dopant was changed to the compound (BD2).
  • BD2 the dopant was changed to the compound (BD2).
  • Example 9 An organic EL device was obtained by the same procedure and configuration as in Example 1 except that the host was changed to the compound (BO2-0264 / 0511S) and the dopant was changed to the compound (BD2).
  • the host was changed to the compound (BO2-0264 / 0511S) and the dopant was changed to the compound (BD2).
  • the structures of the compounds used as the host and the dopant of the light emitting layer are as follows.
  • a glass substrate (manufactured by OptoScience Corp.) of 26 mm ⁇ 28 mm ⁇ 0.7 mm, which is obtained by polishing ITO formed to a thickness of 200 nm by sputtering to 50 nm, is used as a transparent support substrate.
  • This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Choshu Sangyo Co., Ltd.), and tantalum made of HI, HT, EB, compound (BO2-0511S), compound (BD3), and ET, respectively.
  • the following layers were sequentially formed on the ITO film of the transparent support substrate.
  • the pressure in the vacuum chamber was reduced to 5 ⁇ 10 ⁇ 4 Pa.
  • HI was heated to deposit a film to a thickness of 40 nm
  • HT was heated to deposit a film to a thickness of 15 nm to form holes.
  • An injection layer and a hole transport layer were formed, respectively.
  • EB was heated to be deposited to a thickness of 15 nm to form an electron blocking layer.
  • the compound (BO2-0511S) and BD3 were simultaneously heated and evaporated to a thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted such that the weight ratio of the compound (BO2-0511S) to the compound (BD3) became 99: 1.
  • the ET was heated and vapor-deposited so as to have a thickness of 30 nm to form an electron transport layer.
  • the deposition rate for each layer was 0.01-1 nm / sec.
  • LiF is heated to deposit a film at a deposition rate of 0.01 to 0.1 nm / sec to a thickness of 1 nm, and then aluminum is heated to deposit a film to a thickness of 100 nm to form a cathode.
  • an organic EL device was obtained.
  • the deposition rate of aluminum was adjusted to be 1 to 10 nm / sec.
  • the light emission spectrum had a peak wavelength of 451 nm, and deep blue light emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 14.8%, and high quantum efficiency was obtained.
  • Example 11 An organic EL device was obtained in the same procedure and configuration as in Example 10, except that the dopant was changed to the compound (BD4).
  • BD4 the dopant was changed to the compound (BD4).
  • Example 12 An organic EL device was obtained in the same procedure and configuration as in Example 10, except that the dopant was changed to the compound (BD5).
  • BD5 the dopant was changed to the compound (BD5).
  • the light emission spectrum had a peak wavelength of 468 nm, and deep blue light emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 17.5%, and high quantum efficiency was obtained.
  • Example 13 An organic EL device was obtained in the same procedure and configuration as in Example 10, except that the dopant was changed to the compound (BD5).
  • BD5 the dopant was changed to the compound (BD5).
  • Example 14 An organic EL device was obtained in the same procedure and configuration as in Example 10, except that the dopant was changed to the compound (BD7).
  • BD7 the dopant was changed to the compound (BD7).
  • the light emission spectrum had a peak wavelength of 468 nm, and deep blue light emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 11.6%, and high quantum efficiency was obtained.
  • Example 8 An organic EL device was obtained in the same procedure and configuration as in Example 12, except that the host was changed to the compound (EMH1). A direct current voltage was applied using the ITO electrode as the anode and the aluminum electrode as the cathode. The emission spectrum was at a peak wavelength of 468 nm, and deep blue emission was observed. However, no emission was observed at 100 cd / m 2 due to deterioration.
  • the structures of the compounds used as the host and the dopant of the light emitting layer are as follows.
  • a glass substrate (manufactured by OptoScience Corp.) of 26 mm ⁇ 28 mm ⁇ 0.7 mm, which is obtained by polishing ITO formed to a thickness of 200 nm by sputtering to 50 nm, is used as a transparent support substrate.
  • This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Choshu Sangyo Co., Ltd.), and tantalum made of HI, HT, EB, compound (BO2-0231), compound (BD2), and ET, respectively.
  • the following layers were sequentially formed on the ITO film of the transparent support substrate.
  • the pressure in the vacuum chamber was reduced to 5 ⁇ 10 ⁇ 4 Pa.
  • HI was heated to deposit a film to a thickness of 40 nm
  • HT was heated to deposit a film to a thickness of 15 nm to form holes.
  • An injection layer and a hole transport layer were formed, respectively.
  • EB was heated to be deposited to a thickness of 15 nm to form an electron blocking layer.
  • the compound (BO2-0231) and the compound (BD2) were simultaneously heated and evaporated to a thickness of 20 nm to form a light-emitting layer.
  • the deposition rate was adjusted such that the weight ratio of the compound (BO2-0231) to the compound (BD2) became 99: 1.
  • the ET was heated and vapor-deposited so as to have a thickness of 30 nm to form an electron transport layer.
  • the deposition rate for each layer was 0.01-1 nm / sec.
  • LiF is heated to deposit a film at a deposition rate of 0.01 to 0.1 nm / sec to a thickness of 1 nm, and then aluminum is heated to deposit a film to a thickness of 100 nm to form a cathode.
  • an organic EL device was obtained.
  • the deposition rate of aluminum was adjusted to be 1 to 10 nm / sec.
  • the light emission spectrum had a peak wavelength of 476 nm, and deep blue light emission was observed.
  • the external quantum efficiencies at the time of light emission of 100 cd / m 2 and 1000 cd / m 2 were 27.7% and 24.5%, and high quantum efficiency was obtained.
  • the roll-off between 100 cd / m 2 and 1000 cd / m 2 was as small as -11.6%.
  • Example 16 An organic EL device was obtained by the same procedure and configuration as in Example 15 except that the host was changed to the compound (BO2-0431).
  • a DC voltage was applied using the ITO electrode as an anode and the aluminum electrode as a cathode, and the characteristics at the time of light emission of 1000 cd / m 2 were measured, the light emission spectrum had a peak wavelength of 474 nm, and deep blue light emission was observed.
  • the external quantum efficiencies at the time of light emission of 100 cd / m 2 and 1000 cd / m 2 were 29.4% and 25.3%, and high quantum efficiency was obtained.
  • the roll-off between 100 cd / m 2 and 1000 cd / m 2 was as small as -14%.
  • the structures of the host and the dopant of the light emitting layer and the compound used as the material for forming the electron transport layer are as follows.
  • the structure of the compound used as a material for forming each layer other than the light emitting layer and the electron transporting layer is as described above.
  • Example 17 A glass substrate (manufactured by OptoScience Corp.) of 26 mm ⁇ 28 mm ⁇ 0.7 mm, which is obtained by polishing ITO formed to a thickness of 200 nm by sputtering to 50 nm, is used as a transparent support substrate.
  • This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Choshu Sangyo Co., Ltd.), and HI, HT, EB, compound (BO2-0431), compound (BD2), 2CzBN and BPy-TP2 were respectively placed therein.
  • the following layers were sequentially formed on the ITO film of the transparent support substrate.
  • the pressure in the vacuum chamber was reduced to 5 ⁇ 10 ⁇ 4 Pa.
  • HI was heated to deposit a film to a thickness of 40 nm
  • HT was heated to deposit a film to a thickness of 15 nm to form holes.
  • An injection layer and a hole transport layer were formed, respectively.
  • EB was heated to be deposited to a thickness of 15 nm to form an electron blocking layer.
  • the compound (BO2-0231) and the compound (BD2) were simultaneously heated and evaporated to a thickness of 20 nm to form a light-emitting layer.
  • the deposition rate was adjusted such that the weight ratio of the compound (BO2-0231) to the compound (BD2) became 99: 1.
  • the light emission spectrum was at a peak wavelength of 473 nm, and deep blue light emission was observed.
  • the external quantum efficiencies at the time of light emission of 100 cd / m 2 and 1000 cd / m 2 were 28.0% and 25.1%, and high quantum efficiency was obtained.
  • the roll-off between 100 cd / m 2 and 1000 cd / m 2 was as small as -10.4%.
  • the time until the luminance 80 cd / m 2 when is continuously driven at a current value of the luminance 100cd / m 2 (LT 80) was 83 hours.
  • Example 18 An organic EL device was obtained in the same procedure and configuration as in Example 17, except that the host was changed to the compound (BO2-0520).
  • a DC voltage was applied using the ITO electrode as the anode and the aluminum electrode as the cathode, and the characteristics at the time of light emission of 1000 cd / m 2 were measured, the light emission spectrum was at a peak wavelength of 473 nm, and deep blue light emission was observed. Further, the external quantum efficiencies at the time of light emission of 100 cd / m 2 and 1000 cd / m 2 were 28.6% and 25.7%, and high quantum efficiency was obtained.
  • the roll-off between 100 cd / m 2 and 1000 cd / m 2 was as small as -9.2%.
  • the time until the luminance 80 cd / m 2 when is continuously driven at a current value of the luminance 100cd / m 2 (LT 80) was 90 hours.
  • Example 19 An organic EL device was obtained in the same procedure and configuration as in Example 17, except that the host was changed to the compound (BO2-0220).
  • a DC voltage was applied using the ITO electrode as the anode and the aluminum electrode as the cathode, and the characteristics at the time of light emission of 1000 cd / m 2 were measured, the light emission spectrum was at a peak wavelength of 473 nm, and deep blue light emission was observed.
  • the external quantum efficiencies at the time of light emission of 100 cd / m 2 and 1000 cd / m 2 were 29.3% and 26.6%, and high quantum efficiency was obtained.
  • the roll-off between 100 cd / m 2 and 1000 cd / m 2 was as small as -10.1%.
  • the time until the luminance cd / m 2 when is continuously driven at a current value of the luminance 100cd / m 2 (LT 80) was 30 hours.
  • Example 20 An organic EL device was obtained in the same procedure and configuration as in Example 17, except that the host was changed to the compound (BO2-0220-4).
  • a DC voltage was applied using the ITO electrode as the anode and the aluminum electrode as the cathode, and the characteristics at the time of light emission of 1000 cd / m 2 were measured, the light emission spectrum was at a peak wavelength of 473 nm, and deep blue light emission was observed.
  • the external quantum efficiencies at the time of light emission of 100 cd / m 2 and 1000 cd / m 2 were 24.3% and 20.9%, and high quantum efficiency was obtained.
  • the roll-off between 100 cd / m 2 and 1000 cd / m 2 was as small as -14.0%.
  • the time until the luminance 80 cd / m 2 when is continuously driven at a current value of the luminance 100cd / m 2 (LT 80) was 100 hours.
  • Example 21 An organic EL device was obtained in the same procedure and configuration as in Example 17, except that the host was changed to the compound (BO2-0431-1).
  • a DC voltage was applied using the ITO electrode as the anode and the aluminum electrode as the cathode, and the characteristics at the time of light emission of 1000 cd / m 2 were measured, the light emission spectrum was at a peak wavelength of 473 nm, and deep blue light emission was observed.
  • the external quantum efficiencies at the time of light emission of 100 cd / m 2 and 1000 cd / m 2 were 26.1% and 23.5%, and high quantum efficiency was obtained.
  • the roll-off between 100 cd / m 2 and 1000 cd / m 2 was as small as -10.0%.
  • the time until the luminance 80 cd / m 2 when is continuously driven at a current value of the luminance 100cd / m 2 (LT 80) was 90 hours.
  • Example 22 An organic EL device was obtained in the same procedure and configuration as in Example 17, except that the host was changed to the compound (BO2-0431-2).
  • a DC voltage was applied using the ITO electrode as the anode and the aluminum electrode as the cathode, and the characteristics at the time of light emission of 1000 cd / m 2 were measured, the light emission spectrum was at a peak wavelength of 473 nm, and deep blue light emission was observed.
  • the external quantum efficiencies at the time of light emission of 100 cd / m 2 and 1000 cd / m 2 were 26.3% and 23.5%, and high quantum efficiency was obtained.
  • the roll-off between 100 cd / m 2 and 1000 cd / m 2 was as small as -10.6%.
  • the time until the luminance 80 cd / m 2 when is continuously driven at a current value of the luminance 100cd / m 2 (LT 80) was 98 hours.
  • Example 23 An organic EL device was obtained in the same procedure and configuration as in Example 17, except that the host was changed to the compound (BO2-0220 / 0511S-1).
  • the host was changed to the compound (BO2-0220 / 0511S-1).
  • the ITO electrode As the anode and the aluminum electrode as the cathode
  • the characteristics at the time of light emission of 1000 cd / m 2 were measured, the light emission spectrum was at a peak wavelength of 473 nm, and deep blue light emission was observed.
  • the external quantum efficiencies at the time of light emission of 100 cd / m 2 and 1000 cd / m 2 were 24.7% and 21.1%, and high quantum efficiency was obtained.
  • the roll-off between 100 cd / m 2 and 1000 cd / m 2 was as small as -14.6%.
  • the time until the luminance 80 cd / m 2 when is continuously driven at a current value of the luminance 100cd / m 2 (LT 80) was 67 hours.
  • Example 24 An organic EL device was obtained in the same procedure and configuration as in Example 18, except that the dopant was changed to the compound (BD8).
  • BD8 the dopant was changed to the compound (BD8).
  • the light emission spectrum had a peak wavelength of 470 nm, and deep blue light emission was observed.
  • the external quantum efficiencies at the time of light emission of 100 cd / m 2 and 1000 cd / m 2 were 24.6% and 22.5%, and high quantum efficiency was obtained.
  • the roll-off between 100 cd / m 2 and 1000 cd / m 2 was as small as -8.5%.
  • the time until the luminance 80 cd / m 2 when is continuously driven at a current value of the luminance 100cd / m 2 (LT 80) was 80 hours.
  • Example 25 An organic EL device was obtained in the same procedure and configuration as in Example 18, except that the dopant was changed to the compound (BD9).
  • BD9 the dopant was changed to the compound (BD9).
  • the light emission spectrum had a peak wavelength of 462 nm, and deep blue light emission was observed.
  • the external quantum efficiencies at the time of light emission of 100 cd / m 2 and 1000 cd / m 2 were 23.9% and 21.0%, and high quantum efficiency was obtained.
  • the roll-off between 100 cd / m 2 and 1000 cd / m 2 was as small as -12.1%.
  • the time until the luminance 80 cd / m 2 when is continuously driven at a current value of the luminance 100cd / m 2 (LT 80) was 61 hours.
  • Example S-1 to Example S-10 and Comparative Example S-1> Composition for forming light emitting layer ⁇ Example S-1 to Example S-10 and Comparative Example S-1>
  • Table 6 0.99% by mass of the host of the first component, 0.01% by mass of the dopant of the second component, and 99% by mass of the solvent of the third component were mixed to emit light at a solid concentration of 1% by mass.
  • Each layer-forming composition was prepared.
  • the viscosity and surface tension of the composition for forming a light emitting layer of Example S-9 among these prepared compositions were measured, the viscosity was 3.5 mPa ⁇ s, and the surface tension was 36.3 mN / m. Met.
  • the solubility was evaluated by confirming the presence or absence of turbidity and precipitation of the prepared composition for forming a light emitting layer.
  • the composition without turbidity or precipitation was designated as "A”
  • the composition with turbidity or precipitation was designated as "F”
  • the solubility was evaluated.
  • the film formability was evaluated as "." (Film formation method by spin coating) A UV-O 3 treatment was performed by irradiating a clean glass substrate having a thickness of 0.5 mm and a size of 28 ⁇ 26 mm with irradiation energy of 1000 mJ / cm 2 (low-pressure mercury lamp (254 nanometers)). Next, 0.3 to 0.6 mL of the composition for forming a light emitting layer is dropped on glass, and spin-coated (slope (increase to a predetermined number of revolutions in 5 seconds)) ⁇ applied at 500 to 5000 rpm (at a predetermined number of revolutions). 10 seconds) ⁇ slope (rotation speed is reduced in 5 seconds and rotation speed is set to 0 rpm).
  • the film was dried on a hot plate at 120 ° C. for 10 minutes to form a film.
  • the composition for forming a light emitting layer was discharged into a pixel of 100 ppi using an inkjet, and dried at 100 ° C. to form a film.
  • XLP-101 ⁇ Synthesis of Polymeric Hole Transport Compound: XLP-101> According to the method described in JP-A-2018-61028, XLP-101 was synthesized as follows. A copolymer having M5 or M6 bonded thereto is obtained next to M4, and it is estimated from the charging ratio that each unit is 40:10:50 (molar ratio). In the following formula, Bpin is pinacolate boryl.
  • Table 7 shows the material constitution of each layer in the organic EL device.
  • PEDOT: PSS which is a material for forming the hole injection layer is a commercially available PEDOT: PSS solution (Clevios (TM) P VP AI4083, an aqueous dispersion of PEDOT: PSS represented by the following formula, Heraeus (Holdings) was used.
  • OTPD which is a material for forming the hole transport layer includes OTPD (LT-N159, manufactured by Luminescence Technology Corp.) and IK-2 (photo cationic polymerization initiator, manufactured by San Apro was dissolved in toluene to obtain an OTPD solution having an OTPD concentration of 0.7% by mass and an IK-2 concentration of 0.007% by mass.
  • XLP-101 as the material for forming the hole transport layer was obtained by dissolving XLP-101, which is the above-described polymer hole transport compound, in xylene at a concentration of 0.6% by mass. An XLP-101 solution was obtained.
  • PCz polyvinyl carbazole represented by the following formula was dissolved in dichlorobenzene to obtain a 0.7% by mass PCz solution.
  • Example SD-1> A PEDOT: PSS solution was spin-coated on a glass substrate on which ITO was deposited to a thickness of 50 nm, and baked on a hot plate at 200 ° C. for 1 hour to form a PEDOT: PSS film having a thickness of 40 nm. (Hole injection layer). Next, the OTPD solution is spin-coated, dried on a hot plate at 80 ° C. for 10 minutes, exposed to light at an exposure intensity of 100 mJ / cm 2 with an exposure machine, and baked on a hot plate at 100 ° C. for 1 hour to obtain a solution. A OTPD film having a thickness of 30 nm, which was insoluble in the above, was formed (hole transport layer). Next, the composition for forming a light-emitting layer prepared in Example S-9 was spin-coated and baked on a hot plate at 120 ° C. for 1 hour to form a light-emitting layer having a thickness of 20 nm.
  • the produced multilayer film was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing 2CzBN and BPy-TP2, a molybdenum vapor deposition boat containing LiF, and aluminum
  • the inserted tungsten deposition boat was mounted.
  • 2CzBN was heated and vapor-deposited to a thickness of 10 nm to form the electron transport layer 1.
  • BPy-TP2 was heated and vapor-deposited to a thickness of 20 nm to form an electron transport layer 2.
  • the deposition rate at the time of forming the electron transport layer was 1 nm / sec. Thereafter, LiF was heated to be deposited at a deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm. Next, aluminum was heated and vapor-deposited to a thickness of 100 nm to form a cathode. Thus, an organic EL device was obtained.
  • the light emitting surface was uniform, and the light emission spectrum was 472 nm at peak wavelength, 21 nm at half maximum width, and deep. Blue light emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 10.1%.
  • Example SD-2> The same procedures and procedures as in Example SD-1 were performed, except that the hole transport layer was spin-coated with an XLP-101 solution and baked on a hot plate at 200 ° C. for 1 hour to form a 30 nm-thick film.
  • An organic EL device was obtained with the above configuration.
  • a direct current voltage was applied using the ITO electrode as the anode and the aluminum electrode as the cathode, and the characteristics at the time of emission of 100 cd / m 2 were measured, the emission surface was uniform, and the emission spectrum was 472 nm at the peak wavelength, 20 nm at half width at half maximum, and deep. Blue light emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 12.1%.
  • Example SD-3 The hole transport layer was spin-coated with a PCz solution and baked on a hot plate at 120 ° C. for 1 hour to form a 30 nm-thick film, with the same procedure and configuration as in Example SD-1. Thus, an organic EL device was obtained.
  • a direct current voltage was applied using the ITO electrode as the anode and the aluminum electrode as the cathode, and the characteristics at the time of light emission of 100 cd / m 2 were measured, the light emitting surface was uniform, and the light emission spectrum was 472 nm at the peak wavelength, 20 nm at half width at half maximum, and deep. Blue light emission was observed.
  • the external quantum efficiency at the time of light emission of 100 cd / m 2 was 11.5%.
  • the coating-type organic EL devices prepared in Examples SD-1 to SD-3 had an external quantum efficiency of 10% or more, emitted deep blue light and a narrow half-value width, and were excellent in color.
  • the organic EL device of the present invention may be configured to have a light-emitting layer containing a polymer compound or a crosslinked polymer.
  • Examples of the high molecular compound contained in such a light emitting layer include the high molecular compound described in Example PS-1.
  • Example PS-1 According to the method described in International Patent Publication No. WO2019 / 004248, a polymer compound having the following structure of the host as the first component, the dopant as the second component, and the emitting dopant can be synthesized.
  • the following polymer compound polymerizes the first component and the second component, and has a structural unit derived from each.
  • a polycyclic aromatic compound represented by the formula (1) as a host of the first component and boron as a dopant of the second component which have not been specifically known before
  • the organic EL characteristics such as light emission characteristics can be further enhanced by forming a light emitting layer containing a combination of a polycyclic aromatic compound containing

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Abstract

La présente invention concerne un élément électroluminescent qui comprend une couche électroluminescente qui contient un composé aromatique polycyclique représenté par la formule générale (1) comme matériau hôte (un premier composant) et un composé aromatique polycyclique contenant du boron comme matériau dopant (un second composant), présente des caractéristiques EL organiques excellentes ainsi que des caractéristiques d'émission. Dans la formule (1), chacun des R1-R11 représente de manière indépendante un atome d'hydrogène, un groupe aryle, un groupe hétéroaryle, un groupe aminodiaryle, un groupe diarylboryle (où deux fractions d'aryle peuvent être liées l'une à l'autre par l'intermédiaire d'une seule liaison ou d'un seul groupe de liaison), un groupe alkyle, un groupe cycloalkyle, un groupe alcoxyle ou un groupe aryloxyle ; au moins un atome d'hydrogène dans le groupe aryle, le groupe hétéroaryle et le groupe diaminoaryle peut être remplacé par un groupe aryle, un groupe hétéroaryle, un groupe alkyle ou un groupe cycloalkyle ; et au moins un atome d'hydrogène dans le composé représenté par la formule (1) peut être remplacé par un groupe cyano, un atome halogène ou un atome deuterium).
PCT/JP2019/034473 2018-08-31 2019-09-02 Élément électroluminescent organique utilisant un matériau électroluminescent constitué d'un composé aromatique polycyclique WO2020045681A1 (fr)

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CN201980072016.4A CN112997334A (zh) 2018-08-31 2019-09-02 使用了多环芳香族化合物的发光材料的有机电致发光元件
JP2020539658A JPWO2020045681A1 (ja) 2018-08-31 2019-09-02 多環芳香族化合物の発光材料を用いた有機電界発光素子

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020203212A1 (fr) * 2019-03-29 2020-10-08 住友化学株式会社 Élément électroluminescent et son procédé de fabrication, et composition pour élément électroluminescent et son procédé de production
WO2021187507A1 (fr) * 2020-03-18 2021-09-23 株式会社Ｋｙｕｌｕｘ Composé, matériau électroluminescent et dispositif électroluminescent organique
CN113493474A (zh) * 2020-04-03 2021-10-12 三星显示有限公司 缩合环化合物以及包括其的有机发光元件
WO2021230658A1 (fr) * 2020-05-12 2021-11-18 머티어리얼사이언스 주식회사 Diode électroluminescente organique
KR20210138512A (ko) * 2020-05-12 2021-11-19 머티어리얼사이언스 주식회사 유기 전계 발광 소자
WO2022084505A1 (fr) * 2020-10-23 2022-04-28 Cynora Gmbh Molécules organiques pour dispositifs optoélectroniques
WO2022102877A1 (fr) * 2020-11-11 2022-05-19 경희대학교 산학협력단 Dispositif électroluminescent organique ayant des caractéristiques de durée de vie améliorées
JP2022077011A (ja) * 2020-11-10 2022-05-20 エルジー ディスプレイ カンパニー リミテッド 有機発光ダイオードおよび有機発光装置
EP4059915A3 (fr) * 2021-02-26 2022-12-28 Universal Display Corporation Matériaux et dispositifs électroluminescents organiques
WO2023094936A1 (fr) * 2021-11-26 2023-06-01 株式会社半導体エネルギー研究所 Dispositif électroluminescent, appareil électroluminescent, composé organique, instrument électronique et appareil d'éclairage
KR20230093426A (ko) 2020-10-26 2023-06-27 미쯔비시 케미컬 주식회사 유기 전계 발광 소자, 유기 el 표시 장치 및 유기 el 조명
US11919914B2 (en) 2019-10-25 2024-03-05 Universal Display Corporation Organic electroluminescent materials and devices

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230051852A (ko) * 2021-10-12 2023-04-19 엘지디스플레이 주식회사 유기발광다이오드 및 이를 포함하는 유기발광장치
CN116218283B (zh) * 2023-04-13 2024-04-05 义乌清越光电技术研究院有限公司 一种用于tfb空穴传输层的量子点墨水及其应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016152418A1 (fr) * 2015-03-25 2016-09-29 学校法人関西学院 Composé aromatique polycyclique et composition de formation de couche d'émission de lumière
JP2018076281A (ja) * 2016-10-28 2018-05-17 学校法人関西学院 ボロン酸またはボロン酸エステル、もしくはそれらを用いて多環芳香族化合物または多環芳香族多量体化合物を製造する方法
WO2018095394A1 (fr) * 2016-11-23 2018-05-31 广州华睿光电材料有限公司 Mélange organique, composition, dispositif électronique organique, et application
WO2019004248A1 (fr) * 2017-06-30 2019-01-03 住友化学株式会社 Composé macromoléculaire, et élément luminescent mettant en œuvre celui-ci
WO2019009052A1 (fr) * 2017-07-07 2019-01-10 学校法人関西学院 Composé aromatique polycyclique
WO2019151204A1 (fr) * 2018-02-05 2019-08-08 学校法人関西学院 Élément électroluminescent à effet de champ organique utilisant un matériau électroluminescent de composé aromatique polycyclique

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3735703B2 (ja) 1999-12-21 2006-01-18 大阪大学長 エレクトロルミネッセンス素子
US20040131881A1 (en) 2002-12-31 2004-07-08 Eastman Kodak Company Complex fluorene-containing compounds for use in OLED devices
JP2005170911A (ja) 2003-12-15 2005-06-30 Idemitsu Kosan Co Ltd 芳香族化合物およびそれを用いた有機エレクトロルミネッセンス素子
DE102010009903A1 (de) 2010-03-02 2011-09-08 Merck Patent Gmbh Verbindungen für elektronische Vorrichtungen
JP5591996B2 (ja) 2011-03-03 2014-09-17 国立大学法人九州大学 新規化合物、電荷輸送材料および有機デバイス
TWI636056B (zh) 2014-02-18 2018-09-21 學校法人關西學院 多環芳香族化合物及其製造方法、有機元件用材料及其應用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016152418A1 (fr) * 2015-03-25 2016-09-29 学校法人関西学院 Composé aromatique polycyclique et composition de formation de couche d'émission de lumière
JP2018076281A (ja) * 2016-10-28 2018-05-17 学校法人関西学院 ボロン酸またはボロン酸エステル、もしくはそれらを用いて多環芳香族化合物または多環芳香族多量体化合物を製造する方法
WO2018095394A1 (fr) * 2016-11-23 2018-05-31 广州华睿光电材料有限公司 Mélange organique, composition, dispositif électronique organique, et application
WO2019004248A1 (fr) * 2017-06-30 2019-01-03 住友化学株式会社 Composé macromoléculaire, et élément luminescent mettant en œuvre celui-ci
WO2019009052A1 (fr) * 2017-07-07 2019-01-10 学校法人関西学院 Composé aromatique polycyclique
WO2019151204A1 (fr) * 2018-02-05 2019-08-08 学校法人関西学院 Élément électroluminescent à effet de champ organique utilisant un matériau électroluminescent de composé aromatique polycyclique

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020167392A (ja) * 2019-03-29 2020-10-08 住友化学株式会社 発光素子及びその製造方法並びに発光素子用組成物及びその製造方法
WO2020203212A1 (fr) * 2019-03-29 2020-10-08 住友化学株式会社 Élément électroluminescent et son procédé de fabrication, et composition pour élément électroluminescent et son procédé de production
US11919914B2 (en) 2019-10-25 2024-03-05 Universal Display Corporation Organic electroluminescent materials and devices
WO2021187507A1 (fr) * 2020-03-18 2021-09-23 株式会社Ｋｙｕｌｕｘ Composé, matériau électroluminescent et dispositif électroluminescent organique
CN113493474A (zh) * 2020-04-03 2021-10-12 三星显示有限公司 缩合环化合物以及包括其的有机发光元件
KR102550442B1 (ko) 2020-05-12 2023-07-03 머티어리얼사이언스 주식회사 유기 전계 발광 소자
WO2021230658A1 (fr) * 2020-05-12 2021-11-18 머티어리얼사이언스 주식회사 Diode électroluminescente organique
KR20210138512A (ko) * 2020-05-12 2021-11-19 머티어리얼사이언스 주식회사 유기 전계 발광 소자
WO2022084505A1 (fr) * 2020-10-23 2022-04-28 Cynora Gmbh Molécules organiques pour dispositifs optoélectroniques
KR20230093426A (ko) 2020-10-26 2023-06-27 미쯔비시 케미컬 주식회사 유기 전계 발광 소자, 유기 el 표시 장치 및 유기 el 조명
JP7246453B2 (ja) 2020-11-10 2023-03-27 エルジー ディスプレイ カンパニー リミテッド 有機発光ダイオードおよび有機発光装置
JP2022077011A (ja) * 2020-11-10 2022-05-20 エルジー ディスプレイ カンパニー リミテッド 有機発光ダイオードおよび有機発光装置
WO2022102877A1 (fr) * 2020-11-11 2022-05-19 경희대학교 산학협력단 Dispositif électroluminescent organique ayant des caractéristiques de durée de vie améliorées
EP4059915A3 (fr) * 2021-02-26 2022-12-28 Universal Display Corporation Matériaux et dispositifs électroluminescents organiques
WO2023094936A1 (fr) * 2021-11-26 2023-06-01 株式会社半導体エネルギー研究所 Dispositif électroluminescent, appareil électroluminescent, composé organique, instrument électronique et appareil d'éclairage

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