WO2019239897A1 - アルキル置換多環芳香族化合物を含有する電子輸送材料または電子注入材料 - Google Patents

アルキル置換多環芳香族化合物を含有する電子輸送材料または電子注入材料 Download PDF

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WO2019239897A1
WO2019239897A1 PCT/JP2019/021341 JP2019021341W WO2019239897A1 WO 2019239897 A1 WO2019239897 A1 WO 2019239897A1 JP 2019021341 W JP2019021341 W JP 2019021341W WO 2019239897 A1 WO2019239897 A1 WO 2019239897A1
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ring
aryl
carbon atoms
alkyl
cycloalkyl
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PCT/JP2019/021341
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English (en)
French (fr)
Japanese (ja)
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琢次 畠山
笹田　康幸
一志 枝連
明子 影山
今井　宏之
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学校法人関西学院
Jnc株式会社
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Priority to KR1020207025612A priority Critical patent/KR20210019987A/ko
Priority to JP2020525425A priority patent/JP7530593B2/ja
Priority to CN201980024051.9A priority patent/CN111937175B/zh
Publication of WO2019239897A1 publication Critical patent/WO2019239897A1/ja

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    • 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/33—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being semiconductor devices, e.g. diodes
    • 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
    • H10K50/171—Electron injection layers
    • 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
    • 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

Definitions

  • the present invention relates to an electron transport material or an electron injection material (hereinafter collectively referred to as “electron transport material”) containing an alkyl-substituted polycyclic aromatic compound and a multimer thereof (hereinafter collectively referred to as “polycyclic aromatic compound”). And an organic electroluminescent element using the same, a display device, and a lighting device.
  • electron transport material an electron transport material or an electron injection material (hereinafter collectively referred to as “electron transport material”) containing an alkyl-substituted polycyclic aromatic compound and a multimer thereof (hereinafter collectively referred to as “polycyclic aromatic compound”).
  • organic electroluminescent element using the same, a display device, and a lighting device.
  • organic electroluminescent device may be referred to as “organic EL device” or simply “device”.
  • the organic EL element has a structure composed of a pair of electrodes composed of an anode and a cathode, and one layer or a plurality of 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 compound has been developed (International Publication No. 2004/061047).
  • a hole transport material for example, a triphenylamine compound has been developed (Japanese Patent Laid-Open No. 2001-172232).
  • an anthracene compound has been developed (Japanese Patent Laid-Open No. 2005-170911).
  • the charge transport property of a NO-linked compound (Compound 1 on page 63) is evaluated, but a method for producing a material other than the NO-linked compound is not described, and the element to be linked is not described. Since the electronic state of the entire compound is different if it is different, the characteristics obtained from materials other than NO-linked compounds are not yet known. Other examples of such compounds can be found (WO 2011/107186).
  • a compound having a conjugated structure with a large triplet exciton energy (T1) can emit phosphorescence having a shorter wavelength, and thus is useful as a blue light-emitting layer material.
  • a compound having a novel conjugated structure having a large T1 is also required as an electron transport material or a hole transport material sandwiching the light emitting layer.
  • Patent Document 6 a polycyclic aromatic compound containing boron and an organic EL device using the same are reported. However, in order to further improve device characteristics, an electron that can improve luminous efficiency and device lifetime. Transport materials are needed.
  • the present inventors have established an electron transport layer containing a polycyclic aromatic compound having an alkyl group introduced at a specific position (specifically, ortho position) between a pair of electrodes.
  • a specific position specifically, ortho position
  • this invention provides the electron transport material of the organic EL element containing the following alkyl-substituted polycyclic aromatic compounds or multimers thereof.
  • the chemical structure or substituent may be represented by the number of carbons.
  • the number of carbons in the case where a substituent is substituted on the chemical structure or the substituent is further substituted on the chemical group is the chemical structure.
  • the number of carbon atoms of each substituent and does not mean the total number of carbon atoms of the chemical structure and the substituent, or the total number of carbon atoms of the substituent and the substituent.
  • “substituent B of carbon number Y substituted by substituent A of carbon number X” means that “substituent B of carbon number Y” is substituted for “substituent B of carbon number Y”.
  • the carbon number Y is not the total carbon number of the substituent A and the substituent B.
  • substituted with substituent A means that “substituent A having no carbon number” is substituted for “substituent B having carbon number Y”.
  • the carbon number Y is not the total carbon number of the substituent A and the substituent B.
  • Item 1 An electron transport material or an electron injection material comprising a polycyclic aromatic compound represented by the following general formula (1) or a multimer of polycyclic aromatic compounds having a plurality of structures represented by the following general formula (1).
  • a ring, B ring and C ring are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted;
  • Y 1 is B, P, P ⁇ O, P ⁇ S, Al, Ga, As, Si—R or Ge—R, wherein R in Si—R and Ge—R is aryl, alkyl or cycloalkyl
  • X 1 and X 2 are each independently>O,>N—R,> C (—R) 2 ,> S or> Se, and R in> N—R may be substituted
  • the groups may be bonded together to form an aryl ring or heteroaryl ring together with the benzene ring, and at least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, alkyl or cycloalkyl
  • the group represented by the above formula (oR) is substituted with at least one hydrogen in the compound or structure represented by the above formula (1) in *. )
  • a ring, B ring and C ring are each independently an aryl ring or heteroaryl ring, and at least one hydrogen in these rings is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted Or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (the two aryls are bonded via a single bond or a linking group).
  • a 5- or 6-membered ring that shares a bond with Y 1 is B, P, P ⁇ O, P ⁇ S, Al, Ga, As, Si—R or Ge—R, wherein R in Si—R and Ge—R is aryl, alkyl or cycloalkyl
  • X 1 and X 2 are each independently>O,>N—R,> C (—R) 2 ,> S or> Se, wherein R in> N—R is alkyl or cycloalkyl Heteroaryl, alkyl or cycloalkyl optionally substituted with aryl, alkyl or cycloalkyl, wherein R in> C (—R)
  • An alkyl having 1 to 24 carbon atoms or a cycloalkyl having 3 to 24 carbon atoms, and adjacent groups of R 22 to R 25 are bonded to each other to form an aryl ring having 9 to 16 carbon atoms or a carbon number together with a benzene ring.
  • heteroaryl ring 6 to 15 heteroaryl ring may be formed, and at least one hydrogen in the formed ring is aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, alkyl having 1 to 24 carbon atoms
  • the group represented by the above formula (oR) may be substituted with cycloalkyl having 3 to 24 carbon atoms, and at least one hydrogen in the compound or structure represented by the above formula (1) in * Replace with Item 2.
  • Item 3 The electron transport material or electron injection material according to Item 1, wherein the polycyclic aromatic compound is represented by the following general formula (2).
  • R 1 to R 11 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls are bonded via a single bond or a linking group).
  • Aryl, alkyl having 1 to 6 carbons or cycloalkyl having 3 to 14 carbons; X 1 and X 2 are each independently>O,>N—R,> C (—R) 2 ,> S or> Se, and R in> N—R has 6 to 12 carbon atoms Aryl, C 2 -C 15 heteroaryl, C 1 -C 6 alkyl or C 3 -C 14 cycloalkyl, wherein R in> C (—R) 2 is hydrogen, C 6 -C 12 Aryl, C 1-6 alkyl or C 3-14 cycloalkyl, and R of> N—R and / or R of> C (—R) 2 is —O—, — S—, —C (—R) 2 — or a single bond may be attached to at least one of the a ring, b ring and c ring, and R of —C (—R) 2 — represents carbon An alkyl having 1 to 6 carbon atoms or a cycloal
  • R 1 is alkyl having 1 to 12 carbons
  • R 22 to R 25 are each independently hydrogen, aryl having 6 to 16 carbons, or heteroaryl having 2 to 20 carbons.
  • An alkyl having 1 to 12 carbons or a cycloalkyl having 3 to 16 carbons, and adjacent groups of R 22 to R 25 are bonded to each other to form a naphthalene ring, a phenanthrene ring, a fluorene ring or a carbazole ring together with a benzene ring.
  • At least one hydrogen in the ring formed is aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 20 carbon atoms, alkyl having 1 to 12 carbon atoms, or 3 to 16 carbon atoms It may be substituted with cycloalkyl.
  • R 1 to R 11 are each independently hydrogen, aryl having 6 to 30 carbon atoms (the aryl may be substituted with heteroaryl having 2 to 15 carbon atoms), heteroaryl having 2 to 30 carbon atoms , Diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diarylboryl (where aryl is aryl having 6 to 12 carbon atoms, and two aryls may be bonded via a single bond or a linking group) ), An alkyl having 1 to 24 carbon atoms or a cycloalkyl having 3 to 24 carbon atoms, and adjacent groups of R 1 to R 11 are bonded to each other to form a carbon number together with a ring, b ring or c ring.
  • An aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms may be formed, and at least one hydrogen in the formed ring is aryl having 6 to 30 carbon atoms
  • Aryl may be substituted with heteroaryl having 2 to 15 carbon atoms), heteroaryl having 2 to 30 carbon atoms, diarylamino (where aryl is aryl having 6 to 12 carbon atoms), diarylboryl (where aryl is carbon)
  • Y 1 is B, P, P ⁇ O, P ⁇ S or Si—R, wherein R in Si—R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or 5 to 5 carbon atoms.
  • X 1 and X 2 are each independently>O,>N—R,> C (—R) 2 or> S, where R in> N—R is aryl having 6 to 10 carbon atoms, An alkyl having 1 to 4 carbons or a cycloalkyl having 5 to 10 carbons, wherein R in> C (—R) 2 is hydrogen, aryl having 6 to 10 carbons, alkyl having 1 to 4 carbons or carbon A cycloalkyl having a number of 5 to 10, At least one hydrogen in the compound of formula (2) may be substituted with deuterium, cyano or halogen, and The group represented by the general formula (oR) is bonded to at least one of the a ring, the b ring, the c ring, and the aryl ring and heteroaryl ring formed together with these rings in *.
  • R 1 is alkyl having 1 to 6 carbons
  • R 22 to R 25 are each independently hydrogen, aryl having 6 to 12 carbons, or heteroaryl having 2 to 15 carbons.
  • An alkyl having 1 to 6 carbons or a cycloalkyl having 3 to 14 carbons, and adjacent groups of R 22 to R 25 are bonded to each other to form a naphthalene ring, a phenanthrene ring, a fluorene ring, or a carbazole ring together with a benzene ring.
  • At least one hydrogen in the formed ring is an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, an alkyl having 1 to 6 carbon atoms, or an alkyl having 3 to 14 carbon atoms
  • cycloalkyl Item 4.
  • R 1 is alkyl having 1 to 4 carbons
  • R 22 to R 25 are each independently hydrogen, aryl having 6 to 10 carbons, alkyl having 1 to 4 carbons or A cycloalkyl having 5 to 10 carbon atoms, Item 4.
  • R 1 to R 11 are each independently hydrogen, aryl having 6 to 16 carbon atoms (the aryl may be substituted with heteroaryl having 2 to 10 carbon atoms), heteroaryl having 2 to 20 carbon atoms , Diarylamino (where aryl is aryl having 6 to 10 carbon atoms), diarylboryl (where aryl is aryl having 6 to 10 carbon atoms, and two aryls may be bonded via a single bond or a linking group) ), Alkyl having 1 to 12 carbons or cycloalkyl having 3 to 16 carbons, Y 1 is B, X 1 and X 2 are each independently> O or> N—R, and R in> N—R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or 5 to 10 carbon atoms Of cycloalkyl, and The group represented by the general formula (oR) is bonded to at least one of the a ring,
  • R 1 to R 11 are each independently hydrogen, aryl having 6 to 16 carbon atoms (the aryl may be substituted with heteroaryl having 2 to 10 carbon atoms), heteroaryl having 2 to 20 carbon atoms , Diarylamino (where aryl is aryl having 6 to 10 carbon atoms), diarylboryl (where aryl is aryl having 6 to 10 carbon atoms, and two aryls may be bonded via a single bond or a linking group) ), Alkyl having 1 to 12 carbons or cycloalkyl having 3 to 16 carbons, Y 1 is B, X 1 and X 2 are> O and The group represented by the general formula (oR) is bonded to at least one of the a ring, b ring, and c ring in *, In the above formula (oR), R 1 is alkyl having 1 to 4 carbons, and R 22 to R 25 are each independently hydrogen, aryl having 6 to 10 carbons, al
  • At least one of the a ring, the b ring and the c ring may be a diphenylamino group, a carbazolyl group or a benzo group which may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms.
  • a carbazolyl group may be substituted, and these groups may be substituted with at least one of the a ring, b ring and c ring via a phenylene group;
  • a group represented by the above general formula (oR) is bonded to * at least one of the a ring, b ring and c ring;
  • Item 9 The electron transport material or electron injection material according to any one of Items 3 to 8.
  • Item 10 In the above formula (2), The a ring is substituted with a diphenylamino group, a carbazolyl group or a benzocarbazolyl group, which may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and these groups are
  • the ring a may be substituted via a phenylene group, and A group represented by the above general formula (oR) is bonded to the b ring and c ring at *.
  • Item 9 The electron transport material or electron injection material according to any one of Items 3 to 8.
  • Item 11 The electron transport material or electron injection material according to any one of Items 1 to 10, wherein in the formula (1) or formula (2), the halogen is fluorine.
  • Item 12 The electron transport material or electron injection material according to Item 1, wherein the polycyclic aromatic compound is represented by the following structural formula. (“Me” in each formula is methyl.)
  • Item 13 The electron transport material according to any one of Items 1 to 12, which is disposed between the pair of electrodes including an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and the cathode and the light emitting layer.
  • An organic electroluminescence device having an electron transport layer and / or an electron injection layer containing an electron injection material.
  • At least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, a fluoranthene derivative, a BO-based derivative, an anthracene derivative, a benzofluorene derivative, a phosphine oxide derivative, a pyrimidine derivative, a carbazole derivative, a triazine derivative, or a benzimidazole derivative.
  • the electron transport layer and / or the electron injection layer further includes an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or an alkaline earth metal.
  • Item 14 contains at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes.
  • Item 16 A display device or illumination device comprising the organic electroluminescent element according to any one of Items 13 to 15.
  • an excellent organic EL device can be provided by using a polycyclic aromatic compound having an alkyl group introduced at a specific position (specifically, ortho position) as an electron transport material. .
  • a polycyclic aromatic compound (basic skeleton portion) in which aromatic rings are connected with heteroelements such as boron, phosphorus, oxygen, nitrogen, and sulfur has a large HOMO-LUMO gap (in a thin film). It has been found that it has a band gap Eg) and a high triplet excitation energy (E T ). This is because a 6-membered ring containing a hetero element has low aromaticity, so that the reduction of the HOMO-LUMO gap accompanying the expansion of the conjugated system is suppressed, and the triplet excited state (T1 ) SOMO1 and SOMO2 are considered to be localized.
  • the polycyclic aromatic compound (basic skeleton portion) containing a hetero element according to the present invention has less exchange interaction between both orbitals due to localization of SOMO1 and SOMO2 in the triplet excited state (T1). Therefore, since the energy difference between the triplet excited state (T1) and the singlet excited state (S1) is small and shows thermally activated delayed fluorescence, it is also useful as a fluorescent material for organic EL elements.
  • a material having a high triplet excitation energy (E T ) is also useful as an electron transport layer or a hole transport layer of a phosphorescent organic EL device or an organic EL device using thermally activated delayed fluorescence.
  • these polycyclic aromatic compounds (basic skeleton parts) can move the energy of HOMO and LUMO arbitrarily by introducing substituents, the ionization potential and electron affinity are optimized according to the surrounding materials. It is possible.
  • the compound represented by the general formula (oR) is introduced into the compound of the present invention, so that an alkyl group is present at a specific position (specifically, ortho position). Will be substituted, and the glass transition temperature of the compound can be increased, whereby the heat resistance of the organic thin film can be improved, and in particular, the device life can be improved.
  • the present invention is not particularly limited to these principles.
  • the electron transport material or electron injection material according to the present invention is a polycyclic aromatic compound represented by the following general formula (1) or the following general formula (1). Containing a multimer of polycyclic aromatic compounds having a plurality of structures represented, preferably a polycyclic aromatic compound represented by the following general formula (2), or a structure represented by the following general formula (2) In the compound or structure, at least one hydrogen is substituted with a group represented by the following general formula (oR).
  • “B” in the ring together with “A” and “C” are symbols indicating the ring structure represented by the ring, and the other symbols are the same as those defined above.
  • the A ring, B ring and C ring in the general formula (1) are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted with a substituent.
  • the substituent is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino (aryl and Amino group having heteroaryl), substituted or unsubstituted diarylboryl (two aryls may be bonded via a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl , Substituted or unsubstituted alkoxy, or substituted or unsubstituted aryloxy is preferred.
  • substituents include aryl, heteroaryl, alkyl and cycloalkyl.
  • the aryl ring or heteroaryl ring may have a 5-membered or 6-membered ring sharing a bond with the central condensed bicyclic structure composed of Y 1 , X 1 and X 2. preferable.
  • the “fused bicyclic structure” means a structure in which two saturated hydrocarbon rings composed of Y 1 , X 1 and X 2 shown in the center of the general formula (1) are condensed.
  • the “six-membered ring sharing a bond with the condensed bicyclic structure” means, for example, an a ring (benzene ring (6-membered ring)) condensed to the condensed bicyclic structure as shown in the general formula (2). means.
  • the aryl ring or heteroaryl ring (which is A ring) has this 6-membered ring” means that the A ring is formed only by this 6-membered ring or includes this 6-membered ring.
  • aryl ring or heteroaryl ring having a 6-membered ring means that the 6-membered ring constituting all or part of the A ring is fused to the condensed bicyclic structure.
  • a ring (or B ring, C ring) in the general formula (1) is a ring in the general formula (2) and its substituents R 1 to R 3 (or b ring and its substituents R 8 to R 11 , c Corresponding to the ring and its substituents R 4 to R 7 ). That is, the general formula (2) corresponds to a structure in which “A to C rings having a 6-membered ring” are selected as the A to C rings of the general formula (1). In that sense, each ring of the general formula (2) is represented by lower case letters a to c.
  • adjacent groups of the substituents R 1 to R 11 of the a ring, b ring, and c ring are bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring, or c ring.
  • at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are connected via a single bond or a linking group).
  • the polycyclic aromatic compound represented by the general formula (2) has the following formulas (2-1) and (2-2) depending on the mutual bonding form of the substituents in the a-ring, b-ring and c-ring. As shown, the ring structure constituting the compound changes. A ′ ring, B ′ ring and C ′ ring in each formula correspond to A ring, B ring and C ring in general formula (1), respectively. In addition, the definitions of R 1 to R 11 , a, b, c, Y 1 , X 1 and X 2 in each formula are the same as those in the general formula (2).
  • the A ′ ring, the B ′ ring and the C ′ ring are adjacent to the substituents R 1 to R 11 in the general formula (2).
  • the aryl ring or heteroaryl ring formed together with the a ring, b ring and c ring, respectively the condensed ring formed by condensing another ring structure to the a ring, b ring or c ring. It can also be said).
  • b-ring R 8 and c-ring R 7 , b-ring R 11 and a-ring R 1 , c-ring R 1 R 4 and R 3 in the a ring do not correspond to “adjacent groups” and they are not bonded. That is, “adjacent group” means an adjacent group on the same ring.
  • the compound represented by the above formula (2-1) or formula (2-2) 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 condensation of a benzothiophene ring, and a formed condensed ring A ′ (or condensed ring B ′ or condensed ring C ′) are respectively a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring.
  • Y 1 in the general formula (1) is B, P, P ⁇ O, P ⁇ S, Al, Ga, As, Si—R or Ge—R, and R in Si—R and Ge—R is Aryl, alkyl or cycloalkyl.
  • the atom bonded to the A ring, B ring or C ring is P, Si or Ge.
  • Y 1 is preferably B, P, P ⁇ O, P ⁇ S or Si—R, more preferably B or P ⁇ O, and particularly preferably B. This explanation is the same for Y 1 in the general formula (2).
  • X 1 and X 2 in the general formula (1) are each independently>O,>N—R,> C (—R) 2 ,> S or> Se, and R in> N—R is ,
  • R of> N—R and / or R of> C (—R) 2 are each represented by the above A ring, B ring and R It may be bonded to at least one of the C rings, and the linking group is preferably —O—, —S— or —C (—R) 2 —.
  • R in the “—C (—R) 2 —” is hydrogen, alkyl, or cycloalkyl.
  • X 1 and X 2 are each independently preferably>O,> N—R or> C (—R) 2, more preferably> O or> N—R, and particularly preferably> O. This description is the same for X 1 and X 2 in the general formula (2).
  • R of> N—R and / or R of> C (—R) 2 is at least one of the A ring, B ring and C ring by a linking group or a single bond.
  • the definition of “bonded to one” is that in the general formula (2), “R of> N—R and / or R of> C (—R) 2 is —O—, —S—, —C (—R) 2 — or a single bond to at least one of the a ring, b ring and c ring ”.
  • This definition can be expressed by a compound having a ring structure represented by the following formula (2-3-1) in which X 1 and X 2 are incorporated into the condensed ring B ′ and the condensed ring C ′. That is, for example, a B ′ ring (or a ring formed by condensation of another ring so as to incorporate X 1 (or X 2 ) into the benzene ring which is the b ring (or c ring) in the general formula (2) (or C ′ ring).
  • 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 is a compound having a ring structure in which X 1 and / or X 2 is incorporated into the condensed ring A ′, which is represented by the following formula (2-3-2) or formula (2-3-3) But it can be expressed. That is, for example, a compound having an A ′ ring formed by condensing another ring so as to incorporate X 1 (and / or X 2 ) into the benzene ring which is the a ring in the general formula (2). .
  • the formed condensed ring A ′ is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.
  • R 1 to R 11 , a, b, c, Y 1 , X 1 and X 2 in the above formulas are the same as those in the general formula (2).
  • Examples of the “aryl ring” that is A ring, B ring and C ring in the general formula (1) include aryl rings having 6 to 30 carbon atoms, preferably aryl rings having 6 to 16 carbon atoms, An aryl ring having 6 to 12 carbon atoms is more preferable, and an aryl ring having 6 to 10 carbon atoms is particularly preferable.
  • the “aryl ring” is defined as “an aryl ring formed by bonding adjacent groups of R 1 to R 11 together with a ring, b ring or c ring” defined in the general formula (2).
  • the total number of carbon atoms of the condensed ring in which a 5-membered ring is condensed is a carbon having a lower limit. Number.
  • aryl rings include monocyclic benzene rings, bicyclic biphenyl rings, condensed bicyclic naphthalene rings, tricyclic terphenyl rings (m-terphenyl, o -Terphenyl, p-terphenyl), condensed tricyclic systems such as acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, condensed tetracyclic systems such as triphenylene ring, pyrene ring, naphthacene ring, condensed pentacyclic system Examples include a perylene ring and a pentacene ring.
  • heteroaryl ring that is A ring, B ring and C ring in the general formula (1) include heteroaryl rings having 2 to 30 carbon atoms, preferably heteroaryl rings having 2 to 25 carbon atoms.
  • a heteroaryl ring having 2 to 20 carbon atoms is more preferable, a heteroaryl ring having 2 to 15 carbon atoms is more preferable, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferable.
  • heteroaryl ring include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom.
  • the “heteroaryl ring” is a heteroaryl formed together with a ring, b ring or c ring by bonding adjacent groups of “R 1 to R 11 ” defined in the general formula (2).
  • the a ring (or b ring, c ring) is already composed of a benzene ring having 6 carbon atoms, the total number of carbon atoms of the condensed ring in which a 5-membered ring is condensed is lower limit. The number of carbons.
  • heteroaryl ring examples include pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, Pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring Cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, p
  • At least one hydrogen in the above “aryl ring” or “heteroaryl ring” is the first substituent, which is substituted or unsubstituted “aryl”, substituted or unsubstituted “heteroaryl”, substituted or unsubstituted “Diarylamino”, substituted or unsubstituted “diheteroarylamino”, substituted or unsubstituted “arylheteroarylamino”, substituted or unsubstituted “diarylboryl” (two aryls are connected via a single bond or a linking group)
  • Optionally substituted) ", substituted or unsubstituted” alkyl ", substituted or unsubstituted” cycloalkyl ", substituted or unsubstituted” alkoxy ", or substituted or unsubstituted” aryloxy "
  • an aryl group such as “aryl”, “heteroaryl”, or “diarylamin
  • alkyl as the first substituent may be either linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms and branched alkyl having 3 to 24 carbon atoms.
  • Alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons) is preferable, alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons) is more preferable, and alkyl having 1 to 6 carbons. (Branched alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms) is particularly preferable.
  • alkyl having 1 to 4 carbon atoms a methyl group and a t-butyl group are more preferable, but a t-butyl group is more preferable.
  • alkyl examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, and 1-methyl.
  • Pentyl 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n- Tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hepta Sill, n- octadecyl, such as n- eicosyl, and the like
  • Cycloalkyl as the first substituent includes cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, and cycloalkyl having 3 to 14 carbon atoms. Cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, cycloalkyl having 5 carbon atoms and the like.
  • cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (particularly methyl) substituents having 1 to 4 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 [2.2.2] octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.
  • alkoxy as the first substituent includes, for example, straight-chain alkoxy having 1 to 24 carbon atoms or branched alkoxy having 3 to 24 carbon atoms.
  • C1-C18 alkoxy (C3-C18 branched alkoxy) is preferred, C1-C12 alkoxy (C3-C12 branched alkoxy) is more preferred, and C1-C6 Of alkoxy (C3-C6 branched chain alkoxy) is more preferable, and C1-C4 alkoxy (C3-C4 branched chain alkoxy) is particularly preferable.
  • alkoxy examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.
  • aryl in the “diarylboryl” as the first substituent, the above description of aryl can be cited.
  • the two aryls may be bonded via a single bond or a linking group (eg,> C (—R) 2 ,>O,> S or> N—R).
  • R in> C (—R) 2 and> N—R is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy (hereinafter, the first substituent), and the first The substituent may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl (hereinafter, the second substituent).
  • Specific examples of these groups include aryl, hetero as the first substituent described above. References can be made to aryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy.
  • 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 preferably the following structural formulas (S-1) to (S-94) And more preferably a group represented by formula (S-1), formula (S-2), formula (S-5), formula (S-9) to formula (S-19), A group represented by any one of formulas (S-24) to (S-50) and (S-51) to (S-94), more preferably formula (S-1), (S-2), Formula (S-5), Formula (S-9), Formula (S-10), Formula (S-15), Formula (S-16), Formula (S-24), Formula (S-30), formula (S-46), formula (S-48), formula (S-50), formula (S-51), formula (S-56) to formula (S-58), formula (S -70), formula (S-71), formula (S-73), formula S-74), formula (S-76), formula (S-79), formula (S-80), a group represented by any one of formulas (S-1)
  • second substituent examples include aryl, heteroaryl, alkyl, and cycloalkyl, and specific examples thereof include a monovalent group of the above-described “aryl ring” or “heteroaryl ring”, Reference can also be made to the description of “alkyl” or “cycloalkyl” as the first substituent.
  • aryl and heteroaryl as the first and second substituents, at least one hydrogen in them is aryl such as phenyl (specific examples are the groups described above), alkyl such as methyl (specific examples are described above) Group) or a group substituted with cycloalkyl such as cyclohexyl (specific examples are the groups described above) is also included in the aryl and heteroaryl as the first and second substituents.
  • aryl such as phenyl
  • alkyl such as methyl (specific examples are described above) Group
  • a group substituted with cycloalkyl such as cyclohexyl specifically examples are the groups described above
  • at least one hydrogen at the 9-position is substituted with aryl such as phenyl, alkyl such as methyl, or cycloalkyl such as cyclohexyl.
  • Groups are also included in heteroaryl as the first and second substituents.
  • the first and second substituents are benzimidazole groups
  • at least one hydrogen in the group is substituted with aryl such as phenyl, alkyl such as methyl, or cycloalkyl such as cyclohexyl.
  • aryl such as phenyl, alkyl such as methyl, or cycloalkyl such as cyclohexyl.
  • alkyl, cycloalkyl or alkoxy in R 1 to R 11 see the description of “alkyl”, “cycloalkyl” or “alkoxy” as the first substituent in the description of the general formula (1). can do.
  • aryl, heteroaryl, alkyl or cycloalkyl as a substituent for these groups.
  • adjacent groups of R 1 to R 11 are bonded to form an aryl ring or a heteroaryl ring together with a ring, b ring or c ring, heteroaryl which is a substituent for these rings.
  • R in Si—R and Ge—R in Y 1 in the general formula (1) is aryl, alkyl or cycloalkyl, and examples of the aryl, alkyl or cycloalkyl include the groups described above.
  • aryl having 6 to 10 carbon atoms for example, phenyl, naphthyl, etc.
  • alkyl having 1 to 4 carbon atoms for example, methyl, ethyl, t-butyl, etc., especially t-butyl
  • cycloalkyl having 5 to 10 carbon atoms preferably Is preferably cyclohexyl or adamantyl.
  • This explanation is the same for Y 1 in the general formula (2).
  • R in> N—R in X 1 and X 2 in the general formula (1) is aryl, heteroaryl, alkyl or cycloalkyl, which may be substituted with the second substituent described above. At least one hydrogen in aryl may be substituted, for example with alkyl or cycloalkyl. Examples of the aryl, heteroaryl, alkyl and cycloalkyl include the groups described above.
  • aryl having 6 to 10 carbon atoms eg, phenyl, naphthyl, etc.
  • heteroaryl having 2 to 15 carbon atoms eg, carbazolyl, etc.
  • alkyl having 1 to 4 carbon atoms eg, methyl, ethyl, t-butyl, etc.
  • cycloalkyl having 5 to 10 carbon atoms preferably cyclohexyl or adamantyl.
  • C (-R) 2 of R in X 1 and X 2 in the general formula (1) is hydrogen, may be substituted with a second substituent described above, aryl, alkyl or cycloalkyl, aryl At least one hydrogen in may be substituted, for example with alkyl or cycloalkyl.
  • aryl, alkyl or cycloalkyl include the groups described above.
  • aryl having 6 to 10 carbon atoms for example, phenyl, naphthyl, etc.
  • alkyl having 1 to 4 carbon atoms for example, methyl, ethyl, t-butyl, etc., especially t-butyl
  • cycloalkyl having 5 to 10 carbon atoms preferably Is preferably cyclohexyl or adamantyl.
  • R in “—C (—R) 2 —” which is the linking group in the general formula (1) is hydrogen, alkyl or cycloalkyl, and examples of the alkyl or cycloalkyl include the groups described above.
  • alkyl having 1 to 4 carbon atoms for example, methyl, ethyl, t-butyl, etc., especially t-butyl) or cycloalkyl having 5 to 10 carbon atoms (preferably cyclohexyl or adamantyl) is preferable.
  • This explanation is the same for “—C (—R) 2 —” which is a linking group in the general formula (2).
  • the present invention also provides a multimer of polycyclic aromatic compounds having a plurality of unit structures represented by the general formula (1), preferably a polycyclic aromatic having a plurality of unit structures represented by the general formula (2).
  • the multimer is preferably a dimer to hexamer, more preferably a dimer to trimer, and particularly preferably a dimer.
  • the multimer may be in a form having a plurality of the above unit structures in one compound.
  • the unit structure is a single bond, a linking group such as an alkylene group having 1 to 3 carbon atoms, a phenylene group, or a naphthylene group.
  • any ring (A ring, B ring or C ring, a ring, b ring or c ring) contained in the unit structure is shared by the multiple unit structures
  • the bonded form (ring-shared multimer) may be used, and any ring (A ring, B ring or C ring, a ring, b ring or c ring) included in the unit structure may be May be combined in a condensed form (ring-condensed multimer), but a ring-shared multimer and a ring-condensed multimer are preferable, and a ring-shared multimer is more preferable.
  • Examples of such multimers include the following formula (2-4), formula (2-4-1), formula (2-4-2), formula (2-5-1) to formula (2-5). -4) or a multimeric compound represented by formula (2-6).
  • the multimeric compound represented by the following formula (2-4) can be represented by a plurality of general formulas (2) so as to share a benzene ring which is a ring, as explained by the general formula (2). It is a multimeric compound (ring-shared multimer) having a unit structure in one compound.
  • the multimeric compound represented by the following formula (2-4-1) can be expressed by two general formulas (2) such that a benzene ring which is a ring is shared, as explained by the general formula (2).
  • the multimeric compound represented by the following formula (2-4-2) can be described by the general formula (2), so that the benzene ring which is the a ring is shared, so that the three general formulas (2)
  • the multimeric compound represented by the following formulas (2-5-1) to (2-5-4) can be represented by the general formula (2) as a benzene ring which is a b ring (or a c ring). Is a multimeric compound (ring-sharing multimer) having a plurality of unit structures represented by the general formula (2) in one compound.
  • the multimeric compound represented by the following formula (2-6) can be represented by the general formula (2), for example, a benzene ring which is a b ring (or a ring or c ring) of a certain unit structure and a certain unit
  • Type multimer ).
  • the multimeric compound includes a multimerized form represented by formula (2-4), formula (2-4-1) or formula (2-4-2), and formulas (2-5-1) to (2) -5-4) or a multimer in combination with a multimerized form represented by formula (2-6) may be used, and may be represented by formula (2-5-1) to formula (2-5) 4) may be a multimer in which the multimerized form represented by any one of 4) and the multimerized form represented by formula (2-6) are combined.
  • Formula (2-4) and formula (2) -4-1) or the multimerized form represented by formula (2-4-2) and the multimerized form represented by any of formulas (2-5-1) to (2-5-4) A multimer combined with the multimerized form represented by the formula (2-6) may be used.
  • all or part of the polycyclic aromatic compounds represented by the general formula (1) or (2) and the chemical structures of the multimers thereof may be deuterium, cyano, or halogen.
  • the hydrogen in the group of the general formula (oR) described later can be substituted with deuterium, cyano or halogen, but among these, all or part of hydrogen in aryl or heteroaryl is substituted with deuterium, cyano or halogen Is mentioned.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine
  • At least one hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (1) or (2) and the multimer thereof is substituted with a group represented by the following general formula (oR).
  • all hydrogen or part of hydrogen may be a group represented by the following formula (oR).
  • R 21 is alkyl
  • R 22 to R 25 are each independently hydrogen, aryl, heteroaryl, alkyl or cycloalkyl, and adjacent to R 22 to R 25.
  • the groups may be bonded together to form an aryl ring or heteroaryl ring together with the benzene ring, and at least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, alkyl or cycloalkyl
  • the group represented by the above formula (oR) is substituted with at least one hydrogen in the compound or structure represented by the above formula (1) in *.
  • the “alkyl” for R 21 may be either linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms and branched alkyl having 3 to 24 carbon atoms.
  • Alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons) is preferable, alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons) is more preferable, and alkyl having 1 to 6 carbons. (Branched alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms) is particularly preferable.
  • alkyl having 1 to 4 carbon atoms a methyl group and a t-butyl group are more preferable, but a methyl group is more preferable.
  • alkyl examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, and 1-methyl.
  • Pentyl 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n- Tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hepta Sill, n- octadecyl, such as n- eicosyl, and the like
  • adjacent groups of R 22 to R 25 may be bonded to each other to form an aryl ring or a heteroaryl ring together with the benzene ring, and at least one hydrogen in the formed ring is aryl, heteroaryl , Alkyl or cycloalkyl may be substituted, but also in these explanations, in the above general formula (2), adjacent groups of R 1 to R 11 are bonded to each other to form a ring, b ring or c
  • the description of forming an aryl ring or a heteroaryl ring together with the ring can be cited.
  • aryl ring or heteroaryl ring formed together with the benzene ring include a naphthalene ring, a phenanthrene ring, a fluorene ring, and a carbazole ring.
  • the group represented by the formula (oR) may be substituted with at least one hydrogen in the compound or structure represented by the above formula (1).
  • the A ring, B in the general formula (1), At least one of ring and C ring (in general formula (2), a ring, b ring, c ring, and adjacent groups of R 1 to R 11 are bonded together to form a ring, b At least one of an aryl ring and a heteroaryl ring formed together with the ring or c ring).
  • the B ring and / or the C ring of the general formula (1) are An aryl ring and / or a heteroaryl ring formed together with a ring b or c). More preferably, both the B ring and the C ring of the general formula (1) (in the general formula (2), both the b ring and the c ring, or adjacent groups of R 8 to R 11 are bonded to each other.
  • a diarylamino group (particularly a diphenylamino group), a carbazolyl group or a benzocarbazolyl group is substituted.
  • These groups may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and these groups may be substituted with a polycyclic aromatic compound and a large amount thereof via a phenylene group.
  • the body may be substituted.
  • These groups are preferably at least one of A ring, B ring and C ring of general formula (1) (in general formula (2), a ring, b ring, c ring, and R 1 To adjacent groups of R 11 and bonded to at least one of an aryl ring and a heteroaryl ring formed together with a ring, b ring or c ring) directly or via a phenylene group Yes.
  • the A ring of the general formula (1) in the case of the general formula (2), an a ring or an aryl formed by bonding adjacent groups of R 1 to R 3 together with the a ring A ring or a heteroaryl ring
  • a phenylene group is preferably at least one of A ring, B ring and C ring of general formula (1) (in general formula (2), a ring, b ring, c ring, and R 1 To adjacent groups of R 11 and bonded to at least one of an aryl ring and a heteroaryl ring formed together with a
  • alkyl-substituted polycyclic aromatic compound of the present invention include compounds represented by the following structural formula.
  • “Me” is a methyl group
  • “Et” is an ethyl group
  • “iPr” is a propyl group
  • “Hep” is a heptyl group
  • “tBu” is a t-butyl group
  • “CN” is a cyano group. Indicates.
  • a general reaction such as a nucleophilic substitution reaction and an Ullmann reaction can be used for an etherification reaction, and a general reaction such as a Buchwald-Hartwig reaction can be used for an amination reaction.
  • a tandem hetero Friedel-Crafts reaction continuous aromatic electrophilic substitution reaction, the same applies hereinafter
  • the second reaction is a reaction for introducing Y 1 that connects the A ring (a ring), the B ring (b ring), and the C ring (c ring).
  • Y 1 is a boron atom and X 1 and X 2 are oxygen atoms is shown below.
  • a hydrogen atom and n- butyllithium between X 1 and X 2 ortho-metalated with sec- butyllithium or t- butyl lithium, and the like.
  • the said scheme (1) and (2) mainly show the manufacturing method of the polycyclic aromatic compound represented by General formula (1) or (2), about the multimer, about several It can manufacture by using the intermediate body which has A ring (a ring), B ring (b ring), and C ring (c ring). Details will be described in the following schemes (3) to (5).
  • the target product can be obtained by setting the amount of the reagent such as butyl lithium to be doubled or tripled.
  • lithium is introduced to a desired position by orthometalation.
  • a halogen such as a bromine atom at a position where lithium is to be introduced and introduce lithium to the desired position by halogen-metal exchange. it can.
  • the group represented by the general formula (oR) is bonded to the a ring, b ring and / or c ring (particularly the a ring) in the general formula (2), and further, the a ring, b ring and / or c ring A diphenylamino group, a carbazolyl group or a benzocarbazolyl group, which may be substituted with an alkyl having 1 to 4 carbon atoms (especially b ring and / or c ring)
  • a polycyclic aromatic compound in which a ring, b ring and / or c ring may be substituted can also be produced according to the above scheme.
  • the intermediate before cyclization in Scheme (6) can also be synthesized by the method shown in Scheme (1) and the like. That is, an intermediate having a desired substituent can be synthesized by appropriately combining Buchwald-Hartwig reaction, Suzuki coupling reaction, or etherification reaction such as nucleophilic substitution reaction or Ullmann reaction. In these reactions, a commercially available product can be used as the precursor material.
  • FIG. 1 is a schematic cross-sectional view showing an organic EL element according to this embodiment.
  • An 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, and a hole injection layer 103.
  • the hole transport layer 104 provided, the light emitting layer 105 provided on the hole transport layer 104, the electron transport layer 106 provided on the light emitting layer 105, and the electron transport layer 106 are provided.
  • the electron injection layer 107 and the cathode 108 provided on the electron injection layer 107 are provided.
  • the organic EL element 100 is manufactured in the reverse order, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer 107.
  • An electron transport layer 106 provided on the light emitting layer 105, 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 a hole transport layer 104.
  • the hole injection layer 103 provided on the hole injection layer 103 and the anode 102 provided on the hole injection layer 103 may be used.
  • each said layer may consist of a single layer, respectively, and may consist of multiple layers.
  • the layer constituting the organic EL element in addition to the above-described configuration aspect of “substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode”, “Substrate / anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode”, “substrate / Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode ”,“ substrate / Anode / light emitting layer / electron transport layer / electron injection layer / cathode ”,“ substrate / Anode /
  • the substrate 101 is a support for the organic EL element 100, and quartz, glass, metal, plastic, or the like is usually used.
  • the substrate 101 is formed into a plate shape, a film shape, or a sheet shape according to the purpose.
  • a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used.
  • glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable.
  • soda lime glass, non-alkali glass, or the like is used, and the thickness only needs to be sufficient to maintain the mechanical strength.
  • the upper limit value of the thickness is, for example, 2 mm or less, preferably 1 mm or less.
  • the glass material is preferably alkali-free glass because it is better to have less ions eluted from the glass.
  • soda lime glass with a barrier coat such as SiO 2 is also commercially available, so it can be used. it can.
  • the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one surface in order to improve the gas barrier property, and a synthetic resin plate, film or sheet having a low gas barrier property is used as the substrate 101. When used, it is preferable to provide a gas barrier film.
  • the anode 102 serves to inject holes into the light emitting layer 105.
  • the hole injection layer 103 and / or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. .
  • Examples of the material for forming the anode 102 include inorganic compounds and organic compounds.
  • Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide) Products (IZO), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, and the like.
  • Examples of the organic compound include polythiophene such as poly (3-methylthiophene), conductive polymer such as polypyrrole and polyaniline, and the like. In addition, it can select suitably from the substances used as an anode of an organic EL element.
  • the resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but is preferably low resistance from the viewpoint of power consumption of the light emitting element.
  • an ITO substrate of 300 ⁇ / ⁇ or less functions as an element electrode, but at present, since it is possible to supply a substrate of about 10 ⁇ / ⁇ , 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 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104.
  • the hole transport layer 104 serves to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 via 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 kind or two or more kinds of hole injection / transport materials or a mixture of the hole injection / transport material and the polymer binder. Is done.
  • an inorganic salt such as iron (III) chloride may be added to the hole injection / transport material to form a layer.
  • a hole injection / transport material As a hole injection / transport material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes to which an electric field is applied. The hole injection efficiency is high, and the injected holes are transported efficiently. It is desirable to do. For this purpose, it is preferable to use a substance that has a low ionization potential, a high hole mobility, excellent stability, and is less likely to generate trapping impurities during production and use.
  • a compound conventionally used as a charge transport material for holes in a photoconductive material, a p-type semiconductor, and a hole injection layer of an organic EL element are used.
  • any compound can be selected and used from known compounds used in the hole transport layer. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (aromatic tertiary class).
  • polycarbonates, styrene derivatives, polyvinylcarbazole, polysilanes, etc. having the aforementioned monomers in the side chain are preferred, but light emitting devices There is no particular limitation as long as it is a compound that can form a thin film necessary for the fabrication, inject holes from the anode, and further transport holes.
  • organic semiconductors are strongly influenced by the doping.
  • Such 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 tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known for doping of electron donor materials.
  • TCNQ tetracyanoquinone dimethane
  • F4TCNQ 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane
  • the light-emitting layer 105 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 a compound that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state It is preferable that the compound exhibits a strong light emission (fluorescence) efficiency.
  • the light emitting layer may be either a single layer or a plurality of layers, each formed of a light emitting layer material (host material, dopant material). Each of the host material and the dopant material may be one kind or a plurality of combinations.
  • the dopant material may be included in the host material as a whole, or may be included partially.
  • As a doping method it can be formed by a co-evaporation method with a host material. However, it can be formed by a wet film formation method after being pre-mixed with a host material and simultaneously vapor-depositing or pre-mixed with an organic solvent and a host material. A film may be formed.
  • the amount of host material used depends on the type of host material and can be determined according to the characteristics of the host material.
  • the standard of the amount of the host material used is preferably 50 to 99.999% by weight of the entire light emitting layer material, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight. It is.
  • the amount of dopant material used depends on the type of dopant material, and can be determined according to the characteristics of the dopant material.
  • the standard of the amount of dopant used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and further preferably 0.1 to 10% by weight of the entire material for the light emitting layer. is there.
  • the above range is preferable in that, for example, the concentration quenching phenomenon can be prevented.
  • Host materials include fused ring derivatives such as anthracene, pyrene, dibenzochrysene or fluorene that have been known as light emitters, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, and cyclopentadiene derivatives.
  • fused ring derivatives such as anthracene, pyrene, dibenzochrysene or fluorene that have been known as light emitters
  • bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives
  • tetraphenylbutadiene derivatives tetraphenylbutadiene derivatives
  • cyclopentadiene derivatives cyclopentadiene derivatives.
  • an anthracene compound, a fluorene compound, or a dibenzochrysene compound
  • the electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106.
  • the electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105.
  • the electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport / injection materials or a mixture of the electron transport / injection material and the polymer binder.
  • the electron injection / transport layer is a layer that is responsible for injecting electrons from the cathode and further transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. For this purpose, it is preferable to use a substance that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate trapping impurities during production and use. However, considering the transport balance between holes and electrons, if the role of effectively preventing the holes from the anode from flowing to the cathode side without recombination is mainly played, the electron transport capability is much higher. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material having a high electron transport capability. Therefore, the electron injection / transport layer in this embodiment may include a function of a layer that can efficiently block the movement of holes.
  • a material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107 a compound conventionally used as an electron transport compound in a photoconductive material, used for an electron injection layer and an electron transport layer of an organic EL element It can be used by arbitrarily selecting from known compounds.
  • the polycyclic aromatic compound represented by the general formula (1) and a multimer thereof can be used as the electron transport material and the electron injection material.
  • the material used for the electron transport layer or the electron injection layer is an aromatic ring or a heteroaromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus. It is preferable to contain at least one selected from a compound consisting of: a pyrrole derivative and its condensed ring derivative, and a metal complex having 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, naphthalimide derivatives Quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives and indole derivatives.
  • metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials can 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, oxadiazoles.
  • metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. can give.
  • the above-mentioned materials can be used alone, but they may be mixed 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 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, cycloalkyl, aryl that may be substituted, silyl that is substituted, or nitrogen that may be substituted A heterocyclic ring, or at least one of cyano
  • R 13 to R 16 are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl, 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 Are each independently an integer of 0 to 3.
  • substituents in the case of “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, and cycloalkyl.
  • R 11 and R 12 are each independently hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which is substituted, nitrogen which may be substituted
  • a heterocycle containing at least one of cyano and R 13 to R 16 are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl or an optionally substituted aryl.
  • R 21 and R 22 are each independently at least one of hydrogen, alkyl, aryl optionally substituted with cycloalkyl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano.
  • X 1 is substituted carbon atoms and optionally more than 20 arylene
  • n is independently an integer of 0 to 3
  • Te is an integer of 0 to 4 independently.
  • substituent in the case of “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, and cycloalkyl.
  • R 11 and R 12 are each independently hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which is substituted, nitrogen which may be substituted
  • a heterocycle containing at least one of cyano and R 13 to R 16 are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl or an optionally substituted aryl.
  • X 1 is an optionally substituted arylene having 20 or less carbon atoms, and n is each independently an integer of 0 to 3.
  • substituent in the case of “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). (In each formula, each R a is independently an alkyl group, a cycloalkyl group, or an optionally substituted phenyl group.)
  • this borane derivative include the following compounds.
  • 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 the formula (ETM-2-1) or the formula (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 carbons), cycloalkyl (preferably cyclohexane having 3 to 12 carbons). 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 cyclohexane having 3 to 12 carbon atoms). Alkyl) or aryl (preferably aryl having 6 to 30 carbon atoms), and R 11 and R 12 may be bonded to form a ring.
  • the “pyridine substituent” is any of the following formulas (Py-1) to (Py-15), and each pyridine substituent is independently an alkyl or carbon having 1 to 4 carbon atoms. It may be substituted with cycloalkyl of several 5-10. Further, the pyridine-based substituent may be bonded to ⁇ , anthracene ring or fluorene ring in each formula through a phenylene group or a naphthylene group.
  • the pyridine-based substituent is any one of the above formulas (Py-1) to (Py-15), and among these, any of the following formulas (Py-21) to (Py-44) It is preferable.
  • At least one hydrogen in each pyridine derivative may be substituted with deuterium, and among the two “pyridine substituents” in the above formula (ETM-2-1) and formula (ETM-2-2) One of these may be replaced by aryl.
  • Alkyl in R 11 to R 18 may be either linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms and branched alkyl having 3 to 24 carbon atoms.
  • Preferred “alkyl” is alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms). More preferable “alkyl” is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More preferable “alkyl” is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred “alkyl” is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).
  • alkyl 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, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -Propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecy
  • alkyl having 1 to 4 carbon atoms to be substituted on the pyridine-based substituent As the above description of alkyl can be cited.
  • cycloalkyl in R 11 to R 18 examples include 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 examples of “cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.
  • 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 preferred is aryl having 6 to 12 carbon atoms.
  • aryl having 6 to 30 carbon atoms include monocyclic aryl phenyl, condensed bicyclic aryl (1-, 2-) naphthyl, condensed tricyclic aryl acenaphthylene- ( 1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1-, 2 -, 3-, 4-, 9-) phenanthryl, condensed tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, naphthacene- (1- , 2-, 5-) yl, perylene- (1-, 2-, 3-) yl which is a fused pentacyclic aryl, pentacene- (1-, 2-, 5-, 6-) yl and the like. .
  • aryl having 6 to 30 carbon atoms includes phenyl, naphthyl, phenanthryl, chrycenyl, triphenylenyl and the like, more preferably phenyl, 1-naphthyl, 2-naphthyl and phenanthryl, particularly preferably phenyl, 1 -Naphthyl or 2-naphthyl.
  • R 11 and R 12 in the above formula (ETM-2-2) may be bonded to form a ring.
  • the 5-membered ring of the fluorene skeleton includes cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, Cyclohexane, fluorene, indene and the like may be spiro-bonded.
  • pyridine derivative examples include the following compounds.
  • 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 International Publication No. 2010/134352.
  • X 12 to X 21 are hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted Represents heteroaryl.
  • substituent when substituted include aryl, heteroaryl, alkyl, and cycloalkyl.
  • fluoranthene derivative examples include the following compounds.
  • the BO derivative is, for example, a polycyclic aromatic compound represented by the following formula (ETM-4) or a multimer of polycyclic aromatic compounds 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, diarylboryl (the two aryls are bonded via a single bond or a linking group).
  • alkyl, cycloalkyl, alkoxy or aryloxy, wherein at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
  • adjacent groups of R 1 to R 11 may be bonded to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, and at least one hydrogen in the formed ring Is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be linked via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryl It may be substituted with oxy and at least one hydrogen in them may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.
  • At least one hydrogen in the compound or structure represented by the formula (ETM-4) may be substituted with halogen or deuterium.
  • this BO derivative include the following compounds.
  • 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, and R 1 to R 4 are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons or carbon number 6 to 20 aryls.
  • Ar can be independently selected as appropriate from divalent benzene or naphthalene, and the two Ar may be different or the same, but the same from the viewpoint of the ease of synthesis of the anthracene derivative. It is preferable that Ar is bonded to pyridine to form a “part consisting of Ar and pyridine”. This part is an anthracene as a group represented by any of the following formulas (Py-1) to (Py-12), for example. Is bound to.
  • a group represented by any one of the above formulas (Py-1) to (Py-9) is preferable, and any one of the above formulas (Py-1) to (Py-6) may be used. More preferred are the groups
  • the two “sites consisting of Ar and pyridine” bonded to anthracene may have the same structure or different structures, but are preferably the same structure from the viewpoint of ease of synthesis of the anthracene derivative. However, from the viewpoint of device characteristics, it is preferable that the structures of the two “sites composed of Ar and pyridine” are the same or different.
  • the alkyl having 1 to 6 carbon atoms in R 1 to R 4 may be linear or branched. That is, it is a linear alkyl having 1 to 6 carbon atoms or a branched alkyl having 3 to 6 carbon atoms. More preferred is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).
  • 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, Examples include 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc., preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. More preferred are methyl, ethyl, or t-butyl.
  • cycloalkyl having 3 to 6 carbon atoms in R 1 to R 4 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.
  • 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 monocyclic aryl phenyl, (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, bicyclic aryl (2 -, 3-, 4-) biphenylyl, (1-, 2-) naphthyl which is a condensed bicyclic aryl, terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4) which is a tricyclic aryl '-Yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2
  • 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 preferred is phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, and most preferred is 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 an 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.
  • Aryl having 6 to 16 carbon atoms is preferred, aryl having 6 to 12 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred.
  • Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, 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) The explanation in can be cited.
  • anthracene derivatives include the following compounds.
  • 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 an 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.
  • Aryl having 6 to 16 carbon atoms is preferred, aryl having 6 to 12 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred.
  • Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl and the like.
  • Ar 2 is independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably aryl having 6 to 30 carbon atoms). And two Ar 2 may be bonded to form a ring.
  • Alkyl in Ar 2 may be either linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms and branched alkyl having 3 to 24 carbon atoms.
  • Preferred “alkyl” is alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms). More preferable “alkyl” is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More preferable “alkyl” is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred “alkyl” is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).
  • alkyl 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, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like.
  • cycloalkyl in Ar 2 examples include 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 examples of “cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.
  • aryl in Ar 2 , preferred aryl is aryl having 6 to 30 carbon atoms, more preferred aryl is aryl having 6 to 18 carbon atoms, still more preferred is aryl having 6 to 14 carbon atoms, Preferred is aryl having 6 to 12 carbon atoms.
  • aryl having 6 to 30 carbon atoms include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, naphthacenyl, perylenyl, pentacenyl and the like.
  • Two Ar 2 may be bonded to form a ring.
  • cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, or indene is spiro-bonded to the 5-membered ring of the fluorene skeleton. May be.
  • benzofluorene derivative examples include the following compounds.
  • 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). Details are also described in International Publication No. 2013/079217.
  • R 5 is substituted or unsubstituted alkyl having 1 to 20 carbons, cycloalkyl having 3 to 20 carbons, aryl having 6 to 20 carbons or heteroaryl having 5 to 20 carbons;
  • R 6 is CN, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or 5 to 5 carbon atoms.
  • R 7 and R 8 are each independently substituted or unsubstituted aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms;
  • R 9 is oxygen or sulfur;
  • j is 0 or 1
  • k is 0 or 1
  • r is an integer of 0 to 4, and
  • q is an integer of 1 to 3.
  • substituent when substituted include aryl, heteroaryl, alkyl, and cycloalkyl.
  • 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 are hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, alkylthio group, cycloalkylthio group, aryl ether group , Arylthioether group, aryl group, heterocyclic group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, amino group, nitro group, silyl group, and a condensed ring formed between adjacent substituents Chosen from.
  • 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, and when n is 3, R 1 does not exist.
  • the alkyl group represents, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or a butyl group, which may be unsubstituted or substituted.
  • the substituent in the case of being substituted is not particularly limited, and examples thereof include an alkyl group, an aryl group, and a heterocyclic group, and this point is common to the following description.
  • the number of carbon atoms of 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 represents a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, adamantyl and the like, which may be unsubstituted or substituted.
  • the number of carbon atoms in the alkyl group moiety is not particularly limited, but is usually in the range of 3-20.
  • the aralkyl group refers to an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group, and both the aliphatic hydrocarbon and the aromatic hydrocarbon are unsubstituted or substituted. It doesn't matter.
  • the number of carbon atoms in the aliphatic moiety is not particularly limited, but is usually in the range of 1-20.
  • the alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, which may be unsubstituted or substituted.
  • the number of carbon atoms of the alkenyl group is not particularly limited, but is usually in the range of 2-20.
  • the cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexene group, which may be unsubstituted or substituted. It doesn't matter.
  • the alkynyl group represents 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 of the alkynyl group is not particularly limited, but is usually in the range of 2-20.
  • the alkoxy group represents an aliphatic hydrocarbon group via an ether bond such as a methoxy group, and the aliphatic hydrocarbon group may be unsubstituted or substituted.
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is usually in the range of 1-20.
  • the alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom.
  • the cycloalkylthio group is a group in which an oxygen atom of an ether bond of a cycloalkoxy group is substituted with a sulfur atom.
  • aryl ether group refers to 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 of the aryl ether group is not particularly limited, but is usually in the range of 6 to 40.
  • the aryl thioether group is a group in which the oxygen atom of the ether bond of the aryl ether group is substituted with a sulfur atom.
  • the aryl group represents an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a terphenyl group, or a pyrenyl group.
  • the aryl group may be unsubstituted or substituted.
  • the number of carbon atoms of the aryl group is not particularly limited, but is usually in the range of 6 to 40.
  • the heterocyclic group refers to, for example, a cyclic structural group having an atom other than carbon, such as a furanyl group, a thiophenyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, or a carbazolyl group, which is unsubstituted or substituted. It doesn't matter.
  • the number of carbon atoms of the heterocyclic group is not particularly limited, but is usually in the range of 2-30.
  • Halogen means fluorine, chlorine, bromine and iodine.
  • aldehyde group, carbonyl group, and amino group can also include groups substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic rings, and the like.
  • aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, and heterocyclic ring may be unsubstituted or substituted.
  • the silyl group refers to, for example, a silicon compound group such as a trimethylsilyl group, which may be unsubstituted or substituted.
  • the carbon number of the silyl group is not particularly limited, but is usually in the range of 3-20.
  • the number of silicon is usually 1-6.
  • the condensed ring formed between adjacent substituents includes, 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 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 a nitrogen, oxygen, or sulfur atom in the ring structure, or may be further condensed with another ring.
  • phosphine oxide derivative examples include the following compounds.
  • 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). Details are also described in International Publication No. 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 in “optionally substituted aryl” include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferred is aryl having 6 to 12 carbon atoms.
  • aryl include monocyclic aryl phenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, condensed bicyclic aryl (1-, 2-) naphthyl.
  • 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-3-yl, o-terpheny
  • heteroaryl in the “optionally substituted heteroaryl” include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms.
  • Aryl is more preferred, heteroaryl having 2 to 15 carbons is more preferred, and heteroaryl having 2 to 10 carbons is particularly preferred.
  • heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring constituent atoms.
  • heteroaryl includes, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naph
  • the aryl and heteroaryl may be substituted, and may be substituted with, for example, the aryl or heteroaryl.
  • this pyrimidine derivative include the following compounds.
  • 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 such carbazole derivatives are bonded by a single bond or the like. Details are described in US Publication No. 2014/0197386.
  • Ar is each independently an optionally substituted aryl or an optionally substituted heteroaryl.
  • n is an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably 0 or 1.
  • aryl in “optionally substituted aryl” include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferred is aryl having 6 to 12 carbon atoms.
  • aryl include monocyclic aryl phenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, condensed bicyclic aryl (1-, 2-) naphthyl.
  • 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-3-yl, o-terpheny
  • heteroaryl in the “optionally substituted heteroaryl” include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms.
  • Aryl is more preferred, heteroaryl having 2 to 15 carbons is more preferred, and heteroaryl having 2 to 10 carbons is particularly preferred.
  • heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring constituent atoms.
  • heteroaryl includes, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naph
  • the aryl and heteroaryl may be substituted, and may be substituted with, for example, the aryl or 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.
  • an aryl ring preferably a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring
  • 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 the following compounds.
  • 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 US 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, preferably 2 or 3.
  • aryl in “optionally substituted aryl” include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferred is aryl having 6 to 12 carbon atoms.
  • aryl include monocyclic aryl phenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, condensed bicyclic aryl (1-, 2-) naphthyl.
  • 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-3-yl, o-terpheny
  • heteroaryl in the “optionally substituted heteroaryl” include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms.
  • Aryl is more preferred, heteroaryl having 2 to 15 carbons is more preferred, and heteroaryl having 2 to 10 carbons is particularly preferred.
  • heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring constituent atoms.
  • heteroaryl includes, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naph
  • the aryl and heteroaryl may be substituted, and may be substituted with, for example, the aryl or heteroaryl.
  • triazine derivative examples include the following compounds.
  • 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 substituent” means that the pyridyl group in the “pyridine substituent” in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) is benzo It is a substituent substituted with 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 carbon atoms, cycloalkyl having 3 to 12 carbon atoms or aryl having 6 to 30 carbon atoms, and the above formula (ETM-2-1) and the formula ( The description of R 11 in ETM-2-2) can be cited.
  • ⁇ is preferably an anthracene ring or a fluorene ring, and the structure in this case can be referred to the description in the above formula (ETM-2-1) or formula (ETM-2-2), In the formula, R 11 to R 18 can be referred to the description of the above formula (ETM-2-1) or formula (ETM-2-2). Further, in the above formula (ETM-2-1) or formula (ETM-2-2), it is explained in a form in which two pyridine-based substituents are bonded.
  • this benzimidazole derivative 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 formula (ETM-12-1). Details are described in International Publication No. 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 independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably carbon (Aryl of formula 6 to 30).
  • alkyl preferably alkyl having 1 to 24 carbon atoms
  • cycloalkyl preferably cycloalkyl having 3 to 12 carbon atoms
  • aryl preferably carbon (Aryl of formula 6 to 30).
  • any of R 11 to R 18 is bonded to ⁇ which is an aryl ring.
  • At least one hydrogen in 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).
  • ⁇ includes the following structural formula, for example.
  • each R is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl.
  • this phenanthroline derivative 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), bathocuproin, 1,3-bis (2-phenyl-1,10-phenanthroline-9-yl) benzene and compounds represented by the following structural formula can give.
  • 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, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy or aryl
  • M is Li, Al, Ga, Be or Zn
  • n is an integer of 1 to 3.
  • quinolinol metal complexes include 8-quinolinol lithium, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl-8-quinolinolato) aluminum, tris (3 , 4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) ( Phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolato) aluminum, bis (2-methyl-8- Quinolinolato) (4- Tylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolate)
  • 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” are “pyridine-based” in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2).
  • the pyridyl group in the “substituent” is a substituent in which the following thiazole group or benzothiazole group is substituted, and at least one hydrogen in the thiazole derivative and the benzothiazole derivative may be substituted with deuterium.
  • ⁇ is preferably an anthracene ring or a fluorene ring, and the structure in this case can be referred to the description in the above formula (ETM-2-1) or formula (ETM-2-2), In the formula, R 11 to R 18 can be referred to the description of the above formula (ETM-2-1) or formula (ETM-2-2). In addition, in the above formula (ETM-2-1) or formula (ETM-2-2), it is described in the form of two pyridine-based substituents bonded together.
  • at least one of R 11 to R 18 in the above formula (ETM-2-1) is replaced with a thiazole substituent (or benzothiazole substituent) to replace the “pyridine substituent” with R 11 to R 18. May be replaced.
  • 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 the material forming the electron transport layer or the electron injection layer.
  • a substance capable of reducing the material forming the electron transport layer or the electron injection layer various substances can be used as long as they have a certain reducing ability.
  • alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkalis From the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes At least one selected can be suitably used.
  • Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2. 9eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and alkaline earth metals such as those having a work function of 2.9 eV or less are particularly preferable.
  • a more preferable reducing substance is an alkali metal of K, Rb or Cs, more 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 transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended.
  • a reducing substance having a work function of 2.9 eV or less a combination of two or more alkali metals is also preferable.
  • a combination containing Cs such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred.
  • Cs such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred.
  • the cathode 108 plays a role of injecting electrons into the light emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.
  • the material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as the material for forming the anode 102 can be used.
  • metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or alloys thereof (magnesium-silver alloy, magnesium -Indium alloys, aluminum-lithium alloys such as lithium fluoride / aluminum, etc.) are preferred.
  • Lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective for increasing the electron injection efficiency and improving device characteristics.
  • metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride Lamination of hydrocarbon polymer compounds and the like is a preferred example.
  • the method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam evaporation, sputtering, ion plating, and coating.
  • the materials used for the hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can form each layer alone, but as a polymer binder, polyvinyl chloride, polycarbonate, Polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin It can also be used by dispersing it in solvent-soluble resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, etc. is there.
  • solvent-soluble resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins,
  • Each layer constituting the organic EL element is a thin film formed by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coat method or cast method, coating method, etc. Thus, it can be formed.
  • the film thickness of each layer thus formed is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like.
  • the vapor deposition conditions vary depending on the type of material, the target crystal structure and association structure of the film, and the like.
  • Deposition conditions generally include boat heating temperature +50 to + 400 ° C., vacuum degree 10 ⁇ 6 to 10 ⁇ 3 Pa, deposition rate 0.01 to 50 nm / second, substrate temperature ⁇ 150 to + 300 ° C., film thickness 2 nm to 5 ⁇ m. It is preferable to set appropriately within the range.
  • an organic EL element composed of an anode / hole injection layer / hole transport layer / a light emitting layer composed of a host material and a dopant material / electron transport layer / electron injection layer / cathode
  • a manufacturing method of will be described.
  • a thin film of an anode material is formed on a suitable substrate by vapor deposition 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 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 vapor deposition. By forming it as a cathode, a target organic EL element can be obtained.
  • 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 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 with a negative polarity. When a voltage of about 2 to 40 V is applied, a transparent or translucent electrode is applied. Luminescence 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 alternating current waveform to be applied may be arbitrary.
  • the present invention can also be applied to a display device including an organic EL element or a lighting device including an organic EL element.
  • the display device or 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 and a known driving device, such as DC driving, pulse driving, or AC driving. It can drive using a well-known drive method suitably.
  • 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 and JP-A-2003-321546). Gazette, JP-A-2004-281086, etc.).
  • Examples of the display method of the display include a matrix and / or 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 a grid or a mosaic, and characters and images are displayed using a set of pixels.
  • the shape and size of the pixel are determined by the application. For example, square pixels with a side of 300 ⁇ m or less are usually used for displaying images and characters on personal computers, monitors, and televisions. Also, for large displays such as display panels, pixels with a side of the order of mm are used. become.
  • monochrome display pixels of the same color may be arranged, but in 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 driving method may be either a line sequential driving method or an active matrix.
  • the line-sequential driving has an advantage that the structure is simple. However, the active matrix may be superior in consideration of the operation characteristics, so that it is necessary to use them depending on the application.
  • a pattern is formed so as to display predetermined information, and a predetermined region is caused to emit light.
  • a predetermined region is caused to emit light.
  • the time and temperature display in a digital clock or a thermometer the operation state display of an audio device or an electromagnetic cooker, the panel display of an automobile, etc.
  • the illuminating device examples include an illuminating device such as a room illuminator, a backlight of a liquid crystal display device, and the like (for example, Japanese Patent Laid-Open Nos. 2003-257621, 2003-277741, and 2004-119211). Etc.)
  • the backlight is used mainly 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 board, a sign, and the like.
  • this embodiment As a backlight for a liquid crystal display device, especially a personal computer application where thinning is an issue, considering that it is difficult to thin the conventional method because it is made of a fluorescent lamp or a light guide plate, this embodiment
  • the backlight using the light emitting element according to the present invention is thin and lightweight.
  • 1,3-dibromo-5-fluorobenzene 80.0 g
  • 4- (9H-carbazol-9-yl) phenylboronic acid 130.9 g
  • dichlorobis [(di-t-butyl (4- Dimethylaminophenyl) phosphino) palladium (Pd-132, 1.47 g)
  • potassium phosphate 176 g
  • toluene 600 mL
  • isopropyl alcohol (IPA, 150 mL) and water (70 mL) are placed in a flask under a nitrogen atmosphere, Stir at reflux for 2 hours.
  • polycyclic aromatic compounds of the present invention can be synthesized by a method according to the synthesis example described above by appropriately changing the raw material compound.
  • Organic EL devices according to Examples 1 and 2 and Comparative Examples 1 and 2 were prepared and measured as voltage (V) and external quantum efficiency (%), which are characteristics at 1000 cd / m 2 emission, and then 10 mA / cm. The time for maintaining a luminance of 90% or more of the initial luminance when driven at a constant current at a current density of 2 was measured.
  • the quantum efficiency of a light emitting device includes an internal quantum efficiency and an external quantum efficiency.
  • the internal quantum efficiency is that the external energy injected as electrons (or holes) into the light emitting layer of the light emitting device is converted into pure photons. The ratio is shown.
  • the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light emitting device, and some of the photons generated in the light emitting layer continue to be absorbed or reflected inside the light emitting device. In other words, the external quantum efficiency is lower than the internal quantum efficiency because it is not emitted to the outside of the light emitting element.
  • the external quantum efficiency is measured as follows.
  • a voltage / current generator R6144 manufactured by Advantest Corporation was used to apply a voltage at which the luminance of the element was 1000 cd / m 2 to cause the element to emit light.
  • 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 completely diffusing surface, the value obtained by dividing the measured spectral radiance value of each wavelength component by the wavelength energy and multiplying by ⁇ is the number of photons at each wavelength.
  • the value obtained by dividing the applied current value by the elementary charge is the number of carriers injected into the device, and the number obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency.
  • Table 1 below shows the material configuration of each layer and the EL characteristic data in the organic EL elements according to Examples 1-2 and Comparative Examples 1-2.
  • HI is N 4 , N 4 ′ -diphenyl-N 4 , N 4 ′ -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4 , 4′-diamine
  • IL is 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile
  • HT-1 is N-([1,1′-biphenyl].
  • Example 1 ⁇ Device in which electron transport material is compound (1-101)> A glass substrate of 26 mm ⁇ 28 mm ⁇ 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Choshu Sangyo Co., Ltd.), and HI, IL, HT-1, HT-2, BH-1, BD-1 and compound (1-101)
  • a tantalum vapor deposition boat containing each of the above and an aluminum nitride vapor deposition boat each containing Liq, Mg, and Ag were mounted.
  • the vacuum chamber is depressurized to 5 ⁇ 10 ⁇ 4 Pa, first, HI is heated to deposit to a film thickness of 40 nm, then IL is heated to deposit to a film thickness of 5 nm, and then HT-1 was heated and evaporated to a film thickness of 15 nm, and then HT-2 was heated and evaporated to a film thickness of 10 nm to form a four-layer hole layer. Next, BH-1 and BD-1 were heated at the same time and evaporated to a thickness of 25 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH-1 to BD-1 was approximately 98 to 2.
  • the compound (1-101) and Liq were heated at the same time and evaporated to a film thickness of 5 nm to form an electron transport layer.
  • the deposition rate was adjusted so that the weight ratio of the compound (1-101) to Liq was about 50:50.
  • the deposition rate of each layer was 0.01 to 1 nm / second.
  • Liq is heated and deposited at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm, and then magnesium and silver are simultaneously heated and deposited so as to have a film thickness of 100 nm.
  • a cathode was formed to obtain an organic EL device.
  • the deposition rate was adjusted between 0.1 nm and 10 nm / second so that the atomic ratio of magnesium and silver was 10: 1.
  • Example 2> ⁇ Device in which electron transport material is compound (1-201)> An organic EL device was obtained by the method according to Example 1 except that the material of the electron transport layer was changed to the compound (1-201). When the characteristics at 1000 cd / m 2 emission were measured, blue emission was obtained. The driving voltage was 3.5 V, the external quantum efficiency was 6.3%, and the device lifetime was 332 hours.
  • the light emission efficiency and the device lifetime are excellent.
  • an organic EL element having an excellent element lifetime can be provided.

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PCT/JP2019/021341 2018-06-14 2019-05-29 アルキル置換多環芳香族化合物を含有する電子輸送材料または電子注入材料 WO2019239897A1 (ja)

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