WO2019235452A1 - ターシャリーアルキル置換多環芳香族化合物 - Google Patents

ターシャリーアルキル置換多環芳香族化合物 Download PDF

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WO2019235452A1
WO2019235452A1 PCT/JP2019/022071 JP2019022071W WO2019235452A1 WO 2019235452 A1 WO2019235452 A1 WO 2019235452A1 JP 2019022071 W JP2019022071 W JP 2019022071W WO 2019235452 A1 WO2019235452 A1 WO 2019235452A1
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ring
alkyl
substituted
aryl
carbon atoms
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PCT/JP2019/022071
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English (en)
French (fr)
Japanese (ja)
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琢次 畠山
一志 枝連
孝弘 小林
笹田　康幸
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学校法人関西学院
Jnc株式会社
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Priority to KR1020207035722A priority Critical patent/KR102661365B1/ko
Priority to JP2020523107A priority patent/JP7445923B2/ja
Priority to CN201980024838.5A priority patent/CN111936505A/zh
Publication of WO2019235452A1 publication Critical patent/WO2019235452A1/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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants

Definitions

  • the present invention relates to a tertiary alkyl-substituted polycyclic aromatic compound, an organic electroluminescent element, an organic field effect transistor and an organic thin film solar cell using the same, and 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.
  • the host material of the organic EL element is generally a molecule in which a plurality of existing aromatic rings such as benzene and carbazole are connected by a single bond, phosphorus atom or silicon atom. This is because a large HOMO-LUMO gap (band gap Eg in a thin film) required for the host material is secured by connecting a large number of relatively conjugated aromatic rings. Furthermore, a host material of an organic EL device using a phosphorescent material or a thermally activated delayed fluorescent material also requires high triplet excitation energy (E T ), but the molecule has a donor or acceptor aromatic ring or substituent.
  • E T triplet excitation energy
  • Patent Document 6 a polycyclic aromatic compound containing boron and an organic EL device using the same are reported.
  • layer materials particularly dopant materials.
  • the present inventors have arranged a layer containing a polycyclic aromatic compound into which a tertiary alkyl group having a specific structure is introduced between a pair of electrodes, for example, organic EL It has been found that an excellent organic EL device can be obtained by configuring the device, and the present invention has been completed. That is, the present invention provides the following tertiary alkyl-substituted polycyclic aromatic compounds or multimers thereof, and further, organic EL device materials containing the following tertiary alkyl-substituted polycyclic aromatic compounds or multimers thereof, etc. The material for organic devices is provided.
  • 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.
  • 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
  • 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 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).
  • Y 1 A 5-membered ring sharing a bond with the fused bicyclic structure in the center of the above formula, consisting of X 1 and X 2 Or a 6-membered ring 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 And 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
  • Item 3 The polycyclic aromatic compound according to item 1, represented by the following general formula (2): (In the above 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 bonded to the a ring, b ring and / or c ring, and R in the —C (—R) 2 — may have 1 to 6 alkyl or cycloalkyl having 3 to 14
  • R 1 to R 11 are each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diarylboryl (provided that Aryl is aryl having 6 to 12 carbons, and two aryls may be bonded via a single bond or a linking group), alkyl having 1 to 24 carbons or cycloalkyl having 3 to 24 carbons
  • adjacent groups of R 1 to R 11 are bonded to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a ring, b ring or c ring.
  • At least one hydrogen in the ring formed may be substituted with aryl having 6 to 10 carbon atoms, alkyl having 1 to 12 carbon atoms or cycloalkyl having 3 to 16 carbon atoms.
  • 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 At least one hydrogen in the compound represented by the formula (2) is substituted with a group represented by the general formula (tR); In the above formula (tR), R a is alkyl having 2 to 24 carbon atoms, R b and R c are each independently alkyl having 1 to 24 carbon atoms, and any —CH 2 — in the alkyl is -O- may be
  • R a is alkyl having 2 to 24 carbon atoms
  • R b and R c are each independently alkyl having 1 to 24 carbon atoms, and any —CH 2 — in the alkyl is -O- may be substituted
  • the group represented by the above formula (tR) is substituted with at least one hydrogen in the compound represented by the above formula (2) in *.
  • Item 4. The polycyclic aromatic compound according to Item 3.
  • R 1 to R 11 are each independently hydrogen, aryl having 6 to 16 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 both> N—R, or X 1 is> N—R and X 2 is> O, and the R of> N—R has 6 to 10 carbon atoms Aryl, alkyl having 1 to 4 carbons or cycloalkyl having 5 to 10 carbons, and At least one hydrogen in the compound represented by the formula (2) is substituted with a group represented by the general formula (tR); In the above formula (tR), R a is alkyl having 2 to 24 carbon atoms, R b and R c are each
  • Item 7 Substituted with a diarylamino group substituted with a group represented by the general formula (tR), a carbazolyl group substituted with a group represented by the general formula (tR), or a group represented by the general formula (tR) Item 7.
  • the polycyclic aromatic compound or the multimer thereof according to any one of Items 1 to 6, which is substituted with a selected benzocarbazolyl group.
  • Item 8 Any one of Items 3 to 6, wherein R 2 is a diarylamino group substituted with a group represented by the general formula (tR) or a carbazolyl group substituted with a group represented by the general formula (tR) The polycyclic aromatic compound described in 1.
  • Item 9 The polycyclic aromatic compound or the multimer thereof according to any one of Items 1 to 8, wherein the halogen is fluorine.
  • Item 10 The polycyclic aromatic compound according to Item 1, represented by any of the following structural formulas. (“TBu” in each formula is a t-butyl group, and “tAm” is a t-amyl group.)
  • Item 11 The polycyclic aromatic compound according to Item 1, represented by any of the following structural formulas. (In each formula, “Me” is a methyl group, “tBu” is a t-butyl group, and “tAm” is a t-amyl group.)
  • Item 12. A reactive compound, wherein the polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 11 is substituted with a reactive substituent.
  • Item 13 A polymer compound obtained by polymerizing the reactive compound described in Item 12 as a monomer, or a polymer crosslinked product obtained by further crosslinking the polymer compound.
  • Item 14 A pendant polymer compound obtained by substituting the reactive compound described in Item 12 for a main chain polymer, or a pendant polymer crosslinked product obtained by further crosslinking the pendant polymer compound.
  • Item 15. An organic device material containing the polycyclic aromatic compound or the multimer thereof according to any one of Items 1 to 11.
  • Item 16 An organic device material comprising the reactive compound according to Item 12.
  • Item 17. An organic device material comprising the polymer compound or polymer crosslinked product according to Item 13.
  • Item 18 An organic device material containing the pendant polymer compound or the pendant polymer crosslinked product according to Item 14.
  • Item 19 The organic device material according to any one of Items 15 to 18, wherein the organic device material is an organic electroluminescent element material, an organic field effect transistor material, or an organic thin film solar cell material.
  • Item 20 The organic device material according to Item 19, wherein the organic electroluminescent element material is a light emitting layer material.
  • Item 21 Item 12. An ink composition comprising the polycyclic aromatic compound or the multimer thereof according to any one of Items 1 to 11 and an organic solvent.
  • Item 22 Item 13. An ink composition comprising the reactive compound according to Item 12 and an organic solvent.
  • Item 23 An ink composition comprising a main chain type polymer, the reactive compound described in Item 12, and an organic solvent.
  • Item 24 Item 14.
  • An ink composition comprising the polymer compound or polymer crosslinked product according to Item 13 and an organic solvent.
  • Item 25 Item 15. An ink composition comprising the pendant polymer compound or the pendant polymer crosslinked product according to Item 14, and an organic solvent.
  • Item 26 A pair of electrodes consisting of an anode and a cathode, a polycyclic aromatic compound or a multimer thereof according to any one of claims 1 to 11, disposed between the pair of electrodes, a reactive compound according to claim 12, 13.
  • An organic electroluminescent device comprising the polymer compound or crosslinked polymer described in Item 13 or the organic layer containing the pendant polymer compound or pendant crosslinked polymer described in Item 14.
  • Item 27 A pair of electrodes composed of an anode and a cathode, a polycyclic aromatic compound according to any one of Items 1 to 11 or a multimer thereof disposed between the pair of electrodes, a reactive compound according to Item 12, an item 13
  • An organic electroluminescent device comprising the polymer compound or crosslinked polymer described in 1) or the light-emitting layer containing the pendant polymer compound or pendant crosslinked polymer described in Item 14.
  • the light emitting layer includes a host and the polycyclic aromatic compound as a dopant, a multimer thereof, a reactive compound, a polymer compound, a polymer crosslinked body, a pendant polymer compound, or a pendant polymer crosslinked body.
  • Item 27 The organic electroluminescent device according to Item 27.
  • Item 29 The organic electroluminescence device according to Item 28, wherein the host is an anthracene compound, a fluorene compound, a dibenzochrysene compound or a pyrene compound.
  • Item 30 An electron transport layer and / or an electron injection layer disposed between the cathode and the light emitting layer, wherein at least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, a fluoranthene derivative, BO Item 26 containing at least one selected from the group consisting of a series derivative, anthracene derivative, benzofluorene derivative, phosphine oxide derivative, pyrimidine derivative, carbazole derivative, triazine derivative, benzimidazole derivative, phenanthroline derivative, and quinolinol metal complex 30.
  • the organic electroluminescent device as described in any one of.
  • 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 30 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 32 A polymer compound in which at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer is polymerized using a low molecular compound capable of forming each layer as a monomer, or A polymer crosslinked product obtained by further crosslinking the polymer compound, or a pendant polymer compound obtained by reacting a low molecular compound capable of forming each layer with a main chain polymer, or the pendant polymer compound.
  • the organic electroluminescent device according to any one of Items 26 to 31, further comprising a crosslinked pendant polymer crosslinked body.
  • Item 33 A display device or illumination device comprising the organic electroluminescent element according to any one of Items 26 to 32.
  • Item 34 A composition for forming a light emitting layer for coating and forming a light emitting layer of an organic electroluminescent device, As the first component, at least one polycyclic aromatic compound or a multimer thereof according to any one of Items 1 to 11, As a second component, at least one host material; As a third component, at least one organic solvent; A composition for forming a light emitting layer.
  • Item 35 An organic electroluminescence device comprising: a pair of electrodes composed of an anode and a cathode; and a light emitting layer disposed between the pair of electrodes and formed by applying and drying the composition for forming a light emitting layer described in Item 34.
  • a novel tertiary alkyl-substituted polycyclic aromatic compound that can be used as an organic device material such as an organic EL element material can be provided.
  • an organic device material such as an organic EL element material
  • an excellent organic device such as an organic EL element can be provided.
  • 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 basic skeleton part of the polycyclic aromatic compound has high molecular planarity, and the interaction between molecules is large.
  • it when it is used as a dopant material for the light emitting layer of an organic EL device, it is derived from molecular aggregation.
  • the luminous efficiency of the device may be reduced. Therefore, conventionally, the light emission efficiency has been improved by introducing an alkyl group into the basic skeleton portion to reduce the interaction between molecules.
  • the t-butyl group is not an alkyl chain length that increases the solubility of the compound. If the solubility of the compound is low, an enormous amount of organic solvent is required for processing such as synthesis and purification, and man-hours and production are reduced. This is not preferable because the cost increases.
  • Tertiary alkyl substituted polycyclic aromatic compounds and multimers thereof has a plurality of polycyclic aromatic compounds represented by the following general formula (1) or structures represented by the following general formula (1).
  • a polycyclic aromatic compound preferably a polycyclic aromatic compound represented by the following general formula (2), or a polycyclic aromatic compound having a plurality of structures represented by the following general formula (2) And at least one hydrogen in these compounds or structures is substituted with a group represented by the following general formula (tR).
  • 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.
  • This substituent is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino (with aryl Amino groups having heteroaryl), substituted or unsubstituted diarylboryl (two aryls may be linked via a single bond or linking group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl Preferred are substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy.
  • 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.
  • 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, 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 , An optionally substituted aryl, an optionally substituted heteroaryl, an optionally substituted alkyl or an optionally substituted cycloalkyl, wherein R in> C (—R) 2 is hydrogen , An optionally substituted aryl, an optionally substituted alkyl or an optionally substituted cycloalkyl, wherein R of> N—R and / or R of> C (—R) 2 are linked It may be bonded to the B ring and / or C ring by a group or a single bond, and the linking group is preferably —O—, —S— or —C (—R) 2 —.
  • R in the “—C (—R) 2 —” is hydrogen, alkyl or cycloalkyl. This description is the same for X 1 and X 2 in
  • R of> N—R and / or R of> C (—R) 2 is bonded to the A ring, B ring and / or C ring by a linking group or a single bond.
  • the R of> N—R and / or R of> C (—R) 2 is —O—, —S—, —C (—R”. 2 ) or a single bond to the ring a, b and / or c ”.
  • 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.
  • 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” of the first substituent, the above-mentioned explanation 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 second substituent may be substituted with a second substituent.
  • the second substituent include aryl, heteroaryl, alkyl, and cycloalkyl. Specific examples thereof include the above-described monovalent group of “aryl ring” or “heteroaryl ring”, and Reference may be made to the description of “alkyl” or “cycloalkyl” as one substituent.
  • 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 the groups described above) or cyclohexyl.
  • a structure substituted with cycloalkyl (specific examples are the groups described above) is also included in the aryl and heteroaryl as the second substituent.
  • the second substituent is a carbazolyl group
  • a carbazolyl group in which at least one hydrogen at the 9-position is substituted with an aryl such as phenyl, an alkyl such as methyl, or a cycloalkyl such as cyclohexyl is also used.
  • 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 , Diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be linked via a single bond or linking group), alkyl, cycloalkyl, alkoxy or aryloxy, and further The same applies to the substituents aryl, heteroaryl, alkyl or cycloalkyl.
  • the emission wavelength can be adjusted by the steric hindrance, electron donating property, and electron withdrawing property of the structure of the first substituent, preferably a group represented by the following structural formula, more preferably , Methyl, t-butyl, phenyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, di-p- Tolylamino, bis (p- (t-butyl) phenyl) amino, carbazolyl, 3,6-dimethylcarbazolyl, 3,6-di-t-butylcarbazolyl and phenoxy, more preferably methyl, t -Butyl, phenyl, o-tolyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis (p- (t-but
  • t-butyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5 -Xylyl, 2,6-xylyl, 2,4,6-mesityl, di-p-tolylamino, bis (p- (t-butyl) phenyl) amino, 3,6-dimethylcarbazolyl and 3,6-di- -T-Butylcarbazolyl is preferred.
  • 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 or 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) having 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.
  • Hydrogen may be substituted with deuterium, cyano or halogen, and among these, an embodiment in which all or part of hydrogen in aryl or heteroaryl is substituted with deuterium, cyano or halogen can be mentioned.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine
  • the polycyclic aromatic compound and its multimer according to the present invention can be used as a material for organic devices.
  • an organic device an organic electroluminescent element, an organic field effect transistor, an organic thin film solar cell, etc. are mention
  • compound is R, Y 1 is B, X 1 and X 2> O compounds wherein preferably, as an electron transport material, compound Y 1 is B, X 1 and X 2 is> O, Y 1 is P Compounds in which ⁇ O, X 1 and X 2 are> O are preferably used.
  • 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 (tR).
  • all hydrogen or part of hydrogen may be a group represented by the following formula (tR).
  • R a is alkyl having 2 to 24 carbon atoms
  • R b and R c are each independently alkyl having 1 to 24 carbon atoms
  • any —CH 2 — in the alkyl is The group represented by the above formula (tR) may be substituted with —O—, and is substituted with at least one hydrogen in the compound or structure represented by the above formula (1) or (2) in *.
  • the “alkyl having 2 to 24 carbon atoms” for R a may be either a straight chain or branched chain, for example, a straight chain alkyl having 2 to 24 carbon atoms, a branched alkyl having 3 to 24 carbon atoms, or a carbon number of 2 Alkyl having 18 to 18 carbons (branched alkyl having 3 to 18 carbon atoms), alkyl having 2 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms), alkyl having 2 to 6 carbon atoms (branching having 3 to 6 carbon atoms) Chain alkyl) and alkyl having 2 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).
  • alkyl having 1 to 24 carbon atoms may be either linear or branched, for example, linear alkyl having 1 to 24 carbons or branched alkyl having 3 to 24 carbons, C1-C18 alkyl (C3-C18 branched alkyl), C1-C12 alkyl (C3-C12 branched alkyl), C1-C6 alkyl (C3-C3) 6 branched-chain alkyl) and alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).
  • the total number of carbon atoms of R a , R b and R c in the formula (tR) of the general formula (1) is preferably 4 to 20 carbon atoms, and particularly preferably 4 to 10 carbon atoms.
  • R a , R b and R c includes methyl (excluding R a ), ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, Isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t -Octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl
  • Examples of the group represented by the formula (tR) include a t-amyl group, 1-ethyl-1-methylpropyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-ethyl-1 -Methylbutyl, 1,1,3,3-tetramethylbutyl, 1,1,4-trimethylpentyl, 1,1,2-trimethylpropyl, 1,1-dimethyloctyl, 1,1-dimethyl Pentyl group, 1,1-dimethylheptyl group, 1,1,5-trimethylhexyl group, 1-ethyl-1-methylhexyl group, 1-ethyl-1,3-dimethylbutyl group, 1,1,2,2 -Tetramethylpropyl group, 1-butyl-1-methylpentyl group, 1,1-diethylbutyl group, 1-ethyl-1-methylpentyl group, 1,1,3-trimethylbutyl group, 1-prop
  • the polycyclic aromatic compound represented by the general formula (1) or (2) and a multimer thereof are substituted with, for example, a group of the formula (tR)
  • a group of the formula (tR) examples are substituted with a diarylamino group, a carbazolyl group substituted with a group of formula (tR), or a benzocarbazolyl group substituted with a group of formula (tR).
  • Examples of the “diarylamino group” include the groups described above as the “first substituent”.
  • Examples of the substitution form of the group of the formula (tR) for the diarylamino group, carbazolyl group and benzocarbazolyl group include a part or all of the aryl ring or benzene ring in these groups as the group of the formula (tR).
  • a substituted example is given.
  • R 2 in the polycyclic aromatic compound represented by the general formula (2) and its multimer is a diarylamino group substituted with a group of the formula (tR) or a formula (tR ) Is a carbazolyl group substituted with a group.
  • tR is a group of the formula (tR), each n is independently an integer of 1 to 5 (preferably 1), and the definition of each symbol in the structural formula is the same as the definition of each symbol in the general formula (2) It is.
  • tertiary alkyl-substituted polycyclic aromatic compounds and multimers thereof according to the present invention include one or more hydrogen atoms in one or more aromatic rings in the compound. And a compound substituted with 1 to 2 groups of the formula (tR).
  • N in the following formulas are each independently 0 to 2 (however, all n are not 0), preferably 1.
  • tR represents a group represented by the formula (tR)
  • OPh represents a phenoxy group
  • Me represents a methyl group.
  • tertiary alkyl-substituted polycyclic aromatic compound of the present invention include compounds represented by the following structural formula.
  • D is deuterium
  • Me is a methyl group
  • Et is an ethyl group
  • Pr is a propyl group
  • Hep is a heptyl group
  • tBu is a t-butyl group.
  • Tm represents a t-amyl group.
  • the polycyclic aromatic compound represented by the general formula (1) and the multimer thereof according to the present invention are a polymer compound obtained by polymerizing a reactive compound having a reactive substituent substituted thereon as a monomer (this polymer The monomer for obtaining a molecular compound has a polymerizable substituent), or a polymer crosslinked product obtained by further crosslinking the polymer compound (the polymer compound for obtaining the polymer crosslinked product is a crosslinking substituent) Or a pendant polymer compound obtained by reacting a main chain polymer and the reactive compound (the reactive compound for obtaining the pendant polymer compound has a reactive substituent), Alternatively, a pendant polymer crosslinked product obtained by further crosslinking the pendant polymer compound (the pendant polymer compound for obtaining this pendant polymer crosslinked product is a crosslinkable compound).
  • an organic device material for example, can be used a material for an organic electroluminescence device, an organic field effect transistor materials or organic thin film solar cell material.
  • reactive substituent including the polymerizable substituent, the crosslinkable substituent, and the reactive substituent for obtaining a pendant polymer, hereinafter, also simply referred to as “reactive substituent”.
  • a substituent capable of increasing the molecular weight of the polycyclic aromatic compound or a multimer thereof, a substituent capable of further crosslinking the polymer compound thus obtained, and a substituent capable of pendant reaction with a main chain polymer Although it will not specifically limit if it is group, the substituent of the following structures is preferable. * In each structural formula indicates a bonding position.
  • L is each independently a single bond, —O—, —S—,> C ⁇ O, —O—C ( ⁇ O) —, alkylene having 1 to 12 carbons, or oxyalkylene having 1 to 12 carbons. And polyoxyalkylene having 1 to 12 carbon atoms.
  • substituents they are represented by the formula (XLS-1), the formula (XLS-2), the formula (XLS-3), the formula (XLS-9), the formula (XLS-10), or the formula (XLS-17).
  • a group represented by the formula (XLS-1), the formula (XLS-3) or the formula (XLS-17) is more preferable.
  • polymer compound and polymer crosslinked product Details of the uses of such a polymer compound, polymer crosslinked product, pendant polymer compound and pendant polymer crosslinked product (hereinafter also simply referred to as “polymer compound and polymer crosslinked product”) will be described later.
  • a step of using a raw material substituted with a tertiary alkyl group represented by the formula (tR) or introducing a tertiary alkyl group represented by the formula (tR) is added.
  • the compound of the present invention in which the desired position is tertiary alkyl substituted can be produced.
  • 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 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 a raw material to become a tertiary alkyl-substituted precursor.
  • the compound of the general formula (2-A) having a tertiary alkyl-substituted diphenylamino group can also be synthesized, for example, by the following method. That is, after introducing a tertiary alkyl-substituted diphenylamino group by amination reaction such as Buchwald-Hartwig reaction between tertiary alkyl-substituted bromobenzene and trihalogenated aniline, X 1 and X 2 are N—R.
  • X 1 and X 2 are O, they are induced to an intermediate (M-3) by etherification with phenol, and then
  • tandem volatilization can be achieved by applying a metalation reagent such as butyllithium to transmetallate, then applying a boron halide such as boron tribromide, and then using a Bronsted base such as diethylisopropylamine.
  • a metalation reagent such as butyllithium to transmetallate
  • a boron halide such as boron tribromide
  • Bronsted base such as diethylisopropylamine.
  • Compound of general formula (2-A) by Friedel-Crafts reaction It can be synthesized.
  • Organic Device The tertiary alkyl-substituted polycyclic aromatic compound according to the present invention can be used as a material for an organic device.
  • an organic device an organic electroluminescent element, an organic field effect transistor, an organic thin film solar cell, etc. are mention
  • 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 hole injection layer material and the hole transport layer material described above are a polymer compound obtained by polymerizing a reactive compound substituted with a reactive substituent on the monomer as a monomer, or a crosslinked polymer thereof, or A pendant polymer compound obtained by reacting a main chain polymer and the reactive compound, or a pendant polymer crosslinked product thereof, can also be used for the material for the hole layer.
  • the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited. Details of the use of such a polymer compound and polymer crosslinked product will be described later.
  • 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.
  • a host material and, for example, a polycyclic aromatic compound represented by the general formula (1) as a dopant material can be used as the material for the light emitting layer.
  • 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
  • An anthracene compound as a host is, for example, a compound represented by the following general formula (3).
  • X and Ar 4 are each independently hydrogen, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted diarylamino, optionally substituted diheteroarylamino, Arylheteroarylamino which may be substituted, alkyl which may be substituted, cycloalkyl which may be substituted, alkenyl which may be substituted, alkoxy which may be substituted, which may be substituted Aryloxy, optionally substituted arylthio or optionally substituted silyl, and all X and Ar 4 are not simultaneously hydrogen; At least one hydrogen in the compound represented by the formula (3) may be substituted with halogen, cyano, deuterium or an optionally substituted heteroaryl.
  • a multimer may be formed with the structure represented by the formula (3) as a unit structure.
  • X include a single bond, arylene (such as phenylene, biphenylene, and naphthylene), and heteroarylene (a pyridine ring, A group having a divalent valence such as a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring and a phenyl-substituted carbazole ring).
  • aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio or silyl will be described in the following preferred embodiments.
  • substituent to these include aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio or silyl. Details will also be described in the preferred embodiments below.
  • each X is independently a group represented by the above formula (3-X1), formula (3-X2) or formula (3-X3), and the formula (3-X1), formula (3)
  • the group represented by (3-X2) or formula (3-X3) is bonded to the anthracene ring of formula (3) at *.
  • two Xs do not become a group represented by the formula (3-X3) at the same time. More preferably, two Xs do not simultaneously become a group represented by the formula (3-X2).
  • a multimer may be formed with the structure represented by the formula (3) as a unit structure.
  • X include a single bond, arylene (such as phenylene, biphenylene, and naphthylene), and heteroarylene (a pyridine ring, A group having a divalent valence such as a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring and a phenyl-substituted carbazole ring).
  • the naphthylene moiety in formula (3-X1) and formula (3-X2) may be condensed with one benzene ring.
  • the structure thus condensed is as follows.
  • Ar 1 and Ar 2 are each independently hydrogen, phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrycenyl, triphenylenyl, pyrenylyl, or the above formula (A) Represented groups (including carbazolyl, benzocarbazolyl and phenyl-substituted carbazolyl groups).
  • the group represented by the formula (A) is the same as that in the formula (3-X1) or (3-X2) Bonds with the naphthalene ring.
  • Ar 3 is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (carbazolyl group, benzocarbyl group) A zolyl group and a phenyl-substituted carbazolyl group).
  • Ar 3 is a group represented by the formula (A)
  • the group represented by the formula (A) is bonded to a single bond represented by a straight line in the formula (3-X3) at *. . That is, the anthracene ring of formula (3) and the group represented by formula (A) are directly bonded.
  • Ar 3 may have a substituent, and at least one hydrogen in Ar 3 is further alkyl having 1 to 4 carbons, cycloalkyl having 5 to 10 carbons, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl. , Fluorenyl, chrycenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (including a carbazolyl group and a phenyl-substituted carbazolyl group). Note that when the substituent that Ar 3 has is a group represented by the formula (A), the group represented by the formula (A) is bonded to Ar 3 in the formula (3-X3) at *.
  • Ar 4 is each independently substituted with hydrogen, phenyl, biphenylyl, terphenylyl, naphthyl, or alkyl having 1 to 4 carbon atoms (methyl, ethyl, t-butyl, etc.) and / or cycloalkyl having 5 to 10 carbon atoms. Has been silyl.
  • alkyl having 1 to 4 carbon atoms to be substituted with silyl examples include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, cyclobutyl and the like. Are substituted with these alkyls.
  • sil substituted with alkyl having 1 to 4 carbon atoms include trimethylsilyl, triethylsilyl, tripropylsilyl, trii-propylsilyl, tributylsilyl, trisec-butylsilyl, tri-t-butylsilyl, ethyl Dimethylsilyl, propyldimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyl Diethylsilyl, t-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, buty
  • Cycloalkyl having 5 to 10 carbon atoms to be substituted with silyl is cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornenyl, 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, decahydronaphthalenyl, decahydro Azulenyl and the like, and the three hydrogens in silyl are each independently substituted with these cycloalkyls.
  • sil substituted with a cycloalkyl having 5 to 10 carbon atoms include tricyclopentylsilyl, tricyclohexylsilyl and the like.
  • Substituted silyls include dialkylcycloalkylsilyl substituted with two alkyls and one cycloalkyl, and alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyls.
  • Substituted alkyls and cycloalkyls Specific examples of these include the groups described above.
  • hydrogen in the chemical structure of the anthracene compound represented by the general formula (3) may be substituted with a group represented by the above formula (A).
  • the group represented by formula (A) substitutes at least one hydrogen in the compound represented by formula (3) at *.
  • the group represented by the formula (A) is one of the substituents that the anthracene compound represented by the formula (3) may have.
  • Y is —O—, —S— or> N—R 29
  • R 21 to R 28 are each independently hydrogen, optionally substituted alkyl, or optionally substituted.
  • R 29 may be hydrogen or substituted A reel.
  • alkyl of “optionally substituted alkyl” in R 21 to R 28 may be either linear or branched, for example, linear alkyl having 1 to 24 carbon atoms or 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 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
  • Cycloalkyl of “optionally substituted cycloalkyl” for R 21 to R 28 is cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, or cycloalkyl having 3 to 16 carbon atoms. 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 (especially methyl) substituents thereof 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, decahydroazurenyl and the like.
  • Examples of the “aryl” of “optionally substituted aryl” in R 21 to R 28 include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 16 carbon atoms, and 6 to 12 carbon atoms. Are more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable.
  • aryl includes monocyclic phenyl, bicyclic biphenylyl, fused bicyclic naphthyl, tricyclic terphenylyl (m-terphenylyl, o-terphenylyl, p-terphenylyl) And condensed tricyclic systems such as acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, condensed tetracyclic systems such as triphenylenyl, pyrenyl, naphthacenyl, and condensed pentacyclic systems such as perylenyl and pentacenyl.
  • heteroaryl in the “optionally substituted heteroaryl” in R 21 to R 28 include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, A heteroaryl having 2 to 20 carbon atoms is more preferred, a heteroaryl having 2 to 15 carbon atoms is more preferred, and a heteroaryl having 2 to 10 carbon atoms is particularly preferred.
  • heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.
  • heteroaryl examples include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H— Indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxaziny
  • alkoxy of “optionally substituted alkoxy” in R 21 to R 28 include 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.
  • Aryloxy of “optionally substituted aryloxy” in R 21 to R 28 is a group in which hydrogen of —OH group is substituted with aryl, and this aryl is the above-mentioned R 21 to R 28 . Reference may be made to groups described as “aryl”.
  • arylthio of the “optionally substituted arylthio” in R 21 to R 28 is a group in which the hydrogen of the —SH group is substituted with aryl, and this aryl is the “aryl” in R 21 to R 28 described above. Can be cited.
  • Examples of “trialkylsilyl” in R 21 to R 28 include groups in which three hydrogens in the silyl group are each independently substituted with alkyl, and this alkyl is referred to as “alkyl” in R 21 to R 28 described above.
  • the groups described can be cited.
  • Preferable alkyl for substitution is alkyl having 1 to 4 carbon atoms, and specific examples include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, cyclobutyl and the like.
  • trialkylsilyl include trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, trisec-butylsilyl, tri-t-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i-propyl Dimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, t-butyldiethylsilyl, methyl Dipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, butyl
  • Preferred cycloalkyl for substitution is cycloalkyl having 5 to 10 carbon atoms, specifically, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, 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, Decahydronaphthalenyl, decahydroazulenyl and the like can be mentioned.
  • tricycloalkylsilyl includes tricyclopentylsilyl, tricyclohexylsilyl and the like.
  • dialkylcycloalkylsilyl substituted with two alkyls and one cycloalkyl and alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyls are selected from the specific alkyls and cycloalkyls described above And silyl substituted with the above group.
  • Examples of the “substituted amino” of the “optionally substituted amino” in R 21 to R 28 include an amino group in which two hydrogens are substituted with aryl or heteroaryl.
  • An amino in which two hydrogens are substituted with aryl is a diaryl-substituted amino
  • an amino in which two hydrogens are substituted with a heteroaryl is a diheteroaryl-substituted amino
  • an amino in which two hydrogens are substituted with aryl and heteroaryl Is an arylheteroaryl-substituted amino.
  • the groups described as “aryl” and “heteroaryl” in R 21 to R 28 described above can be cited.
  • substituted amino include diphenylamino, dinaphthylamino, phenylnaphthylamino, dipyridylamino, phenylpyridylamino, naphthylpyridylamino, and the like.
  • halogen in R 21 to R 28 include fluorine, chlorine, bromine and iodine.
  • R 21 to R 28 some may be substituted as described above, and examples of the substituent in this case include alkyl, cycloalkyl, aryl, and heteroaryl.
  • This alkyl, cycloalkyl, aryl or heteroaryl can refer to the groups described as “alkyl”, “cycloalkyl”, “aryl” or “heteroaryl” in R 21 to R 28 described above.
  • R 29 in the "> N-R 29" as Y is hydrogen or aryl which may be substituted, be cited a group described as the "aryl” in R 21 ⁇ R 28 described above as the aryl Further, as the substituent, the groups described as the substituents for R 21 to R 28 can be cited.
  • Adjacent groups of R 21 to R 28 may be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring.
  • the case where no ring is formed is a group represented by the following formula (A-1), and the case where a ring is formed includes, for example, groups represented by the following formulas (A-2) to (A-14): It is done.
  • At least one hydrogen in the group represented by any of formulas (A-1) to (A-14) is alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl, It may be substituted with tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, diaryl-substituted amino, diheteroaryl-substituted amino, arylheteroaryl-substituted amino, halogen, hydroxy or cyano.
  • Examples of the ring formed by bonding adjacent groups to each other include a cyclohexane ring as long as it is a hydrocarbon ring, and examples of the aryl ring and heteroaryl ring include “aryl” and “heteroaryl” in R 21 to R 28 described above. And the ring is formed so as to be condensed with one or two benzene rings in the above formula (A-1).
  • Examples of the group represented by the formula (A) include groups represented by any of the above formulas (A-1) to (A-14), and the above formulas (A-1) to (A ⁇ 5) and a group represented by any of formulas (A-12) to (A-14) are preferred, and a group represented by any of the above formulas (A-1) to (A-4) Is more preferable, a group represented by any one of the above formulas (A-1), (A-3) and (A-4) is more preferable, and a group represented by the above formula (A-1) is more preferable. Particularly preferred.
  • the group represented by the formula (A) is represented by * in the formula (A), a naphthalene ring in the formula (3-X1) or the formula (3-X2), a single bond in the formula (3-X3), a formula As described above, it binds to Ar 3 in (3-X3) and substitutes at least one hydrogen in the compound represented by formula (3).
  • formula (3-X1) Alternatively, a form in which the naphthalene ring in the formula (3-X2), the single bond in the formula (3-X3) and / or Ar 3 in the formula (3-X3) is bonded is preferable.
  • the position at which Ar 3 is bonded to at least one hydrogen in the compound represented by the formula (3) is Any one of the two benzene rings in the structure of the formula (A) or an adjacent group among R 21 to R 28 in the structure of the formula (A) Any ring formed by bonding to each other, or any position in R 29 in “> NR 29 ” as Y in the structure of formula (A) can be bonded.
  • Examples of the group represented by the formula (A) include the following groups. Y and * in the formula are as defined above.
  • all or part of the hydrogen in the chemical structure of the anthracene compound represented by the general formula (3) may be deuterium.
  • anthracene compound examples include compounds represented by the following formulas (3-1) to (3-72).
  • “Me” represents a methyl group
  • “D” represents deuterium
  • “tBu” represents a t-butyl group.
  • the anthracene compound represented by the formula (3) includes a compound having a reactive group at a desired position of the anthracene skeleton and a compound having a reactive group in a partial structure such as the structure of X, Ar 4 and the formula (A) Can be produced by applying Suzuki coupling, Negishi coupling, and other known coupling reactions.
  • Examples of the reactive group of these reactive compounds include halogen and boronic acid.
  • the synthesis method in paragraphs [0089] to [0175] of International Publication No. 2014/141725 can be referred to.
  • R 1 to R 10 are each independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the fluorene skeleton in the above formula (4) via a linking group), diarylamino, dihetero Arylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, wherein at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl; R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 or R 9 and R 10 are bonded independently.
  • Examples of the alkenyl in R 1 to R 10 include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and 2 to 6 carbon atoms. Alkenyl is more preferable, and alkenyl having 2 to 4 carbon atoms is particularly preferable.
  • Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl.
  • any one of the compounds of the following formula (4-Ar1), formula (4-Ar2), formula (4-Ar3), formula (4-Ar4) or formula (4-Ar5) may be used. Also included are monovalent groups represented by removing one hydrogen atom.
  • Y 1 is each independently O, S or N—R, R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen; At least one hydrogen in the structures of the above formulas (4-Ar1) to (4-Ar5) may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.
  • heteroaryls may be bonded to the fluorene skeleton in the above formula (4) via a linking group. That is, not only the fluorene skeleton in the formula (4) and the heteroaryl are directly bonded but also a bond between them may be bonded.
  • this linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, —OCH 2 CH 2 —, —CH 2 CH 2 O—, or —OCH 2 CH 2 O—.
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are bonded independently.
  • R 9 and R 10 may be combined to form a spiro ring.
  • the condensed ring formed by R 1 to R 8 is a ring condensed with the benzene ring in the formula (4), and is an aliphatic ring or an aromatic ring.
  • An aromatic ring is preferred, and examples of the structure including the benzene ring in formula (4) include a naphthalene ring and a phenanthrene ring.
  • the spiro ring formed by R 9 and R 10 is a ring that is spiro-bonded to the 5-membered ring in formula (4), and is an aliphatic ring or an aromatic ring. Preferred is an aromatic ring, such as a fluorene ring.
  • the compound represented by the general formula (4) is preferably a compound represented by the following formula (4-1), formula (4-2), or formula (4-3). ) In which R 1 and R 2 are combined to form a condensed benzene ring, in general formula (4), a compound in which R 3 and R 4 are combined to form a condensed benzene ring, general formula (4 ) In which none of R 1 to R 8 is bonded.
  • R 1 to R 10 in Formula (4-1), Formula (4-2), and Formula (4-3) are the same as the corresponding R 1 to R 10 in Formula (4).
  • the definitions of R 11 to R 14 in 1) and formula (4-2) are the same as R 1 to R 10 in formula (4).
  • the compound represented by the general formula (4) is more preferably a compound represented by the following formula (4-1A), formula (4-2A), or formula (4-3A). -1), a compound having a spiro-fluorene ring formed by combining R 9 and R 10 in formula (4-1) or formula (4-3).
  • R 2 to R 7 in formula (4-1A), formula (4-2A), and formula (4-3A) are defined in formula (4-1), formula (4-2), and formula (4-3). corresponding the same from R 2 and R 7, R in the formula also defined formula (4-1) of the R 14 from R 11 in (4-1A) and (4-2A) and (4-2) 11 from is the same as R 14.
  • all or part of the hydrogen in the compound represented by the formula (4) may be substituted with halogen, cyano or deuterium.
  • the dibenzochrysene-type compound as a host is a compound represented, for example by following General formula (5).
  • R 1 to R 16 are each independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the dibenzochrysene skeleton in the above formula (5) via a linking group), diarylamino, diaryl Heteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl; Further, adjacent groups of R 1 to R 16 may be bonded to form a condensed ring, and at least one hydrogen in the formed ring is aryl or heteroaryl (the heteroaryl is connected via a linking group).
  • alkenyl in the definition of the above formula (5) examples include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and 2 to 2 carbon atoms. More preferred is alkenyl having 6 carbon atoms, and particularly preferred is alkenyl having 2 to 4 carbon atoms.
  • Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl.
  • any one of the compounds of the following formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) may be used. Also included are monovalent groups represented by removing one hydrogen atom.
  • Y 1 is each independently O, S or N—R, R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen; At least one hydrogen in the structures of the above formulas (5-Ar1) to (5-Ar5) may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.
  • heteroaryls may be bonded to the dibenzochrysene skeleton in the above formula (5) via a linking group. That is, not only the dibenzochrysene skeleton in the formula (5) and the heteroaryl are directly bonded, but may be bonded via a linking group between them. Examples of this linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, —OCH 2 CH 2 —, —CH 2 CH 2 O—, or —OCH 2 CH 2 O—.
  • R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are preferably hydrogen.
  • R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 in formula (5) are each independently hydrogen, phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl.
  • a monovalent group having the structure of the above formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) (1 having the structure)
  • the valent group is represented by the above formula (5) via phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, —OCH 2 CH 2 —, —CH 2 CH 2 O—, or —OCH 2 CH 2 O—. And may be bonded to the dibenzochrysene skeleton), methyl, ethyl, propyl, or butyl.
  • the compound represented by the general formula (5) is more preferably R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 , R 15 and R. 16 is hydrogen.
  • at least one (preferably one or two, more preferably one) of R 3 , R 6 , R 11 and R 14 in formula (5) is a single bond, phenylene, biphenylene, naphthylene, Via the anthracenylene, methylene, ethylene, —OCH 2 CH 2 —, —CH 2 CH 2 O—, or —OCH 2 CH 2 O—, the above formula (5-Ar1), formula (5-Ar2), formula A monovalent group having a structure of (5-Ar3), formula (5-Ar4) or formula (5-Ar5);
  • Other than the at least one (that is, other than the position where the monovalent group having the structure is substituted) is hydrogen, phenyl, biphenylyl, nap
  • R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 in the formula (5) are represented by the above formulas (5-Ar1) to (5-Ar5).
  • at least one hydrogen in the structure may be bonded to any one of R 1 to R 16 in formula (5) to form a single bond. .
  • the pyrene compound as the host is, for example, a compound represented by the following general formula (6).
  • s pyrene moieties and p Ar moieties are bonded at any position of * of the pyrene moiety and any position of the Ar moiety;
  • At least one hydrogen of the pyrene moiety is independently an aryl having 6 to 10 carbon atoms, a heteroaryl having 2 to 11 carbon atoms, an alkyl having 1 to 30 carbon atoms, a cycloalkyl having 3 to 24 carbon atoms, or a carbon number.
  • Heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryl having 6 to 30 carbon atoms May be substituted with oxy
  • Ar is each independently an aryl having 14 to 40 carbon atoms or a heteroaryl having 12 to 40 carbon atoms, and at least one hydrogen in these is each independently an aryl having 6 to 10 carbon atoms
  • Substituted with 2-11 heteroaryl, alkyl with 1-30 carbons, cycloalkyl with 3-24 carbons, alkenyl with 2-30 carbons, alkoxy with 1-30 carbons or aryloxy with 6-30 carbons May have been s and p are each independently an integer of 1 or 2, and s and p are not simultaneously 2; when s is 2, the two pyrene moieties are structurally identical including the substituent And when
  • alkenyl examples include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and further preferably alkenyl having 2 to 6 carbon atoms. Particularly preferred is alkenyl having 2 to 4 carbon atoms.
  • Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl.
  • heteroaryl a monovalent having a structure of the following formula (6-Ar1), formula (6-Ar2), formula (6-Ar3), formula (6-Ar4) or formula (6-Ar5)
  • Y 1 is each independently>O,> S or> N—R, where R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen.
  • At least one hydrogen in the structures of the above formulas (6-Ar1) to (6-Ar5) may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.
  • heteroaryls may be bonded to the pyrene moiety in the above formula (6) through a linking group. That is, not only the pyrene moiety in the formula (6) and the heteroaryl are directly bonded, but also a bond may be bonded between them.
  • this linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, —OCH 2 CH 2 —, —CH 2 CH 2 O—, or —OCH 2 CH 2 O—.
  • the light emitting layer material (host material and dopant material) described above is a polymer compound obtained by polymerizing a reactive compound substituted with a reactive substituent thereon as a monomer, or a crosslinked polymer thereof, or a main chain.
  • a pendant polymer compound obtained by reacting a reactive polymer with the reactive polymer, or a pendant polymer crosslinked product thereof, can also be used for the light emitting layer material.
  • the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited. Details of the use of such a polymer compound and polymer crosslinked product will be described later.
  • MU is each independently a divalent aromatic compound
  • EC is each independently a monovalent aromatic compound
  • two hydrogens in MU are replaced with EC or MU
  • k is an integer of 2 to 50000 is there.
  • MUs are each independently arylene, heteroarylene, diarylene arylamino, diarylene arylboryl, oxaborin-diyl, azaborin-diyl,
  • Each EC is independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy; At least one hydrogen in MU and EC may be further substituted with aryl, heteroaryl, diarylamino, alkyl and cycloalkyl;
  • k is an integer of 2 to 50,000.
  • k is preferably an integer of 20 to 50,000, more preferably an integer of 100 to 50,000.
  • At least one hydrogen in MU and EC in the formula (SPH-1) may be substituted with alkyl having 1 to 24 carbons, cycloalkyl having 3 to 24 carbons, halogen or deuterium, and Any —CH 2 — in the alkyl may be substituted with —O— or —Si (CH 3 ) 2 —, and —CH 2 — directly connected to EC in the formula (SPH-1) in the alkyl Any —CH 2 — except for may be substituted with arylene having 6 to 24 carbon atoms, and any hydrogen in the alkyl may be substituted with fluorine.
  • Examples of MU include a divalent group represented by removing any two hydrogen atoms from any of the following compounds.
  • the MU binds to other MUs or ECs in *.
  • examples of EC include monovalent groups represented by any of the following structures. In these, EC binds to MU at *.
  • 10 to 100% of the MU total number (k) in the molecule has 1 to 24 carbon atoms alkyl. More preferably, 30 to 100% of the MU total number (k) in the molecule has alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms), and the total number of MUs in the molecule ( More preferably, 50 to 100% of MU of k) has alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms).
  • the MU total number (k) in the molecule has alkyl having 7 to 24 carbon atoms
  • the MU total number (k) It is more preferable that 30 to 100% of MU of the compound has an alkyl having 7 to 24 carbon atoms (branched alkyl having 7 to 24 carbon atoms).
  • the polycyclic aromatic compound represented by the general formula (1) can also be used as a composition for forming a light emitting layer together with an organic solvent.
  • the composition contains at least one polycyclic aromatic compound as a first component, at least one host material as a second component, and at least one organic solvent as a third component.
  • a 1st component functions as a dopant component of the light emitting layer obtained from this composition
  • a 2nd component functions as a host component of a light emitting layer.
  • the third component functions as a solvent that dissolves the first component and the second component in the composition, and gives a smooth and uniform surface shape at the time of application due to the controlled evaporation rate of the third component itself.
  • the composition for forming a light emitting layer contains at least one organic solvent as a third component.
  • the film formability, the presence or absence of defects in the coating film, the surface roughness, and the smoothness can be controlled and improved.
  • the meniscus stability at the pinhole of the ink jet head can be controlled, and the discharge performance can be controlled and improved.
  • the drying speed of the film and the orientation of the derivative molecules the electrical characteristics, light emitting characteristics, efficiency, and lifetime of the organic EL device having a light emitting layer obtained from the composition for forming a light emitting layer are improved. Can do.
  • the boiling point of at least one organic solvent is 130 ° C to 300 ° C, more preferably 140 ° C to 270 ° C, and further preferably 150 ° C to 250 ° C.
  • the boiling point is higher than 130 ° C., it is preferable from the viewpoint of ink jetting properties.
  • a boiling point is lower than 300 degreeC, it is preferable from a viewpoint of the defect of a coating film, surface roughness, a residual solvent, and smoothness.
  • the third component is more preferably composed of two or more organic solvents from the viewpoints of good ink jet discharge properties, film-forming properties, smoothness and low residual solvent.
  • the composition may be a solid state by removing the solvent from the composition for forming the light emitting layer in consideration of transportability and the like.
  • the third component comprises a good solvent (GS) and poor solvent (PS) for the host material of the second component
  • the good boiling (BP PS solvent boiling (GS) BP GS
  • PS poor solvent
  • Is particularly preferred By adding a poor solvent having a high boiling point, a good solvent having a low boiling point is volatilized first at the time of film formation, and the concentration of inclusions in the composition and the concentration of the poor solvent are increased, thereby promptly forming a film. Thereby, a coating film with few defects, a small surface roughness, and high smoothness is obtained.
  • the solubility difference (S GS ⁇ S PS ) is preferably 1% or more, more preferably 3% or more, and further preferably 5% or more.
  • the difference in boiling points (BP PS -BP GS ) is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and further preferably 50 ° C. or higher.
  • the organic solvent is removed from the coating film by a drying process such as vacuum, reduced pressure or heating after the film formation.
  • a drying process such as vacuum, reduced pressure or heating after the film formation.
  • Tg glass transition temperature
  • Tg glass transition point
  • Tg glass transition point
  • drying may be performed a plurality of times at different temperatures, or a plurality of drying methods may be used in combination.
  • organic solvents used in the composition for forming a light emitting layer include alkylbenzene solvents, phenyl ether solvents, alkyl ether solvents, cyclic ketone solvents, aliphatic ketone solvents, monocyclic Examples include ketone solvents, solvents having a diester skeleton, and fluorine-containing solvents.
  • composition for light emitting layer formation may contain arbitrary components in the range which does not impair the property.
  • optional components include a binder and a surfactant.
  • the composition for light emitting layer formation may contain the binder.
  • the binder forms a film at the time of film formation and bonds the obtained film to the substrate.
  • it plays a role of dissolving, dispersing and binding other components in the composition for forming a light emitting layer.
  • binder used in the composition for forming a light emitting layer examples include acrylic resin, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, acrylonitrile-ethylene-styrene copolymer (AES) resin, Ionomer, chlorinated polyether, diallyl phthalate resin, unsaturated polyester resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, Teflon, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile -Styrene copolymer (AS) resin, phenol resin, epoxy resin, melamine resin, urea resin, alkyd resin, polyurethane, and copolymer of the above resin and polymer, Re not limited to.
  • AES acrylonitrile-ethylene-styren
  • the binder used in the composition for forming a light emitting layer may be only one kind or a mixture of plural kinds.
  • the composition for forming a light emitting layer contains, for example, a surfactant for controlling the film surface uniformity, solvophilicity and liquid repellency of the film forming composition. Also good.
  • Surfactants are classified into ionic and nonionic based on the structure of the hydrophilic group, and further classified into alkyl, silicon, and fluorine based on the structure of the hydrophobic group. Further, the molecular structure is classified into a monomolecular system having a relatively small molecular weight and a simple structure, and a polymer system having a large molecular weight and having a side chain and a branch.
  • surfactant for example, Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, polyflow no. 95 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181 and Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, manufactured by Big Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF -50-100CS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Footent 222F, Footage 251, FTX-218 (trade name,
  • the surfactant may be used alone or in combination of two or more.
  • composition and physical properties of composition for forming light emitting layer The content of each component in the composition for forming a light emitting layer is obtained from the good solubility, storage stability and film formability of each component in the composition for forming a light emitting layer, and the composition for forming a light emitting layer. Good film quality of the coating film, good dischargeability when using the ink jet method, and good electrical characteristics, light emission characteristics, efficiency, and lifetime of the organic EL device having a light emitting layer manufactured using the composition
  • the first component is 0.0001% by weight to 2.0% by weight relative to the total weight of the light emitting layer forming composition
  • the second component is based on the total weight of the light emitting layer forming composition.
  • the amount is preferably 0.0999 wt% to 8.0 wt%
  • the third component is preferably 90.0 wt% to 99.9 wt% with respect to the total weight of the light emitting layer forming composition.
  • the first component is 0.005 wt% to 1.0 wt% with respect to the total weight of the light emitting layer forming composition
  • the second component is with respect to the total weight of the light emitting layer forming composition, 0.095 wt% to 4.0 wt%
  • the third component is 95.0 wt% to 99.9 wt% with respect to the total weight of the light emitting layer forming composition.
  • the first component is 0.05% by weight to 0.5% by weight relative to the total weight of the light emitting layer forming composition
  • the second component is based on the total weight of the light emitting layer forming composition.
  • the amount of the third component is 97.0% by weight to 99.7% by weight with respect to the total weight of the composition for forming a light emitting layer.
  • the composition for forming a light emitting layer can be produced by appropriately selecting the above-mentioned components by stirring, mixing, heating, cooling, dissolution, dispersion, and the like by a known method. Further, after preparation, filtration, degassing (also referred to as degas), ion exchange treatment, inert gas replacement / encapsulation treatment, and the like may be selected as appropriate.
  • the viscosity of the composition for forming a light emitting layer As the viscosity of the composition for forming a light emitting layer, a higher viscosity can provide better film formability and good dischargeability when an ink jet method is used. On the other hand, it is easier to make a thin film with a low viscosity. Accordingly, the viscosity of the composition for forming a light emitting layer is preferably 0.3 mPa ⁇ s to 3 mPa ⁇ s at 25 ° C., more preferably 1 mPa ⁇ s to 3 mPa ⁇ s. In the present invention, the viscosity is a value measured using a conical plate type rotational viscometer (cone plate type).
  • the viscosity of the composition for forming a light emitting layer is preferably 20 mN / m to 40 mN / m, more preferably 20 mN / m to 30 mN / m, at 25 ° C.
  • the surface tension is a value measured using the hanging drop method.
  • 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.
  • a compound composed of 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 pyrrole derivatives, condensed ring derivatives thereof, and metal complexes having electron-accepting nitrogen.
  • condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives 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 It is at least one of a heterocycle or 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 is 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 -Containing heterocycle, or at least one of cyano, and R 13 to R 16 each independently represents an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl.
  • R 21 and R 22 are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. at least one a and, X 1 is substituted carbon atoms and optionally more than 20 arylene, n are each independently an integer of 0 to 3 And, m 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 -Containing heterocycle, or at least one of cyano, and R 13 to R 16 each independently represents 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, alkyl, cycloalkyl, alkoxy or aryloxy, in which 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 May be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, wherein at least one hydrogen is aryl, heteroaryl, alkyl or It may be substituted with cycloalkyl.
  • At least one hydrogen in the compound or structure represented by the formula (ETM-4) may be substituted with halogen or deuterium.
  • 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 16 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 16 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 structure group having an atom other than carbon, such as a furanyl group, a thiophenyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, 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). Further, in the above formula (ETM-2-1) or formula (ETM-2-2), it is described in the form of two pyridine-based substituents bonded to each other, but these are represented by thiazole-based substituents (or benzothiazole-based substituents).
  • 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 electron injecting layer material and the electron transport layer material described above are a polymer compound obtained by polymerizing a reactive compound substituted with a reactive substituent thereon as a monomer, or a crosslinked polymer thereof, A pendant polymer compound obtained by reacting a chain polymer with the reactive compound, or a pendant polymer crosslinked product thereof, can also be used for the electronic layer material.
  • the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited. Details of the use of such a polymer compound and polymer crosslinked product will be described later.
  • 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.
  • 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.
  • 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 wet film forming method is carried out by preparing a low molecular compound capable of forming each organic layer of an organic EL element as a liquid organic layer forming composition and using it. If there is no suitable organic solvent that dissolves the low molecular weight compound, the reactive compound obtained by substituting a reactive substituent on the low molecular weight compound is highly reactive along with other monomers having a solubility function and main chain type polymers.
  • a composition for forming an organic layer may be prepared from a polymerized polymer compound.
  • a coating film is formed by performing a coating process for coating the substrate with the organic layer forming composition and a drying process for removing the solvent from the coated organic layer forming composition.
  • the polymer compound has a crosslinkable substituent (also referred to as a crosslinkable polymer compound)
  • the polymer is further crosslinked by this drying step to form a polymer crosslinked product.
  • the spin coater method is the spin coat method
  • the slit coater method is the slit coat method
  • the plate method is the gravure, offset, reverse offset, flexographic printing method
  • the ink jet printer method is the ink jet method.
  • the method of spraying in a mist form is called a spray method.
  • the drying process include air drying, heating, and drying under reduced pressure.
  • the drying step may be performed only once, or may be performed a plurality of times using different methods and conditions. Further, for example, different methods may be used together, such as firing under reduced pressure.
  • the wet film forming method is a film forming method using a solution, for example, a partial printing method (ink jet method), a spin coating method or a casting method, a coating method, or the like.
  • a solution for example, a partial printing method (ink jet method), a spin coating method or a casting method, a coating method, or the like.
  • the wet film formation method does not require the use of an expensive vacuum vapor deposition apparatus and can form a film at atmospheric pressure.
  • the wet film-forming method enables large area and continuous production, leading to reduction in manufacturing cost.
  • the wet film formation method may be difficult to stack.
  • orthogonal solvent Orthogonal solvent, which dissolves each other
  • a method is employed in which only a few layers are formed using a wet film forming method, and the rest are formed using a vacuum vapor deposition method.
  • layer formation including the material for the electron transport layer and the material for the electron injection layer They can be prepared as a composition for coating, and they can be formed by a wet film forming method.
  • a laser heating drawing method can be used for forming the organic layer forming composition into a film.
  • LITI is a method in which a compound attached to a base material is heated and vapor-deposited with a laser, and an organic layer forming composition can be used as a material applied to the base material.
  • ⁇ Arbitrary process> Appropriate treatment steps, washing steps, and drying steps may be appropriately added before and after each step of film formation.
  • the treatment process include exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, cleaning treatment using an appropriate solvent, and heat treatment.
  • a series of steps for producing a bank is also included.
  • Photolithography technology can be used for the production of the bank.
  • a bank material that can be used for photolithography a positive resist material and a negative resist material can be used.
  • a patternable printing method such as an inkjet method, gravure offset printing, reverse offset printing, or screen printing can also be used.
  • a permanent resist material can be used.
  • Materials used for the bank include polysaccharides and derivatives thereof, homopolymers and copolymers of hydroxyl-containing ethylenic monomers, biopolymer compounds, polyacryloyl compounds, polyesters, polystyrenes, polyimides, polyamideimides, polyetherimides , Polysulfide, polysulfone, polyphenylene, polyphenyl ether, polyurethane, epoxy (meth) acrylate, melamine (meth) acrylate, polyolefin, cyclic polyolefin, acrylonitrile-butadiene-styrene copolymer (ABS), silicone resin, polyvinyl chloride, chlorine Polyethylene, chlorinated polypropylene, polyacetate, polynorbornene, synthetic rubber, polyfluorovinylidene, polytetrafluoroethylene, polyhexa Le Oro propylene fluoride such as polymers, fluoroolefin - hydrocarbonoxy ole
  • composition for forming organic layer used in wet film formation method The composition for forming an organic layer is obtained by dissolving, in an organic solvent, a low molecular compound capable of forming each organic layer of an organic EL element or a high molecular compound obtained by polymerizing the low molecular compound.
  • the composition for forming a light emitting layer includes a polycyclic aromatic compound (or a polymer compound thereof) that is at least one dopant material as a first component, at least one host material as a second component, and a third component. It contains at least one organic solvent as a component.
  • a 1st component functions as a dopant component of the light emitting layer obtained from this composition
  • a 2nd component functions as a host component of a light emitting layer.
  • the third component functions as a solvent that dissolves the first component and the second component in the composition, and gives a smooth and uniform surface shape at the time of application due to the controlled evaporation rate of the third component itself.
  • the composition for forming an organic layer contains at least one organic solvent.
  • the evaporation rate of the organic solvent at the time of film formation the film formability, the presence or absence of defects in the coating film, the surface roughness, and the smoothness can be controlled and improved.
  • the meniscus stability at the pinhole of the ink jet head can be controlled, and the discharge performance can be controlled and improved.
  • the drying speed of the film and the orientation of the derivative molecules the electrical characteristics, light emitting characteristics, efficiency, and lifetime of the organic EL device having an organic layer obtained from the organic layer forming composition are improved. Can do.
  • the boiling point of at least one organic solvent is 130 ° C to 300 ° C, more preferably 140 ° C to 270 ° C, and further preferably 150 ° C to 250 ° C.
  • the organic solvent is more preferably composed of two or more organic solvents from the viewpoints of good ink jet discharge properties, film formability, smoothness and low residual solvent.
  • the composition may be a solid state by removing the solvent from the organic layer forming composition in consideration of transportability and the like.
  • the organic solvent contains a good solvent (GS) and a poor solvent (PS) for at least one kind of solute, and the boiling point (BP GS ) of the good solvent (GS) is higher than the boiling point (BP PS ) of the poor solvent (PS).
  • a low configuration is particularly preferred.
  • the solubility difference (S GS ⁇ S PS ) is preferably 1% or more, more preferably 3% or more, and further preferably 5% or more.
  • the difference in boiling points (BP PS -BP GS ) is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and further preferably 50 ° C. or higher.
  • the organic solvent is removed from the coating film by a drying process such as vacuum, reduced pressure or heating after the film formation.
  • a drying process such as vacuum, reduced pressure or heating after the film formation.
  • Tg glass transition temperature
  • Tg glass transition point
  • organic solvents used in the organic layer forming composition include alkylbenzene solvents, phenyl ether solvents, alkyl ether solvents, cyclic ketone solvents, aliphatic ketone solvents, and monocyclic solvents. Examples include ketone solvents, solvents having a diester skeleton, and fluorine-containing solvents.
  • composition for forming an organic layer may contain an optional component as long as its properties are not impaired.
  • optional components include a binder and a surfactant.
  • Binder The composition for forming an organic layer may contain a binder.
  • the binder forms a film at the time of film formation and bonds the obtained film to the substrate. In addition, it plays a role of dissolving, dispersing and binding other components in the organic layer forming composition.
  • binder used in the organic layer forming composition examples include acrylic resin, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, acrylonitrile-ethylene-styrene copolymer (AES) resin, Ionomer, chlorinated polyether, diallyl phthalate resin, unsaturated polyester resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, Teflon, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile -Styrene copolymer (AS) resin, phenol resin, epoxy resin, melamine resin, urea resin, alkyd resin, polyurethane, and copolymer of the above resin and polymer, Re not limited to.
  • AES acrylonitrile-ethylene-styrene copolymer
  • the binder used in the composition for forming an organic layer may be only one kind or a mixture of plural kinds.
  • the composition for forming an organic layer contains, for example, a surfactant for controlling film surface uniformity, lyophilicity and liquid repellency of the composition for forming an organic layer. Also good.
  • Surfactants are classified into ionic and nonionic based on the structure of the hydrophilic group, and further classified into alkyl, silicon, and fluorine based on the structure of the hydrophobic group. Further, the molecular structure is classified into a monomolecular system having a relatively small molecular weight and a simple structure, and a polymer system having a large molecular weight and having a side chain and a branch.
  • surfactant for example, Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, polyflow no. 95 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181 and Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, manufactured by Big Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF -50-100CS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Footent 222F, Footage 251, FTX-218 (trade name,
  • the surfactant may be used alone or in combination of two or more.
  • composition and physical properties of organic layer forming composition The content of each component in the composition for forming an organic layer is obtained from the good solubility, storage stability and film formability of each component in the composition for forming an organic layer, and the composition for forming an organic layer. Good film quality of the coating film, good dischargeability when using the ink jet method, and good electrical characteristics, light emission characteristics, efficiency, and lifetime of the organic EL device having an organic layer produced using the composition It is decided in consideration of the viewpoint.
  • the first component is 0.0001% to 2.0% by weight and the second component is for forming the light emitting layer with respect to the total weight of the composition for forming the light emitting layer.
  • the third component is 90.0 wt% to 99.9 wt% based on the total weight of the composition for forming the light emitting layer. preferable.
  • the first component is 0.005 wt% to 1.0 wt% with respect to the total weight of the light emitting layer forming composition
  • the second component is with respect to the total weight of the light emitting layer forming composition, 0.095 wt% to 4.0 wt%
  • the third component is 95.0 wt% to 99.9 wt% with respect to the total weight of the light emitting layer forming composition.
  • the first component is 0.05% by weight to 0.5% by weight relative to the total weight of the light emitting layer forming composition
  • the second component is based on the total weight of the light emitting layer forming composition.
  • the amount of the third component is 97.0% by weight to 99.7% by weight with respect to the total weight of the composition for forming a light emitting layer.
  • the composition for forming an organic layer can be produced by appropriately selecting and stirring the above-described components by a known method such as stirring, mixing, heating, cooling, dissolution, and dispersion. Further, after preparation, filtration, degassing (also referred to as degas), ion exchange treatment, inert gas replacement / encapsulation treatment, and the like may be selected as appropriate.
  • the viscosity of the composition for forming an organic layer is preferably 0.3 to 3 mPa ⁇ s, more preferably 1 to 3 mPa ⁇ s at 25 ° C.
  • the viscosity is a value measured using a conical plate type rotational viscometer (cone plate type).
  • the viscosity of the composition for forming an organic layer is preferably 20 to 40 mN / m, more preferably 20 to 30 mN / m, at a surface tension at 25 ° C.
  • the surface tension is a value measured using the hanging drop method.
  • ⁇ Crosslinkable polymer compound compound represented by general formula (XLP-1)>
  • a crosslinkable polymer compound is, for example, a compound represented by the following general formula (XLP-1).
  • MUx, ECx and k have the same definitions as MU, EC and k in the above formula (SPH-1), provided that the compound represented by the formula (XLP-1) has at least one crosslinkable substituent (XLS).
  • the content of the monovalent or divalent aromatic compound having a crosslinkable substituent is 0.1 to 80% by weight in the molecule.
  • the content of the monovalent or divalent aromatic compound having a crosslinkable substituent is preferably 0.5 to 50% by weight, and more preferably 1 to 20% by weight.
  • crosslinkable substituent is not particularly limited as long as it can further crosslink the above-described polymer compound, but a substituent having the following structure is preferable. * In each structural formula indicates a bonding position.
  • L is each independently a single bond, —O—, —S—,> C ⁇ O, —O—C ( ⁇ O) —, alkylene having 1 to 12 carbons, or oxyalkylene having 1 to 12 carbons. And polyoxyalkylene having 1 to 12 carbon atoms.
  • substituents they are represented by the formula (XLS-1), the formula (XLS-2), the formula (XLS-3), the formula (XLS-9), the formula (XLS-10), or the formula (XLS-17).
  • a group represented by the formula (XLS-1), the formula (XLS-3) or the formula (XLS-17) is more preferable.
  • divalent aromatic compound having a crosslinkable substituent examples include compounds having the following partial structure.
  • solvent used in the reaction examples include aromatic solvents, saturated / unsaturated hydrocarbon solvents, alcohol solvents, ether solvents, and the like, for example, dimethoxyethane, 2- (2-methoxyethoxy) ethane, 2- (2 -Ethoxyethoxy) ethane and the like.
  • reaction may be performed in a two-phase system.
  • a phase transfer catalyst such as a quaternary ammonium salt may be added as necessary.
  • the compound of formula (SPH-1) and the compound of (XLP-1) are produced, they may be produced in one step or may be produced through multiple steps. Moreover, it may be carried out by a batch polymerization method in which the reaction is started after all the raw materials are put in the reaction vessel, or may be carried out by a dropping polymerization method in which the raw material is dropped into the reaction vessel and the product is used for the progress of the reaction. It may be carried out by a precipitation polymerization method in which precipitation is accompanied, and they can be synthesized by appropriately combining them.
  • the target product is obtained by carrying out the reaction with the monomer unit (MU) and the end cap unit (EC) added to the reaction vessel.
  • the monomer unit (MU) is polymerized to the target molecular weight, and then the end cap unit (EC) is added and reacted. Get things. If the reaction is carried out by adding different types of monomer units (MU) in multiple stages, a polymer having a concentration gradient with respect to the structure of the monomer units can be produced.
  • a target polymer can be obtained by a post reaction.
  • the primary structure of the polymer can be controlled. For example, as shown in Synthesis Schemes 1 to 3, it is possible to synthesize polymers with random primary structures (Synthesis Scheme 1), regular primary structures (Synthesis Schemes 2 and 3), etc. And can be used in appropriate combination depending on the object. Furthermore, if a monomer unit having three or more polymerizable groups is used, a hyperbranched polymer or a dendrimer can be synthesized.
  • Examples of monomer units that can be used in the present invention include JP 2010-189630 A, International Publication No. 2012/086671, International Publication No. 2013/191088, International Publication No. 2002/045184, International Publication No. 2011/049241. No., International Publication No. 2013/146806, International Publication No. 2005/049546, International Publication No. 2015/145871, Japanese Unexamined Patent Publication No. 2010-215886, Japanese Unexamined Patent Publication No. 2008-106241, Japanese Unexamined Patent Publication No. 2010-215886, International Publication No. It can be synthesized according to the methods described in Published 2016/031639, JP 2011-174062, Published 2016/031639, Published 2016/031639, Published 2002/045184 .
  • JP 2012-036388 A International Publication No. 2015/008851, JP 2012-36381 A, JP 2012-144722 A, International Publication No. 2015/194448.
  • International Publication No. 2013/146806 International Publication No. 2015/145871, International Publication No. 2016/031639, International Publication No. 2016/125560, International Publication No. 2016/031639, International Publication No. 2016/031639, International Publication No.
  • the compound can be synthesized according to the methods described in Publication No. 2016/125560, International Publication No. 2015/145871, International Publication No. 2011/049241, and Japanese Unexamined Patent Publication No. 2012-144722.
  • 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 mosaic, and characters and images are displayed with a set of pixels.
  • the shape and size of the pixel are determined by the application. For example, a square pixel with a side of 300 ⁇ m or less is usually used for displaying images and characters on a personal computer, monitor, TV, and a pixel with a side of mm order for a large display such as a display panel. become.
  • monochrome display pixels of the same color may be arranged. However, 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 properly use it 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, and the like can be mentioned.
  • the illuminating device examples include an illuminating device such as indoor lighting, a backlight of a liquid crystal display device, and the like (for example, JP 2003-257621 A, JP 2003-277741 A, JP 2004-119211 A). 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 panel, 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.
  • the polycyclic aromatic compound according to the present invention can be used for producing an organic field effect transistor or an organic thin film solar cell in addition to the above-described organic electroluminescent element.
  • An organic field effect transistor is a transistor that controls current by an electric field generated by voltage input, and a gate electrode is provided in addition to a source electrode and a drain electrode. When a voltage is applied to the gate electrode, an electric field is generated, and the current can be controlled by arbitrarily blocking the flow of electrons (or holes) flowing between the source electrode and the drain electrode.
  • Field effect transistors are easier to miniaturize than simple transistors (bipolar transistors), and are often used as elements constituting integrated circuits and the like.
  • the structure of the organic field effect transistor is usually provided with a source electrode and a drain electrode in contact with the organic semiconductor active layer formed using the polycyclic aromatic compound according to the present invention, and further in contact with the organic semiconductor active layer.
  • the gate electrode may be provided with the insulating layer (dielectric layer) interposed therebetween. Examples of the element structure include the following structures.
  • Substrate / gate electrode / insulator layer / source electrode / drain electrode / organic semiconductor active layer (2) Substrate / gate electrode / insulator layer / organic semiconductor active layer / source electrode / drain electrode (3) substrate / organic Semiconductor active layer / source electrode / drain electrode / insulator layer / gate electrode (4) substrate / source electrode / drain electrode / organic semiconductor active layer / insulator layer / gate electrode It can be applied as a pixel driving switching element for an active matrix driving type liquid crystal display or an organic electroluminescence display.
  • Organic thin-film solar cells have a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are laminated on a transparent substrate such as glass.
  • the photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side.
  • the polycyclic aromatic compound according to the present invention can be used as a material for a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, and an electron transport layer, depending on its physical properties.
  • the polycyclic aromatic compound according to the present invention can function as a hole transport material or an electron transport material in an organic thin film solar cell.
  • the organic thin film solar cell may appropriately include a hole block layer, an electron block layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like.
  • known materials used for the organic thin film solar cell can be appropriately selected and used in combination.
  • intermediate (IB) (10.0 g), bis (4-t-butylphenyl) amine (18.2 g), dichlorobis [(di-t-butyl (4-dimethylaminophenyl) as a palladium catalyst ) Phosphino) palladium (Pd-132, 0.21 g), sodium t-butoxide (NaOtBu, 7.1 g) and xylene (100 ml) were placed in a flask and heated at 100 ° C. for 1 hour. After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product. The crude product was purified with a silica gel short column (eluent: toluene) to obtain intermediate (IC) (18.0 g).
  • intermediate (ID) (15.0 g)
  • bis (4-tert-butylphenyl) amine (8.4 g)
  • Pd-132 (0.21 g) as a palladium catalyst
  • NaOtBu 4.3 g
  • xylene 60 ml
  • water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product.
  • the crude product was purified with a silica gel short column (eluent: toluene) to obtain intermediate (IE) (15.0 g).
  • intermediate (ID) (15.0 g)
  • bis (4-t-amylphenyl) amine 9.3 g
  • Pd-132 (0.21 g) as a palladium catalyst
  • NaOtBu 4.3 g
  • xylene 60 ml
  • water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product.
  • the crude product was purified with a silica gel short column (eluent: toluene) to obtain Intermediate (IF) (14.5 g).
  • intermediate (IB) (7.0 g), bis (4-tertamylphenyl) amine (14.0 g), Pd-132 (0.15 g) as a palladium catalyst, NaOtBu (4.9 g) And xylene (80 ml) were placed in a flask and heated at 100 ° C. for 1 hour. After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product. The crude product was purified with a silica gel short column (eluent: toluene) to obtain Intermediate (IG) (9.8 g).
  • intermediate (IH) (10.0 g), bis (4-tertamylphenyl) amine (19.5 g), bis (dibenzylideneacetone) palladium (0) (Pd (dba)) as a palladium catalyst 2 , 0.33 g), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (Sphos, 0.59 g), NaOtBu (6.9 g) and xylene (80 ml) were placed in a flask and stirred at 100 ° C. for 1 hour. Heated.
  • intermediate (IK) (15.0 g), bis (4-t-amylphenyl) amine (8.0 g), Pd-132 (0.19 g) as a palladium catalyst, NaOtBu (3.9 g) ) And xylene (60 ml) were placed in a flask and heated at 120 ° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product. The crude product was purified with a silica gel short column (eluent: toluene) to obtain intermediate (IL) (15.2 g).
  • intermediate (IM) (11.0 g), bis (4-t-amylphenyl) amine (6.1 g), Pd-132 (0.17 g) as a palladium catalyst, NaOtBu (3.4 g) ) And xylene (50 ml) were placed in a flask and heated at 120 ° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product. The crude product was purified with a silica gel short column (eluent: toluene) to obtain Intermediate (IN) (12.5 g).
  • intermediate (IK) 8.0 g
  • bis (4-t-octylphenyl) amine 6.5 g
  • Pd-132 0.13 g
  • NaOtBu 2.6 g
  • xylene 40 ml
  • water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product.
  • the crude product was purified with a silica gel short column (eluent: toluene) to obtain intermediate (IO) (11.5 g).
  • intermediate (IS) (22.4 g), bis (4-tertamylphenyl) amine (28.4 g), [(t-Bu) 3 PH] BF 4 (0.53 g), palladium Pd (dba) 2 (0.84 g), NaOtBu (11.0 g) and xylene (225 ml) were placed in a flask as a catalyst and heated at 100 ° C. for 1 hour. After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product. The crude product was purified with a silica gel short column (eluent: toluene) to obtain intermediate (IT) (31.2 g).
  • intermediate (IU) 8.0 g
  • bis (4-t-octylphenyl) amine 7.0 g
  • Pd-132 0.13 g
  • NaOtBu 2.6 g
  • xylene 40 ml
  • water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product.
  • the crude product was purified with a silica gel short column (eluent: toluene) to obtain intermediate (IV) (10.5 g).
  • 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.
  • 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 outside 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 1A and Table 1B below show the material configuration of each layer and EL characteristic data in the produced organic EL elements according to Example 1-1 to Example 1-8.
  • HI refers to N 4 , N 4 ′ -diphenyl-N 4 , N 4 ′ -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4, 4'-diamine
  • HAT-CN is 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile
  • HT-1 is N-([1,1'-biphenyl ] -4-yl-9,9-dimethyl-N- [4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine [1,1′-biphenyl] -4
  • An amine, “HT-2” being N, N-bis (4- (dibenzo [b, d] furan-4-yl) phenyl)-[1,1 ′: 4 ′, 1 ′′ -terphenyl] -4-amine
  • BH 1,4 n
  • Example 1-1 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, HAT-CN, HT-1, HT-2, BH-1, compound (1-151), ET A tantalum vapor deposition boat containing -1 and ET-2, and an aluminum nitride vapor deposition boat each containing Liq, LiF, and aluminum were mounted.
  • the following layers were sequentially formed on the ITO film of the transparent support substrate.
  • the vacuum chamber was depressurized to 5 ⁇ 10 ⁇ 4 Pa, first, HI was heated and evaporated to a film thickness of 40 nm, then HAT-CN was heated and evaporated to a film thickness of 5 nm, Next, HT-1 is heated and evaporated to a film thickness of 45 nm, and then HT-2 is heated and evaporated to a film thickness of 10 nm to form a four-layer hole layer. did. Next, BH-1 and the compound (1-151) 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 compound (1-151) was approximately 98 to 2. Further, ET-1 was heated and evaporated to a thickness of 5 nm, and then ET-2 and Liq were simultaneously heated to a thickness of 25 nm to form a two-layer electronic layer. Formed. The deposition rate was adjusted so that the weight ratio of ET-2 to Liq was approximately 50:50. The deposition rate of each layer was 0.01 to 1 nm / second. Thereafter, LiF is heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm, and then aluminum is heated to deposit to a film thickness of 100 nm to form a cathode. Thus, an organic EL element was obtained.
  • Examples 1-2 to 1-8> An organic EL device was produced by a method according to Example 1-1 (Table 1A), and EL characteristics were measured (Table 1B).
  • Example 2 a compound dissolution test was performed. After putting 1 g of the test compound in 30 ml of toluene at 100 ° C. and stirring, it was verified whether or not the test compound was dissolved. The results are shown in Table 2.
  • SPH-101 was synthesized according to the method described in International Publication No. 2015/008851. Next to M1, a copolymer having M2 or M3 bonded thereto is obtained, and each unit is estimated to be 50:26:24 (molar ratio) from the charging ratio.
  • XLP-101 was synthesized according to the method described in JP-A-2018-61028. Next to M7, a copolymer having M2 or M3 bonded thereto is obtained, and each unit is estimated to be 40:10:50 (molar ratio) from the charging ratio.
  • Examples 3 to 10 A coating solution of a material for forming each layer is prepared to prepare a coating type organic EL element.
  • Table 3 shows the material structure of each layer in the organic EL element.
  • a light emitting layer forming composition (1) is prepared by stirring the following components until a uniform solution is obtained.
  • the prepared light emitting layer forming composition is spin-coated on a glass substrate and dried by heating under reduced pressure, whereby a coating film free from film defects and excellent in smoothness can be obtained.
  • Compound (A) 0.04% by weight SPH-101 1.96 wt% Xylene 69.00 wt% Decalin 29.00 wt%
  • the compound (A) is a polycyclic aromatic compound represented by the general formula (1), a multimer thereof, the polycyclic aromatic compound or the multimer as a monomer (that is, the monomer has a reactive substituent). ), Or a crosslinked polymer obtained by further crosslinking the polymer compound.
  • the polymer compound for obtaining a crosslinked polymer has a crosslinkable substituent.
  • PEDOT PSS solution>
  • a commercially available PEDOT: PSS solution (Clevios TM PVP AI4083, PEDOT: PSS aqueous dispersion, manufactured by Heraeus Holdings) is used.
  • OTPD LT-N159, manufactured by Luminescence Technology Corp
  • IK-2 photo cation polymerization initiator, manufactured by San Apro
  • XLP-101 is dissolved in xylene at a concentration of 0.6% by weight to prepare a 0.7% by weight XLP-101 solution.
  • PCz polyvinylcarbazole
  • a PEDOT: PSS solution is spin-coated on a glass substrate on which ITO is deposited to a thickness of 150 nm, and baked on a hot plate at 200 ° C. for 1 hour to form a PEDOT: PSS film having a thickness of 40 nm. (Hole injection layer).
  • the OTPD solution is spin-coated, dried on an 80 ° C. hot plate for 10 minutes, exposed to an exposure intensity of 100 mJ / cm 2 with an exposure machine, and baked on the hot plate at 100 ° C. for 1 hour.
  • An OTPD film having a thickness of 30 nm which is insoluble in the film is formed (hole transport layer).
  • the light emitting layer forming composition (1) is spin-coated and baked on a hot plate at 120 ° C. for 1 hour to form a light emitting layer having a thickness of 20 nm.
  • the produced multilayer film is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing ET1, a molybdenum vapor deposition boat containing LiF, and tungsten containing aluminum.
  • a vapor deposition boat is installed.
  • ET1 is heated and evaporated to a film thickness of 30 nm to form an electron transport layer.
  • the deposition rate for forming the electron transport layer is 1 nm / second.
  • LiF 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.
  • aluminum is heated and evaporated to a thickness of 100 nm to form a cathode. In this way, an organic EL element is obtained.
  • Example 4 An organic EL element is obtained in the same manner as in Example 2. Note that the hole-transporting layer is spin-coated with an XLP-101 solution and baked on a hot plate at 200 ° C. for 1 hour to form a film with a thickness of 30 nm.
  • Example 5 An organic EL element is obtained in the same manner as in Example 2. Note that the hole-transporting layer is formed by spin-coating a PCz solution and baking on a hot plate at 120 ° C. for 1 hour to form a film with a thickness of 30 nm.
  • Table 4 shows the material structure of each layer in the organic EL element.
  • the light emitting layer forming composition (2) is prepared by stirring the following components until a uniform solution is obtained.
  • Compound (A) 0.02% by weight mCBP 1.98 wt% Toluene 98.00 wt%
  • composition for light emitting layer formation (3) is prepared by stirring the following components until it becomes a uniform solution.
  • Compound (A) 0.02% by weight SPH-101 1.98 wt% Xylene 98.00 wt%
  • composition for light emitting layer formation (4) is prepared by stirring the following components until it becomes a uniform solution.
  • Compound (A) 0.02% by weight DOBNA 1.98 wt% Toluene 98.00 wt%
  • mCBP is 3,3′-bis (N-carbazolyl) -1,1′-biphenyl
  • DOBNA 3,11-di-o-tolyl-5,9-dioxa- 13b-Bolanaphtho [3,2,1-de] anthracene
  • TSPO1 diphenyl [4- (triphenylsilyl) phenyl] phosphine oxide.
  • ND-3202 (Nissan Chemical Industries) solution was spin-coated on a glass substrate on which ITO was deposited to a thickness of 45 nm, and then heated at 50 ° C. for 3 minutes in an air atmosphere, and further 230 ° C., 15 By heating for 50 minutes, an ND-3202 film having a thickness of 50 nm is formed (hole injection layer).
  • an XLP-101 solution is spin-coated and heated on a hot plate at 200 ° C. for 30 minutes in a nitrogen gas atmosphere to form an XLP-101 film having a thickness of 20 nm (hole transport layer).
  • the light emitting layer forming composition (2) is spin-coated, and heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere to form a 20 nm light emitting layer.
  • the produced multilayer film is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing TSPO1, a molybdenum vapor deposition boat containing LiF, and tungsten containing aluminum.
  • a vapor deposition boat is installed. After depressurizing the vacuum chamber to 5 ⁇ 10 ⁇ 4 Pa, TSPO1 is heated and evaporated to a film thickness of 30 nm to form an electron transport layer.
  • the deposition rate for forming the electron transport layer is 1 nm / second.
  • LiF 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.
  • aluminum is heated and evaporated to a thickness of 100 nm to form a cathode. In this way, an organic EL element is obtained.
  • Examples 7 and 8> An organic EL device is obtained in the same manner as in Example 6 using the light emitting layer forming composition (3) or (4).
  • Table 5 shows the material structure of each layer in the organic EL element.
  • composition for light emitting layer formation is prepared by stirring the following component until it becomes a uniform solution.
  • Compound (A) 0.02% by weight 2PXZ-TAZ 0.18 wt% mCBP 1.80 wt% Toluene 98.00 wt%
  • composition for light emitting layer formation is prepared by stirring the following component until it becomes a uniform solution.
  • Compound (A) 0.02% by weight 2PXZ-TAZ 0.18 wt% SPH-101 1.80 wt% Xylene 98.00 wt%
  • composition for light emitting layer formation is prepared by stirring the following component until it becomes a uniform solution.
  • Compound (A) 0.02% by weight 2PXZ-TAZ 0.18 wt% DOBNA 1.80 wt% Toluene 98.00 wt%
  • Example 9 An ND-3202 (Nissan Chemical Industries) solution was spin-coated on a glass substrate on which ITO was deposited to a thickness of 45 nm, and then heated at 50 ° C. for 3 minutes in an air atmosphere, and further 230 ° C., 15 By heating for 50 minutes, an ND-3202 film having a thickness of 50 nm is formed (hole injection layer).
  • an XLP-101 solution is spin-coated and heated on a hot plate at 200 ° C. for 30 minutes in a nitrogen gas atmosphere to form an XLP-101 film having a thickness of 20 nm (hole transport layer).
  • the light emitting layer forming composition (5) is spin-coated, and heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere to form a 20 nm light emitting layer.
  • the produced multilayer film is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing TSPO1, a molybdenum vapor deposition boat containing LiF, and tungsten containing aluminum.
  • a vapor deposition boat is installed. After depressurizing the vacuum chamber to 5 ⁇ 10 ⁇ 4 Pa, TSPO1 is heated and evaporated to a film thickness of 30 nm to form an electron transport layer.
  • the deposition rate for forming the electron transport layer is 1 nm / second.
  • LiF 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.
  • aluminum is heated and evaporated to a thickness of 100 nm to form a cathode. In this way, an organic EL element is obtained.
  • Example 10 and 11 An organic EL device is obtained in the same manner as in Example 9 using the light emitting layer forming composition (6) or (7).
  • a novel tertiary alkyl-substituted polycyclic aromatic compound by providing a novel tertiary alkyl-substituted polycyclic aromatic compound, it is possible to increase options for materials for organic devices such as materials for organic EL elements.
  • a novel tertiary alkyl-substituted polycyclic aromatic compound as a material for an organic EL element, for example, an organic EL element having excellent luminous efficiency, a display device including the same, a lighting device including the same, and the like are provided. can do.

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