WO2015093551A1 - 化合物、有機エレクトロルミネッセンス素子用材料、インク組成物、有機エレクトロルミネッセンス素子、電子機器、及び化合物の製造方法 - Google Patents
化合物、有機エレクトロルミネッセンス素子用材料、インク組成物、有機エレクトロルミネッセンス素子、電子機器、及び化合物の製造方法 Download PDFInfo
- Publication number
- WO2015093551A1 WO2015093551A1 PCT/JP2014/083486 JP2014083486W WO2015093551A1 WO 2015093551 A1 WO2015093551 A1 WO 2015093551A1 JP 2014083486 W JP2014083486 W JP 2014083486W WO 2015093551 A1 WO2015093551 A1 WO 2015093551A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- substituted
- carbon atoms
- ring
- unsubstituted
- Prior art date
Links
- 0 CN(C(*=*C(C(*)=***)=*)=C(*)C1=C)C1=**=** Chemical compound CN(C(*=*C(C(*)=***)=*)=C(*)C1=C)C1=**=** 0.000 description 37
- VPQYVESMDVMIRJ-UHFFFAOYSA-N CC1(C)c(cc(c(c2c3cccc2)c2)[n]3-c3cccc(-c4cc(-c5ccccc5)nc(-[n]5c(ccc(-c(cc6)cc(c7ccccc77)c6[n]7-c6ccccc6)c6)c6c6c5cccc6)n4)c3)c2-c2ccccc12 Chemical compound CC1(C)c(cc(c(c2c3cccc2)c2)[n]3-c3cccc(-c4cc(-c5ccccc5)nc(-[n]5c(ccc(-c(cc6)cc(c7ccccc77)c6[n]7-c6ccccc6)c6)c6c6c5cccc6)n4)c3)c2-c2ccccc12 VPQYVESMDVMIRJ-UHFFFAOYSA-N 0.000 description 1
- YDATWWTXEKOGAG-SLKWPDKUSA-N Cc(cc1)ccc1/N=C(\C=C1)/C=C/C1=N/C Chemical compound Cc(cc1)ccc1/N=C(\C=C1)/C=C/C1=N/C YDATWWTXEKOGAG-SLKWPDKUSA-N 0.000 description 1
- YRBLWYZSTBTUSP-XXOFKJKPSA-N N=C(/C=C(/c1cc(-[n]2c3cc(-c(cc4c5ccccc55)ccc4[n]5-c4ccccc4)ccc3c3c2cccc3)ccc1)\N[n](c(cccc1)c1c1c2)c1ccc2-c(cc1)cc(c2ccccc22)c1[n]2-c1ccccc1)c1ccccc1 Chemical compound N=C(/C=C(/c1cc(-[n]2c3cc(-c(cc4c5ccccc55)ccc4[n]5-c4ccccc4)ccc3c3c2cccc3)ccc1)\N[n](c(cccc1)c1c1c2)c1ccc2-c(cc1)cc(c2ccccc22)c1[n]2-c1ccccc1)c1ccccc1 YRBLWYZSTBTUSP-XXOFKJKPSA-N 0.000 description 1
- YFXIAQSBAZXKIN-JQCFUMKPSA-N N=C(/C=C(/c1cccc(-[n]2c(cc(c(cccc3)c3[n]3-c4ccccc4)c3c3)c3c3ccccc23)c1)\N[n](c(cccc1)c1c1c2)c1ccc2-c(cc1)cc(c2ccccc22)c1[n]2-c1ccccc1)c1ccccc1 Chemical compound N=C(/C=C(/c1cccc(-[n]2c(cc(c(cccc3)c3[n]3-c4ccccc4)c3c3)c3c3ccccc23)c1)\N[n](c(cccc1)c1c1c2)c1ccc2-c(cc1)cc(c2ccccc22)c1[n]2-c1ccccc1)c1ccccc1 YFXIAQSBAZXKIN-JQCFUMKPSA-N 0.000 description 1
- UZQRVXRKOWKPGG-UHFFFAOYSA-N c(cc1)ccc1-[n]1c(ccc(-c(cc2)cc(c3c4cccc3)c2[n]4-c2nc(-c3ccc(c4ccccc4[o]4)c4c3)cc(-c(cc3)ccc3-[n]3c(cc(cc4)-c(cc5)cc(c6c7cccc6)c5[n]7-c5ccccc5)c4c4ccccc34)n2)c2)c2c2ccccc12 Chemical compound c(cc1)ccc1-[n]1c(ccc(-c(cc2)cc(c3c4cccc3)c2[n]4-c2nc(-c3ccc(c4ccccc4[o]4)c4c3)cc(-c(cc3)ccc3-[n]3c(cc(cc4)-c(cc5)cc(c6c7cccc6)c5[n]7-c5ccccc5)c4c4ccccc34)n2)c2)c2c2ccccc12 UZQRVXRKOWKPGG-UHFFFAOYSA-N 0.000 description 1
- MODJYHJOAKVCLR-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-[n](c(cccc2)c2c2c3)c2ccc3-c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)nc(-c2cccc(-[n]3c(c4c(cc5)c6ccccc6[n]4-c4ccccc4)c5c4c3cccc4)c2)c1 Chemical compound c(cc1)ccc1-c1nc(-[n](c(cccc2)c2c2c3)c2ccc3-c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)nc(-c2cccc(-[n]3c(c4c(cc5)c6ccccc6[n]4-c4ccccc4)c5c4c3cccc4)c2)c1 MODJYHJOAKVCLR-UHFFFAOYSA-N 0.000 description 1
- WYUFZDBUDUTIJK-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-[n](c(cccc2)c2c2c3)c2ccc3-c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)nc(-c2cccc(-[n]3c4cccc(-c(cc5)cc(c6ccccc66)c5[n]6-c5ccccc5)c4c4ccccc34)c2)c1 Chemical compound c(cc1)ccc1-c1nc(-[n](c(cccc2)c2c2c3)c2ccc3-c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)nc(-c2cccc(-[n]3c4cccc(-c(cc5)cc(c6ccccc66)c5[n]6-c5ccccc5)c4c4ccccc34)c2)c1 WYUFZDBUDUTIJK-UHFFFAOYSA-N 0.000 description 1
- MATYAWNNFXKLKV-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-[n](c(cccc2)c2c2ccc3c4ccccc44)c2c3[n]4-c2ccccc2)nc(-c2cccc(-[n]3c(ccc(-c(cc4c5c6cccc5)ccc4[n]6-c4ccccc4)c4)c4c4ccccc34)c2)c1 Chemical compound c(cc1)ccc1-c1nc(-[n](c(cccc2)c2c2ccc3c4ccccc44)c2c3[n]4-c2ccccc2)nc(-c2cccc(-[n]3c(ccc(-c(cc4c5c6cccc5)ccc4[n]6-c4ccccc4)c4)c4c4ccccc34)c2)c1 MATYAWNNFXKLKV-UHFFFAOYSA-N 0.000 description 1
- WPQADKDNEWEKFO-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-[n]2c(ccc(-[n]3c4ccccc4c4c3cccc4)c3)c3c3c2ccc(-[n]2c(cccc4)c4c4c2cccc4)c3)nc(-c2cccc(-[n]3c(ccc(-c(cc4)cc(c5c6cccc5)c4[n]6-c4ccccc4)c4)c4c4ccccc34)c2)c1 Chemical compound c(cc1)ccc1-c1nc(-[n]2c(ccc(-[n]3c4ccccc4c4c3cccc4)c3)c3c3c2ccc(-[n]2c(cccc4)c4c4c2cccc4)c3)nc(-c2cccc(-[n]3c(ccc(-c(cc4)cc(c5c6cccc5)c4[n]6-c4ccccc4)c4)c4c4ccccc34)c2)c1 WPQADKDNEWEKFO-UHFFFAOYSA-N 0.000 description 1
- RBXNDTHCNFLDIM-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-[n]2c(ccc(-c(cc3)cc(c4ccccc44)c3[n]4-c3ccccc3)c3)c3c3c2cccc3)nc(-c2cc(-[n]3c(ccc(-c4cccc5c4c4ccccc4[s]5)c4)c4c4ccccc34)ccc2)c1 Chemical compound c(cc1)ccc1-c1nc(-[n]2c(ccc(-c(cc3)cc(c4ccccc44)c3[n]4-c3ccccc3)c3)c3c3c2cccc3)nc(-c2cc(-[n]3c(ccc(-c4cccc5c4c4ccccc4[s]5)c4)c4c4ccccc34)ccc2)c1 RBXNDTHCNFLDIM-UHFFFAOYSA-N 0.000 description 1
- MTWITBJDGIMCHN-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-[n]2c3cc(-c(cc4c5c6cccc5)ccc4[n]6-c4ccccc4)ccc3c3c2cccc3)nc(-c2cccc(-[n]3c(ccc(-c(cc4c5c6cccc5)ccc4[n]6-c4ccccc4)c4)c4c4c3cccc4)c2)c1 Chemical compound c(cc1)ccc1-c1nc(-[n]2c3cc(-c(cc4c5c6cccc5)ccc4[n]6-c4ccccc4)ccc3c3c2cccc3)nc(-c2cccc(-[n]3c(ccc(-c(cc4c5c6cccc5)ccc4[n]6-c4ccccc4)c4)c4c4c3cccc4)c2)c1 MTWITBJDGIMCHN-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
-
- 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
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- 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
- C09D11/50—Sympathetic, colour changing or similar inks
-
- 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
- C09D11/52—Electrically conductive inks
-
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- 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
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- 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
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
Definitions
- the present invention relates to a compound, a material for an organic electroluminescence element, an organic electroluminescence element, an ink composition, an electronic device, and a method for producing the compound.
- An organic electroluminescence device comprising an organic thin film layer including a light emitting layer between an anode and a cathode, and emitting light from exciton energy generated by recombination of holes and electrons injected into the light emitting layer (It may be described as “organic EL element”).
- An organic EL element is expected as a light-emitting element that takes advantage of a self-luminous element and is excellent in high luminous efficiency, high image quality, low power consumption, and thin design.
- the light emitting layer is a host / dopant light emitting layer in which a host is doped with a light emitting material as a dopant.
- excitons can be efficiently generated from the charge injected into the host. And the energy of the produced
- Patent Documents 1 to 10 describe various compounds in which a carbazole structure is bonded to a non-condensed or condensed azine ring directly or via a linking group.
- the method for forming each layer of the organic EL element is roughly classified into a deposition method such as a vacuum deposition method and a molecular beam deposition method, and a coating method such as a dipping method, a spin coating method, a casting method, a bar coating method, and a roll coating method.
- the material for forming a layer by the coating method is required to have different characteristics from the material used in the vapor deposition method, such as temperature resistance and solubility in a solvent. Therefore, a material useful in the vapor deposition method is not always useful in the coating method.
- Patent Documents 1 to 8 disclose compounds in which one or more biscarbazole- or tricarbazole-containing groups are substituted on a non-condensed nitrogen-containing ring. However, Patent Documents 1 to 8 disclose compounds in which a condensed nitrogen-containing ring is substituted with a plurality of different biscarbazole-containing groups, a plurality of different tricarbazole-containing groups, or a biscarbazole-containing group and a tricarbazole-containing group. Absent. Patent Document 9 describes a compound having a condensed nitrogen-containing ring substituted with a biscarbazole-containing group, but does not describe a condensed nitrogen-containing ring compound having a plurality of biscarbazole-containing groups.
- Patent Document 10 verifies that a compound in which a plurality of biscarbazole or tricarbazole-containing groups are substituted on a non-condensed or condensed nitrogen-containing ring can be applied to an organic EL device. Some of the compounds are soluble in a solvent, and a layer is formed by a coating method to form an organic EL element. However, all of the compounds applied to the organic EL element by forming a layer by the coating method have a plurality of biscarbazole-containing groups substituted with non-condensed nitrogen-containing rings, each having the same structure.
- the characteristics of the compound verified in Patent Document 10 are limited to a range in which a plurality of biscarbazole-containing groups having the same structure and a non-condensed nitrogen-containing ring are combined, and meet various required characteristics of organic EL elements. Was insufficient.
- the present invention provides a compound that can form a layer by a coating method and can meet various characteristic requirements of an EL element.
- the present invention provides a material for an organic electroluminescence device containing the compound, an organic electroluminescence device using the compound, and an ink composition containing the compound.
- the present invention provides a method for producing the compound.
- the present inventors have found a compound represented by the following formula (1) that can be formed into a layer by a coating method and has various substituents. Moreover, the method of manufacturing this compound efficiently and simply was discovered. The present invention is based on these findings.
- a compound represented by the following formula (1) (hereinafter sometimes referred to as “compound (1)”) is provided.
- R 1 represents a hydrogen atom or a substituent
- X 1 represents N or CR 2
- R 2 represents a hydrogen atom or a substituent
- R 2 may be bonded to R 1 to form a ring
- * b is bonded to the carbon atom * c2
- X 1 represents CR 2 and R 2 is bonded to R 1 to form a ring
- R a represents a hydrogen atom or a substituent
- two adjacent R a may be bonded to each other to form a
- X 22 ′ represents NR 4 , CR 5 R 6 , O, S, Se, or SiR 7 R 8 ; R 4 to R 8 are the same as described above. ) (In Formula (3), * 5 is bonded to carbon atom * c1, carbon atom * c2, L 1 (when n is 0) or L 2 (when n is an integer of 1 to 3) of formula (1);
- One of X 37 to X 41 is a carbon atom bonded to * 6;
- the other X 37 to X 41 , X 32 to X 36 , and X 42 to X 51 each independently represent N or CR 9 ;
- R 9 represents a hydrogen atom or a substituent, and a plurality of R 9 may be bonded to each other to form a ring;
- X 36 and X 41 may be carbon atoms bonded to each other, and X 46 and X 51 may be carbon atoms bonded to each other.
- An atom, X 22 ′′ represents NR 4 , CR 5 R 6 , O, S, Se, or SiR 7 R 8 ; R 4 to R 8 are the same as described above. ) (In Formula (4), * 7 is bonded to carbon atom * c1, carbon atom * c2, L 1 (when n is 0) or L 2 (when n is an integer of 1 to 3) of formula (1); In one adjacent pair selected from X 67 to X 71 , one represents a carbon atom bonded to * 8, and the other represents a carbon atom bonded to * 9; The other X 67 to X 71 , X 62 to X 66 and X 72 to X 75 each independently represent N or CR 10 ; R 10 represents a hydrogen atom or a substituent, and a plurality of R 10 may be bonded to each other to form a ring, X 66 and X 71 may be carbon atoms bonded to each other, X 76 represents NR 11
- an organic electroluminescence device material containing the compound (1).
- an ink composition comprising a solvent and the compound (1) is provided.
- an organic electroluminescence device having a cathode, an anode, and one or more organic thin film layers disposed between the cathode and the anode, wherein the one or more organic thin film layers are provided.
- an organic electroluminescent device comprising a light emitting layer, and at least one of the one or more organic thin film layers comprising the compound (1).
- an electronic apparatus including the organic electroluminescence element is provided.
- a method for producing the compound (1) comprising the following coupling reaction 1 and the following coupling reaction 2 is provided.
- a compound represented by the following formula (I) (Wherein R 1 , X 1 , L 1 , L 2 and n are as defined in formula (1); One of * c and * d is bonded to carbon atom * c1, the other is bonded to carbon atom * c2, Hal 1 and Hal 2 represent the same or different halogen atoms.
- the compound (1) can be formed into a layer by a coating method, and can meet various characteristic requirements of an organic EL element. Moreover, this compound (1) can be efficiently and simply manufactured by the synthesis method described below.
- carbon number XX to YY in the expression “substituted or unsubstituted ZZ group having XX to YY” represents the number of carbon atoms when the ZZ group is unsubstituted. When the group is substituted, the carbon number of the substituent is not included.
- atom number XX to YY in the expression “a ZZ group having a substituted or unsubstituted atom number XX to YY” represents the number of atoms when the ZZ group is unsubstituted. In this case, the number of substituent atoms is not included.
- unsubstituted ZZ group in the case of “substituted or unsubstituted ZZ group” means that the hydrogen atom of the ZZ group is not substituted with a substituent.
- the “ring-forming carbon number” means the ring itself of a compound having a structure in which atoms are bonded in a cyclic manner (for example, a monocyclic compound, a condensed ring compound, a bridged compound, a carbocyclic compound, or a heterocyclic compound). This represents the number of carbon atoms among the constituent atoms.
- the carbon contained in the substituent is not included in the ring-forming carbon.
- the “ring-forming carbon number” described below is the same unless otherwise specified.
- the benzene ring has 6 ring carbon atoms
- the naphthalene ring has 10 ring carbon atoms
- the pyridinyl group has 5 ring carbon atoms
- the furanyl group has 4 ring carbon atoms.
- the carbon number of the alkyl group is not included in the number of ring-forming carbons.
- the carbon number of the fluorene ring as a substituent is not included in the ring-forming carbon number.
- the “number of ring-forming atoms” means a compound (for example, a monocyclic compound, a condensed ring compound, a bridging compound, or a carbocyclic compound) having a structure in which atoms are bonded in a cyclic manner (for example, a monocyclic ring, a condensed ring, or a ring assembly).
- a heterocyclic compound represents the number of atoms constituting the ring itself.
- An atom that does not constitute a ring for example, a hydrogen atom that terminates a bond of an atom that constitutes a ring
- an atom contained in a substituent when the ring is substituted by a substituent is not included in the number of ring-forming atoms.
- the “number of ring-forming atoms” described below is the same unless otherwise specified.
- the pyridine ring has 6 ring atoms
- the quinazoline ring has 10 ring atoms
- the furan ring has 5 ring atoms.
- the hydrogen atoms bonded to the ring-forming carbon atoms of the pyridine ring and quinazoline ring and the atoms constituting the substituent are not included in the number of ring-forming atoms. Further, when, for example, a fluorene ring is bonded to the fluorene ring as a substituent (including a spirofluorene ring), the number of atoms of the fluorene ring as a substituent is not included in the number of ring-forming atoms.
- hydroxide atom includes isotopes having different numbers of neutrons, that is, light hydrogen (protium), deuterium (deuterium) and tritium (tritium).
- an arbitrary substituent referred to as “substituted or unsubstituted” is an alkyl group having 1 to 50 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms; A cycloalkyl group having a number of 3 to 50, preferably 3 to 10, more preferably 3 to 8, more preferably 5 or 6, and a ring forming carbon number of 6 to 50, preferably 6 to 25, more preferably 6 to 18.
- An aryl group an aralkyl group having 6 to 50 ring-forming carbon atoms, preferably 6 to 25, more preferably 6 to 18 carbon atoms, and an aryl group having 7 to 51 carbon atoms, preferably 7 to 30 carbon atoms, and more preferably 7 to 20 carbon atoms;
- An amino group selected from an alkyl group having 1 to 50 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, and an aryl group having 6 to 50 ring carbon atoms, preferably 6 to 25 carbon atoms, more preferably 6 to 18 carbon atoms.
- An aryl group a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, and a substituted or unsubstituted carbon atom having 6 to 50, preferably 6 to 25 carbon atoms.
- the heteroaryl group 5-13; a and a cyano group; a halogen atom.
- the above arbitrary substituents may be further substituted with the above arbitrary substituents.
- Arbitrary substituents may combine to form a ring.
- the compound (1) is preferably represented by the following formula (1a), (1b) or (1c), more preferably represented by the formula (1a) or (1c).
- R 1 represents a hydrogen atom or a substituent.
- the substituent represented by R 1 is a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, a substituted or unsubstituted ring.
- An aryl group an aryl group having 6 to 50 ring carbon atoms, preferably 6 to 25, more preferably 6 to 18 carbon atoms, and an aryl group having 7 to 51 carbon atoms, preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms.
- An amino group a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, and a substituted or unsubstituted carbon atom number 6 to 60, preferably 6 to 25, More preferably a mono- or di-substituted amino group having a substituent selected from 6 to 18 aryl groups, a substituted or unsubstituted alkoxy group having 1 to 50, preferably 1 to 18, more preferably 1 to 8 carbon atoms.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
- alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group.
- Each group, if present, includes isomeric groups.
- Each group, if present, includes isomeric groups.
- cycloalkyl group examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group, and a cyclopentyl group and a cyclohexyl group are preferable.
- aryl group examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a naphthylphenyl group, a biphenylyl group, a terphenylyl group, a quaterphenylyl group, a kinkphenylyl group, an acenaphthylenyl group, an anthryl group, and a benzoanthryl group.
- Each group includes isomeric groups.
- preferred examples and more preferred examples of the aryl moiety of the aralkyl group are the same as those of the aryl group.
- preferred examples and more preferred examples of the alkyl moiety are the same as the above alkyl group.
- alkyl group of the mono-substituted or di-substituted amino group and specific examples, preferred examples and more preferred examples of the aryl group are the same as those of the alkyl group and aryl group, respectively.
- the mono-substituted, di-substituted or tri-substituted silyl group is a monoalkylsilyl group, a dialkylsilyl group, a trialkylsilyl group, a monoarylsilyl group, a diarylsilyl group, a triarylsilyl group, an alkyldiarylsilyl group, and a dialkylarylsilyl group.
- a monoalkylsilyl group preferably a dialkylsilyl group, a trialkylsilyl group, a monoarylsilyl group, a diarylsilyl group, and a triarylsilyl group, more preferably a trialkylsilyl group and a triarylsilyl group It is.
- preferred examples and more preferred examples of the alkyl group, and specific examples, preferred examples and more preferred examples of the aryl group are the same as those of the alkyl group and aryl group, respectively.
- trimethylsilyl group triethylsilyl group, t-butyldimethylsilyl group, propyldimethylsilyl group, isopropyldimethylsilyl group, triphenylsilyl group, phenyldimethylsilyl group, t-butyldiphenylsilyl group, and tolylyl
- silyl group preferably a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and a phenyldimethylsilyl group, and more preferably a trimethylsilyl group and a triphenylsilyl group.
- the heteroaryl group has at least one, preferably 1 to 5, more preferably 1 to 3, more preferably 1 to 2, the same or different heteroatoms such as nitrogen, sulfur, oxygen, phosphorus Contains atoms.
- the heteroaryl group include a pyrrolyl group, a furyl group, a thienyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a pyrazolyl group, an isoxazolyl group, and an isothiazolyl group.
- the substituted or unsubstituted carbazolyl group includes the following carbazolyl group, In addition to the above-described substituted carbazolyl group having an optional substituent, for example, the following substituted carbazolyl group is also included.
- the substituted or unsubstituted dibenzofuranyl group and the substituted or unsubstituted dibenzothiophenyl group include the following dibenzofuranyl group and dibenzothiophenyl group.
- the above-mentioned substituted dibenzofuranyl group and substituted dibenzothiophenyl group having an optional substituent for example, the following substituted dibenzofuranyl group and substituted dibenzothiophenyl group are also included.
- X represents an oxygen atom or a sulfur atom
- Y represents an oxygen atom, a sulfur atom, NH, NR b (R b is an alkyl group or an aryl group), CH 2 , or CR c 2 (R c is an alkyl group) Group or aryl group).
- the haloalkyl group is one or more, preferably 1 to 15, more preferably 1 to 7 hydrogen atoms or all hydrogen atoms of an alkyl group, the same or different halogen atoms (fluorine atom, chlorine atom, bromine atom, A group substituted with an iodine atom).
- halogen atoms fluorine atom, chlorine atom, bromine atom, A group substituted with an iodine atom.
- preferred examples and more preferred examples of the alkyl group are the same as the above alkyl group.
- Specific examples include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group.
- R 1 is preferably a hydrogen atom, the substituted or unsubstituted alkyl group, the substituted or unsubstituted aryl group, or the substituted or unsubstituted heteroaryl group.
- the hydrogen atom, the substituted or unsubstituted group is preferable.
- a substituted or unsubstituted heteroaryl group a hydrogen atom, a phenyl group, a naphthyl group (including an isomer group), a biphenyl group (including an isomer group), a terphenyl group ( An isomer group), a phenylterphenyl group (including an isomer group), a dibenzofuranyl group (including an isomer group), or a dibenzothiophenyl group (including an isomer group). It is particularly preferred.
- X 1 represents N or CR 2 .
- R 2 represents a hydrogen atom or a substituent, and R 2 may combine with R 1 to form a ring.
- the substituent represented by R 2 its specific examples, preferred examples, and more preferred examples are selected from the substituents described for R 1 , its specific examples, preferred examples, and more preferred examples.
- R 2 is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a hydrogen atom, a substituted or unsubstituted alkyl group, or A substituted or unsubstituted aryl group is more preferred, and a hydrogen atom is particularly preferred.
- R 2 may combine with R 1 to form a ring.
- Such rings include fused or non-fused aromatic rings having 6 to 50 carbon atoms, partially hydrogenated fused or non-fused aromatic rings having 6 to 50 carbon atoms, fused or Non-condensed aromatic heterocycles with 5 to 50 ring atoms, partially hydrogenated condensed or non-fused aromatic heterocycles with 5 to 50 ring atoms, benzene ring, naphthalene ring , Anthracene ring, phenanthrene ring, pyridine ring, pyrimidine ring, quinoline ring, quinazoline ring, carbazole ring, dibenzofuran ring, or dibenzothiophene ring, benzene ring, naphthalene ring, pyridine ring, or pyrimidine ring is more preferable, benzene A ring is particularly preferred. These rings may be substituted with any of the above-described substituents.
- X 1 represents CR 2 and R 2 is bonded to R 1 to form a ring
- R 1 represents CR 2 and R 2 is bonded to R 1 to form a ring
- X a to X d each independently represent N or CR a , preferably CR a .
- R a represents a hydrogen atom or a substituent, and two adjacent R a may be bonded to each other to form a ring.
- the substituent represented by R a its specific examples, preferred examples, and more preferred examples are selected from the substituents described for R 1 , its specific examples, preferred examples, and more preferred examples.
- R a is preferably a hydrogen atom, the substituted or unsubstituted alkyl group, the substituted or unsubstituted aryl group, or the substituted or unsubstituted heteroaryl group.
- the hydrogen atom, the substituted or unsubstituted group is preferable.
- a substituted or unsubstituted heteroaryl group a hydrogen atom, a phenyl group, a naphthyl group (including an isomer group), a biphenyl group (including an isomer group), a terphenyl group ( An isomer group), a phenylterphenyl group (including an isomer group), a dibenzofuranyl group (including an isomer group), or a dibenzothiophenyl group (including an isomer group), more preferably a hydrogen atom or More preferred is a phenyl group, and particularly preferred is a hydrogen atom.
- Two adjacent R a may be bonded to each other to form a ring.
- Specific examples, preferred examples, more preferred examples, and particularly preferred examples of such a ring are as described for the ring formed by combining R 1 and R 2 .
- L 1 is preferably an atom that forms a ring by combining with a substituted or unsubstituted arylene group or R 2 Represents a group.
- the arylene group preferably has 6 to 50 ring carbon atoms, more preferably 6 to 25 carbon atoms, and still more preferably 6 to 18 carbon atoms.
- the arylene group is selected from arylene groups obtained by removing one hydrogen atom from the specific examples, preferred examples and more preferred examples of the aryl group described for R 1 , preferably a phenylene group, an m-phenylene group and A p-phenylene group is particularly preferred.
- Ring A includes fused or non-fused aromatic rings having 6 to 50 carbon atoms, partially hydrogenated fused or non-fused aromatic rings having 6 to 50 carbon atoms, condensed or non-fused And aromatic heterocycles having 5 to 50 ring atoms, partially hydrogenated fused or non-fused aromatic heterocycles having 5 to 50 ring atoms, such as benzene ring, naphthalene ring, anthracene Ring, phenanthrene ring, pyridine ring, pyrimidine ring, quinoline ring, quinazoline ring, carbazole ring, dibenzofuran ring, or dibenzothiophene ring are preferable, benzene ring, naphthalene ring, pyridine ring, or pyrimidine ring is more preferable, and benzene ring is Particularly preferred.
- L 1 preferably represents a divalent linking group.
- the divalent linking group is a substituted or unsubstituted alkylene group having 1 to 50 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, or substituted or unsubstituted ring forming carbon atoms having 3 to 50 carbon atoms, preferably A cycloalkylene group having 3 to 10, more preferably 3 to 8, a substituted or unsubstituted arylene group having 6 to 60, preferably 6 to 25, more preferably 6 to 18 ring-forming carbon atoms, and a substituted or unsubstituted And a heteroarylene group having 5 to 60, preferably 5 to 30, and more preferably 5 to 26 ring-forming atoms.
- alkylene group, cycloalkylene group, arylene group, and heteroarylene group include the specific examples of the alkyl group, cycloalkyl group, aryl group, and heteroaryl group described for R 1 , It is a group obtained by removing one hydrogen atom from preferred and more preferred examples.
- L 1 is preferably the substituted or unsubstituted alkylene group having 1 to 50 carbon atoms or the substituted or unsubstituted arylene group having 6 to 60 ring carbon atoms, and more preferably the substituted or unsubstituted ring.
- the divalent linking group represented by L 2 is a substituted or unsubstituted alkylene group having 1 to 50 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, substituted or unsubstituted ring forming carbon atoms having 3 to 50 carbon atoms.
- it is selected from an unsubstituted heteroarylene group having 5 to 60, preferably 5 to 30, more preferably 5 to 26 ring-forming atoms.
- alkylene group, cycloalkylene group, arylene group, and heteroarylene group include the specific examples of the alkyl group, cycloalkyl group, aryl group, and heteroaryl group described for R 1 , It is a group obtained by removing one hydrogen atom from preferred and more preferred examples.
- L 2 is preferably a single bond, the substituted or unsubstituted alkylene group having 1 to 50 carbon atoms, or the substituted or unsubstituted arylene group having 6 to 60 ring carbon atoms, more preferably the substituted or unsubstituted group.
- the substituted arylene group having 6 to 60 ring carbon atoms is more preferably a phenylene group, particularly preferably an m-phenylene group or a p-phenylene group.
- n represents an integer of 0 to 3, particularly preferably 0.
- L 2 represents a single bond.
- L 1 and L 2 may be the same or different, and L 1 and L 2 may be cross-linked with each other.
- L 1 is a substituted or unsubstituted ring-forming arylene group having 6 to 50 carbon atoms, and, when n is 1, L 1 and L 2 may be the same or different, L 1 and L 2 may be mutually cross-linked.
- L 1 and 2 or 3 L 2 may be the same or different, and L 1 and L 2 and 2 L 2 may be cross-linked with each other.
- L 1 is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms and n is 2 or 3
- L 1 and 2 or 3 L 2 are the same or different.
- L 1 and L 2 and the two L 2 may be cross-linked with each other.
- the bridging group include a methylene group, a dimethylmethylene group, a diphenylmethylene group, an imino group (> NH), a phenylimino group, —O—, —S— and the like.
- a 1 and A 2 are different from each other and are groups represented by any of the following formulas (2), (2 ′), (3), (3 ′), (3 ′′), and (4).
- * 2 is the carbon atom * c1, carbon atom * c2, L 1 (when n is 0) or L 2 (where n is an integer of 1 to 3) of formula (1) )
- One of X 7 to X 11 is a carbon atom bonded to * 3;
- One of X 12 to X 16 is a carbon atom bonded to * 4;
- the other X 7 to X 11 , the other X 12 to X 16 , X 2 to X 6 , and X 17 to X 21 each independently represent N or CR 3 , preferably CR 3 .
- X 6 and X 11 are preferably carbon atoms bonded to each other, and X 16 and X 21 are preferably carbon atoms bonded to each other.
- R 3 represents a hydrogen atom or a substituent, and a plurality of R 3 may be bonded to each other to form a ring.
- the substituent represented by R 3 its specific examples, preferred examples, and more preferred examples are selected from the substituents described for R 1 , its specific examples, preferred examples, and more preferred examples.
- R 3 is preferably a hydrogen atom.
- one of X 2 to X 6 preferably X 3 or X 4 represents CR 3
- R 3 represents a carbazolyl group or an N-substituted carbazolyl group (preferably an N-phenylcarbazolyl group) ).
- X 22 represents NR 4 , CR 5 R 6 , O, S, Se, or SiR 7 R 8 .
- R 4 to R 8 each independently represents a hydrogen atom or a substituent.
- R 5 and R 6 or R 7 and R 8 may be bonded to each other to form a ring.
- the substituent represented by R 4 to R 8 is a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 50, preferably 3 to 10, more preferably 3 to 8 carbon atoms, a substituted or unsubstituted ring carbon having 6 to 60, preferably 6 to 25, more preferably 6 An aryl group having ⁇ 18, a ring-forming carbon number of 6-50, preferably 6-25, more preferably 7-18, preferably 7-30, more preferably 7-20 having an aryl group of 6-18.
- Specific examples, preferred examples, and more preferred examples of the substituent represented by R 4 to R 8 are selected from the specific examples, preferred examples, and more preferred examples of the substituent described for R 1 .
- X 22 represents an imino group (> NH), a phenylimino group, a methylene group, a dimethylmethylene group, a diphenylmethylene group, a 9,9-dimethylfluorenylimino group, a biphenylimino group, a naphthylimino group, —O—, —S—. , -Se-, silylene (> SiH 2 ), or dimethylsilylene group, preferably imino group, phenylimino group, dimethylmethylene group, 9,9-dimethylfluorenylimino group, biphenylimino group, naphthylimino group -O- or -S- is more preferable.
- X 7 to X 11 , X 12 to X 16 , X 17 to X 21 , and X 22 are as defined in Formula (2), One of X 2 ′ to X 6 ′ is a carbon atom bonded to * 3 ′; One of X 12 ′ to X 16 ′ is a carbon atom bonded to * 4 ′; The other X 2 ′ to X 6 ′, the other X 12 ′ to X 16 ′, and X 17 ′ to X 21 ′ each independently represent N or CR 3 , preferably CR 3 .
- X 6 ′ and X 11 are preferably bonded to each other, X 16 and X 21 are preferably bonded to each other, and X 16 ′ and X 21 ′ are bonded to each other. It is preferable.
- R 3 is as defined in Formula (2), and is preferably a hydrogen atom.
- X 22 ′ represents NR 4 , CR 5 R 6 , O, S, Se, or SiR 7 R 8 .
- R 4 to R 8 are as defined in Formula (2).
- * 5 is carbon atom * c1, carbon atom * c2, L 1 (when n is 0) or L 2 (where n is an integer of 1 to 3) in formula (1) )
- One of X 37 to X 41 is a carbon atom bonded to * 6;
- the other X 37 to X 41 , X 32 to X 36 , and X 42 to X 51 each independently represent N or CR 9 , preferably CR 9 .
- X 36 and X 41 are preferably carbon atoms bonded to each other, and X 46 and X 51 are preferably carbon atoms bonded to each other.
- R 9 represents a hydrogen atom or a substituent, and a plurality of R 9 may be bonded to each other to form a ring.
- the substituent represented by R 9 its specific examples, preferred examples, and more preferred examples are selected from the substituents described for R 1 , its specific examples, preferred examples, and more preferred examples.
- the ring formed by bonding a plurality of R 9 to each other is the same as that described for R 1 .
- R 9 is preferably a hydrogen atom.
- one of X 32 to X 36 preferably X 34 represents CR 9 and R 9 represents an N-carbazolyl group.
- X 37 to X 41 , and X 42 to X 51 are as defined in Formula (3),
- One of X 32 'to X 36 ' is a carbon atom bonded to * 6 ';
- the other X 32 ′ to X 36 ′ and X 42 ′ to X 51 ′ each independently represent N or CR 9 .
- R 9 is as defined in Formula (3), and is preferably a hydrogen atom.
- X 36 ′ and X 41 are preferably bonded carbon atoms
- X 46 and X 51 are preferably bonded carbon atoms
- X 46 ′ and X 51 ′ are bonded carbon atoms. It is preferable.
- One of X 32 ′′ to X 36 ′′ is a carbon atom bonded to * 3 ′′;
- One of X 12 ′′ to X 16 ′′ is a carbon atom bonded to * 4 ′′;
- the other X 12 ′′ to X 16 ′′ and X 17 ′′ to X 21 ′′ each independently represent N or CR 3 , preferably CR 3 .
- the other X 32 ′′ to X 36 ′′ represents N or CR 9 , preferably CR 9 .
- R 3 is as defined in Formula (2), and is preferably a hydrogen atom.
- R 9 is as defined in Formula (3), and is preferably a hydrogen atom.
- X 36 ′′ and X 41 are preferably bonded carbon atoms, X 46 and X 51 are preferably bonded carbon atoms, and X 16 ′′ and X 21 ′′ are bonded carbon atoms. An atom is preferred.
- X 22 ′′ represents NR 4 , CR 5 R 6 , O, S, Se, or SiR 7 R 8 ; R 4 to R 8 are as defined in Formula (2).
- * 7 is carbon atom * c1, carbon atom * c2, L 1 (when n is 0) or L 2 (where n is an integer of 1 to 3) in formula (1) ).
- one adjacent pair selected from X 67 to X 71 one represents a carbon atom bonded to * 8, and the other represents a carbon atom bonded to * 9.
- the other X 67 to X 71 , X 62 to X 66 and X 72 to X 75 each independently represent N or CR 10 , preferably CR 10 .
- X 66 and X 71 are preferably carbon atoms bonded to each other.
- R 10 represents a hydrogen atom or a substituent, and a plurality of R 10 may be bonded to each other to form a ring.
- the substituent represented by R 10 its specific examples, preferred examples, and more preferred examples are selected from the substituents described for R 1 , its specific examples, preferred examples, and more preferred examples.
- the ring formed by bonding a plurality of R 10 to each other is the same as described for R 1 .
- R 10 is preferably a hydrogen atom.
- X 76 represents NR 11 , CR 12 R 13 , O, S, Se, or SiR 14 R 15 .
- R 11 to R 15 each independently represents a hydrogen atom or a substituent.
- R 12 and R 13 or R 14 and R 15 may combine with each other to form a ring.
- the substituents represented by R 11 to R 15 specific examples, preferred examples, and more preferred examples thereof are selected from the substituents described for R 4 to R 8 , specific examples, preferred examples, and more preferred examples thereof.
- X 76 is an imino group (> NH), a phenylimino group, a methylene group, a dimethylmethylene group, a diphenylmethylene group, —O—, —S—, —Se—, a silylene (> SiH 2 ), or a dimethylsilylene group. It is preferably an imino group, a phenylimino group, a dimethylmethylene group, —O—, or —S—.
- a 1 and A 2 are different” means the following.
- One of A 1 and A 2 is selected from any one of the formulas (2), (2 ′), (3), (3 ′), (3 ′′), and (4), The other is chosen from the remaining equations.
- (2) A 1 and A 2 are both selected from formula (2), (2a) The bonding position of at least one of * 3 and * 4 is different.
- a 1 and A 2 are both selected from the formula (2 ′), (3a) at least one binding position of * 3, * 3 ′, * 4 and * 4 ′ is different; (3b) At least one of X 7 to X 21 , X 2 ′ to X 6 ′, and X 12 ′ to X 21 ′ is different, or (3c) At least one of X 22 and X 22 ′ is different.
- a 1 and A 2 are both selected from formula (3), (4a) The bonding position of * 6 is different, or (4b) At least one of X 32 to X 51 is different.
- a 1 and A 2 are both selected from the formula (3 ′), (5a) The bonding position of at least one of * 6 and * 6 ′ is different, or (5b) At least one of X 37 to X 51 , X 32 ′ to X 36 ′, and X 42 ′ to X 51 ′ is different.
- a 1 and A 2 are both selected from the formula (3 ′′), (6a) * 6, * 3 ′′ and * 4 ′′ at least one binding position is different, (6b) At least one of X 37 to X 51 , X 32 ′′ to X 36 ′′, and X 12 ′′ to X 21 ′′ is different, or (6c) X 22 ′′ is different.
- a 1 and A 2 are both selected from formula (4), (7a) The bonding position of at least one of * 8 and * 9 is different. (7b) At least one of X 62 to X 75 is different, or (7c) X 76 is different.
- a 1 and A 2 are (1), (2a), (2c), (3a), (3c), (4a), (5a), (6a), (6c), (7a), or (7c) It is preferably different depending on (1), (2a), (3a), (4a), (5a), (6a), or (7a).
- the group represented by the formula (2) is preferably represented by the following formulas (2a) to (2c). (Wherein * 2 and X 2 to X 22 are the same as described above.)
- the group represented by the formula (2a) is preferably represented by the following formulas (2a-1) to (2a-3). (In the formula, * 2 and each X group are the same as above.)
- the group represented by the formula (2b) is preferably represented by the following formulas (2b-1) to (2b-3). (In the formula, * 2 and each X group are the same as above.)
- the group represented by the formula (2c) is preferably represented by the following formulas (2c-1) to (2c-3). (In the formula, * 2 and each X group are the same as above.)
- the group represented by the formula (2 ′) is preferably represented by the following formulas (2′a) to (2′i). (In the formula, * 2, X 7 to X 22 , X 2 ′ to X 6 ′, and X 12 ′ to X 22 ′ are the same as described above.)
- the group represented by the formula (2′a) is preferably represented by the following formulas (2′a-1) to (2′a-5). (In the formula, * 2 and each X group are the same as above.)
- the group represented by the formula (2′b) is preferably represented by the following formulas (2′b-1) to (2′b-7). (In the formula, * 2 and each X group are the same as above.)
- the group represented by the formula (2′c) is preferably represented by the following formulas (2′c-1) to (2′c-7). (In the formula, * 2 and each X group are the same as above.)
- the group represented by the formula (2′d) is preferably represented by the following formulas (2′d-1) to (2′d-5). (In the formula, * 2 and each X group are the same as above.)
- the group represented by the formula (2′e) is preferably represented by the following formulas (2′e-1) to (2′e-7). (In the formula, * 2 and each X group are the same as above.)
- the group represented by the formula (2′f) is preferably represented by the following formulas (2′f-1) to (2′f-7). (In the formula, * 2 and each X group are the same as above.)
- the group represented by the formula (2′g) is preferably represented by the following formulas (2′g-1) to (2′g-5). (In the formula, * 2 and each X group are the same as above.)
- the group represented by the formula (2′h) is preferably represented by the following formulas (2′h-1) to (2′h-7). (In the formula, * 2 and each X group are the same as above.)
- the group represented by the formula (2′i) is preferably represented by the following formulas (2′i-1) to (2′i-7). (In the formula, * 2 and each X group are the same as above.)
- the group represented by the formula (3) is preferably represented by the following formula (3a) or (3b). (Wherein * 5 and X 32 to X 51 are the same as described above.)
- the group represented by the formula (3a) is preferably represented by the following formulas (3a-1) to (3a-3). (In the formula, * 5 and each X group are the same as described above.)
- the group represented by the formula (3b) is preferably represented by the following formulas (3b-1) to (3b-3). (In the formula, * 5 and each X group are the same as described above.)
- the group represented by the formula (3 ′) is preferably represented by the following formulas (3′a) to (3′c). (In the formula, 5 * , X 37 to X 51 , X 32 ′ to X 36 ′, and X 42 ′ to X 51 ′ are the same as described above.)
- the group represented by the formula (3′a) is preferably represented by the following formulas (3′a-1) to (3′a-5). (In the formula, * 5 and each X group are the same as described above.)
- the group represented by the formula (3′b) is preferably represented by the following formulas (3′b-1) to (3′b-7). (In the formula, * 5 and each X group are the same as described above.)
- the group represented by the formula (3′c) is preferably represented by the following formulas (3′c-1) to (3′c-5). (In the formula, * 5 and each X group are the same as described above.)
- the group represented by the formula (3 ′′) is preferably represented by the following formulas (3 ′′ a) to (3 ′′ f). (In the formula, 5 * , X 37 to X 51 , X 32 ′′ to X 36 ′′, and X 12 ′′ to X 22 ′′ are the same as described above.)
- the group represented by the formula (3 ′′ a) is preferably represented by the following formulas (3 ′′ a-1) to (3 ′′ a-7). (In the formula, * 5 and each X group are the same as described above.)
- the group represented by the formula (3 ′′ b) is preferably represented by the following formulas (3 ′′ b-1) to (3 ′′ b-7). (In the formula, * 5 and each X group are the same as described above.)
- the group represented by the formula (3 ′′ c) is preferably represented by the following formulas (3 ′′ c-1) to (3 ′′ c-7). (In the formula, * 5 and each X group are the same as described above.)
- the group represented by the formula (3 ′′ d) is preferably represented by the following formulas (3 ′′ d-1) to (3 ′′ d-7). (In the formula, * 5 and each X group are the same as described above.)
- the group represented by the formula (3 ′′ e) is preferably represented by the following formulas (3 ′′ e-1) to (3 ′′ e-7). (In the formula, * 5 and each X group are the same as described above.)
- the group represented by the formula (3 ′′ f) is preferably represented by the following formulas (3 ′′ f-1) to (3 ′′ f-7). (In the formula, * 5 and each X group are the same as described above.)
- the group represented by the formula (4) is preferably represented by the following formulas (4a) to (4f). (Wherein * 7 and X 62 to X 76 are the same as described above.)
- the groups represented by formulas (4a) to (4f) are preferably represented by the following formulas (4a-1) to (4f-1), respectively. (Wherein * 7 and each X group are the same as above)
- a method for producing compound (1) will be described below.
- a first substituent is introduced into one active site of a starting compound having two active sites and a second substituent different from the first substituent is introduced into the other active site, It is necessary to control the reaction so that the first substituent is not introduced into both active sites.
- the reaction in the Ullmann reaction and Buchwald reaction, which are widely used for coupling of aryl halides and amines, it is difficult to control the reaction so that the first substituent is not introduced into both of the two active sites. It was difficult to obtain a compound in which different substituents were introduced at each site simply and with good yield.
- the present inventors (1) selectively introduce the first substituent only into the carbon atom to which Hal 1 is bonded under the specific reaction conditions, and then (2) Hal 2 Different substitutions by introducing a second substituent different from the first substituent into the carbon atom to which Hal 2 is bonded under conditions that increase the reaction activity with respect to the amine compound and carbazole compound, for example, under the conditions of the Buchwald reaction. It has been found that a compound having a group introduced therein can be synthesized with good yield.
- compound (1) can be produced as follows. Synthesis method 1
- L 1 When n is 0, L 1 may be substituted with one, or the same or different halogen atoms, When n is an integer of 1 to 3, L 2 may be substituted with one or a plurality of the same or different halogen atoms.
- H * is Hal 1 in formula (I). It is a hydrogen atom that reacts with.
- the first reaction is carried out in an organic solvent, preferably an aprotic polar organic solvent, in the presence of a basic catalyst and in the absence of a transition metal catalyst.
- Basic catalysts catalyze the extraction of H * in formulas (II), (II ′), (III), (III ′), (III ′′), and (IV), but with halogenated aromatic carbon atoms It is preferable that the catalyst has a low nucleophilicity.
- Examples of such basic catalysts include alkali metal carbonates such as K 2 CO 3 and Na 2 Co 3 ; alkali metal hydrogen carbonates such as KHCO 3 and NaHCO 3 ; alkaline earth metal carbonates such as CaCO 3 and CsCO 3.
- the organic solvent used in the first reaction is not limited as long as it does not react with the above basic catalyst.
- amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, and non-solvents such as dimethylsulfoxide are used.
- Protic polar organic solvents are preferred from the standpoint of solubility of the basic catalyst.
- an aprotic polar organic solvent and an aromatic solvent such as benzene, toluene and xylene may be mixed and used.
- the amine compound represented by any one of formulas (II), (II ′), (III), (III ′), (III ′′), and (IV) is directly connected to the azine ring of compound (I). It is preferable to use 1 to 2 moles per 1 mole of Hal 1 .
- the amount of the basic catalyst used is preferably 1 to 10 equivalents relative to 1 mol of Hal 1 directly bonded to the azine ring of compound (I).
- the amount of the organic solvent used depends on the solubility of the compound (I), but it is preferably used so that its concentration is generally from 0.01 to 2.0 mol / L.
- the reaction temperature is preferably room temperature to 200 ° C. The reaction time varies depending on the type of compound (I) used, amine compound, basic catalyst, amount used, etc., but is usually 1 to 24 hours.
- the target compound (V) By carrying out the first reaction under the above reaction conditions, the target compound (V) can be obtained in a high yield of 50 to 100%. Further, when the first reaction is carried out in the presence of a transition metal catalyst such as palladium, copper, platinum, rhodium, ruthenium, nickel, iron, etc., the reaction activity of Hal 2 of the formula (I) increases, and Hal 1 is bound.
- a transition metal catalyst such as palladium, copper, platinum, rhodium, ruthenium, nickel, iron, etc.
- the amine compounds (II), (II ′), (III), (III ′), (III ′′), and (IV) are introduced not only to the carbon atom that is bonded to but also to the carbon atom to which Hal 2 is bonded. May end up. Therefore, it is desirable to perform the first reaction in the absence of a transition metal catalyst.
- the compound (V) is represented by any one of the formulas (II), (II ′), (III), (III ′), (III ′′), and (IV).
- the compound (1) is synthesized by reacting an amine compound to be produced, which is different from the amine compound used in the first reaction.
- the second reaction is performed under conditions where the reaction activity of Hal 2 is higher than that in the first reaction, for example, amination reaction conditions such as Buchwald reaction and Ullmann reaction. That is, the second reaction includes a transition metal catalyst selected from palladium, copper, platinum, rhodium, ruthenium, nickel, iron, and the like, and a ligand such as monophosphines, diphosphines, diamines, pyridines, quinolines, and the like. And, if necessary, in an organic solvent in the presence of a base such as alkoxides, carbonates, and phosphates.
- amination reaction conditions such as Buchwald reaction and Ullmann reaction. That is, the second reaction includes a transition metal catalyst selected from palladium, copper, platinum, rhodium, ruthenium, nickel, iron, and the like, and a ligand such as monophosphines, diphosphines, diamines, pyridines, quinolines, and the like.
- Pd 2 (dba) 3 tris (dibenzylideneacetone) dipalladium (0)
- Pd (OAc) 2 palladium acetate or the like is usually used as the palladium catalyst.
- the ligand various phosphines are mainly used.
- P (oTol) 3 tri (ortho-tolyl) phosphine
- PtBu 3 tri (t-butyl) phosphine
- BINAP bis (diphenylphosphino)- 1,1′-binaphthyl
- DPPF bis (diphenylphosphino) ferrocene
- XantPhos 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene
- DPEPhos oxydi-2,1-phenylene) Bis (diphenylphosphine)
- DavePhos (2-dicyclohexylphosphino2 '-(N, N-dimethylamino) biphenyl
- X-Phos (2-dicyclohexylphosphine) Fino-2 ', 4', 6'-triisoprop
- a complex in which phosphine is coordinated with palladium in advance such as PdCl 2 (P (oTol) 3 ) 2 , PdCl 2 (dppf), or the like can also be preferably used.
- the base strong basic alkoxides such as tBuONa (sodium tertiary butoxide) are most preferably used.
- weak bases such as CsCO 3 and K 3 PO 4 are used. It is also possible to use a base.
- the copper catalyst copper metal, cuprous chloride, cuprous bromide, cuprous iodide, cuprous oxide, cupric oxide and the like are used, and as the ligand, Diamines such as tetramethylethylenediamine and 1,2-bisdimethylaminocyclohexane, pyridines and quinolines are preferably used.
- an organic hydrocarbon solvent such as benzene, toluene, xylene and mesitylene is generally preferably used as the organic solvent, but tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane is preferable.
- Ether solvents such as anisole and amide solvents such as dimethylformamide and dimethylacetamide can be used alone or as a cosolvent.
- the amine compound represented by any one of the formulas (II), (II ′), (III), (III ′), (III ′′), and (IV) is 1 mol of Hal 2 of the compound (V).
- the amount used is preferably 1 to 1.5 mol.
- the amount of the transition metal catalyst used is 0.01 to 100 mol, preferably 0.5 to 10 mol, based on 1 mol of Hal 2 , and the amount of ligand used is 1 to 5 mol based on the transition metal catalyst.
- the amount of base used is preferably 1 to 20 equivalents per mole of Hal 2 .
- the amount of the organic solvent used depends on the solubility of the compound (V), but it is preferably used so that its concentration is generally 0.01 to 2.0 mol / L.
- the second reaction is preferably performed at room temperature to 200 ° C.
- the reaction time varies depending on the type of compound (V), amine compound, transition metal catalyst, ligand, base used, amount used, etc., but is usually 1 to 24 hours.
- the halogen atom of the compound (V) is represented by any one of the formulas (II), (II ′), (III), (III ′), (III ′′), and (IV).
- the hydrogen atom H * of the amine compound is eliminated and the compound (1) is obtained.
- the obtained compound (1) is isolated from the reaction mixture by a known separation operation, extraction operation, purification operation or the like.
- the overall yield of the compound (1) obtained by the first reaction and the second reaction is about 50 to 95% based on the compound (I).
- the compound (1) is a compound that can meet such various characteristic requirements, and according to the above production method, the compound (1) can be provided in a high yield by a simpler method.
- An organic EL element has one or more organic thin film layers between a cathode and an anode.
- the organic thin film layer includes a light emitting layer, and at least one layer of the organic thin film layer includes the compound represented by the formula (1) (compound (1)).
- Examples of the organic thin film layer containing the compound (1) include an anode-side organic thin film layer (hole transport layer, hole injection layer, etc.) provided between the anode and the light emitting layer, a light emitting layer, a cathode and light emission.
- Examples include, but are not limited to, a cathode-side organic thin film layer (electron transport layer, electron injection layer, etc.), a space layer, a barrier layer, and the like provided between the layers.
- the compound (1) may be contained in any of the above layers, for example, a host material or a dopant material in the light emitting layer of the fluorescent light emitting unit, a host material in the light emitting layer of the phosphorescent light emitting unit, or a hole transport of the light emitting unit. It can be used as a layer material, an electron transport layer material or the like.
- the organic EL element may be a fluorescent or phosphorescent monochromatic light emitting element, a fluorescent / phosphorescent hybrid white light emitting element, or a simple type having a single light emitting unit.
- a tandem type having a plurality of light emitting units may be used, and among them, a phosphorescent type is preferable.
- the “light emitting unit” refers to a minimum unit that includes one or more organic layers, one of which is a light emitting layer, and can emit light by recombination of injected holes and electrons.
- typical element configurations of simple organic EL elements include the following element configurations.
- Anode / light emitting unit / cathode The above light emitting unit may be a laminated type having a plurality of phosphorescent light emitting layers and fluorescent light emitting layers. In that case, the light emitting unit is generated by a phosphorescent light emitting layer between the light emitting layers. In order to prevent the excitons from diffusing into the fluorescent light emitting layer, a space layer may be provided. A typical layer structure of the light emitting unit is shown below.
- A Hole transport layer / light emitting layer (/ electron transport layer)
- B Hole transport layer / first phosphorescent light emitting layer / second phosphorescent light emitting layer (/ electron transport layer)
- C Hole transport layer / phosphorescent layer / space layer / fluorescent layer (/ electron transport layer)
- D Hole transport layer / first phosphorescent light emitting layer / second phosphorescent light emitting layer / space layer / fluorescent light emitting layer (/ electron transport layer)
- E Hole transport layer / first phosphorescent light emitting layer / space layer / second phosphorescent light emitting layer / space layer / fluorescent light emitting layer (/ electron transport layer)
- F Hole transport layer / phosphorescent layer / space layer / first fluorescent layer / second fluorescent layer (/ electron transport layer)
- G Hole transport layer / electron barrier layer / light emitting layer (/ electron transport layer)
- H Hole transport layer / light emitting layer / hole barrier layer (
- Each phosphorescent or fluorescent light-emitting layer may have a different emission color.
- hole transport layer / first phosphorescent light emitting layer (red light emitting) / second phosphorescent light emitting layer (green light emitting) / space layer / fluorescent light emitting layer (blue light emitting) / Examples include a layer configuration such as an electron transport layer.
- An electron barrier layer may be appropriately provided between each light emitting layer and the hole transport layer or space layer.
- a hole blocking layer may be appropriately provided between each light emitting layer and the electron transport layer.
- the following element structure can be mentioned as a typical element structure of a tandem type organic EL element.
- the intermediate layer is generally called an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate insulating layer, and has electrons in the first light emitting unit and holes in the second light emitting unit.
- a known material structure to be supplied can be used.
- FIG. 1 shows a schematic configuration of an example of the organic EL element.
- the organic EL element 1 includes a substrate 2, an anode 3, a cathode 4, and a light emitting unit 10 disposed between the anode 3 and the cathode 4.
- the light emitting unit 10 includes a light emitting layer 5 including at least one phosphorescent light emitting layer including a phosphorescent host material and a phosphorescent dopant material (phosphorescent light emitting material).
- electron injection / transport layer (cathode-side organic thin film layer) 7 between the light-emitting layer 5 and the cathode 4 May be formed.
- an electron barrier layer (not shown) may be provided on the anode 3 side of the light emitting layer 5, and a hole barrier layer (not shown) may be provided on the cathode 4 side of the light emitting layer 5.
- a host material combined with a fluorescent dopant material is referred to as a fluorescent host material
- a host material combined with a phosphorescent dopant material is referred to as a phosphorescent host material.
- the fluorescent host material and the phosphorescent host material are not distinguished only by the molecular structure. That is, the phosphorescent host material means a material for forming a phosphorescent light emitting layer containing a phosphorescent dopant material, and does not mean that it cannot be used as a material for forming a fluorescent light emitting layer. The same applies to the fluorescent host material.
- the organic EL element is formed over a light-transmitting substrate.
- the light-transmitting substrate is a substrate that supports the organic EL element, and is preferably a smooth substrate having a light transmittance in the visible region of 400 nm to 700 nm of 50% or more.
- a glass plate, a polymer plate, etc. are mentioned. Examples of the glass plate include those using soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like as raw materials.
- Examples of the polymer plate include those using polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like as raw materials. Further, a flexible substrate may be used.
- the flexible substrate is a substrate that can be bent (flexible), and examples thereof include a plastic substrate made of polycarbonate or polyvinyl chloride.
- the anode formed on the anode substrate plays a role of injecting holes into the hole transport layer or the light emitting layer, and is a metal, an alloy having a work function of 4.0 eV or more, preferably 4.5 eV or more, It is effective to use an electrically conductive compound and a mixture thereof.
- anode materials include indium tin oxide alloy (ITO), indium tin oxide alloy containing silicon or silicon oxide, tin oxide (NESA), indium zinc oxide, tungsten oxide, graphene, gold, silver, platinum , Copper, metal nitride (for example, titanium nitride), and the like.
- the anode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
- a method such as vapor deposition or sputtering.
- the transmittance of light in the visible region of the anode is greater than 10%.
- the sheet resistance of the anode is preferably several hundred ⁇ / ⁇ or less.
- the film thickness of the anode depends on the material, but is usually selected in the range of 10 nm to 1 ⁇ m, preferably 10 nm to 200 nm.
- the cathode plays a role of injecting electrons into the electron injection layer, the electron transport layer, or the light emitting layer, and has a low work function (specifically, 3.8 eV or less) material such as metal, alloy, electrical conductivity Forming with compounds and mixtures thereof is preferred.
- the cathode material is not particularly limited.
- elements belonging to Group 1 or Group 2 of the periodic table of elements that is, alkali metals such as lithium and cesium, alkaline earth metals such as magnesium, and metals such as rare earth metals
- alkali metals such as lithium and cesium
- alkaline earth metals such as magnesium
- metals such as rare earth metals
- indium, aluminum, magnesium, magnesium-indium alloy, magnesium-aluminum alloy, aluminum-lithium alloy, aluminum-scandium-lithium alloy, magnesium-silver alloy, and the like can be used.
- the cathode can be produced by forming a thin film by a method such as vapor deposition or sputtering. Moreover, you may take out light emission from the cathode side as needed.
- Light-emitting layer An organic layer having a light-emitting function, and when a doping system is employed, includes a host material and a dopant material (a substance having a high light-emitting property).
- a dopant material for example, a fluorescent material or a phosphorescent material can be used.
- the fluorescent light-emitting material is a compound that can emit light from a singlet excited state
- the phosphorescent compound is a compound that can emit light from a triplet excited state.
- the host material mainly has the function of encouraging recombination of electrons and holes and confining excitons in the light emitting layer, and the dopant material has the function of efficiently emitting the excitons obtained by recombination. .
- the host material mainly has a function of confining excitons generated from the dopant material in the light emitting layer.
- the light emitting layer employs a double host (also referred to as a host co-host) that adjusts the carrier balance in the light emitting layer by combining, for example, an electron transporting host material and a hole transporting host material. May be.
- a double host also referred to as a host co-host
- the host material, the red dopant material, and the green dopant material may be co-evaporated to form a common light emitting layer and realize yellow light emission.
- the above light-emitting layer is a laminate in which a plurality of light-emitting layers are stacked, so that electrons and holes are accumulated at the light-emitting layer interface, and the recombination region is concentrated at the light-emitting layer interface to improve quantum efficiency. Can do.
- the ease of injecting holes into the light emitting layer may be different from the ease of injecting electrons, and the hole transport ability and electron transport ability expressed by the mobility of holes and electrons in the light emitting layer may be different. May be different.
- the phosphorescent dopant material (phosphorescent material) forming the light emitting layer is a compound that can emit light from the triplet excited state, and is not particularly limited as long as it emits light from the triplet excited state, but Ir, Pt, Os, Au, Cu , Re, and Ru are preferably organometallic complexes containing at least one metal and a ligand.
- Ir, Pt, Os, Au, Cu , Re, and Ru are preferably organometallic complexes containing at least one metal and a ligand.
- blue phosphorescent dopant materials such as iridium complexes, osmium complexes and platinum complexes
- green phosphorescent dopant materials such as iridium complexes
- red phosphorescent dopant materials such as iridium complexes, platinum complexes and terbium complexes.
- Metal complexes such as europium complexes are used.
- the ligand preferably has an ortho metal bond.
- a metal complex containing a metal atom selected from Ir, Os and Pt is preferred in that the phosphorescent quantum yield is high and the external quantum efficiency of the light emitting device can be further improved, and an iridium complex, an osmium complex, or a platinum complex.
- iridium complexes and platinum complexes are more preferable, and orthometalated iridium complexes are particularly preferable.
- the content of the phosphorescent dopant material in the light emitting layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 0.1 to 70% by mass, and more preferably 1 to 30% by mass. When the content of the phosphorescent dopant material is 0.1% by mass or more, sufficient light emission is obtained, and when it is 70% by mass or less, concentration quenching can be avoided.
- a complex represented by the following formula (X) or (Y) is preferable as the phosphorescent dopant material.
- R 10 is a hydrogen atom or a substituent
- k is an integer of 1 to 4.
- M is Ir, Os, or Pt. Examples of the substituent group represented by R 10, those similar to the substituents exemplified for R 0 ⁇ R 8 or the like in the formula (1).
- the organic EL element may have a light emitting layer containing a fluorescent light emitting material, that is, a fluorescent light emitting layer.
- a fluorescent light emitting layer known fluorescent light emitting materials can be used.
- a blue fluorescent material a pyrene derivative, a styrylamine derivative, a chrysene derivative, a fluoranthene derivative, a fluorene derivative, a diamine derivative, a triarylamine derivative, or the like is used as a green fluorescent material.
- Tetracene derivatives, diamine derivatives, and the like are used as red-based fluorescent light-emitting materials such as group amine derivatives.
- the fluorescent material is preferably at least one selected from anthracene derivatives, fluoranthene derivatives, styrylamine derivatives and arylamine derivatives, more preferably anthracene derivatives and arylamine derivatives.
- the host material is preferably an anthracene derivative
- the dopant material is preferably an arylamine derivative.
- suitable materials described in International Publication Nos. 2010/134350 and 2010/134352 are selected.
- the compound (1) and the organic EL device material may be used as a fluorescent light emitting material of the fluorescent light emitting layer or as a host material of the fluorescent light emitting layer.
- the substance having high light-emitting property (dopant material) described above may be dispersed in another substance (host material).
- host material various materials can be used, and it is preferable to use a substance having a lowest lowest orbital level (LUMO level) and a lower highest occupied orbital level (HOMO level) than the dopant material. .
- host materials include (1) metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes, (2) heterocyclic compounds such as oxadiazole derivatives, benzimidazole derivatives, and phenanthroline derivatives, (3 ) Condensed aromatic compounds such as carbazole derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, chrysene derivatives, and (4) aromatic amine compounds such as triarylamine derivatives and condensed polycyclic aromatic amine derivatives are used.
- metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes
- heterocyclic compounds such as oxadiazole derivatives, benzimidazole derivatives, and phenanthroline derivatives
- Condensed aromatic compounds such as carbazole derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, chrysene derivatives
- aromatic amine compounds such
- the phosphorescent host is a compound having a function of efficiently emitting the phosphorescent dopant by efficiently confining the triplet energy of the phosphorescent dopant in the light emitting layer.
- the compound (1) and the organic EL device material containing the compound (1) are useful as a phosphorescent host, but compounds other than the compound (1) may be appropriately selected as the phosphorescent host depending on the purpose. it can.
- the compound (1) and the organic EL device material are not limited to application to a phosphorescent host.
- the compound (1) and other compounds may be used in combination as a phosphorescent host material in the same light emitting layer.
- the phosphorescent host material of one of the light emitting layers is used as the phosphorescent host material.
- the compound (1) may be used, and a compound other than the compound (1) may be used as the phosphorescent host material of another light emitting layer.
- the compound (1) can also be used in an organic layer other than the light emitting layer. In that case, a compound other than the compound (1) may be used as the phosphorescent host of the light emitting layer.
- compounds other than the compound (1) and suitable as a phosphorescent host include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, Phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, Anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives Various metals typified by metal complexes of dist
- Electron-donating dopant in one embodiment of the present invention, it is also preferable to have an electron-donating dopant in the interface region between the cathode and the light-emitting unit. According to such a configuration, it is possible to improve the light emission luminance and extend the life of the organic EL element.
- the electron donating dopant means a material containing a metal having a work function of 3.8 eV or less, and specific examples thereof include alkali metals, alkali metal complexes, alkali metal compounds, alkaline earth metals, alkaline earths. Examples thereof include at least one selected from metal complexes, alkaline earth metal compounds, rare earth metals, rare earth metal complexes, rare earth metal compounds, and the like.
- alkali metal examples include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), Cs (work function: 1.95 eV), and the like.
- a function of 2.9 eV or less is particularly preferable. Of these, K, Rb, and Cs are preferred, Rb and Cs are more preferred, and Cs is most preferred.
- alkaline earth metals include Ca (work function: 2.9 eV), Sr (work function: 2.0 eV to 2.5 eV), Ba (work function: 2.52 eV), and the like. The thing below 9 eV is especially preferable.
- rare earth metals examples include Sc, Y, Ce, Tb, Yb, and the like, and those having a work function of 2.9 eV or less are particularly preferable.
- alkali metal compound examples include alkali oxides such as Li 2 O, Cs 2 O, and K 2 O, and alkali halides such as LiF, NaF, CsF, and KF, and LiF, Li 2 O, and NaF are preferable.
- alkaline earth metal compound examples include BaO, SrO, CaO, and Ba x Sr 1-x O (0 ⁇ x ⁇ 1), Ba x Ca 1-x O (0 ⁇ x ⁇ 1) mixed with these. BaO, SrO, and CaO are preferable.
- the rare earth metal compound, YbF 3, ScF 3, ScO 3, Y 2 O 3, Ce 2 O 3, GdF 3, TbF 3 and the like, YbF 3, ScF 3, TbF 3 are preferable.
- the alkali metal complex, alkaline earth metal complex, and rare earth metal complex are not particularly limited as long as each metal ion contains at least one of an alkali metal ion, an alkaline earth metal ion, and a rare earth metal ion.
- the ligands include quinolinol, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyl oxazole, hydroxyphenyl thiazole, hydroxydiaryl thiadiazole, hydroxydiaryl thiadiazole, hydroxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzotriazole, Hydroxyfulborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, ⁇ -diketones, azomethines, and derivatives thereof are preferred, but not limited thereto.
- the electron donating dopant is preferably formed in a layered or island shape in the interface region.
- an organic compound light emitting material or electron injecting material
- the electron donating dopant in a layered form, it is preferable to form the organic compound (light emitting material or electron injecting material) that forms the interface region in a layered form, and then deposit the electron donating dopant alone by a resistance heating vapor deposition method. Is formed with a layer thickness of 0.1 nm to 15 nm.
- the electron donating dopant is formed in an island shape, an organic compound (a light emitting material or an electron injection material) that forms the interface region is formed in an island shape, and then the electron donating dopant is deposited by a resistance heating vapor deposition method alone.
- the island is formed with a thickness of 0.05 nm to 1 nm.
- the ratio of the organic compound to the electron-donating dopant is preferably 5: 1 to 1: 5, and more preferably 2: 1 to 1: 2.
- the electron injection layer is a layer containing a substance having a high electron injection property.
- the electron injection layer includes an alkali metal such as lithium (Li), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF2), lithium oxide (LiOx), an alkaline earth metal, Alternatively, those compounds can be used.
- the electron transport layer is an organic layer formed between the light emitting layer and the cathode, and has a function of transporting electrons from the cathode to the light emitting layer.
- an organic layer close to the cathode may be defined as an electron injection layer.
- the electron injection layer has a function of efficiently injecting electrons from the cathode into the organic layer unit.
- the compound (1) and the organic EL device material can also be used as an electron transport material contained in the electron transport layer.
- numerator is used preferably, and a nitrogen-containing ring derivative is especially preferable.
- the nitrogen-containing ring derivative is preferably an aromatic ring having a nitrogen-containing 6-membered ring or 5-membered ring skeleton, or a condensed aromatic ring compound having a nitrogen-containing 6-membered ring or 5-membered ring skeleton.
- a nitrogen-containing ring metal chelate complex represented by the following formula (A) is preferable.
- R 101 to R 106 in formula (A) are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, 1 to 40 carbon atoms (preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5) hydrocarbon group, 1 to 40 carbon atoms (preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5) alkoxy group, and 6 to 50 ring carbon atoms (preferably 6 carbon atoms).
- aryloxy group 2-40 carbon atoms (preferably 2-20, more preferably 2-10, more preferably 2-5) alkoxycarbonyl groups or ring-forming atoms 5 to 50 (preferably 5 to 30, more preferably 5 to 20) aromatic heterocyclic groups, which may be substituted.
- Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.
- the amino group which may be substituted include an alkylamino group, an arylamino group and an aralkylamino group.
- the alkylamino group and the aralkylamino group are represented as —NQ 1 Q 2 .
- Q 1 and Q 2 each independently represents an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 1 to 20 carbon atoms.
- One of Q 1 and Q 2 may be a hydrogen atom.
- the arylamino group is represented as —NAr 1 ′ Ar 2 ′, and Ar 1 ′ and Ar 2 ′ each independently represent a non-condensed aromatic hydrocarbon group or a condensed aromatic hydrocarbon group having 6 to 50 carbon atoms. .
- One of Ar 1 ′ and Ar 2 ′ may be a hydrogen atom.
- the hydrocarbon group having 1 to 40 carbon atoms includes an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group.
- the alkoxycarbonyl group is represented as —COOY ′, and Y ′ represents an alkyl group having 1 to 20 carbon atoms.
- M is aluminum (Al), gallium (Ga) or indium (In), and is preferably In.
- L 100 is a group represented by the following formula (A ′) or (A ′′).
- R 107 to R 111 are each independently a hydrogen atom or a substituted or unsubstituted carbon number of 1 to 40 (preferably 1 to 20, more preferably 1 to 10, more preferably 1). To 5), and two or more of R 107 to R 111 may combine to form a cyclic structure.
- R 112 to R 126 are each independently a hydrogen atom or a substituted or unsubstituted carbon number of 1 to 40 (preferably 1 to 20, more preferably 1 to 10, more preferably Is a hydrocarbon group of 1 to 5), and two or more of R 112 to R 126 may combine to form a cyclic structure.
- the hydrocarbon group having 1 to 40 carbon atoms represented by R 107 to R 126 in formula (A ′) and formula (A ′′) is the same as the hydrocarbon group represented by R 101 to R 106 in formula (A).
- two or more of R 107 to R 111 or two or more of R 112 to R 126 are combined to form a cyclic structure, and examples of the divalent group include a tetramethylene group and a pentamethylene group.
- 8-hydroxyquinoline or a metal complex of its derivative, an oxadiazole derivative, or a nitrogen-containing heterocyclic derivative is preferable.
- a metal chelate oxinoid compound containing a chelate of oxine (generally 8-quinolinol or 8-hydroxyquinoline), for example, tris (8-quinolinol) aluminum is used.
- 8-quinolinol or 8-hydroxyquinoline a metal chelate oxinoid compound containing a chelate of oxine
- tris (8-quinolinol) aluminum is used.
- an oxadiazole derivative the following can be mentioned.
- Ar 17 , Ar 18 , Ar 19 , Ar 21 , Ar 22 and Ar 25 each represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms or a condensed aromatic hydrocarbon group
- Ar 17 and Ar 18 , Ar 19 and Ar 21 , Ar 22 and Ar 25 may be the same or different.
- the aromatic hydrocarbon group or the condensed aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthranyl group, a perylenyl group, and a pyrenyl group.
- substituents include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and cyano groups.
- Ar 20 , Ar 23 and Ar 24 each represent a substituted or unsubstituted divalent aromatic hydrocarbon group or condensed aromatic hydrocarbon group having 6 to 60 carbon atoms, and Ar 23 and Ar 24 are identical to each other. But it can be different.
- the divalent aromatic hydrocarbon group or condensed aromatic hydrocarbon group include a phenylene group, a naphthylene group, a biphenylene group, an anthranylene group, a peryleneylene group, and a pyrenylene group.
- substituents include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and cyano groups.
- electron transfer compounds those having good thin film forming properties are preferably used.
- Specific examples of these electron transfer compounds include the following.
- the nitrogen-containing heterocyclic derivative as the electron transfer compound is a nitrogen-containing heterocyclic derivative composed of an organic compound having the following formula, and includes a nitrogen-containing compound that is not a metal complex. Examples thereof include a 5-membered ring or 6-membered ring containing a skeleton represented by the following formula (B) and a structure represented by the following formula (C).
- X 1 represents a carbon atom or a nitrogen atom.
- Z 1 and Z 2 each independently represents an atomic group capable of forming a nitrogen-containing heterocycle.
- the nitrogen-containing heterocyclic derivative is more preferably an organic compound having a nitrogen-containing aromatic polycyclic group consisting of a 5-membered ring or a 6-membered ring. Further, in the case of such a nitrogen-containing aromatic polycyclic group having a plurality of nitrogen atoms, the nitrogen-containing compound having a skeleton in which the above formulas (B) and (C) or the above formula (B) and the following formula (D) are combined. Aromatic polycyclic organic compounds are preferred.
- the nitrogen-containing group of the nitrogen-containing aromatic polycyclic organic compound is selected from, for example, nitrogen-containing heterocyclic groups represented by the following formulae.
- R ′ ′′ represents an aromatic hydrocarbon group having 6 to 40 ring carbon atoms (preferably 6 to 30, more preferably 6 to 20 and even more preferably 6 to 12) or ring carbon atoms.
- 6 to 40 (preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 12) condensed aromatic hydrocarbon group, 5 to 40 ring atoms (preferably 5 to 30, more preferably 5)
- aromatic heterocyclic groups or 5 to 40 ring atoms preferably 5 to 30, more preferably 5 to 20, more preferably 5 to 12) condensed aromatic heterocyclic rings Group, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), or an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5).
- n 1 is an integer of 0 to 5, and when n 1 is an integer of 2 or more, the plurality of R ′ ′′ may be the same or different from each other.
- preferred specific compounds include nitrogen-containing heterocyclic derivatives represented by the following formula (D1). HAr-L 101 -Ar 101 -Ar 102 (D1)
- HAr is a nitrogen-containing heterocyclic group having a substituted or unsubstituted ring-forming atom number of 5 to 40 (preferably 5 to 30, more preferably 5 to 20, more preferably 5 to 12).
- L 101 is a single bond, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 (preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 12) ring-forming carbon atoms or a condensed aromatic carbon group.
- Ar 101 is a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 40 ring carbon atoms (preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 12), and Ar 102 Is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 ring carbon atoms (preferably 6 to 30, more preferably 6 to 20 and even more preferably 6 to 14), substituted or unsubstituted ring carbon atoms 6 to 40 (preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 12) condensed aromatic hydrocarbon group, substituted or unsubstituted ring-forming atoms 5 to 40 (preferably 5 to 30) More preferably 5 to 20, more preferably 5 to 12) aromatic heterocyclic groups or substituted or unsubstituted ring-forming atoms of 5 to 40 (preferably 5 to 30, more preferably 5 to 20, more preferably Ku is a fused aromatic heterocyclic group having 5 to 12).
- HAr is selected from the following group, for example.
- L 101 is selected from the following group, for example.
- Ar 101 is selected from, for example, groups represented by the following formulas (D2) and (D3).
- R 201 to R 214 each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted carbon number of 1 to 20 (preferably 1 to 10, more preferably 1-5) alkyl group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), substituted or unsubstituted ring carbon atoms 6 to 40 (preferably Is an aryloxy group having 6 to 30, more preferably 6 to 20, and more preferably 6 to 12, a substituted or unsubstituted ring-forming carbon number of 6 to 40 (preferably 6 to 30, more preferably 6 to 20, More preferably 6-12) aromatic hydrocarbon group, substituted or unsubstituted ring-forming carbon atoms of 6-40 (preferably 6-30, more preferably 6-20, still more preferably 6-12).
- Ar 103 represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 ring carbon atoms (preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12), a substituted or unsubstituted ring.
- a condensed aromatic hydrocarbon group having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 20 and even more preferably 6 to 12), a substituted or unsubstituted ring atom number of 5 to 40 (preferably 5-30, more preferably 5-20, more preferably 5-12, aromatic heterocyclic groups or substituted or unsubstituted ring-forming atoms of 5-40 (preferably 5-30, more preferably 5-20) More preferably, it is a condensed aromatic heterocyclic group of 5 to 12).
- Ar 102 is selected from the following group, for example.
- the following compounds are also preferably used as the nitrogen-containing aromatic polycyclic organic compound as the electron transporting compound.
- R 231 to R 234 are each independently a hydrogen atom, a substituted or unsubstituted aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted aliphatic group having 3 to 20 carbon atoms.
- X 21 and X 22 each independently represents an oxygen atom, Represents a sulfur atom or a dicyanomethylene group.
- the following compounds are also preferably used as the electron transfer compound.
- R 221 , R 222 , R 223 and R 224 are the same or different groups, and are an aromatic hydrocarbon group or a condensed aromatic hydrocarbon group represented by the following formula (D6). It is.
- R 225 , R 226 , R 227 , R 228 and R 229 are the same or different from each other, and are a hydrogen atom, a saturated or unsaturated C 1-20 alkoxyl group, saturated or An unsaturated alkyl group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 carbon atoms. At least one of R 225 , R 226 , R 227 , R 228 and R 229 is a group other than a hydrogen atom.
- the electron transfer compound may be a polymer compound containing the nitrogen-containing heterocyclic group or the nitrogen-containing heterocyclic derivative.
- the electron transport layer of the organic EL device particularly preferably contains at least one nitrogen-containing heterocyclic derivative represented by the following formulas (E) to (G).
- Z 201 , Z 202, and Z 203 are each independently a nitrogen atom or a carbon atom.
- R 301 and R 302 are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms (preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 12), substituted or unsubstituted An unsubstituted heteroaryl group having 5 to 50 ring atoms (preferably 5 to 30, more preferably 5 to 20 and even more preferably 5 to 12), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted haloalkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.
- v is an integer of 0 to 5, and when v is an integer of 2 or more, the plurality of R 301 may be the same or different from each other.
- a plurality of R 301 may be bonded to each other to form a substituted or unsubstituted hydrocarbon ring.
- Ar 201 represents a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms (preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 12), or a substituted or unsubstituted ring atom number. 5 to 50 (preferably 5 to 30, more preferably 5 to 20, and still more preferably 5 to 12) heteroaryl groups.
- Ar 202 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), a substituted or unsubstituted carbon atom having 1 to 20 carbon atoms (preferably 1 to 1 carbon atoms). 10, more preferably 1 to 5) haloalkyl group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted ring forming carbon atoms 6 to 50 (preferably 6 to 30, more preferably 6).
- any one of Ar 201 and Ar 202 is a substituted or unsubstituted condensed aromatic hydrocarbon ring group having 10 to 50 ring carbon atoms (preferably 10 to 30, more preferably 10 to 20), It is an unsubstituted aromatic heterocyclic group having 9 to 50 ring atoms (preferably 9 to 30, more preferably 9 to 20).
- Ar 203 represents a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms (preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 12), or a substituted or unsubstituted ring-forming atom number. 5 to 50 (preferably 5 to 30, more preferably 5 to 20, and still more preferably 5 to 12) heteroarylene groups.
- L 201 , L 202 and L 203 are each independently a single bond or a substituted or unsubstituted ring-forming carbon number of 6 to 50 (preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 12). Or a divalent condensed aromatic heterocyclic group having 9 to 50 (preferably 9 to 30, more preferably 9 to 20) ring-forming atoms which are substituted or unsubstituted. )
- aryl group having 6 to 50 ring carbon atoms examples include phenyl group, naphthyl group, anthryl group, phenanthryl group, naphthacenyl group, chrysenyl group, pyrenyl group, biphenyl group, terphenyl group, tolyl group, fluoranthenyl group, fluorenyl Group and the like.
- heteroaryl group having 5 to 50 ring atoms examples include pyrrolyl group, furyl group, thienyl group, silolyl group, pyridyl group, quinolyl group, isoquinolyl group, benzofuryl group, imidazolyl group, pyrimidyl group, carbazolyl group, selenophenyl Group, oxadiazolyl group, triazolyl group, pyrazinyl group, pyridazinyl group, triazinyl group, quinoxalinyl group, acridinyl group, imidazo [1,2-a] pyridinyl group, imidazo [1,2-a] pyrimidinyl group and the like.
- Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
- Examples of the haloalkyl group having 1 to 20 carbon atoms include groups obtained by substituting one or more hydrogen atoms of the alkyl group with at least one halogen atom selected from fluorine, chlorine, iodine and bromine.
- Examples of the alkoxy group having 1 to 20 carbon atoms include groups having the above alkyl group as an alkyl moiety.
- Examples of the arylene group having 6 to 50 ring carbon atoms include groups obtained by removing one hydrogen atom from the aryl group.
- Examples of the divalent condensed aromatic heterocyclic group having 9 to 50 ring atoms include groups obtained by removing one hydrogen atom from the condensed aromatic heterocyclic group described as the heteroaryl group.
- the thickness of the electron transport layer is not particularly limited, but is preferably 1 nm to 100 nm. Moreover, it is preferable to use an insulator or a semiconductor as an inorganic compound in addition to the nitrogen-containing ring derivative as a component of the electron injection layer that can be provided adjacent to the electron transport layer. If the electron injection layer is made of an insulator or a semiconductor, current leakage can be effectively prevented and the electron injection property can be improved.
- an insulator it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. If the electron injection layer is composed of these alkali metal chalcogenides or the like, it is preferable in that the electron injection property can be further improved.
- preferable alkali metal chalcogenides include, for example, Li 2 O, K 2 O, Na 2 S, Na 2 Se, and Na 2 O
- preferable alkaline earth metal chalcogenides include, for example, CaO, BaO. , SrO, BeO, BaS and CaSe.
- preferable alkali metal halides include, for example, LiF, NaF, KF, LiCl, KCl, and NaCl.
- preferable alkaline earth metal halides include fluorides such as CaF 2 , BaF 2 , SrF 2 , MgF 2 and BeF 2 , and halides other than fluorides.
- the inorganic compound constituting the electron injection layer is preferably a microcrystalline or amorphous insulating thin film. If the electron injection layer is composed of these insulating thin films, a more uniform thin film is formed, and pixel defects such as dark spots can be reduced. Examples of such inorganic compounds include alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides.
- the preferred thickness of the layer is about 0.1 nm to 15 nm.
- the electron injecting layer preferably contains the above-described electron donating dopant.
- the hole injection layer is a layer containing a substance having a high hole injection property.
- Substances with high hole injection properties include molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, Tungsten oxide, manganese oxide, aromatic amine compound, or high molecular compound (oligomer, dendrimer, polymer, etc.) can also be used.
- Hole transport layer An organic layer formed between the light emitting layer and the anode, and has a function of transporting holes from the anode to the light emitting layer.
- an organic layer close to the anode may be defined as a hole injection layer.
- the hole injection layer has a function of efficiently injecting holes from the anode into the organic layer unit. 1 aspect of this invention WHEREIN:
- the said compound (1) and the said organic EL element material can also be used as a material (hole transport layer material) which forms a hole transport layer.
- hole transport layer materials for forming the hole transport layer include aromatic amine compounds, carbazole derivatives, anthracene derivatives, poly (N-vinylcarbazole) (abbreviation: PVK) and poly (4-vinyltriphenylamine) (abbreviation: PVTPA). ) And the like can be used. Any other substance may be used as long as it has a property of transporting more holes than electrons. Note that the layer containing a substance having a high hole-transport property is not limited to a single layer, and two or more layers containing the above substances may be stacked.
- an aromatic amine compound for example, an aromatic amine derivative represented by the following formula (H) is preferably used.
- Ar 211 to Ar 214 each independently represents a substituted or unsubstituted ring-forming carbon number of 6 to 50 (preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 12). ) Or a substituted or unsubstituted condensed aromatic hydrocarbon group having 6 to 50 ring carbon atoms (preferably 6 to 30, more preferably 6 to 20 and even more preferably 6 to 12). Alternatively, an aromatic heterocyclic group having 5 to 50 unsubstituted ring atoms (preferably 5 to 30, more preferably 5 to 20 and even more preferably 5 to 12) or substituted or unsubstituted ring atoms having 5 to 5 atoms.
- Ar 211 and Ar 212 , Ar 213 and Ar 214 may combine with each other to form a saturated or unsaturated ring structure.
- L 211 represents an aromatic carbon atom having 6 to 50 (preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12) ring-substituted carbon atoms.
- An aromatic amine represented by the following formula (J) is also preferably used for forming the hole transport layer.
- the hole transport layer may be formed using a hole transport layer composition containing a hole transport layer material and a solvent.
- the hole transport layer material may be a high molecular compound such as a polymer or a low molecular compound such as a monomer.
- a compound having an ionization potential of 4.5 eV to 6.0 eV is preferable from the viewpoint of a charge injection barrier.
- hole transport layer materials include aromatic amine derivatives, phthalocyanine derivatives, porphyrin derivatives, oligothiophene derivatives, polythiophene derivatives, benzylphenyl derivatives, compounds in which tertiary amines are linked by a fluorene group, hydrazone derivatives, silazane derivatives, silanamines Derivatives, phosphamine derivatives, quinacridone derivatives, polyaniline derivatives, polypyrrole derivatives, polyphenylene vinylene derivatives, polythienylene vinylene derivatives, polyquinoline derivatives, polyquinoxaline derivatives, carbon and the like.
- the derivative includes, for example, an aromatic amine derivative, and includes an aromatic amine itself and a compound having an aromatic amine as a main skeleton.
- an aromatic amine compound is preferable from the viewpoint of amorphousness and visible light transmittance, and an aromatic tertiary amine compound is particularly preferable.
- the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and includes a compound having a group derived from an aromatic tertiary amine.
- the type of the aromatic tertiary amine compound is not particularly limited, but from the viewpoint of uniform light emission due to the surface smoothing effect, a polymer compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less (a polymerizable compound in which repeating units are linked) is further included. preferable.
- a polymer compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less a polymerizable compound in which repeating units are linked
- the aromatic tertiary amine polymer compound include a polymer compound having a repeating unit represented by the following formula (I).
- Ar 1 and Ar 2 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group.
- Ar 3 to Ar 5 each independently represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group.
- two groups bonded to the same N atom may be bonded to each other to form a ring.
- Y represents a linking group selected from the following.
- Ar 6 to Ar 16 each independently represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group.
- R 1 and R 2 each independently represents a hydrogen atom or a substituent.
- the aromatic hydrocarbon group and aromatic heterocyclic group represented by Ar 1 to Ar 16 include a benzene ring, a naphthalene ring, a phenanthrene ring, and a thiophene from the viewpoint of the solubility, heat resistance, hole injection / transport properties of the polymer compound.
- a group having a ring selected from a ring and a pyridine ring is preferable, and a group having a ring selected from a benzene ring and a naphthalene ring is more preferable.
- the molecular weight of the optional substituent of the aromatic hydrocarbon group and aromatic heterocyclic group of Ar 1 to Ar 16 is usually 400 or less, and preferably about 250 or less.
- an alkyl group, an alkenyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group and the like are preferable.
- the substituent represented by R 1 and R 2 include an alkyl group, an alkenyl group, an alkoxy group, a silyl group, a siloxy group, an aromatic hydrocarbon group, and an aromatic heterocyclic group.
- a conductive polymer obtained by polymerizing polythiophene derivative 3,4-ethylenedioxythiophene) in high molecular weight polystyrene sulfonic acid is also preferable. Moreover, the end of this polymer may be capped with methacrylate or the like.
- the concentration of the hole transport layer material in the composition for a hole transport layer is arbitrary, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably in terms of film thickness uniformity. It is 0.5 mass% or more, and is usually 70 mass% or less, preferably 60 mass% or less, more preferably 50 mass% or less. If it is this range, a film thickness nonuniformity will not arise or a defect will not arise in a hole transport layer.
- the composition for a hole transport layer may contain an electron accepting compound.
- the electron-accepting compound is preferably a compound having an oxidizing power and the ability to accept one electron from the above-described hole transport layer material. Specifically, a compound having an electron affinity of 4 eV or more is preferable, and 5 eV or more is preferable. The compound which is the compound of these is further more preferable.
- electron-accepting compounds include triarylboron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acids.
- examples thereof include one or more compounds selected from the group. More specifically, onium salts having an organic group such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and triphenylsulfonium tetrafluoroborate; iron (III) chloride, ammonium peroxodisulfate, etc.
- cyano compounds such as tetracyanoethylene
- aromatic boron compounds such as tris (pendafluorophenyl) borane
- fullerene derivatives iodine
- polystyrene sulfonate ions alkylbenzene sulfonate ions, camphor sulfonate ions, etc.
- the sulfonate ion etc. are mentioned.
- These electron-accepting compounds can improve the conductivity of the hole transport layer by oxidizing the hole transport material.
- the content of the electron-accepting compound in the hole transport layer composition with respect to the hole transport material is usually 0.1 mol% or more, preferably 1 mol% or more. However, it is usually 100 mol% or less, preferably 40 mol% or less.
- hole transport layer material and electron accepting compound In addition to the above-described hole transport layer material and electron accepting compound, other components may be further contained in the hole transport layer composition.
- other components include various light emitting materials, electron transporting compounds, binder resins, and coating property improving agents.
- 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.
- a hole transport layer material suitable for a coating method is preferably used.
- a hole transport layer material include polyvinyl carbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having aromatic amine residues in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyl derivatives.
- Phenyldiamine derivative polyaniline or derivative thereof, polythiophene or derivative thereof, polypyrrole or derivative thereof, polyarylamine or derivative thereof, poly (p-phenylene vinylene) or derivative thereof, polyfluorene derivative, polymer having aromatic amine residue Compounds, and poly (2,5-thienylene vinylene) or derivatives thereof.
- the hole transport layer material is preferably a polymer compound such as a polymer. This is because when the polymer compound is used, the film-forming property is improved and the light-emitting property of the organic EL element can be made uniform.
- the number average molecular weight determined by standard polystyrene of such a hole transport layer material is 10,000 or more, preferably 3.0 ⁇ 10 4 to 5.0 ⁇ 10 5 , more preferably 6.0. ⁇ 10 4 to 1.2 ⁇ 10 5 .
- the weight average molecular weight of the hole transport layer material is 1.0 ⁇ 10 4 or more, preferably 5.0 ⁇ 10 4 to 1.0 ⁇ 10 6 , more preferably 1.0 ⁇ 10 5. ⁇ 6.0 ⁇ 10 5 .
- the hole transport layer material examples include polyvinyl carbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having an aromatic amine residue in the side chain or main chain, polyaniline or derivatives thereof, polythiophene or derivatives thereof, and polyfluorene derivatives.
- a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine residue in a side chain or a main chain, a polyfluorene derivative, or a polymer compound having an aromatic amine residue is preferably used by being dispersed in a polymer binder.
- the polyvinyl carbazole or a derivative thereof can be obtained, for example, by cationic polymerization of a vinyl monomer or radical polymerization.
- a compound having a residue of the low molecular hole transport layer material in the side chain or main chain is preferably used because the siloxane skeleton structure has almost no hole transport property.
- compounds having a hole transporting aromatic amine residue in the side chain or main chain can be mentioned.
- a polymer having a fluorenediyl unit represented by the following formula (J) is preferable. This is because when the hole transport layer of the organic EL device is brought into contact with an organic compound having a condensed ring or a plurality of aromatic rings, the hole injection efficiency is improved and the current density during driving is increased.
- R 1 and R 2 may be the same or different and each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group.
- the alkyl group include groups having 1 to 10 carbon atoms.
- the alkoxy group include groups having 1 to 10 carbon atoms.
- the aryl group include a phenyl group and a naphthyl group.
- monovalent heterocyclic groups include pyridyl groups.
- the aryl group and the monovalent heterocyclic group may have a substituent.
- the substituent include an alkyl group having 1 to 10 carbon atoms and a carbon atom from the viewpoint of improving the solubility of the polymer compound. Examples thereof include an alkoxy group having 1 to 10 atoms.
- the aryl group and the monovalent heterocyclic group may have a crosslinkable group.
- the crosslinking group include vinyl group, ethynyl group, butenyl group, group having acrylic structure, group having acrylate structure, group having acrylamide structure, group having methacrylic structure, group having methacrylate structure, and methacrylamide structure.
- a group having a small ring for example, cyclopropane, cyclobutane, epoxide, oxetane, diketene, episulfide, etc.
- a particularly preferable hole transport layer material is a polymer containing the fluorenediyl unit and the aromatic tertiary amine compound unit as repeating units, for example, a polyarylamine polymer.
- aromatic tertiary amine compound unit examples include a repeating unit represented by the following formula (K).
- Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represent an arylene group or a divalent heterocyclic group.
- Ar 5 , Ar 6 and Ar 7 each independently represents an aryl group or a monovalent heterocyclic group. Alternatively, Ar 6 and Ar 7 may form a ring together with the nitrogen atom to which Ar 6 and Ar 7 are bonded.
- m and n each independently represents 0 or 1.
- Examples of the arylene group include a phenylene group.
- Examples of the divalent heterocyclic group include a pyridinediyl group. These groups may have a substituent.
- Examples of the aryl group include a phenyl group and a naphthyl group.
- Examples of the monovalent heterocyclic group include a pyridyl group. These groups may have a substituent.
- Examples of the monovalent heterocyclic group include thienyl group, furyl group, pyridyl group and the like.
- an alkyl group, an alkoxy group, or an aryl group is preferable as the optional substituent for the arylene group, aryl group, divalent heterocyclic group, and monovalent heterocyclic group.
- Groups are more preferred.
- the alkyl group include groups having 1 to 10 carbon atoms.
- the alkoxy group include groups having 1 to 10 carbon atoms.
- the aryl group include a phenyl group and a naphthyl group.
- the substituent may have a crosslinkable group.
- the crosslinkable group include vinyl group, ethynyl group, butenyl group, group having acrylic structure, group having acrylate structure, group having acrylamide structure, group having methacrylic structure, group having methacrylate structure, methacrylamide structure , A group having a vinyl ether structure, a vinylamino group, a group having a silanol structure, a group having a small ring (for example, cyclopropane, cyclobutane, epoxide, oxetane, diketene, episulfide, etc.).
- Ar 1 , Ar 2 , Ar 3 and Ar 4 are preferably arylene groups, and more preferably phenylene groups.
- Ar 5 , Ar 6 and Ar 7 are preferably aryl groups, and more preferably phenyl groups.
- the carbon atom in Ar 2 and the carbon atom in Ar 3 may be directly bonded, or may be bonded via a divalent group such as —O— or —S—. From the viewpoint of ease of synthesis of the monomer, m and n are preferably 0.
- repeating unit represented by the formula (K) include a repeating unit represented by the following formula.
- crosslinker having a crosslinkable group.
- the crosslinking agent include vinyl group, acetyl group, butenyl group, acrylic group, acrylamide group, methacryl group, methacrylamide group, vinyl ether group, vinylamino group, silanol group, cyclopropyl group, cyclobutyl group, epoxy group, oxetane.
- a compound having a polymerizable substituent selected from the group consisting of a group, a diketene group, an episulfide group, a lactone group, and a lactam group.
- a polyfunctional acrylate is preferable, and examples thereof include dipentaerythritol hexaacrylate (DPHA) and trispentaerythritol octaacrylate (TPEA).
- DPHA dipentaerythritol hexaacrylate
- TPEA trispentaerythritol octaacrylate
- a hole transport layer material having a hole transport site and having a crosslinkable group is preferably used.
- the hole transport site include a triarylamine structure, a fluorene ring, an anthracene ring, a pyrene ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, a phenoxazine ring, and a phenanthroline ring, and a thiophene ring structure.
- aromatic heterocyclic structures such as rings and silole rings, and metal complex structures.
- a triarylamine structure as a hole transport site in terms of improving electrochemical stability and hole transport ability.
- it is a polymer at the point which becomes easy to become insoluble in an organic solvent by crosslinking reaction.
- a polymer containing a repeating unit represented by the following formula (L) is preferable from the viewpoint of improving electrochemical stability and hole transport ability.
- m represents an integer of 0 to 3
- Ar 1 and Ar 2 each independently represent a single bond, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic complex.
- Ar 3 to Ar 5 each independently represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group.
- Ar 1 and Ar 2 are not simultaneously a single bond.
- aromatic hydrocarbon group examples include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
- Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, and a pyrrolopyrazole ring.
- Ar 1 to Ar 5 each independently comprises a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a thiophene ring, a pyridine ring, and a fluorene ring from the viewpoint of solubility in solvents and heat resistance.
- a monovalent group of a ring selected from the group is preferred.
- Ar 1 to Ar 5 a group in which one or two or more rings selected from the above groups are connected by a single bond is preferable, and a biphenyl group, a biphenylene group, a terphenyl group, and a terphenylene group are more preferable.
- Examples of the optional substituent of the aromatic hydrocarbon group and aromatic heterocyclic group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a sec-butyl group.
- arylthio group having 4 or more carbon atoms, preferably 5 or more, and 36 or less, preferably 24 or less
- arylthio group a silyl group having 2 or more, preferably 3 or more, and 36 or less, preferably 24 or less, such as a trimethylsilyl group or a triphenylsilyl group; a carbon such as a trimethylsiloxy group or a triphenylsiloxy group
- a siloxy group having a number of 2 or more, preferably 3 or more, 36 or less, preferably 24 or less; a cyano group; a fragrance having 6 to 36 carbon atoms, preferably 6 to 24, such as a phenyl group or a naphthyl group Group hydrocarbon ring group; and thienyl group, pyridyl group and the like having 3 or more carbon atoms, preferably 4 or more, and 36 or less, preferably 2 An aromatic heterocyclic group which is 4 or less is mentioned.
- an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms are preferable from the viewpoint of solubility.
- each said arbitrary substituent may have a substituent further, and the example is selected from an above-described group as an arbitrary substituent.
- Ar 1 to Ar 5 including the substituent, have 3 or more, preferably 5 or more, more preferably 6 or more, and 72 or less, preferably 48 or less. More preferably, it is 25 or less.
- M in the formula (L) represents an integer of 0 to 3, and m is preferably 0 from the viewpoint of improving the film formability. Further, m is preferably 1 to 3 from the viewpoint of improving hole transport ability.
- m is 2 or more, two or more Ar 4 and two or more Ar 5 may be the same or different. Further, Ar 4 and Ar 5 may be bonded to each other directly or via a linking group to form a cyclic structure.
- a crosslinkable group refers to a group that reacts with the same or different groups of other molecules located nearby by irradiation with heat and / or active energy rays to form a new chemical bond.
- Examples of the crosslinkable group include the following crosslinkable groups from the viewpoint of easy insolubilization.
- R 21 to R 23 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- Ar 21 represents a substituted or unsubstituted aromatic group.
- X 1 , X 2 and X 3 each independently represent a hydrogen atom or a halogen atom.
- R 24 represents a hydrogen atom or a vinyl group.
- the benzocyclobutene ring may have a substituent, and the substituents may be bonded to each other to form a ring.
- Examples of the alkyl group of R 21 to R 23 include alkyl groups having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, such as a methyl group and an ethyl group.
- Examples of the aromatic group for Ar 21 include the same groups as the aromatic groups represented by Ar 1 to Ar 5 .
- the optional substituents for R 21 to R 23 and Ar 21 are not particularly limited, and examples thereof include groups selected from the aforementioned arbitrary substituents.
- a crosslinkable group a group that undergoes insolubilization reaction by cationic polymerization such as a cyclic ether group such as an epoxy group or an oxetane group, or a vinyl ether group is preferable in terms of high reactivity and easy insolubilization.
- an oxetane group is particularly preferable from the viewpoint that the rate of cationic polymerization can be easily controlled, and a vinyl ether group is preferable from the viewpoint that a hydroxyl group that may cause deterioration of the device during the cationic polymerization is hardly generated.
- a group that undergoes a cycloaddition reaction such as an arylvinylcarbonyl group such as a cinnamoyl group or a group having a benzocyclobutene ring, is preferred from the viewpoint of further improving electrochemical stability.
- a group having a benzocyclobutene ring is particularly preferable in that the structure after insolubilization is particularly stable.
- a group represented by the following formula (M) is preferable.
- the benzocyclobutene ring in the formula (M) may have a substituent.
- the substituents may be bonded to each other to form a ring.
- the crosslinkable group may be directly bonded to a monovalent or divalent aromatic group in the molecule, or may be bonded via a divalent group.
- the divalent group 1 to 30 groups selected from —O—, —C ( ⁇ O) —, and optionally substituted —CH 2 — are linked in any order.
- a divalent group is preferred.
- bonded through these bivalent groups is shown below, it is not limited to these.
- n represents an integer from 1 to 12.
- the hole transport layer material preferably contains a conductive polymer or an oligomer.
- the conductive polymer or oligomer is usually a mixture with an electron donating compound, an electron accepting compound, or an acidic compound.
- the mixture may be in the form of a solid or liquid, but a solution, dispersion, colloid, ink, varnish and the like suitably used in a method for forming a film by a coating method to obtain a solid film are preferable.
- an additive may be added to the mixture for the purpose of improving the hole transporting property or improving the film forming property. Examples of conductive polymers and oligomers that can be used in one embodiment of the present invention are shown below.
- Typical examples of the electron donating compound include aromatic amine derivatives, phthalocyanine derivatives, porphyrin derivatives, thiophene derivatives, benzylphenyl derivatives, compounds in which tertiary amines are linked by a fluorene group, hydrazone derivatives, silazane derivatives, and silanamine derivatives.
- These derivatives may be any of low molecules having a molecular weight of less than 1000, oligomers and dendrimers having a molecular weight of 1000 to 10,000, and polymers having a molecular weight of 10,000 or more.
- aromatic amine derivatives, polythiophene derivatives, polyaniline derivatives, and oligoaniline derivatives are preferably used.
- the electron-accepting compound and the acidic compound include triaryl boron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, arylamines and Lewis acids, 1 type, or 2 or more types of compounds chosen from the group which consists of these salts are mentioned. More specifically, onium salts having an organic group such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and triphenylsulfonium tetrafluoroborate; iron (III) chloride, ammonium peroxodisulfate, etc.
- High valent inorganic compounds such as tetracyanoethylene; aromatic boron compounds such as tris (pentafluorophenyl) borane; fullerene derivatives; iodine; polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, etc.
- the sulfonate ion etc. are mentioned.
- these derivatives may be any of a low molecular weight molecular weight of less than 1000, an oligomer and a dendrimer having a molecular weight of 1000 to 10,000, and a polymer having a molecular weight of 10,000 or more.
- These electron-accepting compounds can improve the conductivity of the hole transport layer by oxidizing the hole transport layer material.
- the content of the electron-accepting compound in the hole transport layer or the composition for the hole transport layer with respect to the hole transport layer material is usually 0.1 mol% or more, preferably 1 mol% or more, usually 100 mol% or less, Preferably it is 40 mol% or less.
- the following are representative examples (i) to (x) of hole transport layer materials that can be used in one embodiment of the present invention. These can be used alone or in combination, but it is desirable to mix a relatively electron-donating material and a relatively electron-accepting material.
- an additive for promoting charge transfer between the electron donating compound and the electron accepting compound or improving the coating film formability can be added as a third component. A plurality of third components may be used.
- R 1 and R 1 ′ are each independently selected from a hydrogen atom and alkyl having 1 to 4 carbon atoms.
- R 1 and R 1 ′ may be bonded to each other to represent an alkylene chain having 1 to 4 carbon atoms.
- the alkylene chain may be optionally substituted with an alkyl group having 1 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a 1,2-cyclohexylene group.
- n represents a number greater than about 6.
- n is an integer of 0 to 4
- m ⁇ 1 is an integer of 1 to 5
- n + (m ⁇ 1) 5
- R 1 is the same or different and each independently represents an alkyl group, alkenyl group, alkoxy group, cycloalkyl group, cycloalkenyl group, alkanoyl group, alkylthio group, aryloxy group, alkylthioalkyl group, alkylaryl group, arylalkyl Group, amino group, alkylamino group, dialkylamino group, aryl group, alkylsulfinyl group, alkoxyalkyl group, alkylsulfonyl group, arylthio group, arylsulfinyl group, alkoxycarbonyl group, arylsulfonyl group, carboxyl group, halogen atom, cyano A group or an alkyl group substituted by one or more sulfonic acid groups, carboxyl groups,
- R 1 is independently a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkanoyl group, alkylthio group, aryloxy group, alkylthioalkyl group, alkylaryl group, arylalkyl group, amino group, alkyl Amino group, dialkylamino group, aryl group, alkylsulfinyl group, alkoxyalkyl group, alkylsulfonyl group, arylthio group, arylsulfinyl group, alkoxycarbonyl group, arylsulfonyl group, acrylic acid group, phosphoric acid group, phosphonic acid group, halogen Atoms, nitro groups, cyano groups, hydroxyl groups, epoxy groups, silyl groups, siloxane groups, alcohol groups, benzyl groups, carboxylate groups, ether groups, ether carboxylate groups, amide sulfonate groups, ether sul
- the two R 1 groups are joined together to form an alkylene or alkenylene chain that completes a 3-membered, 4-membered, 5-membered, 6-membered or 7-membered aromatic or alicyclic ring.
- the ring may contain one or more divalent nitrogen, sulfur or oxygen atoms.
- R 2 is independently a hydrogen atom, alkyl group, alkenyl group, aryl group, alkanoyl group, alkylthioalkyl group, alkylaryl group, arylalkyl group, amino group, epoxy group, silyl group, siloxane group, amide sulfonate group , Alcohol groups, benzyl groups, carboxylate groups, ether groups, ether carboxylate groups, amide sulfonate groups, ether sulfonate groups, and urethane groups.
- Q is selected from the group consisting of S, Se, and Te
- R 1 is independently a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkanoyl group, an alkthio group, an aryloxy group, Alkylthioalkyl group, alkylaryl group, arylalkyl group, amino group, alkylamino group, dialkylamino group, aryl group, alkylsulfinyl group, alkoxyalkyl group, alkylsulfonyl group, arylthio group, arylsulfinyl group, alkoxycarbonyl group, aryl Sulfonyl group, acrylic acid group, phosphoric acid group, phosphonic acid group, halogen atom, nitro group, cyano group, hydroxyl group, epoxy group, silyl group, siloxane group, alcohol group, benzyl group, carboxylate group, ether group,
- R 1 groups may be joined together to form an alkylene or alkenylene chain that completes a 3, 4, 5, 6, or 7 membered aromatic or alicyclic ring, wherein the ring is 1
- One or more divalent nitrogen, selenium, tellurium, sulfur, or oxygen atoms may be included.
- R 1 and R 2 each independently represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group, a t-butoxycarbonyl group, or a benzyloxycarbonyl group
- R 3 to R 34 are Each independently a hydrogen atom, hydroxyl group, silanol group, thiol group, carboxyl group, phosphate group, phosphate ester group, ester group, thioester group, amide group, nitro group, substituted or unsubstituted monovalent hydrocarbon group ,
- m and n are each independently an integer of 1 or more and satisfy m + n ⁇ 20.
- X represents O, S or NH
- A represents a naphthalene ring or anthracene ring which may have a substituent other than X and n SO 3 H groups
- B represents a substituted group.
- B is a divalent or higher-valent substituted or unsubstituted hydrocarbon group containing one or more aromatic rings, divalent or trivalent 1, considering the improvement in durability and charge transportability.
- a 3,5-triazine group, a substituted or unsubstituted divalent diphenylsulfone group is preferred, and in particular, a divalent or trivalent substituted or unsubstituted benzyl group, a divalent substituted or unsubstituted p-xylylene group, Divalent or trivalent substituted or unsubstituted naphthyl group, divalent or trivalent 1,3,5-triazine group, divalent substituted or unsubstituted diphenylsulfone group, or divalent to tetravalent perfluorobiphenyl group
- the compound represented by the formula (vii) is particularly preferably represented by the formula (vii-3).
- R 1 , R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a silanol group, a thiol group, a carboxyl group, a phosphate group, a phosphate group, or an ester group.
- a and B are each independently A divalent group represented by the formula (viii-1) or (viii-2) is shown.
- R 4 to R 11 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a silanol group, a thiol group, a carboxyl group, a phosphate group, a phosphate ester group, an ester group, or a thioester group.
- m and n are each independently an integer of 1 or more and satisfy m + n ⁇ 20.
- a phenylamine-based polymer represented by the following formula (X) can also be used as a hole transport layer material.
- n represents an integer of 3 or more.
- the hole transport layer may have a two-layer structure of a first hole transport layer (anode side) and a second hole transport layer (cathode side).
- the thickness of the hole transport layer is not particularly limited, but is preferably 10 to 200 nm.
- a layer containing an acceptor material may be bonded to an anode side of the hole transport layer or the first hole transport layer. This is expected to reduce drive voltage and manufacturing costs.
- the acceptor material a compound represented by the following formula (K) is preferable.
- R 311 to R 316 may be the same as or different from each other, and each independently represents a cyano group, —CONH 2 , a carboxyl group, or —COOR 317 (R 317 has 1 to 20 carbon atoms) Represents an alkyl group or a cycloalkyl group having 3 to 20 carbon atoms, provided that one or more pairs of R 311 and R 312 , R 313 and R 314 , and R 315 and R 316 are taken together— A group represented by CO—O—CO— may be formed.)
- R 317 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, and a cyclohexyl group.
- the thickness of the layer containing the acceptor material is not particularly limited, but is
- n / p doping In the above-described hole transport layer and electron transport layer, as described in Japanese Patent No. 3695714, by doping (n) of donor material and doping (p) of acceptor material, The carrier injection ability can be adjusted.
- a typical example of n doping is a method of doping a metal such as Li or Cs into an electron transport material, and a typical example of p doping is F 4 TCNQ (2, 3, 5, 6) in a hole transport material. -Tetrafluoro-7,7,8,8-tetracyanoquinodimethane) and the like.
- the space layer is, for example, in the case of laminating a fluorescent light emitting layer and a phosphorescent light emitting layer, for the purpose of adjusting the carrier balance so as not to diffuse excitons generated in the phosphorescent light emitting layer into the fluorescent light emitting layer.
- This is a layer provided between the fluorescent light emitting layer and the phosphorescent light emitting layer.
- the space layer can be provided between the plurality of phosphorescent light emitting layers. Since the space layer is provided between the light emitting layers, a material having both electron transport properties and hole transport properties is preferable. In order to prevent diffusion of triplet energy in the adjacent phosphorescent light emitting layer, the triplet energy is preferably 2.6 eV or more. Examples of the material used for the space layer include the same materials as those used for the above-described hole transport layer. 1 aspect of this invention WHEREIN: The said compound (1) and the said organic EL element material can also be used as a material for space layers.
- a barrier layer such as an electron barrier layer, a hole barrier layer, or a triplet barrier layer is preferably provided adjacent to the light-emitting layer.
- the electron barrier layer is a layer that prevents electrons from leaking from the light emitting layer to the hole transport layer
- the hole barrier layer is a layer that prevents holes from leaking from the light emitting layer to the electron transport layer. is there.
- the compound (1) and the organic EL device material may be used as a material for a hole blocking layer.
- the triplet barrier layer prevents the triplet excitons generated in the light emitting layer from diffusing into the surrounding layers, and confins the triplet excitons in the light emitting layer, thereby transporting electrons other than the light emitting dopant of the triplet excitons. It has a function of suppressing energy deactivation on the molecules of the layer.
- the triplet energy of the phosphorescent dopant in the light emitting layer is E T d and the triplet energy of the compound used as the triplet barrier layer is E T TB , E T d ⁇ If the energy magnitude relationship of E T TB is satisfied, the triplet exciton of the phosphorescent dopant is confined (cannot move to other molecules) and the energy deactivation path other than light emission on the dopant is interrupted. It is assumed that light can be emitted with high efficiency.
- the energy difference ⁇ E T E T TB ⁇ E T d is small, under the environment of room temperature, which is the actual element driving environment, , endothermically triplet excitons overcame this energy difference Delta] E T by thermal energy near is considered to be possible to move to another molecule.
- the exciton lifetime is longer than that of fluorescence emission, so that the influence of the endothermic exciton transfer process is likely to appear.
- the energy difference ⁇ E T is preferably as large as possible relative to the thermal energy at room temperature, more preferably 0.1 eV or more, and particularly preferably 0.2 eV or more.
- the compound (1) and the material for an organic EL device can be used as a material for a triplet barrier layer of a TTF fluorescent device described in International Publication WO2010 / 134350A1.
- the electron mobility of the material constituting the triplet barrier layer is desirably 10 ⁇ 6 cm 2 / Vs or more in the range of electric field strength of 0.04 to 0.5 MV / cm.
- the electron mobility is determined by impedance spectroscopy.
- the electron injection layer is desirably 10 ⁇ 6 cm 2 / Vs or more in the range of electric field strength of 0.04 to 0.5 MV / cm. This facilitates the injection of electrons from the cathode into the electron transport layer, and also promotes the injection of electrons into the adjacent barrier layer and the light emitting layer, thereby enabling driving at a lower voltage.
- each layer of the organic EL element can be formed by a conventionally known vacuum deposition method, spin coating method, or the like.
- vacuum deposition molecular beam deposition (MBE), or coating methods such as dipping, spin coating, casting, bar coating, roll coating, etc., using a solution of a compound that forms a layer. It can be formed by a known method.
- MBE molecular beam deposition
- each organic layer is not particularly limited. Generally, if the film thickness is too thin, defects such as pinholes are likely to occur. On the other hand, if it is too thick, a high drive voltage is required and the efficiency deteriorates. A range of 1 ⁇ m is preferred.
- a solution (ink composition) containing the compound (1) and other materials such as a dopant as required is used. It is preferable to form a film by the above coating method.
- a known coating method can be used effectively.
- spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, slit coating method, wire bar examples thereof include a coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink jet method, and a nozzle printing method.
- a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method are preferable. Film formation by these methods can be performed under conditions well known to those skilled in the art.
- heating upper limit 250 ° C.
- drying under vacuum may be performed to remove the solvent, and polymerization reaction by light or high temperature heating exceeding 250 ° C. is unnecessary. Therefore, it is possible to suppress deterioration of the performance of the element due to light or high temperature heating exceeding 250 ° C.
- the film-forming solution (ink composition) only needs to contain at least one kind of the compound (1), and also includes known hole transport materials, electron transport materials, light-emitting materials, acceptor materials, stabilizers, and the like.
- An additive may be included.
- the film-forming solution contains additives for adjusting the viscosity and / or surface tension, such as thickeners (high molecular weight compounds, etc.), viscosity reducing agents (low molecular weight compounds, etc.), surfactants, and the like. May be.
- the content of the compound (1) in the film-forming solution (ink composition) is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass with respect to the entire film-forming solution. .
- High molecular weight compounds that can be used as thickeners include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, copolymers thereof, poly Examples thereof include photoconductive resins such as —N-vinylcarbazole and polysilane, and conductive resins such as polythiophene and polypyrrole.
- Examples of the solvent for the film-forming solution include chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, and o-dichlorobenzene; tetrahydrofuran, dioxane, dioxolane, anisole, and the like.
- Ether solvents such as: aromatic hydrocarbon solvents such as toluene and xylene; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane Aliphatic hydrocarbon solvents such as acetone; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, benzophenone and acetophenone; ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate and phenyl acetate; Ethylene glycol, ethylene glycol Polyhydric alcohols such as nobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, dieth
- aromatic hydrocarbon solvents aromatic hydrocarbon solvents, ether solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents are preferable from the viewpoints of solubility, film formation uniformity, viscosity characteristics, and the like.
- an organic electroluminescence element is used in display devices such as an organic EL panel module, display devices such as a television, a mobile phone, and a personal computer, and electronic devices such as a light emitting device for lighting and a vehicle lamp. it can.
- Synthesis Example 1 Synthesis of Compound H-1 Compound H-1 was synthesized according to the following synthesis route.
- pyrimidine intermediate B1 (9.76 g, yield 81%).
- bicarbazolyl intermediate A1 (12.26 g, 30 mmol)
- pyrimidine intermediate B1 (9.04 g, 30 mmol)
- potassium carbonate (4.35 g, 31.5 mmol) were added to 30 mL of dry DMF, and at 120 ° C. for 8 hours. Stir with heating. After cooling the reaction solution to room temperature, 30 mL of water was added, and the precipitated solid was collected by filtration, washed with water and methanol, and dried under reduced pressure.
- Synthesis Example 2 Synthesis of Compound H-2 Compound H-2 was synthesized according to the following synthesis route.
- pyrimidine intermediate B2 (9.40 g, yield 78%).
- bicarbazolyl intermediate A1 (12.26 g, 30 mmol)
- pyrimidine intermediate B2 (9.04 g, 30 mmol)
- potassium carbonate (4.35 g, 31.5 mmol) were added to 30 mL of dry DMF, and at 120 ° C. for 8 hours. Stir with heating. After cooling the reaction solution to room temperature, 30 mL of water was added, and the precipitated solid was collected by filtration, washed with water and methanol, and dried under reduced pressure.
- bicarbazolyl intermediate A2 (12.26 g, 30 mmol), pyrimidine intermediate B2 (9.04 g, 30 mmol) and potassium carbonate (4.35 g, 31.5 mmol) were added to 30 mL of dry DMF, and at 120 ° C. for 8 hours. Stir with heating. After cooling the reaction solution to room temperature, 30 mL of water was added, and the precipitated solid was collected by filtration, washed with water and methanol, and dried under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain the target intermediate C3 (13.13 g, yield 65%).
- intermediate C3 (2.02 g, 3.0 mmol), bicarbazolyl intermediate A1 (1.23 g, 3.0 mmol), tris (dibenzylideneacetone) dipalladium (0.055 g, 0.06 mmol), xanthophos (0.069 g, 0.12 mmol), sodium t-butoxy (0.43 g, 4.5 mmol), and anhydrous xylene (60 mL) were sequentially added, and the mixture was heated to reflux for 8 hours. After cooling the reaction solution to room temperature, insolubles were removed by filtration, and the organic solvent was distilled off under reduced pressure.
- Synthesis Example 4 Synthesis of Compound H-4 Compound H-4 was synthesized according to the following synthesis route.
- intermediate C2 (2.02 g, 3.0 mmol), tricarbazolyl intermediate A3 (1.95 g, 3.0 mmol), tris (dibenzylideneacetone) dipalladium (0.055 g, 0.06 mmol), xanthophos (0.069 g, 0.12 mmol), sodium t-butoxy (0.43 g, 4.5 mmol), and anhydrous xylene (60 mL) were sequentially added, and the mixture was heated to reflux for 8 hours. After cooling the reaction solution to room temperature, insolubles were removed by filtration, and the organic solvent was distilled off under reduced pressure.
- intermediate C2 (2.02 g, 3.0 mmol), carbazole intermediate A4 (1.00 g, 3.0 mmol), tris (dibenzylideneacetone) dipalladium (0.055 g, 0.06 mmol), xanthphos (0.069 g, 0.12 mmol), sodium t-butoxy (0.43 g, 4.5 mmol), and anhydrous xylene (60 mL) were sequentially added, and the mixture was heated to reflux for 8 hours. After cooling the reaction solution to room temperature, insolubles were removed by filtration, and the organic solvent was distilled off under reduced pressure.
- intermediate C2 (2.02 g, 3.0 mmol), carbazole intermediate A5 (0.85 g, 3.0 mmol), tris (dibenzylideneacetone) dipalladium (0.055 g, 0.06 mmol), xanthphos (0.069 g, 0.12 mmol), sodium t-butoxy (0.43 g, 4.5 mmol), and anhydrous xylene (60 mL) were sequentially added, and the mixture was heated to reflux for 8 hours. After cooling the reaction solution to room temperature, insolubles were removed by filtration, and the organic solvent was distilled off under reduced pressure.
- bicarbazolyl intermediate A6 (10.49 g, 20 mmol), pyrimidine intermediate B2 (6.02 g, 20 mmol) and potassium carbonate (3.32 g, 24 mmol) were added to 20 mL of dry DMF, and the mixture was heated and stirred at 120 ° C. for 8 hours. did. After cooling the reaction solution to room temperature, 30 mL of water was added, and the precipitated solid was collected by filtration, washed with water and methanol, and dried under reduced pressure. The target intermediate C4 (15.31 g, yield 97%) was obtained.
- intermediate C4 (2.37 g, 3.0 mmol), bicarbazolyl intermediate A1 (1.23 g, 3.0 mmol), tris (dibenzylideneacetone) dipalladium (0.055 g, 0.06 mmol), xanthophos (0.069 g, 0.12 mmol), sodium t-butoxy (0.43 g, 4.5 mmol), and anhydrous xylene (60 mL) were sequentially added, and the mixture was heated to reflux for 8 hours. After cooling the reaction solution to room temperature, insolubles were removed by filtration, and the organic solvent was distilled off under reduced pressure.
- intermediate C2 (2.02 g, 3.0 mmol), carbazole intermediate A7 (1.46 g, 3.0 mmol), tris (dibenzylideneacetone) dipalladium (0.055 g, 0.06 mmol), xanthophos (0.069 g, 0.12 mmol), sodium t-butoxy (0.43 g, 4.5 mmol), and anhydrous xylene (60 mL) were sequentially added, and the mixture was heated to reflux for 8 hours. After cooling the reaction solution to room temperature, insolubles were removed by filtration, and the organic solvent was distilled off under reduced pressure.
- intermediate C2 (2.02 g, 3.0 mmol), carbazole intermediate A8 (1.38 g, 3.0 mmol), tris (dibenzylideneacetone) dipalladium (0.055 g, 0.06 mmol), xanthphos (0.069 g, 0.12 mmol), sodium t-butoxy (0.43 g, 4.5 mmol), and anhydrous xylene (60 mL) were sequentially added, and the mixture was heated to reflux for 8 hours. After cooling the reaction solution to room temperature, insolubles were removed by filtration, and the organic solvent was distilled off under reduced pressure.
- 2-Amino-4′-chlorobenzophenone (23.17 g, 100 mmol) and urea (12.01 g, 200 mmol) were dissolved in 100 mL of acetic acid and heated to reflux for 8 hours. After cooling the reaction solution to room temperature, 200 mL of water was added, and the precipitated solid was collected by filtration, washed with water and methanol, and dried under reduced pressure. To this, 200 mL of phosphoryl chloride was added and heated to reflux for 3 hours. After cooling the reaction solution to room temperature, the reaction solution was poured into ice water and extracted with methylene chloride. The organic layer was washed with water and dried over magnesium sulfate, and the organic solvent was distilled off under reduced pressure.
- the obtained residue was purified by silica gel column chromatography to obtain quinazoline intermediate B4 (20.6 g, yield 75%). Under an argon atmosphere, add bicarbazolyl intermediate A1 (8.58 g, 21.0 mmol), quinazoline intermediate B4 (5.50 g, 20.0 mmol), potassium carbonate (2.76 g, 20.0 mmol) to 20 mL of dry DMF, The mixture was heated and stirred at 0 ° C. for 8 hours. After cooling the reaction solution to room temperature, 10 mL of water was added, and the precipitated solid was collected by filtration, washed with water and methanol, and dried under reduced pressure.
- intermediate C6 (9.06 g, yield 70%).
- intermediate C6 (1.94 g, 3.0 mmol)
- tricarbazolyl intermediate A3 (1.95 g, 3.0 mmol)
- tris dibenzylideneacetone
- dipalladium 0.055 g, 0.06 mmol
- xanthphos 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene
- t-butoxy sodium (0.43 g, 4.5 mmol
- anhydrous xylene 60 mL
- 2-Amino-5-chlorobenzophenone (23.17 g, 100 mmol) and urea (12.01 g, 200 mmol) were dissolved in 100 mL of acetic acid and heated to reflux for 8 hours. After cooling the reaction solution to room temperature, 200 mL of water was added, and the precipitated solid was collected by filtration, washed with water and methanol, and dried under reduced pressure. To this, 200 mL of phosphoryl chloride was added and heated to reflux for 3 hours. After cooling the reaction solution to room temperature, the reaction solution was poured into ice water and extracted with methylene chloride. The organic layer was washed with water and dried over magnesium sulfate, and the organic solvent was distilled off under reduced pressure.
- the obtained residue was purified by silica gel column chromatography to obtain quinazoline intermediate B5 (19.3 g, yield 70%). Under an argon atmosphere, add bicarbazolyl intermediate A1 (8.58 g, 21.0 mmol), quinazoline intermediate B5 (5.50 g, 20.0 mmol), potassium carbonate (2.76 g, 20.0 mmol) to 20 mL dry DMF, The mixture was heated and stirred at 0 ° C. for 8 hours. After cooling the reaction solution to room temperature, 10 mL of water was added, and the precipitated solid was collected by filtration, washed with water and methanol, and dried under reduced pressure.
- intermediate C9 (3.01 g, yield 87%) was obtained.
- intermediate C9 (2.07 g, 3.0 mmol)
- intermediate A2 (1.23 g, 3.0 mmol)
- tris (dibenzylideneacetone) dipalladium (0.055 g, 0.06 mmol)
- xanthphos 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene) (0.069 g, 0.12 mmol)
- sodium t-butoxy (0.43 g, 4.5 mmol
- anhydrous xylene 60 mL
- intermediate C10 (2.94 g, yield 85%) was obtained.
- intermediate C2 (2.07 g, 3.0 mmol)
- intermediate A2 (1.23 g, 3.0 mmol)
- tris dibenzylideneacetone) dipalladium (0.055 g, 0.06 mmol)
- xanthphos 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene
- sodium t-butoxy (0.43 g, 4.5 mmol
- anhydrous xylene 60 mL
- intermediate C9 (2.07 g, 3.0 mmol), intermediate A3 (1.94 g, 3.0 mmol), tris (dibenzylideneacetone) dipalladium (0.055 g, 0.06 mmol), xanthphos ( 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene) (0.069 g, 0.12 mmol), sodium t-butoxy (0.43 g, 4.5 mmol), and anhydrous xylene (60 mL) were sequentially added. And heated at reflux for 8 hours. After cooling the reaction solution to room temperature, insolubles were removed by filtration, and the organic solvent was distilled off under reduced pressure.
- intermediate C11 (2.80 g, 3.0 mmol), intermediate A1 (1.23 g, 3.0 mmol), tris (dibenzylideneacetone) dipalladium (0.055 g, 0.06 mmol), xanthphos ( 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene) (0.069 g, 0.12 mmol), sodium t-butoxy (0.43 g, 4.5 mmol), and anhydrous xylene (60 mL) were sequentially added. And heated at reflux for 8 hours. After cooling the reaction solution to room temperature, insolubles were removed by filtration, and the organic solvent was distilled off under reduced pressure.
- intermediate C9 (2.07 g, 3.0 mmol), intermediate A5 (0.85 g, 3.0 mmol), tris (dibenzylideneacetone) dipalladium (0.055 g, 0.06 mmol), xanthphos ( 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene) (0.069 g, 0.12 mmol), sodium t-butoxy (0.43 g, 4.5 mmol), and anhydrous xylene (60 mL) were sequentially added. And heated at reflux for 8 hours. After cooling the reaction solution to room temperature, insolubles were removed by filtration, and the organic solvent was distilled off under reduced pressure.
- Example 1 (Washing the substrate) A glass substrate with an ITO transparent electrode (manufactured by Geomat Co., Ltd.) having a size of 25 mm ⁇ 25 mm ⁇ thickness 1.1 mm was ultrasonically cleaned in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 5 minutes.
- CLEVIOUS AI4083 (trade name) manufactured by HERAEUS Co. was formed on the ITO substrate with a thickness of 30 nm by spin coating. After film formation, unnecessary portions were removed with acetone, and then baked on a hot plate at 200 ° C. in the atmosphere for 10 minutes to prepare a base substrate.
- the compound H-4 obtained in Synthesis Example 4 was used as the host material, the following compound D-1 was used as the dopant material, and the compound H-4: compound D-1 was mixed at a weight ratio of 90:10.
- a 1.6 mass% toluene solution was prepared. Using this toluene solution, it was applied and laminated on the base substrate by spin coating so as to have a film thickness of 50 nm. After the coating film formation, unnecessary portions were removed with toluene, and dried by heating on a hot plate at 150 ° C. to prepare a coated laminated substrate on which a light emitting layer was formed. Note that all operations for forming the light emitting layer were performed in a glove box in a nitrogen atmosphere.
- Example 2 An organic EL device was produced in the same manner as in Example 1 except that Compound D-2 was used as the dopant material. The measurement results are shown in Table 1.
- Comparative Example 1 An organic EL device was produced in the same manner as in Example 1 except that the following comparative compound Ha was used as the host material. The measurement results are shown in Table 1.
- Comparative Example 2 An organic EL device was produced in the same manner as in Example 2 except that the following comparative compound Ha was used as the host material. The measurement results are shown in Table 1.
- Example 3 The compound H-13 obtained in Synthesis Example 13 was used as the host material, the following compound D-1 was used as the dopant material, and the compound H-13: compound D-1 was 1 in a mixing ratio of 95: 5 by weight.
- a device EL device was produced in the same manner as in Example 1 except that a 6 wt% toluene solution was prepared. The measurement results are shown in Table 1.
- Comparative Example 3 An organic EL device was produced in the same manner as in Example 3 except that the compound Q-1 described in WO2012 / 086170 was used as the host material. The measurement results are shown in Table 1.
- Comparative Example 4 An organic EL device was produced in the same manner as in Example 3 except that the compound Q-2 described in WO2012 / 086170 was used as the host material. The measurement results are shown in Table 1.
- compounds in which A 1 and A 2 in formula (1) are different that is, compounds having various skeletons can be produced easily and with high yield.
- a compound that can be applied to an organic EL device using different dopants that is, different emission characteristics
- a compound in which the groups corresponding to A 1 and A 2 in the formula (1) are the same that is, a compound in which a plurality of the same biscarbazole-containing groups are substituted on the nitrogen-containing heterocyclic ring (for example, comparative compounds Ha, Q-1, In Q-2), it is difficult to obtain the above effect.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
- Plural Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
ホスト/ドーパント発光層では、ホストに注入された電荷から効率よく励起子を生成することができる。そして、生成された励起子のエネルギーをドーパントに移動させ、ドーパントから高効率の発光を得ることができる。
特に、大型の有機ELディスプレイ、照明パネルなどの製造には塗布法による層形成が適用され得るため、塗布法に用いることができる有機EL素子用材料の開発が望まれている。
特許文献9には、ビスカルバゾール含有基で置換された縮合含窒素環を有する化合物が記載されているが、ビスカルバゾール含有基を複数有する縮合含窒素環化合物は記載されていない。又、塗布法による層形成に関しても何ら記載されていない。
特許文献10には、非縮合又は縮合含窒素環にビスカルバゾールまたはトリカルバゾール含有基が複数置換した化合物が、有機EL素子に適用できることが検証されている。そして、その一部の化合物は溶媒に可溶であり、塗布法により層形成して有機EL素子を形成している。しかしながら、塗布法により層形成して有機EL素子に適用された化合物は、全て、非縮合含窒素環に置換する複数のビスカルバゾール含有基が、それぞれ同じ構造のものに留まっている。従って、特許文献10で検証された化合物の特性は、同一構造の複数のビスカルバゾール含有基と非縮合含窒素環とを組み合わせた範囲内に限定され、有機EL素子の多様な要求特性に応えるには不十分であった。
*a及び*bの一方は炭素原子*c1に結合し、他方は炭素原子*c2に結合し、
R1は水素原子又は置換基を表し、
X1はN又はCR2を表し、R2は水素原子又は置換基を表し、R2はR1に結合して環を形成してもよく、
*bが炭素原子*c2に結合し、X1がCR2を表し、かつ、R2がR1に結合して環を形成する場合、-R1-R2-は-Xa=Xb-Xc=Xd-を表し、
Xa~Xdは、それぞれ独立して、N又はCRaを表し、Raは水素原子又は置換基を表し、隣接する2個のRaは互いに結合して環を形成してもよく、
L1は連結基を表し、
L2は2価の連結基を表し、
nは0~3の整数を表し、nが0の場合、L2は単結合を表し、
A1及びA2は互いに異なり、下記式(2)、(2’)、(3)、(3’)、(3’’)、及び(4)のいずれかで表される基である。
*2は式(1)の炭素原子*c1、炭素原子*c2、L1(nが0である場合)、又は、L2(nが1~3の整数である場合)に結合し、
X7~X11の1つは*3に結合する炭素原子であり、
X12~X16の1つは*4に結合する炭素原子であり、
他のX7~X11、他のX12~X16、X2~X6、及びX17~X21はそれぞれ独立にN又はCR3を表し、
R3は水素原子又は置換基を表し、複数のR3が互いに結合して環を形成してもよく、
X6とX11は互いに結合する炭素原子であってもよく、X16とX21は互いに結合する炭素原子であってもよく、
X22は、NR4、CR5R6、O、S、Se、又はSiR7R8を表し、
R4~R8はそれぞれ独立に水素原子又は置換基を表し、R5とR6又はR7とR8は互いに結合して環を形成してもよい。)
*2、X7~X11、X12~X16、X17~X21、及びX22は前記と同様であり、
X2’~X6’の1つは*3’に結合する炭素原子であり、
X12’~X16’の1つは*4’に結合する炭素原子であり、
他のX2’~X6’、他のX12’~X16’、及びX17’~X21’はそれぞれ独立にN又はCR3を表し、
R3は前記と同様であり、
X6’とX11は互いに結合する炭素原子であってもよく、X16とX21は互いに結合する炭素原子であってもよく、X16’とX21’は互いに結合する炭素原子であってもよく、
X22’は、NR4、CR5R6、O、S、Se、又はSiR7R8を表し、
R4~R8は前記と同様である。)
*5は式(1)の炭素原子*c1、炭素原子*c2、L1(nが0である場合)、又は、L2(nが1~3の整数である場合)に結合し、
X37~X41の1つは*6に結合する炭素原子であり、
他のX37~X41、X32~X36、及びX42~X51はそれぞれ独立にN又はCR9を表し、
R9は水素原子又は置換基を表し、複数のR9は互いに結合して環を形成してもよく、
X36とX41は互いに結合する炭素原子であってもよく、X46とX51は互いに結合する炭素原子であってもよい。)
*5、X37~X41、及びX42~X51は前記と同様であり、
X32’~X36’の1つは*6’に結合する炭素原子であり、
他のX32’~X36’及びX42’~X51’はそれぞれ独立にN又はCR9を表し、
R9は前記と同様であり、
X36’とX41は互いに結合する炭素原子であってもよく、X46とX51は互いに結合する炭素原子であってもよく、X46’とX51’は互いに結合する炭素原子であってもよい。)
*5、X37~X41、及びX42~X51は前記と同様であり、
X32’’~X36’’の1つは*3’’に結合する炭素原子であり、
X12’’~X16’’の1つは*4’’に結合する炭素原子であり、
他のX32’’~X36’’、他のX12’’~X16’’、及びX17’’~X21’’はそれぞれ独立にN又はCR3を表し、
R3は前記と同様であり、
X36’’とX41は互いに結合する炭素原子であってもよく、X46とX51は互いに結合する炭素原子であってもよく、X16’’とX21’’は互いに結合する炭素原子であってもよく、
X22’’は、NR4、CR5R6、O、S、Se、又はSiR7R8を表し、
R4~R8は前記と同様である。)
*7は式(1)の炭素原子*c1、炭素原子*c2、L1(nが0である場合)、又は、L2(nが1~3の整数である場合)に結合し、
X67~X71から選ばれる1つの隣接する対において、一方は*8に結合する炭素原子を表し、他方は*9に結合する炭素原子を表し、
他のX67~X71、X62~X66及びX72~X75はそれぞれ独立にNまたはCR10を表し、
R10は水素原子又は置換基を表し、複数のR10は互いに結合して環を形成してもよく、
X66とX71は互いに結合する炭素原子であってもよく、
X76は、NR11、CR12R13、O、S、Se、又はSiR14R15を表し、
R11~R15はそれぞれ独立に水素原子又は置換基を表し、R11とR12及びR13とR14は互いに結合して環を形成してもよい。))。
(1)前記カップリング反応1では、下記式(I)で表される化合物
*c及び*dの一方は炭素原子*c1に結合し、他方は炭素原子*c2に結合し、
Hal1及びHal2は同一又は異なるハロゲン原子を表す。)
と下記式(II)、(II’)、(III)、(III’)、(III’’)、及び(IV)のいずれかで表されるアミン化合物
を塩基性触媒の存在下、かつ、遷移金属触媒の不存在下で、有機溶媒中で反応させて下記式(V)で表される化合物
を合成し、
(2)前記カップリング反応2では、前記式(V)で表される化合物と前記式(II)、(II’)、(III)、(III’)、(III’’)、及び(IV)のいずれかで表されるアミン化合物(ただし、前記カップリング反応1で用いたアミン化合物とは異なる)を遷移金属触媒と配位子の存在下、かつ、塩基の存在下又は不存在下、有機溶媒中で反応させて、前記式(V)で表される化合物のHal2と前記アミン化合物の水素原子H*の脱離下に前記式(V)で表される化合物と前記アミン化合物をカップリングさせて、式(1)で表される化合物を合成する。
上記置換基の中でも、より好ましくは、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のアルキル基;置換もしくは無置換の環形成炭素数3~50、好ましくは3~10、より好ましくは3~8、さらに好ましくは5又は6のシクロアルキル基;置換もしくは無置換の環形成炭素数6~50、好ましくは6~25、より好ましくは6~18のアリール基;置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のアルキル基及び置換もしくは無置換の環形成炭素数6~50、好ましくは6~25、より好ましくは6~18のアリール基から選ばれる置換基を有するモノ置換又はジ置換アミノ基;置換もしくは無置換の環形成原子数5~50、好ましくは5~24、より好ましくは5~13のヘテロアリール基;ハロゲン原子;及びシアノ基である。
上記任意の置換基は、さらに上述の任意の置換基により置換されていてもよい。また、任意の置換基同士が結合して環を形成していてもよい。
R1が表す置換基は、ハロゲン原子、シアノ基、ニトロ基、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のアルキル基、置換もしくは無置換の環形成炭素数3~50、好ましくは3~10、より好ましくは3~8のシクロアルキル基、置換もしくは無置換の環形成炭素数6~60、好ましくは6~25、より好ましくは6~18のアリール基、環形成炭素数6~50、好ましくは6~25、より好ましくは6~18のアリール基を有する炭素数7~51、好ましくは7~30、より好ましくは7~20のアラルキル基、アミノ基、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のアルキル基及び置換もしくは無置換の環形成炭素数6~60、好ましくは6~25、より好ましくは6~18のアリール基から選ばれる置換基を有するモノ置換又はジ置換アミノ基、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のアルコキシ基、置換もしくは無置換の環形成炭素数3~50、好ましくは3~10、より好ましくは3~8のシクロアルコキシ基、置換もしくは無置換の環形成炭素数6~60、好ましくは6~25、より好ましくは6~18のアリールオキシ基、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のアルキルチオ基、置換もしくは無置換の環形成炭素数6~60、好ましくは6~25、より好ましくは6~18のアリールチオ基、シリル基、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のアルキル基及び置換もしくは無置換の環形成炭素数6~60、好ましくは6~25、より好ましくは6~18のアリール基から選ばれる置換基を有するモノ置換、ジ置換又はトリ置換シリル基、置換もしくは無置換の環形成原子数5~60、好ましくは5~30、より好ましくは5~26のヘテロアリール基、及び、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のハロアルキル基から選ばれる。
好ましくは、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、及びオクタデシル基であり、より好ましくはメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、及びオクチル基である。前記各基は、存在する場合には、異性体基を含む。
好ましくは、フェニル基、1-ナフチル基、2-ナフチル基、ビフェニリル基、ターフェニリル基、フェナントリル基、ベンゾフェナントリル基、フルオレニル基、9,9’-スピロビフルオレニル基、ベンゾフルオレニル基、ジベンゾフルオレニル基、クリセニル基、ベンゾクリセニル基、s-インダニル基、as-インダニル基、トリフェニレニル基、ベンゾトリフェニレニル基、アントリル基、9,9-ジメチルフルオレニル基、及び9,9-ジフェニルフルオレニル基であり、より好ましくは、フェニル基、ビフェニリル基、ターフェニリル基、1-ナフチル基、2-ナフチル基、フェナントリル基、フルオレニル基、9,9’-スピロビフルオレニル基、クリセニル基、トリフェニレニル基、9,9-ジメチルフルオレニル基、及び9,9-ジフェニルフルオレニル基である。
アルキル基の具体例、好ましい例及びより好ましい例、及び、アリール基の具体例、好ましい例及びより好ましい例は、上記アルキル基及びアリール基とそれぞれ同様である。
より具体的には、トリメチルシリル基、トリエチルシリル基、t-ブチルジメチルシリル基、プロピルジメチルシリル基、イソプロピルジメチルシリル基、トリフェニルシリル基、フェニルジメチルシリル基、t-ブチルジフェニルシリル基、及びトリトリルシリル基が挙げられ、好ましくはトリメチルシリル基、トリエチルシリル基、トリフェニルシリル基、及びフェニルジメチルシリル基であり、より好ましくはトリメチルシリル基、及びトリフェニルシリル基である。
該へテロアリール基としては、例えば、ピローリル基、フリル基、チエニル基、ピリジル基、ピリダジニル基、ピリミジニル基、ピラジニル基、トリアジニル基、イミダゾリル基、オキサゾリル基、チアゾリル基、ピラゾリル基、イソオキサゾリル基、イソチアゾリル基、オキサジアゾリル基、チアジアゾリル基、トリアゾーリル基、テトラゾリル基、インドリル基、イソインドリル基、ベンゾフラニル基、イソベンゾフラニル基、ベンゾチオフェニル基、イソベンゾチオフェニル基、インドリジニル基、キノリジニル基、キノリル基、イソキノリル基、シンノリル基、フタラジニル基、キナゾリニル基、キノキサリニル基、ベンゾイミダゾリル基、ベンゾオキサゾリル基、ベンゾチアゾリル基、インダゾリル基、ベンゾイソキサゾリル基、ベンゾイソチアゾリル基、ジベンゾフラニル基、ジベンゾチオフェニル基、カルバゾリル基、ビスカルバゾリル基、フェナントリジニル基、アクリジニル基、フェナントロリニル基、フェナジニル基、フェノチアジニル基、フェノキサジニル基、アザトリフェニレニル基、ジアザトリフェニレニル基、キサンテニル基、アザカルバゾリル基、アザジベンゾフラニル基、アザジベンゾチオフェニル基、ベンゾフラノベンゾチオフェニル基、ベンゾチエノベンゾチオフェニル基、ジベンゾフラノナフチル基、ジベンゾチエノナフチル基、ジナフトチエノチオフェニル基、及びジナフト[2’,3’:2,3:2’,3’:6,7]カルバゾリル基が挙げられる。
好ましくは、ピリジル基、ピリダジニル基、ピリミジニル基、ピラジニル基、トリアジニル基、イミダゾリル基、インドリル基、イソインドリル基、ベンゾフラニル基、イソベンゾフラニル基、ベンゾチオフェニル基、イソベンゾチオフェニル基、インドリジニル基、キノリジニル基、キノリル基、イソキノリル基、キナゾリニル基、キノキサリニル基、ベンズイミダゾリル基、ベンズオキサゾリル基、ベンズチアゾリル基、ベンズイソキサゾリル基、ベンズイソチアゾリル基、ジベンゾフラニル基、ジベンゾチオフェニル基、カルバゾリル基、ビカルバゾリル基、フェナントリジニル基、アクリジニル基、フェナントロリニル基、アザトリフェニレニル基、ジアザトリフェニレニル基、キサンテニル基、アザカルバゾリル基、アザジベンゾフラニル基、及びアザジベンゾチオフェニル基であり、より好ましくは、ピリジル基、ピリミジニル基、トリアジニル基、ベンゾフラニル基、イソベンゾフラニル基、キノリル基、イソキノリル基、キナゾリニル基、ベンゾチオフェニル基、イソベンゾチオフェニル基、インドリジニル基、ジベンゾフラニル基、ジベンゾチオフェニル基、カルバゾリル基、ビカルバゾリル基、アザトリフェニレニル基、ジアザトリフェニレニル基、キサンテニル基、アザカルバゾリル基、アザジベンゾフラニル基、及びアザジベンゾチオフェニル基である。
R2は水素原子又は置換基を表し、R2はR1と結合して環を形成してもよい。
R2が表す置換基、その具体例、好ましい例、及びより好ましい例は、R1に関して記載した置換基、その具体例、好ましい例、及びより好ましい例から選択される。
R2は、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロアリール基であることが好ましく、水素原子、置換もしくは無置換のアルキル基、又は、置換もしくは無置換のアリール基であることがより好ましく、水素原子であることが特に好ましい。
Raが表す置換基、その具体例、好ましい例、及びより好ましい例は、R1に関して記載した置換基、その具体例、好ましい例、及びより好ましい例から選択される。
該アリーレン基は、R1に関して記載したアリール基の具体例、好ましい例及びより好ましい例から1個の水素原子を除くことによって得られるアリーレン基から選ばれ、フェニレン基が好ましく、m-フェニレン基及びp-フェニレン基が特に好ましい。
L2(nが1~3の整数の場合)又はA2(nが0でありL2が単結合を表す場合)が環Aに結合する位置は特に限定されない。
上記アルキレン基、シクロアルキレン基、アリーレン基、及びヘテロアリーレン基の具体例、好ましい例及びより好ましい例は、R1に関して記載したアルキル基、シクロアルキル基、アリール基、及びヘテロアリール基の具体例、好ましい例及びより好ましい例から1個の水素原子を除くことにより得られる基である。
L1は、好ましくは前記置換もしくは無置換の炭素数1~50のアルキレン基又は前記置換もしくは無置換の環形成炭素数6~60のアリーレン基であり、より好ましくは前記置換もしくは無置換の環形成炭素数6~60のアリーレン基、さらに好ましくはフェニレン基、特に好ましくはm-フェニレン基又はp-フェニレン基である。
上記アルキレン基、シクロアルキレン基、アリーレン基、及びヘテロアリーレン基の具体例、好ましい例及びより好ましい例は、R1に関して記載したアルキル基、シクロアルキル基、アリール基、及びヘテロアリール基の具体例、好ましい例及びより好ましい例から1個の水素原子を除くことにより得られる基である。
L2は、好ましくは単結合、前記置換もしくは無置換の炭素数1~50のアルキレン基又は前記置換もしくは無置換の環形成炭素数6~60のアリーレン基であり、より好ましくは前記置換もしくは無置換の環形成炭素数6~60のアリーレン基、さらに好ましくはフェニレン基、特に好ましくはm-フェニレン基又はp-フェニレン基である。
nが1である場合、L1とL2は同一でも異なっていてもよく、L1とL2は互いに架橋されていてもよい。例えば、L1が置換もしくは無置換の環形成炭素数6~50のアリーレン基であり、かつ、nが1である場合、L1とL2は同一でも異なっていてもよく、L1とL2は互いに架橋されていてもよい。
nが2又は3である場合、L1と2又は3個のL2は同一でも異なっていてもよく、L1とL2及び2個のL2は、互いに架橋されていてもよい。例えば、L1が置換もしくは無置換の環形成炭素数6~50のアリーレン基であり、かつ、nが2又は3である場合、L1と2又は3個のL2は同一でも異なっていてもよく、L1とL2及び2個のL2は、互いに架橋されていてもよい。
架橋基としては、メチレン基、ジメチルメチレン基、ジフェニルメチレン基、イミノ基(>NH)、フェニルイミノ基、-O-、-S-などが挙げられる。
X7~X11の1つは*3に結合する炭素原子であり、
X12~X16の1つは*4に結合する炭素原子であり、
他のX7~X11、他のX12~X16、X2~X6、及びX17~X21はそれぞれ独立にN又はCR3、好ましくはCR3を表す。X6とX11は互いに結合する炭素原子であることが好ましく、X16とX21は互いに結合する炭素原子であることが好ましい。
R3は水素原子又は置換基を表し、複数のR3は互いに結合して環を形成してもよい。
R3が表す置換基、その具体例、好ましい例、及びより好ましい例は、R1に関して記載した置換基、その具体例、好ましい例、及びより好ましい例から選択される。
R3は好ましくは水素原子である。
R4~R8はそれぞれ独立に水素原子又は置換基を表す。R5とR6又はR7とR8は互いに結合して環を形成してもよい。
R4~R8が表す置換基は、ハロゲン原子、シアノ基、ニトロ基、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のアルキル基、置換もしくは無置換の環形成炭素数3~50、好ましくは3~10、より好ましくは3~8のシクロアルキル基、置換もしくは無置換の環形成炭素数6~60、好ましくは6~25、より好ましくは6~18のアリール基、環形成炭素数6~50、好ましくは6~25、より好ましくは6~18のアリール基を有する炭素数7~51、好ましくは7~30、より好ましくは7~20のアラルキル基、アミノ基、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のアルキル基及び置換もしくは無置換の環形成炭素数6~60、好ましくは6~25、より好ましくは6~18のアリール基から選ばれる置換基を有するモノ置換又はジ置換アミノ基、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のアルコキシ基、置換もしくは無置換の環形成炭素数3~50、好ましくは3~10、より好ましくは3~8のシクロアルコキシ基、置換もしくは無置換の環形成炭素数6~60、好ましくは6~25、より好ましくは6~18のアリールオキシ基、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のアルキルチオ基、置換もしくは無置換の環形成炭素数6~60、好ましくは6~25、より好ましくは6~18のアリールチオ基、シリル基、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のアルキル基及び置換もしくは無置換の環形成炭素数6~60、好ましくは6~25、より好ましくは6~18のアリール基から選ばれる置換基を有するモノ置換、ジ置換又はトリ置換シリル基、置換もしくは無置換の環形成原子数5~60、好ましくは5~30、より好ましくは5~26のヘテロアリール基、及び、置換もしくは無置換の炭素数1~50、好ましくは1~18、より好ましくは1~8のハロアルキル基から選ばれる。
R4~R8が表す置換基の具体例、好ましい例、及びより好ましい例は、R1に関して記載した置換基の具体例、好ましい例、及びより好ましい例から選択される。
X22はイミノ基(>NH)、フェニルイミノ基、メチレン基、ジメチルメチレン基、ジフェニルメチレン基、9,9-ジメチルフルオレニルイミノ基、ビフェニルイミノ基、ナフチルイミノ基、-O-、-S-、-Se-、シリレン(>SiH2)、又はジメチルシリレン基であることが好ましく、イミノ基、フェニルイミノ基、ジメチルメチレン基、9,9-ジメチルフルオレニルイミノ基、ビフェニルイミノ基、ナフチルイミノ基、-O-、又は-S-であることがより好ましい。
*2、X7~X11、X12~X16、X17~X21、及びX22は式(2)で定義したとおりであり、
X2’~X6’の1つは*3’に結合する炭素原子であり、
X12’~X16’の1つは*4’に結合する炭素原子であり、
他のX2’~X6’、他のX12’~X16’、及びX17’~X21’はそれぞれ独立にN又はCR3、好ましくはCR3を表す。X6’とX11は互いに結合する炭素原子であることが好ましく、X16とX21は互いに結合する炭素原子であることが好ましく、X16’とX21’は互いに結合する炭素原子であることが好ましい。
R3は式(2)で定義したとおりであり、好ましくは水素原子である。
X22’は、NR4、CR5R6、O、S、Se、又はSiR7R8を表す。
R4~R8は式(2)で定義したとおりである。
X37~X41の1つは*6に結合する炭素原子であり、
他のX37~X41、X32~X36、及びX42~X51はそれぞれ独立にN又はCR9、好ましくはCR9を表す。X36とX41は互いに結合する炭素原子であることが好ましく、X46とX51は互いに結合する炭素原子であることが好ましい。
R9は水素原子又は置換基を表し複数のR9は互いに結合して環を形成してもよい。
R9が表す置換基、その具体例、好ましい例、及びより好ましい例は、R1に関して記載した置換基、その具体例、好ましい例、及びより好ましい例から選択される。
複数のR9が互いに結合して形成する環は、R1に関して記載したものと同様である。
R9は好ましくは水素原子である。
*5、X37~X41、及びX42~X51は式(3)で定義したとおりであり、
X32’~X36’の1つは*6’に結合する炭素原子であり、
他のX32’~X36’及びX42’~X51’はそれぞれ独立にN又はCR9を表す。
R9は式(3)で定義したとおりであり、好ましくは水素原子である。
X36’とX41は互いに結合する炭素原子であることが好ましく、X46とX51は互いに結合する炭素原子であることが好ましく、X46’とX51’は互いに結合する炭素原子であることが好ましい。
*5、X37~X41、及びX42~X51式(3)で定義したとおりであり、
X32’’~X36’’の1つは*3’’に結合する炭素原子であり、
X12’’~X16’’の1つは*4’’に結合する炭素原子であり、
他のX12’’~X16’’及びX17’’~X21’’はそれぞれ独立にN又はCR3、好ましくはCR3を表す。他のX32’’~X36’’はN又はCR9、好ましくはCR9を表す。
R3は式(2)で定義したとおりであり、好ましくは水素原子である。R9は式(3)で定義したとおりであり、好ましくは水素原子である。
X36’’とX41は互いに結合する炭素原子であることが好ましく、X46とX51は互いに結合する炭素原子であることが好ましく、X16’’とX21’’は互いに結合する炭素原子であることが好ましい。
X22’’は、NR4、CR5R6、O、S、Se、又はSiR7R8を表し、
R4~R8は式(2)で定義したとおりである。
X67~X71から選ばれる1つの隣接する対において、一方は*8に結合する炭素原子を表し、他方は*9に結合する炭素原子を表す。
他のX67~X71、X62~X66及びX72~X75はそれぞれ独立にN又はCR10、好ましくはCR10を表す。X66とX71は互いに結合する炭素原子であることが好ましい。
R10は水素原子又は置換基を表し、複数のR10は互いに結合して環を形成してもよい。
R10が表す置換基、その具体例、好ましい例、及びより好ましい例は、R1に関して記載した置換基、その具体例、好ましい例、及びより好ましい例から選択される。
複数のR10が互いに結合して形成する環は、R1に関して記載したものと同様である。
R10は好ましくは水素原子である。
R11~R15はそれぞれ独立に水素原子又は置換基を表す。R12とR13又はR14とR15は互いに結合して環を形成してもよい。
R11~R15が表す置換基、その具体例、好ましい例、及びより好ましい例は、R4~R8に関して記載した置換基、その具体例、好ましい例、及びより好ましい例から選択される。
X76は、イミノ基(>NH)、フェニルイミノ基、メチレン基、ジメチルメチレン基、ジフェニルメチレン基、-O-、-S-、-Se-、シリレン(>SiH2)、又はジメチルシリレン基であることが好ましく、イミノ基、フェニルイミノ基、ジメチルメチレン基、-O-、又は-S-であることがより好ましい。
(1)A1とA2の一方が式(2)、(2’)、(3)、(3’)、(3’’)、及び(4)のいずれか1つの式から選ばれ、他方が残りの式から選ばれる。
(2)A1とA2が共に式(2)から選ばれ、
(2a)*3と*4の少なくとも一方の結合位置が異なる、
(2b)X2~X21の少なくとも1つが異なる、又は
(2c)X22が異なる。
(3)A1とA2が共に式(2’)から選ばれ、
(3a)*3、*3’、*4及び*4’の少なくとも1つの結合位置が異なる、
(3b)X7~X21、X2’~X6’、及びX12’~X21’の少なくとも1つが異なる、又は
(3c)X22及びX22’の少なくとも一方が異なる。
(4)A1とA2が共に式(3)から選ばれ、
(4a)*6の結合位置が異なる、又は
(4b)X32~X51の少なくとも1つが異なる。
(5)A1とA2が共に式(3’)から選ばれ、
(5a)*6及び*6’の少なくとも一方の結合位置が異なる、又は
(5b)X37~X51、X32’~X36’、及びX42’~X51’の少なくとも1つが異なる。
(6)A1とA2が共に式(3’’)から選ばれ、
(6a)*6、*3’’及び*4’’の少なくとも一方の結合位置が異なる、
(6b)X37~X51、X32’’~X36’’、及びX12’’~X21’’の少なくとも1つが異なる、又は
(6c)X22’’が異なる。
(7)A1とA2が共に式(4)から選ばれ、
(7a)*8と*9の少なくとも一方の結合位置が異なる、
(7b)X62~X75の少なくとも1つが異なる、又は
(7c)X76が異なる。
A1とA2は(1)、(2a)、(2c)、(3a)、(3c)、(4a)、(5a)、(6a)、(6c)、(7a)、又は(7c)により異なることが好ましく、(1)、(2a)、(3a)、(4a)、(5a)、(6a)、又は(7a)により異なることがより好ましい。
通常、2つの活性部位を有する出発化合物の1つの活性部位に第1の置換基を導入し、他方の活性部位に第1の置換基とは異なる第2の置換基を導入する場合、2つの活性部位の双方に第1の置換基が導入されないように反応を制御する必要がある。
例えば、ハロゲン化アリールとアミンのカップリングに汎用されているウルマン反応やブッフバルト反応では、2つの活性部位の双方に第1の置換基が導入されないように反応を制御することが難しく、2つの活性部位に異なる置換基がそれぞれ導入された化合物を簡便かつ収率良く得ることは難しかった。
では、特定の反応条件において、Hal2のアミン化合物及びカルバゾール化合物に対する反応活性がHal1のそれより著しく低く、Hal1が結合する炭素原子のみに第1の置換基を選択的に導入できることを見出した。この知見に基づいて、本発明者等は、(1)前記特定の反応条件において、Hal1が結合する炭素原子のみに第1の置換基を選択的に導入し、次いで、(2)Hal2のアミン化合物及びカルバゾール化合物に対する反応活性が高くなる条件、例えば、ブッフバルト反応の条件で第1の置換基とは異なる第2の置換基をHal2が結合する炭素原子に導入することにより、異なる置換基が導入された化合物を収率良く合成出来ることを見出した。
第1の反応
第1の反応では、下記式(I)で表される化合物(化合物(I)と記載することもある)
*c及び*dの一方は炭素原子*c1に結合し、他方は炭素原子*c2に結合し、
Hal1及びHal2は同一又は異なるハロゲン原子を表し、フッ素、塩素、臭素、及びヨウ素から選ばれる、
nが0である場合、L1は1個、又は、同一又は異なる複数のハロゲン原子で置換されていてもよく、
nが1~3の整数である場合、L2は1個、又は、同一又は異なる複数のハロゲン原子で置換されていてもよい。)
と下記式(II)、(II’)、(III)、(III’)、(III’’)、及び(IV)のいずれかで表されるアミン化合物を反応させる。
塩基性触媒は、式(II)、(II’)、(III)、(III’)、(III’’)、及び(IV)のH*の引き抜きを触媒するが、ハロゲン化芳香族炭素原子に対する求核性が低い触媒であることが好ましい。そのような塩基性触媒としては、K2CO3、Na2Co3等のアルカリ金属炭酸塩類;KHCO3、NaHCO3等のアルカリ金属炭酸水素塩類;CaCO3、CsCO3等のアルカリ土類金属炭酸塩類;K3PO4等の金属りん酸塩類;KH,NaH,LiH等のアルカリ金属ヒドリド類;LDA(リチウムジイソプロピルアミド)等の金属アミド類等が挙げられるが、特にK2CO3、Na2CO3,CaCO3、CsCO3、KH,NaH,LiH、LDA等が好ましい。
第1の反応に使用する有機溶媒は、上記の塩基性触媒と反応しない溶媒であれば制限はないが、例えば、ジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン等アミド系溶媒、ジメチルスルホキシドなどの非プロトン性極性有機溶媒が塩基性触媒の溶解性の点から好ましい。さらには非プロトン性極性有機溶媒とベンゼン、トルエン、キシレン等の芳香族溶媒とを混合して用いても良い。
反応温度は室温~200℃が好ましい。反応時間は使用する化合物(I)、アミン化合物、塩基性触媒の種類、使用量などにより異なるが、通常1~24時間である。
また、第1の反応をパラジウム、銅、白金、ロジウム、ルテニウム、ニッケル、鉄等の遷移金属触媒の存在下で行うと、式(I)のHal2の反応活性が高くなり、Hal1が結合する炭素原子だけでなく、Hal2が結合する炭素原子にも前記アミン化合物(II)、(II’)、(III)、(III’)、(III’’)、及び(IV)が導入されてしまう場合がある。従って、第1の反応は遷移金属触媒の不存在下で行うことが望ましい。
例えば、第1の反応をPd2(dba)3(トリス(ジベンジリデンアセトン)ジパラジウム(0))等の遷移金属触媒及びtBuONa(ナトリウムt-ブトキシド)等の強塩基の存在下で行うと、Hal1、Hal2双方のハロゲン原子がカルバゾール化合物で置換された化合物、一方のハロゲン原子がカルバゾール化合物で置換され、他方のハロゲン原子がtBuOで置換された化合物、一方のハロゲン原子がtBuOで置換された化合物などが副成し、分離、精製操作が煩雑になるだけでなく、式(V)で表される目的化合物を工業的実施に十分な程度の収率で得ることが出来ない。
第2の反応では、化合物(V)と前記式(II)、(II’)、(III)、(III’)、(III’’)、及び(IV)のいずれかで表されるアミン化合物、ただし、第1の反応で用いたアミン化合物とは異なる、を反応させて前記化合物(1)を合成する。
すなわち、第2の反応は、パラジウム、銅、白金、ロジウム、ルテニウム、ニッケル、鉄等から選ばれる遷移金属触媒と、モノホスフィン類、ジホスフィン類、ジアミン類、ピリジン類、キノリン類等の配位子と、また必要に応じてアルコキシド類、炭酸塩類、燐酸塩類等の塩基の存在下、有機溶媒中で行う。
ブッフバルト反応の場合、パラジウム触媒としては、Pd2(dba)3(トリス(ジベンジリデンアセトン)ジパラジウム(0))、Pd(OAc)2(酢酸パラジウム)等が通常用いられる。配位子としては、各種ホスフィン類が主に用いられ、例えばP(oTol)3(トリ(オルトトリル)ホスフィン)、PtBu3(トリ(t-ブチル)ホスフィン)、BINAP(ビス(ジフェニルホスフィノ)-1,1’-ビナフチル),DPPF(ビス(ジフェニルホスフィノ)フェロセン),XantPhos(4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン)、DPEPhos(オキシジ-2,1-フェニレン)ビス(ジフェニルホスフィン)、JhonPhos(2-(ジターシャリーブチルホスフィノ)ビフェニル)、DavePhos(2-ジシクロヘキシルホスフィノー2’-(N,N-ジメチルアミノ)ビフェニル)、X-Phos(2-ジシクロヘキシルホスフィノ-2’,4’、6’-トリイソプロピルビフェニル)、AmPhos(N,N-ジメチル-4-(ジターシャリーブチルホスフィノ)アニリン)等が好適に用いることができる。また、あらかじめパラジウムにホスフィンが配位した錯体、例えばPdCl2(P(oTol)3)2、PdCl2(dppf)等も好ましく用いることができる。塩基としてはtBuONa(ナトリウムターシャリーブトキシド)等の強塩基性のアルコキド類が最も好ましく用いられるが、強塩基と反応しやすい官能基が存在する場合等にはCsCO3、K3PO4等の弱塩基を用いることも可能である。
ウルマン反応の場合、銅触媒としては、銅金属、塩化第一銅、臭化第一銅、沃化第一銅、酸化第一銅、酸化第二銅等が用いられ、配位子としては、テトラメチルエチレンジアミン、1,2-ビスジメチルアミノシクロヘキサン等のジアミン類、ピリジン類、キノリン類等が好適に用いられる。
いずれの反応に於いても有機溶媒としては一般的にはベンゼン、トルエン、キシレン、メシチレン等の芳香族炭化水素溶媒が好適に用いられるが、テトラヒドロフラン、1,2-ジメトキシエタン、1,4-ジオキサン、アニソール等のエーテル系溶媒、ジメチルホルムアミド、ジメチルアセトアミド等のアミド系溶媒も単独または共溶媒として用いることができる。
有機EL素子においては、例えば、蒸着法や塗布法などの層形成方法の違い、蛍光発光層、燐光発光層、電子輸送層、正孔輸送層などの材料が使用される層の違い、発光層であっても発光色の違いなどにより、材料に求められる特性は異なる。化合物(1)はこのような多様な特性要求に応え得る化合物であり、上記製造方法によれば化合物(1)をより簡便な方法で高収率で提供することができる。
次に、本発明の一態様の有機EL素子について説明する。
有機EL素子は、陰極と陽極の間に一層以上の有機薄膜層を有する。この有機薄膜層は発光層を含み、有機薄膜層の少なくとも1層が前記式(1)で表される化合物(化合物(1))を含む。
前記化合物(1)が含まれる有機薄膜層の例としては、陽極と発光層との間に設けられる陽極側有機薄膜層(正孔輸送層、正孔注入層等)、発光層、陰極と発光層との間に設けられる陰極側有機薄膜層(電子輸送層、電子注入層等)、スペース層、障壁層等が挙げられるが、これらに限定されるものではない。前記化合物(1)は、上記いずれの層に含まれていてもよく、例えば、蛍光発光ユニットの発光層におけるホスト材料やドーパント材料、燐光発光ユニットの発光層におけるホスト材料、発光ユニットの正孔輸送層材料、電子輸送層材料等として用いることができる。
(1)陽極/発光ユニット/陰極
また、上記発光ユニットは、燐光発光層や蛍光発光層を複数有する積層型であってもよく、その場合、各発光層の間に、燐光発光層で生成された励起子が蛍光発光層に拡散することを防ぐ目的で、スペース層を有していてもよい。発光ユニットの代表的な層構成を以下に示す。
(a)正孔輸送層/発光層(/電子輸送層)
(b)正孔輸送層/第一燐光発光層/第二燐光発光層(/電子輸送層)
(c)正孔輸送層/燐光発光層/スペース層/蛍光発光層(/電子輸送層)
(d)正孔輸送層/第一燐光発光層/第二燐光発光層/スペース層/蛍光発光層(/電子輸送層)
(e)正孔輸送層/第一燐光発光層/スペース層/第二燐光発光層/スペース層/蛍光発光層(/電子輸送層)
(f)正孔輸送層/燐光発光層/スペース層/第一蛍光発光層/第二蛍光発光層(/電子輸送層)
(g)正孔輸送層/電子障壁層/発光層(/電子輸送層)
(h)正孔輸送層/発光層/正孔障壁層(/電子輸送層)
(i)正孔輸送層/蛍光発光層/トリプレット障壁層(/電子輸送層)
なお、各発光層と正孔輸送層あるいはスペース層との間には、適宜、電子障壁層を設けてもよい。また、各発光層と電子輸送層との間には、適宜、正孔障壁層を設けてもよい。電子障壁層や正孔障壁層を設けることで、電子又は正孔を発光層内に閉じ込めて、発光層における電荷の再結合確率を高め、発光効率を向上させることができる。
(2)陽極/第一発光ユニット/中間層/第二発光ユニット/陰極
ここで、上記第一発光ユニット及び第二発光ユニットとしては、例えば、それぞれ独立に上述の発光ユニットと同様のものを選択することができる。
上記中間層は、一般的に、中間電極、中間導電層、電荷発生層、電子引抜層、接続層、中間絶縁層とも呼ばれ、第一発光ユニットに電子を、第二発光ユニットに正孔を供給する、公知の材料構成を用いることができる。
本発明の一態様において、有機EL素子は透光性基板上に作製する。透光性基板は有機EL素子を支持する基板であり、400nm~700nmの可視領域の光の透過率が50%以上で平滑な基板が好ましい。具体的には、ガラス板、ポリマー板等が挙げられる。ガラス板としては、特にソーダ石灰ガラス、バリウム・ストロンチウム含有ガラス、鉛ガラス、アルミノケイ酸ガラス、ホウケイ酸ガラス、バリウムホウケイ酸ガラス、石英等を原料として用いてなるものを挙げられる。またポリマー板としては、ポリカーボネート、アクリル、ポリエチレンテレフタレート、ポリエーテルサルファイド、ポリサルフォン等を原料として用いてなるものを挙げることができる。
また、可撓性基板を用いてもよい。可撓性基板とは、折り曲げることができる(フレキシブル)基板のことであり、例えば、ポリカーボネート、ポリ塩化ビニルからなるプラスチック基板等が挙げられる。
基板上に形成される陽極は、正孔を正孔輸送層又は発光層に注入する役割を担うものであり、4.0eV以上、好ましくは4.5eV以上の仕事関数を有する金属、合金、電気伝導性化合物、およびこれらの混合物などを用いることが効果的である。陽極材料の具体例としては、酸化インジウム錫合金(ITO)、珪素若しくは酸化珪素を含有する酸化インジウム錫合金、酸化錫(NESA)、酸化インジウム亜鉛酸化物、酸化タングステン、グラフェン、金、銀、白金、銅、金属の窒化物(例えば、窒化チタン)等が挙げられる。陽極はこれらの電極物質を蒸着法やスパッタリング法等の方法で薄膜を形成させることにより作製することができる。発光層からの発光を陽極から取り出す場合、陽極の可視領域の光の透過率を10%より大きくすることが好ましい。また、陽極のシート抵抗は、数百Ω/□以下が好ましい。陽極の膜厚は、材料にもよるが、通常10nm~1μm、好ましくは10nm~200nmの範囲で選択される。
陰極は電子注入層、電子輸送層又は発光層に電子を注入する役割を担うものであり、仕事関数の小さい(具体的には3.8eV以下)材料、例えば、金属、合金、電気伝導性化合物、およびこれらの混合物により形成するのが好ましい。陰極材料は特に限定されないが、具体的には、元素周期表の第1族または第2族に属する元素、すなわちリチウムやセシウム等のアルカリ金属、マグネシウム等のアルカリ土類金属、希土類金属等の金属、及びこれらの金属を含む合金など、例えば、インジウム、アルミニウム、マグネシウム、マグネシウム-インジウム合金、マグネシウム-アルミニウム合金、アルミニウム-リチウム合金、アルミニウム-スカンジウム-リチウム合金、マグネシウム-銀合金等が使用できる。陰極も、陽極と同様に、蒸着法やスパッタリング法等の方法で薄膜を形成させることにより作製することができる。また、必要に応じて、陰極側から発光を取り出してもよい。
発光機能を有する有機層であって、ドーピングシステムを採用する場合、ホスト材料とドーパント材料(発光性の高い物質)を含んでいる。ドーパント材料としては、例えば、蛍光発光材料や燐光発光材料を用いることができる。蛍光発光材料は一重項励起状態から発光可能な化合物であり、燐光性化合物は三重項励起状態から発光可能な化合物である。ホスト材料は、主に電子と正孔の再結合を促し、励起子を発光層内に閉じ込める機能を有し、ドーパント材料は、再結合で得られた励起子を効率的に発光させる機能を有する。
燐光素子の場合、ホスト材料は主にドーパント材料で生成された励起子を発光層内に閉じ込める機能を有する。
また、量子収率の高いドーパント材料を二種類以上入れることによって、それぞれのドーパント材料が発光するダブルドーパントを採用してもよい。具体的には、ホスト材料、赤色ドーパント材料及び緑色ドーパント材料を共蒸着することによって、発光層を共通化して黄色発光を実現する態様が挙げられる。
発光層への正孔の注入し易さと電子の注入し易さは異なっていてもよく、また、発光層中での正孔と電子の移動度で表される正孔輸送能と電子輸送能が異なっていてもよい。
前記配位子は、オルトメタル結合を有することが好ましい。燐光量子収率が高く、発光素子の外部量子効率をより向上させることができるという点で、Ir,Os及びPtから選ばれる金属原子を含有する金属錯体が好ましく、イリジウム錯体、オスミウム錯体、白金錯体等の金属錯体、特にオルトメタル化錯体がより好ましく、イリジウム錯体及び白金錯体がさらに好ましく、オルトメタル化イリジウム錯体が特に好ましい。
R10の示す置換基としては、上記式(1)のR0~R8等で例示した置換基と同様のものが挙げられる。
本発明の一態様においては、青色系の蛍光発光材料として、ピレン誘導体、スチリルアミン誘導体、クリセン誘導体、フルオランテン誘導体、フルオレン誘導体、ジアミン誘導体、トリアリールアミン誘導体等、緑色系の蛍光発光材料として、芳香族アミン誘導体等、赤色系の蛍光発光材料として、テトラセン誘導体、ジアミン誘導体等が使用される。
本発明の他の態様においては、該蛍光発光材料としては、アントラセン誘導体、フルオランテン誘導体、スチリルアミン誘導体及びアリールアミン誘導体から選択される少なくとも1種が好ましく、アントラセン誘導体、アリールアミン誘導体がより好ましい。特に、ホスト材料としてはアントラセン誘導体が好ましく、ドーパント材料としてはアリールアミン誘導体が好ましい。具体的には、国際公開第2010/134350号や国際公開第2010/134352号に記載する好適な材料が選択される。前記化合物(1)及び前記有機EL素子用材料は、蛍光発光層の蛍光発光材料として用いてもよく、蛍光発光層のホスト材料として用いてもよい。
本発明の一態様において、ホスト材料としては、(1)アルミニウム錯体、ベリリウム錯体、亜鉛錯体等の金属錯体、(2)オキサジアゾール誘導体、ベンゾイミダゾール誘導体、フェナントロリン誘導体等の複素環化合物、(3)カルバゾール誘導体、アントラセン誘導体、フェナントレン誘導体、ピレン誘導体、クリセン誘導体等の縮合芳香族化合物、(4)トリアリールアミン誘導体、縮合多環芳香族アミン誘導体等の芳香族アミン化合物が使用される。
前記化合物(1)とそれ以外の化合物を同一の発光層内の燐光ホスト材料として併用してもよいし、複数の発光層がある場合には、そのうちの一つの発光層の燐光ホスト材料として前記化合物(1)を用い、別の一つの発光層の燐光ホスト材料として前記化合物(1)以外の化合物を用いてもよい。また、前記化合物(1)は発光層以外の有機層にも使用しうるものであり、その場合には発光層の燐光ホストとして、前記化合物(1)以外の化合物を用いてもよい。
本発明の一態様において、陰極と発光ユニットとの界面領域に電子供与性ドーパントを有することも好ましい。このような構成によれば、有機EL素子における発光輝度の向上や長寿命化が図られる。ここで、電子供与性ドーパントとは、仕事関数3.8eV以下の金属を含有するものをいい、その具体例としては、アルカリ金属、アルカリ金属錯体、アルカリ金属化合物、アルカリ土類金属、アルカリ土類金属錯体、アルカリ土類金属化合物、希土類金属、希土類金属錯体、及び希土類金属化合物等から選ばれた少なくとも一種類が挙げられる。
前記有機化合物と電子供与性ドーパントの割合は、モル比で5:1~1:5であると好ましく、2:1~1:2であるとさらに好ましい。
電子注入層は、電子注入性の高い物質を含む層である。電子注入層には、リチウム(Li)、フッ化リチウム(LiF)、フッ化セシウム(CsF)、フッ化カルシウム(CaF2)、リチウム酸化物(LiOx)等のようなアルカリ金属、アルカリ土類金属、またはそれらの化合物を用いることができる。
電子輸送層は、発光層と陰極との間に形成される有機層であって、電子を陰極から発光層へ輸送する機能を有する。電子輸送層が複数層で構成される場合、陰極に近い有機層を電子注入層と定義することがある。電子注入層は、陰極から電子を効率的に有機層ユニットに注入する機能を有する。前記化合物(1)及び前記有機EL素子用材料は、電子輸送層に含有される電子輸送材料として用いることもできる。
この含窒素環誘導体としては、例えば、下記式(A)で表される含窒素環金属キレート錯体が好ましい。
置換されていてもよいアミノ基の例としては、アルキルアミノ基、アリールアミノ基、アラルキルアミノ基が挙げられる。
アルキルアミノ基及びアラルキルアミノ基は-NQ1Q2と表される。Q1及びQ2は、それぞれ独立に、炭素数1~20のアルキル基又は炭素数1~20のアラルキル基を表す。Q1及びQ2の一方は水素原子であってもよい。
アリールアミノ基は-NAr1’Ar2’と表され、Ar1’及びAr2’は、それぞれ独立に、炭素数6~50の非縮合芳香族炭化水素基又は縮合芳香族炭化水素基を表す。Ar1’及びAr2’の一方は水素原子であってもよい。
アルコキシカルボニル基は-COOY’と表され、Y’は炭素数1~20のアルキル基を表す。
Mは、アルミニウム(Al)、ガリウム(Ga)又はインジウム(In)であり、Inであると好ましい。
L100は、下記式(A’)又は(A”)で表される基である。
n1は0~5の整数であり、n1が2以上の整数であるとき、複数のR’’’は互いに同一又は異なっていてもよい。
HAr-L101-Ar101-Ar102 (D1)
前記式(D1)中、HArは、置換もしくは無置換の環形成原子数5~40(好ましくは5~30、より好ましくは5~20、さらに好ましくは5~12)の含窒素複素環基であり、
L101は単結合、置換もしくは無置換の環形成炭素数6~40(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)の芳香族炭化水素基又は縮合芳香族炭化水素基、置換もしくは無置換の環形成原子数5~40(好ましくは5~30、より好ましくは5~20、さらに好ましくは5~12)の芳香族複素環基又は置換もしくは無置換の環形成炭素数6~40(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)の縮合芳香族複素環基である。
Ar101は置換もしくは無置換の環形成炭素数6~40(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)の2価の芳香族炭化水素基であり、Ar102は置換もしくは無置換の環形成炭素数6~40(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~14)の芳香族炭化水素基、置換もしくは無置換の環形成炭素数6~40(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)の縮合芳香族炭化水素基、置換もしくは無置換の環形成原子数5~40(好ましくは5~30、より好ましくは5~20、さらに好ましくは5~12)の芳香族複素環基又は置換もしくは無置換の環形成原子数5~40(好ましくは5~30、より好ましくは5~20、さらに好ましくは5~12)の縮合芳香族複素環基である。
Ar103は、置換もしくは無置換の環形成炭素数6~40(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)の芳香族炭化水素基、置換もしくは無置換の環形成炭素数6~40(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)の縮合芳香族炭化水素基、置換もしくは無置換の環形成原子数5~40(好ましくは5~30、より好ましくは5~20、さらに好ましくは5~12)の芳香族複素環基又は置換もしくは無置換の環形成原子数5~40(好ましくは5~30、より好ましくは5~20、さらに好ましくは5~12)の縮合芳香族複素環基である。
R301及びR302は、それぞれ独立に、置換もしくは無置換の環形成炭素数6~50(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)のアリール基、置換もしくは無置換の環形成原子数5~50(好ましくは5~30、より好ましくは5~20、さらに好ましくは5~12)のヘテロアリール基、置換もしくは無置換の炭素数1~20のアルキル基、置換もしくは無置換の炭素数1~20のハロアルキル基又は置換もしくは無置換の炭素数1~20のアルコキシ基である。
vは、0~5の整数であり、vが2以上の整数であるとき、複数のR301は互いに同一でも異なっていてもよい。また、複数のR301同士が互いに結合して、置換もしくは無置換の炭化水素環を形成していてもよい。
Ar201は、置換もしくは無置換の環形成炭素数6~50(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)のアリール基又は置換もしくは無置換の環形成原子数5~50(好ましくは5~30、より好ましくは5~20、さらに好ましくは5~12)のヘテロアリール基である。
Ar202は、水素原子、置換もしくは無置換の炭素数1~20(好ましくは1~10、より好ましくは1~5)のアルキル基、置換もしくは無置換の炭素数1~20(好ましくは1~10、より好ましくは1~5)のハロアルキル基、置換もしくは無置換の炭素数1~20のアルコキシ基、置換もしくは無置換の環形成炭素数6~50(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)のアリール基又は置換もしくは無置換の環形成原子数5~50(好ましくは5~30、より好ましくは5~20、さらに好ましくは5~12)のヘテロアリール基である。
但し、Ar201、Ar202のいずれか一方は、置換もしくは無置換の環形成炭素数10~50(好ましくは10~30、より好ましくは10~20)の縮合芳香族炭化水素環基又は置換もしくは無置換の環形成原子数9~50(好ましくは9~30、より好ましくは9~20)の縮合芳香族複素環基である。
Ar203は、置換もしくは無置換の環形成炭素数6~50(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)のアリーレン基又は置換もしくは無置換の環形成原子数5~50(好ましくは5~30、より好ましくは5~20、さらに好ましくは5~12)のヘテロアリーレン基である。
L201、L202及びL203は、それぞれ独立に、単結合、置換もしくは無置換の環形成炭素数6~50(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)のアリーレン基、又は置換もしくは無置換の環形成原子数9~50(好ましくは9~30、より好ましくは9~20)の2価の縮合芳香族複素環基である。)
環形成原子数5~50のヘテロアリール基としては、ピローリル基、フリル基、チエニル基、シローリル基、ピリジル基、キノリル基、イソキノリル基、べンゾフリル基、イミダゾリル基、ピリミジル基、カルバゾリル基、セレノフェニル基、オキサジアゾリル基、トリアゾーリル基、ピラジニル基、ピリダジニル基、トリアジニル基、キノキサリニル基、アクリジニル基、イミダゾ[1,2-a]ピリジニル基、イミダゾ[1,2-a]ピリミジニル基などが挙げられる。
炭素数1~20のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、へキシル基などが挙げられる。
炭素数1~20のハロアルキル基としては、前記アルキル基の1又は2以上の水素原子をフッ素、塩素、ヨウ素及び臭素から選ばれる少なくとも1のハロゲン原子で置換して得られる基が挙げられる。
炭素数1~20のアルコキシ基としては、前記アルキル基をアルキル部位としては有する基が挙げられる。
環形成炭素数6~50のアリーレン基としては、前記アリール基から水素原子1個を除去して得られる基が挙げられる。
環形成原子数9~50の2価の縮合芳香族複素環基としては、前記ヘテロアリール基として記載した縮合芳香族複素環基から水素原子1個を除去して得られる基が挙げられる。
また、電子輸送層に隣接して設けることができる電子注入層の構成成分として、含窒素環誘導体の他に無機化合物として、絶縁体又は半導体を使用することが好ましい。電子注入層が絶縁体や半導体で構成されていれば、電流のリークを有効に防止して、電子注入性を向上させることができる。
正孔注入層は、正孔注入性の高い物質を含む層である。正孔注入性の高い物質としては、モリブデン酸化物、チタン酸化物、バナジウム酸化物、レニウム酸化物、ルテニウム酸化物、クロム酸化物、ジルコニウム酸化物、ハフニウム酸化物、タンタル酸化物、銀酸化物、タングステン酸化物、マンガン酸化物、芳香族アミン化合物、又は高分子化合物(オリゴマー、デンドリマー、ポリマー等)等も使用できる。
発光層と陽極との間に形成される有機層であって、正孔を陽極から発光層へ輸送する機能を有する。正孔輸送層が複数層で構成される場合、陽極に近い有機層を正孔注入層と定義することがある。正孔注入層は、陽極から正孔を効率的に有機層ユニットに注入する機能を有する。本発明の一態様において、前記化合物(1)及び前記有機EL素子用材料は、正孔輸送層を形成する材料(正孔輸送層材料)として用いることもできる。
また、前記式(H)において、L211は、置換もしくは無置換の環形成炭素数6~50(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)の芳香族炭化水素基又は置換もしくは無置換の環形成炭素数6~50(好ましくは6~30、より好ましくは6~20、さらに好ましくは6~12)の縮合芳香族炭化水素基、又は置換もしくは無置換の環形成原子数5~50(好ましくは5~30、より好ましくは5~20、さらに好ましくは5~12)の芳香族複素環基又は置換もしくは無置換の環形成原子数5~50(好ましくは5~30、より好ましくは5~20、さらに好ましくは5~12)の縮合芳香族複素環基を表す。
正孔輸送層材料は重合体などの高分子化合物であっても、単量体などの低分子化合物であってもよい。また、電荷注入障壁の観点から4.5eV~6.0eVのイオン化ポテンシャルを有する化合物が好ましい。正孔輸送層材料の例としては、芳香族アミン誘導体、フタロシアニン誘導体、ポルフィリン誘導体、オリゴチオフェン誘導体、ポリチオフェン誘導体、ベンジルフェニル誘導体、フルオレン基で3級アミンを連結した化合物、ヒドラゾン誘導体、シラザン誘導体、シラナミン誘導体、ホスファミン誘導体、キナクリドン誘導体、ポリアニリン誘導体、ポリピロール誘導体、ポリフェニレンビニレン誘導体、ポリチエニレンビニレン誘導体、ポリキノリン誘導体、ポリキノキサリン誘導体、カーボン等が挙げられる。
上記例示した中でも非晶質性、可視光の透過率の点から、芳香族アミン化合物が好ましく、特に芳香族三級アミン化合物が好ましい。ここで、芳香族三級アミン化合物とは、芳香族三級アミン構造を有する化合物であって、芳香族三級アミン由来の基を有する化合物も含む。
芳香族三級アミン化合物の種類は特に制限されないが、表面平滑化効果による均一な発光の点から、重量平均分子量が1000以上、1000000以下の高分子化合物(繰り返し単位が連なる重合型化合物)がさらに好ましい。芳香族三級アミン高分子化合物の好ましい例として、下記式(I)で表される繰り返し単位を有する高分子化合物が挙げられる。
Ar1~Ar16の芳香族炭化水素基および芳香族複素環基としては、高分子化合物の溶解性、耐熱性、正孔注入・輸送性の点から、ベンゼン環、ナフタレン環、フェナントレン環、チオフェン環、及びピリジン環から選ばれる環を有する基が好ましく、ベンゼン環及びナフタレン環から選ばれる環を有する基がさらに好ましい。
R1およびR2が表す置換基としては、アルキル基、アルケニル基、アルコキシ基、シリル基、シロキシ基、芳香族炭化水素基、芳香族複素環基などが挙げられる。
電子受容性化合物とは、酸化力を有し、上述の正孔輸送層材料から一電子受容する能力を有する化合物が好ましく、具体的には、電子親和力が4eV以上である化合物が好ましく、5eV以上の化合物である化合物がさらに好ましい。
正孔輸送層用組成物中の電子受容性化合物の正孔輸送材料に対する含有量は、通常0.1モル%以上、好ましくは1モル%以上である。但し、通常100モル%以下、好ましくは40モル%以下である。
アリーレン基の例としては、フェニレン基等が挙げられる。2価の複素環基の例としては、ピリジンジイル基等が挙げられる。これらの基は置換基を有していてもよい。
アリール基の例としては、フェニル基、ナフチル基等が挙げられる。1価の複素環基の例としては、ピリジル基等が挙げられる。これらの基は置換基を有していてもよい。
1価の複素環基の例としては、チエニル基、フリル基、ピリジル基等が挙げられる。
さらにAr2中の炭素原子とAr3中の炭素原子とが直接結合するか、または-O-、-S-等の2価の基を介して結合していてもよい。
モノマーの合成し易さの観点からは、mおよびnが0であることが好ましい。
このように架橋性基を有する材料を用いるか、または架橋剤を用いることにより、下層(正孔輸送層)上にさらに別の機能層(上層)を塗布法により形成したとしても、上層形成用の溶媒等による下層の溶解を効果的に抑制することができる。
また、架橋反応によって有機溶剤に不溶になりやすい点で、重合体であることが好ましい。特に、電気化学的安定性及び正孔輸送能を向上させる点で、下記式(L)で表される繰り返し単位を含む重合体であることが好ましい。
前記芳香族複素環基としては、例えばフラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの、5又は6員環の単環又は2~4個の5又は6員環を含む縮合環の一価の基が挙げられる。
また、Ar1~Ar5としては、前記群から選ばれる1種又は2種以上の環を単結合により連結した基も好ましく、ビフェニル基、ビフェニレン基及びターフェニル基、ターフェニレン基がさらに好ましい。
また、上記各任意の置換基がさらに置換基を有していてもよく、その例としては任意の置換基として上記した基から選択される。
正孔輸送性に優れる点から、Ar1~Ar5は、置換基を含めて、その炭素数は3以上、好ましくは5以上、さらに好ましくは6以上であり、72以下、好ましくは48以下、さらに好ましくは25以下である。
なお、mが2以上である場合、2個以上のAr4及び2個以上のAr5は、それぞれ同じでも異なっていてもよい。さらに、Ar4同士、Ar5同士は、それぞれ互いに直接又は連結基を介して結合して環状構造を形成していてもよい。
架橋性基とは、熱及び/又は活性エネルギー線の照射により近傍に位置するほかの分子の同一又は異なる基と反応して、新規な化学結合を生成する基のことをいう。
架橋性基としては、不溶化がしやすいという点で、例えば、下記の架橋性基が挙げられる。
X1、X2及びX3は、各々独立して水素原子又はハロゲン原子を示す。
R24は水素原子又はビニル基を示す。
ベンゾシクロブテン環は、置換基を有していてもよく、該置換基同士が、互いに結合して環を形成してもよい。
R21~R23のアルキル基としては、例えばメチル基、エチル基等の炭素数が1~24、好ましくは1~12であるアルキル基等が挙げられる。
なお、R21~R23、及びAr21の任意の置換基としては、特に制限はないが、例えば、前記した任意の置換基から選ばれる基が挙げられる。
さらに、架橋性基として、エポキシ基、オキセタン基等の環状エーテル基、ビニルエーテル基などのカチオン重合によって不溶化反応する基が、反応性が高く不溶化が容易な点で好ましい。中でも、カチオン重合の速度を制御しやすい点でオキセタン基が特に好ましく、カチオン重合の際に素子の劣化をまねくおそれのあるヒドロキシル基が生成しにくい点でビニルエーテル基が好ましい。
又、架橋性基の中でも、不溶化後の構造が特に安定な点で、ベンゾシクロブテン環を有する基が特に好ましい。
具体的には、下記式(M)で表される基であることが好ましい。
以下に本発明の一態様に用いることのできる導電性ポリマーやオリゴマーの例を示す。
前記電子供与性化合物の代表的な例としては、芳香族アミン誘導体、フタロシアニン誘導体、ポルフィリン誘導体、チオフェン誘導体、ベンジルフェニル誘導体、フルオレン基で3級アミンを連結した化合物、ヒドラゾン誘導体、シラザン誘導体、シラナミン誘導体、ホスファミン誘導体、キナクリドン誘導体、アニリン誘導体、ピロール誘導体、フェニレンビニレン誘導体、チエニレンビニレン誘導体、キノリン誘導体、キノキサリン誘導体、カーボン等が挙げられる。これらの誘導体は分子量が1000未満の低分子、分子量が1000~10000のオリゴマー及びデンドリマー、及び分子量が10000以上の高分子のいずれであってもよい。中でも芳香族アミン誘導体やポリチオフェン誘導体、ポリアニリン誘導体、オリゴアニリン誘導体が好適に用いられる。
電子供与性化合物の場合と同様に、これらの誘導体は分子量が1000未満の低分子、分子量が1000~10000のオリゴマー及びデンドリマー、及び分子量が10000以上のポリマーのいずれであってもよい。
以下、本発明の一態様に用いることができる正孔輸送層材料の代表例(i)~(x)を示す。なお、これらは単独、あるいは、混合して用いることもできるが、相対的に電子供与性のものと、相対的に電子受容性のものを混合することが望ましい。さらに、電子供与性化合物と電子受容性化合物との間での電荷移動を促進させたり、塗布成膜性を向上させるための添加剤などを第三の成分として添加することもできる。第三の成分は複数用いることもできる。
m-1は、1~5の整数で、n+(m-1)=5であり、
R1は、同一又は異なり、それぞれ独立して、アルキル基、アルケニル基、アルコキシ基、シクロアルキル基、シクロアルケニル基、アルカノイル基、アルキルチオ基、アリールオキシ基、アルキルチオアルキル基、アルキルアリール基、アリールアルキル基、アミノ基、アルキルアミノ基、ジアルキルアミノ基、アリール基、アルキルスルフィニル基、アルコキシアルキル基、アルキルスルホニル基、アリールチオ基、アリールスルフィニル基、アルコキシカルボニル基、アリールスルホニル基、カルボキシル基、ハロゲン原子、シアノ基、または1つまたは複数のスルホン酸基、カルボキシル基、ハロゲン原子、ニトロ基、シアノ基もしくはエポキシ基によって置換されたアルキル基から選択される。隣接する2つのR1基が互いに結合して、1つまたは複数の二価の窒素原子、イオウ原子または酸素原子を含んでもよい3、4、5、6または7員の芳香族環もしくは脂環式環を完成するアルキレン鎖またはアルケニレン鎖を形成してもよい。
R2は、独立して、水素原子、アルキル基、アルケニル基、アリール基、アルカノイル基、アルキルチオアルキル基、アルキルアリール基、アリールアルキル基、アミノ基、エポキシ基、シリル基、シロキサン基、アミドスルホネート基、アルコール基、ベンジル基、カルボキシレート基、エーテル基、エーテルカルボキシレート基、アミドスルホネート基、エーテルスルホネート基、およびウレタン基から選択される基である。
正孔輸送層の膜厚は特に限定されないが、10~200nmであるのが好ましい。
前記アクセプター材料としては下記式(K)で表される化合物が好ましい。
R317としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。
アクセプター材料を含有する層の膜厚は特に限定されないが、5~20nmであるのが好ましい。
前記アクセプター材料として下記の材料を用いてもよい。
上述の正孔輸送層や電子輸送層においては、特許第3695714号明細書に記載されているように、ドナー性材料のドーピング(n)やアクセプター性材料のドーピング(p)により、キャリア注入能を調整することができる。
nドーピングの代表例としては、電子輸送材料にLiやCs等の金属をドーピングする方法が挙げられ、pドーピングの代表例としては、正孔輸送材料にF4TCNQ(2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane)等のアクセプター材料をドーピングする方法が挙げられる。
上記スペース層とは、例えば、蛍光発光層と燐光発光層とを積層する場合に、燐光発光層で生成する励起子を蛍光発光層に拡散させない、あるいは、キャリアバランスを調整する目的で、蛍光発光層と燐光発光層との間に設けられる層である。また、スペース層は、複数の燐光発光層の間に設けることもできる。
スペース層は発光層間に設けられるため、電子輸送性と正孔輸送性を兼ね備える材料であることが好ましい。また、隣接する燐光発光層内の三重項エネルギーの拡散を防ぐため、三重項エネルギーが2.6eV以上であることが好ましい。スペース層に用いられる材料としては、上述の正孔輸送層に用いられるものと同様のものが挙げられる。本発明の一態様において、前記化合物(1)及び前記有機EL素子用材料をスペース層用の材料として用いることもできる。
本発明の一態様において、電子障壁層、正孔障壁層、トリプレット障壁層などの障壁層を発光層に隣接して設けることが好ましい。ここで、電子障壁層とは、発光層から正孔輸送層へ電子が漏れることを防ぐ層であり、正孔障壁層とは、発光層から電子輸送層へ正孔が漏れることを防ぐ層である。本発明の一態様において、前記化合物(1)及び前記有機EL素子用材料を正孔障壁層用の材料として用いることもできる。
トリプレット障壁層は、発光層で生成する三重項励起子が、周辺の層へ拡散することを防止し、三重項励起子を発光層内に閉じ込めることによって三重項励起子の発光ドーパント以外の電子輸送層の分子上でのエネルギー失活を抑制する機能を有する。
トリプレット障壁層を設ける場合、燐光素子においては、発光層中の燐光発光性ドーパントの三重項エネルギーをET d、トリプレット障壁層として用いる化合物の三重項エネルギーをET TBとすると、ET d<ET TBのエネルギー大小関係であれば、エネルギー関係上、燐光発光性ドーパントの三重項励起子が閉じ込められ(他分子へ移動できなくなり)、該ドーパント上で発光する以外のエネルギー失活経路が断たれ、高効率に発光することができると推測される。ただし、ET d<ET TBの関係が成り立つ場合であってもこのエネルギー差ΔET=ET TB-ET dが小さい場合には、実際の素子駆動環境である室温程度の環境下では、周辺の熱エネルギーにより吸熱的にこのエネルギー差ΔETを乗り越えて三重項励起子が他分子へ移動することが可能であると考えられる。特に燐光発光の場合は蛍光発光に比べて励起子寿命が長いため、相対的に吸熱的励起子移動過程の影響が現れやすくなる。室温の熱エネルギーに対してこのエネルギー差ΔETは大きい程好ましく、0.1eV以上であるとさらに好ましく、0.2eV以上であると特に好ましい。本発明の一態様において、前記化合物(1)及び前記有機EL素子用材料を、国際公開WO2010/134350A1に記載するTTF蛍光素子のトリプレット障壁層用の材料として用いることもできる。
電子注入層は、電界強度0.04~0.5MV/cmの範囲において、10-6cm2/Vs以上であることが望ましい。これにより陰極からの電子輸送層への電子注入が促進され、ひいては隣接する障壁層、発光層への電子注入も促進し、より低電圧での駆動を可能にするためである。
塗布後は、真空下に加熱(上限250℃)乾燥して、溶媒を除去すればよく、光や250℃を超える高温加熱による重合反応は不要である。従って、光や250℃を超える高温加熱による素子の性能劣化の抑制が可能である。
成膜用溶液は、粘度及び/又は表面張力を調節するための添加剤、例えば、増粘剤(高分子量化合物等)、粘度降下剤(低分子量化合物等)、界面活性剤等を含有していてもよい。また、保存安定性を改善するために、フェノール系酸化防止剤、リン系酸化防止剤等、有機EL素子の性能に影響しない酸化防止剤を含有していてもよい。
上記成膜用溶液(インク組成物)中の前記化合物(1)の含有量は、成膜用溶液全体に対して0.1~15質量%が好ましく、0.5~10質量%がより好ましい。
アルゴン雰囲気下、ビカルバゾリル中間体A1(12.26g、30mmol)、ピリミジン中間体B1(9.04g、30mmol)、炭酸カリウム(4.35g、31.5mmol)を乾燥DMF30mLに加え、120℃で8時間加熱撹拌した。室温まで反応液を冷却した後、水30mLを加え、析出した固体を濾取し、水及びメタノールで洗浄し、減圧乾燥した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、目的とする中間体C1(15.14g,収率75%)を得た。
アルゴン雰囲気下、中間体C1(2.02g、3.0mmol)、ビカルバゾリル中間体A2(1.23g、3.0mmol)、トリス(ジベンジリデンアセトン)ジパラジウム(0.055g、0.06mmol)、キサントホス(4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン)(0.069g、0.12mmol)、t-ブトキシナトリウム(0.43g、4.5mmol)、無水キシレン(60mL)を順次加えて8時間加熱還流した。
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-1(2.86g,収率91%)を得た。
HPLC:純度99.1%
FD-MS:calcd for C76H48N6=1045、
found m/z=1045(M+,100)
アルゴン雰囲気下、ビカルバゾリル中間体A1(12.26g、30mmol)、ピリミジン中間体B2(9.04g、30mmol)、炭酸カリウム(4.35g、31.5mmol)を乾燥DMF30mLに加え、120℃で8時間加熱撹拌した。室温まで反応液を冷却した後、水30mLを加え、析出した固体を濾取し、水及びメタノールで洗浄し、減圧乾燥した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、目的とする中間体C2(14.74g,収率73%)を得た。
アルゴン雰囲気下、中間体C2(2.02g、3.0mmol)、ビカルバゾリル中間体A2(1.23g、3.0mmol)、トリス(ジベンジリデンアセトン)ジパラジウム(0.055g、0.06mmol)、キサントホス(0.069g、0.12mmol)、t-ブトキシナトリウム(0.43g、4.5mmol)、無水キシレン(60mL)を順次加えて8時間加熱還流した。
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-2(2.76g,収率88%)を得た。
HPLC:純度99.6%
FD-MS:calcd for C76H48N6=1045、
found m/z=1045(M+,100)
アルゴン雰囲気下、中間体C3(2.02g、3.0mmol)、ビカルバゾリル中間体A1(1.23g、3.0mmol)、トリス(ジベンジリデンアセトン)ジパラジウム(0.055g、0.06mmol)、キサントホス(0.069g、0.12mmol)、t-ブトキシナトリウム(0.43g、4.5mmol)、無水キシレン(60mL)を順次加えて8時間加熱還流した。
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-3(2.70g,収率86%)を得た。
HPLC:純度99.8%
FD-MS:calcd for C76H48N6=1045、
found m/z=1045(M+,100)
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-4(1.85g,収率48%)を得た。
HPLC:純度99.2%
FD-MS:calcd for C94H59N7=1286、
found m/z=1286(M+,100)
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-5(1.85g,収率86%)を得た。
HPLC:純度98.8%
FD-MS:calcd for C70H44N6=969、
found m/z=969(M+,100)
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-6(1.69g,収率61%)を得た。
HPLC:純度98.9%
FD-MS:calcd for C67H45N5=920、
found m/z=920(M+,100)
アルゴン雰囲気下、中間体C4(2.37g、3.0mmol)、ビカルバゾリル中間体A1(1.23g、3.0mmol)、トリス(ジベンジリデンアセトン)ジパラジウム(0.055g、0.06mmol)、キサントホス(0.069g、0.12mmol)、t-ブトキシナトリウム(0.43g、4.5mmol)、無水キシレン(60mL)を順次加えて8時間加熱還流した。
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-7(3.06g,収率88%)を得た。
HPLC:純度99.3%
FD-MS:calcd for C85H58N6=1161、
found m/z=1161(M+,100)
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-8(2.81g,収率83%)を得た。
HPLC:純度98.9%
FD-MS:calcd for C82H54N6=1123、
found m/z=1123(M+,100)
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-9(2.44g,収率74%)を得た。
HPLC:純度99.2%
FD-MS:calcd for C80H52N6=1097、
found m/z=1097(M+,100)
アルゴン雰囲気下、ビカルバゾリル中間体A1(8.58g、21.0mmol)、キナゾリン中間体B4(5.50g、20.0mmol)、炭酸カリウム(2.76g、20.0mmol)を乾燥DMF20mLに加え、120℃で8時間加熱撹拌した。室温まで反応液を冷却した後、水10mLを加え、析出した固体を濾取し、水及びメタノールで洗浄し、減圧乾燥した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、目的とする中間体C6(9.06g,収率70%)を得た。
アルゴン雰囲気下、中間体C6(1.94g、3.0mmol)、トリカルバゾリル中間体A3(1.95g、3.0mmol)、トリス(ジベンジリデンアセトン)ジパラジウム(0.055g、0.06mmol)、キサントホス(4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン)(0.069g、0.12mmol)、t-ブトキシナトリウム(0.43g、4.5mmol)、無水キシレン(60mL)を順次加えて8時間加熱還流した。
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-10(2.76g,収率73%)を得た。
HPLC:純度99.4%
FD-MS:calcd for C92H57N7=1260、
found m/z=1260(M+,100)
アルゴン雰囲気下、ビカルバゾリル中間体A1(8.58g、21.0mmol)、キナゾリン中間体B5(5.50g、20.0mmol)、炭酸カリウム(2.76g、20.0mmol)を乾燥DMF20mLに加え、120℃で8時間加熱撹拌した。室温まで反応液を冷却した後、水10mLを加え、析出した固体を濾取し、水及びメタノールで洗浄し、減圧乾燥した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、目的とする中間体C7(9.32g,収率72%)を得た。
アルゴン雰囲気下、中間体C7(1.94g、3.0mmol)、トリカルバゾリル中間体A9(1.49g、3.0mmol)、トリス(ジベンジリデンアセトン)ジパラジウム(0.055g、0.06mmol)、キサントホス(4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン)(0.069g、0.12mmol)、t-ブトキシナトリウム(0.43g、4.5mmol)、無水キシレン(60mL)を順次加えて8時間加熱還流した。
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-11(2.74g,収率82%)を得た。
HPLC:純度99.5%
FD-MS:calcd for C80H49N7=1108、
found m/z=1108(M+,100)
アルゴン雰囲気下、トリカルバゾリル中間体A3(3.41g、5.25mmol)、キナゾリン中間体B6(1.85g、5.00mmol)、炭酸カリウム(0.83g、6.0mmol)を乾燥DMF5mLに加え、120℃で8時間加熱撹拌した。室温まで反応液を冷却した後、水10mLを加え、析出した固体を濾取し、水及びメタノールで洗浄し、減圧乾燥した。目的とする中間体C8(3.98g,収率81%)を得た。
アルゴン雰囲気下、中間体C8(2.95g、3.0mmol)、ビカルバゾリル中間体A1(1.23g、3.0mmol)、トリス(ジベンジリデンアセトン)ジパラジウム(0.055g、0.06mmol)、キサントホス(4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン)(0.069g、0.12mmol)、t-ブトキシナトリウム(0.43g、4.5mmol)、無水キシレン(60mL)を順次加えて8時間加熱還流した。
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-12(3.38g,収率86%)を得た。
HPLC:純度99.21%
FD-MS:calcd for C96H59N7=1310、
found m/z=1310(M+,100)
アルゴン雰囲気下、中間体A1(2.14g、5.25mmol)、中間体B7(1.60g、5.00mmol)、炭酸カリウム(0.83g、6.0mmol)を乾燥DMF5mLに加え、120℃で8時間加熱撹拌した。室温まで反応液を冷却した後、水10mLを加え、析出した固体を濾取し、水及びメタノールで洗浄し、減圧乾燥した。目的とする中間体C9(3.01g,収率87%)を得た。
アルゴン雰囲気下、中間体C9(2.07g、3.0mmol)、中間体A2(1.23g、3.0mmol)、トリス(ジベンジリデンアセトン)ジパラジウム(0.055g、0.06mmol)、キサントホス(4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン)(0.069g、0.12mmol)、t-ブトキシナトリウム(0.43g、4.5mmol)、無水キシレン(60mL)を順次加えて8時間加熱還流した。
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-13(2.85g,収率93%)を得た。
HPLC:純度99.4%
FD-MS:calcd for C74H46N6=1019
found m/z=1019(M+,100)
HPLC:High performance liquid chromatography
FD-MS:Field Desorption Mass Spectrometry
アルゴン雰囲気下、中間体A1(2.14g、5.25mmol)、中間体B8(1.60g、5.00mmol)、炭酸カリウム(0.83g、6.0mmol)を乾燥DMF5mLに加え、120℃で8時間加熱撹拌した。室温まで反応液を冷却した後、水10mLを加え、析出した固体を濾取し、水及びメタノールで洗浄し、減圧乾燥した。目的とする中間体C10(2.94g,収率85%)を得た。
アルゴン雰囲気下、中間体C2(2.07g、3.0mmol)、中間体A2(1.23g、3.0mmol)、トリス(ジベンジリデンアセトン)ジパラジウム(0.055g、0.06mmol)、キサントホス(4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン)(0.069g、0.12mmol)、t-ブトキシナトリウム(0.43g、4.5mmol)、無水キシレン(60mL)を順次加えて8時間加熱還流した。
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-14(2.90g,収率95%)を得た。
HPLC:純度99.3%
FD-MS:calcd for C74H46N6=1019
found m/z=1019(M+,100)
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-15(3.37g,収率89%)を得た。
HPLC:純度99.4%
FD-MS:calcd for C92H57N7=1260
found m/z=1260(M+,100)
アルゴン雰囲気下、中間体C11(2.80g、3.0mmol)、中間体A1(1.23g、3.0mmol)、トリス(ジベンジリデンアセトン)ジパラジウム(0.055g、0.06mmol)、キサントホス(4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン)(0.069g、0.12mmol)、t-ブトキシナトリウム(0.43g、4.5mmol)、無水キシレン(60mL)を順次加えて8時間加熱還流した。
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-16(3.40g,収率90%)を得た。
HPLC:純度99.5%
FD-MS:calcd for C92H57N7=1260
found m/z=1260(M+,100)
室温まで反応液を冷却した後、不溶物を濾過して除き、有機溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィーにて精製し、化合物H-17(2.33g,収率87%)を得た。
HPLC:純度99.1%
FD-MS:calcd for C65H43N5=894
found m/z=894(M+,100)
(基板の洗浄)
25mm×25mm×厚さ1.1mmのITO透明電極付きガラス基板(ジオマテック株式会社製)をイソプロピルアルコール中で超音波洗浄を5分間行った後、UVオゾン洗浄を5分間行った。
(下地層の形成)
正孔輸送材料としてHERAEUS社製CLEVIOUS AI4083(商品名)を30nmの厚さで前記のITO基板上にスピンコート法により成膜した。成膜後、アセトンにより不要部分を除去し、次いで大気中200℃のホットプレートで10分間焼成し、下地基板を作製した。
(発光層の形成)
ホスト材料として合成実施例4で得た化合物H-4、ドーパント材料として下記化合物D-1を用い、化合物H-4:化合物D-1が重量比で90:10となるような混合比で、1.6質量%のトルエン溶液を作製した。このトルエン溶液を用い、前記下地基板上にスピンコート法により、50nmの膜厚になるように塗布積層した。塗布成膜後、不要部分をトルエンにて除去し、150℃のホットプレート上で加熱乾燥し、発光層を成膜した塗布積層基板を作製した。なお、発光層の成膜にかかる全ての操作は窒素雰囲気のグローブボックス中で実施した。
(蒸着、封止)
塗布積層基板を蒸着チャンバー中に搬送し、電子輸送層として下記化合物ET-1を50nm蒸着した。さらに、フッ化リチウムを1nm、アルミニウムを80nm蒸着積層した。全ての蒸着工程を完了させた後、窒素雰囲気のグローブボックス中でザグリガラスによる封止を行い、有機EL素子を製造した。
得られた有機EL素子を、直流電流駆動により発光させ、電流密度10mA/cm2における外部量子収率(EQE)を測定した。測定結果を表1に示す。
ドーパント材料として化合物D-2を用いたこと以外は、実施例1と同様の方法で有機EL素子を作製した。測定結果を表1に示す。
ホスト材料として下記比較化合物H-aを用いたこと以外は、実施例1と同様の方法で有機EL素子を作製した。測定結果を表1に示す。
ホスト材料として下記比較化合物H-aを用いたこと以外は、実施例2と同様の方法で有機EL素子を作製した。測定結果を表1に示す。
ホスト材料として合成実施例13で得た化合物H-13、ドーパント材料として下記化合物D-1を用い、化合物H-13:化合物D-1が重量比で95:5となるような混合比で1.6重量%のトルエン溶液を調製した以外は実施例1と同様の方法で機EL素子を作製した。測定結果を表1に示す。
ホスト材料として合成実施例で得た化合物H-14(実施例4)、化合物H-15(実施例5)、化合物H-16(実施例6)、化合物H-17(実施例7)をそれぞれ用いたこと以外は、実施例3と同様の方法で有機EL素子を作製した。測定結果を表1に示す。
ホスト材料としてWO2012/086170に記載の化合物Q-1を用いたこと以外は、実施例3と同様の方法で有機EL素子を作製した。測定結果を表1に示す。
2 基板
3 陽極
4 陰極
5 発光層
6 陽極側有機薄膜層
7 陰極側有機薄膜層
10 発光ユニット
Claims (31)
- 下記式(1)で表される化合物。
*a及び*bの一方は炭素原子*c1に結合し、他方は炭素原子*c2に結合し、
R1は水素原子又は置換基を表し、
X1はN又はCR2を表し、R2は水素原子又は置換基を表し、R2はR1に結合して環を形成してもよく、
*bが炭素原子*c2に結合し、X1がCR2を表し、かつ、R2がR1に結合して環を形成する場合、-R1-R2-は-Xa=Xb-Xc=Xd-を表し、
Xa~Xdは、それぞれ独立して、N又はCRaを表し、Raは水素原子又は置換基を表し、隣接する2個のRaは互いに結合して環を形成してもよく、
L1は連結基を表し、
L2は2価の連結基を表し、
nは0~3の整数を表し、nが0の場合、L2は単結合を表し、
A1及びA2は互いに異なり、下記式(2)、(2’)、(3)、(3’)、(3’’)、及び(4)のいずれかで表される基である。
*2は式(1)の炭素原子*c1、炭素原子*c2、L1(nが0である場合)、又は、L2(nが1~3の整数である場合)に結合し、
X7~X11の1つは*3に結合する炭素原子であり、
X12~X16の1つは*4に結合する炭素原子であり、
他のX7~X11、他のX12~X16、X2~X6、及びX17~X21はそれぞれ独立にN又はCR3を表し、
R3は水素原子又は置換基を表し、複数のR3が互いに結合して環を形成してもよく、
X6とX11は互いに結合する炭素原子であってもよく、X16とX21は互いに結合する炭素原子であってもよく、
X22は、NR4、CR5R6、O、S、Se、又はSiR7R8を表し、
R4~R8はそれぞれ独立に水素原子又は置換基を表し、R5とR6又はR7とR8は互いに結合して環を形成してもよい。)
*2、X7~X11、X12~X16、X17~X21、及びX22は前記と同様であり、
X2’~X6’の1つは*3’に結合する炭素原子であり、
X12’~X16’の1つは*4’に結合する炭素原子であり、
他のX2’~X6’、他のX12’~X16’、及びX17’~X21’はそれぞれ独立にN又はCR3を表し、
R3は前記と同様であり、
X6’とX11は互いに結合する炭素原子であってもよく、X16とX21は互いに結合する炭素原子であってもよく、X16’とX21’は互いに結合する炭素原子であってもよく、
X22’は、NR4、CR5R6、O、S、Se、又はSiR7R8を表し、
R4~R8は前記と同様である。)
*5は式(1)の炭素原子*c1、炭素原子*c2、L1(nが0である場合)、又は、L2(nが1~3の整数である場合)に結合し、
X37~X41の1つは*6に結合する炭素原子であり、
他のX37~X41、X32~X36、及びX42~X51はそれぞれ独立にN又はCR9を表し、
R9は水素原子又は置換基を表し、複数のR9は互いに結合して環を形成してもよく、
X36とX41は互いに結合する炭素原子であってもよく、X46とX51は互いに結合する炭素原子であってもよい。)
*5、X37~X41、及びX42~X51は前記と同様であり、
X32’~X36’の1つは*6’に結合する炭素原子であり、
他のX32’~X36’及びX42’~X51’はそれぞれ独立にN又はCR9を表し、
R9は前記と同様であり、
X36’とX41は互いに結合する炭素原子であってもよく、X46とX51は互いに結合する炭素原子であってもよく、X46’とX51’は互いに結合する炭素原子であってもよい。)
*5、X37~X41、及びX42~X51は前記と同様であり、
X32’’~X36’’の1つは*3’’に結合する炭素原子であり、
X12’’~X16’’の1つは*4’’に結合する炭素原子であり、
他のX32’’~X36’’、他のX12’’~X16’’、及びX17’’~X21’’はそれぞれ独立にN又はCR3を表し、
R3は前記と同様であり、
X36’’とX41は互いに結合する炭素原子であってもよく、X46とX51は互いに結合する炭素原子であってもよく、X16’’とX21’’は互いに結合する炭素原子であってもよく、
X22’’は、NR4、CR5R6、O、S、Se、又はSiR7R8を表し、
R4~R8は前記と同様である。)
*7は式(1)の炭素原子*c1、炭素原子*c2、L1(nが0である場合)、又は、L2(nが1~3の整数である場合)に結合し、
X67~X71から選ばれる1つの隣接する対において、一方は*8に結合する炭素原子を表し、他方は*9に結合する炭素原子を表し、
他のX67~X71、X62~X66及びX72~X75はそれぞれ独立にNまたはCR10を表し、
R10は水素原子又は置換基を表し、複数のR10は互いに結合して環を形成してもよく、
X66とX71は互いに結合する炭素原子であってもよく、
X76は、NR11、CR12R13、O、S、Se、又はSiR14R15を表し、
R11~R15はそれぞれ独立に水素原子又は置換基を表し、R11とR12及びR13とR14は互いに結合して環を形成してもよい。))。 - *bが炭素原子*c1に結合する場合、L1は置換もしくは無置換の環形成炭素数6~50のアリーレン基、又は、R2と結合して環を形成する原子群を表し、
L1が置換もしくは無置換の環形成炭素数6~50のアリーレン基であり、かつ、nが1である場合、L1とL2は同一でも異なっていてもよく、互いに架橋されていてもよく、
L1が置換もしくは無置換の環形成炭素数6~50のアリーレン基であり、かつ、nが2又は3である場合、L1と2又は3個のL2は同一でも異なっていてもよく、L1とL2及び2個のL2は互いに架橋されていてもよい請求項1に記載の化合物。 - *bが炭素原子*c2に結合し、かつ、nが1である場合、L1とL2は同一でも異なっていてもよく、互いに架橋されていてもよく、又、*bが炭素原子*c2に結合し、かつ、nが2又は3である場合、L1と2又は3個のL2は同一でも異なっていてもよく、L1とL2及び2個のL2は互いに架橋されていてもよい請求項1に記載の化合物。
- 前記A1及びA2が下記式のいずれかで表される基である請求項1~6のいずれか1項に記載の化合物。
- 前記A1及びA2が下記式のいずれかで表される基である請求項1~7のいずれか1項に記載の化合物。
- R1が表す置換基が、ハロゲン原子、シアノ基、ニトロ基、置換もしくは無置換の炭素数1~50のアルキル基、置換もしくは無置換の環形成炭素数3~50のシクロアルキル基、置換もしくは無置換の環形成炭素数6~60のアリール基、環形成炭素数6~50のアリール基を有する炭素数7~51のアラルキル基、アミノ基、置換もしくは無置換の炭素数1~50のアルキル基及び置換もしくは無置換の環形成炭素数6~60のアリール基から選ばれる置換基を有するモノ置換又はジ置換アミノ基、置換もしくは無置換の炭素数1~50のアルコキシ基、置換もしくは無置換の環形成炭素数3~50のシクロアルコキシ基、置換もしくは無置換の環形成炭素数6~60のアリールオキシ基、置換もしくは無置換の炭素数1~50のアルキルチオ基、置換もしくは無置換の環形成炭素数6~60のアリールチオ基、シリル基、置換もしくは無置換の炭素数1~50のアルキル基及び置換もしくは無置換の環形成炭素数6~60のアリール基から選ばれる置換基を有するモノ置換、ジ置換又はトリ置換シリル基、置換もしくは無置換の環形成原子数5~60のヘテロアリール基、及び、置換もしくは無置換の炭素数1~50のハロアルキル基からなる群から選ばれる請求項1~5、7及び8のいずれか1項に記載の化合物。
- Raが表す置換基が、ハロゲン原子、シアノ基、ニトロ基、置換もしくは無置換の炭素数1~50のアルキル基、置換もしくは無置換の環形成炭素数3~50のシクロアルキル基、置換もしくは無置換の環形成炭素数6~60のアリール基、環形成炭素数6~50のアリール基を有する炭素数7~51のアラルキル基、アミノ基、置換もしくは無置換の炭素数1~50のアルキル基及び置換もしくは無置換の環形成炭素数6~60のアリール基から選ばれる置換基を有するモノ置換又はジ置換アミノ基、置換もしくは無置換の炭素数1~50のアルコキシ基、置換もしくは無置換の環形成炭素数3~50のシクロアルコキシ基、置換もしくは無置換の環形成炭素数6~60のアリールオキシ基、置換もしくは無置換の炭素数1~50のアルキルチオ基、置換もしくは無置換の環形成炭素数6~60のアリールチオ基、シリル基、置換もしくは無置換の炭素数1~50のアルキル基及び置換もしくは無置換の環形成炭素数6~60のアリール基から選ばれる置換基を有するモノ置換、ジ置換又はトリ置換シリル基、置換もしくは無置換の環形成原子数5~60のヘテロアリール基、及び、置換もしくは無置換の炭素数1~50のハロアルキル基からなる群から選ばれる請求項1、3及び5~8のいずれか1項に記載の化合物。
- R2、R3、R9、及びR10が表す置換基が、それぞれ独立に、ハロゲン原子、シアノ基、ニトロ基、置換もしくは無置換の炭素数1~50のアルキル基、置換もしくは無置換の環形成炭素数3~50のシクロアルキル基、置換もしくは無置換の環形成炭素数6~60のアリール基、環形成炭素数6~50のアリール基を有する炭素数7~51のアラルキル基、アミノ基、置換もしくは無置換の炭素数1~50のアルキル基及び置換もしくは無置換の環形成炭素数6~60のアリール基から選ばれる置換基を有するモノ置換又はジ置換アミノ基、置換もしくは無置換の炭素数1~50のアルコキシ基、置換もしくは無置換の環形成炭素数3~50のシクロアルコキシ基、置換もしくは無置換の環形成炭素数6~60のアリールオキシ基、置換もしくは無置換の炭素数1~50のアルキルチオ基、置換もしくは無置換の環形成炭素数6~60のアリールチオ基、シリル基、置換もしくは無置換の炭素数1~50のアルキル基及び置換もしくは無置換の環形成炭素数6~60のアリール基から選ばれる置換基を有するモノ置換、ジ置換又はトリ置換シリル基、置換もしくは無置換の環形成原子数5~60のヘテロアリール基、及び、置換もしくは無置換の炭素数1~50のハロアルキル基からなる群から選ばれる請求項1~10のいずれか1項に記載の化合物。
- R4~R8及びR11~R15が表す置換基が、それぞれ独立に、ハロゲン原子、シアノ基、ニトロ基、置換もしくは無置換の炭素数1~50のアルキル基、置換もしくは無置換の環形成炭素数3~50のシクロアルキル基、置換もしくは無置換の環形成炭素数6~60のアリール基、環形成炭素数6~50のアリール基を有する炭素数7~51のアラルキル基、アミノ基、置換もしくは無置換の炭素数1~50のアルキル基及び置換もしくは無置換の環形成炭素数6~60のアリール基から選ばれる置換基を有するモノ置換又はジ置換アミノ基、置換もしくは無置換の炭素数1~50のアルコキシ基、置換もしくは無置換の環形成炭素数3~50のシクロアルコキシ基、置換もしくは無置換の環形成炭素数6~60のアリールオキシ基、置換もしくは無置換の炭素数1~50のアルキルチオ基、置換もしくは無置換の環形成炭素数6~60のアリールチオ基、シリル基、置換もしくは無置換の炭素数1~50のアルキル基及び置換もしくは無置換の環形成炭素数6~60のアリール基から選ばれる置換基を有するモノ置換、ジ置換又はトリ置換シリル基、置換もしくは無置換の環形成原子数5~60のヘテロアリール基、及び、置換もしくは無置換の炭素数1~50のハロアルキル基からなる群から選ばれる請求項1~11のいずれか1項に記載の化合物。
- L1が、m-フェニレン基又はp-フェニレン基である請求項1~12のいずれか1項に記載の化合物。
- L1がR2と結合して形成する環が、縮合もしくは非縮合の環形成炭素数6~50の芳香族環、部分的に水素化された縮合もしくは非縮合の環形成炭素数6~50の芳香族環、縮合もしくは非縮合の環形成原子数5~50の芳香族複素環、及び部分的に水素化された縮合もしくは非縮合の環形成原子数5~50の芳香族複素環からなる群から選ばれる請求項2、4、7~9及び11~13のいずれか1項に記載の化合物。
- R2がR1と結合して形成する環が、縮合もしくは非縮合の環形成炭素数6~50の芳香族環、部分的に水素化された縮合もしくは非縮合の環形成炭素数6~50の芳香族環、縮合もしくは非縮合の環形成原子数5~50の芳香族複素環、及び部分的に水素化された縮合もしくは非縮合の環形成原子数5~50の芳香族複素環からなる群から選ばれる請求項1~4、7~9及び11~13のいずれか1項に記載の化合物。
- 隣接する2個のRaが互いに結合して形成する環が、縮合もしくは非縮合の環形成炭素数6~50の芳香族環、部分的に水素化された縮合もしくは非縮合の環形成炭素数6~50の芳香族環、縮合もしくは非縮合の環形成原子数5~50の芳香族複素環、及び部分的に水素化された縮合もしくは非縮合の環形成原子数5~50の芳香族複素環からなる群から選ばれる請求項1、3、5~8及び10~13のいずれか1項に記載の化合物。
- Xa~XdのすべてがCRaを表し、Raが水素原子を表す請求項1、3、5~8、10~13及び16のいずれか1項に記載の化合物。
- 請求項1~17のいずれか1項に記載の化合物を含有する有機エレクトロルミネッセンス素子用材料。
- 溶媒及び請求項1~17のいずれか1項に記載の化合物を含むインク組成物。
- 陰極、陽極、及び該陰極と該陽極の間に配置された一層以上の有機薄膜層を有する有機エレクトロルミネッセンス素子であって、
前記一層以上の有機薄膜層が発光層を含み、前記一層以上の有機薄膜層の少なくとも1層が請求項1~17のいずれか1項に記載の化合物を含む有機エレクトロルミネッセンス素子。 - 前記発光層が、前記化合物をホスト材料として含む請求項20に記載の有機エレクトロルミネッセンス素子。
- 前記発光層が、燐光発光材料を含有する請求項20又は21に記載の有機エレクトロルミネッセンス素子。
- 前記燐光発光材料が、イリジウム(Ir),オスミウム(Os)及び白金(Pt)からなる群から選択される金属原子のオルトメタル化錯体である請求項22に記載の有機エレクトロルミネッセンス素子。
- 前記陰極と前記発光層の間に電子輸送層を有し、該電子輸送層が前記化合物を含む請求項20~23のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 前記陽極と前記発光層の間に正孔輸送層を有し、該正孔輸送層が前記化合物を含む請求項20~24のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 前記陰極と前記有機薄膜層との界面領域に、電子供与性ドーパントが添加されてなる請求項20~25のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 請求項20~26のいずれか1項に記載の有機エレクトロルミネッセンス素子を備える電子機器。
- 下記カップリング反応1及び下記カップリング反応2を含む請求項1~17のいずれか1項に記載の式(1)で表される化合物の製造方法であって、
(1)前記カップリング反応1では、下記式(I)で表される化合物
*c及び*dの一方は炭素原子*c1に結合し、他方は炭素原子*c2に結合し、
Hal1及びHal2は同一又は異なるハロゲン原子を表す。)
と下記式(II)、(II’)、(III)、(III’)、(III’’)、及び(IV)のいずれかで表されるアミン化合物
を塩基性触媒の存在下、かつ、遷移金属触媒の不存在下で、有機溶媒中で反応させて下記式(V)で表される化合物
を合成し、
(2)前記カップリング反応2では、前記式(V)で表される化合物と前記式(II)、(II’)、(III)、(III’)、(III’’)、及び(IV)のいずれかで表されるアミン化合物(ただし、前記カップリング反応1で用いたアミン化合物とは異なる)を遷移金属触媒と配位子の存在下、かつ、塩基の存在下又は不存在下、有機溶媒中で反応させて、前記式(V)で表される化合物のHal2と前記アミン化合物の水素原子H*の脱離下に前記式(V)で表される化合物と前記アミン化合物をカップリングさせて、式(1)で表される化合物を合成する。 - 前記塩基性触媒が、アルカリ金属炭酸塩類、アルカリ金属炭酸水素塩類、アルカリ土類金属炭酸塩類、金属りん酸塩類、アルカリ金属ヒドリド類、及び属アミド類からなる群より選ばれる少なくとも1種である請求項28に記載の製造方法。
- 前記遷移金属触媒が、パラジウム、銅、白金、ロジウム、ルテニウム、ニッケル、及び鉄からなる群より選ばれる少なくとも1種の遷移金属を含む触媒である請求項28又は29に記載の製造方法。
- 前記塩基が、アルコキシド類、炭酸塩類、及び燐酸塩類からなる群より選ばれる少なくとも1種である請求項28~30のいずれか1項に記載の製造方法
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020167002909A KR102145784B1 (ko) | 2013-12-18 | 2014-12-17 | 화합물, 유기 전기발광 소자용 재료, 잉크 조성물, 유기 전기발광 소자, 전자 기기, 및 화합물의 제조 방법 |
US14/911,606 US10032991B2 (en) | 2013-12-18 | 2014-12-17 | Compound, organic electroluminescence element material, ink composition, organic electroluminescence element, electronic device, and method for producing compound |
CN201480044515.XA CN105431424B (zh) | 2013-12-18 | 2014-12-17 | 化合物、有机电致发光元件用材料、油墨组合物、有机电致发光元件、电子机器及制造方法 |
JP2015553594A JP6589241B2 (ja) | 2013-12-18 | 2014-12-17 | 化合物、有機エレクトロルミネッセンス素子用材料、インク組成物、有機エレクトロルミネッセンス素子、電子機器、及び化合物の製造方法 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013261799 | 2013-12-18 | ||
JP2013-261799 | 2013-12-18 | ||
JP2014-074090 | 2014-03-31 | ||
JP2014074090 | 2014-03-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015093551A1 true WO2015093551A1 (ja) | 2015-06-25 |
Family
ID=53402895
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/083486 WO2015093551A1 (ja) | 2013-12-18 | 2014-12-17 | 化合物、有機エレクトロルミネッセンス素子用材料、インク組成物、有機エレクトロルミネッセンス素子、電子機器、及び化合物の製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US10032991B2 (ja) |
JP (1) | JP6589241B2 (ja) |
KR (1) | KR102145784B1 (ja) |
CN (1) | CN105431424B (ja) |
WO (1) | WO2015093551A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015190789A1 (en) * | 2014-06-09 | 2015-12-17 | Rohm And Haas Electronic Materials Korea Ltd. | An organic electroluminescent compound and an organic electroluminescent device comprising the same |
WO2016129694A1 (ja) * | 2015-02-13 | 2016-08-18 | 出光興産株式会社 | 化合物、有機エレクトロルミネッセンス素子用材料、インク組成物、有機エレクトロルミネッセンス素子、及び電子機器 |
WO2017004405A1 (en) * | 2015-07-01 | 2017-01-05 | Northwestern University | Substituted quinazoline compounds and uses thereof for modulating glucocerebrosidase activity |
JP2017518986A (ja) * | 2014-06-09 | 2017-07-13 | ローム・アンド・ハース・エレクトロニック・マテリアルズ・コリア・リミテッド | 有機電界発光化合物及びそれを含む有機電界発光デバイス |
JP2017210464A (ja) * | 2016-05-26 | 2017-11-30 | 三星ディスプレイ株式會社Samsung Display Co.,Ltd. | 含窒素化合物及び含窒素化合物を含む有機電界発光素子 |
WO2018186340A1 (ja) * | 2017-04-05 | 2018-10-11 | 日産化学株式会社 | 電荷輸送性ワニス |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10461260B2 (en) * | 2014-06-03 | 2019-10-29 | Universal Display Corporation | Organic electroluminescent materials and devices |
JP5981577B2 (ja) * | 2014-12-08 | 2016-08-31 | 古河電気工業株式会社 | 電子デバイス封止用樹脂組成物および電子デバイス |
US11264576B2 (en) * | 2016-12-19 | 2022-03-01 | Idemitsu Kosan Co., Ltd. | Specifically substituted ladder type compounds for organic light emitting devices |
CN110299461A (zh) * | 2019-06-25 | 2019-10-01 | 南昌航空大学 | 一种量子点发光二极管及其制作方法 |
CN114031609A (zh) * | 2021-12-14 | 2022-02-11 | 北京燕化集联光电技术有限公司 | 一种含咔唑及喹唑啉类结构化合物及其应用 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011503006A (ja) * | 2007-11-06 | 2011-01-27 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 殺菌性複素環アミン |
JP2012508718A (ja) * | 2008-11-13 | 2012-04-12 | バイエル・クロップサイエンス・アーゲー | 殺真菌剤ヘテロシクリル−トリアジニル−アミノ誘導体 |
WO2012086170A1 (ja) * | 2010-12-20 | 2012-06-28 | 出光興産株式会社 | 芳香族複素環誘導体及びそれを用いた有機エレクトロルミネッセンス素子 |
WO2012134124A1 (en) * | 2011-03-25 | 2012-10-04 | Rohm And Haas Electronic Materials Korea Ltd. | Novel compounds for organic electronic material and organic electroluminescent device using the same |
WO2013012297A1 (en) * | 2011-07-21 | 2013-01-24 | Rohm And Haas Electronic Materials Korea Ltd. | Novel organic electroluminescence compounds and organic electroluminescence device using the same |
WO2013165192A1 (en) * | 2012-05-02 | 2013-11-07 | Rohm And Haas Electronic Materials Korea Ltd. | Novel organic electroluminescence compounds and organic electroluminescence device containing the same |
WO2015020217A1 (ja) * | 2013-08-09 | 2015-02-12 | 出光興産株式会社 | 有機エレクトロルミネッセンス用組成物、有機エレクトロルミネッセンス素子用材料、有機エレクトロルミネッセンス素子用材料溶液及び有機エレクトロルミネッセンス素子 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR200442811Y1 (ko) | 2008-05-28 | 2008-12-11 | 여운남 | 파워메터 겸용 콘센트 장치 |
JP5338184B2 (ja) | 2008-08-06 | 2013-11-13 | コニカミノルタ株式会社 | 有機エレクトロルミネッセンス素子、表示装置、照明装置 |
WO2010033678A2 (en) * | 2008-09-18 | 2010-03-25 | Ceramoptec Industries, Inc. | Novel method and application of unsymmetrically meso-substituted porphyrins and chlorins for pdt |
JP5707665B2 (ja) | 2008-12-03 | 2015-04-30 | コニカミノルタ株式会社 | 有機エレクトロルミネッセンス素子、該素子を備えた照明装置及び表示装置 |
KR20100094415A (ko) * | 2009-02-17 | 2010-08-26 | 에스에프씨 주식회사 | 시클로아르알킬 유도체 및 이를 이용한 유기전계발광소자 |
KR101902917B1 (ko) | 2009-07-27 | 2018-10-02 | 에스에프씨 주식회사 | 인돌로카바졸 유도체 및 이를 이용한 유기전계발광소자 |
WO2012077520A1 (ja) | 2010-12-09 | 2012-06-14 | 新日鐵化学株式会社 | 有機電界発光素子 |
KR20120122813A (ko) | 2011-04-29 | 2012-11-07 | 롬엔드하스전자재료코리아유한회사 | 신규한 유기 발광 화합물 및 이를 채용하고 있는 유기 전계 발광 소자 |
KR20120122812A (ko) | 2011-04-29 | 2012-11-07 | 롬엔드하스전자재료코리아유한회사 | 신규한 유기 발광 화합물 및 이를 채용하고 있는 유기 전계 발광 소자 |
JP5679496B2 (ja) | 2011-12-02 | 2015-03-04 | 国立大学法人九州大学 | 有機発光素子ならびにそれに用いる遅延蛍光材料および化合物 |
JPWO2013108589A1 (ja) | 2012-01-16 | 2015-05-11 | 出光興産株式会社 | 新規化合物、有機エレクトロルミネッセンス素子用材料及び有機エレクトロルミネッセンス素子 |
-
2014
- 2014-12-17 JP JP2015553594A patent/JP6589241B2/ja not_active Expired - Fee Related
- 2014-12-17 US US14/911,606 patent/US10032991B2/en active Active
- 2014-12-17 KR KR1020167002909A patent/KR102145784B1/ko active IP Right Grant
- 2014-12-17 WO PCT/JP2014/083486 patent/WO2015093551A1/ja active Application Filing
- 2014-12-17 CN CN201480044515.XA patent/CN105431424B/zh not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011503006A (ja) * | 2007-11-06 | 2011-01-27 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 殺菌性複素環アミン |
JP2012508718A (ja) * | 2008-11-13 | 2012-04-12 | バイエル・クロップサイエンス・アーゲー | 殺真菌剤ヘテロシクリル−トリアジニル−アミノ誘導体 |
WO2012086170A1 (ja) * | 2010-12-20 | 2012-06-28 | 出光興産株式会社 | 芳香族複素環誘導体及びそれを用いた有機エレクトロルミネッセンス素子 |
WO2012134124A1 (en) * | 2011-03-25 | 2012-10-04 | Rohm And Haas Electronic Materials Korea Ltd. | Novel compounds for organic electronic material and organic electroluminescent device using the same |
WO2013012297A1 (en) * | 2011-07-21 | 2013-01-24 | Rohm And Haas Electronic Materials Korea Ltd. | Novel organic electroluminescence compounds and organic electroluminescence device using the same |
WO2013165192A1 (en) * | 2012-05-02 | 2013-11-07 | Rohm And Haas Electronic Materials Korea Ltd. | Novel organic electroluminescence compounds and organic electroluminescence device containing the same |
WO2015020217A1 (ja) * | 2013-08-09 | 2015-02-12 | 出光興産株式会社 | 有機エレクトロルミネッセンス用組成物、有機エレクトロルミネッセンス素子用材料、有機エレクトロルミネッセンス素子用材料溶液及び有機エレクトロルミネッセンス素子 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015190789A1 (en) * | 2014-06-09 | 2015-12-17 | Rohm And Haas Electronic Materials Korea Ltd. | An organic electroluminescent compound and an organic electroluminescent device comprising the same |
JP2017518986A (ja) * | 2014-06-09 | 2017-07-13 | ローム・アンド・ハース・エレクトロニック・マテリアルズ・コリア・リミテッド | 有機電界発光化合物及びそれを含む有機電界発光デバイス |
WO2016129694A1 (ja) * | 2015-02-13 | 2016-08-18 | 出光興産株式会社 | 化合物、有機エレクトロルミネッセンス素子用材料、インク組成物、有機エレクトロルミネッセンス素子、及び電子機器 |
JPWO2016129694A1 (ja) * | 2015-02-13 | 2017-11-24 | 出光興産株式会社 | 化合物、有機エレクトロルミネッセンス素子用材料、インク組成物、有機エレクトロルミネッセンス素子、及び電子機器 |
WO2017004405A1 (en) * | 2015-07-01 | 2017-01-05 | Northwestern University | Substituted quinazoline compounds and uses thereof for modulating glucocerebrosidase activity |
JP2018525345A (ja) * | 2015-07-01 | 2018-09-06 | ノースウェスタン ユニバーシティ | 置換キナゾリン化合物及びグルコセレブロシダーゼ活性の調節のためのその使用 |
US10501435B2 (en) | 2015-07-01 | 2019-12-10 | Northwestern University | Substituted quinazoline compounds and uses thereof for modulating glucocerebrosidase activity |
US10934270B2 (en) | 2015-07-01 | 2021-03-02 | Northwestern University | Substituted quinazoline compounds and uses thereof for modulating glucocerebrosidase activity |
JP2017210464A (ja) * | 2016-05-26 | 2017-11-30 | 三星ディスプレイ株式會社Samsung Display Co.,Ltd. | 含窒素化合物及び含窒素化合物を含む有機電界発光素子 |
US10686139B2 (en) | 2016-05-26 | 2020-06-16 | Samsung Display Co., Ltd. | Nitrogen-containing compound and organic electroluminescence device including the same |
WO2018186340A1 (ja) * | 2017-04-05 | 2018-10-11 | 日産化学株式会社 | 電荷輸送性ワニス |
Also Published As
Publication number | Publication date |
---|---|
CN105431424B (zh) | 2019-09-06 |
JP6589241B2 (ja) | 2019-10-16 |
KR20160092983A (ko) | 2016-08-05 |
KR102145784B1 (ko) | 2020-08-19 |
US10032991B2 (en) | 2018-07-24 |
CN105431424A (zh) | 2016-03-23 |
US20160197288A1 (en) | 2016-07-07 |
JPWO2015093551A1 (ja) | 2017-03-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6589241B2 (ja) | 化合物、有機エレクトロルミネッセンス素子用材料、インク組成物、有機エレクトロルミネッセンス素子、電子機器、及び化合物の製造方法 | |
JP5802854B2 (ja) | 縮合フルオランテン化合物、これを用いた有機エレクトロルミネッセンス素子用材料、並びにこれを用いた有機エレクトロルミネッセンス素子及び電子機器 | |
KR101896729B1 (ko) | 방향족 복소 고리 유도체 및 그것을 사용한 유기 일렉트로 루미네선스 소자 | |
KR102282551B1 (ko) | 카바졸 유도체, 이것을 이용한 유기 전기발광 소자용 재료, 및 이것을 이용한 유기 전기발광 소자 및 전자 기기 | |
JP5877273B2 (ja) | 複素環化合物、これを用いた有機エレクトロルミネッセンス素子用材料、並びにこれを用いた有機エレクトロルミネッセンス素子及び電子機器 | |
JP6114232B2 (ja) | 複素環化合物、これを用いた有機エレクトロルミネッセンス素子用材料、並びにこれを用いた有機エレクトロルミネッセンス素子及び電子機器 | |
WO2014192950A1 (ja) | 縮合フルオランテン化合物、これを含む有機エレクトロルミネッセンス素子用材料、並びにこれを用いた有機エレクトロルミネッセンス素子及び電子機器 | |
JP6375308B2 (ja) | 化合物、有機エレクトロルミネッセンス素子用材料、インク組成物、有機エレクトロルミネッセンス素子、及び電子機器 | |
US10763442B2 (en) | Compound, organic electroluminescent element material using same, organic electroluminescent element using this material, and electronic device | |
KR101882592B1 (ko) | 화합물, 유기 일렉트로루미네선스 소자용 재료, 유기 일렉트로루미네선스 소자 및 전자 기기 | |
WO2016129694A1 (ja) | 化合物、有機エレクトロルミネッセンス素子用材料、インク組成物、有機エレクトロルミネッセンス素子、及び電子機器 | |
JP2018123083A (ja) | 新規アントラセン誘導体、有機エレクトロルミネッセンス素子用材料、有機エレクトロルミネッセンス素子用材料溶液、有機エレクトロルミネッセンス素子及び電子機器 | |
WO2014157230A1 (ja) | 有機エレクトロルミネッセンス素子及びその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480044515.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14872145 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015553594 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20167002909 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14911606 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14872145 Country of ref document: EP Kind code of ref document: A1 |