WO2022209891A1 - Polymère et son utilisation - Google Patents

Polymère et son utilisation Download PDF

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WO2022209891A1
WO2022209891A1 PCT/JP2022/011837 JP2022011837W WO2022209891A1 WO 2022209891 A1 WO2022209891 A1 WO 2022209891A1 JP 2022011837 W JP2022011837 W JP 2022011837W WO 2022209891 A1 WO2022209891 A1 WO 2022209891A1
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group
carbon atoms
groups
charge
represented
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光平 寺谷
雄大 森元
圭介 首藤
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日産化学株式会社
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Priority to JP2023510908A priority Critical patent/JPWO2022209891A1/ja
Priority to CN202280022193.3A priority patent/CN116997575A/zh
Priority to KR1020237036905A priority patent/KR20230161502A/ko
Publication of WO2022209891A1 publication Critical patent/WO2022209891A1/fr

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    • 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
    • H10K50/155—Hole transporting layers comprising dopants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/36—Amides or imides
    • C08F22/40—Imides, e.g. cyclic imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/36—Amides or imides
    • C08F122/40—Imides, e.g. cyclic imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • 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
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • 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
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE

Definitions

  • the present invention relates to polymers and their uses.
  • a charge-transporting thin film made of an organic compound is used as a light-emitting layer or charge injection layer in an organic electroluminescence (EL) device.
  • the hole-injecting layer is responsible for transferring charges between the anode and the hole-transporting layer or the light-emitting layer, and plays an important role in achieving low-voltage driving and high luminance of the organic EL device.
  • organic EL elements are required to have high heat resistance
  • charge-transporting materials used in organic EL elements are required to have high heat resistance.
  • the method of forming the hole injection layer is roughly divided into a dry process typified by vapor deposition and a wet process typified by spin coating. Comparing these processes, the wet process can efficiently produce a thin film having a large area and high flatness. Therefore, at present, where organic EL displays are becoming larger in area, wet process materials that can be formed by wet processes and provide charge-transporting thin films with excellent refractive index, transparency, and heat resistance are always in demand. It is
  • the present invention has been made in view of the above circumstances, and provides a thin film having high heat resistance, good charge transport properties, a high refractive index and high transparency, and applying this thin film to a hole injection layer or the like.
  • An object of the present invention is to provide a polymer capable of realizing an organic EL device having excellent properties when the polymer is used.
  • the inventors of the present invention have made intensive studies to achieve the above objects, and found that a charge-transporting varnish containing a polymer having a triarylamine structure, a diarylether structure, or a diarylsulfide structure and a dialkylfluorene structure in side chains
  • the organic EL element has high heat resistance, exhibits excellent charge transport properties, and provides a thin film with high transparency and high refractive index, and has excellent properties when this thin film is applied to a hole injection layer or the like.
  • the present invention was completed by finding that it gives.
  • RA is a hydrogen atom or a methyl group.
  • R 1 to R 4 are each independently a single bond or a phenylene group, and some or all of the hydrogen atoms in the phenylene group are cyano, nitro, halogen, vinyl, trifluorovinyl, acryloyl group, methacryloyl group, oxetane group, epoxy group, alkyl group having 1 to 20 carbon atoms or halogenated alkyl group having 1 to 20 carbon atoms.
  • X 1 is -N(Ar 3 )-, -S- or -O-.
  • X 2 is -N(Ar 6 )-, -S- or -O-.
  • Ar 1 and Ar 4 each independently represent an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 3 to 20 carbon atoms, or two hydrogen atoms on the aromatic ring of dialkylfluorene represented by the following formula (3);
  • a divalent group obtained by removing one, and some or all of the hydrogen atoms on the aromatic rings of these groups are cyano group, nitro group, halogen atom, vinyl group, trifluorovinyl group, acryloyl group, methacryloyl group, oxetane group, epoxy group, alkyl group having 1 to 20 carbon atoms or halogenated alkyl group having 1 to 20 carbon atoms.
  • Ar 2 , Ar 3 , Ar 5 and Ar 6 are each independently obtained by removing one hydrogen atom from the aromatic ring of an aryl group having 6 to 20 carbon atoms or a dialkylfluorene represented by the following formula (3). and some or all of the hydrogen atoms on the aromatic rings of these groups are cyano groups, nitro groups, halogen atoms, vinyl groups, trifluorovinyl groups, acryloyl groups, methacryloyl groups, oxetane groups , an epoxy group, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms.
  • Ar 2 and Ar 3 may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded
  • X 2 is -N(Ar 6 )-
  • Ar 5 and Ar 6 may be bonded together to form a ring with the nitrogen atom to which they are bonded
  • R 2 is a phenylene group
  • R 2 and Ar 2 may be bonded to each other to form a ring together with the nitrogen atom, sulfur atom or oxygen atom to which they are bonded
  • R 4 is a phenylene group
  • R 4 and Ar 5 may bond with each other to form a ring together with the nitrogen atom, sulfur atom or oxygen atom to which they bond.
  • At least one of Ar 1 to Ar 3 is a group obtained by removing a hydrogen atom on the aromatic ring of the dialkylfluorene represented by the following formula (3)
  • at least one of Ar 4 to Ar 6 One is a group obtained by removing a hydrogen atom on the aromatic ring of the dialkylfluorene represented by the following formula (3).
  • R 5 and R 6 are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms containing at least one ether structure; be.
  • Polymer 1 wherein the repeating unit represented by formula (1) is represented by the following formula (1A), and the repeating unit represented by formula (2) is represented by the following formula (2A) .
  • R A , R 1 to R 4 and Ar 1 to Ar 6 are the same as above.
  • a charge-transporting substance comprising the polymer of any one of 1-5. 7.
  • the polymer of the present invention has high heat resistance, high transparency, and a high refractive index, and has a triarylamine structure, a diaryl ether structure, or a diaryl sulfide structure and a dialkylfluorene structure in the side chains, so that it has excellent electric charge. It has transportability.
  • a thin film with high heat resistance, high transparency and high refractive index can be produced.
  • the charge-transporting thin film obtained from the charge-transporting varnish of the present invention can be suitably used as a thin film for electronic devices such as organic EL devices, and can be used as a hole-injecting layer or hole-transporting layer of an organic EL device. By using it as a hole injection layer, an organic EL device with excellent characteristics can be obtained.
  • polymer The polymer of the present invention contains at least one selected from repeating units represented by the following formula (1) and repeating units represented by the following formula (2).
  • RA is a hydrogen atom or a methyl group.
  • R 1 to R 4 are each independently a single bond or a phenylene group, and some or all of the hydrogen atoms in the phenylene group are cyano, nitro, halogen, vinyl, trifluorovinyl, acryloyl group, methacryloyl group, oxetane group, epoxy group, alkyl group having 1 to 20 carbon atoms or halogenated alkyl group having 1 to 20 carbon atoms.
  • the phenylene group includes a 1,2-phenylene group, a 1,3-phenylene group and a 1,4-phenylene group, with the 1,4-phenylene group being preferred.
  • the alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl.
  • straight groups having 1 to 20 carbon atoms such as group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group; Chain or branched alkyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group , a bicyclooctyl group, a bicyclononyl group, a bicyclodecyl group, and other cyclic alkyl groups having 3 to 20 carbon atoms.
  • the halogenated alkyl group having 1 to 20 carbon atoms is not particularly limited as long as it is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 20 carbon atoms have been substituted with halogen atoms.
  • Specific examples thereof include a trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 3,3,3-trifluoropropyl group, 2, 2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4 ,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group, etc. is mentioned.
  • R 1 and R 3 are preferably single bonds, and R 2 and R 4 are preferably phenylene groups.
  • X 1 is -N(Ar 3 )-, -S- or -O-.
  • X 2 is -N(Ar 6 )-, -S- or -O-.
  • Ar 1 and Ar 4 are each independently an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 3 to 20 carbon atoms, or a dialkyl represented by the following formula (3)
  • a divalent group obtained by removing two hydrogen atoms on the aromatic ring of fluorene, and part or all of the hydrogen atoms on the aromatic ring of these groups are a cyano group, a nitro group, a halogen atom, and a vinyl group.
  • the arylene group having 6 to 20 carbon atoms includes a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,2-naphthalene-diyl group, a 2,3-naphthalenediyl group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group, 1,8-naphthalenediyl group, 1,2-anthracenediyl group, 1, 3-anthracenediyl group, 1,4-anthracenediyl group, 1,5-anthracenediyl group, 1,6-anthracenediyl group, 1,7-anthracenediyl group, 1,8-anthracenediyl group, 2,3- anthracenediyl group, 2,6-anthracenediyl group, 2,7-anthracenediyl group, 2,9-anth
  • heteroarylene group having 3 to 20 carbon atoms examples include 9-phenylcarbazole-3,6-diyl group, 9-phenylcarbazole-2,7-diyl group, 9-phenylcarbazole-3,6-dimethyl-2, Examples thereof include a 7-diyl group and groups represented by the following formulas (H1) to (H33).
  • R 5 and R 6 are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms containing at least one ether structure. is the base.
  • the alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl.
  • straight groups having 1 to 20 carbon atoms such as group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group; Chain or branched alkyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group , a bicyclooctyl group, a bicyclononyl group, a bicyclodecyl group, and other cyclic alkyl groups having 3 to 20 carbon atoms.
  • the alkoxy group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, C1 such as isobutoxy, sec-butoxy, tert-butoxy, n-pentyl, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy to 20 linear or branched alkoxy groups; cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy, cyclodecyloxy, Cyclic alkoxy groups having 3 to 20 carbon atoms such as a bicyclobutyloxy group, a bicyclopentyloxy group, a bi
  • Examples of the alkyl group having 2 to 20 carbon atoms containing at least one ether structure include linear or branched alkyl groups in which at least one methylene group is substituted with an oxygen atom.
  • the methylene group bonded to the fluorene skeleton is not substituted with an oxygen atom, and the adjacent methylene groups are not simultaneously substituted with an oxygen atom.
  • the group represented by the formula (A) is preferable, and among these, the group represented by the formula (B) is more preferable.
  • R 7 represents a linear or branched alkylene group having 1 to 4 carbon atoms
  • R 8 represents a linear or branched chain having 1 to [20-(the number of carbon atoms in R) ⁇ p].
  • p is an integer of 1 to 9.
  • p is preferably 2 or more, more preferably 3 or more, from the viewpoint of compatibility with the dopant, and from the viewpoint of availability of the raw material compound Therefore, it is preferably 5 or less, more preferably 4 or less.
  • alkyl groups having 2 to 20 carbon atoms containing at least one ether structure include -CH2OCH3 , -CH2OCH2CH3 , -CH2O ( CH2 ) 2CH3 , -CH2OCH ( CH 3 ) 2 , -CH2O( CH2 ) 3CH3, -CH2OCH2CH(CH3)2 , -CH2OC ( CH3 ) 3 , -CH2O ( CH2 ) 4CH3 , -CH2OCH ( CH3 )( CH2 ) 2CH3, -CH2O(CH2)2CH(CH3)2 , -CH2OCH ( CH3 ) ( CH2 ) 3CH3 , -CH 2O ( CH2 ) 5CH3 , -CH2OCH2CH ( CH3 )( CH2 ) 2CH3 , -CH2O ( CH2 ) 2CH ( CH3 ) CH2CH3 , -CH2 O( CH2 )3
  • Examples of the divalent group obtained by removing two hydrogen atoms on the aromatic ring of the dialkylfluorene represented by formula (3) include 9,9-dimethyl-9H-fluorene-2,7-diyl group, 9, 9-diethyl-9H-fluorene-2,7-diyl group, 9,9-dipropyl-9H-fluorene-2,7-diyl group, 9,9-dibutyl-9H-fluorene-2,7-diyl group, 9 ,9-dihexyl-9H-fluorene-2,7-diyl group, 9,9-dioctyl-9H-fluorene-2,7-diyl group, 9,9-bis(2-ethylhexyl)-9H-fluorene- 2,7-diyl group, 9,9-dimethoxy-9H-fluorene-2,7-diyl group, 9,9-diethoxy-9H-fluoren
  • Ar 1 and Ar 4 are preferably groups obtained by removing two hydrogen atoms on the aromatic ring of the dialkylfluorene represented by formula (3), particularly 9,9-dimethyl-9H-fluorene.
  • a -2,7-diyl group is preferred.
  • Ar 2 , Ar 3 , Ar 5 and Ar 6 are each independently an aryl group having 6 to 20 carbon atoms or on the aromatic ring of dialkylfluorene represented by formula (3). are monovalent groups obtained by removing one hydrogen atom from, and some or all of the hydrogen atoms on the aromatic rings of these groups are cyano groups, nitro groups, halogen atoms, vinyl groups, trifluorovinyl groups , an acryloyl group, a methacryloyl group, an oxetane group, an epoxy group, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms and the halogenated alkyl group having 1 to 20 carbon atoms are the same as those described above.
  • Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group and the like.
  • Examples of the monovalent group obtained by removing one hydrogen atom on the aromatic ring of the dialkylfluorene represented by formula (3) include 9,9-dimethyl-9H-fluoren-2-yl group, 9,9- dimethyl-9H-fluoren-3-yl group, 9,9-diethyl-9H-fluoren-2-yl group, 9,9-diethyl-9H-fluoren-3-yl group, 9,9-dipropyl-9H-fluorene -2-yl group, 9,9-dipropyl-9H-fluoren-3-yl group, 9,9-dibutyl-9H-fluoren-2-yl group, 9,9-dibutyl-9H-fluoren-3-yl group , 9,9-dihexyl-9H-fluoren-2-yl group, 9,9-dihexyl-9H-fluoren-3-yl group, 9,9-dioctyl-9H-fluoren-2-yl group, 9,
  • Ar 2 and Ar 3 may combine with each other to form a ring together with the nitrogen atom to which they are bonded.
  • X 2 is --N(Ar 6 )--
  • Ar 5 and Ar 6 may combine with each other to form a ring together with the nitrogen atom to which they are bonded.
  • the ring structure is preferably a carbazole ring.
  • R 2 is a phenylene group
  • R 2 and Ar 2 may combine with each other to form a ring together with the nitrogen atom, sulfur atom or oxygen atom to which they are bonded.
  • R 4 is a phenylene group
  • R 4 and Ar 5 may combine with each other to form a ring together with the nitrogen atom, sulfur atom or oxygen atom to which they are bonded.
  • the ring structure is preferably a carbazole ring, a dibenzothiophene ring, or a dibenzofuran ring.
  • At least one of Ar 1 to Ar 3 is a group obtained by removing a hydrogen atom on the aromatic ring of the dialkylfluorene represented by formula (3)
  • at least one of Ar 4 to Ar 6 is a group obtained by removing a hydrogen atom on the aromatic ring of the dialkylfluorene represented by formula (3).
  • X 1 is preferably -N(Ar 3 )-
  • X 2 is -N(Ar 6 )-
  • the repeating unit represented by the formula (1) is preferably represented by the following formula (1A)
  • the repeating unit represented by the formula (2) is represented by the following formula (2A). things are preferred. (In the formula, R A , R 1 to R 4 and Ar 1 to Ar 6 are the same as above.)
  • the polymer of the present invention may contain either the repeating unit represented by formula (1) or the repeating unit represented by formula (2), or may contain both of them.
  • repeating units other than the repeating unit represented by formula (1) and the repeating unit represented by formula (2) may be included within a range that does not impair the effects of the present invention.
  • Other repeating units include compounds containing polymerizable functional groups such as acryloyl groups, acrylamide groups, methacryloyl groups, methacrylamide groups, vinyl ether groups, and maleic anhydride.
  • the polymer of the present invention may be a random copolymer, an alternating copolymer, or a block copolymer.
  • the content of the repeating unit represented by formula (1) and the repeating unit represented by formula (2) is preferably 50 mol% or more, more preferably 80 mol% or more, of all repeating units contained in the polymer. More preferably 90 mol % or more, still more preferably 95 mol % or more, most preferably 100 mol %.
  • the content ratio of these units is the molar ratio of the repeating unit represented by formula (1):
  • the repeating unit represented by formula (2) is preferably 1:99 to 99:1, more preferably 5:95 to 95:5, and even more preferably 10:90 to 90:10.
  • the expression that the content of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) is 100 mol% is due to impurity monomers in the raw materials and side reactions during polymer synthesis. However, the existence of impurity repeating units contained in a trace amount is not denied.
  • a polymer is synthesized using, a polymer containing 100 mol % of the repeating units represented by the formula (1) and the repeating units represented by the formula (2) can be obtained.
  • the weight average molecular weight (Mw) of the polymer of the present invention is usually 2,000 to 1,000,000. 500,000 or less, more preferably 200,000 or less. Further, its dispersity (Mw/Mn) is not particularly limited, but is usually 1.0 to 10.0, preferably 1.1 to 5.0, more preferably 1.2. ⁇ 3.0.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer are, for example, Shimadzu Corporation GPC device, auto sampler SIL-10AF, degasser DGU-20As, column oven CTO-20A.
  • the polymer of the present invention can be produced by polymerizing at least one selected from monomers represented by the following formula (1') and monomers represented by the following formula (2'). (wherein R A , R 1 to R 4 , X 1 , X 2 , Ar 1 , Ar 2 , Ar 4 and Ar 5 are the same as above).
  • the polymerization reaction is not particularly limited, and radical polymerization, anionic polymerization, cationic polymerization, etc. may be employed.
  • radical polymerization is particularly preferred, and specifically, the monomer may be polymerized by heating in a solvent in the presence of a polymerization initiator.
  • the polymerization initiator can be appropriately selected and used from conventionally known ones.
  • peroxides such as benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide
  • persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate
  • azobisisobutyronitrile (AIBN) azo
  • examples include azo compounds such as bismethylbutyronitrile and azobisisovaleronitrile. These may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the amount of polymerization initiator used is preferably about 0.01 to 0.05 mol per 1 mol of the monomer.
  • the reaction temperature may be appropriately set from 0°C to the boiling point of the solvent used, but is preferably about 20 to 100°C.
  • the reaction time is preferably about 0.1 to 30 hours.
  • the solvent used for the polymerization reaction may be appropriately selected from various solvents commonly used in this type of reaction. Specifically, water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, iso Alcohols such as pentanol, tert-pentanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol, cyclohexanol; diethyl ether, diisopropyl Ethers such as ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane; Halogenated hydrocarbons such as chloroform
  • acetals fatty acids such as formic acid, acetic acid and propionic acid; nitropropane, nitrobenzene, dimethylamine, monoethanolamine, pyridine, N-methyl-2-pyrrolidone, N,N-dimethylformamide, dimethylsulfoxide, acetonitrile mentioned. These may be used individually by 1 type, and may be used in mixture of 2 or more types.
  • the method for synthesizing the polymer includes the above-described Polymerization may be carried out in the presence of monomers and monomers that provide other repeating units.
  • the monomer represented by Formula (1') can be synthesized using a conventionally known reaction.
  • a conventionally known reaction for example, as shown in Scheme A below, maleic anhydride and an amine compound represented by formula (1'') are mixed in a solvent, optionally in the presence of a catalyst.
  • a method of reacting can be mentioned. (In the formula, R 1 , R 2 , X 1 , Ar 1 and Ar 2 are the same as above.)
  • solvent examples include acetic acid, toluene, ethyl acetate, tetrahydrofuran, methanol, ethanol, dimethylformamide, dimethylsulfoxide and the like.
  • the catalyst examples include acetic acid, sodium acetate, potassium acetate, toluenesulfonic acid, camphorsulfonic acid, and the like.
  • the amount of the catalyst used is preferably 1.0 to 10.0, more preferably 2.0 to 5.0 in terms of molar ratio to the amine compound represented by formula (1'').
  • acetic acid is used as the solvent, no catalyst may be used.
  • the charging ratio of maleic anhydride and the amine compound represented by formula (1'') is such that the molar ratio of the amine compound represented by formula (1'') to maleic anhydride is 0.
  • An amount of 0.5 to 3.0 is preferred, and an amount of 1.0 to 1.5 is more preferred.
  • the reaction temperature is appropriately set within a range from the melting point to the boiling point of the solvent, taking into account the type and amount of the raw material compound and catalyst used, and is usually about 40 to 150°C, preferably 80 to 120°C. .
  • the reaction time varies depending on the raw material compound used, the reaction temperature, etc., and cannot be defined unconditionally, but is usually about 2 to 24 hours.
  • the target monomer can be obtained by post-processing according to the usual method.
  • the monomer represented by Formula (2') can be synthesized by combining various coupling reactions.
  • a coupling reaction between a styrene compound represented by the formula (2'') and an amine compound represented by the following formula (2'') There is a method to make (In the formula, R A , R 3 , R 4 , X 2 , Ar 4 and Ar 5 are the same as above.)
  • XA is any group used in the coupling reaction.
  • groups include boronic acid groups such as —B(OH) 2 and boronic acid ester groups when Suzuki-Miyaura coupling reaction is used.
  • each X B is independently a halogen atom or a pseudohalogen group.
  • the halogen atom represented by X B includes fluorine, chlorine, bromine and iodine atoms, preferably bromine or iodine.
  • Pseudohalogen groups represented by X B include fluoroalkylsulfonyloxy groups such as methanesulfonyloxy, trifluoromethanesulfonyloxy and nonafluorobutanesulfonyloxy groups; aromatic groups such as benzenesulfonyloxy and toluenesulfonyloxy groups; A sulfonyloxy group and the like can be mentioned.
  • the solvent used in the coupling reaction is not particularly limited as long as it does not adversely affect the reaction.
  • examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), Halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), ethers (diethyl ether , diisopropyl ether, tert-butyl methyl ether, THF, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.), amides (N,N-dimethylformamide (DMF), N,N-dimethylacetamide
  • lactams and lactones N-methylpyrrolidone, ⁇ -butyrolactone, etc.
  • urea derivatives N,N-dimethylimidazolidinone, tetramethylurea, etc.
  • sulfoxides dimethylsulfoxide, sulfolane, etc.
  • nitriles acetonitrile, propio nitrile, butyronitrile, etc.
  • preferred solvents are aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), aromatic hydrocarbons (benzene, nitrobenzene, toluene, etc.) from the viewpoint of efficiently obtaining the desired product. , o-xylene, m-xylene, p-xylene, mesitylene, etc.), ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, THF, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.
  • aliphatic hydrocarbons penentane, n-hexane, n-octane, n-decane, decalin, etc.
  • aromatic hydrocarbons benzene, nitrobenzene, toluene, etc.
  • ethers diethyl
  • aromatic hydrocarbons benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.
  • ethers diethyl ether, diisopropyl ether, tert-butyl methyl ether, THF, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.
  • the amount of the catalyst used is preferably an amount that provides a molar ratio of 0.01 to 0.2, more preferably 0.03 to 0.1, relative to the amine compound represented by formula (2''). preferable.
  • the amount thereof can be 0.1 to 3.0 equivalents, preferably 0.8 to 1.5 equivalents, relative to the metal complex used.
  • a base may also be used in the coupling reaction.
  • the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkoxy alkali metals such as tert-butoxylithium, tert-butoxysodium and tert-butoxypotassium; alkali metal carbonate; alkali metal hydrogen carbonate such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkaline earth metal carbonate such as calcium carbonate; organic lithium such as n-butyllithium, sec-butyllithium and tert-butyllithium; triethylamine, Examples thereof include amines such as diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine, but are not particularly limited as long as they can be used for this type of reaction.
  • sodium carbonate and potassium carbonate are suitable because they are easy to handle.
  • the amount of the base to be used is usually about 1 to 20, preferably 4 to 8,
  • the charging ratio of the styrene compound represented by the formula (2'') to the amine compound represented by the following formula (2'') is styrene represented by the formula (2'')
  • the molar ratio of the amine compound represented by formula (2''') to the compound is preferably from 0.2 to 2.0, more preferably from 0.5 to 1.0.
  • the reaction temperature is appropriately set within the range from the melting point to the boiling point of the solvent, taking into account the type and amount of the raw material compounds and catalysts used, and is usually about 20 to 120° C., preferably 60 to 100°C.
  • the reaction time varies depending on the raw material compound used, the reaction temperature, etc., and cannot be generally specified, but is usually about 0.5 to 12 hours.
  • the target monomer can be obtained by post-processing according to the usual method.
  • the polymer of the present invention can be suitably used as a charge-transporting substance, particularly as a hole-transporting substance.
  • charge transportability is synonymous with conductivity.
  • a charge-transporting substance itself has a charge-transporting property.
  • the charge-transporting varnish may itself have charge-transporting properties, or the solid film obtained therefrom may have charge-transporting properties.
  • the charge-transporting varnish of the present invention contains a charge-transporting substance comprising the polymer and an organic solvent.
  • the charge-transporting substance may be used singly or in combination of two or more.
  • the charge-transporting substance may contain a charge-transporting polymer compound other than the polymer, a charge-transporting low-molecular-weight compound, or a charge-transporting oligomer compound.
  • Organic solvent a highly polar solvent that can dissolve the polymer well can be used. Also, if desired, less polar solvents may be used because they are more process compatible than highly polar solvents.
  • a low polar solvent is defined as having a dielectric constant of less than 7 at a frequency of 100 kHz
  • a highly polar solvent is defined as having a dielectric constant of 7 or more at a frequency of 100 kHz.
  • low-polarity solvent examples include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene; 1-octanol, 1-nonanol, 1-decanol, and the like.
  • Ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether Solvent; Methyl benzoate, Ethyl benzoate, Butyl benzoate, Isoamyl benzoate, Bis(2-ethylhexyl) phthalate, Dimethyl phthalate, Diisopropyl malonate, Dibutyl maleate, Dibutyl oxalate, Hexyl acetate, Propylene glycol monomethyl ether Ester-based solvents such as acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like are included.
  • Examples of the highly polar solvent include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.
  • ketone solvents such as ethyl methyl ketone, isophorone and cyclohexanone; cyano solvents such as acetonitrile and 3-methoxypropionitrile; ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, Polyhydric alcohol solvents such as 2,3-butanediol; diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyl monohydric alcohol solvents other than aliphatic alcohols such as oxyethanol, 3-phenoxybenzyl alcohol and tetrahydrofurfuryl alcohol; sulfoxide solvents such as dimethylsulfoxide;
  • the amount of the organic solvent used is preferably such that the solid content concentration in the varnish of the present invention is usually about 0.1 to 20% by mass, from the viewpoint of suppressing deposition of the charge-transporting substance and ensuring a sufficient film thickness. is an amount of 0.5 to 10% by mass.
  • solid content means the components other than a solvent among the components contained in a varnish.
  • the said organic solvent may be used individually by 1 type, and may be used in mixture of 2 or more types.
  • the charge-transporting varnish of the present invention may contain water as a solvent, but usually contains only an organic solvent as a solvent.
  • only organic solvent means that only the organic solvent is intended to be used as a solvent, and denies even the presence of hydration water and solid content of the compound and the presence of trace amounts of water contained in the organic solvent. Do not mean.
  • the charge-transporting varnish of the present invention may contain a dopant for the purpose of improving the charge-transporting property of the thin film obtained from the charge-transporting varnish of the present invention.
  • the dopant is not particularly limited as long as it dissolves in at least one solvent used in the varnish, and either an inorganic dopant or an organic dopant can be used.
  • the dopant exhibits or improves its function as a dopant for the first time when part of the molecule is removed by an external stimulus such as heating during firing.
  • it may be an arylsulfonate ester compound in which the sulfonic acid group is protected with a group that is easy to leave.
  • heteropolyacids are preferable, and specific examples thereof include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, phosphotungstomolybdic acid, and silicotungstic acid.
  • Heteropolyacids typically have a structure in which a heteroatom is located at the center of the molecule, represented by a Keggin-type chemical structure represented by the following formula (HPA1) or a Dawson-type chemical structure represented by the following formula (HPA2). It is a polyacid obtained by condensing an isopolyacid, which is an oxyacid such as vanadium (V), molybdenum (Mo), tungsten (W), and an oxyacid of a different element.
  • Oxygen acids of such dissimilar elements mainly include oxyacids of silicon (Si), phosphorus (P), and arsenic (As).
  • heteropolyacid examples include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, and phosphotungstomolybdic acid. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the heteropolyacid used in the present invention is available as a commercial product, and can also be synthesized by a known method.
  • the one type of heteropolyacid is preferably phosphotungstic acid or phosphomolybdic acid, most preferably phosphotungstic acid.
  • one of the two or more heteropolyacids is preferably phosphotungstic acid or phosphomolybdic acid, more preferably phosphotungstic acid.
  • the heteropolyacid is obtained as a commercially available product, or a known synthetic As long as it is synthesized appropriately according to the method, it can be used in the present invention.
  • phosphotungstic acid is generally represented by the chemical formula H 3 (PW 12 O 40 ) ⁇ nH 2 O
  • phosphomolybdic acid is represented by the chemical formula H 3 (PMo 12 O 40 ) ⁇ nH 2 O, respectively.
  • P phosphorus
  • O oxygen
  • W tungsten
  • Mo molybdenum
  • the mass of the heteropolyacid defined in the present invention is not the mass of pure phosphotungstic acid (phosphotungstic acid content) in the synthetic product or commercial product, but the form available as a commercial product and a known synthesis In a form that can be isolated by the method, it means the total mass in a state containing water of hydration and other impurities.
  • organic dopant examples include arylsulfonic acid compounds, arylsulfonic acid esters, and ionic compounds composed of a predetermined anion and its countercation.
  • the arylsulfonic acid compound is preferably represented by the following formula (A) or (B).
  • a 1 is -O- or -S-, but -O- is preferred.
  • a 2 is a (p 2 +1) valent group derived from naphthalene or anthracene (that is, a group obtained by removing (p 2 +1) hydrogen atoms from naphthalene or anthracene), but is preferred.
  • a 3 is a divalent to tetravalent perfluorobiphenyl group.
  • p 1 is the number of bonds between A 1 and A 3 and is an integer satisfying 2 ⁇ p 1 ⁇ 4, where A 3 is a divalent perfluorobiphenyl group and p 1 is 2; is preferred.
  • p 2 is the number of sulfonic acid groups bonded to A 2 and is an integer satisfying 1 ⁇ p 2 ⁇ 4, with 2 being preferred.
  • a 4 to A 8 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 2 to 2 carbon atoms. 20 alkenyl halide groups, but at least 3 of A 4 -A 8 are halogen atoms.
  • q is the number of sulfonic acid groups bonded to the naphthalene ring and is an integer satisfying 1 ⁇ q ⁇ 4, preferably 2 to 4, more preferably 2.
  • the alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl.
  • Examples of the halogenated alkyl group having 1 to 20 carbon atoms include trifluoromethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, 3,3,3-trifluoropropyl group, 2,2, 3,3,3-pentafluoropropyl group, perfluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3, 4,4,4-heptafluorobutyl group, perfluorobutyl group and the like.
  • Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include perfluoroethenyl group, 1-perfluoropropenyl group, perfluoroallyl group and perfluorobutenyl group.
  • the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • a 4 to A 8 are hydrogen atom, halogen atom, cyano group, alkyl group having 1 to 10 carbon atoms, halogenated alkyl group having 1 to 10 carbon atoms or alkenyl halide having 2 to 10 carbon atoms. and at least three of A 4 to A 8 are preferably fluorine atoms, such as a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, and a fluorinated group having 1 to 5 carbon atoms.
  • it is an alkyl group or a fluorinated alkenyl group having 2 to 5 carbon atoms, and at least 3 of A 4 to A 8 are fluorine atoms, and hydrogen atom, fluorine atom, cyano group, and 1 to 1 carbon atoms.
  • the perfluoroalkyl group is a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms
  • the perfluoroalkenyl group is a group in which all hydrogen atoms of an alkenyl group are substituted with fluorine atoms.
  • Suitable arylsulfonic acid compounds include, but are not limited to, those shown below.
  • the arylsulfonate ester compound disclosed in International Publication No. 2017/217455, International Publication No. 2017/217457 No. 2017-243631, aryl sulfonate ester compounds disclosed in No. 2017-243631, and the like.
  • the arylsulfonate compound is preferably represented by any one of the following formulas (C) to (E).
  • m is an integer that satisfies 1 ⁇ m ⁇ 4, but 2 is preferred.
  • n is an integer that satisfies 1 ⁇ n ⁇ 4, preferably 2.
  • a 11 is an m-valent group derived from perfluorobiphenyl (that is, a group obtained by removing m fluorine atoms from perfluorobiphenyl).
  • a 12 is -O- or -S-, but -O- is preferred.
  • a 13 is an (n+1)-valent group derived from naphthalene or anthracene (that is, a group obtained by removing (n+1) hydrogen atoms from naphthalene or anthracene), preferably a group derived from naphthalene. .
  • R s1 to R s4 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R s5 is optionally substituted 1 having 2 to 20 carbon atoms. is a valent hydrocarbon group.
  • Linear or branched C 1-6 alkyl groups represented by R s1 to R s4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -butyl group, tert-butyl group, n-hexyl group and the like.
  • alkyl groups having 1 to 3 carbon atoms are preferred.
  • R s1 to R s4 R s1 or R s3 is a linear alkyl group having 1 to 3 carbon atoms and the rest are hydrogen atoms, or R s1 is a linear alkyl group having 1 to 3 carbon atoms.
  • R s2 to R s4 are preferably hydrogen atoms.
  • the straight-chain alkyl group having 1 to 3 carbon atoms is preferably a methyl group.
  • the monovalent hydrocarbon group having 2 to 20 carbon atoms represented by R s5 may be linear, branched or cyclic, and specific examples thereof include ethyl, n-propyl, isopropyl, n Alkyl groups such as -butyl group, isobutyl group, sec-butyl group and tert-butyl group; and aryl groups such as phenyl, naphthyl and phenanthryl groups.
  • R s5 is preferably a linear alkyl group having 2 to 4 carbon atoms or a phenyl group.
  • a 14 is an optionally substituted m-valent hydrocarbon group having 6 to 20 carbon atoms and containing one or more aromatic rings, and the hydrocarbon group contains one or more It is a group obtained by removing m hydrogen atoms from a hydrocarbon compound having 6 to 20 carbon atoms containing an aromatic ring.
  • the hydrocarbon compounds include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, and phenanthrene.
  • a 14 is preferably a group derived from benzene, biphenyl or the like.
  • some or all of the hydrogen atoms may be further substituted with a substituent, and such substituents include a fluorine atom, a chlorine atom and a bromine atom. , iodine atom, nitro group, cyano group, hydroxy group, amino group, silanol group, thiol group, carboxy group, sulfonate ester group, phosphate group, phosphate ester group, ester group, thioester group, amide group, monovalent hydrocarbon groups, organooxy groups, organoamino groups, organosilyl groups, organothio groups, acyl groups, sulfo groups and the like.
  • a 15 is -O- or -S-, but -O- is preferred.
  • a 16 is an (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and this aromatic hydrocarbon group is an aromatic hydrocarbon compound having 6 to 20 carbon atoms. It is a group obtained by removing (n+1) hydrogen atoms on the ring.
  • the aromatic carbonized compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene.
  • a 16 is preferably a group derived from naphthalene or anthracene, more preferably a group derived from naphthalene.
  • R s6 and R s7 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group, and R s8 is a linear or branched 1 It is a valent aliphatic hydrocarbon group.
  • the total number of carbon atoms of R s6 , R s7 and R s8 is 6 or more.
  • the upper limit of the total number of carbon atoms in R s6 , R s7 and R s8 is not particularly limited, it is preferably 20 or less, more preferably 10 or less.
  • linear or branched monovalent aliphatic hydrocarbon groups represented by R s6 , R s7 and R s8 include methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group.
  • R s6 is preferably a hydrogen atom
  • R s7 and R s8 are each independently preferably an alkyl group having 1 to 6 carbon atoms.
  • R s9 to R s13 are each independently a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or carbon It is a halogenated alkenyl group of number 2-10.
  • the alkyl group having 1 to 10 carbon atoms represented by R s9 to R s13 may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl and isopropyl. group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group , n-decyl group and the like.
  • Halogenated alkyl groups having 1 to 10 carbon atoms represented by R s9 to R s13 are groups in which some or all of the hydrogen atoms of the alkyl groups having 1 to 10 carbon atoms are substituted with halogen atoms, especially Not limited.
  • Specific examples thereof include a trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 3,3,3-trifluoropropyl group, 2, 2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4 ,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group, etc. is mentioned.
  • the halogenated alkenyl group having 2 to 10 carbon atoms represented by R s9 to R s13 is a group in which some or all of the hydrogen atoms in the alkenyl group having 2 to 10 carbon atoms are substituted with halogen atoms, It is not particularly limited, and specific examples include perfluorovinyl group, perfluoro-1-propenyl group, perfluoro-2-propenyl group, perfluoro-1-butenyl group, perfluoro-2-butenyl group, perfluoro -3-butenyl group and the like.
  • R s9 is preferably a nitro group, a cyano group, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms. and a halogenated alkenyl group having 2 to 4 carbon atoms are more preferred, and a nitro group, a cyano group, a trifluoromethyl group and a perfluoropropenyl group are even more preferred.
  • R s10 to R s13 are preferably halogen atoms, more preferably fluorine atoms.
  • a 17 is -O-, -S- or -NH-, but -O- is preferred.
  • a 18 is an (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and this aromatic hydrocarbon group is an aromatic hydrocarbon compound having 6 to 20 carbon atoms. It is a group obtained by removing (n+1) hydrogen atoms on the ring.
  • the aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene.
  • a 18 is preferably a group derived from naphthalene or anthracene, more preferably a group derived from naphthalene.
  • R s14 to R s17 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms.
  • the monovalent aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and cyclopentyl group.
  • n-hexyl group cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and other alkyl groups having 1 to 20 carbon atoms; vinyl 1-propenyl group, 2-propenyl group, isopropenyl group, 1-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, hexenyl group, etc. Alkenyl group etc. are mentioned. Among these, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 8 carbon atoms is even more preferred.
  • R s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or —OR s19 .
  • R s19 is an optionally substituted monovalent hydrocarbon group having 2 to 20 carbon atoms.
  • Examples of the linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R s18 include those exemplified in the description of R s14 to R s17 .
  • R s18 is a monovalent aliphatic hydrocarbon group
  • R s18 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Even more preferable.
  • Examples of the monovalent hydrocarbon group having 2 to 20 carbon atoms represented by R s19 include, among the monovalent aliphatic hydrocarbon groups described above, those other than a methyl group, and aryl groups such as phenyl, naphthyl and phenanthryl groups. mentioned. Among these, R s19 is preferably a linear alkyl group having 2 to 4 carbon atoms or a phenyl group.
  • substituents that the monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, and the like.
  • Suitable arylsulfonate ester compounds include, but are not limited to, those shown below.
  • An electrically neutral onium borate salt consisting of is preferred.
  • Ar 11 to Ar 16 are each independently an optionally substituted aryl group or an optionally substituted heteroaryl group.
  • L is an alkylene group, -NH-, oxygen atom, sulfur atom or -CN + -.
  • aryl group examples include aryl groups having 6 to 20 carbon atoms. Specific examples include a phenyl group, a tolyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, and a 3-phenanthryl group. group, 4-phenanthryl group, 9-phenanthryl group, and the like. Among these, a phenyl group, a tolyl group, and a naphthyl group are preferred.
  • heteroaryl group examples include heteroaryl groups having 2 to 20 carbon atoms. Specific examples thereof include a 2-thienyl group, a 3-thienyl group, a 2-furanyl group, a 3-furanyl group, a 2-oxazolyl group, a 4-oxazolyl group, a 5-oxazolyl group, a 3-isoxazolyl group, and a 4-isoxazolyl group.
  • substituents examples include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl.
  • straight groups having 1 to 20 carbon atoms such as group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group; chain or branched alkyl groups; cyclic alkyl groups having 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl groups.
  • an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.
  • the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
  • the alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include ethenyl, n-1-propenyl, n-2-propenyl and 1-methylethenyl. group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl- 1-propenyl group, 1-methyl-2-propenyl group, n-1-pentenyl group, n-1-decenyl group and the like.
  • the alkynyl group having 2 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples include ethynyl, n-1-propynyl, n-2-propynyl, n-1 -butynyl group, n-2-butynyl group, n-3-butynyl group, 1-methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n- 4-pentynyl group, 1-methyl-n-butynyl group, 2-methyl-n-butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, n-1-decynyl group and the like.
  • the aryl group and heteroaryl group preferably have one or more electron-withdrawing groups as substituents.
  • the electron-withdrawing group include a halogen atom, a nitro group, a cyano group, etc.
  • a halogen atom is preferred, and a fluorine atom is particularly preferred.
  • L is an alkylene group, -NH-, an oxygen atom, a sulfur atom or -CN + -, but -CN + - is preferred.
  • the alkylene group may be linear, branched, or cyclic, and includes alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples include methylene, methylmethylene, dimethylmethylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, and hexamethylene groups.
  • anion represented by the formula (F1) that can be suitably used in the present invention include, but are not limited to, those represented by the formula (F1').
  • the onium borate salt may be used singly or in combination of two or more.
  • other known onium borate salts may be used in combination, if necessary.
  • the onium borate salt can be synthesized, for example, by referring to the known method described in JP-A-2005-314682.
  • the onium borate salt may be dissolved in an organic solvent in advance when preparing the varnish in order to facilitate dissolution in the charge-transporting varnish.
  • organic solvents include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; ethylene; Glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of dipropylene glycol monoacetate, etc.
  • polyhydric alcohols and their derivatives polyhydric alcohols and their derivatives; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3 -Esters such as methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate; Aromatic hydrocarbons such as toluene, xylene, 3-phenoxytoluene, 4-meth
  • the content of the dopant varies depending on the type of dopant and the desired degree of charge-transporting property, and cannot be defined unconditionally. Range.
  • the charge-transporting varnish of the present invention may further contain an organic silane compound for the purpose of adjusting the physical properties of the resulting charge-transporting thin film.
  • organic silane compounds include dialkoxysilane compounds, trialkoxysilane compounds, and tetraalkoxysilane compounds.
  • the organosilane compound is preferably a dialkoxysilane compound or a trialkoxysilane compound, more preferably a trialkoxysilane compound.
  • An organic silane compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the organic silane compound is usually about 0.1 to 50% by mass with respect to the total mass of the charge-transporting substance and the dopant.
  • a layer e.g., a hole transport layer or a light-emitting layer laminated on the opposite side of the anode so as to be in contact with the hole injection layer made of the charge-transporting thin film of is about 0.5 to 40% by mass, more preferably about 0.8 to 30% by mass, and even more preferably about 1 to 20% by mass.
  • the method for preparing the charge-transporting varnish is not particularly limited, but includes, for example, a method in which the polymer and, if necessary, a dopant, etc. are added in any order or simultaneously to an organic solvent.
  • the polymer and, if necessary, a dopant or the like may be first dissolved in one organic solvent, and another organic solvent may be added thereto.
  • the polymer and, if necessary, the dopant and the like may be dissolved sequentially or simultaneously.
  • the charge-transporting varnish of the present invention is prepared by dissolving the polymer and, if necessary, a dopant or the like in an organic solvent, followed by filtering through a submicrometer order filter or the like. It is recommended to filter
  • the viscosity of the charge-transporting varnish of the present invention is usually 1-50 mPa ⁇ s at 25°C.
  • the surface tension of the charge-transporting varnish of the present invention is usually 20 to 50 mN/m at 25°C.
  • the viscosity is a value measured with a TVE-25 viscometer manufactured by Toki Sangyo Co., Ltd.
  • the surface tension is a value measured with an automatic surface tensiometer CBVP-Z type manufactured by Kyowa Interface Science Co., Ltd.
  • the viscosity and surface tension of the varnish can be adjusted by considering various factors such as the desired film thickness and changing the types of solvents, their ratios, solid content concentration, and the like.
  • the solid content is usually uniformly dispersed or dissolved in an organic solvent.
  • the charge-transporting thin film of the present invention can be formed by applying the charge-transporting varnish of the present invention onto a base material and baking it.
  • varnish coating method examples include, but are not limited to, dipping, spin coating, transfer printing, roll coating, brush coating, inkjet, spraying, and slit coating. Depending on the method of application it is preferred to adjust the viscosity and surface tension of the varnish.
  • the firing atmosphere of the charge-transporting varnish after application is not particularly limited, and a thin film having a uniform film-forming surface and high charge-transporting properties can be obtained not only in an air atmosphere but also in an inert gas such as nitrogen or in a vacuum. can.
  • a thin film having charge transport properties may be obtained with good reproducibility by firing the varnish in an air atmosphere.
  • the firing temperature is appropriately set within a range of about 100 to 260° C. in consideration of the use of the obtained thin film, the degree of charge transport property to be imparted to the obtained thin film, the type and boiling point of the solvent, etc.
  • the temperature is preferably about 140 to 250°C, more preferably about 145 to 240°C. It should be noted that, during the firing, the temperature may be changed in two or more stages for the purpose of expressing a higher uniform film-forming property or promoting the reaction on the substrate. Suitable equipment such as an oven may be used.
  • the thickness of the charge-transporting thin film is not particularly limited, but when it is used as a functional layer provided between the anode and the light-emitting layer, such as a hole injection layer, a hole transport layer, or a hole injection transport layer of an organic EL device. , 5 to 300 nm.
  • a method for changing the film thickness there are methods such as changing the solid content concentration in the varnish and changing the amount of liquid on the substrate during coating.
  • the charge-transporting thin film of the present invention exhibits a refractive index of 1.6 or more and an extinction coefficient of 0.030 or less in the average value in the wavelength range of 400 to 800 nm. In another embodiment, it exhibits a refractive index of 1.70 or more, and in another embodiment, it exhibits an extinction coefficient of 0.020 or less, and in another embodiment, it exhibits an extinction coefficient of 0.015 or less. show.
  • the refractive index and the extinction coefficient can be measured using, for example, JA Woollam's multi-angle spectroscopic ellipsometer VASE.
  • Organic EL element The organic EL device of the present invention has a pair of electrodes and a functional layer comprising the charge-transporting thin film of the present invention between these electrodes.
  • Typical structures of the organic EL device include (a) to (f) below, but are not limited to these.
  • an electron blocking layer or the like may be provided between the light emitting layer and the anode, and a hole blocking layer or the like may be provided between the light emitting layer and the cathode, if necessary.
  • the hole injection layer, the hole transport layer or the hole injection transport layer may also function as an electron blocking layer or the like, and the electron injection layer, the electron transport layer or the electron injection transport layer may function as the hole blocking layer or the like. may also have the functions of Furthermore, it is also possible to provide arbitrary functional layers between each layer as needed.
  • Hole injection layer is layers formed between a light-emitting layer and an anode that transport holes from the anode to the light-emitting layer. It has a function. When only one layer of hole-transporting material is provided between the light-emitting layer and the anode, it is the “hole-injection-transporting layer”, and two layers of hole-transporting material are provided between the light-emitting layer and the anode. When more than one layer is provided, the layer closer to the anode is the “hole injection layer” and the other layers are the “hole transport layers”.
  • the hole-injecting (transporting) layer is a thin film that is excellent not only in the ability to accept holes from the anode but also in the ability to inject holes into the hole-transporting (light-emitting) layer.
  • Electrode layer is layers formed between a light-emitting layer and a cathode and have the function of transporting electrons from the cathode to the light-emitting layer. is.
  • the electron injection-transporting layer is the layer closest to the cathode.
  • the other layer is the “electron transport layer”.
  • a "light-emitting layer” is an organic layer having a light-emitting function, and includes a host material and a dopant material when a doping system is employed.
  • the host material mainly promotes recombination of electrons and holes and has the function of confining excitons in the light-emitting layer, and the dopant material efficiently emits the excitons obtained by recombination. have a function.
  • the host material mainly functions to confine excitons generated by the dopant within the light-emitting layer.
  • the charge-transporting thin film of the present invention can be suitably used as a functional layer provided between an anode and a light-emitting layer in an organic EL device, and can be used as a hole-injecting layer, a hole-transporting layer, or a hole-injecting-transporting layer. It can be used more preferably, and can be used even more preferably as a hole injection layer.
  • Examples of the materials to be used and the production method for producing an organic EL element using the charge-transporting varnish of the present invention include, but are not limited to, the following.
  • An example of a method for producing an organic EL device having a hole injection layer composed of a charge-transporting thin film obtained from the charge-transporting varnish of the present invention is as follows.
  • the electrodes are preferably cleaned with alcohol, pure water, or the like, or surface-treated with UV ozone treatment, oxygen-plasma treatment, or the like in advance, as long as the electrodes are not adversely affected.
  • a hole injection layer is formed on the anode substrate using the charge-transporting varnish of the present invention by the method described above. This is introduced into a vacuum vapor deposition apparatus, and a hole transport layer, a light-emitting layer, an electron transport layer/hole blocking layer, an electron injection layer, and a cathode metal are sequentially vapor-deposited.
  • a composition for forming a hole-transporting layer containing a hole-transporting polymer and a composition for forming a light-emitting layer containing a light-emitting polymer are used. to form these layers by a wet process.
  • An electron blocking layer may be provided between the light-emitting layer and the hole-transporting layer, if necessary.
  • anode material examples include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and metal anodes composed of metals typified by aluminum, alloys thereof, and the like. , preferably subjected to a flattening treatment. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used. Other metals constituting the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.
  • Materials for forming the hole transport layer include (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spirodimer, N,N'-bis(naphthalen-1-yl)-N,N'- Bis(phenyl)-benzidine ( ⁇ -NPD), 4,4′,4′′-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), 4,4′,4′′- triarylamines such as tris[1-naphthyl(phenyl)amino]triphenylamine (1-TNATA), 5,5′′-bis- ⁇ 4-[bis(4-methylphenyl)amino]phenyl ⁇ -2 ,2':5',2''-terthiophene (BMA-3T) and other oligothiophenes.
  • TPD N,N'-bis(naphthalen-1-yl)-N,N'- Bis(phenyl)-benzidine
  • Materials for forming the light-emitting layer include metal complexes such as aluminum complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo[h]quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, and (2-hydroxyphenyl).
  • Low-molecular-weight light-emitting materials such as benzothiazole metal complexes and silole derivatives; Examples include, but are not limited to, a system in which a light-emitting material and an electron transfer material are mixed with a polymer compound such as alkylthiophene) or polyvinylcarbazole.
  • the light-emitting layer when it is formed by vapor deposition, it may be co-deposited with a light - emitting dopant.
  • a light - emitting dopant examples include complexes, naphthacene derivatives such as rubrene, quinacridone derivatives, and condensed polycyclic aromatic rings such as perylene, but are not limited thereto.
  • Materials for forming the electron-transporting layer/hole-blocking layer include, but are not limited to, oxydiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, pyrimidine derivatives, and the like.
  • Materials for forming the electron injection layer include metal oxides such as lithium oxide (Li 2 O), magnesium oxide (MgO), alumina (Al 2 O 3 ), lithium fluoride (LiF), sodium fluoride (NaF ) and the like, but are not limited to these.
  • cathode material examples include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like.
  • Materials for forming the electron blocking layer include, but are not limited to, tris(phenylpyrazole) iridium.
  • Examples of the light-emitting polymer include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), poly(2-methoxy-5-(2′-ethylhexoxy)-1,4-phenylene vinylene) (MEH -PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).
  • PDAF poly(9,9-dialkylfluorene)
  • MEH -PPV poly(2-methoxy-5-(2′-ethylhexoxy)-1,4-phenylene vinylene)
  • PAT poly(3-alkylthiophene)
  • PVCz polyvinylcarbazole
  • Materials constituting the anode, the cathode and the layers formed therebetween differ depending on whether the device has a bottom emission structure or a top emission structure. .
  • a transparent anode is used on the substrate side, and light is extracted from the substrate side
  • a reflective anode made of metal is used, and light is emitted in the opposite direction to the substrate.
  • Light is extracted from a certain transparent electrode (cathode) side. Therefore, as for the anode material, for example, a transparent anode such as ITO is used when manufacturing an element with a bottom emission structure, and a reflective anode such as Al/Nd is used when manufacturing an element with a top emission structure.
  • the organic EL element of the present invention may be sealed together with a water capturing agent or the like according to a standard method in order to prevent deterioration of its properties.
  • Reagents and solvents used in the synthesis include Pd(dba) 2 , Pd(dppf)Cl 2 .CH 2 Cl 2 , potassium acetate, bis(pinacolato)diboron, 2-amino-N-[(1,1′- Biphenyl)-4-yl]-N-(4-bromophenyl)-9,9 dimethylfluorene, trimethyl borate, lithium bis(trimethylsilyl)amide 1.3 mol/L tetrahydrofuran solution, maleic anhydride, triethylamine, 4-vinyl Phenylboronic acid, tetrakistriphenylphosphine palladium and anisole are those manufactured by Tokyo Chemical Industry Co., Ltd., toluene, hexane, ethyl acetate, ethanol, acetonitrile, dimethylformamide and those manufactured by Methanol Junsei Chemical Co., Ltd., AIBN and Tri-tert-but
  • 4-aminotriphenylamine was synthesized by a method according to the method of Synthesis Example 1 of WO 2014/132834.
  • a ligand trifetri-tert-butylphosphonium tetrafluoroborate was used instead of tri(tert-butyl)phosphine.
  • 4-aminotriphenylamine and 2.06 g of maleic anhydride were added and stirred well, to which 35 mL of acetic acid was added slowly and stirring was continued until the mixture was uniformly dispersed. The resulting mixture was then heated to 120° C. and heated to reflux for 20 hours, and the reaction mixture was allowed to cool.
  • a reaction vessel was charged with 10 g of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, 0.89 g of Pd(dba) 2 and triphetri-tert-butylphosphonium. After adding 0.45 g of tetrafluoroborate and degassing the inside of the reaction vessel, a nitrogen atmosphere was created.
  • a reaction vessel was charged with 7 g of 2-amino-N-[(1,1′-biphenyl)-4-yl]-N-(4-bromophenyl)-9,9 dimethylfluorene, 0.39 g of Pd(dba) 2 and 0.20 g of trifetri-tert-butylphosphonium tetrafluoroborate was added, and after degassing the inside of the reaction vessel, a nitrogen atmosphere was created.
  • the reaction mixture was cooled to 0°C. 20 mL of 1N hydrochloric acid aqueous solution was added to the cooled reaction mixture to adjust the pH of the mixture to 3, then sodium chloride aqueous solution (concentration 2 mol/L) was added to adjust the mixture to pH 12.
  • the pH-adjusted mixture was subjected to suction filtration using KC flocs, the KC flocs were washed with toluene, and this toluene was also collected as a filtrate.
  • a reaction vessel was charged with 10 g of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, 5.4 g of bis(pinacolato)diboron, and Pd(dppf)Cl 2 . - 0.32 g of CH 2 Cl 2 , 4.8 g of potassium acetate and 80 mL of dioxane were added, and after the inside of the reaction vessel was deaerated, a nitrogen atmosphere was created. Then, the inside of the reaction vessel was heated to 100°C.
  • the reaction mixture in the reaction vessel was stirred for 5 hours while monitoring the reaction by TLC, and the raw material 3-(9,9-dimethyl-(4,4,5,5-tetramethyl-1,3,2-
  • the reaction mixture was allowed to cool to room temperature.
  • the cooled reaction mixture was subjected to suction filtration using KC flocs, the KC flocs were washed with toluene, and this toluene was also collected as a filtrate.
  • a reaction vessel was charged with 1.0 g of monomer MD, 0.080 g of AIBN and 5.3 g of dimethylformamide, and after purging the inside of the reaction vessel with nitrogen, the mixture was stirred at 80° C. for 20 hours. After allowing the reaction mixture to cool to room temperature, the cooled reaction mixture was added dropwise to 75 g of a mixed solvent of ethyl acetate and dimethylformamide (5/1 (V/V)) and stirred at room temperature. Finally, the precipitated solid was collected by filtration and dried under reduced pressure to obtain polymer PD (yield: 0.42 g, yield: 42%). As a result of GPC measurement, Polymer PD had an Mw of 4,000 and a polydispersity Mw/Mn of 1.12.
  • a reaction vessel was charged with 0.5 g of monomer M-C, 0.5 g of monomer M-B, 0.050 g of AIBN and 7.0 g of anisole. After allowing the reaction mixture to cool to room temperature, the cooled reaction mixture was added dropwise to 50 g of a mixed solvent of methanol and ethyl acetate (1/4 (V/V)) and stirred at room temperature. Finally, the precipitated solid was collected by filtration and dried under reduced pressure to obtain the copolymer P-CB (yield: 0.42 g, yield: 42%). As a result of GPC measurement, the copolymer P-CB had an Mw of 277,000 and a polydispersity Mw/Mn of 3.38.
  • the polymer of the present invention showed better heat resistance than the polymer of the comparative example.
  • the monomers of the polymers of the invention also exhibited excellent heat resistance.
  • Example 2-2 139 mg of polymer P-B and 278 mg of arylsulfonate ester SE-A were added to 10 g of 4-methoxytoluene and dissolved by stirring at room temperature. The resulting solution was filtered using a PTFE filter with a pore size of 0.2 ⁇ m to obtain a charge-transporting varnish B.
  • Example 2-3 139 mg of copolymer P-AB and 292 mg of arylsulfonate ester SE-A were added to 10 g of 4-methoxytoluene and dissolved by stirring at room temperature. The resulting solution was filtered using a PTFE filter with a pore size of 0.2 ⁇ m to obtain a charge-transporting varnish C.
  • Example 2-4 208 mg of polymer PC and 208 mg of arylsulfonate SE-A were added to 10 g of 4-methoxytoluene and dissolved by stirring at room temperature. The resulting solution was filtered using a PTFE filter with a pore size of 0.2 ⁇ m to obtain a charge-transporting varnish D.
  • Example 2-5 139 mg of polymer P-D and 278 mg of arylsulfonate ester SE-A were added to 10 g of 4-methoxytoluene and dissolved by stirring at room temperature. The resulting solution was filtered using a PTFE filter with a pore size of 0.2 ⁇ m to obtain a charge-transporting varnish E.
  • Example 2-6 139 mg of polymer PE and 278 mg of arylsulfonate ester SE-A were added to 10 g of 4-methoxytoluene and dissolved by stirring at room temperature. The resulting solution was filtered using a PTFE filter with a pore size of 0.2 ⁇ m to obtain a charge-transporting varnish F.
  • Example 2-7 139 mg of copolymer P-AE and 278 mg of arylsulfonic acid ester SE-A were added to 10 g of 4-methoxytoluene and dissolved by stirring at room temperature. The resulting solution was filtered using a PTFE filter with a pore size of 0.2 ⁇ m to obtain a charge-transporting varnish G.
  • Example 2-8 139 mg of the copolymer P-CB and 278 mg of the arylsulfonate ester SE-A were added to 10 g of 4-methoxytoluene and dissolved by stirring at room temperature. The resulting solution was filtered using a PTFE filter with a pore size of 0.2 ⁇ m to obtain a charge-transporting varnish H.
  • Example 2-9 139 mg of copolymer P-DB and 278 mg of arylsulfonate SE-A were added to 10 g of 4-methoxytoluene and dissolved by stirring at room temperature. The resulting solution was filtered using a PTFE filter with a pore size of 0.2 ⁇ m to obtain a charge-transporting varnish I.
  • the charge-transporting thin film of the present invention had a higher refractive index and a lower extinction coefficient than the comparative example. Moreover, the refractive index was as high as 1.65 or more, and the extinction coefficient was as low as 0.020 or less. This is because the skeleton containing alkylfluorene is highly refractive and highly transparent.
  • An aluminum thin film having a thickness of 80 nm was formed thereon at a rate of 0.2 nm/sec using a vapor deposition apparatus (degree of vacuum: 1.0 ⁇ 10 ⁇ 5 Pa). After that, in order to prevent characteristic deterioration due to the influence of oxygen, water, etc. in the air, it was sealed with a sealing substrate. Sealing was performed by the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of ⁇ 76° C. or less, the SLD was placed between the sealing substrates, and the sealing substrates were attached with an adhesive (manufactured by MORESCO Co., Ltd., MORESCO Moisture Cut WB90US (P)). Matched.
  • a water capturing agent (HD-071010W-40 manufactured by Dainic Co., Ltd.) was placed in the sealing substrate together with the SLD.
  • the bonded sealing substrates were irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ/cm 2 ) and then annealed at 80° C. for 1 hour to cure the adhesive.
  • a current density was measured when a voltage of 4 V was applied to the fabricated SLD. Table 3 shows the results.
  • the charge-transporting thin film produced from the charge-transporting varnish of the present invention exhibited good charge-transporting properties.
  • a thin film of ⁇ -NPD with a thickness of 30 nm was formed at 0.2 nm/sec using a vapor deposition apparatus (degree of vacuum: 1.0 ⁇ 10 ⁇ 5 Pa), and further a thin film of 0.2 nm was formed thereon.
  • a thin film of aluminum having a film thickness of 80 nm was formed at a rate of 0.001 m/sec.
  • a HOD was obtained by sealing with a sealing substrate in the same manner as in Example 1-1. A current density was measured when a voltage of 4 V was applied to the fabricated HOD. Table 4 shows the results.
  • the charge-transporting thin film produced from the charge-transporting varnish of the present invention exhibited good hole injection properties into ⁇ -NPD, which is often used as a hole-transporting layer.

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Abstract

L'invention concerne un polymère contenant au moins une unité de répétition choisie parmi une unité de répétition représentée par la formule (1) et une unité de répétition représentée par la formule (2).
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