WO2023189399A1 - Polymère et son utilisation - Google Patents

Polymère et son utilisation Download PDF

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WO2023189399A1
WO2023189399A1 PCT/JP2023/009226 JP2023009226W WO2023189399A1 WO 2023189399 A1 WO2023189399 A1 WO 2023189399A1 JP 2023009226 W JP2023009226 W JP 2023009226W WO 2023189399 A1 WO2023189399 A1 WO 2023189399A1
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group
carbon atoms
charge transporting
formula
och
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PCT/JP2023/009226
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Japanese (ja)
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陽介 倉田
圭介 首藤
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日産化学株式会社
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    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/32—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, 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; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • 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
    • 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

Definitions

  • the present invention relates to polymers and their uses.
  • organic EL organic electroluminescent
  • the hole injection layer transfers charge between the anode and the hole transport layer or the light emitting layer, and plays an important function in achieving low voltage driving and high brightness of the organic EL element.
  • Formation methods for hole injection layers can be broadly divided into dry processes, typified by vapor deposition, and wet processes, typified by spin coating and inkjet methods. Comparing these processes, wet processes are generally superior. Thin films with high area flatness can be efficiently manufactured. Therefore, as organic EL displays are becoming larger in size, there is a demand for a hole injection layer that can be formed by a wet process, and there have been reports on technology related to hole injection materials that can be formed by a wet process. (Patent Document 1).
  • quantum dot electroluminescent (hereinafter referred to as quantum dot EL) elements that use quantum dot materials as light emitting layers have appeared, and are showing prospects for wide application.
  • Quantum dot EL devices can be manufactured at low cost using a wet process, while their properties include control of emission wavelength, high color purity, high luminous efficiency, and use in flexible applications, making them ideal for use in display technology, lighting, etc. is attracting a lot of attention in the field of
  • the present applicant has developed a charge transporting material that can be applied to various wet processes and provides a thin film that can realize excellent EL device characteristics when applied to the hole injection layer of an organic EL device.
  • compounds suitable as charge transporting substances and dopants that exhibit solubility in organic solvents used therein have been developed (see Patent Documents 2 to 8 and Non-Patent Document 1).
  • the present invention also aims to provide a polymer that can be suitably used for forming charge transporting thin films used in organic EL devices and the like.
  • a polymer containing a repeating unit having a group and an aryl group containing at least one sulfonic acid ester group in its side chain has high solubility in organic solvents, has excellent functions as a charge transport substance, and has a high charge transport property.
  • R M is a hydrogen atom or a methyl group.
  • R 1a and R 2a each independently represent a single bond or a phenylene group, and some or all of the hydrogen atoms of the phenylene group are a cyano group, a nitro group, a halogen atom, a vinyl group, a trifluorovinyl group, or an acryloyl group.
  • X 1a is -N(Ar 3a )-, -S- or -O-.
  • Ar 1a is a divalent group obtained by removing two hydrogen atoms on the aromatic ring of an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 3 to 20 carbon atoms, or a dialkylfluorene represented by the following formula (A2).
  • a group in which some or all of the hydrogen atoms on the aromatic rings of these groups are a cyano group, nitro group, halogen atom, vinyl group, trifluorovinyl group, acryloyl group, methacryloyl group, oxetanyl group, or epoxy group. , may be substituted with an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group having 1 to 20 carbon atoms.
  • Ar 2a and Ar 3a are each independently an aryl group having 6 to 20 carbon atoms or a monovalent group obtained by removing one hydrogen atom on the aromatic ring of dialkylfluorene represented by the following formula (A2).
  • Some or all of the hydrogen atoms on the aromatic ring of these groups are cyano group, nitro group, halogen atom, vinyl group, trifluorovinyl group, acryloyl group, methacryloyl group, oxetanyl group, epoxy group, carbon number It may be substituted with an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group having 1 to 20 carbon atoms.
  • X 1a is -N(Ar 3a )-
  • Ar 2a and Ar 3a may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded.
  • R 2a is a phenylene group
  • R 2a and Ar 2a 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.
  • at least one of Ar 1a to Ar 3a is a group obtained by removing the hydrogen atom on the aromatic ring of dialkylfluorene represented by the following formula (A2).
  • R 3a and R 4a 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.
  • Ar F represents a fluorinated arylene group
  • X 1b represents O, S, NH, CONH or NHCO
  • Ar S represents at least one SO 3 D 1 D 2 on the ring.
  • D 1 represents a substituted or unsubstituted divalent hydrocarbon group
  • D 2 represents a single bond, O, S, or a substituted or unsubstituted divalent amino group.
  • D 3 represents a substituted or unsubstituted monovalent hydrocarbon group, but if D 2 is a single bond, it may be a hydrogen atom.
  • Polymer 1 wherein the repeating unit represented by the above formula (A1) is represented by the following formula (A1-1). (In the formula, R M , R 1a , R 2a and Ar 1a to Ar 3a represent the same meanings as above.) 3. 1 or 2 polymers in which the above R 1a is a single bond. 4. Any one of the polymers 1 to 3, wherein R 2a is a phenylene group. 5. Any one of the polymers 1 to 4, wherein Ar 1a is a 9,9-dimethyl-9H-fluorene-2,7-diyl group. 6. Any one of the polymers 1 to 5, wherein Ar F is a perfluoroarylene group. 7. 6.
  • Electronic device comprising 15 charge transporting thin films.
  • An organic electroluminescent device comprising 15 charge transporting thin films.
  • the charge transporting thin film is a hole injection layer or a hole transport layer.
  • Quantum dot electroluminescent device comprising 15 charge transporting thin films.
  • the polymer of the present invention has high solubility in organic solvents and has excellent functions as a charge transporting substance, so it provides a charge transporting thin film with excellent electrical properties, and an organic EL device equipped with the thin film has the following properties: It exhibits good characteristics and is particularly excellent in life performance. Furthermore, since the obtained thin film has high solvent resistance, film thinning and swelling when other functional films are formed thereon are reduced.
  • the polymer of the present invention having such characteristics can be suitably used in thin films for electronic devices such as organic EL devices and quantum dot EL devices, particularly in compositions for forming thin films for organic EL displays and quantum dot EL displays. I can do it.
  • the polymer of the present invention is characterized by containing a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (B1).
  • R M is a hydrogen atom or a methyl group.
  • R 1a and R 2a each independently represent a single bond or a phenylene group, and some or all of the hydrogen atoms of the phenylene group are a cyano group, a nitro group, a halogen atom, a vinyl group, a trifluorovinyl group, or an acryloyl group. may be substituted with a methacryloyl group, an oxetanyl group, an epoxy group, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms.
  • phenylene group examples include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group, with a 1,4-phenylene group being preferred.
  • the above alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group.
  • a straight group having 1 to 20 carbon atoms such as sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc.
  • 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 a cyclic alkyl group 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 are substituted with halogen atoms.
  • Specific examples include 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. can be mentioned.
  • R 1a is preferably a single bond, and R 2a is preferably a phenylene group.
  • X 1a is -N(Ar 3a )-, -S- or -O-.
  • Ar 1a represents 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 (A2). It is a divalent group obtained by removing a part or all of the hydrogen atoms on the aromatic ring of these groups, such as a cyano group, a nitro group, a halogen atom, a vinyl group, a trifluorovinyl group, an acryloyl group, or a methacryloyl group.
  • an oxetanyl group an epoxy group, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms.
  • an alkyl group having 1 to 20 carbon atoms and the halogenated alkyl group having 1 to 20 carbon atoms include those mentioned above.
  • R 3a and R 4a 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.
  • the above arylene groups having 6 to 20 carbon atoms include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-naphthalene-diyl group, 2,3-naphthalene-diyl group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 2,6-naphthalenediyl, 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- Examples include anthracenediyl group, 2,6-anthracenediyl group, 2,7-anthracenediyl group, 2,9-anthracenediyl
  • Examples of the above heteroarylene group having 3 to 20 carbon atoms include 9-phenylcarbazole-3,6-diyl group, 9-phenylcarbazole-2,7-diyl group, 9-phenylcarbazole-3,6-dimethyl-2, Examples include a 7-diyl group, groups represented by the following formulas (H1) to (H33), and the like.
  • R 3a and R 4a 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. It is the basis.
  • the above alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group.
  • a straight group having 1 to 20 carbon atoms such as sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc.
  • 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 a cyclic alkyl group having 3 to 20 carbon atoms.
  • methyl group and ethyl group are preferred, and methyl group is more preferred.
  • the above alkoxy group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, 1 carbon number such as isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyl group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, etc.
  • ⁇ 20 linear or branched alkoxy groups cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group, cyclodecyloxy group
  • Examples include cyclic alkoxy groups having 3 to 20 carbon atoms such as bicyclobutyloxy, bicyclopentyloxy, bicyclohexyloxy, bicycloheptyloxy, bicyclooctyloxy, bicyclononyloxy, and bicyclodecyloxy.
  • 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 substituted with oxygen atoms at the same time.
  • a group represented by formula (A2-1) is preferable, and a group represented by formula (A2-2) is more preferable, considering the availability of the raw material compound.
  • R 5a represents a linear or branched alkylene group having 1 to 4 carbon atoms
  • R 6a represents a linear or branched alkylene group having 1 to 20 carbon atoms (number of carbon atoms in R) x p).
  • p is an integer of 1 to 9. From the viewpoint of compatibility with the dopant, p is preferably 2 or more, more preferably 3 or more, and from the viewpoint of the ease of obtaining the raw material compound. , preferably 5 or less, more preferably 4 or less.
  • alkyl group having 2 to 20 carbon atoms containing at least one ether structure examples include -CH 2 OCH 3 , -CH 2 OCH 2 CH 3 , -CH 2 O(CH 2 ) 2 CH 3 , -CH 2 OCH(CH 3 ) 2 , -CH 2 O(CH 2 ) 3 CH 3 , -CH 2 OCH 2 CH(CH 3 ) 2 , -CH 2 OC(CH 3 ) 3 , -CH 2 O(CH 2 ) 4 CH 3 , -CH 2 OCH(CH 3 )(CH 2 ) 2 CH 3 , -CH 2 O(CH 2 ) 2 CH(CH 3 ) 2 , -CH 2 OCH 2 CH(CH 3 )CH 2 CH 3 , -CH 2 OCH 2 C(CH 3 ) 3 , -CH 2 OCH(CH 3 )CH(CH 3 ) 2 , -CH 2 OC(CH 3 ) 2 CH 2 CH 3 , -CH 2 OCH(CH(
  • Divalent groups obtained by removing two hydrogen atoms on the aromatic ring of dialkylfluorene represented by formula (A2) 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-fluorene-2
  • Ar 1a a group obtained by removing two hydrogen atoms on the aromatic ring of dialkylfluorene represented by formula (A2) is preferable, and in particular, 9,9-dimethyl-9H-fluorene-2, 7-diyl group is preferred.
  • Ar 2a and Ar 3a are each independently obtained by removing one hydrogen atom on the aromatic ring of the aryl group having 6 to 20 carbon atoms or the dialkylfluorene represented by formula (A2). It is a monovalent group, and some or all of the hydrogen atoms on the aromatic ring of these groups are a cyano group, a nitro group, a halogen atom, a vinyl group, a trifluorovinyl group, an acryloyl group, a methacryloyl group, an oxetanyl group, It may be substituted with 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 include those mentioned above.
  • the above aryl group having 6 to 20 carbon atoms includes phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, Examples include 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, and the like.
  • Monovalent groups obtained by removing one hydrogen atom on the aromatic ring of dialkylfluorene represented by formula (A2) 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, 9,9-
  • Ar 2a and Ar 3a may be bonded to each other to form a ring with the nitrogen atom to which they are bonded.
  • the structure of the ring is preferably a carbazole ring.
  • R 2a is a phenylene group
  • R 2a and Ar 2a 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.
  • the structure of the above ring is preferably a carbazole ring, a dibenzothiophene ring or a dibenzofuran ring.
  • At least one of Ar 1a to Ar 3a is a group obtained by removing a hydrogen atom on the aromatic ring of dialkylfluorene represented by formula (A2).
  • the repeating unit represented by formula (A1) is preferably one in which X 1a is -N(Ar 3a )-, and more preferably one represented by the following formula (A1-1).
  • repeating unit represented by formula (A1-1) one represented by the following formula (A1-2) is even more preferable.
  • Ar F represents a fluorinated arylene group.
  • the fluorinated arylene group of Ar F is not particularly limited as long as at least one hydrogen atom on the arylene group is replaced with a fluorine atom, but at least one of the remaining hydrogen atoms is an electron-withdrawing group other than a sulfo group. It is preferable that it is substituted with.
  • electron-withdrawing groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; nitro group; cyano group; acyl group; carboxy group; carboxylic acid ester group; acyl group such as formyl group and acetyl group.
  • the fluorinated arylene group of Ar F is preferably an arylene group substituted with two or more fluorine atoms, and more preferably a perfluoroarylene group.
  • Ar F is preferably a tetrafluorophenylene group, more preferably a 2,3,5,6-tetrafluoro-1,4-phenylene group.
  • X represents O, S, NH, CONH or NHCO, preferably O or S, and more preferably O.
  • repeating unit represented by the above formula (B1) includes those represented by the following formula (B1-1).
  • n1 represents an integer from 1 to 4.
  • repeating unit represented by the above formula (B1) include those represented by the following formula (B1-2).
  • n1 represents an integer from 1 to 4.
  • repeating unit represented by the above formula (B1) include those represented by the following formula (B1-3).
  • Ar S represents an aryl group having at least one SO 3 D 1 D 2 D 3 group on the ring, D 1 represents a substituted or unsubstituted divalent hydrocarbon group, D 2 represents a single bond, O, S, or a substituted or unsubstituted divalent amino group, and D 3 represents a substituted or unsubstituted monovalent hydrocarbon group, but if D 2 is a single bond, even if it is a hydrogen atom. good.
  • the number of carbon atoms in the aryl group constituting Ar S is not particularly limited, but preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
  • Specific examples include 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, etc., but naphthyl group is preferable, and 1-naphthyl group is more preferable.
  • the number of SO 3 D 1 D 2 D 3 groups that Ar S has may be one or more, but preferably 2 to 4, and more preferably 2.
  • the substituted or unsubstituted divalent hydrocarbon group for D 1 is, for example, a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, alkylene group having 1 to 2 carbon atoms, alkylene group having 1 to 2 carbon atoms, or 1 to 2 carbon atoms; ⁇ 2 Alkylenethio Alkylene group with 1 to 2 carbon atoms, Alkylene carbonyl group with 1 to 2 carbon atoms, Alkylene group with 1 to 2 carbon atoms, and some or all of the hydrogen atoms of these groups can further be hydroxyl group, amino group, silanol group, Thiol group, carboxyl group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, ester group, thioester group, amide group, nitro group, monovalent hydrocarbon group, organooxy group, organoamino group, organosilyl group, Examples include those substituted with an organothio group, an
  • an alkylene group having 1 to 5 carbon atoms is preferred.
  • the alkylene group having 1 to 5 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene and pentamethylene groups, with methylene, ethylene, propylene and trimethylene groups being preferred.
  • D 2 is a single bond, O, S, or a substituted or unsubstituted divalent amino group, and O is preferred in the present invention.
  • examples of the divalent substituted amino group include -N(CH 3 )-, -N(C 2 H 5 )-, and -N(C 3 H 7 )-.
  • D 3 represents a substituted or unsubstituted monovalent hydrocarbon group, but may be a hydrogen atom when D 2 is a single bond.
  • Substituted or unsubstituted monovalent hydrocarbon groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, decyl.
  • Alkyl groups such as groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; bicycloalkyl groups such as bicyclohexyl groups; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, Alkenyl groups such as 2-butenyl, 3-butenyl, hexenyl groups; aromatic ring groups (aryl groups) such as phenyl, xylyl, tolyl, biphenyl, naphthyl groups; aralkyl groups such as benzyl, phenylethyl, phenylcyclohexyl groups; Examples include those in which some or all of the hydrogen atoms of the group are further substituted with the above-mentioned substituents. According to the invention, methyl, ethyl, n-propyl, n-butyl and phenyl groups are preferred.
  • the above D 1 to D 3 more preferably have a structure represented by the following formula (D).
  • R 1d and R 2d each independently represent a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group, and R 3d represents a linear or branched monovalent aliphatic hydrocarbon group. Represents an aliphatic hydrocarbon group or an alkoxy group.
  • the total number of carbon atoms in R 1d , R 2d and R 3d is 2 or more.
  • the total number of carbon atoms in R 1d , R 2d and R 3d is not particularly limited, but is preferably 20 or less, more preferably 10 or less.
  • the linear or branched monovalent aliphatic hydrocarbon group is not particularly limited, but includes methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-hexyl. , n-octyl, 2-ethylhexyl, alkyl groups having 1 to 18 carbon atoms such as decyl; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl , 3-butenyl, hexenyl, and other alkenyl groups having 2 to 18 carbon atoms.
  • an alkoxy group having 1 to 10 carbon atoms is preferable, and specifically, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, t-butoxy, n-pentoxy and phenoxy Examples include groups.
  • R 1d a methyl group is more preferable.
  • R 2d a hydrogen atom is preferable.
  • R 3d is preferably an alkoxy group, more preferably a methoxy, ethoxy, n-propoxy, n-butoxy and phenoxy group, even more preferably an ethoxy, n-butoxy and phenoxy group.
  • the structure represented by the above formula (D) is obtained by converting a predetermined arylsulfonic acid halide into a predetermined alcohol compound, for example, with reference to the method described in International Publication No. 2020/218316 (Patent Document 7). , can be introduced by esterification using an alcohol compound represented by the following formula (D').
  • the repeating unit represented by formula (B1) has such a sulfonic acid ester group, thereby improving solubility in an organic solvent.
  • the sulfonic acid ester groups are decomposed by the heating process and sulfonic acid groups are generated, which improves the hydrophilicity of the thin film and improves its resistance to low polar solvents such as toluene. improves. This reduces thinning and swelling of the resulting charge transporting thin film.
  • R 1d to R 3d represent the same meanings as above.
  • Ar S examples include those represented by the following formulas (Ar S -1) to (Ar S -6).
  • n an integer from 2 to 4.
  • Ar S More preferred embodiments of the above Ar S include those represented by the following formulas (Ar S -7) to (Ar S -12).
  • R 1d to R 3d represent the same meanings as above.
  • n represents an integer from 2 to 4.
  • R 1d to R 3d represent the same meanings as above.
  • R 1d to R 3d have the same meanings as above.
  • R 1d to R 3d represent the same meanings as above.
  • the polymer of the present invention may be a polymer containing only the repeating unit represented by the above formula (A1) and the repeating unit represented by the above formula (B1). Further, the polymer of the present invention may be a random copolymer, an alternating copolymer, or a block copolymer.
  • repeating units other than the repeating unit represented by formula (A1) and the repeating unit represented by formula (B1) may be included as long as the effects of the present invention are not impaired.
  • Other repeating units include those containing polymerizable functional groups such as an acryloyl group, an acrylamide group, a methacryloyl group, a methacrylamide group, a vinyl ether group, and maleic anhydride.
  • a repeating unit represented by the following formula (B2) is preferred.
  • R' represents a monovalent organic group.
  • the monovalent organic group include a monovalent hydrocarbon group, a heteroaryl group, a -COOR" group (R" represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), and the like.
  • R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, Alkyl groups such as n-nonyl and n-decyl groups; phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl , aryl groups such as 9-phenanthryl group, and the like.
  • heteroaryl groups include 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2 - Thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, etc. with 2 to 20 carbon atoms
  • heteroaryl groups include 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2 - Thiazolyl, 4-thiazolyl, 5-thiazolyl
  • Examples of the alkyl group having 1 to 10 carbon atoms for R'' include the same groups as exemplified above, but among them, an alkyl group having 1 to 5 carbon atoms is preferred.
  • halogen atom examples include a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, a hydroxyl group, etc.
  • halogen atom examples include the same atoms as exemplified above.
  • R' is preferably an aryl group substituted with a halogen atom, more preferably a fluorinated aryl group, in consideration of improving the device characteristics and life characteristics of the resulting organic EL device or quantum dot EL device.
  • perfluoroaryl groups are even more preferred.
  • a phenyl group substituted with a halogen atom is preferred, a fluorinated phenyl group is more preferred, and a perfluorophenyl group is even more preferred.
  • the molecular weight of the polymer of the present invention is not particularly limited, but from the viewpoint of improving heat resistance and ensuring solubility in solvents, the weight average molecular weight Mw is preferably 1,000 to 50,000, 1,500 to 10, 000 is more preferable, and 2,000 to 10,000 is even more preferable. Further, the molecular weight distribution (Mw/Mn) is not particularly limited, but is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. Note that this weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard sample.
  • GPC gel permeation chromatography
  • the polymer of the present invention is produced by a known radical polymerization method using a monomer represented by the following formula (a1) and a monomer represented by the following formula (b1) in the presence of a solvent and a radical polymerization initiator. It can be obtained by polymerization.
  • the monomers represented by formula (a1) may be used in combination of two or more types
  • the monomers represented by formula (b1) may be used in combination of two or more types.
  • R M , R 1a , R 2a , Ar 1a , Ar 2a , Ar F , Ar S , X 1a and X 1b represent the same meanings as above.
  • a monomer represented by the following formula (a2) may be added as necessary.
  • radical thermal polymerization initiator known compounds such as radical thermal polymerization initiators and radical photopolymerization initiators can be used.
  • a radical thermal polymerization initiator is a compound that generates radicals when heated above the decomposition temperature.
  • radical thermal polymerization initiators include, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxide Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxycyclohexane) ), alkyl peresters (peroxyneodecanoic acid tert-
  • the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
  • Such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(
  • the solvent used in the polymerization reaction is not particularly limited as long as it dissolves the produced polymer.
  • Specific examples include water; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl- ⁇ -caprolactam, dimethylsulfoxide, tetra Methylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 2-propanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve , methyl cellosolve acetate, ethyl cellosolve acetate, buty
  • the polymerization temperature during radical polymerization can be any temperature in the range of 30 to 150°C, but is preferably in the range of 50 to 100°C.
  • the monomer represented by the above formula (a1) can be synthesized by combining various coupling reactions.
  • a styrene compound represented by formula (a1-1) and an amine compound represented by formula (a1-2) below are subjected to a coupling reaction. There are several methods.
  • R M , R 1a , R 2a , X 1a , Ar 1a and Ar 2a have the same meanings as above.
  • X A is any group used in the coupling reaction.
  • groups include, for example, boronic acid groups such as -B(OH) 2 and boronic acid ester groups when using the Suzuki-Miyaura coupling reaction.
  • each X B is independently a halogen atom or a pseudohalogen group.
  • the halogen atom represented by X B include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a bromine atom or an iodine atom being preferred.
  • the pseudohalogen group represented by Examples include sulfonyloxy group.
  • the solvent used in the coupling reaction is not particularly limited as long as it does not adversely affect the reaction, but 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, etc.) , diisopropyl ether, tert-butyl methyl ether, THF, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.), amides (N,N-dimethylformamide (DMF), N,N-dimethyl
  • preferred solvents are aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.) and aromatic hydrocarbons (benzene, nitrobenzene, toluene, etc.) from the viewpoint of efficiently obtaining the target product.
  • ethers diethyl ether, diisopropyl ether, tert-butyl methyl ether, THF, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.) ), more preferably 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.).
  • Catalysts used in the above coupling reaction include [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (PdCl 2 (dppf)), tetrakis(triphenylphosphine)palladium (Pd(PPh 3 )), 4 ), bis(triphenylphosphine)dichloropalladium (Pd(PPh 3 ) 2 Cl 2 ), bis(benzylideneacetone)palladium (Pd(dba) 2 ), tris(benzylideneacetone)dipalladium (Pd 2 (dba) 3 ) ), bis(tri-tert-butylphosphine)palladium (Pd(Pt-Bu 3 ) 2 ), palladium(II) acetate (Pd(OAc) 2 ), and other palladium catalysts. These catalysts may be used with known suitable ligands.
  • the amount of the catalyst used is preferably an amount such that the molar ratio is 0.01 to 0.2, more preferably 0.03 to 0.1 with respect to the amine compound represented by formula (a1-2). .
  • the amount used can be 0.1 to 3.0 equivalents, preferably 0.8 to 1.5 equivalents, relative to the metal complex used.
  • a base may be used in the above coupling reaction.
  • the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkoxyalkali metals such as tert-butoxylithium, tert-butoxysodium, and tert-butoxypotassium; sodium carbonate, potassium carbonate, etc.
  • the amount of the base used is usually about 1 to 20, preferably 4 to 8, in molar ratio to the amine compound represented by formula (a1-2).
  • the charging ratio of the styrene compound represented by the formula (a1-1) and the amine compound represented by the following formula (a1-2) is such that the styrene compound represented by the formula (a1-1)
  • the amount of the amine compound represented by formula (a1-2) is preferably 0.2 to 2.0 in terms of molar ratio, and more preferably 0.5 to 1.0.
  • the reaction temperature is appropriately set in the range from the melting point to the boiling point of the solvent, taking into consideration the type and amount of the raw material compounds and catalysts used, but is usually about 20 to 120°C, preferably The temperature is 60-100°C.
  • the reaction time cannot be absolutely defined because it varies depending on the raw material compounds used, the reaction temperature, etc., but is usually about 0.5 to 12 hours.
  • the desired monomer can be obtained by post-treatment according to a conventional method.
  • the monomer of formula (b1) above can be obtained by esterifying an arylsulfonic acid compound, which can be produced by a known method disclosed in Patent Document 6, by a known method. Esterification of the above-mentioned arylsulfonic acid compound can be carried out by esterifying a predetermined arylsulfonic acid halide using a predetermined alcohol compound, for example, International Publication No. 2020/218316 (Patent Document 7) The method disclosed in can be adopted.
  • charge-transporting varnish of the present invention contains a charge-transporting substance made of the above-mentioned polymer and a solvent.
  • charge transport property is synonymous with electroconductivity, and is synonymous with hole transport property.
  • the charge-transporting varnish may be one that itself has charge-transporting properties, or the solid film obtained therefrom may have charge-transporting properties.
  • the content of the above polymer in the charge transporting varnish of the present invention is preferably 0.1 to 100% by mass, more preferably 10 to 100% by mass, based on the solid content, from the viewpoint of the electrical properties and solvent resistance of the obtained thin film. Even more preferably, it is 20 to 100% by mass.
  • the upper limit of the content of the polymer is usually 100% by mass or less, but when it contains optional components such as thiophene derivatives and arylamine derivatives described below, it is preferably 99.95% by mass or less, more preferably 99.95% by mass or less. .90% by mass or less.
  • the present invention may further contain charge transporting substances other than the above-mentioned polymers.
  • the other charge-transporting substances mentioned above are not particularly limited, and may be appropriately selected from charge-transporting compounds, charge-transporting oligomers, charge-transporting polymers, etc. used in the fields of organic EL and quantum dot EL. Can be used.
  • arylamine derivatives such as oligoaniline derivatives, N,N'-diarylbenzidine derivatives, N,N,N',N'-tetraarylbenzidine derivatives (excluding the above polymers); oligothiophene derivatives , thiophene derivatives such as thienothiophene derivatives, thienobenzothiophene derivatives; various charge transport compounds such as pyrrole derivatives such as oligopyrrole; charge transport polymers such as charge transport oligomers, polythiophene derivatives, polyaniline derivatives, polypyrrole derivatives, etc. Among these, polythiophene derivatives and arylamine derivatives are preferred.
  • a charge transporting compound low molecular weight compound
  • a charge transporting oligomer such as an arylamine compound represented by the formula (T2) or (T3) described below is useful from the viewpoint of producing a thin film with high flatness. Therefore, it is preferably monodisperse (that is, the molecular weight distribution is 1).
  • the molecular weight of the charge transporting substance is usually about 200 to 9,000 from the viewpoint of preparing a uniform varnish that provides a thin film with high flatness, but from the viewpoint of obtaining a thin film with even better charge transportability, It is preferably 300 or more, more preferably 400 or more, and from the viewpoint of preparing a uniform varnish that provides a highly flat thin film with good reproducibility, it is preferably 8,000 or less, more preferably 7,000 or less, and 6,000 or less. is even more preferable, and even more preferably 5,000 or less.
  • charge transporting substances include, for example, JP2002-151272A, WO2004/105446, WO2005/043962, WO2008/032617, and WO2008/032616. , International Publication No. 2013/042623, International Publication No. 2014/141998, International Publication No. 2014/185208, International Publication No. 2015/050253, International Publication No. 2015/137391, International Publication No. 2015/137395, International Publication No. Examples include those disclosed in Publication No. 2015/146912, International Publication No. 2015/146965, International Publication No. 2016/190326, International Publication No. 2016/136544, International Publication No. 2016/204079, etc.
  • the other charge transporting substance is a polythiophene derivative containing a repeating unit represented by formula (T1) or an amine adduct thereof.
  • R 1t and R 2t each independently represent a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a C 1 to 40 alkoxy group.
  • Y is an alkylene group having 1 to 40 carbon atoms which may contain an ether bond and may be substituted with a sulfo group, and Z may be substituted with a halogen atom.
  • the alkyl group having 1 to 40 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and s-butyl.
  • t-butyl n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n -hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosanyl, behenyl, triacontyl, tetracontyl groups and the like.
  • an alkyl group having 1 to 18 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms is more preferred.
  • the fluoroalkyl group having 1 to 40 carbon atoms is not particularly limited as long as it is an alkyl group having 1 to 40 carbon atoms in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom, and the specific Examples include fluoromethyl, difluoromethyl, perfluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,2-difluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 1,1,2 -Trifluoroethyl, 1,2,2-trifluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 1,2,2,2-tetrafluoroethyl, perfluoroethyl Fluoroethyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1,1-di
  • the alkyl group therein may be linear, branched, or cyclic, and specific examples include methoxy, ethoxy, n-propoxy, i-propoxy, c -Propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy , n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, n-eicosanyl
  • the fluoroalkoxy group having 1 to 40 carbon atoms is not particularly limited as long as it is an alkoxy group having 1 to 40 carbon atoms in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom, and the specific Examples include fluoromethoxy, difluoromethoxy, perfluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 1,2-difluoroethoxy, 1,1-difluoroethoxy, 2,2-difluoroethoxy, 1,1,2 -Trifluoroethoxy, 1,2,2-trifluoroethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 1,2,2,2-tetrafluoroethoxy, perfluoroethoxy, Fluoroethoxy, 1-fluoropropoxy, 2-fluoropropoxy, 3-fluoropropoxy, 1,1-difluoropropoxy, 1,2-diflu
  • the alkylene group having 1 to 40 carbon atoms may be linear, branched, or cyclic, and specific examples include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and heptamethylene. , octamethylene, nonamethylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, eicosanylene groups, and the like.
  • aryl group having 6 to 20 carbon atoms include phenyl, tolyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, Examples include 4-phenanthryl and 9-phenanthryl groups, with phenyl, tolyl and naphthyl groups being preferred.
  • aryloxy group having 6 to 20 carbon atoms include phenoxy, anthracenoxy, naphthoxy, phenanthrenoxy, and fluorenoxy groups.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
  • R 1t and R 2t each independently represent a hydrogen atom, a fluoroalkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, -O[C(R a R b ) -C(R c R d )-O] h -R e , -OR f , or a sulfo group, or -O-Y-O- formed by combining R 1t and R 2t is preferred.
  • R a to R d each independently represent a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms; Examples include the same groups as listed above. Among these, R a to R d are each independently preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenyl group.
  • R e is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenyl group, and preferably a hydrogen atom, a methyl group, a propyl group, or a butyl group.
  • h is preferably 1 to 5, more preferably 1, 2 or 3.
  • R f is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms; A fluoroalkyl group having 1 to 8 carbon atoms or a phenyl group is preferred, and -CH 2 CF 3 is more preferred.
  • R 1t is preferably a hydrogen atom or a sulfo group, more preferably a sulfo group
  • R 2t is preferably an alkoxy group having 1 to 40 carbon atoms or -O-[Z-O] h -R e , more preferably -O[C(R a R b )-C(R c R d )-O] h -R e or -OR f , even more preferably -O[C(R a R b )-C (R c R d )-O] h -R e , -O-CH 2 CH 2 -O-CH 2 CH 2 -O-CH 3 , -O-CH 2 CH 2 -O-CH 2 CH 2 -OH or -O-CH 2 CH 2 -OH, or -O-Y-O- formed by combining R 1t and R 2t with each other.
  • the polythiophene derivative according to a preferred embodiment of the present invention contains a repeating unit in which R 1t is a sulfo group and R 2t is other than a sulfo group, or is formed by combining R 1t and R 2t . -O-Y-O-.
  • the polythiophene derivative contains a repeating unit in which R 1t is a sulfo group and R 2t is an alkoxy group having 1 to 40 carbon atoms or -O-[Z-O] h -R e , Or it includes a repeating unit that is -O-Y-O- formed by combining R 1t and R 2t .
  • R 1t is a sulfo group
  • R 2t is -O[C(R a R b )-C(R c R d )-O] h -R e or -OR Contains a repeating unit that is f .
  • R 1t is a sulfo group
  • R 2t is -O[C(R a R b )-C(R c R d )-O] h -R e It contains a repeating unit, or it contains a repeating unit which is -O-Y-O- formed by combining R 1t and R 2t .
  • R 1t is a sulfo group
  • R 2t is -O-CH 2 CH 2 -O-CH 2 CH 2 -O-CH 3
  • -O-CH 2 CH 2 - Contains a repeating unit that is O-CH 2 CH 2 -OH or -O-CH 2 CH 2 -OH, or R 1t and R 2t are bonded to each other and are represented by the following formulas (Y1) and (Y2). Contains repeating units that are groups.
  • polythiophene derivatives include polythiophenes containing at least one type of repeating unit represented by the following formulas (T1-1) to (T1-5).
  • each unit may be bonded randomly or may be bonded as a block polymer.
  • polythiophene derivatives may be homopolymers or copolymers (including statistical, random, gradient, and block copolymers).
  • block copolymers include, for example, AB diblock copolymers, ABA triblock copolymers, and (AB) k -multiblock copolymers.
  • Polythiophenes also contain repeating units derived from other types of monomers, such as thienothiophenes, selenophenes, pyrroles, furans, tellurophenes, anilines, arylamines, and arylenes (such as phenylene, phenylene vinylene, and fluorene). May contain.
  • the content of the repeating unit represented by formula (T1) in the polythiophene derivative is preferably more than 50 mol%, more preferably 80 mol% or more, and more preferably 90 mol% or more, based on all the repeating units contained in the polythiophene derivative. It is more preferably 95 mol% or more, and most preferably 100 mol%.
  • the above polythiophene derivative may contain repeating units derived from impurities, depending on the purity of the starting monomer used for polymerization.
  • the term "homopolymer” above refers to a polymer containing repeat units derived from one type of monomer, but may also contain repeat units derived from impurities.
  • the polythiophene derivative is preferably a polymer in which basically all of the repeating units are repeating units represented by the above formula (T1), and the polythiophene derivative is preferably a polymer in which basically all repeating units are repeating units represented by the above formula (T1-1) to (T1-5). More preferably, it is a polymer containing at least one repeating unit.
  • the polythiophene derivative contains a repeating unit having a sulfo group, from the viewpoint of further improving solubility and dispersibility in organic solvents, the polythiophene derivative has an amine compound added to at least a part of the sulfo group contained therein. Amine adducts are preferred.
  • Amine compounds that can be used to form amine adducts include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine, n-hexylamine.
  • n-heptylamine, n-octylamine 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-penta Monoalkylamine compounds such as decylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-eicosanylamine; aniline, tolylamine, 1-naphthylamine, 2-naphthylamine, 1- Anthrylamine, 2-anthrylamine, 9-anthrylamine, 1-phenanthrylamine, 2-phenanthrylamine, 3-phenanthrylamine, 4-phenanthrylamine, 9-phenanthrylamine Primary
  • the amine adduct can be obtained by adding the polythiophene derivative to the amine itself or its solution and stirring well.
  • polythiophene derivative or its amine adduct may be treated with a reducing agent.
  • some of their constituent repeating units may have an oxidized chemical structure called a "quinoid structure.”
  • the term ⁇ quinoid structure'' is used for the term ⁇ benzenoid structure.'' The latter is a structure containing an aromatic ring, whereas the former is a structure in which the double bond within the aromatic ring moves outside the ring (its (As a result, the aromatic ring disappears), meaning a structure in which two extracyclic double bonds are formed that are conjugated with other double bonds remaining in the ring.
  • This quinoid structure is produced by a process in which a polythiophene derivative containing the repeating unit represented by the above formula (T1) undergoes an oxidation reaction with a dopant, a so-called doping reaction, and a "polaron structure” and " It forms part of a structure called "bipolaron structure”.
  • T1 a polythiophene derivative containing the repeating unit represented by the above formula (T1) undergoes an oxidation reaction with a dopant, a so-called doping reaction, and a "polaron structure” and " It forms part of a structure called "bipolaron structure”.
  • the reason why the polythiophene derivative contains a quinoid structure before undergoing this doping reaction is that the polythiophene derivative undergoes an unintended oxidation reaction equivalent to the doping reaction during its manufacturing process (especially in the sulfonation step). This is thought to be due to the
  • polythiophene derivatives vary in their solubility and dispersibility in organic solvents, and one of the reasons for this is that the amount of quinoid structure introduced into polythiophene due to the above-mentioned unintended oxidation reaction is This is thought to vary depending on differences in the manufacturing conditions of each polythiophene derivative. Therefore, when the above polythiophene derivative is subjected to a reduction treatment using a reducing agent, even if an excessive amount of quinoid structure is introduced into the polythiophene derivative, the reduction reduces the quinoid structure, improving the solubility and dispersibility of the polythiophene derivative in organic solvents. As a result, it becomes possible to stably produce a varnish with good charge transport properties that provides a thin film with excellent homogeneity.
  • the conditions for the reduction treatment are such that the quinoid structure is reduced and appropriately converted to a non-oxidized structure, that is, the benzenoid structure (for example, in a polythiophene derivative containing a repeating unit represented by the above formula (T1), There is no particular restriction as long as the quinoid structure represented by the above formula (T1') can be converted into the structure represented by the above formula (T1), but for example, in the presence of a suitable solvent or This treatment can be carried out simply by contacting the polythiophene derivative or amine adduct with a reducing agent in the absence of the reducing agent.
  • Such a reducing agent is not particularly limited as long as the reduction is carried out appropriately, but suitable examples include aqueous ammonia, hydrazine, etc., which are easily available commercially.
  • the amount of the reducing agent cannot be unconditionally defined as it varies depending on the amount of the reducing agent used, but from the viewpoint that the reduction is usually appropriate for 100 parts by mass of the polythiophene derivative or amine adduct to be treated, The content is 0.1 parts by mass or more, and from the viewpoint of preventing excessive reducing agent from remaining, the content is 10 parts by mass or less.
  • a polythiophene derivative or an amine adduct is stirred in 28% ammonia water at room temperature overnight.
  • the reduction treatment under such relatively mild conditions sufficiently improves the solubility and dispersibility of the polythiophene derivative and amine adduct in organic solvents.
  • the above reduction treatment may be performed before or after forming the amine adduct.
  • the solubility and dispersibility of the polythiophene derivative or its amine adduct in the solvent changes, and as a result, the polythiophene derivative or its amine adduct that was not dissolved in the reaction system at the start of the treatment is Sometimes it is dissolved.
  • an organic solvent that is incompatible with the polythiophene derivative or its amine adduct (for sulfonated polythiophene, acetone, 2-propanol, etc.) is added to the reaction system to dissolve the polythiophene derivative or its amine adduct.
  • the polythiophene derivative or its amine adduct can be recovered by a method such as precipitation and filtration.
  • the weight average molecular weight of the polythiophene derivative containing the repeating unit represented by formula (T1) or its amine adduct is preferably about 1,000 to 1,000,000, more preferably about 5,000 to 100,000, Even more preferred is about 10,000 to about 50,000.
  • this weight average molecular weight is a polystyrene equivalent value determined by GPC.
  • the polythiophene derivative or its amine adduct contained in the charge-transporting varnish used in the present invention may be only one type of polythiophene derivative or its amine adduct containing the repeating unit represented by formula (T1), or may be two types. It may be more than that.
  • the polythiophene derivative containing the repeating unit represented by formula (T1) may be a commercially available product or one polymerized by a known method using a thiophene derivative as a starting material, but in either case, It is also preferable to use one purified by a method such as reprecipitation or ion exchange. By using a purified product, the characteristics of an organic EL device or a quantum dot EL device including a thin film obtained from the charge transporting varnish of the present invention can be further improved.
  • the polythiophene derivative or an amine adduct thereof containing a repeating unit represented by formula (T1) when used, the polythiophene derivative or an amine adduct thereof and another charge transporting compound are used as charge transporting substances.
  • a charge transporting substance consisting of the following may be used in combination, it is preferable that only a polythiophene derivative containing a repeating unit represented by formula (T1) or an amine adduct thereof is included.
  • the content is usually 0.05% in the solid content, taking into consideration the desired film thickness and viscosity of the varnish. It is preferably determined in the range of 0.1 to 35% by weight, more preferably 0.1 to 35% by weight.
  • the aniline derivative represented by formula (T2) may be an oxidized aniline derivative (quinone diimine derivative) having a quinone diimine structure represented by the following formula in its molecule.
  • Examples of the method of oxidizing an aniline derivative to obtain a quinone diimine derivative include the methods described in International Publication No. 2008/010474 and International Publication No. 2014/119782.
  • R 1 to R 6 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, or an alkyl group having 1 to 20 carbon atoms, which may be substituted with Z 1 .
  • Y 1 to Y 5 are each independently an alkyl group having 1 to 20 carbon atoms, which may be substituted with Z 1 group, an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with Z 2 .
  • Z 1 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with a halogen atom, nitro group, cyano group, amino group, or Z 3
  • Z 2 is a halogen atom, a nitro group, a cyano group, an amino group, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, which may be substituted with Z 3 represents an alkynyl group
  • Z 3 represents a halogen atom, a nitro group, a cyano group, or an amino group
  • k and l are each independently an integer of 1 to 5.
  • R 7 to R 10 are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfo group, a carboxy group, or a Z 1 an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms; , represents an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms, which may be substituted with hydrogen atom, phenyl group, naphthyl group, pyridyl group, pyrimidinyl group, pyri
  • R 15 to R 18 are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfo group, a carboxy group, or a Z 1 an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms; , represents an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms, which may be substituted with phenyl group, naphthyl group, anthryl group, pyridyl group, pyrimidinyl group,
  • alkyl group having 1 to 20 carbon atoms alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, 7 to 20 carbon atoms (Optionally substituted with 20 aralkyl groups or acyl groups having 1 to 20 carbon atoms.)
  • Z 1 and Z 2 have the same meanings as above.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl.
  • n-pentyl n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and other linear or branched alkyl groups having 1 to 20 carbon atoms; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, and other cyclic alkyl groups having 3 to 20 carbon atoms.
  • alkenyl groups having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-Methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, n- Examples include 1-eicosenyl group.
  • alkynyl groups having 2 to 20 carbon atoms include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl, 1-methyl- 2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n- Examples include butynyl, 1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n-1-pentadecynyl, n-1-eicosynyl and the like.
  • aryl groups having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4- Examples include phenanthryl and 9-phenanthryl groups.
  • aralkyl groups having 7 to 20 carbon atoms include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl, naphthylpropyl groups, and the like.
  • heteroaryl groups having 2 to 20 carbon atoms include 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl.
  • 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl group, etc. can be mentioned.
  • haloalkyl group having 1 to 20 carbon atoms examples include those in which at least one hydrogen atom of the above alkyl group having 1 to 20 carbon atoms has been replaced with a halogen atom. Among them, a fluoroalkyl group is preferred, and a perfluoro Alkyl groups are more preferred.
  • alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, c-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy , n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, n-eicosanyloxy and the like.
  • thioalkoxy (alkylthio) groups having 1 to 20 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio, t-butylthio, n-pentylthio, n- hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio, n-undecylthio, n-dodecylthio, n-tridecylthio, n-tetradecylthio, n-pentadecylthio, n-hexadecylthio, n-heptadecylthio, Examples include n-octadecylthio,
  • acyl group having 1 to 20 carbon atoms include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and benzoyl groups.
  • R 1 to R 6 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 1 , or an alkyl group having 6 to 20 carbon atoms which may be substituted with Z 2 20 aryl groups, -NHY 1 , -NY 2 Y 3 , -OY 4 , or -SY 5 are preferred, and in this case, Y 1 to Y 5 have 1 to 1 carbon atoms, which may be substituted with Z 1 10 alkyl group or an aryl group having 6 to 10 carbon atoms which may be substituted with Z 2 is preferable, and an alkyl group having 1 to 6 carbon atoms which may be substituted with Z 1 or an aryl group having 6 to 6 carbon atoms which may be substituted with Z 2 is preferable.
  • a phenyl group is more preferred, and an alkyl group having 1 to 6 carbon atoms or a phenyl group is even more preferred.
  • R 1 to R 6 are more preferably a hydrogen atom, a fluorine atom, a methyl group, a phenyl group, or a diphenylamino group (-NY 2 Y 3 in which Y 2 and Y 3 are phenyl groups), and R 1 to R 4 is a hydrogen atom, and it is even more preferable that R 5 and R 6 are both hydrogen atoms or diphenylamino groups.
  • Z 1 is preferably a halogen atom or an aryl group having 6 to 10 carbon atoms which may be substituted with Z 3 , and more preferably a fluorine atom or a phenyl group. Preferably, it is not present (that is, it is an unsubstituted group), and Z 2 is preferably a halogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 3 .
  • a fluorine atom or an alkyl group having 1 to 6 carbon atoms is more preferred, and its absence (ie, an unsubstituted group) is even more preferred.
  • Z 3 is preferably a halogen atom, more preferably a fluorine atom, and even more preferably absent (that is, an unsubstituted group).
  • k and l preferably satisfy k+l ⁇ 8, and more preferably k+l ⁇ 5.
  • R 7 to R 10 are preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; Hydrogen atoms are more preferred. Further, in consideration of increasing the solubility of the aniline derivative represented by formula (T3) in a solvent and increasing the uniformity of the obtained thin film, it is preferable that R 11 and R 13 are both hydrogen atoms.
  • R 11 and R 13 are both hydrogen atoms
  • R 12 and R 14 are each independently a phenyl group (this phenyl group can be a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, group, sulfo group, carboxy group, alkoxy group having 1 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, 2 to 20 carbon atoms may be substituted with an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms.) or a group represented by the above formula (T
  • m is preferably 2 to 4 in consideration of the ease of obtaining the compound, ease of production, cost, etc., and more preferably 2 or 3 in consideration of increasing the solubility in the solvent. Considering the balance of availability, ease of manufacture, manufacturing cost, solubility in solvents, transparency of the obtained thin film, etc., 2 is optimal.
  • the aniline derivatives represented by formulas (T2) and (T3) may be commercially available products or those produced by known methods such as those described in the above publications; In this case, it is preferable to use a varnish purified by recrystallization, vapor deposition, etc. before preparing the charge transporting varnish. By using a purified varnish, the characteristics of an electronic device including a thin film obtained from the varnish can be further improved.
  • a purified varnish By using a purifying by recrystallization, for example, 1,4-dioxane, tetrahydrofuran, etc. can be used as the solvent.
  • the charge transport substance represented by formulas (T2) and (T3) is one type of compound selected from the compounds represented by formulas (T2) and (T3) (i.e., the dispersity of molecular weight distribution 1) may be used alone or in combination of two or more compounds.
  • charge transporting substances represented by formulas (T2) and (T3) that can be suitably used in the present invention include, but are not limited to, the following.
  • DPA represents a diphenylamino group.
  • the content thereof is usually determined in consideration of the desired film thickness, viscosity of the varnish, etc. in the solid content. It is preferably 0.05 to 90% by mass, more preferably 0.1 to 75% by mass, determined as appropriate.
  • the charge transporting varnish of the present invention may contain a known organic dopant substance or inorganic dopant substance.
  • a highly polar solvent that can satisfactorily dissolve the charge transporting substance, dopant substance, etc. to be used can be used.
  • a low polarity solvent may be used because it has better process compatibility than a highly polar solvent.
  • a low polar solvent is defined as one having a dielectric constant of less than 7 at a frequency of 100 kHz
  • a high polar solvent is defined as one having a dielectric constant of 7 or more at a frequency of 100 kHz.
  • low polar solvents examples include: Chlorinated solvents such as chloroform and chlorobenzene; Aromatic hydrocarbon solvents such as toluene, xylene, tetralin, cyclohexylbenzene, decylbenzene; Aliphatic alcohol solvents such as 1-octanol, 1-nonanol, 1-decanol; Ether 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; Methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, dimethyl phthalate, bis(2-ethylhexyl) phthalate, dibutyl maleate, di
  • Amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone; Ketone solvents such as methyl ethyl ketone, isophorone, and cyclohexanone; Cyano solvents such as acetonitrile and 3-methoxypropionitrile; Polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 2,3-butanediol; Other than aliphatic alcohols such as diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxy
  • the charge transporting varnish of the present invention may contain one or more metal oxide nanoparticles.
  • Nanoparticles refer to fine particles whose average primary particle diameter is on the order of nanometers (typically 500 nm or less).
  • Metal oxide nanoparticles refer to metal oxides shaped into nanoparticles.
  • the primary particle diameter of the metal oxide nanoparticles is not particularly limited as long as it is nanosized, but is preferably from 2 to 150 nm, more preferably from 3 to 100 nm, and even more preferably from 5 to 50 nm. Note that the particle diameter is a value measured using a nitrogen adsorption isotherm according to the BET method.
  • the metal constituting the metal oxide nanoparticles includes not only metals in the usual sense but also metalloids.
  • Metals in the usual sense include, but are not limited to, tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum ( It is preferable to use one or more selected from the group consisting of Ta) and W (tungsten).
  • metalloid means an element whose chemical and/or physical properties are intermediate between metals and nonmetals.
  • metalloids boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).
  • B boron
  • Si silicon
  • Ge germanium
  • As arsenic
  • Sb antimony
  • Te tellurium
  • the element is a metalloid.
  • These metalloids may be used alone or in combination of two or more types, or may be used in combination with metals in the usual sense.
  • metal oxide nanoparticles include boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), tin (Sn), titanium (Ti), aluminum It is preferable that the metal oxide contains one or more metal oxides selected from (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten). Note that when the metals are a combination of two or more types, the metal oxide may be a mixture of oxides of individual metals, or may be a composite oxide containing a plurality of metals.
  • metal oxides include B 2 O 3 , B 2 O, SiO 2 , SiO, GeO 2 , GeO, As 2 O 4 , As 2 O 3 , As 2 O 5 , Sb 2 O 3 , Sb 2 Examples include O 5 , TeO 2 , SnO 2 , SnO, ZrO 2 , Al 2 O 3 , ZnO, etc., but B 2 O 3 , B 2 O, SiO 2 , SiO, GeO 2 , GeO, As 2 O 4 , As 2 O 3 , As 2 O 5 , SnO 2 , SnO, Sb 2 O 3 , TeO 2 and mixtures thereof are preferred, and SiO 2 is more preferred.
  • the amount of metal oxide nanoparticles is not particularly limited, but from the viewpoint of improving the transparency of the thin film obtained and the uniformity of the film, the lower limit of the amount of metal oxide nanoparticles in the solid content is usually 50%. It is preferably 60% by mass, more preferably 65% by mass, and its upper limit is usually 95% by mass, preferably 90% by mass.
  • silica sol in which SiO 2 nanoparticles are dispersed in a dispersion medium as the metal oxide nanoparticles.
  • the silica sol is not particularly limited, and can be appropriately selected from known silica sols. Commercially available silica sols are usually in the form of dispersions. Commercially available silica sols include SiO2 nanoparticles in various solvents, such as water, methanol, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylacetamide, ethylene glycol, isopropanol, methanol, ethylene glycol monopropyl ether, cyclohexanone, acetic acid. Examples include those dispersed in ethyl, toluene, propylene glycol monomethyl ether acetate, and the like.
  • silica sols include Snowtex (registered trademark) ST-O, ST-OS, ST-O-40, ST-OL manufactured by Nissan Chemical Co., Ltd., and Silicadol 20 manufactured by Nippon Kagaku Kogyo Co., Ltd. , 30, 40, etc.; methanol silica sol manufactured by Nissan Chemical Co., Ltd., MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST-ZL, EG- Examples include, but are not limited to, organosilica sols such as ST.
  • the solid content concentration of the silica sol is also not particularly limited, but is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 30% by mass.
  • the amount of silica sol used is appropriately determined in consideration of its concentration so that the amount of silica ultimately contained in the charge transporting varnish corresponds to the amount of metal oxide nanoparticles described above.
  • the charge transporting varnish of the present invention improves the injection property to the hole transport layer and improves the life characteristics of the device.
  • an organic silane compound may be included. Its content is usually about 1 to 30% by mass based on the total mass of the charge transport material and the dopant material.
  • the organic silane compound include dialkoxysilane compounds, trialkoxysilane compounds, and tetraalkoxysilane compounds.
  • the viscosity of the charge transporting varnish is determined appropriately depending on the thickness of the thin film to be produced and the solid content concentration, but it is usually 1 to 50 mPa ⁇ s at 25°C.
  • the solid content refers to components other than the solvent contained in the charge transporting varnish.
  • the solid content concentration of the charge transporting varnish is determined as appropriate by taking into account the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, etc., but it is usually 0.1 to 20.0% by mass. %, and in consideration of improving the coatability of the varnish, it is preferably about 0.2 to 10.0% by mass, more preferably about 0.5 to 8.0% by mass.
  • the method for preparing the charge-transporting varnish is not particularly limited, but for example, a charge-transporting substance and a dopant substance are dissolved in a highly polar solvent, and a low-polar solvent and surface-treated metal oxide nanoparticles, etc. are added thereto. Examples include a method in which a highly polar solvent and a low polar solvent are mixed, a charge transporting substance and a dopant substance are dissolved therein, and further surface-treated metal oxide nanoparticles are added.
  • the charge-transporting varnish described above can be used to easily produce a charge-transporting thin film, and therefore can be suitably used in producing electronic devices, particularly organic EL devices and quantum dot EL devices.
  • the charge-transporting thin film can be formed by applying the above-described charge-transporting varnish onto a base material and baking it.
  • the varnish application method is not particularly limited, and examples include dip method, spin coating method, transfer printing method, roll coating method, brush coating, inkjet method, spray method, slit coating method, etc. It is preferable to adjust the viscosity and surface tension of the varnish accordingly.
  • the firing atmosphere of the charge transporting varnish after application is not particularly limited, and a thin film with a uniform coating surface and high charge transporting properties can be produced not only in the air but also in an inert gas such as nitrogen or in a vacuum.
  • an inert gas such as nitrogen or in a vacuum.
  • a thin film having charge transporting properties may be obtained with good reproducibility by firing the varnish in the atmosphere.
  • the firing temperature is determined as appropriate within the range of about 100 to 260°C, taking into account the purpose of the thin film to be obtained, the degree of charge transport property to be imparted to the 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, but when the above-mentioned arylamine compound is used as a charge transporting substance, Even when firing at a low temperature of 200° C. or lower, a thin film having good charge transport properties can be obtained.
  • the temperature may be changed in two or more steps in order to develop more uniform film formation or to advance the reaction on the substrate, and the heating may be performed using, for example, a hot plate or This may be done using a suitable device such as an oven.
  • the thickness of the charge transporting thin film is not particularly limited, but it may be provided between an anode and a light emitting layer such as a hole injection layer, a hole transport layer, a hole injection transport layer, etc. of an organic EL element or a quantum dot EL element. When used as a functional layer, the thickness is preferably 5 to 300 nm.
  • a method for changing the film thickness there are methods such as changing the solid content concentration in the varnish or changing the amount of solution on the substrate during coating.
  • Organic EL device and quantum dot EL device When applying the above charge transporting thin film to an organic EL device or a quantum dot EL device, the above-mentioned It can be configured to include a charge transporting thin film.
  • Typical configurations of organic EL devices and quantum dot EL devices include (a) to (f) below, but are not limited to these.
  • an electron blocking layer etc. can also be provided between a light emitting layer and an anode
  • a hole (hole) blocking layer etc. can also be provided between a light emitting layer and a cathode as needed.
  • the hole injection layer, the hole transport layer, or the hole injection transport layer may also have a function as an electron blocking layer, etc., and the electron injection layer, the electron transport layer, or the electron injection transport layer may block holes. It may also have a function as a block layer or the like. Furthermore, it is also possible to provide an arbitrary functional layer between each layer as necessary.
  • Hole injection layer is layers formed between the light emitting layer and the anode, and transport holes from the anode to the light emitting layer. If only one layer of hole transporting material is provided between the light emitting layer and the anode, it is a “hole injection transport layer”, and between the light emitting layer and the anode, When two or more layers of hole-transporting materials are provided, the layer close to the anode is the “hole-injection layer” and the other layers are the “hole-transporting layers.”
  • the hole injection (transport) layer a thin film is used 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 transport (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. If only one layer of electron transport material is provided between the light emitting layer and the cathode, it is an “electron injection transport layer”, and the layer of electron transport material is provided between the light emitting layer and the cathode. When two or more layers are provided, the layer close to the cathode is the “electron injection layer”, and the other layers are the “electron transport layers”.
  • the "light-emitting layer” is an organic layer having a light-emitting function, and may be an organic light-emitting layer or a quantum dot light-emitting layer.
  • the light emitting layer is an EL device of an organic light emitting layer, it is an organic EL device, and when the light emitting layer is an EL device of a quantum dot light emitting layer, it is a quantum dot EL device.
  • a doping system when a doping system is adopted, it includes a host material and a dopant material.
  • the host material mainly has the function of promoting recombination of electrons and holes and confining excitons within the light emitting layer, and the dopant material makes the excitons obtained by recombination efficiently emit light.
  • the host material mainly has the function of confining excitons generated by the dopant within the light emitting layer.
  • the charge transporting thin film of the present invention can be used as a functional layer provided between an anode and a light emitting layer in an organic EL device or a quantum dot EL device. It is suitable as a layer, more suitable as a hole injection layer or a hole transport layer, and even more suitable as a hole injection layer.
  • Examples of the materials used and the manufacturing method for manufacturing an EL device 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 or a quantum dot EL device having a hole injection layer made of a thin film obtained from the charge transporting varnish of the present invention is as follows. Note that it is preferable that the electrode is previously subjected to surface treatment such as cleaning with alcohol, pure water, etc., UV ozone treatment, oxygen-plasma treatment, etc. within a range that does not adversely affect the electrode.
  • a hole injection layer made of the charge transporting thin film of the present invention is formed on the anode substrate by the method described above.
  • 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 deposited.
  • a composition for forming a hole transport layer containing a hole transporting polymer and a composition for forming a light emitting layer containing a light emitting polymer may be used. These layers are formed using a wet process. Note that, if necessary, an electron blocking layer may be provided between the light emitting layer and the hole transport layer.
  • an example (sequential structure) in which the anode, hole injection layer, hole transport layer, light emitting layer, electron transport layer/hole blocking layer, electron injection layer, and cathode are laminated in this order has been described, but the present invention is not limited to this.
  • a cathode, an electron injection layer, an electron transport layer/hole blocking layer, a light emitting layer, a hole transport layer, a hole injection layer, and an anode may be laminated in this order (reverse structure).
  • anode materials include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and metal anodes made of metals typified by aluminum and their alloys. Preferably, the material has been subjected to chemical treatment. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used. Note that 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"-tris[1 -Triarylamines such as naphthyl(phenyl)amino]triphenylamine (1-TNATA), 5,5''-bis- ⁇ 4-[bis(4-methylphenyl)amino]phenyl ⁇ -2,2': Examples include, but are not limited to, oligothiophenes such as 5',2''-terthiophene (BMA-3T).
  • Examples of materials 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)benzo Low-molecular luminescent materials such as thiazole metal complexes and silole derivatives; poly(p-phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly(3-alkyl) Examples include, but are not limited to, systems in which a light-emitting material and an electron transfer material are mixed with a polymer compound such as thiophene) or polyvinylcarbazole.
  • metal complexes such as aluminum complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo[h]quinoline, bisstyrylbenzene derivatives, bisstyryl
  • a light-emitting layer when forming a light-emitting layer by vapor deposition, it may be co-deposited with a light-emitting dopant, and examples of the light-emitting dopant include metal complexes such as tris(2-phenylpyridine)iridium(III) (Ir(ppy) 3 ). Examples include, but are not limited to, naphthacene derivatives such as rubrene, quinacridone derivatives, and fused polycyclic aromatic rings such as perylene.
  • Materials for forming the electron transport 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), and alumina (Al 2 O 3 ), lithium fluoride (LiF), and sodium fluoride (NaF). metal fluorides, but are not limited to these.
  • metal oxides such as lithium oxide (Li 2 O), magnesium oxide (MgO), and alumina (Al 2 O 3 ), lithium fluoride (LiF), and sodium fluoride (NaF).
  • metal fluorides but are not limited to these.
  • Examples of the cathode material include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like.
  • Examples of the material for forming the electron block layer include tris(phenylpyrazole)iridium, but are not limited thereto.
  • hole-transporting polymers include poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid), poly[(9,9-dihexylfluorenyl-2,7-diyl)-co-( N,N'-bis ⁇ p-butylphenyl ⁇ -1,4-diaminophenylene)], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(N,N'-bis ⁇ p-butylphenyl ⁇ -1,1'-biphenylene-4,4-diamine)], poly[(9,9-bis ⁇ 1'-penten-5'-yl ⁇ fluorenyl-2,7-diyl)- co-(N,N'-bis ⁇ p-butylphenyl ⁇ -1,4-diaminophenylene)], poly[N,N'-bis(4-butylphenyl)-N,
  • luminescent polymers include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), poly(2-methoxy-5-(2'-ethylhexoxy)-1,4-phenylenevinylene) (MEH- Examples include, but are not limited to, polyphenylene vinylene derivatives such as PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).
  • PDAF poly(9,9-dialkylfluorene)
  • MEH- Examples include, but are not limited to, polyphenylene vinylene derivatives such as PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).
  • the quantum dot material may include a II-VI group semiconductor, a III-V group semiconductor, an I-III-VI group semiconductor, a group IV semiconductor, and a semiconductor material. It can contain at least one semiconductor material selected from the group consisting of Group I-II-IV-VI semiconductors.
  • the semiconductor materials include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS , CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgST e, HgZnSeS, CdHgSeTe, CdHgST e, HgZnSeS, HgZnS
  • the charge transporting varnish of the present invention can be used to connect an anode and a light emitting layer such as a hole injection layer, a hole transport layer, a hole injection transport layer, etc. of an organic EL device or a quantum dot EL device (quantum dot light emitting diode).
  • a light emitting layer such as a hole injection layer, a hole transport layer, a hole injection transport layer, etc. of an organic EL device or a quantum dot EL device (quantum dot light emitting diode).
  • organic photoelectric conversion elements organic thin film solar cells, organic perovskite photoelectric conversion elements, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, It can also be used to form charge-transporting thin films in electronic devices such as organic optical analyzers, organic photoreceptors, organic field quenchers, light-emitting electrochemical cells, quantum lasers, organic laser diodes, and organic plasmon light-emitting devices. .
  • compound 3 (2.4 g) and 7.68 g of 1-ethoxy-2-propanol (manufactured by Junsei Kagaku Co., Ltd., the same hereinafter) were added to a 20 mL two-necked flask, and stirred at 0 to 5 °C. .
  • Example 2-2 Add 60 mg of P2 obtained in Example 1-2, 0.97 g of triethylene glycol butyl methyl ether, 0.58 g of butyl benzoate, and 0.39 g of dimethyl phthalate to a sample tube, and stir at room temperature for 30 minutes using a stirrer. Stirred. Thereafter, it was filtered through a PP syringe filter with a pore size of 0.2 ⁇ m to obtain a charge transporting varnish (solid content concentration: 3.0% by mass).
  • Example 2-3 In a sample tube, 30 mg of P2 obtained in Example 1-2, 30 mg of arylsulfonic acid ester compound A of the following formula, 0.97 g of triethylene glycol butyl methyl ether, 0.58 g of butyl benzoate, and 0.39 g of dimethyl phthalate. was added and stirred for 30 minutes at room temperature using a stirrer. Thereafter, it was filtered through a PP syringe filter with a pore size of 0.2 ⁇ m to obtain a charge transporting varnish (solid content concentration: 3.0% by mass).
  • the following arylsulfonic acid ester compound was synthesized according to the method described in International Publication No. 2017/217457.
  • Example 2-4 In a sample tube, 36 mg of P2 obtained in Example 1-2, 0.12 g of silica sol dispersed in triethylene glycol butyl methyl ether obtained in Preparation Example 1-1, 0.88 g of triethylene glycol butyl methyl ether, and benzoic acid. 0.58 g of butyl and 0.39 g of dimethyl phthalate were added, and the mixture was stirred at room temperature for 30 minutes using a stirrer. Thereafter, it was filtered through a PP syringe filter with a pore size of 0.2 ⁇ m to obtain a charge transporting varnish (solid content concentration: 3.0% by mass).
  • Example 2-5 In a sample tube, 18 mg of P2 obtained in Example 1-2, 18 mg of the above arylsulfonic acid ester compound A, 0.12 g of the triethylene glycol butyl methyl ether-dispersed silica sol obtained in Preparation Example 1-1, and triethylene glycol. 0.88 g of butyl methyl ether, 0.58 g of butyl benzoate, and 0.39 g of dimethyl phthalate were added, and the mixture was stirred at room temperature using a stirrer for 30 minutes. Thereafter, it was filtered through a PP syringe filter with a pore size of 0.2 ⁇ m to obtain a charge transporting varnish (solid content concentration: 3.0% by mass).
  • the thickness of the charge-transporting thin film of the ITO substrate with the charge-transporting thin film prepared above was measured using a stylus-type thin-film profilometer. Thereafter, the ITO substrate with the charge transporting thin film after the film thickness measurement was completely immersed in a petri dish filled with toluene solvent, and left to stand for 15 minutes. Thereafter, the substrate was pulled up, the solvent was removed by air blowing, and then the solvent was completely removed by heating and drying at 100° C. for 5 minutes. Thereafter, the thickness of the charge transporting thin film of each substrate was measured again using a stylus meter, and changes in the film thickness before and after immersion in toluene solvent were evaluated. Table 1 shows the results of the film thickness change rate (remaining film rate) before and after immersion in the solvent.
  • P1 and P2 used in the charge transporting varnishes of Examples 2-1 to 2-5 have an arylsulfonic acid ester moiety inside the polymer, so when the charge transporting thin film is fired, the sulfonic acid It is speculated that solvent resistance to toluene was developed by deprotecting the ester moiety and forming a sulfonic acid group. On the other hand, since Comparative Example 2-1 does not have an arylsulfonic acid ester moiety inside the polymer, it is presumed that the charge transporting thin film after firing lacked solvent resistance to toluene.
  • Example 3-1 Fabrication and characteristic evaluation of organic EL device
  • the charge transporting varnish obtained in Example 2-1 was applied to an ITO substrate using a spin coater, and then dried at 120° C. for 1 minute in the atmosphere. Next, the dried ITO substrate was baked at 180° C. for 15 minutes in an air atmosphere to form a uniform thin film of 50 nm on the ITO substrate.
  • the ITO substrate used was a 25 mm x 25 mm x 0.7 t glass substrate with a patterned 150 nm thick ITO film formed on the surface, and the surface was cleaned using an O 2 plasma cleaning device (150 W, 30 seconds) before use. The impurities above were removed.
  • ⁇ -NPD N,N'-di(1- naphthyl )-N,N'- diphenylbenzidine
  • HTEB-01 electronic block material
  • a light-emitting layer host material NS60 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • Ir(ppy) 3 light-emitting layer dopant material
  • the deposition rate was 0.2 nm/sec for Alq 3 and aluminum, and 0.02 nm/sec for lithium fluoride, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively.
  • the organic EL element was sealed with a sealing substrate, and then its characteristics were evaluated.
  • the sealing was performed according to 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 organic EL element is placed between the sealing substrates, and the sealing substrate is bonded with an adhesive (Moresco Moisture Cut WB90US (P) manufactured by MORESCO Co., Ltd.). It was pasted together. At this time, a water absorbing agent (manufactured by Dynic Co., Ltd., HD-071010W-40) was placed in the sealing substrate together with the organic EL element. 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.
  • UV light wavelength: 365 nm, irradiation amount: 6,000 mJ/cm 2
  • Example 3-2 The procedure of Example 3-1 was repeated except that the charge-transporting varnish obtained in Example 2-2 was used instead of the charge-transporting varnish obtained in Example 2-1, and an organic EL element was manufactured. Obtained.
  • Example 3-3 The procedure of Example 3-1 was repeated except that the charge-transporting varnish obtained in Example 2-3 was used instead of the charge-transporting varnish obtained in Example 2-1, and an organic EL element was manufactured. Obtained.
  • Example 3-4 An organic EL element was obtained by repeating the procedure of Example 3-1, except that the charge transporting varnish obtained in Example 2-4 was used instead of the charge transporting varnish obtained in Example 2-1. Ta.
  • Example 3-5 An organic EL element was obtained by repeating the procedure of Example 3-1, except that the charge transporting varnish obtained in Example 2-5 was used instead of the charge transporting varnish obtained in Example 2-1. Ta.
  • the organic EL devices produced in Examples 3-1 to 3-5 all exhibited good organic EL device characteristics.
  • the results of Examples 3-1 and 3-2 show that polymers P1 and P2 have good charge transport properties even when used alone, that is, polymers P1 and P2 have aryl sulfonic acid esters inside the polymer. This indicates that the site functions as a dopant. It is inferred that by containing a dopant function inside the polymer, doping occurs smoothly in the charge transporting site made of arylamine, and the polymer exhibits good charge transporting properties.

Abstract

L'invention concerne un polymère approprié pour être utilisé dans la formation de films minces de transport de charge destinés à être utilisés dans des éléments EL organiques, etc, ledit polymère étant caractérisé en ce qu'il comprend, par exemple, les unités de répétition représentées par les formules.
PCT/JP2023/009226 2022-03-28 2023-03-10 Polymère et son utilisation WO2023189399A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017217455A1 (fr) * 2016-06-16 2017-12-21 日産化学工業株式会社 Composé d'ester d'acide sulfonique et son utilisation
JP2020500417A (ja) * 2016-11-04 2020-01-09 ダウ グローバル テクノロジーズ エルエルシー アミニウムラジカルカチオンを含有する有機発光ダイオード
WO2020067288A1 (fr) * 2018-09-28 2020-04-02 日産化学株式会社 Polymère et son utilisation
WO2022209891A1 (fr) * 2021-03-29 2022-10-06 日産化学株式会社 Polymère et son utilisation
WO2023008176A1 (fr) * 2021-07-26 2023-02-02 日産化学株式会社 Composé polymère d'arylsulfonate fluoré et son utilisation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017217455A1 (fr) * 2016-06-16 2017-12-21 日産化学工業株式会社 Composé d'ester d'acide sulfonique et son utilisation
JP2020500417A (ja) * 2016-11-04 2020-01-09 ダウ グローバル テクノロジーズ エルエルシー アミニウムラジカルカチオンを含有する有機発光ダイオード
WO2020067288A1 (fr) * 2018-09-28 2020-04-02 日産化学株式会社 Polymère et son utilisation
WO2022209891A1 (fr) * 2021-03-29 2022-10-06 日産化学株式会社 Polymère et son utilisation
WO2023008176A1 (fr) * 2021-07-26 2023-02-02 日産化学株式会社 Composé polymère d'arylsulfonate fluoré et son utilisation

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