WO2022181587A1 - Composition d'encre de transport de charges - Google Patents

Composition d'encre de transport de charges Download PDF

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WO2022181587A1
WO2022181587A1 PCT/JP2022/007152 JP2022007152W WO2022181587A1 WO 2022181587 A1 WO2022181587 A1 WO 2022181587A1 JP 2022007152 W JP2022007152 W JP 2022007152W WO 2022181587 A1 WO2022181587 A1 WO 2022181587A1
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group
carbon atoms
charge
transporting
ink composition
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PCT/JP2022/007152
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English (en)
Japanese (ja)
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陽介 倉田
裕太 菅野
知佳 牧島
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日産化学株式会社
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Priority to CN202280016523.8A priority Critical patent/CN116888223A/zh
Priority to JP2023502422A priority patent/JPWO2022181587A1/ja
Priority to KR1020237030032A priority patent/KR20230147645A/ko
Publication of WO2022181587A1 publication Critical patent/WO2022181587A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/165—Electron transporting layers comprising dopants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources

Definitions

  • the present invention relates to a charge-transporting ink composition.
  • organic electroluminescence (hereinafter referred to as organic EL) elements are attracting attention for their various advantages such as high contrast, energy saving, and flexibility, and are being put to practical use in fields such as displays and lighting.
  • An organic EL element uses a plurality of functional thin films, and one of them, the hole injection layer, is responsible for the transfer of electric charges between the anode and the hole transport layer or the light emitting layer. It has an important role to achieve voltage drive and high brightness.
  • the manufacturing methods of organic EL elements are roughly divided into dry processes, typified by vapor deposition, and wet processes, typified by spin coating and inkjet methods. Comparing the two processes from the viewpoint of increasing the area of the device, the wet process can efficiently manufacture a film with high flatness over a large area compared to the dry process. Therefore, at present, when there is a demand for large-area production of organic EL devices, it is important to provide a hole injection layer or the like having excellent functions that can be formed by a wet process.
  • Patent Document 1 achieves formation of a charge-transporting thin film having high transparency in the visible light region by using a composition containing metal oxide nanoparticles.
  • Non-Patent Document 1 shows that the characteristics of an organic EL element are improved by reducing the surface roughness of a film.
  • charge-transporting inks are generally susceptible to oxygen and moisture, and there is concern that their performance may change due to oxidation or decomposition of compounds in the ink. Therefore, it is important from the viewpoint of reliability that the charge-transporting ink is stable against atmospheric exposure.
  • the present invention has been made in view of the above background, and an object of the present invention is to provide a charge-transporting ink composition that has charge-transporting properties, provides a film with excellent flatness, and is stable against exposure to the atmosphere.
  • a charge-transporting ink composition comprising an amine compound represented by the following formula (P1), a charge-transporting substance, and an organic solvent.
  • P1 an amine compound represented by the following formula (P1)
  • P1 a charge-transporting substance
  • organic solvent an organic solvent.
  • R m represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • R n represents an alkylene group having 1 to 20 carbon atoms
  • R m and R n are bonded to each other to represent an alkanetriyl group having 3 to 40 carbon atoms, and the number of carbon atoms in R n
  • R 1 and R 2 are each independently 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, an alkoxy group having 1 to 40 carbon atoms, or 1 ⁇ 40 fluoroalkoxy group, C6-C20 aryloxy group, -O-[Z-O] p -R e , or sulfonic acid group, or formed by combining R 1 and R 2 —O—Y—O—, Y is an alkylene group having 1 to 40 carbon atoms which may contain an ether bond and may be substituted with a sulfonic acid group, and Z is substituted with a halogen atom is an alkylene group having 1 to 40 carbon atoms which may be substituted, p is an integer of 1 or more, R e is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, or
  • R 1 is a sulfonic acid group and R 2 is an alkoxy group having 1 to 40 carbon atoms or -O-[Z-O] p -R e , or R 1 and R 2 are bonded
  • 11. A method for improving storage stability of a charge-transporting ink composition containing an amine compound, a charge-transporting substance, and an organic solvent, wherein an amine compound represented by the following formula (P1) is used as the amine compound.
  • a method for improving the storage stability of a charge-transporting ink composition characterized by: (Wherein, R m represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R n represents an alkylene group having 1 to 20 carbon atoms, represents an alkenylene group having 2 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, or R m and R n are bonded to each other to represent an alkanetriyl group having 3 to 40 carbon atoms, and the number of carbon atoms in R n When an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, and an alkanetriyl group of R m and R n are bonded to —NH 2 in formula (P1), the —CH 2 —NH 2 group is limited to those that are formed.) 12.
  • a method for improving flatness of a charge-transporting thin film obtained from a charge-transporting ink composition containing an amine compound, a charge-transporting substance, and an organic solvent comprising: A method for improving flatness of a charge-transporting thin film, wherein an amine compound represented by the following formula (P1) is used as the amine compound.
  • R m represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • R n represents an alkylene group having 1 to 20 carbon atoms
  • R m and R n are bonded to each other to represent an alkanetriyl group having 3 to 40 carbon atoms, and the number of carbon atoms in R n
  • the —CH 2 —NH 2 group is limited to those that are formed.
  • a charge-transporting thin film with excellent flatness can be obtained by using the charge-transporting ink composition of the present invention. Also, the charge-transporting ink composition of the present invention has excellent stability against atmospheric exposure. This charge-transporting thin film can be suitably used as a thin film for electronic devices such as organic EL devices.
  • the charge-transporting ink composition of the present invention contains an amine compound represented by formula (P1) below, a charge-transporting substance, and an organic solvent.
  • the “solid content” in relation to the charge-transporting ink composition of the present invention means components other than the solvent contained in the composition.
  • charge transportability is synonymous with conductivity, and is also synonymous with hole transportability.
  • the charge-transporting ink composition of the present invention may itself have charge-transporting properties, or a solid film obtained by using the composition may have charge-transporting properties.
  • R m represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • R n represents an alkylene group having 1 to 20 carbon atoms
  • a carbon represents an alkenylene group having 2 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms
  • R m and R n bonded together to represent an alkanetriyl group having 3 to 40 carbon atoms
  • -20 alkylene groups and C2-20 alkenylene groups and R m and R n alkanetriyl groups form a -CH 2 -NH 2 group when combined with -NH 2 in formula (P1). limited to
  • the alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n- dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosanyl group and the like.
  • alkenyl groups having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, and n-3.
  • -butenyl group 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n-1-pentenyl group, n-1-decenyl group, n-1-eicosenyl group and the like.
  • Aryl groups having 6 to 20 carbon atoms include phenyl, tolyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl and 2-phenanthryl. group, 3-phenanthryl group, 4-phenanthryl group, and 9-phenanthryl group, with phenyl group, tolyl group and naphthyl group being preferred.
  • the alkylene group having 1 to 20 carbon atoms is a divalent group derived by removing two hydrogen atoms from an alkane, and may be linear, branched or cyclic. methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, eicosanylene group and the like.
  • the alkenylene group having 2 to 20 carbon atoms is a divalent group derived by removing two hydrogen atoms from an alkene, and includes a vinylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group and an octenylene group.
  • nonenylene group decenylene group, undecenylene group, dodecenylene group, tridecenylene group, tetradecenylene group, pentadecenylene group, hexadecenylene group, heptadecenylene group, octadecenylene group, nonadecenylene group, icosenylene group and the like.
  • Examples of the arylene group having 6 to 20 carbon atoms include groups obtained by removing one hydrogen atom from the above specific examples of aryl groups having 6 to 12 carbon atoms, such as a phenylene group, a naphthylene group, and a biphenylylene group. be done.
  • the alkanetriyl group having 3 to 40 carbon atoms is a trivalent group derived by removing a hydrogen atom from an alkane, and includes groups represented by the following formula (K1).
  • n r represents an integer of 0 to 10
  • n c represents an integer of 1 to 10
  • * represents a bond.
  • R m is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 8 carbon atoms, and further an alkyl group having 1 to 5 carbon atoms. preferable.
  • R n is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 5 carbon atoms. More preferred.
  • n r is preferably 1 to 3, more preferably 1 to 2, still more preferably 1, and the above n c is preferably 1 to 3, more preferably 1 to 2, still more preferably 1. be.
  • both nr and nc are preferably 1 to 3, more preferably both nr and nc are 1 to 2, and even more preferably nr is 1 to 2.
  • nc is 1, more preferably both n r and nc are 1.
  • amine compound represented by formula (P1) include, but are not limited to, the following compounds.
  • the content of the amine compound represented by the formula (P1) is not particularly limited.
  • the mass ratio is about 0.01 to 10 times, preferably about 0.01 to 8 times, more preferably about 0.01 to 6 times the mass of the charge-transporting substance 1. , and more preferably about 0.01 to 4 times the mass.
  • the charge-transporting substance used in the present invention is not particularly limited, and may be appropriately selected from charge-transporting compounds, charge-transporting oligomers, charge-transporting polymers, etc. used in the field of organic EL devices and the like. can be done. Specific examples thereof include arylamine derivatives such as oligoaniline derivatives, N,N'-diarylbenzidine derivatives, N,N,N',N'-tetraarylbenzidine derivatives, oligothiophene derivatives, thienothiophene derivatives, and thienobenzothiophene.
  • arylamine derivatives such as oligoaniline derivatives, N,N'-diarylbenzidine derivatives, N,N,N',N'-tetraarylbenzidine derivatives, oligothiophene derivatives, thienothiophene derivatives, and thienobenzothiophene.
  • charge-transporting compounds such as thiophene derivatives such as derivatives, pyrrole derivatives such as oligopyrrole, charge-transporting oligomers, charge-transporting polymers such as polythiophene derivatives, polyaniline derivatives, and polypyrrole derivatives, etc., and polythiophene derivatives are particularly preferred.
  • the charge-transporting substance is a polythiophene derivative containing a repeating unit represented by formula (1) or an amine adduct thereof.
  • R 1 and R 2 are each independently 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 an alkoxy group having 1 to 40 carbon atoms.
  • Y is an alkylene group having 1 to 40 carbon atoms which may contain an ether bond and may be substituted with a sulfonic acid group
  • Z is substituted with a halogen atom is an alkylene group having 1 to 40 carbon atoms
  • p is an integer of 1 or more
  • R e is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, or a fluoroalkyl group having 1 to 40 carbon atoms.
  • the alkyl group having 1 to 40 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include the above-exemplified alkyl groups having 1 to 20 carbon atoms, behenyl group, and triacontyl group. and tetracontyl groups.
  • 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 the carbon atoms is substituted with a fluorine atom.
  • the alkyl group therein may be linear, branched or cyclic. Specific examples thereof include methoxy, ethoxy, n-propoxy, i- propoxy group, c-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group , n-heptadecyloxy, n-octadecyloxy, n-non
  • 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 the carbon atoms is substituted with a fluorine atom.
  • fluoromethoxy group difluoromethoxy group, perfluoromethoxy group, 1-fluoroethoxy group, 2-fluoroethoxy group, 1,2-difluoroethoxy group, 1,1-difluoroethoxy group, 2,2-difluoroethoxy group, 1,1,2-trifluoroethoxy group, 1,2,2-trifluoroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, 1,2, 2,2-tetrafluoroethoxy group, perfluoroethoxy group, 1-fluoropropoxy group, 2-fluoropropoxy group, 3-fluoropropoxy group, 1,1-difluoropropoxy group, 1,2-difluoropropoxy group, 1, 3-difluoropropoxy group, 2,2-difluoropropoxy group, 2,3-difluoropropoxy group, 3,3-difluoropropoxy group, 1,1,2-
  • the alkylene group having 1 to 40 carbon atoms may be straight-chain, branched-chain or cyclic, and specific examples thereof include the same as those exemplified above.
  • aryl group having 6 to 20 carbon atoms examples are the same as those exemplified above. Phenyl, tolyl and naphthyl groups are preferred in the present invention.
  • Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, anthracenoxy group, naphthoxy group, phenanthrenoxy group and fluorenoxy group.
  • Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
  • R 1 and R 2 are each independently 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] p —R e , —OR f , or a sulfonic acid group, or —O—Y—O— formed by combining R 1 and R 2 is preferable.
  • 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; Specific examples are the same as those mentioned above. Among them, 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, preferably a hydrogen atom, a methyl group, a propyl group or a butyl group. Also, p 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, but 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 is preferred, and -CH 2 CF 3 is more preferred.
  • R 1 is preferably a hydrogen atom or a sulfonic acid group, more preferably a sulfonic acid group
  • R 2 is preferably an alkoxy group having 1 to 40 carbon atoms or -O-[Z- O] p -R e , more preferably -O[C(R a R b )-C(R c R d )-O] p -R e or -OR f , even more preferably -O[C(R a R b )—C(R c R d )—O] p —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 R 1 and R 2 joining together.
  • the polythiophene derivative according to a preferred embodiment of the present invention contains a repeating unit in which R 1 is a sulfonic acid group and R 2 is other than a sulfonic acid group, or R 1 and R 2 are linked Including repeating units that are -O-Y-O- formed.
  • the polythiophene derivative contains a repeating unit in which R 1 is a sulfonic acid group and R 2 is an alkoxy group having 1 to 40 carbon atoms or -O-[ZO] p -R e , or —O—Y—O— formed by combining R 1 and R 2 .
  • R 1 is a sulfonic acid group and R 2 is —O[C(R a R b )–C(R c R d )–O] p —R e or — Contains repeat units that are OR f .
  • R 1 is a sulfonic acid group and R 2 is —O[C(R a R b )–C(R c R d )–O] p —R e It includes a repeating unit or a repeating unit where R 1 and R 2 are joined to form -O-Y-O-.
  • R 1 is a sulfonic acid group and R 2 is --O--CH 2 CH 2 --O--CH 2 CH 2 --O--CH 3 or --O--CH 2 CH 2 —O—CH 2 CH 2 —OH or —O—CH 2 CH 2 —OH, or R 1 and R 2 are bonded to each other, and the following formulas (Y1) and (Y2) Includes repeat units that are represented groups.
  • polythiophene derivatives include polythiophenes containing at least one repeating unit represented by the following formulas (1-1) to (1-5).
  • examples of suitable structures of the above polythiophene derivatives include polythiophene derivatives having a structure represented by the following formula (1a).
  • each unit may be combined randomly or may be combined 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) m -multiblock copolymers.
  • Polythiophenes contain repeat units derived from other types of monomers such as thienothiophenes, selenophenes, pyrroles, furans, tellurophenes, anilines, arylamines, and arylenes such as phenylenes, phenylene vinylenes, and fluorenes. may contain.
  • the content of the repeating unit represented by formula (1) in the polythiophene derivative is preferably more than 50 mol%, more preferably 80 mol% or more, more preferably 90 mol% of all repeating units contained in the polythiophene derivative.
  • the above is more preferable, 95 mol % or more is more preferable, and 100 mol % is most preferable.
  • the polymer formed may contain repeating units derived from impurities, depending on the purity of the starting monomers used for polymerization.
  • the term "homopolymer” means a polymer containing repeating units derived from one type of monomer, but may contain repeating units derived from impurities.
  • the polythiophene derivative is preferably a polymer in which basically all the repeating units are the repeating units represented by the above formula (1). ) is more preferably a polymer containing at least one repeating unit.
  • the polythiophene derivative contains a repeating unit having a sulfonic acid group
  • at least part of the sulfonic acid group contained in the polythiophene derivative is an amine compound. is preferably an amine adduct to which is added.
  • 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 above polythiophene derivative or its amine adduct may be treated with a reducing agent.
  • some of the repeating units constituting them may have an oxidized chemical structure called a "quinoid structure".
  • the term "quinoid structure” is used for the term “benzenoid structure”, the latter being a structure containing an aromatic ring, whereas the former is a structure in which the double bond within the aromatic ring moves out of the ring (the As a result, the aromatic ring disappears), meaning a structure in which two exocyclic double bonds conjugated with other double bonds remaining in the ring are formed.
  • R 1 and R 2 are as defined in formula (1) above.
  • This quinoid structure is generated by a process in which the polythiophene derivative containing the repeating unit represented by the above formula (1) undergoes an oxidation reaction by a dopant, a so-called doping reaction, and imparts charge transport properties to the polythiophene derivative. It forms part of a structure called "bipolaron structure". These structures are known. Introduction of a "polaron structure” and/or a “bipolaron structure” is essential in the production of an organic EL element, and in fact, when the thin film formed from the charge-transporting ink composition is baked when the organic EL element is produced. In addition, the above doping reaction is intentionally caused to achieve this.
  • the reason why the quinoid structure is included in the polythiophene derivative before the doping reaction is that the polythiophene derivative undergoes an unintended oxidation reaction equivalent to the doping reaction during the manufacturing process (especially the sulfonation step therein). This is thought to be due to the
  • the polythiophene derivative when the polythiophene derivative is subjected to a reduction treatment using a reducing agent, even if the quinoid structure is excessively introduced into the polythiophene derivative, the quinoid structure is reduced by the reduction, and the solubility and dispersibility of the polythiophene derivative in an organic solvent are improved. is improved, it becomes possible to stably produce a good charge-transporting ink composition that gives a thin film with excellent uniformity.
  • the conditions for the reduction treatment are such that the quinoid structure is reduced to appropriately convert to the non-oxidized structure, that is, the benzenoid structure (for example, in the polythiophene derivative containing the repeating unit represented by the above formula (1),
  • the quinoid structure represented by the above formula (1′) is not particularly limited as long as it can be converted to the structure represented by the above formula (1), 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 thereof.
  • a reducing agent is not particularly limited as long as the reduction is performed properly, but suitable examples include aqueous ammonia, hydrazine, etc., which are readily available on the market.
  • the amount of the reducing agent varies depending on the amount of the reducing agent to be used, and cannot be categorically defined. It is 0.1 parts by mass or more and 10 parts by mass or less from the viewpoint of preventing excess reducing
  • a polythiophene derivative or an amine adduct is stirred overnight at room temperature in 28% ammonia water.
  • the reduction treatment under such relatively mild conditions sufficiently improves the solubility and dispersibility of the polythiophene derivatives and amine adducts in organic solvents.
  • the reduction treatment may be performed before forming the amine adduct or after forming the amine adduct.
  • the solubility and dispersibility of the polythiophene derivative or its amine adduct in the solvent change, and as a result, the polythiophene derivative or its amine adduct, which was not dissolved in the reaction system at the start of the treatment, will be removed after the treatment is completed. Sometimes dissolved. In such a case, an organic solvent (acetone, isopropyl alcohol, etc. in the case of sulfonated polythiophene) incompatible with the polythiophene derivative or its amine adduct is added to the reaction system to obtain the polythiophene derivative or its amine adduct.
  • the polythiophene derivative or its amine adduct can be recovered by a method such as causing precipitation and filtering.
  • the weight average molecular weight of the polythiophene derivative containing the repeating unit represented by formula (1) or its amine adduct is preferably about 1,000 to 1,000,000, more preferably about 5,000 to 100,000, About 10,000 to about 50,000 is even more preferred.
  • a weight average molecular weight is a polystyrene conversion value by a gel permeation chromatography.
  • the polythiophene derivative or its amine adduct contained in the charge-transporting ink composition of the present invention may be only one polythiophene derivative or its amine adduct containing a repeating unit represented by formula (1). It may be more than seeds.
  • a commercially available product or a product obtained by polymerizing a thiophene derivative or the like as a starting material by a known method may be used. It is also preferable to use those purified by methods such as reprecipitation and ion exchange. By using a purified product, the properties of the organic EL device provided with the thin film obtained from the charge-transporting ink composition of the present invention can be further enhanced.
  • conjugated polymers and sulfonated conjugated polymers are described in US Pat. No. 8,017,241 to Seshadri et al. Sulfonated polythiophenes are also described in WO2008/073149 and WO2016/171935.
  • At least part of the polythiophene derivative containing the repeating unit represented by formula (1) or its amine adduct contained in the charge-transporting ink composition is dissolved in an organic solvent.
  • a polythiophene derivative containing a repeating unit represented by formula (1) or an amine adduct thereof and a charge-transporting substance other than the polythiophene derivative containing the repeating unit may be used in combination.
  • the content of the charge-transporting substance in the charge-transporting ink composition of the present invention is usually 0.05 to 40% by mass, preferably 0.05 to 40% by mass, based on the solid content, taking into account the desired film thickness, the viscosity of the ink composition, and the like. is appropriately determined in the range of 0.1 to 35% by mass.
  • the charge-transporting ink composition of the invention contains an organic solvent.
  • an organic solvent is not particularly limited as long as it disperses or dissolves the solid content.
  • aromatic or halogenated aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and chlorobenzene; aliphatic hydrocarbons such as n-heptane, n-hexane and cyclohexane; diethyl ether, Ether solvents such as tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ethyl acetate, n-hexyl acetate, ethyl lactate, ⁇ -butyrolactone, propylene carbonate, malonic acid ester solvents such as diisoprop
  • amide solvents 1,3-dimethyl-2-imidazolidinone, dipropylene glycol and dipropylene glycol monomethyl ether are more preferred.
  • these organic solvents can be used individually or in mixture of 2 or more types, respectively.
  • the charge-transporting ink composition of the present invention may contain water as a solvent, and the content of water is 10% by mass or less based on the total solvent from the viewpoint of obtaining an organic EL device having excellent durability with good reproducibility. It is preferable, more preferably 5% by mass or less, and it is optimal to use only an organic solvent as the solvent.
  • “only organic solvent” means that only organic solvent is used as a solvent, and even the existence of "water” contained in a trace amount in the organic solvent or solid content used is denied. not something to do.
  • the charge-transporting ink composition of the present invention may contain metal oxide nanoparticles.
  • a nanoparticle means a fine particle having an average primary particle size of the order of nanometers (typically 500 nm or less).
  • Metal oxide nanoparticles refer to metal oxides shaped into nanoparticles.
  • the primary particle size of the metal oxide nanoparticles used in the present invention is not particularly limited as long as it is nano-sized, but considering obtaining a thin film with good reproducibility and excellent flatness, it is preferably 2 to 150 nm. , 3 to 100 nm, and even more preferably 5 to 50 nm.
  • the particle size is a measured value using a nitrogen adsorption isotherm by the BET method.
  • the metals constituting the metal oxide nanoparticles used in the present invention include not only metals in the usual sense, but also semimetals.
  • 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 tungsten (W).
  • metalloids refer to elements whose chemical and/or physical properties are intermediate between those of metals and nonmetals. A universal definition of metalloids has not been established, but in the present invention, a total of six Let the elements be semimetals. These semimetals may be used alone or in combination of two or more, and may also be used in combination with metals in the usual sense.
  • Metal oxide nanoparticles used in the present invention include boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), tin (Sn), titanium (Ti) , aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta) and tungsten (W).
  • the metal oxide may be a mixture of oxides of individual single metals, or a composite oxide containing a plurality of metals.
  • metal oxides include B2O3 , B2O , SiO2 , SiO, GeO2 , GeO , As2O4 , As2O3 , As2O5 , Sb2O3 , Sb2 . O5, TeO2, SnO2 , ZrO2 , Al2O3 , ZnO and the like, but also B2O3 , B2O , SiO2 , SiO , GeO2 , GeO , As2O4 , As2 . O3 , As2O5 , SnO2 , SnO, Sb2O3, TeO2 , and mixtures thereof are preferred, with SiO2 being more preferred.
  • the metal oxide nanoparticles contained in the charge-transporting ink composition of the present invention may be of one type or two or more types.
  • the metal oxide nanoparticles contained in the charge-transporting ink composition of the present invention are preferably uniformly dispersed in the composition.
  • the metal oxide nanoparticles may contain one or more organic capping groups.
  • This organic capping group may be reactive or non-reactive.
  • Examples of reactive organic capping groups include organic capping groups that can be crosslinked by UV light or radical initiators.
  • the content of the metal oxide nanoparticles is not particularly limited.
  • the solid content of the charge-transporting ink composition is preferably 40 to 95% by mass, more preferably 50 to 95% by mass, and most preferably 60 to 90% by mass. .
  • a composition in which metal oxide nanoparticles are uniformly dispersed can be prepared with good reproducibility. That is, rather than mixing and dispersing the metal oxide nanoparticles themselves in a solvent together with the charge-transporting substance or the like, a metal oxide nanoparticle sol is prepared in advance, and the charge-transporting substance or the like is dissolved or dissolved in the solvent. By mixing with the dispersed mixture, a charge-transporting ink composition in which the metal oxide nanoparticles are uniformly dispersed can be produced with good reproducibility.
  • a metal oxide nanoparticle sol may be a commercially available product, or may be prepared by a known method using a solvent and metal oxide nanoparticles that may be contained in the charge-transporting ink composition of the present invention. .
  • silica sol in which SiO 2 nanoparticles are dispersed in a dispersion medium.
  • the silica sol is not particularly limited, and can be appropriately selected from known silica sols and used. Commercially available silica sols are usually in the form of dispersions.
  • SiO2 nanoparticles are mixed with 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.
  • 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.
  • solvents such as water, methanol, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylacetamide, ethylene glycol, isopropanol, methanol, ethylene glycol monopropyl ether, cyclo
  • a silica sol whose dispersion medium is an alcohol solvent, a glycol solvent or water is preferable, and a silica sol whose dispersion medium is an alcohol solvent or a glycol solvent is more preferable.
  • a water-soluble alcohol or glycol-based solvent is preferable, and methanol, 2-propanol, and ethylene glycol are more preferable.
  • silica sols include Snowtex (registered trademark) ST-O, ST-OS, ST-O-40 and ST-OL manufactured by Nissan Chemical Industries, Ltd., Silidodol 20 manufactured by Nippon Chemical Industries, Ltd., Water-dispersed silica sol such as 30, 40; Methanol silica sol, MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST-ZL, EG-ST manufactured by Nissan Chemical Co., Ltd.
  • organosilica sols such as
  • the concentration of SiO 2 nanoparticles in silica sol is usually about 5 to 50% by mass.
  • SiO 2 nanoparticles may aggregate, so this point should be taken into consideration when preparing the composition.
  • the charge-transporting ink composition of the present invention contains an amine compound represented by formula (P1), a charge-transporting substance, and an organic solvent. may also contain dopant materials.
  • the dopant substance is not particularly limited as long as it can be dispersed or dissolved in at least one solvent used in the charge-transporting ink composition, and both inorganic dopant substances and organic dopant substances can be used.
  • the charge-transporting ink composition of the present invention contains a dopant substance, the content thereof is appropriately set in consideration of the type and amount of the charge-transporting substance. It ranges from 0.1 to 20.0 for the charge-transporting substance 1.
  • Inorganic dopant substances include inorganic acids such as hydrogen chloride , sulfuric acid , nitric acid and phosphoric acid; ), boron trifluoride etherate (BF 3 OEt 2 ), iron chloride (III) (FeCl 3 ), copper chloride (II) (CuCl 2 ), antimony pentachloride (V) (SbCl 5 ), pentafluoride metal halides such as antimony (V) (SbF 5 ), arsenic pentafluoride (V) (AsF 5 ), phosphorus pentafluoride (PF 5 ), tris(4-bromophenyl)aluminum hexachloroantimonate (TBPAH); Halogens such as Cl 2 , Br 2 , I 2 , ICl, ICl 3 , IBr and IF 4 ; heteropolyacids such as phosphomolybdic acid and phosphotungstic acid;
  • inorganic acids
  • organic dopant substances include 7,7,8,8-tetracyanoquinodimethane (TCNQ), tetracyanoquinodimethane such as 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane.
  • TCNQ 7,7,8,8-tetracyanoquinodimethane
  • tetracyanoquinodimethane such as 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane.
  • arylsulfonic acid compounds such as dinonylnaphthalenesulfonic acid derivatives described in JP-A-2005-108828 and aromatic sulfone compounds such as polystyrenesulfonic acid; and non-aromatic sulfone compounds such as 10-camphorsulfonic acid.
  • aromatic sulfone compounds such as polystyrenesulfonic acid
  • non-aromatic sulfone compounds such as 10-camphorsulfonic acid.
  • arylsulfonic acid compounds are preferred in the present invention, and examples of preferred arylsulfonic acid compounds include arylsulfonic acid compounds represented by formula (H1) or (H2).
  • a 1 represents O or S, with O being preferred.
  • a 2 represents a naphthalene ring or an anthracene ring, preferably a naphthalene ring.
  • a 3 represents a divalent to tetravalent perfluorobiphenyl group, s represents the number of bonds between A 1 and A 3 and is an integer satisfying 2 ⁇ s ⁇ 4, where A 3 is perfluorobiphenyldiyl is preferably a perfluorobiphenyl-4,4'-diyl group and s is 2.
  • q represents the number of sulfonic acid groups bonded to A 2 and is an integer that satisfies 1 ⁇ q ⁇ 4, with 2 being optimal.
  • a 4 to A 8 each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated group having 2 to 20 carbon atoms. It represents an alkenyl group, but at least three of A 4 to A 8 are halogen atoms.
  • halogenated alkyl groups having 1 to 20 carbon atoms 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, A 4-nonafluorobutyl group and the like can be mentioned.
  • halogenated alkenyl group having 2 to 20 carbon atoms examples include perfluorovinyl group, perfluoropropenyl group (allyl group), perfluorobutenyl group and the like.
  • Other examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms are the same as those mentioned above, but the halogen atom is preferably a fluorine atom.
  • a 4 to A 8 are a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms.
  • a 4 to A 8 are preferably fluorine atoms, such as hydrogen atom, fluorine atom, cyano group, alkyl group having 1 to 5 carbon atoms, and It is more preferably a fluorinated alkyl group or a fluorinated alkenyl group having 2 to 5 carbon atoms, and at least three of A 4 to A 8 are fluorine atoms, a hydrogen atom, a fluorine atom, a cyano group, More preferably, it is a perfluoroalkyl group having 1 to 5 carbon atoms or a perfluoroalkenyl group having 1 to 5 carbon atoms, and A 4 , A 5 and A 8 are fluorine atoms.
  • fluorine atoms such as hydrogen atom, fluorine atom, cyano group, alkyl group having 1 to 5 carbon atoms
  • It is more preferably a fluorinated alkyl group or a fluorinated alkenyl group having 2 to 5
  • the perfluoroalkyl group is a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms
  • the perfluoroalkenyl group is a group in which all hydrogen atoms of an alkenyl group are substituted with fluorine atoms.
  • r represents the number of sulfonic acid groups bonded to the naphthalene ring and is an integer that satisfies 1 ⁇ r ⁇ 4, preferably 2 to 4, and most preferably 2.
  • the molecular weight of an organic compound is preferably 3,000 or less, more preferably 2,500 or less, considering its solubility in organic solvents.
  • the molecular weight of the arylsulfonic acid compound used as the dopant substance is not particularly limited, but is preferably 2,000 or less, more preferably 1,500 or less, in consideration of solubility in organic solvents.
  • amine compound represented by formula (P1) for the purpose of improving the dispersibility and solubility of a charge-transporting substance such as a polythiophene derivative or an amine adduct thereof, together with an amine compound represented by formula (P1), Other amine compounds may also be included.
  • Such other amine compound is not particularly limited as long as it dissolves in at least one solvent used in the ink composition, and may be one kind alone or two or more kinds.
  • primary amine compounds include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine, n-hexylamine and n-heptyl.
  • n-octylamine 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n -monoalkylamine compounds such as hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-eicosanylamine; aniline, tolylamine, 1-naphthylamine, 2-naphthylamine, 1-anthrylamine, Monoaryls such as 2-anthrylamine, 9-anthrylamine, 1-phenanthrylamine, 2-phenanthrylamine, 3-phenanthrylamine, 4-phenanthrylamine and 9-phenanthrylamine
  • secondary amine compounds include N-ethylmethylamine, N-methyl-n-propylamine, N-methylisopropylamine, N-methyl-n-butylamine, N-methyl-s-butylamine, N-methyl -t-butylamine, N-methylisobutylamine, diethylamine, N-ethyl-n-propylamine, N-ethylisopropylamine, N-ethyl-n-butylamine, N-ethyl-s-butylamine, N-ethyl-t- Butylamine, dipropylamine, Nn-propylisopropylamine, Nn-propyl-n-butylamine, Nn-propyl-s-butylamine, diisopropylamine, Nn-butylisopropylamine, Nt-butyl Isopropylamine, di(n-butyl)amine, di(s-butyl)
  • tertiary amine compounds include N,N-dimethylethylamine, N,N-dimethyl-n-propylamine, N,N-dimethylisopropylamine, N,N-dimethyl-n-butylamine, N,N- Dimethyl-s-butylamine, N,N-dimethyl-t-butylamine, N,N-dimethylisobutylamine, N,N-diethylmethylamine, N-methyldi(n-propyl)amine, N-methyldiisopropylamine, N- methyldi(n-butyl)amine, N-methyldiisobutylamine, triethylamine, N,N-diethyl-n-butylamine, N,N-diisopropylethylamine, N,N-di(n-butyl)ethylamine, tri(n-propyl) ) trialkylamine compounds such as amine, tri
  • the charge-transporting ink composition of the present invention contains other amine compounds, it should be excellent in the ability to improve the dispersibility and solubility of the charge-transporting substance such as the polythiophene derivative or its amine adduct used in the present invention. Therefore, the other amine compound preferably contains a primary amine compound, preferably a monoalkylamine, particularly a monoalkylamine having 2 to 20 carbon atoms.
  • the content thereof is usually about 10 times the mass of the charge-transporting substance such as the polythiophene derivative or its amine adduct used in the present invention. It is below.
  • Heteropolyacids can also be suitably used as dopant substances.
  • Heteropolyacid has a structure in which a heteroatom is located at the center of the molecule, typically represented by a Keggin-type chemical structure represented by formula (A) or a Dawson-type chemical structure represented by formula (B), and vanadium ( V), molybdenum (Mo), tungsten (W), and other oxyacid isopolyacids are polyacids formed by condensation with oxyacids of different elements.
  • Oxygen acids of such dissimilar elements mainly include oxyacids of silicon (Si), phosphorus (P), and arsenic (As).
  • heteropolyacid examples include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, phosphotungstomolybdic acid, etc. These may be used alone or in combination of two or more. good.
  • the heteropolyacid used in the present invention is available as a commercial product, and can also be synthesized by a known method.
  • the one type of heteropolyacid preferably includes tungsten. That is, phosphotungstic acid, silicotungstic acid, phosphotungstomolybdic acid and the like are preferred, and phosphotungstic acid and silicotungstic acid are more preferred.
  • the heteropolyacid may be obtained as a commercial product, or may be obtained as an appropriate product according to a known synthesis method, even if the number of elements is large or small from the structure represented by the general formula.
  • phosphotungstic acid is generally represented by the chemical formula H 3 (PW 12 O 40 ) ⁇ nH 2 O, but in quantitative analysis, P (phosphorus), O (oxygen) or W Even if the number of (tungsten) is large or small, it can be used in the present invention as long as it is commercially available or synthesized appropriately according to a known synthesis method.
  • the mass of the heteropolyacid defined in the present invention is not the mass of pure phosphotungstic acid (phosphotungstic acid content) in synthetic products or commercial products, but the commercially available form and known synthesis In a form that can be isolated by the method, it means the total mass in a state containing water of hydration and other impurities.
  • the charge-transporting ink composition of the invention may contain a known organic silane compound.
  • a known organic silane compound By including such an organic silane compound in the charge-transporting ink composition, when the charge-transporting thin film obtained from the ink composition is used as a hole injection layer of an organic EL device, holes are provided so as to be in contact with the hole injection layer. The hole injection property to the transport layer can be improved.
  • alkoxysilane is preferable, and trialkoxysilane and tetraalkoxysilane are more preferable.
  • alkoxysilanes include tetraethoxysilane, tetramethoxysilane, tetraisopropoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane.
  • Examples include silane, dimethyldiethoxysilane, dimethyldimethoxysilane, and the like.
  • tetraethoxysilane TEOS
  • tetramethoxysilane tetramethoxysilane
  • tetraisopropoxysilane can be preferably used in the present invention.
  • organic silane compounds can be used singly or in combination of two or more.
  • the charge-transporting ink composition of the present invention contains an organic silane compound
  • the content thereof is usually about 0.1 to 50% by mass based on the solid content. Considering the balance of suppressing deterioration of transportability, etc., it is preferably about 0.5 to 40% by mass, more preferably about 0.8 to 30% by mass, and even more preferably about 1 to 20% by mass.
  • the viscosity of the charge-transporting ink composition of the invention is usually 1 to 50 mPa ⁇ s at 25°C, and the surface tension is usually 20 to 50 mN/m at 25°C.
  • the viscosity and surface tension of the charge-transporting ink composition of the present invention are determined by changing the type of organic solvent used, their ratio, the solid content concentration, etc., in consideration of various factors such as the coating method used and the desired film thickness. can be adjusted by
  • the solid content concentration of the charge-transporting ink composition of the present invention is appropriately set in consideration of the viscosity and surface tension of the charge-transporting ink composition, the thickness of the thin film to be produced, and the like. It is usually about 0.1 to 15% by mass, preferably 10% by mass or less, more preferably 8% by mass, from the viewpoint of suppressing aggregation of the charge-transporting substance and metal oxide nanoparticles in the ink composition. Below, it is more preferably 6% by mass or less.
  • the amine compound represented by formula (P1), the charge-transporting substance and the solvent, and optionally the , metal oxide nanoparticles and dopant materials can be mixed in any order. That is, for example, a method of dissolving a charge-transporting substance and an amine compound represented by formula (P1) in a solvent to obtain a solution, and then dissolving a dopant substance in the solution; , a method of dissolving the charge-transporting substance and the amine compound represented by formula (P1) in the solution, mixing the amine compound represented by formula (P1), the charge-transporting substance, and the dopant substance, Any method of dissolving the mixture by adding it to a solvent can be employed as long as the solid content is uniformly dissolved or dispersed in the solvent.
  • a method of adding an aqueous dispersion or an organic solvent dispersion of the metal oxide nanoparticles at any time in the above method, or a method of adding an aqueous dispersion or an organic solvent of the metal oxide nanoparticles A method of adding a previously prepared solution containing the amine compound represented by the formula (P1) and the charge-transporting substance and other components or a solution thereof to the dispersion is included. It should be noted that the charge-transporting substance and metal oxide nanoparticles may aggregate or precipitate when mixed, depending on the type and amount of the solvent used together. In the preparation of the charge-transporting ink composition, the composition may be appropriately heated as long as the components are not decomposed or altered.
  • the charge-transporting ink composition is prepared in a submicron state during the production of the charge-transporting ink composition or after all components are mixed, for the purpose of obtaining a highly flat thin film with good reproducibility. It may be filtered using a meter-order filter or the like.
  • a charge-transporting thin film can be formed on the substrate by applying the charge-transporting ink composition described above onto the substrate and baking it.
  • the method for applying the ink composition is not particularly limited, and includes dipping, spin coating, transfer printing, roll coating, brush coating, inkjet, spraying, slit coating, and the like. It is preferable to adjust the viscosity and surface tension of the ink composition according to the method.
  • the firing atmosphere is not particularly limited.
  • a thin film having properties can be obtained.
  • the firing temperature is appropriately set within a range of about 100 to 260° C. in consideration of the use of the obtained thin film, the degree of charge transport property to be imparted to the obtained thin film, the type and boiling point of the solvent, etc.
  • the temperature is preferably about 140 to 250°C, more preferably about 145 to 240°C. It should be noted that, during the firing, the temperature may be changed in two or more stages for the purpose of expressing a higher uniform film-forming property or promoting the reaction on the substrate. Suitable equipment such as an oven may be used.
  • the thickness of the charge-transporting thin film is not particularly limited, but when it is used as a functional layer provided between the anode and the light-emitting layer, such as a hole injection layer, a hole transport layer, and a hole injection transport layer of an organic EL device. , 5 to 300 nm.
  • a method for changing the film thickness there are methods such as changing the solid content concentration in the charge-transporting ink composition and changing the amount of the solution on the substrate during coating.
  • the organic EL device of the present invention has a pair of electrodes, and between these electrodes a charge transport layer comprising the charge transport thin film of the present invention.
  • Typical structures of the organic EL element include (a) to (f) below, but are not limited to these.
  • an electron blocking layer or the like may be provided between the light emitting layer and the anode, and a hole blocking layer or the like may be provided between the light emitting layer and the cathode, if necessary.
  • the hole injection layer, the hole transport layer or the hole injection transport layer may also function as an electron blocking layer or the like, and the electron injection layer, the electron transport layer or the electron injection transport layer may contain holes (holes). It may also have a function as a block layer or the like.
  • anode/hole-injection layer/hole-transport layer/light-emitting layer/electron-transport layer/electron-injection layer/cathode (b) anode/hole-injection layer/hole-transport layer/light-emitting layer/electron-injection-transport layer/ Cathode (c) anode/hole injection transport layer/light emitting layer/electron transport layer/electron injection layer/cathode (d) anode/hole injection transport layer/light emitting layer/electron injection transport layer/cathode (e) anode/positive Hole-injection layer/hole-transport layer/light-emitting layer/cathode (f) Anode/hole-injection-transport layer/light-emitting layer/cathode
  • Hole injection layer is layers formed between a light-emitting layer and an anode that transport holes from the anode to the light-emitting layer.
  • a 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,
  • the layer close to the anode is the “hole-injecting layer” and the other layer is the “hole-transporting layer”.
  • the hole-injecting (transporting) layer is a thin film that is excellent not only in the ability to accept holes from the anode but also in the ability to inject holes into the hole-transporting (light-emitting) layer.
  • Electrode injection 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.
  • a “light-emitting layer” is an organic layer having a light-emitting function, and includes a host material and a dopant material when a doping system is employed.
  • the host material mainly promotes recombination of electrons and holes and has the function of confining excitons in the light-emitting layer, and the dopant material efficiently emits the excitons obtained by recombination. have a function.
  • the host material mainly functions to confine excitons generated by the dopant within the light-emitting layer.
  • a charge-transporting thin film prepared from the charge-transporting ink composition of the present invention can be used as a functional layer formed between an anode and a light-emitting layer in an organic EL device. It is suitable as a layer and a hole injection transport layer, more suitable as a hole injection layer and a hole transport layer, and even more suitable as a hole injection layer.
  • Examples of the materials to be used and the manufacturing method for manufacturing an EL element using the charge-transporting ink composition of the present invention include, but are not limited to, the following.
  • An example of a method for producing an OLED device having a hole injection layer made of a thin film obtained from the charge-transporting ink composition of the present invention is as follows.
  • the electrodes are preferably cleaned with alcohol, pure water, or the like, or surface-treated with UV ozone treatment, oxygen-plasma treatment, or the like in advance, as long as the electrodes are not adversely affected.
  • a hole injection layer is formed on the anode substrate using the charge-transporting ink composition by the method described above. This is introduced into a vacuum vapor deposition apparatus, and a hole transport layer, a light-emitting layer, an electron transport layer/hole blocking layer, an electron injection layer, and a cathode metal are sequentially vapor-deposited.
  • a composition for forming a hole-transporting layer containing a hole-transporting polymer and a composition for forming a light-emitting layer containing a light-emitting polymer are used. are used to form these layers by a wet process.
  • An electron blocking layer may be provided between the light-emitting layer and the hole-transporting layer, if necessary.
  • Anode materials include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and metal anodes composed of metals typified by aluminum, alloys thereof, etc. Those subjected to planarization treatment are preferable. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used. Other metals constituting the metal anode include gold, silver, copper, indium, and alloys thereof, but are not limited to these.
  • Materials for forming the hole transport layer include (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spirodimer, N,N'-bis(naphthalene-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′: oligothiophenes such as 5′,2′′-terthiophene (BMA-3T);
  • Materials for forming the light-emitting layer include metal complexes such as aluminum complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo[h]quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, (2-hydroxyphenyl)benzo Low-molecular light-emitting materials such as thiazole metal complexes and silol derivatives; poly(p-phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], poly(3-alkyl thiophene), polyvinyl carbazole, etc., mixed with a light-emitting material and an electron transfer material, but not limited to these.
  • metal complexes such as aluminum complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo[h]quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, (2-hydroxyphenyl)benz
  • the light-emitting layer when it is formed by vapor deposition, it may be co-deposited with a light - emitting dopant.
  • a light - emitting dopant such as rubrene, quinacridone derivatives, condensed polycyclic aromatic rings such as perylene, and the like, but are not limited thereto.
  • Materials for forming the electron-transporting layer/hole-blocking layer include, but are not limited to, oxydiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, pyrimidine derivatives, and the like.
  • Materials for forming the electron injection layer include metal oxides such as lithium oxide (Li 2 O), magnesium oxide (MgO), alumina (Al 2 O 3 ), lithium fluoride (LiF), and sodium fluoride (NaF). and the like, but are not limited to these.
  • Cathode materials include, but are not limited to, aluminum, magnesium-silver alloys, aluminum-lithium alloys, and the like.
  • Materials for forming the electron blocking layer include, but are not limited to, tris(phenylpyrazole) iridium.
  • hole-transporting polymers include 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,N'-bis(phenyl)-benzidine]-endcapped with polysilsiquinoxane,
  • light-emitting polymers examples include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), poly(2-methoxy-5-(2′-ethylhexoxy)-1,4-phenylene vinylene) (MEH- PPV) and other polyphenylene vinylene derivatives, poly(3-alkylthiophene) (PAT) and other polythiophene derivatives, and polyvinylcarbazole (PVCz).
  • PDAF poly(9,9-dialkylfluorene)
  • MEH- PPV poly(2-methoxy-5-(2′-ethylhexoxy)-1,4-phenylene vinylene)
  • PAT poly(3-alkylthiophene)
  • PVCz polyvinylcarbazole
  • the materials for the anode, cathode, and layers formed between them differ depending on whether the device has a bottom emission structure or a top emission structure.
  • a transparent anode is used on the substrate side, and light is extracted from the substrate side
  • a reflective anode made of metal is used, and light is emitted in the opposite direction to the substrate. Since light is extracted from a certain transparent electrode (cathode) side, for example, regarding the anode material, a transparent anode such as ITO is used when manufacturing an element with a bottom emission structure, and Al is used when manufacturing an element with a top emission structure.
  • a reflective anode such as /Nd is used, respectively.
  • the organic EL element of the present invention may be sealed together with a water capturing agent or the like according to a standard method in order to prevent property deterioration.
  • the charge-transporting ink composition of the present invention is suitably used for forming the functional layer formed between the anode and the light-emitting layer of the organic EL element as described above, but it can also be used for organic photoelectric conversion elements and organic thin films.
  • a method for improving the storage stability of a charge-transporting ink composition of the present invention is a method for improving the storage stability of a charge-transporting ink composition containing an amine compound, a charge-transporting substance, and an organic solvent,
  • the amine compound an amine compound represented by the above formula (P1) is used, and suitable conditions such as the type and amount of the solid content of the amine compound, the charge-transporting substance, etc. and the organic solvent are the same as above. be.
  • the improvement in the storage stability of the charge-transporting ink composition can be evaluated by the change in absorbance.
  • the absorbance of the charge-transporting ink composition before exposure to the atmosphere is a (initial)
  • the absorbance of the charge-transporting ink composition after exposure for 10 days is a (exposure to the atmosphere) at the maximum absorption (for example, wavelength of 620 nm).
  • the rate of change in absorbance (%) ⁇ a/a (initial) as an absolute value, usually 10 % or less, preferably 9% or less, more preferably 8% or less, still more preferably 7% or less, and even more preferably 6% or less.
  • the method for improving the flatness of a charge-transporting thin film of the present invention is a method for improving the flatness of a charge-transporting thin film obtained from a charge-transporting ink composition containing an amine compound, a charge-transporting substance, and an organic solvent.
  • the solid content of the amine compound, the charge-transporting substance, etc. and the preferred conditions such as the type and amount of the organic solvent and the conditions for forming the charge-transporting thin film are the same as above.
  • the improvement in the flatness of the charge-transporting thin film can be evaluated by the average surface roughness Ra.
  • the average surface roughness Ra (nm) is usually 2.80 nm or less, It is preferably 2.70 nm or less, more preferably 2.60 nm or less, and preferably 2.50 nm or less.
  • the average surface roughness (Ra) of the charge-transporting thin film is determined by, for example, an atomic force microscope Park-NX10 manufactured by Park Systems and a cantilever for measuring average surface roughness OMCL-AC 160TS 10M manufactured by Olympus. can be measured using
  • Preparation Example 2 100 g of ST-OS (manufactured by Nissan Chemical Co., Ltd.), which is a water-dispersed silica sol, and dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd., hereinafter the same) are placed in an eggplant flask, and the ST-OS is evaporated using an evaporator. Water contained in was replaced with dipropylene glycol monomethyl ether to obtain a silica sol (silica concentration: 9.43% by mass) using dipropylene glycol monomethyl ether as a dispersion medium.
  • ST-OS manufactured by Nissan Chemical Co., Ltd.
  • dipropylene glycol monomethyl ether manufactured by Kanto Chemical Co., Ltd., hereinafter the same
  • Example 1-2 3.24 g of 1,3-dimethyl-2-imidazolidinone, 5.17 g of dipropylene glycol and 3.55 g of dipropylene glycol monomethyl ether were placed in an Erlenmeyer flask and stirred at room temperature for 30 minutes using a stirrer. After that, 0.21 g of the 1,3-dimethyl-2-imidazolidinone solution of the arylsulfonic acid compound A obtained in Preparation Example 1 was added and stirred at room temperature for 30 minutes using a stirrer.
  • Example 2-1 Preparation of charge-transporting thin film and evaluation of average surface roughness Ra
  • the charge-transporting ink composition obtained in Example 1-1 was applied to an ITO substrate using a spin coater, heated at 120° C. for 1 minute in the air, and then heated at 230° C. for 15 minutes. A uniform thin film with a thickness of 30 nm was formed thereon.
  • As the ITO substrate a 25 mm ⁇ 25 mm ⁇ 0.7 t glass substrate on which indium tin oxide (ITO) was patterned to a thickness of 50 nm was used. , for 30 seconds) to remove impurities on the surface.
  • ITO indium tin oxide
  • Example 2-2 Comparative Examples 2-1 to 2-2
  • Example 1-1 the charge-transporting ink compositions obtained in Example 1-2 and Comparative Examples 1-1 and 1-2 were used.
  • a uniform thin film with a thickness of 30 nm was formed on an ITO substrate in the same manner as in 2-1.
  • Example 2-1 For the charge-transporting thin films on the ITO substrates formed in Example 2-1, Example 2-2, Comparative Examples 2-1 and 2-2, the average surface roughness Ra was evaluated using an atomic force microscope. did. The measurement range of the atomic force microscope was 3 ⁇ m ⁇ 3 ⁇ m. Table 1 shows the results.
  • the average surface roughness of the thin film formed from the charge-transporting ink composition of the present invention was lower than that of the thin film formed from the charge-transporting ink composition of the comparative example.
  • the use of the amine compound represented by the formula (P1) contained in the charge-transporting ink composition of the present invention makes it possible to realize a more stable interaction between the amine compound and the charge-transporting substance, resulting in It is presumed that this is because aggregation of the charge-transporting substance was alleviated or suppressed in the heating process after the application of the substance.
  • Example 3-1 Evaluation of stability of charge-transporting ink composition against atmospheric exposure
  • 0.2 g of the charge-transporting ink composition obtained in Example 1-1 was mixed with 4.14 g of 1,3-dimethyl-2-imidazolidinone, 4.83 g of dipropylene glycol and 4.83 g of dipropylene glycol monomethyl ether. and the absorption spectrum of the resulting mixture was measured.
  • 3.0 g of the charge-transporting ink composition obtained in Example 1-1 was added to a 20-mL glass vial, and the vial was left open for 10 days at room temperature in the atmosphere. exposed to air.
  • Example 3-2 Comparative Examples 3-1 to 3-2
  • the charge-transporting ink compositions obtained in Example 1-2 and Comparative Examples 1-1 and 1-2 were used instead of the charge-transporting ink composition obtained in Example 1-1.
  • the absorption spectrum was measured in the same manner as in Example 3-1.
  • Fig. 1 shows the measured absorption spectrum.
  • the absorbance of the charge-transporting ink composition before exposure to the atmosphere (a (initial)
  • the absorbance of the charge-transporting ink composition after exposure for 10 days (a (exposure to atmosphere)
  • Table 2 shows the difference in absorbance ( ⁇ a) before and after exposure to the atmosphere and the rate of change in absorbance (%).
  • the change in absorbance of the charge-transporting ink composition of the present invention was smaller than that of the charge-transporting ink composition of the comparative example. This is because by using the amine compound represented by formula (P1) contained in the charge-transporting ink composition of the present invention, a stable interaction between the amine compound and the charge-transporting substance in the composition can be realized. It is presumed that this is because the oxidation of the charge-transporting substance is suppressed.
  • Example 4-1 Fabrication and property evaluation of organic EL device
  • the charge-transporting ink composition obtained in Example 1-1 was applied to an ITO substrate using a spin coater, heated at 120° C. for 1 minute in the air, and then heated at 230° C. for 15 minutes. A uniform charge-transporting thin film having a thickness of 30 nm was formed thereon.
  • As the ITO substrate a 25 mm ⁇ 25 mm ⁇ 0.7 t glass substrate having a patterned ITO film with a thickness of 150 nm formed on the surface was used. to remove impurities on the surface.
  • ⁇ -NPD N,N'-di(1-naphthyl)-N
  • a vapor deposition apparatus degree of vacuum: 1.0 ⁇ 10 -5 Pa
  • N′-diphenylbenzidine was deposited at a rate of 0.2 nm/second to a thickness of 30 nm.
  • an electron block material HTEB-01 manufactured by Kanto Kagaku Co., Ltd.
  • the vapor deposition rate was 0.2 nm/sec for Alq 3 and aluminum, and 0.02 nm/sec for lithium fluoride, respectively, and the film thicknesses were 20 nm, 0.5 nm and 80 nm, respectively.
  • the characteristics of the organic EL element were evaluated after being sealed with a sealing substrate. Sealing was performed by the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of ⁇ 76° C. or less, the organic EL element was placed between the sealing substrates, and the sealing substrates were coated with an adhesive (manufactured by MORESCO Co., Ltd., MORESCO Moisture Cut WB90US (P)). pasted together by At this time, a water capturing agent (HD-071010W-40 manufactured by Dainic Co., Ltd.) 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.
  • an adhesive manufactured by MORESCO Co., Ltd., MORESCO Moisture Cut WB90US (P)
  • Example 4-2 In the same manner as in Example 4-1, except that the charge-transporting ink composition obtained in Example 1-2 was used instead of the charge-transporting ink composition obtained in Example 1-1. An organic EL device was obtained.

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Abstract

La présente invention concerne une composition d'encre de transport de charge qui permet l'obtention d'un film qui a des caractéristiques de transport de charge, une transparence élevée dans la région de lumière visible et une excellente planéité, tout en étant stable en termes d'exposition à l'atmosphère, la présente invention concerne une composition d'encre de transport de charge qui est caractérisée en ce qu'elle contient un composé amine représenté par la formule (P1), un matériau de transport de charge et un solvant organique. (Dans la formule, Rm représente un groupe alkyle ayant de 1 à 20 atomes de carbone, un groupe alcényle ayant de 2 à 20 atomes de carbone ou un groupe aryle ayant de 6 à 20 atomes de carbone ; Rn représente un groupe alkylène ayant de 1 à 20 atomes de carbone, un groupe alcénylène ayant de 2 à 20 atomes de carbone ou un groupe arylène ayant de 6 à 20 atomes de carbone ; ou, en variante, Rm et Rn se combinent l'un à l'autre pour former un groupe alcane triyle ayant 3 à 40 atomes de carbone. Pendant ce temps, le groupe alkylène ayant de 1 à 20 atomes de carbone et le groupe alcénylène ayant de 2 à 20 atomes de carbone pour Rn, et le groupe alcane triyle pour Rm et Rn combinés sont limités à ceux qui forment un groupe -CH2-NH2 en cas de combinaison à -NH2 dans la formule (P1).)
PCT/JP2022/007152 2021-02-25 2022-02-22 Composition d'encre de transport de charges WO2022181587A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004204114A (ja) * 2002-12-26 2004-07-22 Dainippon Printing Co Ltd インクジェット用インク組成物
JP4573363B1 (ja) * 2010-06-01 2010-11-04 テイカ株式会社 有機溶剤系導電性高分子分散液の製造方法およびその応用
JP2018523722A (ja) * 2015-07-17 2018-08-23 日産化学株式会社 有機電子デバイスに使用するのに適した金属ナノ粒子を含有する非水性インク組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3573117A4 (fr) 2017-01-18 2020-10-28 Nissan Chemical Corporation Composition d'encre

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004204114A (ja) * 2002-12-26 2004-07-22 Dainippon Printing Co Ltd インクジェット用インク組成物
JP4573363B1 (ja) * 2010-06-01 2010-11-04 テイカ株式会社 有機溶剤系導電性高分子分散液の製造方法およびその応用
JP2018523722A (ja) * 2015-07-17 2018-08-23 日産化学株式会社 有機電子デバイスに使用するのに適した金属ナノ粒子を含有する非水性インク組成物

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