WO2020027262A1 - Composition de transport de charge - Google Patents

Composition de transport de charge Download PDF

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Publication number
WO2020027262A1
WO2020027262A1 PCT/JP2019/030221 JP2019030221W WO2020027262A1 WO 2020027262 A1 WO2020027262 A1 WO 2020027262A1 JP 2019030221 W JP2019030221 W JP 2019030221W WO 2020027262 A1 WO2020027262 A1 WO 2020027262A1
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group
carbon atoms
substituted
charge transporting
composition
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PCT/JP2019/030221
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English (en)
Japanese (ja)
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歳幸 遠藤
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日産化学株式会社
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Priority to KR1020217005351A priority Critical patent/KR20210040081A/ko
Priority to JP2020534740A priority patent/JP7414001B2/ja
Priority to CN201980051435.XA priority patent/CN112534599A/zh
Publication of WO2020027262A1 publication Critical patent/WO2020027262A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/611—Charge transfer complexes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants

Definitions

  • the present invention relates to a charge transporting composition.
  • the present invention has been made in view of the above circumstances, and provides a thin film having good charge transportability, low extinction coefficient (k), good transparency, and high refractive index (n). It is an object of the present invention to provide a charge transporting composition capable of realizing an organic EL device having excellent characteristics when applied to a hole injection layer or the like.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, have found that certain anilines having an N, N, N ', N'-tetra (carbazol-2-yl) -paraphenylenediamine structure in the molecule
  • the charge-transporting composition containing the derivative only provides a charge-transporting thin film having a low extinction coefficient (k), good transparency, and a high refractive index (n), as compared with the case of using an aniline derivative having a similar structure.
  • the present inventors have found that the composition itself has excellent storage stability, and that the present invention provides an organic EL device having excellent characteristics when the charge transporting thin film is applied to a hole injection layer or the like. I let it.
  • a charge transport composition containing an aniline derivative represented by the following formula (1) is independently a group represented by any of the following formulas (Ar1) to (Ar9).
  • R 1 to R 21 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 1 , or a C 2 to 20 carbon atom which may be substituted by Z 1 alkenyl groups, Z 1 at carbon atoms which may be substituted have 2-20 alkynyl group, which may prime be substituted by an aryl group, or Z 2 of which may 6 carbon atoms also be ⁇ 20 substituted by Z 2 2-20 heteroaryl groups, Z 1 is a halogen atom, a nitro group, a cyano group, a heteroaryl group aryl or Z 3 which do 2-20 carbon atoms substituted with Z 3 are carbon atoms that may 6 to be 20 substituted with Yes, Z
  • the charge transporting composition of the present invention By using the charge transporting composition of the present invention, compared to the case of using a composition containing an aniline derivative having a similar structure, a charge having high transparency (low extinction coefficient (k)) and high refractive index (n) is used. A transportable thin film can be manufactured. Further, the charge transporting composition of the present invention is superior in storage stability to a composition containing an aniline derivative having a similar structure.
  • the charge transporting thin film obtained from the charge transporting composition of the present invention can be suitably used as a thin film for an electronic element such as an organic EL element, and is provided between an anode and a light emitting layer of the organic EL element.
  • An organic EL device having excellent characteristics can be obtained by using it as a functional layer, in particular, a hole injection layer.
  • the charge transporting composition of the present invention contains an aniline derivative represented by the following formula (1).
  • each Ar is independently a group represented by any of the following formulas (Ar1) to (Ar9).
  • R 1 to R 21 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 1 , and which may be substituted by Z 1.
  • an alkenyl group having 2 to 20 carbon atoms, substituted with an aryl group, or Z 2 alkynyl group, Z 2 is optionally carbon atoms 6 to be 20 substituted with Z 1 to 2 carbon atoms which may be ⁇ 20 substituted by And a heteroaryl group having 2 to 20 carbon atoms.
  • Z 1 is a halogen atom, a nitro group, a cyano group, a heteroaryl group aryl or Z 3 which do 2-20 carbon atoms substituted with Z 3 are carbon atoms that may 6 to be 20 substituted with is there.
  • Z 2 is a halogen atom, a nitro group, a cyano group, Z 3-substituted of having 1 to 20 carbon atoms in the alkyl group, an alkenyl group of Z 3 is 1-2 carbon atoms which may be 20 substituted by or Z An alkynyl group having 2 to 20 carbon atoms which may be substituted by 3 ;
  • Z 3 is a halogen atom, a nitro group or a cyano group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl.
  • Group having 1 to 20 carbon atoms such as a s-butyl group, a s-butyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group and a n-decyl group.
  • a chain or branched alkyl group and a cyclic alkyl group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.
  • the alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl Group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl- Examples thereof include a 1-propenyl group, a 1-methyl-2-propenyl group, an n-1-pentenyl group, and an n-1-decenyl group.
  • the alkynyl group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include an ethynyl group, an n-1-propynyl group, an n-2-propynyl group, and an n-1 -Butynyl group, n-2-butynyl group, n-3-butynyl group, 1-methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n- 4-pentynyl group, 1-methyl-n-butynyl group, 2-methyl-n-butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, and n-1-decynyl group.
  • aryl group having 6 to 20 carbon atoms include phenyl, tolyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, and 1-phenanthryl. , 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl and the like.
  • heteroaryl group having 2 to 20 carbon atoms examples include a 2-thienyl group, a 3-thienyl group, a 2-furanyl group, a 3-furanyl group, a 2-oxazolyl group, a 4-oxazolyl group, and a 5-oxazolyl group.
  • an aryl group Z 2 are carbon atoms 6 also be ⁇ 20 substituted with a heteroaryl group Z 2 is optionally 2-20 carbon atoms preferably substituted with, Z more preferably an aryl group which may having 6 to 20 carbon atoms optionally substituted by 2 phenyl group which may be substituted with Z 2, which may be substituted with Z 2 1-naphthyl group, substituted with Z 2 An optionally substituted 2-naphthyl group is even more preferred.
  • a halogen atom an alkyl group of Z 3 are optionally to 1 to 20 carbon atoms substituted with an alkenyl group Z 3 are optionally 2-20 carbon atoms substituted with preferred.
  • a halogen atom is preferable, and a fluorine atom is more preferable.
  • Ars are all the same. Further, from the viewpoint of improving the solubility of the aniline derivative in an organic solvent and obtaining a highly uniform composition with good reproducibility, a group represented by any one of formulas (Ar1) to (Ar5) is preferable.
  • the group represented by Ar1) is optimal.
  • the aniline derivative used in the present invention may be a paraphenylenediamine (1,4-phenylenediamine) and a halogenated or pseudohalogenated carbazole derivative Ar-X (where Ar is the same as described above; X is a halogen atom) in the presence of a catalyst. Or a pseudohalogen group).
  • halogen atom examples include the same as described above, but a chlorine atom, a bromine atom and an iodine atom are preferable.
  • pseudohalogen group examples include a (fluoro) alkylsulfonyloxy group such as a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and a nonafluorobutanesulfonyloxy group; and an aromatic sulfonyloxy group such as a benzenesulfonyloxy group and a toluenesulfonyloxy group. And the like.
  • the charge ratio of the 1,4-phenylenediamine to the halogenated or pseudohalogenated carbazole derivative is such that the halogenated or pseudohalogenated carbazole derivative is at least equivalent to the total amount of NH groups in 1,4-phenylenediamine. However, about 1 to 1.2 equivalents are preferred.
  • Examples of the catalyst used in the reaction include copper catalysts such as copper chloride, copper bromide, and copper iodide; tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ), bis (triphenylphosphine) dichloropalladium (Pd (PPh 3 ) 2 Cl 2 ), bis (dibenzylideneacetone) palladium (Pd (dba) 2 ), tris (dibenzylideneacetone) dipalladium (Pd 2 (dba) 3 ), bis [tri (t-butyl) Phosphine)] palladium catalysts such as palladium (Pd (Pt-Bu 3 ) 2 ) and palladium acetate (Pd (OAc) 2 ). These catalysts may be used alone or in combination of two or more.
  • Such catalysts may be used together with a known suitable ligand.
  • ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-t-butylphosphine, di-t-butyl ( Phenyl) phosphine, di-t-butyl (4-dimethylaminophenyl) phosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenyl) Examples include tertiary phosphines such as phosphino) butane and 1,1′-bis (diphenylphosphino) ferrocene, and tertiary phosphites such as trimethyl
  • the amount of the catalyst used can be about 0.01 to 0.2 mol, preferably about 0.15 mol, per 1 mol of the halogenated or pseudohalogenated carbazole derivative.
  • the amount of the ligand used can be 0.1 to 5 equivalents to the catalyst to be used, but is preferably 1 to 2 equivalents.
  • aliphatic hydrocarbons penentane, n-hexane, n-octane, n-decane, decalin, etc.
  • halogenated aliphatic hydrocarbons chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.
  • aromatics Aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethan
  • the reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, but is usually in the range of about 0 to 200 ° C, preferably in the range of 20 to 150 ° C.
  • a post-treatment is carried out according to a conventional method to obtain a desired aniline derivative.
  • the charge transporting composition of the present invention contains an organic solvent.
  • an organic solvent a highly soluble solvent that can satisfactorily dissolve the aniline derivative represented by the formula (1), which is a charge transporting substance, can be used.
  • the highly soluble solvent include, for example, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutyramide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazo Examples include, but are not limited to, organic solvents such as lydinone and diethylene glycol monomethyl ether. These solvents may be used alone or in a combination of two or more. The amount used can be 5 to 100% by mass based on the whole solvent used in the composition.
  • the composition has a viscosity of 10 to 200 mPa ⁇ s at 25 ° C., particularly 35 to 150 mPa ⁇ s, and a high viscosity organic solvent having a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure (atmospheric pressure).
  • the viscosity of the composition can be easily adjusted, and as a result, it is possible to prepare a composition that gives a highly planar thin film with good reproducibility and that is suitable for the application method used.
  • the high-viscosity organic solvent examples include cyclohexanol, ethylene glycol, ethylene glycol diglycidyl ether, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, Examples include, but are not limited to, 2,3-butanediol, 1,4-butanediol, propylene glycol, hexylene glycol, and the like. These solvents may be used alone or in a combination of two or more.
  • the addition ratio of the high-viscosity organic solvent to the entire solvent used in the composition is preferably within a range in which no solid precipitates, and as long as no solid precipitates, the addition ratio is preferably 5 to 80% by mass.
  • another solvent is used in an amount of 1 to 90% by mass, preferably 1 to 90% by mass based on the whole solvent used in the composition. Can be mixed at a ratio of 1 to 50% by mass.
  • Examples of such a solvent include propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol.
  • Examples include, but are not limited to, monoethyl ether, diacetone alcohol, ⁇ -butyrolactone, ethyl lactate, n-hexyl acetate, and the like. These solvents may be used alone or in a combination of two or more.
  • the aniline derivative represented by the formula (1) has an aryl group on the nitrogen atom at the 9-position of the carbazole moiety in the molecule, the aniline derivative is substituted on at least one nitrogen atom in the molecule.
  • the aniline derivative represented by the formula (1) has an aryl group on the nitrogen atom at the 9-position of the carbazole moiety in the molecule.
  • low-polarity solvents include chlorinated solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene; 1-octanol, 1-nonanol, -Aliphatic alcohol solvents such as decanol; 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, etc.
  • chlorinated solvents such as chloroform and chlorobenzene
  • aromatic hydrocarbon-based solvents such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene
  • Ether solvents methyl benzoate, ethyl benzoate, butyl benzoate, dimethyl phthalate, diethyl maleate, isoamyl benzoate, bis (2 -Ethylhexyl), dibutyl maleate, dibutyl oxalate, hexyl acetate, ester solvents such as diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like, but are not limited thereto. These solvents may be used alone or in a combination of two or more.
  • the charge transporting composition of the present invention may contain water as a solvent, but when the charge transporting thin film obtained from the composition is used as a hole injection layer of an organic EL device, a highly durable device can be reproducibly prepared.
  • the content of water is preferably 10% by mass or less, more preferably 5% by mass or less of the whole solvent, and it is optimal to use only an organic solvent as the solvent.
  • “only organic solvent” means that only the organic solvent is used as the solvent, and denies the existence of "water” contained in a trace amount in the organic solvent or solid content used. It does not do.
  • the solid content means components other than the solvent contained in the charge transporting composition.
  • the charge transporting composition of the present invention may contain other charge transporting substances in addition to the charge transporting substance comprising the aniline derivative represented by the formula (1).
  • the charge transporting composition of the present invention contains a charge transporting substance composed of the aniline derivative represented by the formula (1) and an organic solvent.
  • the charge transporting ability is improved depending on the use of the obtained thin film. It may contain a dopant (charge-accepting substance) for the purpose.
  • the dopant is not particularly limited as long as it is soluble in at least one kind of solvent used in the composition, and either an inorganic dopant or an organic dopant can be used. Further, the inorganic and organic dopants may be used alone or in combination of two or more. Further, during the process of obtaining a charge-transporting thin film as a solid film from the composition, for example, the function as a dopant is expressed for the first time because a part of the molecule comes off due to an external stimulus such as heating during baking. Alternatively, a substance capable of improving, for example, an arylsulfonic acid ester compound in which a sulfonic acid group is protected with a group which is easily eliminated may be used.
  • the amount of the dopant substance in the composition cannot be specified unconditionally because it differs depending on the desired degree of charge transporting property and the kind of the dopant substance, but usually, the amount of the dopant substance is based on the mass of the aniline derivative 1 represented by the formula (1).
  • the ratio is in the range of 0.0001 to 100.
  • heteropolyacid is preferred as the inorganic dopant.
  • the heteropolyacid typically has a structure in which a hetero atom is located at the center of a molecule, represented by a Keggin-type chemical structure represented by the following formula (H1) or a Dawson-type chemical structure represented by the following formula (H2). Further, it is a polyacid obtained by condensing isopolyacid which is an oxygen acid such as vanadium (V), molybdenum (Mo), and tungsten (W) with oxygen acid of a different element. Examples of such different types of oxyacids include oxyacids of silicon (Si), phosphorus (P), and arsenic (As).
  • heteropolyacid examples include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, and phosphorus tungstomolybdic acid. These heteropoly acids may be used alone or in combination of two or more. These heteropoly acids are available as commercial products, and can also be synthesized by known methods.
  • the one kind of heteropolyacid is preferably phosphotungstic acid or phosphomolybdic acid, and most preferably phosphotungstic acid.
  • one of the two or more heteropoly acids is preferably phosphotungstic acid or phosphomolybdic acid, more preferably phosphotungstic acid.
  • the heteropolyacid in a quantitative analysis such as elemental analysis, the number of elements is large or small from the structure represented by the general formula, even if it is obtained as a commercial product, or a known synthetic As long as it is appropriately synthesized according to the method, it can be used in the present invention. That is, for example, phosphotungstic acid is generally represented by the chemical formula H 3 (PW 12 O 40 ) ⁇ nH 2 O, and phosphomolybdic acid is generally represented by the chemical formula H 3 (PMo 12 O 40 ) ⁇ nH 2 O.
  • the mass of the heteropolyacid specified in the present invention is not the mass of pure phosphotungstic acid (phosphotungstic acid content) in a synthetic product or a commercial product, but a commercially available product and a known synthetic polytungstic acid. In the form that can be isolated by the method, it means the total mass in the state containing water of hydration and other impurities.
  • the amount of the heteropolyacid can be about 0.001 to 50.0 in terms of a mass ratio with respect to the aniline derivative 1 represented by the formula (1). It is about 0.01 to 20.0, more preferably about 0.1 to 10.0.
  • preferable organic dopants include a tetracyanoquinodimethane derivative and a benzoquinone derivative.
  • tetracyanoquinodimethane derivative include 7,7,8,8-tetracyanoquinodimethane (TCNQ) and halotetracyanoquinodimethane represented by the following formula (H3).
  • benzoquinone derivative examples include tetrafluoro-1,4-benzoquinone (F4BQ), tetrachloro-1,4-benzoquinone (chloranil), tetrabromo-1,4-benzoquinone, 2,3-dichloro-5, 6-dicyano-1,4-benzoquinone (DDQ) and the like.
  • R 101 to R 104 independently represent a hydrogen atom or a halogen atom, but at least one is a halogen atom, preferably at least two are halogen atoms, and at least three are halogen atoms. More preferably, all are halogen atoms.
  • the halogen atom include the same as described above, but a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.
  • halotetracyanoquinodimethane examples include 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2-chloro-7,7,8,8-tetracyanoquinodimethane 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane, 2,5-dichloro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetra Chloro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and the like.
  • the amount thereof is 0.01 to 20.0 in terms of the amount (mol) of the aniline derivative 1 represented by the formula (1).
  • it can be about 0.1 to 10.0, it is preferably about 0.1 to 10.0, and more preferably about 0.5 to 5.0.
  • aryl sulfonic acid compounds include benzenesulfonic acid, tosylic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzenesulfonic acid, dihexylbenzenesulfonic acid, and 5,5-dihexylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, 6,7-dibutyl-2-naphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, 3-dodecyl-2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 4-hexyl-1 -Naphthalenesulfonic acid, octylnaphthalenes
  • a 1 represents O or S, and O is preferable.
  • a 2 is a (q + 1) -valent group derived from naphthalene or anthracene (that is, a group obtained by removing (q + 1) hydrogen atoms from naphthalene or anthracene), and a group derived from naphthalene is preferable.
  • a 3 is a p-valent group derived from perfluorobiphenyl (that is, a group obtained by removing p fluorine atoms from perfluorobiphenyl). p represents the number of bonds between A 1 and A 3 and is an integer satisfying 2 ⁇ p ⁇ 4, preferably 2.
  • a 3 is a perfluorobiphenyldiyl group, preferably a perfluorobiphenyl-4,4′-diyl group.
  • q represents the number of sulfonic acid groups bonded to A 2 and is an integer satisfying 1 ⁇ q ⁇ 4, and 2 is most preferable.
  • 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 group having 2 to 2 carbon atoms.
  • the 20 alkenyl halide groups at least three of A 4 to A 8 are halogen atoms.
  • halogenated alkyl group having 1 to 20 carbon atoms examples include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4 , 4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluorobutyl and the like
  • halogenated alkenyl group having 2 to 20 carbon atoms examples include a perfluorovinyl group, a perfluoro-1-propenyl group, a perfluoro-2-propenyl group, a perfluorobutenyl group, and the like.
  • a 4 to A 8 include 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, and a halogenated alkenyl having 2 to 10 carbon atoms.
  • at least three of A 4 to A 8 are preferably a fluorine atom, such as a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, and a fluorine atom having 1 to 5 carbon atoms.
  • a perfluoroalkyl group is a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms
  • a 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 satisfying 1 ⁇ r ⁇ 4, preferably 2 to 4, and most preferably 2.
  • the amount of the aryl sulfonic acid compound is preferably about 0.01 to 20.0 in terms of a substance amount (mole) ratio to the aniline derivative 1 represented by the formula (1). It is preferably about 0.4 to 5.0.
  • the arylsulfonic acid compound may be a commercially available product, but can also be synthesized by a known method described in International Publication No. WO 2006/025342, International Publication No. 2009/096352, and the like.
  • arylsulfonic acid ester compounds include arylsulfonic acid ester compounds. Specific examples thereof include an arylsulfonic acid ester compound disclosed in International Publication No. 2017/217455 and an arylsulfonic acid ester compound disclosed in International Publication No. 2017/217457.
  • arylsulfonic acid ester compound a compound represented by any of the following formulas (H6) to (H8) is preferable.
  • n is an integer satisfying 1 ⁇ n ⁇ 4, preferably 2.
  • a 11 is an m-valent group derived from perfluorobiphenyl.
  • a 12 is —O— or —S—, preferably —O—.
  • a 13 is a (n + 1) -valent group derived from naphthalene or anthracene, and is preferably a group derived from naphthalene.
  • R s1 to R s4 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms
  • R s5 represents an optionally substituted 2 to 20 carbon atoms.
  • the linear or branched alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group and a t-butyl group. , N-hexyl group and the like.
  • an alkyl group having 1 to 3 carbon atoms is preferable.
  • the monovalent hydrocarbon group having 2 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. And an alkyl group such as a t-butyl group; and an aryl group such as a phenyl, naphthyl and phenanthryl group.
  • R s1 to R s4 is a straight-chain alkyl group having 1 to 3 carbon atoms, and the remainder is a hydrogen atom, or R s1 is a straight-chain alkyl group having 1 to 3 carbon atoms.
  • R s2 to R s4 are hydrogen atoms.
  • the straight-chain alkyl group having 1 to 3 carbon atoms is preferably a methyl group.
  • R s5 a linear alkyl group having 2 to 4 carbon atoms or a phenyl group is preferable.
  • a 14 is an optionally substituted m-valent hydrocarbon group having 6 to 20 carbon atoms and containing one or more aromatic rings, wherein the hydrocarbon group is one or more A group obtained by removing m hydrogen atoms from a hydrocarbon compound having 6 to 20 carbon atoms including an aromatic ring.
  • a hydrocarbon compound having 6 to 20 carbon atoms including an aromatic ring.
  • examples of such a hydrocarbon compound include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, and phenanthrene.
  • part or all of the hydrogen atoms may be further substituted with a substituent.
  • Examples of such a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a nitro atom.
  • a 14 is preferably a group derived from benzene, biphenyl and the like.
  • a 15 is —O— or —S—, preferably —O—.
  • a 16 is a (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms
  • the aromatic hydrocarbon group is an aromatic hydrocarbon compound having 6 to 20 carbon atoms. It is a group obtained by removing (n + 1) hydrogen atoms from the ring.
  • aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene.
  • a 16 is preferably a group derived from naphthalene or anthracene, and more preferably a group derived from naphthalene.
  • R s6 and R s7 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group
  • R s8 is a linear or branched monovalent aliphatic hydrocarbon group. It is a valent aliphatic hydrocarbon group.
  • the total number of carbon atoms of R s6 , R s7 and R s8 is 6 or more.
  • the upper limit of the total number of carbon atoms of R s6 , R s7 and R s8 is not particularly limited, but is preferably 20 or less, and more preferably 10 or less.
  • linear or branched monovalent aliphatic hydrocarbon group examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t- C1-C20 alkyl groups such as butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group and decyl group; vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1- Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as a methyl-2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and a hexenyl group.
  • R s6 is preferably a hydrogen atom
  • R s7 and R s8 are each independently preferably an alkyl group having 1 to 6 carbon atom
  • R s9 to R s13 each independently represent a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or It is a halogenated alkenyl group having 2 to 10 carbon atoms.
  • the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group.
  • the halogenated alkyl group having 1 to 10 carbon atoms is not particularly limited as long as part or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms are substituted with halogen atoms.
  • Specific examples thereof include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, a 3,3,3-trifluoropropyl group, 2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4 , 4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group, etc. Is mentioned.
  • the halogenated alkenyl group having 2 to 10 carbon atoms is not particularly limited as long as part or all of the hydrogen atoms of the alkenyl group having 2 to 10 carbon atoms are substituted with halogen atoms.
  • Specific examples thereof include a perfluorovinyl group, a perfluoro-1-propenyl group, a perfluoro-2-propenyl group, a perfluoro-1-butenyl group, a perfluoro-2-butenyl group, and a perfluoro-3-butenyl group. And the like.
  • R s9 a nitro group, a cyano group, a halogenated alkyl group having 1 to 10 carbon atoms and an alkenyl halide group having 2 to 10 carbon atoms are preferable, and a nitro group, a cyano group, and a carbon atom having 1 to 4 carbon atoms are preferable.
  • a nitro group, a cyano group, a trifluoromethyl group and a perfluoropropenyl group are more preferable.
  • R s10 to R s13 are preferably a halogen atom, more preferably a fluorine atom.
  • a 17 is —O—, —S— or —NH—, preferably —O—.
  • a 18 is an (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and this aromatic hydrocarbon group is an aromatic hydrocarbon compound having 6 to 20 carbon atoms. It is a group obtained by removing (n + 1) hydrogen atoms from the ring.
  • aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene.
  • a 18 is preferably a group derived from naphthalene or anthracene, and more preferably a group derived from naphthalene.
  • R s14 to R s17 each independently represent a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms.
  • the monovalent aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, C1-C20 alkyl groups such as cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group A group having 2 to 2 carbon atoms such as a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropen
  • R s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or OR s19 .
  • R s19 is an optionally substituted monovalent hydrocarbon group having 2 to 20 carbon atoms.
  • Examples of the linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R s18 include the same as described above.
  • R s18 is a monovalent aliphatic hydrocarbon group
  • R s18 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Even more preferred.
  • Examples of the monovalent hydrocarbon group having 2 to 20 carbon atoms represented by R s19 include the above-mentioned monovalent aliphatic hydrocarbon groups other than methyl group, and aryl groups such as phenyl group, naphthyl group and phenanthryl group. And the like. Among them, R s19 is preferably a straight-chain alkyl group having 2 to 4 carbon atoms or a phenyl group. Examples of the substituent which the monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group and a cyano group.
  • Suitable arylsulfonic acid ester compounds include, but are not limited to, the following.
  • the amount of the arylsulfonic acid ester compound to be used is about 0.01 to 20.0 based on the aniline derivative 1 represented by the formula (1) in a substance amount (molar) ratio. However, it is preferably about 0.1 to 10.0, more preferably about 0.5 to 5.0.
  • an organic dopant When an organic dopant is used as the dopant, its molecular weight is not particularly limited, but when used together with the aniline derivative represented by the formula (1), good solubility in an organic solvent is ensured, and uniformity is ensured. From the viewpoint of obtaining a high composition with good reproducibility, it is preferably 5,000 or less, more preferably 3,000 or less, and even more preferably 2,000 or less. In particular, the molecular weight of the arylsulfonic acid compound used as the dopant is preferably 2,000 or less, more preferably 1,500 or less from the same viewpoint.
  • arylsulfonic acid compounds considering that a thin film with high charge transportability can be obtained with good reproducibility, availability of dopants, etc.
  • dopant arylsulfonic acid compounds, arylsulfonic acid ester compounds, halotetracyanoquinodimethane and benzoquinone
  • an arylsulfonic acid ester compound When further considering obtaining a charge transporting composition having excellent stability, it is more preferable to use an arylsulfonic acid ester compound.
  • the charge transporting substance and the dopant are preferably completely dissolved or uniformly dispersed in the solvent, and most preferably completely dissolved.
  • the charge transporting composition of the present invention is used for improving the injection property into the hole transporting layer when the obtained thin film is used as a hole injecting layer of an organic EL device, and improving the life characteristics of the device. It may contain a compound or a nonionic fluorinated surfactant, and its content is usually about 1 to 30 parts by mass based on 100 parts by mass of the total of the charge transporting substance and the dopant.
  • the concentration of the solid content in the charge transporting composition of the present invention is generally about 0.1 to 20% by mass, preferably 0.5, from the viewpoint of securing a sufficient film thickness while suppressing the deposition of the charge transporting substance. 1515% by mass.
  • the viscosity of the charge transporting composition of the present 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 composition of the present invention are determined by changing the type of the organic solvent used, their ratio, the solid content, and the like, in consideration of various factors such as a coating method to be used and a desired film thickness. Can be adjusted.
  • the charge transporting composition of the present invention can be produced by dissolving the aniline derivative represented by the formula (1) in an organic solvent.
  • the aniline derivative may be dissolved in an organic solvent in advance, and the other organic solvent may be sequentially added thereto.
  • a mixed solvent of all the solvents to be used may be prepared in advance, and the aniline derivative may be dissolved therein.
  • the components contained in the composition may be heated so as to accelerate the dissolution of the aniline derivative and the like, while taking care not to decompose or deteriorate the components.
  • the same method is followed when the charge transporting composition of the present invention contains components other than the aniline derivative and the solvent.
  • the charge transporting composition of the present invention is obtained by dissolving the charge transporting substance in an organic solvent from the viewpoint of obtaining a thinner film having higher flatness with good reproducibility, and then filtering using a submicrometer-order filter or the like. May be.
  • the method of applying the composition is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, an ink jet method, a spray method, and a slit coating method. It is preferable to adjust the viscosity and surface tension of the composition according to the application method.
  • the firing atmosphere is not particularly limited, and a uniform thin film surface and a thin film having a charge transporting property can be obtained not only in an air atmosphere (under air) but also in an inert gas such as nitrogen or in a vacuum. Bake in an atmosphere.
  • firing conditions are not particularly limited. For example, heating and firing are performed using a hot plate.
  • the firing temperature is appropriately determined within the range of 100 to 260 ° C.
  • the firing time is appropriately determined within the range of 1 minute to 1 hour in consideration of the desired charge transporting property.
  • multi-stage firing may be performed at two or more different temperatures.
  • the thickness of the charge transporting thin film is not particularly limited, but is preferably 5 to 300 nm when used as a functional layer of an organic EL device.
  • a method of changing the film thickness for example, there is a method of changing a solid concentration in the charge transporting composition or a method of changing a liquid amount at the time of application.
  • Organic EL device has a pair of electrodes, and has the charge transporting thin film of the present invention as a functional layer between these electrodes.
  • an electron block layer or the like may be provided between the light emitting layer and the anode, and a hole (hole) block layer or the like may be provided between the light emitting layer and the cathode as necessary.
  • the hole injection layer, the hole transport layer, or the hole injection / transport layer may also have a 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 be a hole (hole). It may have a function as a block layer or the like.
  • an optional functional layer can be provided between the layers as needed.
  • A anode / hole injection layer / hole transport layer / emission layer / electron transport layer / electron injection layer / cathode
  • b anode / hole injection layer / hole transport layer / emission layer / electron injection transport layer / Cathode
  • c anode / hole injection / transport layer / emission layer / electron transport layer / electron injection layer / cathode
  • d anode / hole injection / transport layer / emission layer / electron injection / transport layer / cathode
  • e anode / positive Hole injection layer / hole transport layer / emission layer / cathode
  • f anode / hole injection / transport layer / emission layer / cathode
  • “Hole injection layer”, “hole transport layer” and “hole injection transport layer” are layers formed between the light emitting layer and the anode, and transport holes from the anode to the light emitting layer. It has a function. When only one layer of the hole transporting material is provided between the light emitting layer and the anode, it is a “hole injection / transport layer”, and the layer of the hole transporting material is provided between the light emitting layer and the anode. Is provided, two or more layers are a "hole injection layer” and a layer near the anode is a "hole transport layer".
  • the hole injection (transport) layer a thin film that is excellent in not only the property of accepting holes from the anode but also the property of injecting holes into the hole transport (emission) layer is used.
  • Electrode layer is layers formed between the light emitting layer and the cathode, and have a function of transporting electrons from the cathode to the light emitting layer. It is. When only one layer of the electron transporting material is provided between the light emitting layer and the cathode, it is an “electron injection and transport layer”, and two layers of the electron transporting material are provided between the light emitting layer and the cathode. When provided as described above, the layer close to the cathode is an “electron injection layer”, and the other layers are “electron transport layers”.
  • the “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 has a function of promoting recombination of electrons and holes and confining excitons in the light-emitting layer, and the dopant material efficiently emits excitons obtained by the recombination.
  • a host material has a function of mainly confining excitons generated by a dopant in a light-emitting layer.
  • the charge transporting thin film of the present invention is suitable as a functional layer provided between an anode and a light emitting layer in an organic EL device, and is more suitable as a hole injection layer, a hole transport layer, and a hole injection transport layer. It is even more suitable as a hole injection layer.
  • Materials and methods for producing an organic EL device using the charge transporting 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 transport layer comprising a thin film obtained from the charge transport composition of the present invention is as follows.
  • the electrode is preferably subjected to cleaning with alcohol, pure water, or the like, or surface treatment such as UV ozone treatment or oxygen-plasma treatment in advance within a range that does not adversely affect the electrode.
  • a hole injection layer composed of the charge transporting thin film of the present invention is formed by the method described above. This is introduced into a vacuum evaporation apparatus, and a hole transport layer, a light emitting layer, an electron transport layer, an electron transport layer / hole block layer, and a cathode metal are sequentially deposited.
  • a composition for forming a hole transporting layer containing a hole transporting polymer and a composition for forming a light emitting layer containing a light emitting polymer are used to form these layers by a wet process. Note that, if necessary, an electron block layer may be provided between the light emitting layer and the hole transport layer.
  • anode material examples include a transparent electrode typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and a metal anode composed of a metal typified by aluminum, an alloy thereof, and the like. It is preferable that the material has been subjected to a chemical treatment. A polythiophene derivative or a polyaniline derivative having a high charge transporting property can also be used.
  • the other metal constituting the metal anode includes, but is not limited to, gold, silver, copper, indium and alloys thereof.
  • Examples of the material for forming the light emitting layer include aluminum complexes of 8-hydroxyquinoline such as tris (8-quinolinolato) aluminum (III) (Alq 3 ) and bis (8-quinolinolato) zinc (II), and metal complexes such as zinc complex.
  • 8-hydroxyquinoline such as tris (8-quinolinolato) aluminum (III) (Alq 3 ) and bis (8-quinolinolato) zinc (II)
  • metal complexes such as zinc complex.
  • Low molecular light emitting materials such as metal complexes of 10,10-hydroxybenzo [h] quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, metal complexes of (2-hydroxyphenyl) benzothiazole, and silole derivatives; poly (p-phenylenevinylene) ), Poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene], poly (3-alkylthiophene), polyvinylcarbazole, and other high molecular compounds mixed with a light emitting material and an electron transfer material And the like, but are not limited thereto.
  • the light emitting layer When the light emitting layer is formed by vapor deposition, the light emitting layer may be co-deposited with a light emitting dopant.
  • the light emitting dopant may be a metal complex such as tris (2-phenylpyridine) iridium (III) (Ir (PPy) 3 ). And naphthacene derivatives 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 transport layer / hole block layer include, but are not limited to, oxydiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, and pyrimidine derivatives.
  • 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). But not limited to metal fluorides
  • cathode material examples include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy and the like.
  • a material for forming the electron blocking layer includes, but is not limited to, tris (phenylpyrazole) iridium and the like.
  • the luminescent polymer examples include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene) (MEH- Polyphenylene vinylene derivatives such as PPV); polythiophene derivatives such as poly (3-alkylthiophene) (PAT); and polyvinyl carbazole (PVCz).
  • polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene) (MEH- Polyphenylene vinylene derivatives such as PPV)
  • polythiophene derivatives such as poly (3-alkylthiophene) (PAT); and polyvinyl carbazole (PVCz).
  • the materials constituting the anode, the cathode, and the layers formed between them differ depending on whether an element having a bottom emission structure or a top emission structure is manufactured. Therefore, the material is appropriately selected in consideration of this point.
  • a transparent anode is used on the substrate side, and light is extracted from the substrate side, whereas in a top emission structure element, a reflective anode made of metal is used, and in a direction opposite to the substrate. Since light is extracted from a certain transparent electrode (cathode) side, regarding the anode material, a transparent anode such as ITO is used when manufacturing a device having a bottom emission structure, and Al / is used when manufacturing a device having a top emission structure. A reflective anode such as Nd is used.
  • the organic EL device of the present invention may be sealed together with a water catching agent, if necessary, according to a standard method, in order to prevent deterioration in characteristics.
  • LDI-MS Bruker AutoFlex
  • 1 H-NMR JNM-ECP300 FT NMR SYSTEM manufactured by JEOL Ltd.
  • Substrate cleaning Choshu Sangyo Co., Ltd. substrate cleaning system (reduced pressure plasma method)
  • Application of the composition Spin coater MS-A100 manufactured by Mikasa Corporation
  • Film thickness measurement Surfcorder ET-4000, a fine shape measuring instrument manufactured by Kosaka Laboratory Co., Ltd.
  • Fabrication of element Choshu Sangyo Co., Ltd.
  • Multi-channel IVL measurement device manufactured by EC Corporation (8) Measurement of refractive index (n) and extinction coefficient (k): manufactured by JA Woollam Japan Multi-entry angle spectroscopic ellipsometer VASE
  • Example 1-2 To a mixture of 0.243 g of the aniline derivative A and 0.283 g of the arylsulfonic acid ester B, 5 g of triethylene glycol butyl methyl ether, 3 g of butyl benzoate and 2 g of dimethyl phthalate were added and stirred at room temperature to dissolve the resulting solution. The mixture was filtered through a syringe filter having a pore size of 0.2 ⁇ m to obtain a charge transporting composition.
  • Example 1-3 To a mixture of 0.243 g of the aniline derivative A and 0.283 g of the arylsulfonic acid ester B, 3 g of 3-phenoxytoluene and 7 g of butyl benzoate were added, and the mixture was stirred and dissolved at room temperature to obtain a solution having a pore size of 0.2. The mixture was filtered with a 2 ⁇ m syringe filter to obtain a charge transporting composition.
  • Example 1-1 Preparation of a charge transporting composition was attempted in the same manner as in Example 1-1, except that an aniline derivative C represented by the following formula was used instead of the aniline derivative A.
  • an aniline derivative C represented by the following formula was used instead of the aniline derivative A.
  • the solid content did not dissolve even when stirred at room temperature, and the solid content did not dissolve even when heated and stirred at 50 ° C., and the solid content was dissolved when heated and stirred at 80 ° C.
  • the obtained solution was filtered with a syringe filter having a pore size of 0.2 ⁇ m to obtain a charge transporting composition.
  • the aniline derivative C was synthesized according to the method described in International Publication No. 2015/137395.
  • Example 1-2 An attempt was made to prepare a charge transporting composition in the same manner as in Example 1-2, except that aniline derivative C was used instead of aniline derivative A. However, the solid content does not dissolve even when stirred at room temperature, and does not dissolve even when heated and stirred at any temperature of 50 ° C. or 80 ° C., so that a charge transporting thin film can be produced. A uniform charge transporting composition was not obtained.
  • Example 1-3 An attempt was made to prepare a charge transporting composition in the same manner as in Example 1-3, except that aniline derivative C was used instead of aniline derivative A. However, the solid content did not dissolve even when stirred at room temperature, and the solid content did not dissolve even when heated and stirred at 50 ° C., and the solid content was dissolved when heated and stirred at 80 ° C. The obtained solution was filtered with a syringe filter having a pore size of 0.2 ⁇ m to obtain a charge transporting composition.
  • Example 2 and Comparative Example 2 Each of the charge transporting compositions obtained in Example 1-1 and Comparative Example 1-1 was applied to a quartz substrate using a spin coater, and then dried at 80 ° C. for 1 minute in an air atmosphere. Firing at 15 ° C. for 15 minutes produced a uniform thin film of 60 nm on the substrate.
  • the extinction coefficient k (average extinction coefficient at a wavelength of 400 nm to 800 nm) and the refractive index n (average refractive index at a wavelength of 400 nm to 800 nm) of each thin film were measured. Table 2 shows the results.
  • the thin film obtained from the composition of the present invention exhibited a lower extinction coefficient, was highly transparent, and had a high refractive index, as compared with the thin film obtained from the composition of the comparative example.
  • Table 2 the thin film obtained from the composition of the present invention exhibited a lower extinction coefficient, was highly transparent, and had a high refractive index, as compared with the thin film obtained from the composition of the comparative example.
  • ITO indium tin oxide
  • Example 3 The composition obtained in Example 1-1 was applied to an ITO substrate using a spin coater, dried at 80 ° C. for 1 minute in the air, and baked at 200 ° C. for 15 minutes to obtain a film having a thickness of 60 nm.
  • ⁇ -NPD N, N′-di (1-naphthyl
  • a vapor deposition device vacuum degree: 1.0 ⁇ 10 ⁇ 5 Pa, vapor deposition rate: 0.2 nm / sec).
  • -N, N'-diphenylbenzidine was formed at a thickness of 0.2 nm / sec to form a 30 nm film, and an 80 nm aluminum thin film was further formed thereon to produce a device.
  • Comparative Example 3 A device was produced in the same manner as in Example 3, except that the composition obtained in Comparative Example 1-1 was used instead of the composition obtained in Example 1-1.
  • Example 4 In the same manner as in Example 3, a charge transporting thin film was formed on an ITO substrate. A 0.6% by mass xylene solution of a TFB polymer (LT-N148, manufactured by Luminescence Technology) was applied thereon by spin coating in a glove box under a nitrogen atmosphere, and then baked at 130 ° C. for 10 minutes to obtain a charge of 20 nm. A transportable thin film was formed as a hole transport layer. Further, an 80 nm aluminum thin film was formed thereon in the same manner as in Example 3 to fabricate a device.
  • TFB polymer LT-N148, manufactured by Luminescence Technology
  • Comparative Example 4 A device was manufactured in the same manner as in Example 4, except that the composition obtained in Comparative Example 1-1 was used instead of the composition obtained in Example 1-1.
  • the charge transporting thin film obtained from the composition of the present invention was more excellent in hole injection into the hole transporting layer than the charge transporting thin film obtained from the composition of Comparative Example. .
  • an organic EL device having high characteristics can be expected.

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Abstract

L'invention concerne, par exemple, une composition de transport de charge comprenant le dérivé d'aniline représenté dans la formule qui suit. (Dans La formule, Ph représente un groupe phényle.)
PCT/JP2019/030221 2018-08-03 2019-08-01 Composition de transport de charge WO2020027262A1 (fr)

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WO2015137395A1 (fr) * 2014-03-14 2015-09-17 日産化学工業株式会社 Dérivé d'aniline et utilisation de ce dérivé d'aniline
JP2016025360A (ja) * 2014-07-24 2016-02-08 ドク サン ネオルクス カンパニーリミテッド 有機電子素子及びこれを含む電子装置
WO2017146405A1 (fr) * 2016-02-23 2017-08-31 덕산네오룩스 주식회사 Composé pour élément électronique organique, élément électronique organique l'utilisant, et dispositif électronique associé

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