WO2018012416A1 - Vernis destiné à former une couche mince de transport de charges - Google Patents

Vernis destiné à former une couche mince de transport de charges Download PDF

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WO2018012416A1
WO2018012416A1 PCT/JP2017/024896 JP2017024896W WO2018012416A1 WO 2018012416 A1 WO2018012416 A1 WO 2018012416A1 JP 2017024896 W JP2017024896 W JP 2017024896W WO 2018012416 A1 WO2018012416 A1 WO 2018012416A1
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group
thin film
charge transporting
carbon atoms
varnish
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PCT/JP2017/024896
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English (en)
Japanese (ja)
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将之 東
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日産化学工業株式会社
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Priority to JP2018527571A priority Critical patent/JP6927214B2/ja
Publication of WO2018012416A1 publication Critical patent/WO2018012416A1/fr

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    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • 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
    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants

Definitions

  • the present invention relates to a varnish for forming a charge transporting thin film.
  • a charge transporting thin film made of an organic compound is used as a light emitting layer or a charge injection layer.
  • the method for forming the charge transporting thin film is roughly classified into a dry process typified by vapor deposition and a wet process typified by spin coating. Compared with the dry process and the wet process, the wet process can efficiently produce a thin film with a large area and high flatness. Therefore, the thin film is formed by the wet process in a field where a large area of the thin film such as an organic EL is desired. Often formed.
  • the present invention has been made in view of the above circumstances, and shows a high charge transport property even when fired at a low temperature.
  • An object of the present invention is to provide a varnish for forming a charge transporting thin film containing a pentavalent hypervalent iodine compound, which can reduce drive voltage and improve luminance characteristics while maintaining it.
  • Another object of the present invention is to provide a method for reducing the driving voltage of an organic EL element, a method for improving luminance, and a method for improving luminance life using such a varnish for forming a charge transporting thin film. To do.
  • the inventor of the present invention has a pentavalent hypervalent iodine compound having excellent solubility in an organic solvent and excellent oxidizability for a charge transporting substance, Even when the varnish is fired at a low temperature by using a charge transporting thin film obtained from a varnish prepared by dissolving it in an organic solvent together with a charge transporting substance as a hole injection layer of the organic EL element, The inventors have found that the drive voltage can be reduced and the luminance characteristics can be improved without impairing the current efficiency of the element, and the present invention has been completed.
  • “baking at a low temperature” means “baking at a temperature of 180 ° C. or lower”.
  • a varnish for forming a charge-transporting thin film comprising a 1.5-valent hypervalent iodine compound, a charge-transporting substance, and an organic solvent;
  • the pentavalent hypervalent iodine compound is selected from the group consisting of Dess-Martin periodinane, 2-iodoxybenzoic acid, 2-iodoxybenzenesulfonic acid, and compounds represented by the following formulas (X1) and (X2) 1 or more varnish for forming a charge transporting thin film, 3.
  • the varnish for forming a charge transporting thin film, wherein the pentavalent hypervalent iodine compound is Dess-Martin periodinane; 4).
  • the varnish for forming a charge transporting thin film according to 6, wherein the dopant contains an aryl sulfonic acid A charge transporting thin film produced using the charge transporting thin film forming varnish of any one of 8.1 to 7, An organic EL device having a charge-transporting thin film of 9.8, 10.
  • 11. A method for producing an organic EL device, characterized by using any one of the charge transporting thin film forming varnishes of 11.1 to 7.
  • a method for reducing the driving voltage of an organic EL device having a charge transporting thin film manufactured using a charge transporting thin film forming varnish A method comprising using any one of charge transporting thin film forming varnishes 1 to 7 as the charge transporting thin film forming varnish; 13.
  • a method for improving the luminance of an organic EL device having a charge transporting thin film manufactured using a charge transporting thin film forming varnish A method comprising using any one of charge transporting thin film forming varnishes 1 to 7 as the charge transporting thin film forming varnish; 14 A method for improving the luminance life of an organic EL device having a charge transporting thin film produced using a charge transporting thin film forming varnish, One of the charge transporting thin film forming varnishes 1 to 7 is used as the charge transporting thin film forming varnish.
  • the varnish for forming a charge transporting thin film of the present invention has a high charge transporting property even when baked at a low temperature as compared with the case of using a varnish not containing this or a varnish containing another organic oxidizing agent. Can be obtained. Furthermore, by using the thin film as a hole injection layer, the driving voltage of the organic EL element can be reduced and the luminance characteristics can be improved. Further, the thin film obtained from the varnish for forming a charge transporting thin film of the present invention is expected to be used as an antistatic film, a hole collection layer of an organic thin film solar cell, or the like.
  • the varnish for forming a charge transporting thin film according to the present invention contains a pentavalent hypervalent iodine compound.
  • the pentavalent hypervalent iodine compound is Dess-Martin periodinane (1,1,1-triacetoxy-1,1-dihydro-1,2-benzoiodoxol-3- (1H) -One), 2-iodoxybenzoic acid (IBX), 2-iodoxybenzenesulfonic acid (IBS), and one or more selected from the group consisting of compounds represented by the following formulas (X1) and (X2) are preferred, Dess-Martin periodinane is more preferred.
  • the content of the pentavalent hypervalent iodine compound in the varnish of the present invention is about 10 to 80% by mass with respect to the charge transporting substance (in the case of containing a dopant, the charge transporting substance and the dopant), preferably About 20 to 60% by mass.
  • charge transport material included in the varnish for forming a charge transport thin film according to the present invention those used in the field of organic EL and the like can be used.
  • Specific examples thereof include oligoamine derivatives, N, N′-diarylbenzidine derivatives, arylamine derivatives such as N, N, N ′, N′-tetraarylbenzidine derivatives, oligothiophene derivatives, thienothiophene derivatives, thienobenzothiophenes.
  • charge transporting compounds such as thiophene derivatives such as derivatives and pyrrole derivatives such as oligopyrrole.
  • arylamine derivatives and thiophene derivatives are preferable and arylamine derivatives are more preferable because they exhibit excellent dissolution in organic solvents.
  • the molecular weight of the charge transporting compound is usually about 200 to 9,500 from the viewpoint of preparing a uniform varnish that gives a thin film with high flatness, but is 300 or more from the viewpoint of obtaining a thin film with more excellent charge transportability. From the viewpoint of preparing a uniform varnish that gives a highly flat thin film with better reproducibility, preferably 8,000 or less, more preferably 7,000 or less, and more preferably 6,000 or less. More preferred is 5,000 or less.
  • the charge transporting compound preferably has no molecular weight distribution (dispersity is 1) (that is, preferably has a single molecular weight). ).
  • arylamine derivative examples include those represented by the formula (1).
  • X 201 represents —NY 201 —, —O—, —S—, — (CR 207 R 208 ) L — or a single bond, and when m 1 or m 2 is 0, , -NY 201 - represents a.
  • Y 201 is independently of each other a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 201 , or An aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z 202 is represented.
  • alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic.
  • Straight chain having 1 to 20 carbon atoms such as s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group Or a branched alkyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohex
  • alkenyl group having 2 to 20 carbon atoms include ethenyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n- Examples thereof include a 1-pentenyl group, an n-1-decenyl group, and an n-1-eicosenyl group.
  • alkynyl group having 2 to 20 carbon atoms examples include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n-2-butynyl group, and n-3-butynyl.
  • aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group. Group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.
  • heteroaryl group having 2 to 20 carbon atoms examples include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, Examples include 4-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, and the like.
  • R 207 and R 208 are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, or Z 201.
  • Y 202 to Y 213 are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 201 , or An aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z 202 is represented.
  • Z 201 is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, or an aryl group having 6 to 20 carbon atoms that may be substituted with Z 203 Represents a group or a heteroaryl group having 2 to 20 carbon atoms.
  • Z 202 is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, or an alkyl group having 1 to 20 carbon atoms that may be substituted with Z 203 Group, an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms.
  • Z 203 represents a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, or a carboxy group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl group of R 207 to R 208 and Y 202 to Y 213 are the same as those described above.
  • a hydrogen atom or an alkyl group Z 201 has been having 1 to 20 carbon atoms substituted by are preferred, and a methyl group which may be substituted with a hydrogen atom or Z 201 More preferred are both hydrogen atoms.
  • L represents the number of divalent groups represented by — (CR 207 R 208 ) — and is an integer of 1 to 20, preferably 1 to 10, more preferably 1 to 5, and more preferably 1 to 2. Even more preferred, 1 is optimal.
  • the plurality of R 207 may be the same as or different from each other, and the plurality of R 208 may be the same as or different from each other.
  • X 201 is preferably —NY 201 — or a single bond.
  • Y 201 a hydrogen atom or an alkyl group Z 201 has been having 1 to 20 carbon atoms substituted with, more preferably a methyl group which may be substituted with a hydrogen atom or Z 201, hydrogen atom Is the best.
  • R 201 to R 206 are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, or Z 201.
  • R 201 to R 204 may be substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 201 , or Z 202.
  • An aryl group having 6 to 14 carbon atoms is preferable, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom is more preferable, and all hydrogen atoms are optimal.
  • R 205 and R 206 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms that may be substituted with Z 201 , or an aryl group having 6 to 14 carbon atoms that may be substituted with Z 202 Or a diphenylamino group optionally substituted by Z 202 (Y 203 and Y 204 are phenyl groups optionally substituted by Z 202 —NY 203 Y 204 group), a hydrogen atom, a fluorine atom Or a diphenylamino group optionally substituted with a fluorine atom, more preferably a hydrogen atom or a diphenylamino group.
  • R 201 to R 204 are hydrogen atoms, fluorine atoms, alkyl groups having 1 to 10 carbon atoms that may be substituted with fluorine atoms, and R 205 and R 206 are substituted with hydrogen atoms, fluorine atoms, or fluorine atoms.
  • X 201 is —NY 201 — or a single bond
  • Y 201 is preferably a hydrogen atom or a combination of methyl groups
  • R 201 to R 204 are hydrogen atoms
  • R 205 and R 206 are At the same time, a hydrogen atom or a diphenylamino group
  • X 201 is more preferably a combination of —NH— or a single bond.
  • m 1 and m 2 each independently represent an integer of 0 or more, and satisfy 1 ⁇ m 1 + m 2 ⁇ 20, but the charge transportability of the resulting thin film and the dissolution of the arylamine derivative In consideration of the balance with property, it is preferable to satisfy 2 ⁇ m 1 + m 2 ⁇ 8, more preferably 2 ⁇ m 1 + m 2 ⁇ 6, and more preferably 2 ⁇ m 1 + m 2 ⁇ 4. Even more preferred.
  • Z 201 is preferably a halogen atom or an aryl group having 6 to 20 carbon atoms which may be substituted with Z 203 , and is substituted with a halogen atom or Z 203
  • An optionally substituted phenyl group is more preferred and optimally absent (ie, unsubstituted).
  • Z 202 is a halogen atom, or preferably an alkyl group which may having 1 to 20 carbon atoms optionally substituted by Z 203, halogen atom, or an alkyl group which 1 carbon atoms which may be 1-4 substituted with Z 203 More preferably, not present (ie, unsubstituted) is optimal.
  • Z 203 is preferably a halogen atom, more preferably fluorine, and most preferably not (ie, unsubstituted).
  • the carbon number of the alkyl group, alkenyl group, and alkynyl group is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.
  • the carbon number of the aryl group and heteroaryl group is preferably 14 or less, more preferably 10 or less, and even more preferably 6 or less.
  • the molecular weight of the arylamine derivative represented by the formula (1) is preferably 9,500 or less, more preferably 8,000 or less, and even more preferably from the viewpoint of ensuring solubility in an organic solvent. It is 7,000 or less, more preferably 6,000 or less, and still more preferably 5,000 or less. Further, from the viewpoint of improving charge transportability, the molecular weight is preferably 300 or more, more preferably 400 or more. From the viewpoint of preventing the charge transporting material from separating when the film is thinned, the arylamine derivative represented by the formula (1) preferably has no molecular weight distribution (dispersity is 1) (that is, a single substance). Preferably having a molecular weight of
  • the method for synthesizing the arylamine derivative is not particularly limited, but Bulletin of Chemical Society of Japan, 67, pp. 1749-175275 (1994), Synthetic Metals, 84, pp. 119-120 (1997), Thin Solid Films, 520 (24), pp. 7157-7163, (2012), International Publication No. 2008/032617, International Publication No. 2008/032616, International Publication No. 2008/129947, International Publication No. 2013/084664, etc. The method described is mentioned.
  • arylamine derivative represented by the formula (1) include, but are not limited to, those represented by the following formula.
  • DPA represents a diphenylamino group.
  • Ph represents a phenyl group
  • TPA represents a p- (diphenylamino) phenyl group.
  • arylamine derivative examples include those represented by the formula (2) or (3).
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom,
  • An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms is represented.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • alkyl group having 1 to 20 carbon atoms examples include the alkenyl group having 2 to 20 carbon atoms, the alkynyl group having 2 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms.
  • heteroaryl group having 2 to 20 carbon atoms include 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, Oxygen-containing heteroaryl group such as 5-isoxazolyl group; 2-thienyl group, 3-thienyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group A sulfur-containing heteroaryl group such as a group; 2-imidazolyl group, 4-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazyl group, 3-pyrazyl group, 5-pyrazyl group, 6 -Pyrazyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyr
  • R 1 and R 2 a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, or a carbon number which may be substituted with a halogen atom
  • An aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with a halogen atom is preferred, and one carbon atom which may be substituted with a hydrogen atom, a fluorine atom, a cyano group or a halogen atom
  • An alkyl group of ⁇ 10 or a phenyl group which may be substituted with a halogen atom is more preferable, a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group is still more preferable, and a hydrogen atom is most preferable.
  • Ph 1 represents a group represented by formula (P1).
  • R 3 to R 6 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, or 2 carbon atoms Represents an alkenyl group having 20 carbon atoms, an alkynyl group having 2-20 carbon atoms, an aryl group having 6-20 carbon atoms, or a heteroaryl group having 2-20 carbon atoms. Specific examples thereof are the same as those described for R 1 and R 2 above.
  • R 3 to R 6 a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, or a carbon atom having 6 to 6 carbon atoms which may be substituted with a halogen atom
  • a 20 aryl group or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with a halogen atom is preferable, and 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a fluorine atom, a cyano group or a halogen atom.
  • a phenyl group which may be substituted with an alkyl group or a halogen atom is more preferred, a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group is even more preferred, and a hydrogen atom is most preferred.
  • Ar 1 independently represents a group represented by any one of the formulas (B1) to (B11), and in particular, any one of the formulas (B1 ′) to (B11 ′) The group represented by these is preferable.
  • R 7 to R 27 , R 30 to R 51 and R 53 to R 154 may each independently be substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a halogen atom.
  • R 28 and R 29 each independently represent an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with Z 1 .
  • R 52 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 4 , or substituted with Z 1.
  • an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms are independently represent an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with Z 1 .
  • R 52 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted
  • Z 1 represents a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 2.
  • Z 2 represents a halogen atom, a nitro group, a cyano group, or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z 3 .
  • Z 3 represents a halogen atom, a nitro group or a cyano group.
  • Z 4 represents a halogen atom, a nitro group, a cyano group, or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z 5 .
  • Z 5 represents a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 3. Represents.
  • halogen atoms alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and heteroaryl groups having 2 to 20 carbon atoms
  • alkyl groups having 1 to 20 carbon atoms alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and heteroaryl groups having 2 to 20 carbon atoms
  • Specific examples include the same as those described for R 1 and R 2 .
  • R 7 to R 27 , R 30 to R 51 and R 53 to R 154 are each substituted with a hydrogen atom, a fluorine atom, a cyano group, a diphenylamino group which may be substituted with a halogen atom, or a halogen atom.
  • a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom is more preferable.
  • a methyl group, or a trifluoromethyl group is more preferable, and a hydrogen atom is most preferable.
  • an aryl group Z 1 ⁇ carbon atoms 6 be replaced by 14, or a heteroaryl group Z 1 ⁇ 2 carbon atoms which may be substituted with 14 preferably, Z 1 substituted in the aryl group of ⁇ 14 6 carbon atoms which may be substituted are more preferred, and phenyl group which may be substituted with Z 1, which may be substituted with Z 1 1-naphthyl group, or Z 1 An optionally substituted 2-naphthyl group is even more preferred.
  • R 52 heteroaryl group of a hydrogen atom, Z 1 substituted by good carbon number of 6 to 20 even though aryl group, Z 1 is optionally 2-20 carbon atoms substituted with, or Z 4 preferably an alkyl group which may having 1 to 20 carbon atoms also be a hydrogen atom, Z 1 aryl group is optionally carbon atoms of 6 to 14 substituted, 2 carbon atoms which may be substituted with Z 1 - 14 heteroaryl groups, or an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 4 , more preferably a hydrogen atom, an aryl group having 6 to 14 carbon atoms which may be substituted with Z 1 , Z even more preferably an alkyl group having a nitrogen-containing heteroaryl group, or Z 4 carbon atoms which may be substituted with 1 to 10 carbon atoms which may 2-14 optionally substituted with 1, hydrogen atom, substituted with Z 1 Optionally substituted phenyl group, substituted with Z 1 Which may be 1-
  • Ar 4 independently represents a C 6-20 aryl group in which each aryl group may be substituted with a diarylamino group which is a C 6-20 aryl group.
  • aryl group having 6 to 20 carbon atoms are the same as those described for R 1 and R 2.
  • diarylamino group include a diphenylamino group, 1-naphthylphenyl, and the like. Examples include an amino group, a di (1-naphthyl) amino group, a 1-naphthyl-2-naphthylamino group, and a di (2-naphthyl) amino group.
  • Ar 4 includes phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4- Phenanthryl group, 9-phenanthryl group, p- (diphenylamino) phenyl group, p- (1-naphthylphenylamino) phenyl group, p- (di (1-naphthyl) amino) phenyl group, p- (1-naphthyl- A 2-naphthylamino) phenyl group, a p- (di (2-naphthyl) amino) phenyl group and the like are preferable, and a p- (diphenylamino) phenyl group is more preferable.
  • Ar 2 independently of each other represents a group represented by any one of the formulas (A1) to (A18), and in particular, the formulas (A1′-1) to (A18′-2) ) Is preferred.
  • R 155 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 4 , or Z 1 Represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with.
  • R 156 and R 157 each independently represent an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with Z 1 .
  • DPA, Ar 4 , Z 1 and Z 4 represent the same meaning as described above.
  • halogen atoms alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and heteroaryl groups having 2 to 20 carbon atoms
  • alkyl groups having 1 to 20 carbon atoms alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and heteroaryl groups having 2 to 20 carbon atoms
  • Specific examples include the same as those described for R 1 and R 2 .
  • heteroaryl group are optionally 2-20 carbon atoms substituted with Z 1
  • Z 4 in the alkyl group is preferably a substituted 1 carbon atoms which may be 1-20, hydrogen atom, Z 1 substituted by carbon atoms and optionally 6-14 aryl carbon atoms, which may be substituted with Z 1
  • a heteroaryl group having 2 to 14 or an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 4 is more preferable
  • a hydrogen atom or an aryl group having 6 to 14 carbon atoms which may be substituted with Z 1 More preferably a nitrogen-containing heteroaryl group having 2 to 14 carbon atoms which may be substituted with Z 1 or an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 4 , a hydrogen atom, Z 1 in an optionally substituted phenyl group, substituted with
  • R 155 and DPA have the same meaning as described above.
  • Ph 1 represents the same meaning as described above. x will be described later.
  • Ar 5 simultaneously represents a group represented by any one of formulas (D1) to (D13), and in particular, may be a group represented by any one of formulas (D1 ′) to (D13 ′). preferable.
  • R 28 , R 29 , R 52 , Ar 4 and DPA have the same meaning as described above.
  • Specific examples of Ar 5 include the same groups as those described above as specific examples of groups suitable as Ar 1 .
  • the arylamine derivative represented by the formula (2) is preferably the one represented by the formula (2-2).
  • Ar 6 simultaneously represents a group represented by any one of formulas (E1) to (E14).
  • R 52 represents the same meaning as described above.
  • Ar 3 represents a group represented by any one of the formulas (C1) to (C8), and particularly preferred is a group represented by any of (C1 ′) to (C8 ′).
  • DPA represents the same meaning as described above.
  • x represents an integer of 1 to 10, preferably 1 to 5, more preferably 1 to 3, from the viewpoint of increasing the solubility of the compound in an organic solvent. 1 or 2 is even more preferred and 1 is optimal.
  • y represents 1 or 2.
  • Z 1 is a halogen atom, a nitro group, a cyano group, an alkyl group which 1 carbon atoms which may be ⁇ 10 substituted by Z 2, with Z 2
  • An alkenyl group having 2 to 10 carbon atoms which may be substituted or an alkynyl group having 2 to 10 carbon atoms which may be substituted with Z 2 is preferable, substituted with a halogen atom, a nitro group, a cyano group or Z 2.
  • Z 4 is preferably a halogen atom, a nitro group, a cyano group, or an aryl group having 6 to 14 carbon atoms which may be substituted with Z 5 ,
  • a halogen atom, a nitro group, a cyano group, or an aryl group having 6 to 10 carbon atoms which may be substituted with Z 5 is more preferable, and a fluorine atom or an aryl group having 6 to 10 carbon atoms which may be substituted with Z 5
  • An aryl group is even more preferable, and a fluorine atom or a phenyl group optionally substituted with Z 5 is more preferable.
  • Z 2 is preferably a halogen atom, a nitro group, a cyano group, or an aryl group having 6 to 14 carbon atoms which may be substituted with Z 3 ,
  • a halogen atom, a nitro group, a cyano group, or an aryl group having 6 to 10 carbon atoms which may be substituted with Z 3 is more preferable, and a fluorine atom or an aryl group having 6 to 10 carbon atoms which may be substituted with Z 3
  • An aryl group is even more preferable, and a fluorine atom or a phenyl group optionally substituted with Z 3 is more preferable.
  • Z 5 is a halogen atom, a nitro group, a cyano group, an alkyl group which 1 carbon atoms which may be ⁇ 10 substituted by Z 3, with Z 3
  • An alkenyl group having 2 to 10 carbon atoms which may be substituted or an alkynyl group having 2 to 10 carbon atoms which may be substituted with Z 3 is preferable, and substituted with a halogen atom, a nitro group, a cyano group or Z 3 carbon atoms that may 1 be ⁇ 3 alkyl group, an alkenyl group of Z 3 - 2 carbon atoms which may be substituted with 3 or alkynyl groups of Z 3 - 2 carbon atoms which may be substituted with 3 more preferably, a fluorine atom, substituted by Z 3 in alkyl group having 1 carbon atoms which may be 3 substituents, alkenyl group of Z 3 - 2 carbon atoms which
  • Z 3 is preferably a halogen atom, more preferably a fluorine atom.
  • Z 1 is a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms which may be substituted with Z 2 , Z 2-substituted 2 carbon atoms which may be 1-3 alkenyl group, or an alkynyl group having 2 to 3 carbon atoms are preferable optionally substituted by Z 2, optionally substituted with a halogen atom, or Z 2
  • the alkyl group having 1 to 3 carbon atoms may be more preferable, and a fluorine atom or a methyl group optionally substituted with Z 2 is more preferable.
  • Z 4 represents a halogen atom, a nitro group, a cyano group, or an aryl group having 6 to 10 carbon atoms which may be substituted with Z 5.
  • a halogen atom or an aryl group having 6 to 10 carbon atoms which may be substituted with Z 5 is more preferable, and a fluorine atom or a phenyl group which may be substituted with Z 5 is even more preferable.
  • Z 2 is a halogen atom, a nitro group, a cyano group, or an aryl group having 6 to 10 carbon atoms that may be substituted with Z 3
  • a halogen atom or an aryl group having 6 to 10 carbon atoms which may be substituted with Z 3 is more preferable
  • a fluorine atom or a phenyl group which may be substituted with Z 3 is even more preferable.
  • Z 5 is a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms which may be substituted with Z 3 , Z 3-substituted 2 carbon atoms which may be 1-3 alkenyl group, or an alkynyl group having 2 to 3 carbon atoms are preferable optionally substituted by Z 3, substituted with a halogen atom, or Z 3
  • the alkyl group having 1 to 3 carbon atoms may be more preferable, and a fluorine atom or a methyl group which may be substituted with Z 3 is more preferable.
  • Z 3 is preferably a halogen atom, more preferably a fluorine atom.
  • R 52 and R 155 include, but are not limited to, those shown below.
  • the carbon number of the alkyl group, alkenyl group and alkynyl group is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.
  • carbon number of the said aryl group and heteroaryl group becomes like this.
  • it is 14 or less, More preferably, it is 10 or less, More preferably, it is 6 or less.
  • the molecular weight of the arylamine derivative represented by the formula (2) and the arylamine derivative represented by the formula (3) is usually about 200 to 9,500 from the viewpoint of preparing a uniform varnish that gives a thin film with high flatness.
  • it is preferably 8,000 or less, more preferably 7,000 or less, even more preferably 6,000 or less. 000 or less is more preferable, and from the viewpoint of obtaining a thin film having more excellent charge transportability, 300 or more is preferable, and 400 or more is more preferable.
  • the charge transporting compound has no molecular weight distribution (dispersity is 1) from the viewpoint of preventing the charge transporting material from being separated when the film is thinned (that is, having a single molecular weight). Is preferred).
  • the arylamine derivative represented by the formula (2) and the arylamine derivative represented by the formula (3) can be produced according to the method described in International Publication No. 2015/050253.
  • the content of the charge transporting substance in the varnish of the present invention is appropriately set in consideration of the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, etc., but is usually 0.1 to 10 in the varnish. In consideration of improving the coatability of the varnish, it is preferably about 0.5 to 5.0% by mass, more preferably about 1.0 to 3.0% by mass.
  • the varnish for forming a charge transporting thin film of the present invention may contain a dopant from the viewpoint of further improving the charge transporting property of the obtained thin film.
  • a dopant Aryl sulfonic acid is suitable.
  • One example thereof is an aryl sulfonic acid represented by the formula (4) or (5).
  • a 1 represents —O— or —S—, preferably —O—.
  • a 2 represents a naphthalene ring or an anthracene ring, and a naphthalene ring is preferable.
  • a 3 represents a divalent to tetravalent perfluorobiphenyl group, j 1 represents the number of bonds between A 1 and A 3, is an integer satisfying 2 ⁇ j 1 ⁇ 4, A 3 is a divalent par It is preferably a fluorobiphenyl group and j 1 is 2.
  • j 2 represents the number of sulfonic acid groups bonded to A 2 , and is an integer satisfying 1 ⁇ j 2 ⁇ 4, but 2 is preferable.
  • a 4 to A 8 are independently of each other a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 2 carbon atoms.
  • k represents the number of sulfonic acid groups bonded to the naphthalene ring and is an integer satisfying 1 ⁇ k ⁇ 4, preferably 2 to 4, and more preferably 2.
  • Examples of the halogenated alkyl group 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, Examples include 4-nonafluorobutyl group.
  • Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include perfluorovinyl group, 1-perfluoropropenyl group, perfluoroallyl group, perfluorobutenyl group and the like.
  • halogen atom and the alkyl group having 1 to 20 carbon atoms include the same ones as described 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.
  • at least three of A 4 to A 8 are preferably fluorine atoms, hydrogen atom, fluorine atom, cyano group, alkyl group having 1 to 5 carbon atoms, fluorinated alkyl having 1 to 5 carbon atoms.
  • a alkenyl fluoride group having 2 to 5 carbon atoms, and at least three of A 4 to A 8 are more preferably fluorine atoms, a hydrogen atom, a fluorine atom, a cyano group, and 1 to 5 carbon atoms. More preferably, the perfluoroalkyl group or the perfluoroalkenyl group having 1 to 5 carbon atoms, and A 4 , A 5 and A 8 are fluorine atoms.
  • the perfluoroalkyl group is a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms
  • the perfluoroalkenyl group is a group in which all hydrogen atoms of the alkenyl group are substituted with fluorine atoms.
  • the content of the dopant in the varnish of the present invention is appropriately set in consideration of the type and amount of the charge transporting material, but is usually about 0.5 to 10 with respect to the charge transporting material in mass ratio. It is.
  • organosilane compounds such as trimethoxysilane and triethoxysilane
  • hole injection of the thin film Other components such as a fluorine atom-containing oligoaniline derivative may be contained for the purpose of improving the above.
  • the content of other components in the charge transporting thin film forming varnish of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and is determined according to the properties, functions, etc. of the other components.
  • the fluorine atom-containing oligoaniline derivative is usually about 5 to 50% by mass, preferably about 10 to 30% by mass with respect to the charge transporting substance.
  • fluorine atom-containing oligoaniline derivative examples include those represented by the formula (6).
  • R 301 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z.
  • Z is a halogen atom, a nitro group, a cyano group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, an aryl group having 6 to 20 carbon atoms which may be substituted with Z ′, or substituted with Z ′.
  • Z ′ represents a halogen atom, nitro group, cyano group, aldehyde group, hydroxy group, thiol group, sulfonic acid group or carboxy group.
  • R 302 to R 310 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms, optionally substituted with a halogen atom, An alkenyl group, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms is represented.
  • halogen atoms alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and heteroaryl groups having 2 to 20 carbon atoms The thing similar to what was mentioned above is mentioned.
  • R 301 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with Z, considering the solubility of the fluorine atom-containing oligoaniline derivative in an organic solvent.
  • An atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with Z is more preferable, and a hydrogen atom is most preferable.
  • a plurality of R 301 may be the same or different.
  • R 302 to R 310 are substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a halogen atom in consideration of the solubility of the fluorine atom-containing oligoaniline derivative in an organic solvent.
  • An optionally substituted alkyl group having 1 to 10 carbon atoms is preferable, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom is more preferable, and a hydrogen atom is most preferable.
  • the plurality of R 302 to R 305 may be the same or different.
  • A represents a cyano group, a chlorine atom, a bromine atom, an iodine atom, a nitro group or a fluoroalkyl group having 1 to 20 carbon atoms which may be substituted with a fluoroalkoxy group having 1 to 20 carbon atoms.
  • the fluoroalkyl group is not particularly limited as long as it is a linear or branched alkyl group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom.
  • the fluorocycloalkyl group is not particularly limited as long as it is a cycloalkyl group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom.
  • a 1-fluorocyclopropyl group a 2-fluorocyclopropyl group 2,2-difluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, pentafluorocyclopropyl group, 2,2-difluorocyclobutyl group, 2,2,3,3-tetrafluorocyclo Butyl group, 2,2,3,3,4,4-hexafluorocyclobutyl group, heptafluorocyclobutyl group, 1-fluorocyclopentyl group, 3-fluorocyclopentyl group, 3,3-difluorocyclopentyl group, 3,3 , 4,4-tetrafluorocyclopentyl group, nonafluoro
  • the fluorobicycloalkyl group is not particularly limited as long as it is a bicycloalkyl group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom.
  • the fluoroalkenyl group is not particularly limited as long as it is an alkenyl group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom.
  • the fluoroalkynyl group is not particularly limited as long as it is an alkynyl group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom.
  • a fluoroethynyl group, a 3-fluoro-1-propynyl group, 3, Examples include a 3-difluoro-1-propynyl group, a 3,3,3-trifluoro-1-propynyl group, a 1-fluoro-2-propynyl group, and a 1,1-difluoro-2-propynyl group.
  • the fluoroaryl group is not particularly limited as long as it is an aryl group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom.
  • fluoroaryl group a cyano group, a chlorine atom, a bromine atom, iodine, etc. are considered in consideration of the balance of the solubility of the fluorine atom-containing oligoaniline derivative in an organic solvent, the availability of raw materials for the fluorine atom-containing oligoaniline derivative, and the like.
  • Substituted with 3 or more fluorine atoms which may be substituted with an atom, a nitro group, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkoxy group having 1 to 20 carbon atoms
  • a phenyl group is preferred.
  • the fluoroalkoxy group is not particularly limited as long as it is an alkoxy group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom.
  • the fluoroalkyl group having 1 to 20 carbon atoms, the fluorocycloalkyl group having 3 to 20 carbon atoms, the fluorobicycloalkyl group having 4 to 20 carbon atoms, the fluoroalkenyl group having 2 to 20 carbon atoms, or the fluoro having 2 to 20 carbon atoms As an aryl group having 6 to 20 carbon atoms that may be substituted with an alkynyl group and optionally substituted with a cyano group, a halogen atom, or a fluoroalkoxy group having 1 to 20 carbon atoms (hereinafter also referred to as a substituted aryl group for convenience)
  • at least one hydrogen atom on the carbon atom is a fluoroalkyl group having 1 to 20 carbon atoms, a fluorocycloalkyl group having 3 to 20 carbon atoms, a fluorobicycloalkyl group having 4 to 20 carbon atoms, or 2 to 20 carbon atoms.
  • the substituted aryl group includes a fluorocycloalkyl group having 3 to 20 carbon atoms in consideration of the balance between the solubility of the fluorine atom-containing oligoaniline derivative in an organic solvent and the availability of the raw material for the fluorine atom-containing oligoaniline derivative.
  • a fluorobicycloalkyl group having 4 to 20 carbon atoms a fluoroalkenyl group having 2 to 20 carbon atoms, or a fluoroalkynyl group having 2 to 20 carbon atoms, and a cyano group, a halogen atom, or a fluoro having 1 to 20 carbon atoms
  • a phenyl group which may be substituted with an alkoxy group (hereinafter also referred to as a substituted phenyl group for convenience) is preferred, and a phenyl group substituted with 1 to 3 trifluoromethyl groups is more preferred, and p-trifluoromethylphenyl Groups are even more preferred.
  • the fluoroaralkyl group is not particularly limited as long as it is an aralkyl group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom.
  • the aralkyl group having 7 to 20 carbon atoms that is substituted with an alkynyl group and optionally substituted with a cyano group, a halogen atom, or a fluoroalkoxy group having 1 to 20 carbon atoms includes at least one hydrogen on the carbon atom
  • A is preferably the optionally substituted fluoroalkyl group having 1 to 20 carbon atoms, the optionally substituted fluoroaryl group having 6 to 20 carbon atoms, or the substituted aryl group.
  • the optionally substituted fluoroaryl group having 6 to 20 carbon atoms or the substituted aryl group is more preferable, the optionally substituted fluorophenyl group or the substituted phenyl group is more preferable, and the substituted aryl group may be substituted.
  • n 1 is an integer of 1 to 20, preferably 2 to 10, more preferably 2 to 8, even more preferably 3 to 5, and still more preferably 3 to 4.
  • the fluorine atom-containing oligoaniline derivative is obtained by reacting an amine compound represented by the formula (7) with a fluorine atom-containing acid halide represented by the formula (8), as represented by Scheme A below. Can be synthesized. At this time, the reaction is preferably performed in the presence of a base for the purpose of allowing the reaction to proceed more efficiently.
  • X represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a chlorine atom or a bromine atom.
  • Examples of the amine compound represented by the formula (7) include, but are not limited to, those represented by the following formula.
  • Examples of the fluorine atom-containing acid halide represented by the formula (8) include 2-fluorobenzoyl chloride, 3-fluorobenzoyl chloride, 4-fluorobenzoyl chloride, 2-fluoro-4-methylbenzoyl chloride, 2-fluoro-5.
  • Examples of the base include alkoxides such as t-butoxy sodium (t-BuONa) and t-butoxy potassium; fluoride salts such as lithium fluoride, potassium fluoride and cesium fluoride; sodium carbonate, potassium carbonate, sodium bicarbonate, Carbonates such as potassium hydrogen carbonate; trimethylamine, triethylamine, diisopropylethylamine, tetramethylethylenediamine, pyridine, morpholine, N-methylmorpholine, quinuclidine, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, etc.
  • the amines are not particularly limited as long as they are used for this kind of reaction. In particular, triethylamine, pyridine, diisopropylethylamine and the like are preferable because they are easy to handle.
  • the reaction solvent is preferably an aprotic polar organic solvent, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, tetrahydrofuran And dioxane.
  • N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dioxane and the like are preferable.
  • the reaction temperature is appropriately set in the range from the melting point to the boiling point of the solvent in consideration of the type and amount of the raw material compound and catalyst used, but is usually about 0 to 200 ° C., preferably 20 to 150 ° C. .
  • the reaction time varies depending on the starting compound used, the type and amount of the catalyst, the reaction temperature, and the like, and thus cannot be generally defined, but is usually about 1 to 24 hours.
  • the target fluorine atom-containing oligoaniline derivative can be obtained by post-treatment according to a conventional method.
  • the fluorine atom-containing acid halide represented by the formula (8) is a corresponding fluorine atom-containing carboxylic acid such as thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, etc. It can be obtained by reacting with an electrophilic halogenating agent.
  • a commercially available product may be used, and a known method (for example, JP-A-9-67303, JP-A-9-67304, JP-A-2002-284733, etc.) may be used. It can also be synthesized by the method described.
  • organic solvent used when preparing the varnish for forming a charge transporting thin film a good solvent capable of dissolving the charge transporting substance and the dopant well can be used.
  • solvents examples include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylbutyramide, N, N-diethylbutyramide, N, N-methylethylbutyramide, N , N-dimethylisobutyramide, N, N-diethylisobutyramide, N-ethyl-N-methylisobutyramide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and the like, It is not limited to these. These solvents can be used alone or in combination of two or more. The amount used can be 5 to 100% by mass in the solvent used for the varnish.
  • the charge transporting substance, the dopant and the like are completely dissolved in the solvent.
  • organic solvents may be included in addition to the organic solvent for the purpose of improving the wettability to the substrate, adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, and the like.
  • organic solvents Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol (hexylene glycol), 1,3-octylene glycol, 3,6-octyl Glycols such as lenglycol; Triols such as glycerin; Ethylene glycol monoalkyl ethers such as ethylene glycol
  • Alkylene glycol monoaryl ethers such as ethylene glycol monoaryl ethers such as ethylene glycol monophenyl ether, propylene glycol monoaryl ethers such as propylene glycol monophenyl ether; Alkylene glycol monoaralkyl ethers such as ethylene glycol monoaralkyl ethers such as ethylene glycol monobenzyl ether and propylene glycol monoaralkyl ethers such as propylene glycol monobenzyl ether; Alkylene glycol alkoxyalkyl ethers such as ethylene glycol alkoxyalkyl ethers such as ethylene glycol butoxyethyl ether, propylene glycol alkoxyalkyl ethers such as propylene glycol butoxyethyl ether; Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropy
  • Alkyl aryl ethers Alkyl aralkyl ethers such as ethyl benzyl ether; Cyclic alkyl monoethers such as 2-methylfuran, tetrahydrofuran, tetrahydropyran; Cyclic alkyl diethers such as 1,4-dioxane; Cyclic alkyl triethers such as trioxane; Diepoxyalkyl ethers such as diglycidyl ether; Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, s-butyl acetate, t-butyl acetate, n-pentyl acetate, (3-methylbutyl) acetate, n-hexyl acetate, (2-ethylbutyl ) Alkyl acetates such as linear or branched alkyl acetate
  • organic solvents other than good solvents may include glycols, triols, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, dialkylene glycol monoalkyl ethers, dialkylene glycol dialkyl ethers.
  • glycols, alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers are more preferable, and diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol Ethyl ether, ethylene glycol propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol mono Butyl ether, propylene glycol monoisobut
  • Ethylene glycol, dipropylene glycol, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, ethylene Containing glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether Are more preferable.
  • a varnish having desired liquid properties can be easily prepared by selecting a solvent to be used from such solvents while considering the type and amount of the charge transporting substance and the dopant.
  • the viscosity of the varnish of the present invention is appropriately set according to the thickness of the thin film to be produced and the solid content concentration, but is usually 1 to 50 mPa ⁇ s at 25 ° C., and its surface tension is usually 20 to 50 mN. / M.
  • the method for preparing the varnish for forming a charge transporting thin film is not particularly limited.
  • a method in which a charge transporting substance is first dissolved in a solvent and a dopant and a pentavalent hypervalent iodine compound are sequentially added thereto examples thereof include a method of dissolving a mixture of a transporting substance, a dopant, and a pentavalent hypervalent iodine compound in a solvent.
  • organic solvents when there are a plurality of organic solvents, these may be first dissolved in a solvent that dissolves the charge transporting substance, the dopant, and the pentavalent hypervalent iodine compound, and other solvents may be added thereto.
  • a charge transporting substance, a dopant, and a pentavalent hypervalent iodine compound may be dissolved sequentially or simultaneously in a mixed solvent of organic solvents.
  • the charge transporting thin film varnish is prepared by dissolving a charge transporting substance, a dopant, etc. in an organic solvent, and then using a sub-micron order filter or the like. It is desirable to filter.
  • a charge transporting thin film can be formed on a substrate by applying the varnish for forming a charge transporting thin film of the present invention on a substrate and baking it.
  • Examples of the varnish coating method include, but are not limited to, a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an ink jet method, a spray method, and a slit coating method.
  • a spin coating method, an ink jet method, and a spray method are preferable.
  • the varnish of the present invention in order to obtain a thin film having a uniform film formation surface and high charge transportability, considering the charge transporting substance, dopant, type of solvent, etc. included in the present invention, It is necessary to select a firing atmosphere (under an air atmosphere, under an inert gas such as nitrogen, under vacuum, etc.), but in most cases, a uniform thin film having excellent charge transportability is obtained by firing in the air atmosphere. be able to.
  • 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 transportability imparted to the obtained thin film, and the like. When used as, it is preferably about 140 to 250 ° C, more preferably about 150 to 230 ° C.
  • the varnish of the present invention is characterized by being capable of low-temperature baking at less than 200 ° C., particularly 150 to 190 ° C., so that a thin film having excellent charge transportability can be realized even when baking at a relatively low temperature. .
  • two or more steps of temperature change may be applied for the purpose of expressing higher uniform film forming property or allowing the reaction to proceed on the substrate. The heating may be performed using an appropriate device such as a hot plate or an oven.
  • the film thickness of the charge transporting thin film is not particularly limited, but is preferably 5 to 200 nm when used as a hole injection layer of an organic EL device.
  • a method for changing the film thickness there are methods such as changing the concentration of a charge transporting substance or the like in the varnish, or changing the amount of the solution on the substrate during coating.
  • the charge transporting thin film of the present invention can be suitably used as a hole injection layer in an organic EL device, but can also be used as a charge transporting functional layer such as a hole injection transport layer.
  • the organic EL device of the present invention has a pair of electrodes, and has the above-described charge transporting thin film of the present invention between these electrodes.
  • Typical configurations of the organic EL element include (a) to (f) below, but are not limited thereto.
  • an electron blocking layer or the like can be provided between the light emitting layer and the anode
  • a hole (hole) blocking layer or the like can be provided between the light emitting layer and the cathode.
  • the hole injection layer, the hole transport layer, or the hole injection transport layer may have a function as an electron block layer or the like
  • the electron injection layer, the electron transport layer, or the electron injection transport layer is a hole. It may have a function as a block layer or the like.
  • A 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 emission 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”, “hole transport layer” and “hole injection transport layer” are layers formed between a light emitting layer and an anode, and transport holes from the anode to the light emitting layer. It has a function. When only one layer of a hole transporting material is provided between the light emitting layer and the anode, it is a “hole injection transporting layer”, and a layer of the hole transporting material is provided between the light emitting layer and the anode. When two or more layers are provided, the layer close to the anode is a “hole injection layer”, and the other layers are “hole transport layers”. In particular, for the hole injection layer and the hole injection transport layer, a thin film that is excellent not only in accepting holes from the anode but also injecting holes into the hole transport layer and the light emitting layer is used.
  • Electrode “Electron injection layer”, “electron transport layer” and “electron injection transport layer” are layers formed between a light emitting layer and a 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 injecting and transporting 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 encouraging recombination of electrons and holes and confining excitons in the light emitting layer, and the dopant material efficiently emits excitons obtained by recombination. It has a function.
  • the host material mainly has a function of confining excitons generated by the dopant in the light emitting layer.
  • Examples of materials and methods for producing an organic EL device using the charge transporting thin film forming varnish of the present invention include the following, but are not limited thereto.
  • the electrode substrate to be used is preferably cleaned in advance by cleaning with a liquid such as a detergent, alcohol, or pure water.
  • a liquid such as a detergent, alcohol, or pure water.
  • the anode substrate is subjected to surface treatment such as UV ozone treatment or oxygen-plasma treatment immediately before use. It is preferable.
  • the surface treatment may not be performed.
  • An example of the method for producing the organic EL device of the present invention when the thin film obtained from the varnish for forming a charge transporting thin film of the present invention is a hole injection layer is as follows.
  • the charge transporting thin film forming varnish of the present invention is applied onto the anode substrate and baked to form a hole injection layer on the electrode.
  • a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are provided in this order.
  • the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer may be formed by either a vapor deposition method or a coating method (wet process) depending on the characteristics of the material used.
  • anode material examples include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), metal anodes typified by aluminum, alloys thereof, and the like. What performed the chemical conversion process is preferable. Polythiophene derivatives and polyaniline derivatives having high charge transporting properties can also be used.
  • metals constituting the metal anode include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, cadmium.
  • Materials for forming the hole transport layer include (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spirodimers, N, N′-bis (naphthalen-1-yl) -N, N′-bis (Phenyl) -benzidine ( ⁇ -NPD), N, N′-bis (naphthalen-2-yl) -N, N′-bis (phenyl) -benzidine, N, N′-bis (3-methylphenyl)- N, N′-bis (phenyl) -benzidine, N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -9,9-spirobifluorene, N, N′-bis ( Naphthalen-1-yl) -N, N′-bis (phenyl) -9,9-spirobifluorene, N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -9,9-s
  • Materials for forming the light emitting layer include tris (8-quinolinolato) aluminum (III) (Alq 3 ), bis (8-quinolinolato) zinc (II) (Znq 2 ), bis (2-methyl-8-quinolinolato)- 4- (p-phenylphenolate) aluminum (III) (BAlq), 4,4′-bis (2,2-diphenylvinyl) biphenyl, 9,10-di (naphthalen-2-yl) anthracene, 2-t -Butyl-9,10-di (naphthalen-2-yl) anthracene, 2,7-bis [9,9-di (4-methylphenyl) -fluoren-2-yl] -9,9-di (4- Methylphenyl) fluorene, 2-methyl-9,10-bis (naphthalen-2-yl) anthracene, 2- (9,9-spirobifluoren-2-yl) -9,9-spir
  • Materials for forming the electron injection layer include lithium oxide (Li 2 O), magnesium oxide (MgO), alumina (Al 2 O 3 ), lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride ( MgF 2 ), cesium fluoride (CsF), strontium fluoride (SrF 2 ), molybdenum trioxide (MoO 3 ), aluminum, lithium acetylacetonate (Li (acac)), lithium acetate, lithium benzoate, etc. .
  • cathode material examples include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, cesium and the like.
  • the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer are formed by sequentially forming the hole transport layer and the light emitting layer, instead of performing the vacuum deposition operation.
  • An organic EL device having a charge transporting thin film formed by the transportable thin film forming varnish can be produced.
  • the charge transporting thin film forming varnish of the present invention is applied on the anode substrate to prepare a hole injection layer by the above method, and a hole transport layer and a light emitting layer are sequentially formed thereon, Further, a cathode material is deposited to form an organic EL element.
  • the same materials as described above can be used, and the same cleaning treatment and surface treatment can be performed.
  • a hole transporting polymer material or a light emitting polymer material, or a material obtained by adding a dopant to these materials is dissolved or uniformly dispersed.
  • coating on a positive hole injection layer or a positive hole transport layer is mentioned.
  • Examples of the light-emitting polymer material include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene) (MEH). -PPV) and the like, polythiophene derivatives such as poly (3-alkylthiophene) (PAT), polyvinylcarbazole (PVCz) and the like.
  • PDAF poly (9,9-dialkylfluorene)
  • MEH 2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene
  • PVT polythiophene derivatives
  • PVCz polyvinylcarbazole
  • Examples of the solvent include toluene, xylene, chloroform and the like.
  • Examples of the dissolution or uniform dispersion method include methods such as stirring, heating and stirring, and ultrasonic dispersion.
  • the coating method is not particularly limited, and examples thereof include an inkjet method, a spray method, a dip method, a spin coating method, a transfer printing method, a roll coating method, and a brush coating.
  • the application is preferably performed under an inert gas such as nitrogen or argon.
  • the firing method a method of heating with an oven or a hot plate under an inert gas or in a vacuum can be mentioned.
  • An example of the method for producing the organic EL device of the present invention when the thin film obtained from the varnish for forming a charge transporting thin film of the present invention is a hole injection transport layer is as follows.
  • a hole injection transport layer is formed on the anode substrate, and a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are provided in this order on the hole injection transport layer.
  • Examples of the formation method and specific examples of the light emitting layer, the electron transport layer, and the electron injection layer include the same ones as described above.
  • Examples of the anode material, the light emitting layer, the luminescent dopant, the material for forming the electron transport layer and the electron block layer, and the cathode material include the same materials as described above.
  • a hole block layer, an electron block layer, or the like may be provided between the electrode and any of the layers as necessary.
  • a material for forming the electron blocking layer tris (phenylpyrazole) iridium and the like can be given.
  • the materials constituting the anode and the cathode and the layer formed between them differ depending on whether a device 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
  • a reflective anode made of metal is used in the opposite direction to the substrate.
  • Light is extracted from a certain transparent electrode (cathode) side. Therefore, for example, regarding the anode material, a transparent anode such as ITO is used when manufacturing an element having a bottom emission structure, and a reflective anode such as Al / Nd is used when manufacturing an element having a top emission structure.
  • the organic EL device of the present invention may be sealed together with a water catching agent or the like according to a standard method in order to prevent deterioration of characteristics.
  • Example 1-2 A varnish was obtained in the same manner as in Example 1-1 except that the content of Dess-Martin periodinane was changed to 20% by mass with respect to the charge transporting substance.
  • Example 1-3 A varnish was obtained in the same manner as in Example 1-1 except that the content of Dess-Martin periodinane was changed to 40% by mass with respect to the charge transporting substance.
  • Example 1-4 A varnish was obtained in the same manner as in Example 1-1 except that the content of Dess-Martin periodinane was changed to 60% by mass with respect to the charge transporting substance.
  • Example 2-1 The varnish 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 then baked at 150 ° C. for 15 minutes, and then 65 nm on the ITO substrate. A thin film was formed. On top of that, an aluminum thin film was formed using a vapor deposition device (degree of vacuum: 4.0 ⁇ 10 ⁇ 5 Pa) to obtain a single layer element. Vapor deposition was performed at a deposition rate of 0.2 nm / second. The film thickness of the aluminum thin film was 80 nm. In order to prevent characteristic deterioration due to the influence of oxygen, water, etc.
  • the single layer element was sealed with a sealing substrate, and then the characteristics were evaluated. Sealing was performed according to the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -85 ° C or less, the single layer element is placed between the sealing substrates, and the sealing substrate is bonded with an adhesive (MORESCO's Mores Moisture Cut WB90US (P)). Pasted together. At this time, a water catching agent (HD-071010W-40 manufactured by Dynic Co., Ltd.) was placed in a sealing substrate together with the single layer element. The bonded sealing substrate was irradiated with UV light (wavelength 365 nm, irradiation amount 6,000 mJ / cm 2 ), and then annealed at 80 ° C. for 1 hour to cure the adhesive.
  • UV light wavelength 365 nm, irradiation amount 6,000 mJ / cm 2
  • Example 2-2 to 2-4 Comparative Example 2-1
  • Example 2-1 In the same manner as in Example 2-1, except that the varnish obtained in Examples 1-2 to 1-4 and Comparative Example 1-1 was used instead of the varnish obtained in Example 1-1.
  • a single layer device was fabricated.
  • ITO substrate ITO was patterned with a film thickness of 150 nm on the surface in the same manner as in the above [2].
  • a 7 t glass substrate was used, and impurities on the surface were removed by an O 2 plasma cleaning apparatus (150 W, 30 seconds) before use.
  • Example 3-1 The varnish obtained in Example 1-1 was applied to an ITO substrate using a spin coater, then dried at 80 ° C. for 1 minute, and further baked at 150 ° C. for 15 minutes in an air atmosphere. A uniform thin film of 65 nm was formed. Subsequently, ⁇ -NPD was formed to a thickness of 30 nm at 0.2 nm / second on the ITO substrate on which the thin film was formed using a vapor deposition apparatus (vacuum degree: 1.0 ⁇ 10 ⁇ 5 Pa). Next, CBP and Ir (PPy) 3 were co-evaporated.
  • the deposition rate was controlled so that the concentration of Ir (PPy) 3 was 6%, and the layers were laminated to 40 nm.
  • a thin film of tris (8-quinolinolato) aluminum (III) (Alq 3 ), lithium fluoride and aluminum was sequentially laminated to obtain an organic EL device.
  • the deposition rate was 0.2 nm / second for Alq 3 and aluminum and 0.02 nm / second for lithium fluoride, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively.
  • the characteristic was evaluated. Sealing was performed according to the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -85 ° C or less, the organic EL element is placed between the sealing substrates, and the sealing substrate is bonded with an adhesive (XNR5516Z-B1 manufactured by Nagase ChemteX Corporation). It was. At this time, a water-absorbing agent (manufactured by Dynic Co., Ltd., HD-071010W-40) was placed in the sealing substrate together with the organic EL element. The bonded sealing substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ / cm 2 ), and then annealed at 80 ° C. for 1 hour to cure the adhesive.
  • UV light wavelength: 365 nm, irradiation amount: 6,000 mJ / cm 2
  • Examples 3-2 to 3-4, Comparative Example 3-1 In the same manner as in Example 3-1, except that the varnish obtained in Examples 1-2 to 1-4 and Comparative Example 1-1 was used instead of the varnish obtained in Example 1-1. An organic EL element was produced.
  • Table 23 shows drive voltage, current density, and current efficiency when the device was made to emit light at 5,000 cd / m 2 .
  • Table 24 shows the current density, luminance, and current efficiency when the device was driven at 9V.
  • Table 25 shows the half life of the element luminance (initial luminance of 5,000 cd / m 2 ).
  • the varnish containing the pentavalent hypervalent iodine compound as compared with the device comprising the thin film obtained from the varnish not containing the pentavalent hypervalent iodine compound (Comparative Example 3-1)
  • the device including the thin film obtained from the above has a low driving voltage when the light is emitted with the same luminance, and the luminance is improved when the light is emitted with the same driving voltage.
  • the element provided with a thin film obtained from a varnish containing a pentavalent hypervalent iodine compound was excellent in durability.

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  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne un vernis destiné à former une couche mince de transport de charges, comprenant un composé d'iode hypervalent pentavalent, une substance de transport de charges et un solvant organique.
PCT/JP2017/024896 2016-07-14 2017-07-07 Vernis destiné à former une couche mince de transport de charges WO2018012416A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004014511A (ja) * 2002-06-03 2004-01-15 Eastman Kodak Co 有機発光ダイオードデバイス
WO2005089024A1 (fr) * 2004-03-11 2005-09-22 Mitsubishi Chemical Corporation Composition pour une couche transportant des charges et pour un composé ionique, couche transportant des charges et composant électroluminescent organique utilisant celle-ci, procédé de fabrication d'un composant électroluminescent organique et procédé de fabrication de
JP2008297196A (ja) * 2007-05-30 2008-12-11 Samsung Electronics Co Ltd 伝導性の改善されたカーボンナノチューブ、その製造方法および該カーボンナノチューブを含有する電極
WO2013019021A2 (fr) * 2011-07-29 2013-02-07 주식회사 엘엠에스 Stratifié à base de graphène contenant un dopant et son procédé de fabrication
US20140061625A1 (en) * 2012-09-06 2014-03-06 Plextronics, Inc. Electroluminescent devices comprising insulator-free metal grids
JP2014169418A (ja) * 2013-03-05 2014-09-18 Toppan Printing Co Ltd 電荷輸送膜用インク、電荷輸送膜用インクに使用可能な芳香族オリゴヨードニウム塩および電荷輸送膜用インクを用いた電荷輸送膜の製造方法
WO2015050253A1 (fr) * 2013-10-04 2015-04-09 日産化学工業株式会社 Dérivés d'aniline et leurs utilisations
JP2015533184A (ja) * 2012-09-25 2015-11-19 メルク パテント ゲーエムベーハー 導電性ポリマーを含む配合物および有機電子素子におけるその使用
WO2016117521A1 (fr) * 2015-01-20 2016-07-28 日産化学工業株式会社 Vernis pour la formation de film mince de transport de charge

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004014511A (ja) * 2002-06-03 2004-01-15 Eastman Kodak Co 有機発光ダイオードデバイス
WO2005089024A1 (fr) * 2004-03-11 2005-09-22 Mitsubishi Chemical Corporation Composition pour une couche transportant des charges et pour un composé ionique, couche transportant des charges et composant électroluminescent organique utilisant celle-ci, procédé de fabrication d'un composant électroluminescent organique et procédé de fabrication de
JP2008297196A (ja) * 2007-05-30 2008-12-11 Samsung Electronics Co Ltd 伝導性の改善されたカーボンナノチューブ、その製造方法および該カーボンナノチューブを含有する電極
WO2013019021A2 (fr) * 2011-07-29 2013-02-07 주식회사 엘엠에스 Stratifié à base de graphène contenant un dopant et son procédé de fabrication
US20140061625A1 (en) * 2012-09-06 2014-03-06 Plextronics, Inc. Electroluminescent devices comprising insulator-free metal grids
JP2015533184A (ja) * 2012-09-25 2015-11-19 メルク パテント ゲーエムベーハー 導電性ポリマーを含む配合物および有機電子素子におけるその使用
JP2014169418A (ja) * 2013-03-05 2014-09-18 Toppan Printing Co Ltd 電荷輸送膜用インク、電荷輸送膜用インクに使用可能な芳香族オリゴヨードニウム塩および電荷輸送膜用インクを用いた電荷輸送膜の製造方法
WO2015050253A1 (fr) * 2013-10-04 2015-04-09 日産化学工業株式会社 Dérivés d'aniline et leurs utilisations
WO2016117521A1 (fr) * 2015-01-20 2016-07-28 日産化学工業株式会社 Vernis pour la formation de film mince de transport de charge

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