WO2020122113A1 - Vernis à transport de charges - Google Patents

Vernis à transport de charges Download PDF

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Publication number
WO2020122113A1
WO2020122113A1 PCT/JP2019/048452 JP2019048452W WO2020122113A1 WO 2020122113 A1 WO2020122113 A1 WO 2020122113A1 JP 2019048452 W JP2019048452 W JP 2019048452W WO 2020122113 A1 WO2020122113 A1 WO 2020122113A1
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group
carbon atoms
charge
transporting
substituted
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PCT/JP2019/048452
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Japanese (ja)
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倉田　陽介
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日産化学株式会社
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Priority to JP2020559279A priority Critical patent/JP7351314B2/ja
Publication of WO2020122113A1 publication Critical patent/WO2020122113A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C07C309/43—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having at least one of the sulfo groups bound to a carbon atom of a six-membered aromatic ring being part of a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • 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]
    • H10K50/17—Carrier injection layers

Definitions

  • the present invention relates to a charge-transporting varnish.
  • organic electroluminescence (hereinafter referred to as "organic EL”) devices are expected to be put to practical use in the fields of displays and lighting, and various developments related to materials and device structures are aimed at low voltage drive, high brightness, long life, etc. Has been done.
  • a plurality of functional thin films are used in this organic EL element, and the hole injection layer, which is one of the functional thin films, transfers charge between the anode and the hole transport layer or the light emitting layer, and is a low layer of the organic EL element. It plays an important role in achieving voltage driving and high brightness.
  • the method of forming the hole injection layer is roughly classified into a dry process represented by vapor deposition and a wet process represented by spin coating. Comparing these processes, the wet process can efficiently manufacture a thin film having a large area and high flatness. Therefore, particularly in the field of displays, the wet process is often used not only for forming the hole injection layer but also for forming the upper layers such as the hole transport layer and the light emitting layer (see Patent Document 1).
  • the underlayer such as the hole injection layer is required to have resistance to the solvent used for coating the upper layer.
  • the present invention has been made in view of the above circumstances, and provides a thin film having good solvent resistance, and can realize an organic EL device having good characteristics when the thin film is applied to a hole injection layer or the like.
  • the purpose is to provide a charge transporting varnish.
  • the present inventor has conducted extensive studies in order to achieve the above-mentioned object, and as a result, a charge-transporting varnish containing a charge-transporting substance and a predetermined polymer compound having an NH group in the molecule thereof has a thin film excellent in solvent resistance.
  • the present invention has been completed by finding that an organic EL device having good characteristics can be obtained when this thin film is applied to a hole injection layer or the like.
  • a charge-transporting varnish comprising a charge-transporting substance, a polymer compound represented by the following formula (I), and an organic solvent:
  • R a1 to R a8 each independently have a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or may have an ether bond, a ketone bond or an ester bond, and have 1 to 20 carbon atoms. It represents an alkyl group, an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R a4 and R a8 are bonded to each other to form a single bond, a methylene group, —O—, or —NR.
  • R d1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • R b1 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with a halogen atom, a nitro group, an amino group or a hydroxy group
  • R b2 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl having 2 to 20 carbon atoms, which may be substituted with a halogen atom, a nitro group, an amino group or a hydroxy group.
  • the polymer compound is a charge-transporting varnish represented by the following formula (II): (In the formula, R a1 to R a3 , R a5 to R a7 , R b1 , R b2 and n have the same meanings as described above.) 3.
  • the polymer compound is a charge-transporting varnish represented by the following formula (III): (In the formula, R a1 to R a3 , R a5 to R a7 and n have the same meanings as described above.
  • R c1 to R c8 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, Or represents a hydroxy group.) 4.
  • An organic electroluminescence device comprising the charge transporting thin film of 8, 11.
  • the organic electroluminescent device according to 10, wherein the charge transporting thin film is a hole injecting layer or a hole transporting layer.
  • the charge-transporting varnish of the present invention contains a predetermined polymer compound having an NH group in the molecule, and by using this varnish, a charge-transporting thin film excellent in solvent resistance can be obtained.
  • a charge transporting thin film having excellent transparency and a high refractive index can be obtained.
  • This charge transporting thin film can be suitably used as a thin film for an electronic device such as an organic EL device, particularly as a thin film for an electronic device in which a thin film is laminated on the upper layer by a wet process.
  • the charge-transporting varnish of the present invention is characterized by containing a charge-transporting substance, a polymer compound represented by the formula (I), and an organic solvent.
  • charge transportability is synonymous with electroconductivity.
  • the charge-transporting varnish may be one having a charge-transporting property by itself, or a solid film obtained therefrom having a charge-transporting property.
  • R a1 to R a8 each independently have a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an ether bond, a ketone bond or an ester bond, and a carbon number of 1 to It represents an alkyl group having 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R a4 and R a8 are bonded to each other to form a single bond, a methylene group, —O—, or A —NR d1 — group (R d1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms) may be formed. ..
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl.
  • alkenyl group having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, n- Examples thereof include a 1-eicosenyl group.
  • aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4- Examples thereof include phenanthryl and 9-phenanthryl groups.
  • R a1 to R a8 are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or R a1 to R a a3 and R a5 to R a7 are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, and R a4 and R a8 are mutually A bonded single bond is preferable, and a single bond in which R a1 to R a3 and R a5 to R a7 are hydrogen atoms and R a4 and R a8 are bonded to each other is more preferable. Therefore, the polymer compound represented by formula (I) is preferably represented by formula (II), and more preferably represented by formula (II)-1.
  • R a1 to R a3 and R a5 to R a7 have the same meanings as described above.
  • R b1 is an aryl having 6 to 20 carbon atoms, which may be substituted with a halogen atom, a nitro group, an amino group or a hydroxy group.
  • R b2 represents an alkyl group having 1 to 20 carbon atoms, which may be substituted with a halogen atom, a nitro group, an amino group or a hydroxy group, and 6 to 6 carbon atoms.
  • R b1 and R b2 may be bonded to each other to form a ring together with the carbon atom to which they are bonded.
  • heteroaryl group having 2 to 20 carbon atoms examples include 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl.
  • examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms include those similar to the atoms and groups exemplified for R a1 to R a8 above.
  • the ring structure formed by R b1 and R b2 being bonded to each other and the carbon atom to which they are bonded is such that the benzene ring therein is substituted with a halogen atom, a nitro group, an amino group or a hydroxy group.
  • optionally a 9H-fluorene-9,9-diyl group and the like is optionally.
  • R b1 and R b2 are each an aryl group having 6 to 20 carbon atoms, or R b1 and R b2 are bonded to each other to form together with the carbon atom to which they are bonded, benzene therein.
  • a 9H-fluorene-9,9-diyl group whose ring may be substituted with a halogen atom, a nitro group, an amino group or a hydroxy group is preferable, and the above 9H-fluorene in which R b1 and R b2 are bonded to each other.
  • a -9,9-diyl group is more preferred. Therefore, the polymer compound represented by the formula (I) is more preferably the compound represented by the formula (III), and further preferably the compound represented by the formula (III)-1.
  • R a1 to R a3 and R a5 to R a7 have the same meanings as described above.
  • the bonding position of the bond in the diphenylamino skeleton or the carbazole skeleton is not particularly limited, but both the left and right bonds have a diphenylamino skeleton or a carbazole skeleton.
  • Para position is preferred with respect to NH.
  • n represents an integer of 2 or more, preferably 2 to 1000, and preferably 5 to 500. More preferable.
  • R c1 to R c8 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, or a hydroxy group, but a hydrogen atom is preferable.
  • the weight average molecular weight Mw of the polymer compound represented by the formula (I) used in the present invention is preferably 600 to 1,000,000, more preferably 600 to 200,000.
  • the weight average molecular weight in the present invention is a polystyrene conversion value by gel permeation chromatography.
  • Examples of the polymer compound represented by the formula (I) used in the present invention include, but are not limited to, those represented by the following formula.
  • n represents the same meaning as described above.
  • the polymer compound represented by the formula (I) includes a monomer represented by the formula (Ia) and a monomer represented by the formula (Ib), (Ic) or (Id), It can be synthesized by polymerizing by a known method such as an addition condensation reaction (for example, the method described in WO 2010/147155).
  • R a1 to R a8 , R b1 and R b2 have the same meanings as described above.
  • X 0 to X 4 each independently represent a hydrogen atom, a halogen atom or a pseudohalogen group.
  • the pseudohalogen group include (fluoro)alkylsulfonyloxy groups and aromatic sulfonyloxy groups.
  • the halogen atom are the same as above.
  • R b2 ′ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hetero group having 2 to 20 carbon atoms, which may be substituted with a halogen atom, a nitro group, an amino group or a hydroxy group.
  • R b2′′ represents a hydrogen atom. Examples of these halogen atom, alkyl group, aryl group and heteroaryl group include the same ones as described above.
  • the content ratio of the polymer compound in the charge-transporting varnish of the present invention is not particularly limited as long as it does not affect the charge-transporting property of the obtained thin film, but the solvent resistance and the charge of the obtained thin film are not limited.
  • the proportion of solids contained in the varnish is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, still more preferably 5 to 25% by mass, 10 to 20 mass% is more preferable.
  • solid content means a component other than a solvent.
  • the charge-transporting substance contained in the charge-transporting varnish of the present invention can be appropriately selected and used from various charge-transporting substances which are conventionally used in the field of organic EL.
  • charge-transporting substances which are conventionally used in the field of organic EL.
  • Specific examples thereof include oligoaniline derivatives, N,N'-diarylbenzidine derivatives, aniline derivatives such as N,N,N',N'-tetraarylbenzidine derivatives; oligothiophene derivatives, thienothiophene derivatives, thienobenzothiophene derivatives.
  • Derivatives such as thiophene derivatives; various hole transporting substances such as pyrrole derivatives such as oligopyrrole.
  • aniline derivatives and thiophene derivatives are preferable, aniline derivatives are more preferable, and charge transport with good transparency and refractive index is preferable.
  • an aniline derivative represented by the following formula (1) or (2) described in WO 2015/050253 is more preferable.
  • the molecular weight of the charge-transporting substance is not particularly limited, but from the viewpoint of preparing a uniform varnish that gives a thin film having high flatness, 200 to 9000 is preferable, and from the viewpoint of obtaining a thin film having high solvent resistance. , 300 or more is more preferable, 400 or more is more preferable, and from the viewpoint of preparing a uniform varnish that gives a highly flat thin film with high reproducibility, 8000 or less is more preferable, 7,000 or less is still more preferable, and 6000 or less is More preferably, 5000 or less is the most suitable.
  • the charge-transporting substance does not have a molecular weight distribution (dispersion degree is 1) (that is, a single molecular weight is preferable). ).
  • 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, Represents 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, and these halogen atoms and alkyl having 1 to 20 carbon atoms.
  • the group, the alkenyl group having 2 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the heteroaryl group having 2 to 20 carbon atoms are the same as those exemplified for the polymer compound represented by the above formula (I). The ones are listed.
  • alkynyl group having 2 to 20 carbon atoms examples include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl, 1-methyl- 2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n- Examples include butynyl, 1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n-1-pentadecynyl, n-1-eicosinyl groups and the like.
  • Ph 1 in the above formulas (1) and (2) represents a group represented by the 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, and a carbon number of 2 Represents an alkenyl group having 20 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, and specific examples thereof are the same as those described above. The ones are listed.
  • R 3 to R 6 are each 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 and a heteroaryl group having 2 to 20 carbon atoms which may be substituted with a halogen atom are preferable, and a hydrogen atom, a fluorine atom, a cyano group, or 1 carbon atoms which may be substituted with a halogen atom.
  • the alkyl group of 10 and a phenyl group which may be substituted with a halogen atom are more preferable, a hydrogen atom, a fluorine atom, a methyl group and a trifluoromethyl group are even more preferable, and a hydrogen atom is most preferable.
  • Ar 1 in the above formula (1) independently represents a group represented by any of the formulas (B1) to (B11), and particularly, in any one of the formulas (B1′) to (B11′).
  • the groups represented are preferred.
  • R 7 to R 27 , R 30 to R 51 and R 53 to R 154 may be each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a halogen atom, Diphenylamino group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms represents, R 28 and R 29 each independently may be substituted with Z 1, represents a heteroaryl group an aryl group or a C 2-20 carbon atoms 6 ⁇ 20, R 52 is hydrogen Atom, an alkyl group having 1 to 20 carbon atoms, which may be substituted with Z 4 , an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, or the number of carbon atoms which may be substituted
  • Z 1 is a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms, which may be substituted with Z 2.
  • Z 2 has 6 to 6 carbon atoms which may be substituted with a halogen atom, a nitro group, a cyano group or Z 3.
  • Z 20 represents an aryl group or a heteroaryl group having 2 to 20 carbon atoms
  • Z 3 represents a halogen atom, a nitro group or a cyano group
  • Z 4 is substituted with a halogen atom, a nitro group, a cyano group, or Z 5 .
  • Z 5 may be substituted with a halogen atom, a nitro group, a cyano group, or Z 3.
  • 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 those similar to the groups described above.
  • R 7 to R 27 , R 30 to R 51 and R 53 to R 154 are each a hydrogen atom, a fluorine atom, a cyano group, a diphenylamino group which may be substituted with a halogen atom, or a halogen atom.
  • Preferred are an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms optionally substituted with a halogen atom, and a heteroaryl group having 2 to 20 carbon atoms optionally substituted with 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, and a phenyl group which may be substituted with a halogen atom are more preferable, and a hydrogen atom, a fluorine atom, methyl More preferred are groups and trifluoromethyl groups, with hydrogen atoms being most preferred.
  • a 3-pyridyl group which may be substituted, a 4-pyridyl group which may be substituted by Z 1 and a methyl group which may be substituted by Z 4 are more preferable.
  • Ar 4's each independently represent an aryl group having 6 to 20 carbon atoms which may be substituted with an arylamino group having 6 to 20 carbon atoms.
  • aryl group having 6 to 20 carbon atoms include those similar to the groups described above.
  • Specific examples of the arylamino group having 6 to 20 carbon atoms include diphenylamino group, 1-naphthylphenylamino group, di(1-naphthyl)amino group, 1-naphthyl-2-naphthylamino group, di(2- Naphthyl)amino group and the like.
  • Ar 4 is 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.
  • R 52 has the same meaning as above.
  • Ar 2 in the above formula (1) each independently represents a group represented by any of the formulas (A1) to (A18).
  • DPA represents a diphenylamino group
  • Ar 4 , Z 1 , and Z 3 to Z 5 have the same meanings as described above.
  • R 155 represents 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 . Alternatively, it 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 Z 1 .
  • 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 .
  • 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 thereof include the same groups as those described above.
  • an aryl group of Z 1 is carbon atoms 6 also be ⁇ 20 substituted with a heteroaryl group which have 2-20 carbon atoms substituted with Z 1, with Z 4 alkyl group substituted-1 carbon atoms which may be 20, more preferably a hydrogen atom, Z 1 substituted by optionally 6 carbon atoms which may be ⁇ 14 aryl group, Z 1 carbon atoms which may be substituted with 2 More preferably, it is a heteroaryl group having 14 to 14 carbon atoms, an alkyl group having 1 to 10 carbon atoms which may be substituted by Z 4 , a hydrogen atom, an aryl group having 6 to 14 carbon atoms which may be substituted by Z 1 , and Z.
  • an alkyl group having a nitrogen-containing heteroaryl group Z 4 carbon atoms which may be substituted with 1 to 10 also 1-2 carbon atoms 14 substituted with 1, hydrogen atom is substituted with Z 1
  • Z 1 Optionally substituted phenyl group, 1 -naphthyl group optionally substituted by Z 1 , 2-naphthyl group optionally substituted by Z 1 , 2-pyridyl group optionally substituted by Z 1 ,
  • a 3-pyridyl group optionally substituted with 1 , a 4-pyridyl group optionally substituted with Z 1 , and a methyl group optionally substituted with Z 4 are more preferable.
  • Z more preferably an aryl group which may having 6 to 14 carbon atoms optionally substituted with 1, a phenyl group which may be substituted with Z 1, which may be substituted with Z 1 1-naphthyl group, substituted with Z 1
  • 2-naphthyl groups which may be present.
  • the aniline derivative represented by the formula (1) is more preferably the aniline derivative represented by the formula (1-1).
  • the aniline represented by the formula (1) can be synthesized relatively easily using a relatively inexpensive bis(4-aminophenyl)amine as a raw material compound and has excellent solubility in an organic solvent.
  • the derivative is preferably an aniline derivative represented by the formula (1-1).
  • Ph 1 and k have the same meanings as described above, and Ar 5 at the same time represents a group represented by any one of formulas (D1) to (D13).
  • ) To (D13') are preferred, and in particular, since a charge-transporting thin film having high transparency and a high refractive index is obtained, the group represented by the formula (D11) is More preferably, the group represented by formula (D11′-1) is even more preferable.
  • Specific examples of Ar 5 include the same groups as those described above as specific examples of groups suitable as Ar 1 .
  • the aniline derivative represented is preferably the aniline derivative represented by the formula (1-2).
  • Ar 6 at the same time represents a group represented by any one of the formulas (E1) to (E14). Also in this case, a charge-transporting thin film having high transparency and a high refractive index can be obtained.
  • the group represented by (E14) is preferable.
  • R 52 has the same meaning as above.
  • Ar 3 in the above formula (2) represents a group represented by any of the formulas (C1) to (C8), and particularly preferably a group represented by any of (C1′) to (C8′). .
  • K in the above formula (1) represents an integer of 1 to 10, but from the viewpoint of enhancing the solubility of the compound in an organic solvent, 1 to 5 is preferable, 1 to 3 is more preferable, and 1 or 2 is further Preferably, 1 is optimum.
  • 1 in the above formula (2) represents 1 or 2.
  • Z 1 is a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 2 , or Z.
  • alkenyl group having 2 to 10 carbon atoms which may have, alkynyl group which 2 carbon atoms which may be ⁇ 10 substituted with Z 2 preferably substituted by 2, halogen atom, nitro group, cyano group, substituted with Z 2 is 1 carbon atoms which may be 1-3 alkyl group, Z 2 substituted by 2 carbon atoms which may be 1-3 alkenyl group, an alkynyl group having Z 2 ⁇ 2 carbon atoms which may be substituted with 3 more preferably, a fluorine atom, an alkyl group of Z 2 ⁇ 1 carbon atoms which may be substituted by 3, alkenyl groups of Z 2 ⁇ 2 carbon atoms which may be substituted by 3, optionally substituted by Z 2 A good alkynyl group having 2 to 3 carbon atoms is even more preferable.
  • 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.
  • Z 2 is a halogen atom, a nitro group, a cyano group, an aryl group of Z 3 may be substituted having from 6 to 14 carbon atoms preferably, a halogen atom , A nitro group, a cyano group, and an aryl group having 6 to 10 carbon atoms which may be substituted with Z 3 are more preferable, and a fluorine atom and an aryl group having 6 to 10 carbon atoms which may be substituted with Z 3 are more preferable. More preferred is a phenyl group which may be substituted with a fluorine atom or Z 3 , and further preferred.
  • 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, and an alkynyl group having 2 to 10 carbon atoms which may be substituted by Z 3 are preferable, and are substituted with a halogen atom, a nitro group, a cyano group or Z 3.
  • an alkyl group having 1 to 3 carbon atoms may be, more preferably an alkynyl group Z 3 in the optionally substituted alkenyl group having a carbon number of 2 to 3 also, Z 3 ⁇ 2 carbon atoms which may be substituted with 3 , a fluorine atom, an alkyl group of Z 3 ⁇ carbon atoms 1 be replaced by 3, an optionally substituted alkenyl group having 2 to 3 carbon atoms in Z 3, which may be substituted with Z 3 carbon Alkynyl groups of the number 2-3 are even more preferred.
  • Z 3 is preferably a halogen atom, more preferably a fluorine atom.
  • Z 1 is a halogen atom, a nitro group, a cyano group or an alkyl group having 1 to 3 carbon atoms which may be substituted with Z 2.
  • group an alkenyl group of Z 2 ⁇ 2 carbon atoms which may be substituted with 1-3, an alkynyl group having 2 to 3 carbon atoms are preferable optionally substituted by Z 2, a halogen atom, optionally substituted by Z 2 More preferably, it is an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group optionally substituted with a fluorine atom or Z 2 .
  • Z 4 is 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 and an aryl group having 6 to 10 carbon atoms which may be substituted with Z 5 are more preferable, and a phenyl group which may be substituted with a fluorine atom and Z 5 are 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 which may be substituted with Z 3.
  • a halogen atom and an aryl group having 6 to 10 carbon atoms which may be substituted with Z 3 are more preferable, and a phenyl group which may be substituted with a fluorine atom and Z 3 are even more preferable.
  • Z 5 is a halogen atom, a nitro group, a cyano group, or 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 is preferably an alkynyl group which may having 2 or 3 carbon atoms optionally substituted by Z 3, halogen atom, optionally substituted by Z 3
  • An alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group optionally substituted with a fluorine atom or Z 3 is even more preferable.
  • Z 3 is preferably a halogen atom, more preferably a fluorine atom.
  • R 52 and R 155 include the following groups, but are not limited thereto. Among these, the formula (N1) is preferable.
  • the alkyl group, alkenyl group and alkynyl group preferably have 10 or less carbon atoms, more preferably 6 or less carbon atoms, and even more preferably 4 or less carbon atoms.
  • the carbon number of the aryl group and the heteroaryl group is preferably 14 or less, more preferably 10 or less, still more preferably 6 or less.
  • the aniline derivative represented by the formula (1), the formula (1-1), the formula (1-2) and the formula (2) should be produced by the method described in the above-mentioned WO 2015/050253. You can
  • the charge-transporting varnish of the present invention may contain a dopant substance for the purpose of improving its charge-transporting ability or the like depending on the use of the resulting thin film.
  • the dopant substance is not particularly limited as long as it is soluble in at least one solvent used for the varnish, and either an inorganic dopant substance or an organic dopant substance can be used.
  • the inorganic and organic dopant substances may be used alone or in combination of two or more.
  • the dopant substance exhibits its function as a dopant substance for the first time when, for example, a part of the molecule is removed by an external stimulus such as heating during firing in the process of obtaining a charge transporting thin film that is a solid film from varnish.
  • it may be an improved substance, for example, an aryl sulfonic acid ester compound in which a sulfonic acid group is protected by a group capable of leaving easily.
  • heteropolyacid is preferable as the inorganic dopant substance.
  • the heteropoly acid has a structure in which a hetero atom is located at the center of the molecule, which is represented by a Keggin type chemical structure represented by the formula (H1) or a Dawson type chemical structure represented by the formula (H2). It is a polyacid formed by condensation of isopoly acid, which is an oxygen acid such as vanadium (V), molybdenum (Mo), and tungsten (W), and an oxygen acid of a different element. Examples of such oxyacids of different elements 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, which may be used alone or in combination of two or more kinds. Good.
  • these heteropolyacids are available as commercial products, or can be synthesized by a known method.
  • the one kind of heteropolyacid is preferably phosphotungstic acid or phosphomolybdic acid, and phosphotungstic acid is most suitable.
  • one of the two or more heteropolyacids is preferably phosphotungstic acid or phosphomolybdic acid, more preferably phosphotungstic acid.
  • the heteropolyacid in the quantitative analysis such as elemental analysis, those having a large number of elements from the structure represented by the general formula, or those having a small number, those obtained as commercial products, or known synthesis As long as it is appropriately synthesized according to the method, it can be used in the present invention.
  • phosphotungstic acid is represented by the chemical formula H 3 (PW 12 O 40 ).nH 2 O
  • phosphomolybdic acid is represented by the chemical formula H 3 (PMo 12 O 40 ).nH 2 O.
  • P (phosphorus), O (oxygen) or W (tungsten) or Mo (molybdenum) in this formula or those obtained as commercial products Alternatively, it can be used in the present invention as long as it is appropriately synthesized according to a known synthesis method.
  • the mass of the heteropolyacid defined in the present invention does not mean the mass of pure phosphotungstic acid in the synthetic product or the commercial product (phosphotungstic acid content), but a commercially available form and a known synthesis. In the form that can be isolated by the method, it means the total mass in the state of containing water of hydration and other impurities.
  • the amount of the heteropolyacid used can be about 0.001 to 50.0 with respect to the charge transporting substance 1 in terms of mass ratio, preferably about 0.01 to 20.0, more preferably about 0.02. It is about 1 to 10.0.
  • a tetracyanoquinodimethane derivative or a benzoquinone derivative can be used as the organic dopant substance.
  • the tetracyanoquinodimethane derivative include 7,7,8,8-tetracyanoquinodimethane (TCNQ) and halotetracyanoquinodimethane represented by the formula (H3).
  • the benzoquinone derivative include tetrafluoro-1,4-benzoquinone (F4BQ), tetrachloro-1,4-benzoquinone (chloranil), tetrabromo-1,4-benzoquinone and 2,3-dichloro-5. 6-dicyano-1,4-benzoquinone (DDQ) and the like can be mentioned.
  • R 500 to R 503 each independently represent a hydrogen atom or a halogen atom, at least one of which is preferably a halogen atom, at least two of which are halogen atoms, and at least three of which are halogen atoms. It is more preferable that all are halogen atoms.
  • the halogen atom include the same ones 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 and 2-chloro-7,7,8,8-tetracyanoquinodimethane.
  • Examples include chloro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and the like.
  • the amount of the tetracyanoquinodimethane derivative and the benzoquinone derivative used is preferably 0.0001 to 100 equivalents, more preferably 0.01 to 50 equivalents, still more preferably 1 to 20 equivalents, relative to the charge transporting substance. is there.
  • the organic dopant substance is an electrically neutral onium comprising a monovalent or divalent anion represented by the following formula (a1) and a counter cation represented by the formulas (c1) to (c5). It is also possible to use borate salts.
  • each Ar independently represents an aryl group having 6 to 20 carbon atoms which may have a substituent or a heteroaryl group having 2 to 20 carbon atoms which may have a substituent; Represents an alkylene group having 1 to 20 carbon atoms, —NH—, an oxygen atom, a sulfur atom or —CN + —.
  • the alkylene group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methylene, methylmethylene, dimethylmethylene, ethylene, trimethylene and propylene. , Tetramethylene, pentamethylene, hexamethylene groups and the like.
  • the aryl group and the heteroaryl group the same ones as described above can be mentioned.
  • Suitable examples of the anion of the above formula (a1) include those represented by the formula (a2), but the anion is not limited thereto.
  • the amount of the onium borate salt used can be about 0.1 to 10 with respect to the charge transporting substance in terms of the substance amount (molar ratio).
  • the onium borate salt can be synthesized with reference to a known method described in, for example, JP-A-2005-314682.
  • an aryl sulfonic acid compound or an aryl sulfonic acid ester compound can also be preferably used.
  • arylsulfonic acid compound examples include benzenesulfonic acid, tosylic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzenesulfonic acid, dihexylbenzene.
  • aryl sulfonic acid compounds examples include aryl sulfonic acid compounds represented by formula (H4) or (H5).
  • a 1 represents O or S, and O is preferable.
  • a 2 represents a naphthalene ring or an anthracene ring, but a naphthalene ring is preferable.
  • a 3 represents a divalent to tetravalent perfluorobiphenyl group, p represents the number of bonds between A 1 and A 3, and is an integer satisfying 2 ⁇ p ⁇ 4, but A 3 is perfluorobiphenyldiyl It is preferably a group, preferably a perfluorobiphenyl-4,4′-diyl group, and p is 2.
  • q represents the number of sulfonic acid groups bonded to A 2 , and is an integer satisfying 1 ⁇ q ⁇ 4, and 2 is optimal.
  • a 4 to A 8 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated group having 2 to 20 carbon atoms. It represents an alkenyl group, and 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 group, etc. Be done.
  • halogenated alkenyl group having 2 to 20 carbon atoms examples include perfluorovinyl, perfluoropropenyl (allyl) and perfluorobutenyl groups.
  • Other examples of the 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 hydrogen atom, halogen atom, cyano group, alkyl group having 1 to 10 carbon atoms, halogenated alkyl group having 1 to 10 carbon atoms, or alkenyl halide having 2 to 10 carbon atoms. It is preferable that at least three of A 4 to A 8 are a fluorine atom, and are a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 5 carbon atoms.
  • it is a fluorinated alkyl group or a fluorinated alkenyl group having 2 to 5 carbon atoms, and at least three of A 4 to A 8 are fluorine atoms, and a hydrogen atom, a fluorine atom, a cyano group, It is even more preferable that it is a perfluoroalkyl group having 1 to 5 carbon atoms or a perfluoroalkenyl group having 1 to 5 carbon atoms, and A 4 , A 5 and A 8 are fluorine atoms.
  • the perfluoroalkyl group is a group in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms
  • the perfluoroalkenyl group is a group in which all the hydrogen atoms of the 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, but 2 to 4 is preferable, and 2 is optimal.
  • the molecular weight of the aryl sulfonic acid compound used as the dopant substance is not particularly limited, but considering the solubility in an organic solvent when used together with the aniline derivative used in the present invention, preferably 2000 or less, more preferably It is 1500 or less.
  • the amount of the arylsulfonic acid compound used is, in terms of a substance amount (molar ratio), preferably about 0.01 to 20.0, and more preferably about 0.4 to 5.0 with respect to the charge transporting substance 1. ..
  • a commercially available product may be used, but it can also be synthesized by a known method described in WO 2006/025342, WO 2009/096352 and the like.
  • the aryl sulfonic acid ester compound the aryl sulfonic acid ester compound disclosed in International Publication No. 2017/217455, the aryl sulfonic acid ester compound disclosed in International Publication No. 2017/217457, and Japanese Patent Application No. 2017-243631 are disclosed. Examples thereof include the aryl sulfonate compound described above, and specifically, compounds represented by any of the following formulas (H6) to (H8) are preferable.
  • n is an integer satisfying 1 ⁇ n ⁇ 4, but 2 is preferable.
  • a 11 is an m-valent group derived from perfluorobiphenyl.
  • a 12 is —O— or —S—, but —O— is preferable.
  • a 13 is a (n+1)-valent group derived from naphthalene or anthracene, but a group derived from naphthalene is preferable.
  • R s1 to R s4 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R s5 is optionally substituted 2 to 20 carbon atoms. Is a monovalent hydrocarbon group.
  • linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl and n-hexyl groups.
  • 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 ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl.
  • alkyl groups such as groups; aryl groups such as phenyl, naphthyl and phenanthryl groups.
  • R s1 to R s4 is a straight chain alkyl group having 1 to 3 carbon atoms and the rest 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 linear alkyl group having 1 to 3 carbon atoms is preferably a methyl group.
  • R s5 is preferably a linear alkyl group having 2 to 4 carbon atoms or a phenyl group.
  • a 14 is an optionally substituted m-valent hydrocarbon group having 6 to 20 carbon atoms and containing one or more aromatic rings, and the hydrocarbon group is one or more. It is a group obtained by removing m hydrogen atoms from a hydrocarbon compound having 6 to 20 carbon atoms and containing an aromatic ring. Examples of such a hydrocarbon compound include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, phenanthrene and the like.
  • the hydrocarbon group may have a part or all of its hydrogen atoms further substituted with a substituent, and as such a substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a nitro atom.
  • a 14 is preferably a group derived from benzene, biphenyl or the like.
  • a 15 is —O— or —S—, but —O— is preferred.
  • a 16 is a (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and this aromatic hydrocarbon group is (n+1) from the aromatic ring of the aromatic hydrocarbon compound having 6 to 20 carbon atoms. It is a group obtained by removing individual hydrogen atoms. Examples of such an aromatic carbon compound include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene. Among them, A 16 is preferably a group derived from naphthalene or anthracene, more preferably a group derived from naphthalene.
  • R s6 and R s7 each independently represent a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group, and R s8 represents a linear or branched monovalent aliphatic group. It is a hydrocarbon group. However, the total carbon number 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, more preferably 10 or less.
  • linear or branched monovalent aliphatic hydrocarbon group examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, n-octyl, Alkyl groups having 1 to 20 carbon atoms such as 2-ethylhexyl and decyl groups; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as 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 atoms.
  • 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, Alternatively, 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 methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, Examples thereof include t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups.
  • the halogenated alkyl group having 1 to 10 carbon atoms is not particularly limited as long as it is a group in which some or all of the hydrogen atoms of the above alkyl group having 1 to 10 carbon atoms are replaced with halogen atoms.
  • Specific 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 group and the like.
  • the halogenated alkenyl group having 2 to 10 carbon atoms is not particularly limited as long as it is a group in which some or all of the hydrogen atoms of the alkenyl group having 2 to 10 carbon atoms are replaced with halogen atoms.
  • Specific examples include perfluorovinyl, perfluoro-1-propenyl, perfluoro-2-propenyl, perfluoro-1-butenyl, perfluoro-2-butenyl, perfluoro-3-butenyl groups and the like.
  • R s9 is preferably a nitro group, a cyano group, a halogenated alkyl group having 1 to 10 carbon atoms, a halogenated alkenyl group having 2 to 10 carbon atoms, and a nitro group, a cyano group, or 1 to 4 carbon atoms.
  • the halogenated alkyl group and the alkenyl group having 2 to 4 carbon atoms are more preferable, and the nitro group, the cyano group, the trifluoromethyl group, and the perfluoropropenyl group are even more preferable.
  • R s10 to R s13 a halogen atom is preferable, and a fluorine atom is more preferable.
  • a 17 is —O—, —S— or —NH—, but —O— is preferred.
  • a 18 is a (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and this aromatic hydrocarbon group is (n+1) from the aromatic ring of the aromatic hydrocarbon compound having 6 to 20 carbon atoms. It is a group obtained by removing individual hydrogen atoms. Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene. Among these, A 18 is preferably a group derived from naphthalene or anthracene, and more preferably a group derived from naphthalene.
  • R s14 to R s17 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms.
  • Specific examples of the monovalent aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n.
  • -Alkyl group having 1 to 20 carbon atoms such as heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl group; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl Examples thereof include alkenyl groups having 2 to 20 carbon atoms such as 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and hexenyl groups, and the like. Alkyl groups having 1 to 20 carbon atoms are preferable, and those having 1 to 20 carbon atoms are preferable. An alkyl group having 10 carbon atoms is more preferable, and an alkyl group having 1 to 8 carbon atoms is still more preferable.
  • 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 C 1 to C 20 monovalent aliphatic hydrocarbon group for R s18 include the same ones as described above.
  • R s18 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Even more preferable.
  • Examples of the monovalent hydrocarbon group having 2 to 20 carbon atoms of R s19 include the monovalent aliphatic hydrocarbon groups described above other than the methyl group, and aryl groups such as phenyl, naphthyl, and phenanthryl groups. Among these, R s19 is preferably a linear alkyl group having 2 to 4 carbon atoms or a phenyl group. Examples of the substituent that the above 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 aryl sulfonic acid ester compounds include, but are not limited to, those shown below.
  • the amount of the arylsulfonic acid ester compound used is preferably about 0.01 to 20 and more preferably about 0.05 to 10 with respect to the charge transporting substance 1 in terms of a substance amount (molar ratio).
  • aryl sulfonic acid compound or an aryl sulfonic acid ester compound as a dopant substance, which is soluble in a solvent.
  • the above charge transporting varnish is an organic silane compound for the purpose of improving the injection property into the hole transporting layer and improving the life characteristics of the device. May be included.
  • the content thereof is usually about 1 to 30 mass% with respect to the total mass of the charge transporting material and the dopant material.
  • a highly soluble solvent that can satisfactorily dissolve the charge-transporting substance and the dopant substance used as necessary can be used.
  • a highly soluble solvent include cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone and 1,3-dimethyl-2-imidazo.
  • organic solvents such as ridinone and diethylene glycol monomethyl ether, but are not limited thereto. These solvents may be used alone or in combination of two or more, and the amount thereof used may be 5 to 100% by mass based on the whole solvent used for the varnish. It is preferable that both the charge transporting substance and the dopant substance are completely dissolved in the above solvent.
  • the varnish contains a high-viscosity organic solvent having a viscosity of 10 to 200 mPa ⁇ s at 25° C., particularly 35 to 150 mPa ⁇ s, and a boiling point of 50 to 300° C., particularly 150 to 250° C. under normal pressure (atmospheric pressure).
  • a high-viscosity organic solvent having a viscosity of 10 to 200 mPa ⁇ s at 25° C., particularly 35 to 150 mPa ⁇ s, and a boiling point of 50 to 300° C., particularly 150 to 250° C. under normal pressure (atmospheric pressure).
  • 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 thereof include, but are not limited to, 2,3-butanediol, 1,4-butanediol, propylene glycol and hexylene glycol. These solvents may be used alone or in combination of two or more.
  • the addition ratio of the high-viscosity organic solvent to the entire solvent used in the varnish is preferably within a range in which solid does not precipitate, and the addition ratio is preferably 5 to 80% by mass as long as solid does not precipitate.
  • another solvent is used in an amount of 1 to 90% by mass, preferably 1 to 90% by mass, based on the total amount of the solvent used in the varnish. It is also possible to mix them in a proportion 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 thereof include, but are not limited to, monoethyl ether, diacetone alcohol, ⁇ -butyrolactone, ethyl lactate, and n-hexyl acetate. These solvents may be used alone or in combination of two or more.
  • the aniline derivative represented by the above formula (1) or (2) is used as the charge transporting substance, the case where the aniline derivative has a substituent on the nitrogen atom at the 9-position of carbazole, for example, When it does not have an NH structure in the molecule, preferably when it has substituents on all nitrogen atoms, it becomes easy to prepare a varnish using only the low polar solvent shown below.
  • the low polar solvent include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon solvents such as toluene, xylene, tetralin, cyclohexylbenzene and decylbenzene; 1-octanol, 1-nonanol, 1-decanol and the like.
  • Aliphatic alcoholic solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, etc.
  • Solvents methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, dimethyl phthalate, bis(2-ethylhexyl phthalate), dibutyl maleate, diisopropyl malonate, dibutyl oxalate, hexyl acetate, diethylene glycol monoethyl ether Examples thereof include ester solvents such as acetate and diethylene glycol monobutyl ether acetate. These may be used alone or in combination of two or more kinds.
  • the viscosity of the charge-transporting varnish is appropriately determined depending on 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.
  • the solid content concentration of the charge transporting varnish 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 10.0 mass. %, and from the viewpoint of improving the coating property 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 method for preparing the charge-transporting varnish is not particularly limited, but for example, solid components such as the polymer compound of formula (I) and the charge-transporting substance are dissolved in a highly soluble solvent, A method of adding a viscous organic solvent, a method of mixing a high-solubility solvent and a high-viscosity organic solvent, and dissolving the polymer compound of formula (I) or a charge-transporting substance therein, charge transport that can use a low-polarity solvent In the case of a volatile substance or a polymer compound, a method of dissolving a solid content in a low polar solvent may be used.
  • the charge-transporting varnish described above can be easily used to produce a charge-transporting thin film by using the varnish, and thus can be suitably used when producing an electronic element, particularly an organic EL element.
  • the charge-transporting thin film can be formed by applying the above-mentioned charge-transporting varnish on a base material and firing it.
  • the method for applying the varnish is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an inkjet method, a spray method, a slit coating method, and the like. It is preferable to adjust the viscosity and surface tension of the varnish accordingly.
  • the firing atmosphere of the charge-transporting varnish after coating is not particularly limited, and a thin film having a uniform film-forming surface and a high charge-transporting property can be formed not only in the air atmosphere but also in an inert gas such as nitrogen or vacuum. Although it can be obtained, depending on the type of the dopant substance used, firing the varnish in the atmosphere may provide a thin film having charge transportability with good reproducibility.
  • the firing temperature is appropriately set within the range of about 100 to 260° C. in consideration of the use of the obtained thin film, the degree of charge transporting property imparted to the obtained thin film, the type of solvent and the boiling point, etc.
  • the obtained thin film is used as a hole injection layer of an organic EL device, it is preferably about 140 to 250° C., more preferably about 145 to 240° C., but represented by the above formula (1) or formula (2).
  • the aniline derivative is used as the charge transporting substance, a thin film having a good charge transporting property can be obtained even by firing at a low temperature of 200° C. or lower.
  • the temperature may be changed in two or more steps for the purpose of exhibiting a higher uniform film-forming property or advancing the reaction on the base material during the baking. It suffices to use an appropriate device such as an oven.
  • the thickness of the charge transporting thin film is not particularly limited, but when used as a hole injecting layer, a hole transporting layer or a hole injecting and transporting layer of an organic EL device, the thickness thereof is usually 3 to 300 nm, preferably 5 nm. ⁇ 200 nm.
  • a method of changing the film thickness there are methods such as changing the solid content concentration in the varnish and changing the amount of the solution on the substrate at the time of coating.
  • the above charge transporting thin film When the above charge transporting thin film is applied to an organic EL element, the above charge transporting thin film can be provided between a pair of electrodes forming the organic EL element.
  • Typical configurations of the organic EL element include the following (a) to (f), but the invention is not limited thereto.
  • an electron blocking layer or the like may be provided between the light emitting layer and the anode, and a hole blocking layer or the like may be provided between the light emitting layer and the cathode.
  • the hole injecting layer, the hole transporting layer or the hole injecting and transporting layer may also have a function as an electron blocking layer, and the electron injecting layer, the electron transporting layer or the electron injecting and transporting layer may be holes (holes).
  • the "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.
  • the hole-transporting material is a “hole-injecting and transporting layer”, and between the light-emitting layer and the anode,
  • the layer close to the anode is the “hole injecting layer” and the other layers are the “hole transporting layer”.
  • the hole injecting (transporting) layer a thin film that is excellent not only in the hole accepting property from the anode but also in the hole injecting property to the hole transporting (light emitting) layer is used.
  • Electrode injection layer is layers formed between a light emitting layer and a cathode and having a function of transporting electrons from the cathode to the light emitting layer.
  • electron injecting and transporting layer 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 a layer of the electron transporting material is provided between the light emitting layer and the cathode.
  • 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 adopted.
  • 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. Have a function.
  • the host material has a function of mainly confining excitons generated by the dopant in the light emitting layer.
  • a charge-transporting thin film prepared from the charge-transporting varnish of the present invention has a function of being provided between an anode and a light-emitting layer such as a hole injection layer, a hole transport layer, and a hole injection transport layer in an organic EL device.
  • a light-emitting layer such as a hole injection layer, a hole transport layer, and a hole injection transport layer in an organic EL device.
  • it can be used as a film, it is usually suitable for a hole injection layer in which an upper layer is formed by coating because it has excellent solvent resistance as described above.
  • Examples of the materials and manufacturing method used for manufacturing an EL device using the charge transporting varnish of the present invention include, but are not limited to, the following materials.
  • An example of a method for manufacturing an OLED element having a hole injection layer made of a thin film obtained from the above charge transporting varnish is as follows.
  • the electrode is previously subjected to cleaning with alcohol, pure water, or the like, or surface treatment such as UV ozone treatment or oxygen-plasma treatment, to the extent that the electrode is not adversely affected.
  • a hole injection layer is formed on the anode substrate by the above method using the charge transporting varnish.
  • a hole transport layer, a light emitting layer, an electron transport layer/hole block layer, an electron injection layer, and a cathode metal are sequentially deposited.
  • a hole transport layer forming composition containing the hole transporting polymer and a light emitting layer forming composition containing the light emitting polymer are provided. Are used to form these layers by a wet process. If necessary, an electron blocking 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), a metal typified by aluminum, a metal anode composed of an alloy thereof, or the like. Those subjected to a flattening treatment are preferable. A polythiophene derivative or a polyaniline derivative having a high charge transporting property can also be used. Note that examples of the other metal forming the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.
  • (triphenylamine) dimer derivative As a material for forming the hole transport layer, (triphenylamine) dimer derivative, [(triphenylamine) dimer] spiro dimer, N,N'-bis(naphthalen-1-yl)-N,N'-bis (Phenyl)-benzidine ( ⁇ -NPD), 4,4′,4′′-Tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), 4,4′,4′′-Tris[1 -Triarylamines such as naphthyl(phenyl)amino]triphenylamine (1-TNATA), 5,5"-bis- ⁇ 4-[bis(4-methylphenyl)amino]phenyl ⁇ -2,2': Examples include oligothiophenes such as 5′,2′′-terthiophene (BMA-3T).
  • a metal complex such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo[h]quinoline, a bisstyrylbenzene derivative, a bisstyrylarylene derivative, (2-hydroxyphenyl)benzo.
  • Low-molecular light emitting materials such as metal complexes of thiazole and silole derivatives; poly(p-phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly(3-alkyl) Examples thereof include, but are not limited to, a system in which a light emitting material and an electron transfer material are mixed with a polymer compound such as thiophene) and polyvinylcarbazole.
  • 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, and the light emitting dopant may be a metal complex such as tris(2-phenylpyridine)iridium (III) (Ir(ppy) 3 ). Examples thereof include, but are not limited to, naphthacene derivatives such as rubrene, quinacridone derivatives, condensed polycyclic aromatic rings such as perylene, and the like.
  • Examples of the material for forming the electron transport layer/hole blocking layer include, but are not limited to, oxydiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, 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), sodium fluoride (NaF). But not limited thereto.
  • metal oxides such as lithium oxide (Li 2 O), magnesium oxide (MgO), and alumina (Al 2 O 3 ), lithium fluoride (LiF), sodium fluoride (NaF).
  • cathode materials include, but are not limited to, aluminum, magnesium-silver alloys, aluminum-lithium alloys, and the like.
  • Examples of the material forming the electron blocking layer include, but are not limited to, tris(phenylpyrazole)iridium and the like.
  • Examples of the hole transporting polymer include poly[(9,9-dihexylfluorenyl-2,7-diyl)-co-(N,N′-bis ⁇ p-butylphenyl ⁇ -1,4-diaminophenylene )], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(N,N′-bis ⁇ p-butylphenyl ⁇ -1,1′-biphenylene-4,4-diamine )], poly[(9,9-bis ⁇ 1′-penten-5′-yl ⁇ fluorenyl-2,7-diyl)-co-(N,N′-bis ⁇ p-butylphenyl ⁇ -1,4 -Diaminophenylene)], poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine]-endcapped with polysilcisquinoxane,
  • Examples of the light emitting polymer include poly(9,9-dialkylfluorene) (PDAF) and other polyfluorene derivatives, poly(2-methoxy-5-(2'-ethylhexoxy)-1,4-phenylenevinylene) (MEH- Examples thereof include polyphenylene vinylene derivatives such as PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).
  • PDAF poly(9,9-dialkylfluorene)
  • MEH- poly(2-methoxy-5-(2'-ethylhexoxy)-1,4-phenylenevinylene)
  • MEH- Examples thereof include polyphenylene vinylene derivatives such as PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).
  • the apparatus used is as follows. (1) MALDI-TOF-MS: manufactured by Bruker, autoflex III smartbeam (2) 1 H-NMR: JNM-ECP300 FT NMR SYSTEM manufactured by JEOL Ltd. (3) Substrate cleaning: Choshu Sangyo Co., Ltd. substrate cleaning equipment (depressurized plasma method) (4) Application of varnish: Spin coater MS-A100 manufactured by Mikasa Co., Ltd. (5) Film thickness measurement: manufactured by Kosaka Laboratory Co., Ltd. Fine shape measuring instrument Surfcoder ET-4000 (6) Fabrication of element: Choshu Sangyo Co., Ltd.
  • Multifunctional evaporation system C-E2L1G1-N (7) Measurement of current density of device: Multichannel IVL measuring device manufactured by E-HTC Co., Ltd. (8) Measurement of refractive index (n): Multi incident angle spectroscopic ellipsometer VASE manufactured by JA Woollam Japan (9) Measurement of extinction coefficient (k): Multi incident angle spectroscopic ellipsometer VASE manufactured by JA Woollam Japan
  • Examples 1-2 to 1-4 The addition amount of the polymer compound C was 0.037 g (ratio to solid content: 10% by mass), 0.144 g (ratio to solid content: 30% by mass), 0.223 g (ratio to solid content: 40% by mass). ), and a charge-transporting varnish was obtained in the same manner as in Example 1-1, except that the weight of the solvent was adjusted so that the solid content in the varnish was 5% by mass.
  • Example 1-1 A charge-transporting varnish was obtained in the same manner as in Example 1-1, except that the polymer compound C was not added and the weight of the solvent was adjusted so that the solid content in the varnish was 5% by mass. ..
  • the thin film obtained from the charge-transporting varnish of the present invention has a high refractive index and is obtained from the charge-transporting varnish of Comparative Example 2-1 containing no polymer compound C. It can be seen that the extinction coefficient is lower than that of the thin film.
  • Example 3-1 and Comparative example 3-1 The varnishes prepared in Example 1-1 and Comparative Example 1-1 were applied on an ITO substrate using a spin coater (500 rpm, 5 seconds ⁇ 2000 rpm, 20 seconds), respectively, and then dried at 120° C. for 1 minute, and further, The film was baked at 200° C. for 15 minutes to prepare a charge transporting thin film.
  • ITO indium tin oxide
  • Example 3-1 As shown in Table 2, since the charge-transporting thin film produced in Example 3-1 was produced from the varnish containing the polymer compound C, the film loss after applying toluene was small and the solvent resistance was high. It turns out to be excellent. In the thin film produced in Comparative Example 3-1, film roughness of about 5 nm occurred after dropping toluene, but in the thin film of Example 3-1, the film roughness did not occur.
  • Example 4-1 A charge transporting thin film was prepared in the same manner as in Example 3-1. An aluminum thin film was formed on this using a vapor deposition device (vacuum degree 4.0 ⁇ 10 ⁇ 5 Pa) to obtain a single layer element. The vapor deposition was performed under the conditions of a vapor deposition rate of 0.2 nm/sec. The thickness of the aluminum thin film was 80 nm.
  • Example 4-1 A single-layer element was produced in the same manner as in Example 4-1, except that the charge transporting thin film produced by the same method as in Comparative example 3-1 was used.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
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Abstract

La présente invention concerne un vernis à transport de charge, qui comprend un matériau de transport de charge, un composé à poids moléculaire élevé représenté par la formule (I) et un solvant organique, peut fournir un film mince hautement résistant aux solvants. Le film mince peut être appliqué à une couche d'injection de trous, etc., ce qui permet d'obtenir un élément électroluminescent organique ayant d'excellentes caractéristiques. (Ra1 à Ra8 représentent indépendamment un atome d'hydrogène, un groupe alkyle ayant de 1 à 20 atomes de carbone, un groupe alcényle ayant de 2 à 20 atomes de carbone, un groupe aryle ayant de 6 à 20 atomes de carbone, etc, à condition que Ra4 et Ra8 puissent être liés l'un à l'autre pour former une liaison simple, etc ; Rb1 représente un groupe aryle ayant de 6 à 20 atomes de carbone ou un groupe hétéroaryle ayant de 2 à 20 atomes de carbone ; Rb2 représente un groupe alkyle ayant de 1 à 20 atomes de carbone, un groupe aryle ayant de 6 à 20 atomes de carbone, un groupe hétéroaryle ayant de 2 à 20 atomes de carbone ou un atome d'hydrogène, à condition que Rb1 et Rb2 puissent être liés l'un à l'autre pour former un cycle conjointement avec l'atome de carbone auquel ces groupes sont attachés ; et n représente un nombre entier supérieur ou égal à 2.)
PCT/JP2019/048452 2018-12-13 2019-12-11 Vernis à transport de charges WO2020122113A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022018572A1 (fr) * 2020-07-24 2022-01-27 株式会社半導体エネルギー研究所 Dispositif électroluminescent, appareil électroluminescent, dispositif électronique et dispositif d'éclairage
WO2022034421A1 (fr) * 2020-08-12 2022-02-17 株式会社半導体エネルギー研究所 Dispositif électroluminescent, appareil électroluminescent, équipement électronique et appareil d'éclairage

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JPS61151545A (ja) * 1984-12-26 1986-07-10 Canon Inc 電子写真感光体
WO2010147155A1 (fr) * 2009-06-19 2010-12-23 日産化学工業株式会社 Novolaque de carbazole
WO2015050253A1 (fr) * 2013-10-04 2015-04-09 日産化学工業株式会社 Dérivés d'aniline et leurs utilisations
WO2015146957A1 (fr) * 2014-03-27 2015-10-01 日産化学工業株式会社 Vernis de transport de charge
WO2017217455A1 (fr) * 2016-06-16 2017-12-21 日産化学工業株式会社 Composé d'ester d'acide sulfonique et son utilisation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61151545A (ja) * 1984-12-26 1986-07-10 Canon Inc 電子写真感光体
WO2010147155A1 (fr) * 2009-06-19 2010-12-23 日産化学工業株式会社 Novolaque de carbazole
WO2015050253A1 (fr) * 2013-10-04 2015-04-09 日産化学工業株式会社 Dérivés d'aniline et leurs utilisations
WO2015146957A1 (fr) * 2014-03-27 2015-10-01 日産化学工業株式会社 Vernis de transport de charge
WO2017217455A1 (fr) * 2016-06-16 2017-12-21 日産化学工業株式会社 Composé d'ester d'acide sulfonique et son utilisation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022018572A1 (fr) * 2020-07-24 2022-01-27 株式会社半導体エネルギー研究所 Dispositif électroluminescent, appareil électroluminescent, dispositif électronique et dispositif d'éclairage
WO2022034421A1 (fr) * 2020-08-12 2022-02-17 株式会社半導体エネルギー研究所 Dispositif électroluminescent, appareil électroluminescent, équipement électronique et appareil d'éclairage

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