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WO2018173801A1 - Polymère contenant un atome de fluor et utilisation associée - Google Patents

Polymère contenant un atome de fluor et utilisation associée Download PDF

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Publication number
WO2018173801A1
WO2018173801A1 PCT/JP2018/009208 JP2018009208W WO2018173801A1 WO 2018173801 A1 WO2018173801 A1 WO 2018173801A1 JP 2018009208 W JP2018009208 W JP 2018009208W WO 2018173801 A1 WO2018173801 A1 WO 2018173801A1
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group
carbon atoms
bis
charge transporting
diyl
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PCT/JP2018/009208
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English (en)
Japanese (ja)
Inventor
博史 太田
直樹 中家
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日産化学株式会社
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Priority to CN201880002966.5A priority Critical patent/CN109563243B/zh
Priority to KR1020197000951A priority patent/KR102476004B1/ko
Priority to JP2019507543A priority patent/JP7056644B2/ja
Publication of WO2018173801A1 publication Critical patent/WO2018173801A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers

Definitions

  • the present invention relates to a fluorine atom-containing polymer and use thereof.
  • an organic electroluminescence (EL) element a charge transporting thin film made of an organic compound is used as a light emitting layer or a charge injection layer.
  • the hole injection layer is responsible for charge transfer between the anode and the hole transport layer or the light emitting layer, and plays an important function to achieve low voltage driving and high luminance of the organic EL element.
  • the method of forming the hole injection layer is roughly divided into a dry process typified by vapor deposition and a wet process typified by spin coating. Compared with these processes, the wet process is flatter in a larger area. A highly efficient thin film can be produced efficiently. Therefore, at the present time when the area of the organic EL display is being increased, a hole injection layer that can be formed by a wet process is desired.
  • the present inventors are applicable to various wet processes and charge transport that provides a thin film capable of realizing excellent organic EL element characteristics when applied to a hole injection layer of an organic EL element.
  • Compounds having good solubility in organic materials and organic solvents used therefor have been developed (see, for example, Patent Documents 1 to 4).
  • Patent Documents 1 to 4 there is a constant demand for improvements in wet process materials for hole injection layers, and in particular, there is a need for wet process materials that provide thin films with excellent charge transport properties.
  • the present invention has been made in view of the above circumstances, and provides a charge transporting varnish that gives a charge transporting thin film excellent in charge transporting property, flatness and uniformity with good reproducibility, and a material for the charge transporting varnish.
  • the object is to provide a compound.
  • a predetermined fluorine atom-containing polymer has excellent solubility in an organic solvent, and charge transportability comprising the fluorine atom-containing polymer.
  • a thin film obtained from a charge transporting varnish containing a substance, a dopant, and an organic solvent is excellent in charge transporting property, flatness and uniformity, and further, by using the thin film as a hole injection layer, an organic EL having excellent luminance characteristics. The inventors found that an element can be obtained and completed the present invention.
  • a fluorine atom-containing polymer represented by the following formula (1) or (2).
  • a 1 to A 3 each independently represents a fluoroalkanediyl group having 1 to 6 carbon atoms
  • Ar 1 to Ar 3 each independently represent an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms, and may be substituted with a halogen atom, a nitro group, a cyano group, or Z 1
  • Each Ar 1 , each Ar 2 and each Ar 3 may be the same or different from each other, and may be substituted with a heteroaryl group of 2 to 20;
  • R 1 to R 10 are each independently a halogen atom, a nitro group or a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a carbon atom optionally substituted with Z 1
  • An alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, or a carbon number optionally substituted with Z 2 Represents a 6 to 20 aryl group, a C2 to C20 heteroaryl group, a C6 to C20 aryloxy group or a C2 to C20 heteroaryloxy group, each having two or more R 1 to R 10 If so, each R 1 to R 10 may be the same or different from each other; Z 1 is a halogen atom, a nitro group or a cyano group, or an
  • Z 2 represents a halogen atom, a nitro group or 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.
  • Z 3 represents a halogen atom, a nitro group or a cyano group
  • p, q, t, u, w and x each independently represents an integer of 0 to 4
  • r, s, y and z each independently represents an integer of 0 to 4
  • k represents an integer of 1 or more.
  • A is a perfluoromethanediyl group, a perfluoroethane-1,2-diyl group, a perfluoropropane-1,3-diyl group, a perfluoropropane-2,2-diyl group, a perfluorobutane-1,4- 1.
  • a polymer compound according to 1 or 2 which is a diyl group, a perfluoropentane-1,5-diyl group or a perfluorohexane-1,6-diyl group. 4).
  • Ar 1 to Ar 3 are groups represented by the following formula (3).
  • R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or 6 to 20 carbon atoms.
  • R 13 and R 14 are each independently a halogen atom, a nitro group or a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or a carbon atom optionally substituted with Z 1
  • a and b each independently represents an integer of 0 to 3. ) 6).
  • a charge transport material comprising a fluorine atom-containing polymer of any one of 1 to 7.
  • a charge transporting varnish comprising 9.8 charge transporting material, a dopant, and an organic solvent.
  • An electronic device comprising the charge transporting thin film of 10.10.
  • An organic EL device comprising the charge transporting thin film of 12.10.
  • the charge transporting varnish containing the fluorine atom-containing polymer of the present invention By using the charge transporting varnish containing the fluorine atom-containing polymer of the present invention, a charge transporting thin film excellent in charge transporting property, flatness and uniformity can be obtained.
  • the charge transporting thin film having such characteristics can be suitably used as a thin film for electronic devices including organic EL elements.
  • this thin film by applying this thin film to a hole injection layer of an organic EL element, an organic EL element with a low driving voltage can be obtained.
  • the charge transporting varnish of the present invention can produce a thin film with excellent charge transportability with good reproducibility even when using various wet processes that can be formed into a large area, such as a spin coating method and a slit coating method, It can sufficiently cope with recent progress in the field of organic EL elements.
  • the charge transporting thin film of the present invention can be used as an antistatic film, an anode buffer layer of an organic thin film solar cell, or the like.
  • fluorine atom-containing polymer The fluorine atom-containing polymer of the present invention is represented by the following formula (1) or (2).
  • the nitrogen atom is preferably bonded to the meta position or the para position with respect to the bonding position of A 1 to A 3 in the benzene ring.
  • a 1 to A 3 represent a fluoroalkanediyl group having 1 to 6 carbon atoms.
  • the fluoroalkanediyl group is not particularly limited as long as part or all of the hydrogen atoms bonded to the carbon atoms of the alkanediyl group are substituted with fluorine atoms.
  • fluoroalkanediyl group examples include a monofluoromethanediyl group, a perfluoromethanediyl group, a 2,2,2-trifluoroethane-1,1-diyl group, a perfluoroethane-1,1-diyl group, Perfluoroethane-1,2-diyl group, 3-fluoropropane-1,2-diyl group, 3,3,3-trifluoropropane-1,1-diyl group, 1,1-difluoropropane-1,3 -Diyl group, perfluoropropane-1,1-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane-1,3-diyl group, perfluoropropane-2,2-diyl group, 2- Methyl-2-fluoropropane-1,3-diyl group, 3,4,4-trifluor
  • fluoroalkanediyl group a perfluoroalkanediyl group having 1 to 6 carbon atoms (that is, all hydrogen atoms bonded to carbon atoms of the alkanediyl group are substituted with fluorine atoms) is preferable.
  • Methanediyl group perfluoroethane-1,2-diyl group, perfluoropropane-1,3-diyl group, perfluoropropane-2,2-diyl group, perfluorobutane-1,4-diyl group, perfluoro Pentane-1,5-diyl group, perfluorohexane-1,6-diyl group and the like are preferable.
  • Ar 1 to Ar 3 each independently represents an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms. These groups are 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 1. Or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with Z 2 . Further, each Ar 1 , each Ar 2 and Ar 3 may be the same or different from each other, but are preferably the same group from the viewpoint of ease of synthesis of the polymer.
  • Ar 1 to Ar 3 are preferably groups derived from fluorene, benzene, naphthalene, biphenyl or derivatives thereof.
  • a group represented by the following formula (3) is preferable.
  • R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a carbon number of 6 Represents an aryl group having ⁇ 20 or a heteroaryl group having 2 to 20 carbon atoms.
  • R 11 and R 12 are both alkyl groups from the viewpoint of solubility in the solvent used for the varnish.
  • the alkyl group those having 4 to 10 carbon atoms are particularly preferable.
  • R 13 and R 14 are each independently a halogen atom, a nitro group or a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or a carbon atom optionally substituted with Z 1 It represents an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z 2 . When two or more R 13 and R 14 are present, each R 13 and R 14 may be the same as or different from each other.
  • a and b each independently represent an integer of 0 to 3, but from the viewpoint of improving the availability of the raw material compound, the solubility of the polymer of the present invention, the charge transportability, and the like. 0 to 2 are preferred, 0 or 1 is more preferred, and 0 is optimal. In particular, both a and b are preferably 0.
  • X 1 to X 4 each independently represent a crosslinkable group.
  • the crosslinkable group is preferably a polymerizable carbon-carbon double bond, or a group containing an oxirane ring or an oxetane ring. Specifically, those selected from groups represented by the following formula are preferred.
  • R a represents a hydrogen atom or a methyl group.
  • R b and R d each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group.
  • R c , R e and R f each independently represents an alkylene group having 1 to 8 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom.
  • R c , R e and R f are preferably an alkylene group having 1 to 8 carbon atoms which may contain an oxygen atom.
  • a broken line represents a bond.
  • Y 1 to Y 4 each independently represents a single bond or an arylene group having 6 to 20 carbon atoms.
  • the arylene group include 1,3-phenylene group, 1,4-phenylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 2,6-naphthylene group, 4, Examples include 4′-biphenylylene group.
  • Y 1 to Y 4 are preferably a single bond, a 1,3-phenylene group, or a 1,4-phenylene group.
  • Each Y 1 , each Y 2 , each Y 3 and each Y 4 may be the same or different from each other, but are preferably the same group from the viewpoint of ease of monomer synthesis.
  • R 1 to R 10 are each independently a halogen atom, a nitro group or a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 1 ,
  • An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, or Z 2 Represents an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a heteroaryloxy group having 2 to 20 carbon atoms, which may be substituted with When two or more R 1 to R 10 are present, each R 1 to R 10 may be the same as or different from each other.
  • Z 1 is a halogen atom, a nitro group or a cyano group, or an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkoxy having 1 to 20 carbon atoms, which may be substituted with Z 3.
  • Z 2 represents a halogen atom, a nitro group or 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.
  • Z 3 represents a halogen atom, a nitro group or a cyano group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group.
  • 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, bicyclohexyl group, bicycloheptyl group, Examples thereof include cyclic alkyl groups having 3 to 20 carbon atoms such as a bicyclooctyl group, a bicyclononyl group, and a bicyclodecyl group.
  • the alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include ethenyl group, n-1-propenyl group, n-2-propenyl group and 1-methylethenyl group.
  • the alkynyl group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1- Butynyl group, n-2-butynyl group, n-3-butynyl group, 1-methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n-4 -Pentynyl group, 1-methyl-n-butynyl group, 2-methyl-n-butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, n Examples include a -1-decynyl group, an n-1-pentadecynyl group, and
  • 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.
  • the alkoxy group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group.
  • the alkenyloxy group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include ethenyloxy group, n-1-propenyloxy group, n-2-propenyloxy group, -Methylethenyloxy group, n-1-butenyloxy group, n-2-butenyloxy group, n-3-butenyloxy group, 2-methyl-1-propenyloxy group, 2-methyl-2-propenyloxy group, 1- Ethylethenyloxy group, 1-methyl-1-propenyloxy group, 1-methyl-2-propenyloxy group, n-1-pentenyloxy group, n-1-decenyloxy group, n-1-eicocenyloxy group Etc.
  • the alkynyloxy group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include ethynyloxy group, n-1-propynyloxy group, n-2-propynyloxy group, n-1-butynyloxy group, n-2-butynyloxy group, n-3-butynyloxy group, 1-methyl-2-propynyloxy group, n-1-pentynyloxy group, n-2-pentynyloxy group, n -3-pentynyloxy group, n-4-pentynyloxy group, 1-methyl-n-butynyloxy group, 2-methyl-n-butynyloxy group, 3-methyl-n-butynyloxy group, 1,1-dimethyl- n-propynyloxy group, n-1-hexynyloxy group, n-1-decynyloxy group, n-1
  • aryloxy group having 6 to 20 carbon atoms include phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthryloxy group, 2-anthryloxy group, 9-anthryloxy Group, 1-phenanthryloxy group, 2-phenanthryloxy group, 3-phenanthryloxy group, 4-phenanthryloxy group, 9-phenanthryloxy group and the like.
  • heteroaryloxy group having 2 to 20 carbon atoms include 2-thienyloxy group, 3-thienyloxy group, 2-furanyloxy group, 3-furanyloxy group, 2-oxazolyloxy group, 4-oxazolyl Ruoxy group, 5-oxazolyloxy group, 3-isoxazolyloxy group, 4-isoxazolyloxy group, 5-isoxazolyloxy group, 2-thiazolyloxy group, 4-thiazolyloxy group, 5 -Thiazolyloxy group, 3-isothiazolyloxy group, 4-isothiazolyloxy group, 5-isothiazolyloxy group, 2-imidazolyloxy group, 4-imidazolyloxy group, 2-pyridyloxy group, 3-pyridyloxy group Group, 4-pyridyloxy group and the like.
  • R 1 to R 10 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.
  • p, q, t, u, w and x each independently represent an integer of 0 to 4
  • r, s, y and z each independently represent 0 to Represents an integer of 5, preferably 0 to 2, more preferably 0 or 1, from the viewpoint of improving the availability of the raw material compound, the solubility of the polymer of the present invention, the charge transporting property, and the like.
  • m and n represent the composition ratio of the left repeating unit (hereinafter referred to as repeating unit m) and the right repeating unit (hereinafter referred to as repeating unit n) in formula (1), respectively.
  • the fluorine atom-containing polymer represented by the formula (1) includes the repeating unit n as an essential unit, may include only the repeating unit n, or may include both the repeating units m and n.
  • m and n preferably satisfy 0.1 ⁇ m ⁇ 1, 0 ⁇ n ⁇ 0.9. 0.5 ⁇ m ⁇ 0.99 and 0.01 ⁇ n ⁇ 0.5 are more preferable, and 0.8 ⁇ m ⁇ 0.99 and 0.01 ⁇ n ⁇ 0.2 are satisfied. Even more preferred.
  • k represents an integer of 1 or more. k is preferably 500 or less, more preferably 100 or less, and even more preferably 50 or less.
  • the lower limit of the weight average molecular weight (Mw) of the fluorine atom-containing polymer of the present invention is preferably 1,000, more preferably 3,000, and still more preferably 5 from the viewpoint of improving the charge transport property of the polymer.
  • the upper limit is preferably 500,000, more preferably 100,000, and even more preferably 50,000, from the viewpoint of improving the solubility of the polymer.
  • Mw is a measured value in terms of polystyrene by gel permeation chromatography (GPC).
  • a 1 , A 2 , Ar 1 , X 1 , X 2 , Y 1 , Y 2 , R 1 to R 6 , p, q, r, s, t and u are the same as described above.
  • X A and X B each independently represent a halogen atom or a pseudohalogen group.
  • X C each independently represents a group represented by the following formula (7) or (8). (Wherein A 11 and A 12 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
  • a 13 represents an alkanediyl group having 1 to 20 carbon atoms. Represents a group or an arylene group having 6 to 20 carbon atoms.)
  • halogen atom alkyl group and aryl group are the same as those described above.
  • pseudohalogen group examples include fluoroalkylsulfonyloxy groups such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group, and nonafluorobutanesulfonyloxy group; aromatic sulfonyloxy groups such as benzenesulfonyloxy group and toluenesulfonyloxy group, and the like. It is done.
  • alkanediyl group having 1 to 20 carbon atoms represented by A 13 examples include an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, and 2,2-dimethylpropane-1,3- Diyl group, 2-ethyl-2-methylpropane-1,3-diyl group, 2,2-diethylpropane-1,3-diyl group, 2-methyl-2-propylpropane-1,3-diyl group, butane -1,3-diyl group, butane-2,3-diyl group, butane-1,4-diyl group, 2-methylbutane-2,3-diyl group, 2,3-dimethylbutane-2,3-diyl group Pentane-1,3-diyl group, pentane-1,5-diyl group, pentane-2,3-diyl group, pentane-2,4-d
  • Examples of the arylene group having 6 to 20 carbon atoms include 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 1,8-naphthylene group, 1,2-anthrylene group, and 2,3- Examples include an anthrylene group, a 1,2-phenanthrylene group, a 3,4-phenanthrylene group, and a 9,10-phenanthrylene group.
  • the reaction of Scheme A can be performed without a solvent, but is usually performed using a solvent. Any solvent can be used as long as it does not inhibit the reaction. Examples thereof include cyclic ethers such as tetrahydrofuran and 1,4-dioxane; N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc ), Amides such as N-methyl-2-pyrrolidone (NMP); ketones such as methyl isobutyl ketone and cyclohexanone; halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene; benzene, toluene, xylene and the like And aromatic hydrocarbons. These solvent can be used individually by 1 type or in mixture of 2 or more types. Of these, 1,4-dioxane, toluene, xylene and the like are particularly preferable.
  • the catalyst used in the above reaction includes [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride (PdCl 2 (dppf)), tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ).
  • the charging ratio of the aromatic compound represented by the formula (6) is 0.83 to 1 in terms of a molar ratio with respect to the total of the amine derivative represented by the formula (4) and the amine derivative represented by the formula (5). .2 is preferred.
  • what is necessary is just to set suitably the preparation ratio of the amine derivative represented by Formula (4), and the amine derivative represented by Formula (5) so that the composition ratio of the repeating units m and n may become the range mentioned above. .
  • the reaction temperature of the reaction is usually 40 to 200 ° C.
  • the reaction time is appropriately set depending on the reaction temperature, but is usually about 30 minutes to 50 hours.
  • the amine derivative represented by the formula (4) comprises an amine compound represented by the formula (9) and a halogenated compound represented by the formula (10) in the presence of a catalyst, as represented by Scheme B below.
  • An amine derivative represented by the formula (4-1) is subjected to a condensation reaction with the halogenated compound represented by the formula (11) and the halogenated compound represented by the formula (12).
  • a 1 , R 1 to R 4 , Y 1 , X A , p, q, r and s are the same as described above.
  • Y 1 ′ represents an aryl group having 6 to 20 carbon atoms.
  • Hal represents Represents a halogen atom or a pseudohalogen group.
  • the amine derivative represented by the formula (4) includes a halogenated compound represented by the formula (13), an amine compound represented by the formula (14), and the formula (15) as represented by the following scheme C.
  • the amine compound represented by formula (4-1) is subjected to a condensation reaction in the presence of a catalyst to synthesize the amine derivative represented by formula (4-1), and then the obtained amine derivative is reacted with a known halogenating agent. Can also be synthesized.
  • the charging ratio of the amine compound to the halogenated compound may be such that the total Hal group of the total halogenated compound is equal to or more than the equivalent of the total amount of NH groups of the total amine compound, but about 1 to 1.5 equivalent Is preferred.
  • the catalyst examples include copper catalysts such as copper chloride, copper bromide, copper iodide; Pd (PPh 3 ) 4 , Pd (PPh 3 ) 2 Cl 2 , Pd (dba) 2 , Pd 2 (dba) 3 , Examples thereof include palladium catalysts such as Pd (Pt-Bu 3 ) 2 and Pd (OAc) 2 . These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type. These catalysts may be used together with a known appropriate ligand.
  • the amount of the catalyst used can be 0.0001 to 0.5 mol with respect to 1 mol of the halogenated compound, but is preferably about 0.001 to 0.1 mol.
  • the amount used can be 0.5 to 50 equivalents relative to the metal complex to be used, but 1 to 10 equivalents is preferred.
  • halogenating agent known ones can be used, and specific examples include N-bromosuccinimide.
  • the amount of the halogenating agent used is preferably about 4 to 6 mol with respect to 1 mol of the compound represented by the formula (4-1).
  • Each reaction shown in Schemes B and C may be performed in a solvent.
  • a solvent the kind will not be specifically limited if it does not have a bad influence on reaction.
  • specific examples of solvents that can be suitably used in the condensation reaction include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, Dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether) , Tetrahydrofuran (THF), dioxane, 1,2-dimethoxye
  • the solvent that can be suitably used in the reaction with the halogenating agent include those exemplified as the solvent that can be used in the condensation reaction, and halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dibenzene). Chlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc.).
  • a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent to be used, and is particularly preferably about 0 to 200 ° C, more preferably 20 to 150 ° C.
  • the target amine derivative can be obtained by post-treatment according to a conventional method.
  • the amine derivative represented by the formula (5) is represented by the amine compound represented by the formula (16), the halogenated compound represented by the formula (17), and the formula (18) as represented by the following scheme D.
  • the resulting halogenated compound is reacted in the presence of a catalyst, and the resulting compound is further reacted with the halogenated compound represented by formula (10) to synthesize an amine derivative represented by formula (5-1).
  • the obtained amine derivative can be synthesized by reacting with a known halogenating agent.
  • Y 2 ′ represents an aryl group having 6 to 20 carbon atoms.
  • the charging ratio of the amine compound to the halogenated compound may be such that the total Hal group of the total halogenated compound is equal to or more than the equivalent of the total amount of NH groups of the total amine compound, but about 1 to 1.5 equivalent Is preferred.
  • the aromatic compound represented by the formula (6) can be synthesized by a conventionally known method.
  • a 1 , A 2 , Ar 1 , X 1 , X 2 , R 1 to R 6 , p, q, r, s, t and u are the same as above.
  • X D is independently Represents a halogen atom or a pseudohalogen group.
  • the amine derivative represented by the formula (4 ′) can be synthesized according to the methods shown in Schemes B and C. Further, the phenylamine derivative represented by the formula (5 ′) can be synthesized according to the method shown in Scheme D.
  • the compound represented by the formula (6 ′) can be synthesized by a conventionally known method.
  • the fluorine atom-containing polymer represented by the formula (2) is represented by, for example, an amine derivative represented by the formula (4 ′′) and a formula (6 ′′) as represented by the following scheme F.
  • a polymer obtained by condensation polymerization of an aromatic compound in the presence of a catalyst is reacted with a compound represented by formulas (9) and (10) to synthesize a terminal. it can.
  • R 7 to R 10 , A 3 , Ar 3 , X 3 , X 4 , Y 3 , Y 4 , X A , X C , w, x, y and z are the same as above)
  • the fluorine atom-containing polymer of the present invention can be suitably used as a charge transport material.
  • charge transportability is synonymous with conductivity and is synonymous with hole transportability.
  • the charge transporting substance may be a substance having a charge transporting property per se, or a substance having a charge transporting property when used together with a dopant.
  • the charge transporting varnish may be one that has charge transporting property itself, and the solid film obtained thereby may have charge transporting property.
  • the charge transporting varnish of the present invention comprises a charge transporting substance comprising the fluorine atom-containing polymer, a dopant, and an organic solvent.
  • the content of the charge transport material comprising the fluorine atom-containing polymer is preferably about 0.1 to 20% by mass in the varnish from the viewpoint of suppressing the precipitation of the charge transport material.
  • E represents a Group 13 element of the long-period periodic table
  • Ar 101 to Ar 104 are each independently an aryl group having 6 to 20 carbon atoms or a heteroaryl having 2 to 20 carbon atoms.
  • a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, an acyl group having 2 to 12 carbon atoms such as a cyano group, a nitro group or an acetyl group, or a halogen having 1 to 10 carbon atoms such as a trifluoromethyl group May be substituted with an alkyl group.
  • the group 13 element is preferably a boron atom, an aluminum atom, or a gallium atom, and more preferably a boron atom.
  • Examples of the aryl group having 6 to 20 carbon atoms and the heteroaryl group having 2 to 20 carbon atoms are the same as those described above.
  • M + represents an onium ion.
  • the onium ions include iodonium ions, sulfonium ions, ammonium ions, phosphonium ions, and the like, and iodonium ions represented by the following formula (10) are particularly preferable.
  • R 101 and R 102 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or an alkyl group having 6 to 20 carbon atoms.
  • the aryl group having 6 to 20 carbon atoms or the heteroaryl group having 2 to 20 carbon atoms may be substituted.
  • the content of the dopant is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3 with respect to the charge transporting substance.
  • the charge transporting varnish of the present invention may contain a charge transporting material that does not contain a fluorine atom, if necessary.
  • a charge transporting substance include charge transporting oligomers such as aniline derivatives, thiophene derivatives, and pyrrole derivatives.
  • the molecular weight of the charge transporting oligomer is usually 200 to 5,000, but from the viewpoint of preparing a varnish that gives a thin film having a high charge transporting property, it is preferably 300 or more, more preferably 400 or more, and even more preferably 500 or more. From the viewpoint of preparing a uniform varnish that gives a thin film with high flatness, it is preferably 4,000 or less, more preferably 3,000 or less, and even more preferably 2,000 or less.
  • an aniline derivative is preferable in consideration of the balance between solubility in an organic solvent and charge transporting property of the obtained thin film.
  • aniline derivatives include oligoaniline derivatives described in JP-A No. 2002-151272, oligoaniline compounds described in WO 2004/105446, oligoaniline compounds described in WO 2008/032617, Examples include oligoaniline compounds described in 2008/032616 and aryldiamine compounds described in International Publication No. 2013/042623. Examples thereof include aniline derivatives described in International Publication No. 2016/006674.
  • the usage ratio of the charge transporting material comprising the fluorine atom-containing polymer of the present invention to the charge transporting material containing no fluorine atom is determined by the organic EL obtained.
  • the charge transporting material comprising the fluorine atom-containing polymer of the present invention is preferably 0.1 to 5 by mass ratio with respect to the charge transporting material containing no fluorine atom.
  • Organic solvent As the organic solvent used when preparing the charge transporting varnish, a highly soluble solvent that can dissolve the charge transporting substance and the dopant well can be used. Since the fluorine atom-containing polymer of the present invention has high solubility even in a low polarity solvent, it is possible to use a low polarity solvent as a high solubility solvent.
  • examples of the low polarity solvent include cyclohexanone, anisole, chloroform, chlorobenzene, toluene, xylene, tetralin, cyclohexylbenzene, 3-phenoxytoluene, methyl benzoate and the like.
  • examples of the polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. These solvents can be used singly or in combination of two or more, and the amount used can be 5 to 100% by mass in the total solvent used in the varnish.
  • both the charge transporting substance and the dopant are completely dissolved in the solvent.
  • the varnish has a viscosity of 10 to 200 mPa ⁇ s, particularly 35 to 150 mPa ⁇ s at 25 ° C., and a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure (atmospheric pressure).
  • At least one high-viscosity organic solvent can be contained.
  • Examples of the high viscosity organic solvent include cyclohexanol, ethylene glycol, ethylene glycol diglycidyl ether, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, Examples include 2,3-butanediol, 1,4-butanediol, propylene glycol, hexylene glycol, and the like, but are not limited thereto.
  • the content thereof is preferably within a range where no solid is precipitated, and is preferably 5 to 90% by mass in the total solvent used for the varnish as long as no solid is precipitated.
  • solvents are used in an amount of 1 to 90% by weight, preferably 1 to 90%, based on the total solvent used in the varnish. It is also possible to mix at a ratio of 50% by mass.
  • solvents examples include propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether
  • solvents include, but are not limited to, ether acetate, diethylene glycol monoethyl ether, diacetone alcohol, ⁇ -butyrolactone, ethyl lactate, and n-hexyl acetate. These solvent can be used individually by 1 type or in mixture of 2 or more types.
  • 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.
  • the solid content concentration of the charge transporting varnish in 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 10.0 mass. In consideration of improving the coatability of the varnish, it is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 3.0% by mass.
  • solid content means what remove
  • a charge transporting thin film can be formed on a base material by applying the charge transporting varnish of the present invention on the base material and baking it.
  • Examples of the varnish coating method include, but are not limited to, a dip 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. It is preferable to adjust the viscosity and surface tension of the varnish depending on the coating method.
  • the firing atmosphere is not particularly limited, and a thin film having a uniform film formation surface and high charge transportability can be obtained not only in the air atmosphere but also in an inert gas such as nitrogen or in a vacuum. it can.
  • 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 in that it can be fired at a low temperature of less than 200 ° C. Even a thin film manufactured under such firing conditions has high flatness and high charge transportability.
  • two or more steps of temperature change may be applied for the purpose of developing a higher uniform film forming property or causing 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 can be about 5 to 200 nm when used in an organic EL device, and particularly 10 to 100 nm when used as a hole injecting and transporting layer. ⁇ 50 nm is more preferred, and 25 to 45 nm is even more preferred.
  • Examples of the method of changing the film thickness include a method of changing the solid content concentration in the varnish or changing the amount of the solution on the substrate at the time of application.
  • Organic EL device 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 used and methods for producing an organic EL device using the charge transporting 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 charge transporting varnish of the present invention is a hole injection layer is as follows.
  • the charge transporting varnish of the present invention is applied on 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 of a transporting varnish can be produced.
  • the charge transporting varnish of the present invention is applied onto the anode substrate, a hole injection layer is prepared by the above-described method, a hole transport layer and a light emitting layer are sequentially formed thereon, and further a cathode material Is evaporated to obtain 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 charge transporting varnish 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 light emitting 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.
  • ITO substrate As a substrate for evaluating electrical characteristics, a glass substrate of 25 mm ⁇ 25 mm ⁇ 0.7 t (hereinafter referred to as “indium tin oxide”) having a thickness of 150 nm patterned on its surface , Abbreviated as ITO substrate).
  • the ITO substrate was used after removing impurities on the surface using an O 2 plasma cleaning apparatus (150 W, 30 seconds).
  • Example 9 Production of organic EL device using charge transporting varnish A
  • the charge transporting varnish A prepared in Example 5 was applied to an ITO substrate using a spin coater, and then at 150 ° C in an air atmosphere. Baking for 10 minutes formed a uniform thin film of 50 nm on the ITO substrate. 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.
  • an organic EL device was obtained by sequentially laminating thin films of Alq 3 , lithium fluoride, and aluminum.
  • 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 adhesive (MORESCO Co., Ltd., Mores Moisture Cut WB90US (P)) Was pasted together. At this time, a water-absorbing agent (manufactured by Dynic Co., Ltd., HD-071010W-40) was placed in the sealing substrate together with the organic EL element. The bonded sealing 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 10 Preparation of organic EL device using charge transporting varnish B An organic EL device was prepared in the same manner as in Example 9 except that charge transporting varnish B was used instead of charge transporting varnish A. did.
  • Example 11 Preparation of organic EL device using charge transporting varnish C An organic EL device was prepared in the same manner as in Example 9 except that charge transporting varnish C was used instead of charge transporting varnish A. did.
  • Example 12 Preparation of organic EL device using charge transporting varnish D An organic EL device was prepared in the same manner as in Example 9 except that charge transporting varnish D was used instead of charge transporting varnish A. did.

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Abstract

L'invention concerne un polymère contenant un atome de fluor représenté par la formule (1) ou (2). (Dans les formules, A1 à A3 représentent chacun indépendamment un groupe fluoroalcanediyle en C1-6 ; X1 à X4 représentent chacun indépendamment un groupe de réticulation ; Ar1 à Ar3 représentent chacun indépendamment un groupe arylène en C6-20 facultativement substitué ou un groupe hétéroarylène en C2-20 ; Y1 à Y4 représentent chacun indépendamment une liaison simple ou un groupe arylène en C6-20 ; et R1 à R10 représentent chacun indépendamment un groupe halogéno, nitro, cyano, ou un groupe alkyle, alcényle, alcynyle, alcoxy, alcényloxy, alcynyloxy, aryle, hétéroaryle, aryloxy, ou hétéroaryloxy éventuellement substitué.)
PCT/JP2018/009208 2017-03-24 2018-03-09 Polymère contenant un atome de fluor et utilisation associée WO2018173801A1 (fr)

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KR20190125282A (ko) 2019-11-06
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TWI780131B (zh) 2022-10-11
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