WO2017164158A1 - アリールアミン誘導体とその利用 - Google Patents
アリールアミン誘導体とその利用 Download PDFInfo
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- WO2017164158A1 WO2017164158A1 PCT/JP2017/011169 JP2017011169W WO2017164158A1 WO 2017164158 A1 WO2017164158 A1 WO 2017164158A1 JP 2017011169 W JP2017011169 W JP 2017011169W WO 2017164158 A1 WO2017164158 A1 WO 2017164158A1
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- NKCKVJVKWGWKRK-UHFFFAOYSA-N Brc(cc1)ccc1-c(cc1)ccc1N(c1ccccc1)c1ccccc1 Chemical compound Brc(cc1)ccc1-c(cc1)ccc1N(c1ccccc1)c1ccccc1 NKCKVJVKWGWKRK-UHFFFAOYSA-N 0.000 description 1
- COIDWLFXQNJMNO-UHFFFAOYSA-N C=Cc(cc1)ccc1N(c1ccc(C(C(F)(F)F)(C(F)(F)F)c(cc2)ccc2N(c2ccc(C=C)cc2)c(cc2)ccc2-c(cc2)ccc2N(c2ccccc2)c2ccccc2)cc1)c(cc1)ccc1-c(cc1)ccc1N(c1ccccc1)c1ccccc1 Chemical compound C=Cc(cc1)ccc1N(c1ccc(C(C(F)(F)F)(C(F)(F)F)c(cc2)ccc2N(c2ccc(C=C)cc2)c(cc2)ccc2-c(cc2)ccc2N(c2ccccc2)c2ccccc2)cc1)c(cc1)ccc1-c(cc1)ccc1N(c1ccccc1)c1ccccc1 COIDWLFXQNJMNO-UHFFFAOYSA-N 0.000 description 1
- INVXRXNAMKSBDO-UHFFFAOYSA-N C=Cc(cc1)ccc1Nc1ccc(C(C(F)(F)F)(C(F)(F)F)c(cc2)ccc2Nc2ccc(C=C)cc2)cc1 Chemical compound C=Cc(cc1)ccc1Nc1ccc(C(C(F)(F)F)(C(F)(F)F)c(cc2)ccc2Nc2ccc(C=C)cc2)cc1 INVXRXNAMKSBDO-UHFFFAOYSA-N 0.000 description 1
- 0 CN(*[Al])c1ccc(C(*)(*)c(cc2)ccc2N([Al]*)[Al]I)cc1 Chemical compound CN(*[Al])c1ccc(C(*)(*)c(cc2)ccc2N([Al]*)[Al]I)cc1 0.000 description 1
- GQALJPWSTONBJO-UHFFFAOYSA-N Cc1cc(N(c2ccccc2)c2ccccc2)ccc1-c(cc1)c(C)cc1N(c1ccc(C(C(F)(F)F)(C(F)(F)F)c(cc2)ccc2N(c2ccc(C=C)cc2)c(cc2)cc(C)c2-c(c(C)c2)ccc2N(c2ccccc2)c2ccccc2)cc1)c1ccc(C=C)cc1 Chemical compound Cc1cc(N(c2ccccc2)c2ccccc2)ccc1-c(cc1)c(C)cc1N(c1ccc(C(C(F)(F)F)(C(F)(F)F)c(cc2)ccc2N(c2ccc(C=C)cc2)c(cc2)cc(C)c2-c(c(C)c2)ccc2N(c2ccccc2)c2ccccc2)cc1)c1ccc(C=C)cc1 GQALJPWSTONBJO-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/56—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/156—Hole transporting layers comprising a multilayered structure
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/166—Electron transporting layers comprising a multilayered structure
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
Definitions
- the present invention relates to an arylamine derivative and its use.
- organic EL organic electroluminescence
- 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 have a charge transport property that provides a thin film that can realize excellent EL element characteristics when applied to a hole injection layer of an organic EL element.
- Compounds having good solubility in materials and organic solvents used therefor have been developed (see, for example, Patent Documents 1 to 4).
- the hole transport layer and the hole injection layer are required to be prepared by a wet process.
- the underlying hole transport layer and the hole injection / transport layer include Although the solvent resistance used in the composition for forming a light emitting layer is required, the materials of Patent Documents 1 to 4 have room for improvement in this respect.
- the present invention has been made in view of the above circumstances, and provides an organic solvent that exhibits good solubility in organic solvents and provides a thin film having solvent resistance, and also exhibits good characteristics when applied as a hole transport layer. It is an object to provide an arylamine derivative that provides an EL element.
- a given arylamine derivative having a crosslinkable group-containing aryl group has excellent solubility in an organic solvent, and converts it into an organic solvent.
- the varnish prepared by dissolving is heated to thermally crosslink the arylamine derivative, a thin film excellent in solvent resistance can be obtained, and when the thin film is applied to a hole transport layer of an organic EL device, it is good
- the present invention has been completed by finding that an element exhibiting excellent luminous efficiency can be obtained.
- Ar 2 independently represents at least one aryl group selected from the formulas (2) to (4)
- Z 1 represents a halogen atom, a nitro group, a cyano group A group, an amino group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 4
- Ar 3 represents a hydrogen atom or an aryl group having 6 to 20 carbon atoms which may be substituted with Z 2
- R 1 to R 39 each independently represents a hydrogen atom, a halogen atom, A nitro group, a cyano group, an amino group, 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 , and a carbon number which may be substituted with Z 3 alkyl group of 1 to 20, an alkenyl group or an alkynyl group having 2 to 20 carbon atoms carbon atoms
- arylamine derivative wherein R is a perfluoroalkyl group and R 1 to R 39 are all hydrogen atoms; 3. 1 or 2 arylamine derivatives in which the bridging group is a vinyl group, 4). Any one of arylamine derivatives 1 to 3, wherein Ar 1 is a 4-vinylphenyl group; 5.
- a charge transporting varnish comprising a charge transporting material comprising any of the arylamine derivatives 1 to 4 and an organic solvent, 6).
- a charge transporting thin film prepared from 5 charge transporting varnishes; 7).
- 6 or 7 charge transporting thin film for a hole transporting layer of an organic electroluminescence device 9.
- An organic electroluminescence device comprising 6 or 7 charge transporting thin films; 10.
- Organic electroluminescence device composed, 11.
- a step of applying a hole injection layer forming varnish on the anode and drying it to form a hole injection layer; and a charge transporting varnish of any one of 1 to 5 on the hole injection layer Applying and heating this to thermally crosslink the crosslinkable group of the arylamine derivative represented by the formula (1) to form a hole transport layer, and a method for producing an organic electroluminescence device, 12
- the manufacturing method of 11 organic electroluminescent elements including the process of apply
- the arylamine derivative of the present invention is easily soluble in an organic solvent, and it can be easily dissolved in an organic solvent to prepare a charge transporting varnish.
- the thin film prepared from the charge transporting varnish of the present invention exhibits high solvent resistance by cross-linking and curing in the arylamine derivative, so that it can be used for manufacturing a coating type device in which other functional layers are laminated by a coating method. Is suitable.
- the light emitting layer can be easily formed by a coating method.
- the thin film produced from the charge transportable varnish of the present invention exhibits high charge transportability, it can be suitably used as a thin film for electronic devices including organic EL elements.
- 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 arylamine derivative according to the present invention is represented by the formula (1).
- R independently represents a fluorine atom-containing alkyl group having 1 to 5 carbon atoms
- Ar 1 independently represents a carbon having a bridging group and optionally substituted with Z 1.
- Ar 2 independently represents at least one aryl group selected from formulas (2) to (4)
- Z 1 represents a halogen atom, a nitro group, or a cyano group
- Ar 1 is preferably the same as each other
- Ar 2 is preferably the same as each other, but is not limited thereto.
- the groups represented by formulas (2) to (4) are preferably the following groups from the viewpoint of ease of synthesis, but are not limited thereto.
- Ar 3 represents a hydrogen atom or an aryl group having 6 to 20 carbon atoms which may be substituted with Z 2
- R 1 to R 39 independently represent a hydrogen atom, a halogen atom, a nitro A group, a cyano group, an amino group, 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 , and an optionally substituted carbon atom with 1 Z 3
- Y 1 to Y 5 is each independently 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 , or a
- fluorine atom-containing alkyl group having 1 to 5 carbon atoms include fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2,2 -Pentafluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1, Examples include 2,2,3,3,4,4,4-nonafluorobutyl groups.
- 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.
- the crosslinking group possessed by the aryl group having 6 to 20 carbon atoms is not particularly limited as long as it is a group that can react with each other to form a crosslinked structure, but in the present invention, a vinyl group, an epoxy group, or an oxetane is used.
- acryloyl group (meth) acryloyl group, (meth) acryloyloxy group, cyclobutenyl group and the like are preferable, and among these, vinyl group is more preferable.
- the bridging group having a cyclic structure such as an epoxy group or a cyclobutenyl group may be condensed with an aryl 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.
- 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.
- alkenyl group having 2 to 20 carbon atoms include ethenyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n- Examples thereof include a 1-pentenyl group, an n-1-decenyl group, and an n-1-eicosenyl group.
- alkynyl group having 2 to 20 carbon atoms examples include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n-2-butynyl group, and n-3-butynyl.
- R is preferably a perfluoroalkyl group, and more preferably a trifluoromethyl group.
- Ar 1 includes 2-vinylphenyl group, 3-vinylphenyl group, 4-vinylphenyl group, 2-oxiranylphenyl group, 3-oxiranylphenyl group, 4-oxiranylphenyl group, 2-glycidyl A phenyl group, 3-glycidylphenyl group, 4-glycidylphenyl group, benzocyclobutenyl group and the like are preferable, and 4-vinylphenyl group is more preferable.
- Ar 3 is preferably a hydrogen atom or a phenyl group, and more preferably a phenyl group.
- R 1 to R 39 are preferably hydrogen atoms. Therefore, as Ar 2 , groups represented by the following formulas (10) to (12) are preferable, and groups represented by the formulas (13) to (15) are more preferable.
- R is a perfluoroalkyl group
- Ar 1 is a 4-vinylphenyl group
- Ar 2 is any group of the formulas (10) to (12).
- R 2 is preferably a perfluoroalkyl group
- Ar 1 is a 4-vinylphenyl group
- Ar 2 is any group of the formulas (13) to (15)
- both R are trifluoromethyl groups.
- the group, Ar 1 is a 4-vinylphenyl group
- Ar 2 is any group of the formulas (13) to (15).
- the arylamine derivative represented by the above formula (1) includes a diamine compound represented by the formula (5) and an aryl compound represented by the formula (6) or the formula (7), as shown in the following scheme: Are reacted in the presence of a catalyst to obtain a compound represented by formula (8) or formula (9), and then the compound represented by formula (8) or formula (9) and formula (7) or It can be produced by reacting an aryl compound represented by the formula (6).
- Examples of the halogen atom are the same as described above.
- Examples of pseudohalogen groups include (fluoro) alkylsulfonyloxy groups such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group, and nonafluorobutanesulfonyloxy group; aromatic sulfonyloxy groups such as benzenesulfonyloxy group and toluenesulfonyloxy group Is mentioned.
- the charging ratio of the diamine compound represented by the formula (5) and the aryl compound represented by the formula (6) or the formula (7), the diamine compound represented by the formula (9), the formula (7) or The charge ratio of the aryl compound represented by the formula (6) is preferably about 2 to 2.4 for the diamine compound 1 with respect to the diamine compound 1 in terms of substance amount (mol).
- Examples of the catalyst used in the above reaction include copper catalysts such as copper chloride, copper bromide, copper iodide; Pd (PPh 3 ) 4 (tetrakis (triphenylphosphine) palladium), Pd (PPh 3 ) 2 Cl 2 (bis (triphenylphosphine) dichloropalladium), Pd (dba) 2 (bis (dibenzylideneacetone) palladium), Pd 2 (dba) 3 (tris (dibenzylideneacetone) dipalladium), Pd (Pt Examples thereof include palladium catalysts such as —Bu 3 ) 2 (bis (tri (t-butylphosphine)) palladium) and Pd (OAc) 2 (palladium acetate).
- copper catalysts such as copper chloride, copper bromide, copper iodide
- Pd (PPh 3 ) 4 tetrakis (triphenylphosphine) palladium
- These catalysts may be used alone or in combination of two or more. These catalysts may be used together with a known appropriate ligand.
- ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-t-butylphosphine.
- the amount of the catalyst used can be about 0.2 mol with respect to 1 mol of the aryl compound represented by formula (6) or (7), but about 0.15 mol is preferable.
- the amount used can be 0.1 to 5 equivalents relative to the metal complex to be used, but 1 to 2 equivalents is preferred.
- the above reactions are carried out in a solvent.
- a solvent the type is not particularly limited as long as it does not adversely affect the reaction.
- Specific examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic Group hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene
- the reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used.
- the desired arylamine derivative can be obtained by post-treatment according to a conventional method.
- the charge transporting varnish of the present invention contains a charge transporting substance comprising an arylamine derivative represented by the formula (1) and an organic solvent.
- the organic solvent used for preparing the charge transporting varnish is not particularly limited as long as it can dissolve or disperse the arylamine derivative represented by the formula (1).
- the solid content concentration of the charge transporting varnish of the present invention is appropriately set in consideration of the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, etc., but is usually 0.1 to 10.0. It is about mass%, preferably 0.5 to 5.0 mass%, more preferably 1.0 to 3.0 mass%.
- solid content means components other than the organic solvent which comprises a varnish.
- the arylamine derivative and the organic solvent can be mixed in any order as long as the solid content is uniformly dissolved or dispersed in the solvent.
- varnish preparation is usually performed in an inert gas atmosphere at normal temperature and pressure, but in an air atmosphere (in the presence of oxygen) unless the compounds in the varnish are decomposed or the composition changes significantly. It may be performed while heating.
- the charge transporting varnish described above can be suitably used as a varnish for forming a charge transporting thin film such as an organic EL element.
- the charge transporting thin film can be produced by applying the charge transporting varnish of the present invention on a base and baking it.
- the charge transporting varnish of the present invention is preferably used as a varnish for forming a hole transport layer laminated on the hole injection layer.
- the coating method of 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, an ink jet method, a spray method, and a slit coating method. Accordingly, it is preferable to adjust the viscosity and surface tension of the varnish.
- the firing atmosphere is not particularly limited, and a thin film having a uniform film formation surface and a high charge transport property not only in the air atmosphere but also in an inert gas such as nitrogen or in a vacuum.
- the firing temperature is appropriately set within a range of about 100 to 260 ° C. in consideration of the intended use of the obtained thin film, the degree of charge transportability imparted to the obtained thin film, the type and boiling point of the solvent, and the like.
- the crosslinking reaction of the arylamine derivative represented by the formula (1) by the crosslinking group sufficiently proceeds to form a strong crosslinked structure, it is preferably about 180 to 250 ° C., preferably about 190 to 240 ° C. More preferred.
- a temperature change of two or more steps may be applied, and the heating may be performed using an appropriate device such as a hot plate or an oven. .
- the thickness of the charge transporting thin film is not particularly limited, but is preferably 5 to 200 nm when used as a hole transporting layer of an organic EL device.
- 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 during coating.
- the organic EL device of the present invention has a pair of electrodes, and has a hole transport layer or a hole injection transport layer made of the above-described charge transport thin film of the present invention between these electrodes.
- this hole transport layer when the light emitting layer laminated
- Typical examples 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, and 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, and 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.
- a hole injection transport layer In the case where only one layer of a hole transporting material is provided between the light emitting layer and the anode, it is a “hole injection transport layer”, and between the light emitting layer and the anode,
- the layer close to the anode is a “hole injection layer”, and the other layers are “hole transport layers”.
- 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 (light emitting) layer is used.
- Electrode injection layer “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.
- the layer of the electron transporting material is disposed between the light emitting layer and the cathode.
- 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 liquid cleaning with a detergent, alcohol, pure water or the like.
- 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.
- the example of the manufacturing method of the organic EL element which has a positive hole transport layer which consists of a thin film obtained from the charge transportable varnish of this invention is as follows. First, a hole injection layer is formed on the anode substrate, and the charge transporting varnish of the present invention is applied onto the hole injection layer by the method described above and baked to form a hole transport layer. On this, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are provided in this order.
- the hole injection layer, the light emitting layer, the electron transport layer, and the electron injection layer may be formed by any one of a vapor deposition method and 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. Other 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 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
- luminescent dopants examples include 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H-10-.
- Materials for forming the electron transport layer include 8-hydroxyquinolinolate-lithium, 2,2 ′, 2 ′′-(1,3,5-benztolyl) -tris (1-phenyl-1-H-benzimidazole) ), 2- (4-biphenyl) 5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 4, 7-diphenyl-1,10-phenanthroline, bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum, 1,3-bis [2- (2,2′-bipyridin-6-yl) -1,3,4-oxadiazo-5-yl] benzene, 6,6′-bis [5- (biphenyl-4-yl) -1,3,4-oxadiazo-2-yl] -2,2′- Bipyridine, 3- ( -Biphenyl
- 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, Li (acac), lithium acetate, lithium benzoate and the like.
- Examples of the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, cesium and the like.
- Materials for forming the hole injection layer include copper phthalocyanine, titanium oxide phthalocyanine, platinum phthalocyanine, pyrazino [2,3-f] [1,10] phenanthroline-2,3-dicarbonitrile, N, N, N ′.
- N′-tetrakis (4-methoxyphenyl) benzidine 2,7-bis [N, N-bis (4-methoxy-phenyl) amino] -9,9-spirobifluorene, 2,2′-bis [N , N-bis (4-methoxy-phenyl) amino] -9,9-spirobifluorene, N, N′-diphenyl-N, N′-di [4- (N, N-ditolylamino) phenyl] benzidine, N , N′-diphenyl-N, N′-di [4- (N, N-diphenylamino) phenyl] benzidine, N 4 , N 4 ′ -(biphenyl-4,4′-diyl) bis (N 4 , N 4 ', N 4' - birds E sulfonyl-biphenyl-4,4'-diamine) N 1, N 1 '- ( biphenyl
- 2010/058777 International Publication No. 2010/058776, International Publication No. 2013/042623, International Publication No. Examples thereof include charge transport materials described in 2013/129249, International Publication No. 2014/115865, International Publication No. 2014/12917, International Publication No. 2014/141998, and International Publication No. 2014/132934.
- aniline derivatives and thiophene derivatives disclosed in International Publication No. 2005/043962, International Publication No. 2013/042623, International Publication No. 2014/141998, and the like are preferable, aniline derivatives are more preferable, and the following formula (H1 ) To (H2) are more preferable.
- the molecular weight of the charge transporting material constituting the hole injection layer is preferably 200 to 2,000, but considering the conductivity, the lower limit is preferably 300 or more, more preferably 400 or more.
- the upper limit is preferably 1,500 or less, and more preferably 1,000 or less.
- the aniline derivative represented by the formula (H1) may be an oxidized aniline derivative (quinonediimine derivative) having a quinonediimine structure represented by the following formula in its molecule.
- Examples of the method for oxidizing an aniline derivative into a quinonediimine derivative include the methods described in International Publication Nos. 2008/010474 and 2014/119882.
- R 40 to R 45 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 3
- a alkenyl group having 2 to 20 carbon atoms or 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 which may be substituted with Z 2 Represents an NHY 1 , —NY 2 Y 3 , —OY 4 , or —SY 5 group, and Y 1 to Y 5 each independently represents an alkyl having 1 to 20 carbon atoms which may be substituted with Z 3.
- Z 2 and Z 3 are the same meaning as above
- the stands, k and l are each independently an integer of 1-5.
- R 46 to R 49 are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, or Z 3 .
- R 54 to R 57 are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, or Z 3 .
- a group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms, which may be substituted with Z 2 , R 58 and R 59 are each represented by Independently, phenyl group, naphthyl group, anthryl group, pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, furanyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, thienyl group (this These groups may be bonded to each other to form a ring, and may be a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, having 1 to 20 carbon atoms.
- Z 2 and Z 3 represent the same meaning as described above.
- a halogen 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, an aryl group having 6 to 20 carbon atoms, and an aryl group having 2 to 20 carbon atoms
- the heteroaryl group include those similar to the above.
- Specific examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, phenylethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group, naphthylpropyl group and the like.
- haloalkyl group having 1 to 20 carbon atoms examples include those obtained by substituting at least one hydrogen atom of the alkyl group having 1 to 20 carbon atoms with a halogen atom. Among them, a fluoroalkyl group is preferable, and perfluoro An alkyl group is more preferred.
- fluoromethyl group examples thereof include fluoromethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, 2,2,3,3,3- Pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, nonafluorobutyl group, 4,4,4-trifluoro Butyl group, undecafluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5-octafluoro Pentyl group, tridecafluorohexyl group, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, 2,2,3,3,4,4,4 5,5,6,6-Decafluo Hexyl group
- alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, c-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-eicosa Nyl
- thioalkoxy (alkylthio) group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, s-butylthio group, t-butylthio group.
- n-pentylthio group n-hexylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetra
- acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.
- R 40 to R 45 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms that may be substituted with Z 3 , or 6 to C carbon atoms that may be substituted with Z 2.
- aryl groups —NHY 1 , —NY 2 Y 3 , —OY 4 , or —SY 5 are preferable, and in this case, Y 1 to Y 5 are each a group having 1 to 3 carbon atoms that may be substituted with Z 3 10 alkyl groups or aryl groups having 6 to 10 carbon atoms which may be substituted with Z 2 are preferred, and alkyl groups having 1 to 6 carbon atoms which may be substituted with Z 3 or substituted with Z 2. More preferred are phenyl groups, and even more preferred are alkyl groups having 1 to 6 carbon atoms or phenyl groups.
- R 40 to R 45 are more preferably a hydrogen atom, a fluorine atom, a methyl group, a phenyl group or a diphenylamino group (—NY 2 Y 3 wherein Y 2 and Y 3 are phenyl groups), and R 42 to R 45.
- R 40 and R 41 are more preferably a hydrogen atom or a diphenylamino group at the same time.
- Z 3 is preferably a halogen atom or an aryl group having 6 to 10 carbon atoms which may be substituted with Z 4 , more preferably a fluorine atom or a phenyl group.
- Z 2 is preferably a halogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 4 ,
- a fluorine atom or an alkyl group having 1 to 6 carbon atoms is more preferable, and it is even more preferable that it is not present (that is, an unsubstituted group).
- Z 4 is preferably a halogen atom, more preferably a fluorine atom, and even more preferably not (ie, an unsubstituted group).
- k and l are preferably k + 1 ⁇ 8 and more preferably k + 1 ⁇ 5 from the viewpoint of enhancing the solubility of the aniline derivative represented by the formula (H1).
- R 46 to R 49 are preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, A hydrogen atom is more preferable.
- both R 50 and R 52 are preferably hydrogen atoms.
- R 50 and R 52 are both hydrogen atoms
- R 51 and R 53 are each independently a phenyl group
- this phenyl group is a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, phosphoric acid, Group, sulfonic acid group, carboxyl group, alkoxy group having 1 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, 2 to 2 carbon atoms (It may be substituted with an alkenyl group having 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms.) Or a group represented by the above formula (H3)
- m is preferably 2 to 4 in view of availability of the compound, ease of production, cost, etc., and 2 or 3 is more preferable in consideration of enhancing solubility in a solvent. Considering the balance of availability, ease of production, production cost, solubility in a solvent, transparency of the resulting thin film, etc., 2 is optimal.
- R 54 to R 57 are preferably a hydrogen atom, a fluorine atom, a sulfonic acid group, an alkyl group having 1 to 8 carbon atoms, a —OY 4 group, a —SiY 6 Y 7 Y 8 group, Atoms are more preferred.
- the aniline derivatives represented by the formulas (H1) and (H2) may be commercially available products or those produced by known methods such as the methods described in the above publications, Even in this case, it is preferable to use one purified by recrystallization or vapor deposition before preparing the varnish for forming the hole injection layer. By using the purified one, the characteristics of the optical sensor element including the thin film obtained from the composition can be further enhanced.
- purification by recrystallization for example, 1,4-dioxane, tetrahydrofuran or the like can be used as the solvent.
- the aniline derivative represented by the formulas (H1) and (H2) is one compound selected from the compounds represented by the formulas (H1) and (H2) (that is, The dispersion of molecular weight distribution 1) may be used alone, or two or more compounds may be used in combination.
- an aniline derivative represented by the formula (H2) from the viewpoint of enhancing the transparency of the hole injection layer, and it is more preferable to use a benzidine derivative in which the m is 2, and the following formula (g) It is even more preferable to use diphenylbenzidine represented by
- aniline derivatives suitable as the hole injecting material include the following, but are not limited thereto.
- the electron-accepting dopant substance is not particularly limited as long as it is soluble in at least one solvent used for the hole injection layer forming varnish.
- the electron-accepting dopant material include inorganic strong acids such as hydrogen chloride, sulfuric acid, nitric acid and phosphoric acid; aluminum chloride (III) (AlCl 3 ), titanium tetrachloride (IV) (TiCl 4 ), boron tribromide (BBr 3 ), boron trifluoride ether complex (BF 3 ⁇ OEt 2 ), iron chloride (III) (FeCl 3 ), copper (II) chloride (CuCl 2 ), antimony pentachloride (V) (SbCl 5 ), Lewis acids such as arsenic pentafluoride (V) (AsF 5 ), phosphorus pentafluoride (PF 5 ), tris (4-bromophenyl) aluminum hexachloroantimonate (TBPAH); benzenesulfonic acid, tosylic acid, camphorsulfonic acid , Naphthalene disulfuric acid such as hydroxybenzobenz
- naphthalene trisulfonic acid such as 1,3,6-naphthalene trisulfonic acid, polystyrene sulfonic acid, 1,4 described in International Publication No.
- 2005/000832 -Aryl sulfonic acid compounds such as benzodioxane disulfonic acid compounds, naphthalene or anthracene sulfonic acid compounds described in WO 2006/025342, and dinonyl naphthalene sulfonic acid compounds described in JP-A-2005-108828
- Strong organic acids such as 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), organic oxidants such as iodine, Phosphomolybdic acid and phosphorus described in WO2010 / 058777
- organic oxidants such as iodine, Phosphomolybdic acid and phosphorus described in WO2010 / 058777
- examples thereof include inorganic oxidizing agents such as heteropolyacids such as tungstic acid and phosphotungstomolybdic
- aryl sulfonic acid compounds are preferable, and in particular, naphthalene or anthracene sulfonic acid compound represented by the formula (D1), 1,3,5-naphthalene trisulfonic acid, 1,3,6-naphthalene trisulfonic acid, etc.
- naphthalene trisulfonic acid and polystyrene sulfonic acid are preferred.
- Z represents O
- A represents a naphthalene ring or an anthracene ring
- B represents a divalent to tetravalent perfluorobiphenyl group
- s represents the number of sulfonic acid groups bonded to A
- It is an integer that satisfies 1 ⁇ s ⁇ 4
- t represents the number of bonds between B and Z, and is an integer that satisfies 2 to 4.
- naphthalene or anthracene sulfonic acid compound represented by the formula (D1) include the following naphthalene sulfonic acid compounds (formula (D2)), but are not limited thereto.
- a highly soluble solvent capable of satisfactorily dissolving the hole injecting material and the electron-accepting dopant substance used as necessary can be used.
- Highly soluble solvents can be used singly or in combination of two or more, and the amount used can be 5-100% by mass with respect to the total solvent used in the varnish.
- Examples of such highly soluble solvents include N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1, Examples include 3-dimethyl-2-imidazolidinone. It is preferable that both the charge transporting substance and the electron-accepting dopant substance are completely dissolved or uniformly dispersed in the organic solvent, thereby providing an organic EL device having good characteristics. In view of obtaining the hole injection layer with good reproducibility, it is more preferable that these substances are completely dissolved in the organic solvent.
- the varnish for forming a hole injection layer has a viscosity of 10 to 200 mPa ⁇ s, particularly 35 to 150 mPa ⁇ s at 25 ° C., and a high viscosity organic material having a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure. It is preferable to contain at least one solvent.
- the high-viscosity organic solvent is not particularly limited.
- cyclohexanol ethylene glycol, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol 2,3-butanediol, 1,4-butanediol, propylene glycol, hexylene glycol and the like.
- the addition ratio of the high-viscosity organic solvent to the entire solvent used in the hole injection layer forming varnish is preferably within a range in which no solid precipitates. As long as no solid precipitates, the addition ratio is 5 to 80 masses. % Is preferred.
- adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, etc. 1 to 90% by mass, preferably 1 to 50% by mass can be mixed.
- a solvent include butyl cellosolve, 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, propylene glycol monomethyl ether acetate, ethyl carbitol,
- Examples include, but are not limited to, diacetone alcohol, ⁇ -butyrolactone, ethyl lactate, and n-hexyl acetate.
- the solid content concentration of the varnish for forming the hole injection layer 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 usually 0.1 to 10.0. It is about mass%, preferably 0.5 to 5.0 mass%, more preferably 1.0 to 3.0 mass%.
- solid content means components other than an organic solvent.
- the substance amount (mol) ratio between the hole injecting material and the electron-accepting dopant substance is appropriately set in consideration of the type of charge transporting property, hole injecting material, etc.
- the electron-accepting dopant substance is 0.1 to 10, preferably 0.2 to 5.0, more preferably 0.5 to 3.0 with respect to the hole injecting material 1.
- the viscosity of the varnish for forming a hole injection layer used in the present invention is appropriately adjusted according to the coating method in consideration of the thickness of the thin film to be produced and the solid content concentration. About 1 to 50 mPa ⁇ s.
- the hole injecting material, the electron-accepting dopant substance, and the organic solvent can be mixed in any order as long as the solid content is uniformly dissolved or dispersed in the solvent.
- varnish is usually prepared in an inert gas atmosphere at normal temperature and pressure, but in an air atmosphere (in the presence of oxygen) unless the compound in the varnish is decomposed or the composition changes significantly. Or may be performed while heating.
- the hole injection layer of the present invention can be formed by applying the hole injection layer varnish to the anode of the organic EL element and baking it.
- the coating method and the firing conditions the same conditions as the hole transport layer forming conditions described above can be adopted.
- the film thickness is usually about 1 to 200 nm, preferably about 3 to 100 nm, more preferably 5 to 30 nm.
- a method for changing the film thickness there are methods such as changing the solid content concentration in the composition or changing the amount of the solution at the time of coating.
- the other example of the manufacturing method of the organic EL element which has a positive hole transport layer which consists of a thin film obtained from the charge transportable varnish of this invention is as follows.
- the light transport layer varnish is used to form the light transport layer varnish of the present invention.
- An organic EL device having a charge transporting thin film can be produced. Specifically, the charge transporting varnish of the present invention is applied on the anode substrate on which the hole injection layer is formed, and the hole transporting layer is formed by the above method, and the light emitting polymer layer is formed thereon. Further, a cathode electrode is deposited to obtain an organic EL element.
- the cathode and anode material to be used the same ones as described above can be used, and the same cleaning treatment and surface treatment can be performed.
- the light-emitting polymer layer is formed by adding a solvent to a light-emitting polymer material or a material obtained by adding a dopant substance to the light-emitting polymer material, or after uniformly dispersing and applying the solution on a hole transport layer. And a method of forming a film by firing each.
- 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). And polyphenylene vinylene derivatives such as -PPV), polythiophene derivatives such as poly (3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).
- polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene) (MEH).
- polyphenylene vinylene derivatives such as -PPV
- polythiophene derivatives such as poly (3-alkylthiophene) (PAT)
- 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 application method is not particularly limited, and examples thereof include an inkjet method, a spray method, a dipping method, a spin coating method, a transfer printing method, a roll coating method, and a brush coating method.
- the application is preferably performed under an inert gas such as nitrogen or argon.
- Examples of the firing method include a method of heating in an oven or a hot plate under an inert gas or in a vacuum.
- a hole block layer, an electron block layer, or the like may be provided between the electrode and any of the above layers as necessary.
- a hole block layer, an electron block layer, or the like may be provided between the electrode and any of the above layers as necessary.
- tris (phenylpyrazole) iridium etc. are mentioned as a material which forms an electronic block layer.
- the materials constituting the anode and the cathode and the layer formed between them differ depending on whether the element having the bottom emission structure or the 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. Because light is extracted from a certain transparent electrode (cathode) side, for example, regarding the anode material, a transparent anode such as ITO is used when manufacturing a device with a bottom emission structure, and Al is used when manufacturing a device with a top emission structure.
- a reflective anode such as / Nd is used.
- the organic EL device of the present invention may be sealed together with a water catching agent or the like according to a standard method in order to prevent deterioration of characteristics.
- the reaction mixture was cooled to room temperature, and ethyl acetate and ion-exchanged water were mixed to carry out a liquid separation treatment.
- the reaction mixture was cooled to room temperature, mixed with ion-exchanged water and subjected to a liquid separation treatment.
- the obtained organic layer was washed with ion-exchanged water and saturated brine in that order, and dried over magnesium sulfate.
- the solvent was distilled off under reduced pressure.
- the obtained solid was washed with methanol and dried to obtain arylamine derivative 3 (yield: 1.15 g, yield: 39%).
- the reaction mixture was cooled to room temperature, mixed with toluene, ethyl acetate, and ion-exchanged water, and subjected to liquid separation treatment.
- the solvent was distilled off under reduced pressure.
- Example 2-2 A hole transport layer forming varnish 2 was obtained in the same manner as in Example 2-1, except that the arylamine derivative 2 obtained in Example 1-2 was used.
- Example 2-3 A hole transport layer forming varnish 3 was obtained in the same manner as in Example 2-1, except that the arylamine derivative 3 obtained in Example 1-3 was used.
- Example 2-4 Hole transport layer in the same manner as in Example 2-1, except that 16 mg of the arylamine derivative 3 obtained in Example 1-3 and 8 mg of the arylamine derivative 4 obtained in Example 1-4 were used. A forming varnish 4 was obtained.
- Example 2-5 Hole transport layer in the same manner as in Example 2-1, except that 12 mg of the arylamine derivative 3 obtained in Example 1-3 and 12 mg of the arylamine derivative 4 obtained in Example 1-4 were used. A forming varnish 5 was obtained.
- Example 2-6 A hole transport layer forming varnish 6 was obtained in the same manner as in Example 2-1, except that 24 mg of the arylamine derivative 4 obtained in Example 1-4 was used.
- the charge transporting thin film containing the crosslinked arylamine derivative of the present invention can be applied to a device in which the upper light emitting layer is a coating type.
- Example 4-1 Fabrication and characteristic evaluation of organic EL device
- the hole injection layer forming varnish 1 obtained in Reference Example 1 was applied to an ITO substrate using a spin coater, dried at 80 ° C. for 1 minute, and further baked at 230 ° C. for 15 minutes in an air atmosphere.
- a uniform thin film (hole injection layer) of 100 nm was formed on the ITO substrate.
- As the ITO substrate a glass substrate of 25 mm ⁇ 25 mm ⁇ 0.7 t in which indium tin oxide (ITO) is patterned on the surface with a film thickness of 150 nm is used, and an O 2 plasma cleaning apparatus (150 W, 30 seconds) before use. To remove impurities on the surface.
- ITO indium tin oxide
- the hole transport layer forming varnish 1 obtained in Example 2-1 was applied to the ITO substrate on which the thin film was formed using a spin coater, and then baked at 200 ° C. for 30 minutes to inject holes.
- a uniform thin film (hole transport layer) having a thickness of 20 nm was formed on the layer.
- CBP and Ir (PPy) 3 were co-evaporated using a vapor deposition apparatus (degree of vacuum: 1.0 ⁇ 10 ⁇ 5 Pa). In the co-evaporation, the deposition rate was controlled so that the concentration of Ir (PPy) 3 was 6%, and the layers were laminated to 40 nm.
- the organic EL element is placed between the sealing substrates, and the sealing substrate is bonded with an adhesive (XNR5516Z-B1 manufactured by Nagase ChemteX Corporation). It was. At this time, a water catching 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.
- Examples 4-2, 4-3 An organic EL device was obtained in the same manner as in Example 4-1, except that the hole transport layer forming varnishes 2 and 3 obtained in Examples 2-2 and 2-3 were used.
- Example 4-4 to 4-6 Organic EL devices were obtained in the same manner as in Example 4-1, except that the hole transport layer forming varnishes 4 to 6 obtained in Examples 2-4 to 2-6 were used.
- Example 4-1 An organic EL device was obtained in the same manner as in Example 4-1, except that CBP and Ir (PPy) 3 were directly co-deposited on the hole injection layer.
- Example 3-2 With respect to the devices manufactured in Examples 4-1 to 4-6 and Comparative Example 4-1, the driving voltage and current efficiency when driving at a luminance of 500 cd / m 2 , and the half life of the luminance (initial luminance 500 cd / m 2) , The time required to reach half, Example 3-2 was not carried out) was measured. The results are shown in Table 2.
- the EL device provided with the charge transporting thin film of the present invention as a hole transporting layer is excellent in current efficiency and life characteristics.
Abstract
Description
正孔注入層の形成方法は、蒸着法に代表されるドライプロセスと、スピンコート法に代表されるウェットプロセスとに大別され、これら各プロセスを比べると、ウェットプロセスの方が大面積に平坦性の高い薄膜を効率的に製造できる。それゆえ、有機ELディスプレイの大面積化が進められている現在、ウェットプロセスで形成可能な正孔注入層が望まれている。
しかし、近年、正孔輸送層や正孔注入層だけでなく、発光層等もウェットプロセスで作製することが求められ、その際、下地となる正孔輸送層や正孔注入/輸送層には、発光層形成用組成物に用いられる溶剤耐性が求められることになるが、上記特許文献1~4の材料には、この点で改良の余地があった。
1. 式(1)で表されることを特徴とするアリールアミン誘導体、
2. 前記Rが、ともにパーフルオロアルキル基であり、R1~R39が、すべて水素原子である1のアリールアミン誘導体、
3. 前記架橋基が、ビニル基である1または2のアリールアミン誘導体、
4. 前記Ar1が、4-ビニルフェニル基である1~3のいずれかのアリールアミン誘導体、
5. 1~4のいずれかのアリールアミン誘導体からなる電荷輸送性物質と、有機溶媒とを含む電荷輸送性ワニス、
6. 5の電荷輸送性ワニスから作製される電荷輸送性薄膜、
7. 5の電荷輸送性ワニスから作製され、その中に、前記式(1)で表されるアリールアミン誘導体の架橋基が反応してなる架橋構造を有する電荷輸送性薄膜、
8. 有機エレクトロルミネッセンス素子の正孔輸送層用である6または7の電荷輸送性薄膜、
9. 6または7の電荷輸送性薄膜を備える有機エレクトロルミネッセンス素子、
10. 陽極および陰極と、これら各極間に介在する、正孔注入層、正孔輸送層および発光層を含む複数の機能層と、を備え、前記正孔輸送層が、7の電荷輸送性薄膜から構成される有機エレクトロルミネッセンス素子、
11. 陽極上に、正孔注入層形成用ワニスを塗布し、これを乾燥して正孔注入層を形成する工程と、この正孔注入層上に、1~5のいずれかの電荷輸送性ワニスを塗布し、これを加熱して前記式(1)で表されるアリールアミン誘導体が有する架橋基を熱架橋させて正孔輸送層を形成する工程と、を有する有機エレクトロルミネッセンス素子の製造方法、
12. さらに、前記正孔輸送層の上に、発光層形成用組成物を塗布し、これを乾燥して発光層を形成する工程を含む11の有機エレクトロルミネッセンス素子の製造方法、
13. 式(5)
で表されるジアミン化合物を、触媒存在下、式(6)または式(7)
で表されるアリール化合物と反応させて式(8)または式(9)
で表される化合物を得た後、これら式(8)または式(9)で表される化合物と、前記式(7)または式(6)で表されるアリール化合物とを反応させる1のアリールアミン誘導体の製造方法
を提供する。
本発明の電荷輸送性ワニスから作製した薄膜は、上記アリールアミン誘導体中の架橋基が架橋硬化して高い溶剤耐性を示すため、塗布法にて他の機能層を積層する塗布型デバイスの作製に適している。特に、この薄膜を有機EL素子の正孔輸送層に適用することで、塗布法にて容易に発光層を形成することができる。
また、本発明の電荷輸送性ワニスから作製した薄膜は、高い電荷輸送性を示すため、有機EL素子をはじめとした電子デバイス用薄膜として好適に用いることができる。
さらに、本発明の電荷輸送性ワニスは、スピンコート法やスリットコート法等、大面積に成膜可能な各種ウェットプロセスを用いた場合でも電荷輸送性に優れた薄膜を再現性よく製造できるため、近年の有機EL素子の分野における進展にも十分対応できる。
本発明に係るアリールアミン誘導体は、式(1)で表される。
合成の観点から、Ar1は互いに同一、かつ、Ar2は互いに同一であることが好ましいがこれに限定されない。
炭素数6~20のアリール基が有する架橋基としては、相互に反応して架橋構造を形成し得る基であれば特に限定されるものではないが、本発明では、ビニル基、エポキシ基、オキセタン基、(メタ)アクリロイル基、(メタ)アクリロイルオキシ基、シクロブテニル基等が好ましく、これらの中でも、ビニル基がより好ましい。なお、エポキシ基、シクロブテニル基等の環状構造を有する架橋基は、アリール基と縮環していてもよい。
炭素数1~20のアルキル基としては、直鎖状、分岐鎖状、環状のいずれでもよく、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、n-ノニル基、n-デシル基等の炭素数1~20の直鎖または分岐鎖状アルキル基;シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、ビシクロブチル基、ビシクロペンチル基、ビシクロヘキシル基、ビシクロヘプチル基、ビシクロオクチル基、ビシクロノニル基、ビシクロデシル基等の炭素数3~20の環状アルキル基などが挙げられる。
Ar1としては、2-ビニルフェニル基、3-ビニルフェニル基、4-ビニルフェニル基、2-オキシラニルフェニル基、3-オキシラニルフェニル基、4-オキシラニルフェニル基、2-グリシジルフェニル基、3-グリシジルフェニル基、4-グリシジルフェニル基、ベンゾシクロブテニル基等が好ましく、特に、4-ビニルフェニル基がより好ましい。
Ar3としては、水素原子またはフェニル基が好ましく、フェニル基がより好ましい。
R1~R39としては、水素原子が好ましい。
したがって、Ar2としては、下記式(10)~(12)で表される基が好ましく、式(13)~(15)で表される基がより好ましい。
擬ハロゲン基としては、メタンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、ノナフルオロブタンスルホニルオキシ基等の(フルオロ)アルキルスルホニルオキシ基;ベンゼンスルホニルオキシ基、トルエンスルホニルオキシ基等の芳香族スルホニルオキシ基などが挙げられる。
このような配位子としては、トリフェニルフォスフィン、トリ-o-トリルフォスフィン、ジフェニルメチルフォスフィン、フェニルジメチルフォスフィン、トリメチルフォスフィン、トリエチルフォスフィン、トリブチルフォスフィン、トリ-t-ブチルフォスフィン、ジ-t-ブチル(フェニル)フォスフィン、ジ-t-ブチル(4-ジメチルアミノフェニル)フォスフィン、1,2-ビス(ジフェニルフォスフィノ)エタン、1,3-ビス(ジフェニルフォスフィノ)プロパン、1,4-ビス(ジフェニルフォスフィノ)ブタン、1,1’-ビス(ジフェニルフォスフィノ)フェロセン等の3級フォスフィン、トリメチルフォスファイト、トリエチルフォスファイト、トリフェニルフォスファイト等の3級フォスファイトなどが挙げられる。
また、配位子を用いる場合、その使用量は、使用する金属錯体に対し0.1~5当量とすることができるが、1~2当量が好適である。
反応終了後は、常法にしたがって後処理をし、目的とするアリールアミン誘導体を得ることができる。
電荷輸送性ワニス調製に用いられる有機溶媒としては、式(1)で表されるアリールアミン誘導体を溶解または分散可能なものであれば特に限定されるものではなく、例えば、ベンゼン、トルエン、o-キシレン、m-キシレン、p-キシレン、N-メチルホルムアミド、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、N-メチルアセトアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン、1,3-ジメチル-2-イミダゾリジノン、シクロヘキサノール、エチレングリコール、1,3-オクチレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール、1,3-ブタンジオール、2,3-ブタンジオール、1,4-ブタンジオール、プロピレングリコール、へキシレングリコール、ブチルセロソルブ、ジエチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、エチルカルビトール、ジアセトンアルコール、γ-ブチロラクトン、エチルラクテート、n-ヘキシルアセテート等が挙げられ、これらは1種単独で用いても、2種以上組み合わせて用いてもよい。
これらの中でも、トルエン、キシレン等の芳香族炭化水素系溶媒が好ましい。
また、通常、ワニス調製は、常温、常圧の不活性ガス雰囲気下で行われるが、ワニス中の化合物が分解したり、組成が大きく変化したりしない限り、大気雰囲気下(酸素存在下)で行ってもよく、加熱しながら行ってもよい。
特に、本発明の電荷輸送性ワニスは、正孔注入層上に積層される正孔輸送層形成用ワニスとして用いることが好ましい。
ワニスの塗布方法としては、特に限定されるものではなく、ディップ法、スピンコート法、転写印刷法、ロールコート法、刷毛塗り、インクジェット法、スプレー法、スリットコート法等が挙げられ、塗布方法に応じてワニスの粘度および表面張力を調節することが好ましい。
焼成温度は、得られる薄膜の用途、得られる薄膜に付与する電荷輸送性の程度、溶媒の種類や沸点等を勘案して、100~260℃程度の範囲内で適宜設定されるものではあるが、式(1)で表されるアリールアミン誘導体の架橋基による架橋反応を十分に進行させて強固な架橋構造を形成させることを考慮すると、180~250℃程度が好ましく、190~240℃程度がより好ましい。
なお、焼成の際、より高い均一成膜性を発現させる目的で、2段階以上の温度変化をつけてもよく、加熱は、例えば、ホットプレートやオーブン等、適当な機器を用いて行えばよい。
有機EL素子の代表的な構成としては、以下(a)~(f)が挙げられるが、これらに限定されるわけではない。なお、下記構成において、必要に応じて、発光層と陽極の間に電子ブロック層等を、発光層と陰極の間にホール(正孔)ブロック層等を設けることもできる。また、正孔注入層、正孔輸送層あるいは正孔注入輸送層が電子ブロック層等としての機能を兼ね備えていてもよく、電子注入層、電子輸送層あるいは電子注入輸送層がホール(正孔)ブロック層等としての機能を兼ね備えていてもよい。
(a)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
(b)陽極/正孔注入層/正孔輸送層/発光層/電子注入輸送層/陰極
(c)陽極/正孔注入輸送層/発光層/電子輸送層/電子注入層/陰極
(d)陽極/正孔注入輸送層/発光層/電子注入輸送層/陰極
(e)陽極/正孔注入層/正孔輸送層/発光層/陰極
(f)陽極/正孔注入輸送層/発光層/陰極
「電子注入層」、「電子輸送層」および「電子注入輸送層」とは、発光層と陰極との間に形成される層であって、電子を陰極から発光層へ輸送する機能を有するものであり、発光層と陰極の間に、電子輸送性材料の層が1層のみ設けられる場合、それが「電子注入輸送層」であり、発光層と陰極の間に、電子輸送性材料の層が2層以上設けられる場合、陰極に近い層が「電子注入層」であり、それ以外の層が「電子輸送層」である。
「発光層」とは、発光機能を有する有機層であって、ドーピングシステムを採用する場合、ホスト材料とドーパント材料を含んでいる。このとき、ホスト材料は、主に電子と正孔の再結合を促し、励起子を発光層内に閉じ込める機能を有し、ドーパント材料は、再結合で得られた励起子を効率的に発光させる機能を有する。燐光素子の場合、ホスト材料は主にドーパントで生成された励起子を発光層内に閉じ込める機能を有する。
使用する電極基板は、洗剤、アルコール、純水等による液体洗浄を予め行って浄化しておくことが好ましく、例えば、陽極基板では使用直前にUVオゾン処理、酸素-プラズマ処理等の表面処理を行うことが好ましい。ただし陽極材料が有機物を主成分とする場合、表面処理を行わなくともよい。
まず、陽極基板上に正孔注入層を形成し、この正孔注入層の上に、上述した方法によって本発明の電荷輸送性ワニスを塗布して焼成し、正孔輸送層を形成する。
この上に、発光層、電子輸送層、電子注入層、陰極をこの順で設ける。正孔注入層、発光層、電子輸送層および電子注入層は、用いる材料の特性等に応じて、蒸着法、塗布法(ウェットプロセス)のいずれかで形成すればよい。
なお、金属陽極を構成するその他の金属としては、スカンジウム、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、ガリウム、イットリウム、ジルコニウム、ニオブ、モリブデン、ルテニウム、ロジウム、パラジウム、カドミウム、インジウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ハフニウム、タリウム、タングステン、レニウム、オスミウム、イリジウム、プラチナ、金、チタン、鉛、ビスマスやこれらの合金等が挙げられるが、これらに限定されるわけではない。
陰極材料としては、アルミニウム、マグネシウム-銀合金、アルミニウム-リチウム合金、リチウム、ナトリウム、カリウム、セシウム等が挙げられる。
この場合、正孔注入層を構成する電荷輸送性物質の分子量は200~2,000が好適であるが、導電性という点を考慮すると、下限として好ましくは300以上、より好ましくは400以上であり、溶媒に対する溶解性向上という点を考慮すると、上限として好ましくは1,500以下、より好ましくは1,000以下である。
炭素数7~20のアラルキル基の具体例としては、ベンジル基、フェニルエチル基、フェニルプロピル基、ナフチルメチル基、ナフチルエチル基、ナフチルプロピル基等が挙げられる。
その具体例としては、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、ペンタフルオロエチル基、2,2,2-トリフルオロエチル基、ヘプタフルオロプロピル基、2,2,3,3,3-ペンタフルオロプロピル基、2,2,3,3-テトラフルオロプロピル基、2,2,2-トリフルオロ-1-(トリフルオロメチル)エチル基、ノナフルオロブチル基、4,4,4-トリフルオロブチル基、ウンデカフルオロペンチル基、2,2,3,3,4,4,5,5,5-ノナフルオロペンチル基、2,2,3,3,4,4,5,5-オクタフルオロペンチル基、トリデカフルオロヘキシル基、2,2,3,3,4,4,5,5,6,6,6-ウンデカフロオロヘキシル基、2,2,3,3,4,4,5,5,6,6-デカフルオロヘキシル基、3,3,4,4,5,5,6,6,6-ノナフルオロヘキシル基等が挙げられる。
特に、R40~R45は、水素原子、フッ素原子、メチル基、フェニル基またはジフェニルアミノ基(Y2およびY3がフェニル基である-NY2Y3)がより好ましく、R42~R45が水素原子であり、かつ、R40およびR41が同時に水素原子またはジフェニルアミノ基がより一層好ましい。
また、Z4は、ハロゲン原子が好ましく、フッ素原子がより好ましく、存在しないこと(すなわち、非置換の基であること)がより一層好ましい。
kおよびlとしては、式(H1)で表されるアニリン誘導体の溶解性を高める観点から、好ましくは、k+l≦8であり、より好ましくは、k+l≦5である。
また、式(H2)で表されるアニリン誘導体の溶媒に対する溶解性を高めるとともに、得られる薄膜の均一性を高めることを考慮すると、R50およびR52が共に水素原子であることが好ましい。
特に、R50およびR52が共に水素原子であり、R51およびR53が、それぞれ独立して、フェニル基(このフェニル基は、ハロゲン原子、ニトロ基、シアノ基、水酸基、チオール基、リン酸基、スルホン酸基、カルボキシル基、炭素数1~20のアルコキシ基、炭素数1~20のチオアルコキシ基、炭素数1~20のアルキル基、炭素数1~20のハロアルキル基、炭素数2~20のアルケニル基、炭素数2~20のアルキニル基、炭素数6~20のアリール基、炭素数7~20のアラルキル基、または炭素数1~20のアシル基で置換されていてもよい。)、または上記式(H3)で表される基であることが好ましく、R50およびR52が共に水素原子であり、R51およびR53が、それぞれ独立して、フェニル基、またはR58’およびR59’が共にフェニル基である下記式(H3′)で表される基であることがより好ましく、R50およびR52が共に水素原子であり、R51およびR53が、共にフェニル基であることがより一層好ましい。
また、mとしては、化合物の入手容易性、製造の容易性、コスト面などを考慮すると、2~4が好ましく、溶媒への溶解性を高めることを考慮すると、2または3がより好ましく、化合物の入手容易性、製造の容易性、製造コスト、溶媒への溶解性、得られる薄膜の透明性等のバランスを考慮すると、2が最適である。
特に、正孔注入層の透明性を高めるという点から、式(H2)で示されるアニリン誘導体を用いることが好ましく、中でも上記mが2であるベンジジン誘導体を用いることがより好ましく、下記式(g)で示されるジフェニルベンジジンを用いることがより一層好ましい。
電子受容性ドーパント物質は、正孔注入層形成用ワニスに使用する少なくとも一種の溶媒に溶解するものであれば、特に限定されない。
電荷輸送性物質および電子受容性ドーパント物質は、いずれも上記有機溶媒に完全に溶解しているか、均一に分散している状態となっていることが好ましく、良好な特性を備える有機EL素子を与える正孔注入層を再現性よく得ることを考慮すると、これらの物質は上記有機溶媒に完全に溶解していることがより好ましい。
高粘度有機溶媒は、特に限定されるものではなく、例えば、シクロヘキサノール、エチレングリコール、1,3-オクチレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール、1,3-ブタンジオール、2,3-ブタンジオール、1,4-ブタンジオール、プロピレングリコール、へキシレングリコールなどが挙げられる。
このような溶媒としては、例えば、ブチルセロソルブ、ジエチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、エチルカルビトール、ジアセトンアルコール、γ-ブチロラクトン、エチルラクテート、n-ヘキシルアセテートなどが挙げられるが、これらに限定されるものではない。
また、正孔注入性材料と電子受容性ドーパント物質の物質量(mol)比も、発現する電荷輸送性、正孔注入性材料等の種類を考慮して適宜設定されるものではあるが、通常、正孔注入性材料1に対し、電子受容性ドーパント物質0.1~10、好ましくは0.2~5.0、より好ましくは0.5~3.0である。
そして、本発明において用いる正孔注入層形成用ワニスの粘度は、作製する薄膜の厚み等や固形分濃度を考慮し、塗布方法に応じて適宜調節されるものではあるが、通常25℃で0.1~50mPa・s程度である。
また、通常、ワニスの調製は、常温、常圧の不活性ガス雰囲気下で行われるが、ワニス中の化合物が分解したり、組成が大きく変化したりしない限り、大気雰囲気下(酸素存在下)で行ってもよく、加熱しながら行ってもよい。
塗布法や、焼成条件としては、上述した正孔輸送層形成条件と同様のものを採用できる。
膜厚は、通常1~200nm程度であるが、好ましくは3~100nm程度、より好ましくは5~30nmである。膜厚を変化させる方法としては、組成物中の固形分濃度を変化させたり、塗布時の溶液量を変化させたりするなどの方法がある。
上記EL素子作製において、発光層、電子輸送層、電子注入層の真空蒸着操作を行う代わりに、発光層(以下、発光性高分子層)を形成することによって本発明の電荷輸送性ワニスによって形成される電荷輸送性薄膜を有する有機EL素子を作製することができる。
具体的には、正孔注入層が形成された陽極基板上に本発明の電荷輸送性ワニスを塗布して上記の方法により正孔輸送層を作製し、その上に発光性高分子層を形成し、さらに陰極電極を蒸着して有機EL素子とする。
発光性高分子層の形成法としては、発光性高分子材料、またはこれらにドーパント物質を加えた材料に溶媒を加えて溶解するか、均一に分散し、正孔輸送層の上に塗布した後、それぞれ焼成することで成膜する方法が挙げられる。
塗布方法としては、特に限定されるものではなく、インクジェット法、スプレー法、ディップ法、スピンコート法、転写印刷法、ロールコート法、刷毛塗り等が挙げられる。なお、塗布は、窒素、アルゴン等の不活性ガス下で行うことが好ましい。
焼成する方法としては、不活性ガス下または真空中、オーブンまたはホットプレートで加熱する方法が挙げられる。
通常、ボトムエミッション構造の素子では、基板側に透明陽極が用いられ、基板側から光が取り出されるのに対し、トップエミッション構造の素子では、金属からなる反射陽極が用いられ、基板と反対方向にある透明電極(陰極)側から光が取り出されることから、例えば陽極材料について言えば、ボトムエミッション構造の素子を製造する際はITO等の透明陽極を、トップエミッション構造の素子を製造する際はAl/Nd等の反射陽極を、それぞれ用いる。
(1)1H-NMR:ブルカー・バイオスピン(株)製 核磁気共鳴分光計 AVANCE III HD 500MHz
(2)基板洗浄:長州産業(株)製 基板洗浄装置(減圧プラズマ方式)
(3)ワニスの塗布:ミカサ(株)製 スピンコーターMS-A100
(4)膜厚測定:(株)小坂研究所製 微細形状測定機サーフコーダET-4000
(5)膜の表面観察:レーザーテック社製 共焦点レーザー顕微鏡 リアルタイム走査型レーザー顕微鏡 1LM21D
(6)EL素子の作製:長州産業(株)製 多機能蒸着装置システムC-E2L1G1-N
(7)EL素子の輝度等の測定:(有)テック・ワールド製 I-V-L測定システム
(8)EL素子の寿命測定(輝度半減期測定):(株)イーエッチシー製 有機EL輝度寿命評価システムPEL-105S
1H-NMR (500MHz, DMSO-d6) δ [ppm]: 8.56(s, 2H), 7.37(d, J=8.5Hz,4H), 7.20(d, J=8.5Hz, 4H), 7.12(d, J=8.5Hz, 4H), 7.11(d, J=8.5Hz, 4H), 6.65(dd, J=17.7, 11.0Hz, 2H), 5.65(d, J=17.7Hz, 2H), 5.10(d, J=11.0Hz, 2H).
1H-NMRの測定結果を以下に示す。
1H-NMR (500MHz, THF-d8) δ [ppm]: 8.06(d, J=7.9Hz, 2H), 8.03(d, J=1.8Hz, 2H), 7.59-7.65(m, 8H), 7.47-7.49(m, 2H), 7.31-7.39(m, 10H), 7.16-7.24(m, 8H), 7.12(d, J=8.9Hz, 4H), 7.02(d, J=8.9Hz, 4H), 6.66(dd, J=17.7, 11.0Hz, 2H), 5.64(d, J=17.7Hz, 2H), 5.10(d, J=11.0Hz, 2H).
1H-NMRの測定結果を以下に示す。
1H-NMR (500MHz, THF-d8) δ [ppm]: 7.35(d, J=8.5Hz, 4H), 7.21-7.25(m, 12H), 6.96-7.11(m, 28H), 6.67(dd, J=17.4, 11.0Hz, 2H), 5.66(d, J=17.4Hz, 2H), 5.13(d, J=11.0Hz, 2H).
1H-NMRの測定結果を以下に示す。
1H-NMR (500MHz, THF-d8) δ [ppm]: 7.54(d, J=8.5Hz, 4H), 7.49(d, J=8.5Hz, 4H), 7.37(d, J=8.2Hz, 4H), 7.28(d, J=8.5Hz, 4H), 7.23(t, J=7.6Hz, 8H), 7.17(d, J=8.5Hz, 4H), 7.06-7.11(m, 20H), 6.99(t, J=7.6Hz, 4H), 6.68(dd, J=17.4, 11.0Hz, 2H), 5.68(d, J=17.4Hz, 2H), 5.14(d, J=11.0Hz, 2H).
濃縮液にメタノールを加えて白色固体を析出させた後、再び溶媒を減圧留去し、乾燥して4′-ヨード-2,2′-ジメチル-N,N-ジフェニル-(1,1′-ビフェニル)-4-アミンを得た(収量:1.25g、収率:26%)。
1H-NMRの測定結果を以下に示す。
1H-NMR (500MHz, DMSO-d6) δ [ppm]: 7.69(d, J=1.2Hz, 1H), 7.57(dd, J=7.9, 1.2Hz, 1H), 7.30-7.33(m, 4H), 7.03-7.06(m, 6H), 6.97(d, J=7.9Hz, 1H), 6.93(d, J=2.1Hz, 1H), 6.90(d, J=7.9Hz 1H), 6.84(dd, J=7.9, 2.1Hz, 1H), 2.01(s, 3H), 1.90(s, 3H).
1H-NMRの測定結果を以下に示す。
1H-NMR (500MHz, THF-d8) δ [ppm]: 7.37(d, J=8.5Hz, 4H), 7.27(d, J=8.5Hz, 4H), 7.21-7.24(m, 8H), 7.04-7.13(m, 20H), 6.96-7.00(m, 10H), 6.90(dd, J=8.2, 2.1Hz, 2H), 6.69(dd, J=17.7, 11.0Hz, 2H), 5.68(d, J=17.7Hz, 2H), 5.14(d, J=11.0Hz, 2H), 2.03(s, 6H), 1.99(s, 6H).
[2-1]正孔輸送層形成用ワニスの調製
[実施例2-1]
上記実施例1-1で得られたアリールアミン誘導体1 24mgに、キシレン2.0gを加え、室温で撹拌して固形分を溶解させて溶液を得た。得られた溶液を孔径0.2μmのシリンジフィルターでろ過して、正孔輸送層形成用ワニス1を得た。
上記実施例1-2で得られたアリールアミン誘導体2を用いた以外は、実施例2-1と同様にして正孔輸送層形成用ワニス2を得た。
上記実施例1-3で得られたアリールアミン誘導体3を用いた以外は、実施例2-1と同様にして正孔輸送層形成用ワニス3を得た。
上記実施例1-3で得られたアリールアミン誘導体3 16mgと上記実施例1-4で得られたアリールアミン誘導体4 8mgを用いた以外は、実施例2-1と同様にして正孔輸送層形成用ワニス4を得た。
上記実施例1-3で得られたアリールアミン誘導体3 12mgと上記実施例1-4で得られたアリールアミン誘導体4 12mgを用いた以外は、実施例2-1と同様にして正孔輸送層形成用ワニス5を得た。
上記実施例1-4で得られたアリールアミン誘導体4 24mgを用いた以外は、実施例2-1と同様にして正孔輸送層形成用ワニス6を得た。
[参考例1]正孔注入層形成用ワニス
上記式(c)で示されるオリゴアニリン化合物58.9mg(0.086mmol)と上記式(D2)で表されるアリールスルホン酸化合物160.9mg(0.161mmol)との混合物に、DMAc5.00gを加えて、40℃で撹拌して固形分を溶解させた。さらにそこへ、CHN5.0gを加えて撹拌し、濃緑色溶液を得た。得られた濃緑色溶液を、孔径0.2μmのシリンジフィルターでろ過して、正孔注入層形成用ワニス1を得た。
なお、上記式(c)で示されるオリゴアニリン化合物は、国際公開第2014/141998号記載の方法に従って合成した。
[実施例3-1~3-3]
参考例1で得られた正孔注入層形成用ワニス1を、スピンコーターを用いてITO基板に塗布した後、80℃で1分間乾燥し、さらに、大気雰囲気下、230℃で15分間焼成し、ITO基板上に30nmの均一な薄膜を形成した。この薄膜を形成したITO基板に対し、実施例2-1~2-3で得られた正孔輸送層形成用ワニス1~3を、それぞれスピンコーターを用いて塗布した後、N2雰囲気下、表1記載の各条件で焼成し、厚み20nmの均一な薄膜を形成した。
形成した薄膜の上に、トルエン0.5mlを載せて1分放置後、スピンコートにてトルエンを除去し、さらに100℃で1分間加熱乾燥し、膜厚を測定した。トルエンストリッピング前後の膜厚から、残膜率を算出した。結果を表1に示す。
したがって、本発明のアリールアミン誘導体の架橋体を含む電荷輸送性薄膜は、上層の発光層が塗布型の素子にも適用可能であることがわかる。
[実施例4-1]
参考例1で得られた正孔注入層形成用ワニス1を、スピンコーターを用いてITO基板に塗布した後、80℃で1分間乾燥し、さらに、大気雰囲気下、230℃で15分間焼成し、ITO基板上に100nmの均一な薄膜(正孔注入層)を形成した。ITO基板としては、インジウム錫酸化物(ITO)が表面上に膜厚150nmでパターニングされた25mm×25mm×0.7tのガラス基板を用い、使用前にO2プラズマ洗浄装置(150W、30秒間)によって表面上の不純物を除去した。
次いで、薄膜を形成したITO基板に対し、実施例2-1で得られた正孔輸送層形成用ワニス1を、スピンコーターを用いて塗布した後、200℃で30分焼成し、正孔注入層上に、厚み20nmの均一な薄膜(正孔輸送層)を形成した。
作製した正孔輸送層の上に、蒸着装置(真空度1.0×10-5Pa)を用いてCBPとIr(PPy)3を共蒸着した。共蒸着はIr(PPy)3の濃度が6%になるように蒸着レートをコントロールし、40nm積層させた。次いで、Alq3、フッ化リチウムおよびアルミニウムの薄膜を順次積層して有機EL素子を得た。この際、蒸着レートは、Alq3およびアルミニウムについては0.2nm/秒、フッ化リチウムについては0.02nm/秒の条件でそれぞれ行い、膜厚は、それぞれ20nm、0.5nmおよび80nmとした。
なお、空気中の酸素、水等の影響による特性劣化を防止するため、有機EL素子は封止基板により封止した後、その特性を評価した。封止は、以下の手順で行った。酸素濃度2ppm以下、露点-85℃以下の窒素雰囲気中で、有機EL素子を封止基板の間に収め、封止基板を接着材(ナガセケムテックス(株)製,XNR5516Z-B1)により貼り合わせた。この際、捕水剤(ダイニック(株)製,HD-071010W-40)を有機EL素子と共に封止基板内に収めた。貼り合わせた封止基板に対し、UV光を照射(波長:365nm、照射量:6,000mJ/cm2)した後、80℃で1時間、アニーリング処理して接着材を硬化させた。
実施例2-2および2-3で得られた正孔輸送層形成用ワニス2,3をそれぞれ用いた以外は、実施例4-1と同様にして有機EL素子を得た。
実施例2-4~2-6で得られた正孔輸送層形成用ワニス4~6をそれぞれ用いた以外は、実施例4-1と同様にして有機EL素子を得た。
正孔注入層上に、CBPとIr(PPy)3を直接共蒸着した以外は、実施例4-1と同様にして有機EL素子を得た。
Claims (13)
- 式(1)で表されることを特徴とするアリールアミン誘導体。
R1~R39は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、アミノ基、Z2で置換されていてもよい、炭素数6~20のアリール基もしくは炭素数2~20のヘテロアリール基、Z3で置換されていてもよい、炭素数1~20のアルキル基、炭素数2~20のアルケニル基もしくは炭素数2~20のアルキニル基、-NHY1、-NY2Y3、-OY4、または-SY5基を表し、Y1~Y5は、それぞれ独立して、Z2で置換されていてもよい、炭素数6~20のアリール基もしくは炭素数2~20のヘテロアリール基、またはZ3で置換されていてもよい、炭素数1~20のアルキル基、炭素数2~20のアルケニル基もしくは炭素数2~20のアルキニル基を表し、
Z2は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、またはZ4で置換されていてもよい、炭素数1~20のアルキル基、炭素数2~20のアルケニル基もしくは炭素数2~20のアルキニル基を表し、Z3は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、またはZ4で置換されていてもよい、炭素数6~20のアリール基もしくは炭素数2~20のヘテロアリール基を表し、Z4は、ハロゲン原子、ニトロ基、シアノ基、またはアミノ基を表す。)〕 - 前記Rが、ともにパーフルオロアルキル基であり、R1~R39が、すべて水素原子である請求項1記載のアリールアミン誘導体。
- 前記架橋基が、ビニル基である請求項1または2記載のアリールアミン誘導体。
- 前記Ar1が、4-ビニルフェニル基である請求項1~3のいずれか1項記載のアリールアミン誘導体。
- 請求項1~4のいずれか1項記載のアリールアミン誘導体からなる電荷輸送性物質と、有機溶媒とを含む電荷輸送性ワニス。
- 請求項5記載の電荷輸送性ワニスから作製される電荷輸送性薄膜。
- 請求項5記載の電荷輸送性ワニスから作製され、その中に、前記式(1)で表されるアリールアミン誘導体の架橋基が反応してなる架橋構造を有する電荷輸送性薄膜。
- 有機エレクトロルミネッセンス素子の正孔輸送層用である請求項6または7記載の電荷輸送性薄膜。
- 請求項6または7記載の電荷輸送性薄膜を備える有機エレクトロルミネッセンス素子。
- 陽極および陰極と、これら各極間に介在する、正孔注入層、正孔輸送層および発光層を含む複数の機能層と、を備え、
前記正孔輸送層が、請求項7記載の電荷輸送性薄膜から構成される有機エレクトロルミネッセンス素子。 - 陽極上に、正孔注入層形成用ワニスを塗布し、これを乾燥して正孔注入層を形成する工程と、この正孔注入層上に、請求項1~5のいずれか1項記載の電荷輸送性ワニスを塗布し、これを加熱して前記式(1)で表されるアリールアミン誘導体が有する架橋基を熱架橋させて正孔輸送層を形成する工程と、を有する有機エレクトロルミネッセンス素子の製造方法。
- さらに、前記正孔輸送層の上に、発光層形成用組成物を塗布し、これを乾燥して発光層を形成する工程を含む請求項11記載の有機エレクトロルミネッセンス素子の製造方法。
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CN201780019241.2A CN108884016B (zh) | 2016-03-24 | 2017-03-21 | 芳基胺衍生物及其用途 |
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JP2018507325A JP6763425B2 (ja) | 2016-03-24 | 2017-03-21 | アリールアミン誘導体とその利用 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3527632A4 (en) * | 2017-05-29 | 2020-04-22 | LG Chem, Ltd. | INK COMPOSITION, ORGANIC ELECTROLUMINESCENT ELEMENT USING THE SAME, AND MANUFACTURING METHOD THEREOF |
CN111316463A (zh) * | 2018-10-10 | 2020-06-19 | 住友化学株式会社 | 发光元件用膜及使用了它的发光元件 |
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CN111875551B (zh) * | 2019-09-02 | 2022-04-15 | 广东聚华印刷显示技术有限公司 | 有机化合物、电子器件及相应的制备方法 |
Citations (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004043117A1 (ja) | 2002-11-07 | 2004-05-21 | Nissan Chemical Industries,Ltd. | 電荷輸送性ワニス |
WO2004105446A1 (ja) | 2003-05-20 | 2004-12-02 | Nissan Chemical Industries, Ltd. | 電荷輸送性ワニス |
WO2005000832A1 (ja) | 2003-06-25 | 2005-01-06 | Nissan Chemical Industries, Ltd. | 1,4-ベンゾジオキサンスルホン酸化合物及び電子受容性物質としての利用 |
JP2005108828A (ja) | 2003-09-11 | 2005-04-21 | Nissan Chem Ind Ltd | 電荷輸送性ワニス、電荷輸送性薄膜および有機エレクトロルミネッセンス素子 |
WO2005042621A1 (ja) | 2003-10-30 | 2005-05-12 | Nissan Chemical Industries, Ltd. | 電荷輸送性化合物、電荷輸送性材料、電荷輸送性ワニス、電荷輸送性薄膜及び有機エレクトロルミネッセンス素子 |
WO2005043962A1 (ja) | 2003-10-31 | 2005-05-12 | Nissan Chemical Industries, Ltd. | 1,4−ジチイン環を有する化合物を含む電荷輸送性有機材料 |
WO2005107335A1 (ja) | 2004-04-30 | 2005-11-10 | Nissan Chemical Industries, Ltd. | 良溶媒及び貧溶媒を含有するワニス |
WO2006006459A1 (ja) | 2004-07-09 | 2006-01-19 | Nissan Chemical Industries, Ltd. | オリゴアニリン化合物の精製方法およびオリゴアニリン化合物 |
WO2006025342A1 (ja) | 2004-08-31 | 2006-03-09 | Nissan Chemical Industries, Ltd. | アリールスルホン酸化合物及び電子受容性物質としての利用 |
WO2006137473A1 (ja) | 2005-06-24 | 2006-12-28 | Nissan Chemical Industries, Ltd. | 芳香族スルホン酸化合物の製造法 |
WO2007049631A1 (ja) | 2005-10-28 | 2007-05-03 | Nissan Chemical Industries, Ltd. | スプレー又はインクジェット塗布用電荷輸送性ワニス |
WO2007099808A1 (ja) | 2006-02-23 | 2007-09-07 | Nissan Chemical Industries, Ltd. | スルホン酸エステル化合物およびその利用 |
WO2008010474A1 (fr) | 2006-07-18 | 2008-01-24 | Nissan Chemical Industries, Ltd. | Vernis contenant des charges |
WO2008032616A1 (en) | 2006-09-13 | 2008-03-20 | Nissan Chemical Industries, Ltd. | Oligoaniline compounds |
WO2008032617A1 (fr) | 2006-09-13 | 2008-03-20 | Nissan Chemical Industries, Ltd. | Composé d'oligoaniline et son utilisation |
WO2008129947A1 (ja) | 2007-04-12 | 2008-10-30 | Nissan Chemical Industries, Ltd. | オリゴアニリン化合物 |
JP2009522273A (ja) * | 2005-12-29 | 2009-06-11 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 新規な化合物を含む組成物およびそのような組成物を使用して製造された電子デバイス |
WO2009096352A1 (ja) | 2008-01-29 | 2009-08-06 | Nissan Chemical Industries, Ltd. | アリールスルホン酸化合物および電子受容性物質としての利用 |
WO2010041701A1 (ja) | 2008-10-09 | 2010-04-15 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2010058777A1 (ja) | 2008-11-19 | 2010-05-27 | 日産化学工業株式会社 | 電荷輸送性材料および電荷輸送性ワニス |
WO2010058776A1 (ja) | 2008-11-19 | 2010-05-27 | 日産化学工業株式会社 | 電荷輸送性材料および電荷輸送性ワニス |
WO2013042623A1 (ja) | 2011-09-21 | 2013-03-28 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2013129249A1 (ja) | 2012-03-02 | 2013-09-06 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2014073683A1 (ja) * | 2012-11-12 | 2014-05-15 | 三菱化学株式会社 | 有機電界発光素子およびその製造方法 |
WO2014115865A1 (ja) | 2013-01-28 | 2014-07-31 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2014119782A1 (ja) | 2013-02-04 | 2014-08-07 | 日産化学工業株式会社 | 有機薄膜太陽電池用バッファ層及び有機薄膜太陽電池 |
WO2014132917A1 (ja) | 2013-02-28 | 2014-09-04 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2014132834A1 (ja) | 2013-02-26 | 2014-09-04 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2014141998A1 (ja) | 2013-03-11 | 2014-09-18 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2015178407A1 (ja) * | 2014-05-23 | 2015-11-26 | 日産化学工業株式会社 | 電荷輸送性ワニス |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100626823B1 (ko) | 2004-09-16 | 2006-09-20 | 서상진 | 떡 및 제과용 소재 자동 절단 장치 |
US7781550B1 (en) * | 2004-12-30 | 2010-08-24 | E. I. Du Pont De Nemours And Company | Charge transport compositions and their use in electronic devices |
KR100888131B1 (ko) | 2006-10-10 | 2009-03-11 | 한올제약주식회사 | 시간차 투약 원리를 이용한 심혈관계 질환 치료용 복합제제 |
JP2008129947A (ja) | 2006-11-22 | 2008-06-05 | Sharp Corp | 半導体装置 |
KR20100058777A (ko) | 2008-11-25 | 2010-06-04 | 주식회사 동부하이텍 | 반도체소자 및 그 제조방법 |
-
2017
- 2017-03-21 KR KR1020187030140A patent/KR102372197B1/ko active IP Right Grant
- 2017-03-21 JP JP2018507325A patent/JP6763425B2/ja active Active
- 2017-03-21 CN CN201780019241.2A patent/CN108884016B/zh active Active
- 2017-03-21 WO PCT/JP2017/011169 patent/WO2017164158A1/ja active Application Filing
- 2017-03-21 EP EP17770200.8A patent/EP3434666A4/en not_active Withdrawn
- 2017-03-21 US US16/087,747 patent/US20190084920A1/en not_active Abandoned
- 2017-03-24 TW TW106109998A patent/TWI773664B/zh active
Patent Citations (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004043117A1 (ja) | 2002-11-07 | 2004-05-21 | Nissan Chemical Industries,Ltd. | 電荷輸送性ワニス |
WO2004105446A1 (ja) | 2003-05-20 | 2004-12-02 | Nissan Chemical Industries, Ltd. | 電荷輸送性ワニス |
WO2005000832A1 (ja) | 2003-06-25 | 2005-01-06 | Nissan Chemical Industries, Ltd. | 1,4-ベンゾジオキサンスルホン酸化合物及び電子受容性物質としての利用 |
JP2005108828A (ja) | 2003-09-11 | 2005-04-21 | Nissan Chem Ind Ltd | 電荷輸送性ワニス、電荷輸送性薄膜および有機エレクトロルミネッセンス素子 |
WO2005042621A1 (ja) | 2003-10-30 | 2005-05-12 | Nissan Chemical Industries, Ltd. | 電荷輸送性化合物、電荷輸送性材料、電荷輸送性ワニス、電荷輸送性薄膜及び有機エレクトロルミネッセンス素子 |
WO2005043962A1 (ja) | 2003-10-31 | 2005-05-12 | Nissan Chemical Industries, Ltd. | 1,4−ジチイン環を有する化合物を含む電荷輸送性有機材料 |
WO2005107335A1 (ja) | 2004-04-30 | 2005-11-10 | Nissan Chemical Industries, Ltd. | 良溶媒及び貧溶媒を含有するワニス |
WO2006006459A1 (ja) | 2004-07-09 | 2006-01-19 | Nissan Chemical Industries, Ltd. | オリゴアニリン化合物の精製方法およびオリゴアニリン化合物 |
WO2006025342A1 (ja) | 2004-08-31 | 2006-03-09 | Nissan Chemical Industries, Ltd. | アリールスルホン酸化合物及び電子受容性物質としての利用 |
WO2006137473A1 (ja) | 2005-06-24 | 2006-12-28 | Nissan Chemical Industries, Ltd. | 芳香族スルホン酸化合物の製造法 |
WO2007049631A1 (ja) | 2005-10-28 | 2007-05-03 | Nissan Chemical Industries, Ltd. | スプレー又はインクジェット塗布用電荷輸送性ワニス |
JP2009522273A (ja) * | 2005-12-29 | 2009-06-11 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 新規な化合物を含む組成物およびそのような組成物を使用して製造された電子デバイス |
WO2007099808A1 (ja) | 2006-02-23 | 2007-09-07 | Nissan Chemical Industries, Ltd. | スルホン酸エステル化合物およびその利用 |
WO2008010474A1 (fr) | 2006-07-18 | 2008-01-24 | Nissan Chemical Industries, Ltd. | Vernis contenant des charges |
WO2008032617A1 (fr) | 2006-09-13 | 2008-03-20 | Nissan Chemical Industries, Ltd. | Composé d'oligoaniline et son utilisation |
WO2008032616A1 (en) | 2006-09-13 | 2008-03-20 | Nissan Chemical Industries, Ltd. | Oligoaniline compounds |
WO2008129947A1 (ja) | 2007-04-12 | 2008-10-30 | Nissan Chemical Industries, Ltd. | オリゴアニリン化合物 |
WO2009096352A1 (ja) | 2008-01-29 | 2009-08-06 | Nissan Chemical Industries, Ltd. | アリールスルホン酸化合物および電子受容性物質としての利用 |
WO2010041701A1 (ja) | 2008-10-09 | 2010-04-15 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2010058777A1 (ja) | 2008-11-19 | 2010-05-27 | 日産化学工業株式会社 | 電荷輸送性材料および電荷輸送性ワニス |
WO2010058776A1 (ja) | 2008-11-19 | 2010-05-27 | 日産化学工業株式会社 | 電荷輸送性材料および電荷輸送性ワニス |
WO2013042623A1 (ja) | 2011-09-21 | 2013-03-28 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2013129249A1 (ja) | 2012-03-02 | 2013-09-06 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2014073683A1 (ja) * | 2012-11-12 | 2014-05-15 | 三菱化学株式会社 | 有機電界発光素子およびその製造方法 |
WO2014115865A1 (ja) | 2013-01-28 | 2014-07-31 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2014119782A1 (ja) | 2013-02-04 | 2014-08-07 | 日産化学工業株式会社 | 有機薄膜太陽電池用バッファ層及び有機薄膜太陽電池 |
WO2014132834A1 (ja) | 2013-02-26 | 2014-09-04 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2014132917A1 (ja) | 2013-02-28 | 2014-09-04 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2014141998A1 (ja) | 2013-03-11 | 2014-09-18 | 日産化学工業株式会社 | 電荷輸送性ワニス |
WO2015178407A1 (ja) * | 2014-05-23 | 2015-11-26 | 日産化学工業株式会社 | 電荷輸送性ワニス |
Non-Patent Citations (1)
Title |
---|
See also references of EP3434666A4 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3527632A4 (en) * | 2017-05-29 | 2020-04-22 | LG Chem, Ltd. | INK COMPOSITION, ORGANIC ELECTROLUMINESCENT ELEMENT USING THE SAME, AND MANUFACTURING METHOD THEREOF |
US11236246B2 (en) | 2017-05-29 | 2022-02-01 | Lg Chem, Ltd. | Ink composition, organic light-emitting element using same, and fabrication method thereof |
CN111316463A (zh) * | 2018-10-10 | 2020-06-19 | 住友化学株式会社 | 发光元件用膜及使用了它的发光元件 |
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KR20180128017A (ko) | 2018-11-30 |
US20190084920A1 (en) | 2019-03-21 |
CN108884016B (zh) | 2022-11-01 |
JPWO2017164158A1 (ja) | 2019-02-14 |
CN108884016A (zh) | 2018-11-23 |
JP6763425B2 (ja) | 2020-09-30 |
EP3434666A1 (en) | 2019-01-30 |
TWI773664B (zh) | 2022-08-11 |
KR102372197B1 (ko) | 2022-03-08 |
TW201808881A (zh) | 2018-03-16 |
EP3434666A4 (en) | 2019-11-27 |
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