Aniline derivatives

Abstract

For example, an aniline derivative represented by the following formula is provided. (In the formula, Ph is a phenyl group.)

Description

Technical Field

[0001] The present invention relates to aniline derivatives. Background Art

[0002] In an organic electroluminescent (hereinafter also referred to as organic EL) element, a charge-transporting thin film containing an organic compound is used as a light-emitting layer and a charge injection layer. In particular, the hole injection layer undertakes the transfer of charges between the anode and the hole transport layer or the light-emitting layer, and plays an important role in achieving low-voltage driving and high brightness of the organic EL element.

[0003] The formation methods of the hole injection layer are roughly classified into a dry method represented by vapor deposition and a wet method represented by spin coating. If these methods are compared, the wet method can produce a thin film with high flatness over a large area with high efficiency. Therefore, at present when the area of organic EL displays is increasing, there is a need for a hole injection layer that can be formed by a wet method.

[0004] Under such circumstances, the present inventors have developed a material that imparts charge transport properties and a compound that can be used for such a material. The material that imparts charge transport properties can be applied to various wet methods, and can achieve excellent characteristics when applied to the hole injection layer of an organic EL element (for example, Patent Documents 1 to 3). At present when efforts are concentrated on the development of organic EL displays, there is still an urgent need for new materials for wet methods. In addition, there is also a strong urgent need for cheaper materials.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: International Publication No. 2008 / 129947

[0008] Patent Document 2: International Publication No. 2015 / 050253

[0009] Patent Document 3: International Publication No. 2017 / 217457 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] In view of the above actual situation, the present invention has been completed, and an object thereof is to provide an aniline derivative that can be easily synthesized from a simple raw material compound, gives a thin film with excellent charge transport properties, and can achieve an organic EL element with excellent characteristics when the thin film is applied to a hole injection layer or the like.

[0012] Means for Solving the Problems

[0013] The inventors of the present invention conducted repeated and in-depth studies to achieve the above object, and as a result, it was found that a specified aniline derivative having an N,N,N',N'-tetrakis(carbazol-2-yl)-p-phenylenediamine structure in the molecule can not only be easily synthesized from inexpensive and simple 1,4-phenylenediamine and a halogenated or pseudohalogenated carbazole derivative, but also gives a film having excellent charge transport properties. When this film is applied to a hole injection layer or the like, an organic EL element having excellent characteristics can be realized, and the present invention has been completed.

[0014] Therefore, the present invention provides the following aniline derivatives.

[0015] 1. An aniline derivative represented by the following formula (1).

[0016] [Chemical formula 1]

[0017]

[0018] [In the formula, each Ar is independently a group represented by any one of the following formulas (Ar1) to (Ar9).

[0019] [Chemical formula 2]

[0020]

[0021] (In the formula, R 1 ~R 21 are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 1 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 1 , an alkynyl group having 2 to 20 carbon atoms which may be substituted by Z 1 , an aryl group having 6 to 20 carbon atoms which may be substituted by Z 2 or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z 2 .

[0022] Z 1 is a halogen atom, a nitro group, a cyano group, an aryl group having 6 to 20 carbon atoms which may be substituted by Z 3 or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z 3 .

[0023] Z 2 is a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 3 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 3 or an alkynyl group having 2 to 20 carbon atoms which may be substituted by Z 3 .

[0024] Z 3 is a halogen atom, a nitro group or a cyano group.)]

[0025] An aniline derivative of 2.1, wherein all Ar are the same group.

[0026] An aniline derivative of 3.2, wherein Ar is a group represented by any one of the formulas (Ar1) to (Ar5).

[0027] An aniline derivative of 4.3, wherein Ar is a group represented by the formula (Ar1).

[0028] A method for producing an aniline derivative of 5.1, wherein p-phenylenediamine is reacted with a carbazole derivative represented by the following formula (N1) in the presence of a catalyst.

[0029] [Chemical formula 3]

[0030] Ar-X (N1)

[0031] (In the formula, Ar is the same as above, and X is a halogen atom or a pseudohalogen group.)

[0032] Effects of the invention

[0033] The aniline derivative of the present invention is easily soluble in an organic solvent, and when it is dissolved alone or together with a dopant in an organic solvent, a charge-transporting composition can be easily prepared. In addition, the aniline derivative of the present invention gives a thin film with high charge transportability, and this thin film can be suitably applied to electronic components such as organic EL elements. Detailed implementation manners

[0034] The aniline derivative of the present invention is represented by the following formula (1).

[0035] [Chemical formula 4]

[0036]

[0037] In formula (1), each Ar is independently a group represented by any one of the following formulas (Ar1) to (Ar9).

[0038] [Chemical formula 5]

[0039]

[0040] In formulas (Ar1) to (Ar9), R 1 ~R 21 are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 1 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 1 , an alkynyl group having 2 to 20 carbon atoms which may be substituted by Z 1 , an aryl group having 6 to 20 carbon atoms which may be substituted by Z 2 or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z 2 . Z1 is a halogen atom, nitro group, cyano group, an aryl group having 6 to 20 carbon atoms which may be substituted by Z 3 or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z 3 . Z 2 is a halogen atom, nitro group, cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 3 or an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 3 or an alkynyl group having 2 to 20 carbon atoms which may be substituted by Z 3 . Z 3 is a halogen atom, nitro group or cyano group.

[0041] As the above-mentioned halogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. can be cited, and fluorine atom is preferred.

[0042] Regarding the above-mentioned alkyl group having 1 to 20 carbon atoms, it may be linear, branched or cyclic. As specific examples thereof, linear or branched alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. can be cited; cyclic alkyl groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, etc.

[0043] Regarding the above-mentioned alkenyl group having 2 to 20 carbon atoms, it may be linear, branched or cyclic. As specific examples thereof, vinyl 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-1-pentenyl group, n-1-decenyl group, etc. can be cited.

[0044] Regarding the above-mentioned alkynyl group having 2 to 20 carbon atoms, it may be linear, branched or cyclic. As specific examples thereof, 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-1-decynyl group, etc. can be cited.

[0045] As specific examples of the above-mentioned aryl group having 6 to 20 carbon atoms, phenyl group, tolyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc. can be cited.

[0046] As specific examples of the heteroaryl group having 2 to 20 carbon atoms described above, oxygen-containing heteroaryl groups such as 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, sulfur-containing heteroaryl groups such as 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, nitrogen-containing heteroaryl groups such as 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 3-pyrazinyl, 5-pyrazinyl, 6-pyrazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6-pyrimidinyl, 3-pyridazinyl, 4-pyridazinyl, 5-pyridazinyl, 6-pyridazinyl, 1,2,3-triazin-4-yl, 1,2,3-triazin-5-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,2,4-triazin-6-yl, 1,3,5-triazin-2-yl, 1,2,4,5-tetrazin-3-yl, 1,2,3,4-tetrazin-5-yl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, 8-quinazolinyl, 3-cinnolinyl, 4-cinnolinyl, 5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8-cinnolinyl, etc. may be mentioned.

[0047] Among them, as R 1 ~R 21 , an aryl group having 6 to 20 carbon atoms which may be substituted by Z 2 , a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z 2 are preferred, an aryl group having 6 to 20 carbon atoms which may be substituted by Z 2 is more preferred, a phenyl group which may be substituted by Z 2 , a 1-naphthyl group which may be substituted by Z 2 , a 2-naphthyl group which may be substituted by Z 2 are further preferred. In addition, as Z 2 , a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 3 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 3 are preferred. As Z 3 , a halogen atom is preferred, and a fluorine atom is more preferred.

[0048] In the present invention, from the viewpoint of the ease of synthesis of aniline derivatives, it is preferred that all of Ar are the same group. Further, from the viewpoint of obtaining a highly homogeneous composition with good reproducibility when preparing the charge transporting composition, a group represented by any one of the formulas (Ar1) to (Ar5) is more preferred, and a group represented by the formula (Ar1) is most preferred.

[0049] The following lists preferred specific examples of the aniline derivatives of the present invention, but are not limited thereto.

[0050] [Chemical formula 6]

[0051]

[0052] (In the formula, Ph is a phenyl group.)

[0053] The aniline derivative of the present invention can be produced by reacting p-phenylenediamine (1,4-phenylenediamine) with a halogenated or pseudohalogenated carbazole derivative represented by the following formula (N1) in the presence of a catalyst.

[0054] [Chemical formula 7]

[0055] Ar-X (N1)

[0056] (In the formula, Ar is the same as above, and X is a halogen atom or a pseudohalogen group.)

[0057] Examples of the above-mentioned halogen atom include the same halogen atoms as above, preferably a chlorine atom, a bromine atom, and an iodine atom. Examples of the above-mentioned pseudohalogen group include (fluoro)alkylsulfonyloxy groups such as methanesulfonyloxy, trifluoromethanesulfonyloxy, and nonafluorobutanesulfonyloxy; and aromatic sulfonyloxy groups such as benzenesulfonyloxy and toluenesulfonyloxy.

[0058] Regarding the feeding ratio of 1,4-phenylenediamine to the halogenated or pseudohalogenated carbazole derivative, the halogenated or pseudohalogenated carbazole derivative can be made equivalent or more, preferably about 1 to 1.2 equivalents, relative to the total amount of NH groups of 1,4-phenylenediamine.

[0059] Examples of the catalyst used in the above reaction include copper catalysts such as copper chloride, copper bromide, and copper iodide; palladium catalysts such as tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), bis(triphenylphosphine)palladium dichloride (Pd(PPh3)2Cl2), bis(dibenzylideneacetone)palladium (Pd(dba)2), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3), bis[tris(tert-butylphosphine)]palladium (Pd(P-t-Bu3)2), and palladium acetate (Pd(OAc)2). These catalysts can be used alone or in combination of two or more.

[0060] In addition, these catalysts can be used together with a known appropriate ligand. Examples of such ligands include tertiary phosphines such as triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-tert-butylphosphine, di-tert-butyl(phenyl)phosphine, di-tert-butyl(4-dimethylaminophenyl)phosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, and 1,1'-bis(diphenylphosphino)ferrocene, and triesters of phosphites such as trimethyl phosphite, triethyl phosphite, and triphenyl phosphite.

[0061] The amount of the catalyst used can be about 0.01 to 0.2 mol, preferably about 0.15 mol, relative to 1 mol of the halogenated or pseudo-halogenated carbazole derivative. In addition, when a ligand is used, the amount thereof can be 0.1 to 5 equivalents, preferably 1 to 2 equivalents, relative to the catalyst used.

[0062] In the case where all the raw material compounds are solid or from the viewpoint of efficiently obtaining the target aniline derivative, the above-mentioned reactions are carried out in a solvent. When a solvent is used, its type is not particularly limited as long as it does not adversely affect the reaction. As specific examples, aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decahydronaphthalene, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, 1,2 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.), amides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), lactams and lactones (N-methylpyrrolidone, γ-butyrolactone, etc.), ureas (N,N-dimethylimidazolidinone, tetramethylurea, etc.), sulfoxides (dimethyl sulfoxide, cyclopentane, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.), etc., but are not limited to these. These solvents may be used alone or in combination of two or more.

[0063] The reaction temperature can be appropriately set within the range of the melting point to boiling point of the solvent used, and is usually about 0 to 200° C., preferably 20 to 150° C. After the reaction, post-treatment is performed according to a conventional method to obtain the target aniline derivative.

[0064] The aniline derivatives of the present invention are suitable as charge transporting materials and, moreover, exhibit excellent solubility in organic solvents. Therefore, by dissolving the aniline derivatives of the present invention in an organic solvent, a charge transporting composition can be easily prepared.

[0065] As such an organic solvent, a highly soluble solvent capable of dissolving the aniline derivatives of the present invention well can be used. Specific examples of the highly soluble solvent include, for example, organic solvents such as cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and diethylene glycol monomethyl ether, but are not limited thereto. These solvents can be used alone or in combination of two or more. Regarding the amount used, it can be set to 5 to 100% by mass relative to all the solvents used in the composition.

[0066] In addition, by making the composition contain at least one highly viscous organic solvent having 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, under normal pressure (atmospheric pressure), the adjustment of the viscosity of the composition becomes easy. As a result, it becomes possible to prepare a composition that gives a film with high flatness and good reproducibility in accordance with the coating method used. Examples of the highly viscous organic solvent include, for example, cyclohexanol, ethylene glycol, ethylene glycol diglycidyl ether, 1,3-octanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, propylene glycol, hexanediol, etc., but are not limited thereto. These solvents can be used alone or in combination of two or more. The addition ratio of the highly viscous organic solvent relative to all the solvents used in the composition is preferably within the range where no solid precipitates, and as long as no solid precipitates, the addition ratio is preferably 5 to 80% by mass.

[0067] Furthermore, for the purposes of improving the wettability to the substrate, adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, etc., other solvents can also be mixed in a ratio of 1 to 90% by mass, preferably 1 to 50% by mass, relative to all the solvents used in the composition. Examples of such solvents include, for example, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diacetone alcohol, γ-butyrolactone, ethyl lactate, n-hexyl acetate, etc., but are not limited thereto. These solvents can be used alone or in combination of two or more.

[0068] In addition, in the case where the aniline derivative of the present invention has a substituent on at least one nitrogen atom in the molecule, such as having an aryl group on the nitrogen atom at the 9-position of the carbazole moiety in the molecule, preferably when having substituents on all nitrogen atoms, the preparation of a composition using only a low-polarity solvent becomes easy. Specific examples of such low-polarity solvents include chloroform, chlorobenzene and other chlorine-based solvents; toluene, xylene, tetralin, cyclohexylbenzene, decylbenzene and other aromatic hydrocarbon-based solvents; 1-octanol, 1-nonanol, 1-decanol and other aliphatic alcohol-based solvents; tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether and other ether-based solvents; methyl benzoate, ethyl benzoate, butyl benzoate, dimethyl phthalate, diethyl maleate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and other ester-based solvents, etc., but are not limited to these. These solvents may be used alone or in combination of two or more.

[0069] The charge transporting composition of the present invention may also contain water as a solvent. From the viewpoint of obtaining a highly durable element with good reproducibility when the charge transporting film obtained from the composition is used as the hole injection layer of an organic EL element, the content of water is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably only organic solvents are used as the solvent. It should be noted that "using only organic solvents" in this case means that only organic solvents are used as the solvent, and it does not deny the existence of "water" contained in trace amounts in the used organic solvents, solid components, etc. In addition, in the present invention, the solid component means the components other than the solvent contained in the charge transporting composition.

[0070] The charge transporting composition of the present invention may contain other charge transporting substances while containing a charge transporting substance containing the aniline derivative of the present invention.

[0071] The above charge transporting composition contains a charge transporting substance containing the aniline derivative of the present invention and an organic solvent, and may contain a dopant (charge accepting substance) for the purpose of improving its charge transporting ability, etc., according to the use of the obtained film.

[0072] As the dopant, as long as it is soluble in at least one solvent used in the composition, there is no particular limitation, and both inorganic dopants and organic dopants can be used. In addition, the inorganic and organic dopants may be used alone or in combination of two or more.

[0073] The amount of the dopant in the composition varies depending on the degree of desired charge transportability and the type of dopant, and thus cannot be generally specified. Usually, it is in the range of 0.0001 to 100 in terms of mass ratio with respect to the aniline derivative 1 represented by the formula (1).

[0074] In the present invention, as an example of a preferred dopant, an ionic compound can be cited. As specific examples thereof, anions represented by the following formula (2a), anions represented by the following formula (2b), hydroxide ions, fluoride ions, chloride ions, bromide ions, iodide ions, cyanide ions, nitrate ions, nitrite ions, sulfate ions, sulfite ions, perchlorate ions, perbromate ions, periodate ions, chlorate ions, chlorite ions, hypochlorite ions, phosphate ions, phosphite ions, hypophosphite ions, borate ions, isocyanate ions, hydrosulfide ions, tetrafluoroborate ions, hexafluorophosphate ions, hexafluoroantimonate ions; carboxylate ions such as acetate ions, trifluoroacetate ions, benzoate ions; sulfonate ions such as methanesulfonic acid, trifluoromethanesulfonate ions; and salts composed of alcoholate ions such as methoxide ions, tert-butoxide ions and their counter cations can be cited.

[0075] [Chemical formula 8]

[0076]

[0077] In formula (2a), E 1 is an element belonging to Group 13 or Group 15 of the long-period type periodic table. Among them, boron, gallium, phosphorus, and antimony are preferred, and boron is more preferred.

[0078] In formula (2a), Ar 1 ~Ar 4 are independently an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. As the above aromatic hydrocarbon group and aromatic heterocyclic group, monovalent groups derived from a 5- or 6-membered single ring or 2-4 fused rings can be cited. Among them, from the viewpoints of the stability and heat resistance of the compound, monovalent groups derived from benzene, naphthalene, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, etc. are preferred.

[0079] Furthermore, at least one of the groups of Ar 1 ~Ar 4 more preferably has one or two or more fluorine atoms or chlorine atoms as substituents. In particular, more preferably, all hydrogen atoms of Ar 1 ~Ar 4 are substituted with fluorine atoms to form a perfluoroaryl group or a perfluoroheteroaryl group, and most preferably, all hydrogen atoms of Ar 1 ~Ar 4A perfluoroaryl group in which all hydrogen atoms are replaced by fluorine atoms. Specific examples of the perfluoroaryl group include a pentafluorophenyl group, a heptafluoro-2-naphthyl group, a tetrafluoro-4-pyridyl group, etc.

[0080] In formula (2b), E 2 is an element belonging to Group 15 of the long-period type periodic table. Among them, a phosphorus atom, an arsenic atom, and an antimony atom are preferred, and a phosphorus atom is preferred from the viewpoints of the stability of the compound, ease of synthesis and purification, and toxicity. X a is a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom. From the viewpoints of the stability of the compound, ease of synthesis and purification, a fluorine atom and a chlorine atom are preferred, and a fluorine atom is most preferred.

[0081] As the above counter cation, a metal ion and an onium ion are preferred. As the above metal ion, a monovalent metal ion is preferred, and examples include Li + , Na + , K + and Ag + etc., and Ag + is particularly preferred. As the above onium ion, an iodonium ion, a sulfonium ion, an ammonium ion, a phosphonium ion, etc. can be mentioned.

[0082] As the above onium ion, an iodonium ion represented by the following formula (2c) is preferred.

[0083] [Chemical formula 9]

[0084]

[0085] In formula (2c), R 101 and R 102 are independently 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, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and a part or all of the hydrogen atoms of these groups may be substituted by a halogen atom, a cyano group, a nitro group, 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, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms.

[0086] As the above onium ion, an ion represented by the following formula (2d) can also be used.

[0087] [Chemical formula 10]

[0088]

[0089] In formula (2d), E 3Elements after the 3rd period (3rd to 6th periods) of the periodic table, and elements belonging to Group 16 of the long-period type periodic table. In the present invention, among these, from the viewpoints of electron acceptability and ease of acquisition, elements before the 5th period (3rd to 5th periods) of the periodic table are preferred. That is, as E 3 , a sulfur atom, a selenium atom, or a tellurium atom is preferred, and a sulfur atom is more preferred.

[0090] In formula (2d), R 103 is an organic group bonded to E 3 via a carbon atom, and R 104 and R 105 are each independently an arbitrary substituent. Two or more adjacent groups among R 103 to R 105 may be bonded to each other to form a ring.

[0091] R 103 is not particularly limited as long as it is an organic group having a carbon atom at the bonding portion with E 3 and does not violate the gist of the present invention. The molecular weight of R 103 is usually 1000 or less, preferably in the range of 500 or less. Preferred examples of R 103 include, from the aspect of delocalizing positive charges, alkyl, alkenyl, alkynyl, aromatic hydrocarbon group, and aromatic heterocyclic group. Among them, from the viewpoints of delocalizing positive charges and thermal stability, aromatic hydrocarbon or aromatic heterocyclic group is preferred.

[0092] As the above-mentioned aromatic hydrocarbon group, it is a monovalent group derived from a 5- or 6-membered ring or 2 to 5 fused rings, and groups that can delocalize positive charges on the group can be cited. As specific examples thereof, monovalent groups derived from benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, (chrysene), benzo[9,10]phenanthrene, acenaphthene, fluorene, etc. can be cited. More specifically, phenyl, tolyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, etc. can be cited. Among these, phenyl and tolyl are preferred, and tolyl is more preferred.

[0093] As the above-mentioned aromatic heterocyclic group, a monovalent group of a monocyclic or 2-4 fused rings from a 5- or 6-membered ring, groups that can delocalize a positive charge on the group can be cited. As specific examples thereof, monovalent groups derived from furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxadiazole, indole, carbazole, pyrroloimidazole, pyrrolopyrazole, pyrrolopyrrole, thiophenopyrrole, thiophenothiophene, furanopyrrole, furanofuran, thiophenofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, cinnoline, quinoxaline, phenanthridine, benzimidazole, pyrimidine, quinazoline, quinazolinone, azulene, etc. can be cited.

[0094] As the above-mentioned alkyl group, it can be linear, branched, or cyclic, and alkyl groups having usually 1 or more, usually 12 or less, preferably 6 or less carbon atoms can be cited. As specific examples thereof, methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, etc. can be cited.

[0095] As the above-mentioned alkenyl group, alkenyl groups having usually 2 or more, usually 12 or less, preferably 6 or less carbon atoms can be cited. As specific examples thereof, vinyl, allyl, 1-butenyl, etc. can be cited.

[0096] As the above-mentioned alkynyl group, alkynyl groups having usually 2 or more, usually 12 or less, preferably 6 or less carbon atoms can be cited. As specific examples thereof, ethynyl, propargyl, etc. can be cited.

[0097] R 104 and R 105 are not particularly limited as long as they do not violate the gist of the present invention. The molecular weights of R 104 and R 105 are usually in the range of 1000 or less, preferably 500 or less. As examples of R 104 and R 105 , alkyl, alkenyl, alkynyl, aromatic hydrocarbon group, aromatic heterocyclic group, organic amino group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonyloxy group, arylsulfonyloxy group, cyano group, hydroxy group, mercapto group, organosilyl group, etc. can be cited. Among them, similar to R 103 , from the aspect of large electron accepting property, an organic group having a carbon atom at the binding portion with E 3 is preferred, for example, an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, and an aromatic heterocyclic group are preferred. In particular, from the aspect of large electron accepting property and thermal stability, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferred.

[0098] As the above-mentioned alkyl group, alkenyl group, alkynyl group, aromatic hydrocarbon group, and aromatic heterocyclic group, those similar to R 103The same groups as those described in the description.

[0099] As the above-mentioned organic amino group, amino groups substituted with organic groups such as alkyl, aryl, heteroaryl, aralkyl, acyl, etc. can be cited. As the amino group substituted with the above-mentioned alkyl group, amino groups having one or more alkyl groups with a carbon number usually of 1 or more, usually 12 or less, preferably 6 or less can be cited. As specific examples thereof, methylamino, dimethylamino, diethylamino, etc. can be cited.

[0100] As the amino group substituted with the above-mentioned aryl or heteroaryl group, amino groups having one or more aromatic hydrocarbon groups or aromatic heterocyclic groups with a carbon number usually of 3 or more, preferably 4 or more, usually 25 or less, preferably 15 or less can be cited. As specific examples thereof, phenylamino, diphenylamino, tolylamino, pyridylamino, thienylamino, etc. can be cited.

[0101] As the amino group substituted with the above-mentioned aralkyl group, amino groups having one or more aralkyl groups with a carbon number usually of 7 or more, usually 25 or less, preferably 15 or less can be cited. As specific examples thereof, benzylamino, dibenzylamino, etc. can be cited.

[0102] As the amino group substituted with the above-mentioned acyl group, acylamino groups having one or more acyl groups with a carbon number usually of 2 or more, usually 25 or less, preferably 15 or less can be cited. As specific examples thereof, acetylamino, benzoylamino, etc. can be cited.

[0103] As the above-mentioned alkoxy group, alkoxy groups with a carbon number usually of 1 or more, usually 12 or less, preferably 6 or less can be cited. As specific examples thereof, methoxy, ethoxy, butoxy, etc. can be cited.

[0104] As the above-mentioned aryloxy group, aryloxy groups having aromatic hydrocarbon groups or aromatic heterocyclic groups with a carbon number usually of 3 or more, preferably 4 or more, usually 25 or less, preferably 15 or less can be cited. As specific examples thereof, phenoxy, naphthoxy, pyridyloxy, thienyloxy, etc. can be cited.

[0105] As the above-mentioned acyl group, acyl groups with a carbon number usually of 1 or more, usually 25 or less, preferably 15 or less can be cited. As specific examples thereof, formyl, acetyl, benzoyl, etc. can be cited.

[0106] As the above-mentioned alkoxycarbonyl group, alkoxycarbonyl groups with a carbon number usually of 2 or more, usually 10 or less, preferably 7 or less can be cited. As specific examples thereof, methoxycarbonyl, ethoxycarbonyl, etc. can be cited.

[0107] As the above aryloxycarbonyl group, an aryloxycarbonyl group having an aromatic hydrocarbon group or an aromatic heterocyclic group with usually 3 or more, preferably 4 or more, usually 25 or less, and preferably 15 or less carbon atoms can be mentioned. Specific examples thereof include phenoxycarbonyl group, pyridyloxycarbonyl group and the like.

[0108] As the above alkylcarbonyloxy group, an alkylcarbonyloxy group having usually 2 or more, and usually 10 or less, preferably 7 or less carbon atoms can be mentioned. Specific examples thereof include acetoxy group, trifluoroacetoxy group and the like.

[0109] As the above alkylthio group, an alkylthio group having usually 1 or more, and usually 12 or less, preferably 6 or less carbon atoms can be mentioned. Specific examples thereof include methylthio group, ethylthio group and the like.

[0110] As the above arylthio group, an arylthio group having usually 3 or more, preferably 4 or more, usually 25 or less, and preferably 14 or less carbon atoms can be mentioned. Specific examples thereof include phenylthio group, naphthylthio group, pyridylthio group and the like.

[0111] Specific examples of the above alkylsulfonyl group and arylsulfonyl group include methanesulfonyl group, toluenesulfonyl group and the like.

[0112] Specific examples of the above alkylsulfonyloxy group and arylsulfonyloxy group include methanesulfonyloxy group, toluenesulfonyloxy group and the like.

[0113] Specific examples of the above organosilyl group include trimethylsilyl group, triphenylsilyl group and the like.

[0114] The groups exemplified above as R 103 , R 104 and R 105 As long as the exemplified groups do not violate the gist of the present invention, they may be further substituted with other substituents. The type of the substituent is not particularly limited. For example, in addition to the groups exemplified as R 103 , R 104 and R 105 , halogen atoms, cyano group, thiocyanato group, nitro group and the like can be mentioned. Among them, from the viewpoints of heat resistance and prevention of hindrance to electron acceptability that will not become an ionic compound (electron-accepting ionic compound), an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferred.

[0115] Among the above, an ionic compound represented by the following formulas (2-1) to (2-4) can be preferably used (refer to Japanese Patent No. 5381931).

[0116] [Chemical Formula 11]

[0117]

[0118] [Chemical formula 12]

[0119]

[0120] Furthermore, it is also possible to preferably use an onium borate (a neutral salt) composed of a monovalent or divalent anion represented by formula (3a) and a counter cation represented by any one of formulas (4a) to (4e).

[0121] [Chemical formula 13]

[0122]

[0123] [Chemical formula 14]

[0124]

[0125] In formula (3a), Ar 11 ~Ar 16 are each independently an aryl group which may have a substituent or a heteroaryl group which may have a substituent. L is an alkylene group, -NH-, an oxygen atom, a sulfur atom or -CN + -.

[0126] Examples of the above-mentioned aryl group include aryl groups having 6 to 20 carbon atoms. Specific examples thereof include the same groups as those exemplified in the description of R 1 ~R 21 , and phenyl, tolyl and naphthyl are preferred. Examples of the above-mentioned heteroaryl group include heteroaryl groups having 2 to 20 carbon atoms. Specific examples thereof include the same groups as those exemplified in the description of R 1 ~R 21 .

[0127] Examples of the above-mentioned substituent include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms and an alkynyl group having 2 to 20 carbon atoms.

[0128] Specific examples of the above-mentioned alkyl group include the same groups as those exemplified in the description of R 1 ~R 21 , an alkyl group having 1 to 18 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms is more preferred. Specific examples of the above-mentioned halogen atom, alkenyl group and alkynyl group include the same groups as those exemplified in the description of R 1 ~R 21 .

[0129] As the above-mentioned aryl group and heteroaryl group, a group having one or two or more electron-withdrawing groups as substituents is preferred. Examples of the electron-withdrawing group in the above-mentioned substituents include a halogen atom, a nitro group, a cyano group, etc., a halogen atom is preferred, and a fluorine atom is particularly preferred.

[0130] In formula (3a), L is an alkylene group, -NH-, an oxygen atom, a sulfur atom or -CN + -, preferably -CN + -.

[0131] Regarding the above-mentioned alkylene group, it can be linear, branched or cyclic, and alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, can be mentioned. Specific examples thereof include methylene, methylmethylene, dimethylmethylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, etc.

[0132] As the anion represented by formula (3a) that can be preferably used in the present invention, the anion represented by formula (3b) can be mentioned, but it is not limited thereto.

[0133] [Chemical 15]

[0134]

[0135] In the present invention, the above-mentioned onium borate can be used alone as one kind, or two or more kinds can be used in combination. In addition, according to need, other known onium borates can be used in combination. It should be noted that the above-mentioned onium borate can be synthesized, for example, with reference to the known methods described in Japanese Patent Application Laid-Open No. 2005-314682 and the like.

[0136] Regarding the above-mentioned onium borate, in order to facilitate dissolution in the charge transport composition, it can be pre-dissolved in an organic solvent during the preparation of the composition. Examples of such organic solvents include propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate and other carbonates; acetone, methyl ethyl ketone, cyclohexanone, methyl isopentyl ketone, 2-heptanone and other ketones; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of dipropylene glycol monoacetate and other polyhydric alcohols and their derivatives; dioxane and other cyclic ethers; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and other esters; toluene, xylene, 3-phenoxytoluene, 4-methoxytoluene, methyl benzoate, cyclohexylbenzene, tetralin, isophorone and other aromatic hydrocarbons, etc. These solvents can be used alone or in combination of two or more. Regarding the amount used, it is preferably 15 to 1000 parts by mass, more preferably 30 to 500 parts by mass, relative to 100 parts by mass of the above-mentioned onium borate.

[0137] When the above charge transport composition contains the above onium borate as a dopant, regarding its content, in terms of mass ratio, it is preferably in an amount such that the charge transport material (the aniline derivative of the present invention): onium borate is about 1:0.01 to 20, more preferably about 1:0.01 to 10, further preferably about 1:0.01 to 2, and further preferably about 1:0.1 to 2.

[0138] In the above charge transport composition, the above charge transport material and dopant are preferably in a state of being completely dissolved or uniformly dispersed in the above solvent, and most preferably completely dissolved.

[0139] Regarding the above charge transport composition, for the purpose of improving the injectability into the hole transport layer when using the obtained film as the hole injection layer of an organic EL element and improving the life characteristics of the element, etc., an organosilane compound and a nonionic fluorosurfactant can be included. Regarding the amount, it is usually about 1 to 30 parts by mass relative to 100 parts by mass in total of the charge transport material and the dopant.

[0140] Regarding the solid component concentration in the above charge transport composition, from the viewpoints of suppressing precipitation of the charge transport material and ensuring a sufficient film thickness, it is generally about 0.1 to 20% by mass, preferably 0.5 to 15% by mass.

[0141] The viscosity of the above charge transport composition is generally 1 to 50 mPa·s at 25°C, and the surface tension is generally 20 to 50 mN / m at 25°C. Regarding the viscosity and surface tension of the above charge transport composition, various factors such as the coating method to be used and the desired film thickness are considered, and they can be adjusted by changing the types of organic solvents used, their ratios, the solid component concentration, etc.

[0142] The above charge transport composition can be produced by dissolving the aniline derivative of the present invention in an organic solvent. The aniline derivative of the present invention can be dissolved in an organic solvent in advance, and other organic solvents can be sequentially added thereto, or a mixed solvent of all the solvents to be used can be prepared in advance, and the aniline derivative of the present invention can be dissolved therein. In addition, if necessary, while paying attention not to decompose or deteriorate the components contained in the composition, heating can be performed to promote the dissolution of the aniline derivative of the present invention and the like. The same method is also applicable when the above charge transport composition contains components other than the aniline derivative and the solvent of the present invention. Furthermore, regarding the above charge transport composition, from the viewpoint of obtaining a film with higher flatness with good reproducibility, after dissolving the charge transport material in an organic solvent, it can be filtered using a submicron filter or the like.

[0143] By coating and firing the above-described charge transport composition on a substrate, a charge transport film can be formed on the substrate.

[0144] As the coating method of the composition, there is no particular limitation, and examples include dipping method, spin coating method, transfer printing method, roll coating method, inkjet method, spraying method, slot coating method, etc. It is preferable to adjust the viscosity and surface tension of the composition according to the coating method.

[0145] There is no particular limitation on the firing atmosphere either. Not only in an atmospheric atmosphere (under air), but also in an inert gas such as nitrogen or in a vacuum, a film having a uniform film-forming surface and charge transport properties can be obtained, and it is usually fired in an atmospheric atmosphere.

[0146] In addition, there is no particular limitation on the firing conditions either. For example, heating and firing are performed using a hot plate. Generally, also considering the desired charge transport properties and the like, the firing temperature is appropriately determined within the range of 100 to 260°C, and the firing time is within the range of 1 minute to 1 hour. Furthermore, if necessary, multi-stage firing can be performed at two or more different temperatures.

[0147] There is no particular limitation on the film thickness of the charge-transporting film. When it is used as a functional layer of an organic EL element, a thickness of 5 to 300 nm is preferred. As a method of changing the film thickness, for example, there are methods of changing the solid content concentration in the charge-transporting composition or changing the liquid amount during coating.

[0148] The above charge-transporting film can preferably be used as a functional layer of an organic EL element. When the above charge-transporting film is applied to an organic EL element, the organic EL element has a pair of electrodes, and the above charge-transporting film is provided between these electrodes.

[0149] As representative configurations of an organic EL element, the following (a) to (f) can be cited, but are not limited thereto. It should be noted that in the following configurations, an electron blocking layer or the like can be provided between the light-emitting layer and the anode as needed, and a hole (hole) blocking layer or the like can be provided between the light-emitting layer and the cathode. In addition, the hole injection layer, hole transport layer, or hole injection transport layer can also function as an electron blocking layer or the like, and the electron injection layer, electron transport layer, or electron injection transport layer can also function as a hole (hole) blocking layer or the like. Furthermore, as needed, an arbitrary functional layer can be provided between each layer.

[0150] (a) Anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode

[0151] (b) Anode / hole injection layer / hole transport layer / light-emitting layer / electron injection transport layer / cathode

[0152] (c) Anode / hole injection transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode

[0153] (d) Anode / hole injection transport layer / light-emitting layer / electron injection transport layer / cathode

[0154] (e) Anode / hole injection layer / hole transport layer / light-emitting layer / cathode

[0155] (f) Anode / hole injection transport layer / light-emitting layer / cathode

[0156] The "hole injection layer", "hole transport layer", and "hole injection transport layer" are layers formed between the light-emitting layer and the anode, and have the function of transporting holes from the anode to the light-emitting layer. When only one layer of hole-transporting material is provided between the light-emitting layer and the anode, it is the "hole injection transport layer". When two or more layers of hole-transporting material are provided between the light-emitting layer and the anode, the layer close to the anode is the "hole injection layer", and the other layers are the "hole transport layer". In particular, the hole injection (transport) layer uses a film that is excellent not only in hole acceptability from the anode but also in hole injectability into the hole transport (light-emitting) layer.

[0157] "Electron injection layer", "electron transport layer", and "electron injection transport layer" are layers formed between the light-emitting layer and the cathode, and have the function of transporting electrons from the cathode to the light-emitting layer. When only one layer of electron-transporting material is provided between the light-emitting layer and the cathode, it is an "electron injection transport layer". When two or more layers of electron-transporting material are provided between the light-emitting layer and the cathode, the layer closer to the cathode is the "electron injection layer", and the other layers are the "electron transport layer".

[0158] The "light-emitting layer" is an organic layer having a light-emitting function. In the case of using a doping system, it contains a host material and a dopant material. At this time, the host material mainly has the functions of promoting the recombination of electrons and holes and confining excitons within the light-emitting layer, and the dopant material has the function of efficiently emitting light from the excitons obtained by recombination. In the case of a phosphorescent element, the host material mainly has the function of confining the excitons generated by the dopant within the light-emitting layer.

[0159] The above charge-transporting thin film is preferably used as a functional layer provided between the anode and the light-emitting layer in an organic EL element, more preferably used as a hole injection layer, a hole transport layer, a hole injection transport layer, and further preferably used as a hole injection layer.

[0160] As the materials and manufacturing methods for manufacturing an organic EL element using the above charge-transporting composition, the following materials and manufacturing methods can be cited, but are not limited thereto.

[0161] An example of a manufacturing method of an OLED element having a hole transport layer including a thin film obtained by including the above charge-transporting composition is as follows. Further, for the electrodes, it is preferable to perform cleaning using alcohol, pure water, etc. and surface treatment using UV ozone treatment, oxygen-plasma treatment, etc. in a range that does not cause adverse effects on the electrodes.

[0162] On the anode substrate, using the above method, a hole injection layer composed of the above charge-transporting thin film is formed. It is introduced into a vacuum evaporation apparatus, and a hole transport layer, a light-emitting layer, an electron transport layer, an electron transport layer / hole blocking layer, and a cathode metal are sequentially evaporated. Alternatively, in this method, instead of forming the hole transport layer and the light-emitting layer by evaporation, a hole transport layer-forming composition containing a hole-transporting polymer and a light-emitting layer-forming composition containing a light-emitting polymer are used, and these layers are formed by a wet method. Further, if necessary, an electron blocking layer can be provided between the light-emitting layer and the hole transport layer.

[0163] As the anode material, transparent electrodes represented by indium tin oxide (ITO) and indium zinc oxide (IZO), metals represented by aluminum, their alloys, etc., and preferably an anode material that has been planarized can be cited. A polythiophene derivative or a polyaniline derivative having high charge transportability can also be used. Further, as other metals constituting the metal anode, gold, silver, copper, indium, their alloys, etc. can be cited, but it is not limited to these.

[0164] As the material for forming the light-emitting layer, tris(8-hydroxyquinoline)aluminum(III) (Alq3), zinc(II) bis(8-hydroxyquinoline), etc., metal complexes such as aluminum complexes and zinc complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo[h]quinoline, distyrylbenzene derivatives, distyrylarylene derivatives, metal complexes of (2-hydroxyphenyl)benzothiazole, low molecular weight light-emitting materials such as silole derivatives; systems in which a light-emitting material and an electron transport material are mixed in a polymer compound such as poly(p-phenylene vinylene), poly[2-methoxy-5-(2-ethylhexoxy)-1,4-phenylene vinylene], poly(3-alkylthiophene), polyvinylcarbazole, etc. can be cited, but it is not limited to these. Further, in the case of forming the light-emitting layer by vapor deposition, it can be co-vapor deposited with a light-emitting dopant. As the light-emitting dopant, metal complexes such as tris(2-phenylpyridine)iridium(III) (Ir(PPy)3), tetracene derivatives such as rubrene, quinacridone derivatives, condensed polycyclic aromatic rings such as perylene, etc. can be cited, but it is not limited to these.

[0165] As the material for forming the electron transport layer / hole blocking layer, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, pyrimidine derivatives, etc. can be cited, but it is not limited to these.

[0166] As the material for forming the electron injection layer, metal oxides such as lithium oxide (Li2O), magnesium oxide (MgO), aluminum oxide (Al2O3), metal fluorides such as lithium fluoride (LiF), sodium fluoride (NaF) can be cited, but it is not limited to these.

[0167] As the cathode material, aluminum, magnesium-silver alloy, aluminum-lithium alloy, etc. can be cited, but it is not limited to these.

[0168] As the material for forming the electron blocking layer, tris(phenylpyrazole)iridium, etc. can be cited, but it is not limited thereto.

[0169] Examples of hole-transporting polymers include poly[(9,9-dihexylfluorene-2,7-diyl)-co-(N,N'-bis{4-butylphenyl}-1,4-diaminophenylene)], poly[(9,9-dioctylfluorene-2,7-diyl)-co-(N,N'-bis{4-butylphenyl}-1,1'-biphenyl-4,4-diamine)], poly[(9,9-bis{1'-penten-5'-yl}fluorene-2,7-diyl)-co-(N,N'-bis{4-butylphenyl}-1,4-diaminophenylene)], poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine] capped with polysilsesquioxane, poly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-butylphenyl))diphenylamine)], and the like.

[0170] Examples of light-emitting polymers include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), poly(phenylenevinylene) derivatives such as poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), poly(thiophene) derivatives such as poly(3-alkylthiophene) (PAT), polyvinylcarbazole (PVCz), and the like.

[0171] The materials constituting the anode, the cathode, and the layers formed therebetween vary depending on whether the element to be manufactured has a bottom-emission structure or a top-emission structure. Therefore, the materials are appropriately selected in consideration of this point.

[0172] Generally, in an element with a bottom-emission structure, a transparent anode is used on the substrate side, and light is extracted from the substrate side. In an element with a top-emission structure, a reflective anode made of metal is used, and light is extracted from the transparent electrode (cathode) side on the side opposite to the substrate. Therefore, for the anode material, when manufacturing an element with a bottom-emission structure, a transparent anode such as ITO is used, and when manufacturing an element with a top-emission structure, a reflective anode such as Al / Nd is used.

[0173] Regarding the organic EL element of the present invention, in order to prevent deterioration of characteristics, it is sealed together with a water scavenger or the like according to a conventional method as needed.

[0174] The aniline derivative of the present invention has sublimability, and a vapor deposition film can be easily formed using it. Therefore, depending on the use, instead of the charge-transporting thin film obtained from the above charge-transporting composition, a charge-transporting thin film obtained by a vapor deposition method using the aniline derivative of the present invention can be used.

[0175] Examples

[0176] Examples are listed below to illustrate the present invention more specifically, but the present invention is not limited to the following examples. It should be noted that the devices used are as described below.

[0177] (1) LDI-MS: AutoFlex manufactured by Bruker

[0178] (2) 1 ¹H-NMR: JNM-ECP300 FT NMR SYSTEM manufactured by JEOL Ltd.

[0179] (3) Substrate cleaning: Substrate cleaning apparatus (vacuum plasma method) manufactured by Choshu Sangyo Co., Ltd.

[0180] (4) Coating of the composition: Spin coater MS-A100 manufactured by Mikasa Co., Ltd.

[0181] (5) Film thickness measurement: Micro shape measuring instrument SURFCORDER ET-4000 manufactured by Kosaka Laboratory Ltd.

[0182] (6) Fabrication of components: Multifunctional evaporation apparatus system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd.

[0183] (7) Measurement of current density etc. of components: Multi-channel IVL measuring apparatus manufactured by EHC Co., Ltd.

[0184] [1] Manufacture of compounds

[0185] [Example 1]

[0186] [Chemical 16]

[0187]

[0188] 0.502 g of 1,4-phenylenediamine, 6.26 g of 2-bromo-9-phenyl-9H-carbazole, 0.106 g of bis(dibenzylideneacetone)palladium, and 2.24 g of sodium tert-butoxide were placed in a flask, and the inside of the flask was purged with nitrogen. 10 mL of toluene and 1.3 mL of a toluene solution of phenyl di-tert-butylphosphine prepared in advance (concentration: 62.5 g / L) were added thereto, and the mixture was stirred at 90 °C for 3 hours. After cooling the reaction mixture to room temperature, toluene and saturated brine were placed in a separatory funnel together with the cooled reaction mixture, and liquid separation was performed to recover the organic layer. Activated carbon was added to the recovered organic layer, and the mixture was stirred at room temperature for 0.5 hour and then filtered through silica gel, and the resulting filtrate was concentrated.

[0189] The obtained concentrated solution was dropped into a mixed solvent of methanol and ethyl acetate and stirred for a while. The obtained slurry solution was filtered, and the obtained filtrate was dried to obtain 2.96 g (yield: 59%) of the target aniline derivative A. The obtained target product was identified by 1 ¹H-NMR.

[0190] 1 H-NMR (500 MHz, DMSO-d6) δ [ppm]: 8.09 - 8.15 (m, 8H), 7.54 - 7.57 (m, 8H), 7.43 - 7.47 (m, 12H), 7.33 - 7.37 (m, 4H), 7.24 - 7.30 (m, 8H), 7.05 (m, 8H), 6.92 - 6.94 (m, 4H).

[0191] [Synthesis Example 1] Preparation of Onium Borate

[0192] (1) Synthesis of Intermediate

[0193] [Chemical Formula 17]

[0194]

[0195] 6068 mL of diethyl ether, 151.7 g of tris(pentafluorophenyl)borane, and 9.4 g of potassium cyanide were placed in a flask and stirred at 34 - 36 °C for 3 hours. Then, the reaction mixture was concentrated under normal pressure to obtain 267.2 g of a brown liquid. The obtained brown liquid was concentrated under reduced pressure at 55 °C. The obtained solid was dried under reduced pressure at 35 °C for 16 hours to obtain 157.7 g of the intermediate represented by the formula (Q-1). The obtained target product was identified by LDI-MS.

[0196] LDI-MS m / Z measured value: 1050.12 ([M] - Calculated value: 1049.97).

[0197] (2) Synthesis of Onium Borate P

[0198] [Chemical Formula 18]

[0199]

[0200] 11.043 g of diphenyl[4-(phenylthio)phenyl]sulfonium trifluoromethanesulfonate, 22.000 g of the intermediate represented by the formula (Q-1), 110 mL of ion-exchanged water, and 110 mL of diethyl ether were placed in a flask and stirred at 25 °C for 16 hours. Then, the reaction mixture was placed in a separatory funnel, the organic layer was left, the aqueous layer was removed, and the remaining organic layer was washed with ion-exchanged water (100 mL × 5 times) and then recovered. From the recovered organic layer, the organic solvent was distilled off under reduced pressure at 40 - 45 °C, and the obtained residue was dried under reduced pressure for 20 hours to obtain 24 g of onium borate P. The obtained target product was identified by 1 H-NMR and LDI-MS.

[0201] 1H-NMR (300 MHz, DMSO-D6): δ 7.40 - 7.80 (19H, m)

[0202] LDI-MS m / Z found: 371.04 ([M] + calculated: 371.09).

[0203] LDI-MS m / Z found: 1050.11 ([M] - calculated: 1049.97).

[0204] [2] Preparation of Charge Transport Composition

[0205] [Reference Example 1]

[0206] To a mixture of 113 mg of aniline derivative A1 and 150 mg of onium borate P was added 5.0 g of xylene, and the mixture was stirred at room temperature until dissolved. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain a charge transport composition.

[0207] [3] Fabrication and Property Evaluation of Organic EL Device

[0208] [Reference Example 2]

[0209] The charge transport composition obtained in Reference Example 1 was coated on an ITO substrate using a spin coater and then dried at 120 °C for 1 minute in an air atmosphere. Next, the dried ITO substrate was inserted into a glove box and fired at 150 °C for 10 minutes in an air atmosphere to form a 50-nm-thick film on the ITO substrate. As the ITO substrate, a 25 mm × 25 mm × 0.7 t glass substrate with indium tin oxide (ITO) patterned on the surface with a film thickness of 150 nm was used. Before use, impurities on the surface were removed using an O2 plasma cleaning device (150 W, 30 s).

[0210] Next, for the ITO substrate on which the film was formed, a vapor deposition apparatus (vacuum degree 1.0 × 10 -5Pa) An α-NPD (N,N'-bis(1-naphthyl)-N,N'-diphenylbenzidine) film with a thickness of 120 nm was formed at a rate of 0.2 nm / second. Next, a 10-nm film of the electron blocking material HTEB-01 manufactured by Kanto Chemical Co., Inc. was formed. Next, the host material NS60 for the light-emitting layer and the dopant material Ir(PPy)3 for the light-emitting layer manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. were co-evaporated. Regarding the co-evaporation, the evaporation rate was controlled so that the concentration of Ir(PPy)3 became 6%, and a 40-nm layer was stacked. Next, thin films of Alq3, lithium fluoride, and aluminum were stacked in sequence to obtain an organic EL element. At this time, regarding the evaporation rate, for Alq3 and aluminum, it was carried out under the condition of 0.2 nm / second, and for lithium fluoride, it was carried out under the condition of 0.02 nm / second. The film thicknesses were set to 20 nm, 0.5 nm, and 80 nm, respectively.

[0211] It should be noted that in order to prevent deterioration of the characteristics caused by the influence of oxygen, water, etc. in the air, after the organic EL element was sealed with a sealing substrate, its characteristics were evaluated. The sealing was carried out according to the following steps. The organic EL element was placed between the sealing substrates in a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76°C or less, and the sealing substrates were pasted with an adhesive (MORESCO MOISTURE CUT Wb90US(P) manufactured by MORESCO Co., Ltd.). At this time, a water scavenger (HD-071010W-40 manufactured by Dainic Co., Ltd.) was placed inside the sealing substrate together with the organic EL element. For the pasted sealing substrates, UV light (wavelength: 365 nm, irradiation dose: 6000 mJ / cm 2 ) was irradiated, and then annealed at 80°C for 1 hour to cure the adhesive.

[0212] The measurement was carried out at 5000 cd / m 2 The driving voltage, current density, current efficiency, luminous efficiency, and external luminous quantum yield (EQE) were measured when the obtained element emitted light. The results are shown in Table 1.

[0213] [Table 1]

[0214]

[0215] As shown in Table 1, it can be seen that the organic EL element using the aniline derivative of the present invention is suitably driven.

Claims

1. An aniline derivative represented by the following formula (1): [Chemical formula 1] In the formula, each Ar is independently a group represented by the following formula (Ar1), [Chemical formula 2] In the formula, R 1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 1 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 1 , an alkynyl group having 2 to 20 carbon atoms which may be substituted by Z 1 , an aryl group having 6 to 20 carbon atoms which may be substituted by Z 2 , or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z 2 . Z 1 is a halogen atom, nitro group, cyano group, aryl group having 6 to 20 carbon atoms which may be substituted by Z 3 or heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z 3 and Z 2 is a halogen atom, nitro group, cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 3 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 3 or an alkynyl group having 2 to 20 carbon atoms which may be substituted by Z 3 . Z 3 is a halogen atom, nitro group or cyano group, Among them, All of the Ars are the same group.

2. The aniline derivative according to claim 1, wherein, R 1 is an aryl group having 6 to 20 carbon atoms which can be substituted by Z 2 or a heteroaryl group having 2 to 20 carbon atoms which can be substituted by Z 2 and is substituted by Z 3. The aniline derivative according to claim 2, wherein R 1 is an aryl group having 6 to 20 carbon atoms that can be replaced by Z 2 and substituted with a carbon number of 6 to 20 aryl group.

4. The aniline derivative according to claim 3, wherein, R 1 is a phenyl group which may be substituted by Z 2 a 1-naphthyl group which may be substituted by Z 2 or a 2-naphthyl group which may be substituted by Z 2 .

5. The method for producing an aniline derivative according to claim 1, wherein, React p-phenylenediamine with a carbazole derivative represented by the following formula (N1) in the presence of a catalyst, [Chemical formula 3] In the formula, Ar is the same as that described in claim 1, and X is a halogen atom or a pseudohalogen group.

Images