Biodiversity

Abstract

For example, an aniline derivative represented by the following formula having a repeating unit of a meta-phenylene group in the molecule exhibits good solubility in organic solvents and provides a thin film having good transparency. When the thin film is used as a hole injection layer, an organic EL element having excellent characteristics is provided.

Description

Technical Field

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

[0002] Due to the actual situation that the coloring of the charge transport film used in the organic electroluminescent (hereinafter referred to as organic EL) element reduces the color purity and color reproducibility of the organic EL element, in recent years, it is desired that the charge transport film used in the organic EL element have a high transmittance in the visible region and high transparency (see patent document 1).

[0003] In view of this, the present inventors have found a material for a wet process that provides a charge transporting thin film having suppressed coloration in the visible region and excellent transparency (see Patent Documents 1 and 2).

[0004] However, as organic EL displays are now being developed on a larger scale, efforts are being focused on the development of organic EL displays using a wet process for practical use, and there is a constant demand for wet process materials that provide a charge transport thin film with high transparency.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2013 / 042623

[0008] Patent Document 2: International Publication No. 2008 / 032616 Summary of the invention

[0009] Problems to be solved by the invention

[0010] The present invention has been made in view of such actual circumstances, and an object of the present invention is to provide an aniline derivative which exhibits good solubility in an organic solvent and gives a thin film having good transparency, and when the thin film is used as a hole injection layer or the like, an organic EL element having excellent characteristics can be realized.

[0011] Means for solving problems

[0012] The present inventors have repeatedly conducted in-depth studies to achieve the above-mentioned purpose, and as a result, have found that a specified aniline derivative having a repeating unit of meta-phenylene in the molecule shows good solubility in an organic solvent and provides a thin film with a low extinction coefficient (k) and good transparency, and that when the thin film is applied to a hole injection layer, etc., an organic EL element with excellent characteristics is provided, thereby completing the present invention.

[0013] That is, the present invention provides:

[0014] 1. Aniline derivative, characterized in that it is represented by formula (1):

[0015] [Chemistry 1]

[0016]

[0017] [Where Ph 1 Each independently represents a group represented by formula (P1) or formula (P2), at least one of which is a group represented by formula (P1),

[0018] [Chemistry 2]

[0019]

[0020] (Where R 1 ~R 4 Each independently represents a hydrogen atom, a cyano group, or 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, or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by a cyano group.

[0021] Ar 0 Each independently represents a group represented by formula (B0),

[0022] [Chemistry 3]

[0023]

[0024] (Where Ar B represents a single bond or a phenylene group which may be substituted by any substituent other than the E group (excluding substituents containing a pyridine ring; the same applies hereinafter). B In the case of the phenylene group, it can be G or a part of a fused ring formed by combining with other aromatic rings,

[0025] Ar G each independently represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with any substituent other than the E group,

[0026] E represents a single bond, -C(R a )2-、-NR b -, -NH-, N, -O- or -S-,

[0027] R a Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, and in R a When it is the monovalent hydrocarbon group, R a They can combine with each other and form a ring with carbon atoms. b represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom,

[0028] In ArB When E is a single bond and Ar G is a naphthyl group which may be substituted with any substituent other than the E group,

[0029] In E is -C(R a )2-yl, Ar B and Ar G Combined with each other to form a fused ring, in which case Ar B and Ar G may combine with each other to form a fused ring,

[0030] n G Ar combined with E G The number of bases is 2 when E is N and 1 in other cases. G In the case of a nitrogen atom, they may be combined with each other to form a condensed ring.

[0031] k represents an integer greater than or equal to 1.]

[0032] 2.1 Aniline derivatives, wherein the Ar 0 are each independently a group represented by any one of formulae (B1) to (B16),

[0033] [Chemistry 4]

[0034]

[0035] (Where R 5 ~R 25 , R 28 ~R 49 and R 51 ~R 194 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a diphenylamino group which may be substituted with a halogen atom, a nitro group or a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and R 26 and R 27 Each independently represents a hydrogen atom, which can be replaced by Z 1 The substituted alkyl group having 1 to 20 carbon atoms may be Z 1 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 1 The substituted alkynyl group having 2 to 20 carbon atoms may be Z 2 The substituted aryl group having 6 to 20 carbon atoms may be Z 2 Substituted heteroaryl having 2 to 20 carbon atoms, R 50 Represents hydrogen atoms, which can be Z 1 The substituted alkyl group having 1 to 20 carbon atoms may be Z 1The substituted alkenyl group having 2 to 20 carbon atoms may be Z 1 The substituted alkynyl group having 2 to 20 carbon atoms may be Z 2 The substituted aryl group having 6 to 20 carbon atoms may be Z 2 Substituted heteroaryl having 2 to 20 carbon atoms, Z 1 Represents halogen atoms, nitro groups, cyano groups, diphenylamino groups, and Z 3 The substituted aryl group having 6 to 20 carbon atoms may be Z 3 Substituted heteroaryl having 2 to 20 carbon atoms, Z 2 Represents halogen atoms, nitro groups, cyano groups, diphenylamino groups, and Z 3 The substituted alkyl group having 1 to 20 carbon atoms may be Z 3 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 3 Substituted alkynyl having 2 to 20 carbon atoms, Z 3 represents a halogen atom, a nitro group, a cyano group or a diphenylamino group, Ar 4 Each independently represents an aryl group having 6 to 20 carbon atoms which may be substituted with a di(aryl group having 6 to 20 carbon atoms)amino group.

[0036] 3.2 Aniline derivative represented by any one of formulas (1-1) to (1-4),

[0037] [Chemistry 5]

[0038]

[0039] (Ar 1 ~Ar 3 are different from each other and are groups represented by any one of the formulae (B1) to (B16), wherein Ar 1 All represent the same group, Ar 2 All represent the same group, Ar 3 All represent the same group. )

[0040] 4. The aniline derivative according to any one of 1 to 3, wherein the number (n m ) and the number of groups represented by the formula (P2) (n p ) satisfies 0.5≤n m / (n m +n p ),

[0041] 5. A method for producing an aniline derivative according to 5.1, comprising reacting an amine compound represented by the formula (4) with an aryl compound represented by the formula (5) in the presence of a catalyst.

[0042] [Chemistry 6]

[0043]

[0044] (Where Ph 1 and k have the same meanings as above. )

[0045] [Chemistry 7]

[0046] Ar 0 -X (5)

[0048] (wherein, X represents a halogen atom or a pseudohalogen group, Ar 0 Means the same as above.)

[0049] Effects of the Invention

[0050] The aniline derivative of the present invention is easily soluble in an organic solvent, and a charge-transporting varnish can be easily prepared by dissolving it alone or together with a dopant substance in an organic solvent.

[0051] Furthermore, the aniline derivative of the present invention provides a thin film having a low extinction coefficient (k), excellent transparency and high charge transport properties, and the thin film can be suitably used as a thin film for electronic devices including organic EL devices. DETAILED DESCRIPTION

[0052] The present invention is described in more detail below.

[0053] The aniline derivative of the present invention is represented by formula (1).

[0054] [Chemistry 8]

[0055]

[0056] In formula (1), Ph 1 Each independently represents a group represented by formula (P1) or formula (P2), as described later, (k+1) Ph 1 At least one of the groups is a group represented by formula (P1).

[0057] [Chemistry 9]

[0058]

[0059] Among them, R 1 ~R 4 Each independently represents a hydrogen atom, a cyano group, or 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, or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by a cyano group.

[0060] The alkyl group having 1 to 20 carbon atoms may be straight-chain, branched or cyclic. Examples thereof include straight-chain or branched alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl; and cyclic alkyl groups having 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl and bicyclodecyl.

[0061] Specific examples of the alkenyl group having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, and n-1-eicosenyl.

[0062] Specific examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl, 1-methyl-2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n-butynyl, 1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n-1-pentadecenyl, and n-1-eicosynyl.

[0063] Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, and 9-phenanthrenyl.

[0064] Specific examples of heteroaryl groups having 2 to 20 carbon atoms include oxygen-containing heteroaryl groups such as 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, and 5-isoxazolyl; sulfur-containing heteroaryl groups such as 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, and 5-isothiazolyl; 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 -triazine-3-yl, 1,2,4-triazine-5-yl, 1,2,4-triazine-6-yl, 1,3,5-triazine-2-yl, 1,2,4,5-tetrazine-3-yl, 1,2,3,4-tetrazine-5-yl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-iso ...6-quinolyl, 7-quinolyl, 8-quinolyl, -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 and the like nitrogen-containing heteroaryl groups.

[0065] Among these, R 1 ~R 4 , preferably a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted by a cyano group, an aryl group having 6 to 20 carbon atoms which may be substituted by a cyano group, or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by a cyano group; more preferably a hydrogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a cyano group, or a phenyl group which may be substituted by a cyano group; further preferably a hydrogen atom and a methyl group; most preferably a hydrogen atom.

[0066] That is, the group represented by the formula (P1) is most preferably an unsubstituted m-phenylene (benzene-1,3-diyl), and the group represented by the formula (P2) is most preferably an unsubstituted p-phenylene (benzene-1,4-diyl).

[0067] In the above formula (1), Ar 0 Each independently represents a group represented by formula (B0).

[0068] [Chemistry 10]

[0069]

[0070] In the formula, Ar B represents a single bond or a phenylene group which may be substituted by any substituent other than the E group (excluding substituents containing a pyridine ring; the same applies hereinafter). B In the case of the above-mentioned phenylene group, it may be G or a part of a condensed ring formed by combining with other aromatic rings.

[0071] Examples of the phenylene group in the phenylene group which may be substituted with any substituent other than the E group include o-phenylene, m-phenylene and p-phenylene. From the viewpoint of ease of synthesis of the aniline derivative, m-phenylene and p-phenylene are preferred, and in consideration of the solubility of the aniline derivative, p-phenylene is more preferred.

[0072] Ar G Each independently represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with any substituent other than the E group. Specific examples of these aryl groups and heteroaryl groups include the same groups as exemplified above, but are not limited thereto.

[0073] Among them, as Ar G , preferably an aryl group having 6 to 10 carbon atoms or a heteroaryl group having 2 to 10 carbon atoms which may be substituted with a substituent other than an E group, more preferably an aryl group having 6 to 10 carbon atoms which may be substituted with a substituent other than an E group, and further preferably a phenyl group, a 1-naphthyl group, or a 2-naphthyl group which may be substituted with a substituent other than an E group.

[0074] As a substitute for Ar B and Ar G Substituents other than the E group of the pyridine ring are not particularly limited as long as they are substituents other than those containing the pyridine ring, and examples thereof include halogen atoms, nitro groups, cyano groups, diphenylamino groups, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and diphenylamino groups, alkyl groups, alkenyl groups, alkynyl groups substituted with these groups; alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms substituted with aryl groups, and the like. Specific examples of the alkyl group, alkenyl group, alkynyl group, and aryl group include the same groups as those exemplified above, but are not limited thereto.

[0075] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0076] E represents a single bond, -C(R a )2-、-NR b -, -NH-, N, -O-, or -S-.

[0077] Among them, R aEach independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, and in R a When it is the above-mentioned monovalent hydrocarbon group, R a They may be combined with each other to form a ring together with the carbon atom. b It represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0078] Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom include 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 a heteroaryl group having 2 to 20 carbon atoms, and specific examples thereof include the same groups as those exemplified above. These groups may be further substituted with a substituent.

[0079] Examples of such substituents include a halogen atom, a nitro group, a cyano group, a diphenylamino group, 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, a heteroaryl group having 2 to 20 carbon atoms, and groups in which these groups are further substituted.

[0080] Furthermore, in Ar B When Ar is a single bond, E is also a single bond, and G It is a naphthyl group which may be substituted with an arbitrary substituent group other than the E group. Examples of such a naphthyl group include 1-naphthyl group and 2-naphthyl group.

[0081] In addition, when E is -C(R a )2-yl, Ar B and Ar G Combined with each other to form a fused ring, in which case Ar B and Ar G may combine with each other to form a fused ring.

[0082] n G Ar combined with E G The number of bases is 2 when E is N and 1 in other cases. G In the case of a nitrogen atom, they may be bonded to each other to form a condensed ring together with the nitrogen atom.

[0083] k represents an integer of 1 or more, and is preferably 10 or less, more preferably 5 or less, further preferably 4 or less, and further preferably 3 or less, from the viewpoint of the solubility of the aniline derivative.

[0084] As described above, the aniline derivative of the present invention contains at least one meta-phenylene structure in its straight chain, and the (k+1) Ph in formula (1) 1At least one of the groups represents a group represented by formula (P1).

[0085] The number (n) of the groups represented by the formula (P1) in the formula (1) is m ) and the number of groups represented by formula (P2) (n p ) satisfies n m +n p = k + 1. If the balance among the solubility of the aniline derivative, the charge transport property of the obtained charge transport thin film, transparency, etc. is taken into consideration, n m and n p Preferably, 0.5≤n m / (n m +n p ), preferably satisfying 0.6≤n m / (n m +n p ), preferably satisfying 0.8≤n m / (n m +n p ), and further preferably satisfying 0.9≤n m / (n m +n p ), preferably satisfying 1=n m / (n m +n p ).

[0086] In a preferred embodiment of the present invention, Ar in formula (1) 0 Each independently represents a group represented by any one of formulae (B1) to (B16), and is particularly preferably a group represented by any one of formulae (B1′) to (B16′-5).

[0087] [Chemistry 11]

[0088]

[0089] [Chemistry 12]

[0090]

[0091] [Chemistry 13]

[0092]

[0093] Among them, R 5 ~R 25 , R 28 ~R 49 and R 51 ~R 194each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a diphenylamino group which may be substituted with a halogen atom, a nitro group or a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and R 26 and R 27 Each independently represents a hydrogen atom, which can be replaced by Z 1 The substituted alkyl group having 1 to 20 carbon atoms may be Z 1 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 1 The substituted alkynyl group having 2 to 20 carbon atoms may be Z 2 The substituted aryl group having 6 to 20 carbon atoms may be Z 2 Substituted heteroaryl having 2 to 20 carbon atoms, R 50 Represents hydrogen atoms, which can be Z 1 The substituted alkyl group having 1 to 20 carbon atoms may be Z 1 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 1 The substituted alkynyl group having 2 to 20 carbon atoms may be Z 2 The substituted aryl group having 6 to 20 carbon atoms may be Z 2 Substituted heteroaryl having 2 to 20 carbon atoms, Z 1 Represents halogen atoms, nitro groups, cyano groups, diphenylamino groups, and Z 3 The substituted aryl group having 6 to 20 carbon atoms may be Z 3 Substituted heteroaryl having 2 to 20 carbon atoms, Z 2 Represents halogen atoms, nitro groups, cyano groups, diphenylamino groups, and Z 3 The substituted alkyl group having 1 to 20 carbon atoms may be Z 3 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 3 Substituted alkynyl having 2 to 20 carbon atoms, Z 3 represents a halogen atom, a nitro group, a cyano group or a diphenylamino group. Specific examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms, the alkynyl group having 2 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms and the heteroaryl group having 2 to 20 carbon atoms include the same groups as described above.

[0094] In particular, as R 5 ~R 25 , R 28 ~R 49 and R 51 ~R 194, preferably a hydrogen atom, a fluorine atom, a cyano group, a diphenylamino group which may be substituted with a fluorine atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a fluorine atom, or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom; more preferably a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, or a phenyl group which may be substituted with a fluorine atom; further preferably a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; and most preferably a hydrogen atom.

[0095] As R 26 and R 27 , preferably can be Z 2 The substituted aryl group having 6 to 14 carbon atoms may be Z 2 The substituted heteroaryl group having 2 to 14 carbon atoms may be more preferably substituted by Z 2 The substituted aryl group having 6 to 14 carbon atoms may be further preferably 2 Substituted phenyl, Z 2 Substituted 1-naphthyl, which may be Z 2 Substituted 2-naphthyl.

[0096] As R 50 , preferably hydrogen atoms, which can be Z 2 The substituted aryl group having 6 to 20 carbon atoms is preferably a hydrogen atom, which may be substituted by Z 2 The substituted aryl group having 6 to 14 carbon atoms is preferably a hydrogen atom, which may be Z 2 Substituted phenyl, Z 2 Substituted 1-naphthyl, which may be Z 2 Substituted 2-naphthyl.

[0097] In addition, Ar 4 Each independently represents an aryl group having 6 to 20 carbon atoms which may be substituted with a di(aryl group having 6 to 20 carbon atoms)amino group.

[0098] Specific examples of the aryl group having 6 to 20 carbon atoms include the same groups as described above, and specific examples of the di(aryl group having 6 to 20 carbon atoms)amino group include diphenylamino, 1-naphthylphenylamino, di(1-naphthyl)amino, 1-naphthyl-2-naphthylamino, di(2-naphthyl)amino, and the like.

[0099] As Ar 4 , preferably phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, p-(diphenylamino)phenyl, p-(1-naphthylphenylamino)phenyl, p-(di(1-naphthyl)amino)phenyl, p-(1-naphthyl-2-naphthylamino)phenyl, p-(di(2-naphthyl)amino)phenyl, more preferably p-(diphenylamino)phenyl.

[0100] The following are listed as Ar 0 Specific examples of preferred groups are shown below, but are not limited to these.

[0101] [Chemistry 14]

[0102]

[0103] (Wherein, DPA represents diphenylamino.)

[0104] [Chemistry 15]

[0105]

[0106] [Chemistry 16]

[0107]

[0108] [Chemistry 17]

[0109]

[0110] (Where R 50 Means the same as above.)

[0111] [Chemistry 18]

[0112]

[0113] [Chemistry 19]

[0114]

[0115] [Chemistry 20]

[0116]

[0117] [Chemistry 21]

[0118]

[0119] [Chemistry 22]

[0120]

[0121] In the present invention, as R 50 Specific examples of preferred groups include the following groups, but are not limited to these.

[0122] [Chemistry 23]

[0123]

[0124] [Chemistry 24]

[0125]

[0126] [Chemistry 25]

[0127]

[0128] [Chemistry 26]

[0129]

[0130] [Chemistry 27]

[0131]

[0132] [Chemistry 28]

[0133]

[0134] In the present invention, the carbon number of the alkyl group, alkenyl group and alkynyl group is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.

[0135] The aryl group and the heteroaryl group preferably have 14 or less carbon atoms, more preferably 10 or less carbon atoms, and even more preferably 6 or less carbon atoms.

[0136] In the present invention, the aniline derivative represented by the formula (1) is preferably an aniline derivative represented by any one of the formulae (1-1) to (1-4) in view of ease of synthesis.

[0137] [Chemistry 29]

[0138]

[0139] (Ar 1 ~Ar 3 are different from each other and are groups represented by any one of the above formulae (B1) to (B16), wherein Ar 1 All represent the same group, Ar 2 All represent the same group, Ar 3 All represent the same group. )

[0140] The aniline derivative represented by the formula (1) of the present invention can be produced by reacting an amine compound represented by the formula (4) with an aryl compound represented by the formula (5) in the presence of a catalyst.

[0141] [Chemistry 30]

[0142]

[0143] (wherein, X represents a halogen atom or a pseudohalogen group, Ar 0 Ph 1 and k have the same meanings as above. )

[0144] Examples of the halogen atom include the same halogen atoms as mentioned above.

[0145] Examples of the pseudohalogen group include (fluoro)alkylsulfonyloxy groups such as a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and a nonafluorobutanesulfonyloxy group; and aromaticsulfonyloxy groups such as a benzenesulfonyloxy group and a toluenesulfonyloxy group.

[0146] The feed ratio of the amine compound represented by formula (4) to the aryl compound represented by formula (5) can be an equivalent or more of the aryl compound relative to the amount of all NH groups of the amine compound, preferably about 1 to 1.2 equivalents.

[0147] As the catalyst used in the above reaction, for example, copper catalysts such as copper chloride, copper bromide, and copper iodide can be listed; palladium catalysts such as Pd(PPh3)4(tetrakis(triphenylphosphine)palladium), Pd(PPh3)2Cl2(bis(triphenylphosphine)palladium dichloride), Pd(dba)2(bis(dibenzylideneacetone)palladium), Pd2(dba)3(tris(dibenzylideneacetone)dipalladium), Pd(Pt-Bu3)2(bis(tri(tert-butylphosphine))palladium), and Pd(OAc)2(palladium acetate) can be used. These catalysts can be used alone or in combination of two or more. In addition, these catalysts can be used together with known appropriate ligands.

[0148] 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 such as trimethyl phosphite, triethyl phosphite, and triphenyl phosphite.

[0149] The amount of the catalyst used can be about 0.1 to 0.2 mol, preferably about 0.15 mol, based on 1 mol of the aryl compound represented by the formula (5).

[0150] When a ligand is used, the amount of the ligand used can be 0.1 to 5 equivalents, preferably 1 to 2 equivalents, based on the metal complex used.

[0151] In the case where all the raw material compounds are solid or from the viewpoint of efficiently obtaining the target aniline derivative, each of the above reactions is 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-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. These solvents may be used alone or in combination of two or more.

[0152] The reaction temperature can be appropriately set within the range from the melting point to the boiling point of the solvent used, and is particularly preferably about 0 to 200°C, more preferably 20 to 150°C.

[0153] After the reaction is completed, post-treatment can be performed according to a conventional method to obtain the target aniline derivative.

[0154] The aniline derivative represented by the above formula (1-1) can also be produced by the following method.

[0155] First, a dinitro compound represented by the formula (1-1-4) and an aryl compound represented by the formula (6) are reacted to obtain a dinitro compound represented by the formula (1-1-3).

[0156] [Chemistry 31]

[0157]

[0158] (Where Ar 1 Ph 1 , X and k have the same meanings as above. )

[0159] The feed ratio of the dinitro compound represented by formula (1-1-4) to the aryl compound represented by formula (6) is such that the aryl compound is an equivalent or more, preferably about 1 to 1.2 equivalents, relative to the amount of all NH groups of the dinitro compound.

[0160] The conditions for the coupling reaction, such as the amount of the catalyst relative to the aromatic compound, the solvent, the reaction temperature, etc., are the same as those described above for the method for producing the aniline derivative represented by the formula (1).

[0161] Next, the nitro group in the dinitro compound represented by the formula (1-1-3) is reduced by hydrogenation to obtain the amine compound represented by the formula (1-1-2). The hydrogenation reaction may be a hydrogenation reaction using Pd / C or the like, and can be carried out by a known method.

[0162] [Chemistry 32]

[0163]

[0164] (Where Ar 1 Ph 1 and k have the same meanings as above. )

[0165] Secondly, the amine compound represented by formula (1-1-2) is reacted with the aromatic compound represented by formula (7) to obtain the amine compound represented by formula (1-1-1), and the obtained amine compound represented by formula (1-1-1) is reacted with the aromatic compound represented by formula (8) to obtain the aniline derivative represented by formula (1-1).

[0166] [Chemistry 33]

[0167]

[0168] (Where Ar 1 ,Ar 2 ,Ar 3 Ph 1 , X and k have the same meanings as above. )

[0169] With regard to the feed ratio of the amine compound represented by formula (1-1-2) to the aromatic compound represented by formula (7) or the feed ratio of the amine compound represented by formula (1-1-1) to the aromatic compound represented by formula (8), the aromatic compound can be present in an amount of 2 or more equivalents, preferably about 2 to 2.4 equivalents, relative to the amine compound.

[0170] The conditions for the coupling reaction, such as the amount of the catalyst relative to the aromatic compound, the solvent, the reaction temperature, etc., are the same as those described above for the method for producing the aniline derivative represented by the formula (1).

[0171] In addition, the aniline derivative represented by the formula (1-2) can also be produced by the following method.

[0172] The aniline derivative represented by the formula (1-2) can be obtained by reacting the amine compound represented by the formula (1-1-1) obtained by the above method with the aryl compound represented by the formula (6).

[0173] [Chemistry 34]

[0174]

[0175] (Where Ar 1 ,Ar 2 Ph 1 , X and k have the same meanings as above. )

[0176] The conditions for the coupling reaction, such as the feed ratio of the amine compound and the aryl compound, the amount of the catalyst relative to the aryl compound, the solvent, the reaction temperature, etc., are the same as those described above for the production method of the aniline derivative represented by the formula (1).

[0177] In addition, the aniline derivative represented by the formula (1-3) can also be produced by the following method.

[0178] The amine compound represented by the formula (1-1-2) obtained by the above method is reacted with the aryl compound represented by the formula (7) to obtain the aniline derivative represented by the formula (1-3).

[0179] [Chemistry 35]

[0180]

[0181] (Where Ar 1 ,Ar 2 Ph 1 , X and k have the same meanings as above. )

[0182] The feed ratio of the amine compound represented by formula (1-1-2) to the aryl compound represented by formula (7) is such that the aryl compound is at least an equivalent, preferably about 1 to 1.2 equivalents, relative to the amount of all NH groups of the amine compound.

[0183] The conditions for the coupling reaction, such as the amount of the catalyst relative to the aromatic compound, the solvent, the reaction temperature, etc., are the same as those described above for the method for producing the aniline derivative represented by the formula (1).

[0184] In addition, the aniline derivative represented by the formula (1-4) can also be produced by the following method.

[0185] By reacting the amine compound represented by the formula (4) with the aryl compound represented by the formula (6), the aniline derivative represented by the formula (1-4) can be obtained.

[0186] [Chemistry 36]

[0187]

[0188] (Where Ar 1 Ph 1 , X and k have the same meanings as above. )

[0189] The conditions for the coupling reaction, such as the feed ratio of the amine compound and the aryl compound, the amount of the catalyst relative to the aryl compound, the solvent, the reaction temperature, etc., are the same as those described above for the production method of the aniline derivative represented by the formula (1).

[0190] Furthermore, the amine compound that can be used as a raw material for the aniline derivative of the present invention can be obtained by (A) a coupling reaction of an amine compound represented by formula (1-1-4) or formula (1-1-5) with an aromatic compound represented by formula (9) and (B) a reduction reaction of a hydrogenated nitro group as shown in the following scheme. By repeating the reactions (A) and (B), the chain length (the number of meta- or para-phenylene groups) can be increased.

[0191] [Chemistry 37]

[0192]

[0193] (Where Ph 1 , X and k have the same meanings as above. )

[0194] [Chemistry 38]

[0195]

[0196] (Where Ph 1 , X and k have the same meanings as above. )

[0197] To give a more specific example, the amine compound contained in formula (4) can be obtained by (A) a coupling reaction of m-phenylenediamine or 3-nitroaniline with 3-halonitrobenzene and (B) a reduction reaction of a nitro group using hydrogenation, as shown in the following scheme. By repeating the reactions (A) and (B), the chain length (the number of m-phenylene groups) can be increased.

[0198] [Chemistry 39]

[0199] Odd-numbered phenylene

[0200]

[0201] Even-numbered phenylene

[0202]

[0203] (In the formula, X has the same meaning as above.)

[0204] By selecting the upper reaction and the lower reaction of the above scheme respectively, the even and odd numbers of phenylene groups can be produced respectively. Therefore, it is not necessary to use a method with high synthetic difficulty such as protecting one amino group with a protecting group, and the amine compound represented by formula (4) having the desired number of phenylene groups can be freely produced.

[0205] In this case, as for the feed ratio of the amine compound or meta-phenylenediamine represented by formula (1-1-4) to the aromatic compound or 3-halonitrobenzene represented by formula (9), expressed as the mass ratio, the aromatic compound or 3-halonitrobenzene represented by formula (9) is preferably about 2 to 2.4 relative to 1 of the amine compound or meta-phenylenediamine represented by formula (1-1-4).

[0206] In addition, with respect to the feed ratio of the amine compound or 3-nitroaniline represented by formula (1-1-5) to the aromatic compound or 3-halonitrobenzene represented by formula (9), expressed as a mass ratio, the aromatic compound or 3-halonitrobenzene represented by formula (9) is preferably about 1 to 1.2 relative to 1 of the amine compound or 3-nitroaniline represented by formula (1-1-5).

[0207] Furthermore, as the palladium catalyst for the coupling reaction, the same palladium catalyst as above can be listed. In addition, in this case, a ligand can also be used. As a ligand, in addition to the ligands exemplified above, biphenylphosphine compounds such as JohnPhos, CyjohnPhos, DavePhos, XPhos, SPhos, tBuXPhos, RuPhos, Me4tBuXPhos, sSPhos, tBuMePhos, MePhos, tBuDavePhos, PhDavePhos, 2'-dicyclohexylphosphino-2,4,6-trimethoxybiphenyl, BrettPhos, tBuBrettPhos, AdBrettPhos, Me3(OMe)tBuXPhos, (2-biphenyl)di-1-adamantylphosphine, RockPhos, CPhos, etc. commercially available from Aldrich can also be preferably used.

[0208] Examples of the base used in the coupling reaction include alkali metal elements such as lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, tert-butoxylithium, tert-butoxysodium, tert-butoxypotassium, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, alkali metal hydrides, alkali metal hydroxides, alkali metal alkoxides, alkali metal carbonates, alkali metal hydrogencarbonates; alkaline earth metal carbonates such as calcium carbonate; organic lithiums such as n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamine (LDA), 2,2,6,6-tetramethylpiperidinium lithium (LiTMP), and lithium hexamethyldisilazane (LHMDS); and amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine.

[0209] The conditions for the coupling reaction, such as the solvent and the reaction temperature, are the same as those described above for the method for producing the aniline derivative represented by the formula (1).

[0210] The hydrogenation reaction using Pd / C can be performed by a known method.

[0211] When p-phenylene is introduced in place of m-phenylene, 4-halonitrobenzene may be used in place of 3-halonitrobenzene.

[0212] The aniline derivative of the present invention can be preferably used as a charge transporting substance. In this case, it can be used as a charge transporting varnish comprising the aniline derivative of the present invention and an organic solvent, in which a dopant substance may be contained for the purpose of improving the charge transporting ability of the obtained film, etc., depending on the application of the film.

[0213] The dopant substance is not particularly limited as long as it is soluble in at least one solvent used in the varnish, and both inorganic and organic dopant substances can be used.

[0214] Inorganic and organic dopant substances may be used alone or in combination of two or more.

[0215] Furthermore, the dopant substance may be a substance that, in the process of obtaining a charge transporting thin film as a solid film from a varnish, causes a part of the molecule to be released due to external stimulation such as heating during firing, thereby causing the function as a dopant substance to be initially manifested or enhanced, such as an aromatic sulfonate compound in which the sulfonic acid group is protected with an easily release group.

[0216] In the present invention, heteropolyacids are particularly preferred as inorganic dopant substances.

[0217] The so-called heteropoly acid is a structure in which a heteroatom is located at the center of the molecule, which is typically represented by a Keggin-type chemical structure represented by formula (H1) or a Dawson-type chemical structure represented by formula (H2), and is a polyacid formed by condensation of an isopoly acid of an oxygen-containing acid such as vanadium (V), molybdenum (Mo), tungsten (W), etc. with an oxygen-containing acid of a different element. As such an oxygen-containing acid of a different element, oxygen-containing acids of silicon (Si), phosphorus (P), and arsenic (As) can be mainly listed.

[0218] [Chemistry 40]

[0219]

[0220] As the specific example of heteropolyacid, phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, phosphotungstic molybdic acid etc. can be listed, and these heteropolyacids can be used alone, and two or more combinations can also be used. Furthermore, these heteropolyacids can be obtained as commercially available products, and in addition, known method synthesis can also be adopted.

[0221] In particular, when one heteropoly acid is used, the one heteropoly acid is preferably phosphotungstic acid or phosphomolybdic acid, and most preferably phosphotungstic acid. In addition, when two or more heteropoly acids are used, one of the two or more heteropoly acids is preferably phosphotungstic acid or phosphomolybdic acid, and more preferably phosphotungstic acid.

[0222] In addition, the heteropolyacid can be used in the present invention as long as it is a commercially available product or a product appropriately synthesized by a known synthesis method even if the number of elements relative to the structure represented by the general formula is large or small in quantitative analysis such as elemental analysis.

[0223] That is, for example, phosphotungstic acid is generally represented by the chemical formula H3(PW 12 O 40 )·nH2O, phosphomolybdic acid is represented by the chemical formula H3(PMo 12 O 40 )·nH2O represents that, in quantitative analysis, even if the number of P (phosphorus), O (oxygen) or W (tungsten) or Mo (molybdenum) in the formula is large or small, as long as it is a product obtained as a commercial product or a product appropriately synthesized according to a known synthesis method, it can be used in the present invention. In this case, the mass of the heteropoly acid specified in the present invention is not the mass (phosphotungstic acid content) of pure phosphotungstic acid in the synthetic product or commercial product, but means the total mass in the state including hydration water, other impurities, etc. in the form available as a commercial product and the form separable by a known synthesis method.

[0224] The amount of the heteropolyacid used can be about 0.001 to 50.0, preferably about 0.01 to 20.0, and more preferably about 0.1 to 10.0, expressed as a mass ratio, relative to the charge transporting material 1 composed of the aniline derivative represented by formula (1).

[0225] On the other hand, as the organic dopant substance, in particular, a tetracyanoquinodimethane derivative or a benzoquinone derivative can be used.

[0226] Specific examples of the tetracyanoquinodimethane derivative include 7,7,8,8-tetracyanoquinodimethane (TCNQ) and halogenated tetracyanoquinodimethane represented by the formula (H3).

[0227] Specific examples of benzoquinone derivatives include tetrafluoro-1,4-benzoquinone (F4BQ), tetrachloro-1,4-benzoquinone (tetrachlorobenzoquinone), tetrabromo-1,4-benzoquinone, and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ).

[0228] [Chemistry 41]

[0229]

[0230] In the formula, R 500 ~R 503 Each independently represents a hydrogen atom or a halogen atom, at least one is a halogen atom, preferably at least two are halogen atoms, more preferably at least three are halogen atoms, and most preferably all are halogen atoms.

[0231] Examples of the halogen atom include the same halogen atoms as mentioned above, and a fluorine atom or a chlorine atom is preferred, and a fluorine atom is more preferred.

[0232] Specific examples of such halogenated tetracyanoquinodimethanes include 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2-chloro-7,7,8,8-tetracyanoquinodimethane, 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane, 2,5-dichloro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrachloro-7,7,8,8-tetracyanoquinodimethane, and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ).

[0233] The amount of the tetracyanoquinodimethane derivative and the benzoquinone derivative used is preferably 0.0001 to 100 equivalents, more preferably 0.01 to 50 equivalents, and even more preferably 1 to 20 equivalents relative to the aniline derivative represented by the formula (1).

[0234] As the organic dopant substance, an electrically neutral onium borate composed of a monovalent or divalent anion represented by the following formula (a1) and a counter cation represented by formulae (c1) to (c5) can also be used.

[0235] [Chemistry 42]

[0236]

[0237] (wherein, Ar each independently represents an aryl group having 6 to 20 carbon atoms which may have a substituent or a heteroaryl group having 2 to 20 carbon atoms which may have a substituent, and L represents an alkylene group having 1 to 20 carbon atoms, -NH-, an oxygen atom, a sulfur atom or -CN + -. )

[0238] [Chemistry 43]

[0239]

[0240] In formula (a1), the alkylene group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methylene, methylmethylene, dimethylmethylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, etc. Further, the aryl group and heteroaryl group may be the same as those mentioned above.

[0241] Preferred examples of the anion of the above formula (a1) include anions represented by formula (a2), but the anion is not limited thereto.

[0242] [Chemistry 44]

[0243]

[0244] The amount of the onium borate used can be about 0.1 to 10, expressed as a mass (molar) ratio, relative to the aniline derivative 1 represented by the formula (1).

[0245] The onium borate can be synthesized by referring to a known method described in, for example, JP-A-2005-314682.

[0246] In addition, as the organic dopant substance, an arylsulfonic acid compound or an arylsulfonic acid ester compound can also be preferably used.

[0247] Specific examples of the arylsulfonic acid compound include benzenesulfonic acid, p-toluenesulfonic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzenesulfonic acid, dihexylbenzenesulfonic acid, 2,5-dihexylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, 6,7-dibutyl-2-naphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, 3-dodecyl-2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 4-hexyl-1-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalenesulfonic acid, hexyl Naphthalenesulfonic acid, 7-hexyl-1-naphthalenesulfonic acid, 6-hexyl-2-naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, 2,7-dinonyl-4-naphthalenesulfonic acid, dinonylnaphthalene disulfonic acid, 2,7-dinonyl-4,5-naphthalene disulfonic acid, 1,4-benzodioxane disulfonic acid compounds described in International Publication No. 2005 / 000832, arylsulfonic acid compounds described in International Publication No. 2006 / 025342, arylsulfonic acid compounds described in International Publication No. 2009 / 096352, and the like.

[0248] Preferred examples of the arylsulfonic acid compound include arylsulfonic acid compounds represented by the formula (H4) or (H5).

[0249] [Chemistry 45]

[0250]

[0251] A 1 represents O or S, preferably O.

[0252] A 2 represents a naphthalene ring or an anthracene ring, preferably a naphthalene ring.

[0253] A 3 represents a 2- to 4-valent perfluorobiphenyl group, and p represents A 1 With A 3 The combination number is an integer satisfying 2≤p≤4, preferably A 3 is perfluorobiphenylene, preferably perfluorobiphenyl-4,4′-diyl, and p is 2.

[0254] q means 2 The number of sulfonic acid groups to be bonded is an integer satisfying 1≤q≤4, and 2 is most preferred.

[0255] A 4 ~A 8 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated alkenyl group having 2 to 20 carbon atoms, and A 4 ~A 8 At least three of them are halogen atoms.

[0256] Examples of the halogenated alkyl group having 1 to 20 carbon atoms include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl and 1,1,2,2,3,3,4,4,4-nonafluorobutyl.

[0257] Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include perfluorovinyl group, perfluoropropenyl group (allyl group), and perfluorobutenyl group.

[0258] Examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms include the same examples as described above, and the halogen atom is preferably a fluorine atom.

[0259] Among these, A 4 ~A 8 is preferably a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms, and A 4 ~A 8 At least three of them are fluorine atoms, more preferably hydrogen atoms, fluorine atoms, cyano groups, alkyl groups having 1 to 5 carbon atoms, fluoroalkyl groups having 1 to 5 carbon atoms, or fluoroalkenyl groups having 2 to 5 carbon atoms, and A 4 ~A 8 At least three of them are fluorine atoms, more preferably a hydrogen atom, a fluorine atom, a cyano group, a perfluoroalkyl group having 1 to 5 carbon atoms, or a perfluoroalkenyl group having 1 to 5 carbon atoms, and A 4 , A 5 and A 8 A fluorine atom.

[0260] The perfluoroalkyl group is a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms, and the perfluoroalkenyl group is a group in which all hydrogen atoms of the alkenyl group are substituted with fluorine atoms.

[0261] r represents the number of sulfonic acid groups bonded to the naphthalene ring and is an integer satisfying 1≤r≤4, preferably 2 to 4, and most preferably 2.

[0262] The molecular weight of the arylsulfonic acid compound used as a dopant substance is not particularly limited, but is preferably 2000 or less, more preferably 1500 or less, in consideration of solubility in an organic solvent when used together with the aniline derivative of the present invention.

[0263] Specific examples of preferred arylsulfonic acid compounds are listed below, but the compounds are not limited to these.

[0264] [Chemistry 46]

[0265]

[0266] The amount of the arylsulfonic acid compound used is preferably about 0.01 to 20.0, more preferably about 0.4 to 5.0, relative to the aniline derivative 1 represented by the formula (1), expressed as a mass (molar) ratio.

[0267] As the arylsulfonic acid compound, a commercially available product may be used, or the arylsulfonic acid compound may be synthesized by a known method described in International Publication No. 2006 / 025342, International Publication No. 2009 / 096352, and the like.

[0268] On the other hand, examples of the aryl sulfonate compound include the aryl sulfonate compounds disclosed in International Publication No. 2017 / 217455, the aryl sulfonate compounds disclosed in International Publication No. 2017 / 217457, and the aryl sulfonate compounds described in Japanese Patent Application No. 2017-243631. Specifically, the aryl sulfonate compound represented by any one of the following formulas (H6) to (H8) is preferred.

[0269] [Chemistry 47]

[0270]

[0271] (In the formula, m is an integer satisfying 1≤m≤4, preferably 2. n is an integer satisfying 1≤n≤4, preferably 2.)

[0272] In formula (H6), A 11 It is an m-valent group derived from perfluorobiphenyl.

[0273] A 12 It is -O- or -S-, preferably -O-.

[0274] A 13 It is a (n+1)-valent group derived from naphthalene or anthracene, and is preferably a group derived from naphthalene.

[0275] R s1 ~R s4 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, s5 It is a monovalent hydrocarbon group having 2 to 20 carbon atoms which may be substituted.

[0276] Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-hexyl. An alkyl group having 1 to 3 carbon atoms is preferred.

[0277] The monovalent hydrocarbon group having 2 to 20 carbon atoms may be linear, branched or cyclic. Specific examples thereof include alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl; and aryl groups such as phenyl, naphthyl and phenanthryl.

[0278] In particular, R s1 ~R s4 Among them, R is preferred s1 or R s3 is a straight-chain alkyl group having 1 to 3 carbon atoms, the remainder of which are hydrogen atoms, or R s1 is a straight-chain alkyl group having 1 to 3 carbon atoms, R s2 ~R s4 In this case, the linear alkyl group having 1 to 3 carbon atoms is preferably a methyl group.

[0279] In addition, as R s5 , preferably a straight-chain alkyl group having 2 to 4 carbon atoms or a phenyl group.

[0280] In formula (H7), A 14 It is an m-valent hydrocarbon group having 6 to 20 carbon atoms and containing one or more aromatic rings which may be substituted, and the hydrocarbon group is a group obtained by removing m hydrogen atoms from a hydrocarbon compound having 6 to 20 carbon atoms and containing one or more aromatic rings.

[0281] Examples of such hydrocarbon compounds include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, and phenanthrene.

[0282] Furthermore, with respect to the above-mentioned hydrocarbon group, part or all of its hydrogen atoms may be further substituted by a substituent, and examples of such substituents include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a silanol group, a thiol group, a carboxyl group, a sulfonate group, a phosphoric acid group, a phosphate ester group, an ester group, a thioester group, an acylamino group, a monovalent hydrocarbon group, an organic oxygen group, an organic amino group, an organic silyl group, an organic thio group, an acyl group, a sulfonic acid group, and the like.

[0283] Among these, as A 14 , preferably a group derived from benzene, biphenyl, etc.

[0284] In addition, A 15 It is -O- or -S-, preferably -O-.

[0285] A 16 An (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, wherein the aromatic hydrocarbon group is a group obtained by removing (n+1) hydrogen atoms from an aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms.

[0286] Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene.

[0287] Among them, as A 16 , preferably a group derived from naphthalene or anthracene, more preferably a group derived from naphthalene.

[0288] R s6 and R s7 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group, R s8 is a linear or branched monovalent aliphatic hydrocarbon group. s6 , R s7 and R s8 The total number of carbon atoms in R is 6 or more. s6 , R s7 and R s8 The upper limit of the total number of carbon atoms is not particularly limited, but is preferably 20 or less, and more preferably 10 or less.

[0289] Specific examples of the above-mentioned straight-chain or branched monovalent aliphatic hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, and decyl; and alkenyl groups having 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and hexenyl.

[0290] Among these, R s6 Preferably, a hydrogen atom, R s7 and R s8 Each independently is preferably an alkyl group having 1 to 6 carbon atoms.

[0291] In formula (H8), R s9 ~R s13 Each is independently a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkenyl group having 2 to 10 carbon atoms.

[0292] The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl.

[0293] The haloalkyl group having 1 to 10 carbon atoms is not particularly limited as long as a part or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms are substituted with halogen atoms. Specific examples thereof include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, and 1,1,2,2,3,3,4,4,4-nonafluorobutyl.

[0294] The haloalkenyl group having 2 to 10 carbon atoms is not particularly limited as long as it is a group in which a part or all of the hydrogen atoms of the alkenyl group having 2 to 10 carbon atoms are substituted by halogen atoms. Specific examples thereof include perfluorovinyl, perfluoro-1-propenyl, perfluoro-2-propenyl, perfluoro-1-butenyl, perfluoro-2-butenyl, and perfluoro-3-butenyl.

[0295] Among these, R s9 , preferably nitro, cyano, haloalkyl having 1 to 10 carbon atoms, or haloalkenyl having 2 to 10 carbon atoms, more preferably nitro, cyano, haloalkyl having 1 to 4 carbon atoms, or haloalkenyl having 2 to 4 carbon atoms, further preferably nitro, cyano, trifluoromethyl, or perfluoropropenyl.

[0296] As R s10 ~R s13 , preferably a halogen atom, more preferably a fluorine atom.

[0297] A 17 It is -O-, -S- or -NH-, preferably -O-.

[0298] A 18 An (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, wherein the aromatic hydrocarbon group is a group obtained by removing (n+1) hydrogen atoms from an aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms.

[0299] Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene.

[0300] Among them, as A 18 , preferably a group derived from naphthalene or anthracene, more preferably a group derived from naphthalene.

[0301] R s14 ~R s17 Each independently represents a hydrogen atom, or a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms.

[0302] Specific examples of the monovalent aliphatic hydrocarbon group include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl; and alkenyl groups having 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and hexenyl. Preferably, the alkyl group has 1 to 20 carbon atoms, more preferably, the alkyl group has 1 to 10 carbon atoms, and still more preferably, the alkyl group has 1 to 8 carbon atoms.

[0303] R s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or OR s19 . R s19 It is a monovalent hydrocarbon group having 2 to 20 carbon atoms which may be substituted.

[0304] As R s18 Examples of the linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms include the same groups as described above.

[0305] In R s18 When it is a monovalent aliphatic hydrocarbon group, R s18 An alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 8 carbon atoms is further preferred.

[0306] As R s19 The monovalent hydrocarbon group having 2 to 20 carbon atoms includes, in addition to the groups other than the methyl group among the above-mentioned monovalent aliphatic hydrocarbon groups, aryl groups such as phenyl, naphthyl, and phenanthryl.

[0307] Among them, as R s19 , preferably a straight-chain alkyl group having 2 to 4 carbon atoms or a phenyl group.

[0308] Examples of the substituent that the monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, and a cyano group.

[0309] Specific examples of preferred arylsulfonate compounds include the following, but are not limited to these.

[0310] [Chemistry 48]

[0311]

[0312] In the present invention, if the reproducibility of a thin film with high charge transport properties and the ease of obtaining the dopant material are taken into consideration, it is preferred to use at least one of an aromatic sulfonic acid compound, an aromatic sulfonic acid ester compound, an onium borate, a halogenated tetracyanoquinodimethane and a quinone derivative as the dopant material. If the thin film with a small extinction coefficient is taken into consideration, it is more preferred to use an onium borate.

[0313] In the present invention, the amount of the dopant substance in the varnish is preferably about 0.01 to 20, more preferably about 0.05 to 15, relative to the aniline derivative 1 represented by the formula (1), expressed in terms of molar ratio.

[0314] Furthermore, when the obtained thin film is used as a hole injection layer of an organic EL element, the charge transporting varnish may contain an organic silane compound for the purpose of improving the injectability into the hole transporting layer and the life characteristics of the element, and the content of the organic silane compound is generally about 1 to 30% by mass relative to the total mass of the aniline derivative and the dopant substance of the present invention.

[0315] In addition, in the charge-transporting varnish, other known charge-transporting substances can be used in addition to the charge-transporting substance composed of the aniline derivative of the present invention.

[0316] As the organic solvent used in preparing the charge-transporting varnish, a high-solubility solvent that can well dissolve the charge-transporting substance and the dopant substance can be used.

[0317] As such a highly soluble solvent, for example, organic solvents such as cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and diethylene glycol monomethyl ether can be cited, but are not limited to these. These solvents can be used alone or in combination of two or more, and their usage can be set to 5 to 100% by mass relative to all solvents used in the varnish.

[0318] Furthermore, it is preferred that both the charge transporting substance and the dopant substance are completely dissolved in the above-mentioned solvent.

[0319] In addition, by making the varnish contain at least one high-viscosity organic solvent having a viscosity of 10 to 200 mPa·s, especially 35 to 150 mPa·s at 25°C and a boiling point of 50 to 300°C, especially 150 to 250°C at normal pressure (atmospheric pressure), the viscosity of the varnish can be easily adjusted, and as a result, it becomes possible to prepare a varnish that is consistent with the coating method used while giving a highly flat film with good reproducibility.

[0320] Examples of high viscosity organic solvents include, but are not limited to, 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, and hexylene glycol. These solvents may be used alone or in combination of two or more.

[0321] The addition ratio of the high-viscosity organic solvent to the total solvent used in the varnish is preferably within a range where solids do not precipitate. As long as solids do not precipitate, the addition ratio is preferably 5 to 80% by mass.

[0322] Furthermore, other solvents may be mixed in a ratio of 1 to 90% by mass, preferably 1 to 50% by mass, based on the total solvents used in the varnish for the purpose of improving wettability to the substrate, adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, etc.

[0323] As such a solvent, 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. can be listed, but it is not limited to these. These solvents can be used alone or in combination of two or more.

[0324] When the aniline derivative of the present invention does not have an NH structure in the molecule, such as when it has a substituent on the nitrogen atom at the 9-position of carbazole, and preferably has substituents on all nitrogen atoms, it becomes easy to prepare a varnish using only the low-polarity solvent shown below.

[0325] Specific examples of low-polarity solvents include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene; aliphatic alcohol-based solvents such as 1-octanol, 1-nonanol, and 1-decanol; ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; ester-based solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isopentyl benzoate, di(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. These solvents may be used alone or in combination of two or more.

[0326] The viscosity of the charge transport varnish is appropriately determined depending on the thickness of the film to be produced and the solid content concentration, and is usually 1 to 50 mPa·s at 25°C.

[0327] In addition, the solid content concentration of the charge transporting varnish is appropriately set in consideration of the viscosity and surface tension of the varnish, the thickness of the film to be produced, etc., and is usually about 0.1 to 10.0 mass %. If considering improving the coating properties of the varnish, it is preferably about 0.5 to 5.0 mass %, and more preferably about 1.0 to 3.0 mass %.

[0328] In addition, in the present invention, the solid content means components other than the solvent.

[0329] In the present invention, the method for preparing the charge transporting varnish is not particularly limited, and examples thereof include a method of dissolving the above-mentioned aniline derivative in a part of the solvent used and adding the remaining solvent thereto; a method of first mixing all the solvents used and dissolving the above-mentioned aniline derivative therein, etc.

[0330] In particular, when preparing a charge transport varnish, it is preferred to filter using a submicron filter or the like after dissolving a charge transport material, a dopant material, etc. in an organic solvent from the viewpoint of obtaining a thin film with higher flatness with good reproducibility.

[0331] Furthermore, the varnish may be heated as required as long as the components thereof do not deteriorate.

[0332] The charge transporting substance and charge transporting varnish described above can be used to easily produce a charge transporting thin film, and thus can be preferably used in the production of electronic devices, particularly organic EL devices.

[0333] In this case, the charge transporting thin film can be formed by applying the above-mentioned charge transporting varnish on a substrate and firing it.

[0334] The coating method of the varnish is not particularly limited, and examples thereof include dipping, spin coating, transfer printing, roller coating, brush coating, inkjet, spray coating, and slit coating. The viscosity and surface tension of the varnish are preferably adjusted according to the coating method.

[0335] In addition, there is no particular limitation on the firing atmosphere of the charge transport varnish after coating. Not only in the air atmosphere, but also in an inert gas such as nitrogen or a vacuum, a thin film having a uniform film-forming surface and high charge transport properties can be obtained. Depending on the type of dopant substance used together with the aniline derivative of the present invention, by firing the varnish in the air atmosphere, a thin film having charge transport properties can sometimes be obtained with good reproducibility.

[0336] The firing temperature is appropriately set within the range of about 100 to 260°C, taking into account the purpose of the obtained film, the degree of charge transport properties imparted to the obtained film, the type of solvent, the boiling point, etc. When the obtained film is used as a hole injection layer of an organic EL element, it is preferably about 140 to 250°C, and more preferably about 145 to 240°C. For the charge transport varnish containing the aniline derivative of the present invention, even low-temperature firing at below 200°C can obtain a film with good charge transport properties.

[0337] During firing, in order to develop a more uniform film-forming property or to advance the reaction on the substrate, two or more temperature changes may be applied, and heating may be performed using appropriate equipment such as a hot plate or an oven.

[0338] The film thickness of the charge transport thin film is not particularly limited. When used as a hole injection layer, a hole transport layer or a hole injection transport layer of an organic EL element, it is usually 3 to 300 nm, preferably 5 to 200 nm. As a method for changing the film thickness, there are methods such as changing the solid content concentration in the varnish or changing the amount of solution on the substrate during coating.

[0339] Furthermore, the aniline derivative of the present invention has sublimation properties and can be used to easily form a vapor-deposited film. Therefore, depending on the application, a charge transport thin film obtained by a vapor deposition method using the aniline derivative of the present invention may be used instead of a charge transport thin film obtained from the charge transport varnish described above.

[0340] When the charge transporting thin film is applied to an organic EL element, the charge transporting thin film may be provided between a pair of electrodes constituting the organic EL element.

[0341] As a representative structure of an organic EL element, the following (a) to (f) can be listed, but it is not limited to these. It should be noted that in the following structure, as needed, an electron blocking layer can be provided between the light-emitting layer and the anode, and a hole (hole) blocking layer can be provided between the light-emitting layer and the cathode. In addition, the hole injection layer, the hole transport layer or the hole injection transport layer can also have the function of an electron blocking layer, and the electron injection layer, the electron transport layer or the electron injection transport layer can also have the function of a hole (hole) blocking layer. Furthermore, as needed, any functional layer can also be provided between the layers.

[0342] (a) Anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode

[0343] (b) Anode / hole injection layer / hole transport layer / light-emitting layer / electron injection transport layer / cathode

[0344] (c) Anode / HIT / Emission layer / Electron transport layer / Electron injection layer / Cathode

[0345] (d) Anode / hole injection and transport layer / light-emitting layer / electron injection and transport layer / cathode

[0346] (e) Anode / hole injection layer / hole transport layer / light-emitting layer / cathode

[0347] (f) Anode / HIT Injection and Transport Layer / Light Emitting Layer / Cathode

[0348] "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 transport material is provided between the light-emitting layer and the anode, it is a "hole injection transport layer". When two or more layers of hole transport material are provided 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". In particular, the hole injection (transport) layer uses a thin film that is excellent not only in hole acceptance from the anode but also in hole injection into the hole transport (light-emitting) layer.

[0349] “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 transport 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 transport material are provided between the light-emitting layer and the cathode, the layer close to the cathode is the “electron injection layer”, and the layers other than the cathode are “electron transport layers”.

[0350] The "light-emitting layer" is an organic layer having a light-emitting function, and in the case of a doping system, it includes a host material and a dopant material. In this case, the host material mainly has the function of promoting the recombination of electrons and holes and confining excitons in the light-emitting layer, and the dopant material has the function of making the excitons obtained by recombination emit light efficiently. In the case of a phosphorescent element, the host material mainly has the function of confining the excitons generated by the dopant in the light-emitting layer.

[0351] The charge transporting thin film made of the charge transporting varnish containing the aniline derivative of the present invention can be used as a functional layer provided between the anode and the light emitting layer, such as a hole injection layer, a hole transport layer, or a hole injection transport layer in an organic EL element, and is preferably used as a hole injection layer.

[0352] As materials used and production methods when producing an organic EL device using the charge-transporting varnish containing the aniline derivative of the present invention, the following materials used and production methods can be cited, but the present invention is not limited to these.

[0353] An example of a method for producing an OLED element having a hole injection layer composed of a thin film obtained from the above-mentioned charge transport varnish is as follows. In addition, as for the electrode, it is preferred to perform a cleaning with alcohol, pure water, etc. in advance within a range that does not adversely affect the electrode; and to perform a surface treatment with UV ozone treatment, oxygen-plasma treatment, etc.

[0354] On the anode substrate, the above-mentioned method is used to form a hole injection layer using the above-mentioned charge transport varnish. It is introduced into a vacuum evaporation device, and a hole transport layer, a light-emitting layer, an electron transport layer / hole blocking layer, an electron injection layer, and a cathode metal are sequentially evaporated. Alternatively, in this method, instead of using evaporation to form a hole transport layer and a light-emitting layer, a hole transport layer forming composition containing a hole transport polymer and a light-emitting layer forming composition containing a light-emitting polymer are used to form these layers by a wet method. In addition, as needed, an electron blocking layer can be provided between the light-emitting layer and the hole transport layer.

[0355] As anode materials, transparent electrodes represented by indium tin oxide (ITO) and indium zinc oxide (IZO), metal anodes composed of metals represented by aluminum, or alloys thereof, etc. are listed, preferably anode materials that have been flattened. Polythiophene derivatives and polyaniline derivatives with high charge transport properties can also be used.

[0356] In addition, examples of other metals constituting the metal anode include gold, silver, copper, indium, and alloys thereof, but are not limited to these.

[0357] As materials for forming the hole transport layer, there can be listed (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spirodimer, N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-benzidine (α-NPD), 4,4',4"-tri[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), 4,4',4"-tri[1-naphthyl(phenyl)amino]triphenylamine (1-TNATA) and other triarylamines, 5,5"-bis-{4-[bis(4-methylphenyl)amino]phenyl}-2,2':5',2"-terthiophene (BMA-3T) and other oligothiophenes, etc.

[0358] As materials for forming the light-emitting layer, there can be listed low molecular light-emitting materials such as metal complexes such as aluminum complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo[h]quinoline, bisphenylene benzene derivatives, bisphenylene arylene derivatives, metal complexes of (2-hydroxyphenyl)benzothiazole, and silole derivatives; and systems in which light-emitting materials and electron transfer materials are mixed in polymer compounds such as poly(p-phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly(3-alkylthiophene), and polyvinylcarbazole.

[0359] In addition, when the light-emitting layer is formed by vapor deposition, it can be co-deposited with a light-emitting dopant. Examples of the light-emitting dopant include metal complexes such as tris(2-phenylpyridine)iridium(III) (Ir(ppy)3), tetracene derivatives such as rubrene, quinacridone derivatives, and condensed polycyclic aromatic rings such as perylene.

[0360] Examples of the material for forming the electron transport layer / hole blocking layer include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, and pyrimidine derivatives.

[0361] Examples of materials for forming the electron injection layer include metal oxides such as lithium oxide (Li2O), magnesium oxide (MgO), and aluminum oxide (Al2O3), and metal fluorides such as lithium fluoride (LiF) and sodium fluoride (NaF), but are not limited thereto.

[0362] Examples of the cathode material include aluminum, magnesium-silver alloys, and aluminum-lithium alloys, but are not limited thereto.

[0363] Examples of the material for forming the electron blocking layer include tris(phenylpyrazole)iridium and the like.

[0364] Examples of hole transport polymers include poly[(9,9-dihexylfluorene-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene)], poly[(9,9-dioctylfluorene-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,1'-biphenylene-4,4-diamine)], poly[(9,9-bis{1'-pentene [(9,9-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine)], poly[(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine] terminated with polysilsesquioxane, poly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine)], etc.

[0365] Examples of the light-emitting polymer include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), polyphenylenevinylene derivatives such as poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).

[0366] Example

[0367] The present invention is described in more detail below by way of synthesis examples, working examples, and reference examples, but the present invention is not limited to the following working examples.

[0368] (1) MALDI-TOF-MS: Bruker, autoflex III smartbeam

[0369] (2) LDI-MS: AutoFlex manufactured by Bruker

[0370] (3) 1 H-NMR: JNM-ECP300 FT NMR SYSTEM manufactured by JEOL Ltd.

[0371] (4) Substrate cleaning: Substrate cleaning equipment manufactured by Choshu Industry Co., Ltd. (reduced pressure plasma method)

[0372] (5) Varnish coating: Spin coater MS-A100 manufactured by Mikasa Corporation

[0373] (6) Film thickness measurement: (Fine shape measuring device SURFCORDER (サーフコーダ) ET-4000 manufactured by Kosaka Laboratory Co., Ltd.

[0374] (7) Component production: Multifunctional evaporation equipment system C-E2L1G1-N manufactured by Choshu Industry Co., Ltd.

[0375] (8) Measurement of current density, etc. of the device: Multi-channel IVL measuring device manufactured by EHC Corporation

[0376] (9) Determination of extinction coefficient (k): Multi-incident angle spectroscopic ellipsometer VASE manufactured by JA Woollam Japan

[0377] [1] Production of onium borates

[0378] [Synthesis Example 1] Preparation of Onium Borate (P-3)

[0379] [Chemistry 49]

[0380]

[0381] (1) Synthesis of intermediate (Q-2)

[0382] [Chemistry 50]

[0383]

[0384] In a 10L four-necked flask, 6068mL of diethyl ether, 151.7g of the compound represented by the above formula (Q-1), and 9.4g of KCN were placed and reacted at 34-36°C for 3 hours. After the reaction, the mixture was concentrated under normal pressure to obtain 267.2g of a brown liquid. The brown liquid was concentrated at 55°C using an evaporator and then dried under reduced pressure at 35°C for 16 hours to obtain 157.7g of an intermediate (Q-2) as a light brown solid. The intermediate (Q-2) obtained was identified using LDI-MS.

[0385] LDI-MS m / Z measured value: 1050.12 ([M] - Calculated value: 1049.97).

[0386] (2) Synthesis of onium borate (P-3)

[0387] In a 300mL Erlenmeyer flask were placed 11.043g of diphenyl[4-(phenylthio)phenyl]sulfonium trifluoromethanesulfonate, 22.000g of the intermediate (Q-2) obtained above, 110mL of ion exchange water, and 110mL of diethyl ether, and the mixture was reacted at 25°C for 16 hours. After the reaction, the contents of the flask were transferred to a 300mL separatory funnel to separate the aqueous layer. The ether layer was washed five times with 100mL of ion exchange water. The ether layer was concentrated with an evaporator at 40-45°C, and dried under reduced pressure for 20 hours to obtain 24g of the target product (P-3) as a light yellow solid. The target product obtained was prepared using 1 Identification by H-NMR and LDI-MS.

[0388] 1 H-NMR (300MHz, DMSO-D6): δ7.40~7.80 (19H, m)

[0389] LDI-MS m / Z measured value: 371.04 ([M] + Calculated value: 371.09).

[0390] LDI-MS m / Z measured value: 1050.11 ([M] - Calculated value: 1049.97).

[0391] [2] Production of aniline derivatives

[0392] [Example 1] Preparation of aniline derivative A

[0393] [Chemistry 51]

[0394]

[0395] (1) Synthesis of bis(3-nitrophenyl)amine

[0396] 6.00 g of m-nitroaniline, 9.65 g of 1-bromo-3-nitrobenzene, 0.749 g of bis(dibenzylideneacetone)palladium, 1.10 g of di-tert-butyl(2',4',6'-triisopropyl-[1,1'-diphenyl]-2-yl)phosphine (tBuXPhos), 18.0 g of potassium carbonate, and 60 mL of toluene were added to a reaction vessel, purged with nitrogen, and stirred at 80°C for 2 hours. After cooling to room temperature, the mixture was filtered. Ion exchange water and methanol were added to the filtrate, stirred at room temperature, and then further filtered. The filtrate was dried to obtain 8.54 g of the target bis(3-nitrophenyl)amine (yield: 76%).

[0397] 1 H-NMR (500MHz, DMSO-d6) δ [ppm]: 9.23 (brs), 7.88 (s, 2H), 7.73-7.77 (m, 2H), 7.56-7.60 (m, 4H).

[0398] (2) Synthesis of bis(3-aminophenyl)amine / 2HCl

[0399] 3.00 g of the bis(3-nitrophenyl)amine obtained above, 0.300 g of 5% palladium / carbon (manufactured by NE Chemcat, AER type, 50% water content) and 30 mL of tetrahydrofuran were placed in a reaction vessel, the interior of the reaction vessel was replaced with hydrogen, and stirred at 50°C for 7 hours. After cooling to room temperature, the reaction solution was filtered with Celite (Celite 545 was used). After the filtrate was cooled to 0°C, 35 mL of 1M HCl ethyl acetate solution was added dropwise and stirred. The reaction solution was filtered, and the filtrate was dried to obtain the target bis(3-aminophenyl)amine / 2HCl (bis(3-aminophenyl)amine dihydrochloride 3.02 g (yield: 3.03 g).

[0400] 1 H-NMR (500MHz, CDCl3) δ [ppm]: 7.00-7.04 (m, 2H), 6.44-6.46 (m, 2H), 6.42-6.43 (m, 2H), 6.25-6.27 (m, 2H), 5.54 (brs, 1H), 3.61 (brs, 4H).

[0401] (3) Synthesis of aniline derivative A

[0402] 0.500 g of the above-obtained bis(3-aminophenyl)amine / 2HCl, 4.03 g of 3-(4-bromophenyl)-9-phenyl-9H-carbazole, 0.106 g of bis(dibenzylideneacetone)palladium, and 1.77 g of sodium tert-butoxide were placed in a reaction vessel, purged with nitrogen, and then 30 mL of toluene and 1.45 mL of a toluene solution of phenyldi-tert-butylphosphine prepared in advance (concentration: 50.3 g / L) were added, and stirred at 80°C for 3.5 hours. After cooling to room temperature, toluene and saturated brine were added to separate the liquids. The organic layer was filtered with silica gel, and the filtrate was concentrated. The obtained concentrated solution was dropped into a mixed solvent of methanol / ethyl acetate and stirred at room temperature. The slurry solution was filtered, and the obtained filtrate was dried to obtain 3.19 g of the target aniline derivative A (yield: 97%).

[0403] MALDI-TOF-MS m / z measured value: 1786.06 ([M] + Calculated value: 1784.71)

[0404] [Example 2] Preparation of aniline derivative B

[0405] [Chemistry 52]

[0406]

[0407] (1) Synthesis of 4'-(3-bromo-9H-carbazole-9-yl)-N,N-diphenyl-[1,1'-biphenyl]-4-amine

[0408] 2.00 g of 3-bromo-9-(4-iodophenyl)-9H-carbazole, 1.35 g of (4-(diphenylamino)phenyl)boric acid, 0.103 g of tetrakis(triphenylphosphine)palladium, 0.569 g of Aliquat336, 25 mL of tetrahydrofuran and 17 mL of 2M potassium carbonate aqueous solution were placed in a reaction vessel, replaced with nitrogen, and stirred at 60°C for 22 hours. After cooling to room temperature, the liquid was separated, and the organic phase was concentrated to dryness. 1,4-dioxane was added to the dry solid, and after dissolving at 80°C, methanol was added, and after cooling to room temperature, stirring was continued for 2 hours. After the stirring was completed, the filtrate obtained by filtration was dried to obtain 2.15 g of the target 4'-(3-bromo-9H-carbazole-9-yl)-N,N-diphenyl-[1,1'-biphenyl]-4-amine (yield: 85%).

[0409] 1H-NMR (500MHz, CDCl3) δ [ppm]: 8.26 (d, J = 2.0Hz, 1H), 8.09 (d, J = 8.0Hz, 1H), 7.78 (d, J = 8.5Hz, 2H), 7.54-7.58 ( m, 4H), 7.49 (dd, J=8.5, 2.0Hz, 1H), 7.44-7.45 (m, 2H), 7.28-7.33 (m, 6H), 7.16-7.20 (m, 6H), 7.05-7.08 (m, 2H).

[0410] (2) Synthesis of aniline derivative B

[0411] 0.163 g of N1-(3-aminophenyl)benzene-1,3-diamine dihydrochloride, 1.81 g of the above-obtained 4'-(3-bromo-9H-carbazole-9-yl)-N,N-diphenyl-[1,1'-biphenyl]-4-amine, 0.0355 g of bis(dibenzylideneacetone)palladium and 0.600 g of sodium tert-butoxide were placed in a reaction vessel, purged with nitrogen, and then 9 mL of toluene and 0.88 mL of a toluene solution of phenyldi-tert-butylphosphine prepared in advance (concentration: 32.3 g / L) were added, and stirred at 100°C for 3 hours. After cooling to room temperature, toluene and ion exchange water were added and the mixture was separated. The organic layer was filtered with silica gel, and the filtrate was concentrated. The obtained concentrated solution was dropped into a mixed solvent of methanol / ethyl acetate and stirred at room temperature. The slurry solution was filtered, and the obtained filtrate was dried to obtain 1.34 g of the target aniline derivative B (yield: 85%).

[0412] MALDI-TOF-MS m / z measured value: 2620.94 ([M] + Calculated value: 2620.08)

[0413] [Example 3] Preparation of Aniline Derivative C

[0414] [Chemistry 53]

[0415]

[0416] (1) Synthesis of N,N-bis(3-nitrophenyl)-9-phenyl-9H-carbazole-3-amine

[0417] 1.00 g of bis(3-nitrophenyl)amine, 1.37 g of 3-bromo-9-phenyl-9H-carbazole, 0.0678 g of bis(dibenzylideneacetone)palladium, 0.0983 g of di-tert-butyl(2',4',6'-triisopropyl-[1,1'-diphenyl]-2-yl)phosphine (tBuXPhos), 1.61 g of potassium carbonate and 10 mL of toluene were placed in a reaction vessel, purged with nitrogen, and stirred at 100° C. for 24.5 hours. After the reaction was completed, toluene and saturated brine were added for separation. The organic layer was filtered with silica gel, and the filtrate was concentrated. Chloroform and hexane were added to the concentrated residue to prepare a solution, which was then purified by column chromatography (the eluent was a mixed solvent of chloroform / hexane) to obtain 1.02 g (yield: 53%) of the target N,N-bis(3-nitrophenyl)-9-phenyl-9H-carbazole-3-amine.

[0418] MALDI-TOF-MS m / z measured value: 499.86 ([M] + Calculated value: 500.15)

[0419] (2) Synthesis of N1-(3-aminophenyl)-N1-(9-phenyl-9H-carbazole-3-yl)benzene-1,3-diamine

[0420] After N, N-bis (3-nitrophenyl) -9-phenyl-9H-carbazole-3-amine 0.603g, 5% palladium / carbon (NE Chem Caterpillar, AER type, water content 50%) 0.0582g and tetrahydrofuran 9mL were placed in a reaction container, the reaction container was replaced with hydrogen, and stirred at 50 ° C for 24 hours. After cooling to room temperature, the reaction solution was filtered with Celite (using Celite 545). The filtrate was dried to obtain the target N1- (3-aminophenyl) -N1- (9-phenyl-9H-carbazole-3-yl) benzene-1,3-diamine 0.486g (yield: 92%).

[0421] 1 H-NMR (500MHz, CDCl3) δ [ppm]: 8.00 (d, J=8.0Hz, 1H), 7.92 (m, 1H), 7.56-7.60 (m, 4H), 7.45 (m, 1H), 7.37-7.38 (m, 2H) , 7.32 (d, J = 8.5Hz, 1H), 7.20-7.23 (m, 2H), 6.98-7.02 (m, 2H), 6.52 (d, J = 8.0Hz, 2H), 6.45 (m, 2H), 6.29-6.31 (m, 2H).

[0422] (3) Synthesis of aniline derivative C

[0423] 0.451 g of the above-obtained N1-(3-aminophenyl)-N1-(9-phenyl-9H-carbazole-3-yl)benzene-1,3-diamine, 1.45 g of 3-bromo-9-phenyl-9H-carbazole, 0.0234 g of palladium acetate and 0.539 g of sodium tert-butoxide were placed in a reaction vessel, purged with nitrogen, and then 10 mL of toluene and 0.84 mL of a toluene solution of phenyl di-tert-butylphosphine prepared in advance (concentration: 54.0 g / L) were added, and stirred at 90°C for 1.5 hours. After cooling to room temperature, toluene and saturated brine were added for separation. The organic layer was filtered with silica gel, and the filtrate was concentrated. The obtained concentrated solution was dropped into a mixed solvent of methanol / ethyl acetate and stirred at room temperature. The slurry solution was filtered, and the obtained filtrate was dried to obtain 0.855 g of the target aniline derivative C (yield: 59%). MALDI-TOF-MS m / z measured value: 2620.94 ([M] + Calculated value: 2620.08)

[0424] [3] Preparation of charge transport varnish

[0425] [Reference Example 1-1]

[0426] 5.0 g of xylene was added to a mixture of 77 mg of the aniline derivative C obtained in Example 3 and 78 mg of the onium borate (P-3) obtained in Synthesis Example 1, and the mixture was stirred at room temperature to dissolve the mixture. The obtained solution was filtered with a syringe filter having a pore size of 0.2 μm to obtain a charge transport varnish.

[0427] [Reference Examples 1-2 to 1-4]

[0428] A charge-transporting varnish was obtained in the same manner as in Reference Example 1-1 except that the used amounts of the aniline derivative C and the onium borate (P-3) were 113 mg and 150 mg, 147 mg and 117 mg, and 100 mg and 54 mg, respectively.

[0429] [Comparative Reference Example 1-1]

[0430] 5.0 g of xylene was added to a mixture of 131 mg of an aniline derivative D represented by the following formula synthesized according to the method described in International Publication No. 2015 / 050253 and 132 mg of an onium borate (P-3), and the mixture was stirred at room temperature to dissolve the mixture. The obtained solution was filtered with a syringe filter having a pore size of 0.2 μm to obtain a charge transport varnish.

[0431] [Chemistry 54]

[0432]

[0433] [4] Thin film production and film property evaluation

[0434] [Reference Examples 2-1 to 2-4 and Comparative Reference Example 2-1]

[0435] The varnishes obtained in Reference Examples 1-1 to 1-4 and Comparative Reference Example 1-1 were applied to a quartz substrate using a spin coater and dried at 120° C. for 1 minute in an atmospheric firing. Next, the dried quartz substrate was fired at 150° C. for 10 minutes in an atmospheric atmosphere to form a uniform thin film of 50 nm on the quartz substrate.

[0436] The extinction coefficient k was measured using the obtained quartz substrate with a film. The results are shown in Table 1.

[0437] [Table 1]

[0438]

[0439] As shown in Table 1, it is found that the extinction coefficient of a film obtained from a varnish containing the aniline derivative of the present invention is lower than that of a film obtained using an aniline derivative having a similar structure.

[0440] [5] Fabrication and characteristic evaluation of organic EL elements

[0441] [Reference Example 3-1]

[0442] After applying the varnish obtained in Reference Example 1-1 to the ITO substrate using a spin coater, it was dried at 120°C for 1 minute in an atmospheric atmosphere. Next, the dried ITO substrate with the coating was inserted into a glove box and fired at 150°C for 10 minutes in an atmospheric atmosphere to form a 50nm thin film on the ITO substrate. As the ITO substrate, a 25mm×25mm×0.7t glass substrate with indium tin oxide (ITO) patterned on the surface with a film thickness of 150nm was used, and impurities on the surface were removed using an O2 plasma cleaning device (150W, 30 seconds) before use.

[0443] Next, the ITO substrate with the thin film formed thereon was subjected to a vacuum deposition apparatus (vacuum degree 1.0×10 -5Pa), and a 120nm α-NPD (N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine) film was formed at 0.2nm / sec. Next, a 10nm film of electron blocking material HTEB-01 manufactured by Kanto Chemical Co., Ltd. was formed. Next, the light-emitting layer main material NS60 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. and the light-emitting layer dopant material Ir(PPy)3 were co-evaporated. For co-evaporation, the evaporation rate was controlled in such a way that the concentration of Ir(PPy)3 became 6%, and 40nm was stacked. Next, thin films of Alq3, lithium fluoride and aluminum were stacked in sequence to obtain an organic EL element. At this time, with regard to the evaporation rate, for Alq3 and aluminum, it was carried out under the condition of 0.2nm / sec, and for lithium fluoride, it was carried out under the condition of 0.02nm / sec, and the film thicknesses were set to 20nm, 0.5nm and 80nm, respectively.

[0444] It should be noted that in order to prevent the degradation of characteristics due to the influence of oxygen, water, etc. in the air, the organic EL element was sealed with a sealing substrate, and its characteristics were evaluated. The sealing was performed according to the following steps. The organic EL element was placed between the sealing substrates in a nitrogen atmosphere with an oxygen concentration of less than 2 ppm and a dew point of less than -76°C, and the sealing substrates were pasted with an adhesive (MORESCO MOISTURE CUT WB90US(P)). At this time, a water scavenger (HD-071010W-40, manufactured by DYNIC CO., LTD.) was placed in the sealing substrate together with the organic EL element. The pasted sealing substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6000 mJ / cm 2 ) and then annealed at 80°C for 1 hour to cure the adhesive.

[0445] [Chemistry 55]

[0446]

[0447] [Reference Examples 3-2, 3-3]

[0448] Each layer was formed in the same manner as in Reference Example 3-1, thereby producing an organic EL element, except that the varnishes obtained in Reference Examples 1-2 and 1-3 were used instead of the varnish obtained in Reference Example 1-1.

[0449] For each element obtained above, the 2 The driving voltage, current density, current efficiency, luminous efficiency, and external light emission quantum yield (EQE) when the light was emitted were shown in Table 2.

[0450] [Table 2]

[0451]

[0452] As shown in Table 2, it was found that the EL element including the charge-transporting thin film produced from the charge-transporting varnish containing the aniline derivative of the present invention as a hole injection layer can be driven appropriately.

Claims

1. Aniline derivative, characterized in that It is represented by formula (1) or (1'): [Chemistry 1] Where Ph 1 represents a group represented by formula (P1), [Chemistry 2] In the formula, R 1 ~R 4 represents a hydrogen atom, Ar 0 are all the same group, representing a group represented by formula (B4), [Chemistry 3] In the formula, R 43 ~R 49 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and R 50 represents a hydrogen atom or an aryl group having 6 to 20 carbon atoms which may be substituted with a diphenylamino group, k represents 1.

2. The aniline derivative according to claim 1, wherein the aniline derivative represented by formula (1) is any one of the following formulae: [Chemistry 4] 3. The method for producing an aniline derivative according to claim 1, wherein An amine compound represented by the formula (4) is reacted with an aryl compound represented by the formula (5) in the presence of a catalyst, [Chemistry 5] Where Ph 1 and k have the same meanings as above, [Chemistry 6] Ar 0 -X (5) In the formula, X represents a halogen atom or a pseudohalogen group, Ar 0 It means the same as above or the following formula:

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