阅读说明：本技术 聚合物及其利用 (Polymer and use thereof ) 是由 太田博史 仓田阳介 于 2019-07-29 设计创作，主要内容包括：例如包含下述的重复单元的聚合物兼具优异的电荷传输性和在有机溶剂中的优异的溶解性,通过使该聚合物单独地或者与掺杂剂物质一起溶解在有机溶剂中,从而在以有机EL元件为首的电子元件中应用的情况下能够实现优异的特性。(For example, a polymer containing a repeating unit described below has both excellent charge transport properties and excellent solubility in an organic solvent, and by dissolving the polymer in an organic solvent alone or together with a dopant substance, excellent characteristics can be realized when the polymer is applied to electronic devices such as organic EL devices.)

1. A polymer comprising a repeat unit represented by formula (P1):

[ solution 1]

Wherein Ph represents a1, 4-phenylene group, G represents a group having a valence of 1 represented by any one of the formulae (A01) to (A18),

[ solution 2]

[ solution 3]

[ solution 4]

[ solution 5]

In the formula, L⁰¹represents-S-, -O-, -CO-, -CH₂-、-(CH₂)₂-、-C(CH₃)₂-、-CF₂-、-(CF₂)₂-、-C(CF₃)₂-or fluorene-9, 9-diyl,

L⁰²independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, or an aryl group having 6 to 20 carbon atoms which may be substituted with R,

L⁰³and L⁰⁴Independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, or an aryl group having 6 to 20 carbon atoms which may be substituted with R,

Z⁰¹～Z¹⁸independently represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, or an alkynyl group having 2 to 20 carbon atoms,

r represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, or an alkynyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom,

ar represents a group represented by any one of formulae (S1) to (S6),

[ solution 6]

a⁰¹¹～a¹⁸³Independently of one another, are integers representing the number of substituents substituted on the aromatic ring,

a⁰⁷¹、a⁰⁸¹、a⁰⁹¹、a¹⁰¹and a¹¹¹Is in the range of 0 to 3,

a⁰⁵¹、a⁰⁶¹、a⁰⁷²、a⁰⁸²、a⁰⁹²、a¹⁰²、a¹¹²、a¹¹³、a¹¹⁴、a¹²¹、a¹³¹、a¹⁴¹、a¹⁵¹、a¹⁶¹、a¹⁷¹、a¹⁸¹、a¹⁸²and a¹⁸³Is in the range of 0 to 4,

a⁰¹¹、a⁰⁵²、a⁰⁶²、a¹²²、a¹²³and a¹³²Is in the range of 0 to 5,

a⁰²¹、a¹³³、a¹⁴²、a¹⁴³、a¹⁵²、a¹⁵³、a¹⁶²and a¹⁶³Is in the range of 0 to 7,

a⁰³¹and a⁰⁴¹Is 0 to 9.

2. The polymer according to claim 1, wherein G is a group represented by any one of formulae (A01-1) to (A01-3),

[ solution 7]

In the formula, Z⁰¹The same meanings as described above are indicated.

3. A polymer comprising a repeating unit represented by formula (E1),

[ solution 8]

4. A charge transport composition comprising: a charge transporting material comprising the polymer according to any one of claims 1 to 3, and an organic solvent.

5. The charge transport composition of claim 4 further comprising a charge accepting substance or charge accepting substance precursor.

6. A charge-transporting film obtained from the charge-transporting composition according to claim 4 or 5.

7. An organic electroluminescent element having the charge-transporting thin film according to claim 6.

8. The method for producing a polymer according to claim 1, wherein a triphenylamine derivative represented by the formula (A1) is reacted with a triphenylamine derivative represented by the formula (H1),

[ solution 9]

Wherein X independently represents a chlorine atom, a bromine atom, an iodine atom or a pseudohalogen group, and Ph and G represent the same meanings as described above.

Technical Field

The present invention relates to a polymer and use thereof.

Background

Low molecular weight compounds and high molecular weight compounds having charge transport properties are used in various electronic devices such as organic Electroluminescence (EL) devices and organic solar cells.

Among them, there are many reports of polymers having triarylamines such as triphenylamine contributing to high charge transport property in the repeating unit (hereinafter referred to as triarylamine polymers) because of their high charge transport property (for example, patent documents 1 to 3).

On the other hand, organic EL devices that have been put into practical use in the field of displays and the like include organic functional layers such as a hole injection layer and a hole transport layer, and these organic functional layers play an important role in achieving high performance such as reduction in driving voltage and improvement in lifetime of the devices.

Methods for forming an organic functional layer of an organic EL element can be roughly classified into a dry method typified by a vapor deposition method and a wet method typified by a spin coating method, and it is necessary to form an organic functional layer having a larger area as the area of a display is increased. Under such circumstances, development of organic EL devices in which an organic functional layer is formed by a wet process has been carried out (for example, patent documents 4 to 6).

Under such a background, development of materials for a wet process for forming an organic functional layer such as a hole injection layer and a hole transport layer has been intensively carried out, and a new material having high functionality is often required for realizing a higher-performance organic EL display.

In addition, although a new material for a wet process using a triarylamine polymer having a high charge transport property, which is expected to contribute to a high function, is one of promising candidate materials, a polymer having only triphenylamine in a repeating unit has low solubility depending on the kind of a solvent, and thus there is a problem that the selection range of a solvent to be used for preparing a composition using the polymer is narrow.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-105790

Patent document 2: japanese patent laid-open No. 2012 and 102286

Patent document 3: japanese patent laid-open No. 2014-001399

Patent document 4: international publication No. 2015/050253

Patent document 5: international publication No. 2017/047644

Patent document 6: international publication No. 2018/110535

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a polymer having good solubility in an organic solvent, a method for producing the same, a charge-transporting composition containing a charge-transporting substance containing the polymer, a charge-transporting thin film obtained from the charge-transporting composition, and an organic EL element having the charge-transporting thin film.

Means for solving the problems

The present inventors have made extensive studies to achieve the above object, and as a result, have found that: the present inventors have completed the present invention by finding that a polymer having a repeating unit containing a predetermined triphenylamine structure and an-NH-structure has good solubility in an organic solvent.

Namely, the present invention provides:

1. a polymer comprising a repeat unit represented by formula (P1):

[ solution 1]

[ in the formula, Ph represents a1, 4-phenylene group, and G represents a group having a valence of 1 represented by any one of formulas (A01) to (A18).

[ solution 2]

[ solution 3]

[ solution 4]

[ solution 5]

(in the formula, L⁰¹represents-S-, -O-, -CO-, -CH₂-、-(CH₂)₂-、-C(CH₃)₂-、-CF₂-、-(CF₂)₂-、-C(CF₃)₂-or fluorene-9, 9-diyl,

L⁰²independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, or an aryl group having 6 to 20 carbon atoms which may be substituted with R,

L⁰³and L⁰⁴Independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, or an aryl group having 6 to 20 carbon atoms which may be substituted with R,

Z⁰¹～Z¹⁸independently represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, or an alkynyl group having 2 to 20 carbon atoms,

r represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, or an alkynyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom,

ar represents a group represented by any one of formulae (S1) to (S6),

[ solution 6]

a⁰¹¹～a¹⁸³Independently of one another, are integers representing the number of substituents substituted on the aromatic ring,

a⁰⁷¹、a⁰⁸¹、a⁰⁹¹、a¹⁰¹and a¹¹¹Is in the range of 0 to 3,

a⁰⁵¹、a⁰⁶¹、a⁰⁷²、a⁰⁸²、a⁰⁹²、a¹⁰²、a¹¹²、a¹¹³、a¹¹⁴、a¹²¹、a¹³¹、a¹⁴¹、a¹⁵¹、a¹⁶¹、a¹⁷¹、a¹⁸¹、a¹⁸²and a¹⁸³Is in the range of 0 to 4,

a⁰¹¹、a⁰⁵²、a⁰⁶²、a¹²²、a¹²³and a¹³²Is in the range of 0 to 5,

a⁰²¹、a¹³³、a¹⁴²、a¹⁴³、a¹⁵²、a¹⁵³、a¹⁶²and a¹⁶³Is in the range of 0 to 7,

a⁰³¹and a⁰⁴¹Is 0 to 9. )]

2.1A polymer wherein G is a group represented by any one of the formulae (A01-1) to (A01-3),

[ solution 7]

(in the formula, Z⁰¹The same meanings as described above are indicated. )

3. A polymer comprising a repeating unit represented by formula (E1),

[ solution 8]

4. A charge transport composition comprising: a charge transporting material comprising a polymer of any one of 1 to 3, and an organic solvent,

5.4, further comprising a charge accepting substance or a charge accepting substance precursor,

6. a charge-transporting film obtained from the charge-transporting composition of 4 or 5,

7. an organic electroluminescent element having a charge-transporting thin film of 6,

8.1A method for producing a polymer, characterized by reacting a triphenylamine derivative represented by the formula (A1) with a triphenylamine derivative represented by the formula (H1),

[ solution 9]

(wherein X independently represents a chlorine atom, a bromine atom, an iodine atom or a pseudohalogen group, and Ph and G represent the same meanings as described above).

ADVANTAGEOUS EFFECTS OF INVENTION

The polymer of the present invention has both excellent charge transport properties and excellent solubility in an organic solvent because it contains a predetermined triphenylamine structure and an — NH-structure in its repeating unit, and can be dissolved in an organic solvent alone or together with a dopant substance or a dopant substance precursor, thereby easily preparing a charge transport composition that can provide a charge transport thin film that can realize excellent properties when applied to electronic devices such as organic EL devices.

In particular, by using the charge transporting thin film of the present invention as a hole injection layer of an organic EL element, an organic EL element having excellent characteristics can be obtained.

Detailed Description

The present invention will be described in more detail below.

The polymer of the present invention comprises a repeating unit represented by formula (P1).

[ solution 10]

Ph represents a1, 4-phenylene group, and G represents a group having a valence of 1 represented by any one of formulae (A01) to (A18).

[ solution 11]

[ solution 12]

[ solution 13]

[ solution 14]

L⁰¹represents-S-, -O-, -CO-, -CH₂-、-(CH₂)₂-、-C(CH₃)₂-、-CF₂-、-(CF₂)₂-、-C(CF₃)₂-or fluorene-9, 9-diyl.

L⁰²Independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, or an aryl group having 6 to 20 carbon atoms which may be substituted with R.

The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include linear 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-pentan-2-yl, n-pentan-3-yl, n-hexyl, n-hexan-2-yl, n-hexan-3-yl, n-heptyl, n-heptan-2-yl, n-heptan-3-yl, n-heptan-4-yl, n-octyl, n-octan-2-yl, n-octan-3-yl, n-octan-4-yl, n-nonyl and n-decyl; and C3-20 cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include vinyl, 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 and n-1-decenyl.

The alkynyl group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof, examples thereof 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-dimethyl-n-propynyl, n-1-hexynyl and n-1-decynyl groups.

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-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl.

L⁰³And L⁰⁴Independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, or an aryl group having 6 to 20 carbon atoms which may be substituted with R.

Z⁰¹～Z¹⁸The substituent is a substituent substituted on the aromatic ring, and independently represents an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted by a fluorine atom, or an alkynyl group having 2 to 20 carbon atoms which may be substituted by a fluorine atom.

R represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, or an alkynyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom.

L⁰³And L⁰⁴、Z⁰¹～Z¹⁸And R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or L⁰³And L⁰⁴Specific examples of the C6-20 aryl group in (A) areThe same groups as described above are exemplified.

Preferred examples of the group represented by the formula (a01) include the following, but are not limited thereto.

[ solution 15]

(in the formula, Z⁰¹The same meanings as described above are indicated. )

In the formulae (A01-1) to (A01-3), Z is a linear or branched structure derived from the solubility and charge transport properties of the resulting polymer⁰¹Preferably an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, and an alkynyl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom, more preferably an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, still more preferably an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and still more preferably an alkyl group having 1 to 8 carbon atoms which may be substituted with a fluorine atom.

Further, the substituent Z in the formulae (A01-1) to (A01-3)⁰¹In the case of an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, the bond end of the alkyl group to the aromatic ring is preferably located on a secondary or tertiary carbon atom of the alkyl group, and more preferably located on a secondary carbon atom.

Specifically, in the formulae (A01-1) to (A01-3), Z⁰¹Preferred examples thereof include, but are not limited to, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentan-2-yl group, n-pentan-3-yl group, n-hexan-2-yl group, n-hexan-3-yl group, n-heptan-2-yl group, n-heptan-3-yl group, n-heptan-4-yl group, n-octan-2-yl group, n-octan-3-yl group, and n-octan-4-yl group.

In the present invention, the number of carbon atoms of the alkyl group, alkenyl group and alkynyl group in the formula (P1) is preferably 15 or less, more preferably 10 or less, further preferably 8 or less, and further preferably 5 or less, from the viewpoint of solubility in an organic solvent, and the number of carbon atoms of the aryl group is preferably 15 or less, more preferably 10 or less.

Ar represents a group represented by any one of formulae (S1) to (S6).

[ solution 16]

a⁰¹¹～a¹⁸³Independently of each other, is an integer representing the number of substituents substituted on the aromatic ring.

a⁰⁷¹、a⁰⁸¹、a⁰⁹¹、a¹⁰¹And a¹¹¹Is 0 to 3.

a⁰⁵¹、a⁰⁶¹、a⁰⁷²、a⁰⁸²、a⁰⁹²、a¹⁰²、a¹¹²、a¹¹³、a¹¹⁴、a¹²¹、a¹³¹、a¹⁴¹、a¹⁵¹、a¹⁶¹、a¹⁷¹、a¹⁸¹、a¹⁸²And a¹⁸³Is 0 to 4.

a⁰¹¹、a⁰⁵²、a⁰⁶²、a¹²²、a¹²³And a¹³²Is 0 to 5.

a⁰²¹、a¹³³、a¹⁴²、a¹⁴³、a¹⁵²、a¹⁵³、a¹⁶²And a¹⁶³Is 0 to 7.

a⁰³¹And a⁰⁴¹Is 0 to 9.

Considering the balance among availability of the starting compound, ease of synthesis, solubility of the resulting polymer, and charge transport properties of the resulting charge transport film, a⁰¹¹Preferably 0 to 3, more preferably 1 or 2, a⁰²¹～a¹⁸³Preferably 0 or 1, more preferably 0.

The polymer of the present invention does not necessarily have all the repeating units having the same structure, and may include repeating units having different structures contained in the formula (P1). The units may be randomly combined or may be combined as a block polymer.

The content of the repeating unit represented by the formula (P1) in the polymer of the present invention is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, further preferably 95 mol% or more, and most preferably 100 mol% of all repeating units contained in the polymer, from the viewpoint of obtaining a polymer excellent in charge transport property and solubility.

The weight average molecular weight of the polymer of the present invention is usually 1000 to 100000, and from the viewpoint of solubility in an organic solvent, is preferably 20000 or less, more preferably 10000 or less, and from the viewpoint of charge transport property, is preferably 3000 or more, more preferably 5000 or more. The weight average molecular weight in the present invention is an average molecular weight in terms of standard polystyrene analyzed by gel permeation chromatography (hereinafter referred to as GPC).

The polymer of the present invention can be produced by reacting a triphenylamine derivative represented by the formula (a1) with a triphenylamine derivative represented by the formula (H1).

[ solution 17]

(wherein X independently of one another represents a chlorine atom, a bromine atom, an iodine atom or a pseudohalogen group, and Ph and G represent the same meanings as described above.)

Examples of the pseudohalogen group include (fluoro) alkylsulfonyloxy groups such as methylsulfonyloxy, trifluoromethanesulfonyloxy and nonafluorobutanesulfonyloxy; and aromatic sulfonyloxy groups such as benzenesulfonyloxy and toluenesulfonyloxy.

The feeding ratio of the triphenylamine derivative represented by the formula (a1) to the triphenylamine derivative represented by the formula (H1) can be 1 equivalent or more, preferably about 1 to 1.5 equivalents of the triphenylamine derivative represented by the formula (a1) to the triphenylamine derivative represented by the formula (H1).

Examples of the catalyst used in the above reaction include copper catalysts such as copper chloride, copper bromide, and copper iodide; pd (PPh)₃)₄(tetrakis (triphenylphosphine) palladium), Pd (PPh)₃)₂Cl₂(bis (triphenylphosphine) palladium dichloride), Pd (dba)₂(bis (dibenzylideneacetone) palladium), Pd₂(dba)₃(tris (dibenzylideneacetone) dipalladium), Pd (P-t-Bu)₃)₂(bis (tris (t-butylphosphino)) palladium), Pd (OAc)₂Palladium catalysts such as (palladium acetate) and the like. These catalysts may be used alone, or 2 or more of them may be used in combination. In addition, these catalysts may be used together with known appropriate ligands.

Examples of such ligands include tertiary phosphines such as triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-t-butylphosphine, di-t-butyl (phenyl) phosphine, di-t-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, trimethyl phosphite, triethyl phosphite and triphenyl phosphite.

The amount of the catalyst to be used may be about 0.01 to 0.2 mol, preferably about 0.1 mol, based on 1 mol of the triphenylamine derivative represented by the formula (H1).

When the 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 (catalyst) used.

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

The reaction temperature may be suitably set in a range from the melting point to the boiling point of the solvent used, and is preferably about 0 to 200 ℃ and more preferably 20 to 150 ℃.

After the reaction, the target polymer can be obtained by performing post-treatment according to a conventional method.

The triphenylamine derivative represented by the formula (a1) used for producing the polymer of the present invention can be produced by a commercially available method, or by the following method according to the following scheme.

The aniline derivative specified below is reacted with, for example, 4-fluoronitrobenzene by a known method to obtain the corresponding dinitro compound. Then, the nitro group of the obtained dinitro compound is converted into an amino group by, for example, hydrogenation using Pd/C.

[ solution 18]

(wherein Ph and G represent the same meanings as described above.)

The triphenylamine derivative represented by the formula (H1) used for producing the polymer of the present invention may be a commercially available product, or the corresponding triphenylamine derivative may be halogenated or quasi-halogenated according to the following scheme. Halogenation or pseudohalogenation can be carried out according to conventional methods using halogenating or pseudohalogenating agents.

[ solution 19]

(wherein Ph, G and X represent the same meanings as described above.)

The following is a preferred example of the polymer of the present invention, but the present invention is not limited thereto.

[ solution 20]

(k is an integer representing a repeating unit, determined according to the molecular weight of the polymer.)

The polymer of the present invention exhibits good solubility in an organic solvent, and a charge transporting composition can be produced by dissolving the polymer of the present invention as a charge transporting substance in an organic solvent.

As such an organic solvent, a highly soluble organic solvent that can dissolve the polymer of the present invention well can be used.

Specific examples thereof include low-polarity, highly soluble organic solvents such as chlorine-based solvents such as chloroform and chlorobenzene, aromatic hydrocarbon-based solvents such as toluene, xylene, tetrahydronaphthalene, cyclohexylbenzene and 3-phenoxytoluene; polar highly soluble organic solvents such as amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-dimethylisobutyramide, N-methylpyrrolidone, and 1, 3-dimethyl-2-imidazolidinone, ketone solvents such as isophorone and cyclohexanone, ester solvents such as ethyl acetate and methyl benzoate, polyol solvents such as ethylene glycol and diethylene glycol, ether solvents such as tetrahydrofuran, dioxane, and anisole, and sulfoxide solvents such as dimethyl sulfoxide.

These organic solvents may be used alone in 1 kind, or in a mixture of 2 or more kinds, and the amount of the organic solvent used may be 5 to 100% by mass based on the total amount of the solvents used in the charge transporting composition.

The organic solvent may further contain at least 1 high-viscosity organic solvent having a viscosity of 10 to 200 mPas, particularly 35 to 150 mPas, at 25 ℃ and a boiling point of 50 to 300 ℃, particularly 150 to 250 ℃ at normal pressure (atmospheric pressure). By adding such a solvent, the viscosity of the charge transporting composition can be easily adjusted, and the composition can be prepared according to the coating method used, which can give a film having high flatness with good reproducibility.

Examples of the high-viscosity organic solvent include, but are not limited to, cyclohexanol, 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. The high-viscosity organic solvent may double as the high-solubility organic solvent, which is determined according to the structure of the polymer as the charge transporting substance.

When a high-viscosity organic solvent is added, the proportion of the high-viscosity organic solvent is preferably within a range in which no solid precipitates, and 5 to 90% by mass of the total solvent used in the charge transporting composition is preferable as long as no solid precipitates.

Further, for the purpose of improving wettability to the substrate, adjusting surface tension of the solvent, adjusting polarity, adjusting boiling point, and the like, other solvents may be mixed in a proportion of 1 to 90 mass%, preferably 1 to 50 mass%, to all the solvents used in the charge transporting composition.

Examples of such a solvent include, but are not limited to, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diacetone alcohol, γ -butyrolactone, ethyl lactate, and n-hexyl acetate. These solvents can be used alone in 1 kind, or more than 2 kinds of mixed use. Further, the solvent used for this purpose may also function as a highly soluble organic solvent.

The charge transporting composition of the present invention may contain a dopant substance (charge-receiving substance) or a dopant substance precursor (charge-receiving substance precursor) for the purpose of, for example, improving the charge transporting property of the obtained charge transporting thin film.

The dopant substance is not particularly limited as long as it is dissolved in at least one solvent used in the charge transporting composition, and the organic charge-receiving substance is an organic dopant substance such as arylsulfonic acid, an ionic compound composed of an anion and a counter cation thereof, a tetracyanoquinodimethane derivative, or a benzoquinone derivative; organic dopant precursor such as arylsulfonate; inorganic dopant substances such as phosphotungstic acid and phosphomolybdic acid can be used.

A preferred example of the charge transporting composition of the present invention comprises a dopant substance precursor containing a sulfonate compound represented by formula (1).

[ solution 21]

R¹And R²Independently represent a hydrogen atom or a linear or branched aliphatic hydrocarbon group having a valence of 1, R³Represents a linear or branched 1-valent aliphatic hydrocarbon group. However, R¹、R²And R³The total number of carbon atoms of (2) is 6 or more. To R¹、R²And R³The upper limit of the total number of carbon atoms of (3) is not particularly limited, but is preferably 20 or less, and more preferably 10 or less.

The linear or branched 1-valent aliphatic hydrocarbon group is not particularly limited, and examples thereof include alkyl groups having 1 to 18 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, and decyl group; and alkenyl groups having 2 to 18 carbon atoms such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, hexenyl, and the like.

As R¹Preferably a hydrogen atom, as R²And R³Preferably, the alkyl group has 1 to 6 carbon atoms. In this case, R²And R³May be the same or different.

A¹represents-O-or-S-, preferably-O-. A. the²Represents (n +1)) A monovalent aromatic hydrocarbon group. A. the³Represents a substituted or unsubstituted m-valent hydrocarbon group containing 1 or more aromatic rings.

From A²The (n +1) -valent aromatic hydrocarbon group is a group obtained by removing (n +1) hydrogen atoms from the aromatic ring of the aromatic hydrocarbon compound. Examples of the aromatic hydrocarbon compound include benzene, toluene, xylene, naphthalene, anthracene, phenanthrene, and the like. Among these, as A²Preferably a naphthalene or anthracene derived group, more preferably a naphthalene derived group.

From A³The substituted or unsubstituted m-valent hydrocarbon group containing 1 or more aromatic rings represented herein is a group obtained by removing m atoms or atomic groups bonded to a carbon skeleton from a substituted or unsubstituted hydrocarbon compound containing 1 or more aromatic rings. Examples of the hydrocarbon compounds include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, phenanthrene, and the like; some or all of the hydrogen atoms of these groups are further substituted with a hydroxyl group, an amino group, a silanol group, a thiol group, a carboxyl group, a sulfonate group, a phosphate group, an ester group, a thioester group, an amido group, a nitro group, a 1-valent hydrocarbon group, an organooxy group, an organoamino group, an organosilyl group, an organothio group, an acyl group, a sulfone group, a halogen atom, or the like.

If it is considered to achieve an improvement in durability and an improvement in charge transport property of the sulfonate compound represented by the formula (1), A is³Preferably, a 2-or 3-valent group derived from 1,3, 5-triazine, a 2-or 3-valent group derived from substituted or unsubstituted benzene, a 2-or 3-valent group derived from substituted or unsubstituted toluene, a 2-valent group derived from substituted or unsubstituted p-xylene, a 2-or 3-valent group derived from substituted or unsubstituted naphthalene, a 2-to 4-valent group derived from perfluorobiphenyl, etc., more preferably a 2-valent perfluorobiphenyl.

m represents an integer satisfying 2. ltoreq. m.ltoreq.4, preferably 2. n represents an integer satisfying 1. ltoreq. n.ltoreq.4, preferably 2.

The sulfonic acid ester compound represented by the formula (1) can also be synthesized by the method described in international publication No. 2017/217457.

When the charge transporting composition of the present invention contains a dopant substance or a dopant substance precursor, the content thereof is appropriately determined depending on the kind thereof, the desired charge transporting property, and the like, and therefore, it cannot be generally specified that the content is in the range of 0.01 to 10 in terms of the mass ratio, in terms of the total of the dopant substance and the dopant substance precursor, relative to the polymer 1 of the present invention.

Specific examples of the dopant substance or the dopant substance precursor preferable in the present invention will be described below, but the present invention is not limited thereto.

[ solution 22]

[ solution 23]

[ solution 24]

The charge transporting substance, the dopant substance, and the dopant substance precursor are preferably completely dissolved or uniformly dispersed in the solvent, and most preferably completely dissolved.

The charge transporting composition of the present invention may contain water as a solvent, and the content of water is preferably 10% by mass or less, more preferably 5% by mass or less, of the total solvent, and most preferably only an organic solvent is used as a solvent, from the viewpoint of obtaining a highly durable element with good reproducibility when the charge transporting film obtained from the composition is used as a hole injection layer of an organic EL element.

In this case, "only the organic solvent is used" means that only the organic solvent is used as the solvent, and the presence of "water" contained in a small amount in the organic solvent, the solid component, and the like to be used is not denied.

In the present invention, the solid component means a component other than the solvent contained in the charge transporting composition.

In the present invention, from the viewpoint of obtaining a film having a higher flatness with good reproducibility, it is preferable to dissolve the charge transporting substance in an organic solvent and then perform filtration using a submicron filter or the like.

The solid content concentration in the charge transporting composition of the present invention is usually about 0.1 to 20% by mass, preferably 0.5 to 15% by mass, from the viewpoint of suppressing precipitation of the charge transporting material and ensuring a sufficient film thickness.

The charge transporting composition of the present invention has a viscosity of usually 1 to 50 mPas at 25 ℃ and a surface tension of usually 20 to 50mN/m at 25 ℃.

The viscosity and surface tension of the charge transporting composition of the present invention can be adjusted by changing the kind of the organic solvent used, the ratio thereof, the solid content concentration, and the like, in consideration of various factors such as the coating method used and the desired film thickness.

The charge transporting composition of the present invention can be produced by dissolving the polymer of the present invention in an organic solvent. The polymer of the present invention may be dissolved in an organic solvent in advance, and other organic solvents may be sequentially added thereto, or a mixed solvent of all the solvents used may be prepared in advance and the polymer of the present invention may be dissolved therein. The same procedure is followed also in the case where the charge transporting composition of the present invention contains the polymer of the present invention and components other than the solvent.

In addition, if necessary, attention is paid so as not to decompose or deteriorate the components contained in the composition, and heat may be applied to promote dissolution of the polymer or the like.

The charge-transporting film of the present invention can be formed on a substrate by applying the charge-transporting composition of the present invention on a substrate and baking the composition.

Examples of the method for applying the charge transporting composition include, but are not limited to, dipping, spin coating, transfer printing, roll coating, brush coating, ink jet, spray coating, and slit coating. The viscosity and surface tension of the charge transporting composition are preferably adjusted according to the coating method.

The firing conditions are not particularly limited, and firing by heating on a hot plate is used, for example. The firing temperature is usually in the range of 100 to 260 ℃ and the firing time is in the range of 1 minute to 1 hour. The firing atmosphere is not particularly limited, and is preferably under air.

Further, the firing may be performed in multiple stages at 2 or more different temperatures, if necessary.

The thickness of the charge transporting thin film is not particularly limited, and is preferably 5 to 300nm when used as a functional layer of an organic EL element. As a method for changing the film thickness, there are methods of changing the concentration of solid components in the charge transporting composition, changing the amount of liquid at the time of application, and the like.

The organic EL device of the present invention has a pair of electrodes, and the charge transporting thin film of the present invention is provided between the electrodes.

Typical configurations of the organic EL element include the following (a) to (f), but are not limited thereto. In the following configuration, an electron blocking layer or the like may be provided between the light-emitting layer and the anode, and a hole (hole) blocking layer or the like may be provided between the light-emitting layer and the cathode, as necessary. The hole injection layer, the hole transport layer, or the hole injection transport layer may have a function as an electron blocking layer or the like, and the electron injection layer, the electron transport layer, or the electron injection transport layer may have a function as a hole (hole) blocking layer or the like. Further, an arbitrary functional layer may be provided between the layers as necessary.

(a) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode

(b) Anode/hole injection layer/hole transport layer/light emitting layer/electron injection transport layer/cathode

(c) Anode/hole injection transport layer/luminescent layer/electron transport layer/electron injection layer/cathode

(d) Anode/hole injection transport layer/light emitting layer/electron injection transport layer/cathode

(e) Anode/hole injection layer/hole transport layer/light emitting layer/cathode

(f) Anode/hole injection transport layer/light emitting layer/cathode

The "hole injection layer", "hole transport layer" and "hole injection transport layer" are layers formed between the light-emitting layer and the anode, and have a function of transporting holes from the anode to the light-emitting layer, and are "hole injection transport layer" when only 1 layer of a hole-transporting material is provided between the light-emitting layer and the anode, and are "hole injection layer" when 2 or more layers of a hole-transporting material are provided between the light-emitting layer and the anode, the layer close to the anode is the "hole injection layer", and the other layers are the "hole transport layers". In particular, a thin film excellent in hole accepting property from the anode and hole injecting property into the hole transporting (light emitting) layer is used as the hole injecting (transporting) layer.

The "electron injection layer", "electron transport layer" and "electron injection transport layer" are layers formed between the light-emitting layer and the cathode, and have a function of transporting electrons from the cathode to the light-emitting layer, and are the "electron injection transport layer" when only 1 layer of an electron-transporting material is provided between the light-emitting layer and the cathode, and are the "electron injection layer" when 2 or more layers of an electron-transporting material are provided between the light-emitting layer and the cathode, the layer close to the cathode is the "electron injection layer", and the other layers are the "electron transport layers".

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

The charge-transporting thin film of the present invention can be preferably used as an organic functional film provided between an anode and a light-emitting layer in an organic EL device, can be more preferably used as a hole injection layer, a hole transport layer, a hole injection transport layer, and a further preferably used as a hole injection layer.

Examples of the materials and methods for producing the organic EL element using the charge transporting composition of the present invention include, but are not limited to, the following materials and methods.

An example of a method for manufacturing an OLED element having a hole injection layer composed of a thin film obtained from the charge transporting composition of the present invention is as follows. Furthermore, it is preferable that the electrode is previously cleaned with alcohol, pure water, or the like within a range that does not adversely affect the electrode; surface treatment such as UV ozone treatment, oxygen-plasma treatment, or the like is employed.

On the anode substrate, a hole injection layer composed of the charge transporting thin film of the present invention is formed by the above-described method. The organic electroluminescent material is introduced into a vacuum evaporation device, and a hole transport layer, a luminescent layer, an electron transport layer/hole barrier layer and cathode metal are evaporated in sequence. Alternatively, in this method, instead of forming the hole transport layer and the light-emitting layer by vapor deposition, a composition for forming a hole transport layer containing a hole transport polymer and a composition for forming a light-emitting layer containing a light-emitting polymer are used, and these layers are formed by a wet method. Further, an electron blocking layer may be provided between the light-emitting layer and the hole transporting layer as necessary.

Examples of the anode material include a transparent electrode typified by Indium Tin Oxide (ITO) and Indium Zinc Oxide (IZO), a metal anode typified by aluminum, an alloy thereof, and the like, and a flattened anode material is preferable. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used.

Examples of the other metal constituting the metal anode include gold, silver, copper, indium, and alloys thereof, but are not limited thereto.

Examples of the material for forming the hole transport layer include triarylamines such as (triphenylamine) dimer derivatives, [ (triphenylamine) dimer ] spiro dimer, N '-bis (naphthalene-1-yl) -N, N' -bis (phenyl) -benzidine (. alpha. -NPD), 4 '-tris [ 3-methylphenyl (phenyl) amino ] triphenylamine (m-MTDATA), and 4, 4' -tris [ 1-naphthyl (phenyl) amino ] triphenylamine (1-TNATA), and 5, 5 '-bis- {4- [ bis (4-methylphenyl) amino ] phenyl } -2, 2': and oligophenes such as 5 ', 2' -terthiophene (BMA-3T).

Examples of the material for forming the light-emitting layer include low-molecular-weight light-emitting materials such as metal complexes of 8-hydroxyquinoline and the like, metal complexes of 10-hydroxybenzo [ h ] quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, metal complexes of (2-hydroxyphenyl) benzothiazole, silole (シロール) derivatives, and the like; and a system in which a light-emitting material and an electron-transporting material are mixed in a polymer compound such as poly (p-phenylene vinylene), poly [ 2-methoxy-5- (2-ethylhexyloxy) -1, 4-phenylene vinylene ], poly (3-alkylthiophene) or polyvinylcarbazole, but the present invention is not limited thereto.

In addition, when the light-emitting layer is formed by vapor deposition, the light-emitting layer may be co-deposited with a light-emitting dopant, and examples of the light-emitting dopant include tris (2-phenylpyridine) iridium (III) (ir (ppy)₃) And metal complexes thereof, tetracene derivatives such as rubrene, quinacridone derivatives, fused polycyclic aromatic rings such as perylene, and the like, but are not limited thereto.

Examples of the material for forming the electron transport layer/hole blocking layer include, but are not limited to, oxadiazole (オキシジアゾール) derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, and pyrimidine derivatives.

As a material for forming the electron injection layer, lithium oxide (Li) can be mentioned₂O), magnesium oxide (MgO), aluminum oxide (Al)₂O₃) And metal fluorides such as lithium fluoride (LiF) and sodium fluoride (NaF), but the metal fluorides are not limited thereto.

Examples of the cathode material include, but are not limited to, aluminum, magnesium-silver alloy, and aluminum-lithium alloy.

Examples of the material for forming the electron blocking layer include, but are not limited to, tris (phenylpyrazole) iridium.

Examples of the hole-transporting polymer 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' -penten-5 '-yl } fluorene-2, 7-diyl) -co- (N, N' -bis { p-butylphenyl } -1, 4-diaminophenylene) ], poly [ N ] terminated with polysilsesquioxane (ポリシルシスキノキサン), n ' -bis (4-butylphenyl) -N, N ' -bis (phenyl) -benzidine ], poly [ (9, 9-bisdioctylfluorene-2, 7-diyl) -co- (4,4 ' - (N- (p-butylphenyl)) diphenylamine) ], and the like.

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

Examples

The present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. The apparatus used is as follows.

(1) Cleaning a substrate: substrate cleaning device (reduced pressure plasma method) manufactured by Changzhou industry (strain)

(2) Coating of the composition: ミカサ Spreader MS-A100

(3) And (3) manufacturing an element: multifunctional evaporation device system C-E2L1G1-N manufactured by Changzhou industry

(4) Measurement of Current Density and the like: multi-channel IVL measuring device manufactured by (Jobi) EHC

(5) Life measurement (measurement of half-life) of EL element: organic EL Brightness Life evaluation System PEL-105S manufactured by EHC

(6) Weight average molecular weight (Mw) and number average molecular weight (Mn): shimadzu corporation (column: SHODEX GPC KF-803L + GPC KF-804L, column temperature: 40 ℃ C., detector: UV detector (254nm) and RI detector, eluent: 0.5% Et₃N/THF, column flow rate: 1.0mL/min.)

(7)¹H-NMR: ascend500 manufactured by Bruker

(8) LC/MS: ZQ2000 manufactured by Waters corporation

[1] Synthesis of starting Compounds

[ Synthesis example 1]

[ solution 25]

In a three-necked flask, 4-sec-butylaniline (4.48g, 30mmol) and 4-fluoronitrobenzene (8.51g, 60.3mmol) were placed, and further, dimethyl sulfoxide (45mL) and cesium fluoride (9.16g, 60.3mmol) were added thereto, followed by heating and refluxing at 110 ℃ for 48 hours.

After the reaction solution was cooled to room temperature, ethanol (750mL) was added dropwise to the cooled reaction solution, and the precipitated solid was collected by filtration, and the obtained filtrate was washed with water (100mL) and dried to obtain compound 1(8.60g, 73%).

¹H-NMR(500MHz、CDCl3)：δ0.87(t，J＝7.5Hz，3H),1.27(d，J＝7.0Hz，3H),1.62(quin，J＝7.5Hz，2H),2.65(sext，J＝7.0Hz，1H),7.08(d，J＝8.5Hz，2H),7.14(d，J＝9.0Hz，4H),7.23(d，J＝8.5Hz，2H),8.14(d，J＝9.0Hz，4H).

[ Synthesis example 2]

[ solution 26]

An ethanol suspension (65mL) of Compound 1(4.3g, 11mmol) was placed in a three-necked flask, and palladium on carbon (0.21g) and hydrazine monohydrate (6.5mL) were added thereto, followed by heating and refluxing for 5 hours.

After the reaction solution was cooled to room temperature, the cooled reaction solution was subjected to Celite filtration, and the filtrate was washed with ethanol (30mL) to recover a filtrate containing ethanol.

To the recovered filtrate, water (400mL) was added, and the mixture was stirred at 0 ℃ for 30 minutes, and the precipitated solid was collected by filtration and dried to obtain compound 2(3.00g, 82%).

¹H-NMR(500MHz、CDCl₃)：δ0.83(t，J＝7.5Hz，3H),1.19(d，J＝6.5Hz，3H),1.54(quin，J＝7.5Hz，2H),2.49(sext，J＝7.0Hz，1H),3.52(brs,4H),6.60(d，J＝8.5Hz，4H),6.83(d，J＝8.5Hz，2H),6.91-6.95(m,6H).

LC/MS(ESI⁺)m/z；332[M+1]⁺

[2] Synthesis of Polymer (Polymer)

[ example 1]

[ solution 27]

In a three-necked flask, Compound 2(1.50g, 4.5mmol), Compound 3(1.72g, 3.75mmol), and Pd (PPh) were placed₃)₄(0.43g, 0.38mmol) and t-BuONa (0.86g, 9mmol), to which xylene (34mL) was added, and after heating under reflux for 4 hours, 4-sec-butylaniline (0.20g, 1.35mmol) was added, and further the mixture was refluxed for 3 hours.

After the reaction solution was cooled to room temperature, the cooled reaction solution was mixed with water (34mL), and the resulting mixture and toluene (17mL × 2) were used to perform liquid separation treatment, and the organic layer was recovered and dried over sodium sulfate.

Then, the dried organic layer was concentrated, tetrahydrofuran (17mL) was added to the obtained concentrate to dilute the concentrate, and the obtained diluted product was dropped into methanol (340mL) and stirred for 1 hour.

Then, the precipitated powder was recovered by suction filtration, the obtained filtrate was dissolved in tetrahydrofuran (17mL), the solution was dropped into methanol (340mL), stirred for 1 hour, the precipitated powder was recovered by suction filtration, and dried under reduced pressure to obtain polymer a (2.20 g).

Compound 3 was synthesized by the method described in j.mater.chem., 2011,21, 11800.

Mw＝3871Mn(GPC)＝7455Mw/Mn＝1.93

Comparative example 1

[ solution 28]

Into a flask were placed 4-sec-butylbenzenamine (1.51g, 10.1mmol), 1, 4-dibromobenzene (2.36g, 10mmol), Pd (dba)₄(0.43g，0.38mmol)、[(t-Bu)₃Ph]BF₄(0.58g, 2mmol) and t-BuONa (2.88g, 30mmol), toluene (47mL) was added thereto, and after heating under reflux for 3 hours, diphenylamine (0.34g, 2mmol) was added thereto, and further heating under reflux for 2 hours.

After the reaction solution was cooled to room temperature, the cooled reaction solution was mixed with water (50mL), and a liquid separation treatment was performed using the obtained mixture and chloroform (50mL × 2), and the organic layer was recovered and dried over sodium sulfate.

Then, the dried organic layer was concentrated, chloroform (50mL) was added to the obtained concentrate to dilute the concentrate, and the obtained diluted product was dropped into methanol (470mL) and stirred for 1 hour.

Then, the precipitated powder was recovered by suction filtration, the obtained filtrate was dissolved in chloroform (50mL), the solution was dropped into methanol (470mL), stirred for 1 hour, the precipitated powder was recovered by suction filtration, and dried under reduced pressure to obtain polymer X (1.88 g).

Mw＝2043Mn＝3608Mw/Mn＝1.77

[3] Preparation of Charge-transporting compositions

[ example 2]

A charge transporting composition was obtained by dissolving 0.167g of the polymer A and 0.333g of an arylsulfonate compound described below in a mixed solvent of 4.75g of triethylene glycol butyl methyl ether, 2.85g of butyl benzoate and 1.90g of dimethyl phthalate. Further, the aryl sulfonate compound described below was synthesized by the method described in International publication No. 2017/217457.

[ solution 29]

Comparative example 2

Preparation of a composition was attempted in the same manner as in example 2 except that the polymer X was used instead of the polymer a, but the solid was not completely dissolved, and a uniform composition sufficient for producing a charge transporting film could not be obtained.

[4] Fabrication and characterization of Single-layer elements

[ example 3]

The charge-transporting composition obtained in example 2 was applied to an ITO substrate using a spin coater, and then dried at 120 ℃ for 1 minute under the air, and then baked at 230 ℃ for 15 minutes, thereby forming a uniform thin film of 40nm on the ITO substrate. As the ITO substrate, a glass substrate 25 mm. times.25 mm. times.0.7 t having a patterned Indium Tin Oxide (ITO) film of 50nm thickness formed on the surface thereof was used, and O was used before use₂The plasma cleaning apparatus (150W, 30 seconds) removed impurities on the surface.

Next, an evaporation apparatus (degree of vacuum 1.0X 10) was used thereon^-5Pa), an 80nm aluminum film was formed under the condition of 0.2 nm/sec, and a single layer element was obtained. In order to prevent deterioration of characteristics due to the influence of oxygen, water, and the like in the air, the single-layer element was sealed with a sealing substrate, and the characteristics thereof were evaluated. The sealing was performed as follows. The elements were put between the sealing substrates in a nitrogen atmosphere having an oxygen concentration of 2ppm or less and a dew point of-76 ℃ or less, and the sealing substrates were bonded with an adhesive (MORESCO MOISTURE CUT WB90US (P) available from MORESCO Co Ltd.). At this time, the water-capturing agent (HD-071010W-40, manufactured by ダイニック Co., Ltd.) was contained in the sealing substrate together with the element. The pasted sealing substrate was irradiated with UV light (wavelength: 365nm, dose: 6000 mJ/cm)²) Thereafter, the adhesive was cured by annealing at 80 ℃ for 1 hour.

The current density was measured when a voltage of 5V was applied to the obtained element. The results are shown in table 1.

[ Table 1]

	Current Density (mA/cm)2)
		Example 3	807

As shown in table 1, the film obtained from the charge transporting composition of the present invention exhibits excellent charge transporting properties.

[5] Production of organic EL element and evaluation of characteristics

[ example 4]

A thin film was formed on an ITO substrate by using the charge-transporting composition obtained in example 2 in the same manner as in example 3 except that the film thickness was changed to 50 nm.

Then, a deposition apparatus (degree of vacuum of 1.0X 10) was used for the thin film thus formed^-5Pa), a 30nm α -NPD film was formed at 0.2 nm/sec, and a10 nm film of HTEB-01, an electron-blocking material, manufactured by Kanto chemical Co., Ltd, was formed thereon. Further, a light-emitting layer host material NS60 and a light-emitting layer dopant material Ir (PPy) manufactured by Nippon iron King chemical Co., Ltd were placed thereon₃And (4) co-evaporation. For co-evaporation, Ir (PPy)₃The deposition rate was controlled so that the concentration of (2) was 6%, and 40nm was stacked. Finally, Alq is orderly added₃And thin films of lithium fluoride and aluminum were laminated to obtain an organic EL device. At this time, the deposition rate is set to Alq₃And aluminum at 0.2 nm/sec, and lithium fluoride at 0.02 nm/sec, with film thicknesses of 20nm, 0.5nm, and 80nm, respectively.

In order to prevent deterioration of characteristics due to the influence of oxygen, water, and the like in the air, the elements were sealed in the same manner as in example 3, and the characteristics thereof were evaluated.

The luminance of the obtained element was measured to be 10000cd/m²Driving voltage, current density, luminous efficiency and external quantum yield at the time of driving, and half-life of luminance. The results are shown in table 2.

[ Table 2]

As shown in table 2, the organic EL device including the charge-transporting thin film obtained from the charge-transporting composition of the present invention was suitably driven and also excellent in durability.