JP7104518B2 - Polymer materials, materials for electroluminescence devices, liquid compositions, thin films and electroluminescence devices - Google Patents

Description

The present invention relates to polymer materials, materials for electroluminescent devices, liquid compositions, thin films and electroluminescent devices.

In recent years, the development of displays that support a wide color gamut has become active. For example, in an organic EL device, we are trying to improve the color gamut by developing a material for the light emitting layer. (See, for example, Patent Document 1).

However, in principle, it is difficult to obtain a sharp emission spectrum with a fluorescent light emitting material or a phosphorescent light emitting material, which is an organic light emitting material constituting the light emitting layer of the organic EL element.

Quantum dots are known as a material having a sharp emission spectrum, and a quantum dot light emitting element using the quantum dots as a light emitting layer has been developed (see, for example, Patent Document 2).

International Publication No. 2014/042265 Japanese Unexamined Patent Publication No. 2010-199067

However, quantum dot light emitting devices are required to improve the luminous efficiency.

In order to improve the luminous efficiency of the quantum dot light emitting device, it is important to adjust the carrier balance.

Here, in the organic EL element, since the hole injection material, the electron injection material, and the light emitting material are each organic, the hole injection material, the electron injection material, and the light emitting material generally have a small energy difference between energy levels. Therefore, the barrier for injecting charge into the light emitting layer is small.

On the other hand, quantum dots generally have a deep highest occupied molecular orbital level (hereinafter referred to as HOMO level), and when holes are injected from the hole transport layer, which is an organic layer. It is considered that a large barrier is one of the causes of the decrease in light emission efficiency.

In view of the above, one aspect of the present invention is to provide a polymer material capable of improving luminous efficiency in a quantum dot light emitting element.

One aspect of the present invention includes a segment of an alternating copolymer of a structural unit represented by the following formula (1) in a polymer material.

（式（１）中、Ｘは、下記式（２）で表される基であり、Ｙは、置換された若しくは非置換の炭素数６以上６０以下の２価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の２価の芳香族複素環基である。）

(In the formula (1), X is a group represented by the following formula (2), and Y is a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or A divalent aromatic heterocyclic group having a substituted or unsubstituted ring-forming atom number of 3 or more and 60 or less.)

（式（２）中、Ａｒ_１は、置換された若しくは非置換の炭素数６以上６０以下の３価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の３価の芳香族複素環基であり、
Ａｒ_２及びＡｒ_３は、それぞれ独立して、置換された若しくは非置換の炭素数６以上６０以下の１価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の１価の芳香族複素環基であり、
Ｌ_１及びＬ_２は、それぞれ独立して、単結合、置換された若しくは非置換の炭素数６以上６０以下の２価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の２価の芳香族複素環基であり、
Ｒ_１及びＲ_２は、それぞれ独立して、置換された若しくは非置換の炭素数１以上２０以下のアルキル基、置換された若しくは非置換の炭素数１以上２０以下のアルコキシ基、置換された若しくは非置換の炭素数６以上６０以下の１価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の１価の芳香族複素環基であり、
Ｒ_１及びＲ_２は、互いに結合して環を形成してもよく、
ａは、０以上４以下の整数であり、
ｂは、０以上３以下の整数であり、
Ｚ_１～Ｚ_８は、それぞれ独立して、窒素原子又は－ＣＨ＝である。）

(In the formula (2), Ar ₁ is a substituted or unsubstituted trivalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or a substituted or unsubstituted ring-forming atom number of 3 or more and 60 or less. Is a trivalent aromatic heterocyclic group of
Ar ₂ and Ar ₃ are independently substituted or unsubstituted monovalent aromatic hydrocarbon groups having 6 or more and 60 or less carbon atoms, or substituted or unsubstituted ring-forming atoms having 3 or more and 60 atoms, respectively. The following monovalent aromatic heterocyclic groups,
L ₁ and L ₂ are independently single-bonded, substituted or unsubstituted divalent aromatic hydrocarbon groups having 6 to 60 carbon atoms, or substituted or unsubstituted ring-forming atoms. It is a divalent aromatic heterocyclic group of 3 or more and 60 or less.
R ₁ and R ₂ are independently substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or substituted. An unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted ring-forming monovalent aromatic heterocyclic group having 3 to 60 atoms.
R ₁ and R ₂ may be combined with each other to form a ring.
a is an integer of 0 or more and 4 or less,
b is an integer of 0 or more and 3 or less,
Z ₁ to Z ₈ are independently nitrogen atoms or −CH =. )

According to one aspect of the present invention, it is possible to provide a polymer material capable of improving luminous efficiency in a quantum dot light emitting element.

It is a schematic diagram which shows an example of the quantum dot light emitting element which concerns on this embodiment. It is sectional drawing which shows the structure of the quantum dot of Example 6. It is an ultraviolet absorption spectrum of the quantum dot of Example 6. 6 is a photoluminescence spectrum of the quantum dots of Example 6. It is an energy diagram of the quantum dot light emitting element of the comparative example 2. It is an energy diagram of the quantum dot light emitting device of Example 9.

Hereinafter, modes for carrying out the present invention will be described. The present invention is not limited to the following embodiments.

[Polymer material]
The polymer material according to the present embodiment includes a segment of an alternating copolymer of a structural unit represented by the following formula (1).

（式（１）中、Ｘは、下記式（２）で表される基であり、Ｙは、置換された若しくは非置換の炭素数６以上６０以下の２価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の２価の芳香族複素環基である。）

(In the formula (1), X is a group represented by the following formula (2), and Y is a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or A divalent aromatic heterocyclic group having a substituted or unsubstituted ring-forming atom number of 3 or more and 60 or less.)

（式（２）中、Ａｒ_１は、置換された若しくは非置換の炭素数６以上６０以下の３価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の３価の芳香族複素環基であり、
Ａｒ_２及びＡｒ_３は、それぞれ独立して、置換された若しくは非置換の炭素数６以上６０以下の１価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の１価の芳香族複素環基であり、
Ｌ_１及びＬ_２は、それぞれ独立して、単結合、置換された若しくは非置換の炭素数６以上６０以下の２価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の２価の芳香族複素環基であり、
Ｒ_１及びＲ_２は、それぞれ独立して、置換された若しくは非置換の炭素数１以上２０以下のアルキル基、置換された若しくは非置換の炭素数１以上２０以下のアルコキシ基、置換された若しくは非置換の炭素数６以上６０以下の１価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の１価の芳香族複素環基であり、
Ｒ_１及びＲ_２は、互いに結合して環を形成してもよく、
ａは、０以上４以下の整数であり、
ｂは、０以上３以下の整数であり、
Ｚ_１～Ｚ_８は、それぞれ独立して、窒素原子又は－ＣＨ＝である。）
本実施形態に係る高分子材料は、１種以上の式（１）で表される構成単位を含み、１種以上の他の構成単位をさらに含んでいてもよい。ここで、本実施形態に係る高分子材料は、Ｘ及びＹが交互に結合している交互共重合体のセグメントを含むため、製造の再現性が高い。また、本実施形態に係る高分子材料は、Ｘ及びＹの局在がないことから、薄膜として用いた場合に均質な特性が得られる。

(In the formula (2), Ar ₁ is a substituted or unsubstituted trivalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or a substituted or unsubstituted ring-forming atom number of 3 or more and 60 or less. Is a trivalent aromatic heterocyclic group of
Ar ₂ and Ar ₃ are independently substituted or unsubstituted monovalent aromatic hydrocarbon groups having 6 or more and 60 or less carbon atoms, or substituted or unsubstituted ring-forming atoms having 3 or more and 60 atoms, respectively. The following monovalent aromatic heterocyclic groups,
L ₁ and L ₂ are independently single-bonded, substituted or unsubstituted divalent aromatic hydrocarbon groups having 6 to 60 carbon atoms, or substituted or unsubstituted ring-forming atoms. It is a divalent aromatic heterocyclic group of 3 or more and 60 or less.
R ₁ and R ₂ are independently substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or substituted. An unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted ring-forming monovalent aromatic heterocyclic group having 3 to 60 atoms.
R ₁ and R ₂ may be combined with each other to form a ring.
a is an integer of 0 or more and 4 or less,
b is an integer of 0 or more and 3 or less,
Z ₁ to Z ₈ are independently nitrogen atoms or −CH =. )
The polymer material according to the present embodiment contains one or more structural units represented by the formula (1), and may further contain one or more other structural units. Here, since the polymer material according to the present embodiment contains segments of an alternating copolymer in which X and Y are alternately bonded, the reproducibility of production is high. Further, since the polymer material according to the present embodiment does not have X and Y localized, homogeneous characteristics can be obtained when used as a thin film.

[X]
The polymer material according to the present embodiment may contain one kind of X or two or more kinds of X as a constituent unit.

Since the polymer material according to the present embodiment contains a nitrogen-containing aromatic heterocycle (for example, a carbazole skeleton) in which X is substituted with an amino group, hole transportability can be improved.

Further, in the polymer material according to the present embodiment, X is an amino group (N (Ar 1)) in which X is bonded to an aromatic group (Ar ₁ ) in the main chain, a nitrogen-containing aromatic heterocycle and a nitrogen-containing aromatic heterocycle in the side chain. ₂ ) (Ar ₃ )) is included. Therefore, the polymer material according to the present embodiment has a deep HOMO level, and as a result, high luminous efficiency and low drive voltage can be achieved in the quantum dot light emitting element.

In the formula (2), Ar ₁ is a trivalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms substituted or unsubstituted, or a ring-forming atom having 3 or more and 60 or less substituted or unsubstituted. It is a trivalent aromatic heterocyclic group.

Here, the aromatic hydrocarbon group is a group derived from an aromatic hydrocarbon compound containing one or more aromatic hydrocarbon rings. Here, when the aromatic hydrocarbon group contains two or more aromatic hydrocarbon rings, the two or more aromatic hydrocarbon rings may be condensed with each other. Moreover, the aromatic hydrocarbon group may be substituted with one or more substituents.

The aromatic hydrocarbon compound is not particularly limited, but is not limited to benzene, pentalene, inden, naphthalene, anthracene, azulene, heptalene, acenaphthalene, phenalene, fluorene, anthracene, phenalene, biphenyl, triphenylene, pyrene, chrysene, picene, perylene, Examples thereof include pentaphene, pentacene, tetraphene, hexaphene, hexacene, rubicene, trinaphthylene, heptalene, pyrenethan and the like.

Further, the aromatic heterocyclic group has one or more heteroatoms (for example, nitrogen atom (N), oxygen atom (O), phosphorus atom (P), sulfur atom (S)), and the remaining ring formation. It is a group derived from an aromatic heterocyclic compound containing one or more aromatic heterocycles whose atom is a carbon atom (C). When the aromatic heterocyclic group contains two or more aromatic heterocycles, the two or more aromatic heterocycles may be condensed with each other. Further, the aromatic heterocyclic group may be substituted with one or more substituents.

The aromatic heterocyclic compound is not particularly limited, but pyrazoline, imidazoline, oxazoline, thiazolin, triazoline, tetrazoline, oxadiazoline, pyridine, pyridadinin, pyrimidine, triazine, carbazoline, azacarbazoline, indolin, quinolinin, isoquinolin, benzoimidazolin, Examples thereof include imidazole pyridine, imidazolipyrimidine, furan, benzofuran, dibenzofuran, azadibenzofuran, thiophene, benzothiophene, dibenzothiophene, azadibenzothiophene and the like.

Examples of the trivalent aromatic hydrocarbon group in Ar ₁ include a group obtained by removing any three hydrogen atoms from the hydrogen atoms of the above aromatic hydrocarbon compound. In addition, examples of the trivalent aromatic heterocyclic group include groups obtained by removing any three hydrogen atoms from the hydrogen atoms of the aromatic heterocyclic compound.

Of these, Ar ₁ is preferably the group shown below from the viewpoint of adjusting the HOMO level.

（上記式中、Ａは、－Ｏ－、－Ｓ－、－Ｓｅ－、－ＮＲ_１－（ただし、Ｒ_１は、水素原子、重水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基又は置換若しくは無置換のヘテロアリール基である。）又は－ＣＲ_２Ｒ_３－（ただし、Ｒ_２及びＲ_３は、それぞれ独立に、水素原子、重水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基又は置換若しくは無置換のヘテロアリール基である。）であり、＊は、結合部位である。）
３価の芳香族炭化水素基又は３価の芳香族複素環基が置換されている場合の置換基としては、特に限定されないが、ハロゲン原子、アルキル基、アルコキシ基、芳香族炭化水素基、芳香族複素環基等を挙げることができ、二種以上を併用してもよい。

(In the above formula, A is -O-, -S-, -Se-, -NR _1- (where R ₁ is a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted. _Or an aryl group or a _substituted or _{unsubstituted heteroaryl} group of It is a group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group)), and * is a binding site.)
The substituent when the trivalent aromatic hydrocarbon group or the trivalent aromatic heterocyclic group is substituted is not particularly limited, but is not particularly limited, but is limited to a halogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, and an aromatic group. Group heterocyclic groups and the like can be mentioned, and two or more kinds may be used in combination.

Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group and tert-pentyl. Group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1, 4-Dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group , 2-Methyl-1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-Methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecil group, n-eicosyl group, Examples thereof include n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group and the like.

The alkyl group is preferably a linear or branched alkyl group having 1 or more and 24 or less carbon atoms, and more preferably a linear or branched alkyl group having 1 or more and 8 or less carbon atoms.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group and an undecyloxy group. Examples thereof include dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, 2-ethylhexyloxy group, 3-ethylpentyloxy group and the like.

The alkoxy group is preferably a linear or branched alkoxy group having 1 or more and 24 or less carbon atoms, and more preferably a linear or branched alkoxy group having 1 or more and 8 or less carbon atoms.

Examples of the aromatic heterocyclic group (or aromatic hydrocarbon group) that may be introduced into the trivalent aromatic hydrocarbon group (or trivalent aromatic heterocyclic group) include the above-mentioned aromatic heterocycle (or the above-mentioned aromatic heterocyclic group). Examples thereof include a group obtained by removing an arbitrary one hydrogen atom from an aromatic hydrocarbon).

In the formula (2), Ar ₂ and Ar ₃ are independently substituted or unsubstituted monovalent aromatic hydrocarbon groups having 6 to 60 carbon atoms, or substituted or unsubstituted rings. It is a monovalent aromatic heterocyclic group having 3 or more and 60 or less atoms.

Here, the monovalent aromatic hydrocarbon group and the monovalent aromatic heterocyclic group are represented by the formula (2) except that the trivalent aromatic hydrocarbon group and the trivalent aromatic heterocyclic group are monovalent. Since it is the same as Ar ₁ in), the description thereof is omitted here. Further, when the monovalent aromatic hydrocarbon group or the monovalent aromatic heterocyclic group is substituted, the substituent is the same as the substituent in Ar ₁ in the formula (2). The explanation is omitted.

From the viewpoint of increasing the HOMO level, hole transportability, and hole injection property of the polymer material according to the present embodiment, the monovalent aromatic hydrocarbon group includes a phenyl group, a biphenyl group, a fluorenyl group, and a naphthyl group. It is preferably an anthryl group, a phenanthryl group, a naphthacenyl group, a pyrenyl group, a terphenyl group, a trill group, a t-butylphenyl group, or a (phenylpropyl) phenyl group, preferably a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, More preferably, it is an anthryl group, a terphenyl group, or a trill group.

Further, from the viewpoint of increasing the HOMO level, hole transportability and hole injection property of the polymer material according to the present embodiment, the monovalent aromatic heterocyclic group is a pyridyl group, a bipyridyl group, a pyrrolyl group, or a pyrazinyl. Group, pyridinyl group, pyrimidyl group, indolyl group, frill group, benzofuranyl group, dibenzofuranyl group, quinolyl group, quinoxanyl group, carbazolyl group, phenanthridinyl group, acridinyl group, phenazinyl group, phenothiazinyl group, phenoxadinyl group, It is preferably an oxazolyl group, an oxadiazolyl group, a frazayl group, a thienyl group, a thiophenyl group, an isothiophenyl group, or a dibenzothiophenyl group, preferably a pyridyl group, a pyrrolyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, Alternatively, it is more preferably a bipyridyl group.

Further, from the viewpoint of increasing the HOMO level, hole transportability, hole injection property, solubility, and coatability of the polymer material according to the present embodiment, a monovalent aromatic hydrocarbon group or a monovalent aromatic group is used. When the heterocyclic group is substituted, the substituents are an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group and an arylalkylthio. Group, arylalkenyl group, arylalkynyl group, amino group, amino group substituted with substituent, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acidimide group, It is preferably a monovalent heterocyclic group, a carboxyl group, a carboxyl group substituted with a substituent, a cyano group, or a nitro group, and more preferably an alkyl group having 1 or more and 3 or less carbon atoms.

Specific examples of Ar ₂ and Ar ₃ are shown below.

（上記式中、Ｒ_３は、それぞれ独立して、置換された若しくは非置換の炭素数１以上２０以下のアルキル基、置換された若しくは非置換の炭素数１以上２０以下のアルコキシ基、置換された若しくは非置換の炭素数６以上６０以下の１価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の１価の芳香族複素環基であり、＊は、結合部位であり、Ａｌｋｙｌは、アルキル基で置換された又は非置換であることを意味する。）
式（２）において、Ｌ_１及びＬ_２は、それぞれ独立して、単結合、置換された若しくは非置換の炭素数６以上６０以下の２価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の２価の芳香族複素環基である。

(In the above formula, R ₃ is independently substituted with an substituted or unsubstituted alkyl group having 1 or more and 20 or less carbon atoms, a substituted or unsubstituted alkoxy group having 1 or more and 20 or less carbon atoms, and substituted. Alternatively, it is a monovalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or a monovalent aromatic heterocyclic group having 3 or more and 60 or less substituted or unsubstituted ring-forming atoms. Means the binding site and Alkyl is substituted or unsubstituted with an alkyl group.)
In the formula (2), L ₁ and L ₂ are independently single-bonded, substituted or unsubstituted divalent aromatic hydrocarbon groups having 6 to 60 carbon atoms, or substituted or non-substituted. Substituted ring-forming A divalent aromatic heterocyclic group having 3 or more and 60 or less atoms.

Here, the divalent aromatic hydrocarbon group and the divalent aromatic heterocyclic group are represented by the formula (2) except that the trivalent aromatic hydrocarbon group and the trivalent aromatic heterocyclic group are divalent. Since it is the same as Ar ₁ in), the description thereof is omitted here. Further, when the divalent aromatic hydrocarbon group or the divalent aromatic heterocyclic group is substituted, the substituent is the same as the substituent in Ar ₁ in the formula (2). The explanation is omitted.

From the viewpoint of increasing the HOMO level, hole transportability, and hole injection property of the polymer material according to the present embodiment, the divalent aromatic hydrocarbon group includes a phenylene group, a biphenylene group, a fluorenylene group, and a naphthylene group. Anthrylene group, phenanthrylene group, naphthalsenylene group, pyrenylene group, terphenylene group, tolylen group, t-butylphenylene group, or (phenylpropyl) phenylene group is preferable, and phenylene group, biphenylene group, fluorenylene group, naphthylene group, More preferably, it is an anthrylene group, a terphenylene group, or a tolylen group.

Further, from the viewpoint of enhancing the HOMO level, hole transportability and hole injection property of the polymer material according to the present embodiment, the divalent aromatic heterocyclic group is a pyridyl group, a bipyridyl group, a pyrrolyl group or a pyrazinel. Group, pyridinyl group, pyrimidyl group, indolyl group, frill group, benzofuranyl group, dibenzofuranyl group, quinolyl group, quinoxanyl group, carbazolyl group, phenanthridinyl group, acridinyl group, phenazinyl group, phenothiazinyl group, phenoxadinyl group, It is preferably an oxazolyl group, an oxadiazolyl group, a frazayl group, a thienyl group, a thiophenyl group, an isothiophenyl group, or a dibenzothiophenyl group, preferably a pyridyl group, a pyrrolyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, Alternatively, it is more preferably a bipyridyl group.

Further, from the viewpoint of increasing the HOMO level, hole transportability, hole injection property, solubility, and coatability of the polymer material according to the present embodiment, a divalent aromatic hydrocarbon group or a divalent aromatic group is used. When the heterocyclic group is substituted, the substituents are an alkyl group having 1 to 50 carbon atoms, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group and an arylalkylthio. Group, arylalkenyl group, arylalkynyl group, amino group, amino group substituted with substituent, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acidimide group, It is preferably a monovalent heterocyclic group, a carboxyl group, a carboxyl group substituted with a substituent, a cyano group, or a nitro group, and more preferably an alkyl group having 1 or more and 50 or less carbon atoms.

Of these, L ₁ and L ₂ are a single bond, a phenylene group, a biphenylene group, a fluorenylene group, a naphthylene group, an anthrylene group, a phenanthylene group, a naphthacenylene group, a pyrenylene group, a terphenylene group, a trilene group, and a t-butylphenylene group. , Or a (phenylpropyl) phenylene group, more preferably a single bond, a phenylene group, a biphenylene group, a terphenylene group, or a fluorenylene group.

In the formula (2), R ₁ and R ₂ are independently substituted or unsubstituted alkyl groups having 1 or more and 20 or less carbon atoms, and substituted or unsubstituted alkoxy having 1 or more and 20 or less carbon atoms. A group, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or a substituted or unsubstituted ring-forming group having 3 or more and 60 or less monovalent aromatic heterocyclic groups. Is. Here, R ₁ and R ₂ may be bonded to each other to form a ring. R ₁ and R ₂ may be the same or different. Further, when a is 2 or more and 4 or less, the plurality of R _1s may be the same or different. Similarly, if b is 2 or 3, the plurality of R _2s may be the same or different.

Here, the alkyl group having 1 or more and 20 or less carbon atoms is not particularly limited, but is limited to a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl. Group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1, 2-Dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2 -Ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n- Examples thereof include an octadecyl group and an n-eicosyl group.

The alkyl group having 1 to 20 carbon atoms is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and is a linear or branched alkyl group having 1 to 8 carbon atoms. Is more preferable.

The alkoxy group having 1 to 20 carbon atoms is not particularly limited, but is limited to a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and the like. n-pentoxy group, isopentoxy group, tert-pentoxy group, neopentoxy group, 1,2-dimethylpropoxy group, n-hexyloxy group, isohexyloxy group, 1,3-dimethylbutoxy group, 1-isopropylpropoxy group, 1 , 2-Dimethylbutoxy group, n-heptyloxy group, 1,4-dimethylpentyloxy group, 3-ethylpentyloxy group, 2-methyl-1-isopropylpropoxy group, 1-ethyl-3-methylbutoxy group, n -Octyloxy group, 2-ethylhexyloxy group, 3-methyl-1-isopropylbutoxy group, 2-methyl-1-isopropoxy group, 1-tert-butyl-2-methylpropoxy group, n-nonyloxy group, 3, 5,5-trimethylhexyloxy group, n-decyloxy group, isodecyloxy group, n-undecyloxy group, 1-methyldecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyl Examples thereof include an oxy group, an n-pentadecyloxy group, an n-hexadecyloxy group, an n-heptadecyloxy group, an n-octadecyloxy group, an n-eicosyloxy group and the like.

The alkoxy group having 1 or more and 20 or less carbon atoms is preferably a linear or branched alkoxy group having 1 or more and 20 or less carbon atoms, and is a linear or branched alkoxy group having 1 or more and 8 or less carbon atoms. Is more preferable.

Here, the monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms and the monovalent aromatic heterocyclic group having 3 to 60 ring-forming atoms are trivalent aromatic hydrocarbon groups and trivalent. Since it is the same as Ar ₁ in the formula (2) except that the aromatic heterocyclic group is monovalent, the description thereof is omitted here. Further, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group having 1 or more and 20 or less carbon atoms, a monovalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or a monovalent group having 3 or more and 60 or less ring-forming atoms. When the aromatic heterocyclic group of is substituted, the substituent is the same as the substituent in Ar ₁ in the formula (2), and thus the description thereof will be omitted here.

Of these, R ₁ and R ₂ are preferably phenyl groups or fluorenyl groups.

a is a number in which R ₁ in the formula (2) is bonded to the nitrogen-containing aromatic heterocycle located in the side chain, and is an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 2 or less. , More preferably 0 or 1, and particularly preferably 0.

b is the number in which R ₂ in the formula (2) is bonded to the nitrogen-containing aromatic heterocycle located in the side chain, and is an integer of 0 or more and 3 or less, preferably an integer of 0 or more and 2 or less. , More preferably 0 or 1, and particularly preferably 0.

In the formula (2), Z ₁ to Z ₈ constituting the nitrogen-containing aromatic heterocycle are independently nitrogen atoms or −CH =.

The nitrogen-containing aromatic heterocycle preferably has the structure shown below.

（上記式中、＊は、結合部位である。）
本実施形態において、Ｘは、ＨＯＭＯ準位及び正孔輸送能をさらに向上させる観点並びに駆動電圧をさらに低下させる観点から、下記式（２－１）～（２－６）で表される構成単位から選択されることが好ましい。ここで、上記式（１）で表される構成単位の交互共重合体のセグメントに含まれる複数のＸは、同一であってもよいし、異なっていてもよい。

(In the above formula, * is a binding site.)
In the present embodiment, X is a structural unit represented by the following formulas (2-1) to (2-6) from the viewpoint of further improving the HOMO level and hole transporting ability and further reducing the driving voltage. It is preferable to be selected from. Here, the plurality of Xs contained in the alternating copolymer segment of the structural unit represented by the above formula (1) may be the same or different.

（上記式（２－１）～（２－６）中、Ａｒ_４は、置換された若しくは非置換の炭素数６以上６０以下の１価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の１価の芳香族複素環基である。）
Ｘの具体例を以下に示す。

(In the above formulas (2-1) to (2-6), Ar ₄ is a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or substituted or unsubstituted. It is a monovalent aromatic heterocyclic group having 3 or more and 60 or less ring-forming atoms.)
A specific example of X is shown below.

（上記式中、＊は、結合部位であり、Ａｌｋｙｌは、アルキル基で置換された又は無置換であることを意味する。）
［Ｙ］
本実施形態に係る高分子材料は、構成単位として、１種のＹを含んでいてもよいし、２種以上のＹを含んでいてもよい。

(In the above formula, * is a binding site, and Alkyl is substituted or unsubstituted with an alkyl group.)
[Y]
The polymer material according to the present embodiment may contain one kind of Y or two or more kinds of Y as a constituent unit.

Since the polymer material according to this embodiment contains Y as a constituent unit, it has excellent solubility. Therefore, when the polymer material according to the present embodiment is used, a thin film can be easily formed by the coating method.

In the formula (1), Y is a divalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms substituted or unsubstituted, or 2 having a substituted or unsubstituted ring-forming atom number of 3 or more and 60 or less. It is a valent aromatic heterocyclic group.

Here, the divalent aromatic hydrocarbon group and the divalent aromatic heterocyclic group are represented by the formula (2) except that the trivalent aromatic hydrocarbon group and the trivalent aromatic heterocyclic group are divalent. Since it is the same as Ar ₁ in), the description thereof is omitted here.

Of these, from the viewpoint of improving the solubility of the polymer material, Y is a phenylene group, a fluorenylyl group, a biphenylene group, a fluorenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a naphthacenylene group, a pyrenylene group and a terphenylene group. A group, a trilene group, a t-butylphenylene group, or a (phenylpropyl) phenylene group is preferable, and a phenylene group or a fluorinatedyl group is more preferable.

Further, when the divalent aromatic hydrocarbon group or the divalent aromatic heterocyclic group is substituted, the substituent is the same as the substituent in Ar ₁ in the formula (2). The explanation is omitted.

Of these, from the viewpoint of improving the solubility of the polymer material according to the present embodiment, the substituent is preferably a linear or branched alkyl group having 1 or more and 20 or less carbon atoms, and has 3 or more carbon atoms. It is more preferably a linear or branched alkyl group of 10 or less, and particularly preferably a linear alkyl group having 6 or more and 8 or less carbon atoms.

From the viewpoint of adjusting the HOMO level, Y is preferably selected from the structural units represented by the following formulas (2-7) to (2-14). Here, the plurality of Ys contained in the alternate copolymer segment of the structural unit represented by the above formula (1) may be the same or different.

（上記式（２－７）～（２－１４）中、Ａｒ_５１～Ａｒ_５５は、それぞれ独立して、置換された若しくは非置換の炭素数６以上６０以下の１価の芳香族炭化水素基、置換された若しくは非置換の環形成原子数３以上６０以下の１価の芳香族複素環基、炭素数１以上２０以下のアルキル基、又は水素原子であり、
Ａ_１１～Ａ_１３は、それぞれ独立して、－Ｏ－、－Ｓ－、－Ｓｅ－、－ＣＲ_３Ｒ_４－、－ＳｉＲ_３Ｒ_４－（ただし、Ｒ_３及びＲ_４は、それぞれ独立して、水素原子、重水素原子、置換若しくは非置換のアルキル基、置換若しくは非置換のアリール基又は置換若しくは非置換のヘテロアリール基であり、
Ａ_２１～Ａ_２８は、それぞれ独立して、－ＣＲ_５＝、－Ｎ＝、－ＳｉＲ_５＝（ただし、Ｒ_５は、水素原子、重水素原子、置換若しくは非置換のアルキル基、置換若しくは非置換のアリール基又は置換若しくは非置換のヘテロアリール基である。）
Ｙの具体例を以下に示す。

(In the above formulas (2-7) to (2-14), Ar ₅₁ to Ar ₅₅ are independently substituted or unsubstituted monovalent aromatic hydrocarbon groups having 6 to 60 carbon atoms. , A substituted or unsubstituted ring-forming monovalent aromatic heterocyclic group having 3 or more and 60 or less atoms, an alkyl group having 1 or more carbon atoms and 20 or less carbon atoms, or a hydrogen atom.
A ₁₁ to A ₁₃ are independent of each other, -O-, -S-, -Se-, -CR ₃ R _4- , -SiR ₃ R _4- (however, R ₃ and R ₄ are independent of each other. A hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
A ₂₁ to A ₂₈ are independently -CR ₅ =, -N =, -SiR ₅ = (where R ₅ is a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, substituted or non-substituted Substituted aryl group or substituted or unsubstituted heteroaryl group.)
A specific example of Y is shown below.

（上記式中、Ａは、Ｏ、Ｓ又はＳｅであり、Ｘが複数存在する場合、複数のＸは、同一であってもよいし、異なっていてもよい。また、＊は、結合部位であり、Ａｌｋｙｌは、アルキル基で置換されたことを意味する。）
本実施形態に係る高分子材料は、下記式（３）で表されることが好ましい。これにより、量子ドット発光素子の発光寿命が長くなる。

(In the above formula, A is O, S or Se, and when a plurality of Xs are present, the plurality of Xs may be the same or different. In addition, * is a binding site. Yes, Alkyl means substituted with an alkyl group.)
The polymer material according to this embodiment is preferably represented by the following formula (3). As a result, the emission life of the quantum dot light emitting device is extended.

（式（３）中、Ｅは、置換された若しくは非置換の炭素数６以上６０以下の１価の芳香族炭化水素基、又は置換された若しくは非置換の環形成原子数３以上６０以下の１価の芳香族複素環基であり、
ｍは２以上の整数であり、複数のＸ及びＹは、それぞれ独立して、同一であってもよいし、異なっていてもよい。）

(In the formula (3), E is a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or a substituted or unsubstituted ring-forming atom having 3 or more and 60 or less. It is a monovalent aromatic heterocyclic group and
m is an integer of 2 or more, and the plurality of Xs and Ys may be independently the same or different. )

Here, the monovalent aromatic hydrocarbon group and the monovalent aromatic heterocyclic group are represented by the formula (2) except that the trivalent aromatic hydrocarbon group and the trivalent aromatic heterocyclic group are divalent. Since it is the same as Ar ₁ in), the description thereof is omitted here. Further, when the monovalent aromatic hydrocarbon group or the monovalent aromatic heterocyclic group is substituted, the substituent is the same as the substituent in Ar ₁ in the formula (2). The explanation is omitted.

Specific examples of E (terminal group) in the above formula (3) are shown below.

（上記式中、＊は、結合部位である。）
本実施形態に係る高分子材料は、エレクトロルミネッセンス（ＥＬ）素子用材料として用いることができるが、量子ドットを含むＥＬ素子用の正孔輸送材料として用いることが特に有効である。

(In the above formula, * is a binding site.)
The polymer material according to the present embodiment can be used as a material for an electroluminescence (EL) device, but it is particularly effective to use it as a hole transport material for an EL device containing quantum dots.

[Number average molecular weight (Mn) and weight average molecular weight (Mw) of polymer material]
The number average molecular weight (Mn) of the polymer material according to the present embodiment is preferably 10,000 or more and 1,000,000 or less, and more preferably 30,000 or more and 500,000 or less. This makes it possible to appropriately adjust the viscosity of the coating liquid for forming a thin film containing a polymer material (for example, a hole injection layer or a hole transport layer) to form a thin film having a uniform thickness. Is.

The weight average molecular weight (Mw) of the polymer material according to the present embodiment is preferably 10,000 or more, and more preferably 50,000 or more. This makes it possible to appropriately adjust the viscosity of the coating liquid for forming a thin film containing a polymer material (for example, a hole injection layer or a hole transport layer) to form a thin film having a uniform thickness. Is.

Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are not particularly limited, and can be measured by using a known method or by appropriately modifying a known method. In the present specification, the number average molecular weight (Mn) and the weight average molecular weight (Mw) adopt values measured by the following methods.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer material are measured by GPC (Gel Permeation Chromatography) using polystyrene as a standard substance under the following conditions.

Analyzer (GPC): Prominence manufactured by Shimadzu Corporation
Column: Made by Polymer Laboratories, PLgel MIXED-B
Column temperature: 40 ° C
Flow rate: 1.0 mL / min
Injection amount of sample solution: 20 μL (concentration: about 0.05% by mass)
Eluent: tetrahydrofuran (THF)
Detector (UV-VIS detector): Shimadzu, SPD-10AV
Standard sample: Polystyrene [Method for synthesizing polymer materials]
The polymer material according to the present embodiment can be synthesized by appropriately combining known organic synthesis reactions. A specific method for synthesizing the polymer material according to the present embodiment can be easily understood by those skilled in the art with reference to the examples described later. Specifically, the polymer material according to the present embodiment includes one or more monomers represented by the following formula (4) (1) and one or more monomers represented by the following formula (5). 2) can be synthesized by copolymerizing at a molar ratio of 1: 1. The monomers (1) and (2) can be synthesized by appropriately combining known organic synthesis reactions. Further, the monomers (1) and (2) can be identified by using a known analytical method (for example, NMR, LC-MS).

上記式（４）、（５）中、Ａｒ_１、Ａｒ_２、Ａｒ_３、Ｌ_１、Ｌ_２、Ｒ_１、Ｒ_２、ａ、ｂは、式（２）と同様である。Ｗ_１～Ｗ_４は、それぞれ独立して、ハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子、特に臭素原子）又は以下に示す基である。

In the above formulas (4) and (5), Ar ₁ , Ar ₂ , Ar ₃ , L ₁ , L ₂ , R ₁ , R ₂ , a, and b are the same as those in the formula (2). W ₁ to W ₄ are independent halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, particularly bromine atom) or groups shown below.

上記式中、Ｒ_Ａ～Ｒ_Ｄは、それぞれ独立して、炭素数１以上３以下のアルキル基である。

In the above formula, _RA to R _D are independently alkyl groups having 1 or more and 3 or less carbon atoms.

[Material for EL element, EL element]
The EL element material according to the present embodiment includes the polymer material according to the present embodiment.

The EL element according to the present embodiment includes a pair of electrodes and one or more organic layers including the polymer material according to the present embodiment, which are arranged between the pair of electrodes. At this time, it is preferable that the EL element further includes a layer containing quantum dots. Further, it is preferable that at least one of the one or more organic layers of the EL element is formed by a coating method.

Examples of the EL element include a quantum dot light emitting element, an organic EL element, an organic inorganic perovskite light emitting element, and the like.

[Liquid composition, thin film]
The liquid composition according to the present embodiment contains the polymer material according to the present embodiment and a solvent or a dispersion medium. Further, the thin film according to the present embodiment includes the polymer material according to the present embodiment.

Since the polymer material according to the present embodiment has excellent solubility, it can be particularly preferably used when manufacturing an EL element (particularly a thin film) by a coating method (wet process).

Since the polymer material according to the present embodiment has excellent charge mobility, it can be used when forming an organic layer such as a hole injection layer, a hole transport layer, and a light emitting layer. At this time, the polymer material according to the present embodiment can be suitably used when forming the hole injection layer and / or the hole transport layer from the viewpoint of hole transportability, and the hole transport layer can be used. It can be particularly preferably used when forming.

Next, a quantum dot light emitting device will be described as an example of the EL device according to the present embodiment.

[Quantum dot light emitting device]
FIG. 1 shows an example of a quantum dot light emitting device according to the present embodiment.

The quantum dot light emitting device 100 has a first electrode 120, a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, an electron injection layer 170, and a third electrode on the substrate 110. The two electrodes 180 are sequentially arranged.

Here, the polymer material according to the present embodiment is contained in, for example, one or more organic layers arranged between the first electrode 120 and the second electrode 180. Specifically, the polymer material according to the present embodiment is included in the hole injection layer 130, the hole transport layer 140, or the light emitting layer 150 as a hole injection material, a hole transport material, or a light emitting material. Is preferable. Further, the polymer material according to the present embodiment is more preferably contained in the hole injection layer 130 or the hole transport layer 140 as the hole injection material or the hole transport material. Further, it is particularly preferable that the polymer material according to the present embodiment is contained in the hole transport layer 140 as the hole transport material.

Further, the organic layer containing the polymer material according to the present embodiment is formed by a coating method (solution coating method).

The coating method (solution coating method) is not particularly limited, but is limited to a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar cord method, a dip coating method, and a spray coating method. The method, screen printing method, flexographic printing method, offset printing method, inkjet printing method and the like can be mentioned.

The solvent used in the solution coating method is not particularly limited as long as it can dissolve the polymer material according to the present embodiment, but is not particularly limited, but toluene, xylene, diethyl ether, chloroform, ethyl acetate, methylene chloride, and tetrahydrofuran. , Acetone, acetonitrile, N, N-dimethylformamide, dimethylsulfoxide, anisole, hexamethylphosphate triamide, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene, dioxane, cyclohexane, n- Pentan, n-hexane, n-heptane, n-octane, n-nonane, n-decane, methyl ethyl ketone, cyclohexanone, butyl acetate, ethyl cell solvent acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol Monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, methanol, ethanol, propanol, isopropanol, cyclohexanol, N-methyl-2-pyrrolidone and the like. be able to.

Here, in consideration of ease of application, the concentration of the polymer material in the solution is preferably about 0.1% by mass or more and 10% by mass or less, and about 0.5% by mass or more and about 5% by mass or less. Is more preferable.

The method for forming a layer other than the organic layer containing the polymer material according to the present embodiment is not particularly limited, and examples thereof include a vacuum vapor deposition method and a solution coating method.

The substrate 110 is not particularly limited, and a substrate used in a general EL element can be used, and examples thereof include a glass substrate, a semiconductor substrate such as a silicon substrate, and a transparent plastic substrate.

The first electrode 120 is an anode and can be formed by using a material having a large work function among materials such as metals, alloys, and conductive compounds. The first electrode 120 is a transparent conductive material such as indium tin oxide (In ₂ O ₃ -SnO ₂ : ITO), indium zinc oxide (In ₂ O ₃ -ZnO), tin oxide (SnO ₂ ), and zinc oxide (ZnO). Can be formed as a transmissive electrode by forming a film. Further, the first electrode 120 can be formed as a reflective electrode by forming a reflective material such as magnesium (Mg) or aluminum (Al) on the transmissive electrode.

The hole injection layer 130 is a layer that facilitates the injection of holes from the first electrode 120.

The thickness of the hole injection layer 130 is preferably about 10 nm or more and about 1000 nm or less, and more preferably about 10 nm or more and about 100 nm or less.

The hole injection layer 130 can be formed by a vacuum deposition method, a spin coating method, an inkjet method, or the like using a known hole injection material.

Examples of the hole injection material include triphenylamine-containing polyether ketone, 4-isopropyl-4'-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, N, N'-diphenyl-N, N'-bis- [ 4- (Phenyl-m-trill-amino) -phenyl] -biphenyl-4,4'-diamine, copper phthalocyanine, 4,4', 4 "-tris (3-methylphenylphenylamino) triphenylamine, N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine, 4,4', 4 "-tris (diphenylamino) triphenylamine, 4,4', 4" -tris (N, N-2) -Naphtylphenylamino) triphenylamine, polyaniline / dodecylbenzenesulfonic acid, poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate) (PEDOT / PSS), polyaniline / 10-camparsulfonic acid, etc. Can be mentioned.

The hole transport layer 140 is a layer having a function of transporting holes.

The thickness of the hole transport layer 140 is preferably about 10 nm or more and about 150 nm or less.

The hole transport layer 140 is preferably formed by a solution coating method using the polymer material according to the present embodiment. As a result, a polymer material capable of improving the luminous efficiency of the quantum dot light emitting element 100 can be efficiently formed over a large area.

However, when the other organic layer constituting the quantum dot light emitting device 100 contains the polymer material according to the present embodiment, the hole transport layer 140 may be formed by using a known hole transport material.

Examples of the hole transport material include carbazole derivatives such as 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane, N-phenylcarbazole, and polyvinylcarbazole, and N, N'-bis (3-methylphenyl). -N, N'-diphenyl- [1,1-biphenyl] -4,4'-diamine, 4,4', 4 "-tris (N-carbazolyl) triphenylamine, N, N'-di (1-) Naftyl) -N, N'-diphenylbenzidine and the like can be mentioned.

The light emitting layer 150 is a layer that emits light such as fluorescence and phosphorescence.

The thickness of the light emitting layer 150 is preferably about 10 nm or more and about 60 nm or less.

The light emitting layer 150 may have a large number of quantum dots arranged in a single layer, or may be arranged in a plurality of layers. Here, the quantum dots are inorganic nanoparticles having a quantum constraint effect. The diameter of the inorganic nanoparticles is about 1 nm or more and 10 nm or less.

The quantum dots arranged in the light emitting layer 150 can be synthesized by a wet chemical method, an organometallic chemical vapor deposition method, a molecular beam epitaxy method, or the like.

The wet chemical method is a method of growing particles by putting a precursor substance in an organic solvent. At this time, the organic solvent is naturally coordinated on the surface of the quantum dot crystal and acts as a dispersant to regulate the crystal growth. Therefore, the wet chemical method can control the growth of particles more easily and at lower cost than the vapor phase vapor deposition method such as the organometallic chemical vapor deposition (MOCVD) method and the molecular beam epitaxy (MBE) method. At this time, the energy band gap can be adjusted by adjusting the size of the quantum dots, and as a result, the light emitting layer 150 can emit light in various wavelength bands. Therefore, by using a plurality of quantum dots of different sizes, it is possible to manufacture a display that emits light having a plurality of wavelengths. The size of the quantum dots can be appropriately selected so that red light, green light and blue light can be emitted to form a color display. In addition, the size of the quantum dots can be combined so that various color lights emit white light.

The material constituting the quantum dot is not particularly limited, but a semiconductor substance selected from the group consisting of a group II-VI compound, a group III-V compound, a group IV-VI compound, a group IV element or a compound is used. And two or more types may be used together.

Group II-VI compounds include, for example, two-element compounds such as CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, and HgTe; , CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe and other three elemental compounds; can.

Group III-V compounds include, for example, two-element compounds such as GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb; , AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP and other three elemental compounds; Four elemental compounds such as InAlPAs and InAlPSb can be mentioned.

Examples of the IV-VI group compounds include diatomic compounds such as SnS, SnSe, SnTe, PbS, PbSe, and PbTe; Examples thereof include four element compounds such as SnPbSSe, SnPbSeTe, and SnPbSTe.

Examples of the Group IV element or compound include a one-element compound such as Si and Ge; and a two-element compound such as SiC and SiGe.

The quantum dots may have a homogeneous structure or may have a core-shell structure.

The core-shell structure can contain different materials, and the materials that make up the core and shell are different semiconductor materials. However, the semiconductor material constituting the shell has a larger energy bandgap than the semiconductor material constituting the core.

For example, a case where a quantum dot having a core (CdSe) / shell (ZnS) structure is produced will be described. First, a core (CdSe) precursor substance such as (CH ₃ ) ₂ Cd (dimethylcadmium) or TOPSe (trioctylphosphine selenide) is injected into TOPO (trioctylphosphine oxide) as an organic solvent (dispersant). To generate a core. At this time, after maintaining the crystal at a high temperature for a certain period of time so that the crystal grows to a certain size, the precursor substance of the shell (ZnS) is injected to form a shell on the surface of the core. As a result, CdSe / ZnS quantum dots capped by TOPO can be produced.

The electron transport layer 160 is a layer having a function of transporting electrons.

The thickness of the electron transport layer 160 is preferably about 15 nm or more and about 50 nm or less.

The electron transport layer 160 can be formed by a vacuum vapor deposition method, a spin coating method, an inkjet method, or the like using a known electron transport material.

Examples of the electron transporting material include (8-quinolinolato) lithium, tris (8-quinolinolato) aluminum, and compounds having a nitrogen-containing aromatic heterocycle.

Specific examples of the compound having a nitrogen-containing aromatic heterocycle include a compound containing a pyridine ring such as 1,3,5-tri [(3-pyridyl) -phen-3-yl] benzene, and 2,4,6-. Tris (3'-(pyridin-3-yl) biphenyl-3-yl) -1,3,5-triazine and other triazine ring-containing compounds, 2- (4- (N-phenylbenzoinidazolyl-1-) Examples thereof include compounds containing an imidazole ring such as yl-phenyl) -9,10-dinaphthylanthracene.

The electron injection layer 170 is a layer having a function of facilitating the injection of electrons from the second electrode 180.

The thickness of the electron injection layer 170 is preferably about 0.3 nm or more and about 9 nm or less.

The electron injection layer 170 can be formed by a vacuum vapor deposition method or the like using a known electron injection material.

Examples of the electron injection material include lithium compounds such as (8-quinolinolato) lithium and lithium fluoride (LiF), sodium chloride (NaCl), cesium fluoride (CsF), lithium oxide (Li ₂ O), and barium oxide (Lium oxide). BaO) and the like can be mentioned.

The second electrode 180 is a cathode, and can be formed by using a metal, an alloy, a conductive compound, or the like having a small work function. The second electrode 180 is a metal such as lithium (Li), magnesium (Mg), aluminum (Al), calcium (Ca), aluminum-lithium (Al-Li), magnesium-indium (Mg-In), magnesium-silver. It can be formed as a reflective electrode by using an alloy such as (Mg—Ag). Further, the second electrode 180 can be formed as a transmission type electrode having a thickness of 20 nm or less by using the above metal. Further, the second electrode 180 can be formed as a transmissive electrode by using a transparent conductive material such as indium tin oxide (In ₂ O ₃ -SnO ₂ ) and indium zinc oxide (In ₂ O ₃ -ZnO). can.

The laminated structure of the EL element according to the present embodiment is not limited to the laminated structure of the quantum dot light emitting element 100. The EL element according to the present embodiment may have another known laminated structure formed therein. For example, in the quantum dot light emitting device 100, one or more of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, and the electron injection layer 170 may be omitted. Further, the quantum dot light emitting device 100 may further include another layer. Further, in the quantum dot light emitting device 100, each layer may be formed by a laminated structure of a plurality of layers.

For example, the quantum dot light emitting device 100 further includes a hole blocking layer between the hole transport layer 140 and the light emitting layer 150 in order to prevent excitons or holes from diffusing into the electron transport layer 160. You may.

The hole blocking layer can be formed by using an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the like.

Examples of the present invention will be described below. However, the technical scope of the present invention is not limited to the following examples. In the following examples, unless otherwise specified, each operation was carried out at room temperature (25 ° C.). Unless otherwise specified,% and parts mean mass% and parts by mass, respectively.

Synthesis Example 1: Synthesis of compound 1 Compound 1 was synthesized according to the following reaction formula.

詳細には、アルゴン雰囲気下、反応容器中に、１，４－ジヘキシル－２，５－ジブロモベンゼン（８．０８ｇ、２０．０ｍｍｏｌ）、ビス（ピナコレートジボロン）（１２．１９ｇ、４８．０ｍｍｏｌ）、［１，１'－ビス（ジフェニルホスフィノ）フェロセン］パラジウム（ＩＩ）（０．９８ｇ、１．２ｍｍｏｌ）、酢酸カリウム（１１．７８ｇ、１２０．０ｍｍｏｌ）、及びジオキサン（１００ｍｌ）を加え、混合した後、加熱還流下、６時間攪拌した。次に、トルエン及び水を加え、分液した後、水で洗浄した。次に、硫酸ナトリウム及び活性炭を加え、撹拌した後、セライト（Ｃｅｌｉｔｅ：登録商標）で濾過した。次に、濾液を濃縮し、粗生成物（１１．９４ｇ）を得た。次に、粗生成物をヘキサンで再結晶した後、メタノールで洗浄した。得られた結晶を減圧乾燥させることにより、化合物１（４．２３ｇ）を得た。

Specifically, 1,4-dihexyl-2,5-dibromobenzene (8.08 g, 20.0 mmol) and bis (pinacholate diboron) (12.19 g, 48.0 mmol) were placed in a reaction vessel under an argon atmosphere. ), [1,1'-Bis (diphenylphosphino) ferrocene] palladium (II) (0.98 g, 1.2 mmol), potassium acetate (11.78 g, 120.0 mmol), and dioxane (100 ml) were added. After mixing, the mixture was stirred under heating under reflux for 6 hours. Next, toluene and water were added, the liquids were separated, and then the mixture was washed with water. Next, sodium sulfate and activated carbon were added, stirred, and then filtered through Cerite (registered trademark). The filtrate was then concentrated to give the crude product (11.94 g). The crude product was then recrystallized from hexane and then washed with methanol. The obtained crystals were dried under reduced pressure to obtain Compound 1 (4.23 g).

The structure of the obtained compound 1 was identified by a nuclear magnetic resonance apparatus ( ¹ H-NMR).

Synthesis Example 2: Synthesis of Compound 2 2-1. Synthesis of Compound 2-1 Compound 2-1 was synthesized according to the following reaction formula.

詳細には、アルゴン雰囲気下、反応容器中に、２－アミノ－Ｎ－［（１，１'－ビフェニル）－４－イル］－Ｎ－（４－ブロモフェニル）－９，９－ジメチルフルオレン（１５．００ｇ、２９．０４ｍｍｏｌ）、３－（４，４，５，５，－テトラメチル－１，３，２－ジオキサボロラン－２－イル）カルバゾール（７．６６ｇ、２６．１４ｍｍｏｌ）、ビス（トリフェニルホスフィン）パラジウム（ＩＩ）ジクロライド（０．４１ｇ、０．５８ｍｍｏｌ）、炭酸ナトリウム（７．７０ｇ、７２．６１ｍｍｏｌ）、ジオキサン（２９０ｍｌ）、水（１４５ｍｌ）を加えた後、混合した。次に、混合物を８５℃で４時間攪拌し、反応が終了した後、反応混合液を室温まで放冷した。次に、セライト（登録商標）を用いて、反応混合液を濾過し、不純物を濾別した。次に、濾液から溶媒を留去した後、カラムクロマトグラフィーにより精製し、化合物２－１（１２．７ｇ）を得た。

Specifically, 2-amino-N-[(1,1'-biphenyl) -4-yl] -N- (4-bromophenyl) -9,9-dimethylfluorene (in an argon atmosphere, in a reaction vessel). 15.00 g, 29.04 mmol), 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl) carbazole (7.66 g, 26.14 mmol), bis (tri) Phenylphosphine) Palladium (II) dichloride (0.41 g, 0.58 mmol), sodium carbonate (7.70 g, 72.61 mmol), dioxane (290 ml), water (145 ml) were added and then mixed. Next, the mixture was stirred at 85 ° C. for 4 hours, and after the reaction was completed, the reaction mixture was allowed to cool to room temperature. Next, the reaction mixture was filtered using Cerite®, and impurities were filtered off. Next, the solvent was distilled off from the filtrate and then purified by column chromatography to obtain Compound 2-1 (12.7 g).

The structure of the obtained compound 2-1 was identified by a nuclear magnetic resonance apparatus ( ¹ H-NMR).

2-2. Synthesis of Compound 2 Compound 2 was synthesized according to the following reaction formula.

詳細には、アルゴン雰囲気下、反応容器中に、化合物２－１（７．００ｇ、１１．６ｍｍｏｌ）、１，３－ジブロモ－５－ヨードベンゼン（４．６２ｇ、１２．７７ｍｍｏｌ）、ヨウ化銅（Ｉ）（０．１１ｇ、０．５８ｍｍｏｌ）、ｔｒａｎｓ－１，２－シクロヘキサンジアミン（０．２９ｇ、２．５５ｍｍｏｌ）、ナトリウムｔｅｒｔ－ブトキシド（２．２３ｇ、２３．２３ｍｍｏｌ）、ジオキサン（３５ｍｌ）を加えた後、混合した。次に、混合物を９０℃で６時間攪拌し、反応が終了した後、反応混合液を室温まで放冷した。次に、セライト（Ｃｅｌｉｔｅ：登録商標）を用いて、反応混合液を濾過し、不純物を濾別した。次に、濾液から溶媒を留去した後、カラムクロマトグラフィーにより精製し、化合物２（６ｇ）を得た。

Specifically, in an argon atmosphere, in a reaction vessel, compound 2-1 (7.00 g, 11.6 mmol), 1,3-dibromo-5-iodobenzene (4.62 g, 12.77 mmol), copper iodide. (I) (0.11 g, 0.58 mmol), trans-1,2-cyclohexanediamine (0.29 g, 2.55 mmol), sodium tert-butoxide (2.23 g, 23.23 mmol), dioxane (35 ml). After addition, it was mixed. Next, the mixture was stirred at 90 ° C. for 6 hours, and after the reaction was completed, the reaction mixture was allowed to cool to room temperature. Next, the reaction mixture was filtered using Cerite (registered trademark), and impurities were filtered off. Next, the solvent was distilled off from the filtrate and then purified by column chromatography to obtain Compound 2 (6 g).

The structure of the obtained compound 2 was identified by a nuclear magnetic resonance apparatus ( ¹ H-NMR).

Synthesis Example 3: Synthesis of compound 3 Compound 3 was synthesized according to the following reaction formula.

詳細には、アルゴン雰囲気下、反応容器中に、化合物３（４．００ｇ、４．７８ｍｍｏｌ）、ビスピナコレートジボロン（３．６４ｇ、１４．３４ｍｍｏｌ）、酢酸カリウム（２．８２ｇ、２８．６９ｍｍｏｌ）、［ビス（ジフェニルホスフィノ）フェロセン］ジクロロパラジウム（０．１１ｇ、０．１３ｍｍｏｌ）ジオキサン（５０ｍｌ）を加えた後、混合した。次に、混合物を９０℃で６時間攪拌し、反応が終了した後、反応混合液を室温まで放冷した。次に、セライト（Ｃｅｌｉｔｅ：登録商標）を用いて、反応混合液を濾過し、不純物を濾別した。次に、濾液から溶媒を留去した後、カラムクロマトグラフィーにより精製し、化合物３（３ｇ）を得た。

Specifically, in an argon atmosphere, compound 3 (4.00 g, 4.78 mmol), bispinacholate diboron (3.64 g, 14.34 mmol), potassium acetate (2.82 g, 28.69 mmol) were placed in the reaction vessel. ), [Bis (diphenylphosphino) ferrocene] dichloropalladium (0.11 g, 0.13 mmol) dioxane (50 ml) was added and then mixed. Next, the mixture was stirred at 90 ° C. for 6 hours, and after the reaction was completed, the reaction mixture was allowed to cool to room temperature. Next, the reaction mixture was filtered using Cerite (registered trademark), and impurities were filtered off. Next, the solvent was distilled off from the filtrate and then purified by column chromatography to obtain Compound 3 (3 g).

The structure of the obtained compound 3 was identified by a nuclear magnetic resonance apparatus ( ¹ H-NMR).

Synthesis Example 4: Synthesis of Compound 4 Compound 4 was synthesized according to the following reaction formula.

詳細には、アルゴン雰囲気下、反応容器中に、化合物２－１（７．００ｇ、１１．６ｍｍｏｌ）、１，４－ジブロモ－２－フルオロベンゼン（３．０４ｇ、１２．０ｍｍｏｌ）、Ｎ－メチル－２－ピロリドン（ＮＭＰ）１００ｍｌを加えた後、室温で撹拌した。次に、水素化ナトリウム（含有量６０％、０．４７８ｇ、１２．０ｍｍｏｌ）を投入した後、混合した。次に、混合物を１８０℃で５時間撹拌し、反応が終了した後、反応混合物を室温まで放冷した。次に、トルエン１００ｍｌを加えた後、分液ロートに移し、水１００ｍｌを用いて３回洗浄した。次に、反応混合物から溶媒を留去した後、カラムクロマトグラフィーにより精製し、化合物４（６．０８ｇ）を得た。

Specifically, in an argon atmosphere, in a reaction vessel, compound 2-1 (7.00 g, 11.6 mmol), 1,4-dibromo-2-fluorobenzene (3.04 g, 12.0 mmol), N-methyl. After adding 100 ml of -2-pyrrolidone (NMP), the mixture was stirred at room temperature. Next, sodium hydride (content 60%, 0.478 g, 12.0 mmol) was added and then mixed. The mixture was then stirred at 180 ° C. for 5 hours and after the reaction was complete, the reaction mixture was allowed to cool to room temperature. Next, after adding 100 ml of toluene, the mixture was transferred to a separating funnel and washed 3 times with 100 ml of water. Next, the solvent was distilled off from the reaction mixture, and the residue was purified by column chromatography to obtain Compound 4 (6.08 g).

Synthesis Example 5: Synthesis of Compound 5 5-1. Synthesis of Compound 5-1 Compound 5-1 was synthesized according to the following reaction formula.

詳細には、アルゴン雰囲気下、反応容器中に、化合物２－１（４．０ｇ、６．６ｍｍｏｌ）、１－ブロモ－４－ヨードベンゼン（２．０７ｇ、７．３ｍｍｏｌ）ヨウ化銅（Ｉ）（０．０４６ｇ、０．２４ｍｍｏｌ）、ナトリウムｔｅｒｔ－ブトキシド（０．８８ｇ、９．２ｍｍｏｌ）、ジオキサン（４０ｍｌ）を加えた後、混合した。次に、混合物を９０℃で１１時間撹拌し、反応が終了した後、反応混合物を室温まで放冷した。次に、セライト（Ｃｅｌｉｔｅ：登録商標）を用いて、反応混合液を濾過し、不純物を濾別した。次に、濾液から溶媒を留去した後、カラムクロマトグラフィーにより精製し、化合物５－１（３．０ｇ）を得た。

Specifically, in an argon atmosphere, in a reaction vessel, compound 2-1 (4.0 g, 6.6 mmol), 1-bromo-4-iodobenzene (2.07 g, 7.3 mmol) copper iodide (I). (0.046 g, 0.24 mmol), sodium tert-butoxide (0.88 g, 9.2 mmol) and dioxane (40 ml) were added and then mixed. The mixture was then stirred at 90 ° C. for 11 hours and after the reaction was complete the reaction mixture was allowed to cool to room temperature. Next, the reaction mixture was filtered using Cerite (registered trademark), and impurities were filtered off. Next, the solvent was distilled off from the filtrate and then purified by column chromatography to obtain Compound 5-1 (3.0 g).

5-2. Synthesis of Compound 5-2 Compound 5-2 was synthesized according to the following reaction formula.

詳細には、アルゴン雰囲気下、反応容器中に、化合物５－１（２．５ｇ、３．３ｍｍｏｌ）ビスピナコレートジボロン（１．０１ｇ、４．０ｍｍｏｌ）、酢酸カリウム（１．２１ｇ、１２．４ｍｍｏｌ）、［ビス（ジフェニルホスフィノ）フェロセン］ジクロロパラジウム（０．０４９ｇ、０．０６ｍｍｏｌ）、ジオキサン（８０ｍｌ）を加えた後、混合した。次に、混合物を９０℃で１２時間撹拌し、反応が終了した後、反応混合物を室温まで放冷した。次に、セライト（Ｃｅｌｉｔｅ：登録商標）を用いて、反応混合液を濾過し、不純物を濾別した。次に、濾液から溶媒を留去した後、カラムクロマトグラフィーにより精製し、化合物５－２（１．５ｇ）を得た。

Specifically, in an argon atmosphere, compound 5-1 (2.5 g, 3.3 mmol) bispinacholate dichloromethane (1.01 g, 4.0 mmol), potassium acetate (1.21 g, 12.1 mmol) were placed in the reaction vessel. 4 mmol), [bis (diphenylphosphino) ferrocene] dichloropalladium (0.049 g, 0.06 mmol), and dioxane (80 ml) were added and then mixed. The mixture was then stirred at 90 ° C. for 12 hours and after the reaction was complete the reaction mixture was allowed to cool to room temperature. Next, the reaction mixture was filtered using Cerite (registered trademark), and impurities were filtered off. Next, the solvent was distilled off from the filtrate and then purified by column chromatography to obtain Compound 5-2 (1.5 g).

5-3. Synthesis of Compound 5 Compound 5 was synthesized according to the following reaction formula.

詳細には、アルゴン雰囲気下、反応容器中に、化合物５－２（１．４ｇ、１．７４ｍｍｏｌ）、１，４－ジブロモ－２－ヨードベンゼン（０．６５ｇ、１．８ｍｍｏｌ）、ジオキサン（５０ｍｌ）、［テトラキス（トリフェニルホスフィン）］パラジウム（０．０２０ｇ、０．０１８ｍｍｏｌ）、炭酸ナトリウム（０．１９ｇ、１．８ｍｍｏｌ）、水１００ｍｌを加えた後、混合した。次に、混合物を８５℃で３４時間撹拌し、反応が終了した後、反応混合物を室温まで放冷した。次に、セライト（Ｃｅｌｉｔｅ：登録商標）を用いて、反応混合液を濾過し、不純物を濾別した。次に、濾液から溶媒を留去した後、カラムクロマトグラフィーにより精製し、化合物５（０．６０ｇ）を得た。

Specifically, in an argon atmosphere, in a reaction vessel, compound 5-2 (1.4 g, 1.74 mmol), 1,4-dibromo-2-iodobenzene (0.65 g, 1.8 mmol), dioxane (50 ml). ), [Tetrakis (triphenylphosphine)] palladium (0.020 g, 0.018 mmol), sodium carbonate (0.19 g, 1.8 mmol), and 100 ml of water were added and then mixed. The mixture was then stirred at 85 ° C. for 34 hours and after the reaction was complete the reaction mixture was allowed to cool to room temperature. Next, the reaction mixture was filtered using Cerite (registered trademark), and impurities were filtered off. Next, the solvent was distilled off from the filtrate and then purified by column chromatography to obtain Compound 5 (0.60 g).

Example 1: Synthesis of Polymer Material A-1 Using the compound 1 synthesized in Synthesis Example 1 and the compound 2 synthesized in Synthesis Example 2, a polymer material A-1 having the following structural units having the following composition is synthesized. did.

詳細には、アルゴン雰囲気下、化合物１（１．９６ｇ）、化合物２（２．５８ｇ）、酢酸パラジウム（４．３ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２７．０ｍｇ）、トルエン（５５ｍＬ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１５．２ｇ）を加えた後、８時間加熱還流した。次に、フェニルボロン酸（０．０２３ｇ）、酢酸パラジウム（４．３ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２７．０ｍｇ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１５．２ｇ）を加えた後、７時間加熱還流した。次に、反応混合物から水層を除き、Ｎ，Ｎ－ジエチルジチオカルバミド酸ナトリウム三水和物（５．４ｇ）、及びイオン交換水（５０ｍＬ）を加えた後、８５℃で２時間攪拌した。次に、反応混合物を有機層と水層に分離した後、水、３質量％酢酸水溶液、及び水を用いて、有機層を順次洗浄した。次に、有機層をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、粗生成物を得た。次に、粗生成物をトルエンに溶解させて、シリカゲル／アルミナを充填したカラムクロマトグラフを用いて精製した後、溶媒を減圧留去した。次に、得られた液体をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、高分子材料Ａ－１（１．１４ｇ）を得た。

Specifically, under an argon atmosphere, compound 1 (1.96 g), compound 2 (2.58 g), palladium acetate (4.3 mg), tris (2-methoxyphenyl) phosphine (27.0 mg), toluene (55 mL). , And a 20 mass% tetraethylammonium hydroxide aqueous solution (15.2 g) was added, and then the mixture was heated under reflux for 8 hours. Next, phenylboronic acid (0.023 g), palladium acetate (4.3 mg), tris (2-methoxyphenyl) phosphine (27.0 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (15.2 g) were added. After that, the mixture was heated and refluxed for 7 hours. Next, the aqueous layer was removed from the reaction mixture, sodium trihydrate N, N-diethyldithiocarbamate (5.4 g) and ion-exchanged water (50 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. Next, the reaction mixture was separated into an organic layer and an aqueous layer, and then the organic layer was washed sequentially with water, a 3 mass% acetic acid aqueous solution, and water. Next, the organic layer was added dropwise to methanol to precipitate, filtered off, and then dried to obtain a crude product. Next, the crude product was dissolved in toluene, purified using a column chromatograph packed with silica gel / alumina, and then the solvent was distilled off under reduced pressure. Next, the obtained liquid was added dropwise to methanol to precipitate, filtered off, and then dried to obtain a polymer material A-1 (1.14 g).

The polymer material A-1 has the above composition (constituent unit derived from compound 1: structural unit derived from compound 2 = 1: 1 (molar ratio)) based on the charging ratio of the monomers, and the respective structural units are alternately arranged. It is presumed to be an alternating copolymer that is bound. Further, when the number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer material A-1 were estimated using size exclusion chromatography (SEC), Mn = 44. It was 000, Mw = 80,000, and Mw / Mn = 1.83.

Example 2: Synthesis of Polymer Material A-2 Using the compound 3 synthesized in Synthesis Example 3 and p-diiodobenzene, a polymer material A-2 having the following constituent units having the following composition was synthesized.

詳細には、アルゴン雰囲気下、化合物３（２．５３ｇ）、ｐ－ジヨードベンゼン（３．３０ｇ）、酢酸パラジウム（４．３ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２７．０ｍｇ）、トルエン（５５ｍＬ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１５．２ｇ）を加えた後、８時間加熱還流した。次に、フェニルボロン酸（０．０２３ｇ）、酢酸パラジウム（４．３ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２７．０ｍｇ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１５．２ｇ）を加えた後、７時間加熱還流した。次に、反応混合物から水層を除き、Ｎ，Ｎ－ジエチルジチオカルバミド酸ナトリウム三水和物（５．４ｇ）、及びイオン交換水（５０ｍＬ）を加えた後、８５℃で２時間攪拌した。次に、反応混合物を有機層と水層に分離した後、水、３質量％酢酸水溶液、及び水を用いて、有機層を順次洗浄した。次に、有機層をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、粗生成物を得た。次に、粗生成物をトルエンに溶解させて、シリカゲル／アルミナを充填したクロマトグラフを用いて精製した後、溶媒を減圧留去した。次に、得られた液体をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、高分子材料Ａ－２（０．８ｇ）を得た。

Specifically, under an argon atmosphere, compound 3 (2.53 g), p-diiodobenzene (3.30 g), palladium acetate (4.3 mg), tris (2-methoxyphenyl) phosphine (27.0 mg), toluene. After adding (55 mL) and a 20 mass% tetraethylammonium hydroxide aqueous solution (15.2 g), the mixture was heated under reflux for 8 hours. Next, phenylboronic acid (0.023 g), palladium acetate (4.3 mg), tris (2-methoxyphenyl) phosphine (27.0 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (15.2 g) were added. After that, the mixture was heated and refluxed for 7 hours. Next, the aqueous layer was removed from the reaction mixture, sodium trihydrate N, N-diethyldithiocarbamate (5.4 g) and ion-exchanged water (50 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. Next, the reaction mixture was separated into an organic layer and an aqueous layer, and then the organic layer was washed sequentially with water, a 3 mass% acetic acid aqueous solution, and water. Next, the organic layer was added dropwise to methanol to precipitate, filtered off, and then dried to obtain a crude product. Next, the crude product was dissolved in toluene, purified using a chromatograph filled with silica gel / alumina, and then the solvent was distilled off under reduced pressure. Next, the obtained liquid was added dropwise to methanol to precipitate, and the mixture was separated by filtration and dried to obtain a polymer material A-2 (0.8 g).

The polymer material A-2 has the above composition (constituent unit derived from compound 3: constituent unit derived from p-diiodobenzene = 1: 1 (molar ratio)) based on the charging ratio of the monomers, and each constituent unit. Is presumed to be an alternating copolymer in which Further, when the number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer material A-2 were estimated using size exclusion chromatography (SEC), Mn = 14 It was 000, Mw = 26,000, and Mw / Mn = 1.88.

Example 3: Synthesis of Polymer Material A-3 Using the compound 3 synthesized in Synthesis Example 3 and 3,5-dibromobiphenyl, a polymer material A-3 having the following constituent units having the following composition was synthesized.

詳細には、アルゴン雰囲気下、化合物３（３．２１ｇ、３．４５ｍｍｏｌ）、３，５－ジブロモビフェニル（１．０８ｇ）、酢酸パラジウム（５．５ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（３４．３ｍｇ）、トルエン（５５ｍＬ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１９．３ｇ）を加えた後、８時間加熱還流した。次に、フェニルボロン酸（０．０２３ｇ）、酢酸パラジウム（４．３ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２７．０ｍｇ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１５．２ｇ）を加えた後、７時間加熱還流した。次に、反応混合物から水層を除き、Ｎ，Ｎ－ジエチルジチオカルバミド酸ナトリウム三水和物（５．４ｇ）、及びイオン交換水（５０ｍＬ）を加えた後、８５℃で２時間攪拌した。次に、反応混合物を有機層と水層に分離した後、水、３質量％酢酸水溶液、及び水を用いて、有機層を順次洗浄した。次に、有機層をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、粗生成物を得た。粗生成物をトルエンに溶解させて、シリカゲル／アルミナを充填したクロマトグラフを用いて精製した後、溶媒を減圧留去した。次に、得られた液体をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、高分子材料Ａ－３（０．１７ｇ）を得た。

Specifically, under an argon atmosphere, Compound 3 (3.21 g, 3.45 mmol), 3,5-dibromobiphenyl (1.08 g), palladium acetate (5.5 mg), tris (2-methoxyphenyl) phosphine (34). .3 mg), toluene (55 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (19.3 g) were added, and the mixture was heated under reflux for 8 hours. Next, add phenylboronic acid (0.023 g), palladium acetate (4.3 mg), tris (2-methoxyphenyl) phosphine (27.0 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (15.2 g). After that, the mixture was heated and refluxed for 7 hours. Next, the aqueous layer was removed from the reaction mixture, sodium trihydrate N, N-diethyldithiocarbamate (5.4 g) and ion-exchanged water (50 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. Next, the reaction mixture was separated into an organic layer and an aqueous layer, and then the organic layer was washed sequentially with water, a 3 mass% acetic acid aqueous solution, and water. Next, the organic layer was added dropwise to methanol to precipitate, filtered off, and then dried to obtain a crude product. The crude product was dissolved in toluene and purified using a chromatograph filled with silica gel / alumina, and then the solvent was distilled off under reduced pressure. Next, the obtained liquid was added dropwise to methanol to precipitate, and the mixture was separated by filtration and dried to obtain a polymer material A-3 (0.17 g).

The polymer material A-3 has the above composition (constituent unit derived from compound 3: constituent unit derived from 3,5-dibromobiphenyl: = 1: 1 (molar ratio)) based on the charging ratio of the monomers. It is presumed to be an alternating copolymer in which the constituent units are bonded alternately. Further, when the number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer material A-3 were estimated using size exclusion chromatography (SEC), Mn = 15 , 200, Mw = 33,500, Mw / Mn = 2.20.

Example 4: Synthesis of Polymer Material A-4 Polymer Material A-4 having the following constituent units in the following composition using the compound 3 synthesized in Synthesis Example 3 and 1,3-dibromo-5-dodecylbenzene. Was synthesized.

詳細には、アルゴン雰囲気下、化合物３（１．６０ｇ、１．７１ｍｍｏｌ）、１，３－ジブロモ－５－ドデシルベンゼン（０．８４ｇ）、酢酸パラジウム（２．２ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（１３．５ｍｇ）、トルエン（５５ｍＬ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（７．１０ｇ）を加えた後、８時間加熱還流した。次に、フェニルボロン酸（０．０２３ｇ）、酢酸パラジウム（４．３ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２７．０ｍｇ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１５．２ｇ）を加えた後、７時間加熱還流した。次に、反応混合物から水層を除き、Ｎ，Ｎ－ジエチルジチオカルバミド酸ナトリウム三水和物（５．４ｇ）、及びイオン交換水（５０ｍＬ）を加えた後、８５℃で２時間攪拌した。次に、反応混合物を有機層と水層に分離した後、水、３質量％酢酸水溶液、及び水を用いて、有機層を順次洗浄した。次に、有機層をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、粗生成物を得た。粗生成物をトルエンに溶解させて、シリカゲル／アルミナを充填したクロマトグラフを用いて精製した後、溶媒を減圧留去した。次に、得られた液体をメタノールに滴下して沈殿させ、ろ別した後、乾燥させ、高分子材料Ａ－４（０．９８ｇ）を得た。

Specifically, under an argon atmosphere, compound 3 (1.60 g, 1.71 mmol), 1,3-dibromo-5-dodecylbenzene (0.84 g), palladium acetate (2.2 mg), tris (2-methoxyphenyl). ) Phenyl (13.5 mg), toluene (55 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (7.10 g) were added, and the mixture was heated under reflux for 8 hours. Next, phenylboronic acid (0.023 g), palladium acetate (4.3 mg), tris (2-methoxyphenyl) phosphine (27.0 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (15.2 g) were added. After that, the mixture was heated and refluxed for 7 hours. Next, the aqueous layer was removed from the reaction mixture, sodium trihydrate N, N-diethyldithiocarbamate (5.4 g) and ion-exchanged water (50 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. Next, the reaction mixture was separated into an organic layer and an aqueous layer, and then the organic layer was washed sequentially with water, a 3 mass% acetic acid aqueous solution, and water. Next, the organic layer was added dropwise to methanol to precipitate, filtered off, and then dried to obtain a crude product. The crude product was dissolved in toluene and purified using a chromatograph filled with silica gel / alumina, and then the solvent was distilled off under reduced pressure. Next, the obtained liquid was added dropwise to methanol to precipitate, and the mixture was filtered and dried to obtain a polymer material A-4 (0.98 g).

The polymer material A-3 has the above composition (constituent unit derived from compound 3: 1,3-dibromo-5-dodecylbenzene-derived structural unit = 1: 1 (molar ratio)) based on the monomer charging ratio. , It is presumed that the constituent units are alternating copolymers in which they are bonded alternately. Further, when the number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer material A-3 were estimated using size exclusion chromatography (SEC), Mn = 7 , 300, Mw = 16,100, Mw / Mn = 2.18.

Example 5: Synthesis of Polymer Material A-5 Polymer Material A having the following structural units in the following composition using the compound 4 synthesized in Synthesis Example 4 and 1,4-dihexyl-2,5-dibromobenzene. -5 was synthesized.

詳細には、アルゴン雰囲気下、化合物４（２．５８ｇ、３．０８ｍｍｏｌ）、化合物１（１．５４ｇ）、酢酸パラジウム（４．３ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２７．０ｍｇ）、トルエン（５５ｍＬ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１５．２ｇ）を加えた後、８時間加熱還流した。次に、フェニルボロン酸（０．０２３ｇ）、酢酸パラジウム（４．３ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２７．０ｍｇ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１５．２ｇ）を加えた後、７時間加熱還流した。次に、反応混合物から水層を除き、Ｎ，Ｎ－ジエチルジチオカルバミド酸ナトリウム三水和物（５．４ｇ）、及びイオン交換水（５０ｍＬ）を加えた後、８５℃で２時間攪拌した。次に、反応混合物を有機層と水層に分離した後、水、３質量％酢酸水溶液、及び水を用いて、有機層を順次洗浄した。次に、有機層をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、粗生成物を得た。次に、粗生成物をトルエンに溶解させて、シリカゲル／アルミナを充填したクロマトグラフを用いて精製した後、溶媒を減圧留去した。次に、得られた液体をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、高分子材料Ａ－５（０．８４ｇ）を得た。

Specifically, under an argon atmosphere, Compound 4 (2.58 g, 3.08 mmol), Compound 1 (1.54 g), Palladium acetate (4.3 mg), Tris (2-methoxyphenyl) phosphine (27.0 mg), Toluene (55 mL) and a 20 mass% tetraethylammonium hydroxide aqueous solution (15.2 g) were added, and the mixture was heated under reflux for 8 hours. Next, phenylboronic acid (0.023 g), palladium acetate (4.3 mg), tris (2-methoxyphenyl) phosphine (27.0 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (15.2 g) were added. After that, the mixture was heated and refluxed for 7 hours. Next, the aqueous layer was removed from the reaction mixture, sodium trihydrate N, N-diethyldithiocarbamate (5.4 g) and ion-exchanged water (50 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. Next, the reaction mixture was separated into an organic layer and an aqueous layer, and then the organic layer was washed sequentially with water, a 3 mass% acetic acid aqueous solution, and water. Next, the organic layer was added dropwise to methanol to precipitate, filtered off, and then dried to obtain a crude product. Next, the crude product was dissolved in toluene, purified using a chromatograph filled with silica gel / alumina, and then the solvent was distilled off under reduced pressure. Next, the obtained liquid was added dropwise to methanol to precipitate, and the mixture was separated by filtration and dried to obtain a polymer material A-5 (0.84 g).

The polymer material A-5 has the above composition (constituent unit derived from compound 4: structural unit derived from compound 1 = 1: 1 (molar ratio)) based on the charging ratio of the monomers, and the respective structural units are alternately arranged. It is presumed to be an alternating copolymer that is bound. Further, when the number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer material A-5 were estimated using size exclusion chromatography (SEC), Mn = 29. , 300, Mw = 77,500, Mw / Mn = 2.64.

Example 6: Synthesis of Polymer Material A-6 Using the compound 1 synthesized in Synthesis Example 1, the compound 2 synthesized in Synthesis Example 2, and 1,3-dibromoazulene, a high molecular weight material having the following structural units having the following composition. Molecular material A-6 was synthesized.

詳細には、アルゴン雰囲気下、化合物３（２．１０ｇ、２．２６ｍｍｏｌ）、１，４－ジヘキシル－２，５－ジブロモベンゼン（０．８９ｇ、２．１９ｍｍｏｌ）１，３－ジブロモアズレン（１９．４ｍｇ）、酢酸パラジウム（４．４ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２７．８ｍｇ）、トルエン（５５ｍＬ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１５．７ｇ）を加えた後、８時間加熱還流した。次に、フェニルボロン酸（０．０２３ｇ）、酢酸パラジウム（４．３ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２７．０ｍｇ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１５．２ｇ）を加えた後、７時間加熱還流した。次に、反応混合物から水層を除き、Ｎ，Ｎ－ジエチルジチオカルバミド酸ナトリウム三水和物（５．４ｇ）、及びイオン交換水（５０ｍＬ）を加えた後、８５℃で２時間攪拌した。次に、反応混合物を有機層と水層に分離した後、水、３質量％酢酸水溶液、及び水を用いて、有機層を順次洗浄した。次に、有機層をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、粗生成物を得た。次に、粗生成物をトルエンに溶解させて、シリカゲル／アルミナを充填したクロマトグラフを用いて精製した後、溶媒を減圧留去した。次に、得られた液体をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、高分子材料Ａ－６（０．４７ｇ）を得た。

Specifically, in an argon atmosphere, Compound 3 (2.10 g, 2.26 mmol), 1,4-dihexyl-2,5-dibromobenzene (0.89 g, 2.19 mmol) 1,3-dibromoazulene (19. 4 mg), palladium acetate (4.4 mg), tris (2-methoxyphenyl) phosphine (27.8 mg), toluene (55 mL), and 20 mass% tetraethylammonium hydroxide aqueous solution (15.7 g), followed by 8 It was heated and refluxed for hours. Next, phenylboronic acid (0.023 g), palladium acetate (4.3 mg), tris (2-methoxyphenyl) phosphine (27.0 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (15.2 g) were added. After that, the mixture was heated and refluxed for 7 hours. Next, the aqueous layer was removed from the reaction mixture, sodium trihydrate N, N-diethyldithiocarbamate (5.4 g) and ion-exchanged water (50 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. Next, the reaction mixture was separated into an organic layer and an aqueous layer, and then the organic layer was washed sequentially with water, a 3 mass% acetic acid aqueous solution, and water. Next, the organic layer was added dropwise to methanol to precipitate, filtered off, and then dried to obtain a crude product. Next, the crude product was dissolved in toluene, purified using a chromatograph filled with silica gel / alumina, and then the solvent was distilled off under reduced pressure. Next, the obtained liquid was added dropwise to methanol to precipitate, and the mixture was separated by filtration and dried to obtain a polymer material A-6 (0.47 g).

The polymer material A-6 has the above composition (constituent unit derived from compound 2: constituent unit derived from compound 1: constituent unit derived from 1,3-dibromoazulene = 48.5:50: At 1.5 (molar ratio)), it is presumed that the copolymer has segments in which the structural units derived from compound 2 and the structural units derived from compound 1 are alternately bonded. Further, when the number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer material A-6 were estimated using size exclusion chromatography (SEC), Mn = 28200. , Mw = 41,500 and Mw / Mn = 1.47.

Example 7: Synthesis of Polymer Material A-7 Using the compound 2 synthesized in Synthesis Example 2 and 2,7-dibromo-9,9-di-n-octylfluorene, the following constituent units are contained in the following composition. Polymer material A-7 was synthesized.

詳細には、アルゴン雰囲気下、化合物２（２．００ｇ、２．１９ｍｍｏｌ）、２，７－ジブロモ－９，９－ジ－ｎ－オクチルフルオレン（１．２０ｇ）、酢酸パラジウム（３．４ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２１．３ｍｇ）、トルエン（５０ｍＬ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１５．２ｇ）を加えた後、８時間加熱還流した。次に、フェニルボロン酸（０．０２３ｇ）、酢酸パラジウム（４．３ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２７．０ｍｇ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１２．０ｇ）を加えた後、７時間加熱還流した。次に、反応混合物から水層を除き、Ｎ，Ｎ－ジエチルジチオカルバミド酸ナトリウム三水和物（５．４ｇ）、及びイオン交換水（５０ｍＬ）を加えた後、８５℃で２時間攪拌した。次に、反応混合物を有機層と水層に分離した後、水、３質量％酢酸水溶液、及び水を用いて、有機層を順次洗浄した。次に、有機層をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、粗生成物を得た。次に、粗生成物をトルエンに溶解させて、シリカゲル／アルミナを充填したクロマトグラフを用いて精製した後、溶媒を減圧留去した。次に、得られた液体をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、高分子材料Ａ－７（１．２０ｇ）を得た。

Specifically, in an argon atmosphere, Compound 2 (2.00 g, 2.19 mmol), 2,7-dibromo-9,9-di-n-octylfluorene (1.20 g), palladium acetate (3.4 mg), and the like. After adding tris (2-methoxyphenyl) phosphine (21.3 mg), toluene (50 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (15.2 g), the mixture was heated under reflux for 8 hours. Next, phenylboronic acid (0.023 g), palladium acetate (4.3 mg), tris (2-methoxyphenyl) phosphine (27.0 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (12.0 g) are added. After that, the mixture was heated and refluxed for 7 hours. Next, the aqueous layer was removed from the reaction mixture, sodium trihydrate N, N-diethyldithiocarbamate (5.4 g) and ion-exchanged water (50 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. Next, the reaction mixture was separated into an organic layer and an aqueous layer, and then the organic layer was washed sequentially with water, a 3 mass% acetic acid aqueous solution, and water. Next, the organic layer was added dropwise to methanol to precipitate, filtered off, and then dried to obtain a crude product. Next, the crude product was dissolved in toluene, purified using a chromatograph filled with silica gel / alumina, and then the solvent was distilled off under reduced pressure. Next, the obtained liquid was added dropwise to methanol to precipitate, filtered off, and then dried to obtain a polymer material A-7 (1.20 g).

Based on the monomer charging ratio, the polymer material A-7 has the above composition (constituent unit derived from compound 2: 2,7-dibromo-9,9-di-n-octylfluorene-derived structural unit = 1: 1). (Mole ratio)), it is presumed to be an alternating copolymer in which each constituent unit is alternately bonded. Further, when the number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer material A-7 were estimated using size exclusion chromatography (SEC), Mn = 61. It was 000, Mw = 133,000, and Mw / Mn = 1.86.

Example 8: Synthesis of Polymer Material A-8 Using the compound 5 and the compound 1 synthesized in Synthesis Example 5, the polymer material A-8 having the following structural unit having the following composition was synthesized.

詳細には、アルゴン雰囲気下、化合物５（２．００ｇ、２，１９ｍｍｏｌ）、化合物１（１．０９ｇ）、酢酸パラジウム（３．４ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２１．３ｍｇ）、トルエン（５０ｍＬ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１２．０ｇ）を加えた後、８時間加熱還流した。次に、フェニルボロン酸（０．０２３ｇ）、酢酸パラジウム（４．３ｍｇ）、トリス（２－メトキシフェニル）ホスフィン（２７．０ｍｇ）、及び２０質量％テトラエチルアンモニウムヒドロキシド水溶液（１５．２ｇ）を加えた後、７時間加熱還流した。次に、反応混合物から水層を除き、Ｎ，Ｎ－ジエチルジチオカルバミド酸ナトリウム三水和物（５．４ｇ）、及びイオン交換水（５０ｍＬ）を加えた後、８５℃で２時間攪拌した。次に、反応混合物を有機層と水層に分離した後、水、３質量％酢酸水溶液、及び水を用いて、有機層を順次洗浄した。次に、有機層をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、粗生成物を得た。次に、粗生成物をトルエンに溶解させて、シリカゲル／アルミナを充填したクロマトグラフを用いて精製した後、溶媒を減圧留去した。次に、得られた液体をメタノールに滴下して沈殿させ、濾別した後、乾燥させ、高分子材料Ａ－７（１．２０ｇ）を得た。

Specifically, under an argon atmosphere, Compound 5 (2.00 g, 2,19 mmol), Compound 1 (1.09 g), Palladium acetate (3.4 mg), Tris (2-methoxyphenyl) phosphine (21.3 mg), and the like. Toluene (50 mL) and a 20 mass% tetraethylammonium hydroxide aqueous solution (12.0 g) were added, and the mixture was heated under reflux for 8 hours. Next, phenylboronic acid (0.023 g), palladium acetate (4.3 mg), tris (2-methoxyphenyl) phosphine (27.0 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (15.2 g) were added. After that, the mixture was heated and refluxed for 7 hours. Next, the aqueous layer was removed from the reaction mixture, sodium trihydrate N, N-diethyldithiocarbamate (5.4 g) and ion-exchanged water (50 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. Next, the reaction mixture was separated into an organic layer and an aqueous layer, and then the organic layer was washed sequentially with water, a 3 mass% acetic acid aqueous solution, and water. Next, the organic layer was added dropwise to methanol to precipitate, filtered off, and then dried to obtain a crude product. Next, the crude product was dissolved in toluene, purified using a chromatograph filled with silica gel / alumina, and then the solvent was distilled off under reduced pressure. Next, the obtained liquid was added dropwise to methanol to precipitate, filtered off, and then dried to obtain a polymer material A-7 (1.20 g).

The polymer material A-8 has the above composition (constituent unit derived from compound 5: structural unit derived from compound 1 = 1: 1 (molar ratio)) based on the charging ratio of the monomers, and the respective structural units are alternately arranged. It is presumed to be an alternating copolymer that is bound. Further, when the number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer material A-8 were estimated using size exclusion chromatography (SEC), Mn = 29. It was 000, Mw = 70,000, and Mw / Mn = 2.41.

Next, the polymer materials A-1 to A-8 of Examples 1 to 8 and the poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4) having the following structural units The HOMO level and LUMO level of'-(N- (4-sec-butylphenyl) diphenylamine)] (TFB) (manufactured by Luminescence Technology Corp.) (polymer material of Comparative Example 1) were measured.

（ＨＯＭＯ準位の測定方法）
濃度が１質量％となるように、各高分子材料をキシレンに溶解させ、塗布液を調製した。

(Measurement method of HOMO level)
Each polymer material was dissolved in xylene so that the concentration was 1% by mass, and a coating liquid was prepared.

Using the coating solution prepared above on a UV-cleaned glass substrate with ITO, a film was formed by the spin coating method at a rotation speed of 2000 rpm, and then dried on a hot plate at 150 ° C. for 30 minutes. , A sample for measurement was prepared.

The HOMO level of the sample was measured using an atmospheric photoelectron spectrometer (AC-3 manufactured by RIKEN Keiki Co., Ltd.). At this time, the rising tangential intersection was calculated from the measurement result and used as the HOMO level.

The HOMO level is usually a negative number.

(LUMO level measurement method)
Each polymer material was dissolved in toluene so that the concentration was 3.2% by mass, and a coating liquid was prepared.

Using the coating liquid prepared above on a UV-cleaned glass substrate with ITO, a film was formed by the spin coating method at a rotation speed of 1600 rpm, and then dried on a hot plate at 250 ° C. for 60 minutes. , A sample for measurement was prepared. At this time, the film thickness of the film was about 70 nm. The obtained sample was cooled to 77K (-196 ° C.) and the photoluminescence (PL) spectrum was measured. The LUMO level [eV] was calculated from the peak value on the shortest wavelength side of the PL spectrum.

Table 1 shows the HOMO level and LUMO level of the polymer material.

表１の結果から、実施例１～８の高分子材料Ａ－１～Ａ－８は、従来使用されている比較例１の高分子材料（ＴＦＢ）と比較して、ＨＯＭＯ準位が若干深く、ＬＵＭＯ順位が有意に浅いことがわかる。

From the results in Table 1, the polymer materials A-1 to A-8 of Examples 1 to 8 have a slightly deeper HOMO level than the conventionally used polymer materials (TFB) of Comparative Example 1. , It can be seen that the LUMO ranking is significantly shallow.

Example 9: Fabrication of Quantum Dot Light Emitting Element As the first electrode (anode), a glass substrate with ITO patterned with ITO is sequentially washed with a neutral detergent, deionized water, water and isopropyl alcohol, and then washed in sequence. UV-ozone treatment was performed. Next, PEDOT / PSS (manufactured by Sigma-Aldrich) was applied onto a glass substrate with ITO by a spin coating method, and then dried. As a result, a hole injection layer having a thickness (dry film thickness) of 30 nm was formed on the glass substrate with ITO.

A 1.0% by mass toluene solution of the polymer material A-1 (hole transport material) of Example 1 was applied onto the hole injection layer by a spin coating method, and then heat-treated at 150 ° C. for 30 minutes. , A hole transport layer was formed. As a result, a hole transport layer having a thickness (dry film thickness) of 25 nm was formed on the hole injection layer.

Quantum dots (see FIG. 2) of ZnTeSe / ZnSe / ZnS (core / shell / shell) are dispersed on the hole transport layer in cyclohexane in which the hole transport layer is not dissolved so as to be 1.0% by mass. The dispersed dispersion was applied by a spin coating method and then dried. As a result, a quantum dot light emitting layer having a thickness (dry film thickness) of 25 nm was formed on the hole transport layer. The light emitted by irradiating the dispersion liquid of quantum dots with ultraviolet rays had a central wavelength of 458 nm and a half width of 29 nm (see FIGS. 3 and 4).

After the quantum dot light emitting layer was completely dried, lithium quinolate (Liq) and the electron transport material TPBI (manufactured by Sigma-Aldrich) were co-deposited on the quantum dot light emitting layer using a vacuum vapor deposition apparatus. As a result, an electron transport layer having a thickness of 36 nm was formed on the quantum dot light emitting layer.

Liq was deposited on the electron transport layer using a vacuum vapor deposition apparatus. As a result, an electron injection layer having a thickness of 0.5 nm was formed on the electron transport layer.

Aluminum was vapor-deposited on the electron-injected layer using a vacuum-film deposition device. As a result, a second electrode (cathode) having a thickness of 100 nm was formed on the electron injection layer, and a quantum dot light emitting device was obtained.

Examples 10 to 16: Fabrication of quantum dot light emitting device A hole transport layer was formed by using the polymer materials A-2 to A-8 of Examples 2 to 8 instead of the polymer material A-1. Obtained a quantum dot light emitting device in the same manner as in Example 9.

Comparative Example 2: Fabrication of Quantum Dot Light Emitting Element The same as in Example 9 except that the hole transport layer was formed by using the polymer material (TFB) of Comparative Example 1 instead of the polymer material A-1. To obtain a quantum dot light emitting device.

5 and 6 show energy diagrams of the quantum dot light emitting devices of Comparative Examples 2 and 9.

Next, the drive voltage and luminous efficiency of the quantum dot light emitting devices of Examples 9 to 16 and Comparative Example 2 were evaluated.

[Evaluation method of light emitting element]
When a voltage was applied to each quantum dot light emitting element using a DC constant voltage power supply (source meter manufactured by KEYENCE), a current started to flow at a constant voltage, and the quantum dot light emitting element emitted light. At this time, the voltage at a current density of 5 mA / cm ² was defined as the drive voltage (Vop) [V]. Further, the current was gradually increased, and when the brightness reached 100 nits (cd / m ² ), the current was kept constant and left to stand. At this time, the external quantum efficiency (EQE) at a brightness of 100 nits was calculated from the measured spectral radiance spectrum, assuming that Lambersian radiation was performed, and the luminous efficiency was evaluated.

Table 2 shows the evaluation results of Vop and EQE of the quantum dot light emitting device. The EQE is a relative value when the measured value of the quantum dot light emitting device of Comparative Example 1 is 100.

表２から、実施例９～１６の量子ドット発光素子は、正孔輸送材料として、本実施形態に係る高分子材料の具体例としての、高分子材料Ａ－１～Ａ－８が用いられているため、Ｖｏｐが低く、ＥＱＥが高いことがわかる。

From Table 2, in the quantum dot light emitting devices of Examples 9 to 16, polymer materials A-1 to A-8 as specific examples of the polymer material according to the present embodiment are used as the hole transport material. Therefore, it can be seen that the Vop is low and the EQE is high.

On the other hand, in the quantum dot light emitting device of Comparative Example 2, since TFB is used as the hole transport material, Vop is high and EQE is low.

As can be seen from Table 1, FIG. 5, FIG. 6, etc., the reason why these differences occur is that the HOMO levels of the polymer materials A-1 to A-8 are higher than the HOMO levels of the TFB and the HOMO of the quantum dots. It is considered that this is because the barrier for injecting holes from the hole transport layer into the quantum dots is small because it is slightly close to the level.

100 Quantum dot light emitting device 110 Substrate 120 First electrode 130 Hole injection layer 140 Hole transport layer 150 Light emitting layer 160 Electron transport layer 170 Electron injection layer 180 Second electrode

Claims (10)

A polymer material containing a segment of an alternating copolymer of a structural unit represented by the following formula (1).

(In the formula (1), X is a group represented by the following formula (2), and Y is a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or Substituted or unsubstituted ring-forming A divalent aromatic heterocyclic group having 3 or more and 60 or less atoms, and the aromatic hydrocarbon group contains two or more aromatic hydrocarbon rings. The aromatic hydrocarbon rings are condensed with each other .)

(In the formula (2), Ar ₁ is a substituted or unsubstituted trivalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or a substituted or unsubstituted ring-forming atom number of 3 or more and 60 or less. Is a trivalent aromatic heterocyclic group of
Ar ₂ and Ar ₃ are independently substituted or unsubstituted monovalent aromatic hydrocarbon groups having 6 or more and 60 or less carbon atoms, or substituted or unsubstituted ring-forming atoms having 3 or more and 60 atoms, respectively. The following monovalent aromatic heterocyclic groups,
L ₁ and L ₂ are independently single-bonded, substituted or unsubstituted divalent aromatic hydrocarbon groups having 6 to 60 carbon atoms, or substituted or unsubstituted ring-forming atoms. It is a divalent aromatic heterocyclic group of 3 or more and 60 or less.
R ₁ and R ₂ are independently substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or substituted. An unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted ring-forming monovalent aromatic heterocyclic group having 3 to 60 atoms.
R ₁ and R ₂ may be combined with each other to form a ring.
a is an integer of 0 or more and 4 or less,
b is an integer of 0 or more and 3 or less,
Z ₁ to Z ₈ are independently nitrogen atoms or −CH =. ) The polymer material according to claim 1, wherein in the formula (1), X is selected from the group consisting of groups represented by the following formulas (2-1) to (2-6).

(In the above formulas (2-1) to (2-6), Ar ₄ is a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or substituted or unsubstituted. It is a monovalent aromatic heterocyclic group having 3 or more and 60 or less ring-forming atoms.) The polymer material according to claim 1 or 2, wherein in the formula (1), Y is selected from the group consisting of groups represented by the following formulas (2-7) to (2-14).

(In the above formulas (2-7) to (2-14), Ar ₅₁ to Ar ₅₅ are independently substituted or unsubstituted monovalent aromatic hydrocarbon groups having 6 to 60 carbon atoms. , A substituted or unsubstituted ring-forming monovalent aromatic heterocyclic group having 3 or more and 60 or less atoms, an alkyl group having 1 or more carbon atoms and 20 or less carbon atoms, or a hydrogen atom.
A ₁₁ to A ₁₃ are independent of each other, -O-, -S-, -Se-, -CR ₃ R _4- , -SiR ₃ R _4- (however, R ₃ and R ₄ are independent of each other. A hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
A ₂₁ to A ₂₈ are independently -CR ₅ =, -N =, -SiR ₅ = (where R ₅ is a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, substituted or non-substituted Substituted aryl group or substituted or unsubstituted heteroaryl group.) The polymer material according to any one of claims 1 to 3, which is represented by the following formula (3).

(In the formula (3), E is a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or a substituted or unsubstituted ring-forming atom having 3 or more and 60 or less. It is a monovalent aromatic heterocyclic group and
m is an integer of 2 or more, and the plurality of Xs and Ys may be independently the same or different. ) A material for an electroluminescent device, which comprises the polymer material according to any one of claims 1 to 4. A liquid composition containing the polymer material according to any one of claims 1 to 4 and a solvent or dispersion medium. A thin film containing the polymer material according to any one of claims 1 to 4. With a pair of electrodes,
An electroluminescence device including one or more organic layers including the polymer material according to any one of claims 1 to 4, which are arranged between the pair of electrodes. The electroluminescence device according to claim 8, wherein at least one of the organic layers is formed by a coating method. With more layers containing quantum dots,
The electroluminescence device according to claim 8 or 9, wherein the quantum dots are inorganic nanoparticles.

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