CN117887043A

CN117887043A - Polymer compound, electroluminescent device material comprising the same, and electroluminescent device

Info

Publication number: CN117887043A
Application number: CN202311327373.5A
Authority: CN
Inventors: 加藤文昭; 权河一; 车淳旻; 菅沼直俊; 小西悠作; 石井宽人; 藤山高广; 辻雅司
Original assignee: Samsung Electronics Co Ltd
Current assignee: Samsung Electronics Co Ltd
Priority date: 2022-10-14
Filing date: 2023-10-13
Publication date: 2024-04-16

Abstract

The present invention relates to polymer compounds, electroluminescent device materials and electroluminescent devices comprising the same. Techniques are provided that can improve the durability (particularly the light emission lifetime) of electroluminescent devices. A polymer compound comprising a structural unit (a) represented by the chemical formula (1). In the chemical formula (1), the definition of each substituent is as described in the detailed description.

Description

Polymer compound, electroluminescent device material comprising the same, and electroluminescent device

Cross reference to related applications

This application claims priority from japanese patent application nos. 2022-165440, filed by the japanese patent office at 10-month 14, and korean patent application No. 10-2023-0136711, filed by the korean intellectual property office at 10-month 12, 2023, the entire contents of which are incorporated herein by reference.

Technical Field

Disclosed are polymeric compounds, and electroluminescent device materials and electroluminescent devices comprising the polymeric compounds.

Background

Research and development of electroluminescent devices (EL devices) are actively underway. In particular, EL devices are expected to be used as inexpensive and large-area full-color display devices of solid-state light emission type or recording light source arrays. The EL device is a light emitting device including a thin film having a thickness of several nanometers to several hundred nanometers between an anode and a cathode. In addition, the EL device generally further includes a hole transporting layer, a light emitting layer, an electron transporting layer, and the like.

Among these, the light emitting layer includes a fluorescent light emitting material and a phosphorescent light emitting material. Phosphorescent light-emitting materials are materials expected to have higher light-emitting efficiency than fluorescent light-emitting materials. In addition, in order to cover a wide color gamut, an RGB light source is required to have an emission spectrum with a narrow half-value width. Although deep blue is particularly desirable for blue, there is currently no device that has a long lifetime and satisfies color purity.

As a method for solving such a problem, there is a light-emitting device using "quantum dots" as a light-emitting material, the "quantum dots" being inorganic light-emitting materials (see patent document 1, japanese patent laid-open No. 2010-199067). Quantum Dots (QDs) are semiconductor materials having a crystal structure with a size of several nanometers and are composed of hundreds to thousands of atoms. Because quantum dots are very small in size, the surface area per unit volume is large. For this reason, most atoms are present on the surface of nanocrystals and exhibit quantum confinement effects. Due to quantum confinement effects, quantum dots are capable of adjusting emission wavelengths by adjusting their sizes, and have many interests because they have characteristics such as improved color purity and high Photoluminescence (PL) luminous efficiency. The basic quantum dot electroluminescent device (QD LED) is a three-layer device comprising a Hole Transport Layer (HTL) and an Electron Transport Layer (ETL) at both sides and a quantum dot light emitting layer.

In order to improve the characteristics of such a quantum dot electroluminescent device, techniques for improving the hole transport property and the hole injection property of a hole transport material have been proposed. For example, japanese patent laid-open publication No.2021-138915 (patent document 2) proposes an arylamine-fluorene alternating copolymer (polymer compound) having hydrocarbon groups in side chains as a hole-transporting material.

According to the arylamine-fluorene alternating copolymer disclosed in patent document 2, the hole injection property of the hole transporting material is improved, the durability (especially the light emission lifetime) is improved, and sufficient light emission efficiency is achieved.

However, there remains a need for the following techniques: it can further improve durability (particularly light emission lifetime) as compared with an electroluminescent device (particularly a quantum dot electroluminescent device) using the hole transport material disclosed in patent document 2.

Disclosure of Invention

Accordingly, the present invention has been made in view of the above circumstances, and an object thereof is to provide a technique that can improve the durability (particularly the light emission lifetime) of an electroluminescent device (particularly a quantum dot electroluminescent device).

The present inventors have conducted intensive studies to solve the above problems. As a result, it was found that the above problems can be solved by using a polymer compound having a specific structure, and the present invention has been completed.

That is, the above object can be achieved by a polymer compound comprising a structural unit (a) represented by chemical formula (1).

[ Chemical formula (1) ]

In the chemical formula (1), a radical of formula (I),

R ¹¹-R¹⁴ and R ²¹-R²⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, wherein R ¹¹ and R ²¹ may be connected to each other to form a ring,

L ¹ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring member atoms,

Ar ¹ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms,

Ar ² is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring member atoms, or may be attached to Ar ¹ to form a ring,

X ¹ is a substituted or unsubstituted aromatic hydrocarbon radical having 6 to 25 ring member atoms,

Y ¹ is a substituted or unsubstituted aromatic hydrocarbon radical having 6 to 25 ring member atoms, an

At least one of X ¹ and Y ¹ is an aromatic hydrocarbon group having 6 to 25 ring member atoms substituted by: alkyl groups having 1 to 14 carbon atoms substituted with a carboxyl group or alkyl groups having 1 to 14 carbon atoms substituted with a group having a carboxyl group.

Drawings

Fig. 1 is a schematic view showing an electroluminescent device according to an embodiment.

Fig. 2 is a cross-sectional view of an exemplary embodiment of a structure of quantum dots.

Detailed Description

The present disclosure relates to techniques for improving the durability of electroluminescent devices with polymer compounds.

The first embodiment provides a polymer compound including a structural unit (a) represented by chemical formula (1):

[ chemical formula (1) ]

In the chemical formula (1), a radical of formula (I),

L ¹ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring member atoms,

Ar ² is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring member atoms or may be attached to Ar ¹ to form a ring,

In this specification, the structural unit (a) represented by the chemical formula (1) is also simply referred to as "structural unit (a)" or "structural unit (a) according to the embodiment".

In addition, a structural unit having the following structure in the "structural unit (a) represented by the chemical formula (1)" is also simply referred to as "structural unit X" or "structural unit X according to the embodiment".

[ Structural unit X ]

Similarly, the structural unit "-Y ¹ -" in the structural unit (a) "represented by the chemical formula (1) is also simply referred to as" structural unit Y "or" structural unit Y according to the embodiment ".

In addition, the polymer compound having the structural unit (a) represented by the chemical formula (1) is also simply referred to as "polymer compound" or "polymer compound according to an embodiment".

A second embodiment provides an electroluminescent device material comprising a polymer compound according to an embodiment.

A third embodiment provides an electroluminescent device comprising: a first electrode, a second electrode, and one or more layers of an organic film disposed between the first electrode and the second electrode, wherein at least one layer of the organic film comprises a polymer compound according to an embodiment. As used herein, the electroluminescent device is simply referred to as an "LED".

The quantum dot electroluminescent device is also simply referred to as "QLED".

The organic electroluminescent device is also simply referred to as "OLED".

As a material constituting the light emitting layer or the carrier transporting layer of the electroluminescent device, various low molecular materials and polymer materials are used. Among these, the polymer material has an advantage of reducing manufacturing costs because there is no need to manufacture a device by a vacuum process like a low molecular material, but it is difficult to obtain sufficient durability (light emission lifetime). Accordingly, development of a polymer material that can improve durability (light emission lifetime) has been desired. The present inventors have conducted intensive studies on means for solving the above problems (improvement of durability (light emission lifetime)).

As a result, by applying the polymer compound having the structural unit (a) represented by the chemical formula (1) to an electroluminescent device, the light emission lifetime can be improved as compared with the case where a known material (for example, a polymer material disclosed in patent document 2) is used. In addition, by applying the polymer compound having the structural unit (a) represented by the chemical formula (1) to an electroluminescent device, external Quantum Efficiency (EQE) can be improved and high light emitting efficiency can be achieved.

While not intending to be bound by a particular theory, the mechanism by which the above-described effects are exerted by the arrangement is believed to be as follows. According to the energy diagram of a typical electroluminescent device, the energy band of the hole transport layer is shifted to match the fermi level of the light emitting layer (in the case of QLED, the light emitting layer comprising quantum dots). When this occurs, an energy gap is generated between the vacuum level (vacuum level at the interface between the hole transport layer and the light emitting layer) and the energy band of the hole transport layer, which causes holes to be trapped on the interface between the hole transport layer and the light emitting layer and generates a load. As a result, the light emission lifetime becomes short. On the other hand, since the polymer compound having the structural unit (a) represented by the chemical formula (1) includes an alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group (-COOH) or an alkyl group having 1 to 14 carbon atoms substituted with a group having a carboxyl group, it has a large dipole moment. Therefore, when the polymer compound is included in the hole transport layer, polarization occurs between the hole transport layer and the light emitting layer, and the vacuum level changes (vacuum level shift). Therefore, since the energy gap between the vacuum level and the hole transport layer becomes small, holes are not trapped, and as a result, holes become more easily moved and efficiently injected into the quantum dots (hole injection property is enhanced). Therefore, durability (light emission lifetime) can be improved.

In addition, in the structural unit (a) represented by the chemical formula (1), the nitrogen atom breaks the conjugated region of the main chain (cleave). Therefore, the triplet energy level of the polymer compound can be increased, the hole mobility (bulk mobility) along the main chain is high, and high current efficiency can be achieved. Therefore, by using the polymer compound (main chain) having the structural unit (a), excellent light-emitting efficiency can be achieved. In addition, since the main chain of the structural unit (a) represented by the chemical formula (1) is broken by a nitrogen atom, the polymer compound according to the embodiment exhibits properties similar to those of a low-molecular compound having an energy level close to that of a quantum dot even when polymerized. Therefore, by using the polymer compound according to the embodiment, an increase in driving voltage is suppressed, and a low driving voltage becomes possible.

Accordingly, an electroluminescent device (particularly a quantum dot electroluminescent device) using a polymer compound having a structural unit (a) represented by chemical formula (1) can exhibit high durability (light emission lifetime), and can achieve sufficient light emission efficiency at a low driving voltage.

In addition, since the polymer compound according to the embodiment has excellent film forming properties and solvent solubility, a film can be formed using a wet (coating) method. Therefore, by using the polymer compound according to the embodiment, it becomes possible to enlarge the area of the electroluminescent device and achieve high productivity. The above effects can be effectively exhibited when the polymer compound is applied to a hole transport layer or a hole injection layer of an EL device, particularly a QLED.

The mechanism described is theoretical and the disclosure is not limited thereby.

Hereinafter, embodiments are described. This disclosure may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In addition, the drawings are exaggerated for better understanding and ease of description, and the dimensional ratios of the constituent elements in the drawings may be different from reality. In addition, when the embodiments of the present disclosure have been described with reference to the drawings, the same reference numerals are given to the same elements in the description of the drawings, and redundant description is omitted.

It will be understood that when an element is referred to as being "on" another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, including "at least one," unless the context clearly indicates otherwise. "at least one (seed)" will not be interpreted as "one (seed)". "or" means "and/or". As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.

As used herein, "about" or "approximately" includes the stated values and is meant to be within an acceptable range of deviation from the particular values as determined by one of ordinary skill in the art in view of the measurements in question and the errors associated with the measurement of the particular quantities (i.e., limitations of the measurement system). For example, "about" may mean within one or more standard deviations, or within ±5%, relative to the stated value.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the present disclosure and relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

Exemplary embodiments are described herein with reference to cross-sectional illustrations that are schematic illustrations of idealized embodiments. As such, differences from the illustrated shapes as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, the embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, an area illustrated or described as flat may typically have rough and/or nonlinear features. Further, the acute angles illustrated may be rounded. Accordingly, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the claims.

In this specification, unless specifically stated otherwise, the operational and physical properties are measured under the following conditions: room temperature (about 20 ℃ or higher and about 25 ℃ or lower)/relative humidity about 40% RH or greater and about 50% RH or less.

In this specification, "x and y are each independently" means that x and y may be the same or different.

In this specification, "group derived from compound z" or "group derived from compound z" refers to the following group: the hydrogen atom directly bonded to the ring member atom from the cyclic structure (when "compound z" is a cyclic compound) is removed as much as the valence used to represent the free valence.

In this specification, the number of ring member atoms refers to the number of atoms constituting the corresponding ring itself of a compound (e.g., a monocyclic compound, a condensed compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) having a structure in which atoms are bonded in a ring (e.g., a monocyclic ring, a condensed ring, and a ring group). Atoms that do not form a ring (e.g., hydrogen atoms that terminate bonds to atoms that form a ring) or atoms that are included in a substituent when the ring is substituted with a substituent are not included in the number of ring member atoms. The number of ring member atoms described below is considered the same unless specifically stated otherwise.

For example, the benzene ring has 6 ring member atoms, the naphthalene ring has 10 ring member atoms, the pyridine ring has 6 ring member atoms, and the furan ring has 5 ring member atoms.

When the benzene ring is substituted with a substituent such as an alkyl group, the number of carbon atoms of the alkyl group is not included in the number of ring member atoms of the benzene ring. Thus, the number of ring member atoms of the benzene ring taken by the alkyl group is 6. In addition, when the naphthalene ring is substituted with an alkyl group as a substituent, for example, the number of atoms of the alkyl group is not included in the number of ring member atoms of the naphthalene ring. Thus, the number of ring member atoms of the naphthalene ring substituted with an alkyl group is 10.

For example, the number of hydrogen atoms or atoms constituting substituents bonded to the pyridine ring is not included in the number of ring member atoms of the pyridine ring. Thus, the number of ring member atoms of the pyridine ring to which the hydrogen atom or substituent is bonded is 6.

As used herein, "substituted" means substituted as follows, unless specifically stated otherwise: (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) hydroxyalkyl, (C2-C20) alkoxyalkyl, (C1-C20) alkoxy, (C4-C20) cycloalkoxy, (C2-C20) alkenyl, (C2-C20) alkynyl, (C0-C20) amino, (C6-C20) aryl, (C6-C20) aryloxy, (C1-C20) alkylthio, (C3-C20) cycloalkylthio, (C6-C20) arylthio, (C2-C20) alkoxycarbonyl, (C7-C20) aryloxycarbonyl, hydroxy (-OH), carboxy (-COOH), thiol (-SH), cyano (-CN), halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), or combinations thereof. On the other hand, when a group is substituted, the following substituted forms are excluded: wherein substituents are included in the definition prior to substitution. For example, when the substituent is an alkyl group, the alkyl group as the substituent is not substituted with an alkyl group.

Here, the alkyl group as a substituent may be a linear or branched alkyl group, for example, a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms. In particular, the alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, 1, 3-dimethylbutyl, 1-isopropyl propyl, 1, 2-dimethylbutyl, n-heptyl, 1, 4-dimethylpentyl, 3-ethylpentyl, 2-methyl-1-isopropyl, 1-ethyl-3-methylbutyl, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropyl butyl, 2-methyl-1-isopropyl butyl, 1-tert-butyl-2-methylpropyl, n-nonyl, 3, 5-trimethylhexyl, n-decyl, isodecyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, nonadecyl, eicosyl, etc.

As substituents, cycloalkyl groups may include, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

Hydroxyalkyl groups can be, for example, alkyl groups (e.g., hydroxymethyl, hydroxyethyl) substituted with 1-3 (desirably 1 or 2, and particularly desirably 1) hydroxy groups.

Alkoxyalkyl groups may be, for example, alkyl groups substituted with 1 to 3 (desirably 1 or 2, and particularly desirably 1) alkoxy groups.

The alkoxy group as a substituent may be a linear or branched alkoxy group, but is desirably a linear alkoxy group having 1 to 20 carbon atoms or a branched alkoxy group having 3 to 20 carbon atoms. For example, the alkoxy group may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, 2-ethylhexyloxy, 3-ethylpentyloxy and the like.

The cycloalkoxy group as a substituent may be, for example, cyclopropyloxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, or the like.

Alkenyl groups as substituents may include, for example, vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 5-heptenyl, 1-octenyl, 3-octenyl, 5-octenyl and the like.

Alkynyl groups as substituents may include, for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 1-heptynyl, 2-heptynyl, 5-heptynyl, 1-octynyl, 3-octynyl, 5-octynyl and the like.

The aryl group as a substituent may desirably be an aryl group having 6 to 30 carbon atoms. Aryl groups may include, for example, phenyl, naphthyl, biphenyl, fluorenyl, anthracenyl, pyrenyl, azulenyl, acenaphthylenyl, terphenyl, and phenanthryl.

Aryloxy groups as substituents may include, for example, phenoxy and naphthoxy.

Alkylthio as a substituent may include, for example, methylthio, ethylthio, propylthio, pentylthio, hexylthio, octylthio, dodecylthio and the like.

The cycloalkylthio group as a substituent may include, for example, cyclopentylthio and cyclohexylthio.

Arylthio groups as substituents may include, for example, phenylthio, naphthylthio, and the like.

The alkoxycarbonyl group as a substituent may include, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, and the like.

The aryloxycarbonyl group as a substituent may include, for example, phenoxycarbonyl, naphthyloxycarbonyl, and the like.

[ Polymer Compound ]

Structural Unit (A)

The polymer compound according to the embodiment has a structural unit (a) represented by chemical formula (1). The polymer compound having such a structural unit (a) has excellent hole injection property in a vector point and can improve the durability (light emission lifetime) of an electroluminescent device. In addition, high current efficiency and low driving voltage can be achieved. The polymer compound according to the embodiment may include only one type of structural unit (a), or may include two or more types of structural units (a). On the other hand, the plurality of structural units (A) may exist in a block form, a random form, an alternating form, or a periodic form.

[ Chemical formula (1) ]

In chemical formula (1), the structural unit X ((structural unit on the left side of chemical formula (1); structural unit composed of a nitrogen atom between two phenylene groups)) constitutes the polymer compound according to the embodiment similarly, in chemical formula (1), the structural unit Y (structural unit on the right side of chemical formula (1); structural unit represented by "Y ¹") constitutes the polymer compound according to the embodiment.

In chemical formula (1), X ¹ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms, Y ¹ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms, wherein at least one of X ¹ and Y ¹ is an aromatic hydrocarbon group having 6 to 25 ring member atoms substituted as follows: alkyl groups having 1 to 14 carbon atoms substituted with a carboxyl group or alkyl groups having 1 to 14 carbon atoms substituted with a group having a carboxyl group.

In this manner, in the structural unit (a) according to the embodiment, X ¹ and/or Y ¹ has an alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group or an alkyl group having 1 to 14 carbon atoms substituted with a group having a carboxyl group (in this specification, an alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group or an alkyl group having 1 to 14 carbon atoms substituted with a group having a carboxyl group may be simply referred to as "alkyl group substituted with a carboxyl group" or simply as "substituent (a)"). Therefore, the polymer compound according to the embodiment has a large dipole moment, and the hole injection property of the hole transport layer including the same is improved. Therefore, when used in an electroluminescent device, the durability (light emission lifetime) of the device can be improved. On the other hand, when the substituent (a) is included in both of X ¹ and Y ¹, the substituent (a) may be the same or different.

The alkyl group having 1 to 14 carbon atoms included in the alkyl group substituted with a carboxyl group (substituent (a)) according to the embodiment may be a straight-chain or branched alkyl group, for example, 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, tert-pentyl group, neopentyl group, 1, 2-dimethylpropyl group, n-hexyl group, isohexyl group, 1, 3-dimethylbutyl group, 1-isopropyl propyl group, 1, 2-dimethylbutyl group, n-heptyl group, 1, 4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropyl butyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3, 5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, and the like.

Here, the alkyl group included in the alkyl group substituted with a carboxyl group may have a carbon number of 1 to 13, desirably 3 to 12, more desirably 5 to 12, and particularly desirably 7 to 12 from the viewpoints of improvement in durability, excellent solvent solubility, and improved film forming property when a film is formed by a wet (coating) method. In addition, by making the alkyl group constituting the substituent (a) a relatively long-chain alkyl group, the glass transition temperature (T _g) of the polymer compound is in an appropriate range which is desirable in terms of manufacturing an electroluminescent device.

In addition, from the viewpoint of improving durability, the alkyl group included in the substituent (a) (the alkyl group constituting the substituent (a)) is desirably linear.

In addition, in the alkyl group, the substitution position of the carboxyl group is not particularly limited, but desirably at the terminal. That is, the alkyl group substituted with a carboxyl group (substituent (a)) according to the embodiment desirably has a structure represented by chemical formula (i):

[ formula (i) ]

***-C_tH_2t-(Z¹)_u-COOH (i)

In the chemical formula (i), t represents an integer of 1 to 14, u is 0 or 1, z ¹ represents an organic group other than an alkylene group, and is bonded to an aromatic hydrocarbon group having 6 to 25 ring member atoms constituting X ¹ or Y ¹.

For improving durability (especially light emission lifetime), t is desirably an integer of 1 to 13, more desirably 3 to 12, particularly desirably 5 to 12, and most desirably 7 to 12.

In addition, from the viewpoint of further improving durability (particularly, light emission lifetime), the following is desirable: u is 0 (i.e., there is no Z ¹). On the other hand, from the viewpoint of improving External Quantum Efficiency (EQE) and light emission efficiency, the following is desirable: u is 1 (i.e., has Z ¹).

When u is 1, the organic group (divalent organic group) as Z ¹ is not particularly limited as long as it is a group including a carbon atom other than an alkylene group, but is, for example, a substituted or unsubstituted alkenylene group having 2 to 14 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 14 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 16 carbon atoms, and a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

Examples of the alkenylene group having 2 to 14 carbon atoms may include a vinylene group, a 1-propenylene group, a 2-butenylene group, a 1, 3-butadienylene group, a 2-pentenylene group, an isopropenylene group, and the like.

Examples of the alkynylene group having 2 to 14 carbon atoms may include ethynylene group, 1-propynylene group, 1-butynylene group, 1-pentynylene group, 1-hexynylene group, 2-butynylene group, 2-pentynylene group and the like.

Examples of the cycloalkylene group having 3 to 16 carbon atoms may include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and the like.

Examples of the arylene group having 6 to 20 carbon atoms may include o-phenylene, m-phenylene, p-phenylene, naphthalenediyl, anthracenediyl, tetracenediyl, pyrenediyl, biphenyldiyl and the like.

Among them, the organic group as Z ¹ may desirably be a substituted or unsubstituted alkenylene group having 2 to 14 carbon atoms, a more desirably substituted or unsubstituted alkenylene group having 2 to 8 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 6 carbon atoms, or a substituted or unsubstituted vinylene group.

As will be described in detail below, the polymer compound according to the embodiment may be formed into a film by a coating method, but at this time, the alkenylene, alkynylene, cycloalkylene, and arylene groups constituting Z ¹ may be unsubstituted from the viewpoint of improving film forming properties and durability (especially light emission lifetime) by forming a uniform film. In addition, in other embodiments, alkenylene groups or the like constituting Z ¹ may be substituted, and in this case, the same substituents as those described above for the "substituted" may be applied. At this time, the substituent for the alkenylene group as Z ¹ may desirably be selected from the group consisting of an alkoxy group, an amino group, a hydroxyl group (-OH), a thiol group (-SH), and a cyano group (-CN), and more desirably a cyano group.

In the chemical formula (1), X ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms. Herein, "a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms" means any one of the following: an aromatic hydrocarbon group having 6 to 25 ring member atoms substituted with substituent (a); an aromatic hydrocarbon group having 6 to 25 ring member atoms substituted with a substituent other than the substituent (a); or an unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms. Meanwhile, in this specification, "a substituent other than the substituent (a)" refers to a substituent other than an alkyl group substituted with a carboxyl group (-COOH) among the substituents described above for "substituted".

Here, the aromatic hydrocarbon group having 6 to 25 ring member atoms may include, in particular, monovalent groups derived from aromatic hydrocarbons such as benzene, naphthalene, anthracene, pyrene, pentalene, indene, azulene, heptene, acenaphthylene, phenalene, phenanthrene, biphenyl, terphenyl, tetrabiphenyl, fluorene, and 9,9' -spirodi [ fluorene ].

When X ¹ is an aromatic hydrocarbon group substituted with an alkyl group substituted with a carboxyl group (substituent (a)), the aromatic hydrocarbon group may desirably be a monovalent group derived from a compound selected from benzene, biphenyl, terphenyl, and fluorene (a group selected from phenyl, biphenyl, terphenyl, and fluorenyl).

In addition, in the chemical formula (1), when X ¹ is an aromatic hydrocarbon group substituted with the substituent (a), X ¹ may be one of the groups represented by chemical formulas (3-1) to (3-12):

[ formulae (3-1) to (3-12) ]

In the chemical formulas (3-1) to (3-12),

Each R ³⁰¹-R³¹⁵ is independently a substituted or unsubstituted alkylene group having 1 to 14 carbon atoms and is bonded to a nitrogen atom (the nitrogen atom bonded to Ar ¹).

In addition, in the chemical formulas (3-10) to (3-12), R ³¹⁰ and R ³¹¹、R³¹², and R ³¹³、R³¹⁴ and R ³¹⁵ may be the same or different, respectively. Desirably, R ³¹⁰ and R ³¹¹、R³¹² and R ³¹³、R³¹⁴, and R ³¹⁵ can be the same.

The alkylene group having 1 to 14 carbon atoms as R ³⁰¹-R³¹⁵ is not particularly limited, but is, for example, a straight-chain or branched alkylene group such as methylene, ethylene, trimethylene, propylene, 1-dimethylmethylene, n-butylene, isobutyl, sec-butylene, tert-butylene, n-pentylene, isopentylene, tert-pentylene, neopentylene, 1, 2-dimethylpropylene, n-hexylene, isohexylene, 1, 3-dimethylbutylene, 1-isopropylene, 1, 2-dimethylbutylene, n-heptylene, 1, 4-dimethylpentylene, 3-ethylpentylene, 2-methyl-1-isopropylene, 1-ethyl-3-methylbutylene, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropylbutylene, 2-methyl-1-isopropylbutylene, 1-tert-butyl-2-methylpropylene, n-nonylene, 3, 5-trimethylhexylene, n-decylene, isodecylene, 1-undecylene, n-decylene, n-tridecylylene, and the like.

Here, the alkylene group as R ³⁰¹-R³¹⁵ may have desirably 3 to 13 carbon atoms, more desirably 5 to 12 carbon atoms, and particularly desirably 7 to 10 carbon atoms from the viewpoint of improving durability.

In addition, the alkylene group as R ³⁰¹-R³¹⁵ is desirably linear from the viewpoint of improving durability.

In the chemical formula (1), when X ¹ is an aromatic hydrocarbon group substituted with the substituent (a), X ¹ may desirably be any one of the groups represented by the chemical formulas (3-10) to (3-12). When X ¹ has these structures, durability (especially light emission lifetime), external Quantum Efficiency (EQE), and light emission efficiency are further improved. Among them, the following are desirable: x ¹ is a group represented by the formula (3-10).

On the other hand, when X ¹ is an aromatic hydrocarbon group that is not substituted with an alkyl group substituted with a carboxyl group (substituent (a)), the aromatic hydrocarbon group may desirably be a monovalent group derived from: the compound is selected from benzene, biphenyl, terphenyl, and fluorene substituted or unsubstituted with substituents other than substituent (a). X ¹ may more desirably be a monovalent group derived from a compound of the formula: the compound is selected from benzene, biphenyl, and fluorene substituted or unsubstituted with substituents other than substituent (a). X ¹ may particularly desirably be a monovalent group derived from benzene or fluorene substituted or unsubstituted with a substituent other than the substituent (a) (phenyl or fluorenyl substituted or unsubstituted with a substituent other than the substituent (a)).

In addition, from the viewpoint of improving durability, in the chemical formula (1), when X ¹ is an aromatic hydrocarbon group unsubstituted by the substituent (a), the following is desirable: which is any one of the groups represented by chemical formulas (4-1) to (4-4).

[ Formulae (4-1) to (4-4) ]

In the chemical formulas (4-1) to (4-4),

R ⁴⁰¹-R⁴¹³ is each independently an alkyl group having 1 to 14 carbon atoms which is substituted or unsubstituted with a substituent other than a carboxyl group (-COOH),

A is 0, 1, 2, 3,4 or 5,

B. d, and f are each independently 0, 1, 2, or 3,

C. e, and g are each independently 0,1, 2, 3, or 4, and

When any of a, b, c, d, e, f, and g is 2 or greater, each R ⁴⁰¹, each R ⁴⁰⁴, each R ⁴⁰⁵, each R ⁴⁰⁸, each R ⁴⁰⁹, each R ⁴¹², or each R ⁴¹³ may be the same or different and are bonded to a nitrogen atom (a nitrogen atom bonded to Ar ¹).

In addition, in the chemical formulas (4-2) to (4-4), R ⁴⁰² and R ⁴⁰³、R⁴⁰⁶ and R ⁴⁰⁷、R⁴¹⁰ and R ⁴¹¹ may be the same or different, respectively. Desirably, R ⁴⁰² and R ⁴⁰³、R⁴⁰⁶ and R ⁴⁰⁷、R⁴¹⁰, and R ⁴¹¹ can be the same as each other.

In the chemical formulas (4-1) to (4-4), a, b, c, d, e, f, or g is 0 means that the corresponding R ⁴⁰¹、R⁴⁰⁴、R⁴⁰⁵、R⁴⁰⁸、R⁴⁰⁹、R⁴¹², or R ⁴¹³ is not present. That is, the ring member atom to which substituent R ⁴⁰¹、R⁴⁰⁴、R⁴⁰⁵、R⁴⁰⁸、R⁴⁰⁹、R⁴¹², or R ⁴¹³, may be bound is unsubstituted, which means that a hydrogen atom is bound to the ring member atom.

A may desirably be 0, 1, or 2, more desirably 0 or 1, and particularly desirably 1. In addition, when a is 1, the substitution position of R ⁴⁰¹ is desirably para (p-position or 4-position) with respect to the bond to the nitrogen atom (the nitrogen atom bound to Ar ¹). b. c, d, e, f, and g can each independently be desirably 0, 1, or 2, more desirably 0 or 1, and particularly desirably 0.

The alkyl group having 1 to 14 carbon atoms as R ⁴⁰¹-R⁴¹³ is not particularly limited, but is a linear or branched alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, 1, 3-dimethylbutyl, 1-isopropyl propyl, 1, 2-dimethylbutyl, n-heptyl, 1, 4-dimethylpentyl, 3-ethylpentyl, 2-methyl-1-isopropyl propyl, 1-ethyl-3-methylbutyl, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropyl butyl, 2-methyl-1-isopropyl butyl, 1-tert-butyl-2-methylpropyl, n-nonyl, 3, 5-trimethylhexyl, n-decyl, isodecyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, n-tetradecyl and the like.

Here, the alkyl group as R ⁴⁰¹-R⁴¹³ has desirably 1 to 12 carbon atoms, and more desirably 1 to 8 carbon atoms from the viewpoint of improving durability. In particular, the following is desirable: each R ⁴⁰¹-R⁴¹³ is independently an alkyl group having a carbon number within the above range.

In addition, the alkyl group as R ⁴⁰¹-R⁴¹³ is desirably linear from the viewpoint of improving durability.

In the chemical formula (1), when X ¹ is an aromatic hydrocarbon group unsubstituted by the substituent (a), the following is desirable from the viewpoint of improving durability (especially light emission lifetime): x ¹ is any one of the groups represented by the above formulas (4-1) to (4-3). The following is more desirable: x ¹ is a group represented by the formula (4-1) or (4-3).

In the chemical formula (1), Y ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms. Here, "a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms" means any one of the following: an aromatic hydrocarbon group having 6 to 25 ring member atoms substituted with substituent (a); an aromatic hydrocarbon group having 6 to 25 ring member atoms substituted with a substituent other than the substituent (a); or an unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms.

Here, the aromatic hydrocarbon group having 6 to 25 ring member atoms may include, in particular, divalent groups derived from aromatic hydrocarbons such as benzene, naphthalene, anthracene, pyrene, pentalene, indene, azulene, heptene, acenaphthylene, phenalene, phenanthrene, biphenyl, terphenyl, tetrabiphenyl, fluorene, and 9,9' -spirodi [ fluorene ].

When Y ¹ is an aromatic hydrocarbon group substituted with an alkyl group substituted with a carboxyl group (substituent (a)), the aromatic hydrocarbon group may desirably be a divalent group derived from benzene or fluorene (phenylene or fluorenylene).

In addition, in the chemical formula (1), when Y ¹ is an aromatic hydrocarbon group substituted with the substituent (a), Y ¹ may desirably be any one of the groups represented by chemical formulas (5-1) to (5-9):

[ formulae (5-1) to (5-9) ]

In the chemical formulas (5-1) to (5-9), each R ⁵⁰¹-R⁵¹⁵ is independently a substituted or unsubstituted alkylene group having 1 to 14 carbon atoms.

In addition, in the chemical formulas (5-1) to (5-3) and (5-7) to (5-9), R ⁵⁰¹ and R ⁵⁰²、R⁵⁰³ and R ⁵⁰⁴、R⁵⁰⁵ and R ⁵⁰⁶、R⁵¹⁰ and R ⁵¹¹、R⁵¹² and R ⁵¹³、R⁵¹⁴ and R ⁵¹⁵ may be the same or different, respectively. Desirably, R ⁵⁰¹ and R ⁵⁰²、R⁵⁰³ and R ⁵⁰⁴、R⁵⁰⁵ and R ⁵⁰⁶、R⁵¹⁰ and R ⁵¹¹、R⁵¹² and R ⁵¹³、R⁵¹⁴ and R ⁵¹⁵ may be the same.

The alkylene group having 1 to 14 carbon atoms as R ⁵⁰¹-R⁵¹⁵ is not particularly limited, but is, for example, a straight-chain or branched alkylene group such as methylene, ethylene, trimethylene, propylene, 1-dimethylmethylene, n-butylene, isobutyl, sec-butylene, tert-butylene, n-pentylene, isopentylene, tert-pentylene, neopentylene, 1, 2-dimethylpropylene, n-hexylene, isohexylene, 1, 3-dimethylbutylene, 1-isopropylene, 1, 2-dimethylbutylene, n-heptylene, 1, 4-dimethylpentylene, 3-ethylpentylene, 2-methyl-1-isopropylene, 1-ethyl-3-methylbutylene, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropylbutylene, 2-methyl-1-isopropylbutylene, 1-tert-butyl-2-methylpropylene, n-nonylene, 3, 5-trimethylhexylene, n-decylene, isodecylene, 1-undecylene, n-decylene, n-tridecylylene, and the like.

Here, the alkylene group as R ⁵⁰¹-R⁵¹⁵ may have desirably 1 to 13 carbon atoms, more desirably 3 to 12 carbon atoms, particularly desirably 5 to 12 carbon atoms, and particularly desirably 7 to 12 carbon atoms from the viewpoint of improving durability.

In addition, the alkylene group as R ⁵⁰¹-R⁵¹⁵ is desirably linear from the viewpoint of improving durability.

In the chemical formula (1), when Y ¹ is an aromatic hydrocarbon group substituted with the substituent (a), Y ¹ is desirably any one of the groups represented by the chemical formulas (5-1) to (5-3). From the viewpoint of further improving durability (especially light emission lifetime), the following is desirable: y ¹ is a group represented by the formula (5-1). On the other hand, Y ¹ is desirably a group represented by the chemical formula (5-2) or (5-3) from the viewpoint of improving External Quantum Efficiency (EQE) and light-emitting efficiency.

On the other hand, when Y ¹ is an aromatic hydrocarbon group that is not substituted with an alkyl group substituted with a carboxyl group (substituent (a)), the aromatic hydrocarbon group may desirably be a divalent group derived from: the compound is selected from benzene, biphenyl, terphenyl, and fluorene substituted or unsubstituted with substituents other than substituent (a). Y ¹ is more desirably a divalent group derived from biphenyl or fluorene substituted or unsubstituted with substituents other than substituent (a). The following is particularly desirable: y ¹ is a divalent group derived from fluorene that is unsubstituted or substituted with a substituent other than substituent (a) (fluorenylene that is unsubstituted or substituted with a substituent other than substituent (a)).

In addition, from the viewpoint of improving durability, in the chemical formula (1), when Y ¹ is an aromatic hydrocarbon group unsubstituted by the substituent (a), the following is desirable: y ¹ is a group represented by the formula (6-1).

[ Chemical formula (6-1) ]

In the chemical formula (6-1),

R ⁶⁰¹-R⁶⁰⁴ is each independently an alkyl group having 1 to 14 carbon atoms which is substituted or unsubstituted with a substituent other than a carboxyl group (-COOH),

H and i are each independently 0, 1, 2, or 3, and

When h or i is 2 or more, each R ⁶⁰³ or each R ⁶⁰⁴ may be the same or different.

In addition, in the chemical formula (6-1), R ⁶⁰¹ and R ⁶⁰² may be the same or different. Desirably, R ⁶⁰¹ and R ⁶⁰² may be identical to each other.

In formula (6-1), h or i is 0 means that the corresponding R ⁶⁰³ or R ⁶⁰⁴ is absent. That is, the ring member atom to which substituent R ⁶⁰³ or R ⁶⁰⁴ may be bound is unsubstituted, which means that a hydrogen atom is bound to the ring member atom.

H and i may each independently desirably be 0, 1, or 2, more desirably 0 or 1, and particularly desirably 0.

The alkyl group having 1 to 14 carbon atoms as R ⁶⁰¹-R⁶⁰⁴ is not particularly limited, but is a linear or branched alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, 1, 3-dimethylbutyl, 1-isopropyl propyl, 1, 2-dimethylbutyl, n-heptyl, 1, 4-dimethylpentyl, 3-ethylpentyl, 2-methyl-1-isopropyl propyl, 1-ethyl-3-methylbutyl, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropyl butyl, 2-methyl-1-isopropyl butyl, 1-tert-butyl-2-methylpropyl, n-nonyl, 3, 5-trimethylhexyl, n-decyl, isodecyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, n-tetradecyl and the like.

Here, the alkyl group as R ⁶⁰¹-R⁶⁰⁴ may have desirably 1 to 12 carbon atoms, more desirably 1 to 10 carbon atoms, and particularly desirably 2 to 6 carbon atoms from the viewpoint of improving durability. In particular, the following is desirable: r ⁶⁰¹ and R ⁶⁰² are each independently an alkyl group having a carbon number within the above range.

In addition, the alkyl group as R ⁶⁰¹-R⁶⁰⁴ may desirably be linear from the viewpoint of improving durability.

In the chemical formula (1), the alkyl group substituted with a carboxyl group (substituent (a)) may be included in the following: only X ¹, only Y ¹, or both X ¹ and Y ¹. From the viewpoint of improving durability (especially light emission lifetime), the substituent (a) is desirably included only in X ¹, or only in Y ¹, and more desirably included only in X ¹. For example, in chemical formula (1), X ¹ is an aromatic hydrocarbon group having 6 to 25 ring member atoms substituted as follows: an alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group or an alkyl group having 1 to 14 carbon atoms substituted with a group having a carboxyl group (substituent (a)), and in this case, Y ¹ is an aromatic hydrocarbon group having 6 to 25 ring member atoms substituted or unsubstituted with substituents other than the following: alkyl having 1 to 14 carbon atoms substituted with a carboxyl group or alkyl having 1 to 14 carbon atoms substituted with a group having a carboxyl group (substituent (a)).

Similarly, when an alkyl group substituted with a carboxyl group (substituent (a)) is present in a side chain of a polymer compound, it is considered as follows. That is, in a quantum dot electroluminescent device having a hole transport layer including the polymer compound and a light emitting layer including quantum dots, a substituent (a) of a side chain of the polymer compound in the hole transport layer and the quantum dots included in the light emitting layer are more closely present together, and a hydrocarbon group of the side chain of the polymer compound closely interacts with the quantum dots. Accordingly, holes are efficiently injected into the quantum dots (hole injection property is further improved), and durability (light emission lifetime) can be further improved.

In some embodiments, the following is desirable: r ¹¹-R¹⁴、R²¹-R²⁴、L¹、Ar¹ in the chemical formula (1), and Ar ² do not have an alkyl group substituted with a carboxyl group (substituent (a)).

In formula (1), L ¹ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms; or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring member atoms.

Here, the aromatic hydrocarbon group may be specifically a divalent group derived from an aromatic hydrocarbon such as benzene (phenylene), naphthalene, anthracene, pyrene, pentalene, indene, azulene, heptene, acenaphthene, phenalene, phenanthrene, biphenyl, terphenyl, tetrabiphenyl, fluorene, and 9,9' -spirodi [ fluorene ]. In addition, the aromatic heterocyclic group may be specifically a divalent group derived from a heterocyclic aromatic compound such as acridine, phenazine, benzoquinoline, benzisoquinoline, phenanthridine, phenanthroline, anthraquinone, fluorenone, dibenzofuran, dibenzothiophene, carbazole, imidazophenanthridine, benzimidazole benzophenanthridine, azadibenzofuran, azacarbazole, azadibenzothiophene, diazadibenzofuran, diazacarbazole, diazadibenzothiophene, xanthone, thioxanthone, pyridine, quinoline, and anthracoquinoline.

Among these, L ¹ may desirably be a divalent group derived from a substituted or unsubstituted compound selected from benzene, biphenyl, terphenyl, tetrabiphenyl, and fluorene, and the following are more desirable: which is a substituted or unsubstituted divalent radical derived from benzene or biphenyl (substituted or unsubstituted phenylene or biphenylene).

In addition, in the chemical formula (1), L ¹ may desirably be one of the groups represented by the chemical formulas (7-1) to (7-24):

[ formulae (7-1) to (7-24) ]

In the chemical formulas (7-1) to (7-24), are bonded to a nitrogen atom, and are bonded to Ar ¹.

In addition, L ¹ may be any one of the groups represented by formulas (7-1) to (7-3) and formulas (7-13) to (7-16) (i.e., a substituted or unsubstituted phenylene group). L ¹ may desirably be any one of the groups represented by chemical formula (7-1) and chemical formulas (7-13) to (7-16) (i.e., a substituted or unsubstituted p-phenylene group). The following is particularly desirable: l ¹ is a group represented by the formula (7-1) (i.e., unsubstituted p-phenylene). With such L ¹, higher hole injection properties (resulting in high durability) and good film formation properties can be achieved.

In the chemical formula (1), ar ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms. At this time, ar ¹ may form a ring with Ar ². On the other hand, when Ar ¹ forms a ring with Ar ², ar ¹ is a trivalent group. Ar ¹ is a divalent group when Ar ¹ does not form a ring with Ar ².

Here, the aromatic hydrocarbon group as Ar ¹ is not particularly limited. When Ar ¹ does not form a ring with Ar ², specific examples of Ar ¹ include the same divalent groups derived from aromatic hydrocarbons having 6 to 25 ring member atoms described above for L ¹. In addition, when Ar ¹ forms a ring with Ar ², the divalent groups derived from aromatic hydrocarbons having 6 to 25 ring member atoms described above for L ¹ can be converted to trivalent groups.

Among these, ar ¹ is desirably a substituted or unsubstituted divalent or trivalent group derived from a compound selected from benzene, biphenyl and fluorene, more desirably a substituted or unsubstituted divalent or trivalent group derived from benzene or biphenyl, and particularly desirably a divalent (e.g., o-, m-, p-phenylene) or trivalent group (e.g., 1,3, 4-phenylene) derived from substituted or unsubstituted benzene. In addition, ar ¹ is more desirably a substituted or unsubstituted p-phenylene group or a1, 3, 4-phenylene group, and most desirably a substituted or unsubstituted 1,3, 4-phenylene group. That is, the following is desirable: ar ¹ forms a ring with Ar ².

With such Ar ¹, higher hole injection properties (resulting in high durability) and good film formation properties can be achieved. In addition, durability and luminous efficiency can be improved in good balance.

Meanwhile, a substituent that may be present when any one of the hydrogen atoms of Ar ¹ is substituted is not particularly limited, and the same substituent as that described above for "substituted" may be applied. In an embodiment, ar ¹ is unsubstituted.

In formula (1), ar ² is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms; or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring member atoms. At this time, ar ² may form a ring with Ar ¹. On the other hand, when Ar ² forms a ring with Ar ¹, ar ² is a divalent group. Ar ² is a monovalent group when Ar ² does not form a ring with Ar ¹.

Here, the aromatic hydrocarbon group and the aromatic heterocyclic group as Ar ² are not particularly limited. When Ar ² does not form a ring with Ar ¹, a specific example of Ar ² can be exemplified by: the divalent radical from an aromatic hydrocarbon having 6 to 25 ring member atoms described for L ¹ is converted to a monovalent radical. Similarly, in the above case, an aromatic heterocyclic group as Ar ² can be exemplified by: the divalent radical from a heterocyclic aromatic compound having 5 to 25 ring member atoms described for L ¹ is converted to a monovalent radical. In addition, when Ar ² forms a ring with Ar ¹, the same divalent group derived from an aromatic hydrocarbon having 6 to 25 ring member atoms described for L ¹ may be used. Similarly, in the above case, the aromatic heterocyclic group as Ar ² may be exemplified by the same divalent groups derived from heterocyclic aromatic compounds having 5 to 25 ring member atoms described for L ¹.

Among these, ar ² is desirably a substituted or unsubstituted monovalent or divalent group derived from a compound selected from benzene, biphenyl, and fluorene, more desirably a substituted or unsubstituted monovalent or divalent group derived from benzene or biphenyl, particularly desirably a monovalent or divalent group derived from substituted or unsubstituted benzene (e.g., o-, m-, p-phenylene), and most desirably a substituted or unsubstituted o-phenylene. That is, ar ² desirably forms a ring with Ar ¹.

With such Ar ², higher hole injection properties (resulting in high durability) and good film formation properties can be achieved. In addition, durability and luminous efficiency can be improved in good balance.

Meanwhile, a substituent that may be present when any one of the hydrogen atoms of Ar ² is substituted is not particularly limited, and the same substituent as that described above for "substituted" may be applied. In an embodiment, ar ² is unsubstituted.

As described above, ar ¹ and Ar ² desirably combine with each other to form a ring.

In this way, when Ar ¹ and Ar ² form a ring, higher hole injection property can be obtained, durability (particularly, light emission lifetime) can be improved, and good film forming property can be achieved.

When Ar ¹ and Ar ² form a ring, the ring structure formed by Ar ¹ and Ar ² is not particularly limited, but the following is desirable: ar ¹ and Ar ² combine with each other to form a carbazole ring. Further, in an embodiment, ar ¹-N(Ar²)(X¹ in chemical formula (1) has a structure selected from the following groups.

[ Formulas (8-1) and (8-2) ]

In the chemical formulas (8-1) and (8-2),

R ⁸⁰¹-R⁸⁰⁴ is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryl group, or a halogen atom,

J and l are each independently 0, 1, 2, or 3,

K and m are each independently 0, 1, 2,3, or 4, and

When any one of j, k, L, and m is 2 or more, each R ⁸⁰¹, each R ⁸⁰², each R ⁸⁰³, or each R ⁸⁰⁴ may be the same or different, X ¹ is the same as defined in formula (1), and is bonded to L ¹.

The alkyl group as R ⁸⁰¹-R⁸⁰⁴ may be a straight-chain or branched alkyl group, for example a straight-chain alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms. For example, the alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, 1, 3-dimethylbutyl, 1-isopropyl propyl, 1, 2-dimethylbutyl, n-heptyl, 1, 4-dimethylpentyl, 3-ethylpentyl, 2-methyl-1-isopropyl, 1-ethyl-3-methylbutyl, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropyl butyl, 2-methyl-1-isopropyl butyl, 1-tert-butyl-2-methylpropyl, n-nonyl, 3, 5-trimethylhexyl, n-decyl, isodecyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, nonadecyl, eicosyl, etc.

Cycloalkyl groups as R ⁸⁰¹-R⁸⁰⁴ may desirably be cycloalkyl groups having 3 to 16 carbon atoms. In particular, it may include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

The alkoxy group as R ⁸⁰¹-R⁸⁰⁴ may be a straight-chain or branched alkoxy group, but is desirably a straight-chain alkoxy group having 1 to 20 carbon atoms or a branched alkoxy group having 3 to 20 carbon atoms. For example, the alkoxy group may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, 2-ethylhexyloxy, 3-ethylpentyloxy and the like.

The cycloalkoxy group as R ⁸⁰¹-R⁸⁰⁴ may desirably be a cycloalkoxy group having 3 to 16 carbon atoms. For example, it may include cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, and the like.

The aryl group as R ⁸⁰¹-R⁸⁰⁴ may desirably be an aryl group having 6 to 30 carbon atoms. For example, it may include phenyl, naphthyl, biphenyl, fluorenyl, anthracenyl, pyrenyl, azulenyl, acenaphthylenyl, terphenyl, phenanthryl, and the like.

Examples of the halogen atom for R ⁸⁰¹-R⁸⁰⁴ may include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In addition, in the chemical formulas (8-1) and (8-2), j, k, l, or m is 0 means that R ⁸⁰¹、R⁸⁰²、R⁸⁰³ or R ⁸⁰⁴ corresponding to them is not present. That is, the ring member atom to which substituent R ⁸⁰¹、R⁸⁰²、R⁸⁰³ or R ⁸⁰⁴ may be bound is unsubstituted, which means that a hydrogen atom is bound to the ring member atom.

J. k, l, and m may each independently desirably be 0, 1, or 2, more desirably 0 or 1, and particularly desirably 0.

In addition, from the viewpoint of improving durability and film forming property, in the chemical formula (1), the following is desirable: ar ¹ forms a ring with Ar ², and-L ¹-Ar¹-N(Ar²)(X¹) may be any of the groups represented by the chemical formulas (9-1) to (9-3):

[ formulae (9-1) to (9-3) ]

In the chemical formulas (9-1) to (9-3),

R ⁹⁰¹-R⁹⁰⁶ is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryl group, or a halogen atom,

N, p, and r are each independently 0, 1, 2, or 3,

O, q, and s are each independently 0, 1, 2,3, or 4,

When any of n, o, p, q, R, and s is 2 or more, each R ⁹⁰¹, each R ⁹⁰², each R ⁹⁰³, each R ⁹⁰⁴, each R ⁹⁰⁵, or each R ⁹⁰⁶ may be the same or different,

X ¹ is the same as defined in the chemical formula (1), and

* Bonded to the nitrogen atom.

Each substituent as R ⁹⁰¹-R⁹⁰⁶ may be the same as the examples given for R ⁸⁰¹-R⁸⁰⁴ in chemical formulas (8-1) and (8-2).

In the chemical formulas (9-1) to (9-3), n, o, p, q, R, or s is 0 means that R ⁹⁰¹、R⁹⁰²、R⁹⁰³、R⁹⁰⁴、R⁹⁰⁵, or R ⁹⁰⁶ corresponding to them are not present. That is, the ring member atom to which substituent R ⁹⁰¹、R⁹⁰²、R⁹⁰³、R⁹⁰⁴、R⁹⁰⁵, or R ⁹⁰⁶, may be bound is unsubstituted, which means that a hydrogen atom is bound to the ring member atom.

N, o, p, q, r, and s can each independently be desirably 0, 1, or 2, more desirably 0 or 1, and particularly desirably 0.

In the chemical formula (1), R ¹¹-R¹⁴ and R ²¹-R²⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, wherein R ¹¹ and R ²¹ may combine with each other to form a ring.

Here, R ¹¹-R¹⁴ and R ²¹-R²⁴ may be the same or different, respectively.

The alkyl groups as R ¹¹-R¹⁴ and R ²¹-R²⁴ may be straight-chain or branched alkyl groups, for example straight-chain alkyl groups having 1 to 20 carbon atoms or branched alkyl groups having 3 to 20 carbon atoms. For example, the alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, 1, 3-dimethylbutyl, 1-isopropyl propyl, 1, 2-dimethylbutyl, n-heptyl, 1, 4-dimethylpentyl, 3-ethylpentyl, 2-methyl-1-isopropyl, 1-ethyl-3-methylbutyl, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropyl butyl, 2-methyl-1-isopropyl butyl, 1-tert-butyl-2-methylpropyl, n-nonyl, 3, 5-trimethylhexyl, n-decyl, isodecyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, nonadecyl, eicosyl, etc.

Cycloalkyl groups as R ¹¹-R¹⁴ and R ²¹-R²⁴ may desirably be cycloalkyl groups having 3 to 16 carbon atoms. In particular, it may include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

The alkoxy groups as R ¹¹-R¹⁴ and R ²¹-R²⁴ may be straight-chain or branched alkoxy groups, but are desirably straight-chain alkoxy groups having 1 to 20 carbon atoms or branched alkoxy groups having 3 to 20 carbon atoms. For example, the alkoxy group may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, 2-ethylhexyloxy, 3-ethylpentyloxy and the like.

The cycloalkoxy groups as R ¹¹-R¹⁴ and R ²¹-R²⁴ may desirably be cycloalkoxy groups having 3 to 16 carbon atoms. For example, it may include cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, and the like.

The aryl groups as R ¹¹-R¹⁴ and R ²¹-R²⁴ may desirably be aryl groups having 6 to 30 carbon atoms. The aryl group may include, for example, phenyl, naphthyl, biphenyl, fluorenyl, anthracenyl, pyrenyl, azulenyl, acenaphthylenyl, terphenyl, and phenanthryl.

Examples of the halogen atom for R ¹¹-R¹⁴ and R ²¹-R²⁴ may include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In addition, R ¹¹ and R ²¹ may combine with each other to form a ring. At this time, the ring structure formed by R ¹¹ and R ²¹ is not particularly limited, but the following is desirable: r ¹¹ and R ²¹ may combine with each other to form a carbazole ring. That is, as an embodiment, in the chemical formula (1), the structural unit X has the following structure (structural unit X-1).

[ Structural unit X-1]

In structural unit X-1, R ¹²-R¹⁴ and R ²²-R²⁴、L¹、Ar¹、Ar² and X ¹ are each the same as defined in formula (1), bound to an adjacent atom forming the backbone of the polymer compound (i.e., bound to Y ¹ or an adjacent structural unit).

Among these, from the viewpoint of obtaining higher durability (especially light emission lifetime) or excellent film forming properties, R ¹¹ and R ²¹ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, or are combined with each other to form a ring; and R ¹²-R¹⁴ and R ²²-R²⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms is desirable. In addition, R ¹¹ and R ²¹ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, or are combined with each other to form a ring; and R ¹²-R¹⁴ and R ²²-R²⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms is desirable. In addition, R ¹¹ and R ²¹ are both hydrogen atoms or are combined with each other to form a ring; and R ¹²-R¹⁴ and R ²²-R²⁴ are all hydrogen atoms, is particularly desirable. Moreover, it is most desirable that R ¹¹-R¹⁴ and R ²¹-R²⁴ are all hydrogen atoms (unsubstituted).

From the above, the structural unit (A) according to the embodiment is desirably selected from the following groups (structural units (A-1 a) to (A-1 d).

Structural unit (A-1)

In the structural unit (a-1), R ⁵⁷、R⁵⁸、R⁶⁷、R⁶⁸、R⁷⁸、R⁷⁹、R⁹⁴, and R ⁹⁵ each independently represent an alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group or an alkyl group having 1 to 14 carbon atoms substituted with a group having a carboxyl group (substituent (a)), and R ⁵¹-R⁵⁶、R⁵⁹-R⁶⁶、R⁶⁹-R⁷⁷、R⁸⁰-R⁹³、R⁹⁶, and R ⁹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms.

Structural Unit (B)

In addition to the structural unit (a) represented by chemical formula (1), the polymer compound according to the embodiment further includes a structural unit (B) represented by chemical formula (2):

[ chemical formula (2) ]

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In the chemical formula (2), a radical of formula (2),

R ³¹-R³⁴ and R ⁴¹-R⁴⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, wherein R ³¹ and R ⁴¹ may be connected to each other to form a ring,

L ² is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring member atoms,

Ar ³ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms,

Ar ⁴ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring member atoms, or may be attached to Ar ³ to form a ring,

X ² is an aromatic hydrocarbon radical having 6 to 25 ring member atoms which may be substituted by alkyl having 1 to 14 carbon atoms,

Y ² is an aromatic hydrocarbon radical having 6 to 25 ring member atoms which may be substituted by alkyl having 1 to 14 carbon atoms, and

R ³¹-R³⁴、R⁴¹-R⁴⁴、L²、Ar³, and Ar ⁴ do not have an alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group and an alkyl group having 1 to 14 carbon atoms substituted with a group having a carboxyl group.

In this specification, the structural unit (B) represented by the chemical formula (2) is sometimes also referred to as "structural unit (B)" or "structural unit (B) according to the embodiment".

In addition, a structural unit having the following structure in the "structural unit (B) represented by the chemical formula (2)" is also simply referred to as "structural unit X '" or "structural unit X'" according to the embodiment.

[ Structural unit X' ]

Similarly, the structural unit "-Y ² -" in the structural unit (B) "represented by the chemical formula (2) is also simply referred to as" structural unit Y '"or" structural unit Y' "according to the embodiment.

In addition to the structural unit (a) represented by the chemical formula (1), the polymer compound according to the embodiment further includes the structural unit (B) represented by the chemical formula (2), which has excellent hole injection property in the vector sub-point and can further improve the durability (light emission lifetime) of the electroluminescent device. In addition, high current efficiency and low driving voltage can be achieved. When the polymer compound according to the embodiment further includes the structural unit (B), only one type of the structural unit (B) may be included, or two or more types may be included. On the other hand, the plurality of structural units (B) may exist in a block form, a random form, an alternating form, or a periodic form.

[ Chemical formula (2) ]

As described above, in an embodiment, the polymer compound includes the structural unit (B) represented by the chemical formula (2). That is, the structural unit X' (structural unit on the left side of chemical formula (2), i.e., structural unit composed of a nitrogen atom between two phenylene groups) in chemical formula (2) constitutes the polymer compound according to the embodiment. Similarly, the structural unit Y' (structural unit on the right side of chemical formula (2), namely, structural unit represented by "Y ²") in chemical formula (2) constitutes a polymer compound according to an embodiment. That is, the polymer compound according to the embodiment may be a copolymer further including structural units X 'and Y' in addition to structural units X and Y.

In the chemical formula (2), X ² and Y ² do not have an alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group and an alkyl group having 1 to 14 carbon atoms substituted with a group having a carboxyl group (substituent (a)), and thus are different from X ¹ and Y ¹. In addition, in chemical formula (2), the definitions of L ²、Ar³、Ar⁴、R³¹-R³⁴ and R ⁴¹-R⁴⁴ are the same as those of L ¹、Ar¹、Ar²、R¹¹-R¹⁴ and R ²¹-R²⁴ in chemical formula (1), except for the following: each of which does not have a substituent (a) (or is not a substituent (a)). Thus, for L ²、Ar³、Ar⁴、R³¹-R³⁴, and R ⁴¹-R⁴⁴, the term "substituted" refers to a form substituted with substituents other than substituent (a), unless specifically stated otherwise.

In the chemical formula (2), X ² represents an aromatic hydrocarbon group having 6 to 25 ring member atoms which may be substituted with an alkyl group having 1 to 14 carbon atoms.

Among them, the aromatic hydrocarbon group as X ² is desirably a monovalent group derived from a compound selected from benzene, biphenyl, terphenyl, and fluorene, more desirably a monovalent group derived from a compound selected from benzene, biphenyl, and fluorene, and particularly desirably a monovalent group derived from benzene or fluorene (phenyl or fluorenyl).

Moreover, from the viewpoint of improving durability, in the chemical formula (2), the following is desirable: x ² is any one of the groups represented by chemical formulas (4 '-1) to (4' -4).

[ Formulae (4 '-1) to (4' -4) ]

In the chemical formulas (4 '-1) to (4' -4),

R ⁴⁰¹'-R⁴¹³' is each independently an alkyl group having 1 to 14 carbon atoms which is substituted or unsubstituted with a substituent other than a carboxyl group (-COOH),

A' is 0, 1, 2, 3,4, or 5,

B ', d ', and f ' are each independently 0, 1, 2, or 3,

C ', e ', and g ' are each independently 0, 1, 2, 3, or 4, and

When any of a ', b', c ', d', e ', f', and g 'is 2 or greater, each R ⁴⁰¹', each R ⁴⁰⁴ ', each R ⁴⁰⁵', each R ⁴⁰⁸ ', each R ⁴⁰⁹', each R ⁴¹² ', or each R ⁴¹³' may be the same or different and are bonded to a nitrogen atom (a nitrogen atom bonded to Ar ²).

In addition, in the chemical formulas (4 '-1) to (4' -4), R ⁴⁰² 'and R ⁴⁰³'、R⁴⁰⁶' and R ⁴⁰⁷'、R⁴¹⁰ 'and R ⁴¹¹' may be the same or different, respectively. Desirably, R ⁴⁰² 'and R ⁴⁰³'、R⁴⁰⁶' and R ⁴⁰⁷'、R⁴¹⁰ 'and R ⁴¹¹' may be the same as each other.

In the chemical formulas (4-1) to (4-4), a ', b ', c ', d ', e ', f ', or g ' being 0 means that R ⁴⁰¹'、R⁴⁰⁴'、R⁴⁰⁵'、R⁴⁰⁸'、R⁴⁰⁹'、R⁴¹² ' or R ⁴¹³ ' corresponding to them are not present. That is, the ring member atom to which substituent R ⁴⁰¹'、R⁴⁰⁴'、R⁴⁰⁵'、R⁴⁰⁸'、R⁴⁰⁹'、R⁴¹² 'or R ⁴¹³' may be bound is unsubstituted, which means that a hydrogen atom is bound to the ring member atom.

A' may desirably be 0,1, or 2, more desirably 0 or 1, and particularly desirably 1. In addition, when a 'is 1, the substitution position of R ⁴⁰¹' is desirably para (p-position or 4-position) with respect to the bond to the nitrogen atom (nitrogen atom bonded to Ar ²). b ', c', d ', e', f 'and g' may each independently desirably be 0,1, or 2, more desirably 0 or 1, and particularly desirably 0.

The alkyl group having 1 to 14 carbon atoms as R ⁴⁰¹'-R⁴¹³' is not particularly limited, but is a linear or branched alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, 1, 3-dimethylbutyl, 1-isopropyl propyl, 1, 2-dimethylbutyl, n-heptyl, 1, 4-dimethylpentyl, 3-ethylpentyl, 2-methyl-1-isopropyl propyl, 1-ethyl-3-methylbutyl, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropyl butyl, 2-methyl-1-isopropyl butyl, 1-tert-butyl-2-methylpropyl, n-nonyl, 3, 5-trimethylhexyl, n-decyl, isodecyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, n-tetradecyl and the like.

Here, the alkyl group as R ⁴⁰¹'-R⁴¹³' may desirably have 1 to 12 carbon atoms from the viewpoint of improving durability. In particular, the following is desirable: r ⁴⁰¹'-R⁴¹³' are each independently an alkyl group having a carbon number within the above range.

In addition, the alkyl group as R ⁴⁰¹'-R⁴¹³' may desirably be linear from the viewpoint of improving durability.

In the chemical formula (2), from the viewpoint of improving durability (especially, light emission lifetime), the following is desirable: x ² is any one of the groups represented by chemical formulas (4 '-1) to (4' -3), and it is more desirable that: x ² is represented by the formula (4 '-1) or (4' -3).

In the chemical formula (2), Y ² is an aromatic hydrocarbon group having 6 to 25 ring member atoms which may be substituted with an alkyl group having 1 to 14 carbon atoms.

Among them, the aromatic hydrocarbon group as Y ² is desirably a divalent group derived from a compound selected from benzene, biphenyl, terphenyl, and fluorene, more desirably a divalent group derived from biphenyl or fluorene, and particularly desirably a divalent group derived from fluorene (fluorenylene).

Further, from the viewpoint of improving durability, in the chemical formula (2), Y ² is desirably a group represented by the chemical formula (6' -1).

[ Chemical formula (6' -1) ]

In the chemical formula (6' -1),

R ⁶⁰¹'-R⁶⁰⁴' is each independently an alkyl group having 1 to 14 carbon atoms which is substituted or unsubstituted with a substituent other than a carboxyl group (-COOH),

H 'and i' are each independently 0, 1, 2, or 3, and

When either of h 'and i' is 2 or more, each R ⁶⁰³ 'or each R ⁶⁰⁴' may be the same or different.

In addition, in the chemical formula (6 ' -1), R ⁶⁰¹ ' and R ⁶⁰² ' may be the same or different. Desirably, R ⁶⁰¹ and R ⁶⁰²' may be identical to each other.

In the chemical formula (6 ' -1), h ' or i ' is 0 means that R ⁶⁰³ ' or R ⁶⁰⁴ ' corresponding to them is not present. That is, the ring member atom to which substituent R ⁶⁰³ 'or R ⁶⁰⁴' may be bound is unsubstituted, which means that a hydrogen atom is bound to the ring member atom.

H 'and i' may each independently desirably be 0,1, or 2, more desirably 0 or 1, and particularly desirably 0.

The alkyl group having 1 to 14 carbon atoms as R ⁶⁰¹'-R⁶⁰⁴' is not particularly limited, but is a linear or branched alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, 1, 3-dimethylbutyl, 1-isopropyl propyl, 1, 2-dimethylbutyl, n-heptyl, 1, 4-dimethylpentyl, 3-ethylpentyl, 2-methyl-1-isopropyl propyl, 1-ethyl-3-methylbutyl, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropyl butyl, 2-methyl-1-isopropyl butyl, 1-tert-butyl-2-methylpropyl, n-nonyl, 3, 5-trimethylhexyl, n-decyl, isodecyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, n-tetradecyl and the like.

Here, the alkyl group as R ⁶⁰¹'-R⁶⁰⁴' may have desirably 1 to 12 carbon atoms, more desirably 1 to 10 carbon atoms, and particularly desirably 2 to 6 carbon atoms from the viewpoint of improving durability. In particular, the following is desirable: r ⁶⁰¹ 'and R ⁶⁰²' each independently have an alkyl group having a carbon number within the above range.

In addition, the alkyl group as R ⁶⁰¹'-R⁶⁰⁴' may desirably be linear from the viewpoint of improving durability.

In addition, in chemical formula (2), the definitions of L ²、Ar³、Ar⁴、R³¹-R³⁴ and R ⁴¹-R⁴⁴ are the same as those of L ¹、Ar¹、Ar²、R¹¹-R¹⁴ and R ²¹-R²⁴ in chemical formula (1). In addition, the desirable embodiments are the same for each. Hereinafter, it will be described in detail.

In formula (2), L ² is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms; or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring member atoms.

Here, the aromatic hydrocarbon group may be specifically a divalent group derived from an aromatic hydrocarbon such as benzene (phenylene), naphthalene, anthracene, pyrene, pentalene, indene, azulene, heptene, acenaphthene, phenalene, phenanthrene, biphenyl, terphenyl, tetrabiphenyl, fluorene, and 9,9' -spirodi [ fluorene ]. In addition, the aromatic heterocyclic group may include divalent groups derived from heterocyclic aromatic compounds such as acridine, phenazine, benzoquinoline, benzisoquinoline, phenanthridine, phenanthroline, anthraquinone, fluorenone, dibenzofuran, dibenzothiophene, carbazole, imidazophenanthridine, benzimidazole benzophenanthridine, azadibenzofuran, azacarbazole, azadibenzothiophene, diazadibenzofuran, diazacarbazole, diazadibenzothiophene, xanthone, anthraphenone, pyridine, quinoline, and anthracoquinoline.

Among these, L ² is desirably a substituted or unsubstituted divalent group derived from a compound selected from benzene, biphenyl, terphenyl, tetrabiphenyl, and fluorene. L ² is more desirably a substituted or unsubstituted divalent radical derived from benzene or biphenyl (substituted or unsubstituted phenylene or biphenylene).

In addition, in the chemical formula (2), L ² is desirably one of the groups represented by the chemical formulas (7 '-1) to (7' -24):

[ formulae (7 '-1) to (7' -24) ]

In the chemical formulas (7 '-1) to (7' -24), are bonded to a nitrogen atom, and are bonded to Ar ³.

In addition, L ² may desirably be any one of the groups represented by formulas (7 '-1) to (7' -3) and formulas (7 '-13) to (7' -16) (i.e., a substituted or unsubstituted phenylene group), more desirably any one of the groups represented by formulas (7 '-1) and formulas (7' -13) to (7 '-16) (i.e., a substituted or unsubstituted p-phenylene group), and particularly desirably the group represented by formula (7' -1) (i.e., an unsubstituted p-phenylene group). With such L ¹, higher hole injection properties (resulting in high durability) and good film formation properties can be achieved.

In the chemical formula (2), ar ³ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms. At this time, ar ³ may form a ring with Ar ⁴. On the other hand, when Ar ³ forms a ring with Ar ⁴, ar ³ is a trivalent group. Ar ³ is a divalent group when Ar ³ does not form a ring with Ar ⁴.

Here, the aromatic hydrocarbon group as Ar ³ is not particularly limited. When Ar ³ does not form a ring with Ar ⁴, specific examples of Ar ³ include the same divalent groups derived from aromatic hydrocarbons having 6 to 25 ring member atoms described above for L ². In addition, when Ar ³ forms a ring with Ar ⁴, the divalent groups derived from aromatic hydrocarbons having 6 to 25 ring member atoms described above for L ² can be converted to trivalent groups.

Among these, ar ³ is desirably a substituted or unsubstituted divalent or trivalent group derived from a compound selected from benzene, biphenyl, and fluorene. Ar ³ is more desirably a substituted or unsubstituted divalent or trivalent radical derived from benzene or biphenyl. Ar ³ is particularly desirably a divalent group (e.g., o, m, p-phenylene) or trivalent group (e.g., 1,3, 4-phenylene) derived from substituted or unsubstituted benzene. In addition, ar ³ is more desirably a substituted or unsubstituted p-phenylene group or a1, 3, 4-phenylene group, and most desirably a substituted or unsubstituted 1,3, 4-phenylene group. That is, the following is desirable: ar ³ forms a ring with Ar ⁴.

With such Ar ³, higher hole injection properties (resulting in high durability) and good film formation properties can be achieved. In addition, durability and luminous efficiency can be improved in good balance.

Meanwhile, a substituent that may be present when any one of the hydrogen atoms of Ar ³ is substituted is not particularly limited, and the same substituent as that described above for "substituted" may be applied. In an embodiment, ar ³ is unsubstituted.

In formula (2), ar ⁴ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms; or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring member atoms. At this time, ar ⁴ may form a ring with Ar ³. On the other hand, when Ar ⁴ forms a ring with Ar ³, ar ⁴ is a divalent group. Ar ⁴ is a monovalent group when Ar ⁴ does not form a ring with Ar ³.

Here, the aromatic hydrocarbon group and the aromatic heterocyclic group as Ar ⁴ are not particularly limited. When Ar ⁴ does not form a ring with Ar ³, a specific example of Ar ⁴ can be exemplified by: the divalent radical from an aromatic hydrocarbon having 6 to 25 ring member atoms described for L ² is converted to a monovalent radical. Similarly, in the above case, an aromatic heterocyclic group as Ar ⁴ can be exemplified by: the divalent radical from a heterocyclic aromatic compound having 5 to 25 ring member atoms described for L ² is converted to a monovalent radical. In addition, when Ar ⁴ forms a ring with Ar ³, the same divalent group derived from an aromatic hydrocarbon having 6 to 25 ring member atoms described for L ² may be used. Similarly, in the above case, the aromatic heterocyclic group as Ar ⁴ may be exemplified by the same divalent groups derived from heterocyclic aromatic compounds having 5 to 25 ring member atoms described for L ².

Among these, ar ⁴ is desirably a substituted or unsubstituted monovalent or divalent group derived from a compound selected from benzene, biphenyl, and fluorene, more desirably a substituted or unsubstituted monovalent or divalent group derived from benzene or biphenyl, particularly desirably a monovalent or divalent group derived from substituted or unsubstituted benzene (e.g., o-, m-, p-phenylene), and most desirably a substituted or unsubstituted o-phenylene. That is, ar ⁴ desirably forms a ring with Ar ³.

With such Ar ⁴, a higher hole injection property (resulting in high durability) and a good film forming property can be achieved. In addition, durability and luminous efficiency can be improved in good balance.

Meanwhile, a substituent that may be present when any one of the hydrogen atoms of Ar ⁴ is substituted is not particularly limited, and the same substituent as that described above for "substituted" may be applied. In an embodiment, ar ⁴ is unsubstituted.

As described above, ar ³ and Ar ⁴ desirably combine with each other to form a ring.

In this way, when Ar ³ and Ar ⁴ form a ring, higher hole injection property can be obtained, durability (particularly, light emission lifetime) can be improved, and good film forming property can be achieved.

When Ar ³ and Ar ⁴ form a ring, the ring structure formed by Ar ³ and Ar ⁴ is not particularly limited, but the following is desirable: ar ³ and Ar ⁴ combine with each other to form a carbazole ring. Further, in an embodiment, -Ar ³-N(Ar⁴)(X² in chemical formula (2) has a structure selected from the following groups.

[ Formulae (8 '-1) and (8' -2) ]

In the chemical formulas (8 '-1) and (8' -2),

R ⁸⁰¹'-R⁸⁰⁴' are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryl group, or a halogen atom,

J 'and l' are each independently 0,1, 2, or 3,

K 'and m' are each independently 0, 1, 2,3, or 4, and

When any one of j ', k ', L ', and m ' is 2 or more, each R ⁸⁰¹ ', each R ⁸⁰² ', each R ⁸⁰³, or each R ⁸⁰⁴ ' may be the same or different, X ² is the same as defined in formula (2), and is bonded to L ².

The alkyl group as R ⁸⁰¹'-R⁸⁰⁴' may be a straight-chain or branched alkyl group, for example a straight-chain alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms. For example, the alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, 1, 3-dimethylbutyl, 1-isopropyl, 1, 2-dimethylbutyl, n-heptyl, 1, 4-dimethylpentyl, 3-ethylpentyl, 2-methyl-1-isopropyl, 1-ethyl-3-methylbutyl, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropyl butyl, 2-methyl-1-isopropyl butyl, 1-tert-butyl-2-methylpropyl, n-nonyl, 3, 5-trimethylhexyl, n-decyl, isodecyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, nonadecyl, eicosyl, etc.

Cycloalkyl as R ⁸⁰¹'-R⁸⁰⁴' may desirably be cycloalkyl having 3 to 16 carbon atoms. In particular, it may include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

The alkoxy group as R ⁸⁰¹'-R⁸⁰⁴' may be a linear or branched alkoxy group, but is desirably a linear alkoxy group having 1 to 20 carbon atoms or a branched alkoxy group having 3 to 20 carbon atoms. For example, the alkoxy group may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, 2-ethylhexyloxy, 3-ethylpentyloxy and the like.

The cycloalkoxy group as R ⁸⁰¹'-R⁸⁰⁴' may desirably be a cycloalkoxy group having 3 to 16 carbon atoms. For example, it may include cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, and the like.

The aryl group as R ⁸⁰¹'-R⁸⁰⁴' may desirably be an aryl group having 6 to 30 carbon atoms. The aryl group may include, for example, phenyl, naphthyl, biphenyl, fluorenyl, anthracenyl, pyrenyl, azulenyl, acenaphthylenyl, terphenyl, and phenanthryl.

Examples of the halogen atom for R ⁸⁰¹'-R⁸⁰⁴' may include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the formulae (8 '-1) to (8' -2), j ', k', l ', or m' are 0 means that R ⁸⁰¹'、R⁸⁰²'、R⁸⁰³ 'or R ⁸⁰⁴' corresponding to them are not present. That is, the ring member atom to which substituent R ⁸⁰¹'、R⁸⁰²'、R⁸⁰³ ', or R ⁸⁰⁴' may be bound is unsubstituted, which means that a hydrogen atom is bound to the ring member atom.

J ', k', l ', and m' may each independently desirably be 0, 1, or 2, more desirably 0 or 1, and particularly desirably 0.

In addition, from the viewpoint of improving durability and film forming property, in the chemical formula (2), the following is desirable: ar ³ forms a ring with Ar ⁴, and-L ²-Ar³-N(Ar⁴)(X²) may be any of the groups represented by the chemical formulas (9 '-1) to (9' -3):

[ formulae (9 '-1) to (9' -3) ]

In the chemical formulas (9 '-1) to (9' -3),

R ⁹⁰¹'-R⁹⁰⁶' are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryl group, or a halogen atom,

N ', p ', and r ' are each independently 0,1, 2, or 3,

O ', q ', and s ' are each independently 0, 1, 2, 3, or 4,

When any of n ', o', p ', q', R ', and s' is 2 or more, each R ⁹⁰¹ ', each R ⁹⁰²', each R ⁹⁰³ ', each R ⁹⁰⁴', each R ⁹⁰⁵ ', or each R ⁹⁰⁶' may be the same or different,

X ² is the same as defined in the chemical formula (2), and

* Is bonded to the nitrogen atom.

Each substituent as R ⁹⁰¹'-R⁹⁰⁶ 'may be the same as the examples given for R ⁸⁰¹'-R⁸⁰⁴' in the chemical formulas (8-1) and (8-2).

In the chemical formulas (9 '-1) to (9' -3), n ', o', p ', q', R ', or s' are 0 means that R ⁹⁰¹'、R⁹⁰²'、R⁹⁰³'、R⁹⁰⁴'、R⁹⁰⁵ 'or R ⁹⁰⁶' corresponding to them are not present. That is, the ring member atom to which substituent R ⁹⁰¹'、R⁹⁰²'、R⁹⁰³'、R⁹⁰⁴'、R⁹⁰⁵ ', or R ⁹⁰⁶' may be bound is unsubstituted, which means that a hydrogen atom is bound to the ring member atom.

N ', o', p ', q', r ', and s' may each independently desirably be 0, 1, or 2, more desirably 0 or 1, and particularly desirably 0.

In chemical formula (2), R ³¹-R³⁴ and R ⁴¹-R⁴⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, wherein R ³¹ and R ⁴¹ may combine with each other to form a ring.

Here, R ³¹-R³⁴ and R ⁴¹-R⁴⁴ may be the same or different, respectively.

The alkyl groups as R ³¹-R³⁴ and R ⁴¹-R⁴⁴ may be straight-chain or branched alkyl groups, for example straight-chain alkyl groups having 1 to 20 carbon atoms or branched alkyl groups having 3 to 20 carbon atoms. For example, the alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, 1, 3-dimethylbutyl, 1-isopropyl propyl, 1, 2-dimethylbutyl, n-heptyl, 1, 4-dimethylpentyl, 3-ethylpentyl, 2-methyl-1-isopropyl, 1-ethyl-3-methylbutyl, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropyl butyl, 2-methyl-1-isopropyl butyl, 1-tert-butyl-2-methylpropyl, n-nonyl, 3, 5-trimethylhexyl, n-decyl, isodecyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, nonadecyl, eicosyl, etc.

Cycloalkyl groups as R ³¹-R³⁴ and R ⁴¹-R⁴⁴ may desirably be cycloalkyl groups having 3 to 16 carbon atoms. In particular, it may include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

The alkoxy groups as R ³¹-R³⁴ and R ⁴¹-R⁴⁴ may be straight-chain or branched alkoxy groups, but are desirably straight-chain alkoxy groups having 1 to 20 carbon atoms or branched alkoxy groups having 3 to 20 carbon atoms. For example, the alkoxy group may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, 2-ethylhexyloxy, 3-ethylpentyloxy and the like.

The cycloalkoxy groups as R ³¹-R³⁴ and R ⁴¹-R⁴⁴ may desirably be cycloalkoxy groups having 3 to 16 carbon atoms. For example, it may include cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, and the like.

The aryl groups as R ³¹-R³⁴ and R ⁴¹-R⁴⁴ may desirably be aryl groups having 6 to 30 carbon atoms. The aryl group may include, for example, phenyl, naphthyl, biphenyl, fluorenyl, anthracenyl, pyrenyl, azulenyl, acenaphthylenyl, terphenyl, and phenanthryl.

Examples of the halogen atom for R ³¹-R³⁴ and R ⁴¹-R⁴⁴ may include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In addition, R ³¹ and R ⁴¹ may combine with each other to form a ring. At this time, the ring structure formed by R ³¹ and R ⁴¹ is not particularly limited, but the following is desirable: r ³¹ and R ⁴¹ may combine with each other to form a carbazole ring. That is, as an embodiment, in chemical formula (2), the structural unit X' has the following structure.

[ Structural unit X' -1]

In structural unit X' -1, R ³²-R³⁴ and R ⁴²-R⁴⁴、L²、Ar³、Ar⁴, and X ² are each the same as defined in formula (2), bound to an adjacent atom forming the backbone of the polymer compound (i.e., bound to Y ² or an adjacent structural unit).

Among these, from the viewpoint of obtaining higher durability (especially light emission lifetime) or excellent film forming properties, R ³¹ and R ⁴¹ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, or are combined with each other to form a ring; and R ³²-R³⁴ and R ⁴²-R⁴⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms is desirable. In addition, R ³¹ and R ⁴¹ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, or are combined with each other to form a ring; and R ³²-R³⁴ and R ⁴²-R⁴⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms is desirable. In addition, R ³¹ and R ⁴¹ are both hydrogen atoms or are combined with each other to form a ring; and R ³²-R³⁴ and R ⁴²-R⁴⁴ are all hydrogen atoms, is particularly desirable. Moreover, it is most desirable that R ³¹-R³⁴ and R ⁴¹-R⁴⁴ are all hydrogen atoms (unsubstituted).

The following is desirable: the structural unit (B) represented by the chemical formula (2) described above has the same structure and substituents as the structural unit (a) represented by the chemical formula (1), except for the portion including the substituent (a) (i.e., X ¹、Y¹). That is, R ¹¹-R¹⁴、R²¹-R²⁴、L¹、Ar¹ and Ar ² in chemical formula (1) are desirably the same as R ³¹-R³⁴、R⁴¹-R⁴⁴、L²、Ar³ and Ar ⁴ in chemical formula (2). In a more desirable embodiment, when X ¹ includes substituent (a), R ¹¹-R¹⁴、R²¹-R²⁴、L¹、Ar¹、Ar², and Y ¹ in formula (1) are each the same as R ³¹-R³⁴、R⁴¹-R⁴⁴、L²、Ar³、Ar⁴, and Y ² in formula (2). Moreover, in other desirable embodiments, when Y ¹ includes substituent (a), R ¹¹-R¹⁴、R²¹-R²⁴、L¹、Ar¹、Ar², and X ¹ in formula (1) are each the same as R ³¹-R³⁴、R⁴¹-R⁴⁴、L²、Ar³、Ar⁴, and X ² in formula (2).

From the above, the structural unit (B) according to the embodiment is desirably selected from the following groups.

Structural unit (B-1)

In the structural unit (B-1), R ⁵⁷'、R⁵⁸'、R⁶⁷'、R⁶⁸'、R⁷⁸'、R⁷⁹'、R⁹⁴ ' and R ⁹⁵ ' each independently represent an alkyl group ,R⁵¹'-R⁵⁶'、R⁵⁹'-R⁶⁶'、R⁶⁹'-R⁷⁷'、R⁸⁰'-R⁹³'、R⁹⁶' having 1 to 14 carbon atoms and R ⁹⁷ ' each independently represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms.

Other structural units

The polymer compound according to the embodiment may further include structural units other than the structural unit (a) and the structural unit (B). In the case where other structural units are included therein, the other structural units are not particularly limited as long as they do not interfere with the effect (particularly high hole injection property) of the polymer compound. Other structural units include, for example, structural units derived from compounds such as azulene, naphthalene, anthracene, phenanthrene, and pyrene. Meanwhile, hereinafter, such other structural unit is also referred to as "structural unit (C)".

Composition of Polymer Compounds

The composition of the structural units (a) to (C) in the polymer compound according to the embodiment is not particularly limited. In view of durability (light emission lifetime) and excellent film forming property of a layer (e.g., a hole injection layer, a hole transport layer) formed using the resulting polymer compound, the structural unit (a) is desirably greater than or equal to about 5 mol% and less than about 100 mol%, more desirably greater than or equal to about 10 mol% and less than or equal to about 80 mol%, particularly desirably greater than or equal to about 10 mol% and less than or equal to about 70 mol%, and most desirably greater than or equal to about 30 mol% and less than or equal to about 70 mol%, based on the total structural units constituting the polymer compound. That is, in a desirable embodiment, the structural unit (a) is included in a ratio of greater than or equal to about 30 mole% and less than or equal to about 70 mole% based on the total structural units. On the other hand, when the polymer compound includes two or more types of structural units (a), the content of the structural units (a) means the total amount of the structural units (a).

That is, in a desirable embodiment, structural units (a) are included in a ratio of less than about 100 mole percent, based on total structural units. At this time, the following is desirable: further comprising a structural unit (B). In view of durability (light emission lifetime) and excellent film forming property of a layer (e.g., hole injection layer, hole transport layer) formed using the obtained polymer compound, the content of the structural unit (B) may be greater than about 0 mol% and less than or equal to about 95 mol%, more desirably greater than or equal to about 20 mol% and less than or equal to about 90 mol%, particularly desirably greater than or equal to about 30 mol% and less than or equal to about 90 mol%, most desirably greater than or equal to about 30 mol% and less than or equal to about 70 mol%, based on the total structural units constituting the polymer compound. That is, in a desirable embodiment, the structural units (B) are included in a ratio of greater than or equal to about 30 mole% and less than or equal to about 70 mole% based on the total structural units. On the other hand, when the polymer compound includes two or more types of structural units (B), the content of the structural units (B) means the total amount of the structural units (B).

In addition, as described above, the polymer compound according to the embodiment may further include other structural units (C)). In this case, the composition of the other structural unit (C)) is not particularly limited. In view of ease of film formation by the resulting polymer compound and effect of further improving film strength, the structural unit (C) is desirably greater than about 0 mol% and less than or equal to about 10 mol% based on the total structural units constituting the polymer compound. On the other hand, when the polymer compound includes two or more types of structural units (C), the content of the structural units (C) means the total amount of the structural units (C).

As an example, the structural unit (C) may include a structural unit having a crosslinking group. Here, the "crosslinking group" refers to a group that generates a new bond by reacting (crosslinking) with a group of the same or different structural unit existing in the vicinity through heating or irradiation with active energy rays. By including a structural unit having a crosslinking group, a crosslinking reaction can occur by heat or irradiation of active energy rays, and a more durable film can be formed by insolubility in a solvent used for a subsequent process. As a result, productivity and durability of the electroluminescent device can be further improved.

The crosslinking group is not particularly limited as long as it is a group that can cause a crosslinking reaction by heat or active energy rays, but examples may include bicyclo [4.2.0] oct-1, 3, 5-trialkenyl, vinyl, hexenyl, styryl, (3-methyl-3-oxetanyl) methoxy, and the like.

In addition, in view of durability (light-emitting lifetime) and excellent film-forming properties of a layer (e.g., a hole injection layer, a hole transport layer) formed using the obtained polymer compound, when the total molar ratio of the structural unit (a) and the structural unit (B) is 100 mol%, the molar ratio of the structural unit (a) may desirably be greater than or equal to about 10 mol% and less than or equal to about 80 mol%, more desirably greater than or equal to about 10 mol% and less than or equal to about 70 mol%, and particularly desirably greater than or equal to about 30 mol% and less than or equal to about 70 mol%. Similarly, the molar ratio of the structural unit (B) may desirably be greater than or equal to about 20 mol% and less than or equal to about 90 mol%, more desirably greater than or equal to about 30 mol% and less than or equal to about 90 mol%, and particularly desirably greater than or equal to about 30 mol% and less than or equal to about 70 mol% (the total molar ratio of the structural unit (a) and the structural unit (B) is 100 mol%).

The weight average molecular weight (Mw) of the polymer compound according to the present disclosure is not particularly limited as long as the desired effect of the present disclosure is obtained. The weight average molecular weight (Mw) can be, for example, about greater than or equal to about 5,000 grams per mole (g/mol) and less than or equal to about 1,000,000g/mol, desirably greater than or equal to about 8,000g/mol and less than or equal to about 1,000,000g/mol, more desirably greater than or equal to about 10,000g/mol and less than or equal to about 800,000g/mol, and particularly desirably greater than or equal to about 30,000g/mol and less than or equal to about 500,000g/mol. With such a weight average molecular weight, the viscosity of a coating liquid for forming a layer (e.g., a hole injection layer, a hole transport layer) formed using the polymer compound can be appropriately adjusted to form a layer having a uniform film thickness.

Moreover, the number average molecular weight (Mn) of the polymer compound is not particularly limited as long as the desired effect of the present disclosure is obtained. The number average molecular weight (Mn) can be, for example, greater than or equal to about 4,000g/mol and less than or equal to about 300,000g/mol, desirably greater than or equal to about 6,000g/mol and less than or equal to about 250,000g/mol, more desirably greater than or equal to about 10,000g/mol and less than or equal to about 200,000g/mol, and particularly desirably greater than or equal to about 20,000g/mol and less than or equal to about 180,000g/mol. With such a number average molecular weight, the viscosity of a coating liquid for forming a layer (e.g., a hole injection layer, a hole transport layer) using the polymer compound can be appropriately adjusted to form a layer having a uniform film thickness. In addition, the polydispersity (weight average molecular weight/number average molecular weight) of the polymer compound of the present embodiment may be, for example, greater than or equal to about 1.1 and less than or equal to about 5.0, such as greater than or equal to about 1.3 and less than or equal to about 4.0, desirably greater than or equal to about 1.5 and less than or equal to about 3.5.

Here, the measurement of the number average molecular weight (Mn) and the weight average molecular weight (Mw) is not particularly limited, and may be applied by using a known method or by appropriately changing the known method. In the present specification, the number average molecular weight (Mn) and the weight average molecular weight (Mw) use values measured by the following methods. The polydispersity (Mw/Mn) of the polymer is calculated by: the weight average molecular weight (Mw) measured by the following method was divided by the number average molecular weight (Mn).

(Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw))

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer material were measured by SEC (size exclusion chromatography) using polystyrene as a standard material under the following conditions.

(SEC measurement conditions)

Analytical device (SEC): shimadzu Corporation, prominence (registered trademark)

Column: polymer Laboratories PLgel MIXED-B

Column temperature: 40 DEG C

Flow rate: 1.0 mL/min

Sample solution injection amount: 20. Mu.L (concentration of Polymer: about 0.05% by mass)

Eluent: tetrahydrofuran (THF)

Detector (UV-VIS detector): shimadzu Corporation SPD-10AV

Standard sample: and (3) polystyrene.

The terminal of the main chain of the polymer compound according to the present embodiment is not particularly limited, and is appropriately defined depending on the type of raw material used, but is generally a hydrogen atom.

The polymer compound of the present embodiment can be synthesized by using a known organic synthesis method. The specific synthetic method of the polymer compound of the present embodiment can be easily understood by one of ordinary skill in the art with reference to examples to be described later.

In particular, the polymer compound according to the embodiment may be prepared by copolymerization using at least one monomer (I-X) represented by formula (I-X) and at least one monomer (I-Y) represented by formula (I-Y). In addition, at this time, if necessary, a monomer constituting the structural unit (B) according to the embodiment may be further added. In particular, it can be prepared by copolymerization using at least one monomer (II-X) represented by formula (II-X) and at least one monomer (II-Y) represented by formula (II-Y) (i.e., a monomer constituting the structural unit (B) according to the embodiment) in addition to at least one monomer (I-X) represented by formula (I-X) and at least one monomer (I-Y) represented by formula (I-Y) (i.e., a monomer constituting the structural unit (A) according to the embodiment). Here, in the polymer compound, when Y ¹ in the structural unit (a) and Y ² in the structural unit (B) have the same structure, the polymer compound according to the embodiment may also be prepared by copolymerization using at least one monomer (I-X) represented by the formula (I-X), at least one monomer (I-Y) represented by the formula (I-Y), and at least one monomer (II-X) represented by the formula (II-X). In addition, at this time, if necessary, other monomers corresponding to the other structural units (C)) may be further added.

[ Formula (I-X) ]

[ Formula (I-Y) ]

W³-Y¹-W⁴ (I-Y)

[ Formula (II-X) ]

[ Formula (II-Y) ]

W⁷-Y²-W⁸ (II-Y)

Alternatively, the polymer compound according to the embodiment may be prepared by polymerization using one or more monomers represented by formula (1'). Further, at this time, if necessary, a monomer corresponding to the structural unit (B) according to the embodiment may be further added. In particular, when the polymer compound according to the embodiment includes the structural unit (a) and the structural unit (B), it may be prepared by copolymerization using at least one monomer represented by the formula (1 ') and at least one monomer represented by the formula (2'). In addition, at this time, if necessary, other monomers corresponding to the other structural units (C)) may be further added.

[ Formula (1') ]

[ Formula (2') ]

Monomers for polymerization of the polymer compounds according to the present disclosure may be synthesized by appropriately combining known synthetic reactions, and their structures may be confirmed by known methods (e.g., NMR, LC-MS, etc.).

,R¹¹-R¹⁴、R²¹-R²⁴、R³¹-R³⁴、R⁴¹-R⁴⁴、L¹、L²、Ar¹、Ar²、Ar³、Ar⁴、X¹、X²、Y¹、 And Y ² in the formulae (I-X), (I-Y), (II-X), (II-Y), (1 '), and (2') are the same as defined in the formulae (1) or (2), and W ¹-W¹² is each independently a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, especially bromine atom) or a group having a structure represented by the following formula D. Meanwhile, in the following structures, R ^A-R^D each independently represents an alkyl group having 1 to 3 carbon atoms. Desirably, R ^A-R^D can be methyl.

[ Chemical formula D ]

On the other hand, W ¹ and W ² in the formula (I-X), W ³ and W ⁴ in the formula (I-Y), W ⁵ and W ⁶ in the formula (II-X), W ⁷ and W ⁸ in the formula (II-Y), W ⁹ and W ¹⁰ in the formula (1 '), and W ¹¹ and W ¹² in the formula (2') may be the same or different, respectively. However, in order to inhibit polymerization between the monomers (I-x), the following is desirable: w ¹ and W ² in the formula (I-X) are atoms or groups that do not react with each other. Similarly, in order to inhibit polymerization between the monomers (I-Y), W ³ and W ⁴ in the chemical formula (I-Y) are atoms or groups that do not react with each other. In addition, similarly in order to inhibit polymerization between the monomers (II-x) or (II-y), the following is desirable: w ⁵ and W ⁶ in formula (II-X) and W ⁷ and W ⁸ in formula (II-Y) are atoms or groups that do not react with each other. In addition, similarly, in order to suppress polymerization between the monomer represented by the formula (1 ') or the monomer represented by the formula (2'), the following is desirable: w ⁹ and W ¹⁰ in the formula (1 ') and W ¹¹ and W ¹² in the formula (2') are each an atom or a group that do not react with each other. W ¹ and W ² in formula (I-X), W ³ and W ⁴ in formula (I-Y), W ⁵ and W ⁶ in formula (II-X), and W ⁷ and W ⁸ in formula (II-Y), respectively, may be the same. In addition, the following is desirable: w ⁹ and W ¹⁰ in the chemical formula (1') are different. Similarly, the following is desirable: w ¹¹ and W ¹² in the chemical formula (2') are different.

The polymer compound according to the embodiment has a structural unit (a). Thus, the polymer compound has a large dipole moment, and as a result, has high hole injection properties. Therefore, when the polymer compound according to the embodiment is used as a hole injection material or a hole transport material (particularly a hole transport material), high durability (light emission lifetime) can be achieved. In addition, the polymer compound according to the embodiment has a high triplet energy level and a low driving voltage. Therefore, when the polymer compound according to the embodiment is used as a hole injection material or a hole transport material (particularly a hole transport material), high hole mobility can be achieved with a low driving voltage. Therefore, the electroluminescent device using the polymer compound according to the embodiment has excellent durability (light emission lifetime) and light emission efficiency.

[ Electroluminescent device Material ]

The polymer compound according to the embodiment may be used as an electroluminescent device material. According to the polymer compound according to the embodiment, an electroluminescent device material having excellent durability (light emission lifetime) and high hole mobility is provided. In addition, according to the polymer compound according to the embodiment, an electroluminescent device material having a high triplet energy level (current efficiency) and a low driving voltage is also provided. Thus, in a second embodiment, an electroluminescent device material comprising a polymer compound according to an embodiment is provided. Alternatively, there is provided the use of the polymer compound as an electroluminescent device material.

In addition, the polymer compound according to the embodiment has a HOMO level of more than about 5.20 eV. Thus, the polymer compound according to the embodiment may also be suitably used in a quantum dot electroluminescent device (especially a hole transport layer).

The glass transition temperature (T _g) of the polymer compound according to the embodiment is not particularly limited, but is desirably greater than or equal to about 75 ℃, more desirably greater than or equal to about 90 ℃, and particularly desirably greater than or equal to about 100 ℃. On the other hand, the upper limit is not particularly limited, but less than or equal to about 200 ℃ is desirable, less than or equal to about 180 ℃ is more desirable, and less than or equal to about 150 ℃ is particularly desirable.

If the glass transition temperature (T _g) of the polymer is within the above range, it is suitable for device fabrication and devices with improved characteristics can be obtained. The glass transition temperature (T _g) of the polymer can be measured using a Differential Scanning Calorimeter (DSC) (manufactured by Seiko Instruments, brand name: DSC 6000). Meanwhile, details of the measurement method are described in the examples.

[ Electroluminescent device ]

As described above, the polymer compound according to the embodiment may be used in an electroluminescent device. In other words, the electroluminescent device comprises a pair of electrodes, and one or more organic films between the electrodes and comprising a polymer compound or electroluminescent device material according to an embodiment. Such an electroluminescent device may exhibit excellent light emitting efficiency and low driving voltage. Thus, according to a third embodiment, an electroluminescent device comprises a first electrode and a second electrode, and one or more organic films between the first electrode and the second electrode, wherein at least one layer of the organic film comprises a polymer compound according to an embodiment. The object (or effect) of the present disclosure can also be achieved by the electroluminescent device according to the present embodiment. In an embodiment, the electroluminescent device further comprises a light emitting layer between the electrodes and comprising a light emitting material capable of emitting light by triplet excitons. On the other hand, the electroluminescent device of the present embodiment may be an example of an electroluminescent device according to the present disclosure.

In addition, the present embodiment provides a method of manufacturing an electroluminescent device including a pair of electrodes, and at least one organic film disposed between the electrodes and including the polymer compound according to the embodiment, and at least one of the layers is formed by a coating method. Further, by this method, the present embodiment provides an electroluminescent device in which at least one layer of the organic film is formed by a coating method.

The polymer compound according to the embodiment and the electroluminescent device material (EL device material) according to the present embodiment (hereinafter also collectively referred to as "polymer compound/EL device material") have improved solubility in an organic solvent. For this reason, the polymer compound/EL device material according to the present embodiment can be used for manufacturing a device (particularly a thin film) by a coating method (wet process). For this reason, the present embodiment provides a liquid composition comprising the polymer compound according to the embodiment and a solvent or dispersion medium. Such liquid compositions are examples of liquid compositions according to the present disclosure.

In addition, as described above, the electroluminescent device material according to the embodiment may be used for manufacturing devices (particularly thin films) by a coating method (wet process). In view of the above, the present embodiment provides a film including the polymer compound according to the embodiment. Such films are examples of films according to the present disclosure.

In addition, the EL device material according to the present embodiment has improved hole injection properties and hole mobility. For this reason, it can also be desirably used in the formation of any organic film of a hole injecting material, a hole transporting material, or a light emitting material (host). Among them, from the viewpoint of hole transporting property, it can be used as a hole injecting material or a hole transporting material, and particularly a hole transporting material.

In other words, the present embodiment provides a composition including the polymer compound and at least one material selected from a hole transporting material, an electron transporting material, and a light emitting material. Here, the light emitting material included in the composition is not particularly limited, but may include an organometallic complex (light emitting organometallic complex compound) or a semiconductor nanoparticle (semiconductor inorganic nanoparticle).

[ Electroluminescent device ]

Hereinafter, an electroluminescent device according to the present embodiment will be described in detail with reference to fig. 1. Fig. 1 is a schematic view showing an electroluminescent device according to the present embodiment. In addition, in this specification, the "electroluminescent device" may be abbreviated as "EL device".

As shown in fig. 1, the EL device 100 according to the present embodiment includes a substrate 110, a first electrode 120 on the substrate 110, a hole injection layer 130 on the first electrode 120, a hole transport layer 140 on the hole injection layer 130, a light emitting layer 150 on the hole transport layer 140, an electron transport layer 160 on the light emitting layer 150, an electron injection layer 170 on the electron transport layer 160, and a second electrode 180 on the electron injection layer 170.

Here, the polymer compound according to the present embodiment is included in, for example, any one of organic films (organic layers) disposed between the first electrode 120 and the second electrode 180. In particular, the polymer compound may be included in the hole injection layer 130 as a hole injection material, in the hole transport layer 140 as a hole transport material, or in the light emitting layer 150 as a light emitting material (host). The polymer compound may be included in the hole injection layer 130 as a hole injection material or in the hole transport layer 140 as a hole transport material. That is, in an embodiment, the layer including the polymer compound may be a hole transport layer, a hole injection layer, or a light emitting layer. In embodiments, the layer including the polymer compound may be a hole transport layer or a hole injection layer. In embodiments, the layer including the polymer compound may be a hole transport layer.

In addition, a layer including the polymer compound/EL device material according to the present embodiment can be formed by a coating method (solution coating method). In particular, the layer may be formed by a solution coating method such as a spin coating method, a casting method, a micro gravure coating method, a bar coating method, a roll coating method, a bar coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an inkjet printing method, or the like.

As the solvent used in the solution coating method, any solvent may be used as long as it can dissolve the polymer compound/EL device material, and the solvent may be appropriately selected according to the type of the polymer compound. For example, the solvent may be toluene, xylene, ethylbenzene, diethylbenzene, mesitylene, propylbenzene, cyclohexylbenzene, dimethoxybenzene, anisole, ethoxytoluene, phenoxytoluene, isopropylbiphenyl, dimethyl anisole, phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, cyclohexane, and the like. The amount of the solvent used is not particularly limited, but in view of ease of coating, the concentration of the polymer compound may desirably be greater than or equal to about 0.1 mass% and less than or equal to about 10 mass%, or greater than or equal to about 0.5 mass% and less than or equal to about 5 mass%.

In addition, a film forming method of a layer other than the layer including the polymer compound/EL device material is not particularly limited. The layers other than the layer including the polymer compound/EL device material according to the present embodiment may be formed by, for example, a vacuum deposition method or may be formed by a solution coating method.

The substrate 110 may be a substrate used in a general EL device. For example, the substrate 110 may be a semiconductor substrate such as a glass substrate, a silicon substrate, or the like, or a transparent plastic substrate.

On the substrate 110, a first electrode 120 is formed. The first electrode 120 is particularly an anode, and is formed of a material having a large work function among metals, alloys, or conductive compounds. For example, the first electrode 120 may be formed by indium tin oxide (In ₂O₃-SnO₂: ITO), indium zinc oxide (In ₂O₃ -ZnO), tin oxide (SnO ₂), zinc oxide (ZnO), or the like as a transmissive electrode due to improved transparency and conductivity. The first electrode 120 may be formed by laminating magnesium (Mg), aluminum (Al), or the like as a reflective electrode on the transparent conductive layer. After the first electrode 120 is formed on the substrate 110, washing and UV-ozone treatment may be performed as necessary.

On the first electrode 120, a hole injection layer 130 is formed.

The hole injection layer 130 is a layer that facilitates injection of holes from the first electrode 120, and may be formed to have a thickness (dry film thickness; hereinafter) of, in particular, about 10nm or more and about 1000nm or less, or about 20nm or more and about 50nm or less.

The hole injection layer 130 may be formed of a known hole injection material. Known hole injection materials of the hole injection layer 130 may include, for example, poly (ether ketone) (TPAPEK) containing triphenylamine, 4-isopropyl-4 ' -methyldiphenyliodo (PPBI) tetrakis (pentafluorophenyl) borate, N ' -diphenyl-N, N ' -bis- [4- (phenyl-m-tolyl-amino) -phenyl ] -biphenyl-4, 4' -diamine (DNTPD), copper phthalocyanine, 4',4 "-tris (3-methylphenyl-amino) -triphenylamine (m-MTDATA), N ' -bis (1-naphthyl) -N, N ' -diphenyl-benzidine (NPB), 4',4" -tris (diphenylamino) triphenylamine (TDATA), 4',4 "-tris (N, N-2-naphthylphenylamino) triphenylamine (2-TNATA), polyaniline/dodecylbenzenesulfonic acid, poly (3, 4-ethylenedioxythiophene)/poly (4-sulfostyrene) (PEDOT), polyaniline/10-camphorsulfonic acid, and the like.

On the hole injection layer 130, a hole transport layer 140 is formed. The hole transport layer 140 is a layer having a function of transporting holes, and may be formed, for example, to a thickness of about 10nm or more and about 150nm or less, and more particularly about 20nm or more and about 50nm or less. The hole transport layer 140 may be formed by a solution coating method using the polymer compound according to the present embodiment. According to this method, the durability (light emission lifetime) of the EL device 100 can be prolonged. In addition, the current efficiency of the EL device 100 can be improved and the driving voltage can be reduced. In addition, since the hole transport layer can be formed by a solution coating method, a large area can be efficiently formed.

However, when one organic film of the EL device 100 includes a polymer compound according to an embodiment, the hole transport layer 140 may be formed of a known hole transport material. The known hole transport materials may include, for example, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC), carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole, etc., N '-bis (3-methylphenyl) -N, N' -diphenyl- [1, 1-biphenyl ] -4,4 '-diamine (TPD), 4' -tris (N-carbazolyl) triphenylamine (TCTA), and N, N '-bis (1-naphthyl) -N, N' -diphenylbenzidine (NPB).

On the hole transport layer 140, a light emitting layer 150 is formed. The light emitting layer 150 is a layer emitting light by fluorescence, phosphorescence, or the like, and is formed using a vacuum deposition method, a spin coating method, an inkjet printing method, or the like. The light emitting layer 150 may be formed, for example, with a thickness of about 10nm to about 60nm, and more particularly about 20nm to about 50 nm. The luminescent material of the luminescent layer 150 may include a known luminescent material. However, the light emitting material included in the light emitting layer 150 is desirably a light emitting material capable of emitting light (i.e., phosphorescence emission) by triplet excitons. In such a case, the driving lifetime of the EL device 100 can be further improved.

The light emitting layer 150 is not particularly limited and may have a known configuration. Desirably, the light emitting layer may comprise semiconductor nanoparticles or organometallic complexes. That is, in embodiments of the present disclosure, the organic film has a light emitting layer including semiconductor nanoparticles or an organometallic complex. When the light emitting layer includes semiconductor nanoparticles, the EL device may be a quantum dot electroluminescent device (QLED) or a quantum dot light emitting diode. In addition, when the light emitting layer includes an organometallic complex, the EL device is an organic electroluminescent device (OLED).

In the form in which the light emitting layer comprises semiconductor nanoparticles (QLEDs), the light emitting layer may comprise a plurality of semiconductor nanoparticles (quantum dots) arranged in a single layer or in multiple layers. Here, the semiconductor nanoparticle (quantum dot) may be a particle of a predetermined size having a quantum confinement effect. The diameter of the semiconductor nanoparticle (quantum dot) is not particularly limited, but is greater than or equal to about 1nm and less than or equal to about 20nm.

The semiconductor nanoparticles (quantum dots) disposed in the light emitting layer may be synthesized by a wet chemical process, an organometallic chemical deposition process, a molecular beam epitaxy process, or another similar process. Among them, the wet chemical process is a method of growing particles by placing a precursor material in an organic solvent.

In the wet chemical process, when crystals are grown, the organic solvent naturally coordinates to the surface of the quantum dot crystals and acts as a dispersant, thereby controlling the growth of the crystals. For this reason, in the wet chemical process, the growth of semiconductor nanoparticles can be easily controlled at low cost as compared with vapor deposition methods such as Metal Organic Chemical Vapor Deposition (MOCVD) and Molecular Beam Epitaxy (MBE).

The semiconductor nanoparticle (quantum dot) can adjust an energy band gap by adjusting its size so that light of various wavelengths can be obtained from the light emitting layer (quantum dot light emitting layer). Thus, a plurality of quantum dots of different sizes may realize a display that emits (or emits) light of a plurality of wavelengths. The size of the quantum dots may be selected to emit red, green, and blue light to form a color display. In addition, the dimensions of the quantum dots may be combined such that a variety of colored lights emit white light.

The semiconductor nanoparticles (quantum dots) may be a semiconductor material selected from the group consisting of: a group II-VI semiconductor compound; a group III-V semiconductor compound; group IV-VI semiconductor compounds; group IV elements (simple substances) or compounds; and combinations thereof.

The group II-VI semiconductor compound is not particularly limited but includes, for example, a binary compound selected from CdSe, cdTe, znS, znSe, znTe, znO, hgS, hgSe, hgTe, and mixtures thereof; a ternary compound selected from CdSeS、CdSeTe、CdSTe、ZnSeS、ZnTeSe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、 and mixtures thereof; and quaternary compounds selected from CdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe, hgZnSTe, and mixtures thereof.

The group III-V semiconductor compound is not particularly limited but includes, for example, a binary compound selected from GaN, gaP, gaAs, gaSb, alN, alP, alAs, alSb, inN, inP, inAs, inSb, and mixtures thereof; a ternary compound selected from GaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, and mixtures thereof; and quaternary compounds selected from GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs、InAlPSb、 and mixtures thereof.

The group IV-VI semiconductor compound is not particularly limited but includes, for example, a binary compound selected from SnS, snSe, snTe, pbS, pbSe, pbTe, and mixtures thereof; a ternary compound selected from SnSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, and mixtures thereof; and quaternary compounds selected from SnPbSSe, snPbSeTe, snPbSTe, and mixtures thereof.

The group IV element or compound is not particularly limited, but includes, for example, an elemental substance (single element) selected from Si, ge, and a mixture thereof; and a binary compound selected from SiC, siGe, and mixtures thereof.

The semiconductor nanoparticle (quantum dot) may have a uniform single structure or a core-shell dual structure. The core-shell may comprise different materials. The materials constituting each core and shell may be made of different semiconductor compounds. However, the band gap of the shell material is larger than that of the core material. In particular, structures such as ZnTeSe/ZnSe/ZnS, cdSe/ZnS, inP/ZnS, etc. are desirable.

For example, a process for fabricating quantum dots having a core (CdSe) -shell (ZnS) structure is described. The crystal is formed by injecting core (CdSe) precursor material (CH ₃)₂ Cd (dimethyl cadmium), TOPSe (trioctylphosphine selenide), etc. into an organic solvent using TOPO (trioctylphosphine oxide) as a surfactant, at this time, after maintaining for a certain time at a high temperature so that the crystal grows to a certain size, a precursor material of shell (ZnS) is injected to form a shell on the surface of the core that has been produced, as a result, cdSe/ZnS quantum dots capped with TOPO can be manufactured.

In addition, in embodiments (OLEDs) in which the light emitting layer comprises an organometallic complex, the light emitting layer 150 may comprise, for example, 6, 9-diphenyl-9 '- (5' -phenyl- [1,1':3',1 "-terphenyl ] -3-yl) 3,3 '-bis [ 9H-carbazole ], 3, 9-diphenyl-5- (3- (4-phenyl-6- (5' -phenyl- [1,1':3',1 '-terphenyl ] -3-yl) -1,3,5, -triazin-2-yl) phenyl) -9H-carbazole, 9' -diphenyl-3, 3 '-bis [ 9H-carbazole ], tris (8-hydroxyquinoline) aluminum (Alq ₃), 4' -bis (carbazol-9-yl) biphenyl (CBP), poly (N-vinylcarbazole) (PVK), 9, 10-bis (naphtalene) Anthracene (ADN), 4', 4' -tris (N-carbazolyl) triphenylamine (TCTA), 1,3, 5-tris (N-phenyl-benzimidazol-2-yl) benzene (TPBI), 3-tert-butyl-9, 10-bis (naphthalen-2-yl) anthracene (TBADN), distyrylarylene (DSA), a, 4,4 '-bis (9-carbazole) -2,2' -dimethyl-biphenyl (dmCBP) and the like as host materials.

In addition, the light emitting layer 150 may include, for example, perylene and its derivatives, rubrene and its derivatives, coumarin and its derivatives, 4-dicyanomethylene-2- (p-dimethylaminostyryl) -6-methyl-4H-pyran (DCM) and its derivatives, iridium (Ir) complexes such as bis [2- (4, 6-difluorophenyl) pyridine ] picolinic acid iridium (III) (FIrpic)), bis (1-phenylisoquinoline) (acetylacetonate) iridium (III) (Ir (piq) ₂ (acac)), tris (2-phenylpyridine) iridium (III) (Ir (ppy) ₃), tris (2- (3-p-dimethylphenyl) phenyl) pyridine iridium (III), osmium (Os) complexes, platinum complexes, and the like as dopant materials. Among these, the following is desirable: the luminescent material is a luminescent organometallic complex compound.

The method for forming the light emitting layer is not particularly limited. Which can be formed by coating a coating liquid (solution coating method) including semiconductor nanoparticles or an organometallic complex. At this time, it is desirable to select a solvent that does not dissolve a material (hole transport material, particularly the polymer compound) in the hole transport layer as a solvent constituting the coating liquid.

On the light emitting layer 150, an electron transport layer 160 is formed. The electron transport layer 160 is a layer having a function of transporting electrons, and is formed using a vacuum deposition method, a spin coating method, an inkjet method, or the like. For example, the electron transport layer 160 may be formed to have a thickness of greater than or equal to about 15nm and less than or equal to about 50 nm.

The electron transport layer 160 may be formed of a known electron transport material. The known electron transport materials may include, for example, (8-hydroxyquinoline) lithium (lithium hydroxyquinoline) (Liq), tris (8-hydroxyquinoline) aluminum (Alq ₃), and compounds having a nitrogen-containing aromatic ring. Examples of the compound having a nitrogen-containing aromatic ring may include, for example, a compound including a pyridine ring such as 1,3, 5-tris [ (3-pyridyl) -benzene-3-yl ] benzene, a compound including a triazine ring such as 2,4, 6-tris (3' - (pyridin-3-yl) biphenyl-3-yl) -1,3, 5-triazine, a compound including an imidazole ring such as 2- (4- (N-phenylbenzimidazolyl-1-yl-phenyl) -9, 10-dinaphthyl anthracene or 1,3, 5-tris (N-phenyl-benzimidazol-2-yl) benzene (TPBI). The electron transport materials may be used singly or as a mixture of two or more thereof.

On the electron transport layer 160, an electron injection layer 170 is formed. The electron injection layer 170 is a layer having a function of promoting injection of electrons from the second electrode 180. The electron injection layer 170 is formed using a vacuum deposition method or the like. The electron injection layer 170 may be formed to have a thickness of greater than or equal to about 0.1nm and less than or equal to about 5nm, and more particularly greater than or equal to about 0.3nm and less than or equal to about 2 nm. As a material for forming the electron injection layer 170, any known material may be used. For example, the electron injection layer 170 may be formed of a lithium compound such as (8-hydroxyquinoline) lithium (hydroxyquinoline lithium) (Liq) and lithium fluoride (LiF), sodium chloride (NaCl), cesium fluoride (CsF), lithium oxide (Li ₂ O), or barium oxide (BaO).

On the electron injection layer 170, a second electrode 180 is formed. The second electrode 180 is formed using a vacuum deposition method or the like. In particular, the second electrode 180 is a cathode, and is formed of a material having a small work function, such as a metal, an alloy, or a conductive compound. For example, the second electrode 180 may be formed using a metal such as lithium (Li), magnesium (Mg), aluminum (Al), calcium (Ca), or aluminum-lithium (Al-Li), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or the like as a reflective electrode. The second electrode 180 may be formed to have a thickness of greater than or equal to about 10nm and less than or equal to about 200nm, and more particularly greater than or equal to about 50nm and less than or equal to about 150 nm. Alternatively, the second electrode 180 may be formed by a thin film of a metal material of less than or equal to about 20nm or a transparent conductive layer such as indium tin oxide (In ₂O₃-SnO₂) and indium zinc oxide (In ₂O₃ -ZnO) as a transmissive electrode.

The EL device 100 according to the present embodiment has been described above as an example of an electroluminescent device according to the present disclosure. The EL device 100 according to the present embodiment further improves the light emitting efficiency (current efficiency) and reduces the driving voltage by mounting an organic film (particularly, a hole transport layer or a hole injection layer) including a polymer compound. In addition, the light emission efficiency (current efficiency) may be further improved and the driving voltage may be reduced.

The stacked structure of the EL device 100 according to the present embodiment is not limited to the above embodiment. The EL device 100 according to the present embodiment may have another known stacked structure. For example, in EL device 100, one or more of hole injection layer 130, hole transport layer 140, electron transport layer 160, and electron injection layer 170 may be omitted or additional layers may be further included. In addition, each layer of the EL device 100 may be formed as a single layer or as a plurality of layers.

For example, the EL device 100 may further include a hole blocking layer between the electron transport layer 160 and the light emitting layer 150 to prevent excitons or holes from diffusing into the electron transport layer 160. The hole blocking layer may be formed by, for example, an oxadiazole derivative, a triazole derivative, or a phenanthroline derivative.

In addition, the polymer compound according to the present embodiment may be applied to electroluminescent devices other than QLEDs or OLEDs. Additional electroluminescent devices comprising the polymer compound according to embodiments may include, but are not particularly limited to, for example, organic-inorganic perovskite light emitting devices.

The present disclosure includes the following aspects and embodiments.

1. A polymer compound comprising a structural unit (a) represented by chemical formula (1):

[ chemical formula (1) ]

In the chemical formula (1), a radical of formula (I),

2. The polymer compound described in the above 1, further comprising a structural unit (B) represented by the chemical formula (2):

[ chemical formula (2) ]

Wherein, in the chemical formula (2),

3. The polymer compound described in the above 2 wherein the molar ratio of the structural unit (a) is greater than or equal to about 10 mol% and less than or equal to about 70 mol% (the total molar ratio of the structural unit (a) and the structural unit (B) is 100 mol%).

4. The polymer compound described in any one of the above 1 to 3, wherein in the chemical formula (1), X ¹ is an aromatic hydrocarbon group having 6 to 25 ring member atoms substituted as follows: an alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group or an alkyl group having 1 to 14 carbon atoms substituted with a group having a carboxyl group, and Y ¹ is an aromatic hydrocarbon group having 6 to 25 ring member atoms substituted or unsubstituted with a substituent other than: alkyl groups having 1 to 14 carbon atoms substituted with a carboxyl group or alkyl groups having 1 to 14 carbon atoms substituted with a group having a carboxyl group.

5. The polymer compound described in the above 2 or 3, wherein R ¹¹-R¹⁴、R²¹-R²⁴、L¹、Ar¹、Ar² and Y ¹ in the chemical formula (1) are each the same as R ³¹-R³⁴、R⁴¹-R⁴⁴、L²、Ar³、Ar⁴ and Y ² in the chemical formula (2).

6. The polymer compound described in any one of the above 1 to 5, wherein the alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group or the alkyl group having 1 to 14 carbon atoms substituted with a group having a carboxyl group has a structure represented by the formula (i):

[ formula (i) ]

***-C_tH_2t-(Z¹)_u-COOH (i)

Wherein, in the chemical formula (i),

T represents an integer of 1 to 14,

U is 0 or 1, and the number of the elements is,

Z ¹ represents an organic group other than an alkylene group, and

* Bonded to an aromatic hydrocarbon group having 6 to 25 ring member atoms constituting either X ¹ or Y ¹.

7. The polymer compound described in any one of the above 1 to 6, wherein in the chemical formula (1), X ¹ is one of the groups represented by the chemical formulas (3-1) to (3-12):

[ formulae (3-1) to (3-12) ]

Wherein, in the chemical formulas (3-1) to (3-12),

R ³⁰¹-R³¹⁵ is each independently a substituted or unsubstituted alkylene group having 1 to 14 carbon atoms, and

* Bonded to the nitrogen atom.

8. The polymer compound described in the above 7, wherein in the chemical formula (1), X ¹ is one of the groups represented by the chemical formulas (3-10) to (3-12).

9. The polymer compound described in any one of the above 1 to 8, wherein in the chemical formula (1), Y ¹ is any one of the groups represented by the chemical formulas (5-1) to (5-9):

[ formulae (5-1) to (5-9) ]

Wherein, in the chemical formulas (5-1) to (5-9),

R ⁵⁰¹-R⁵¹⁵ is each independently a substituted or unsubstituted alkylene group having 1 to 14 carbon atoms.

10. The polymer compound described in any one of the above 1 to 9, wherein in the chemical formula (1), L ¹ is one of the groups represented by the chemical formulas (7-1) to (7-24):

[ formulae (7-1) to (7-24) ]

Wherein, in the chemical formulas (7-1) to (7-24),

* Is bound to a nitrogen atom and is bound to Ar ¹.

11. The polymer compound described in any one of the above 1 to 10, wherein-L ¹-Ar¹-N(Ar²)(X¹ in the chemical formula (1) is any one of the groups represented by the chemical formulas (9-1) to (9-3):

[ formulae (9-1) to (9-3) ]

Wherein, in the chemical formulas (9-1) to (9-3),

N, p, and r are each independently 0, 1, 2, or 3,

O, q, and s are each independently 0, 1, 2,3, or 4,

When any of n, o, p, q, R, and s is 2 or more, each R ⁹⁰¹, each R ⁹⁰², each R ⁹⁰³, each R ⁹⁰⁴, each R ⁹⁰⁵, or each R ⁹⁰⁶ is the same or different,

X ¹ is the same as defined in the chemical formula (1), and

* Bonded to the nitrogen atom.

12. An electroluminescent device material comprising a polymer compound as described in any one of claims 1 to 11 above.

13. An electroluminescent device comprising: a first electrode and a second electrode, and one or more organic films between the first electrode and the second electrode, wherein at least one layer of the organic films comprises a polymer compound described in any one of 1.to 11.

14. The electroluminescent device described in 13 above, wherein the layer comprising the polymer compound is a hole transporting layer or a hole injecting layer.

15. The electroluminescent device described in 13 above, wherein the organic film comprises a light emitting layer comprising semiconductor nanoparticles or organometallic complexes.

Examples

The present disclosure is described in more detail using the following examples and comparative examples. However, the technical scope of the present disclosure is not limited to the following embodiments. In the following examples, each operation was performed at room temperature (25 ℃) unless specifically described. In addition, "%" and "parts" mean "% by mass" and "parts by mass", respectively, unless specifically indicated otherwise.

Synthesis example 1

(Synthesis of Compound A-1)

Compound A-1 was synthesized according to the following reaction.

[ Reaction scheme A-1]

In a 1L four-necked flask, 10-bromodecanoic acid (50.0 g) and THF (400 mL) were placed, followed by stirring at room temperature under a nitrogen atmosphere. Subsequently, anhydrous trifluoroacetic acid (TFAA) (160 g) was added dropwise thereto, followed by stirring for 1 hour. T-butanol (76.0 g) was then added dropwise thereto, followed by stirring for 12 hours. The resultant was neutralized with a saturated aqueous sodium hydrogencarbonate solution, extracted with ethyl acetate after THF was removed by distillation under reduced pressure, washed with water, and dried over magnesium sulfate. After the solvent was removed by distillation under reduced pressure, the residue was purified by column chromatography (silica gel, hexane/ethyl acetate) to obtain tert-butyl 10-bromodecanoate (37.8 g).

In a 1L four-necked flask, the obtained tert-butyl 10-bromodecanoate (20.0 g) and THF (700 mL) were placed, followed by stirring at 0℃under a nitrogen atmosphere. Subsequently, potassium t-butoxide (t-BuOK) (7.30 g) was added thereto, followed by stirring for 10 minutes. To this was added dropwise a solution prepared by dissolving 2-bromofluorene (5.31 g) in THF (55 mL), followed by stirring for 1 hour. Subsequently, the reaction mixture was allowed to warm to room temperature and stirred at room temperature for 12 hours. After 100mL of water was added thereto and the solvent was removed by distillation under reduced pressure, the residue was washed with ethyl acetate, washed with water, and dried over magnesium sulfate. Subsequently, the solvent was removed by distillation under reduced pressure to obtain di-tert-butyl-10, 10' - (2-bromo-9H-fluorene-9, 9-diyl) bis (decanoate) (12.4 g).

In a 200mL four-necked flask, the obtained di-t-butyl-10, 10' - (2-bromo-9H-fluorene-9, 9-diyl) bis (decanoate) (10.9 g), N- (4- (9H-carbazolyl) phenyl) -4-chloro-N- (4-chlorophenyl) aniline (7.99 g), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂(dba)₃, 0.38 g), tri-t-butylphosphonium tetrafluoroborate (t-Bu ₃PH·BF₄, 0.500 g), sodium t-butoxide (t-Buona) (3.21 g), and toluene (83 mL) were placed, and then stirred under a nitrogen atmosphere at 100℃for 5 hours. After filtration by using Celite (registered trademark, the same applies hereinafter), activated carbon (4.0 g) and zeolite (4.0 g) were added thereto, followed by stirring at 110℃for 30 minutes. The solid was filtered through celite and the filtrate was passed through silica gel. After the solvent was removed by distillation under reduced pressure, the residue was purified by column chromatography (silica gel, hexane/toluene) to obtain di-tert-butyl-10, 10' - (2- (2- (4- (bis (4-chlorophenyl) amino) phenyl) -9H-carbazol-9-yl) -9H-fluorene-9, 9-diyl) bis (decanoate) (3.55 g).

In a 100mL four-necked flask, the obtained di-tert-butyl-10, 10'- (2- (2- (4- (bis (4-chlorophenyl) amino) phenyl) -9H-carbazol-9-yl) -9H-fluorene-9, 9-diyl) bis (decanoate) (3.55 g), dipinacolol diboron (2.89 g), potassium acetate (KOAc) (1.95 g), pd ₂(dba)₃ (0.178 g), 2-dicyclohexylphosphino-2', 4',6' -triisopropylbiphenyl (XPhos) (0.231 g), and 1, 4-dioxane (47 mL) were placed, followed by stirring under nitrogen atmosphere for 4 hours. The reaction solution was cooled to room temperature, and the solid was filtered therefrom by using celite. After the solvent was removed by distillation under reduced pressure, the residue was dissolved in toluene (100 mL), and activated carbon (1 g) and zeolite (1 g) were added thereto, followed by stirring at 120 ℃ for 30 minutes. The solid was filtered therefrom by using celite, and the filtrate therefrom was passed through silica gel. After the solvent was removed by distillation under reduced pressure, ethanol (50 mL) was added thereto, followed by stirring at 70 ℃ for 1 hour, filtration, and drying to obtain compound a-1 (3.82 g).

Synthesis example 2

(Synthesis of Compound A-2)

Compound A-2 was synthesized according to the following reaction.

[ Reaction scheme A-2]

In a 1L four-necked flask, 10-bromodecane (25.0 g) and THF (200 mL) were placed, followed by stirring at 0℃under a nitrogen atmosphere. Subsequently, potassium t-butoxide (12.6 g) was added thereto, followed by stirring for 10 minutes. To this was added dropwise a solution prepared by dissolving 2-bromofluorene (5.31 g) in THF (55 mL), followed by stirring for 1 hour. The reaction mixture was allowed to warm to room temperature and stirred at room temperature for 12 hours. After 100mL of water was added thereto and the solvent was removed by distillation under reduced pressure, the residue was washed with ethyl acetate, washed with water, and dried over magnesium sulfate. The solvent was removed by distillation under reduced pressure to give 2-bromo-9, 9-di-n-decyl-9H-fluorene (18.7 g).

In a 200mL four-necked flask, the obtained 2-bromo-9, 9-di-N-decyl-9H-fluorene (5.26 g), N- (4- (9H-carbazolyl) phenyl) -4-chloro-N- (4-chlorophenyl) aniline (5.88 g), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂(dba)₃, 0.251 g), tri-t-butylphosphonium tetrafluoroborate (t-Bu ₃PH·BF₄, 0.334 g), sodium t-butoxide (4.40 g), and toluene (55 mL) were placed, and then stirred under a nitrogen atmosphere at 100℃for 3 hours. After removing the solids by filtration using celite, activated carbon (3.0 g) and zeolite (3.0 g) were added to the filtrate, followed by stirring at 110 ℃ for 30 minutes. The solid was filtered through the use of celite and the filtrate from it was passed through silica gel. After the solvent was removed by distillation under reduced pressure, the residue was purified by column chromatography (silica gel, hexane/toluene) to obtain 4-chloro-N- (4-chlorophenyl) -N- (4- (9, 9-di-N-decyl-9H-fluoren-2-yl) -9H-carbazol-2-yl) phenyl) aniline (7.35 g).

In a 100mL four-necked flask, the obtained 4-chloro-N- (4-chlorophenyl) -N- (4- (9, 9-di-N-decyl-9H-fluoren-2-yl) -9H-carbazol-2-yl) phenyl) aniline (7.35 g), dipinacol diboron (7.07 g), potassium acetate (4.68 g), pd ₂(dba)₃ (0.436 g), XPhos (0.568 g), and 1, 4-dioxane (65 mL) were placed, followed by reflux under nitrogen atmosphere for 4 hours. The reaction solution was cooled to room temperature, and the solid was filtered therefrom by using celite. After the solvent was removed by distillation under reduced pressure, the residue was dissolved in toluene (100 mL), and activated carbon (2 g) and zeolite (2 g) were added thereto, followed by stirring at 120 ℃ for 30 minutes. The solid was filtered therefrom by using celite, and the filtrate therefrom was passed through silica gel. After the solvent was removed by distillation under reduced pressure, the residue was recrystallized from acetonitrile and dried to obtain compound a-2 (7.35 g).

Synthesis example 3

(Synthesis of Compound B-1)

Compound B-1 was synthesized according to the following reaction.

[ Reaction scheme B-1]

In a 1L four-necked flask, t-butyl bromoacetate (25.0 g) and THF (400 mL) were placed, followed by stirring at 0℃under a nitrogen atmosphere. Subsequently, potassium t-butoxide (14.3 g) was added thereto, followed by stirring for 10 minutes. To this was added dropwise a solution prepared by dissolving 2, 7-dibromofluorene (13.8 g) in THF (80 mL), followed by stirring for 1 hour. The reaction mixture was allowed to warm to room temperature and stirred at room temperature for 12 hours. After adding water (100 mL) thereto and removing the solvent by distillation under reduced pressure, the residue was washed with ethyl acetate, washed with water, and dried over magnesium sulfate. After the solvent was removed by distillation under reduced pressure, the residue was recrystallized from ethyl acetate to obtain compound B-1 (18.2 g).

Synthesis example 4

(Synthesis of Compound B-2)

Compound B-2 was synthesized according to the following reaction.

[ Reaction scheme B-2]

In a 1L four-necked flask, 6-bromohexanoic acid (50.0 g) and THF (400 mL) were placed, followed by stirring at room temperature under a nitrogen atmosphere. Subsequently, anhydrous trifluoroacetic acid (215 g) was added dropwise thereto, followed by stirring for 1 hour. Then, t-butanol (114 g) was added dropwise thereto, followed by stirring for 12 hours. The resultant was neutralized with a saturated aqueous sodium hydrogencarbonate solution, after THF was distilled off under reduced pressure, extracted with ethyl acetate, washed with water, and dried over magnesium sulfate. The solvent was removed by distillation under reduced pressure to give tert-butyl 6-bromohexanoate (58.0 g).

In a 1L four-necked flask, the obtained tert-butyl 6-bromohexanoate (15.0 g) and THF (400 mL) were placed, followed by stirring at 0℃under a nitrogen atmosphere. Subsequently, potassium t-butoxide (6.70 g) was added thereto, followed by stirring for 10 minutes. Then, a solution prepared by dissolving 2, 7-dibromofluorene (6.45 g) in THF (65 mL) was added thereto dropwise, followed by stirring for 1 hour. The reaction mixture was allowed to warm to room temperature and stirred at room temperature for 12 hours. After adding water (100 mL) thereto and removing the solvent by distillation under reduced pressure, the residue was washed with ethyl acetate, washed with water, and dried over magnesium sulfate. After the solvent was removed by distillation under reduced pressure, the residue was recrystallized from ethyl acetate to obtain compound B-2 (7.21 g).

Synthesis example 5

(Synthesis of Compound B-3)

Compound B-3 was synthesized according to the following reaction.

[ Reaction scheme B-3]

Compound B-3 (9.05 g) was obtained in the same manner as in Synthesis example 4, except that: 8-bromooctanoic acid was used instead of 6-bromohexanoic acid in the first step of the synthesis reaction. The molar ratio of each compound used in the synthesis was the same as in synthesis example 4.

Synthesis example 6

(Synthesis of Compound B-4)

Compound B-4 was synthesized according to the following reaction.

[ Reaction scheme B-4]

Compound B-4 (14.6 g) was obtained in the same manner as in Synthesis example 3, except that: instead of tert-butyl bromoacetate in the first step of the synthesis reaction, tert-butyl 10-bromodecanoate was used. The molar ratio of each compound used in the synthesis was the same as in synthesis example 3.

Synthesis example 7

(Synthesis of Compound B-5)

Compound B-5 was synthesized according to the following reaction.

[ Reaction scheme B-5]

Compound B-5 (36.8 g) was obtained in the same manner as in Synthesis example 4, except that: 12-bromododecanoic acid was used instead of 6-bromohexanoic acid in the first step of the synthesis reaction. The molar ratio of each compound used in the synthesis was the same as in synthesis example 4.

Synthesis example 8

(Synthesis of Compound B-6)

Compound B-6 was synthesized according to the following reaction.

[ Reaction scheme B-6]

Compound B-6 (15.8 g) was obtained in the same manner as in Synthesis example 3, except that: instead of tert-butyl bromoacetate in the first step of the synthesis reaction, 2- (4-bromobutyl) -1, 3-dioxolane was used. The molar ratio of each compound used in the synthesis was the same as in synthesis example 3.

Synthesis example 9

(Synthesis of Compound C-1)

Compound C-1 was synthesized according to the following reaction.

[ Reaction scheme C-1]

In a 100mL four-necked flask, 2-bromocarbazole (20.0 g), 4-chloro-N- (4-chlorophenyl) -N- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) aniline (10.0 g), sodium carbonate (4.84 g), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃)₄, 1.31 g), toluene (80 mL), ethanol (EtOH) (30 mL), and water (30 mL) were placed, then stirred at 100 ℃ (bath temperature) for 3 hours.

In a four-necked flask replaced with argon gas, the obtained N- (4- (9-carbazol-2-yl) phenyl) -4-chloro-N- (4-chlorophenyl) aniline (6.00 g), 1-bromo-4-hexylbenzene (3.00 g), tris (dibenzylideneacetone) dipalladium (Pd ₂(dba)₃, 0.580 g), tri-t-butylphosphonium tetrafluoroborate (tBu ₃PH·BF₄, 0.276 g), sodium t-butoxide (t-Buona) (2.43 g), and toluene (60 mL) were placed, and then heated at 110℃for 7 hours. The resultant was cooled to room temperature and then purified by celite to filter the solid. After the solvent was removed by distillation under reduced pressure, the residue was purified by column chromatography to obtain 4-chloro-N- (4-chlorophenyl) -N- (4- (9- (4-hexylphenyl) -9-carbazol-2-yl) phenyl) aniline (1.60 g).

In a 50mL 3-necked flask, the obtained 4-chloro-N- (4-chlorophenyl) -N- (4- (9- (4-hexylphenyl) -9-carbazol-2-yl) phenyl) aniline (1.60 g), dipinacol diboron (1.90 g), potassium acetate (KOAc) (1.47 g), tris (dibenzylideneacetone) dipalladium (Pd ₂(dba)₃, 0.114 g), 2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl (XPh s,0.177 g), and 1, 4-dioxane (16 mL) were placed, followed by stirring under nitrogen atmosphere at 100℃for 3 hours. After cooling to room temperature, insoluble material was removed from it by using diatomaceous earth as a filtration aid. After the solvent was removed by distillation under reduced pressure, the residue was dissolved in a mixed solvent of toluene (20 mL) and hexane (40 mL), and activated carbon (2.0 g) was added thereto, followed by reflux for 30 minutes. After insoluble matter was removed therefrom by using diatomaceous earth as a filtration aid and furthermore the solvent was removed by distillation under reduced pressure, the residue was recrystallized from toluene/acetonitrile to obtain compound C-1 (1.85 g).

Synthesis example 10

(Synthesis of Compound C-2)

Compound C-2 was synthesized according to the following reaction.

[ Reaction scheme C-2]

In a 1L four-necked flask, 9- (4-hexylphenyl) -3-iodo-9-carbazole (20.0 g), 4- (diphenylamino) phenylboronic acid (15.3 g), sodium carbonate (9.51 g), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃)₄, 2.49 g), toluene (221 mL), ethanol (110 mL), and water (110 mL) were placed, followed by stirring at 120 ℃ (bath temperature) for 3 hours.

In a 500mL four-necked flask, the obtained 4- (9- (4-hexylphenyl) -9-carbazol-3-yl) -N, N-diphenyl) aniline (17.7 g) and N, N-dimethylformamide (DMF, 310 mL) were placed, then cooled with ice, and a solution prepared by dissolving N-bromosuccinimide (NBS) (11.7 g) in DMF (30 mL) under a nitrogen atmosphere was added dropwise thereto, followed by stirring for 6 hours. After filtration of insoluble material, 4-bromo-N- (4-bromophenyl) -N- (4- (9- (4-hexylphenyl) -9-carbazol-3-yl) phenyl) aniline (14.0 g) was obtained by washing with methanol (800 mL) and water (800 mL) and drying under vacuum.

The obtained 4-bromo-N- (4-bromophenyl) -N- (4- (9- (4-hexylphenyl) -9-carbazol-3-yl) phenyl) aniline (14.0 g), dipinacolol diboron (14.8 g), potassium acetate (KOAc) (11.4 g), a [1,1' -bis (diphenylphosphino) ferrocene ] palladium (II) dichloride complex with dichloromethane (PdCl ₂(dppf)CH₂Cl₂, 0.477 g), and 1, 4-dioxane (160 mL) were refluxed at 100 ℃ under nitrogen atmosphere for 4 hours in a 500mL four-necked flask. The reaction solution was cooled to room temperature, and after the solid was filtered using celite as a filtration aid, the filtrate therefrom was passed through silica gel. After the solvent was removed by distillation under reduced pressure, the residue was dissolved in toluene (200 mL), and activated carbon (14.2 g) was added thereto, followed by reflux for 30 minutes. After filtering the activated carbon and removing the solvent by distillation under reduced pressure, compound C-2 (11.9 g) was obtained by recrystallization via a mixed solvent of toluene and acetonitrile.

Synthesis example 11

(Synthesis of Compound C-3)

Compound C-3 was synthesized according to the following reaction.

[ Reaction scheme C-3]

In a 500mL four-necked flask, 2- (2-biphenylyl) amino-9, 9-dimethylfluorene (12.0 g), 9- (4 'bromo- [1,1' -biphenyl ] -4-yl) -3, 6-dichloro-9H-carbazole (15.5 g), palladium acetate (Pd (AOc) ₂, 0.372 g), tri-tert-butylphosphonium tetrafluoroborate (tBu ₃PH·BF₄, 0.722 g), sodium t-butoxide (6.38 g), and toluene (330 mL) were placed, followed by stirring at 100℃for 1 hour under a nitrogen atmosphere. After insoluble matters were filtered by using celite, activated carbon (6.0 g) and zeolite (6.0 g) were added thereto, followed by stirring at 110℃for 30 minutes. After filtering the solid by using celite, the filtrate therefrom was passed through silica gel. After removal of the solvent by distillation under reduced pressure, the residue was purified by column chromatography (silica gel, hexane/toluene) to obtain N- ([ 1,1 '-biphenyl ] -2-yl) -N- (4' - (3, 6-dichloro-9H-carbazol-9-yl) - [1,1 '-biphenyl ] -4-yl) -9,9' -dimethyl-9H-fluoren-2-amine (18.2 g, 73.4%).

In a 200mL four-necked flask, the obtained N- ([ 1,1' -biphenyl ] -2-yl) -N- (4 ' - (3, 6-dichloro-9H-carbazol-9-yl) - [1,1' -biphenyl ] -4-yl) -9,9' -dimethyl-9H-fluoren-2-amine (9.00 g), dipinacol diboron (7.64 g), potassium acetate (7.08 g), tris (dibenzylideneacetone) dipalladium (Pd ₂(dba)₃, 0.551 g), 2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl (XPhos, 0.860 g), and 1, 4-dioxane (100 mL) were placed, followed by reflux under nitrogen atmosphere for 4 hours. The reaction solution was cooled to room temperature, and then treated with celite to filter the solid. After the solvent was removed by distillation under reduced pressure, the residue was dissolved in toluene (100 mL), and activated carbon (3 g) and zeolite (3 g) were added thereto, followed by stirring at 130 ℃ for 30 minutes. After filtering the solid by using celite, the filtrate therefrom was passed through silica gel. After the solvent was removed by distillation under reduced pressure, the residue was recrystallized from a mixed solvent of toluene and hexane and dried to obtain compound C-3 (7.88 g, 63.5%).

Example 1-1

Compound C-1 of synthesis example 9 (1.441 g), 2, 7-dibromo-9, 9-di-n-decylfluorene (hereinafter, referred to as "compound D-1") (0.953 g), compound B-4 of synthesis example 6 (0.131 g), palladium acetate (3.90 mg), tris (2-methoxyphenyl) phosphine (36.8 mg), toluene (54 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (5.88 g) were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85 ℃ for 6 hours. Subsequently, phenylboric acid (210 mg), bis (triphenylphosphine) palladium (II) dichloride (73.7 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (5.88 g) and then stirred at 85 ℃ for 6 hours were added thereto. Then, sodium N, N-diethyldithiocarbamate trihydrate (8.97 g) dissolved in ion-exchanged water (50 mL) was added thereto, followed by stirring at 85℃for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water, and dried under vacuum to obtain polymer compound P-1 (1.01 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-1 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-1 were 83,600g/mol and 2.39, respectively.

From the monomer input ratio, it is estimated that the polymer compound P-1 obtained in this manner is a polymer compound having the following structural unit.

[ Polymer Compound P-1]

Examples 1 to 2

Compound C-1 of Synthesis example 9 (1.421 g), compound D-1 (0.825 g), compound B-4 of Synthesis example 6 (0.259 g), palladium acetate (3.90 mg), tris (2-methoxyphenyl) phosphine (36.8 mg), toluene (54 mL), and a 20 mass% aqueous tetraethylammonium hydroxide solution (8.90 g) were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (209 mg), bis (triphenylphosphine) palladium (II) dichloride (72.7 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (8.90 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. Then, sodium N, N-diethyldithiocarbamate trihydrate (8.97 g) dissolved in ion-exchanged water (50 mL) was added thereto, followed by stirring at 85℃for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-2 (1.23 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-2 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-2 were 108,000g/mol and 2.24, respectively.

From the monomer input ratio, it is estimated that the polymer compound P-2 obtained in this manner is a polymer compound having the following structural unit.

[ Polymer Compound P-2]

Examples 1 to 3

Compound C-1 of Synthesis example 9 (1.40 g), compound D-1 (0.721 g), compound B-4 of Synthesis example 6 (0.383 g), palladium acetate (3.80 mg), tris (2-methoxyphenyl) phosphine (36.0 mg), toluene (54 mL), and a 20 mass% aqueous tetraethylammonium hydroxide solution (8.78 g) were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (206 mg), bis (triphenylphosphine) palladium (II) dichloride (71.7 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (8.78 g) were added thereto, followed by stirring at 85 ℃ for 6 hours.

After that, sodium N, N-diethyldithiocarbamate trihydrate (5.76 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85 ℃ for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-3 (1.16 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-3 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-3 were 125,000g/mol and 2.24, respectively.

From the monomer input ratio, it is estimated that the polymer compound P-3 obtained in this manner is a polymer compound having the following structural unit.

[ Polymer Compound P-3]

Examples 1 to 4

Compound C-1 (1.36 g), compound D-1 (0.501 g), compound B-4 (0.621 g), palladium acetate (3.70 mg), tris (2-methoxyphenyl) phosphine (35.1 mg), toluene (54 mL), and a20 mass% aqueous tetraethylammonium hydroxide solution (8.55 g) of Synthesis example 9, synthesis example 6 were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (201 mg), bis (triphenylphosphine) palladium (II) dichloride (69.8 mg), and a20 mass% tetraethylammonium hydroxide aqueous solution (8.55 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. Then, sodium N, N-diethyldithiocarbamate trihydrate (5.60 g) dissolved in ion-exchanged water (50 mL) was added thereto, followed by stirring at 85℃for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-4 (1.00 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-4 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-4 were 383,000g/mol and 3.01, respectively.

From the monomer input ratio, it is estimated that the polymer compound P-4 obtained in this manner is a polymer compound having the following structural unit.

[ Polymer Compound P-4]

Examples 1 to 5

Compound C-1 of Synthesis example 9 (1.33 g), compound D-1 (0.293 g), compound B-4 of Synthesis example 6 (0.846 g), palladium acetate (3.60 mg), tris (2-methoxyphenyl) phosphine (34.1 mg), toluene (54 mL), and a20 mass% aqueous tetraethylammonium hydroxide solution (8.32 g) were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (195 mg), bis (triphenylphosphine) palladium (II) dichloride (68.0 mg), and a20 mass% tetraethylammonium hydroxide aqueous solution (8.32 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. Then, sodium N, N-diethyldithiocarbamate trihydrate (5.46 g) dissolved in ion-exchanged water (50 mL) was added thereto, followed by stirring at 85℃for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-5 (0.458 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-5 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-5 were 393,000g/mol and 2.36, respectively.

From the monomer input ratio, it is estimated that the polymer compound P-5 obtained in this manner is a polymer compound having the following structural unit.

[ Polymer Compound P-5]

Examples 1 to 6

Compound C-2 (1.44 g), compound D-1 (0.953 g), compound B-4 (0.131 g), palladium acetate (3.90 mg), tris (2-methoxyphenyl) phosphine (37.0 mg), toluene (54 mL), and a20 mass% aqueous tetraethylammonium hydroxide solution (9.03 g) of Synthesis example 10, were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (212 mg), bis (triphenylphosphine) palladium (II) dichloride (73.7 mg), and a20 mass% tetraethylammonium hydroxide aqueous solution (9.03 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. Then, sodium N, N-diethyldithiocarbamate trihydrate (5.92 g) dissolved in ion-exchanged water (50 mL) was added thereto, followed by stirring at 85℃for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-6 (1.45 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-6 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-6 were 117,000g/mol and 2.35, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-6 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-6]

Examples 1 to 7

Compound C-2 (1.40 g), compound D-1 (0.721 g) of Synthesis example 10, compound B-4 (0.383 g), palladium acetate (3.90 mg), tris (2-methoxyphenyl) phosphine (37.0 mg), toluene (54 mL), and a 20 mass% aqueous tetraethylammonium hydroxide solution (8.78 g) of Synthesis example 6 were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (206 mg), bis (triphenylphosphine) palladium (II) dichloride (71.7 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (8.78 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. After that, sodium N, N-diethyldithiocarbamate trihydrate (5.76 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85 ℃ for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-7 (1.04 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-7 obtained were measured by SEC. As a result, the Mw and Mw/Mn of polymer compound P-7 were 143,000g/mol and 2.37, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-7 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-7]

Examples 1 to 8

Compound C-2 (1.36 g), compound D-1 (0.501 g), compound B-4 (0.621 g), palladium acetate (3.70 mg), tris (2-methoxyphenyl) phosphine (37.0 mg), toluene (54 mL), and a 20 mass% aqueous tetraethylammonium hydroxide solution (8.55 g) of Synthesis example 10, synthesis example 6 were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (479 mg), bis (triphenylphosphine) palladium (II) dichloride (69.8 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (8.55 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. After that, sodium N, N-diethyldithiocarbamate trihydrate (5.76 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85 ℃ for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-8 (1.01 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-8 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-8 were 99,600g/mol and 1.74, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-8 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-8]

Examples 1 to 9

Compound C-2 (1.32 g), compound D-1 (0.293 g), compound B-4 (0.846 g), palladium acetate (3.60 mg), tris (2-methoxyphenyl) phosphine (34.1 mg), toluene (54 mL), and a 20 mass% aqueous tetraethylammonium hydroxide solution (8.32 g) of Synthesis example 10, were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (467 mg), bis (triphenylphosphine) palladium (II) dichloride (68.0 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (8.32 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. After that, sodium N, N-diethyldithiocarbamate trihydrate (5.76 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85 ℃ for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was removed by distillation under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-9 (1.11 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-9 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-9 were 355,000g/mol and 2.32, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-9 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-9]

Examples 1 to 10

Compound C-1 of Synthesis example 9 (1.50 g), compound D-1 (0.551 g), compound B-1 of Synthesis example 3 (0.503 g), palladium acetate (4.10 mg), tris (2-methoxyphenyl) phosphine (38.5 mg), toluene (54 mL), and a 20 mass% aqueous tetraethylammonium hydroxide solution (9.40 g) were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (220 mg), bis (triphenylphosphine) palladium (II) dichloride (76.8 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (9.40 g), and sodium carbamate trihydrate (6.16 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-10 (1.15 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the resulting polymer compound P-10 were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-10 were 137,000g/mol and 1.63, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-10 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-10]

Examples 1 to 11

Compound C-1 (1.41 g), compound D-1 (0.521 g) of Synthesis example 9, compound B-2 (0.573 g), palladium acetate (3.90 mg), tris (2-methoxyphenyl) phosphine (36.5 mg), toluene (54 mL), and a 20 mass% aqueous tetraethylammonium hydroxide solution (8.89 g) were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (208 mg), bis (triphenylphosphine) palladium (II) dichloride (72.6 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (8.89 g), and sodium carbamate trihydrate (6.16 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-11 (1.10 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the resulting polymer compound P-11 were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-11 were 86,200g/mol and 1.87, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-11 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-11]

Examples 1 to 12

Compound C-1 (1.38 g), compound D-1 (0.508 g), compound B-3 (0.605 g), palladium acetate (3.80 mg), tris (2-methoxyphenyl) phosphine (36.5 mg), toluene (54 mL), and a 20 mass% aqueous tetraethylammonium hydroxide solution (8.66 g) of Synthesis example 9 were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (203 mg), bis (triphenylphosphine) palladium (II) dichloride (70.7 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (8.66 g), and sodium carbamate trihydrate (5.68 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-12 (1.17 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-12 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-12 were 75,100g/mol and 1.83, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-12 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-12]

Examples 1 to 13

Compound C-1 (1.31 g), compound D-1 (0.483 g), compound B-5 (0.665 g), compound B-5 (3.60 mg), tris (2-methoxyphenyl) phosphine (33.7 mg), toluene (54 mL), and a 20 mass% aqueous tetraethylammonium hydroxide solution (8.23 g) of synthetic example 9 were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (193 mg), bis (triphenylphosphine) palladium (II) dichloride (67.2 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (8.23 g), and sodium carbamate trihydrate (5.39 g) were added thereto, followed by stirring at 85 ℃ for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-13 (1.25 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-13 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-13 were 64,900g/mol and 1.84, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-13 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-13]

Examples 1 to 14

Compound A-1 of Synthesis example 1 (0.599 g), compound A-2 of Synthesis example 2 (1.21 g), 2, 7-dibromo-9, 9-di-n-propylfluorene (hereinafter, referred to as "Compound D-2") (0.637 g), palladium acetate (3.50 mg), tris (2-methoxyphenyl) phosphine (33.0 mg), toluene (54 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (8.03 g) were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (169 mg), bis (triphenylphosphine) palladium (II) dichloride (65.7 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (8.03 g), and sodium carbamate trihydrate (5.26 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-14 (1.14 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-14 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-14 were 53,400g/mol and 1.87, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-14 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-14]

Examples 1 to 15

Compound A-1 of Synthesis example 1 (0.534 g), compound A-2 of Synthesis example 2 (1.07 g), 2, 7-dibromo-9, 9-di-n-octylfluorene (hereinafter, referred to as "Compound D-3") (0.763 g), palladium acetate (3.10 mg), tris (2-methoxyphenyl) phosphine (26.5 mg), toluene (54 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (6.80 g) were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (401 mg), bis (triphenylphosphine) palladium (II) dichloride (68.6 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (6.80 g), and sodium carbamate trihydrate (4.70 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-15 (0.906 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the resulting polymer compound P-15 were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-15 were 71,500g/mol and 1.74, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-15 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-15]

Examples 1 to 16

Compound A-1 of Synthesis example 1 (0.512 g), compound A-2 of Synthesis example 2 (1.03 g), compound D-1 (0.806 g), palladium acetate (3.00 mg), tris (2-methoxyphenyl) phosphine (28.3 mg), toluene (54 mL), and a 20 mass% aqueous tetraethylammonium hydroxide solution (6.80 g) were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (369 mg), bis (triphenylphosphine) palladium (II) dichloride (55.1 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (6.80 g), and sodium carbamate trihydrate (4.70 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-16 (0.906 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-16 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-16 were 56,700g/mol and 1.78, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-16 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-16]

Examples 1 to 17

Compound C-3 of Synthesis example 11 (1.364 g), compound B-4 of Synthesis example 6 (0.621 g), compound D-1 (0.501 g), palladium acetate (3.50 mg), tris (2-methoxyphenyl) phosphine (33.0 mg), toluene (49 mL), and a 20 mass% aqueous tetraethylammonium hydroxide solution (8.06 g) were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (189 mg), bis (triphenylphosphine) palladium (II) dichloride (65.8 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (8.06 g), and sodium carbamate trihydrate (4.70 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-17 (0.400 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the resulting polymer compound P-17 were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of polymer compound P-17 were 14,600g/mol and 1.45, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-17 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-17]

Examples 1 to 18

Compound C-3 of Synthesis example 11 (1.44 g), compound B-4 of Synthesis example 6 (0.720 g), compound D-1 (0.281 g), palladium acetate (3.50 mg), tris (2-methoxyphenyl) phosphine (32.7 mg), toluene (49 mL), and a 20 mass% aqueous tetraethylammonium hydroxide solution (87.97 g) were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (187 mg), bis (triphenylphosphine) palladium (II) dichloride (55.1 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (7.97 g), and sodium carbamate trihydrate (5.23 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (20 mL), alumina (9.0 g) and diatomaceous earth (4.5 g) were added, and the mixture was stirred at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain polymer compound P-18 (0.290 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-18 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-18 were 17,500g/mol and 1.45, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-18 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-18]

Examples 1 to 19

Compound C-2 (2.47 g) of Synthesis example 10, compound B-6 (0.519 g) of Synthesis example 8, compound D-1 (1.26 g), palladium acetate (6.8 mg), tris (2-methoxyphenyl) phosphine (63.6 mg), toluene (90 mL), and a 20% by mass aqueous tetraethylammonium hydroxide solution (15.5 g) were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (364 mg), bis (triphenylphosphine) palladium (II) dichloride (126 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (15.5 g), and sodium carbamate trihydrate (10.1 g) were added thereto, followed by stirring at 85 ℃ for 6 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure and reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (30 mL), and alumina (15.0 g) and diatomaceous earth (7.5 g) were added thereto, followed by stirring at 90 ℃ for 1 hour. Alumina and celite were filtered, 12N hydrochloric acid (10 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was separated and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain a polymer compound P-19 precursor (2.42 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the resulting polymer compound P-19 precursor were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-19 precursor were 116,000g/mol and 2.29, respectively.

The polymer compound P-19 precursor (0.400 g), cyanoacetic acid (0.200 g), piperidine (0.1 mL), and toluene (10 mL) were placed in a flask and stirred under nitrogen at 60℃for 6 hours. The solution was treated by distillation under reduced pressure to remove the solvent, and then treated with toluene/methanol to reprecipitate. The precipitated solid was filtered, washed with water and methanol, and dried to obtain polymer compound P-19 (0.316 g). The polymer compound P-19 obtained by SEC analysis, but without elution, failed to obtain its weight average molecular weight and polydispersity (therefore, shown as "-" in table 1).

From the monomer input ratio, it was estimated that the polymer compound P-19 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-19]

Examples 1 to 20

The polymer compound P-19 precursor (0.400 g), malonic acid (0.200 g), piperidine (0.1 mL), and toluene (10 mL) according to examples 1-19 were placed in a flask under a nitrogen atmosphere, and then stirred at 60℃for 6 hours. The solution was treated by distillation under reduced pressure to remove the solvent and treated with toluene/methanol to reprecipitate. The precipitated solid was filtered, washed with water and methanol, and dried to obtain polymer compound P-20 (0.336 g). The polymer compound P-20 obtained by SEC analysis, but without elution, failed to obtain its weight average molecular weight and polydispersity (therefore, shown as "-" in table 1).

From the monomer input ratio, it was estimated that the polymer compound P-20 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-20]

Comparative examples 1 to 1

Compound C-1 (1.49 g), compound D-1 (0.97 g), palladium acetate (3.6 mg), tris (2-methoxyphenyl) phosphine (33.9 mg), toluene (54 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (8.27 g) of Synthesis example 9 were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (194 mg), bis (triphenylphosphine) palladium (II) dichloride (67.6 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (8.27 g), and sodium carbamate trihydrate (5.42 g) were added thereto, followed by stirring at 85 ℃ for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water. The washed organic layer was purified by column chromatography (packing material: silica gel/alumina, eluent: toluene), reprecipitated with toluene/methanol, and dried in vacuo to obtain polymer compound P-21 (1.17 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the polymer compound P-21 obtained were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-21 were 73,000g/mol and 1.40, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-21 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-21]

Comparative examples 1 to 2

Compound C-2 (1.49 g), compound D-1 (0.97 g), palladium acetate (3.6 mg), tris (2-methoxyphenyl) phosphine (33.9 mg), toluene (54 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (8.27 g) of Synthesis example 10 were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (194 mg), bis (triphenylphosphine) palladium (II) dichloride (67.6 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (8.27 g), and sodium carbamate trihydrate (5.42 g) were added thereto, followed by stirring at 85 ℃ for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water. The washed organic layer was purified by column chromatography (packing material: silica gel/alumina, eluent: toluene), reprecipitated with toluene/methanol, and dried in vacuo to obtain polymer compound P-22 (1.25 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the resulting polymer compound P-22 were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-22 were 101,000g/mol and 2.66, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-22 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-22]

Comparative examples 1 to 3

Compound A-2 (1.80 g), compound D-2 (0.667 g), palladium acetate (3.7 mg), tris (2-methoxyphenyl) phosphine (34.5 mg), toluene (54 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (8.42 g) of synthetic example 2 were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (197 mg), bis (triphenylphosphine) palladium (II) dichloride (68.8 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (8.42 g), and sodium carbamate trihydrate (5.23 g) were added thereto, followed by stirring at 85 ℃ for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water. The washed organic layer was purified by column chromatography (packing material: silica gel/alumina, eluent: toluene), reprecipitated with toluene/methanol, and dried in vacuo to obtain polymer compound P-23 (0.78 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the resulting polymer compound P-23 were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-23 were 74,600g/mol and 1.69, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-23 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-23]

Comparative examples 1 to 4

Compound C-3 (1.49 g), compound D-1 (0.970 g), palladium acetate (3.6 mg), tris (2-methoxyphenyl) phosphine (33.9 mg), toluene (54 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (8.27 g) of Synthesis example 11 were placed in a four-necked flask under a nitrogen atmosphere, followed by stirring at 85℃for 6 hours. Subsequently, phenylboric acid (194 mg), bis (triphenylphosphine) palladium (II) dichloride (67.6 mg), a 20 mass% tetraethylammonium hydroxide aqueous solution (8.27 g), and sodium carbamate trihydrate (5.42 g) were added thereto, followed by stirring at 85 ℃ for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water. The washed organic layer was purified by column chromatography (packing material: silica gel/alumina, eluent: toluene), reprecipitated with toluene/methanol, and dried in vacuo to obtain polymer compound P-24 (0.44 g). The weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the resulting polymer compound P-24 were measured by SEC. As a result, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) of the polymer compound P-24 were 20,000g/mol and 1.63, respectively.

From the monomer input ratio, it was estimated that the polymer compound P-24 obtained in this manner was a polymer compound having the following structural unit.

[ Polymer Compound P-24]

[ Evaluation of Properties of Polymer Compounds ]

The HOMO levels (eV), LUMO levels (eV), and glass transition temperatures (T _g) (. Degree. C.) of the polymer compounds P-1 to P-20 according to examples 1-1 to 1-20 and the polymer compounds P-21 to P-24 according to comparative examples 1-1 to 1-4 were measured as follows. The results are shown in Table 1.

(Measurement of HOMO energy level)

Each polymer compound was dissolved in xylene at a concentration of 1 mass%, to prepare a coating liquid. The coating liquid was spin-coated on a UV-cleaned and ITO-attached glass substrate at 2000rpm and dried at 150 ℃ for 30 minutes on a hot plate to manufacture a sample (film thickness: about 70 nm) for measurement. The HOMO level of the sample was measured in air by using a photoelectronic spectrometer (AC-3, riken Keiki Co., ltd.). Here, the measurement result is used to calculate the rising tangent point of the intersection, which is regarded as the HOMO level (eV). The HOMO level is typically negative.

(Measurement of LUMO energy level)

The polymer compounds were each dissolved in toluene at a concentration of 3.2 mass% to prepare a coating solution. On a glass substrate which was UV-washed and attached with ITO, the coating solution was spin-coated at 1600rpm to form a film and dried at 250 ℃ for 60 minutes on a hot plate to manufacture a sample (film thickness: about 70 nm) for measurement. The obtained sample was cooled to 77K (-196 ℃) to measure Photoluminescence (PL) spectrum. The LUMO level (eV) is calculated from the peak on the shortest wavelength side of the PL spectrum.

(Glass transition temperature (T _g))

Each polymer compound was heated to 300 ℃ at 10 ℃/min, held there for 10 minutes, cooled to 25 ℃ at 10 ℃/min, and held there again for 10 minutes, and then heated again to 300 ℃ at 10 ℃/min to measure the glass transition temperature (T _g). When the measurement was completed, the sample was cooled to room temperature (25 ℃) at 10 ℃/min.

TABLE 1

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Example 2-1

For the first electrode (anode), a glass substrate to which Indium Tin Oxide (ITO) patterned to have a thickness of 150nm was attached was used. The glass substrate with ITO attached was washed sequentially with neutral detergent, deionized water, and isopropyl alcohol, and then treated with UV-ozone. Subsequently, on the ITO-attached glass substrate, poly (3, 4-ethylenedioxythiophene)/poly (4-sulfostyrene) (PEDOT/PSS) (Sigma-Aldrich co., ltd.) was spin-coated and dried to have a dry film thickness of 30 nm. As a result, a hole injection layer having a thickness of 30nm (dry film thickness) was formed on the ITO-attached glass substrate.

On this hole injection layer, a 1.0 mass% toluene solution of the polymer compound P-1 (hole transport material) according to example 1-1 was spin-coated to have a dry film thickness of 30nm, and then dried at 230 ℃ for 60 minutes to form a hole transport layer. As a result, a hole transport layer having a thickness (dry film thickness) of 30nm was formed in the hole injection layer.

Subsequently, a quantum dot dispersion was prepared by: blue quantum dots ZnTeSe/ZnSe/ZnS (core/shell quantum dots prepared according to U.S. Pat. No.11,702,593; average diameter=about 10 nm) having the structure shown in fig. 2 were dispersed in cyclohexane at 1.0 mass%.

The hole transport layer (specifically, the polymer compound P-1) is insoluble in cyclohexane. The quantum dot dispersion was spin coated on the hole transport layer to have a dry film thickness of 30nm and dried. As a result, a quantum dot light emitting layer having a thickness (dry film thickness) of 30nm was formed on the hole transport layer. When the quantum dot dispersion is irradiated by Ultraviolet (UV) light, the light generated therefrom has a central wavelength of 462nm and a half width of 30 nm.

The quantum dot light-emitting layer was completely dried. On the quantum dot light emitting layer, lithium hydroxyquinoline (Liq) and 1,3, 5-tris (N-phenylbenzimidazol-2-yl) benzene (TPBI) (Sigma-Aldrich co., ltd.) as electron transport materials were co-deposited by using a vacuum deposition apparatus. As a result, an electron transport layer having a thickness of 36nm was formed on the quantum dot light emitting layer.

On the electron transport layer, lithium (8-hydroxyquinoline) is deposited (lithium hydroxyquinoline, liq) by using the vacuum deposition apparatus. As a result, an electron injection layer of 0.5nm thickness was formed on the electron transport layer.

Aluminum (Al) is deposited on the electron injection layer using a vacuum deposition apparatus. As a result, a second electrode (cathode) having a thickness of 100nm was formed on the electron injection layer. Thus, a quantum dot electroluminescent device 1 was obtained.

Example 2-2

A quantum dot electroluminescent device 2 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-2 of example 1-2 was used instead of the polymer compound P-1.

Examples 2 to 3

A quantum dot electroluminescent device 3 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-3 of example 1-3 was used instead of the polymer compound P-1.

Examples 2 to 4

A quantum dot electroluminescent device 4 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-4 of example 1-4 was used instead of the polymer compound P-1.

Examples 2 to 5

A quantum dot electroluminescent device 5 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-5 of example 1-5 was used instead of the polymer compound P-1.

Examples 2 to 6

A quantum dot electroluminescent device 6 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-6 of examples 1-6 was used instead of the polymer compound P-1.

Examples 2 to 7

A quantum dot electroluminescent device 7 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-7 of examples 1-7 was used instead of the polymer compound P-1.

Examples 2 to 8

A quantum dot electroluminescent device 8 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-8 of examples 1-8 was used instead of the polymer compound P-1.

Examples 2 to 9

A quantum dot electroluminescent device 9 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-9 of examples 1-9 was used instead of the polymer compound P-1.

Examples 2 to 10

A quantum dot electroluminescent device 10 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-10 of examples 1-10 was used in place of the polymer compound P-1.

Examples 2 to 11

A quantum dot electroluminescent device 11 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-11 of examples 1-11 was used instead of the polymer compound P-1.

Examples 2 to 12

A quantum dot electroluminescent device 12 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-12 of examples 1-12 was used instead of the polymer compound P-1.

Examples 2 to 13

A quantum dot electroluminescent device 13 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-13 of examples 1-13 was used in place of the polymer compound P-1.

Examples 2 to 14

A quantum dot electroluminescent device 14 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-14 of examples 1-14 was used in place of the polymer compound P-1.

Examples 2 to 15

A quantum dot electroluminescent device 15 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-15 of examples 1-15 was used instead of the polymer compound P-1.

Examples 2 to 16

A quantum dot electroluminescent device 16 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-16 of examples 1-16 was used in place of the polymer compound P-1.

Examples 2 to 17

A quantum dot electroluminescent device 17 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-17 of examples 1-17 was used in place of the polymer compound P-1.

Examples 2 to 18

A quantum dot electroluminescent device 18 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-18 of examples 1-18 was used instead of the polymer compound P-1.

Examples 2 to 19

A quantum dot electroluminescent device 19 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-19 of examples 1-19 was used in place of the polymer compound P-1.

Examples 2 to 20

A quantum dot electroluminescent device 20 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-20 of examples 1-20 was used in place of the polymer compound P-1.

Comparative example 2-1

A comparative quantum dot electroluminescent device 1 was fabricated in the same manner as in example 2-1, except that: the polymer compound P-21 of comparative example 1-1 was used instead of the polymer compound P-1.

Comparative examples 2 to 2

A comparative quantum dot electroluminescent device 2 was fabricated in the same manner as in example 2-1, except that: polymer compound P-22 of comparative example 1-2 was used instead of polymer compound P-1.

Comparative examples 2 to 3

A comparative quantum dot electroluminescent device 3 was fabricated in the same manner as in example 2-1, except that: polymer compound P-23 of comparative example 1-3 was used instead of polymer compound P-1.

Comparative examples 2 to 4

A comparative quantum dot electroluminescent device 4 was fabricated in the same manner as in example 2-1, except that: polymer compound P-24 of comparative examples 1-4 was used instead of polymer compound P-1.

[ Evaluation of Quantum dot electroluminescent device ]

The light-emitting efficiency and the light-emitting lifetime of the quantum dot electroluminescent devices 1 to 20 according to examples 2-1 to 2-20 and the comparative quantum dot electroluminescent devices 1 to 4 according to comparative examples 2-1 to 2-4 were evaluated as follows. The results are shown in tables 2-1 to 2-4.

(Luminous efficiency)

When a voltage is applied to each quantum dot electroluminescent device and a current starts to flow at a constant voltage, the quantum dot electroluminescent device emits light. The current at that time was measured while gradually increasing the voltage of each device by using a DC constant voltage power supply (source meter), and in addition, the luminance thereof during light emission was measured by using a luminance measuring device (SR-3,Topcom Technology Co, ltd.). Here, when the luminance starts to decrease, the measurement ends. The luminance (cd/m ²) was divided by the current density (a/m ²), which was obtained as a current per unit area from the area of each device, to obtain the current efficiency (cd/a). In tables 2-1 to 2-4, the highest current efficiency in the measured voltage range is regarded as "cd/Amax".

Current efficiency means the efficiency of converting a current into light emission energy (conversion efficiency), wherein the higher the current efficiency, the better the device performance.

In addition, external Quantum Efficiency (EQE) (%) at Cd/Amax was calculated using a spectral emission luminance spectrum considered to be Lambertian (Lambertian) radiation and measured by a luminance measuring apparatus, and the light emission efficiency was evaluated.

In addition, when voltages are applied to each of the quantum dot electroluminescent devices using a DC constant voltage power supply (KEYENCE corp.), such that current can flow at a constant voltage, the quantum dot electroluminescent devices emit light. The light emission of the device was measured by using a luminance measuring apparatus (SR-3,Topcom Technology Co, ltd.) while the current was slowly increased, and the device was allowed to remain with the current constant when the luminance reached 1000 nit (cd/m ²). Here, the voltage at 1000 nit is set to "V @ 1000 nit".

(Luminescence lifetime)

Each quantum dot electroluminescent device emits light by: a predetermined voltage is added thereto with a DC constant voltage power supply (source table). The light emission of the quantum dot electroluminescent device was measured at gradually increasing current by using a luminance measuring apparatus (SR-3,Topcom Technology Co, ltd.) and the device was allowed to remain while the current was made constant when the luminance reached 650 nit (cd/m ²). The time when the luminance measured with the luminance measuring apparatus gradually decreases and reaches 90% of the initial luminance is "LT90 (hr)".

In addition, the time when the luminance measured with the luminance measuring apparatus gradually decreases and reaches 50% of the initial luminance is "LT50 (hr)".

[ Table 2-1]

[ Table 2-2]

[ Tables 2 to 3]

[ Tables 2 to 4]

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Referring to the results of tables 2-1 to 2-4, the quantum dot electroluminescent devices 1 to 20 of examples exhibited substantially higher durability (longer light emission lifetime) than the comparative quantum dot electroluminescent devices 1 to 4 without using the polymer compound according to the embodiment.

In particular, compared with comparative quantum dot electroluminescent device 1 (comparative example 2-1) using a polymer compound consisting of only structural unit (B) not including a carboxyl group, quantum dot electroluminescent devices 1 to 5 and 10 to 13 (examples 2-1 to 2-5, 2-10 to 2-13) using a polymer compound further having structural unit (a) including a carboxyl group in addition to the same structural unit (B) exhibited long light emission lifetime (T90) results. In addition, the quantum dot electroluminescent devices 6 to 9 and 20 (examples 2 to 9 and 2 to 20) using the polymer compound further having the structural unit (a) including a carboxyl group in addition to the same structural unit (B) exhibited excellent light emission efficiency and External Quantum Efficiency (EQE) in addition to the longer light emission lifetime (T90) similarly compared to the comparative quantum dot electroluminescent device 2 (comparative example 2-2) using the polymer compound composed of only the structural unit (B) including no carboxyl group. Further, the quantum dot electroluminescent device 19 (examples 2 to 19) exhibited a slightly deteriorated light emission lifetime (T90) which is still sufficiently longer in terms of light emission lifetime (T50) and excellent light emission efficiency and External Quantum Efficiency (EQE) which are suitable light emission performance (balance between light emission efficiency and light emission lifetime) in practical use, as compared with the comparative quantum dot electroluminescent device 2 (comparative example 2-2). In addition, the quantum dot electroluminescent device 14 (examples 2 to 14) using the polymer compound further having the structural unit (a) including a carboxyl group in addition to the same structural unit (B) exhibited longer light emission lifetime (T90 and T50) and excellent light emission efficiency and External Quantum Efficiency (EQE) similarly compared to the comparative quantum dot electroluminescent device 3 (comparative examples 2 to 3) using the polymer compound consisting of only the structural unit (B) including no carboxyl group.

The comparative quantum dot electroluminescent devices 2 and 3 of comparative examples 2-2 and 2-3 exhibited relatively excellent light emission lifetime (T90), but low light emission efficiency and External Quantum Efficiency (EQE), which are quantum dot electroluminescent devices inferior to the present example embodiment in light emission performance (balance between light emission efficiency and light emission lifetime) in practical use.

Further, the quantum dot electroluminescent devices 17 and 18 (examples 2 to 17 and 2 to 18) using the polymer compound further having the structural unit (a) including a carboxyl group in addition to the same structural unit (B) exhibited very long light emission lifetime (T90 and T50) and excellent light emission efficiency and External Quantum Efficiency (EQE) as compared with the comparative quantum dot electroluminescent device 4 (comparative examples 2 to 4) using the polymer compound composed of only the structural unit (B).

While this disclosure has been described in terms of what are presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

< Description of symbols >

100: Electroluminescent device (EL device)

110: Substrate board

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

[ chemical formula (1) ]

Wherein, in the chemical formula (1),

R ¹¹-R¹⁴ and R ²¹-R²⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, wherein R ¹¹ and R ²¹ are optionally linked to each other to form a ring,

Ar ² is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring member atoms, or is attached to Ar ¹ to form a ring,

2. The polymer compound according to claim 1, wherein

The polymer compound further includes a structural unit (B) represented by chemical formula (2):

[ chemical formula (2) ]

Wherein, in the chemical formula (2),

R ³¹-R³⁴ and R ⁴¹-R⁴⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, wherein R ³¹ and R ⁴¹ are optionally linked to each other to form a ring,

Ar ⁴ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring member atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring member atoms, or is attached to Ar ³ to form a ring,

X ² is an aromatic hydrocarbon radical having 6 to 25 ring member atoms, optionally substituted by alkyl having 1 to 14 carbon atoms,

Y ² is an aromatic hydrocarbon radical having 6 to 25 ring member atoms, optionally substituted by alkyl having 1 to 14 carbon atoms, and

R ³¹-R³⁴、R⁴¹-R⁴⁴、L²、Ar³ and Ar ⁴ do not have an alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group and an alkyl group having 1 to 14 carbon atoms substituted with a group having a carboxyl group.

3. The polymer compound according to claim 2, wherein

The molar ratio of the structural unit (a) is greater than or equal to 10 mol% and less than or equal to 70 mol%, based on the total molar ratio of the structural unit (a) and the structural unit (B) being 100 mol%.

4. The polymer compound according to claim 1, wherein

In chemical formula (1), X ¹ is an aromatic hydrocarbon group having 6 to 25 ring member atoms substituted as follows: an alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group or an alkyl group having 1 to 14 carbon atoms substituted with a group having a carboxyl group, and Y ¹ is an aromatic hydrocarbon group having 6 to 25 ring member atoms substituted or unsubstituted with a substituent other than: alkyl groups having 1 to 14 carbon atoms substituted with a carboxyl group or alkyl groups having 1 to 14 carbon atoms substituted with a group having a carboxyl group.

5. The polymer compound according to claim 2, wherein

R ¹¹-R¹⁴、R²¹-R²⁴、L¹、Ar¹、Ar² and Y ¹ in the chemical formula (1) are each the same as R ³¹-R³⁴、R⁴¹-R⁴⁴、L²、Ar³、Ar⁴ and Y ² in the chemical formula (2).

6. The polymer compound according to claim 1, wherein

The alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group or the alkyl group having 1 to 14 carbon atoms substituted with a group having a carboxyl group has a structure represented by the formula (i):

[ formula (i) ]

***-C_tH_2t-(Z¹)_u-COOH (i)

Wherein, in the chemical formula (i),

T represents an integer of 1 to 14,

U is 0 or 1, and the number of the elements is,

Z ¹ represents an organic group other than an alkylene group, and

7. The polymer compound according to claim 1, wherein

In the chemical formula (1), X ¹ is one of the groups represented by the chemical formulas (3-1) to (3-12):

[ formulae (3-1) to (3-12) ]

Wherein, in the chemical formulas (3-1) to (3-12),

* Bonded to the nitrogen atom.

8. The polymer compound according to claim 7, wherein

In the chemical formula (1), X ¹ is one of the groups represented by the chemical formulas (3-10) to (3-12).

9. The polymer compound according to claim 1, wherein

In the chemical formula (1), Y ¹ is any one of the groups represented by chemical formulas (5-1) to (5-9):

[ formulae (5-1) to (5-9) ]

Wherein, in the chemical formulas (5-1) to (5-9),

10. The polymer compound according to claim 1, wherein

In the chemical formula (1), L ¹ is one of the groups represented by the chemical formulas (7-1) to (7-24):

[ formulae (7-1) to (7-24) ]

Wherein, in the chemical formulas (7-1) to (7-24),

* Is bound to a nitrogen atom and is bound to Ar ¹.

11. The polymer compound according to claim 1, wherein

-L ¹-Ar¹-N(Ar²)(X¹ in the chemical formula (1) is any one of the groups represented by the chemical formulas (9-1) to (9-3):

[ formulae (9-1) to (9-3) ]

Wherein, in the chemical formulas (9-1) to (9-3),

N, p, and r are each independently 0, 1, 2, or 3,

O, q, and s are each independently 0, 1, 2,3, or 4,

X ¹ is the same as defined in the chemical formula (1), and

* Bonded to the nitrogen atom.

12. An electroluminescent device material comprising a polymer compound as claimed in any one of claims 1 to 11.

13. An electroluminescent device comprising

A first electrode and a second electrode, and

One or more organic films between the first electrode and the second electrode,

Wherein at least one layer of the organic film comprises the polymer compound according to any one of claims 1-11.

14. The electroluminescent device of claim 13 wherein the layer comprising the polymer compound is a hole transport layer or a hole injection layer.

15. The electroluminescent device of claim 13 wherein

Wherein the organic film comprises a light emitting layer comprising semiconductor nanoparticles or organometallic complexes.