KR20240053537A - Polymer compound, and electroluminescent device material and electroluminescent device including polymer compound - Google Patents

Abstract

Provided is a polymer compound containing a structural unit (A) represented by Chemical Formula (1) that can improve the durability (particularly the luminescence life) of an electroluminescent device.

Description

Polymer compounds, and electroluminescent device materials and electroluminescent devices using the polymer compounds {POLYMER COMPOUND, AND ELECTROLUMINESCENT DEVICE MATERIAL AND ELECTROLUMINESCENT DEVICE INCLUDING POLYMER COMPOUND}

The present invention relates to polymer compounds, and electroluminescent device materials and electroluminescent devices using the polymer compounds.

Research and development of electroluminescent devices (EL devices) are actively underway. In particular, EL elements are promising for use as solid-state, low-cost, large-area, full-color display elements or recording light source arrays. An EL element is a light emitting element that has a thin film between an anode and a cathode with a thickness of several nanometers to several hundred nanometers. Additionally, the EL element usually further includes a hole transport layer, a light emitting layer, an electron transport layer, etc.

Among these, the light-emitting layer includes fluorescent materials and phosphorescent materials. Phosphorescent materials are materials expected to have high luminous efficiency compared to fluorescent materials. Additionally, because it covers a wide color gamut, RGB light sources require an emission spectrum with a narrow half width. In particular, deep blue is required, but the current situation is that a device that can satisfy the viewpoint of color purity while having a long life has not been found.

As a way to solve this problem, there is a light-emitting device that uses “quantum dots,” an inorganic light-emitting material, as a light-emitting material (Patent Document 1). Quantum dots (QDs) are semiconductor materials with a crystal structure of several nanometers in size 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. Accordingly, most atoms exist on the surface of the nanocrystal and exhibit a quantum confinement effect. Due to this quantum confinement effect, quantum dots can control the emission wavelength simply by adjusting their size, and have characteristics such as excellent color purity and high PL (photoluminescence) luminous efficiency, so they are attracting a lot of attention. A quantum dot electroluminescence device (QD LED) is a device with a three-layer structure that includes a hole transport layer (HTL) and an electron transport layer (ETL) on both sides with a quantum dot electroluminescence layer in between. It is known as a basic element.

In order to improve the characteristics of such quantum dot light emitting devices, technologies for improving the hole transport properties and hole injection properties of hole transport materials have been proposed. For example, Patent Document 2 proposes an arylamine-fluorene alternating copolymer (polymer compound) having a hydrocarbon group in the side chain as a hole transport material.

Patent Document 1: Japanese Patent Application Publication No. 2010-199067

Patent Document 2: Japanese Patent Application Publication No. 2021-138915

According to the arylamine-fluorene alternating copolymer disclosed in Patent Document 2, the hole injection property of the hole transport material is improved, durability (especially luminescence life) is improved, and sufficient luminous efficiency is achieved.

However, there is a demand for a technology that can further improve durability (especially luminescence life) compared to electroluminescent devices (particularly quantum dot electroluminescent devices) using the hole transport material disclosed in Patent Document 2.

Accordingly, the present invention was made in consideration of the above circumstances, and its purpose is to provide a technology that can improve the durability (particularly the luminescence life) of an electroluminescent device (particularly a quantum dot electroluminescent device).

The present inventors conducted intensive research to solve the above problems. As a result, it was discovered that the above problem could be solved by using a polymer compound having a specific structure, and the present invention was completed.

That is, the above objective can be achieved by a polymer compound containing the structural unit (A) represented by the following formula (1).

[Formula (1)]

In the above formula (1),

R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ 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, It is a substituted or unsubstituted aryl group or a halogen atom. In this case, R ¹¹ and R ²¹ may be combined with each other to form a ring,

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

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

Ar ² is a substituted or unsubstituted aromatic hydrocarbon group with 6 to 25 ring atoms, or a substituted or unsubstituted aromatic heterocyclic group with 5 to 25 ring atoms, and in this case, forms a ring with Ar ¹ You can do it,

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

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

At this ^time , at least one ^of It is an aromatic hydrocarbon group.

1 is a schematic diagram showing an electroluminescent device according to this embodiment.
Figure 2 is a cross-sectional view showing the structure of quantum dots.

In one embodiment, the present invention provides a polymer compound comprising a structural unit (A) represented by the following formula (1):

[Formula (1)]

In the above formula (1),

R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ 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, It is a substituted or unsubstituted aryl group, or a halogen atom. In this case, R ¹¹ and R ²¹ may be combined with each other to form a ring,

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

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

Ar ² is a substituted or unsubstituted aromatic hydrocarbon group with 6 to 25 ring atoms, or a substituted or unsubstituted aromatic heterocyclic group with 5 to 25 ring atoms. In this case, Ar ¹ and the ring are can be formed,

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

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

At this ^time , at least one ^of It is an aromatic hydrocarbon group.

In this specification, the structural unit (A) represented by formula (1) is also simply referred to as “structural unit (A)” or “structural unit (A) according to the present invention.” In addition, the structural unit having the following structure among the “structural units (A) represented by formula (1)” is also simply referred to as “structural unit

[Structural unit

Similarly, the structural unit “-Y ¹ -” in the “structural unit (A) represented by formula (1)” is also simply referred to as “structural unit Y” or “structural unit Y according to the present invention.” In addition, the polymer compound having the structural unit (A) represented by the formula (1) is also simply referred to as “polymer compound” or “polymer compound according to the present invention.”

In another embodiment, an electroluminescent device material comprising the polymer compound according to the present invention is provided.

In another embodiment, an electroluminescent device comprising a first electrode, a second electrode, and one or more layers of an organic layer disposed between the first electrode and the second electrode, wherein at least one layer of the organic layer contains the polymer. An electroluminescent device comprising a compound is provided. In this specification, the electroluminescent element is also simply referred to as “LED.” Quantum dot electroluminescent devices are also simply called “QLED.” Organic electroluminescent devices are also simply called “OLED.”

As materials constituting the light-emitting layer or carrier transport layer of the electroluminescent device, various low-molecular materials and high-molecular materials are used. Among these, polymer materials have the advantage of suppressing manufacturing costs because there is no need to fabricate elements through a vacuum process like low molecular materials, but it is difficult to obtain sufficient durability (luminescence life). Accordingly, the development of polymer materials that can improve durability (luminescence life) has been desired. The present inventors have conducted intensive studies on means of solving the above problem (improving durability (light emission life)).

As a result, by applying a polymer compound having the structural unit (A) represented by the above formula (1) to an electroluminescent device, light emission is achieved compared to the case of using a known material (for example, the polymer material disclosed in Patent Document 2). Discovered something that can improve lifespan. In addition, it was discovered that by applying a polymer compound having the structural unit (A) represented by the above formula (1) to an electroluminescent device, the external quantum efficiency (EQE) can be improved and high luminous efficiency can be achieved. .

The mechanism of exerting the above-mentioned effects by the configuration of the present invention is assumed 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 containing quantum dots). When this happens, an energy gap is created between the energy band of the hole transport layer and the vacuum level (vacuum level at the interface between the hole transport layer and the light-emitting layer), which traps holes and places a load on the interface between the hole transport layer and the light-emitting layer. As a result, the luminescence life becomes shorter. Meanwhile, the polymer compound having the structural unit (A) represented by the above formula (1) is 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. Since 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). Accordingly, since the energy gap between the vacuum level and the hole transport layer becomes smaller, holes are not trapped, and as a result, holes become easier to move and are efficiently injected into quantum dots (hole injection properties increase). Therefore, durability (light emission life) can be improved.

Additionally, in the structural unit (A) represented by the above formula (1), the nitrogen atom is cutting the conjugate region of the main chain. Accordingly, the triplet energy level of the polymer compound can be increased, hole mobility (bulk mobility) along the main chain is high, and high current efficiency can be achieved. Therefore, excellent luminous efficiency can be achieved by using a polymer compound (main chain) having the structural unit (A). In addition, since the main chain of the structural unit (A) represented by the formula (1) is cleaved by nitrogen atoms, the polymer compound according to the present invention exhibits properties similar to low molecular compounds whose energy levels are close to quantum dots even when polymerized. Accordingly, by using the polymer compound according to the present invention, an increase in the driving voltage is suppressed, and a low driving voltage becomes possible.

Therefore, electroluminescent devices (especially quantum dot electroluminescent devices) using a polymer compound having the structural unit (A) represented by the above formula (1) can exhibit high durability (luminescence life) and are sufficient under low driving voltages. Luminous efficiency can be achieved.

Additionally, since the polymer compound according to the present invention has excellent film forming properties and solvent solubility, it is possible to form a film using a wet (application) method. Therefore, by using the polymer compound according to the present invention, it becomes possible to enlarge the area of the electroluminescent device and achieve high productivity. The above effect can be effectively exhibited when the polymer compound according to the present invention is applied to the hole transport layer or hole injection layer of an EL device, especially QLED.

Additionally, the mechanism is speculative, and the present invention is not limited to the mechanism at all.

Hereinafter, embodiments of the present invention will be described. Meanwhile, the present invention is not limited to the following embodiments. Additionally, each drawing is exaggerated for convenience of explanation, and the dimensional ratio of each component in each drawing may differ from the actual one. In addition, when the embodiment of the present invention is described with reference to the drawings, like elements are given the same reference numerals in the description of the drawings, and overlapping descriptions are omitted.

In this specification, unless otherwise specified, operations and physical properties are measured under room temperature (20°C or higher and 25°C or lower)/relative humidity of 40%RH or higher and 50%RH or lower.

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 a hydrogen atom that is directly bonded to the ring forming atom from the ring structure when “compound z” is a cyclic compound. is removed as much as the valence, and the free valence is expressed as one group.

In this specification, the number of ring atoms refers to compounds (e.g., monocyclic compounds, condensed ring compounds, cross-linked compounds, carbocyclic compounds) with a structure in which atoms are bonded in a ring (e.g., monocycle, condensed ring, and ring set). , and heterocyclic compounds) indicates the number of atoms constituting the corresponding ring itself. Atoms that do not form a ring (e.g., a hydrogen atom that terminates the bond of the atoms forming a ring) or atoms included in a substituent when the ring is substituted by a substituent are not included in the number of ring forming atoms. No. The number of ring forming atoms described below is assumed to be the same unless otherwise specified.

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

When the benzene ring is substituted with a substituent, for example, an alkyl group, the number of carbon atoms of the alkyl group is not included in the number of ring atoms of the benzene ring. Accordingly, the number of ring atoms of the benzene ring substituted 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 forming atoms of the naphthalene ring. Accordingly, the number of ring atoms of the naphthalene ring substituted by the alkyl group is 10.

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

In this specification, “substitution”, unless specifically defined, means (C1 to C20) alkyl group, (C3 to C20) cycloalkyl group, (C1 to C20) hydroxyalkyl group, (C2 to C20) alkoxyalkyl group, (C1 to C20) C20) alkoxy group, (C4 to C20) cycloalkoxy group, (C2 to C20) alkenyl group, (C2 to C20) alkynyl group, (C0 to C20) amino group, (C6 to C20) aryl group, (C6 to C20) Aryloxy group, (C1 to C20) alkylthio group, (C3 to C20) cycloalkylthio group, (C6 to C20) arylthio group, (C2 to C20) alkoxycarbonyl group, (C7 to C20) aryloxycarbonyl group, hydride Substituted with a hydroxy group (-OH), carboxyl group (-COOH), thiol group (-SH), cyano group (-CN), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), and combinations thereof. On the other hand, when a group is substituted, the form of substitution included in the definition before the substituted structure is substituted is excluded. For example, when the substituent is an alkyl group, the alkyl group as the substituent is not substituted again with an alkyl group. No.

Here, the alkyl group as a substituent may be either straight-chain or branched, and preferably is a straight-chain alkyl group with 1 to 20 carbon atoms or a branched alkyl group with 3 to 20 carbon atoms. Specifically, 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-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1 , 4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1 -Isopropylbutyl group, 2-methyl-1-isopropylbutyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, iso Decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n -Examples include octadecyl group, nonadecyl group, and icosyl group.

Examples of cycloalkyl groups as substituents include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.

As a hydroxyalkyl group as a substituent, for example, the alkyl group is substituted with 1 to 3 hydroxy groups (preferably 1 to 2, particularly preferably 1) hydroxy groups (e.g., hydroxymethyl group, hydroxy Roxyethyl group) is exemplified.

Examples of the alkoxyalkyl group as a substituent include those in which the alkyl group is substituted with 1 to 3 (preferably 1 to 2, particularly preferably 1) alkoxy groups.

The alkoxy group as a substituent may be either straight chain or branched, and is preferably a straight chain alkoxy group with 1 to 20 carbon atoms or a branched alkoxy group with 3 to 20 carbon atoms. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group. There are siloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, 2-ethylhexyloxy group, 3-ethylpentoxy group, etc.

Examples of cycloalkoxy groups as substituents include cyclopropoxy group, cyclobutoxy group, cyclopentoxy group, and cyclohexyloxy group.

Examples of alkenyl groups as substituents include vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 5-heptenyl group, 1-octenyl group, 3-octenyl group, 5- Octenyl group, etc.

Examples of alkynyl groups as substituents include acetylenyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, and 3. -Pentinyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 1-heptinyl group, 2-heptinyl group, 5-heptinyl group, 1-octinyl group, 3-octinyl group, 5-octinyl group, etc. there is.

The aryl group as a substituent is preferably an aryl group having 6 to 30 carbon atoms. For example, there are phenyl group, naphthyl group, biphenyl group, fluorenyl group, anthryl group, pyrenyl group, azulenyl group, acenaphthylenyl group, terphenyl group, phenanthryl group, etc.

Examples of aryloxy groups as substituents include phenoxy groups and naphthyloxy groups.

Examples of alkylthio groups as substituents include methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, and dodecylthio group.

Examples of cycloalkylthio groups as substituents include cyclopentylthio groups and cyclohexylthio groups.

Examples of arylthio groups as substituents include phenylthio groups and naphthylthio groups.

Examples of the alkoxycarbonyl group as a substituent include methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, and dodecyloxycarbonyl group.

Examples of the aryloxycarbonyl group as a substituent include phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.

[Polymer compounds]

《Structural unit (A)》

The polymer compound according to the present invention has a structural unit (A) represented by the following formula (1). A polymer compound having such a structural unit (A) has excellent hole injection properties into quantum dots and can improve the durability (luminescence life) of an electroluminescent device. In addition, high current efficiency and low driving voltage can be achieved. The polymer compound according to the present invention may contain only one type of structural unit (A), or may contain two or more types of structural units (A). On the other hand, a plurality of structural units (A) may exist in a block form, a random form, an alternating form, or a periodic form.

[Formula (1)]

In the formula (1), the structural unit constitutes. Likewise, in the above formula (1), the structural unit Y (the structural unit on the right side of the above formula (1); that is, the structural unit represented by “Y ¹ ”) is a polymer according to one embodiment of the present invention. constitutes a compound. In other words, the polymer compound according to the present invention can be said to be a copolymer containing the structural unit X and the structural unit Y.

In the above formula ⁽ 1 ⁾ , In this case, at least ^{one of} These are the following aromatic hydrocarbon groups.

In this ^way , the structural unit (A) according to the present invention is, ^for (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 is simply referred to as “alkyl group substituted with a carboxyl group” or simply “substituent (a )”). Therefore, the polymer compound according to the present invention has a large dipole moment, and the hole injection property of the hole transport layer containing it is improved. Therefore, when used in an electroluminescent device, the durability (luminescence life) of the device can be improved. On the other hand, when the substituent (a) is included in both 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 (substituent (a)) substituted with a carboxyl group according to the present invention is a straight-chain or branched alkyl group, for example, methyl group, ethyl group, n-propyl group, and isopropyl group. 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 Syl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2- Methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropylbutyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n -Dodecyl group, n-tridecyl group, n-tetradecyl group, etc.

Here, the alkyl group contained in the alkyl group substituted with a carboxyl group has a carbon number of 1 to 13 from the viewpoint of improving durability, excellent solvent solubility and improved film forming properties when forming a film by a wet (application) method. is preferable, it is more preferable that it is 3 or more and 12 or less, it is especially preferable that it is 5 or more and 12 or less, and it is most preferable that it is 7 or more and 12 or less. In addition, by making the alkyl group constituting the substituent (a) a relatively long-chain alkyl group, the glass transition temperature (Tg) of the polymer compound is within an appropriate range, which is preferable in terms of manufacturing an electroluminescent device.

Additionally, the alkyl group included in the substituent (a) (alkyl group constituting the substituent (a)) is preferably straight chain from the viewpoint of improving durability.

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

[Formula (i)]

In the above formula (i), t represents an integer from 1 to 14, u is 0 or 1, Z ¹ represents ^an organic group other than ^an alkylene group, and *** represents It is bonded to an aromatic hydrocarbon group having 6 to 25 ring atoms.

In terms of improving durability (especially luminescence life), t is preferably an integer of 1 to 13, more preferably 3 to 12, especially preferably 5 to 12, and 7 to 12. It is most preferable that it is the following integer.

Additionally, from the viewpoint of further improving durability (especially luminescence life), it is preferable that u is 0 (that is, does not have Z ¹ ). Meanwhile, from the viewpoint of improving external quantum efficiency (EQE) or luminous efficiency, it is desirable for u to be 1 (that is, to have 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 containing carbon atoms other than an alkylene group, for example, a substituted or unsubstituted group with 2 to 14 carbon atoms. Alkenylene group, substituted or unsubstituted alkynylene group with 2 to 14 carbon atoms, substituted or unsubstituted cycloalkylene group with 3 to 16 carbon atoms, substituted or unsubstituted arylene group with 6 to 20 carbon atoms, etc. .

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

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

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

Examples of the arylene group having 6 to 20 carbon atoms include o-phenylene group, m-phenylene group, p-phenylene group, naphthylenediyl group, anthracenediyl group, naphthacynediyl group, pyrenediyl group, and biphenyldiyl group. There are diaries, etc.

Among them, the organic group as Z ¹ is preferably a substituted or unsubstituted alkenylene group having 2 to 14 carbon atoms, more preferably a substituted or unsubstituted alkenylene group having 2 to 8 carbon atoms, and a substituted or unsubstituted alkenylene group having 2 to 8 carbon atoms. Alkenylene groups of 2 or more and 6 or less are particularly preferable, and substituted or unsubstituted vinylene groups are most preferable.

As will be explained in detail below, the polymer compound according to the present invention can be formed into a film by a coating method, but at this time, the film forming property is improved and durability (especially luminescence life) is improved by forming a uniform film. In this regard, it is preferable that the alkenylene group, the alkynylene group, the cycloalkylene group, and the arylene group constituting Z ¹ are unsubstituted. Additionally, in another form, the alkenylene group or the like constituting Z ¹ may be substituted, and in that case, the same substituent as the substituent described for “substitution” can be applied. At this time, the substituent for the alkenylene group as Z ¹ is preferably selected from an alkoxy group, an amino group, a hydroxy group (-OH), a thiol group (-SH), and a cyano group (-CN), and a cyano group It is more preferable to be

In the formula (1), X ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms. Here, “substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms” means an aromatic hydrocarbon group having 6 to 25 ring atoms substituted with a substituent (a); An aromatic hydrocarbon group substituted with a substituent other than substituent (a) and having 6 to 25 ring atoms; or an unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms. Meanwhile, in this specification, “substituent other than substituent (a)” refers to a substituent excluding an alkyl group substituted by a carboxyl group (-COOH) among the substituents described for “substitution” above.

Here, the aromatic hydrocarbon group having 6 to 25 ring atoms specifically includes benzene, naphthalene, anthracene, pyrene, pentalene, indene, azulene, hepthalene, acenaphthene, phenalene, phenanthrene, biphenyl, Examples include monovalent groups derived from aromatic hydrocarbons such as terphenyl, quarterphenyl, fluorene, and 9,9'-spirobi[fluorene].

In ^the case where It is preferable that it is a group selected from the group consisting of a phenyl group, a biphenyl group, a terphenyl group, and a fluorenyl group.

In addition, in the formula (1), when X ¹ is an aromatic hydrocarbon group substituted with a substituent (a) ^, it is preferable that do:

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

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

R ³⁰¹ to R ³¹⁵ are each 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 above formulas (3-10) to (3-12), R ³¹⁰ and R ³¹¹ , R ³¹² and R ³¹³ , R ³¹⁴ and R ³¹⁵ may be the same or different, respectively. Preferably, R ³¹⁰ and R ³¹¹ , R ³¹² and R ³¹³ , R ³¹⁴ and R ³¹⁵ are identical to each other.

The alkylene group having 1 to 14 carbon atoms as R ³⁰¹ to R ³¹⁵ is not particularly limited, but is a straight-chain or branched alkylene group, for example, methylene group, ethylene group, trimethylene group, propylene group, 1,1- Dimethylmethylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, n-pentylene group, isopentylene group, tert-pentylene group, neopentylene group, 1,2-dimethylpropylene group, n -Hexylene group, isohexylene group, 1,3-dimethylbutylene group, 1-isopropylpropylene group, 1,2-dimethylbutylene group, n-heptylene group, 1,4-dimethylpentylene group, 3-ethylpentyl Len group, 2-methyl-1-isopropylpropylene group, 1-ethyl-3-methylbutylene group, n-octylene group, 2-ethylhexylene group, 3-methyl-1-isopropylbutylene group, 2-methyl- 1-isopropylbutylene group, 1-tert-butyl-2-methylpropylene group, n-nonylene group, 3,5,5-trimethylhexylene group, n-decylene group, isodecylene group, n-undecylene group, 1-methyldecylene group, n-dodecylene group, n-tridecylene group, n-tetradecylene group, etc.

Here, from the viewpoint of improving durability, the alkylene group as R ³⁰¹ to R ³¹⁵ preferably has 3 to 13 carbon atoms, more preferably 5 to 12 carbon atoms, and especially preferably 7 to 10 carbon atoms.

In addition, the alkylene groups as R ³⁰¹ to R ³¹⁵ are preferably straight chain from the viewpoint of improving durability.

In the formula (1), when X ¹ is an aromatic hydrocarbon ^group substituted with a substituent (a), it is preferable that When X ¹ has these structures, durability (especially luminescence lifetime), external quantum efficiency (EQE), and luminous efficiency are further improved. Among them, it is preferable that X ¹ is a group represented by the above formula (3-10).

On the ^other hand, when It is preferable that it is a monovalent group derived from a compound selected from terphenyl and fluorene. It is more preferable ^{that and} This is particularly desirable.

In addition, from the viewpoint of improving durability, in Chemical Formula (1), when X ¹ is ^an aromatic hydrocarbon group not substituted with a substituent (a), It is preferable that it is any one of the following groups.

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

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

R ⁴⁰¹ to R ⁴¹³ are each independently an alkyl group having 1 to 14 carbon atoms that is unsubstituted or substituted 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,

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

Additionally, in the above formulas (4-2) to (4-4), R ⁴⁰² and R ⁴⁰³ , R ⁴⁰⁶ and R ⁴⁰⁷ , R ⁴¹⁰ and R ⁴¹¹ may be the same or different, respectively. Preferably, R ⁴⁰² and R ⁴⁰³ , R ⁴⁰⁶ and R ⁴⁰⁷ , R ⁴¹⁰ and R ⁴¹¹ are identical to each other.

In the above formulas (4-1) to (4-4), a, b, c, d, e, f or g is 0 means that the corresponding R ⁴⁰¹ , R ⁴⁰⁴ , R ⁴⁰⁵ , R ⁴⁰⁸ , This means that R ⁴⁰⁹ , R ⁴¹² or R ⁴¹³ do not exist. That is, ring formation described as the substituent R ⁴⁰¹ , R ⁴⁰² , R ⁴⁰³ , R ⁴⁰⁴ , R ⁴⁰⁵ , R ⁴⁰⁶ , R ⁴⁰⁷ , R ⁴⁰⁸ , R ⁴⁰⁹ , R ⁴¹⁰ , R ⁴¹¹ , R ⁴¹² or R ⁴¹³ may be combined The atom is unsubstituted, indicating that a hydrogen atom is bonded to the ring-forming atom.

a is preferably 0, 1, or 2, more preferably 0 or 1, and especially preferably 1. In addition, when a is 1, the substitution position of R ⁴⁰¹ is preferably a para position (p position or 4 position) with respect to the bond (*) to the nitrogen atom (the nitrogen atom bonded to Ar ¹ ). It is preferable that b, c, d, e, f and g are each independently 0, 1 or 2, more preferably 0 or 1, and especially preferably 0.

The alkyl group having 1 to 14 carbon atoms as R ⁴⁰¹ to R ⁴¹³ is not particularly limited, but is a straight-chain or branched alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso Butyl 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-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group , 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropylbutyl group, 1-tert-butyl- 2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group There are actual groups, n-tetradecyl groups, etc.

Here, from the viewpoint of improving durability, the alkyl group as R ⁴⁰¹ to R ⁴¹³ preferably has 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. In particular, it is preferable that R ⁴⁰¹ to R ⁴¹³ are each independently an alkyl group having a carbon number within the above range.

In addition, the alkyl groups as R ⁴⁰¹ to R ⁴¹³ are preferably straight chain from the viewpoint of improving durability.

In the formula (1) ^{, when} Any one of the groups represented by -3) is preferable. It is more preferable that X ¹ is a group represented by the above formula (4-1) or formula (4-3).

In the formula (1), Y ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms. Here, “substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms” means an aromatic hydrocarbon group having 6 to 25 ring atoms substituted with a substituent (a); An aromatic hydrocarbon group substituted with a substituent other than substituent (a) and having 6 to 25 ring atoms; or an unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms.

Here, the aromatic hydrocarbon group having 6 to 25 ring atoms specifically includes benzene, naphthalene, anthracene, pyrene, pentalene, indene, azulene, hepthalene, acenaphthene, phenalene, phenanthrene, biphenyl, Examples include divalent groups derived from aromatic hydrocarbons such as terphenyl, quarterphenyl, fluorene, and 9,9'-spirobi[fluorene].

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

Additionally, in Formula (1), when Y ¹ is an aromatic hydrocarbon group substituted with substituent (a), Y ¹ is preferably any one of the groups represented by the following formulas (5-1) to (5-9). do:

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

In the above formulas (5-1) to (5-9), R ⁵⁰¹ to R ⁵¹⁵ are each independently a substituted or unsubstituted alkylene group having 1 to 14 carbon atoms.

In addition, in the above formulas (5-1) to (5-3) and formulas (5-7) to (5-9), R ⁵⁰¹ and R ⁵⁰² , R ⁵⁰³ and R ⁵⁰⁴ , R ⁵⁰⁵ and R ⁵⁰⁶ , R ⁵¹⁰ and R ⁵¹¹ , R ⁵¹² , R ⁵¹³ , R ⁵¹⁴ and R ⁵¹⁵ may be the same or different, respectively. Preferably, R ⁵⁰¹ and R ⁵⁰² , R ⁵⁰³ and R ⁵⁰⁴ , R ⁵⁰⁵ and R ⁵⁰⁶ , R ⁵¹⁰ and R ⁵¹¹ , R ⁵¹² and R ⁵¹³ , R ⁵¹⁴ and R ⁵¹⁵ are identical to each other.

The alkylene group having 1 to 14 carbon atoms as R ⁵⁰¹ to R ⁵¹⁵ is not particularly limited, but is a straight-chain or branched alkylene group, for example, methylene group, ethylene group, trimethylene group, propylene group, 1,1- Dimethylmethylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, n-pentylene group, isopentylene group, tert-pentylene group, neopentylene group, 1,2-dimethylpropylene group, n -Hexylene group, isohexylene group, 1,3-dimethylbutylene group, 1-isopropylpropylene group, 1,2-dimethylbutylene group, n-heptylene group, 1,4-dimethylpentylene group, 3-ethylpentyl Len group, 2-methyl-1-isopropylpropylene group, 1-ethyl-3-methylbutylene group, n-octylene group, 2-ethylhexylene group, 3-methyl-1-isopropylbutylene group, 2-methyl- 1-isopropylbutylene group, 1-tert-butyl-2-methylpropylene group, n-nonylene group, 3,5,5-trimethylhexylene group, n-decylene group, isodecylene group, n-undecylene group, 1-methyldecylene group, n-dodecylene group, n-tridecylene group, and n-tetradecylene group.

Here, from the viewpoint of improving durability, the alkylene group as R ⁵⁰¹ to R ⁵¹⁵ preferably has 1 to 13 carbon atoms, more preferably 3 to 12 carbon atoms, particularly preferably 5 to 12 carbon atoms, and particularly preferably 7 to 12 carbon atoms. It is most preferable that it is below.

Additionally, the alkylene groups represented by R ⁵⁰¹ to R ⁵¹⁵ are preferably linear from the viewpoint of improving durability.

In the formula (1), when Y ¹ is an aromatic hydrocarbon group substituted with a substituent (a), Y ¹ is preferably any one of the groups represented by the formulas (5-1) to (5-3). From the viewpoint of further improving durability (especially luminescence life), Y ¹ is preferably a group represented by the above formula (5-1). On the other hand, from the viewpoint of improving external quantum efficiency (EQE) or luminous efficiency, Y ¹ is preferably a group represented by the above formula (5-2) or formula (5-3).

On the other hand, when Y ¹ is an aromatic hydrocarbon group unsubstituted by an alkyl group substituted with a carboxyl group (substituent (a)), this aromatic hydrocarbon group is substituted or unsubstituted by a substituent other than the substituent (a), such as benzene, biphenyl, It is preferable that it is a divalent group derived from a compound selected from terphenyl and fluorene. Y ¹ is more preferably a divalent group derived from biphenyl or fluorene, substituted or unsubstituted with a substituent other than substituent (a). It is especially preferable that Y ¹ is a divalent group derived from fluorene that is unsubstituted or substituted with a substituent other than substituent (a) (a fluorenylene group that is unsubstituted or substituted with a substituent other than substituent (a)).

Additionally, from the viewpoint of improving durability, in the general formula (1), when Y ¹ is an aromatic hydrocarbon group not substituted with a substituent (a), it is preferable that Y ¹ is a group represented by the following general formula (6-1) .

[Formula (6-1)]

In the above formula (6-1),

R ⁶⁰¹ to R ⁶⁰⁴ are each independently an alkyl group having 1 to 14 carbon atoms that is unsubstituted or substituted with a substituent other than a carboxyl group (-COOH),

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

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

Additionally, in the above formula (6-1), R ⁶⁰¹ and R ⁶⁰² may be the same or different. Preferably, R ⁶⁰¹ and R ⁶⁰² are identical to each other.

In the above formula (6-1), h or i being 0 means that the corresponding R ⁶⁰³ or R ⁶⁰⁴ does not exist. That is, the ring-forming atom described to which the substituent R ⁶⁰³ or R ⁶⁰⁴ may be bonded is unsubstituted, indicating that a hydrogen atom is bonded to the ring-forming atom.

h and i are each independently preferably 0, 1, or 2, more preferably 0 or 1, and especially preferably 0.

The alkyl group having 1 to 14 carbon atoms as R ⁶⁰¹ to R ⁶⁰⁴ is not particularly limited, but is a straight-chain or branched alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso Butyl 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-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group , 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropylbutyl group, 1-tert-butyl- 2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group There are actual groups, n-tetradecyl groups, etc.

Here, from the viewpoint of improving durability, the alkyl group as R ⁶⁰¹ to R ⁶⁰⁴ preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and especially preferably 2 to 6 carbon atoms. In particular, it is preferable that R ⁶⁰¹ and R ⁶⁰² are each independently an alkyl group having a carbon number within the above range.

In addition, the alkyl groups as R ⁶⁰¹ to R ⁶⁰⁴ are preferably straight chain from the viewpoint of improving durability.

In the formula (1), the alkyl group (substituent (a)) substituted with a carboxyl group may be included only in X ¹ , only in Y ¹ , or in both X ¹ and Y ¹ . From the viewpoint of improving durability (especially luminescence life), the substituent (a) is preferably contained only in X ¹ or only in Y ¹ , and more preferably only in X ¹ . That is, in the above formula (1) ^, It is an aromatic hydrocarbon group with a number of 6 to 25, and in this case, Y ¹ is an alkyl group with 1 to 14 carbon atoms substituted with a carboxyl group or an alkyl group with 1 to 14 carbon atoms substituted with a group having a carboxyl group (substituent (a)) It is more preferable that it is an aromatic hydrocarbon group with 6 to 25 ring atoms substituted or unsubstituted by other substituents. Likewise, when an alkyl group substituted with a carboxyl group (substituent (a)) exists in the side chain of a polymer compound, it is believed to be as follows. That is, in a quantum dot electroluminescent device having a hole transport layer containing a polymer compound and a light emitting layer containing quantum dots, the substituent (a) of the side chain of the polymer compound in the hole transport layer and the quantum dots contained in the light emitting layer are closer together due to the substituent (a). exist, and the hydrocarbon groups of the side chains of the polymer compound interact closely with the quantum dots. Accordingly, holes are efficiently injected into the quantum dots (hole injection properties are further improved), and durability (light emission lifetime) can be further improved.

At this time, it is preferable that R ¹¹ to R ¹⁴ , R ²¹ to R ²⁴ , L ¹ , Ar ¹ and Ar ² in the formula (1) do not have an alkyl group (substituent (a)) substituted with a carboxyl group.

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

Here, the aromatic hydrocarbon group specifically includes benzene (phenylene group), naphthalene, anthracene, pyrene, pentalene, indene, azulene, heptalene, acenaphthene, phenalene, phenanthrene, biphenyl, terphenyl, and quarterphenyl. , fluorene, and 9,9'-spirobi[fluorene], and other divalent groups derived from aromatic hydrocarbons. Additionally, the aromatic heterocyclic group specifically includes acridine, phenazine, benzoquinoline, benzoisoquinoline, phenanthridine, phenanthroline, anthraquinone, fluorenone, dibenzofuran, dibenzothiophene, and carbazole. , imidazophenanthridine, benzimidazophenanthridine, azadibenzofuran, azacarbazole, azadibenzothiophene, diazadibenzofuran, diazacarbazole, diazadibenzothiophene, xanthone, Examples include divalent groups derived from heterocyclic aromatic compounds such as thioxanthone, pyridine, quinoline, and anthraquinoline.

Among these, L ¹ is preferably a divalent group derived from a compound selected from substituted or unsubstituted benzene, biphenyl, terphenyl, quaterphenyl and fluorene, and is preferably a divalent group derived from substituted or unsubstituted benzene or biphenyl. It is more preferable that it is a divalent group (substituted or unsubstituted, phenylene group or biphenylene group).

Additionally, in the formula (1), L ¹ is preferably any one of the groups represented by the following formulas (7-1) to (7-24):

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

In the above formulas (7-1) to (7-24), * is bonded to a nitrogen atom, and ** is bonded to Ar ¹ .

In addition, L ¹ is any one of the groups represented by the formulas (7-1) to (7-3) and the formulas (7-13) to (7-16) (i.e., a substituted or unsubstituted phenylene group) It is desirable to be L ¹ is any one of the groups represented by the above formula (7-1) and the above formulas (7-13) to (7-16) (i.e., a substituted or unsubstituted p-phenylene group). desirable. It is particularly preferable that L ¹ is a group represented by the above 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 forming properties can be achieved.

In the formula (1), Ar ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring 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. When Ar ¹ does not form a ring with Ar ² , Ar ¹ is a divalent group.

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 forming atoms described for L ¹ above. In addition, when Ar ¹ forms a ring with Ar ² , the divalent group derived from an aromatic hydrocarbon with 6 to 25 ring forming atoms described for L ¹ above can be converted into a trivalent group.

Among these, Ar ¹ is preferably a divalent or trivalent group derived from a compound selected from substituted or unsubstituted benzene, biphenyl and fluorene, and is preferably a substituted or unsubstituted divalent group derived from benzene or biphenyl. Or, it is more preferable that it is a trivalent group, and a divalent (e.g., o, m, p-phenylene group) or trivalent group (e.g., 1,3,4-phenylyl) derived from substituted or unsubstituted benzene. Rengi) is particularly preferable. Additionally, Ar ¹ is more preferably a substituted or unsubstituted p-phenylene group or 1,3,4-phenylylene group, and most preferably is a substituted or unsubstituted 1,3,4-phenylylene group. That is, it is preferable that Ar ¹ forms a ring with Ar ² .

With such Ar ¹ , higher hole injection properties (resulting in high durability) and good film forming properties can be achieved. Additionally, durability and luminous efficiency can be improved with a good balance.

Meanwhile, the substituent that may exist when any one hydrogen atom of Ar ¹ is substituted is not particularly limited, and the same substituent as the substituent described for “substitution” above can be applied. In a preferred embodiment, Ar ¹ may be unsubstituted.

In the formula (1), Ar ² is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms; or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring 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. When Ar ² does not form a ring with Ar ¹ , Ar ² is a monovalent group.

Here, the aromatic hydrocarbon group and 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 converting a divalent group derived from an aromatic hydrocarbon with 6 to 25 ring forming atoms described for L ¹ above into a monovalent group. You can. Similarly, in the above case, the aromatic heterocyclic group as Ar ² can be exemplified by converting the divalent group derived from the heterocyclic aromatic compound with 5 to 25 ring forming atoms described for L ¹ into a monovalent group. . In addition, when Ar ² forms a ring with Ar ¹ , examples thereof include the same divalent groups derived from aromatic hydrocarbons having 6 to 25 ring atoms described for L ¹ above. Similarly, in the case described above, the aromatic heterocyclic group as Ar ² can be exemplified as the same divalent group derived from a heterocyclic aromatic compound having 5 to 25 ring atoms described for L ¹ above.

Among these, Ar ² is preferably a substituted or unsubstituted monovalent or divalent group derived from a compound selected from benzene, biphenyl and fluorene, and is preferably a substituted or unsubstituted monovalent or divalent group derived from benzene or biphenyl. It is more preferable that it is a valent group or a divalent group, and it is especially preferable that it is a monovalent or divalent group derived from substituted or unsubstituted benzene (for example, o, m, p-phenylene group), and a substituted or unsubstituted o -It is most preferable that it is a phenylene group. That is, it is preferable that Ar ² forms a ring with Ar ¹ .

With such Ar ² , higher hole injection properties (resulting in high durability) and good film forming properties can be achieved. Additionally, durability and luminous efficiency can be improved with a good balance.

In addition, the substituent that may exist when any one hydrogen atom of Ar ² is substituted is not particularly limited, and the same substituent as the substituent described for “substitution” above can be applied. In a preferred form, Ar ² is unsubstituted.

As described above, Ar ¹ and Ar ² are preferably bonded to each other to form a ring.

In this way, when Ar ¹ and Ar ² form a ring, higher hole injection properties can be obtained, durability (especially luminescence life) can be improved, and good film forming properties 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 Ar ¹ and Ar ² are preferably bonded to each other to form a carbazole ring. Furthermore, in a preferred form of the present invention, -Ar ¹ -N(Ar ² )(X ¹ ) in the above formula (1) has a structure selected from the following group.

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

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

R ⁸⁰¹ to R ⁸⁰⁴ 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 It is 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,

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, and It is the same as defined in Formula (1), and * is bonded to L ¹ .

The alkyl group for R ⁸⁰¹ to R ⁸⁰⁴ may be either straight chain or branched, and is preferably a straight chain alkyl group with 1 to 20 carbon atoms or a branched alkyl group with 3 to 20 carbon atoms. 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-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1 , 4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1 -Isopropylbutyl group, 2-methyl-1-isopropylbutyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, iso Decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n -There are octadecyl groups, nonadecyl groups, and icosyl groups.

The cycloalkyl group as R ⁸⁰¹ to R ⁸⁰⁴ is preferably a cycloalkyl group having 3 to 16 carbon atoms. Specifically, examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.

The alkoxy group as R ⁸⁰¹ to R ⁸⁰⁴ may be either straight chain or branched, and is preferably a straight chain alkoxy group with 1 to 20 carbon atoms or a branched alkoxy group with 3 to 20 carbon atoms. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group. There are siloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, 2-ethylhexyloxy group, 3-ethylpentoxy group, etc.

The cycloalkoxy group as R ⁸⁰¹ to R ⁸⁰⁴ is preferably a cycloalkoxy group having 3 to 16 carbon atoms. For example, there are cyclopropoxy group, cyclobutoxy group, cyclopentoxy group, cyclohexyloxy group, etc.

The aryl group as R ⁸⁰¹ to R ⁸⁰⁴ is preferably an aryl group having 6 to 30 carbon atoms. For example, there are phenyl group, naphthyl group, biphenyl group, fluorenyl group, anthryl group, pyrenyl group, azulenyl group, acenaphthylenyl group, terphenyl group, phenanthryl group, etc.

Examples of the halogen atom for R ⁸⁰¹ to R ⁸⁰⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In addition, in the above formulas (8-1) to (8-2), j, k, l, or m being 0 means that the corresponding R ⁸⁰¹ , R ⁸⁰² , R ⁸⁰³ or R ⁸⁰⁴ does not exist. means that That is, the ring-forming atom described to which the substituent R ⁸⁰¹ , R ⁸⁰² , R ⁸⁰³ or R ⁸⁰⁴ may be bonded is unsubstituted, indicating that a hydrogen atom is bonded to the ring-forming atom.

j, k, l, and m are each independently preferably 0, 1, or 2, more preferably 0 or 1, and especially preferably 0.

In addition, from the viewpoint of improving durability and film forming properties, in the above formula (1), it is preferable that Ar ¹ forms a ring with Ar ² , and -L ¹ -Ar ¹ -N(Ar ² )(X ¹ ) is , it is preferably any one of the groups represented by the following formulas (9-1) to (9-3):

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

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

R ⁹⁰¹ to R ⁹⁰⁶ 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 It is 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 one 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 , each may be the same or different,

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

* is bonded to the nitrogen atom.

Each substituent as R ⁹⁰¹ to R ⁹⁰⁶ can be the same as the example given for R ⁸⁰¹ to R ⁸⁰⁴ in the above formulas (8-1) to (8-2).

In the above formulas (9-1) to (9-3), n, o, p, q, r or s are 0, which means that the corresponding R ⁹⁰¹ , R ⁹⁰² , R ⁹⁰³ , R ⁹⁰⁴ , R ⁹⁰⁵ Or it means that R ⁹⁰⁶ does not exist. That is, the ring-forming atom described to which the substituent R ⁹⁰¹ , R ⁹⁰² , R ⁹⁰³ , R ⁹⁰⁴ , R ⁹⁰⁵ or R ⁹⁰⁶ may be bonded is unsubstituted, indicating that a hydrogen atom is bonded to the ring-forming atom.

n, o, p, q, r, and s are each independently preferably 0, 1, or 2, more preferably 0 or 1, and especially preferably 0.

In formula (1), R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ 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 It represents an unsubstituted cycloalkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, and in this case, R ¹¹ and R ²¹ may be bonded to each other to form a ring.

Here, R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be the same or different, respectively.

The alkyl group as R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be either straight-chain or branched, and is preferably a straight-chain alkyl group with 1 to 20 carbon atoms or a branched alkyl group with 3 to 20 carbon atoms. . 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-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1 , 4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1 -Isopropylbutyl group, 2-methyl-1-isopropylbutyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, iso Decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n -There are octadecyl groups, nonadecyl groups, and icosyl groups.

The cycloalkyl group as R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ is preferably a cycloalkyl group having 3 to 16 carbon atoms. Specifically, examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.

The alkoxy group as R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be either straight chain or branched, and is preferably a straight chain alkoxy group with 1 to 20 carbon atoms or a branched alkoxy group with 3 to 20 carbon atoms. there is. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group. There are siloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, 2-ethylhexyloxy group, 3-ethylpentoxy group, etc.

The cycloalkoxy group as R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ is preferably a cycloalkoxy group having 3 to 16 carbon atoms. For example, there are cyclopropyloxy group, cyclobutoxy group, cyclopentoxy group, cyclohexyloxy group, etc.

As the aryl group as R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ , an aryl group having 6 to 30 carbon atoms is preferably used. For example, there are phenyl group, naphthyl group, biphenyl group, fluorenyl group, anthryl group, pyrenyl group, azulenyl group, acenaphthylenyl group, terphenyl group, phenanthryl group, etc.

Examples of the halogen atom as R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Additionally, R ¹¹ and R ²¹ may be combined 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 it is preferable that R ¹¹ and R ²¹ combine with each other to form a carbazole ring. That is, as a preferred embodiment of the present invention, in the above general formula (1), the structural unit X has the following structure (structural unit X-1).

[Structural unit X-1]

In the structural unit X-1, R ¹² to R ¹⁴ and R ^{22 to} R ²⁴ , L ¹ , Ar ¹ , Ar ² and It bonds with adjacent atoms that form the main skeleton of the polymer compound (i.e., it bonds with Y ¹ or an adjacent structural unit).

Among these, from the viewpoint of obtaining higher durability (especially luminescence life) or excellent film forming properties, R ¹¹ and R ²¹ are each independently a hydrogen atom or a straight-chain or branched alkyl group having 1 to 5 carbon atoms, or are combined with each other to form a ring. forming; R ¹² to R ¹⁴ and R ²² to R ²⁴ are preferably each independently a hydrogen atom or a straight-chain or branched alkyl group having 1 to 5 carbon atoms. In addition, R ¹¹ and R ²¹ are each independently a hydrogen atom or a straight-chain or branched alkyl group having 1 to 3 carbon atoms, or are combined with each other to form a ring; It is more preferable that R ¹² to R ¹⁴ and R ²² to R ²⁴ each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 3 carbon atoms. In addition, R ¹¹ and R ²¹ are both hydrogen atoms or are combined with each other to form a ring; It is particularly preferable that R ¹² to R ¹⁴ and R ²² to R ²⁴ are all hydrogen atoms. In addition, it is most preferable that R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ are all hydrogen atoms (unsubstituted).

From the above, the structural unit (A) according to the present invention is preferably selected from the following group (structural units (A-1a) to (A-1d)).

[Structural unit (A-1)]

In the structural unit (A-1)], R ⁵⁷ , R ⁵⁸ , R ⁶⁷ , R ⁶⁸ , R ⁷⁸ , R ⁷⁹ , R ⁹⁴ and R ⁹⁵ are each independently an alkyl group having 1 to 14 carbon atoms substituted with a carboxyl group. or an alkyl group having 1 to 14 carbon atoms (substituent (a)) substituted with a group having a carboxyl group, and R ⁵¹ to R ⁵⁶ , R ⁵⁹ to R ⁶⁶ , R ⁶⁹ to R ⁷⁷ , R ⁸⁰ to R ⁹³ , R ⁹⁶ and R ⁹⁷ each independently represents 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 the above formula (1), the polymer compound according to the present invention preferably further contains a structural unit (B) represented by the following formula (2):

[Formula (2)]

In the above formula (2),

R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ 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, It is a substituted or unsubstituted aryl group or a halogen atom. In this case, R ³¹ and R ⁴¹ may be combined with each other to form a ring,

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

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

Ar ⁴ is a substituted or unsubstituted aromatic hydrocarbon group with 6 to 25 ring atoms, or a substituted or unsubstituted aromatic heterocyclic group with 5 to 25 ring atoms. In this case, Ar ³ and the ring are can be formed,

^and

Y ² is an aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with an alkyl group having 1 to 14 carbon atoms,

R ³¹ to R ³⁴ , R ⁴¹ to R ⁴⁴ , L ² , Ar ³ and Ar ⁴ do not have 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, the structural unit (B) represented by formula (2) is also simply referred to as “structural unit (B)” or “structural unit (B) according to the present invention.” In addition, the structural unit having the following structural structure among the “structural units (B) represented by formula (2)” is also simply referred to as “structural unit

[Structural unit

Likewise, the structural unit “-Y ² -” in the “structural unit (B) represented by formula (2)” is also simply referred to as “structural unit Y’” or “structural unit Y’ according to the present invention.”

In addition to the structural unit (A) represented by the formula (1), by further comprising the structural unit (B) represented by the formula (2), the polymer compound according to the present invention has hole injection properties for quantum dots. This is excellent, and the durability (light emission life) of the electroluminescent device can be further improved. Additionally, high current efficiency and low driving voltage can be achieved. When the polymer compound according to the present invention further contains a structural unit (B), only one type of structural unit (B) may be contained, or two or more types may be contained. 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.

[Formula (2)]

As described above, in a preferred embodiment of the present invention, the polymer compound includes the structural unit (B) represented by the above formula (2). That is, the structural unit It constitutes a polymer compound according to: In addition, similarly, the structural unit Y' in the above formula (2) (the structural unit on the right side of the above formula (2); that is, the structural unit represented by “Y ² ”) is according to a preferred embodiment of the present invention. It constitutes a polymer compound. That is, the polymer compound according to a preferred embodiment can be said to be a copolymer that further includes the structural unit X' and the structural unit Y' in addition to the structural unit X and the structural unit Y.

In the formula ⁽ 2 ⁾ , , are each different from X ¹ and Y ¹ in Formula (1). In addition, in Formula (2), the definition of L ² , Ar ³ , Ar ⁴ , R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ is that each does not have a substituent (a) (or is not a substituent (a)). ) Except for this point, the definitions of L ¹ , Ar ¹ , Ar ² , R ¹¹ to R ¹⁴ , and R ²¹ to R ²⁴ in the above formula (1) are the same. Therefore, with respect to L ² , Ar ³ , Ar ⁴ , R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ , the term “substituted” means substituted with a substituent other than substituent (a), unless otherwise specified. intended form.

In the general formula (2) ^,

Here, the aromatic hydrocarbon group having 6 to 25 ring atoms specifically includes benzene, naphthalene, anthracene, pyrene, pentalene, indene, azulene, hepthalene, acenaphthene, phenalene, phenanthrene, biphenyl, Examples include monovalent groups derived from aromatic hydrocarbons such as terphenyl, quarterphenyl, fluorene, and 9,9'-spirobi[fluorene].

Among them, the aromatic hydrocarbon group ^as It is more preferable, and it is especially preferable that it is a monovalent group (phenyl group or fluorenyl group) derived from benzene or fluorene.

Additionally, from the viewpoint of improving durability, in the general formula (2), X ² is preferably one of the groups represented by the following general formulas (4'-1) to (4'-4).

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

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

R ^401' to R ^413' are each independently an alkyl group having 1 to 14 carbon atoms unsubstituted or substituted 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,

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

In addition, in the above formulas (4'-2) to (4'-4), R ^402' and R ^403' , R ^406' and R ^407' , R ^410' and R ^411' may be the same or different, respectively. It can be anything. Preferably, R ^402' and R ^403' , R ^406' and R ^407' , R ^410' and R ^411' are identical to each other.

In the above formulas (4-1) to (4-4), a', b', c', d', e', f' or g' being 0 means that the corresponding R ^401' , R It means that ^404' , R ^405' , R ^408' , R ^409' , R ^412' or R ^413' do not exist. That is, the ring-forming atom described to which the substituent R ^401' , R ^404' , R ^405' , R ^408' , R ^409' , R ^412' or R ^413' may be bonded is unsubstituted, and the ring-forming atom It indicates that hydrogen atoms are bonded.

a' is preferably 0, 1, or 2, more preferably 0 or 1, and especially preferably 1. In addition, when a' is 1, the substitution position of R ^401' is preferably para-position (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' are each independently preferably 0, 1, or 2, more preferably 0 or 1, and especially preferably 0.

The alkyl group having 1 to 14 carbon atoms as R ^401' to R ^413' is not particularly limited, but is a straight-chain or branched alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, and 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-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropyl group Propyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropylbutyl group, 1-tert- Butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n- There are tridecyl groups, n-tetradecyl groups, etc.

Here, the alkyl group as R ^401' to R ^413' preferably has 1 to 12 carbon atoms from the viewpoint of improving durability. In particular, it is preferable that R ^401' to R ^413' are each independently an alkyl group having a carbon number within the above range.

In addition, the alkyl groups as R ^401' to R ^413' are preferably straight chain from the viewpoint of improving durability.

In the formula (2), from the viewpoint of improving durability (especially luminescence life), X ² is preferably any one of the groups represented by the formulas (4'-1) to (4'-3), A group represented by the formula (4'-1) or (4'-3) is more preferable.

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

Here, the aromatic hydrocarbon group having 6 to 25 ring atoms specifically includes benzene, naphthalene, anthracene, pyrene, pentalene, indene, azulene, hepthalene, acenaphthene, phenalene, phenanthrene, biphenyl, Examples include divalent groups derived from aromatic hydrocarbons such as terphenyl, quarterphenyl, fluorene, and 9,9'-spirobi[fluorene].

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

Additionally, from the viewpoint of improving durability, in the general formula (2), Y ² is preferably a group represented by the following general formula (6'-1).

[Formula (6'-1)]

In the above formula (6'-1),

R ^601' to R ^604' are each independently an alkyl group having 1 to 14 carbon atoms unsubstituted or substituted with a substituent other than a carboxyl group (-COOH),

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

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

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

In the above formula (6'-1), h' or i' being 0 means that the corresponding R ^603' or R ^604' does not exist. That is, the ring-forming atom described to which the substituent R ^603' or R ^604' may be bonded is unsubstituted, indicating that a hydrogen atom is bonded to the ring-forming atom.

h' and i' are each independently preferably 0, 1, or 2, more preferably 0 or 1, and especially preferably 0.

The alkyl group having 1 to 14 carbon atoms as R ^601' to R ^604' is not particularly limited, but is a straight-chain or branched alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, and 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-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropyl group Propyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropylbutyl group, 1-tert- Butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n- There are tridecyl groups, n-tetradecyl groups, etc.

Here, from the viewpoint of improving durability, the alkyl group as R ^601' to R ^604' preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and especially preferably 2 to 6 carbon atoms. In particular, it is preferable that R ^601' and R ^602' are each independently an alkyl group having a carbon number within the above range.

Additionally, the alkyl groups as R ^601' to R ^604' are preferably straight chain from the viewpoint of improving durability.

As above, in the formula (2), the definitions of L ² , Ar ³ , Ar ⁴ , R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ are L ¹ , Ar ¹ , and Ar in the formula (1). ² , R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ are the same as the definitions, respectively. Additionally, the preferred forms are the same for each. Hereinafter, it will be described in detail.

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

Here, the aromatic hydrocarbon group specifically includes benzene (phenylene group), naphthalene, anthracene, pyrene, pentalene, indene, azulene, heptalene, acenaphthene, phenalene, phenanthrene, biphenyl, terphenyl, and quarterphenyl. , fluorene, and 9,9'-spirobi[fluorene], and other divalent groups derived from aromatic hydrocarbons. Additionally, the aromatic heterocyclic group specifically includes acridine, phenazine, benzoquinoline, benzoisoquinoline, phenanthridine, phenanthroline, anthraquinone, fluorenone, dibenzofuran, dibenzothiophene, and carbazole. , imidazophenanthridine, benzimidazophenanthridine, azadibenzofuran, azacarbazole, azadibenzothiophene, diazadibenzofuran, diazacarbazole, diazadibenzothiophene, xanthone, ti Examples include divalent groups derived from heterocyclic aromatic compounds such as oxanthone, pyridine, quinoline, and anthraquinoline.

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

Additionally, in the formula (2), L ² is preferably any one of the groups represented by the following formulas (7'-1) to (7'-24):

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

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

In addition, L ² is any one of the groups represented by the formulas (7'-1) to (7'-3) and the formulas (7'-13) to (7'-16) (i.e., substituted or unsubstituted) It is preferable that it is a phenylene group), and any one of the groups represented by the formula (7'-1) and the formulas (7'-13) to (7'-16) (i.e., substituted or unsubstituted p-phenyl It is more preferable that it is a lene group), and it is especially preferable that it is a group (namely, an unsubstituted p-phenylene group) represented by the formula (7'-1). With such L ¹ , higher hole injection properties (resulting in high durability) and good film forming properties can be achieved.

In the general formula (2), Ar ³ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms. At this time, Ar ³ may form a ring with Ar ⁴ . On the other hand, when Ar ¹ forms a ring with Ar ² , Ar ³ is a trivalent group. When Ar ³ does not form a ring with Ar ⁴ , Ar ³ is a divalent group.

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 forming atoms described for L ² above. In addition, when Ar ³ forms a ring with Ar ⁴ , the divalent group derived from an aromatic hydrocarbon with 6 to 25 ring forming atoms described for L ² above can be converted into a trivalent group.

Among these, Ar ³ is preferably a substituted or unsubstituted divalent or trivalent group derived from a compound selected from benzene, biphenyl and fluorene. Ar ³ is more preferably a substituted or unsubstituted divalent or trivalent group derived from benzene or biphenyl. In particular, Ar ³ is a divalent (for example, o, m, p-phenylene group) or trivalent group (for example, 1,3,4-phenylylene group) derived from substituted or unsubstituted benzene. desirable. Additionally, Ar ³ is more preferably a substituted or unsubstituted p-phenylene group or 1,3,4-phenylylene group, and most preferably is a substituted or unsubstituted 1,3,4-phenylylene group. That is, Ar ³ preferably forms a ring with Ar ⁴ .

With such Ar ³ , higher hole injection properties (resulting in high durability) and good film forming properties can be achieved. Additionally, durability and luminous efficiency can be improved with a good balance.

Meanwhile, the substituent that may exist when any one hydrogen atom of Ar ³ is substituted is not particularly limited, and the same substituent as the substituent described for “substitution” above can be applied. In a preferred form, Ar ³ is unsubstituted.

In the formula (2), Ar ⁴ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms; or a substituted or unsubstituted aromatic heterocyclic group having 5 to 25 ring 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. When Ar ⁴ does not form a ring with Ar ³ , Ar ⁴ is a monovalent group.

Here, the aromatic hydrocarbon group and 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 converting a divalent group derived from an aromatic hydrocarbon with 6 to 25 ring forming atoms described for L ² above into a monovalent group. You can. Similarly, in the above case, the aromatic heterocyclic group as Ar ⁴ can be exemplified by converting a divalent group derived from a heterocyclic aromatic compound with 5 to 25 ring atoms described for L ² into a monovalent group. 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 forming atoms described for L ² above can be used. Similarly, in the above case, the aromatic heterocyclic group as Ar ⁴ may be the same as the divalent group derived from a heterocyclic aromatic compound having 5 to 25 ring atoms described for L ² above.

Among these, Ar ⁴ is preferably a substituted or unsubstituted monovalent or divalent group derived from a compound selected from benzene, biphenyl and fluorene, and is preferably a substituted or unsubstituted 1 group derived from benzene or biphenyl. It is more preferable that it is a valent group or a divalent group, and it is especially preferable that it is a monovalent or divalent group derived from substituted or unsubstituted benzene (for example, o, m, p-phenylene group), and a substituted or unsubstituted group is more preferable. Most preferably it is an o-phenylene group. That is, it is preferable that Ar ⁴ forms a ring with Ar ³ .

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

In addition, the substituent that may exist when any one of the hydrogen atoms in Ar ⁴ is substituted is not particularly limited, and the same substituent as the substituent described for “substitution” above can be applied. In a preferred form, Ar ⁴ is unsubstituted.

As described above, Ar ³ and Ar ⁴ are preferably combined with each other to form a ring.

In this way, when Ar ³ and Ar ⁴ form a ring, higher hole injection properties can be obtained, durability (especially luminescence life) can be improved, and good film forming properties 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 Ar ³ and Ar ⁴ are preferably bonded to each other to form a carbazole ring. Furthermore, in a preferred form of the present invention, -Ar ³ -N(Ar ⁴ )(X ² ) in the above formula (2) has a structure selected from the following group.

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

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

R ^801' to R ^804' 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, or 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,

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) above, and * is bonded to L ² .

The alkyl group as R ^801' to R ^804' may be either straight chain or branched, and preferably is a straight chain alkyl group with 1 to 20 carbon atoms or a branched alkyl group with 3 to 20 carbon atoms. 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 group, 1,2-dimethylbutyl group, n-heptyl group, 1, 4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1- Isopropylbutyl group, 2-methyl-1-isopropylbutyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isode Syl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n- There are octadecyl groups, nonadecyl groups, and icosyl groups.

The cycloalkyl group as R ^801' to R ^804' is preferably a cycloalkyl group having 3 to 16 carbon atoms. Specifically, examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.

The alkoxy group as R ^801' to R ^804' may be either straight chain or branched, and is preferably a straight chain alkoxy group with 1 to 20 carbon atoms or a branched alkoxy group with 3 to 20 carbon atoms. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group. There are siloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, 2-ethylhexyloxy group, 3-ethylpentoxy group, etc.

The cycloalkoxy group as R ^801' to R ^804' is preferably a cycloalkoxy group having 3 to 16 carbon atoms. For example, there are cyclopropoxy group, cyclobutoxy group, cyclopentoxy group, cyclohexyloxy group, etc.

The aryl group as R ^801' to R ^804' is preferably an aryl group having 6 to 30 carbon atoms. For example, there are phenyl group, naphthyl group, biphenyl group, fluorenyl group, anthryl group, pyrenyl group, azulenyl group, acenaphthylenyl group, terphenyl group, phenanthryl group, etc.

Examples of the halogen atom as R ^801' to R ^804' include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In addition, in the above formulas (8'-1) and (8'-2), j', k', l', or m' being 0 means that the corresponding R ^801' , R ^802' , and R It means that ^803' or R ^804' does not exist. That is, the ring-forming atom described to which the substituent R ^801' , R ^802' , R ^803' or R ^804' may be bonded is unsubstituted, indicating that a hydrogen atom is bonded to the ring-forming atom.

j', k', l', and m' are each independently preferably 0, 1, or 2, more preferably 0 or 1, and especially preferably 0.

Additionally, from the viewpoint of improving durability and film forming properties, in the above formula (2), it is preferable that Ar ³ forms a ring with Ar ⁴ , and -L ² -Ar ³ -N(Ar ⁴ )(X ² ) is , it is preferably any one of the groups represented by the following formulas (9'-1) to (9'-3):

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

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

R ^901' to R ^906' 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, or 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 one 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 formula (2) above,

* is bonded to the nitrogen atom.

Each substituent as R ^901' to R ^906' can be the same as the example given for R ^801' to R ^804' in the above formulas (8-1) to (8-2).

In the above formulas (9'-1) to (9'-3), n', o', p', q', r' or s' being 0 means that the corresponding R ^901' and R ^{902 '} , R ^903' , R ^904' , R ^905' or R ^906' do not exist. That is, the ring-forming atom described as the substituent R ^901' , R ^902' , R ^903' , R ^904' , R ^905' or R ^906' is unsubstituted, and a hydrogen atom is bonded to the ring-forming atom. indicates what exists.

n', o', p', q', r', and s' are each independently preferably 0, 1, or 2, more preferably 0 or 1, and especially preferably 0.

In formula (2), R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ 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 It represents an unsubstituted cycloalkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, and in this case, R ³¹ and R ⁴¹ may be bonded to each other to form a ring.

Here, R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ may be the same or different, respectively.

The alkyl group as R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ may be either straight chain or branched, and is preferably a straight chain alkyl group with 1 to 20 carbon atoms or a branched alkyl group with 3 to 20 carbon atoms. . 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-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1 , 4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1 -Isopropylbutyl group, 2-methyl-1-isopropylbutyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, iso Decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n -There are octadecyl groups, nonadecyl groups, and icosyl groups.

The cycloalkyl group as R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ is preferably a cycloalkyl group having 3 to 16 carbon atoms. Specifically, examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.

The alkoxy group as R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ may be either straight chain or branched, and preferably is a straight chain alkoxy group with 1 to 20 carbon atoms or a branched alkoxy group with 3 to 20 carbon atoms. there is. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group. There are siloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, 2-ethylhexyloxy group, 3-ethylpentoxy group, etc.

The cycloalkoxy group as R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ is preferably a cycloalkoxy group having 3 to 16 carbon atoms. For example, there are cyclopropoxy group, cyclobutoxy group, cyclopentoxy group, cyclohexyloxy group, etc.

The aryl group as R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ preferably includes an aryl group having 6 to 30 carbon atoms. For example, there are phenyl group, naphthyl group, biphenyl group, fluorenyl group, anthryl group, pyrenyl group, azulenyl group, acenaphthylenyl group, terphenyl group, phenanthryl group, etc.

Examples of the halogen atom as R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Additionally, R ³¹ and R ⁴¹ may be combined 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 R ³¹ and R ⁴¹ are preferably bonded to each other to form a carbazole ring. That is, as a preferred embodiment of the present invention, in the above general formula (2), the structural unit X' has the following structure (structural unit X'-1).

[Structural unit X'-1]

In the structural unit X'-1, R ³² to R ³⁴ and R ^{42 to} R ⁴⁴ , L ² , Ar ³ , Ar ⁴ and , binds to adjacent atoms forming the main skeleton of the polymer compound (i.e., binds to Y ² or adjacent structural units).

Among these, from the viewpoint of obtaining higher durability (especially luminescence life) or excellent film forming properties, R ³¹ and R ⁴¹ are each independently a hydrogen atom or a straight-chain or branched alkyl group with 1 to 5 carbon atoms, or are combined with each other to form a ring. forming; R ³² to R ³⁴ and R ⁴² to R ⁴⁴ are preferably each independently a hydrogen atom or a straight-chain or branched alkyl group having 1 to 5 carbon atoms. In addition, R ³¹ and R ⁴¹ are each independently a hydrogen atom or a straight-chain or branched alkyl group having 1 to 3 carbon atoms, or are combined with each other to form a ring; It is more preferable that R ³² to R ³⁴ and R ⁴² to R ⁴⁴ are each independently a hydrogen atom or a straight-chain or branched alkyl group having 1 to 3 carbon atoms. Additionally, R ³¹ and R ⁴¹ are both hydrogen atoms or are bonded to each other to form a ring; It is particularly preferable that R ³² to R ³⁴ and R ⁴² to R ⁴⁴ are all hydrogen atoms. In addition, it is most preferable that R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ are all hydrogen atoms (unsubstituted).

The structural unit (B) represented by the formula (2) described above includes the structural unit (A) represented by the formula (1) and the portion containing the substituent (a) (i.e., X ¹ , Y ¹ ). It is preferable that the structure and substituents are the same. That is, R ¹¹ to R ¹⁴ , R ²¹ to R ²⁴ , L ¹ , Ar ¹ , and Ar ² in the formula (1) are respectively R ³¹ to R ³⁴ , R ⁴¹ to R ⁴⁴ , and L ² in the formula (2). , Ar ³ , and Ar ⁴ are preferably the same. ^{In a more preferred embodiment , when ​ ​} , respectively, are the same as R ³¹ to R ³⁴ , R ⁴¹ to R ⁴⁴ , L ² , Ar ³ , Ar ⁴ and Y ² in the above formula (2). In another preferred form, when Y ¹ includes a substituent (a), R ¹¹ to R ¹⁴ , R ²¹ to R ²⁴ , L ¹ , Ar ¹ , Ar ^{2 and} are the same as R ³¹ to R ³⁴ , R ⁴¹ to R ⁴⁴ , L ² , Ar ³ , Ar ⁴ and X ² in the above formula (2), respectively.

From the above, the structural unit (B) according to the present invention is preferably selected from the following group (structural units (B-1a) to (B-1d)).

[Structural unit (B-1)]

In the structural unit (B-1), R ^57' , R ^58' , R ⁶⁷ ', R ^68' , R ^78' , R ^79' , R ^94' and R ^95' each independently have 1 to 14 carbon atoms. Represents an alkyl group, R ^51' to R ^56' , R ^59' to R ^66' , R ^69' to R ^77' , R ^80' to R ^93' , R ^96' and R ^97' are each independently a hydrogen atom Or it represents an alkyl group having 1 to 14 carbon atoms.

《Other structural units》

The polymer compound of the present invention may further contain structural units other than the structural unit (A) and the structural unit (B). When other structural units are included, the other structural units are not particularly limited as long as they do not impede the effect of the polymer compound (particularly high hole injection properties). Other structural units include, for example, structural units derived from compounds such as azulene, naphthalene, anthracene, phenanthrene, and pyrene. Meanwhile, hereinafter, such other structural units are also referred to as “structural units (C).”

《Composition of polymer compounds》

The composition of structural units (A) to structural units (C) in the polymer compound according to the present invention is not particularly limited. Considering the durability (emission lifetime) and excellent film forming properties of the layers (e.g., hole injection layer, hole transport layer) formed using the resulting polymer compound, the structural unit (A) is the overall structure that constitutes the polymer compound. Per unit, it is preferably 5 mol% or more and less than 100 mol%, more preferably 10 mol% or more and 80 mol% or less, particularly preferably 10 mol% or more and 70 mol% or less, and most preferably 30 mol% or more. It is less than 70 mol%. That is, in a preferred form of the present invention, the structural unit (A) is contained in a ratio of 30 mol% or more and 70 mol% or less with respect to all structural units. On the other hand, when a polymer compound contains 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 preferred form of the present invention, the structural unit (A) is contained in a ratio of less than 100 mol% with respect to all structural units. At this time, it is preferable that the structural unit (B) is further included. Considering the durability (emission life) and excellent film forming properties of the layers (e.g., hole injection layer, hole transport layer) formed using the obtained polymer compound, the structural unit (B) is the overall structure that constitutes the polymer compound. Per unit, it is preferably greater than 0 mol% and less than or equal to 95 mol%, more preferably greater than or equal to 20 mol% and less than or equal to 90 mol%, particularly preferably greater than or equal to 30 mol% and less than or equal to 90 mol%, and most preferably 30 mol%. % or more and 70 mol% or less. That is, in a preferred form of the present invention, the structural unit (B) is contained in a ratio of 30 mol% or more and 70 mol% or less with respect to all structural units. On the other hand, when a polymer compound contains 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 present invention may further contain another structural unit (structural unit (C)). In this case, the composition of the other structural unit (structural unit (C)) is not particularly limited. Considering the ease of film formation by the resulting polymer compound and the effect of further improving film strength, the structural unit (C) is preferably greater than 0 mol% and is 10 mol% relative to all structural units constituting the polymer compound. % or less. On the other hand, when a polymer compound contains 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, “crosslinking group” means a group that creates a new bond by reacting (crosslinking) with the same or different structural unit located nearby by heating or irradiation of active energy rays. Including a structural unit having a crosslinking group. As a result, a crosslinking reaction occurs by heating or irradiation of active energy rays, and a more durable film can be formed by insolubilization in the solvent used in the subsequent process, thereby further improving the productivity and durability of the electroluminescent device. You can.

The crosslinking group is not particularly limited as long as it is a group that can induce a crosslinking reaction by heat or active energy rays, but examples include bicyclo[4.2.0]octa-1,3,5-trienyl group, vinyl group, There are hexenyl group, styryl group, (3-methyl-3-oxetanyl)methoxy group, etc.

In addition, considering the durability (luminescence life) and excellent film forming properties of the layers (e.g., hole injection layer, hole transport layer) formed using the obtained polymer compound, the structural unit (A) and the structural unit (B) When the total molar ratio of is 100 mol%, the molar ratio of structural unit (A) is preferably 10 mol% or more and 80 mol% or less, more preferably 10 mol% or more and 70 mol% or less, and 30 mol% or more. It is particularly preferable that it is 70 mol% or less. Likewise, the mole ratio of the structural unit (B) is preferably 20 mol% or more and 90 mol% or less, more preferably 30 mol% or more and 90 mol% or less, and especially preferably 30 mol% or more and 70 mol% or less (however, , the sum of the 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 one embodiment of the present invention is not particularly limited as long as the objective effect of the present invention is obtained. The weight average molecular weight (Mw), for example, is preferably 5,000 to 1,000,000, more preferably 8,000 to 1,000,000, even more preferably 10,000 to 800,000, and especially preferably 30,000 to 500,000. With such a weight average molecular weight, it is possible to form a layer with a uniform film thickness by appropriately adjusting the viscosity of the coating solution for forming a layer (e.g., hole injection layer, hole transport layer) using a polymer compound. do.

Additionally, the number average molecular weight (Mn) of the polymer compound is not particularly limited as long as the objective effect of the present invention is obtained. The number average molecular weight (Mn) is, for example, preferably between 4,000 and 300,000, more preferably between 6,000 and 250,000, even more preferably between 10,000 and 200,000, and particularly preferably between 20,000 and 180,000. With such a number average molecular weight, it is possible to form a layer with a uniform film thickness by appropriately adjusting the viscosity of the coating solution for forming a layer (e.g., hole injection layer, hole transport layer) using a polymer compound. do. In addition, the polydispersity (weight average molecular weight/number average molecular weight) of the polymer compound according to the present invention is, for example, 1.1 or more and 5.0 or less, preferably 1.3 or more and 4.0 or less, preferably 1.5 or more and 3.5 or less.

In this specification, the measurement of number average molecular weight (Mn) and weight average molecular weight (Mw) is not particularly limited and can be applied using known methods or by appropriately modifying known methods. In this specification, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured by the following method. Meanwhile, the polydispersity (Mw/Mn) of the polymer is calculated by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) measured by the following method.

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

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer material are measured by SEC (Size Exclusion Chromatography) using polystyrene as a standard material under the following conditions:

(SEC measurement conditions)

Analysis equipment (SEC): Shimadzu Works, Prominece (registered trademark)

Column: PLgel MIXED-B, manufactured by Polymer Laboratories Ltd.

Column temperature: 40℃

Flow rate: 1.0 mL/min

Injection volume of sample solution: 20μL (polymer concentration: approximately 0.05% by weight)

Eluent: tetrahydrofuran (THF)

Detector (UV-VIS detector): Shimadzu Works, SPD-10AV

Standard sample: polystyrene

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

The polymer compound according to one embodiment of the present invention can be synthesized using a known organic synthesis method. The specific method for synthesizing a polymer compound according to an embodiment of the present invention can be easily understood by those skilled in the art by referring to the examples described later.

Specifically, the polymer compound according to one embodiment of the present invention is a copolymerization using one or more monomers (Ix) represented by the following formula (IX) and one or more monomers (Iy) represented by the following formula (IY) It can be manufactured by reaction. Also, at this time, if necessary, monomers constituting the structural unit (B) according to the present invention may be further added. Specifically, one or more monomers (Ix) represented by the following formula (IX) and one or more monomers (Iy) represented by the following formula (IY) (i.e., constituting the structural unit (A) according to the present invention In addition to the monomer), one or more monomers (II-x) represented by the following formula (II-X) and one or more monomers (II-y) represented by the following formula (II-Y) (i.e., It can be produced by a copolymerization reaction using the monomers constituting the structural unit (B) according to the invention. 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, one or more monomers (Ix) represented by the following formula (IX) ), one or more monomers (Iy) represented by the following formula (IY), and one or more monomers (II-x) represented by the following formula (II-X). can be manufactured. Also, at this time, if necessary, other monomers corresponding to the other structural units (structural units (C)) may be further added.

[Formula (I-X)]

[Formula (I-Y)]

[Formula (II-X)]

[Formula (II-Y)]

Alternatively, the polymer compound according to one embodiment of the present invention can be produced by a polymerization reaction using one or more monomers represented by the following formula (1'). Also, at this time, if necessary, a monomer corresponding to the structural unit (B) according to the present invention may be further added. Specifically, when the polymer compound according to the present invention contains a structural unit (A) and a structural unit (B), one or more monomers represented by the following formula (1') and one or more monomers represented by the following formula (2') It can be produced by copolymerization using one or more monomers. Also, at this time, if necessary, other monomers corresponding to the other structural units (structural units (C)) may be further added.

[Formula (1')]

[Formula (2')]

In the present invention, the monomer used in the polymerization of a polymer compound can be synthesized by appropriately combining known synthesis reactions, and its structure can also be synthesized by known methods (e.g., NMR, LC-MS, etc.). It can be confirmed by

In Formula (IX), Formula (IY), Formula (II-X), Formula (II-Y), Formula (1'), and Formula (2'), R ¹¹ to R ¹⁴ , R ²¹ to R ²⁴ , R ³¹ to R ³⁴ , R ^{41 to} R ⁴⁴ , L ¹ , L ² , Ar ¹ , ^{Ar 2} , Ar ^{3 , Ar 4 ,} X ¹ , It is the same as defined in (2), and W ¹ to W ¹² are 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 structure below, R ^A to R ^D are each independently an alkyl group having 1 to 3 carbon atoms. Preferably, R ^A to R ^D are methyl groups.

[Formula D]

On the other hand, W ¹ and W ² in the formula (IX), W ³ and W ⁴ in the formula (IY), W ⁵ and W ⁶ in the formula (II-X), and W ⁷ in the formula (II-Y) and W ⁸ , 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 suppress polymerization of monomers (Ix), it is preferable that W ¹ and W ² in the above formula (IX) are atoms or groups that do not react with each other. Similarly, in order to suppress polymerization between monomers (Iy), it is preferable that W ³ and W ⁴ in the above formula (IY) are atoms or groups that do not react with each other. In addition, in order to similarly suppress polymerization between monomers (II-x) or between monomers (II-y), W ⁵ and W ⁶ in the formula (II-X), and W 6 in the formula (II-Y) W ⁷ and W ⁸ are preferably atoms or groups that do not react with each other. In addition, in order to similarly suppress polymerization between the monomers represented by the formula (1') or the monomers represented by the formula (2'), W ⁹ and W ¹⁰ in the formula (1'), and In the formula (2'), W ¹¹ and W ¹² are preferably atoms or groups that do not react with each other. W ¹ and W ² in the formula (IX), W ³ and W ⁴ in the formula (IY), W ⁵ and W ⁶ in the formula (II-X), and W ⁷ in the formula (II-Y) W ⁸ is preferably the same. In addition, it is preferable that W ⁹ and W ¹⁰ in the above formula (1') are different. Likewise, it is preferable that W ¹¹ and W ¹² in the above formula (2') are different.

The polymer compound according to the present invention has a structural unit (A). Accordingly, 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 present invention is used as a hole injection material or a hole transport material (particularly a hole transport material), high durability (luminescence lifetime) can be achieved. Additionally, the polymer compound according to the present invention has a high triplet energy level and a low driving voltage. Therefore, when the polymer compound according to the present invention is used as a hole injection material or a hole transport material (particularly a hole transport material), high hole mobility is achieved with a low driving voltage. Therefore, the electroluminescent device using the polymer compound according to the present invention has excellent durability (luminescence life) and luminous efficiency.

[Electroluminescence device material]

The polymer compound according to the present invention is suitably used as an electroluminescent device material. According to the polymer compound according to the present invention, an electroluminescent device material having excellent durability (luminescence life) and high hole mobility is provided. In addition, according to the polymer compound according to the present invention, an electroluminescent device material having a high triplet energy level (current efficiency) and a low driving voltage is also provided. Accordingly, in the second embodiment, an electroluminescent device material comprising the polymer compound of the present invention is provided. Alternatively, use of the polymer compound as an electroluminescent device material is provided.

Additionally, the polymer compound according to the present invention has a HOMO level exceeding 5.20 eV. Accordingly, the polymer compound according to the present invention can also be suitably used in quantum dot electroluminescent devices (especially hole transport layers).

The glass transition temperature (T _g ) of the polymer compound according to one embodiment of the present invention is not particularly limited, but is preferably 75°C or higher, more preferably 90°C or higher, and particularly preferably 100°C or higher. On the other hand, the upper limit is not particularly limited, but 200°C or lower is preferable, 180°C or lower is more preferable, and 150°C or lower is particularly preferable.

If the glass transition temperature (T _g ) of the polymer is within the above-mentioned range, it is suitable for device fabrication and a device with further 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: DSC6000). Meanwhile, details of the measurement method are described in the examples.

[Electroluminescence device]

As described above, the polymer compound according to the present invention is suitably used in electroluminescent devices. That is, an electroluminescent device is provided, which includes a pair of electrodes and one or more organic layers disposed between the electrodes and containing the polymer compound or the electroluminescent device material according to the present invention.

Such an electroluminescent device can exhibit excellent luminous efficiency with a low driving voltage. Therefore, in one embodiment, the present invention provides an electroluminescent device comprising a first electrode, a second electrode, and one or more layers of organic films disposed between the first electrode and the second electrode, wherein: An electroluminescent device is provided, wherein at least one layer contains the polymer compound of the present invention. The purpose (or effect) of the present invention can also be achieved by the electroluminescent device according to this embodiment. In one embodiment, the electroluminescent device further includes a light-emitting layer disposed between the electrodes and including a light-emitting material capable of emitting light from triplet excitons. Meanwhile, the electroluminescent device of this embodiment is an example of an electroluminescent device according to the present invention.

In addition, this embodiment is a method of manufacturing an electroluminescent device comprising a pair of electrodes and one or more organic layers disposed between the electrodes and containing a polymer compound according to the present invention, wherein at least one of the organic layers A method of forming the first layer by a coating method is provided. Furthermore, 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 present invention and the electroluminescent device material (EL device material) according to this embodiment (hereinafter, collectively referred to as “polymer compound/EL device material”) have excellent solubility in organic solvents. . Accordingly, the polymer compound/EL device material according to the present invention is particularly suitably used for manufacturing devices (particularly thin films) by a coating method (wet process). Accordingly, this embodiment provides a liquid composition containing the polymer compound according to the present invention and a solvent or dispersion medium. Such a liquid composition is an example of a liquid composition according to the present invention.

In addition, the electroluminescent device material according to the embodiment as described above is suitably used for manufacturing devices (particularly thin films) by a coating method (wet process). In view of the above, this embodiment provides a thin film containing the polymer compound according to the present invention. Such a thin film is an example of a thin film according to the present invention.

Additionally, the EL device material according to this embodiment has excellent hole injection properties and hole mobility. Accordingly, it can be suitably used in the formation of any organic film, such as a hole injection material, a hole transport material, or a light-emitting material (host). Among these, from the viewpoint of hole transport properties, it is suitably used as a hole injection material or hole transport material, and is particularly suitably used as a hole transport material.

That is, this embodiment provides a composition containing a polymer compound and at least one material selected from the group consisting of a hole transport material, an electron transport material, and a light emitting material. Here, the light-emitting material included in the composition is not particularly limited, but may contain an organometallic complex (luminescent organometallic complex compound) or semiconductor nanoparticles (semiconductor inorganic nanoparticles).

[Electroluminescence device]

Hereinafter, with reference to FIG. 1, the electroluminescent device according to this embodiment will be described in detail. 1 is a schematic diagram showing an electroluminescent device according to this embodiment. Meanwhile, in this specification, “electroluminescent device” may be abbreviated as “EL device.”

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

Here, the polymer compound according to the present invention is included in, for example, one organic film (organic layer) disposed between the first electrode 120 and the second electrode 180. Specifically, the polymer compound is preferably included in the hole injection layer 130 as a hole injection material, the hole transport layer 140 as a hole transport material, or the light emitting layer 150 as a light emitting material (host). The polymer compound is more preferably included in the hole injection layer 130 as a hole injection material or in the hole transport layer 140 as a hole transport material. It is particularly preferable that the polymer compound is included in the hole transport layer 140 as a hole transport material. That is, in a preferred form of the present invention, the organic film containing a polymer compound is a hole transport layer, a hole injection layer, or a light emitting layer. In a more preferred form of the present invention, the organic film containing a polymer compound is a hole transport layer or a hole injection layer. In a particularly preferred form of the present invention, the organic film containing a polymer compound is a hole transport layer.

Additionally, the organic film containing the polymer compound/EL device material according to the present invention is formed by a coating method (solution coating method). Specifically, the organic film is made using spin coating method, casting/casting method, micro gravure coat method, gravure coat method, bar coat method, and roll method. Roll coat method, wire bar coat method, dip coat method, spray coat method, screen printing method, flexographic printing method, offset ( It is formed using solution application methods such as offset printing and ink jet printing.

On the other hand, the solvent used in the solution application method can be any solvent as long as it can dissolve the polymer compound/EL device material, and can be appropriately selected depending on the type of polymer compound used. For example, toluene, xylene, ethylbenzene, diethylbenzene, mesityle, propylbenzene, cyclohexylbenzene, dimethoxybenzene, anisole, ethoxytoluene, phenoxytoluene, isopropylbiphenyl, dimethylanisole, acetic acid. Examples include phenyl, phenyl pyropionate, methyl benzoate, ethyl benzoate, and cyclohexane. In addition, the amount of solvent used is not particularly limited, but considering ease of application, etc., the concentration of the polymer compound is preferably 0.1% by weight or more and 10% by weight or less, more preferably 0.5% by weight or more and 5% by weight or less. It is the amount that becomes.

On the other hand, there is no particular limitation on the film forming method for layers other than the organic film containing the polymer compound/EL device material. Layers other than the organic film containing the polymer compound/EL device material according to the present invention may be formed by, for example, a vacuum deposition method or a solution coating method.

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

A first electrode 120 is formed on the substrate 110. The first electrode 120 is specifically an anode, and is formed of a metal, alloy, or conductive compound with a high work function. For example, the first electrode 120 is made of indium tin oxide (In ₂ O ₃ -SnO ₂ : ITO), indium zinc oxide (In ₂ O ₃ -ZnO), and tin oxide (SnO ₂ ), which have excellent transparency and conductivity. , zinc oxide (ZnO), etc. may be formed as a transmissive electrode. Additionally, the first electrode 120 may be formed as a reflective electrode by laminating magnesium (Mg), aluminum (Al), etc. on the transparent conductive film. Additionally, after forming the first electrode 120 on the substrate 110, cleaning and UV-ozone treatment may be performed, if necessary.

A hole injection layer 130 is formed on the first electrode 120.

The hole injection layer 130 is a layer that facilitates the injection of holes from the first electrode 120, and is specifically, about 10 nm or more and about 1000 nm or less, more specifically about 20 nm or more and about 50 nm or less (thickness) It may also be formed with a dry film thickness (same as below).

The hole injection layer 130 can be formed from a known hole injection material. Known hole injection materials forming the hole injection layer 130 include, for example, poly(ether ketone)-containing triphenylamine (TPAPEK) and 4-isopropyl-4'-methyldimethylamine. Phenyliodonium tetrakis(pentafluorophenyl)borate (4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate: PPBI), N,N'-diphenyl-N,N'-bis-[4-( Phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine(N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl ]-biphenyl-4,4'-diamine: DNTPD), copper phthalocyanine, 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (4,4',4"-methylphenylphenylamino) )triphenylamine: m-MTDATA), N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine: NPB ), 4,4',4"-tris(diphenylamino)triphenylamine (4,4',4"-triphenylamine: TDATA), 4,4',4"-tris(N,N-2-naph) Tylphenylamino)triphenylamine (4,4',4"-N,N-2-naphthylphenylamino)triphenylamine: 2-TNATA), polyaniline/dodecylbenzenesulphonic acid, poly(3,4- ethylenedioxythiophene)/poly(4-styrenesulfonate) (poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate): PEDOT/PSS), and polyaniline/10-camphorsulfonic acid ), etc.

A hole transport layer 140 is formed on the hole injection layer 130. The hole transport layer 140 is a layer that has the function of transporting holes, and may be formed to have a thickness of, for example, about 10 nm or more and about 150 nm or less, and more specifically, about 20 nm or more and about 50 nm or less. The hole transport layer 140 is preferably formed by a solution coating method using the polymer compound according to the present invention. According to this method, it is possible to extend the durability (light emission life) of the EL element 100. Additionally, it is possible to improve the current efficiency of the EL element 100 and reduce the driving voltage. Additionally, since the hole transport layer can be formed by a solution coating method, it can be efficiently formed into a large area.

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

A light emitting layer 150 is formed on the hole transport layer 140. The light-emitting layer 150 is a layer that emits light by fluorescence, phosphorescence, etc., and is formed using a vacuum deposition method, spin coating method, inkjet printing method, etc. The light emitting layer 150 may be formed to have a thickness of, for example, about 10 nm or more and about 60 nm or less, and more specifically, about 20 nm or more and about 50 nm or less. As the light-emitting material of the light-emitting layer 150, a known light-emitting material can be used. However, it is preferable that the light-emitting material included in the light-emitting layer 150 is a light-emitting material capable of emitting light (i.e., phosphorescence) from triplet excitons. In this case, the driving life of the EL element 100 can be further improved.

The light emitting layer 150 is not particularly limited and can have a known structure. Preferably, the light-emitting layer contains semiconductor nanoparticles or organometallic complexes. That is, in a preferred form of the present invention, the organic film has a light-emitting layer containing semiconductor nanoparticles or an organic metal complex. On the other hand, when the light emitting layer contains semiconductor nanoparticles, the EL device is a quantum dot electroluminescent device (QLED) or a quantum dot light emitting device. In addition, when the light-emitting layer contains an organic metal complex, the EL element is an organic electroluminescent element (OLED).

In a form (QLED) in which the light-emitting layer includes semiconductor nanoparticles, the light-emitting layer is one in which a large number of semiconductor nanoparticles (quantum dots) are arranged in a single layer or multiple layers. Here, semiconductor nanoparticles (quantum dots) are particles of a certain size that have a quantum confinement effect. The diameter of semiconductor nanoparticles (quantum dots) is not particularly limited, but is approximately 1 nm to 20 nm.

Semiconductor nanoparticles (quantum dots) arranged in the light-emitting layer can be synthesized by a wet chemical process, an organometallic chemical deposition process, a molecular beam epitaxy process, or other similar processes. Among them, the wet chemical process is a method of growing particles by adding a precursor material to an organic solvent.

In the wet chemical process, when crystals grow, the organic solvent is naturally coordinated to the surface of the quantum dot crystals and acts as a dispersant, thereby controlling the growth of the crystals. Accordingly, in the wet chemical process, semiconductor nanoparticles can be produced easily and at low cost compared to vapor deposition methods such as Metal Organic Chemical Vapor Deposition (MOCVD) or Molecular Beam Epitaxy (MBE). Growth can be controlled.

By adjusting the size of semiconductor nanoparticles (quantum dots), the energy band gap can be adjusted, and light in various wavelength ranges can be obtained from the light-emitting layer (quantum dot light-emitting layer). Therefore, by using a plurality of quantum dots of different sizes, a display that emits (or emits) light of multiple wavelengths is possible. The size of the quantum dots can be selected to emit red, green, and blue light to create a color display. Additionally, the sizes of quantum dots can be combined to emit white light with various color lights.

Examples of semiconductor nanoparticles (quantum dots) include group II-VI semiconductor compounds; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; Group IV elements or compounds; and semiconductor materials selected from the group consisting of combinations thereof.

Group II-VI semiconductor compounds are not particularly limited, but include, for example, binary compounds selected from the group consisting of CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; A ternary compound selected from the group consisting of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnTeSe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe and mixtures thereof; and a four-element compound selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof.

Group III-V semiconductor compounds are not particularly limited, but include, for example, two elements selected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof. compound; A ternary compound selected from GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, and mixtures thereof; and a four-element compound selected from GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof.

Group IV-VI semiconductor compounds are not particularly limited, but include, for example, binary compounds 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 a four-element compound selected from SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof.

Group IV elements or compounds are not particularly limited, and include, for example, single-element compounds selected from Si, Ge, and mixtures thereof; and a binary compound selected from SiC, SiGe, and mixtures thereof.

Semiconductor nanoparticles (quantum dots) may have a homogeneous single structure or a core/shell dual structure. The core/shell may contain different materials. The materials constituting each core and shell may be made of different semiconductor compounds. However, the energy band gap of the shell material is larger than that of the core material. Specifically, structures such as ZnTeSe/ZnSe/ZnS, InP/ZnSe/ZnS, CdSe/ZnS, and InP/ZnS are preferable.

For example, the case of manufacturing quantum dots with a core (CdSe)/shell (ZnS) structure will be described. First, a core (CdSe) precursor material such as (CH ₃ ) ₂ Cd (dimethylcadmium) and TOPSe (trioctylphosphine selenide) is injected into an organic solvent using trioctylphosphine oxide (TOPO) as a surfactant to generate crystals. At this time, after maintaining the crystal at a high temperature for a certain period of time so that it grows to a certain size, a shell (ZnS) precursor material is injected to form a shell on the surface of the already created core. Accordingly, quantum dots of CdSe/ZnS capped with TOPO can be produced.

In addition, in the form (OLED) in which the light-emitting layer includes an organometallic complex, the light-emitting layer 150 contains, as a host material, for example, 6,9-diphenyl-9'-(5'-phenyl-[1, 1':3',1"-terphenyl]-3-yl)3,3'-bi[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, 9'-diphenyl-3,3'-bi[9H-carbazole], tris(8-quinolinato)aluminium: Alq ₃ ), 4,4'-bis(carbazole -9-yl) biphenyl (4,4'-bis(carbazol-9-yl)biphenyl: CBP), poly(n-vinyl carbazole) (poly(N-vinyl carbazole): PVK), 9,10- Di(naphthalene-2-yl)anthracene (9,10-di(naphthalene)anthracene: ADN), 4,4',4"-tris(N-carbazolyl)triphenylamine (4,4',4" -tris(N-carbazolyl)triphenylamine: TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (1,3,5-tris(N-phenyl-benzimidazol-2-yl) )benzene: TPBI), 3-tert-butyl-9,10-di(naphth-2-yl)anthracene (TBADN), Distyrylarylene (DSA), 4,4'-bis(9-carbazole)-2,2'-dimethyl-biphenyl (4,4'-bis(9-carbazole)-2,2'- dimethyl-bipheny: dmCBP), etc. may be included.

In addition, the light-emitting layer 150 is a dopant material, for example, perylene and its derivatives, rubrene and its derivatives, coumarin and its derivatives, 4-dicyanomethylene-2- (p-dimethylaminostyryl)-6-methyl-4H-pyran (4-dicyanomethylene-2-(pdimethylaminostyryl)-6-methyl-4H-pyran: DCM) and its derivatives, bis[2-(4,6- Difluorophenyl) pyridinate] picolinate iridium (III) (bis [2- (4,6-difluorophenyl) pyridinate] picolinate iridium (III): FIrpic), bis (1-phenylisoquinoline) (acetylaceto nate) iridium (III) (bis (1-phenylisoquinoline) (acetylacetonate) iridium (III): Ir (piq) ₂ (acac)), tris (2-phenylpyridine) iridium (III) (tris (2-phenylpyridine) iridium (III): Even if it contains iridium (Ir) complexes such as Ir(ppy) ₃ ), tris(2-(3-p-xyl)phenyl)pyridine iridium(III), osmium (Os) complex, platinum complex, etc. do. Among these, it is preferable that the luminescent material is a luminescent organic metal complex compound.

The method of forming the light emitting layer is not particularly limited. It can be formed by applying a coating liquid containing semiconductor nanoparticles or an organic metal complex (solution coating method). At this time, as the solvent constituting the coating liquid, it is preferable to select a solvent that does not dissolve the material in the hole transport layer (hole transport material, especially a polymer compound).

An electron transport layer 160 is formed on the light emitting layer 150. The electron transport layer 160 is a layer that has the function of transporting electrons, and is formed using a vacuum deposition method, spin coating method, inkjet method, etc. The electron transport layer 160 may be formed to have a thickness of, for example, about 15 nm or more and about 50 nm or less.

The electron transport layer 160 may be formed of a known electron transport material. Known electron transport materials include, for example, lithium (8-quinolinato) (lithium quinolinoleate) (Liq), tris (8-quinolinato) aluminum (tris (8-quinolinato) aluminum: Alq ₃ ), and compounds having a nitrogen-containing aromatic ring. Specific examples of compounds having a nitrogen-containing aromatic ring include, for example, 1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene (1,3,5-tri[(3-pyridyl )-phen-3-yl]benzene), a compound containing a pyridine ring, 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1, Contains triazine rings such as 3,5-triazine (2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine) A compound, 2-(4-(N-phenylbenzoimidazolyl-1-yl-phenyl)-9,10-dinaphthylanthracene (2-(4-(N-phenylbenzoimidazolyl-1-yl-phenyl)- 9,10-dinaphthylanthracene), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene: TPBI) There are compounds containing an imidazole ring, etc. The above electron transport materials may be used individually or as a mixture of two or more types.

An electron injection layer 170 is formed on the electron transport layer 160. The electron injection layer 170 is a layer that has a function to facilitate 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 about 0.1 nm or more and about 5 nm or less, and more specifically, about 0.3 nm or more and about 2 nm or less. As a material for forming the electron injection layer 170, any known material can be used. For example, the electron injection layer 170 is made of lithium compounds such as (8-)lithium (lithium quinolinato) ((8-quinolinato)lithium: Liq) and lithium fluoride (LiF), and sodium chloride (NaCl). ), cesium fluoride (CsF), lithium oxide (Li ₂ O), or barium oxide (BaO).

A second electrode 180 is formed on the electron injection layer 170. The second electrode 180 is formed using a vacuum deposition method or the like. The second electrode 180 is specifically a cathode, and is formed of a metal, alloy, or conductive compound with a small work function. For example, the second electrode 180 is made of a metal such as lithium (Li), magnesium (Mg), aluminum (Al), or calcium (Ca), or aluminum-lithium (Al-Li) or magnesium-indium (Mg). -In), magnesium-silver (Mg-Ag), etc. may be formed as a reflective electrode. The second electrode 180 may be formed to have a thickness of about 10 nm or more and about 200 nm or less, and more specifically, about 50 nm or more and about 150 nm or less. Alternatively, the second electrode 180 is formed by a transparent conductive film such as a thin film of 20 nm or less of the metal material, indium tin oxide (In ₂ O ₃ -SnO ₂ ), and indium zinc oxide (In ₂ O ₃ -ZnO). It may also be formed as a transmissive electrode.

Above, as an example of an electroluminescent device according to the present invention, the EL device 100 according to this embodiment has been described. The EL device 100 according to this embodiment can further improve durability (emission lifetime) by providing an organic layer (particularly a hole transport layer or hole injection layer) containing a polymer compound. Additionally, luminous efficiency (current efficiency) can be further improved and driving voltage can be reduced.

Additionally, the stacked structure of the EL element 100 according to this embodiment is not limited to the above examples. The EL element 100 according to this embodiment may be formed in another known stacked structure. For example, in the EL device 100, one or more of the hole injection layer 130, hole transport layer 140, electron transport layer 160, and electron injection layer 170 may be omitted, and other layers may be added. It may be provided in layers. Additionally, each layer of the EL element 100 may be formed as a single layer or may be formed as multiple layers.

For example, the EL element 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. . Meanwhile, the hole blocking layer can be formed by, for example, an oxadiazole derivative, a triazole derivative, or a phenanthroline derivative.

Additionally, the polymer compound according to the present invention can be applied to electroluminescent devices other than the QLED or OLED. Other electroluminescent devices to which the polymer compound according to the present invention can be applied are not particularly limited, but include, for example, organic-inorganic perovskite light-emitting devices.

The present invention includes the following aspects and forms.

1. A polymer compound containing a structural unit (A) represented by the following formula (1):

[Formula (1)]

In the above formula (1),

R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ 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, It is a substituted or unsubstituted aryl group or a halogen atom. In this case, R ¹¹ and R ²¹ may be combined with each other to form a ring,

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

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

Ar ² is a substituted or unsubstituted aromatic hydrocarbon group with 6 to 25 ring atoms, or a substituted or unsubstituted aromatic heterocyclic group with 5 to 25 ring atoms. In this case, Ar ¹ and the ring are can be formed,

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

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

At this ^time , at least one ^of It is an aromatic hydrocarbon group.

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

[Formula (2)]

In the above formula (2),

R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ 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, It is a substituted or unsubstituted aryl group or a halogen atom. In this case, R ³¹ and R ⁴¹ may be combined with each other to form a ring,

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

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

Ar ⁴ is a substituted or unsubstituted aromatic hydrocarbon group with 6 to 25 ring atoms, or a substituted or unsubstituted aromatic heterocyclic group with 5 to 25 ring atoms. In this case, Ar ³ and the ring are can be formed,

^and

Y ² is an aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with an alkyl group having 1 to 14 carbon atoms,

R ³¹ to R ³⁴ , R ⁴¹ to R ⁴⁴ , L ² , Ar ³ and Ar ⁴ do not have 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. .

3. 2 above, wherein the molar ratio of the structural unit (A) is 10 mol% or more and 70 mol% or less (however, the total molar ratio of the structural unit (A) and the structural unit (B) is 100 mol%) The polymer compound described in .

4. In the above formula ( ¹ ), It is an aromatic hydrocarbon group, and Y ¹ is 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 the number of unsubstituted ring forming atoms is 6 to 25. The polymer compound according to any one of 1. to 3. above, which is the following aromatic hydrocarbon group.

5. R ¹¹ to R ¹⁴ , R ²¹ to R ²⁴ , L ¹ , Ar ¹ , Ar ² and Y ¹ in the formula (1) are, respectively, R ³¹ to R ³⁴ , R 41 to R ⁴¹ in the formula (2) The polymer compound described in item 2 or 3 above, which is the same as R ⁴⁴ , L ² , Ar ³ , Ar ⁴ and Y ² .

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

[Formula (i)]

In formula (i) above,

t represents an integer from 1 to 14,

u is 0 or 1,

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

*** is bonded to an aromatic hydrocarbon group having 6 to 25 ring atoms constituting X ¹ or Y ¹ .

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

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

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

R ³⁰¹ to R ³¹⁵ are each independently a substituted or unsubstituted alkylene group having 1 to 14 carbon atoms,

* is bonded to the nitrogen atom.

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

9. In the above formula (1), Y ¹ is any one of the groups represented by the following formulas (5-1) to (5-9), the polymer compound according to any one of the above 1. to 8.:

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

In the above formulas (5-1) to (5-9),

R ⁵⁰¹ to R ⁵¹⁵ are each independently a substituted or unsubstituted alkylene group having 1 to 14 carbon atoms.

10. In the above formula (1), L ¹ is any one of the groups represented by the following formulas (7-1) to (7-24), the polymer compound according to any one of 1. to 9. above:

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

In the above formulas (7-1) to (7-24),

* is bonded to a nitrogen atom, and ** is bonded to Ar ¹ .

11. In the above formula (1), -L ¹ -Ar ¹ -N(Ar ² )(X ¹ ) is any one of the groups represented by the following formulas (9-1) to (9-3). The polymer compound according to any one of 1. to 10.:

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

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

R ⁹⁰¹ to R ⁹⁰⁶ 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 It is 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 one 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 , each may be the same or different,

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

* is bonded to the nitrogen atom.

12. An electroluminescent device material containing the polymer compound according to any one of 1. to 11. above.

13. An electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode,

An electroluminescent device, wherein at least one layer of the organic film contains the polymer compound according to any one of 1 to 11 above.

14. The electroluminescent device according to item 13, wherein the organic film containing the polymer compound is a hole transport layer or a hole injection layer.

15. The electroluminescent device according to item 13, wherein the organic film has a light-emitting layer containing semiconductor nanoparticles or an organic metal complex.

Example

The effect of the present invention will be explained using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. Meanwhile, in the following examples, unless otherwise specified, operations were performed at room temperature (25°C). Additionally, unless otherwise specified, “%” and “part” mean “% by weight” and “part by weight”, respectively.

Synthesis Example 1

(Synthesis of Compound A-1)

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

[Scheme A-1]

10-Bromodecanoic acid (50.0 g) and THF (400 mL) were added to a 1L-4-necked flask, and stirred at room temperature under a nitrogen atmosphere. Trifluoroacetic anhydride (TFAA) (160 g) was added dropwise, and stirred for 1 hour. tert-butanol (76.0 g) was added dropwise and stirred for 12 hours. It was neutralized with a saturated aqueous sodium bicarbonate solution, THF was distilled off under reduced pressure, extracted with ethyl acetate, washed with water, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure and purified by column chromatography (silica gel, hexane/ethyl acetate) to obtain tert-butyl 10-decanoate (37.8 g).

The tert-butyl 10-decanoate (20.0 g) and THF (700 mL) obtained above were added to a 1L-4-necked flask, and stirred at 0°C under a nitrogen atmosphere. tert-butoxypotassium (tert-BuOK) (7.30 g) was added and stirred for 10 minutes. 2-Bromofluorene (5.31 g) was dissolved in THF (55 mL), added dropwise, and stirred for 1 hour. After that, it was stirred at room temperature for 12 hours. Water (100 mL) was added, the solvent was distilled off under reduced pressure, extracted with ethyl acetate, washed with water, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain di-tert-butyl-10,10'-(2-bromo-9H-fluorene-9,9-diyl)bis(decanoate) (12.4 g).

In a 200 mL-4-necked flask, N-(4-(9H-carbazole)phenyl)-4-chloro-N-(4-chlorophenyl)aniline (7.99 g), di-tert-butyl-10 obtained above, 10'-(2-bromo-9H-fluorene-9,9-diyl)bis(decanoate) (10.9g), tris(dibenzylideneacetone)dipalladium(0)(Pd ₂ (dba) ₃ ) (0.38 g), tri-tert-butylphosphonium tetrafluoroborate (tert-Bu ₃ PH·BF ₄ ) (0.500 g), sodium tert-butoxide (tert-BuONa) (3.21 g), and toluene ( 83 mL) was added and stirred at 100°C for 5 hours under a nitrogen atmosphere. Insoluble matter was filtered using Celite (registered trademark, same hereinafter), activated carbon (4.0 g) and zeolite (4.0 g) were added, and stirred at 110°C for 30 minutes. The solid was filtered using Celite, and the filtrate was passed through silica gel. The solvent was distilled off under reduced pressure, and the residue was purified using 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) was obtained.

In a 100 mL-4-necked flask, di-tert-butyl-10,10'-(2-(2-(4-(bis(4-chlorophenyl)amino)phenyl)-9H-carbazole-9- obtained above was added. I)-9H-fluorene-9,9-diyl)bis(decanoate) (3.55g), bispinacolatodiborane (2.89g), potassium acetate (KOAc) (1.95g), Pd ₂ (dba) ₃ (0.178g), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos) (0.231g) and 1,4-dioxane (47mL) were added, and nitrogen atmosphere was added. It was refluxed for 4 hours under low temperature. The reaction solution was cooled to room temperature, and the solid was filtered using Celite. The solvent was distilled off under reduced pressure, the residue was dissolved in toluene (100 mL), activated carbon (1 g) and zeolite (1 g) were added, and the mixture was stirred at 120°C for 30 minutes. The solid was filtered using Celite, and the filtrate was passed through silica gel. The solvent was distilled off under reduced pressure, ethanol (50 mL) was added, the mixture was stirred at 70°C for 1 hour, filtered and dried, and compound A-1 was obtained (3.82 g).

Synthesis Example 2

(Synthesis of Compound A-2)

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

[Scheme A-2]

10-Bromodecane (25.0 g) and THF (200 mL) were added to a 1L-4-necked flask, and stirred at 0°C under a nitrogen atmosphere. Potassium tert-butoxy (12.6 g) was added and stirred for 10 minutes. 2-Bromofluorene (5.31 g) was dissolved in THF (55 mL), added dropwise, and stirred for 1 hour. Afterwards, it was stirred at room temperature for 12 hours. Water (100 mL) was added, the solvent was distilled off under reduced pressure, extracted with ethyl acetate, washed with water, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 2-bromo-9,9-di-n-decyl-9H-fluorene (18.7 g).

In a 200 mL-4-necked flask, N-(4-(9H-carbazolyl)phenyl)-4-chloro-N-(4-chlorophenyl)aniline (5.88 g), 2-bromo-9 obtained above, 9-di-n-decyl-9H-fluorene (5.26g), tris(dibenzylideneacetone)dipalladium(0)(Pd ₂ (dba) ₃ ) (0.251g), tri-tert-butylphosphonium tetra Fluoroborate (tert-Bu ₃ PH·BF ₄ ) (0.334 g), tert-butoxy sodium (4.40 g), and toluene (55 mL) were added, and stirred at 100°C for 3 hours under a nitrogen atmosphere. Insoluble matter was filtered using Celite, activated carbon (3.0 g) and zeolite (3.0 g) were added, and stirred at 110°C for 30 minutes. The solid was filtered using Celite, and the filtrate was passed through silica gel. The solvent was distilled off under reduced pressure, and the residue was purified using column chromatography (silica gel, hexane/toluene) to obtain 4-chloro-N-(4-chlorophenyl)-N-(4-(9-(9,9 -di-n-decyl-9H-fluoren-2-yl)-9H-carbazol-2-yl)phenyl)aniline (7.35 g) was obtained.

In a 100 mL-4-necked flask, 4-chloro-N-(4-chlorophenyl)-N-(4-(9-(9,9-di-n-decyl-9H-fluoren-2-yl obtained above) )-9H-carbazol-2-yl)phenyl)aniline (7.35g), bispinacolatodiborane (7.07g), potassium acetate (4.68g), Pd ₂ (dba) ₃ (0.436g), XPhos (0.568) g), 1,4-dioxane (65 mL) was added, and refluxed for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, and the solid was filtered using Celite. The solvent was distilled off under reduced pressure, the residue was dissolved in toluene (100 mL), activated carbon (2 g) and zeolite (2 g) were added, and the mixture was stirred at 120°C for 30 minutes. The solid was filtered using Celite, and the filtrate was passed through silica gel. After the solvent was distilled off under reduced pressure, it was recrystallized with 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.

[Scheme B-1]

Tert-butyl bromoacetate (25.0 g) and THF (400 mL) were added to a 1L-4-necked flask, and stirred at 0°C under a nitrogen atmosphere. Potassium tert-butoxy (14.3 g) was added and stirred for 10 minutes. 2,7-dibromofluorene (13.8 g) was dissolved in THF (80 mL), added dropwise, and stirred for 1 hour. Afterwards, it was stirred at room temperature for 12 hours. Water (100 mL) was added, the solvent was distilled off under reduced pressure, extracted with ethyl acetate, washed with water, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and 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.

[Scheme B-2]

6-Bromohexanoic acid (50.0 g) and THF (400 mL) were added to a 1L-4-necked flask, and stirred at room temperature under a nitrogen atmosphere. Anhydrous trifluoroacetic acid (215 g) was added dropwise and stirred for 1 hour. tert-butanol (114 g) was added dropwise and stirred for 12 hours. It was neutralized with a saturated aqueous sodium bicarbonate solution, THF was distilled off under reduced pressure, extracted with ethyl acetate, washed with water, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain tert-butyl 6-hexanoate (58.0 g).

6-Bromohexanoic acid (15.0 g) and THF (400 mL) obtained above were added to a 1L-4-necked flask, and stirred at 0°C under a nitrogen atmosphere. Potassium tert-butoxy (6.70 g) was added and stirred for 10 minutes. 2,7-dibromofluorene (6.45 g) was dissolved in THF (65 mL), added dropwise, and stirred for 1 hour. Afterwards, it was stirred at room temperature for 12 hours. Water (100 mL) was added, the solvent was distilled off under reduced pressure, extracted with ethyl acetate, washed with water, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and 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.

[Scheme B-3]

In the same manner as Synthesis Example 4, except that 6-bromohexanoic acid used in the first step synthesis reaction was changed to 8-bromooctanoic acid, compound B-3 (9.05 g) was obtained. ) was obtained. Meanwhile, 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.

[Scheme B-4]

Compound B- was prepared in the same manner as in Synthesis Example 3, except that tert-butyl bromoacetate used in the first step synthesis reaction was changed to tert-butyl 10-bromodecanoate. 4 (14.6g) was obtained. Meanwhile, 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.

[Scheme B-5]

Compound B-5 (36.8 g) was obtained. Meanwhile, 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.

[Scheme B-6]

In the above Synthesis Example 3, except that tert-butyl bromoacetate used in the first step synthesis reaction was changed to 2-(4-bromobutyl)-1,3-dioxolane. Compound B-6 (15.8 g) was obtained in the same manner as above. Meanwhile, 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.

[Scheme C-1]

In a 100mL-4-necked flask, 2-bromocarbazole (20.0g), 4-chloro-N-(4-chlorophenyl)-N-(4-(4,4,5,5-tetramethyl-1, 3,2-dioxaboran-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 (30 mL), and water (30 mL) were added, and stirred at 100°C (bath temperature) for 3 hours. After cooling to room temperature, the aqueous layer was separated, and the organic layer was washed with water (100 mL x 2) and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, toluene (200 mL) was added to the residue, refluxed at 60°C for 1 hour, and the solid was filtered and dried to obtain N-(4-(9-carbazol-2-yl)phenyl)-4. -Chloro-N-(4-chlorophenyl)aniline (6.08 g) was obtained.

In a four-necked flask replaced with argon, N-(4-(9-carbazol-2-yl)phenyl)-4-chloro-N-(4-chlorophenyl)aniline (6.00 g) obtained above, 1- Bromo-4-hexylbenzene (3.00g), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ ) (0.580g), tri-tert-butylphosphonium tetrafluoroborate (tert-Bu ₃ PH·BF ₃ ) (0.276 g), sodium tert-butoxide (tert-BuONa) (2.43 g), and toluene (60 mL) were added, and heated at 110°C for 7 hours. It was left to cool to room temperature and filtered for impurities using Celite. The solvent was distilled off under reduced pressure, and 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) was obtained.

In a 50 mL-3-necked flask, 4-chloro-N-(4-chlorophenyl)-N-(4-(9-(4-hexylphenyl)-9-carbazol-2-yl)phenyl)aniline obtained above was added. (1.60g), bispinacolatodiborane (1.90g), potassium acetate (KOAc) (1.47g), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ ) (0.114g), XPhos (0.177 g), and 1,4-dioxane (16 mL) were added, and stirred for 3 hours at a bath temperature of 100°C under a nitrogen atmosphere. It was cooled to room temperature, and insoluble matter was removed using Celite as a filtering aid. The solvent was distilled off under reduced pressure, dissolved in a mixed solvent of 20 mL of toluene and hexane (40 mL), activated carbon (2.0 g) was added, and the mixture was refluxed for 30 minutes. Insoluble matter was filtered using Cerite as a filter aid, the solvent was distilled off under reduced pressure, and 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.

[Scheme C-2]

In a 1L-4-neck flask, 9-(4-hexylphenyl)-3-iodo-9-carbazole (20.0g), 4-(diphenylamino)phenylboronic acid (15.3g), sodium carbonate (9.51g) , tetrakis(triphenylphosphine)palladium(0)(Pd(PPh ₃ ) ₄ ) (2.49 g), toluene (221 mL), ethanol (110 mL), and water (110 mL) were added, and the mixture was heated to 120°C (bath temperature). It was stirred for 3 hours. After cooling to room temperature, the aqueous layer was separated, and the organic layer was washed with water (100 mL x 2) and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 4-(9-(4-hexylphenyl)-9-carbazol-3-yl)-N,N-diphenyl)aniline (17.7 g). got it

In a 500 mL-4-necked flask, 4-(9-(4-hexylphenyl)-9-carbazol-3-yl)-N,N-diphenyl)aniline (17.7 g) and N,N-dimethyl obtained above were added. Formamide (DMF) (310 mL) was added and ice-cooled, and N-bromosuccinimide (NBS) (11.7 g) dissolved in DMF (30 mL) was added dropwise under a nitrogen atmosphere and stirred for 6 hours. The insoluble material was filtered, washed with methanol (800 mL) and water (800 mL), dried under vacuum, and 4-bromo-N-(4-bromophenyl)-N-(4-(9-(4-hexyl) Phenyl)-9-carbazol-3-yl)phenyl)aniline (14.0 g) was obtained.

In a 500 mL-4-necked flask, 4-bromo-N-(4-bromophenyl)-N-(4-(9-(4-hexylphenyl)-9-carbazol-3-yl)phenyl obtained above was added. ) Aniline (14.0g), bispinacolatodiborane (14.8g), potassium acetate (KOAc) (11.4g), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II)dichloridedichloromethane Adduct (PdCl ₂ (dppf)CH ₂ Cl ₂ ) (0.477 g) and 1,4-dioxane (160 mL) were added, and the mixture was refluxed at 100°C for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, the solid was filtered using Cerite as a filtering aid, and the filtrate was passed through silica gel. The solvent was distilled off under reduced pressure, dissolved in toluene (200 mL), activated carbon (14.2 g) was added, and the mixture was refluxed for 30 minutes. Activated carbon was filtered, the solvent was distilled off under reduced pressure, and recrystallized using a mixed solvent of toluene and acetonitrile to obtain compound C-2 (11.9 g).

Synthesis Example 11

(Synthesis of Compound C-3)

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

[Scheme C-3]

In a 500mL-4-necked flask, 2-(2-biphenylyl)amino-9,9-dimethylfluorene (12.0g), 9-(4'bromo-[1,1'-biphenyl]-4- 1) 3,6-dichloro-9H-carbazole (15.5g), palladium acetate (Pd(OAc) ₂ ) (0.372g), tri-tert-butylphosphonium tetrafluoroborate (tert-Bu ₃ PH·BF) ₄ ) (0.722 g), sodium tert-butoxy (6.38 g), and toluene (330 mL) were added, and stirred at 100°C for 1 hour under a nitrogen atmosphere. Insoluble matter was filtered using Celite, activated carbon (6.0 g) and zeolite (6.0 g) were added, and stirred at 110°C for 30 minutes. The solid was filtered using Celite, and the filtrate was passed through silica gel. The solvent was distilled off under reduced pressure, and the residue was purified using 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%) was obtained.

In a 200 mL-4-necked flask, N-([1,1'-biphenyl]-2-yl)-N-(4'-(3,6-dichloro-9H-carbazol-9-yl) obtained above was added. -[1,1'-biphenyl]-4-yl)-9,9'-dimethyl-9H-fluoren-2-amine (9.00g), bispinacolatodiborane (7.64g), 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 added, and refluxed for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, and the solid was filtered using Celite. The solvent was distilled off under reduced pressure, the residue was dissolved in toluene (100 mL), activated carbon (3 g) and zeolite (3 g) were added, and the mixture was stirred at 130°C for 30 minutes. The solid was filtered using Celite, and the filtrate was passed through silica gel. The solvent was distilled off under reduced pressure, and the residue was recrystallized with 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 (1.441 g), 2,7-dibromo-9,9-di-n-decylfluorene (hereinafter also referred to as “Compound D-1”) synthesized in Synthesis Example 9 under nitrogen atmosphere. described) (0.953g), compound B-4 synthesized in Synthesis Example 6 (0.131g), palladium acetate (3.90mg), tris(2-methoxyphenyl)phosphine (36.8mg), toluene (54mL) , and 20% by weight tetraethylammonium hydroxide aqueous solution (5.88g) were added to the four-necked flask, and stirred at 85°C for 6 hours. Phenylboronic acid (210 mg), bis(triphenylphosphine)palladium(II) dichloride (73.7 mg), and 20% by weight tetraethylammonium hydroxide aqueous solution (5.88 g) were added, and stirred at 85°C for 6 hours. Afterwards, sodium N,N-diethyldithiocarbamidate trihydrate (8.97 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-1 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-1 were 83,600 and 2.39, respectively.

The polymer compound P-1 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer Compound P-1]

Example 1-2

Under a nitrogen atmosphere, compound C-1 (1.421 g), compound D-1 (0.825 g) synthesized in Synthesis Example 9, compound B-4 (0.259 g) synthesized in Synthesis Example 6, and palladium acetate (3.90 mg) ), tris(2-methoxyphenyl)phosphine (36.8mg), toluene (54mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.90g) were added to a four-necked flask and stirred at 85°C for 6 hours. did. Phenylboronic acid (209 mg), bis(triphenylphosphine)palladium(II) dichloride (72.7 mg), and 20 wt% tetraethylammonium hydroxide aqueous solution (8.90 g) were added, and stirred at 85°C for 6 hours. After that, sodium N,N-diethyldithiocarbamidate trihydrate (5.84 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-2 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-2 were 108,000 and 2.24, respectively.

The polymer compound P-2 obtained in this way is estimated to be a polymer compound having the following structural units from the monomer input ratio.

[Polymer Compound P-2]

Example 1-3

Under a nitrogen atmosphere, compound C-1 (1.40 g), compound D-1 (0.721 g) synthesized in Synthesis Example 9, compound B-4 (0.383 g) synthesized in Synthesis Example 6, and palladium acetate (3.80 mg) ), tris(2-methoxyphenyl)phosphine (36.0 mg), toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.78 g) were added to a four-necked flask and stirred at 85°C for 6 hours. did. Phenylboronic acid (206 mg), bis(triphenylphosphine)palladium(II) dichloride (71.7 mg), and 20 wt% tetraethylammonium hydroxide aqueous solution (8.78 g) were added, and stirred at 85°C for 6 hours. After that, sodium N,N-diethyldithiocarbamidate trihydrate (5.76 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-3 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-3 were 125,000 and 2.24, respectively.

The polymer compound P-3 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-3]

Example 1-4

Under a nitrogen atmosphere, compound C-1 (1.36 g), compound D-1 (0.501 g) synthesized in Synthesis Example 9, compound B-4 (0.621 g) synthesized in Synthesis Example 6, and palladium acetate (3.70 mg) ), tris(2-methoxyphenyl)phosphine (35.1 mg), toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.55 g) were added to a four-necked flask and stirred at 85°C for 6 hours. did. Phenylboronic acid (201 mg), bis(triphenylphosphine)palladium(II) dichloride (69.8 mg), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.55 g) were added, and stirred at 85°C for 6 hours. Afterwards, sodium N,N-diethyldithiocarbamidate trihydrate (5.60 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-4 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-4 were 383,000 and 3.01, respectively.

The polymer compound P-4 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-4]

Examples 1-5

Under a nitrogen atmosphere, compound C-1 (1.33 g), compound D-1 (0.293 g) synthesized in Synthesis Example 9, compound B-4 (0.846 g) synthesized in Synthesis Example 6, and palladium acetate (3.60 mg) ), tris(2-methoxyphenyl)phosphine (34.1 mg), toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.32 g) were added to a four-necked flask and stirred at 85°C for 6 hours. did. Phenylboronic acid (195 mg), bis(triphenylphosphine)palladium(II) dichloride (68.0 mg), and 20 wt% tetraethylammonium hydroxide aqueous solution (8.32 g) were added, and stirred at 85°C for 6 hours. After that, sodium N,N-diethyldithiocarbamidate trihydrate (5.46 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-5 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-5 were 393,000 and 2.36, respectively.

The polymer compound P-5 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-5]

Example 1-6

Under a nitrogen atmosphere, compound C-2 (1.44 g), compound D-1 (0.953 g) synthesized in Synthesis Example 10, compound B-4 (0.131 g) synthesized in Synthesis Example 6, and palladium acetate (3.90 mg) ), tris(2-methoxyphenyl)phosphine (37.0 mg), toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (9.03 g) were added to a four-necked flask, and stirred at 85°C for 6 hours. did. Phenylboronic acid (212 mg), bis(triphenylphosphine)palladium(II) dichloride (73.7 mg), and 20% by weight tetraethylammonium hydroxide aqueous solution (9.03 g) were added, and stirred at 85°C for 6 hours. Afterwards, sodium N,N-diethyldithiocarbamidate trihydrate (5.92 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-6 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-6 were 117,000 and 2.35, respectively.

The polymer compound P-6 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-6]

Example 1-7

Under a nitrogen atmosphere, compound C-2 (1.40 g), compound D-1 (0.721 g) synthesized in Synthesis Example 10, compound B-4 (0.383 g) synthesized in Synthesis Example 6, and palladium acetate (3.90 mg) ), tris(2-methoxyphenyl)phosphine (37.0 mg), toluene (54 mL), and 20 wt% tetraethylammonium hydroxide aqueous solution (8.78 g) were added to a four-necked flask, and stirred at 85°C for 6 hours. did. Phenylboronic acid (206 mg), bis(triphenylphosphine)palladium(II) dichloride (71.7 mg), and 20 wt% tetraethylammonium hydroxide aqueous solution (8.78 g) were added, and stirred at 85°C for 6 hours. After that, sodium N,N-diethyldithiocarbamidate trihydrate (5.76 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-7 were measured by SEC. As a result, Mw and Mw/Mn of polymer compound P-7 were 143,000 and 2.37, respectively.

The polymer compound P-7 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer Compound P-7]

Examples 1-8

Under a nitrogen atmosphere, compound C-2 (1.36 g), compound D-1 (0.501 g) synthesized in Synthesis Example 10, compound B-4 (0.621 g) synthesized in Synthesis Example 6, and palladium acetate (3.70 mg) ), tris(2-methoxyphenyl)phosphine (37.0 mg), toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.55 g) were added to a four-necked flask and stirred at 85°C for 6 hours. did. Phenylboronic acid (479 mg), bis(triphenylphosphine)palladium(II) dichloride (69.8 mg), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.55 g) were added, and stirred at 85°C for 6 hours. After that, sodium N,N-diethyldithiocarbamidate trihydrate (5.76 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-8 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-8 were 99,600 and 1.74, respectively.

The polymer compound P-8 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-8]

Example 1-9

Under a nitrogen atmosphere, compound C-2 (1.32 g), compound D-1 (0.293 g) synthesized in Synthesis Example 10, compound B-4 (0.846 g) synthesized in Synthesis Example 6, and palladium acetate (3.60 mg) ), tris(2-methoxyphenyl)phosphine (34.1 mg), toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.32 g) were added to a four-necked flask and stirred at 85°C for 6 hours. did. Phenylboronic acid (467 mg), bis(triphenylphosphine)palladium(II) dichloride (68.0 mg), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.32 g) were added, and stirred at 85°C for 6 hours. After that, sodium N,N-diethyldithiocarbamidate trihydrate (5.76 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85°C for 2 hours. After separating the organic layer from the aqueous layer, 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-9 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-9 were 355,000 and 2.32, respectively.

The polymer compound P-9 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-9]

Examples 1-10

Under a nitrogen atmosphere, compound C-1 (1.50 g), compound D-1 (0.551 g) synthesized in Synthesis Example 9, compound B-1 (0.503 g) synthesized in Synthesis Example 3, and palladium acetate (4.10 mg) ), tris(2-methoxyphenyl)phosphine (38.5 mg), toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (9.40 g) were added to a four-necked flask, and stirred at 85°C for 6 hours. did. Phenylboronic acid (220 mg), bis(triphenylphosphine)palladium(II) dichloride (76.8 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (9.40 g), sodium carbamidate trihydrate (6.16 g) ) was added and stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-10 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-10 were 137,000 and 1.63, respectively.

The polymer compound P-10 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-10]

Example 1-11

Under a nitrogen atmosphere, compound C-1 (1.41 g), compound D-1 (0.521 g) synthesized in Synthesis Example 9, compound B-2 (0.573 g) synthesized in Synthesis Example 4, and palladium acetate (3.90 mg) ), tris(2-methoxyphenyl)phosphine (36.5 mg), toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.89 g) were added to a four-necked flask and stirred at 85°C for 6 hours. did. Phenylboronic acid (208 mg), bis(triphenylphosphine)palladium(II) dichloride (72.6 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (8.89 g), sodium carbamidate trihydrate (6.16 g) ) was added and stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-11 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-11 were 86,200 and 1.87, respectively.

The polymer compound P-11 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer Compound P-11]

Examples 1-12

Under a nitrogen atmosphere, compound C-1 (1.38 g), compound D-1 (0.508 g) synthesized in Synthesis Example 9, compound B-3 (0.605 g) synthesized in Synthesis Example 5, and palladium acetate (3.80 mg) ), tris(2-methoxyphenyl)phosphine (35.5 mg), toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.66 g) were added to a four-necked flask and stirred at 85°C for 6 hours. did. Phenylboronic acid (203mg), bis(triphenylphosphine)palladium(II) dichloride (70.7mg), 20% by weight tetraethylammonium hydroxide aqueous solution (8.66g), sodium carbamidate trihydrate (5.68g) ) was added and stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-12 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-12 were 75,100 and 1.83, respectively.

The polymer compound P-12 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-12]

Example 1-13

Under a nitrogen atmosphere, compound C-1 (1.31 g) synthesized in Synthesis Example 9, compound D-1 (0.483 g), compound B-5 (0.665 g) synthesized in Synthesis Example 7, and palladium acetate (3.60 mg) , tris(2-methoxyphenyl)phosphine (33.7 mg), toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.23 g) were added to a four-necked flask and stirred at 85°C for 6 hours. . Phenylboronic acid (193 mg), bis(triphenylphosphine)palladium(II) dichloride (67.2 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (8.23 g), sodium carbamidate trihydrate (5.39 g) ) was added and stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-13 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-13 were 64,900 and 1.84, respectively.

The polymer compound P-13 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-13]

Example 1-14

Under nitrogen atmosphere, Compound A-1 (0.599 g) synthesized in Synthesis Example 1, Compound A-2 (1.21 g) synthesized in Synthesis Example 2, 2,7-dibromo-9,9-di- n-propylfluorene (hereinafter also referred to as “Compound D-2”) (0.637g), palladium acetate (3.50mg), tris(2-methoxyphenyl)phosphine (33.0mg), toluene (54mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.03 g) were added to the four-necked flask, and stirred at 85°C for 6 hours. Phenylboronic acid (169 mg), bis(triphenylphosphine)palladium(II) dichloride (65.7 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (8.03 g), sodium carbamidate trihydrate (5.26 g) ) was added and stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-14 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-14 were 53,400 and 1.87, respectively.

The polymer compound P-14 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-14]

Example 1-15

Under nitrogen atmosphere, Compound A-1 (0.534 g) synthesized in Synthesis Example 1, Compound A-2 (1.07 g) synthesized in Synthesis Example 2, 2,7-dibromo-9,9-di- n-octylfluorene (hereinafter also referred to as “Compound D-3”) (0.763g), palladium acetate (3.10mg), tris(2-methoxyphenyl)phosphine (26.5mg), toluene (54mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (6.80g) were added to the four-necked flask, and stirred at 85°C for 6 hours. Phenylboronic acid (401 mg), bis(triphenylphosphine)palladium(II) dichloride (68.6 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (6.80 g), sodium carbamidate trihydrate (4.70 g) ) was added and stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-15 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-15 were 71,500 and 1.74, respectively.

The polymer compound P-15 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-15]

Example 1-16

Under a nitrogen atmosphere, compound A-1 (0.512 g) synthesized in Synthesis Example 1, compound A-2 (1.03 g) synthesized in Synthesis Example 2, compound D-1 (0.806 g), palladium acetate (3.00 mg) ), tris(2-methoxyphenyl)phosphine (28.3mg), toluene (54mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (6.80g) were added to a four-necked flask and stirred at 85°C for 6 hours. did. Phenylboronic acid (369 mg), bis(triphenylphosphine)palladium(II) dichloride (55.1 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (6.80g), sodium carbamidate trihydrate (4.70g) ) was added and stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-16 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-16 were 56,700 and 1.78, respectively.

The polymer compound P-16 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-16]

Example 1-17

Under a nitrogen atmosphere, compound C-3 (1.364 g) synthesized in Synthesis Example 11, compound B-4 (0.621 g) synthesized in Synthesis Example 6, compound D-1 (0.501 g), palladium acetate (3.50 g) mg), tris(2-methoxyphenyl)phosphine (33.0 mg), toluene (49 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.06 g) were added to a four-necked flask, and incubated at 85°C for 6 hours. It was stirred. Phenylboronic acid (189 mg), bis(triphenylphosphine)palladium(II) dichloride (65.8 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (8.06 g), sodium carbamidate trihydrate (4.70 g) ) was added and stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-17 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-17 were 14,600 and 1.45, respectively.

The polymer compound P-17 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-17]

Example 1-18

Under a nitrogen atmosphere, compound C-3 (1.44 g) synthesized in Synthesis Example 11, compound B-4 (0.720 g) synthesized in Synthesis Example 6, compound D-1 (0.281 g), palladium acetate (3.50 mg) ), tris(2-methoxyphenyl)phosphine (32.7mg), toluene (49mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (7.97g) were added to a four-necked flask and stirred at 85°C for 6 hours. did. Phenylboronic acid (187 mg), bis(triphenylphosphine)palladium(II) dichloride (55.1 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (7.97 g), sodium carbamidate trihydrate (5.23 g) ) was added and stirred at 85°C 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 cerite (4.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-18 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-18 were 17,500 and 1.45, respectively.

The polymer compound P-18 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-18]

Example 1-19

Under a nitrogen atmosphere, compound C-2 (2.47 g) synthesized in Synthesis Example 10, compound B-6 (0.519 g) synthesized in Synthesis Example 8, compound D-1 (1.26 g), palladium acetate (6.8 mg) ), tris(2-methoxyphenyl)phosphine (63.6mg), toluene (90mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (15.5g) were added to a four-necked flask and stirred at 85°C for 6 hours. did. Phenylboronic acid (364 mg), bis(triphenylphosphine)palladium(II) dichloride (126 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (15.5 g), sodium carbamidate trihydrate (10.1 g) was added and stirred at 85°C 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 (30 mL), alumina (15.0 g) and cerite (7.5 g) were added, and the mixture was stirred at 90°C 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 dispersion (Mw/Mn) of the obtained polymer compound P-19 precursor were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the polymer compound P-19 precursor were 116,000 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 at 60°C for 6 hours under nitrogen. After the solution was distilled off under reduced pressure, it was reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried to obtain polymer compound P-19 (0.316 g). Analysis by SEC was attempted for the obtained polymer compound P-19, but since it did not elute, the weight average molecular weight and dispersion degree could not be determined (therefore, written as “-” in Table 1).

The polymer compound P-19 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-19]

Examples 1-20

Under a nitrogen atmosphere, polymer compound P-19 precursor (0.400 g), malonic acid (0.200 g), piperidine (0.1 mL), and toluene (10 mL) synthesized in Example 1-19 were placed in a flask, and the mixture was heated to 60°C. It was stirred for 6 hours. After the solution was distilled off under reduced pressure, it was reprecipitated with toluene/methanol. The precipitated solid was filtered, washed with water and methanol, and dried to obtain polymer compound P-20 (0.336 g). Analysis by SEC was attempted for the obtained polymer compound P-20, but since it did not elute, the weight average molecular weight and dispersion degree could not be determined (therefore, written as “-” in Table 1).

The polymer compound P-20 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-20]

Comparative Example 1-1

Compound C-1 (1.49 g), compound D-1 (0.97 g), palladium acetate (3.6 mg), and tris(2-methoxyphenyl)phosphine (33.9 mg) synthesized in Synthesis Example 9 under a nitrogen atmosphere. , toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.27 g) were added to the four-necked flask, and stirred at 85°C for 6 hours. Phenylboronic acid (194 mg), bis(triphenylphosphine)palladium(II) dichloride (67.6 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (8.27 g), sodium carbamidate trihydrate (5.42 g) ) was added and stirred at 85°C 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 vacuum to obtain polymer compound P-21 (1.17 g). The weight average molecular weight (Mw) and dispersion (Mw/Mn) of the obtained polymer compound P-21 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-21 were 73,000 and 1.40, respectively.

The polymer compound P-21 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-21]

Comparative Example 1-2

Compound C-2 (1.49 g), compound D-1 (0.97 g), palladium acetate (3.6 mg), and tris(2-methoxyphenyl)phosphine (33.9 mg) synthesized in Synthesis Example 10 under a nitrogen atmosphere. , toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.27 g) were added to the four-necked flask, and stirred at 85°C for 6 hours. Phenylboronic acid (194 mg), bis(triphenylphosphine)palladium(II) dichloride (67.6 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (8.27 g), sodium carbamidate trihydrate (5.42 g) ) was added and stirred at 85°C 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: silica gel/alumina, eluent: toluene), reprecipitated with toluene/methanol, and dried in vacuum to obtain polymer compound P-22 (1.25 g). The weight average molecular weight (Mw) and dispersion (Mw/Mn) of the obtained polymer compound P-22 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-22 were 101,000 and 2.66, respectively.

The polymer compound P-22 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-22]

Comparative Example 1-3

Compound A-2 (1.80 g), compound D-2 (0.667 g), palladium acetate (3.7 mg), and tris(2-methoxyphenyl)phosphine (34.5 mg) synthesized in Synthesis Example 2 under a nitrogen atmosphere. , toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.42 g) were added to the four-necked flask, and stirred at 85°C for 6 hours. Phenylboronic acid (197 mg), bis(triphenylphosphine)palladium(II) dichloride (68.8 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (8.42 g), sodium carbamidate trihydrate (5.23 g) ) was added, and stirred at 85°C 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: silica gel/alumina, eluent: toluene), reprecipitated with toluene/methanol, and dried in vacuum to obtain polymer compound P-23 (0.78 g). The weight average molecular weight (Mw) and dispersion (Mw/Mn) of the obtained polymer compound P-23 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-23 were 74,600 and 1.69, respectively.

The polymer compound P-23 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-23]

Comparative Example 1-4

Compound C-3 (1.49 g), compound D-1 (0.970 g), palladium acetate (3.6 mg), and tris(2-methoxyphenyl)phosphine (33.9 mg) synthesized in Synthesis Example 11 under a nitrogen atmosphere. , toluene (54 mL), and 20% by weight tetraethylammonium hydroxide aqueous solution (8.27 g) were added to the four-necked flask, and stirred at 85°C for 6 hours. Phenylboronic acid (194 mg), bis(triphenylphosphine)palladium(II) dichloride (67.6 mg), 20% by weight tetraethylammonium hydroxide aqueous solution (8.27 g), sodium carbamidate trihydrate (5.42 g) ) was added and stirred at 85°C 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: silica gel/alumina, eluent: toluene), reprecipitated with toluene/methanol, and dried in vacuum to obtain polymer compound P-24 (0.44 g). The weight average molecular weight (Mw) and dispersion (Mw/Mn) of the obtained polymer compound P-24 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of polymer compound P-24 were 20,000 and 1.63, respectively.

The polymer compound P-24 obtained in this way is estimated to be a polymer compound having the following structural units based on the monomer input ratio.

[Polymer compound P-24]

[Evaluation of characteristics of each polymer compound]

For the polymer compounds P-1 to P-20 obtained in Examples 1-1 to 20 and the polymer compounds P-21 to P-24 obtained in Comparative Examples 1-1 to 1-4, HOMO was obtained by the following method. Level (eV), LUMO level (eV) and glass transition temperature (Tg) (°C) were measured. The results are shown in Tables 1 and 2 below.

(Measurement of HOMO level)

Each polymer compound was dissolved in xylene so that the concentration was 1% by weight, and a coating liquid was prepared. On a UV-cleaned ITO-coated glass substrate, the coating liquid prepared above was used to form a film by spin coating at a rotation speed of 2000 rpm, and then dried on a hot plate at 150°C for 30 minutes. A sample for measurement (film thickness of the formed film: approximately 70 nm) was produced. The HOMO level of the sample was measured using an atmospheric photoelectron spectroscopy device (AC-3 manufactured by Riken Instruments Co., Ltd.). At this time, from the measurement results, the tangent intersection point of the rise is calculated and set as the HOMO level (eV). On the other hand, the HOMO level is usually a negative value.

(Measurement of LUMO level)

Each polymer compound was dissolved in toluene so that the concentration was 3.2% by weight, and a coating liquid was prepared. On a UV-cleaned ITO-coated glass substrate, a film was formed by spin coating using the coating liquid prepared above at a rotation speed of 1600 rpm, and then dried on a hot plate at 250° C. for 60 minutes. A sample for measurement (film thickness of the formed film: approximately 70 nm) was produced. The obtained sample was cooled to 77K (-196°C), and the photoluminescence (PL) spectrum was measured. The LUMO level (eV) was calculated from the peak value on the shortest wavelength side of the PL spectrum.

(Glass transition temperature (T _g ))

Each polymer compound was heated to 300°C using a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments, brand name: DSC6000) at a temperature increase rate of 10°C/min, and the sample was held for 10 minutes. ) After cooling to 25°C at a rate of 10°C/min and maintaining it for 10 minutes, the temperature was raised to 300°C at a temperature increase rate of 10°C/min and measurement was performed. After completion of measurement, cool to room temperature (25°C) at 10°C/min.

polymer
compound
(polymer) Monomer input cost
(mol%) Mw
(Mw/Mn) HOMO
(eV) LUMO
(eV) Tg
(℃) Example
1-1 P-1 C-1/B-4/D-1
(50/5/45) 83,600
(2.39) 5.54 2.70 119 Example 1-2 P-2 C-1/B-4/D-1
(50/10/40) 108,000
(2.24) 5.50 2.66 134 Example 1-3 P-3 C-1/B-4/D-1
(50/15/35) 125,000
(2.24) 5.49 2.65 135 Example 1-4 P-4 C-1/B-4/D-1
(50/25/25) 383,000
(3.01) 5.47 2.62 129 Example
1-5 P-5 C-1/B-4/D-1
(50/35/15) 393,000
(2.36) 5.44 2.59 120 Example 1-6 P-6 C-2/B-4/D-1
(50/5/45) 117,000
(2.35) 5.44 2.60 120 Example 1-7 P-7 C-2/B-4/D-1
(50/15/35) 143,000
(2.37) 5.39 2.59 123 Example 1-8 P-8 C-2/B-4/D-1
(50/25/25) 99,600
(1.74) 5.23 2.51 106 Example 1-9 P-9 C-2/B-4/D-1
(50/35/15) 355,000
(2.32) 5.35 2.51 106 Example 1-10 P-10 C-1/B-1/D-1
(50/25/25) 137,000
(1.63) 5.47 2.63 151 Example 1-11 P-11 C-1/B-2/D-1
(50/25/25) 86,200
(1.87) 5.47 2.63 150 Example 1-12 P-12 C-1/B-3/D-1
(50/25/25) 75,100
(1.83) 5.46 2.62 114 Example 1-13 P-13 C-1/B-5/D-1
(50/25/25) 64,900
(1.84) 5.45 2.60 110 Example 1-14 P-14 A-2/A-1/D-2
(35/15/50) 53,400
(1.87) 5.50 2.65 149 Example 1-15 P-15 A-2/A-1/D-3
(35/15/50) 71,500
(1.74) 5.50 2.65 101 Example 1-16 P-16 A-2/A-1/D-1
(35/15/50) 56,700
(1.78) 5.50 2.65 79.8 Example 1-17 P-17 C-3/B-4/D-1
(50/25/25) 14,600
(1.45) 5.61 2.56 133 Example
1-18 P-18 C-3/B-4/D-1
(50/35/15) 17,500
(1.45) 5.56 2.51 131 Example 1-19 P-19 C-2/B-6/D-1
(50/15/35) - 5.50 2.65 134 Example 1-20 P-20 C-2/B-6/D-1
(50/15/35) - 5.50 2.65 132

polymer
compound
(polymer) Monomer input cost
(mol%) Mw
(Mw/Mn) HOMO
(eV) LUMO
(eV) Tg
(℃) Comparative example
1-1 P-21 C-1/D-1
(50/50) 73,000
(1.40) 5.52 2.68 125 Comparative Example 1-2 P-22 C-2/D-1
(50/50) 101,000
(2.66) 5.44 2.61 129 Comparative Example 1-3 P-23 A-2/D-2
(50/50) 74,600
(1.69) 5.50 2.71 144 Comparative Example 1-4 P-24 C-3/D-1
(50/50) 20,000
(1.63) 5.65 2.60 149

Example 2-1

As the first electrode (anode), an ITO-coated glass substrate on which indium tin oxide (ITO) was patterned to a film thickness of 150 nm was used. This ITO-adhered glass substrate was sequentially washed using a neutral detergent, deionized water, water, and isopropyl alcohol, and then subjected to UV-ozone treatment. Next, on this ITO-coated glass substrate, poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS) (manufactured by Sigma-Aldrich) was spread at a dry film thickness of 30 nm. It was applied by spin coating as much as possible and then dried. As a result, a hole injection layer with a thickness (dry film thickness) of 30 nm was formed on the ITO attached glass substrate.

On this hole injection layer, a 1.0% by weight toluene solution of polymer compound P-1 (hole transport material) obtained in Example 1-1 was applied by spin coating so that the dry film thickness was 30 nm, and then applied at 230 nm. Heat treatment was performed at ℃ for 60 minutes to form a hole transport layer. As a result, a hole transport layer with a thickness (dry film thickness) of 30 nm was formed on the hole injection layer.

In cyclohexane, blue quantum dots of ZnTeSe/ZnSe/ZnS (core/shell/shell; average diameter = about 10 nm, manufactured according to U.S. Patent 11,702,593) having the structure shown in Figure 2 were dispersed to 1.0% by weight, and the quantum dots were dispersed to 1.0% by weight. A dispersion was prepared. On the other hand, the hole transport layer (particularly polymer compound P-1) does not dissolve in cyclohexane. This quantum dot dispersion was applied on the hole transport layer by spin coating so that the dry film thickness was 30 nm, and then dried. As a result, a quantum dot light-emitting layer with a thickness (dry film thickness) of 30 nm was formed on the hole transport layer. On the other hand, the light generated by irradiating ultraviolet rays to the quantum dot dispersion had a central wavelength of 462 nm and a half width of 30 nm.

This quantum dot emitting layer was completely dried. On this quantum dot emitting layer, using a vacuum deposition device, lithium quinolate (Liq) and 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) as an electron transport material (Sigma- (manufactured by Aldrich) was co-deposited. As a result, an electron transport layer with a thickness of 36 nm was formed on the quantum dot emitting layer.

Using a vacuum deposition device, (8-)lithium (lithium quinolate) (Liq) was deposited on this electron transport layer. As a result, an electron injection layer with a thickness of 0.5 nm was formed on the electron transport layer.

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

Example 2-2

Quantum dot electroluminescent device 2 was produced by performing the same operation as in Example 2-1, except that polymer compound P-2 obtained in Example 1-2 was used instead of polymer compound P-1. Produced.

Example 2-3

In Example 2-1, the same operation as in Example 2-1 was performed, except that polymer compound P-3 obtained in Example 1-3 was used instead of polymer compound P-1, and quantum dot electroluminescent device 3 was produced. Produced.

Example 2-4

Quantum dot electroluminescent device 4 was produced by performing the same operation as in Example 2-1, except that polymer compound P-4 obtained in Example 1-4 was used instead of polymer compound P-1. Produced.

Example 2-5

Quantum dot electroluminescent device 5 was produced in the same manner as in Example 2-1, except that polymer compound P-5 obtained in Example 1-5 was used instead of polymer compound P-1. Produced.

Example 2-6

Quantum dot electroluminescent device 6 was produced by performing the same operation as in Example 2-1, except that polymer compound P-6 obtained in Example 1-6 was used instead of polymer compound P-1. Produced.

Example 2-7

Quantum dot electroluminescent device 7 was produced by performing the same operation as in Example 2-1, except that polymer compound P-7 obtained in Example 1-7 was used instead of polymer compound P-1. Produced.

Example 2-8

Quantum dot electroluminescent device 8 was produced in the same manner as in Example 2-1, except that polymer compound P-8 obtained in Example 1-8 was used instead of polymer compound P-1. Produced.

Example 2-9

In Example 2-1, the same operation as in Example 2-1 was performed, except that polymer compound P-9 obtained in Example 1-9 was used instead of polymer compound P-1, and quantum dot electroluminescent device 9 was produced. Produced.

Example 2-10

In Example 2-1, the same operation as in Example 2-1 was performed, except that polymer compound P-10 obtained in Example 1-10 was used instead of polymer compound P-1, and quantum dot electroluminescent device 10 was produced. Produced.

Example 2-11

Quantum dot electroluminescent device 11 was produced in the same manner as in Example 2-1, except that polymer compound P-11 obtained in Example 1-11 was used instead of polymer compound P-1. Produced.

Example 2-12

Quantum dot electroluminescent device 12 was produced in the same manner as in Example 2-1, except that polymer compound P-12 obtained in Example 1-12 was used instead of polymer compound P-1. Produced.

Example 2-13

Quantum dot electroluminescent device 13 was produced in the same manner as in Example 2-1, except that polymer compound P-13 obtained in Example 1-13 was used instead of polymer compound P-1. Produced.

Example 2-14

Quantum dot electroluminescent device 14 was produced in the same manner as in Example 2-1, except that polymer compound P-14 obtained in Example 1-14 was used instead of polymer compound P-1. Produced.

Example 2-15

Quantum dot electroluminescent device 15 was produced in the same manner as in Example 2-1, except that polymer compound P-15 obtained in Example 1-15 was used instead of polymer compound P-1. Produced.

Example 2-16

Quantum dot electroluminescent device 16 was produced in the same manner as in Example 2-1, except that polymer compound P-16 obtained in Example 1-16 was used instead of polymer compound P-1. Produced.

Example 2-17

Quantum dot electroluminescent device 17 was produced in the same manner as in Example 2-1, except that polymer compound P-17 obtained in Example 1-17 was used instead of polymer compound P-1. Produced.

Example 2-18

Quantum dot electroluminescent device 18 was produced by performing the same operation as in Example 2-1, except that polymer compound P-18 obtained in Example 1-18 was used instead of polymer compound P-1. Produced.

Example 2-19

Quantum dot electroluminescent device 19 was produced in the same manner as in Example 2-1, except that polymer compound P-19 obtained in Example 1-19 was used instead of polymer compound P-1. Produced.

Example 2-20

In Example 2-1, the same operation as in Example 2-1 was performed, except that polymer compound P-20 obtained in Example 1-20 was used instead of polymer compound P-1, and quantum dot electroluminescent device 20 was produced. Produced.

Comparative Example 2-1

Comparative quantum dot electroluminescent device 1 was prepared in the same manner as in Example 2-1, except that polymer compound P-21 obtained in Comparative Example 1-1 was used instead of polymer compound P-1. produced.

Comparative Example 2-2

Comparative quantum dot electroluminescent device 2 was prepared in the same manner as in Example 2-1, except that polymer compound P-22 obtained in Comparative Example 1-2 was used instead of polymer compound P-1. produced.

Comparative Example 2-3

In Example 2-1, the same operation as in Example 2-1 was performed except that polymer compound P-23 obtained in Comparative Example 1-3 was used instead of polymer compound P-1, and comparative quantum dot electroluminescent device 3 was obtained. produced.

Comparative Example 2-4

In Example 2-1, the same operation as in Example 2-1 was performed except that polymer compound P-24 obtained in Comparative Example 1-4 was used instead of polymer compound P-1, and comparative quantum dot electroluminescent device 4 was obtained. produced.

[Evaluation of quantum dot electroluminescent devices]

For the quantum dot electroluminescent devices 1 to 20 manufactured in Examples 2-1 to 2-20 and the comparative quantum dot electroluminescent devices 1 to 4 manufactured in Comparative Examples 2-1 to 2-4, light emission was performed by the following method. Efficiency and luminous lifetime were evaluated. The results are shown in Tables 3 and 4 below.

(Luminous efficiency)

When a voltage is applied to each quantum dot electroluminescent device, a current begins to flow at a certain voltage, and the quantum dot electroluminescent device emits light. Using a direct current constant voltage power supply (source meter, manufactured by KEYENCE), the voltage is gradually increased for each element, the current value is measured, and the luminance when emitting light is measured using a luminance measurement device (manufactured by Topcom). , SR-3) is used to measure. Here, the measurement ends when the luminance starts to decrease. The current value (current density) per unit area is calculated from the area of each element, and the current efficiency (cd/A) is calculated by dividing the luminance (cd/m ² ) by the current density (A/m ² ). . In Tables 3 and 4 below, the highest current efficiency in the measured voltage range is set as “cd/A max”. Meanwhile, current efficiency indicates the efficiency (conversion efficiency) of converting current into luminous energy, and the higher the current efficiency, the higher the device performance.

In addition, from the spectral radiance luminance spectrum measured with a luminance measurement device, assuming that Lambertian radiation is performed, the external quantum efficiency (EQE) (%) at cd/A max is calculated, and the luminous efficiency is evaluated.

Additionally, when voltage is applied to each quantum dot electroluminescent device using a direct current constant voltage power supply (source meter manufactured by KEYENCE), current begins to flow at a constant voltage, and the quantum dot electroluminescent device emits light. While measuring the light emission of each element using a luminance measurement device (SR-3 manufactured by Topcom), the current is gradually increased, and when the luminance reaches 1000 nits (cd/m ² ), the current is kept constant and left to stand. Here, the voltage at 1000 nit is set to “V@1000 nit”.

(Luminous life)

Using a direct current constant voltage power supply (Source Meter, manufactured by Keyence Co., Ltd.), a predetermined voltage is applied to each quantum dot electroluminescent device, causing each quantum dot electroluminescent device to emit light. While measuring the light emission of the quantum dot electroluminescent device with a luminance measurement device (SR-3 manufactured by Topcom Co., Ltd.), the current is gradually increased, and when the luminance reaches 650 nits (cd/m ² ), the current is kept constant and left. The luminance value measured by the luminance measurement device gradually decreases, and the time until it reaches 90% of the initial luminance is set as “LT90 (hr).” Additionally, in the same manner, the time until the initial luminance reaches 50% is set to “LT50 (hr)”.

polymer
compound structural unit
(Ａ)：(Ｂ) Luminous efficiency
[Cd/A] EQE
[%] V
@1000nit T90
[hr] T50
[hr] Example
2-1 P-1 10：90 7.1 8.4 3.0 4 47 Example 2-2 P-2 20：80 8.1 9.4 3.0 3 36 Example 2-3 P-3 30：70 15.1 13.0 3.0 7.8 60 Example 2-4 P-4 50：50 14.9 10.0 3.1 9.1 59 Example 2-5 P-5 70：30 14.5 11.0 3.1 12 52 Example 2-6 P-6 10：90 11.7 10.0 3.0 9.3 - Example 2-7 P-7 30：70 7.8 7.0 2.9 15 61 Example 2-8 P-8 50：50 6.9 6.1 3.0 10 40 Example 2-9 P-9 70：30 7.4 6.1 3.0 11 40 Example 2-10 P-10 50:50 14.5 13.2 3.0 5.3 49 Example 2-11 P-11 50:50 14.2 12.3 3.1 7.2 52 Example 2-12 P-12 50:50 14.1 13.6 3.1 9.3 55 Example 2-13 P-13 50：50 14.0 11.0 3.1 11 56 Example 2-14 P-14 30：70 10.8 9.5 2.9 24 123 Example 2-15 P-15 30：70 12.9 11.2 2.8 15 132 Example
2-16 P-16 30：70 12.8 10.9 2.8 16 132 Example
2-17 P-17 50：50 15.1 15.9 2.8 8 50 Example
2-18 P-18 70：30 13.8 17.7 2.5 16 66 Example
2-19 P-19 30：70 16.4 15.2 3.0 4.8 48 Example 2-20 P-20 30：70 17.3 15.1 3.0 6.8 65

polymer
compound structural unit
(Ａ)：(Ｂ) Luminous efficiency
[Cd/A] EQE
[%] V
@1000nit T90
[hr] T50
[hr] Comparative example
2-1 P-21 - 7.1 8.7 3.3 2 37 Comparative Example 2-2 P-22 - 3.5 3.5 3.2 6 33 Comparative Example 2-3 P-23 - 2.5 3.5 3.2 6 33 Comparative Example 2-4 P-24 - 7.1 8.7 3.3 One 11

From the results of Tables 3 and 4, the quantum dot electroluminescent devices 1 to 20 of the example have generally high durability (generally long luminescence life) compared to the comparative quantum dot electroluminescent devices 1 to 4 that do not use the polymer compound according to the present invention. ) can be demonstrated.

Specifically, compared to Comparative Quantum Dot Electroluminescence Device 1 (Comparative Example 2-1) using a polymer compound consisting only of a structural unit (B) but not containing a carboxyl group, a structure containing not only the same structural unit (B) but also a carboxyl group. Quantum dot electroluminescent devices 1 to 5, 10 to 13 (Examples 2-1 to 2-5, 2-10 to 2-13) using a polymer compound further containing a unit (A) have a luminescence life (T90) of Long results were obtained. Also, similarly, compared to comparative quantum dot electroluminescent device 2 (Comparative Example 2-2) using a polymer compound consisting only of the structural unit (B), not only the same structural unit (B) but also a structural unit (A) containing a carboxyl group is used. Furthermore, the quantum dot electroluminescent devices 6 to 9 and 20 (Examples 2-6 to 9 and 2-20) using the polymer compound include a long luminescence life (T90) and excellent luminous efficiency and external quantum efficiency (EQE). was obtained. In addition, quantum dot electroluminescent device 19 (Example 2-19) is slightly inferior to comparative quantum dot electroluminescent device 2 (Comparative Example 2-2) in terms of emission life (T90), but is superior in terms of emission life (T50). Since it is sufficiently long and has excellent luminous efficiency and external quantum efficiency (EQE), the luminous performance (balance between luminous efficiency and luminous lifetime) is good in actual use. Additionally, similarly, compared to comparative quantum dot electroluminescent device 3 (Comparative Example 2-3) using a polymer compound consisting only of the structural unit (B), not only the same structural unit (B) but also a structural unit (A) containing a carboxyl group is used. Furthermore, quantum dot electroluminescent device 14 (Example 2-14) using a polymer compound including a significantly longer luminous life (T90 and T50) and excellent luminous efficiency and external quantum efficiency (EQE) were obtained.

On the other hand, the comparative quantum dot electroluminescent devices 2 and 3 in Comparative Examples 2-2 and 2-3 can be said to have relatively excellent luminous lifetime (T90), but because the luminous efficiency and external quantum efficiency (EQE) are low, In terms of luminous performance (balance between luminous efficiency and luminous lifetime) in actual use, it is considered to be inferior to the quantum dot electroluminescent device according to this embodiment.

In addition, compared to the comparative quantum dot electroluminescence device 4 (Comparative Example 2-4) using a polymer compound consisting only of the structural unit (B), it further contains not only the same structural unit (B) but also a structural unit (A) containing a carboxyl group. Quantum dot electroluminescent devices 17 and 18 (Examples 2-17 and 2-18) using polymer compounds that have significantly longer luminescence lifetimes (T90 and T50) and excellent luminous efficiency and external quantum efficiency (EQE) were obtained. lost.

Although the present invention has been described above with reference to embodiments and examples, the present invention is not limited to the specific embodiments and examples, and various modifications and changes are possible within the scope of the invention described in the claims. .

100: Electroluminescent element (EL element)
110: substrate
120: first electrode
130: Hole injection layer
140: Hole transport layer
150: light emitting layer
160: Electron transport layer
170: Electron injection layer
180: second electrode

Claims (15)

A polymer compound containing a structural unit (A) represented by the following formula (1):
[Formula 1]

In formula (1) above,
R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ 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, It is a substituted or unsubstituted aryl group or a halogen atom. In this case, R ¹¹ and R ²¹ may be combined with each other to form a ring,
L ¹ is a substituted or unsubstituted aromatic hydrocarbon group with 6 to 25 ring atoms, or a substituted or unsubstituted aromatic heterocyclic group with 5 to 25 ring atoms,
Ar ¹ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms,
Ar ² is a substituted or unsubstituted aromatic hydrocarbon group with 6 to 25 ring atoms, or a substituted or unsubstituted aromatic heterocyclic group with 5 to 25 ring atoms, and in this case, forms a ring with Ar ¹ You can do it,
X ¹ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms,
Y ¹ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms,
At this ^time , at least one ^of It is an aromatic hydrocarbon group. According to paragraph 1,
A polymer compound further comprising a structural unit (B) represented by the following formula (2):
[Formula 2]

In the above formula (2),
R ³¹ to R ³⁴ and R ⁴¹ to R ⁴⁴ 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, It is a substituted or unsubstituted aryl group or a halogen atom. In this case, R ³¹ and R ⁴¹ may be combined with each other to form a ring,
L ² is a substituted or unsubstituted aromatic hydrocarbon group with 6 to 25 ring atoms, or a substituted or unsubstituted aromatic heterocyclic group with 5 to 25 ring atoms,
Ar ³ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms,
Ar ⁴ is a substituted or unsubstituted aromatic hydrocarbon group with 6 to 25 ring atoms, or a substituted or unsubstituted aromatic heterocyclic group with 5 to 25 ring atoms, and in this case, forms a ring with Ar ³ You can do it,
X ² is an aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with an alkyl group having 1 to 14 carbon atoms,
Y ² is an aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with an alkyl group having 1 to 14 carbon atoms,
R ³¹ to R ³⁴ , R ⁴¹ to R ⁴⁴ , L ² , Ar ³ and Ar ⁴ do not have 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. According to paragraph 2,
A polymer compound in which the molar ratio of the structural unit (A) is 10 mol% or more and 70 mol% or less (however, the total molar ratio of the structural unit (A) and the structural unit (B) is 100 mol%). According to paragraph 1,
In the above formula (1) ^, and Y ¹ is 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 carboxyl group, or an unsubstituted ring forming atom having 6 to 25 atoms. A polymer compound that is an aromatic hydrocarbon group. According to paragraph 2,
R ¹¹ to R ¹⁴ , R ²¹ to R ²⁴ , L ¹ , Ar ¹ , Ar ² and Y ¹ in the formula (1) are, respectively, R ³¹ to R ³⁴ , R ⁴¹ to R ⁴⁴ in the formula (2) , L ² , Ar ³ , Ar ⁴ and Y ² , a polymer compound. According to paragraph 1,
The alkyl group having 1 to 14 carbon atoms substituted with the carboxyl group or the alkyl group having 1 to 14 carbon atoms substituted with the group having the carboxyl group is a polymer compound having a structure represented by the following formula (i):
[Formula (i)]

In formula (i) above,
t represents an integer from 1 to 14,
u is 0 or 1,
Z ¹ represents an organic group other than an alkylene group,
*** is bonded to an aromatic hydrocarbon group having 6 to 25 ring atoms constituting X ¹ or Y ¹ . According to paragraph 1,
In the above formula (1), X ¹ is any one of the groups represented by the following formulas (3-1) to (3-12):
[Formula (3-1) to (3-12)]

In the above formulas (3-1) to (3-12),
R ³⁰¹ to R ³¹⁵ are each independently a substituted or unsubstituted alkylene group having 1 to 14 carbon atoms,
* is bonded to the nitrogen atom. In clause 7,
A polymer compound in which X ¹ in the formula (1) is any one of the groups represented by the formulas (3-10) to (3-12). According to paragraph 1,
In the above formula (1), Y ¹ is any one of the groups represented by the following formulas (5-1) to (5-9):
[Formula (5-1) to (5-9)]

In the above formulas (5-1) to (5-9),
R ⁵⁰¹ to R ⁵¹⁵ are each independently a substituted or unsubstituted alkylene group having 1 to 14 carbon atoms. According to paragraph 1,
In the above formula (1), L ¹ is any one of the groups represented by the following formulas (7-1) to (7-24):
[Formula (7-1) to (7-24)]

In the above formulas (7-1) to (7-24),
* is bonded to a nitrogen atom, and ** is bonded to Ar ¹ . According to paragraph 1,
In the above formula (1), -L ¹ -Ar ¹ -N(Ar ² )(X ¹ ) is any one of the groups represented by the following formulas (9-1) to (9-3):
[Formula (9-1) to (9-3)]

In the above formulas (9-1) to (9-3),
R ⁹⁰¹ to R ⁹⁰⁶ 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 It is 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 one 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 , each may be the same or different,
X ¹ is the same as defined in formula (1) above,
* is bonded to the nitrogen atom. An electroluminescent device material comprising the polymer compound according to any one of claims 1 to 11. An electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode,
An electroluminescent device, wherein at least one layer of the organic film contains the polymer compound according to any one of claims 1 to 11. According to clause 13,
An electroluminescent device wherein the organic film containing the polymer compound is a hole transport layer or a hole injection layer. According to clause 13,
An electroluminescent device in which the organic film has a light-emitting layer containing semiconductor nanoparticles or an organic metal complex.