KR20230106525A - A Polymeric Compound, an Electroluminescent Material, an Electroluminescent Device, and an Electronic Device - Google Patents

Abstract

(화학식 2)

단, 상기 화학식 1 및 화학식 2에서, R¹¹ 내지 R¹⁴는 R⁴¹ 내지 R⁴⁴ 와 동일하지 않다. As a technology capable of improving the durability of an electroluminescent device, for example, the lifespan of light emission, a structural unit represented by the following formula (1), or a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) A polymer compound and an electroluminescence material or electroluminescence device including the same are provided:
(Formula 1)

(Formula 2)

However, in Formula 1 and Formula 2, R ¹¹ to R ¹⁴ are not the same as R ⁴¹ to R ⁴⁴ .

Description

A Polymeric Compound, an Electroluminescent Material, an Electroluminescent Device, and an Electronic Device}

One embodiment relates to a polymer compound, an electroluminescence device material and an electroluminescence device including the polymer compound, and an electronic device including the electroluminescence device.

BACKGROUND OF THE INVENTION Research and development on electroluminescence devices (EL devices) are actively progressing. In particular, the use of the EL element as an inexpensive large-area full-color display element of a solid light emitting type or a recording light source array is expected to be promising. An EL element is a light emitting element having a thin film of several nanometers to hundreds of nanometers between an anode and a cathode. In addition, an EL element usually has a hole transport layer, a light emitting layer, an electron transport layer, and the like.

Among these, there are a fluorescent light emitting material and a phosphorescent light emitting material as the light emitting layer. Phosphorescent light emitting materials are materials that are expected to have higher luminous efficiency than fluorescent light emitting materials. In addition, since it covers a wide color gamut, the RGB light source requires an emission spectrum with a narrow half-width. In particular, blue is required to be deep blue, but a device capable of satisfying the viewpoints of long life and color purity at the same time has not yet been found.

As a method to solve these problems, there is a light emitting device using "quantum dots" as an inorganic light emitting material as a light emitting material (Patent Document 1).

A quantum dot (QD) is a semiconductor material having a crystal structure of several nanometers and is composed of hundreds to thousands of atoms. Since quantum dots are very small in size, they have a large surface area per unit volume. For this reason, most of the atoms exist on the surface of the nanocrystal, and exhibit a quantum confinement effect and the like. Due to the quantum confinement effect, quantum dots can control the emission wavelength only by adjusting their size, and have characteristics such as excellent color purity and high photoluminescence (PL) luminous efficiency, and so have attracted much attention.

A quantum dot electroluminescence device (QD LED, or QLED) is known as a basic device having a three-layer structure including a hole transport layer and an electron transport layer at both ends with a quantum dot light emitting layer interposed therebetween.

In addition, for the purpose of improving the durability (particularly, light emitting lifetime) of the electroluminescent element described in Patent Document 1 (particularly, the quantum dot electroluminescent element), a structural unit (A) having a specific structure is used. An electroluminescence device using an alternating arylamine-fluorene copolymer has been reported (Patent Document 2).

JP 2010-199067 A JP 2021-138915 A

The electroluminescent device using the arylamine-fluorene alternating copolymer described in Patent Document 2 as a hole transport material has excellent durability. On the other hand, it is required to further improve the durability due to the recent high performance of the electroluminescence device.

Accordingly, an embodiment is intended to provide a technique capable of improving durability (in particular, light emitting lifetime) of an electroluminescence device (in particular, a quantum dot electroluminescence device).

The inventors of the present application conducted research intensively in order to solve the above problems. As a result, the present inventors have found that the above problems can be solved by using a polymer compound containing a specific structural unit.

That is, one embodiment provides a polymer compound including a structural unit represented by Formula 1 below:

(Formula 1)

In Formula 1,

R ¹¹ to R ¹⁴ , R ²¹ , R ²² , R ³¹ and R ³² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms;

L ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic ring group having 5 or more and 14 or less ring atoms;

x is 0, 1 or 2, and when x is 2, L ¹ may be the same or different, respectively;

L ² represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, and in this case, L ² is Ar ¹ can form a ring,

Ar ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, and Ar ² or L ² and can form a circle,

Ar ² is (i) a straight-chain or branched hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 25 ring atoms, or an aromatic group having 5 to 14 ring atoms An aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with a heterocyclic ring group, or (ii) a straight-chain or branched hydrocarbon group having 3 to 12 carbon atoms and 1 to 12 carbon atoms, or a number of ring atoms Represents an aromatic heterocyclic ring group having 5 or more and 14 or less ring atoms which may be substituted with an aromatic hydrocarbon group of 6 or more and 25 or less or an aromatic heterocyclic ring group of 5 or more and 14 or less ring atoms, wherein Ar ² is You may form a ring with ^Ar1 .

The polymer compound according to one embodiment further includes a structural unit represented by the following Chemical Formula 2 together with the structural unit represented by Chemical Formula 1:

(Formula 2)

In Formula 2,

R ⁴¹ to R ⁴⁴ , R ²³ , R ²⁴ , R ³³ and R ³⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, wherein R ⁴¹ to R ⁴⁴ are represented by the formula (1) is different from R ¹¹ to R ¹⁴ of

L ³ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms or a substituted or unsubstituted aromatic heterocyclic ring group having 5 to 14 ring atoms;

y is 0, 1 or 2, and when y is 2, L ³ may be the same or different, respectively;

L ⁴ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, wherein L ⁴ is Ar ³ can form a ring with

Ar ³ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, and also represents Ar ⁴ or L ⁴ and form a circle,

Ar ⁴ is (i) a straight-chain or branched hydrocarbon group having 1 to 12 carbon atoms, or a branched hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 25 ring atoms, or an aromatic group having 5 to 14 ring atoms An aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with a heterocyclic ring group, or (ii) a straight-chain or branched hydrocarbon group having 3 to 12 carbon atoms and 1 to 12 carbon atoms, or a number of ring atoms Represents an aromatic heterocyclic ring group having 5 or more and 14 or less ring atoms which may be substituted with an aromatic hydrocarbon group of 6 or more and 25 or less or an aromatic heterocyclic ring group of 5 or more and 14 or less ring atoms, wherein Ar ⁴ is You may form a ring with Ar ³ .

According to one embodiment, the durability, for example, the light emission lifespan of the electroluminescence device, in particular, the quantum dot electroluminescence device, may be improved.

1 is a schematic diagram showing an electroluminescence device according to an embodiment.

A first embodiment provides a polymer compound including a structural unit represented by Formula 1 below:

(Formula 1)

In Formula 1,

R ¹¹ to R ¹⁴ , R ²¹ , R ²² , R ³¹ and R ³² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms;

L ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 14 ring atoms;

x is 0, 1 or 2, and when x is 2, L ¹ may be the same or different, respectively;

L ² represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, wherein L ² is Ar ¹ can form a ring with

Ar ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, and Ar ² or L ² and form a circle,

Ar ² is (i) a straight-chain or branched hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 25 ring atoms, or an aromatic group having 5 to 14 ring atoms An aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with a heterocyclic ring group, or (ii) a straight-chain or branched hydrocarbon group having 3 to 12 carbon atoms and 1 to 12 carbon atoms, or a number of ring atoms Represents an aromatic heterocyclic ring group having 5 or more and 14 or less ring atoms which may be substituted with an aromatic hydrocarbon group of 6 or more and 25 or less or an aromatic heterocyclic ring group of 5 or more and 14 or less ring atoms, wherein Ar ² is You may form a ring with ^Ar1 .

The polymer compound according to one embodiment may further include a structural unit represented by the following Chemical Formula 2 together with the structural unit represented by Chemical Formula 1:

(Formula 2)

In Formula 2,

R ⁴¹ to R ⁴⁴ , R ²³ , R ²⁴ , R ³³ and R ³⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, wherein R ⁴¹ to R ⁴⁴ are represented by the formula (1) is different from R ¹¹ to R ¹⁴ of

L ³ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms or a substituted or unsubstituted aromatic heterocyclic ring group having 5 to 14 ring atoms;

y is 0, 1 or 2, and when y is 2, L ³ may be the same or different, respectively;

L ⁴ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, wherein L ⁴ is Ar ³ can form a ring with

Ar ³ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, and also represents Ar ⁴ or L ⁴ and form a circle,

Ar ⁴ is (i) a straight-chain or branched hydrocarbon group having 1 to 12 carbon atoms, or a branched hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 25 ring atoms, or an aromatic group having 5 to 14 ring atoms An aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with a heterocyclic ring group, or (ii) a straight-chain or branched hydrocarbon group having 3 to 12 carbon atoms and 1 to 12 carbon atoms, or a number of ring atoms Represents an aromatic heterocyclic ring group having 5 or more and 14 or less ring atoms which may be substituted with an aromatic hydrocarbon group of 6 or more and 25 or less or an aromatic heterocyclic ring group of 5 or more and 14 or less ring atoms, wherein Ar ⁴ is You may form a ring with Ar ³ .

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

A third embodiment is an electroluminescent device including a first electrode, a second electrode, and one or more layers of an organic film disposed between the first electrode and the second electrode, wherein at least one of the organic films is provided. An electroluminescence device in which the layer includes the polymer compound according to the first embodiment is provided.

In the specification of the present application, the electroluminescent element is simply referred to as "LED". Quantum dot electroluminescence devices are also simply referred to as "QLEDs". An organic electroluminescence device is also simply referred to as "OLED".

In the present specification, the structural unit derived from indenofluorene of the polymer compound according to the first embodiment is referred to as "structural unit A", and the structural unit other than the structural unit derived from indenofluorene is referred to as "structural unit B" .

In addition, a structural unit in which structural units A and B are combined is referred to as "structural unit C". For example, structural units A, B, and C in the structural unit of Chemical Formula 1 are as follows.

Meanwhile, in the present specification, when the polymer compound includes both the structural unit of Chemical Formula 1 and the structural unit of Chemical Formula 2, unless otherwise specified, the structural unit of Chemical Formula 1 and the structural unit of Chemical Formula 2 collectively It is called "structural unit C".

In the present specification, the number of ring-forming atoms refers to compounds (eg, monocyclic compounds, condensed-cyclic compounds, bridged compounds, carbocyclic compounds, and a heterocyclic ring compound) shows the number of atoms constituting the ring itself. Atoms not constituting the ring, for example, hydrogen atoms terminating bonds of atoms constituting the ring, and atoms included as substituents when the ring is substituted by substituents are not included in the number of ring atoms. The number of ring atoms described below has the same meaning 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, for example, an alkyl group as a substituent, the number of carbon atoms in the alkyl group is not included in the number of ring atoms in the benzene ring. Therefore, the number of ring atoms of the benzene ring substituted with an alkyl group is 6. In addition, when the naphthalene ring is substituted with, for example, an alkyl group as a substituent, the number of atoms of the alkyl group is not included in the number of ring atoms of the naphthalene ring. For this reason, the number of ring atoms in the naphthalene ring in which the alkyl group is substituted is 10.

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

Various low-molecular materials and high-molecular materials are used as materials constituting the light emitting layer and the carrier transport layer of the electroluminescence device. For example, as a polymer material, TFB (for example, paragraph "0037") is reported in Patent Document 1, and an alternating copolymer of fluorene and an arylamine having a specific structure (claim) is reported in Patent Document 2, respectively. .

The inventors of the present application have repeatedly studied means for further improving durability, for example, device life, light emitting life, and the like, compared to these polymer materials, particularly, the arylamine-fluorene alternating copolymer of Patent Document 2. As a result, it was found that durability, such as device lifetime and light emission lifetime, could be further improved by changing the structural unit derived from fluorene to the structural unit derived from indenofluorene.

Without being bound by any particular theory, the mechanism of exerting the above action and effect by the above configuration of the present invention is presumed as follows.

Structural unit A and structural unit B, in particular, the arylamine structure in structural unit B {—L ² —N (Ar ¹ ) (Ar ² ) in Formula 1 or —L ⁴ —N (Ar ^{3 ) (Ar 4 in} Formula 2) )}] has a large number of resonance structures such as condensed rings. For this reason, structural unit C has a stable skeleton with high resonance energy. Therefore, the bond dissociation energy (BDE) of the CN bond in the exciton state and the anion state is high (strong for excitons and electrons). In particular, by applying the structural unit derived from indenofluorene to the structural unit A, the bond dissociation energy of the CN bond in the exciton state can be increased compared to the structural unit derived from fluorene as described in Patent Document 2. A hole transport layer or a hole injection layer using a polymer compound according to an embodiment can easily or maintain its structure even when electrons leaked from the electron transport layer or excitons generated by recombination of electrons and holes exist. Accordingly, the electroluminescence device using the polymer compound according to the embodiment, eg, the quantum dot electroluminescence device, can further improve durability, eg, device lifespan, light emitting lifespan, and the like.

Further, in the structural unit (structural unit C) of Formula 1 or Formula 2, a nitrogen atom cuts the conjugate of the main chain. Accordingly, the triplet energy level of the polymer compound can be increased, the bulk mobility of holes along the main chain is high, and high current efficiency can be achieved. Therefore, an electroluminescence device using the polymer compound (main chain) according to the present invention, for example, a quantum dot electroluminescence device, can achieve excellent light emitting efficiency. In addition, since the main chain of the structural unit C is cleaved with a nitrogen atom, the polymer compound according to one embodiment exhibits properties of a low molecular compound having a close energy level to that of the quantum dots even when polymerized. For this reason, an electroluminescence device using a polymer compound according to an embodiment, for example, a quantum dot electroluminescence device, suppresses an increase in driving voltage and makes it possible to lower the driving voltage.

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

On the other hand, the mechanism is based on speculation, and the present invention is not limited to the mechanism at all.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated in detail.

On the other hand, the present invention is not limited only to the following embodiments, and can be variously changed within the scope of the claims. In addition, unless otherwise specified, operation and measurement of physical properties are measured under conditions of room temperature (20°C or more and 25°C or less)/relative humidity of 40% RH or more and 50% RH or less.

In addition, dimensional ratios in the drawings may be exaggerated for convenience of description and may differ from actual ratios.

In this specification, "X and Y are each independently" means that X and Y may be the same or different. In the present specification, "X and/or Y" means including at least one of X and Y, and includes "X alone", "Y alone", and "combination of X and Y".

[Polymer compound]

A polymer compound according to an embodiment includes a structural unit represented by Formula 1 below. Alternatively, the polymer compound according to one embodiment includes a structural unit represented by the following Chemical Formula 1 and a structural unit represented by the following Chemical Formula 2. A polymer compound containing such a structural unit has a stable backbone with high resonance energy and high C-N bond dissociation energy. In addition, the high molecular compound has high hole injection and transport properties into quantum dots. Therefore, durability (device life, light emitting life) can be further improved. In addition, high current efficiency and low driving voltage can be achieved.

(Formula 1)

(Formula 2)

The structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2 have structures different from each other in that at least R ¹¹ to R ¹⁴ are different from R ⁴¹ to R ⁴⁴ .

In the present specification, "a polymer compound containing a structural unit represented by Formula 1" means that the polymer compound contains at least one structural unit C. In addition, "a polymer compound containing a structural unit represented by formula (1) and a structural unit represented by formula (2)" means that the polymer compound contains at least two kinds of structural units C present.

In other words, the polymer compound according to one embodiment may include one type of structural unit C, or may include two or more types of structural unit C. From the viewpoint of further improving the effect according to one embodiment, the structural unit C present in the polymer compound according to one embodiment may be one or two kinds, for example, two kinds. For example, by including two types of different structural units C, desired properties such as durability, glass transition temperature, etc. can be more appropriately and more easily controlled.

In Formula 1, R ¹¹ to R ¹⁴ , R ²¹ , R ²² , R ³¹ and R ³² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. At this time, R ¹¹ to R ¹⁴ , R ²¹ , R ²² , R ³¹ and R ³² may be the same as or different from each other.

From the viewpoint of further improving the effect according to one embodiment, at least one pair of R ¹¹ and R ¹² , and R ¹³ and R ¹⁴ may be identical to each other, for example, all of R ¹¹ to R ¹⁴ may be identical. there is.

For example, R ²¹ and R ²² may be identical to or different from each other, and for example, R ²¹ and R ²² may be identical to each other.

For example, R ³¹ and R ³² may be identical to or different from each other, and for example, R ³¹ and R ³² may be identical to each other.

In Formula 2, R ⁴¹ to R ⁴⁴ , R ²³ , R ²⁴ , R ³³ and R ³⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. In this case, R ⁴¹ to R ⁴⁴ in Formula 2 are different from R ¹¹ to R ¹⁴ in Formula 1.

R ⁴¹ to R ⁴⁴ , R ²³ , R ²⁴ , R ³³ and R ³⁴ may be identical to or different from each other.

From the viewpoint of further improving the effect according to one embodiment, at least one pair of R ⁴¹ and R ⁴² , and R ⁴³ and R ⁴⁴ may be identical to each other, for example, all of R ⁴¹ to R ⁴⁴ may be identical. there is.

For example, R ²³ and R ²⁴ may be identical to or different from each other, and for example, R ²³ and R ²⁴ may be identical to each other.

For example, R ³³ and R ³⁴ may be identical to or different from each other, and for example, R ³³ and R ³⁴ may be identical to each other.

The hydrocarbon group having 1 to 18 carbon atoms is not particularly limited, and examples thereof include straight-chain or branched alkyl groups, straight-chain or branched alkenyl groups, straight-chain or branched alkynyl groups, and cycloalkyl groups. On the other hand, when the hydrocarbon group is an alkenyl group or an alkynyl group, the hydrocarbon group has 2 or more and 18 or less carbon atoms. Similarly, when the hydrocarbon group is a cycloalkyl group, the hydrocarbon group has 3 or more and 18 or less carbon atoms.

Examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropyl propyl group, 1, 2-dimethylbutyl group, n-heptyl group, 1,4-dimethyl pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group , 2-ethylhexyl group, 3-methyl-1-isopropyl butyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methyl propyl group, n-nonyl group, 3,5,5 -trimethyl hexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, and the like, but are not limited thereto.

Examples of the alkenyl group having 2 to 18 carbon atoms include a vinyl group, an allyl group, a 1-propenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, and an isopropanol group. phenyl groups and the like, but is not limited thereto.

Examples of the alkynyl group having 2 to 18 carbon atoms include, but are not limited to, an ethynyl group and a propargyl group.

Examples of the cycloalkyl group having 3 to 18 carbon atoms include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

At least 2 of R ¹¹ to R ¹⁴ and/or at least 2 of R ⁴¹ to R ⁴⁴ may be a hydrocarbon group having 1 to 18 carbon atoms, for example, at least 3 of R ¹¹ to R ¹⁴ and/or R ⁴¹ At least 3 of R ⁴⁴ may be a hydrocarbon group having 1 to 18 carbon atoms, and all of R ¹¹ to R ¹⁴ and all of R ⁴¹ to R ⁴⁴ may be a hydrocarbon group having 1 to 18 carbon atoms.

As described above, as the number of hydrocarbon groups present in the indeno fluorene ring is increased, hole injection and transport properties are improved, and thus durability (device lifespan) can be further improved.

In addition, the hydrocarbon group as R ¹¹ to R ¹⁴ or R ⁴¹ to R ⁴⁴ may be a straight-chain or branched alkyl group having 1 to 18 carbon atoms and 3 to 18 carbon atoms. For example, the hydrocarbon group as R ¹¹ to R ¹⁴ or R ⁴¹ to R ⁴⁴ may be a straight-chain or branched alkyl group having 3 to 14 carbon atoms and 3 to 14 carbon atoms.

In particular, when the polymer compound has only one structural unit C (the polymer compound includes the structural unit of Chemical Formula 1), the hydrocarbon group as R ¹¹ to R ¹⁴ may be a straight-chain alkyl group having 6 to 12 carbon atoms, such as , It may be a straight chain alkyl group having 7 to 9 carbon atoms, for example, an n-octyl group.

As such, when the number of carbon atoms in the hydrocarbon group present in the indenofluorene ring is within the above range, it is a high molecular compound in the hole transport layer in a quantum dot electroluminescent device including a hole transport layer including a polymer compound and a light emitting layer including quantum dots. Hydrocarbon groups present in the no-fluorene ring and quantum dots included in the light emitting layer exist more closely (hydrocarbon groups and quantum dots interact more closely). Accordingly, the hole injection/transport property is further improved, and the durability (device lifetime, light emitting lifetime) can be further improved.

In addition, when two types of structural units C exist in the polymer compound (the polymer compound includes the structural unit of Formula 1 and the structural unit of Formula 2), R ¹¹ to R ¹⁴ of Formula 1 and R of Formula 2 above In the combination of ⁴¹ to R ⁴⁴ , one may be a hydrocarbon group having a low carbon number and the other a hydrocarbon group having a large carbon number. In one embodiment, the polymer compound includes a structural unit represented by Formula 1 and a structural unit represented by Formula 2, wherein R ¹¹ to R ¹⁴ in Formula 1 are hydrocarbon groups having 1 to 9 carbon atoms. and R ⁴¹ to R ⁴⁴ in Formula 2 may represent a hydrocarbon group having 10 or more and 18 or less carbon atoms.

In one embodiment, the polymer compound includes a structural unit represented by Chemical Formula 1 and a structural unit represented by Chemical Formula 2, wherein R ¹¹ to R ¹⁴ in Chemical Formula 1 each independently have 3 or more carbon atoms. It may be a hydrocarbon group having 9 or less carbon atoms, and R ⁴¹ to R ⁴⁴ in Formula 2 may each independently represent a hydrocarbon group having 10 to 14 carbon atoms.

In another embodiment, the polymer compound includes a structural unit represented by Formula 1 and a structural unit represented by Formula 2, wherein R ¹¹ to R ¹⁴ in Formula 1 are each independently represents a straight-chain or branched alkyl group having 5 or more and 7 or less carbon atoms, and R ⁴¹ to R ⁴⁴ in the formula (2) each independently represent a straight-chain or branched alkyl group having 11 or more and 13 or less carbon atoms.

In another embodiment, the polymer compound includes a structural unit represented by Chemical Formula 1 and a structural unit represented by Chemical Formula 2, wherein R ¹¹ to R ¹⁴ in Chemical Formula 1 represent an n-hexyl group, and , R ⁴¹ to R ⁴⁴ in Formula 2 represent an n-dodecyl group.

Meanwhile, in the above embodiments, R ¹¹ to R ¹⁴ may be the same or different, but, for example, may be all the same. Similarly, R ⁴¹ to R ⁴⁴ may be the same as or different from each other, but, for example, they may all be the same. That is, in one embodiment, R ¹¹ to R ¹⁴ are all the same, and also R ⁴¹ to R ⁴⁴ may be all the same.

By combining R ¹¹ to R ¹⁴ and R ⁴¹ to R ⁴⁴ of the two structural units C present in the polymer compound as described above, appropriate hole injection and transport properties, and thus durability and film forming properties, for example, glass transition temperature, can be adjusted. You can adjust the balance.

Further, R ²¹ , R ²² , R ³¹ , R ³² , R ²³ , R ²⁴ , R ³³ and R ³⁴ are each independently a hydrogen atom (unsubstituted) or a straight chain having 1 to 8 carbon atoms or 3 to 8 carbon atoms. The following may be a branched alkyl group, for example, a hydrogen atom (unsubstituted) or a straight-chain alkyl group having 3 or more and 6 or less carbon atoms, for example, a hydrogen atom (unsubstituted).

In Formula 1, L ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 14 ring atoms.

In Formula 2, L ³ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 14 ring atoms.

When the polymer compound includes the structural unit of Formula 1 and the structural unit of Formula 2, L ¹ of Formula 1 and L ³ of Formula 2 may be the same as or different from each other, for example, may be the same as each other. there is.

Here, the aromatic hydrocarbon group includes benzene (phenylene group), pentalene, indene, naphthalene, anthracene, azylene, acenaphthene, phenalene, fluorene, phenanthrin, biphenyl, ter (ter) phenyl, quarterphenyl, pi and groups derived from aromatic hydrocarbons such as ene, 9,9-diphenyl fluorene, 9,9'-spirobi[fluorene], and 9,9-dialkyl fluorene.

In addition, as an aromatic heterocyclic ring group, pyridine, pyrazine, pyridazine, pyrimidine, triadine, quinoline, isoquinoline, quinoxaline, quinazoline, nathylidine, acridine, phenazine, benzoquinoline, benzoiso Quinoline, phenanthridine, phenanthroline, benzoquinone, coumarin, fluorenone, furan, thiophene, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, pyrrole, indole, carbazole, imidazole, benz Imidazole, pyrazole, indazole, oxazole, isoxazole, benzoxazole, benzoisoxazole, thiazole, isothiazole, benzothiazole, benzoisothiazole, imidazolinone, benzimidazolinone , imidazopyridine, imidazo pyrimidine, azadibenzofuran, azacarbazole, azadibenzothiophene, diazadibenzofuran, diazacarbazole, diazadibenzothiophene, xanthone, thioxanthone, etc. and groups derived from cyclic aromatic compounds.

Among these, L ¹ and L ³ may each independently be a group derived from a compound selected from benzene, fluorene, dibenzofuran, dibenzothiophene, or biphenyl. For example, L ¹ and L ³ may each independently be a divalent group derived from a compound selected from benzene (o, m, p-phenylene group), dibenzofuran, or fluorene.

L ¹ and L ³ may each independently be a phenylene group, for example, an m-phenylene group or a p-phenylene group, for example, a p-phenylene group. If it is such L ¹ or L ³ , a higher bond dissociation energy can be achieved. In addition, a higher hole injection transport property and a triplet energy level, a lower drive voltage, and a viewpoint of film forming property, and a balance of any two or more of these (particularly, a balance between hole injection transport property and film forming property) can be achieved. .

On the other hand, in Examples, L ¹ or L ³ may each be unsubstituted, or any one of the hydrogen atoms may be substituted with a substituent.

Here, the number of introduced substituents when any one hydrogen atom of L ¹ or L ³ is substituted is not particularly limited, but is, for example, 1 or more and 3 or less, for example, 1 or more and 2 or less, for example , can be 1.

In one embodiment, L ¹ and L ³ may be unsubstituted.

In another embodiment, L ¹ or L ³ may have one substituent.

When L ¹ or L ³ has a substituent, the binding position of the substituent is not particularly limited.

The substituent may be present at a position as far as possible from the nitrogen atom of the main chain to which L ¹ or L ³ is connected, for example. For example, when L ¹ or L ³ is a p-phenylene group, the substituent may be positioned meta to the bond connected to the nitrogen atom of the main chain. A higher bond dissociation energy can be achieved by the presence of a substituent at such a position. In addition, higher hole injection and transport properties and triplet energy levels, lower driving voltage and film forming properties, and a balance of any two or more of these (particularly, a balance between hole injection and transport properties and film forming properties) can be achieved.

In addition, when any hydrogen atom of L ¹ or L ³ is substituted, the substituent that may be present is not particularly limited, and an alkyl group, a cycloalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, a cycloalkoxy group, an A kenyl group, an alkynyl group, an amino group, an aryl group, an aryloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an alkoxy carbonyl group, an aryloxycarbonyl group, a hydroxy group (-OH), a carboxy group ( -COOH), a thiol group (-SH), a cyano group (-CN), and the like.

Here, the alkyl group may be either straight-chain or branched, but examples thereof include a straight-chain chain having 1 to 18 carbon atoms or a branched alkyl group having 3 to 18 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-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropyl propyl group, 1,2-dimethylbutyl group, n-heptyl group , 1,4-dimethyl pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, 2-ethylhexyl group, 3-methyl -1-isopropyl butyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methyl propyl group, n-nonyl group, 3,5,5-trimethyl hexyl group, n-decyl group, Isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group group, n-octadecyl group, etc. are mentioned.

As a cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group etc. are mentioned, for example.

As a hydroxyalkyl group, for example, the alkyl group may be substituted with 1 or more and 3 or less, such as 1 or more and 2 or less, for example, one hydroxy group (e.g., a hydroxymethyl group, hydroxyethyl group, etc.).

As an alkoxyalkyl group, for example, the above alkyl group may be substituted at 1 or more and 3 or less, such as 1 or more and 2 or less, for example, in one of the following alkoxy groups.

For example, as an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, Decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, 2-ethylhexyloxy group period, 3-ethylpentyloxy group, etc. are mentioned.

As a cycloalkoxy group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group etc. are mentioned, for example.

Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 5-heptenyl group, 1- an octenyl group, 3-octenyl group, 5-octenyl group and the like.

Examples of the alkynyl group include ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2- Pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 1-heptynyl group, 2-heptynyl group, 5-heptynyl group, 1-octynyl group, 3-octinyl group, 5-octinyl group and the like.

Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, an anthryl group, a pyrenyl group, an azrenyl group, an acenaphthylenyl group, a terphenyl group, a phenanthryl group, and the like. can be heard

As an aryloxy group, a phenoxy group, a naphthyloxy group, etc. are mentioned, for example.

Examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, and dodecylthio group.

As a cycloalkyl thio group, a cyclopentyl thio group, a cyclohexyl thio group, etc. are mentioned, for example.

As an arylthio group, a phenylthio group, a naphthylthio group, etc. are mentioned, for example.

Examples of the alkoxycarbonyl group include a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group.

As an aryloxycarbonyl group, a phenyloxycarbonyl group, a naphthyloxycarbonyl group, etc. are mentioned, for example.

Among these, when any one hydrogen atom of L ¹ or L ³ is substituted, the substituent that may be present may be a straight chain or branched alkyl group having 1 to 8 carbon atoms, for example, a straight chain having 1 to 3 carbon atoms. or a branched alkyl group, for example, a methyl group.

Among the above, L ¹ and L ³ may each independently be a divalent group selected from the following groups.

That is, in one embodiment, x in Chemical Formula 1 is 1 or 2 (eg, 1), and L ¹ may each independently be a divalent group selected from the following groups.

In one embodiment, y in Formula 2 is 1 or 2 (eg, 1), and L ³ , each independently, may be a divalent group selected from the following groups.

Meanwhile, in the following structures, R ¹¹¹ to R ¹²⁵ each independently represent a hydrogen atom or a straight-chain or branched hydrocarbon group having 1 to 18 carbon atoms or 3 to 18 carbon atoms (for example, R ¹¹¹ to R ¹²⁵ May be a hydrogen atom or a methyl group, for example, R ¹¹¹ to R ¹²⁵ may be a hydrogen atom).

In Chemical Formula 1, x may be 0, 1 or 2.

Meanwhile, when x is 2, L ¹ may be the same or different.

In addition, when x is 0, L ¹ is a single bond, and the nitrogen atom of the main chain is directly bonded to L ² .

From the viewpoint of further enhancing the effect according to one embodiment, x may be 0 or 1, for example, x may be 1 day.

In Formula 2, y may be 0, 1 or 2.

Meanwhile, when y is 2, L ³ may be the same or different.

In addition, when y is 0, L ³ is a single bond, and the nitrogen atom of the main chain is directly bonded to L ⁴ .

From the viewpoint of further enhancing the effect according to one embodiment, y may be 0 or 1, for example, 1.

x in Formula 1 and y in Formula 2 may be the same or different, but, for example, may be the same.

In Formula 1, L ² is a substituted or unsubstituted divalent or trivalent aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted divalent or trivalent aromatic heterocyclic group having 5 to 14 ring atoms. indicates ventilation. At this time, L ² may form a ring with Ar ¹ .

On the other hand, when L ² forms a ring with Ar ¹ , L ² is a trivalent group. When L ² does not form a ring with Ar ¹ , L ² is a divalent group.

In Formula 2, L ⁴ is a substituted or unsubstituted divalent or trivalent aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted divalent or trivalent aromatic heterocyclic group having 5 to 14 ring atoms. indicates ventilation. At this time, L ⁴ may form a ring with Ar ³ .

On the other hand, when L ⁴ forms a ring with Ar ³ , L ⁴ is a trivalent group. When L ⁴ does not form a ring with Ar ³ , L ⁴ is a divalent group.

When the polymer compound includes the structural unit of Formula 1 and the structural unit of Formula 2, L ² of Formula 1 and L ⁴ of Formula 2 may be the same as or different from each other, for example, may be the same as each other. there is.

Here, the aromatic hydrocarbon group and aromatic heterocyclic ring group as L ² or L ⁴ are not particularly limited.

When L ² does not form a ring with Ar ¹ , or when L ⁴ does not form a ring with Ar ³ , 2 derived from an aromatic hydrocarbon having 6 or more and 25 or less ring atoms defined in L ¹ and L ³ above A group can be exemplified.

Similarly, in the above case, the aromatic heterocyclic ring group as L ² or L ⁴ is not particularly limited, but divalent groups derived from heterocyclic aromatic compounds defined for L ¹ and L ³ can be exemplified.

Further, when L ² forms a ring with Ar ¹ or L ⁴ forms a ring with Ar ³ , a divalent aromatic hydrocarbon derived from an aromatic hydrocarbon having 6 or more and 25 or less ring atoms defined for L ¹ and L ³ above. A group can be converted into a trivalent group and illustrated.

Similarly, in the above case, the aromatic heterocyclic ring group as L ² or L ⁴ is not particularly limited, but exemplified by converting the divalent group derived from the heterocyclic aromatic compound defined for L ¹ and L ³ into a trivalent group can do.

Among these, L ² and L ⁴ may each independently be a divalent or trivalent group derived from a compound selected from benzene, fluorene, dibenzofuran, dibenzothiophene, or biphenyl. For example, L ² and L ⁴ are each independently a group derived from a compound selected from benzene, fluorene, and dibenzofuran, for example, an o, m, p-phenylene group, or a trivalent group; For example, it may be a 1,3,4-phenylylene group. For example, L ² and L ⁴ are each independently a divalent (phenylene group) derived from benzene (particularly, a p-phenylene group) or a trivalent group (particularly, a 1,3,4-phenylylene group). can

If it is such L ² or L ⁴ , a higher bond dissociation energy can be achieved.

In addition, a higher hole injection transport property and triplet energy level, and a lower drive voltage and film forming property, and any of these can achieve a balance of two or more types (particularly, a balance between hole injection and transport property and film forming property). there is.

Meanwhile, in one embodiment, L ² or L ⁴ may be unsubstituted, or any one hydrogen atom may be substituted with a substituent. In addition, when any one hydrogen atom of L ² or L ⁴ is substituted, substituents that may exist are not particularly limited, and the same examples as in L ¹ and L ³ can be applied. For example, L ² or L ⁴ may be unsubstituted.

In Formula 1, Ar ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms.

In Formula 2, Ar ³ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms.

When the polymer compound includes the structural unit of Chemical Formula 1 and the structural unit of Chemical Formula 2, Ar ¹ of Chemical Formula 1 and Ar ³ of Chemical Formula 2 may be identical to or different from each other, for example, may be identical to each other. there is.

Here, the aromatic hydrocarbon group having 6 or more and 25 or less ring atoms as Ar ¹ or Ar ³ is not particularly limited, but exemplifies the group derived from an aromatic hydrocarbon having 6 or more and 25 or less ring atoms defined for L ¹ and L ³ . can do.

Similarly, the aromatic heterocyclic ring group as Ar ¹ or Ar ³ is not particularly limited, but examples of groups derived from heterocyclic aromatic compounds defined for L ¹ and L ³ above can be exemplified. Among these, Ar ¹ and Ar ³ may each independently be selected from a phenylene group, a biphenylene group, a dibenzofuranylene group, a dibenzothiophenylene group, and a fluorenylene group. For example, Ar ¹ and Ar ³ may each independently be a phenylene group (o, m, p-phenylene group). For example, Ar ¹ and Ar ³ may be o-phenylene groups.

If it is such Ar ¹ or Ar ³ , higher bond dissociation energy can be achieved. In addition, a higher hole injection transport property and triplet energy level, a lower drive voltage and film forming property, and a balance of any two or more of these (particularly, a balance between hole injection transport property and film forming property) can be achieved.

Meanwhile, Ar ¹ or Ar ³ may be unsubstituted, or any one hydrogen atom may be substituted with a substituent.

On the other hand, when any one of Ar ¹ and Ar ³ is substituted, substituents that may exist are not particularly limited, and examples such as L ¹ and L ³ may be applied.

For example, Ar ¹ and Ar ³ are each independently unsubstituted or benzene substituted with a straight chain having 3 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, unsubstituted or 3 to 10 carbon atoms. Selected from biphenyl substituted with the following straight-chain or branched alkyl groups having 3 to 10 carbon atoms, and fluorene substituted with unsubstituted or straight-chain or branched alkyl groups with 3 to 10 carbon atoms and 3 to 10 carbon atoms It may be a divalent group derived from a compound that is For example, Ar ¹ and Ar ³ may each independently be an o, m, p-phenylene group substituted with an unsubstituted or straight-chain or branched alkyl group having 3 to 10 carbon atoms and 3 to 10 carbon atoms. there is. Further, for example, Ar ¹ and Ar ³ may each independently be an unsubstituted or o-phenylene group substituted with a straight-chain alkyl group having 5 or more and 8 or less carbon atoms. For example, Ar ¹ and Ar ³ may be an unsubstituted o-phenylene group.

On the other hand, when Ar ¹ or Ar ³ has a substituent, that is, when a substituted aromatic hydrocarbon group having 6 or more and 25 or less carbon atoms or a substituted aromatic heterocyclic ring group, the position of the substituent is not particularly limited, but Ar ¹ or Ar It may be located as far as possible from the nitrogen atom bonded to ³ . For example, when Ar ¹ or Ar ³ is an o-phenylene group, the substituent may be positioned para to the nitrogen atom. With this arrangement, the distance between the polymer compound and the quantum dot becomes closer, and the interaction between the polymer compound in the hole transport layer and the quantum dot in the light emitting layer becomes stronger, so that the hole injection/transport property and thus the durability (device lifetime, light emitting lifetime) are further improved. can make it

In Formula 1, Ar ¹ forms a ring with Ar ² or L ² .

In Formula 2, Ar ³ and Ar ⁴ or L ⁴ form a ring.

In this way, when Ar ¹ forms a ring with Ar ² or L ² and Ar ³ forms a ring with Ar ⁴ or L ⁴ , a higher triplet energy level can be imparted. Among these, from the viewpoint of further improving the effect according to one embodiment, at least one of Ar ¹ forming a ring with L ² and Ar ³ forming a ring with L ⁴ may be satisfied, for example For example, Ar ¹ may form a ring with L ² and Ar ³ may form a ring with L ⁴ .

That is, in one embodiment, Ar ¹ forms a ring with L ² , or Ar ³ forms a ring with L ⁴ .

In another embodiment, Ar ¹ forms a ring with L ² and Ar ³ forms a ring with L ⁴ .

The ring structure formed by Ar ^{1 and} L 2 when Ar ¹ forms a ring with L ² , or the ring structure formed by Ar ³ and L ⁴ when Ar ³ forms a ring with L ⁴ are not particularly limited. However, at least one of Ar ¹ and L ² , and Ar ³ and L ⁴ may form a carbazole ring, and Ar ¹ and L ² , and Ar ³ and L ⁴ may form a carbazole ring.

That is, in one embodiment, -L ² -N (Ar ¹ ) (Ar ² ) of Chemical Formula 1 may have a structure selected from the following groups. Also, in one embodiment, -L ⁴ -N (Ar ³ )(Ar ⁴ ) of Chemical Formula 2 may have a structure selected from the following groups.

Meanwhile, in the structure below, R ²¹¹ to R ²¹⁴ may each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 3 or more and 10 or less carbon atoms. For example, R ²¹¹ to R ²¹⁴ are hydrogen atoms.

In the structure below, “*1” indicates a binding site with L ¹ or L ³ , and “*2” indicates a binding site with Ar ² or Ar ⁴ .

For example, at least one of Ar ¹ and L ² , and Ar ³ and L ⁴ form a carbazole ring having the following structure. For example, a carbazole ring having the following structure may be formed by Ar ¹ and L ² , and Ar ³ and L ⁴ .

Meanwhile, in the structure below, R ²¹¹ to R ²¹⁴ each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 3 or more and 10 or less carbon atoms. For example, R ²¹¹ to R ²¹⁴ are hydrogen atoms. In the structure below, “*1” is a binding site with L ¹ or L ³ , and “*2” is a binding site with Ar ² or Ar ⁴ .

In one embodiment, in Formula 1, Ar ¹ forms a ring with L ² , and -(L ¹ )xL ² -N(Ar ¹ )(Ar ² ) may have a structure selected from the following groups.

In one embodiment, in Formula 2, Ar ³ forms a ring with L ⁴ , and -(L ³ )yL ⁴ -N(Ar ³ )(Ar ⁴ ) may have a structure selected from the following groups.

On the other hand, in the structure below, "*1" is a bonding site with a nitrogen atom of the main chain, and "*2" represents a bonding site with Ar ² or Ar ⁴ .

However, R ²¹¹ to R ²¹⁴ are each independently a hydrogen atom or a straight-chain or branched alkyl group having 3 to 10 carbon atoms and 3 to 10 carbon atoms. For example, R ²¹¹ and R ²¹³ are hydrogen atoms, and R ²¹² and R ²¹⁴ are hydrogen atoms or linear alkyl groups of 5 to 8 carbon atoms.

In Chemical Formula 1, Ar ² is (i) a straight-chain or branched hydrocarbon group having 1 to 12 carbon atoms, or a branched hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 25 ring atoms, or 5 or more ring atoms. An aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with an aromatic heterocyclic ring group of 14 or less, or (ii) a straight-chain or branched hydrocarbon group having 3 to 12 carbon atoms and 1 to 12 carbon atoms, represents an aromatic heterocyclic ring group having 5 to 14 ring atoms which may be substituted with an aromatic hydrocarbon group having 6 to 25 ring atoms or an aromatic heterocyclic ring group with 5 to 14 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.

In Formula 2, Ar ⁴ is (i) a straight-chain or branched hydrocarbon group having 1 to 12 carbon atoms, or a branched hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 25 ring atoms, or 5 or more ring atoms. An aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with an aromatic heterocyclic ring group of 14 or less, or (ii) a straight-chain or branched hydrocarbon group having 3 to 12 carbon atoms and 1 to 12 carbon atoms, An aromatic heterocyclic ring group having 5 to 14 ring atoms which may be substituted with an aromatic hydrocarbon group having 6 to 25 ring atoms or an aromatic heterocyclic ring group to have 5 to 14 ring atoms.

At this time, Ar ⁴ may form a ring with Ar ³ .

On the other hand, when Ar ⁴ and Ar ³ form a ring, Ar ⁴ is a divalent group.

When Ar ⁴ does not form a ring with Ar ³ , Ar ⁴ is a monovalent group.

Ar ² in Formula 1 and Ar ⁴ in Formula 2 may be the same as or different from each other, but, for example, may be the same.

In one embodiment, when the polymer compound according to one embodiment includes the structural unit of Formula 1 and the structural unit of Formula 2, R ²¹ , R ²² , R ³¹ , R ³² , L ^{1 of} Formula 1, x, L ² , Ar ¹ and Ar ² are the same as R ²³ , R ²⁴ , R ³³ , R ³⁴ , L ³ , y, L ⁴ , Ar ³ and Ar ⁴ in Formula 2, respectively.

Here, an aromatic hydrocarbon group having 6 or more and 25 or less ring atoms and an aromatic heterocyclic ring group having 5 or more and 14 or less ring atoms as Ar ² or Ar ⁴ are not particularly limited.

When Ar ² or Ar ⁴ does not form a ring with Ar ¹ or Ar ³ , the divalent group derived from an aromatic hydrocarbon having 6 or more and 25 or less ring atoms defined in L ¹ or L ³ is converted into a monovalent group. can do.

Similarly, in the above case, the aromatic heterocyclic ring group as Ar ² or Ar ⁴ is not particularly limited, but by converting the divalent group derived from the heterocyclic aromatic compound defined for L ¹ or L ³ into a monovalent group, can be exemplified.

Further, when Ar ² or Ar ⁴ forms a ring with Ar ¹ or Ar ³ , divalent groups derived from aromatic hydrocarbons having 6 or more and 25 or less ring atoms defined for L ¹ or L ³ can be exemplified.

Similarly, the aromatic heterocyclic ring group as Ar ² or Ar ⁴ in the above case is not particularly limited, but the divalent group derived from the heterocyclic aromatic compound defined for L ¹ or L ³ can be exemplified.

Among these, Ar ² and Ar ⁴ may each independently be a group derived from a compound selected from benzene, biphenyl, dibenzofuran, dibenzothiophene, and fluorene. For example, Ar ² and Ar ⁴ may each independently be a group derived from benzene, that is, a phenyl group or an o, m, p-phenylene group.

For example, Ar ² or Ar ⁴ is a phenyl group when Ar ² or Ar ⁴ does not form a ring with Ar ¹ or Ar ³ , or when Ar ² or Ar ⁴ forms a ring with Ar ¹ or Ar ³ ; It may be an o-phenylene group.

If such Ar ² or Ar ⁴ (unsubstituted form), a higher bond dissociation energy can be achieved. In addition, from the viewpoints of higher hole injection and transport properties and triplet energy levels, and lower driving voltage and film forming properties, a balance of any two or more of these (particularly, balance of hole injection and transport properties and film forming properties) can be achieved.

In one embodiment of the present invention, Ar ² or Ar ⁴ is a straight-chain or branched hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 25 ring atoms, or a ring-forming atom It has a divalent aromatic heterocyclic ring group of 5 or more and 14 or less as a substituent. By disposing such a substituent at the end of the high molecular compound, the high molecular compound in the hole transport layer can closely interact with the quantum dots in the light emitting layer, so that hole injection and transport properties can be improved. Therefore, the electroluminescence device using the polymer compound according to one embodiment, in particular, the quantum dot electroluminescence device, can more effectively improve durability, for example, device lifespan and light emitting lifespan.

Here, the hydrocarbon group having 1 to 12 carbon atoms is not particularly limited, and examples thereof include straight-chain or branched alkyl groups, straight-chain or branched alkenyl groups, straight-chain or branched alkynyl groups, and cycloalkyl groups.

On the other hand, when Ar ² or Ar ⁴ is an alkenyl group or an alkynyl group, the carbon number of Ar ² or Ar ⁴ is 2 or more and 12 or less. Similarly, when Ar ² or Ar ⁴ is a cycloalkyl group, the number of carbon atoms of Ar ² or Ar ⁴ is 3 or more and 12 or less.

Examples of the alkyl group having 1 or more and 12 or less carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropyl propyl group, 1,2 -Dimethylbutyl group, n-heptyl group, 1,4-dimethyl pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropyl butyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methyl propyl group, n-nonyl group, 3,5,5- trimethyl hexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group and the like.

Examples of the alkenyl group having 2 to 12 carbon atoms include a vinyl group, an allyl group, a 1-propenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, and an isopropanol group. A phenyl group etc. are mentioned.

As a C2-C12 alkynyl group, an ethynyl group, a propargyl group, etc. are mentioned, for example.

As a C3-C12 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group etc. are mentioned, for example.

In addition, the aromatic hydrocarbon group having 6 to 25 ring atoms present in Ar ² or Ar ⁴ is not particularly limited, but is derived from an aromatic hydrocarbon group having 6 to 25 ring atoms specified for L ¹ or L ³ . Examples can be made by converting a divalent group into a monovalent group.

For example, an aromatic hydrocarbon group having 6 or more and 25 or less ring atoms present in Ar ² or Ar ⁴ is a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, and a 9,9-dimethyl fluorenyl group, and A combination of any of these, for example a 9,9-dimethyl-2-phenyl fluorenyl group.

In addition, the divalent aromatic heterocyclic ring group having 5 or more and 14 or less ring atoms present in Ar ² or Ar ⁴ is not particularly limited, but has 5 or more and 14 or less ring atoms specified for L ¹ or L ³ . Examples can be made by converting a divalent group derived from a heterocyclic aromatic compound of , into a monovalent group.

For example, the divalent aromatic heterocyclic ring group having 5 or more and 14 or less ring atoms present in Ar ² or Ar ⁴ may be a pyridine-derived group.

On the other hand, an aromatic hydrocarbon group having 6 or more and 25 or less ring atoms and a divalent aromatic heterocyclic ring group having 5 or more and 14 or less ring atoms may be present in Ar ² or Ar ⁴ in combination.

Among these, the substituent present in Ar ² or Ar ⁴ is a straight-chain or branched alkyl group having 4 or more and 10 or less carbon atoms, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a 9,9- a dimethyl fluorenyl group and a pyridinyl group, or a combination of any of these (eg, a 9,9-dimethyl-2-phenyl fluorenyl group). Accordingly, the high molecular compound in the hole transport layer can exist more closely (and can interact more closely) with the quantum dots in the light emitting layer. Accordingly, hole injection and transport properties can be further improved. Accordingly, the electroluminescence device using the polymer compound according to the embodiment, eg, the quantum dot electroluminescence device, can more effectively improve durability, eg, device lifespan, light emitting lifespan, and the like.

In other words, in one embodiment, Ar ² and Ar ⁴ are each independently a group derived from a compound selected from the group consisting of benzene, biphenyl, dibenzofuran, dibenzothiophene, and fluorene, and carbon atoms 4 or more and 10 or less straight-chain or branched alkyl group of 4 or more and 10 or less carbon atoms, or a phenyl group, biphenyl group, terphenyl group, naphthyl group, 9,9-dimethyl fluorenyl group, 9,9-dimethyl-2 -phenyl fluorenyl group, pyridinyl group, 3-pyridinyl phenyl group, 4-pyridinyl phenyl group, or biphenyl group substituted with a pyridinyl group.

For example, the hydrocarbon group present in Ar ² or Ar ⁴ is a straight-chain alkyl group having 5 or more and 8 or less carbon atoms.

In other words, in one embodiment, Ar ² or Ar ⁴ may be a benzene-derived group (phenyl group, o, m, p-phenylene group) substituted with a straight-chain alkyl group having 5 or more and 8 or less carbon atoms.

For example, the hydrocarbon group present in Ar ² or Ar ⁴ is a straight-chain alkyl group having 6 or more and 8 or less carbon atoms.

In other words, in one embodiment, Ar ² or Ar ⁴ is a phenyl group substituted with a straight-chain alkyl group having 6 to 8 carbon atoms (when Ar ² or Ar ⁴ does not form a ring with Ar ¹ or Ar ³ ) , or an o-phenylene group substituted with a straight-chain alkyl group having 6 to 8 carbon atoms (when Ar ² or Ar ⁴ forms a ring with Ar ¹ or Ar ³ ).

Meanwhile, the position of the substituent present in Ar ² or Ar ⁴ is not particularly limited, but from the nitrogen atom of -L ² -N (Ar ¹ ) (Ar ² ) or -L ⁴ -N (Ar ³ ) (Ar ⁴ ). It can exist in a location as far away as possible. For example, when Ar ¹ forms a ring with L ² and Ar ² is a phenyl group, the hydrocarbon group may exist in a para position with respect to the nitrogen atom. According to this arrangement, since the high molecular compound in the hole transport layer can exist more closely with the quantum dots in the light emitting layer (i.e., can interact more closely), the hole injection and transport properties can be further improved. Therefore, the electroluminescence device using the polymer compound according to the embodiment, for example, the quantum dot electroluminescence device, can more effectively improve durability, for example, device lifetime and light emitting lifetime.

Ar ² or Ar ⁴ may form a ring with Ar ¹ or Ar ³ . When Ar ² or Ar ⁴ forms a ring with Ar ¹ or Ar ³ , the ring structure formed with Ar ² or Ar ⁴ and Ar ¹ or Ar ³ is not particularly limited, but Ar ² or Ar ⁴ and Ar ¹ or A A carbazole ring can be formed with ^r3 . In other words, in one embodiment, Ar ¹ in Formula 1 forms a ring with Ar ² , and -N(Ar ¹ )(Ar ² ) is a group selected from the following groups. In one embodiment, Ar ³ in Formula 2 forms a ring with Ar ⁴ , and -N(Ar ³ )(Ar ⁴ ) is a group selected from the following groups.

However, in the above formulas, R ₃₁₁ to R ₃₂₃ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. At this time, at least one of R ₃₁₁ and R ₃₁₂ , at least one of R ₃₁₃ to R ₃₁₅ , at least one of R ₃₁₆ to R ₃₁₉ , at least one of R ₃₂₀ and R ₃₂₁ , or at least one of R ₃₂₂ and R ₃₂₃ have carbon atoms. 1 to 12 straight chain or branched alkyl group having 3 to 12 carbon atoms (for example, a straight chain or branched alkyl group having 4 to 10 carbon atoms, for example, 5 to 8 carbon atoms) a straight-chain alkyl group, for example, a straight-chain alkyl group having 6 or more and 8 or less carbon atoms).

For example, a carbazole ring having the following structure may be formed by Ar ² or Ar ⁴ and Ar ¹ or Ar ³ . In other words, in one embodiment, -L ² -N (Ar ¹ ) (Ar ² ) of Chemical Formula 1 includes the following structure. In another embodiment, -L ⁴ -N (Ar ³ ) (Ar ⁴ ) in Chemical Formula 2 has the following structure.

However, R ₃₁₁ represents a hydrogen atom or a straight-chain or branched alkyl group having 4 to 10 carbon atoms or 4 to 10 carbon atoms (for example, a hydrogen atom or a straight-chain alkyl group having 5 to 8 carbon atoms), and R ₃₁₂ represents a straight-chain or branched alkyl group having 4 or more and 10 or less carbon atoms (for example, a straight-chain alkyl group having 5 or more and 8 or less carbon atoms, such as a straight-chain alkyl group having 6 or more and 8 or less carbon atoms).

Accordingly, the structural unit B may include the following structure. In other words, in one embodiment, the following structure of Formula 1:

Alternatively, the following structure of Formula 2:

may each independently have a structure selected from the following groups.

In the above structure, R ⁵¹ to R ⁵⁴ each independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 12 carbon atoms, or a group selected from the following groups;

Ar ⁴¹¹ to Ar ⁴¹⁷ each independently represents a group selected from the following groups;

Here, R ⁵⁵ to R ⁵⁷ each independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 12 carbon atoms, or a group selected from the following groups;

R ⁵⁸ and R ⁵⁹ each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms.

For example, structural unit B may include the following structure. In other words, in one embodiment, the following structure in Formula 1:

Alternatively, the following structure in Formula 2:

each independently has a structure selected from the group:

In the above structure, Ar ⁴¹² to Ar ⁴¹⁶ each independently represents a group selected from the following groups:

In the above structure, R ⁵⁵ to R ⁵⁷ each independently represent a straight-chain or branched alkyl group having 4 to 10 carbon atoms and 4 to 10 carbon atoms.

Accordingly, the structural unit of Chemical Formula 1 according to an embodiment may be selected from the following groups:

Among the structural units,

R ¹¹ to R ¹⁴ , R ²¹ and R ²² are defined as in Formula 1 above,

R ⁵¹ to R ⁵⁴ each independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms, or a group selected from the following groups:

Ar ⁴¹¹ to Ar ⁴¹⁷ each independently represents a group selected from the following groups;

In the above formulas, R ⁵⁵ to R ⁵⁷ each independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 12 carbon atoms or 3 to 12 carbon atoms, or a group selected from the following groups;

In the above formulas, R ⁵⁸ and R ⁵⁹ each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms.

In addition, the structural unit of Chemical Formula 2 according to an embodiment may be selected from the following groups:

Among the structural units,

R ⁴¹ to R ⁴⁴ , R ²³ and R ²⁴ are defined as in Formula 2 above,

Ar ⁴¹² to Ar ⁴¹⁶ each independently represent a group selected from the group below:

In the above structure, R ⁵⁵ to R ⁵⁷ each independently represent a straight-chain or branched alkyl group having 4 to 10 carbon atoms and 4 to 10 carbon atoms.

The composition of the structural unit C in the polymer compound according to one embodiment is not particularly limited.

For example, when considering the durability (device lifetime, luminescence lifetime, etc.) of a layer formed using the obtained polymer compound, for example, a hole injection layer, a hole transport layer, or a new improvement effect of hole injection and transport ability, etc. Unit C may be, for example, 10 mol% or more and 100 mol% or less, for example, 50 mol% or more and 100 mol% or less, such as 100 mol%, based on the total structural units constituting the polymer compound. The compound consists only of the structural unit C).

Meanwhile, when the polymer compound includes two or more kinds of structural units C, the content of the structural units C means the total amount of the structural units C.

When the polymer compound according to an embodiment includes the structural unit of Formula 1 and the structural unit of Formula 2, the composition of the structural unit represented by Formula 1 and the structural unit represented by Formula 2 below is The structural unit represented by, for example, is present in an amount of 0.3 mol or more and 10 mol or less with respect to 1 mol of the structural unit represented by the above formula (1), and the structural unit represented by the above formula (2) is represented by the above formula (1) It may be present in an amount of 1 mole or more and 20 moles or less with respect to 1 mole of the structural unit represented by Formula 2, and the structural unit represented by Chemical Formula 2 may be present in an amount of 1 mole or more and 3 moles or less with respect to 1 mole of the structural unit represented by Chemical Formula 1. may exist in proportion. Due to the presence of two types of structural units C in this composition, desired properties, such as durability and film forming properties, can be appropriately adjusted.

As described above, the polymer compound according to one embodiment may be composed only of structural unit C.

Alternatively, the polymer compound of one embodiment may further include structural units other than structural unit C.

In the case of including other structural units, other structural units are not particularly limited as long as they do not impair the effects of the polymer compound (in particular, durability, film forming property, high triplet energy level, and low driving voltage). For example, structural units selected from the following groups may be mentioned.

On the other hand, below, structural units represented by the following groups are also referred to as "structural unit D".

The composition of the structural unit D in the polymer compound of the present embodiment is not particularly limited. Considering the ease of forming a film by the obtained polymer compound and the effect of further improving film strength, the structural unit D may be, for example, 1 mol% or more and 10 mol% or less with respect to all structural units constituting the polymer compound. Meanwhile, when the polymer compound includes two or more kinds of structural units D, the content of the structural units D means the total amount of the structural units D.

The weight average molecular weight (Mw) of the high molecular compound is not particularly limited as long as the desired effect of the present invention is obtained. The weight average molecular weight (Mw) may be, for example, 8,000 g/mol or more and 1,000,000 g/mol or less, 12,000 g/mol or more and 1,000,000 g/mol or less, and, for example, 20,000 g/mol or more and 800,000 g/mol or more. mol or less, and may be 50,000 g/mol or more and 500,000 g/mol or less. With such a weight average molecular weight, it is possible to appropriately adjust the viscosity of a coating solution for forming a layer (eg, a hole injection layer or a hole transport layer) using a polymer compound, and form a layer having a uniform film thickness.

In addition, the number average molecular weight (Mn) of the high molecular compound is not particularly limited as long as the desired effect of the present invention is obtained. The number average molecular weight (Mn) may be, for example, 4,000 g/mol or more and 250,000 g/mol or less, 10,000 g/mol or more and 250,000 g/mol or less, 20,000 g/mol or more and 150,000 g/mol or less, , eg, greater than or equal to 25,000 g/mol and less than or equal to 100,000 g/mol. With such a number average molecular weight, it is possible to appropriately adjust the viscosity of the coating solution for forming a layer (e.g., hole injection layer, hole transport layer) using a polymer compound, and form a layer with a uniform film thickness. .

Further, the polydispersity (weight average molecular weight/number average molecular weight) of the polymer compound of the present embodiment may be, for example, 1.2 or more and 6.0 or less, such as 1.2 or more and 4.0 or less, for example, 1.5 or more and 3.5 or less.

In the present specification, the measurement of the number average molecular weight (Mn) and the weight average molecular weight (Mw) is not particularly limited, and may be applied using a known method or by appropriately modifying a known method.

In the present specification, the number average molecular weight (Mn) and the weight average molecular weight (Mw) employ values measured by the following method.

On the other hand, the polydispersity (Mw/Mn) of the polymer can be calculated by dividing the weight average molecular weight (Mw) from 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 using polystyrene as a standard substance by SEC (Size Exclusion Chromatography) under the following conditions:

(SEC measurement conditions)

Analyzer (SEC): Shimadzu Corporation, Prominence

Column: Polymer Laboratories, PLgel MIXED-B

Column temperature: 40 °C

Flow rate: 1.0mL/min

Injection amount of sample solution: 20 μL (polymer concentration: about 0.05% by mass)

Eluent: tetrahydrofuran (THF)

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

Standard sample: polystyrene.

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

The polymer compound of the present embodiment can be synthesized using a known organic synthesis method.

A specific method for synthesizing the polymer compound of the present embodiment can be easily understood by those skilled in the art by referring to Examples described later. For example, the polymer compound of the present embodiment is obtained by a polymerization reaction using a monomer represented by the following formula (1'), or a monomer represented by the following formula (1') and a monomer represented by the following formula (2'), or represented by the following formula (1'). It can be produced by a copolymerization reaction using monomers or monomers represented by the following formula (1') and monomers represented by the following formula (2') and monomers other than those corresponding to the above other structural units.

(Formula 1')

(Formula 2')

In the present invention, the monomers usable for polymerization of high molecular compounds can be synthesized by appropriately combining known synthesis reactions, and their structures can also be confirmed by known methods such as NMR and LC-MS. For example, the monomer represented by the above formula (1') is obtained by a reaction between a compound represented by the following formula (3') and a compound represented by the following formula (4'). Similarly, the monomer represented by the formula (2') can be obtained by a reaction between a compound represented by the following formula (5') and a compound represented by the following formula (6').

(Formula 3')

(Formula 4')

(Formula 5')

(Formula 6')

R ¹¹ to R ¹⁴ , R ^{21 ,} R ²² , R 31 , R ³² , L ¹ , x, L ² , Ar ¹ and Ar ² in Formulas 1′ to 6′ are as defined in Formula 1 above.

In addition, R ⁴¹ to R ⁴⁴ , R ²³ , R ²⁴ , R ³³ , R ³⁴ , L ³ , y, L ⁴ , Ar ³ and Ar ⁴ in Formulas 1' to 6' are as defined in Formula 2 above. same.

Z ¹ and Z ² , Z ³ and Z ⁴ , Z ^1' and Z ^2' , Z ^3' and Z ^4' , Z ^1” and Z ^2” , and Z ^3” and Z ^3” are each independently, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom such as a bromine atom) or a group having the following structure. In the structure below, R _A to R _D are each independently an alkyl group having 1 to 3 carbon atoms. For example, R _A to R _D are methyl groups.

On the other hand, Z ¹ and Z ² , Z ³ and Z ⁴ , Z 1 'and Z ^2' , Z ³ ' and Z ^{4 '} , Z ^1” and Z ^2” , and Z ³ in Formulas 1' to 6' ^” and Z ^{4 ”} may be the same or different, respectively. For example, in Formula 1', Z ¹ and Z ² are different. For example, in Formula 2', Z ³ and Z ⁴ are different. Alternatively, in Formula 1', Z ¹ and Z ² are different, and in Formula 2', Z ³ and Z ⁴ are different, and in Formula 1', Z ¹ and Z ³ are the same, and in Formula 1', Z ² and Z ⁴ may be the same as each other. For example, in Formula 3', Z ^1' and Z ^2' are the same. For example, Z ^1” and Z ^2” in Formula 4' are the same. In addition, Z ^1' and Z ^2' in Formula 3' are the same, Z ^1” and Z ^2” in Formula 4' are the same, and Z ^1' and Z ^2' in Formula 3' are the same. It may be different from Z ^1” and Z ^2” of 4'. For example, Z ^3' and Z ^4' in Formula 5' are the same. For example, Z ^3” and Z ^4” in Formula 6' are the same. In addition, Z ^3' and Z ^4' in Formula 5' are the same, Z ^3” and Z ^4” in Formula 6' are the same, and Z ^3' and Z ^{4' in Formula 3'} are the same as above. It may be different from Z ^3” and Z ^4” in Formula 6'.

The polymer compound of the present embodiment includes structural unit C. For this reason, the high molecular compound has a large C-N bond dissociation energy and a high hole injection/transport property. Therefore, when the polymer compound according to one embodiment is used as a hole injection material or a hole transport material (particularly a hole transport material), high durability (device lifespan, light emitting lifespan) can be achieved. Further, the polymer compound of the present embodiment has a high triplet energy level and a low drive voltage at the same time. Therefore, when the polymer compound according to one embodiment is used as a hole injection material or a hole transport material (particularly, a hole transport material), high hole mobility can be achieved with a low driving voltage. Therefore, the electroluminescence device using the polymer compound according to the embodiment has excellent durability (device lifespan, light emitting lifespan, etc.) and light emitting efficiency.

[Electroluminescence element material]

A polymer compound according to an embodiment can be advantageously used as an electroluminescence device material.

According to the polymer compound according to an embodiment, an electroluminescence device material having excellent durability (device lifespan, light emitting lifespan, etc.) can be provided. In addition, according to the polymer compound according to an embodiment, an electroluminescence device material having a high triplet energy level (current efficiency) and a low driving voltage may also be provided. In addition, the main chain (structural unit C) of the polymer compound has appropriate flexibility. For this reason, the polymer compound according to one embodiment exhibits high solubility in solvents and high heat resistance. Therefore, it can be easily formed into a film (thin film) by a wet (application) method. Therefore, in the second embodiment, an electroluminescence device material comprising the polymer compound according to the first embodiment is provided. Alternatively, use of the above polymer compound as an electroluminescence device material is provided.

In addition, the polymer compound according to an embodiment has a HOMO energy value exceeding 5.20 eV, for example, exceeding 5.47 eV. For this reason, the polymer compound according to one embodiment can be suitably used for a quantum dot electroluminescence device (particularly, a hole transport layer).

[Electroluminescence element]

As described above, the polymer compound according to one embodiment can be advantageously used in an electroluminescent device. In other words, an electroluminescence device including a pair of electrodes and one or more organic layers disposed between the electrodes and containing the polymer compound or electroluminescence device material of one embodiment is provided. Such an electroluminescence device has excellent durability (device lifetime, luminescence lifetime, etc.). In addition, such an electroluminescent device can exhibit excellent luminous efficiency with a low driving voltage.

Accordingly, in the third embodiment, an electroluminescent device including a first electrode, a second electrode, and one or more layers of an organic film disposed between the first electrode and the second electrode, wherein the organic film An electroluminescence device in which at least one layer includes the polymer compound according to one embodiment is provided.

The object (or effect) of the present invention can also be achieved by the electroluminescence device according to this embodiment. As an example of the above aspect, the electroluminescent element further includes a light emitting layer disposed between the electrodes and containing a light emitting material capable of emitting light as a triplet exciton.

Meanwhile, the electroluminescence device of this embodiment is an example of an electroluminescence device according to an embodiment.

Further, the present embodiment is a method for manufacturing an electroluminescence device including a pair of electrodes and one or more layers of organic films disposed between the electrodes and containing the polymer compound of one embodiment, wherein at least one of the organic films is used. A method for forming a layer by an application method is provided. Further, according to this method, the present embodiment provides an electroluminescent element in which at least one layer of the organic film is formed by a coating method.

The polymer compound of the present embodiment and the electroluminescence device material (EL device material) according to one embodiment (hereinafter collectively referred to as "polymer compound/EL device material") are excellent in solubility in organic solvents. For this reason, the polymer compound/EL element material according to one embodiment can be used particularly advantageously in the manufacture of elements (particularly thin films) by a coating method (wet process). For this reason, this embodiment provides the liquid composition containing the polymer compound of this embodiment, and a solvent or a dispersion medium. This liquid composition is an example of a liquid composition according to an embodiment.

In addition, as described above, the electroluminescence element material according to one embodiment can be advantageously used for manufacturing an element (especially a thin film) by an application method (wet process). In view of the above, the present embodiment provides a thin film containing the polymer compound of the present embodiment. Such a thin film is an example of a thin film according to an embodiment.

In addition, the EL device material according to the embodiment has excellent hole injection and transport properties. For this reason, it can be suitably used also in formation of any organic film, such as a hole injection material, a hole transport material, or a light emitting material (host). Among these, it can be advantageously used as a hole injection material or a hole transport material from the viewpoint of hole transport properties, and can be advantageously used as a hole transport material.

In other words, 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 include organometallic complexes (luminescent organometallic complex compounds) or semiconductor nanoparticles (semiconductor inorganic nanoparticles).

[Electroluminescence element]

Hereinafter, referring to FIG. 1 , an electroluminescence device according to an exemplary embodiment will be described in detail.

1 is a schematic diagram showing an electroluminescence device according to an exemplary embodiment.

On the other hand, in the present specification, "electroluminescence element" is sometimes abbreviated as "EL element".

As shown in FIG. 1, the EL device 100 according to an embodiment includes a substrate 110, a first electrode 120 disposed on the substrate 110, and holes disposed on the first electrode 120. The injection layer 130, the hole transport layer 140 disposed on the hole injection layer 130, the light emitting layer 150 disposed on the hole transport layer 140, and the electron transport layer 160 disposed on the light emitting layer 150, , 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 high molecular compound of this embodiment is contained in any one organic film (organic layer) arrange|positioned between the 1st electrode 120 and the 2nd electrode 180, for example. For example, the polymer compound may be 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). For example, the high molecular compound may be included in the hole injection layer 130 as a hole injection material or in the hole transport layer 140 as a hole transport material. For example, a high molecular compound may be included in the hole transport layer 140 as a hole transport material. In other words, in one embodiment, the organic film containing the polymer compound may be a hole transport layer, a hole injection layer, or a light emitting layer.

In one embodiment of the present invention, the organic film containing the polymer compound is a hole transport layer or a hole injection layer.

In one embodiment of the present invention, the organic film containing the polymer compound is a hole transport layer.

In addition, the organic film containing the polymer compound/EL element material of the present embodiment can be formed by a coating method (solution coating method).

For example, the organic film is a spin coat method, a casting/casting method, a micro gravure coat method, a gravure coat method, a bar coat method, a roll Roll coat method, wire bar coat method, dip coat method, spray coat method, screen printing method, flexographic printing method, offset ) may be formed using a solution coating method such as a printing method or an ink jet printing method.

On the other hand, any solvent can be used for the solvent used in the solution coating method as long as it can dissolve the polymer compound/EL device material, and can be appropriately selected according to the type of polymer compound used. For example, toluene, xylene, ethyl benzene, diethylbenzene, mesitylene, propyl benzene, cyclohexyl benzene, dimethoxy benzene, anisole, ethoxy toluene, phenoxy toluene, isopropyl biphenyl, dimethyl anisole, acetic acid Phenyl, phenyl propionate, methyl benzoate, ethyl benzoate, cyclohexane and the like can be exemplified.

The amount of the solvent used is not particularly limited, but considering ease of application and the like, the concentration of the polymer compound is, for example, 0.1% by mass or more and 10% by mass or less, for example, 0.5% by mass or more and 5% by mass or less. can be an amount

On the other hand, the method for forming a layer other than the organic film containing the polymer compound/EL device material is not particularly limited.

Layers other than the organic film containing the polymer compound/EL element material of the present embodiment may be formed into a film by, for example, a vacuum evaporation method or a solution coating method.

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

Above the substrate 110, a first electrode 120 is formed. The first electrode 120 is, for example, an anode, and may be formed of a metal, an alloy, or a conductive compound having a large work function. For example, the first electrode 120 may include indium tin oxide (In ₂ O ₃ -SnO ₂ : ITO), indium zinc oxide (In ₂ O ₃ -ZnO), or tin oxide (SnO ₂ ) having excellent transparency and conductivity. , zinc oxide (ZnO), or the like may be formed as a transmissive electrode.

Also, the first electrode 120 may be formed as a reflective electrode by laminating magnesium (Mg), aluminum (Al), or the like on the transparent conductive film. Further, 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 hole injection from the first electrode 120, and has a thickness of, for example, about 10 nm or more and about 1000 nm or less, for example, about 20 nm or more and about 50 nm or less (dry film thickness; hereinafter the same).

The hole injection layer 130 can be formed of a known hole injection material. As a known hole injection material forming the hole injection layer 130, for example, poly(ether ketone)-containing triphenylamine (TPAPEK), 4-isopropyl-4'-methyl Diphenyliodonium tetrakis (pentafluorophenyl) borate (4-isopropyl-4'-methyldiphenyliodonium tetrakis ( pentafluorophenyl)borate: PPBI), N, N'-diphenyl-N, N'-bis- [4- (phenyl-m-triyl-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-methylphenyl phenyl amino) triphenylamine (4,4',4” -tris(3-methylphenylphenylamino) triphenylamine:m-MTDATA), N, N'-di(1-naphthyl)-N, N'-diphenylbenzidine (N, N'-di(1-naphthyl)-N, N'-diphenylbenzidine:NPB), 4,4', 4”-tris(diphenylamino)triphenylamine (4,4',4”-tris(diphenylamino) triphenylamine:TDATA), 4,4', 4” -tris(N, N-2-naphthylphenylamino)triphenylamine (4,4',4”-tris(N, N-2-naphthylphenylamino)triphenylamine:2-TNATA), polyaniline/dodecylbenzenesulfonic acid (polyaniline/dodecylbenzenesulphonic acid), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate): PEDOT/PSS), and and polyaniline/10-camphorsulfonic acid.

A hole transport layer 140 is formed on the hole injection layer 130 . The hole transport layer 140 is a layer having a function of transporting holes, and may be formed to a thickness of, for example, about 10 nm or more and about 150 nm or less, for example, about 20 nm or more and about 50 nm or less. The hole transport layer 140 can be formed into a film by a solution coating method using the polymer compound of the present embodiment. According to this method, the durability of the EL element 100 (device life, light emitting life, etc.) can be further improved. It is also possible to improve the current efficiency of the EL element 100 and reduce the driving voltage. In addition, since the hole transport layer can be formed by the solution coating method, it is possible to efficiently form a large-area film.

However, when the organic film other than any one of the EL elements 100 contains the polymer compound of the present embodiment, the hole transport layer 140 may be formed of a known hole transport material. As a known hole transport material, for example, 1,1-bis [(di-4-triylamino) phenyl] cyclohexane (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”-tris(N-carbazolyl) triphenylamine: TCTA), and N, N’-di(1- naphthyl) -N, N'-diphenyl benzidine (N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine: NPB) and the like.

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, or the like, and may be formed using a vacuum deposition method, a spin coating method, an inkjet printing method, or the like. The light emitting layer 150 may be formed to a thickness of, for example, greater than or equal to about 10 nm and less than or equal to about 60 nm, for example, greater than or equal to about 20 nm and less than or equal to about 50 nm. As the light emitting material of the light emitting layer 150, a known light emitting material can be used. However, the light emitting material included in the light emitting layer 150 may be a light emitting material capable of emitting light from triplet excitons (ie, phosphorescent light emission). 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. For example, the light emitting layer may include semiconductor nanoparticles or organometallic complexes. In other words, in the form of an embodiment, the organic film has a light emitting layer containing semiconductor nanoparticles or organometallic complexes. Meanwhile, when the light emitting layer includes semiconductor nanoparticles, the EL device is a quantum dot electroluminescence device (QLED) or a quantum dot light emitting device. In the case where the light emitting layer contains an organometallic complex, the EL element is an organic electroluminescent element (OLED).

In a form (QLED) in which the light emitting layer includes semiconductor nanoparticles, in the light emitting layer, a plurality of semiconductor nanoparticles (quantum dots) may be arranged in a single layer or a plurality of layers. Here, semiconductor nanoparticles (quantum dots) are particles of a predetermined size having a quantum confinement effect. The diameter (average diameter) of the semiconductor nanoparticles (quantum dots) is not particularly limited, but is about 1 nm or more and 10 nm or less.

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

In the wet chemical process, when the crystal grows, the organic solvent is naturally coordinated to the surface of the quantum dot crystal and acts as a dispersant, so that the growth of the crystal can be controlled. For this reason, in the wet chemical process, it is easier than vapor deposition methods such as Metal Organic Chemical Vapor Deposition (MOCVD) or Molecular Beam Epitaxy (MBE), and at the same time, semiconductor nanoparticles at a low cost growth can be controlled.

Semiconductor nanoparticles (quantum dots) can adjust their energy bandgap by adjusting their size, and light of various wavelengths can be obtained as a 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) light of a plurality of wavelengths is possible. The size of the quantum dots can be selected so that red, green, and blue light can be emitted to configure a color display. In addition, the size of the quantum dots can be combined to emit white light from various color lights.

As semiconductor nanoparticles (quantum dots), II-VI group semiconductor compounds; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; Group IV elements or compounds; and a semiconductor material selected from the group consisting of combinations thereof.

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

The group III-V semiconductor compound is not particularly limited, but is, for example, selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof. a binary compound that becomes; A three-element compound selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and a quaternary compound selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. .

The IV-VI group semiconductor compound is not particularly limited, but includes, for example, a binary compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; a ternary compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; and a quaternary compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof.

The Group IV element or compound is not particularly limited, but includes, for example, one-element compounds selected from the group consisting of Si, Ge, and mixtures thereof; and a binary compound selected from the group consisting of 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. Materials constituting the respective cores and shells may include different semiconductor compounds. However, the energy band gap of the shell material is larger than that of the core material.

For example, structures such as ZnTeSe/ZnSe/ZnS, InP/ZnSe/ZnS, CdSe/ZnS, and InP/ZnS may be used.

For example, a case of manufacturing a quantum dot having a core (CdSe) shell (ZnS) structure will be described.

First, trioctylphosphine oxide (TOPO) is used as a surfactant. A core (CdSe) precursor material such as (CH ₃ ) ₂ Cd (dimethylcadmium) or TOPSe (trioctylphosphine selenide) is injected into an organic solvent to form a crystal. At this time, after maintaining the high temperature for a certain time so that the crystal grows to a certain size, the precursor material of the shell (ZnS) is injected, and the shell is formed 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 uses, for example, 6,9-diphenyl-9'-(5'-phenyl-[1,1] as a host material. ':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,-triadin-2-yl)phenyl)-9H-carbazole, 9,9 '-diphenyl-3,3'-bis [9H-carbazole], tris (8-) aluminum (tris (8-quinolinato) aluminum: Alq3), 4,4'-bis (carbazol-9-yl) Biphenyl (4,4'-bis(carbazol-9-yl)biphenyl:CBP), 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-phenyl-benzimidazol-2-yl) benzene: TPBI) , 3-tert-butyl-9,10-di (naphth-2-yl) anthracene (3-tert-butyl-9,10-di (naphth-2-yl) anthracene: TBADN), distryl arylene ( 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)pyridinato] picolinate iridium(III):FIrpic), bis(1-phenyl isoquinoline) (acetylaceto nate) iridium(III) (bis(1-phenylisoquinoline) (acetylacetonate)iridium(III):Ir(piq) 2(acac)), tris(2-phenylpyridine)iridium(III) (tris(2-phenylpyridine)iridium (III):Ir(ppy)3), tris(2-(3-p-xylphenyl)pyridine iridium(III), etc., iridium (Ir) complexes, osmium (Os) complexes, platinum complexes, etc. may be included. Among them, the luminescent material may be a luminescent organometallic complex compound.

A method of forming the light emitting layer is not particularly limited. It can be formed by applying a coating solution containing semiconductor nanoparticles or organometallic complexes (solution coating method). At this time, as the solvent constituting the coating liquid, a solvent that does not dissolve the material in the hole transport layer (hole transport material, particularly a polymer compound) can be selected.

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

The electron transport layer 160 may be formed of a known electron transport material. As the electron transport material, for example, ZnCl ₂ , ZnMgO, (8-) lithium (lithium quinolate) (Liq), tris (8-) aluminum (tris (8-quinolinato) aluminum: Alq3), and nitrogen-containing aromatics compounds having a ring; and the like. 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), compounds containing a pyridine ring such as 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1, Contains a triazine ring such as 3,5-triadine (2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine) 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-phenyl-benzimidazol-2-yl)benzene (TPBI) and compounds containing an imidazole ring, etc. The above electron transport materials may be used singly or as a mixture of two or more.

An electron injection layer 170 is formed on the electron transport layer 160 . The electron injection layer 170 is a layer having a function of facilitating injection of electrons from the second electrode 180 . The electron injection layer 170 may be formed using a vacuum deposition method or the like. The electron injection layer 170 may be formed to a thickness of about 0.1 nm or more and about 5 nm or less, for example, about 0.3 nm or more and about 2 nm or less.

Any known material for forming the electron injection layer 170 can be used. For example, the electron injection layer 170 may include lithium compounds such as (8-)lithium (lithium quinolate) ((8-quinolinato)lithium: Liq) and lithium fluoride (LiF), 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 may be formed using a vacuum deposition method or the like. The second electrode 180 is, for example, a cathode and may be formed of a material having a small work function such as a metal, an alloy, or a conductive compound. For example, the second electrode 180 may be 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 a thickness of about 10 nm or more and about 200 nm or less, for example, about 50 nm or more and about 150 nm or less. Alternatively, the second electrode 180 is a transparent conductive film such as a thin film of the metal material of 20 nm or less, indium tin oxide (In ₂ O ₃ -SnO ₂ ) and indium zinc oxide (In ₂ O ₃ -ZnO), and is a transmissive type. It can also be formed as an electrode.

In the above, the EL device 100 according to an embodiment has been described as an example of an electroluminescence device according to an embodiment. In the EL device 100 according to an embodiment, durability (device lifespan, light emitting lifespan, etc.) can be further improved by installing an organic film (particularly, a hole transport layer or a hole injection layer) containing a polymer compound. In addition, the luminous efficiency (current efficiency) can be further improved and the driving voltage can be reduced.

Meanwhile, the laminated structure of the EL device 100 according to an embodiment is not limited to the above example.

The EL device 100 according to an embodiment may be formed in other known stacked structures. For example, in the EL device 100, at least one layer of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, and the electron injection layer 170 may be omitted, or other layers may be further added. You may have more. Further, each layer of the EL element 100 may be formed of a single layer or a plurality of layers.

For example, since the EL element 100 prevents excitons or holes from diffusing into the electron transport layer 160, even if a hole blocking layer is further provided between the hole transport layer 140 and the light emitting layer 150, do. Meanwhile, the hole blocking layer may be formed of, for example, an oxadiazole derivative, a triazole derivative, or a phenanthroline derivative.

In addition, the polymer compound according to one embodiment can be applied to electroluminescent devices other than the QLED or OLED.

Examples of other electroluminescent devices to which the polymer compound according to an embodiment can be applied are not particularly limited, but examples thereof include organic-inorganic perovskite light emitting devices and the like.

Example

Effects of the present invention are explained using the following Examples and Comparative Examples. However, the technical scope of the present invention is not limited only to the following examples. On the other hand, in the following examples, unless otherwise noted, operations were performed at room temperature (25°C). In addition, "%" and "part" mean "mass %" and "part by mass", respectively, unless otherwise specified.

Synthesis Example 1

(Synthesis of Compound M-1)

Compound M-1 was synthesized according to the following scheme.

(Synthesis of Compound 1a)

In a four-necked flask, 6,12-dihydroindeno [1,2-b] fluorene (39.3 mmol, 10.0 g), DMSO (65 ml), and t-butoxy sodium (NaOtBu) (235 mmol, 22.7 g), and stirred for 10 minutes at room temperature (25° C.) under a nitrogen atmosphere. Then, 1-bromohexane (235mmol, 38.9g) was added dropwise, and the mixture was heated and stirred at 80°C for 3 hours. After completion of the reaction, the obtained solution is cooled to room temperature and extracted with hexane. After concentrating the obtained organic layer, it recrystallizes from hexane and ethanol to obtain compound 1a (amount 19.7g, yield 85%).

(Synthesis of Compound M-1)

In a four-necked flask, the obtained compound 1a (16.9mmol, 10.0g), iron (III) chloride (FeCl ₃ ) (0.25mmol, 15mg), and chloroform (150ml) were put, and stirred at 0° C. for 5 minutes under a nitrogen atmosphere. do. Thereafter, bromine (33.8 mmol, 1.7 mml) was added dropwise, and after the addition was completed, the mixture was stirred at room temperature for 3 hours. After completion of the reaction, an aqueous solution of sodium thiosulfate was added to the reaction system, and then the organic layer that could have been extracted with hexane was concentrated and then recrystallized with hexane and ethanol to obtain compound M-1 (amount 6.1 g, yield 72 %).

Synthesis Example 2

(Synthesis of Compound M-2)

Compound M-2 was synthesized according to the reaction scheme below.

Compound M-2 was obtained in the same manner as in Synthesis Example 1 except for using 1-bromooctane instead of 1-bromohexane in Synthesis Example 1 (amount: 5.9 g, yield: 70%).

Synthesis Example 3

(Synthesis of Compound M-3)

Compound M-3 was synthesized according to the reaction scheme below.

Compound M-3 was obtained in the same manner as in Synthesis Example 1 except for using 1-bromododecane instead of 1-bromohexane in Synthesis Example 1 (amount 5.4 g, yield 74%).

Synthesis Example 4

(Synthesis of M-A1)

Compound M-A1 (Compound M-A1) was synthesized according to the following reaction scheme.

In a 1L-4-necked flask, 9-(4-hexylphenyl)-3-iodo-9-carbazole (20.0 g), 4-(diphenyl amino)phenyl boronic acid (15.3 g), sodium carbonate (9.51 g) , tetrakis(triphenylphosphine)palladium(0) (Pd(PPh ₃ ) ₄ ) (2.49 g), toluene (221 mL), ethanol (110 mL), and water (110 mL) were added, and 120° C. (bath temperature) stirred for 3 hours.

After cooling to room temperature, the aqueous layer was separated, and the organic layer was washed with water (100 L x 2) and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by column chromatography, and 4-(9-(4-hexylphenyl)-9-carbazol-3-yl)-N, N-diphenyl)aniline (17.7 g ) to get

Into a 500 mL-four-necked flask, 4- (9- (4-hexylphenyl) -9-carbazol-3-yl) -N, N-diphenyl) aniline (17.7 g) obtained above, and N, N- Dimethylformamide (DMF) (310 mL) was added, cooled with ice, and N-bromo succinimide (NBS) (11.7 g) dissolved in DMF (30 mL) was added dropwise under a nitrogen atmosphere, followed by stirring for 6 hours.

The insoluble matter was separated by filtration, washed with methanol (800 mL) and water (800 mL), dried under vacuum, and 4-bromo-N- (4-bromophenyl) -N- (4- (9- (4-) -Hexylphenyl)-9-carbazol-3-yl)phenyl)aniline (14.0 g) is obtained.

To a 500 mL-4-necked flask, the above-obtained 4-bromo-N-(4-bromophenyl)-N-(4-(9-(4-hexylphenyl)-9-carbazol-3-yl)phenyl )aniline (14.0g), bis(pinacolato)diboron (14.8g), potassium acetate (KOAc) (11.4g), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) A dichloromethane 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, solids were separated by filtration using Celite as a filter 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 is separated by filtration, the solvent is distilled off under reduced pressure, and recrystallized using a mixed solvent of toluene and acetonitrile to obtain compound M-A1 (11.9 g).

Example 1

(Synthesis of polymeric compound P-1)

Under an argon atmosphere, compound M-A1 (1.777 g) synthesized in Synthesis Example 4, compound M-1 (1.617 g) synthesized in Synthesis Example 1, palladium acetate (4.8 mg), tris (2-methoxy phenyl) ) Phosphine (45.7 g), toluene (64 mL), and 20% by mass tetraethylammonium hydroxide aqueous solution (11.1 g) were mixed and refluxed and stirred for 6 hours. Thereafter, phenyl boronic acid (261.4 mg), bis(triphenylphosphine)palladium(II) dichloride (91.0 mg), and 20% by mass tetraethylammonium hydroxide aqueous solution (11.1 g) were added to the reaction solution, Heat to reflux for 6 hours. Thereafter, to the obtained solution, except for the aqueous layer, N,N-diethyldithiocarbamide sodium trihydrate (6.5 g) and ion-exchanged water (60 mL) were added, and the mixture was stirred at 85°C for 6 hours.

With respect to the obtained solution, after the organic layer was separated from the aqueous layer, the organic layer was washed with water, a 3% by mass aqueous acetic acid solution, and water. The organic layer is added dropwise to methanol to precipitate a polymer, and solid is obtained by drying. This solid was dissolved in toluene, passed through column chromatography packed with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid is added dropwise to methanol, and the precipitated solid is taken and dried to obtain polymer compound P-1 (amount: 1.56 g). The weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the obtained polymer compound P-1 were measured by SEC. As a result, the weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the polymer compound P-1 were 150,600 g/mol and 2.35, respectively.

The polymer compound P-1 obtained in this way is presumed to be a polymer compound having the following structural units from the composition of the monomers.

(Polymer Compound P-1)

Example 2

(Synthesis of polymeric compound P-2)

A polymer compound P-2 was obtained in the same manner as in Example 1, except that the compound M-2 (1.296 g) synthesized in Synthesis Example 2 was used instead of the compound M-1 in Example 1. The weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the obtained polymeric compound P-2 were measured by SEC. As a result, the weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the polymer compound P-2 were 149,000 g/mol and 2.24, respectively.

The polymer compound P-2 obtained in this way is presumed to be a polymer compound having the following structural units from the structure of the monomers.

(Polymer compound P-2)

Example 3

(Synthesis of polymeric compound P-3)

A polymer compound P-3 was obtained in the same manner as in Example 1, except that the compound M-3 (1.673 g) synthesized in Synthesis Example 3 was used instead of the compound M-1 in Example 1. The weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the obtained polymeric compound P-3 were measured by SEC. As a result, the weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the polymer compound P-3 were 134,400 g/mol and 2.23, respectively.

The polymer compound P-3 obtained in this way is presumed to be a polymer compound having the following structural units from the composition of the monomers.

(Polymer compound P-3)

Example 4

(Synthesis of polymeric compound P-4)

Compound M-A1 (0.592 g, 1.0 mol equivalent) synthesized in Synthesis Example 4 under an argon atmosphere, Compound M-1 (0.270 g, 0.5 mol equivalent) synthesized in Synthesis Example 1, Synthesis in Synthesis Example 3 One compound M-3 (0.391 g, 0.5 mol equivalent), palladium acetate (1.6 mg), tris(2-methoxy phenyl)phosphine (15.7 g), toluene (20 mL), and 20 mass % tetraethylanmonium hydrate An aqueous solution of rockoxide (4.1 g) was mixed and stirred under reflux for 6 hours. Thereafter, phenyl boronic acid (261.4 mg), bis(triphenylspin)palladium(II) dichloride (30.1 mg), and 20% by mass tetraethyl ammonium hydroxide aqueous solution (11.1 g) were added to the reaction solution, and 6 Heat to reflux for an hour. After that, the aqueous layer was removed from the obtained solution, sodium N,N-diethyldithiocarbamidate trihydrate (6.5 g) and ion-exchanged water (60 mL) were added, and the mixture was stirred at 85°C for 6 hours. With respect to the obtained solution, after the organic layer was separated from the aqueous layer, the organic layer was washed with water, a 3% by mass aqueous acetic acid solution, and water. The organic layer was dropped into methanol to precipitate a polymer, which was dried to obtain a solid. This solid was dissolved in toluene, passed through column chromatography packed with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was separated and dried to obtain polymer compound P-4 (amount: 0.56 g). The weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the obtained polymer compound P-4 were measured by SEC. As a result, the weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the polymer compound P-4 were 185,000 g/mol and 2.56, respectively.

The polymer compound P-4 obtained in this way is presumed to be a polymer compound having the following structural units from the structure of the monomers.

(Polymer compound P-4)

Example 5

(Synthesis of polymeric compound P-5)

In Example 4, Compound M-A1 (0.790 g, 1.0 mol equivalent) synthesized in Synthesis Example 4, Compound M-1 (0.270 g, 0.375 mol equivalent) synthesized in Synthesis Example 1, and Synthesis Example 3 A polymer compound P-5 was obtained in the same manner as in Example 4, except that one compound M-3 (0.651 g, 0.625 mol equivalent) was used instead. The weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the obtained polymer compound P-5 were measured by SEC. As a result, the weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the polymer compound P-5 were 102,000 g/mol and 2.12, respectively.

The polymer compound P-5 obtained in this way is presumed to be a polymer compound having the following structural units from the structure of the monomers.

(Polymer compound P-5)

Example 6

(Synthesis of polymeric compound P-6)

In Example 4, compound M-A1 (0.592 g, 1.0 mol equivalent) synthesized in Synthesis Example 4, compound M-1 (0.135 g, 0.25 mol equivalent) synthesized in Synthesis Example 1, and Synthesis Example 3 A polymer compound P-6 was obtained in the same manner as in Example 4, except that one compound M-3 (0.586 g, 0.75 mol equivalent) was used instead. The weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the obtained polymer compound P-6 were measured by SEC. As a result, the weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the polymer compound P-6 were 55,000 g/mol and 2.20, respectively.

The polymer compound P-6 obtained in this way is presumed to be a polymer compound having the following structural units from the structure of the monomers.

(Polymer compound P-6)

Comparative Example 1

(Synthesis of polymeric compound P-7)

Compound M-A1 (1.64 g) synthesized in Synthesis Example 4 under an argon atmosphere, 2,7-dibromo-9,9-di-n-hexyl fluorene (0.983 g), palladium acetate (9.0 mg), Tris (2-methoxy phenyl) phosphine (42.2 mg), toluene (53 mL), and 20% by mass tetraethylammonium hydroxide aqueous solution (10.3 g) were placed in a four-necked flask, and the mixture was stirred at 85°C for 6 hours. Next, phenyl boronic acid (241 mg), tetrakis(triphenylphosphino)palladium (140 mg), and 20% by mass tetraethylammonium hydroxide aqueous solution (10.3 g) are added, and the mixture is stirred for 3 hours. Thereafter, sodium N,N-diethyldithiocarbamidate trihydrate (13.5 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 washed with water, a 3% by mass aqueous acetic acid solution, and water. Thereafter, the organic layer was subjected to column chromatography packed with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid is added dropwise to methanol, and the precipitated solid is dissolved in toluene. Thereafter, this solution is added dropwise to methanol to precipitate, and the precipitated solid is separated and dried to obtain polymer compound P-7 (1.35 g). The weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the obtained polymer compound P-7 were measured by SEC. As a result, the weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the polymer compound P-7 were 86,000 g/mol and 2.56, respectively.

The polymer compound P-7 obtained in this way is presumed to be a polymer compound having the following structural units from the structure of the monomers.

(Polymer compound P-7)

Example 7

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

On this hole injection layer, a 1.0% by mass toluene solution of the polymer compound P-1 (hole transport material) of Example 1 was applied by spin coating to a dry film thickness of 30 nm, and then at 230°C for 60 minutes. Heat treatment is performed to form a hole transport layer. As a result, a hole transport layer having a thickness (dry film thickness) of 30 nm was formed over the hole injection layer.

In octane, the following structure:

A quantum dot dispersion is prepared by dispersing blue quantum dots of ZnTeSe/ZnSe/ZnS (core/shell/shell; average diameter = about 10 nm) having 2.0% by mass. On the other hand, the hole transport layer (particularly the polymer compound P-1) is insoluble in octane. This quantum dot dispersion was applied onto the hole transport layer by spin coating to a dry film thickness of 30 nm and then dried. As a result, a quantum dot light emitting layer having a thickness (dry film thickness) of about 30 nm is formed over the hole transport layer. On the other hand, the light generated by irradiating the quantum dot dispersion with ultraviolet light had a central wavelength of 462 nm and a full width at half maximum of 30 nm.

Then, ZnCl ₂ is dissolved in ethanol as a solvent at a concentration of 0.7 mol/L to prepare a ZnCl ₂ coating solution. The prepared ZnCl ₂ coating liquid was slowly dropped so as to cover the light emitting surface formed above, left for 60 seconds, rotated at 1,000 rpm for 40 seconds by spin coating method, and heated and dried at 80° C. for 20 minutes. Subsequently, ethanol was slowly dropped so as to cover the light emitting surface formed above, and the operation of rotating at 1,000 rpm by spin coating was repeated twice, followed by heating and drying at 80 DEG C for 20 minutes.

A ZnMgO dispersion is prepared by dispersing ZnMgO at 1% by mass in ethanol. A ZnMgO dispersion was coated on the quantum dot light emitting layer by spin coating to a dry film thickness of about 20 nm, and dried by heating at 80° C. for 30 minutes. As a result, an electron transport layer having a thickness (dry film thickness) of about 20 nm is formed on the quantum dot light emitting layer.

Aluminum (Al) is deposited on the electron transport layer using a vacuum deposition apparatus. As a result, a second electrode (cathode) having a thickness of about 100 nm is formed over the electron transport layer. In this way, the quantum dot electroluminescence element 1 is obtained.

Example 8

Quantum dot electroluminescent device 2 was fabricated in the same manner as in Example 7, except that the polymer compound P-2 of Example 2 was used instead of the polymer compound P-1 in Example 7.

Example 9

Quantum dot electroluminescence device 3 was fabricated in the same manner as in Example 7, except that the polymer compound P-3 of Example 3 was used instead of the polymer compound P-1 in Example 7.

Example 10

Quantum dot electroluminescent device 4 was fabricated in the same manner as in Example 7, except that the polymer compound P-4 of Example 4 was used instead of the polymer compound P-1 in Example 7.

Example 11

Quantum dot electroluminescent device 5 was fabricated in the same manner as in Example 7, except that the polymer compound P-5 of Example 5 was used instead of the polymer compound P-1 in Example 7.

Example 12

Quantum dot electroluminescence device 6 was fabricated in the same manner as in Example 7, except that the polymer compound P-6 of Example 6 was used instead of the polymer compound P-1 in Example 7.

Comparative Example 2

In Example 7, instead of the polymer compound P-1, poly[(9,9-dioctyl fluorenyl-2,7-diyl)-co- (4,4'-(N- (4-sec-butyl phenyl) diphenyl amine)] (TFB) (manufactured by Luminescence Technology Corp.), but the same operations as in Example 7 were carried out to prepare comparative quantum dot electroluminescent device 1. On the other hand, , The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of TFB were measured by SEC.As a result, the weight average molecular weight and Mw/Mn of TFB were 359,000 g/mol and 3.4, respectively.

(TFB)

Comparative Example 3

Comparative quantum dot electroluminescence device 2 was fabricated in the same manner as in Example 7, except that the polymer compound P-7 of Comparative Example 1 was used instead of the polymer compound P-1 in Example 7.

[Evaluation of quantum dot electroluminescence device 1]

For the quantum dot electroluminescence devices 1 to 6 prepared in Examples 7 to 12 and the comparative quantum dot electroluminescence devices 1 and 2 prepared in Comparative Examples 2 and 3, the emission characteristics (V@5mA) were determined by the following method. (V), ΔV (V)) and luminescence lifetime were evaluated, and the results are shown in Table 1 below.

(V@5mA (V))

When a voltage is applied to each quantum dot electroluminescence element using a DC constant voltage power supply (source meter, manufactured by KEYENCE), a current starts to flow at a constant voltage, and the quantum dot electroluminescence element emits light. . A voltage (V) at a current density of 5 mA/cm ² is defined as a driving voltage “V@5 mA (V)”.

(ΔV (V) and luminous lifetime)

Using a direct current constant voltage power source (source meter manufactured by Keyence Corporation), a predetermined voltage is applied to each quantum dot electroluminescence element to cause each quantum dot electroluminescence element to emit light. While measuring the light emission of the quantum dot electroluminescence device with a luminance measuring device (manufactured by Tafcon Co., Ltd., SR-3), the current is gradually increased, and when the luminance reaches 650 nit (cd/m ² ), the current is left constant. . The time until the luminance value measured by the luminance measuring device gradually decreases to 90% of the initial luminance is referred to as "LT90 (hr)". Further, the difference between the initial voltage (V) when the luminance is 650 nit (cd/m ² ) and the voltage (V) when the luminance is 50% of the initial luminance is ΔV (V). On the other hand, in Table 1 below, LT90 (hr) of each element is a relative value when LT90 (hr) of comparative quantum dot electroluminescence element 2 of Comparative Example 2 is set to 1.0, and "LT90 TFB = 1 It is shown in the column of ".

high molecular compound V@5mA (V) ΔV (V) LT90 TFB=1 Example 7 P-1 2.7 0.37 4.6 Example 8 P-2 2.8 0.37 5.3 Example 9 P-3 2.7 0.38 2.0 Example 10 P-4 2.9 0.36 6.9 Example 11 P-5 2.7 0.38 8.1 Example 12 P-6 2.9 0.36 9.9 Comparative Example 2 TFB 3.0 0.40 1.0 Comparative Example 3 P-7 2.8 0.38 1.1

From the results of Table 1, the quantum dot electroluminescence devices 1 to 6 of the examples are capable of exhibiting significantly higher durability (significantly longer luminescence lifetime) than the comparative quantum dot electroluminescence devices 1 and 2. can know that

[Evaluation of characteristics of each polymer compound]

For the polymer compounds P-1 to P-6 and TFB of Examples 1 to 6, and the polymer compound P-7 of Comparative Example 1, the HOMO level (eV) and glass transition temperature (T _g ) (℃ ) was measured, and the results are shown in Table 2 below.

In addition, the characteristics of the model device were evaluated for the polymer compounds P-1 to P-6 and TFB of Examples 1 to 6 and the polymer compound P-7 of Comparative Example 1 by the following method, and the results are shown in Table 2 below. indicated in

(Measurement of HOMO level)

Each high molecular compound is dissolved in xylene to a concentration of 1% by mass to prepare a coating liquid. A film was formed on a UV-cleaned glass substrate with ITO by spin coating using the coating liquid prepared above at a rotation rate of 2,000 rpm, and then dried on a hot plate at 150°C for 30 minutes for measurement. make a sample The HOMO level of the sample is measured using a photoelectron spectrometer (AC-3, manufactured by Riken Keiki Co., Ltd.) in air. At this time, the rising tangential intersection is calculated from the measurement result and is set as the HOMO level (eV). On the other hand, the HOMO level is usually a negative value.

(Glass transition temperature (T _g ))

Each polymer compound was heated up to 300°C at a temperature rise rate of 10°C/min using a differential scanning calorimeter (DSC) (product name: DSC6000, manufactured by Seiko Scientific Co., Ltd.), and the sample held for 10 minutes was held at a temperature drop rate of 10°C/min. After cooling to 25°C in minutes and holding for 10 minutes, the temperature was raised to 300°C at a temperature rise rate of 10°C/minute and measurement was performed. After completion of the measurement, it is cooled to room temperature (25°C) at 10°C/min.

(Reference experiment: Characteristic evaluation of model device)

(Reference Example 1)

As a first electrode (anode), a glass substrate on which a stripe-shaped indium tin oxide (ITO) film is formed to a film thickness of about 150 nm is prepared. On the glass substrate, PEDOT-PSS (manufactured by Sigma-Aldrich) was applied by spin coating to a dry film thickness of about 30 nm and dried to form a hole injection layer with a dry film thickness of about 30 nm.

Thereafter, the polymer compound P-1 (hole transport material) of Example 1 was dissolved in xylene as a solvent at a concentration of 1% by mass to prepare a polymer coating liquid. The polymer coating liquid prepared above is applied onto the hole injection layer formed above by spin coating to a dry film thickness of about 30 nm, and heat-dried at 150° C. for 30 minutes. This forms a hole transport layer with a dry film thickness of about 30 nm.

Separately, a quantum dot dispersion was prepared in the same manner as in Example 7. This quantum dot dispersion was applied onto the hole transport layer formed above by spin coating to a dry film thickness of about 20 nm, and dried by heating at 80° C. for 30 minutes. In this way, a quantum dot light-emitting layer having a dry film thickness of about 20 nm is formed.

Then, ZnCl ₂ is dissolved in ethanol as a solvent at a concentration of 0.7 mol/L to prepare a ZnCl ₂ coating liquid. The ZnCl ₂ coating solution prepared above is slowly dripped so as to cover the quantum dot light emitting layer formed above, left for 60 seconds, rotated at 1,000 rpm for 40 seconds by spin coating, and heated and dried at 80 ° C. for 20 minutes. Subsequently, ethanol was slowly added dropwise so as to cover the light emitting layer formed above, and the rotation at 1000 rpm by spin coating was repeated twice, followed by heating and drying at 80 DEG C for 20 minutes.

α-NPD (N, N'-di-1-naphthyl-N, N'-diphenyl benzidine) and HAT-CN (di pyrazino [2,3-f:2',3'-h] quinox Saline-2,3,6,7,10,11-hexacarbonitrile) was sequentially deposited on the hole transport layer formed above by a vacuum deposition method to obtain a thickness of about 36 nm and about 10 nm, respectively. layers are formed, and a hole only device 1 is fabricated.

(Reference example 2)

A hole-only device 2 was fabricated in the same manner as in Reference Example 1, except that the polymer compound P-2 of Example 2 was used instead of the polymer compound P-1 in Reference Example 1.

(Reference Example 3)

A hole-only element 3 was fabricated in the same manner as in Reference Example 1, except that the polymer compound P-3 of Example 3 was used instead of the polymer compound P-1 in Reference Example 1.

(Reference example 4)

A hole-only element 4 was fabricated in the same manner as in Reference Example 1, except that the polymer compound P-4 of Example 4 was used instead of the polymer compound P-1 in Reference Example 1.

(Reference Example 5)

A hole-only device 5 was fabricated in the same manner as in Reference Example 1, except that the polymer compound P-5 of Example 5 was used instead of the polymer compound P-1 in Reference Example 1.

(Reference Example 6)

A hole-only device 6 was fabricated in the same manner as in Reference Example 1, except that the polymer compound P-6 of Example 6 was used instead of the polymer compound P-1 in Reference Example 1.

(Comparative reference example 1)

Comparative hole-only device 1 was fabricated in the same manner as in Reference Example 1, except that TFB of Comparative Example 2 was used in place of the polymer compound P-1 in Reference Example 1.

(Comparative reference example 2)

Comparative hole-only device 2 was fabricated in the same manner as in Reference Example 1 except for using the polymer compound P-7 of Comparative Example 1 in place of the polymer compound P-1 in Reference Example 1.

Hole-only devices 1 to 6 obtained above and comparative hole-only devices 1 and 2 were evaluated for Hole Current Density @ 8V by the following method.

(Hole Current Density @8V)

For each hall-only element, the voltage was gradually increased using a direct current constant voltage power supply (source meter, manufactured by Keyence Corporation) to measure the current value at 8 V, and the current value per unit area (current value) from the area of each element Density (A/m ² )) is calculated, and this is referred to as “Hole Current Density @8V”. The results are shown in Table 2 below. On the other hand, in Table 2 below, the current density of each hole-only element is expressed as a relative value when the current density of comparative hole-only element 1 of Reference Comparative Example 1 is set to 1.00, and in Table 2 below, "HOD @ 8V TFB = 1”.

high molecular compound HOD@8V TFB=1 HOMO (eV) T _g (℃) Reference example 1 P-1 3.95 5.49 176 Reference example 2 P-2 4.25 5.49 128 Reference example 3 P-3 16.05 5.49 79 Reference example 4 P-4 4.45 5.49 115 Reference Example 5 P-5 10.08 5.49 97 Reference example 6 P-6 10.22 5.49 88 Comparative Reference Example 1 TFB 1.00 5.54 150 Comparative Reference Example 2 P-7 2.50 5.47 183

As clearly shown from Table 2, it can be seen that the devices of Reference Examples 1 to 6 are superior in hole injection/transport properties compared to the devices of Comparative Reference Examples 1 and 2. In this respect, the device according to one embodiment is considered to have a long lifespan effect.

100... Electroluminescence element (EL element),
110... Board,
120... a 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 (20)

A polymer compound containing a structural unit represented by Formula 1 below:
(Formula 1)

In Formula 1,
R ¹¹ to R ¹⁴ , R ²¹ , R ²² , R ³¹ and R ³² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms;
L ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 14 ring atoms;
x is 0, 1 or 2, and when x is 2, L ¹ are each the same or different;
L ² represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, wherein L ² is Ar ¹ can form a ring with
Ar ¹ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, and Ar ² or L ² and form a circle,
Ar ² is (i) a straight-chain or branched hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 25 ring atoms, or an aromatic group having 5 to 14 ring atoms An aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with a heterocyclic ring group, or (ii) a straight-chain or branched hydrocarbon group having 3 to 12 carbon atoms and 1 to 12 carbon atoms, or a number of ring atoms Represents an aromatic heterocyclic ring group having 5 or more and 14 or less ring atoms which may be substituted with an aromatic hydrocarbon group of 6 or more and 25 or less or an aromatic heterocyclic ring group of 5 or more and 14 or less ring atoms, wherein Ar ² is You may form a ring with ^Ar1 . The polymer compound of claim 1, further comprising a structural unit represented by Formula 2 below:
(Formula 2)

In Formula 2,
R ⁴¹ to R ⁴⁴ , R ²³ , R ²⁴ , R ³³ and R ³⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, wherein R ⁴¹ to R ⁴⁴ are represented by the formula (1) is different from R ¹¹ to R ¹⁴ of
L ³ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms or a substituted or unsubstituted aromatic heterocyclic ring group having 5 to 14 ring atoms;
y is 0, 1 or 2, and when y is 2, L ³ are each the same or different;
L ⁴ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, wherein L ⁴ is Ar ³ can form a ring with
Ar ³ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, and also represents Ar ⁴ or L ⁴ and form a circle,
Ar ⁴ is (i) a straight-chain or branched hydrocarbon group having 1 to 12 carbon atoms, or a branched hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 25 ring atoms, or an aromatic group having 5 to 14 ring atoms An aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with a heterocyclic ring group, or (ii) a straight-chain or branched hydrocarbon group having 3 to 12 carbon atoms and 1 to 12 carbon atoms, or a number of ring atoms Represents an aromatic heterocyclic ring group having 5 or more and 14 or less ring atoms which may be substituted with an aromatic hydrocarbon group of 6 or more and 25 or less or an aromatic heterocyclic ring group of 5 or more and 14 or less ring atoms, wherein Ar ⁴ is You may form a ring with Ar ³ . In claim 2, R ¹¹ to R ¹⁴ in Formula 1 each independently represent a hydrocarbon group having 3 to 9 carbon atoms, and R ⁴¹ to R ⁴⁴ in Formula 2 each independently have 10 to 14 carbon atoms. A polymer compound representing a hydrocarbon group of . In claim 2, R ²¹ , R ²² , R ³¹ , R ³² , L ¹ , x, L ² , Ar ¹ and Ar ² in Formula 1 are each, independently, R ²³ , R ²⁴ in Formula 2 , R ³³ , R ³⁴ , L ³ , y, L ⁴ , Ar ³ and Ar ⁴ , the same polymer compound. The polymer compound of claim 2, wherein the structural unit represented by Chemical Formula 2 is included in an amount of 1 mole or more and 20 moles or less with respect to 1 mole of the structural unit represented by Chemical Formula 1. The polymer compound of claim 1, wherein the following structure of Chemical Formula 1 includes a structure selected from Group 1 below:

(Group 1)

In Group 1, R ⁵¹ to R ⁵⁴ each independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 12 carbon atoms, or a group selected from the following groups,

;
In Group 1, Ar ⁴¹¹ to Ar ⁴¹⁷ each independently represent a group selected from the following groups;

In the above formulas, R ⁵⁵ to R ⁵⁷ each independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 12 carbon atoms or 3 to 12 carbon atoms, or a group selected from the following groups;

In the above formulas, R ⁵⁸ and R ⁵⁹ each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms. The polymer compound of claim 2, wherein the following structure of Chemical Formula 2 includes a structure selected from Group 1 below:

(Group 1)

In Group 1, R ⁵¹ to R ⁵⁴ each independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms, or a group selected from the following groups:

Ar ⁴¹¹ to Ar ⁴¹⁷ in Group 1 each independently represent a group selected from the following groups:

In the above formulas, R ⁵⁵ to R ⁵⁷ each independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms, or a group selected from the following groups:

In the above formulas, R ⁵⁸ and R ⁵⁹ each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms. In claim 2, the following structure of Formula 1:

Or the following structure of Formula 2:

At least one of the polymeric compounds having a structure selected from Group 2 below:
(Group 2)

In Group 2 above, Ar ⁴¹² to Ar ⁴¹⁶ each independently represent a group selected from the following groups:

In the above formulas, R ⁵⁵ to R ⁵⁷ each independently represent a straight-chain or branched alkyl group having 4 to 10 carbon atoms and 4 to 10 carbon atoms. The polymer compound of claim 1, wherein the structural unit represented by Formula 1 is represented by one or more of the following structural units:

In the structural units,
R ¹¹ to R ¹⁴ , R ²¹ , and R ²² are defined as in Formula 1 above,
Ar ⁴¹¹ to Ar ⁴¹⁷ each independently represent a group selected from the following groups:

In the above formulas, R ⁵⁵ to R ⁵⁷ each independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms, or a group selected from the following groups:

In the above formulas, R ⁵⁸ and R ⁵⁹ each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms. The polymer compound of claim 2, wherein the structural unit represented by Formula 2 is represented by one or more of the following structural units:

Among the structural units,
R ⁴¹ to R ⁴⁴ , R ²³ and R ²⁴ are defined as in Formula 2 above,
Ar ⁴¹² to Ar ⁴¹⁶ each independently represents a group selected from the group below:

In the above formula, R ⁵⁵ to R ⁵⁷ each independently represent a straight-chain or branched alkyl group having 4 to 10 carbon atoms and 4 to 10 carbon atoms. An electroluminescent device material comprising the polymer compound of claim 1. 12. The electroluminescent device material according to claim 11, wherein the polymer compound further comprises a structural unit represented by Formula 2 below:
(Formula 2)

In Formula 2,
R ⁴¹ to R ⁴⁴ , R ²³ , R ²⁴ , R ³³ and R ³⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, wherein R ⁴¹ to R ⁴⁴ are represented by the formula (1) is different from R ¹¹ to R ¹⁴ of
L ³ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 ring atoms or a substituted or unsubstituted aromatic heterocyclic ring group having 5 to 14 ring atoms;
y is 0, 1 or 2, and when y is 2, L ³ are each the same or different;
L ⁴ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, wherein L ⁴ is Ar ³ can form a ring with
Ar ³ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 25 or less ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 or more and 14 or less ring atoms, and Ar ⁴ or L ⁴ and form a circle,
Ar ⁴ is (i) a straight-chain or branched hydrocarbon group having 1 to 12 carbon atoms, or a branched hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 25 ring atoms, or an aromatic group having 5 to 14 ring atoms An aromatic hydrocarbon group having 6 to 25 ring atoms which may be substituted with a heterocyclic ring group, or (ii) a straight-chain or branched hydrocarbon group having 3 to 12 carbon atoms and 1 to 12 carbon atoms, or a number of ring atoms Represents an aromatic heterocyclic ring group having 5 to 14 ring atoms which may be substituted with an aromatic hydrocarbon group of 6 or more and 25 or less or an aromatic heterocyclic ring group of 5 to 14 ring atoms, wherein Ar ⁴ is You may form a ring with Ar ³ . An electroluminescence device comprising a first electrode, a second electrode, and one or more layers of organic film 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 claim 1. 14. The electroluminescence device of claim 13, wherein the organic layer containing the polymer compound is a hole transport layer or a hole injection layer. The electroluminescent device of claim 13, wherein the organic layer further comprises a light emitting layer including semiconductor nanoparticles or organometallic complexes. An electroluminescence device comprising a first electrode, a second electrode, and one or more layers of organic film 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 claim 2. 17. The electroluminescent device of claim 16, wherein the organic layer containing the polymer compound is a hole transport layer or a hole injection layer. The electroluminescence device of claim 16, wherein the organic layer further comprises a light emitting layer including semiconductor nanoparticles or organometallic complexes. An electronic device comprising the electroluminescence device of claim 13. An electronic device comprising the electroluminescence device of claim 16.

Images