KR20220074749A - Organic light emitting device - Google Patents

Abstract

The present invention is an anode; cathode; and a light emitting layer provided between the anode and the cathode, wherein the organic light emitting device is provided between the light emitting layer and the anode, the first compound comprising a unit of Formula 1-1 of the present invention; A first organic material layer comprising the second compound of Formula 1-2 of the present invention, and a second composition comprising a composition comprising a copolymer of Formula 2 below, or a cured product thereof, which is provided between the light emitting layer and the first organic layer It relates to an organic light emitting device comprising an organic material layer.

Description

Organic light emitting device {ORGANIC LIGHT EMITTING DEVICE}

The present invention claims the benefit of the filing date of Korean Patent No. 10-2020-0162773 filed with the Korean Intellectual Property Office on November 27, 2020, the entire contents of which are included in the present invention.

The present invention relates to an organic light emitting device.

The organic light emitting phenomenon is one example in which electric current is converted into visible light by an internal process of a specific organic molecule. The principle of the organic light emitting phenomenon is as follows. When the organic material layer is placed between the anode and the cathode, when a current is applied between the two electrodes, electrons and holes are respectively injected into the organic material layer from the cathode and the anode. Electrons and holes injected into the organic material layer recombine to form excitons, and the excitons fall back to the ground state and emit light. An organic light emitting device using this principle may generally include a cathode, an anode, and an organic material layer disposed therebetween, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and an electron transport layer.

Conventionally, a deposition process has been mainly used to manufacture an organic light emitting device. However, when an organic light emitting diode is manufactured by a deposition process, material loss occurs a lot, and thus material use efficiency is low. On the other hand, the solution process is much more economical than the deposition process because in theory 100% of the material can be used. However, conventional organic light emitting device materials for deposition have low solubility and have problems with coating properties in the thin film formation process.

Therefore, there is a need for a material for solution processing capable of securing thin film properties and device performance.

Korean Patent Publication No. 10-2012-0112277

An object of the present invention is to provide an organic light emitting device having excellent efficiency and/or lifetime characteristics.

One embodiment of the present invention is an anode; cathode; and a light emitting layer provided between the anode and the cathode, wherein the organic light emitting device comprises:

A first organic material layer provided between the light emitting layer and the anode and comprising a second compound of Formula 1-2, and

It provides an organic light emitting device that is provided between the light emitting layer and the first organic material layer, and includes a composition including a copolymer of Formula 2 or a second organic material layer including a cured product thereof.

[Formula 1-2]

In Formula 1-2,

R15 to R18 are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted haloaryl group. a group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted arylalkyl group, -ORa, -SRb, -C(=O)Rc, or a curable group, and Ra to Rc are the same as or different from each other, and each independently is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group,

At least one of R15 to R18 is -CH=CH-Rx or an aryl group substituted with -CH=CH-Rx, wherein Rx is an alkyl group or an aryl group,

n15 to n18 are each an integer from 0 to 3, n1 to n4 are each an integer from 0 to 5, n1+n15, n2+n16, n3+n17 and n4+n18 are each an integer from 1 to 5, and m1 to m4 is an integer from 0 to 4, respectively;

[Formula 2]

In Formula 2,

A is a monomer unit comprising at least one triarylamine group,

B' is a monomeric unit having at least three points of attachment in the copolymer,

C' is an aromatic monomer unit or a deuterated analog thereof,

E is the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted germanium group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylamino group; a substituted or unsubstituted siloxane group; And it is selected from the group consisting of a substituted or unsubstituted curable group,

a, b and c are mole fractions, a+b+c=1, a≠0, and b≠0.

The first organic layer material of the organic light emitting diode according to an exemplary embodiment of the present invention has excellent hole injection ability because charge mobility is increased and energy level is well matched.

In addition, in the organic light emitting device according to an exemplary embodiment of the present invention, since the copolymer of Formula 2 is included in the second organic layer together with the first organic layer material, hole injection and hole transport in the device are smoothly performed, resulting in a low driving voltage and / Alternatively, a device having a long life can be obtained.

1 illustrates an example of an organic light emitting device according to an exemplary embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

An exemplary embodiment of the present invention provides the following organic light emitting device.

anode; cathode; and a light emitting layer provided between the anode and the cathode, wherein the organic light emitting device comprises:

A first organic material layer provided between the light emitting layer and the anode and comprising a second compound of Formula 1-2, and

An organic light emitting device that is provided between the light emitting layer and the first organic material layer, and includes a second organic material layer comprising a composition comprising a copolymer of Formula 2 or a cured product thereof:

[Formula 1-2]

In Formula 1-2,

R15 to R18 are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted haloaryl group. a group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted arylalkyl group, -ORa, -SRb, -C(=O)Rc, or a curable group, and Ra to Rc are the same as or different from each other, and each independently is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group,

At least one of R15 to R18 is -CH=CH-Rx or an aryl group substituted with -CH=CH-Rx, wherein Rx is an alkyl group or an aryl group,

n15 to n18 are each an integer from 0 to 3, n1 to n4 are each an integer from 0 to 5, n1+n15, n2+n16, n3+n17 and n4+n18 are each an integer from 1 to 5, and m1 to m4 is an integer from 0 to 4, respectively;

[Formula 2]

In Formula 2,

A is a monomer unit comprising at least one triarylamine group,

B' is a monomeric unit having at least three points of attachment in the copolymer,

C' is an aromatic monomer unit or a deuterated analog thereof,

E is the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted germanium group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylamino group; a substituted or unsubstituted siloxane group; And it is selected from the group consisting of a substituted or unsubstituted curable group,

a, b and c are mole fractions, a+b+c=1, a≠0, and b≠0.

The first organic material layer material of the organic light emitting diode according to an exemplary embodiment of the present invention has excellent hole injection ability by increasing hole mobility and smooth matching between energy levels. In addition, by including the copolymer of Chemical Formula 2 in the second organic layer together with the first organic layer material, hole injection and hole transport in the device are smoothly performed to obtain a device having a low driving voltage, high efficiency and/or long lifespan. have.

In the present invention, when a member (layer) is said to be located “on” another member (layer), this is not only when a member (layer) is in contact with another member but also between two members (layers). (layer) is also included.

In the present invention, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

In the present invention, the 'layer' is a meaning compatible with a 'film' mainly used in the present technical field, and refers to a coating covering a desired area. The size of the 'layers' is not limited, and each of the 'layers' may have the same size or different sizes. According to an exemplary embodiment, the size of the 'layer' may be the same as the entire device, may correspond to the size of a specific functional area, and may be as small as a single sub-pixel.

Unless defined otherwise herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. All publications, patent applications, patents and other references mentioned herein are incorporated herein by reference in their entirety, and in the event of a conflict the present invention, including definitions, will control unless a specific passage is recited. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

In the present invention, the "curable group" refers to a group capable of inducing crosslinking through heat treatment and/or light exposure. Crosslinking may be generated while radicals generated while decomposing carbon-carbon multiple bonds or cyclic structures are connected by heat treatment or light irradiation.

According to an exemplary embodiment of the present invention, the curable group may be selected from the following structures.

In the above structures,

Lc is a direct bond; -O-; -S-; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

lc1 is 1 or 2,

When lc1 is 2, Lc is the same as or different from each other,

R21 is a substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present invention, Lc is a direct bond; methylene group; or an ethylene group.

In another exemplary embodiment, Lc is a direct bond.

According to an exemplary embodiment of the present invention, R21 is a methyl group; or an ethyl group.

According to another exemplary embodiment, R21 is a methyl group.

In the present invention, the term "deuterated" is intended to mean that at least one available H has been replaced by D. A compound or group that is X% deuterated has X% of available H replaced with D. A deuterated compound or group is one in which deuterium is present at greater than 100 times its natural abundance level.

According to an exemplary embodiment of the present invention, at least one of the first compound to be described later, the second compound, and the copolymer of Formula 2 may be deuterated. The deuterated compound is then in a similar manner using deuterated precursor materials, or more generally, a Lewis acid H/D exchange catalyst such as trifluoromethanesulfonic acid, aluminum trichloride or ethyl aluminum die It can be prepared by treating an undeuterated compound with a deuterated solvent such as benzene-d6 in the presence of chloride.

In the present invention, "deuteration rate" or "deuterium substitution rate" is nuclear magnetic resonance (1H NMR), TLC / MS (Thin-Layer Chromatography / Mass Spectrometry), or GC / MS (Gas Chromatography / Mass Spectrometry), such as It can be confirmed by a known method.

As used herein, "deuterated analog" refers to a structural analog of a compound or group in which one or more available hydrogens have been replaced with deuterium.

According to an exemplary embodiment of the present invention, at least one of the first compound to be described later, the second compound, and the copolymer of Formula 2 is 5% to 100% deuterated.

According to an exemplary embodiment of the present invention, at least one of the first compound to be described later, the second compound, and the copolymer of Formula 2 is 10% to 100% deuterated.

According to an exemplary embodiment of the present invention, at least one of the first compound to be described later, the second compound, and the copolymer of Formula 2 is 40% to 100% deuterated.

According to an exemplary embodiment of the present invention, at least one of the first compound to be described later, the second compound, and the copolymer of Formula 2 is 50% to 100% deuterated.

According to an exemplary embodiment of the present invention, at least one of the first compound to be described later, the second compound, and the copolymer of Formula 2 may be deuterated. When deuterium is substituted for the hydrogen position, the chemical properties of the compound hardly change. However, since deuterium has twice the atomic weight of hydrogen, the physical properties of the deuterated compound change. For example, a deuterated compound has a lower vibrational energy level, and a decrease in the vibrational energy level can prevent a decrease in intermolecular van der Waals force or a decrease in quantum efficiency due to collisions due to intermolecular vibration. Thus, devices comprising deuterated compounds have improved efficiency and lifetime.

Examples of substituents in the present invention are described below, but are not limited thereto.

", "-----" 및 "*"는 각각 연결되는 부위를 의미한다.In the present invention, "

", "-----" and "*" mean a site to be connected, respectively.

In the present invention, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent is substitutable, When two or more substituents are substituted, two or more substituents may be the same as or different from each other.

In the present invention, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; an alkyl group; cycloalkyl group; alkoxy group; silyl group; aryl group; germanium group; hardening group; And it means that it is substituted with one or more substituents selected from the group consisting of a heteroaryl group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents.

In the present invention, the halogen group is a fluoro group (-F), a chloro group (-Cl), a bromo group (-Br) or an iodo group (-I).

In the present invention, the alkyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but may be 1 to 20. According to another exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 10. Specific examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, etc. , but not limited to these. Unless otherwise specified, the alkyl group includes a cycloalkyl group.

In the present invention, the cycloalkyl group is not particularly limited, but may have 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. Specific examples of the cycloalkyl group include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.

In the present invention, the alkoxy group may be straight-chain or branched. The number of carbon atoms of the alkoxy group is not particularly limited, but may be 1 to 20 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, n-propoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, n-no It may be a nyloxy group, an n-decyloxy group, or the like, but is not limited thereto.

In the present invention, the amino group means -NRR', and R and R' are the same as or different from each other, and may each independently be an alkyl group, an aryl group, or a deuterated analog thereof.

In the present invention, the aryloxy group means -OR, the R means an aryl group.

In the present invention, the germanium group means -GeRR'R", wherein R, R' and R" are the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group, a deuterated alkyl group, a fluoroalkyl group, a deuterated partially-fluorinated alkyl group, an aryl group, or a deuterated aryl group.

In the present invention, the silyl group means -SiRR'R", wherein R, R' and R" are the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group, a deuterated alkyl group, a fluoroalkyl group, an aryl group or a deuterated aryl group, in some embodiments wherein at least one carbon in the alkyl group is replaced with Si when R, R', R" are each an alkyl group.

In the present invention, the siloxane group means -SiR ₂ OSiR ₃ , wherein R is the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group, a deuterated alkyl group, a fluoroalkyl group, an aryl group, or a deuterated an aryl group, and in some embodiments, when R is an alkyl group, at least one carbon in the alkyl group is replaced with Si.

In the present invention, the siloxy group means -OSiR ₃ , wherein R is the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group, a deuterated alkyl group, a fluoroalkyl group, an aryl group, or a deuterated aryl it's gi

In the present invention, the aryl group is not particularly limited, but may have 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

In the present invention, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

,

등의 스피로플루오레닐기,

(9,9-디메틸플루오레닐기), 및

(9,9-디페닐플루오레닐기) 등의 치환된 플루오레닐기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

spirofluorenyl groups such as

(9,9-dimethyl fluorenyl group), and

a substituted fluorenyl group such as (9,9-diphenylfluorenyl group). However, the present invention is not limited thereto.

In the present invention, the heteroaryl group is an aromatic ring group including at least one of N, O, P, S, Si and Se as heteroatoms, and the number of carbon atoms is not particularly limited, but may be 2 to 60 carbon atoms. According to an exemplary embodiment, the heteroaryl group has 2 to 30 carbon atoms. Examples of the heteroaryl group include a pyridine group, a pyrrole group, a pyrimidine group, a pyridazine group, a furan group, a thiophene group, a benzothiophene group, a benzofuran group, a dibenzothiophene group, a dibenzofuran group, a carbazole group and the like, but is not limited thereto.

In the present invention, the description of the above-described alkyl group is applied except that the alkylene group is divalent.

In the present invention, the description of the above-described aryl group is applied except that the arylene group is divalent.

In the present invention, the description of the above-mentioned heteroaryl group is applied except that the heteroarylene group is divalent.

In the present invention, the haloalkyl group and the haloaryl group are an alkyl group substituted with a halogen group and an aryl group substituted with a halogen group, respectively.

In the present invention, the aliphatic ring is a hydrocarbon ring that is not aromatic, and examples thereof include the above-described cycloalkyl group and adamantyl group.

In the present invention, the content regarding the aryl group described above may be applied to the aromatic ring.

In the present invention, "adjacent" group means a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom in which the substituent is substituted. can For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups.

In the present invention, in the substituted or unsubstituted ring formed by bonding to each other, "ring" is a hydrocarbon ring; or a heterocyclic ring. The hydrocarbon ring may be an aromatic, aliphatic, or condensed ring of aromatic and aliphatic. The description of the heterocyclic group may be applied except that the heterocycle is divalent.

In the present invention, the description of the above-described aryl group may be applied, except that the aromatic hydrocarbon ring is divalent.

In the present invention, the description of the cycloalkyl group described above may be applied, except that the aliphatic hydrocarbon ring is divalent.

In the present invention, the mole fraction means the ratio of the number of moles of a given component to the total number of moles of all components.

In the present invention, "unit" or "monomer unit" is intended to mean a repeating unit in a polymer or copolymer.

Hereinafter, the second compound of Formula 1-2 will be described.

According to an exemplary embodiment, the second compound is represented by the following Chemical Formula 1-2.

[Formula 1-2]

In Formula 1-2,

R15 to R18 are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted haloaryl group. a group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted arylalkyl group, -ORa, -SRb, -C(=O)Rc, or a curable group, and Ra to Rc are the same as or different from each other, and each independently is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group,

At least one of R15 to R18 is -CH=CH-Rx or an aryl group substituted with -CH=CH-Rx, wherein Rx is an alkyl group or an aryl group,

n15 to n18 are each an integer from 0 to 3, n1 to n4 are each an integer from 0 to 5, n1+n15, n2+n16, n3+n17 and n4+n18 are each an integer from 1 to 5, and m1 to m4 is an integer from 0 to 4, respectively;

According to an exemplary embodiment, -CH=CH-Rx in Formula 1-2 may be selected from the following structures.

* is a binding site, and Rx is as defined in claim 1.

According to an exemplary embodiment, in Formula 1-2, the aryl group substituted with -CH=CH-Rx is a phenyl group substituted with -CH=CH-Rx, a biphenyl group substituted with -CH=CH-Rx, or -CH= It may be a terphenyl group substituted with CH-Rx.

According to an exemplary embodiment, the aryl group substituted with -CH=CH-Rx in Formula 1-2 may be selected from the following structures.

In the above structure, Rx and Rx' are the same as or different from each other, and each independently represents an alkyl group or an aryl group.

According to one embodiment, Rx and Rx' are the same as or different from each other, and each independently represents a C1-C6 alkyl group or a C6-C20 aryl group.

According to a specific example, Rx and Rx' are the same as or different from each other, and each independently represents a methyl group, an ethyl group, a phenyl group, a biphenyl group, or a naphthyl group.

According to another specific example, Rx and Rx' are methyl groups.

According to an exemplary embodiment, one or two of R15 to R18 in Formula 1-2 is -CH=CH-Rx or an aryl group substituted with -CH=CH-Rx.

According to another exemplary embodiment, R15 to R18 in Formula 1-2 are the same as or different from each other, and each independently represents an aryl group substituted with -CH=CH-Rx or -CH=CH-Rx.

According to an exemplary embodiment, in R15 to R18 of Formula 1-2, a group other than an aryl group substituted with -CH=CH-Rx or -CH=CH-Rx is a halogen group, a substituted or unsubstituted haloalkyl group, a substituted or an unsubstituted haloaryl group, or a curable group.

According to an exemplary embodiment, in R15 to R18 of Formula 1-2, at least one of the groups other than the aryl group substituted with -CH=CH-Rx or -CH=CH-Rx is a curable group.

According to an exemplary embodiment, in R15 to R18 of Formula 1-2, one or two of the groups other than the aryl group substituted with -CH=CH-Rx or -CH=CH-Rx is a curable group.

When at least one of the groups other than the aryl group substituted with -CH=CH-Rx or -CH=CH-Rx among R15 to R18 of Formula 1-2 is a curable group, the curable group may be selected from the following groups. At this time, since the thermosetting group or the photocurable group, which is the curable group, is crosslinked by heat or light, when an additional layer is laminated on the coating layer, the compound of Formula 1-2 included in the coating composition is washed away by the solvent It plays a role in preventing or preventing diffusion into the upper layer. Accordingly, while maintaining the coating layer, it is possible to laminate an additional layer thereon. Furthermore, there is an effect that the chemical resistance of the coating layer to a solvent is increased, and the film retention rate is high. In addition, the effect of the curable group can be expected from the first compound of Chemical Formula 1-1 to be described later, the copolymer of Chemical Formula 2 to be described later, and other additives into which the curable group is introduced.

According to an exemplary embodiment, n15 to n18 are integers from 0 to 3.

According to an exemplary embodiment, n15 to n18 are 0.

According to an exemplary embodiment, n15 to n18 are 1.

According to an exemplary embodiment, at least one of n15 to n18 is 2.

According to an exemplary embodiment, n15 to n18 are 3.

According to an exemplary embodiment, at least one of n15 to n18 is 3.

According to an exemplary embodiment, m1 to m4 are integers of 0 to 4, respectively.

According to an exemplary embodiment, m1 to m4 are 0.

According to an exemplary embodiment, m1 to m4 are integers of 1 to 4, respectively.

According to an exemplary embodiment, m1 to m4 are integers of 1 to 3, respectively.

According to an exemplary embodiment, m1 to m4 are 1 or 2, respectively.

의 부분은

로 표시될 수 있다. 상기 m1=0일 때의 결합 구조는 m2=0, m3=0 또는 m4=0일 때의 결합 구조에도 동일하게 적용될 수 있다.In a specific embodiment, when m1 is 0, R15 is directly bonded to tetrafluorophenyl of Formula 1-2. That is, when m1 = 0, the formula 1-2

part of

can be displayed as The bonding structure when m1=0 may be equally applied to the bonding structure when m2=0, m3=0, or m4=0.

의 부분은

로 표시될 수 있다. 상기 m1=1일 때의 결합 구조는 m2=1, m3=1 또는 m4=1일 때의 결합 구조에도 동일하게 적용될 수 있다.As a specific embodiment, when m1 is 1, R15 is bonded to phenylene bonded to tetrafluorophenylene of Formula 1-2. That is, when m1 = 1, the formula 1-2

part of

can be displayed as The bonding structure when m1=1 may be equally applied to the bonding structure when m2=1, m3=1, or m4=1.

의 부분은

로 표시될 수 있고, 이때 n1은 각각 0 내지 5의 정수이다. 상기 m1=2일 때의 결합 구조는 m2=2, m3=2 또는 m4=2일 때의 결합 구조에도 동일하게 적용될 수 있다.As a specific embodiment, when m1 = 2, the formula 1-2

part of

may be represented as , where n1 is an integer of 0 to 5, respectively. The bonding structure when m1=2 may be equally applied to the bonding structure when m2=2, m3=2, or m4=2.

의 부분은

로 표시될 수 있고, 이때 n1은 각각 0 내지 5의 정수이다. 상기 m1=3일 때의 결합 구조는 m2=3, m3=3 또는 m4=3일 때의 결합 구조에도 동일하게 적용될 수 있다.As a specific embodiment, when m1 = 3, the formula 1-2

part of

may be represented as , where n1 is an integer of 0 to 5, respectively. The bonding structure when m1=3 may be equally applied to the bonding structure when m2=3, m3=3, or m4=3.

Based on the above-described case where m1 is an integer of 0 to 3, the case where m1 to m4 is 4 may also be similarly applied.

According to an exemplary embodiment, n1 to n4 are 0.

According to an exemplary embodiment, n1 to n4 are integers of 1 to 4, respectively.

According to an exemplary embodiment, n1 to n4 are 4.

According to an exemplary embodiment, examples of the second compound include the following compounds.

.

.

According to an exemplary embodiment, the second compound may further include a counter ion. In this case, the type of the counter ion is not particularly limited, and may include a counter ion having the following structure.

In the above structural formula, R41 and R42 are the same as or different from each other, and each independently represent hydrogen or an alkyl group, and R43 to R45 are the same as or different from each other and each independently represent an alkyl group or an aryl group. For example, R41 and R42 are the same as or different from each other and each independently represent a C1-C6 straight-chain or branched alkyl group, such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. In one example, R41 and R42 are a methyl group, R42 is an isopropyl group, and n41 and n42 are 1. For example, R43 to R45 are phenyl groups.

According to an exemplary embodiment of the present invention, the second compound of Formula 1-2 may be included in the hole injection layer in the organic light emitting device. In this case, the second compound of Formula 1-2 may serve as a host of the hole injection layer.

According to another exemplary embodiment of the present invention, the material serving as a host of the hole injection layer may further include other types of compounds in addition to the second compound of Formula 1-2. The other type of compound may be any one selected from the following group, but is not limited thereto.

.

.

Hereinafter, the first compound of Formula 1-1 will be described.

According to an exemplary embodiment of the present invention, the first organic material layer further includes a first compound including a unit represented by the following Chemical Formula 1-1.

[Formula 1-1]

상기 화학식 1-1에 있어서,

In Formula 1-1,

L1 to L3 are the same as or different from each other, and each independently represents a direct bond, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group,

X is CR, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted fluorenylene group,

R1 to R4 are the same as or different from each other, and are each independently a C4 to C8 alkyl group,

R and R5 to R9 are the same as or different from each other, and each independently represents hydrogen, deuterium, an alkyl group, an aryl group, or a heteroaryl group, n5 and n6 are each an integer of 0 to 7, n7 and n8 are each an integer of 0 to 5 an integer, n9 is an integer from 0 to 9, and m is 0 or 1.

The first compound has a curable group in the compound, similarly to the second compound described above, specifically, the curable group is connected to X through a linking group L3, crosslinking is formed by heat or light to prevent diffusion into the upper layer; Effects such as preventing washing out by solvents, stacking additional layers on top of the coating layer by maintaining the coating, increasing chemical resistance to solvents, and increasing film retention can be expected.

In one example, L1 to L3 are the same as or different from each other, and each independently represents a direct bond, a substituted or unsubstituted C1 to C6 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group.

According to another example, L1 to L3 are the same as or different from each other, and each independently represents a direct bond, a C1 to C6 alkylene group, or a C6 to C20 arylene group.

According to another example, L1 to L3 are the same as or different from each other, and each independently represent a direct bond or a C6 to C20 arylene group.

According to another example, L1 to L3 are the same as or different from each other, and each independently represents a direct bond, phenylene, or biphenylylene.

According to an exemplary embodiment, X in Formula 1-1 is CR, where R is hydrogen, deuterium, an alkyl group, an aryl group, or a heteroaryl group. As a specific example, R may be a methyl group.

When X is CR, since it is a non-conjugated structure, the energy level is changed by controlling a portion in which some conjugation is broken, thereby making excellent hole injection.

According to an exemplary embodiment, X in Formula 1-1 is substituted or unsubstituted phenylene, for example, phenylene. When X is phenylene, the energy level may be changed by controlling the wavelength band by conjugation, and thus hole injection may be made smoothly.

According to an exemplary embodiment, X in Formula 1-1 is a substituted or unsubstituted fluorenylene, for example, the fluorenylene group may be substituted or unsubstituted with an alkyl group substituted or unsubstituted with a curable group.

According to an exemplary embodiment, R1 to R4 are the same as or different from each other, and are each independently a C4 to C8 alkyl group, preferably a hexyl group.

According to an exemplary embodiment, R5 and R6 are the same as or different from each other, and each independently represents hydrogen, deuterium, or an aryl group.

According to an exemplary embodiment, R5 and R6 are the same as or different from each other, each independently an aryl group, and n5 and n6 are 1.

According to an exemplary embodiment, R7 and R8 are the same as or different from each other, and each independently represent a C1 to C8 straight-chain or branched alkyl group.

According to an exemplary embodiment, R7 and R8 are the same as or different from each other, and each independently represents a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group, and n7 and n8 are 1.

According to an exemplary embodiment, Chemical Formula 1-1 may be represented by the following Chemical Formula 1-11:

[Formula 1-11]

화학식 1-11에 있어서, 치환기의 정의는 화학식 1-1에서 정의한 바와 같다.

In Formula 1-11, the definition of a substituent is the same as defined in Formula 1-1.

According to an exemplary embodiment, Chemical Formula 1-1 may be represented by the following Chemical Formula 1-12:

[Formula 1-12]

In Formula 1-12, the definition of a substituent is the same as defined in Formula 1-1.

According to an exemplary embodiment, Chemical Formula 1-1 may be represented by the following Chemical Formulas 1-13 or 1-14:

[Formula 1-13]

[Formula 1-14]

In Formulas 1-13 and 1-14, the definition of a substituent is the same as defined in Formula 1-1.

According to an exemplary embodiment, the first compound including the unit of Formula 1-1 may further include Formula 1-3 below.

[Formula 1-3]

In Formula 1-3,

L11 is a direct bond, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group,

R31 to R34 are the same as or different from each other, and each independently represent a C4 to C8 alkyl group,

R35 to R38 are the same as or different from each other, and each independently represents hydrogen, deuterium, an alkyl group, an aryl group, or a heteroaryl group, n35 and n36 are each an integer of 0 to 7, and n37 and n38 are each an integer of 0 to 5 .

When the first compound includes the unit of Formula 1-1 and the unit of Formula 1-3, they may be included in a molar ratio of 10:90 to 90:10, preferably 20:80 to 80:20. .

According to an example, L11 is a C6 to C20 arylene group.

According to a specific example, L11 is phenylene, biphenylrylene, or terphenylrylene.

According to an exemplary embodiment, R31 to R34 are the same as or different from each other, and each independently represent a C4 to C8 alkyl group, preferably a hexyl group.

According to an exemplary embodiment, R35 and R36 are the same as or different from each other, and each independently represents hydrogen, deuterium, or an aryl group.

According to an exemplary embodiment, R35 and R36 are the same as or different from each other, each independently an aryl group, and n35 and n36 are 1.

According to an exemplary embodiment, R37 and R38 are the same as or different from each other, and each independently represents a C1 to C8 straight-chain or branched alkyl group.

According to an exemplary embodiment, R37 and R38 are the same as or different from each other, and each independently represents a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.

According to an exemplary embodiment, as a terminal group, the first compound may include an aryl group or a heteroaryl group, for example, a phenyl group, but is not limited thereto.

Examples of the first compound include the following compounds.

The first compound may be synthesized by using polymerization methods known in the art, such as Suzuki reaction, Grignard reaction, Yamamoto reaction, Ullman reaction, Buchwald-Hartwig reaction, and the like. As an example, the following polymer 1 may be synthesized using the following starting materials. A person skilled in the art can prepare other compounds of the first compound by changing starting materials based on the following examples.

According to an exemplary embodiment of the present invention, the first compound further includes a unit of Formula 1-1-1 or a unit of Formula 1-1-2 below. According to another exemplary embodiment, the first compound includes a unit of Formula 1-1-1 or a unit of Formula 1-1-2 below. As a specific example, the first compound includes a unit of Formula 1-1, a unit of Formula 1-1 below, or a unit of Formula 1-1-2 below.

[Formula 1-1-1]

[Formula 1-1-2]

In Formulas 1-1-1 and 1-1-2,

R51, R52, R56 and R57 are the same as or different from each other, and each independently represent a substituted or unsubstituted alkyl group;

R53, R54, R58 and R59 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group,

R55 and R60 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group.

According to an exemplary embodiment of the present invention, R51 and R52 are the same as or different from each other, and each independently represent a substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present invention, R51 and R52 are the same as or different from each other, and each independently represents a substituted or unsubstituted C1-C20 alkyl group.

According to an exemplary embodiment of the present invention, R51 and R52 are the same as or different from each other, and each independently represent a substituted or unsubstituted C 1 to C 10 alkyl group.

According to an exemplary embodiment of the present invention, R51 and R52 are the same as or different from each other, and each independently represent an alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present invention, R51 and R52 are the same as or different from each other, and each independently a substituted or unsubstituted methyl group; or a substituted or unsubstituted hexyl group.

According to an exemplary embodiment of the present invention, R51 and R52 are the same as or different from each other, and each independently a methyl group; or a hexyl group.

According to an exemplary embodiment of the present invention, R53 and R54 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present invention, R53 and R54 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted C 1 to C 10 alkyl group.

According to an exemplary embodiment of the present invention, R53 and R54 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted C 1 to C 6 alkyl group.

According to an exemplary embodiment of the present invention, R53 and R54 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted C 1 to C 4 alkyl group.

According to an exemplary embodiment of the present invention, R53 and R54 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or an alkyl group having 1 to 4 carbon atoms.

According to an exemplary embodiment of the present invention, R53 and R54 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted methyl group.

According to an exemplary embodiment of the present invention, R53 and R54 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a methyl group.

According to an exemplary embodiment of the present invention, R53 and R54 are the same as or different from each other, and each independently represents a hydrogen or a methyl group.

According to an exemplary embodiment of the present invention, R56 and R57 are the same as or different from each other, and each independently represent a substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present invention, R56 and R57 are the same as or different from each other, and each independently represent a substituted or unsubstituted C 1 to C 20 alkyl group.

According to an exemplary embodiment of the present invention, R56 and R57 are the same as or different from each other, and each independently represents a substituted or unsubstituted C 1 to C 10 alkyl group.

According to an exemplary embodiment of the present invention, R56 and R57 are the same as or different from each other, and each independently represent an alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present invention, R56 and R57 are the same as or different from each other, and each independently a substituted or unsubstituted methyl group; or a substituted or unsubstituted hexyl group.

According to an exemplary embodiment of the present invention, R56 and R57 are the same as or different from each other, and each independently a methyl group; or a hexyl group.

According to an exemplary embodiment of the present invention, R56 and R57 are methyl groups.

According to an exemplary embodiment of the present invention, R58 and R59 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present invention, R58 and R59 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted methyl group.

According to an exemplary embodiment of the present invention, R58 and R59 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a methyl group.

According to an exemplary embodiment of the present invention, R58 and R59 are the same as or different from each other, and each independently represents hydrogen or deuterium.

According to an exemplary embodiment of the present invention, R55 and R60 are the same as or different from each other, and each independently represent a substituted or unsubstituted aryl group.

According to an exemplary embodiment of the present invention, R55 and R60 are any one or two or more selected from the group consisting of the following structures.

In the above structures, * means a position connected to Formula 1-1-1 or 1-1-2.

According to an exemplary embodiment of the present invention, R55 and R60 are any one selected from the group consisting of the above structures. According to another exemplary embodiment, R55 and R60 are two or more structures selected from the group consisting of the above structures.

According to an exemplary embodiment of the present invention, the first organic material layer further includes at least one compound selected from the group P consisting of the following compounds. According to another exemplary embodiment, the first organic material layer includes at least one compound selected from the group P consisting of the following compounds instead of the compound of Formula 1-1.

[P group]

[Compound 1]

The weight average molecular weight (Mw) of Compound 1 is 40000, the number average molecular weight (Mn) is 29850, and the dispersion degree (Mw/Mn) is 1.34.

[Compound 2]

The weight average molecular weight (Mw) of Compound 2 is 39000, the number average molecular weight (Mn) is 27080, and the dispersion degree (Mw/Mn) is 1.44.

[Compound 3]

The weight average molecular weight (Mw) of Compound 3 is 19500, the number average molecular weight (Mn) is 147700, and the degree of dispersion (Mw/Mn) is 1.32.

[Compound 4]

The weight average molecular weight (Mw) of Compound 4 is 15100, the number average molecular weight (Mn) is 11100, and the degree of dispersion (Mw/Mn) is 1.36.

[Compound 5]

Compound 5 had a weight average molecular weight (Mw) of 38840, a number average molecular weight (Mn) of 28990, and a degree of dispersion (Mw/Mn) of 1.34.

[Compound 6]

Compound 6 had a weight average molecular weight (Mw) of 41300, a number average molecular weight (Mn) of 30150, and a degree of dispersion (Mw/Mn) of 1.37.

[Compound 7]

Compound 7 has a weight average molecular weight (Mw) of 40000, a number average molecular weight (Mn) of 29600, and a degree of dispersion (Mw/Mn) of 1.35.

[Compound 8]

Compound 8 had a weight average molecular weight (Mw) of 39800, a number average molecular weight (Mn) of 29920, and a degree of dispersion (Mw/Mn) of 1.33.

According to an exemplary embodiment, the weight average molecular weight of the first compound may be 10,000 to 100,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC) using a polystyrene standard (PS standard) using an Agilent 1200 series. Specifically, it can be measured using an Agilent 1200 series instrument using a Polymer Laboratories PLgel MIX-B 300 mm long column, and the measurement temperature is 40° C., the solvent used is THF (tetrahydrofuran), and 20 mg/10 mL of After preparing to a concentration, inject in an amount of 100 μL. In this case, the molecular weight of the polystyrene standard foam is 91450 one type.

According to an exemplary embodiment, the viscosity of the first compound is preferably 1cP to 12cP, more preferably 1cP to 10cP.

According to an exemplary embodiment, the first compound preferably has a solubility that can be dissolved in an amount of 0.5 wt% to 10 wt% with respect to a solvent used for manufacturing the device.

According to an exemplary embodiment of the present invention, the first compound including the unit of Formula 1-1 may be included in the hole injection layer in the organic light emitting device. In this case, the first compound including the unit of Formula 1-1 may serve as a host of the hole injection layer.

According to another exemplary embodiment of the present invention, the material serving as a host of the hole injection layer may further include the following compounds in addition to the first compound including the unit of Formula 1-1. According to another exemplary embodiment of the present invention, the first compound including the unit of Formula 1-1, which is a material serving as a host of the hole injection layer, may be replaced with the following compound.

According to another exemplary embodiment of the present invention, the material serving as a host of the hole injection layer includes, in addition to the first compound including the unit of Formula 1-1, metal porphyrin, oligothiophene, and arylamine series. organic matter; hexanitrile hexaazatriphenylene-based organic substances; quinacridone-based organic substances; perylene-based organic substances; phthalocyanine compounds such as copper phthalocyanine disclosed in US Pat. No. 4,356,429; or starburst-type amine derivatives described in Advanced Material, 6, p.677 (1994), such as tris(4-carbazolyl-9-ylphenyl)amine (TCTA), 4,4',4 Hole injection such as "-tri[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB) It may further include a material, in this case, the hole injection material is not limited to the form of a monomolecular or polymer.

According to an exemplary embodiment, the content ratio of the first compound and the second compound in the first organic material layer is 90:10 to 50:50 based on a weight ratio, and may be 85:15 to 60:40, and 80:20 to 70 It could be :30.

The first compound and the second compound may serve as a host and a dopant in the first organic material layer, respectively. The first organic material layer may serve as a hole injection layer. The thickness of the first organic material layer may be determined as needed, for example, may be determined within the range of 1 nm to 500 nm, specifically 10 nm to 200 nm, more preferably 50 nm to 100 nm.

Hereinafter, the copolymer of Formula 2 will be described.

According to an exemplary embodiment of the present invention, the copolymer of Formula 2 is represented as follows.

[Formula 2]

In Formula 2,

A is a monomer unit comprising at least one triarylamine group,

B' is a monomeric unit having at least three points of attachment in the copolymer,

C' is an aromatic monomer unit or a deuterated analog thereof,

E is the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted germanium group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylamino group; a substituted or unsubstituted siloxane group; And it is selected from the group consisting of a substituted or unsubstituted curable group,

a, b and c are mole fractions, a+b+c=1, a≠0, and b≠0.

A, b and c are the same as or different from each other.

According to another exemplary embodiment, Chemical Formula 2 may be represented by the following Chemical Formula 2'.

[Formula 2']

In Formula 2',

A is a monomer unit comprising at least one triarylamine group,

B' is a monomeric unit having at least three points of attachment in the copolymer,

C' is an aromatic monomer unit or a deuterated analog thereof,

E is the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylamino group; a substituted or unsubstituted siloxane group; And selected from the group consisting of a substituted or unsubstituted curable group,

a1, b1, c1 and e1 are mole fractions, a1+b1+c1+e1=1, a1≠0, b1≠0,

z1 is an integer greater than or equal to 3,

* means the point of attachment in the copolymer.

a1, b1, c1 and e1 are the same as or different from each other.

According to an exemplary embodiment of the present invention, all of the embodiments for A, B′, C′ and E described below for Formula 2 apply equally to Formula 2′.

According to an embodiment of the present invention, the A, B' and optional C' units are arranged in a regular alternating pattern.

According to an exemplary embodiment of the present invention, the A, B' and optional C' units are aligned to form a block.

According to an exemplary embodiment of the present invention, the A, B' and optional C' units are randomly arranged.

According to an exemplary embodiment of the present invention, the copolymer of Formula 2 may be deuterated. Here, deuteration may be present on one or more of the monomer units A, B', and C'. In addition, deuteration can be present on the copolymer backbone, on pendant groups (substituents), or both.

According to an exemplary embodiment of the present invention, the weight average molecular weight (Mw) of the copolymer of Formula 2 is 10,000 g/mol to 5,000,000 g/mol, 10,000 g/mol to 2,000,000 g/mol, 10,000 g/mol to 500,000 g /mol.

In the present invention, the term weight average molecular weight (Mw) means a molecular weight converted to standard polystyrene measured using Gel Permeation Chromatography (GPC).

In the present invention, the monomer unit A is a monomer unit including at least one triarylamine group. The monomer unit A has two points of attachment in the copolymer.

According to an exemplary embodiment of the present invention, A is represented by the following formula A-1.

[Formula A-1]

In the formula A-1,

Ar1 is the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group or a deuterated aryl group,

Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group or a deuterated aryl group,

T is a direct bond; a substituted or unsubstituted aryl group; and a deuterated aryl group,

* indicates the point of attachment in the copolymer.

According to an exemplary embodiment of the present invention, A is represented by the following formula A-2.

[Formula A-2]

In Formula A-2,

Ar1 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group or an aryl group substituted with deuterium;

Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group or a deuterated aryl group,

Ar3 is the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group or a deuterated aryl group,

q is an integer greater than or equal to 0,

* indicates the point of attachment in the copolymer.

According to an exemplary embodiment of the present invention, Chemical Formula A-2 is represented by the following Chemical Formula A-2-1.

[Formula A-2-1]

The definitions of the substituents in Formula A-2-1 are the same as in Formula A-2.

According to an exemplary embodiment of the present invention, the formula A-2 is represented by the following formula A-2-2.

[Formula A-2-2]

In the formula A-2-2,

Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group or a deuterated aryl group,

T21 to T25 are the same as or different from each other, and each independently hydrogen; F; cyano group; an alkyl group; fluoroalkyl group; aryl group; heteroaryl group; amino group; silyl group; germanium group; alkoxy group; aryloxy group; fluoroalkoxy group; siloxane group; siloxy group; deuterated alkyl group; deuterated partially-fluorinated alkyl groups; deuterated aryl group; a deuterated heteroaryl group; deuterated amino groups; deuterated silyl group; Deuterated germanium group; deuterated alkoxy groups; a deuterated aryloxy group; a deuterated fluoroalkoxy group; deuterated siloxane groups; selected from the group consisting of a deuterated siloxy group and a curable group, wherein adjacent groups selected from T21 to T25 may combine with each other to form a 5- or 6-membered aromatic ring,

k is an integer from 0 to 4 each, g is an integer from 0 to 3, h and h1 are each 1 or 2,

* indicates the point of attachment in the copolymer.

According to an exemplary embodiment of the present invention, A is represented by the following formula A-3.

[Formula A-3]

In the formula A-3,

Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group or a deuterated aryl group,

Ar4 are the same as or different from each other, and each independently a substituted or unsubstituted phenylene group; a substituted or unsubstituted naphthylene group; and deuterated analogs thereof;

T1 and T2 are the same as or different from each other and are each independently a conjugated moiety connected in a non-planar configuration, or a deuterated analog thereof,

d is an integer from 1 to 6, respectively,

e is an integer from 1 to 6, respectively,

* indicates the point of attachment in the copolymer.

According to an exemplary embodiment of the present invention, A is represented by the following formula A-4 or A-5.

[Formula A-4]

[Formula A-5]

In Formulas A-4 and A-5,

Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group or a deuterated aryl group,

Ar5, Ar6 and Ar7 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group or a deuterated aryl group,

T3 to T5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; F; cyano group; an alkyl group; fluoroalkyl group; aryl group; heteroaryl group; amino group; silyl group; germanium group; alkoxy group; aryloxy group; fluoroalkoxy group; siloxane group; siloxy group; deuterated alkyl group; deuterated partially-fluorinated alkyl groups; deuterated aryl group; a deuterated heteroaryl group; deuterated amino groups; deuterated silyl group; Deuterated germanium group; deuterated alkoxy groups; a deuterated aryloxy group; a deuterated fluoroalkoxy group; deuterated siloxane groups; deuterated siloxy groups; and a curable group, wherein adjacent groups selected from T3, T4 and T5 may combine with each other to form a ring,

k3 is an integer from 0 to 4, k4 and k5 are each an integer from 0 to 3,

* indicates the point of attachment in the copolymer.

According to an exemplary embodiment of the present invention, Ar1 is selected from the group consisting of a naphthyl group, an anthracenyl group, a naphthylphenyl group, a phenylnaphthyl group, a fluorenyl group, substituted derivatives thereof, and deuterated analogs thereof .

According to an exemplary embodiment of the present invention, Ar1 is deuterium; F; cyano group; an alkyl group; fluoroalkyl group; aryl group; heteroaryl group; amino group; silyl group; germanium group; alkoxy group; aryloxy group; fluoroalkoxy group; siloxane group; siloxy group; hardening group; deuterated alkyl group; deuterated partially-fluorinated alkyl groups; deuterated aryl group; a deuterated heteroaryl group; deuterated amino groups; deuterated silyl group; Deuterated germanium group; deuterated alkoxy groups; a deuterated aryloxy group; a deuterated fluoroalkoxy group; deuterated siloxane groups; deuterated siloxy groups; and an aryl group substituted with one or more substituents selected from the group consisting of a deuterated curable group. According to another exemplary embodiment, the substituent is selected from the group consisting of deuterium, an alkyl group, an arylamino group, an aryl group, a deuterated alkyl group, a deuterated arylamino group, and a deuterated aryl group.

According to an exemplary embodiment of the present invention, Ar1 is a substituted or unsubstituted aryl group.

According to an exemplary embodiment of the present invention, Ar1 is a phenyl group; biphenyl group; terphenyl group; 1-naphthyl group; 2-naphthyl group; anthracenyl group; fluorenyl group; deuterated analogs thereof, and derivatives thereof having one or more substituents. According to another exemplary embodiment, the one or more substituents are selected from the group consisting of a fluoro group, an alkyl group, an alkoxy group, a silyl group, a germanium group, a siloxy group, a substituent having a curable group, and deuterated analogs thereof.

According to an exemplary embodiment of the present invention, Ar1 is an aryl group having 6 to 30 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms or an arylamine group having 6 to 30 carbon atoms.

According to another exemplary embodiment, Ar1 is a phenyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms or an arylamine group having 6 to 30 carbon atoms; a biphenyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms or an arylamine group having 6 to 30 carbon atoms; a terphenyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms or an arylamine group having 6 to 30 carbon atoms; or a naphthyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms or an arylamine group having 6 to 30 carbon atoms.

The description of the embodiment of Ar1 above applies equally to Ar3, Ar5, Ar6 and Ar7.

According to an exemplary embodiment of the present invention, Ar2 is selected from the group consisting of a naphthyl group, an anthracenyl group, a naphthylphenyl group, a phenylnaphthyl group, a fluorenyl group, substituted derivatives thereof, and deuterated analogs thereof. .

According to an exemplary embodiment of the present invention, Ar2 is a substituted or unsubstituted aryl group.

According to an exemplary embodiment of the present invention, Ar2 is a phenyl group; biphenyl group; terphenyl group; 1-naphthyl group; 2-naphthyl group; anthracenyl group; fluorenyl group; deuterated analogs thereof, and derivatives thereof having one or more substituents. According to another exemplary embodiment, the one or more substituents are selected from the group consisting of a fluoro group, an alkyl group, an alkoxy group, a silyl group, a germanium group, a siloxy group, a substituent having a curable group, and deuterated analogs thereof.

According to an exemplary embodiment of the present invention, Ar2 is an aryl group having 6 to 30 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms or an arylamine group having 6 to 30 carbon atoms.

According to another exemplary embodiment, Ar2 is a phenyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms or an arylamine group having 6 to 30 carbon atoms; a biphenyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms or an arylamine group having 6 to 30 carbon atoms; a terphenyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms or an arylamine group having 6 to 30 carbon atoms; or a naphthyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms or an arylamine group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present invention, T is a direct bond; or an aryl group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present invention, T3 to T5 are the same as or different from each other, and are each independently hydrogen or deuterium.

According to an exemplary embodiment of the present invention, when d is 2 or more, two or more substituents in parentheses are the same as or different from each other.

According to an exemplary embodiment of the present invention, d is 1 or 2.

According to an exemplary embodiment of the present invention, when e is 2 or more, two or more substituents in parentheses are the same as or different from each other.

According to an exemplary embodiment of the present invention, e is 1 or 2.

According to an exemplary embodiment of the present invention, when k3 to k5 are 2 or more, respectively, two or more substituents in parentheses are the same as or different from each other.

According to an exemplary embodiment of the present invention, when q is 2 or more, two or more substituents in parentheses are the same as or different from each other.

According to an exemplary embodiment of the present invention, q is an integer of 0 to 2.

According to another exemplary embodiment, q is 0 or 1.

According to an exemplary embodiment of the present invention, the T21 to T25 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; C _1-10 alkyl group; or a C _1-10 deuterated alkyl group.

According to another exemplary embodiment, T21 to T25 are the same as or different from each other, and each independently a C _1-10 silyl group; or a deuterated C _1-10 silyl group.

According to another exemplary embodiment, T21 to T25 are the same as or different from each other, and each independently a C _6-20 aryl group; C _6-20 deuterated aryl group; Or a C _3-20 heteroaryl group.

According to another exemplary embodiment, T21 to T25 are the same as or different from each other, and each independently an amino group; or a deuterated amino group.

According to an exemplary embodiment of the present invention, when k, g, h and h1 are 2 or 2 or more, two or more substituents in parentheses are the same as or different from each other.

According to an exemplary embodiment of the present invention, k is an integer of 0 to 2.

According to an exemplary embodiment of the present invention, g is an integer of 0 to 2.

According to an exemplary embodiment of the present invention, g is 1.

According to an exemplary embodiment of the present invention, T1 and T2 are the same as or different from each other, and each independently represents a substituted or unsubstituted C6-C30 aryl group.

According to another exemplary embodiment, T1 and T2 are the same as or different from each other, and each independently represents an aryl group having 6 to 30 carbon atoms that is unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms.

According to another exemplary embodiment, T1 and T2 are the same as or different from each other, and each independently represents a naphthyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms.

According to an exemplary embodiment of the present invention, the monomer unit A may have any one of the following structures.

According to one embodiment of the present invention, the monomer unit B' is a polyfunctional monomer unit having at least three bonding points in the copolymer.

According to another exemplary embodiment, the monomer unit B' has 3 to 6 bonding points.

According to another exemplary embodiment, the monomer unit B' has three bonding points.

According to another exemplary embodiment, the monomer unit B' has four bonding points.

According to another exemplary embodiment, the monomer unit B' has 5 bonding points.

According to another exemplary embodiment, the monomer unit B' has 6 bonding points.

According to an exemplary embodiment of the present invention, the monomer unit B' is represented by the following formula B'-A.

[Formula B'-A]

Cy1-(Cy2-*)s

In the formula B'-A,

Cy1 is selected from the group consisting of C, Si, Ge, N, an aliphatic ring group, an aromatic ring group, a deuterated aliphatic ring group or a deuterated aromatic ring group having at least three bonding positions,

Cy2 are the same as or different from each other, and each independently is a direct bond; an alkyl group; aryl group; deuterated alkyl group; or a deuterated aryl group,

However, when Cy2 is a direct bond, an alkyl group, or a deuterated alkyl group, Cy1 is an aromatic ring group or a deuterated aromatic ring group,

s is an integer from 3 to the maximum number of available binding sites of Cy1,

* indicates the point of attachment in the copolymer.

According to an exemplary embodiment of the present invention, Cy1 is C, Si, N, an aliphatic ring group having 3 to 30 carbon atoms, or an aromatic ring group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present invention, s is an integer of 3 to 5, and the substituents in parentheses are the same as or different from each other.

In another embodiment, s is 3 or 4.

According to an exemplary embodiment of the present invention, the Cy2 are the same as or different from each other, and each independently a direct bond; or an aryl group having 6 to 30 carbon atoms.

According to another exemplary embodiment, the Cy2 are the same as or different from each other, and each independently a direct bond; phenyl group; or a biphenyl group.

According to an exemplary embodiment of the present invention, the monomer unit B' is represented by any one of the following Chemical Formulas B'-1 to B'-9.

[Formula B'-1]

[Formula B'-2]

[Formula B'-3]

[Formula B'-4]

[Formula B'-5]

[Formula B'-6]

[Formula B'-7]

[Formula B'-8]

[Formula B'-9]

In the formulas B'-1 to B'-9,

Ar8 is an aromatic ring group having at least three attachment points or a deuterated aromatic ring group,

T31 to T61 are the same as or different from each other, and each independently deuterium; F; cyano group; an alkyl group; fluoroalkyl group; aryl group; heteroaryl group; amino group; silyl group; germanium group; alkoxy group; aryloxy group; fluoroalkoxy group; siloxane group; siloxy group; deuterated alkyl group; deuterated partially-fluorinated alkyl groups; deuterated aryl group; a deuterated heteroaryl group; deuterated amino groups; deuterated silyl group; Deuterated germanium group; deuterated alkoxy groups; a deuterated aryloxy group; a deuterated fluoroalkoxy group; deuterated siloxane groups; deuterated siloxy groups; and a curable group, wherein adjacent groups selected from T31 to T61 may combine with each other to form a 5-membered or 6-membered aromatic ring,

k6 to k19, k21 to k25 and k27 to k35 are each an integer from 0 to 4, k20 and k26 are integers from 0 to 5, k36 is an integer from 0 to 3,

* indicates the point of attachment in the copolymer.

According to an exemplary embodiment of the present invention, when k6 to k36 are 2 or more, respectively, two or more substituents in parentheses are the same as or different from each other.

According to an exemplary embodiment of the present invention, Ar8 is benzene having at least three bonding points.

According to an exemplary embodiment of the present invention, T31 to T61 are hydrogen or deuterium, respectively.

According to an exemplary embodiment of the present invention, the monomer unit B' may have any one of the following structures.

According to an exemplary embodiment of the present invention, the monomer unit C' is an aromatic monomer unit or a deuterated analog thereof.

According to an exemplary embodiment of the present invention, the monomer unit C' is a difunctional monomer unit having two bonding points.

According to an exemplary embodiment of the present invention, the monomer unit C' includes a curable group or a deuterated curable group.

According to an exemplary embodiment of the present invention, the monomer unit C' may be one of the following formulas.

In the formulas M1 to M20,

R ¹² are the same as or different from each other, and each independently deuterium; an alkyl group; silyl group; germanium group; aryl group; deuterated alkyl group; deuterated silyl group; Deuterated germanium group; and a deuterated aryl group,

R ¹³ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an alkyl group; and a deuterated alkyl group,

R ¹⁴ are the same as or different from each other, and each independently an alkyl group; aryl group; and deuterated analogs thereof;

R ¹⁵ are the same as or different from each other and are each independently selected from the group consisting of an aryl group and a deuterated aryl group,

R is hydrogen; heavy hydrogen; or an alkyl group,

each f is an integer from 0 to the maximum number of available bonding positions of the substituent;

t is an integer from 0 to 20,

** means the point of attachment.

According to an exemplary embodiment of the present invention, when f and t are each 2 or more, the substituents in the two or more parentheses are the same as or different from each other.

According to an exemplary embodiment of the present invention, f is an integer of 0 to 2.

According to an exemplary embodiment of the present invention, t is an integer of 1 to 3.

According to an exemplary embodiment of the present invention, R ¹² Are the same as or different from each other, and each independently deuterium; an alkyl group having 1 to 20 carbon atoms; or an aryl group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present invention, R ¹³ Are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an alkyl group having 1 to 20 carbon atoms; or a deuterated alkyl group having 1 to 20 carbon atoms.

According to an exemplary embodiment of the present invention, R ¹⁵ Are the same as or different from each other, and each independently an aryl group having 6 to 30 carbon atoms; or a deuterated aryl group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present invention, R ¹⁴ are the same as or different from each other, and each independently an alkyl group having 1 to 20 carbon atoms; or an aryl group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present invention, R is hydrogen; heavy hydrogen; or an alkyl group having 1 to 20 carbon atoms.

According to an exemplary embodiment of the present invention, the monomer unit C' may be selected from the following structures.

According to an exemplary embodiment of the present invention, the unit E is an end-capping unit for the copolymer.

According to an exemplary embodiment of the present invention, the unit E is a monofunctional unit having one point of attachment.

According to an exemplary embodiment of the present invention, the unit E is hydrogen or deuterium.

According to an exemplary embodiment of the present invention, the unit E is a monofunctional monomer unit.

According to an exemplary embodiment of the present invention, the unit E is a curable group or a deuterated curable group.

According to an exemplary embodiment of the present invention, the unit E is an aryl group or a deuterated aryl group.

According to an exemplary embodiment of the present invention, the unit E is an aryl group; arylamino group; hardening group; and deuterated analogs thereof.

According to an exemplary embodiment of the present invention, the unit E is a phenyl group; biphenyl group; diphenylamino group; substituted derivatives thereof and deuterated analogs thereof. In this case, the substituent is a C _1-10 alkyl group, a curable group, or a deuterated analog thereof.

According to an exemplary embodiment of the present invention, the unit E may have any one of the following structures.

In this case, * indicates a bonding point in the copolymer.

According to an exemplary embodiment of the present invention, a in Formula 2 is 0.50 or more.

According to an exemplary embodiment of the present invention, a in Formula 2 is 0.50 to 0.99.

According to an exemplary embodiment of the present invention, a in Formula 2 is 0.60 to 0.90.

According to an exemplary embodiment of the present invention, a in Formula 2 is 0.65 to 0.80.

According to an exemplary embodiment of the present invention, b in Formula 2 is 0.05 or more, and according to some embodiments, b is 0.10 or more.

According to an exemplary embodiment of the present invention, b in Formula 2 is 0.01 to 0.50.

According to an exemplary embodiment of the present invention, b in Formula 2 is 0.05 to 0.45.

According to an exemplary embodiment of the present invention, b in Formula 2 is 0.10 to 0.40.

According to an exemplary embodiment of the present invention, b in Formula 2 is 0.20 to 0.35.

According to an exemplary embodiment of the present invention, c in Formula 2 is 0.

According to an exemplary embodiment of the present invention, c in Formula 2 is 0 to 0.20.

According to an exemplary embodiment of the present invention, c in Formula 2 is 0.01 to 0.20.

According to an exemplary embodiment of the present invention, c in Formula 2 is 0.05 to 0.15.

According to an embodiment of the present invention, the molar ratio of A+B' to E is 40:60 to 98:2; or 50:50 to 90:10 or 60:40 to 80:20.

According to an exemplary embodiment of the present invention, in Formula 2', a1 is 0.30 to 0.90.

According to an exemplary embodiment of the present invention, in Formula 2', a1 is 0.40 to 0.80.

According to an exemplary embodiment of the present invention, in Formula 2', a1 is 0.50 to 0.80.

According to an exemplary embodiment of the present invention, in Formula 2', b1 is 0.05 to 0.40.

According to an exemplary embodiment of the present invention, in Formula 2', b1 is 0.10 to 0.30.

According to an exemplary embodiment of the present invention, b1 in Formula 2' is 0.10 to 0.20.

According to an exemplary embodiment of the present invention, in Formula 2', c1 is 0.

According to an exemplary embodiment of the present invention, in Formula 2', c1 is 0 to 0.15.

According to an exemplary embodiment of the present invention, c1 in Formula 2' is 0.01 to 0.15.

According to an exemplary embodiment of the present invention, c1 in Formula 2' is 0.05 to 0.12.

According to an exemplary embodiment of the present invention, c1 in Formula 2' is 0.05 to 0.60.

According to an exemplary embodiment of the present invention, c1 in Formula 2' is 0.10 to 0.50.

According to an exemplary embodiment of the present invention, c1 in Formula 2' is 0.15 to 0.35.

According to an exemplary embodiment of the present invention, e1 in Formula 2' is 0.05 to 0.60.

According to an exemplary embodiment of the present invention, e1 in Formula 2' is 0.10 to 0.50.

According to an exemplary embodiment of the present invention, e1 in Formula 2' is 0.15 to 0.35.

According to an exemplary embodiment of the present invention, in the copolymer of Formula 2 or 2', A is a unit represented by Formula 201a, and B' is preferably a unit represented by Formula 201b.

[Formula 201a]

In Formula 201a, R101 to R106 are the same as or different from each other, each independently an alkyl group, and n105 and n106 are each an integer of 1 to 3.

[Formula 201b]

In Formula 201b, X101 is trivalent benzene, N or SiR108, nx1 to nx3 are each 0 or 1, R108 is phenyl, and R108 may be connected to other structures of the copolymer.

According to an exemplary embodiment of the present invention, in Formula 201a, R101 and R102 are the same as or different from each other, each independently represent a C1-C3 alkyl group, R103 and R104 are the same as or different from each other, and each independently C4 - A C8 alkyl group, R105 and R106 are the same as or different from each other, and each independently represent a C1-C8 alkyl group, and n105 and n106 are each an integer of 1 to 3.

According to an exemplary embodiment of the present invention, in Formula 201a, the number of carbon atoms Ca of the alkyl groups of R101 and R102, the number of carbons Cb of the alkyl groups of R105 and R106, and the number of carbons Cc of the alkyl groups of R103 and R104 may be Ca<Cb<Cc have.

According to an exemplary embodiment of the present invention, Chemical Formula 201b may be selected from the following structures.

이고, 여기서 L101 내지 L103은 서로 같거나 상이하고 각각 독립적으로 직접결합, 아릴렌 또는 알킬렌이고, R107은 경화성기이며, n107은 1 또는 2이다. According to an exemplary embodiment of the present invention, in the copolymer of Formula 2 or 2', A is a unit represented by Formula 201a, B' is a unit represented by Formula 201b, and E is substituted or unsubstituted with an alkyl group aryl group or

wherein L101 to L103 are the same as or different from each other and each independently represent a direct bond, arylene or alkylene, R107 is a curable group, and n107 is 1 or 2.

For example, R107 is preferably selected from the following structural formulas.

According to a specific example, R107 is preferably selected from the following structural formula.

According to an example, L101 to L103 are a direct bond.

In one example, L101 is phenylene, and L102 and L103 are a direct bond.

In one example, L101 and L103 are phenylene, and L102 is C1-C10 alkylene.

According to an exemplary embodiment of the present invention, in the copolymer of Formula 2 or 2', A is a unit represented by Formula 201a, B' is a unit represented by Formula 201b, and E is substituted or unsubstituted with an alkyl group phenyl, biphenyl unsubstituted or substituted with an alkyl group, a curable group, a phenyl group substituted with a curable group, or *-phenylene-alkylene-phenylene-curable group.

According to an exemplary embodiment of the present invention, in the copolymer of Formula 2 or 2', A is a unit represented by Formula 201a, B' is a unit represented by Formula 201b, and E is a phenyl group, a biphenyl group, C1 - A biphenyl group substituted with a C3 alkyl group, a curable group, or a phenyl group substituted with a curable group. Here, the curable group is preferably selected from the following structures.

이고, 여기서 L101 내지 L103은 서로 같거나 상이하고 각각 독립적으로 직접결합, 아릴렌 또는 알킬렌이고, R107은 경화성기이며, n107은 1 또는 2이다. According to an exemplary embodiment of the present invention, in the copolymer of Formula 2 or 2', A is a unit represented by Formula 201a, B' is a unit represented by Formula 201b, c is 0, and E is an alkyl group an aryl group unsubstituted or substituted with or

wherein L101 to L103 are the same as or different from each other and each independently represent a direct bond, arylene or alkylene, R107 is a curable group, and n107 is 1 or 2.

이고, 여기서 L101 내지 L103은 서로 같거나 상이하고 각각 독립적으로 직접결합, 아릴렌 또는 알킬렌이고, R107은 경화성기이며, n107은 1 또는 2이다. According to an exemplary embodiment of the present invention, in the copolymer of Formula 2 or 2', A is a unit represented by Formula 201a, B' is a unit represented by Formula 201b, C' is Formula 201c, E is an aryl group unsubstituted or substituted with an alkyl group or

wherein L101 to L103 are the same as or different from each other and each independently represent a direct bond, arylene or alkylene, R107 is a curable group, and n107 is 1 or 2.

[Formula 201c]

이다.In Formula 201c, R109 is deuterium, an alkyl group, or a curable group, and n109 is an integer of 0 to 5. According to one example, R109 is

to be.

According to an exemplary embodiment of the present invention, in the copolymer of Formula 2 or 2', A may be a unit represented by Formula 202a, and B' may be a unit represented by Formula 201b.

[Formula 202a]

In Formula 202a, R111 to R113 are the same as or different from each other, each independently an alkyl group, R114 to R117 are the same as or different from each other, and each independently represent hydrogen, deuterium or an alkyl group.

According to one embodiment, R111 to R113 in Formula 202a are the same as or different from each other, and each independently represent a C1-C6 alkyl group.

According to an example, R111 to R113 in Formula 202a are the same as or different from each other, and each independently represent a branched alkyl group.

According to an example, R111 to R113 in Formula 202a are tert-butyl groups.

According to an exemplary embodiment of the present invention, in the copolymer of Formula 2 or 2', A may be a unit represented by Formula 203a, and B' may be a unit represented by Formula 201b.

[Formula 203a]

In Formula 203a, R121 to R124 are the same as or different from each other, each independently an alkyl group, R125 to R128 are the same as or different from each other, and each independently an aryl group.

According to an example, in Formula 203a, R121 to R124 are the same as or different from each other, each independently a C1 to C6 alkyl group, such as a methyl group, R125 to R128 are the same as or different from each other, and each independently C6 to C16 of an aryl group, such as a phenyl group.

According to an exemplary embodiment of the present invention, in the copolymer of Formula 2 or 2', A may be a unit represented by Formula 204a, and B' may be a unit represented by Formula 201b.

[Formula 204a]

In Formula 204a, R131 and R132 are the same as or different from each other, and each independently represents an alkyl group.

According to an example, in Formula 204a, R131 and R132 are the same as or different from each other, and each independently represent a C1 to C12 alkyl group, preferably a C4 to C10 alkyl group, more preferably a C6 to C8 alkyl group. .

According to an exemplary embodiment of the present invention, examples of the copolymer of Formula 2 are shown below using the form of Formula 2'.

[Copolymer Type 1]

In the copolymer type 1, c1 is 0 and the monomer unit C' is not present. The end-capping unit E is a curable group.

[Copolymer type 2]

In the copolymer type 2, c1 is 0 and the monomer unit C' is not present. The end-capping unit E is an aryl group.

[Copolymer type 3]

In the copolymer type 3, c1 is 0 and the monomer unit C' is absent. The end-capping unit E is a curable group.

[Copolymer type 4]

In the above copolymer type 4, the monomer unit C' is present and contains a curable group. The end-capping unit E is an aryl group.

[Copolymer type 5]

In the copolymer type 5, c1 is 0 and the monomer unit C' is not present. The end-capping unit E is a curable group.

[Copolymer type 6]

In the above copolymer type 6, c1 is 0 and the monomer unit C' is not present. The end-capping unit E is a curable group.

[Copolymer type 7]

In the above copolymer type 7, c1 is 0 and the monomer unit C' is not present. The end-capping unit E is an aryl group.

[Copolymer type 8]

In the above copolymer type 8, c1 is 0 and the monomer unit C' is not present. The end-capping unit E is a curable group.

[Copolymer type 9]

In the copolymer type 9, c1 is 0 and the monomer unit C' is absent. The end-capping unit E is an aryl group.

[Copolymer type 10]

In the above copolymer type 10, the monomer unit C' is present and contains a curable group. The end-capping unit E is a curable group.

[Copolymer type 11]

In the above copolymer type 11, c1 is 0 and the monomer unit C' is not present. The end-capping unit E is a curable group.

[Copolymer Type 12]

In the copolymer type 12, c1 is 0 and the monomer unit C' is absent. The end-capping unit E comprises a curable group.

[Copolymer type 13]

In the above copolymer type 13, c1 is 0 and the monomer unit C' is absent. The end-capping unit E is an aryl group.

[Copolymer type 14]

In the above copolymer type 14, c1 is 0 and the monomer unit C' is absent. The monomer unit B' is tetrafunctional. The end-capping unit E is an aryl group.

[Copolymer type 15]

In the above copolymer type 15, c1 is 0 and the monomer unit C' is absent. The end-capping unit E is a curable group.

[Copolymer Type 16]

In the copolymer type 16, c1 is 0 and the monomer unit C' is absent. The end-capping unit E is a curable group.

[Copolymer Type 17]

In the copolymer type 17, c1 is 0 and the monomer unit C' is absent. The end-capping unit E is an aryl group.

[Copolymer Type 18]

In the copolymer type 18, c1 is 0 and the monomer unit C' is absent. The end-capping unit E is a curable group.

[Copolymer type 19]

In the above copolymer type 19, c1 is 0 and the monomer unit C' is absent. The end-capping unit E is an aryl group.

[Copolymer Type 20]

In the copolymer type 20, c1 is 0 and the monomer unit C' is absent. The end-capping unit E is a curable group.

[Copolymer Type 21]

In the copolymer type 21, c1 is 0 and the monomer unit C' is absent. The end-capping unit E is a curable group.

The copolymer of Formula 2 may be prepared using any technique that yields a C-C or C-N bond and a known polymerization technique. Various such techniques are known, such as Suzuki, Yamamoto, Stille, and metal-catalyzed C-N coupling as well as metal-catalyzed oxidative direct arylation.

Techniques for controlling the molecular weight of the copolymers of the present invention are well known in the art. The molecular weight of the copolymers described in the present invention can generally be controlled by the ratio of the monomers in the polymerization reaction. According to another exemplary embodiment, the molecular weight may be controlled using a quenching reaction.

The second organic material layer may serve as a hole transport layer. The thickness of the second organic material layer may be determined as needed, for example, may be determined within the range of 1 nm to 500 nm, specifically 10 nm to 200 nm, more preferably within the range of 30 nm to 120 nm.

According to an exemplary embodiment of the present invention, the first organic material layer may be formed of a composition including the second compound.

According to an exemplary embodiment of the present invention, the first organic material layer may be formed of a composition including the first compound and the second compound.

According to an exemplary embodiment of the present invention, the second organic material layer may be formed of a composition including the copolymer of Formula 2 above.

The above-described first organic material layer may be formed of a composition including the first compound and the second compound, and the second organic material layer may be formed of a composition including the copolymer of Formula 2 above.

According to an exemplary embodiment of the present invention, the composition may be liquid. The "liquid phase" means a liquid state at room temperature and pressure.

In one embodiment of the present invention, the composition comprising the second compound further comprises a solvent.

According to an exemplary embodiment of the present invention, the composition including the first compound and the second compound further comprises a solvent.

According to an exemplary embodiment of the present invention, the composition including the copolymer of Formula 2 further includes a solvent.

According to an exemplary embodiment of the present invention, the solvent is, for example, a chlorine-based solvent such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene; ether solvents such as tetrahydrofuran and dioxane; aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, Isophorone, Tetralone, Decalone, and Acetylacetone; ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyvalents such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, and 1,2-hexanediol alcohols and derivatives thereof; alcohol solvents such as methanol, ethanol, propanol, isopropanol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; and amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; A solvent such as tetralin is exemplified, but any solvent capable of dissolving or dispersing the compound of Formula 1 according to an exemplary embodiment of the present invention is sufficient, and the present invention is not limited thereto.

According to another exemplary embodiment, the solvent may be used alone or as a mixture of two or more solvents.

According to another exemplary embodiment, the boiling point of the solvent is preferably 40° C. to 250° C., more preferably 60° C. to 230° C., but is not limited thereto.

According to another exemplary embodiment, the viscosity of the composition including the copolymer of Formula 2 is 2 cP to 15 cP at room temperature.

In an exemplary embodiment of the present invention, the concentration of the composition including the second compound is 0.5 to 10 wt/v%.

According to an exemplary embodiment of the present invention, the concentration of the composition including the first compound and the second compound is 0.5 to 10 wt/v%.

According to an exemplary embodiment of the present invention, the concentration of the composition including the copolymer of Formula 2 is 0.1 to 10 wt/v%.

According to an exemplary embodiment of the present invention, the composition may further include one or more additives selected from the group consisting of a thermal polymerization initiator and a photopolymerization initiator.

The thermal polymerization initiator is methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide , bis-3,5,5-trimethyl hexanoyl peroxide, lauryl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, dicumylperoxide, 2,5-dimethyl-2,5-(t-butyl Oxy)-hexane, 1,3-bis(t-butyl peroxy-isopropyl) benzene, t-butyl cumyl peroxide, di-tbutyl peroxide, 2,5-dimethyl-2,5-( dit-butyl peroxy) hexane-3, tris-(t-butyl peroxy) triazine, 1,1-dit-butyl peroxy-3,3,5-trimethyl cyclohexane, 1,1-dit -Butyl peroxycyclohexane, 2,2-di(t-butyl peroxy)butane, 4,4-di-t-butylpaoxyvaleric acid n-butyl ester, 2,2-bis(4, 4-t-Butyl peroxy cyclohexyl) propane, t-butylperoxyisobutylate, dit-butyl peroxy hexahydro terephthalate, t-butyl peroxy-3,5,5-trimethylhexaate, t- Peroxides such as butyl peroxybenzoate and dit-butyl peroxy trimethyl adipate, or azo-based compounds such as azobis isobutylnitrile, azobisdimethylvaleronitrile, and azobiscyclohexyl nitrile, but are not limited thereto .

The photopolymerization initiator is diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy) Phenyl-(2-hydroxy-2-propyl)ketone,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1,2-hydroxy-2-methyl-1-phenyl Propan-1-one, 2-methyl-2-morpholino (4-methyl thiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime acetophenone-based or ketal-based photopolymerization initiators such as Photoinitiators, benzophenone-based photoinitiators such as benzophenone, 4-hydroxybenzophenone, 2-benzoylnaphthalene, 4-benzoyl biphenyl, 4-benzoylphenyl ether, acrylated benzophenone, and 1,4-benzoylbenzene; -There are thioxanthone-based photopolymerization initiators such as isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. , As other photoinitiators, ethyl anthraquinone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide, bis(2,4,6-trimethylbenzoyl) Phenyl phosphine oxide, bis (2,4-dimethoxy benzoyl) -2,4,4-trimethyl pentyl phosphine oxide, methyl phenyl glyceryl ester, 9, 10-phenanthrene, acridine-based compound, tria ginsic compounds and imidazole-based compounds, but are not limited thereto.

Moreover, what has a photoinitiator effect can also be used individually or in combination with the said photoinitiator. For example, triethanolamine, methyl diethanolamine, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoate isoamyl, benzoate (2-dimethylamino) ethyl, 4,4'-dimethylaminobenzophenone, etc., but this It is not limited.

According to an exemplary embodiment of the present invention, the first organic material layer is a hole injection layer, and the second organic material layer is a hole transport layer.

According to an exemplary embodiment of the present invention, the first organic material layer is provided in contact with the anode, and the second organic material layer is provided in contact with the first organic material layer.

According to another exemplary embodiment, the first organic material layer is a hole injection layer, the second organic material layer is a hole transport layer, the first organic material layer is provided in contact with the anode, and the second organic material layer is in the first organic material layer. provided in contact. As the hole injection layer including the first compound and the second compound and the hole transport layer including the copolymer of Chemical Formula 2 are provided in contact with each other, hole injection and hole transport in the device are smoothly performed, resulting in a low driving voltage and A device having a long life can be obtained.

According to an exemplary embodiment of the present invention, a third organic material layer may be included between the second organic material layer and the light emitting layer.

According to an exemplary embodiment of the present invention, the organic light emitting device includes a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a light emitting layer, an electron injection and transport layer, a hole injection and transport layer in addition to the first organic material layer, the second organic material layer and the light emitting layer; It may further include one or more layers selected from the group consisting of an electron blocking layer and a hole blocking layer.

According to another exemplary embodiment, the organic light emitting device may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

According to another exemplary embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole injection and transport layer, an electron injection and transport layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

For example, the structure of the organic light emitting device according to an exemplary embodiment of the present invention is illustrated in FIG. 1 .

1, an anode 201, a hole injection layer 301, a hole transport layer 401, a light emitting layer 501, an electron injection and transport layer 601 and a cathode 701 are sequentially stacked on a substrate 101. The structure of the light emitting device is illustrated. Here, the electron injection and transport layer means a layer that simultaneously injects and transports electrons. The hole injection layer 301 of FIG. 1 may include a composition including the first compound and the second compound or a cured product thereof, and the hole transport layer 401 may include a composition including the copolymer of Formula 2 or A cured product thereof may be included.

1 illustrates an organic light emitting device, but is not limited thereto.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

In the organic light emitting device of the present invention, a first organic material layer among organic material layers is formed using a composition including the first compound and a second compound, and a second organic material layer is formed using a composition including the copolymer of Formula 2 Except that, it may be prepared by materials and methods known in the art.

For example, the organic light emitting device of the present invention may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. and an organic material layer including at least one layer of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, an electron transport layer, a hole injection and transport layer, and an electron injection and transport layer thereon. It can be prepared by depositing a material that can be used as a cathode on it. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The present invention also provides a method of manufacturing an organic light emitting device formed using the above compositions.

Specifically, according to an exemplary embodiment of the present invention, the method comprising: preparing a substrate; forming an anode on the substrate; forming a first organic material layer on the anode; forming a second organic material layer on the first organic material layer; and forming a light emitting layer on the second organic material layer and forming a cathode on the light emitting layer.

According to an exemplary embodiment of the present invention, the first organic material layer and/or the second organic material layer is formed using spin coating or inkjetting.

According to an exemplary embodiment of the present invention, the first organic material layer and/or the second organic material layer is formed using a printing method.

According to the state of the present invention, the printing method includes, for example, inkjet printing, nozzle printing, offset printing, transfer printing or screen printing, but is not limited thereto.

According to an exemplary embodiment of the present invention, a solution process is suitable as a method for forming the first organic material layer and the second organic material layer, and thus it can be formed by spin coating, ink jetting, or printing method. There is an economic effect.

According to an exemplary embodiment of the present invention, the forming of the first organic material layer comprises the steps of coating a composition of the first organic material layer; and heat-treating or light-treating the coated composition.

According to an exemplary embodiment of the present invention, the forming of the second organic material layer comprises: coating the composition of the second organic material layer; and heat-treating or light-treating the coated composition.

According to an exemplary embodiment of the present invention, the heat treatment may be performed through heat treatment, and the heat treatment temperature in the heat treatment step may be 85° C. to 250° C., and 100° C. to 250° C. according to an exemplary embodiment, According to another exemplary embodiment, it may be 150 °C to 250 °C.

According to another exemplary embodiment, the heat treatment time in the heat treatment step is 1 minute to 2 hours, according to an exemplary embodiment may be 1 minute to 1 hour, according to another exemplary embodiment, 20 minutes to It can be 1 hour.

According to an exemplary embodiment of the present invention, the heat treatment atmosphere in the process of forming the first organic material layer and/or the second organic material layer may be an inert gas atmosphere such as argon or nitrogen, or the atmosphere, but is not limited thereto.

When the heat treatment or light treatment step is included in the step of forming the first organic layer and/or the second organic layer, a plurality of the compounds included in the composition form a cross-link to provide an organic layer including a thinned structure. . In this case, when another layer is laminated on the surface of the organic material layer formed by using the composition, it can be prevented from being dissolved, morphologically affected, or decomposed by a solvent.

Therefore, when the organic material layer formed using the composition is formed including a heat treatment or light treatment step, resistance to solvents increases, so that a multilayer can be formed by repeatedly performing solution deposition and crosslinking methods, and stability is increased to increase the lifespan of the device characteristics can be increased.

According to an exemplary embodiment of the present invention, the composition including the first compound and the second compound, or the composition including the copolymer of Formula 2 may be a composition mixed and dispersed in a polymer binder.

According to one embodiment of the present invention, as the polymer binder, one that does not extremely inhibit charge transport and does not have strong absorption of visible light is preferably used. Examples of the polymer binder include poly(N-vinylcarbazole), polyaniline and its derivatives, polythiophene and its derivatives, poly(p-phenylenevinylene) and its derivatives, poly(2,5-thienylenevinylene) and Derivatives thereof, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like are exemplified.

The composition of the first organic material layer according to an exemplary embodiment of the present invention may further include other monomers (compounds) in addition to the first compound and the second compound.

The composition of the second organic material layer according to an exemplary embodiment of the present invention may use the copolymer of Formula 2 alone, or may include other monomers or other copolymers.

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO:Al or SnO ₂ : a combination of a metal such as Sb and an oxide; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the cathode material include metals such as barium, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multi-layered material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include the compound of Formula 1, metal porphyrin, oligothiophene, an arylamine-based organic material, a hexanitrile hexaazatriphenylene-based organic material, and a quinacridone-based organic material. , perylene-based organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. The hole transport material is a material capable of transporting holes from the anode or hole injection layer to the light emitting layer and has high hole mobility. material is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The hole injection and transport layer may include the material of the hole transport layer and the hole injection layer described above.

The light emitting material is a material capable of emitting light in the visible ray region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

The emission layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a heterocyclic compound containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted in the arylamine, one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. do. Specific examples include Al complex of 8-hydroxyquinoline; complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons as an electron injection material, has an electron injection effect from the cathode, has an excellent electron injection effect on the light emitting layer or the light emitting material, and is generated in the light emitting layer A compound that prevents the excitons from moving to the hole injection layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

The electron injection and transport layer may include the material of the electron transport layer and the electron injection layer described above.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

The hole blocking layer is a layer that blocks the holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but is not limited thereto.

The electron blocking layer is a layer that blocks electrons from reaching the anode, and a material known in the art may be used.

The organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.

Hereinafter, examples will be given to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not to be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

<A first compound comprising a unit of Formula 1-1>

Polymer 1

Polymer 2

<Second compound of Formula 1-2>

dopant 1

dopant 2

dopant 3

<Preparation example of the copolymer of formula 2>

Preparation Example 1. Copolymer type 5 (a1:b1:e1 = 58:12:30)

Step 1) Preparation of Intermediate A

To an oven dried 1 L, three necked round bottom flask under nitrogen was added 1,4-dibromobenzene (55.84 g, 236.71 mmol) and anhydrous THF (400 mL). Once all starting materials had dissolved, the solution was cooled to -67 °C (internal temperature). A slight precipitation of dibromobenzene was observed. Once the solution had cooled, n-butyl lithium (15.16 g, 236.71 mmol) was added via cannula transfer and the solution was left to stir at -67 °C for 15 min, careful observation of agitation due to lithium salt precipitation this was needed 1,6 diiodohexane (40.00 g, 118.35 mmol) was added and the bath was allowed to warm slowly to room temperature resulting in a clear solution. The solution was left to stir at room temperature for 16 hours. The solution was slowly quenched with 1 N HCl (200 mL). A slight exotherm was observed. The layers were separated and the organic layer was dried over NaSO ₄ and concentrated via rotary evaporation. The water bath was raised to 55° C. to achieve distillation of low molecular weight impurities. The crude product remaining was purified using flash chromatography (silica, 100% hexanes isocratic). A second purification was performed using flash chromatography (C18, 10% H ₂ O:90% ACN isocratic). ACN was removed to precipitate the product, which was collected by filtration. Intermediate A was obtained as a white solid in 19% yield (8.871 g).

Step 2) Preparation of Intermediate XL1

In an oven dried 500 mL three neck flask under nitrogen, compound A (8.871 g, 22.39 mmol), benzocyclobutene-4-boronic acid (3.313 g, 22.39 mmol), sodium carbonate (7.12 g, 67.17 mmol) and 1:1 m -Xylene:water (80 mL) was added. The solution was degassed. Tetrakis(triphenylphosphine)Pd(0) (7.12 g, 67.17 mmol) was added to the solution. The resulting mixture was heated to 100° C. for 4 h. Toluene (100 mL) and water (50 mL) were added to the reaction mixture. The layers were separated and the organic layer was dried over NaSO ₄ and filtered through a pad of celite, florisil and silica gel. The crude material was concentrated to give a yellow oil. This was purified using flash chromatography (silica, hexanes:DCM 0-10%). The pure fractions were concentrated to give a white solid. The resulting material was dissolved in 400 mL of acetonitrile. 50 mL of water was added. ACN was removed by rotary evaporation to precipitate the product, which was filtered and collected as a white solid (2.854 g, 30% yield).

Step 3) Preparation of monomer M1

The synthesis of M1 and other monomers is described in WO 2011/159872. The synthesis can be carried out according to the following scheme.

Step 4) Preparation of copolymer type 5 (a1:b1:e1 = 58:12:30)

Compounds M1 (0.765 mmol), M2 (0.158 mmol) and XL1 (0.396 mmol) were added to a scintillation vial and dissolved in 11 mL of toluene. Bis (1,5-cyclooctadiene) nickel (0) (2.42 mmol) was charged to a clean and dry 50 mL Schlenk tube. 2,2'-dipyridyl (2.42 mmol) and 1,5-cyclooctadiene (2.42 mmol) were weighed into a scintillation vial and dissolved in 5.5 mL of N,N'-dimethylformamide and 11 mL of toluene. dissolved. The solution was added to a Schlenk tube, which was then inserted into an aluminum block and heated to an internal temperature of 50°C. The catalyst system was held at 50° C. for 30 minutes. A solution of the monomer in toluene was added to the Schlenk tube and the tube sealed.

The polymerization mixture was stirred at 50° C. for 180 minutes. The Schlenk tube was then removed from the block and allowed to cool to room temperature. The contents were poured into HCl/methanol (5 % v/v, concentrated HCl). After stirring for 45 minutes, the polymer was collected by vacuum filtration and dried under high vacuum. The polymer was dissolved in toluene (1% wt/v) and passed through a column containing basic aluminum oxide (6 grams) layered on silica gel (6 grams). The polymer/toluene filtrate was concentrated (2.5% wt/v toluene) and triturated with 3-pentanone. The toluene/3-pentanone solution was decanted from the semi-solid polymer, which was then dissolved in 15 mL of toluene and then poured into stirring methanol to give copolymer type 5 (a1:b1:e1 = 58:12:30) 60 % yield. (Mw: 32,000)

Other copolymer types can be prepared in a similar manner using the preparation method of copolymer type 5 (a1:b1:e1 = 58:12:30) described above.

Copolymers were characterized by gel permeation chromatography (“GPC”) using a multi-angle light scattering detector as detector and an in-line viscometer and THF as solvent.

Preparation Example 2. Copolymer type 17 (a1:b1:e1 = 47:21:32)

Copolymer type 17 was prepared by Suzuki coupling as shown in the scheme below. In the Suzuki approach, the end-capping monomers are charged last after the monomers for unit A and unit B' have been converted to polymer. This is done in order to consume any residual functional groups remaining on the polymer.

Under inert gas conditions, compound M1 (0.207 mmol), compound B30 (0.092 mmol), Aliquat 336 (0.041 mmol), 1.24 mL of aqueous potassium carbonate solution (0.5 M), 0.1 mmol of bis(di-tert- Butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) and a total of 6.0 mL of toluene were added to a scintillation vial equipped with a magnetic stir bar. The vial was sealed with a screw-cap with a septum, inserted into an aluminum block, heated to an external temperature of 105° C. over a period of 30 minutes, and stirred at that temperature under gentle reflux for 5 hours. The reaction was then charged with 0.05 μmol of bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II), phenylboronic acid pinacol ester E30 (0.138 mmol) and 0.9 ml of toluene. did The reaction was heated again at the temperature specified above for 1.5 hours. Next, iodobenzene (0.092 mmol) and 0.6 mL of toluene were added. The reaction was heated for an additional 1.5 hours and then cooled to room temperature. The aqueous layer was removed and the organic layer was washed twice with 20 mL each of deionized water. The toluene layer was dried by passing it through 10 g of silica gel as a desiccant and the silica was rinsed with toluene. Removal of solvent gave 250 mg of product. The crude product was further purified by passing the toluene solution through alumina, silica gel and Florisil ®. After concentration, the solvent-soaked product was diluted to about 14 mL with toluene, and then added to 150 mL of ethyl acetate to obtain about 200 mg of polymer. The product toluene solution was reprecipitated in 3-pentanone to give 145 mg of final copolymer type 17 (a1:b1:e1 = 47:21:32). (Mw: 232,350)

Preparation Example 3. Copolymer Type 9 (a1:b1:e1 = 42:17:41)

Copolymer type 9 was prepared by Suzuki coupling as shown in the scheme below.

Step 1) Preparation of monomer M3

27.81 g of compound M1 (21.3 mmol), 16.2 g of bis(pinacolato)diboron (63.8 mmol), 8.35 g of potassium acetate (85.1 mmol), 280 mL of 1,4-dioxane were added with an overhead mechanical stirrer And a 1L jacketed-reactor equipped with a reflux condenser was charged and inerted (inerting). Thereafter, 0.70 g of [1,1′-bis(diphenyl-phosphino)ferrocene]dichloropalladium(II), a complex with dichloromethane was charged under an inert atmosphere, and the reaction mixture was allowed to It was heated to an external temperature of about 97° C. The reaction was deemed complete after 10 hours of heating and cooled to 25°C. The reaction mixture was passed through a bed of Celite, then washed with 250 mL of a dichloromethane/hexane mixture (1:1 v/v). The solvent was removed and the residue was diluted with 50 mL of dichloromethane/hexanes (1:1 v/v), the addition of dichloromethane to the crude mixture on a column containing 150 g of silica gel pre-embedded with boric acid. It helped to load the . The collected product fractions were combined and column purification was repeated using 300 g of silica-gel embedded with boric acid. After solvent removal 19.1 g of light colored monomer were obtained. Further purification was achieved by passing the monomers through a column packed with 190 g of Florisil using dichloromethane/hexanes. Finally the monomer was dissolved in toluene/hexane and precipitated in methanol and 15.4 g of solid monomer M3 was isolated in 52% yield.

Step 2) Preparation of copolymer type 9 (a1:b1:e1 = 42:17:41)

Synthesis was performed in a manner similar to Preparation Example 2. (Mw: 461,000)

Additional manufacturing examples

In the same manner as in the above-mentioned Preparation Example, the copolymers of Table 1 below were synthesized.

sphere copolymer copolymer type molar ratio Weight average molecular weight (Mw) HTL1-1 copolymer type 1 58:12:30 69,000 HTL1-2 copolymer type 1 38:12:50 13,000 HTL2-1 copolymer type 2 76:12:12 1,600,000 HTL2-2 copolymer type 2 68:12:20 150,000 HTL3-1 copolymer type 3 58:12:30 22,000 HTL3-2 copolymer type 3 76:12:12 53,000 HTL4-1 copolymer type 7 52:20:28 108,800 HTL4-2 copolymer type 7 54:20:26 130,700 HTL5-1 Copolymer Type 15 58:12:30 15,000 HTL5-2 Copolymer Type 15 52:20:28 14,000

<Experimental example>

Examples 1 to 10

A glass substrate on which ITO was deposited as a thin film to a thickness of 1500 Å was ultrasonically cleaned for 10 minutes using an acetone solvent. Thereafter, the detergent was placed in distilled water, washed with ultrasonic waves for 10 minutes, and repeated twice with distilled water, followed by ultrasonic washing for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol for 10 minutes, followed by drying. The substrate was then transported to a glove box.

A 2 wt% cyclohexanone solution containing the host and dopant materials of the hole injection layer shown in Table 2 below in a weight ratio of 80:20 on the ITO transparent electrode prepared as described above was spin-coated and heat treated at 230°C for 30 minutes to have a thickness of 60 nm of the hole injection layer was formed. A toluene solution containing 0.8 wt% of the hole transport layer material of Table 2 below was spin-coated on the hole injection layer and heat-treated at 230° C. for 25 minutes to form a 140 nm hole transport layer.

After transferring to a vacuum evaporator, the following HOST 1 and the following DOPANT 1 were vacuum-deposited at a weight ratio of 9:1 on the hole transport layer to form a light emitting layer with a thickness of 30 nm. The following ETL was vacuum-deposited on the light emitting layer to form an electron injection and transport layer having a thickness of 40 nm. LiF having a thickness of 0.5 nm and aluminum having a thickness of 100 nm were sequentially deposited on the electron injection and transport layer to form a cathode.

In the above process, the deposition rate of organic material was maintained at 0.4 ~ 1.0 Å/sec, the deposition rate of LiF of the cathode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum degree during deposition was 2×10 ^-8 ~ 5×10 ^-6 torr was maintained.

Comparative Example 1

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the materials shown in Table 2 below were used as the hole injection layer host, dopant, and hole transport layer compound.

[HT-1]

The results of measuring the driving voltage and efficiency of the organic light-emitting device manufactured by the above method at a current density of 10 mA/cm ² are shown in Table 2 below. The time to become 95% of the initial luminance at a current density of 10 mA/cm ² was measured and shown as the lifespan in Table 2 below. The driving voltage, efficiency, and lifespan were expressed as relative values based on Comparative Example 1. The relative voltage indicates the increase or decrease compared to the comparative example, and the relative efficiency and the relative life mean (efficiency/comparative example efficiency X100) and (lifetime/comparative example lifetime X100), respectively.

hole injection layer host hole injection layer
dopant hole transport layer compound Relative voltage (V) Relative Current Efficiency (cd/A) Relative operating life
(95%, h) Example 1 Polymer 1 Dopant 1 HTL1-1 -0.3 140 160 Example 2 Polymer 2 Dopant 2 HTL3-1 -0.25 141 158 Example 3 Polymer 1 Dopant 3 HTL5-2 -0.26 135 165 Example 4 Polymer 2 Dopant 3 HTL2-1 -0.33 132 155 Example 5 Polymer 1 Dopant 2 HTL1-2 -0.4 133 149 Example 6 Polymer 2 Dopant 1 HTL4-2 -0.41 141 158 Example 7 Polymer 1 Dopant 1 HTL3-1 -0.35 138 150 Example 8 Polymer 2 Dopant 2 HTL5-1 -0.38 136 151 Example 9 Polymer 1 Dopant 3 HTL2-2 -0.4 138 144 Example 10 Polymer 2 Dopant 3 HTL3-2 -0.39 142 156 Comparative Example 1 Polymer 2 Dopant 3 HT-1 0 100 100

From the experimental results of Table 2, it was found that the organic light-emitting devices of Examples 1 to 10 including the first organic material layer and the second organic material layer of the present invention had a lower driving voltage than the organic light-emitting device of Comparative Example 1, and had better efficiency and lifespan. can be checked

101: substrate
201: anode
301: hole injection layer
401: hole transport layer
501: light emitting layer
601: electron injection and transport layer
701: cathode

Claims (18)

anode; cathode; and a light emitting layer provided between the anode and the cathode, wherein the organic light emitting device comprises:
A first organic material layer provided between the light emitting layer and the anode and comprising a second compound of Formula 1-2, and
An organic light emitting device that is provided between the light emitting layer and the first organic material layer, and includes a composition including a copolymer of Formula 2 or a second organic material layer including a cured product thereof:
[Formula 1-2]

In Formula 1-2,
R15 to R18 are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted haloaryl group. a group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted arylalkyl group, -ORa, -SRb, -C(=O)Rc, or a curable group, and Ra to Rc are the same as or different from each other, and each independently is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group,
At least one of R15 to R18 is -CH=CH-Rx or an aryl group substituted with -CH=CH-Rx, wherein Rx is an alkyl group or an aryl group,
n15 to n18 are each an integer from 0 to 3, n1 to n4 are each an integer from 0 to 5, n1+n15, n2+n16, n3+n17 and n4+n18 are each an integer from 1 to 5, and m1 to m4 is an integer from 0 to 4, respectively;
[Formula 2]

In Formula 2,
A is a monomer unit comprising at least one triarylamine group,
B' is a monomeric unit having at least three points of attachment in the copolymer,
C' is an aromatic monomer unit or a deuterated analog thereof,
E is the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted germanium group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylamino group; a substituted or unsubstituted siloxane group; And it is selected from the group consisting of a substituted or unsubstituted curable group,
a, b and c are mole fractions, a+b+c=1, a≠0, and b≠0. The method according to claim 1,
The curable group is an organic light emitting device that is any one selected from the following structures:

In the above structures,
Lc is a direct bond; -O-; -S-; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
lc1 is 1 or 2,
When lc1 is 2, Lc is the same as or different from each other,
R21 is a substituted or unsubstituted alkyl group. The method according to claim 1,
In Formula 1-2, -CH=CH-Rx is an organic light emitting device selected from the following structures:

* is a binding site, and Rx is as defined in claim 1. The method according to claim 1,
In Formula 1-2, the aryl group substituted with -CH=CH-Rx is a phenyl group substituted with -CH=CH-Rx, a biphenyl group substituted with -CH=CH-Rx, or substituted with -CH=CH-Rx An organic light-emitting device that is a terphenyl group. The method according to claim 1,
In Formula 1-2, the aryl group substituted with -CH=CH-Rx is an organic light emitting device selected from the following structures:

In the above structure, Rx and Rx' are the same as or different from each other, and each independently represents an alkyl group or an aryl group. The method according to claim 1,
One or two of R15 to R18 in Formula 1-2 is -CH=CH-Rx or an aryl group substituted with -CH=CH-Rx. The method according to claim 1,
R15 to R18 in Formula 1-2 are the same as or different from each other, and each independently represents an aryl group substituted with -CH=CH-Rx or -CH=CH-Rx. The method according to claim 1,
In Formula 2, A is an organic light emitting device represented by any one of Formulas A-1 to A-5:
[Formula A-1]

[Formula A-2]

[Formula A-3]

[Formula A-4]

[Formula A-5]

In the formulas A-1 to A-5,
Ar1 is the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group or a deuterated aryl group,
Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group or a deuterated aryl group,
Ar3 is the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group or a deuterated aryl group,
Ar4 are the same as or different from each other, and each independently a substituted or unsubstituted phenylene group; a substituted or unsubstituted naphthylene group; and deuterated analogs thereof;
Ar5, Ar6 and Ar7 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group or a deuterated aryl group,
T1 and T2 are the same as or different from each other and are each independently a conjugated moiety connected in a non-planar configuration, or a deuterated analog thereof,
T is a direct bond; a substituted or unsubstituted aryl group; and a deuterated aryl group,
T3 to T5 are the same as or different from each other, and each independently hydrogen; F; cyano group; an alkyl group; fluoroalkyl group; aryl group; heteroaryl group; amino group; silyl group; germanium group; alkoxy group; aryloxy group; fluoroalkoxy group; siloxane group; siloxy group; deuterated alkyl group; deuterated partially-fluorinated alkyl groups; deuterated aryl group; a deuterated heteroaryl group; deuterated amino groups; deuterated silyl group; Deuterated germanium group; deuterated alkoxy groups; a deuterated aryloxy group; a deuterated fluoroalkoxy group; deuterated siloxane groups; deuterated siloxy groups; and a curable group, wherein adjacent groups selected from T3, T4 and T5 may combine with each other to form a ring,
d is an integer of 1 to 6, respectively,
e is an integer from 1 to 6, respectively,
k3 is an integer of 0 to 4, k4 and k5 are each an integer of 0 to 3, q is an integer of 0 or more,
* indicates the point of attachment in the copolymer. The method according to claim 1,
The monomer unit B' is an organic light emitting device represented by any one of the following Chemical Formulas B'-1 to B'-9:
[Formula B'-1]

[Formula B'-2]

[Formula B'-3]

[Formula B'-4]

[Formula B'-5]

[Formula B'-6]

[Formula B'-7]

[Formula B'-8]

[Formula B'-9]

In the formulas B'-1 to B'-9,
Ar8 is an aromatic ring group having at least three attachment points or a deuterated aromatic ring group,
T31 to T61 are the same as or different from each other, and each independently deuterium; F; cyano group; an alkyl group; fluoroalkyl group; aryl group; heteroaryl group; amino group; silyl group; germanium group; alkoxy group; aryloxy group; fluoroalkoxy group; siloxane group; siloxy group; deuterated alkyl group; deuterated partially-fluorinated alkyl groups; deuterated aryl group; a deuterated heteroaryl group; deuterated amino groups; deuterated silyl group; Deuterated germanium group; deuterated alkoxy groups; a deuterated aryloxy group; a deuterated fluoroalkoxy group; deuterated siloxane groups; deuterated siloxy groups; and a curable group, wherein adjacent groups selected from T31 to T61 may combine with each other to form a 5-membered or 6-membered aromatic ring,
k6 to k19, k21 to k25 and k27 to k35 are each an integer from 0 to 4, k20 and k26 are integers from 0 to 5, k36 is an integer from 0 to 3,
* indicates the point of attachment in the copolymer. The method according to claim 1,
The copolymer of Formula 2 is an organic light emitting device represented by the following Formula 2':
[Formula 2']

In Formula 2',
A is a monomer unit comprising at least one triarylamine group,
B' is a monomeric unit having at least three points of attachment in the copolymer,
C' is an aromatic monomer unit or a deuterated analog thereof,
E is the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylamino group; a substituted or unsubstituted siloxane group; And selected from the group consisting of a substituted or unsubstituted curable group,
a1, b1, c1 and e1 are mole fractions, a1+b1+c1+e1=1, a1≠0, b1≠0,
z1 is an integer greater than or equal to 3,
* means the point of attachment in the copolymer. The method according to claim 1,
The weight average molecular weight of the copolymer of Formula 2 is 10,000 g/mol to 5,000,000 g/mol organic light emitting device. The method according to claim 1,
The first organic material layer is an organic light emitting device that further comprises a first compound including a unit of Formula 1-1:
[Formula 1-1]

In Formula 1-1,
L1 to L3 are the same as or different from each other, and each independently represents a direct bond, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group,
X is CR, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted fluorenylene group,
R1 to R4 are the same as or different from each other, and are each independently a C4 to C8 alkyl group,
R and R5 to R9 are the same as or different from each other, and each independently represents hydrogen, deuterium, an alkyl group, an aryl group, or a heteroaryl group, n5 and n6 are each an integer of 0 to 7, n7 and n8 are each an integer of 0 to 5 an integer, n9 is an integer from 0 to 9, and m is 0 or 1. 13. The method of claim 12,
Formula 1-1 is an organic light emitting device represented by the following Formula 1-11:
[Formula 1-11]

In Formula 1-11, the definition of a substituent is the same as defined in Formula 1-1. 13. The method of claim 12,
Formula 1-1 is an organic light emitting device represented by the following Formula 1-12:
[Formula 1-12]

In Formula 1-12, the definition of a substituent is the same as defined in Formula 1-1. 13. The method of claim 12,
The first compound including the unit of Formula 1-1 is an organic light emitting device further comprising the following Formula 1-3:
[Formula 1-3]

In Formula 1-3,
L11 is a direct bond, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group,
R31 to R34 are the same as or different from each other, and each independently represent a C4 to C8 alkyl group,
R35 to R38 are the same as or different from each other, and each independently represents hydrogen, deuterium, an alkyl group, an aryl group, or a heteroaryl group, n35 and n36 are each an integer of 0 to 7, and n37 and n38 are each an integer of 0 to 5 . 13. The method of claim 12,
At least one of the first compound, the second compound, and the copolymer of Formula 2 is 5% to 100% deuterated organic light emitting device. The method according to claim 1,
The first organic material layer is a hole injection layer, and the second organic material layer is an organic light emitting device that is a hole transport layer. The method according to claim 1,
The first organic material layer is provided in contact with the anode,
The second organic material layer is an organic light emitting device that is provided in contact with the first organic material layer.

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