KR20220021735A - Organic light emitting device - Google Patents

Abstract

The present specification relates to an organic light emitting element, which includes: an anode; a cathode; and a light emitting layer provided between the anode and the cathode. The organic light emitting element includes a first organic material layer including a composition including the compound of Formula 1 or a cured product thereof between the light emitting layer and the anode, and a second organic material layer including a composition including a copolymer of Formula 2 or a cured product thereof between the first organic layer and the light emitting layer.

Description

Organic light emitting device {ORGANIC LIGHT EMITTING DEVICE}

The present specification 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 an organic material layer is placed between the anode and the cathode, if 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, there are problems in that a lot of material loss occurs and it is difficult to manufacture a device having a large area when manufacturing an organic light emitting device through the deposition process. To solve these problems, a device using a solution process is being developed.

Accordingly, there is a demand for the development of materials and combinations of materials for the organic layer manufactured by the solution process.

Korean Patent Publication No. 10-2012-0112277

An object of the present specification is to provide an organic light emitting device having excellent efficiency and lifespan characteristics.

The present specification is anode; cathode; and a first organic material layer including a composition comprising a compound of Formula 1 or a cured product thereof between the light emitting layer and the anode, wherein the organic light emitting layer is provided between the anode and the cathode. It provides an organic light emitting device comprising a composition comprising a copolymer of Formula 2 or a second organic layer comprising a cured product thereof between the organic layer and the light emitting layer.

[Formula 1]

In Formula 1,

L is a substituted or unsubstituted divalent amine group; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

L1 and L2 are the same as or different from each other, and are each independently a substituted or unsubstituted arylene group,

m1, m2, n1 and n2 are each an integer of 1 to 10, and when n1 and n2 are each 2 or more, the structures in parentheses are the same as or different from each other,

n is an integer from 1 to 10, and when n is 2 or more, L of 2 or more are the same as or different from each other,

[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 organic light emitting device according to an exemplary embodiment of the present specification includes the compound of Formula 1 in the first organic layer, so that curing and film retention are excellent when the first organic layer is formed, and the hole injection ability into the second organic layer is improved.

In addition, the organic light emitting device according to an exemplary embodiment of the present specification improves the efficiency and lifespan of the device by forming the second organic layer including the copolymer of Formula 2 on the first organic layer as described above.

1 illustrates an example of an organic light emitting device according to an exemplary embodiment of the present specification.
2 is a diagram showing the MS spectrum of Compound 1-1.
3 is a diagram showing the MS spectrum of Compound 1-2.

Hereinafter, the present specification will be described in detail.

In the present specification, 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 specification, 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 specification, the 'layer' means 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 specification, 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.

As used herein, the term “curable group” refers to a group capable of inducing crosslinking through heat treatment and/or exposure to light. Crosslinking may be generated while radicals generated while decomposing carbon-carbon multiple bonds or cyclic structures are connected by heat treatment or light irradiation.

In one embodiment of the present specification, the curable group may be selected from the following structures.

In the structure,

L11 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,

k is 1 or 2,

When k is 2, L11 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 specification, L11 is a direct bond; methylene group; or an ethylene group.

In another exemplary embodiment, L11 is a direct bond.

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

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

As used herein, the term “deuterated” is intended to mean that at least one available H has been replaced with 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 specification, at least one of the compound of Formula 1 and the copolymer of Formula 2 may be deuterated, in which case, the deuterated compound is, in a similar manner using a deuterated precursor material, Or more generally, in the presence of a Lewis acid H/D exchange catalyst such as trifluoromethanesulfonic acid, aluminum trichloride or ethyl aluminum dichloride, the undeuterated compound is reacted with a deuterated solvent, for example It can be prepared by treatment with benzene-d6.

In the present specification, "deuterated 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.

In an exemplary embodiment of the present specification, at least one of the compound of Formula 1 and the copolymer of Formula 2 is 10% to 100% deuterated.

In an exemplary embodiment of the present specification, the copolymer of Formula 2 is 5% to 100% deuterated.

In an exemplary embodiment of the present specification, the copolymer of Formula 2 is 40% to 100% deuterated.

In an exemplary embodiment of the present specification, the compound of the copolymer of Formula 2 is 50% to 100% deuterated.

According to an exemplary embodiment of the present specification, at least one of the compound of Formula 1 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.

Throughout this specification, the term "combination of these" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, and the components It is meant to include one or more selected from the group consisting of.

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

", "-----" 및 "*"는 각각 연결되는 부위를 의미한다.In this specification, "

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

In the present specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of the compound is changed to 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.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; an alkyl group; cycloalkyl group; alkoxy group; silyl group; amino 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 specification, the halogen group is a fluoro group (-F), a chloro group (-Cl), a bromo group (-Br) or an iodo group (-I).

In the present specification, the alkyl group may be linear 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.

In the present specification, the cycloalkyl group is not particularly limited, but may have 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group may have 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 specification, the alkoxy group may be linear 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, etc., but is not limited thereto.

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

In the present specification, 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 specification, the silyl group means -SiRR'R", and 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 specification, 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 specification, 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 specification, 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 include, but is not limited to, 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.

In the present specification, 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 specification, the heteroaryl group is an aromatic ring group including at least one of N, O, P, S, Si and Se as a heteroatom, and the number of carbon atoms is not particularly limited, but may be from 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, and the like. However, the present invention is not limited thereto.

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

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

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

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

As used herein, the "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 Formula 1 of the present specification, Ra and Rb may be adjacent groups, and Rc and Rd may be adjacent groups.

In the present specification, in a 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 heterocyclic ring is divalent.

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

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

In this specification, 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 specification, "monomer unit" is intended to mean a repeating unit in a polymer or copolymer.

Hereinafter, Formula 1 will be described.

According to an exemplary embodiment of the present specification, L is a substituted or unsubstituted divalent amine group; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

In an exemplary embodiment of the present specification, L is a substituted or unsubstituted divalent amine group; a substituted or unsubstituted arylene group; and a combination of two or more selected from the group consisting of a substituted or unsubstituted heteroarylene group.

According to an exemplary embodiment of the present specification, L is a substituted or unsubstituted divalent arylamine group; a substituted or unsubstituted divalent arylheteroarylamine group; a substituted or unsubstituted fluorenylene group; Or a substituted or unsubstituted diphenylfluorenylene group.

According to an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted C _6-60 arylene group.

According to an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted C _6-30 arylene group.

In an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted naphthylene group.

According to another exemplary embodiment, L1 and L2 are the same as or different from each other, and are each independently a naphthylene group.

According to an exemplary embodiment of the present specification, n is an integer of 1 to 5.

In an exemplary embodiment of the present specification, n is an integer of 1 to 3.

In the exemplary embodiment of the present specification, m1 and m2 are integers of 1 to 5, respectively.

According to another exemplary embodiment, each of m1 and m2 is 2.

According to an exemplary embodiment of the present specification, n1 and n2 are integers of 1 to 5, respectively.

According to another exemplary embodiment, each of n1 and n2 is 2.

According to an exemplary embodiment of the present specification, m1+m2 / n1+n2 <1.

The sulfonic acid group of Chemical Formula 1 of the present specification can prevent the hole injection layer material from moving to the hole transport layer by using solvent resistance during lamination of the hole injection layer and the hole transport layer in a solution process, so m1, m2, When n1 and n2 are within the above ranges, an excellent effect is exhibited on the device performance and long life.

In an exemplary embodiment of the present specification, -[L]n- is any one of the following Chemical Formulas A-1 to A-3.

In Formulas A-1 to A-3,

L3 to L6 are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted arylene group; a substituted or unsubstituted divalent amine group; Or a substituted or unsubstituted heteroarylene group,

R1 to R18 are 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 cycloalkyl group; a substituted or unsubstituted amine group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

r1, r2, r4, r8, r9, r11 and r14 are integers from 1 to 4;

r3, r12 and r13 are integers from 1 to 3;

r5, r6, r7, r10 and r15 to r18 are integers from 1 to 5;

When each of r1 to r18 is 2 or more, two or more substituents in parentheses are the same as or different from each other.

In an exemplary embodiment of the present specification, L3 to L6 are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted C _6-60 arylene group; a substituted or unsubstituted C _12-60 divalent amine group; Or a substituted or unsubstituted C _2-60 heteroarylene group.

According to an exemplary embodiment of the present specification, L3 is a direct bond; a substituted or unsubstituted phenylene group; a substituted or unsubstituted diphenylamine group; Or a substituted or unsubstituted triphenylamine group.

In an exemplary embodiment of the present specification, L4 is a substituted or unsubstituted phenylene group; a substituted or unsubstituted triphenylamine group; Or a substituted or unsubstituted dimethyl fluorenyl group.

According to an exemplary embodiment of the present specification, L5 and L6 are a direct bond; Or a substituted or unsubstituted diphenylamine group.

According to an exemplary embodiment of the present specification, R1 to R18 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; A substituted or unsubstituted C _1-20 alkyl group; A substituted or unsubstituted C _3-30 cycloalkyl group; a substituted or unsubstituted C _12-60 amine group; A substituted or unsubstituted C _6-60 aryl group; Or a substituted or unsubstituted C _2-60 heterocyclic group.

In another exemplary embodiment, R1 to R18 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted phenyl group.

In the exemplary embodiment of the present specification, Chemical Formula 1 is any one selected from the following structures.

Hereinafter, the copolymer of Formula 2 will be described.

According to an exemplary embodiment of the present specification, 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, b2, c1 and e1 are the same as or different from each other.

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

In one embodiment of the present specification, the A, B' and optional C' units are arranged in a regular alternating pattern.

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

In one embodiment of the present specification, the A, B' and optional C' units are randomly arranged.

According to an exemplary embodiment of the present specification, 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 specification, 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 specification, the term weight average molecular weight (Mw) refers to a molecular weight converted to standard polystyrene measured using a Gel Permeation Chromatograph (GPC).

In the present specification, 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 specification, A is represented by the following Chemical 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.

In an exemplary embodiment of the present specification, A is represented by the following Chemical 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 specification, the 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 specification, the Chemical Formula A-2 is represented by the following Chemical 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.

In an exemplary embodiment of the present specification, A is represented by the following Chemical 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.

In an exemplary embodiment of the present specification, A is represented by the following Chemical 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 specification, 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 specification, 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 specification, Ar1 is an aryl group.

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

In 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 specification, 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 specification, Ar2 is an aryl group.

According to an exemplary embodiment of the present specification, 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 specification, 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.

In 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 specification, T is a direct bond; or an aryl group having 6 to 30 carbon atoms.

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

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

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

According to an exemplary embodiment of the present specification, 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 specification, 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 specification, 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 specification, 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.

In 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.

In 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 specification, 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 specification, k is an integer of 0 to 2.

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

In one embodiment of the present specification, g is 1.

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

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

In one embodiment of the present specification, 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.

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

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

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

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

According to an exemplary embodiment of the present specification, 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 specification, 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 specification, 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 specification, 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.

In 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.

In an exemplary embodiment of the present specification, 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 T6 to T23 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 specification, 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 specification, Ar8 is benzene having at least three bonding points.

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

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

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

In an exemplary embodiment of the present specification, the monomer unit C' is a difunctional monomer unit having two bonding points.

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

In the exemplary embodiment of the present specification, 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.

In the exemplary embodiment of the present specification, 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 specification, f is an integer of 0 to 2.

In an exemplary embodiment of the present specification, t is an integer of 1 to 3.

In an exemplary embodiment of the present specification, 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.

In an exemplary embodiment of the present specification, 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.

In an exemplary embodiment of the present specification, 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.

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

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

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

In an exemplary embodiment of the present specification, the unit E is a monofunctional unit having one attachment point.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

According to an exemplary embodiment of the present specification, 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 herein are well known in the art. The molecular weight of the copolymers described herein 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.

In one embodiment of the present specification, the composition may be in a liquid form. The "liquid phase" means a liquid state at room temperature and pressure.

In an exemplary embodiment of the present specification, the composition including the compound of Formula 1 further includes a solvent.

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

In one embodiment of the present specification, 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.

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

In 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.

In another exemplary embodiment, the viscosity of the composition comprising the compound of Formula 1 is 2 cP to 15 cP at room temperature.

In 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 specification, the concentration of the composition comprising the compound of Formula 1 is 0.5 to 10 wt/v%.

In an exemplary embodiment of the present specification, the concentration of the composition comprising the copolymer of Formula 2 is 0.1 to 10 wt/v%.

In one embodiment of the present specification, 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 butylperoxybenzoate and dit-butyl peroxytrimethyl adipate, or azo-based compounds such as azobisisobutylnitrile, azobisdimethylvaleronitrile, and azobiscyclohexylnitrile, 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 specification, 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 specification, 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.

In the exemplary embodiment of the present specification, 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 specification, 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.

In 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.

In 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 specification 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 specification 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 compound of Formula 1 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 include

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 specification, a first organic material layer among organic material layers is formed using a composition containing the compound of Formula 1, and a second organic material layer is formed using a composition containing a copolymer of Formula 2, except that may be prepared by materials and methods known in the art.

For example, the organic light emitting device of the present specification 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 specification also provides a method of manufacturing an organic light emitting device formed using the above compositions.

Specifically, in one embodiment of the present specification, 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.

In the exemplary embodiment of the present specification, the first organic material layer and/or the second organic material layer is formed using spin coating or inkjetting.

In one embodiment of the present specification, the first organic material layer and/or the second organic material layer is formed using a printing method.

In the present specification, 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 specification, a solution process is suitable as a method for forming the first organic material layer and the second organic material layer, so that it can be formed by spin coating, ink jetting, or printing method. There is an economic effect.

In an exemplary embodiment of the present specification, the forming of the first organic material layer comprises: coating a composition of the first organic material layer; and heat-treating or light-treating the coated composition.

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

In an exemplary embodiment of the present specification, 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, In another exemplary embodiment, it may be 150 °C to 250 °C.

In 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, in another exemplary embodiment, 20 minutes to It can be 1 hour.

According to an exemplary embodiment of the present specification, 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.

In an exemplary embodiment of the present specification, the composition including the compound of Formula 1 or the composition including the copolymer of Formula 2 may be mixed and dispersed in a polymer binder.

In one embodiment of the present specification, as the polymer binder, one that does not extremely inhibit charge transport and does not have strong absorption for 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 specification may further include other monomers (compounds) in addition to the compound of Formula 1 above.

The composition of the second organic material layer according to an exemplary embodiment of the present specification 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, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, and 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 It is a compound in which at least one arylvinyl group is substituted in the arylamine, and 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 specification 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 specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art.

<of the compound of formula 1 production example >

production example 1. Preparation of compound 1-1

Preparation Example 1-1. Preparation of Intermediate 1-1

Degassing in 1,4-dibromobenzene (10 g, 42.4 mmol), 4- (phenylamino) phenol (16.5 g, 89.02 mmol) and sodium-tert-butoxide (NaOtBu, 12.2 g, 127.2 mmol) 150ml of toluene was added and dissolved. After raising the temperature to 100 °C, bis(tri-tert-butylphosphine)palladium (0.866g, 1.69mmol) was added, and the reaction was conducted for about 18 hours. After the temperature was lowered to room temperature, water was added, and the organic layer was extracted using ethyl acetate. After drying with magnesium sulfate (MgSO ₄ ) and adsorbing palladium, it was filtered through celite and silica, respectively. The reaction solution was concentrated and flash column was performed to synthesize Intermediate 1-1.

Preparation 1-2. Preparation of Intermediate 1-2

Intermediate 1-1 (3g, 6.75mmol) and potassium carbonate (2.33g, 16.8mmol) were dissolved in 150ml of DMF (dimethyl formamide). After stirring at 60° C. for about 30 minutes, perfluoro-1,1′-biphenyl (22.5 g, 67.5 mmol) was added, the temperature was raised to 90° C., and the mixture was stirred for about 4 hours, and then the reaction temperature was cooled. After adding water, the organic layer was extracted using ethyl acetate, dried over MgSO ₄ , the reaction product was concentrated and flash column was performed to synthesize Intermediate 1-2.

Preparation Example 1-3. Preparation of Intermediate 1-3

Intermediate 1-2 (2.4g, 2.23mmol), potassium carbonate (0.62g, 4.46mmol) was dissolved in 25ml of DMF. After stirring at 60° C. for about 30 minutes, sodium-4-hydroxynaphthalene-2,7-disulfonate (1.7 g, 4.9 mmol) was added, the temperature was raised to 90° C., and stirred for about 18 hours, and then the reaction temperature was lowered. cooled down After adding 75 mL of DMF, the salt was removed by filtration, and filtration was repeated until the part insoluble in methanol disappeared to synthesize Intermediate 1-3.

Preparation Example 1-4. Preparation of compound 1-1

After dissolving 30 ml of water and 10 ml of methanol in Intermediate 1-3 (1 g), it was flowed into an ion exchange resin (650CDOWEX™ MONOSPHERE™ 650C) to synthesize Compound 1-1.

2 is a diagram showing the MS spectrum of Compound 1-1.

production example 2. Preparation of compound 1-2

Preparation Example 1-1. Preparation of Intermediate 2-1

4,4′-(2-bromo-9H-fluorene-9,9-diyl)diphenol (3.00 g, 6.99 mmol), triphenylbenzene-1,4-diamine (2.59 g, 7.68 mmol) and NaOtBu (3.36 g, 34.9 mmol) was dissolved in 200 mL and 50 mL of degassed toluene and tetrahydrofuran, respectively, after creating a nitrogen atmosphere. After raising the temperature to 60° C. and stirring for about 30 minutes, bis (tri-tert-butylphosphine) palladium (0.18 g, 0.35 mmol) was dissolved in tetrahydrofuran and reacted for about 18 hours. After cooling the reaction product by lowering the temperature to room temperature and removing the solvent, the organic layer was extracted several times with CH ₂ Cl ₂ /H ₂ O. After drying with MgSO ₄ and adsorbing palladium, it was filtered through celite and silica, respectively. The reaction solution was concentrated and flash column was performed to synthesize Intermediate 2-1.

Preparation 1-2. Preparation of Intermediate 2-2

Intermediate 2-1 (1.00 g, 1.46 mmol), perfluoro-1,1'-biphenyl (4.88 g, 14.6 mmol) and potassium carbonate (0.30 g, 2.19 mmol) were dissolved in 50 ml of DMF. Then, the reaction was carried out by stirring at 100° C. for about 3 hours. After cooling the reaction temperature, an excess of water was added, the organic layer was extracted using ethyl acetate, dried over MgSO ₄ , the reaction product was concentrated, and flash column was performed to synthesize Intermediate 2-2.

Preparation Example 1-3. Preparation of Intermediate 2-3

Add 10 mL of DMF to Intermediate 2-2 (0.41 g, 0.31 mmol), sodium-4-hydroxynaphthalene-2,7-disulfonate (0.33 g, 0.94 mmol) and potassium carbonate (0.04 g, 0.31 mmol) melted it After that, the reaction was carried out by stirring at 100° C. for about 5 hours. After cooling the reaction temperature, 75 mL of DMF was added, filtered to remove salt, and filtration was repeated until the insoluble portion in methanol disappeared to synthesize Intermediate 2-3.

Preparation Example 1-4. Preparation of compound 1-2

After dissolving 30 ml of water and 10 ml of methanol in Intermediate 2-3 (0.50 g), it was flowed into an ion exchange resin (650CDOWEX™ MONOSPHERE™ 650C) having a volume of about 100 mL to synthesize Compound 1-2.

3 is a diagram showing the MS spectrum of Compound 1-2.

<The copolymer of Formula 2 production example >

production 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 minutes, careful observation of stirring 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 scheme below.

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)

production 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 a complex with [1,1′-bis(diphenyl-phosphino)ferrocene]dichloropalladium(II), dichloromethane was charged under an inert atmosphere, and the reaction mixture was allowed to react in a period of 1 hour. 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) and the dichloromethane addition was crude on a column containing 150 g of silica gel pre-embedded with boric acid. Assisted in loading the mixture. 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)

In the devices of Examples below, the copolymers shown in Table 1 were used.

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 >

Example One

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 previously prepared compound 1-1 was spin-coated on the ITO transparent electrode prepared as described above, and heat-treated at 230° C. for 30 minutes to form a hole injection layer having a thickness of 60 nm. A hole transport layer having a thickness of 140 nm was formed by spin coating a toluene solution containing 0.8 wt% of the copolymer HTL1-1 prepared above on the hole injection layer.

After transferring to a vacuum evaporator, the following compound A and the following compound B were vacuum-deposited in a weight ratio of 9:1 on the hole transport layer to form a light emitting layer having a thickness of 30 nm. The following compound C 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.

Example 2 to 8 and comparative example One.

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 instead of Compound 1-1 and copolymer HTL1-1 in Example 1.

[Comparative compound 1]

[HT-1]

Experimental example hole injection layer material hole transport layer material Example 1 compound 1-1 HTL1-1 Example 2 compound 1-1 HTL2-2 Example 3 compound 1-1 HTL3-2 Example 4 compound 1-1 HTL4-1 Example 5 compound 1-2 HTL5-1 Example 6 compound 1-2 HTL2-1 Example 7 compound 1-2 HTL3-1 Example 8 compound 1-2 HTL4-2 Comparative Example 1 compound 1-1 compound HT-1 Comparative Example 2 Comparative compound 1 HTL1-1

The driving voltage, current efficiency, and power efficiency values of the organic light emitting devices prepared in Examples 1 to 8 and Comparative Examples 1 to 2 were measured at a current density of 10 mA/cm ² , and initial luminance at a current density of 10 mA/cm ² The time (lifetime) to be 95% of the contrast was measured. The results are shown in Table 3 below.

Experimental example Driving voltage (V) Current efficiency (cd/A) Power efficiency (lm/W) Lifetime (95%, h) Example 1 5.81 4.15 2.24 56 Example 2 5.61 4.22 2.36 55 Example 3 5.49 3.99 2.28 61 Example 4 5.79 4.11 2.23 56 Example 5 5.77 4.05 2.20 59 Example 6 5.53 4 2.27 52 Example 7 5.69 4.25 2.34 63 Example 8 5.51 4.09 2.33 59 Comparative Example 1 5.88 3.78 2.02 16 Comparative Example 2 5.94 3.85 2.03 10

From Table 3, Examples 1 to 8 of the present application are Comparative Example 1 using a monomolecular compound having a structure different from that of Chemical Formula 2 as a hole transport layer material and Comparative Compound 1 having a different structure from Chemical Formula 1 as a material of the hole injection layer. It can be seen that the driving voltage, efficiency, and lifespan of the device are superior to those of Comparative Example 2.

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 (10)

anode; cathode; and an organic light emitting device having a light emitting layer between the anode and the cathode,
A composition comprising the compound of Formula 1 or a first organic material layer comprising a cured product thereof between the light emitting layer and the anode,
An organic light emitting device comprising a second organic layer comprising a composition comprising a copolymer of Formula 2 or a cured product thereof between the first organic layer and the light emitting layer:
[Formula 1]

In Formula 1,
L is a substituted or unsubstituted divalent amine group; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
L1 and L2 are the same as or different from each other, and are each independently a substituted or unsubstituted arylene group,
m1, m2, n1 and n2 are each an integer of 1 to 10, and when n1 and n2 are each 2 or more, the structures in parentheses are the same as or different from each other,
n is an integer from 1 to 10, and when n is 2 or more, L of 2 or more are the same as or different from each other,
[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,
At least one of the compound of Formula 1 and the copolymer of Formula 2 is 10% to 100% deuterated organic light emitting device. The method according to claim 1,
The copolymer of Formula 2 is 5% to 100% deuterated organic light emitting device. The method according to claim 1,
The -[L]n- is an organic light emitting device of any one of Formulas A-1 to A-3:

In Formulas A-1 to A-3,
L3 to L6 are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted arylene group; a substituted or unsubstituted divalent amine group; Or a substituted or unsubstituted heteroarylene group,
R1 to R18 are 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 cycloalkyl group; a substituted or unsubstituted amine group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
r1, r2, r4, r8, r9, r11 and r14 are integers from 1 to 4;
r3, r12 and r13 are integers from 1 to 3;
r5, r6, r7, r10 and r15 to r18 are integers from 1 to 5;
When each of r1 to r18 is 2 or more, two or more substituents in parentheses are the same as or different from each other. The method according to claim 1,
The monomer unit 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 from 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 T6 to T23 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 Chemical Formula 2 is 10,000 g/mol to 5,000,000 g/mol. 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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