KR102466674B1 - Amino fluorene polymer and organic light-emitting device including the same - Google Patents

Abstract

An amino fluorene polymer and an organic light emitting device including the same are presented.

Description

Amino fluorene polymer and organic light-emitting device including the same

An amino fluorene polymer and an organic light emitting device including the same are presented.

An organic light-emitting device is a self-luminous device, and has the advantages of a wide viewing angle, excellent contrast, fast response time, excellent luminance, driving voltage and response speed characteristics, and multi-colorization. .

According to one example, the organic light emitting device may include an anode, a cathode, and an organic layer interposed between the anode and the cathode and including an emission layer. A hole transport region may be provided between the anode and the light emitting layer, and an electron transport region may be provided between the light emitting layer and the cathode. Holes injected from the anode move to the light emitting layer via the hole transport region, and electrons injected from the cathode move to the light emitting layer via the electron transport region. Carriers such as holes and electrons recombine in the light emitting layer region to generate excitons. As these excitons change from the excited state to the ground state, light is generated.

An amino fluorene polymer and an organic light emitting device employing the same are provided.

According to one aspect, an amino fluorene polymer including a first repeating unit represented by Formula 1 is provided:

<Formula 1>

In Formula 1,

R ₁ to R ₃ may each independently represent a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group; is selected from;

m1 is an integer from 1 to 20;

F and F' are each independently selected from a substituted or unsubstituted azafluorenylene group and a substituted or unsubstituted fluorenylene group;

n1 and n2 are each independently selected from 1 and 2;

A is a group represented by the following formula (2);

R ₄ is a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, substituted or unsubstituted C ₆ -C ₃₀ aryloxy group, substituted or An unsubstituted C ₇ -C ₄₀ aralkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, -Si(Q ₁ )(Q ₂ )(Q ₃ ) and -N(Q ₁ )(Q ₂ ) is selected from;

<Formula 2>

In Formula 2,

L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkylene group, a substituted or unsubstituted C ₆ -C ₃₀ Arylene group, substituted or unsubstituted C ₁ -C ₂₀ oxyalkylene group, substituted or unsubstituted C ₃ -C ₁₆ oxycycloalkylene group, substituted or unsubstituted C ₆ -C ₃₀ oxyarylene group, substituted or unsubstituted selected from a C ₇ -C ₄₀ aralkylene group, a substituted or unsubstituted C ₅ -C ₃₀ heteroarylene group, -Si(Q ₄ )(Q ₅ )-, and -N(Q ₄ )-;

n3 and n4 are each independently selected from 1 and 2;

Ar ₁ is a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, substituted or unsubstituted C ₆ -C ₃₀ aryloxy group, substituted or unsubstituted C ₇ -C ₄₀ aralkyl group, substituted or It is selected from an unsubstituted C ₅ -C ₃₀ heteroaryl group and -N(Q ₆ )(Q ₇ );

Ar ₁ is optionally bonded to F, F', L ₁ or L ₂ to form a ring;

Q ₁ to Q ₇ are each independently selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group;

* is a binding site with a neighboring atom.

According to another aspect, the first electrode; a second electrode; and an organic layer interposed between the first electrode and the second electrode; The organic layer is provided with an organic light emitting device including the above-described amino fluorene polymer.

An organic light emitting device employing the amino fluorene polymer has improved light emitting lifetime and current efficiency.

1 is a schematic cross-sectional view of an organic light emitting device according to an exemplary embodiment.

In this specification, "x to y" representing a range means "not less than x and not more than y".

In addition, unless otherwise specified, measurements of operation and physical properties were measured under the conditions of temperature: 20 to 25° C. and humidity: 40 to 50%.

In order to manufacture a large-sized organic light emitting device at a lower cost, a solution coating method can be used. Compared to the vacuum deposition method, the solution coating method has advantages such as high material utilization efficiency, easy fabrication of a large-sized organic light emitting device, and no need for an expensive vacuum deposition apparatus.

As materials used in the solution coating method, there may be, for example, low-molecular materials and high-molecular materials. Among them, the polymeric material has advantages of high application uniformity and easy lamination.

For example, Patent Documents 1 to 10 below disclose materials for an organic light emitting device that are polymerized by substituting a part of a low molecular weight material with a vinyl group and polymerizing the same.

Patent Document 1: Japanese Unexamined Patent Publication No. 7-90255

Patent Document 2: Japanese Unexamined Patent Publication No. 8-54833

Patent Document 3: Japanese Unexamined Patent Publication No. 8-269133

Patent Document 4: Japanese Unexamined Patent Publication No. 2001-098023

Patent Document 5: Japanese Unexamined Patent Publication No. 2002-110359

Patent Document 6: Japanese Unexamined Patent Publication No. 2003-313240

Patent Document 7: Japanese Unexamined Patent Publication No. 2004-059743

Patent Document 8: Japanese Unexamined Patent Publication No. 2006-237592

Patent Document 9: Japanese Unexamined Patent Publication No. 2008-198989

Patent Document 10: Japanese Unexamined Patent Publication No. 2008-218983

However, organic light emitting devices manufactured by a solution coating method using the materials for organic light emitting devices disclosed in Patent Documents 1 to 10 have a problem in that the light emitting lifetime is not sufficient.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described. This invention is not limited only to the following embodiment.

Amino Fluorene Polymer

Amino fluorene polymer according to an embodiment of the present invention is a material for an organic light emitting device that can be formed into a film by a solution coating method. The amino fluorene polymer has high solubility in solvents and high stability of a film formed after application. In addition, the organic light emitting device including the amino fluorene polymer may have an improved light emitting lifetime.

The amino fluorene polymer is a polymer formed by polymerizing a polymerizable monomer and may include a first repeating unit represented by Formula 1 below:

<Formula 1>

In Formula 1, R ₁ to R ₃ are each independently a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group; can be selected from.

For example, in Formula 1, R ₁ to R ₃ may be each independently selected from a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, but are not limited thereto.

As another example, in Formula 1, R ₁ to R ₃ may be each independently selected from a hydrogen atom and a methyl group, but are not limited thereto.

In Formula 1, m1 means the number of repetitions of the moiety represented by *-A-(F') _n2 -*', and m1 may be an integer from 1 to 20.

For example, in Formula 1, m1 may be an integer of 1 to 15, but is not limited thereto.

In Formula 1, F and F' may be each independently selected from a substituted or unsubstituted azafluorenylene group and a substituted or unsubstituted fluorenylene group.

For example, in Formula 1, F and F' may be each independently a group represented by Formula 3 below, but are not limited thereto:

<Formula 3>

In Formula 3,

R ₅ to R ₈ are each independently a bonding site, a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, or a substituted or unsubstituted C ₃ -C ₁₆ cyclo group. An alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, a substituted or unsubstituted C ₆ -C ₃₀ aryloxy group, substituted or unsubstituted C ₇ -C ₄₀ aralkyl group, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, -Si(Q ₁ )(Q ₂ )(Q ₃ ) and - is selected from N(Q ₁ )(Q ₂ );

Adjacent substituents among R ₅ to R ₈ are optionally bonded to each other to form a ring;

two substituents of R ₅ to R ₈ are binding sites;

Q ₁ to Q ₃ are each independently selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group;

a and b are each independently selected from 1, 2, 3 and 4;

Y ₁ to Y ₈ are each independently a carbon atom or a nitrogen atom.

For example, in Formula 3, R ₅ to R ₈ may each independently represent a binding site, a hydrogen atom, a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₃₀ aryl group, and a C ₅ -C ₃₀ heteroaryl group;

a C ₁ -C ₂₀ alkyl group substituted with at least one selected from a halogen atom and a C ₆ -C ₃₀ aryl group; and

A C ₁ -C ₂₀ alkyl group, a C ₆ -C ₃₀ aryl group, and a C ₁ -C ₂₀ alkyl-substituted C ₆ -C ₃₀ aryl group substituted with at least one selected from a C ₃₀ aryl group and a C ₅ -C ₃₀ hetero group. aryl group; is selected from;

Adjacent substituents among R ₅ to R ₈ are optionally bonded to each other to form a ring;

Two substituents of R ₅ to R ₈ may be binding sites, but are not limited thereto.

As another example, in Formula 3, R ₅ to R ₈ are each independently selected from a bonding site, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2-dimethyl butyl group, n-heptyl group, 1,4-dimethyl pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3 -Methyl butyl group, n-octyl group, 2-ethyl hexyl group, 3-methyl-1-isopropyl butyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methyl propyl group, n -Nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group , n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-eicosyl group, phenyl group, naphthyl group, anthracenyl group , A phenanthrenyl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, a triazinyl group, a furanyl group and a thiophenyl group;

-F, a methyl group, an ethyl group, and an n-propyl group, substituted with at least one selected from a phenyl group and a naphthyl group; and

methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-octyl group, phenyl group, naphthyl group, phenyl group substituted with methyl group, and tert- a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, a triazinyl group, a furanyl group, and a thiophenyl group, substituted with at least one selected from a phenyl group substituted with a butyl group; is selected from;

Adjacent substituents among R ₅ to R ₈ are optionally bonded to each other to form a ring;

Two substituents of R ₅ to R ₈ may be binding sites, but are not limited thereto.

As another example, in Formula 3, R ₅ to R ₈ are each independently a bonding site, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. group, tert-butyl group, n-octyl group, n-octadecyl group, phenyl group, pyridinyl group and thiophenyl group;

-A methyl group and an ethyl group substituted with at least one selected from F and a phenyl group; and

A phenyl group substituted with at least one selected from a phenyl group substituted with a methyl group, a tert-butyl group, an n-octyl group, a phenyl group, and a tert-butyl group; is selected from;

Adjacent substituents among R ₅ to R ₈ are optionally bonded to each other to form a ring;

Two substituents of R ₅ to R ₈ may be binding sites, but are not limited thereto.

As another example, in Formula 1, F and F' may be each independently selected from groups represented by Formulas 4-1 to 4-58, but are not limited thereto:

In Formulas 4-1 to 4-58,

Two hydrogen atoms are replaced with binding sites.

In Formula 1, n1 means the number of repetitions of F, n2 means the number of repetitions of F', and n1 and n2 may be independently selected from 1 and 2.

In Formula 1, A may be a group represented by Formula 2 below:

<Formula 2>

In Formula 2,

L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkylene group, a substituted or unsubstituted C ₆ -C ₃₀ Arylene group, substituted or unsubstituted C ₁ -C ₂₀ oxyalkylene group, substituted or unsubstituted C ₃ -C ₁₆ oxycycloalkylene group, substituted or unsubstituted C ₆ -C ₃₀ oxyarylene group, substituted or unsubstituted selected from a C ₇ -C ₄₀ aralkylene group, a substituted or unsubstituted C ₅ -C ₃₀ heteroarylene group, -Si(Q ₄ )(Q ₅ )-, and -N(Q ₄ )-;

n3 and n4 are each independently selected from 1 and 2;

Ar ₁ is a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, substituted or unsubstituted C ₆ -C ₃₀ aryloxy group, substituted or unsubstituted C ₇ -C ₄₀ aralkyl group, substituted or It is selected from an unsubstituted C ₅ -C ₃₀ heteroaryl group and -N(Q ₆ )(Q ₇ );

Ar ₁ is optionally bonded to F, F', L ₁ or L ₂ to form a ring;

Q ₄ to Q ₇ are each independently selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group;

* is a binding site with a neighboring atom.

For example, in Formula 2, L ₁ and L ₂ may each independently represent a single bond, a C ₁ -C ₂₀ alkylene group, and a C ₆ -C ₃₀ arylene group; and

a C ₁ -C ₂₀ alkylene group and a C ₆ -C ₃₀ arylene group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group and a C ₆ -C ₃₀ aryl group; It may be selected from, but is not limited thereto.

As another example, in Formula 2, L ₁ and L ₂ may each independently represent a single bond, a methylene group, or a phenylene group; and

a methylene group and a phenylene group substituted with at least one selected from a methyl group, an n-hexyl group and a phenyl group; It may be selected from, but is not limited thereto.

For example, in Formula 2, Ar ₁ is a hydrogen atom, a C ₁ -C ₂₀ alkyl group, and a C ₆ -C ₃₀ aryl group; and

a C ₆ -C ₃₀ aryl group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₃₀ aryl group, and a C ₁ -C ₂₀ alkoxy group; is selected from;

Ar ₁ may be optionally bonded to F, F', L ₁ or L ₂ to form a ring, but is not limited thereto.

As another example, in Formula 2, Ar ₁ is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or an n-pen ethyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2 -Dimethyl butyl group, n-heptyl group, 1,4-dimethyl pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, 2-Ethyl hexyl group, 3-methyl-1-isopropyl butyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methyl-propyl group, phenyl group, naphthyl group, anthracenyl group and phenan trenyl group; and

methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2-dimethyl butyl group, n-heptyl group, 1,4-dimethyl Pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, phenyl group, naphthyl group, methoxy group, ethoxy group, n-propoxy group group, isopropoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, phenyl group, naphthyl group, substituted with at least one selected from n-heptyloxy group and n-octyloxy group a tyl group, an anthracenyl group and a phenanthrenyl group; is selected from;

Ar ₁ may be optionally bonded to F, F', L ₁ or L ₂ to form a ring, but is not limited thereto.

As another example, in Formula 2, Ar ₁ is selected from a hydrogen atom, a methyl group, an n-hexyl group, a phenyl group, a naphthyl group, and groups represented by Formulas 8-1 to 8-6;

Ar ₁ may be optionally bonded to F, F', L ₁ or L ₂ to form a ring, but is not limited thereto:

In Formulas 8-1 to 8-6

* is a binding site with a neighboring atom.

In Formula 1, R ₄ is a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, or a substituted Or an unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, or a substituted or unsubstituted C ₆ -C ₃₀ aryl group. An oxy group, a substituted or unsubstituted C ₇ -C ₄₀ aralkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, -Si(Q ₁ )(Q ₂ )(Q ₃ ) and -N(Q ₁ )(Q ₂ );

Q ₁ to Q ₃ may be each independently selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group.

For example, in Formula 1, R ₄ is a hydrogen atom, a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₃₀ aryl group, a C ₁ -C ₂₀ alkoxy group, and -N(Q ₁ )(Q ₂ ); and

a C ₆ -C ₃₀ aryl group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₃₀ aryl group, and a C ₁ -C ₂₀ alkoxy group; is selected from;

Q ₁ and Q ₂ are each independently a hydrogen atom, a C ₆ -C ₃₀ aryl group; and

a C ₆ -C ₃₀ aryl group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group; It may be selected from, but is not limited thereto.

As another example, in Formula 1, R ₄ is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pen ethyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2 -Dimethyl butyl group, n-heptyl group, 1,4-dimethyl pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, 2-Ethyl hexyl group, 3-methyl-1-isopropyl butyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methyl-propyl group, phenyl group, naphthyl group, anthracenyl group, phenan Trenyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n- an octyloxy group and -N(Q ₁ )(Q ₂ ); and

methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2-dimethyl butyl group, n-heptyl group, 1,4-dimethyl Pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, phenyl group, naphthyl group, methoxy group, ethoxy group, n-propoxy group group, isopropoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, phenyl group, naphthyl group, substituted with at least one selected from n-heptyloxy group and n-octyloxy group a tyl group, an anthracenyl group and a phenanthrenyl group; is selected from;

Q ₁ and Q ₂ are each independently a hydrogen atom, a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthrenyl group; and

methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group; a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthrenyl group, substituted with at least one selected from; It may be selected from, but is not limited thereto.

As another example, in Formula 1, R ₄ may be selected from a hydrogen atom, a methyl group, an n-hexyl group, a phenyl group, a naphthyl group, a methoxy group, and groups represented by Formulas 8-1 to 8-7 below; It is not limited to:

In Formulas 8-1 to 8-7

* is a binding site with a neighboring atom.

For example, the first repeating unit represented by Chemical Formula 1 may be represented by Chemical Formula 1-1, but is not limited thereto:

<Formula 1-1'>

In Chemical Formula 1-1,

R ₁ to R ₃ may each independently represent a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group; is selected from;

m1 is an integer from 1 to 20;

F and F' are each independently selected from a substituted or unsubstituted azafluorenylene group and a substituted or unsubstituted fluorenylene group;

n1 and n2 are each independently selected from 1 and 2;

A is a group represented by the following formula (2);

R ₄ is a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, substituted or unsubstituted C ₆ -C ₃₀ aryloxy group, substituted or An unsubstituted C ₇ -C ₄₀ aralkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, -Si(Q ₁ )(Q ₂ )(Q ₃ ) and -N(Q ₁ )(Q ₂ ) is selected from;

<Formula 2>

In Formula 2,

L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkylene group, a substituted or unsubstituted C ₆ -C ₃₀ Arylene group, substituted or unsubstituted C ₁ -C ₂₀ oxyalkylene group, substituted or unsubstituted C ₃ -C ₁₆ oxycycloalkylene group, substituted or unsubstituted C ₆ -C ₃₀ oxyarylene group, substituted or unsubstituted selected from a C ₇ -C ₄₀ aralkylene group, a substituted or unsubstituted C ₅ -C ₃₀ heteroarylene group, -Si(Q ₄ )(Q ₅ )-, and -N(Q ₄ )-;

n3 and n4 are each independently selected from 1 and 2;

Ar ₁ is a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, substituted or unsubstituted C ₆ -C ₃₀ aryloxy group, substituted or unsubstituted C ₇ -C ₄₀ aralkyl group, substituted or It is selected from an unsubstituted C ₅ -C ₃₀ heteroaryl group and -N(Q ₆ )(Q ₇ );

Ar ₁ is optionally bonded to F, F', L ₁ or L ₂ to form a ring;

* is a binding site with a neighboring atom;

R ₅ to R ₈ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, or a substituted Or an unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, a substituted or unsubstituted C ₆ -C ₃₀ An aryloxy group, a substituted or unsubstituted C ₇ -C ₄₀ aralkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, -Si(Q ₁ )(Q ₂ )(Q ₃ ) and -N(Q ₁ )(Q ₂ );

Adjacent substituents among R ₅ to R ₈ are optionally bonded to each other to form a ring;

a and b are each independently selected from 1, 2, 3 and 4;

Y ₁ to Y ₈ are each independently a carbon atom or a nitrogen atom;

Q ₁ to Q ₇ are each independently selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group.

For example, the first repeating unit represented by Chemical Formula 1 may be selected from the following Chemical Formulas, but is not limited thereto:

In the above formulas, m is an integer from 1 to 10.

The amino fluorene polymer has a fluorene structure directly bonded to the side chain of the polymer. In addition, i) a substituent containing an amine structure and ii) a substituent containing a fluorene structure are further substituted in the fluorene structure. The amine structure may be successively substituted, the fluorene structure may be successively substituted, or the amine structure and the fluorene structure may be alternately substituted.

An organic light emitting diode including an amino fluorene polymer according to an embodiment of the present invention may have improved light emitting lifetime and current efficiency.

The amino fluorene polymer including the first repeating unit represented by Formula 1 includes a fluorenylene group at the polymerization site, and has three times the carbon-carbon bond dissociation energy compared to a polymer containing a phenylene group at the polymerization site. can be higher than Accordingly, the light emitting lifetime of an organic light emitting device including the organic light emitting diode may be improved.

The number average molecular weight (Mn) of the amino fluorene polymer may be, for example, 10000 or more and 100000 or less, but is not limited thereto. When the above range is satisfied, the viscosity of the coating agent for forming the layer (eg, the hole injection layer and/or the hole transport layer) including the amino fluorene polymer can be appropriately adjusted, and the layer has a uniform film thickness. can form

The weight average molecular weight (Mw) of the amino fluorene polymer may be, for example, 10000 or more and 300000 or less, but is not limited thereto. When the above range is satisfied, the viscosity of the coating agent for forming the layer (eg, the hole injection layer and/or the hole transport layer) including the amino fluorene polymer can be appropriately adjusted, and the layer has a uniform film thickness. can form

The degree of dispersion (weight average molecular weight/number average molecular weight) of the amino fluorene polymer may be, for example, 1.5 or more and 2.5 or less, but is not limited thereto. When the above range is satisfied, the viscosity of the coating agent for forming the layer (eg, the hole injection layer and/or the hole transport layer) including the amino fluorene polymer can be appropriately adjusted, and the layer has a uniform film thickness. can form

Methods for measuring the number average molecular weight (Mn), weight average molecular weight (Mw), and degree of dispersion are not particularly limited, and may be measured and calculated in a known method. In the present specification, the number average molecular weight (Mn), weight average molecular weight (Mw), and degree of dispersion employ values measured in the following examples.

The amino fluorene polymer may further include a second repeating unit derived from a monomer containing at least one crosslinking group. That is, the amino fluorene polymer may be a copolymer including both the first repeating unit and the second repeating unit:

The crosslinking group may be represented by Chemical Formulas 5-1 to 5-10, but is not limited thereto:

In Chemical Formulas 5-1 to 5-10,

R ₁₀ to R ₁₆ are each independently a hydrogen atom or a substituted or unsubstituted C ₁ -C ₂₀ alkyl group;

p is an integer from 1 to 10;

* is a binding site with a neighboring atom.

In one embodiment, the second repeating unit may be represented by Formula 6 below, but is not limited thereto:

<Formula 6>

In Formula 6,

R ₁₇ to R ₁₉ are each independently a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, or a substituted or unsubstituted C ₆ -C ₃₀ aryl group;

R ₂₀ to R ₂₈ are each independently a crosslinking group, a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, or a substituted or unsubstituted C ₁ -C ₂₀ alkyl group represented by Formulas 5-1 to 5-10 below. , a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, a substituted or unsubstituted C ₃ -C ₁₆ A cycloalkoxy group, a substituted or unsubstituted C ₆ -C ₃₀ aryloxy group, a substituted or unsubstituted C ₇ -C ₄₀ aralkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, -Si(Q ₁ ) (Q ₂ ) (Q ₃ ) and -N (Q ₁ ) (Q ₂ );

Adjacent substituents among R ₂₀ to R ₂₈ are optionally bonded to each other to form a ring;

at least one of R ₂₀ to R ₂₈ is selected from crosslinking groups represented by Formulas 5-1 to 5-10;

c, d, e and f are each independently selected from 1, 2 and 3;

A' is a single bond, a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkylene group, a substituted or unsubstituted C ₆ -C ₃₀ arylene group, or a substituted or unsubstituted C 3 -C 16 cycloalkylene group. C ₁ -C ₂₀ oxyalkylene group, substituted or unsubstituted C ₃ -C ₁₆ oxycycloalkylene group, substituted or unsubstituted C ₆ -C ₃₀ oxyarylene group, substituted or unsubstituted C ₇ -C ₄₀ are It is selected from an alkylene group, a substituted or unsubstituted C ₅ -C ₃₀ heteroarylene group, -Si(Q ₄ )(Q ₅ )-, and -N(Q ₄ )-;

n5 is selected from 1, 2, 3, 4 and 5;

m2 is an integer from 0 to 20;

Q ₁ to Q ₅ are each independently selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group;

In Chemical Formulas 5-1 to 5-10,

R ₁₀ to R ₁₆ are each independently a hydrogen atom or a substituted or unsubstituted C ₁ -C ₂₀ alkyl group;

p is an integer from 1 to 10;

* is a binding site with a neighboring atom.

For example, in Formula 6, R ₁₇ to R ₁₉ may be each independently selected from a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, but are not limited thereto.

As another example, in Formula 6, R ₁₇ to R ₁₉ may be each independently selected from a hydrogen atom and a methyl group, but are not limited thereto.

For example, in Formula 6, R ₂₀ to R ₂₈ may independently represent a bridging group represented by Formulas 5-1 to 5-10, a hydrogen atom, a C ₁ -C ₂₀ alkyl group, or a C ₆ -C ₃₀ aryl group. groups, C ₁ -C ₂₀ alkoxy groups and -N(Q ₁ )(Q ₂ ); and

a C ₆ -C ₃₀ aryl group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₃₀ aryl group, and a C ₁ -C ₂₀ alkoxy group; is selected from;

Adjacent substituents among R ₂₀ to R ₂₈ are optionally bonded to each other to form a ring;

at least one of R ₂₀ to R ₂₈ is selected from crosslinking groups represented by Formulas 5-1 to 5-10;

Q ₁ and Q ₂ are each independently a hydrogen atom, a C ₆ -C ₃₀ aryl group; and

a C ₆ -C ₃₀ aryl group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group; It may be selected from, but is not limited thereto.

As another example, in Formula 6, R ₂₀ to R ₂₈ are each independently a crosslinking group represented by Formulas 5-1 to 5-10, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, , n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group , isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2-dimethyl butyl group, n-heptyl group, 1,4-dimethyl pentyl group, 3-ethyl pentyl group, 2-methyl -1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, 2-ethyl hexyl group, 3-methyl-1-isopropyl butyl group, 2-methyl-1-isopropyl group, and 1-tert-butyl-2-methyl-propyl group, phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert- butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group and -N(Q ₁ )(Q ₂ ); and

methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2-dimethyl butyl group, n-heptyl group, 1,4-dimethyl Pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, phenyl group, naphthyl group, methoxy group, ethoxy group, n-propoxy group group, isopropoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, phenyl group, naphthyl group, substituted with at least one selected from n-heptyloxy group and n-octyloxy group a tyl group, an anthracenyl group and a phenanthrenyl group; is selected from;

Adjacent substituents among R ₂₀ to R ₂₈ are optionally bonded to each other to form a ring;

at least one of R ₂₀ to R ₂₈ is selected from crosslinking groups represented by Formulas 5-1 to 5-10;

Q ₁ and Q ₂ are each independently a hydrogen atom, a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthrenyl group; and

methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group; a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthrenyl group, substituted with at least one selected from; It may be selected from, but is not limited thereto.

As another example, in Formula 6, R ₂₀ to R ₂₈ are each independently a crosslinking group represented by Formulas 5-1 to 5-10, a hydrogen atom, a methyl group, an n-hexyl group, a phenyl group, a naphthyl group, It is selected from a methoxy group and groups represented by the following formulas 8-1 to 8-7;

Adjacent substituents among R ₂₀ to R ₂₈ are optionally bonded to each other to form a ring;

At least one of R ₂₀ to R ₂₈ may be selected from crosslinking groups represented by Chemical Formulas 5-1 to 5-10, but is not limited thereto:

In Formulas 8-1 to 8-7

* is a binding site with a neighboring atom.

For example, in Formula 6, A' is a single bond, a C ₁ -C ₂₀ alkylene group, a C ₆ -C ₃₀ arylene group, and -N(Q ₄ ); and

a C ₁ -C ₂₀ alkylene group and a C ₆ -C ₃₀ arylene group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group and a C ₆ -C ₃₀ aryl group; is selected from;

Q ₄ is a hydrogen atom, a C ₁ -C ₂₀ alkyl group and a C ₆ -C ₃₀ aryl group; and

a C ₆ -C ₃₀ aryl group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₃₀ aryl group, and a C ₁ -C ₂₀ alkoxy group; It may be selected from, but is not limited thereto.

As another example, in Formula 6, A' is a single bond, a methylene group, a phenylene group, and -N(Q ₄ ); and

a methylene group and a phenylene group substituted with at least one selected from a methyl group, an n-hexyl group and a phenyl group; is selected from;

Q ₄ is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-phen ethyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2-dimethyl butyl group, n-heptyl group , 1,4-dimethyl pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, 2-ethyl hexyl group, 3-methyl -1-isopropyl butyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methyl-propyl group, phenyl group, naphthyl group, anthracenyl group and phenanthrenyl group; and

methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2-dimethyl butyl group, n-heptyl group, 1,4-dimethyl Pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, phenyl group, naphthyl group, methoxy group, ethoxy group, n-propoxy group group, isopropoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, phenyl group, naphthyl group, substituted with at least one selected from n-heptyloxy group and n-octyloxy group a tyl group, an anthracenyl group and a phenanthrenyl group; It may be selected from, but is not limited thereto.

As another example, in Formula 6, A' is a single bond, a methylene group, a phenylene group, and -N(Q ₄ ); and

a methylene group and a phenylene group substituted with at least one selected from a methyl group, an n-hexyl group and a phenyl group; is selected from;

Q ₄ may be selected from a hydrogen atom, a methyl group, an n-hexyl group, a phenyl group, a naphthyl group, and groups represented by Chemical Formulas 8-1 to 8-6, but is not limited thereto:

In Formulas 8-1 to 8-6

* is a binding site with a neighboring atom.

For example, in Formula 6, (A′) _n5 is a single bond, a C ₁ -C ₂₀ alkylene group, a C ₆ -C ₃₀ arylene group, and a group represented by Formula 2; and

a C ₁ -C ₂₀ alkylene group and a C ₆ -C ₃₀ arylene group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group and a C ₆ -C ₃₀ aryl group; It may be selected from, but is not limited thereto: <Formula 2>

In Formula 2,

L ₁ and L ₂ are each independently a single bond, a C ₁ -C ₂₀ alkylene group and a C ₆ -C ₃₀ arylene group; and

a C ₁ -C ₂₀ alkylene group and a C ₆ -C ₃₀ arylene group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group and a C ₆ -C ₃₀ aryl group; is selected from;

n3 and n4 are each independently selected from 1 and 2;

Ar ₁ is a hydrogen atom, a C ₁ -C ₂₀ alkyl group and a C ₆ -C ₃₀ aryl group; and

a C ₆ -C ₃₀ aryl group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₃₀ aryl group, and a C ₁ -C ₂₀ alkoxy group; is selected from;

* is a binding site with a neighboring atom.

For example, in Formula 6, at least one of R ₂₀ to R ₂₈ may be selected from crosslinking groups represented by Formulas 5-8 to 5-10, but is not limited thereto:

In Chemical Formulas 5-8 to 5-10,

* is a binding site with a neighboring atom.

For example, the second repeating unit represented by Chemical Formula 6 may be represented by Chemical Formula 6-1, but is not limited thereto:

<Formula 6-1>

In Chemical Formula 6-1,

For descriptions of R ₁₇ to R ₂₈ , c, d, e, f, A', n5 and m2, refer to the description in Chemical Formula 6 above.

In another embodiment, the second repeating unit may be selected from the following structures, but is not limited thereto:

Among the above chemical formulas,

n and m are each independently an integer of 1 to 10;

Since the second repeating unit is a triphenyl amine-based unit having a crosslinking group, it may serve as both a unit having a crosslinking group and a charge transport unit. Therefore, the amino fluorene polymer including the second repeating unit may increase the charge transport unit ratio (while ensuring high charge transport performance) and increase crosslinkability. Since the second repeating unit has a crosslinking group, a crosslinking reaction may occur by heating and/or irradiation with active energy rays. Such a crosslinking reaction can form a highly durable film that does not dissolve in a solvent. Accordingly, an organic light emitting device using the amino fluorene polymer including the second repeating unit may have an improved light emitting lifetime.

Further, for example, even if another layer is formed on the layer containing the amino fluorene polymer, the layer containing the amino fluorene polymer cannot or hardly dissolves in the solvent when the other layer is applied. . Insoluble or hardly soluble in the solvent at the time of application.

When the amino fluorene polymer is a copolymer, the structure of the amino fluorene polymer is not particularly limited. For example, the amino fluorene polymer may be any one of a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer, but is not limited thereto.

The ratio of the second repeating unit is the total number of repeating units forming the amino fluorene polymer (for example, when the amino fluorene polymer is composed of the first repeating unit and the second repeating unit, the first repeating unit and the sum of the numbers of the second repeating units) may be 1 mol% or more and 50 mol% or less. If the ratio of the second repeating unit is less than 1 mol %, it may be undesirable because a film insoluble in a solvent cannot be formed by a crosslinking reaction. When the ratio of the second repeating unit exceeds 50 mol%, the effect of improving the light emitting lifetime of the organic light emitting device is lowered, which may be undesirable.

For example, the ratio of the second repeating unit may be 5 mol% or more to 15 mol% or less, or 10 mol% with respect to all repeating units forming the amino fluorene polymer, but is not limited thereto.

In one embodiment, the sum of the content of the first repeating unit and the second repeating unit may be 100 mol%. The amino fluorene polymer according to this embodiment may be a random copolymer represented by Formula 9 below, but is not limited thereto:

<Formula 9>

In Formula 9,

For descriptions of R ₁ to R _{4 ,} F, F', A, n1, n2 and m1, refer to the description of Formula 1 above;

For descriptions of R ₁₇ to R ₂₈ , c, d, e, f, A′, n5 and m2, refer to the description of Chemical Formula 6 above;

q is an integer from 5 to 300;

r is an integer from 1 to 300;

The amino fluorene polymer represented by Chemical Formula 9 may have sufficient resistance (insolubility) to solvents during crosslinking. Therefore, even if another layer is formed on the layer containing the amino fluorene polymer, the layer containing the amino fluorene polymer does not dissolve or hardly dissolves in the solvent.

The ratio of each repeating unit can be arbitrarily adjusted by changing the ratio of monomers used when polymerizing the amino fluorene polymer. The ratio of each repeating unit included in the total number of repeating units can be measured by NMR.

The amino fluorene polymer may be formed by polymerizing a monomer represented by Formula 1' below, but is not limited thereto:

<Formula 1'>

In Formula 1',

For descriptions of R ₁ to R ₄ , F, F', A, n1, n2 and m1, refer to the descriptions in Formula 1 above.

The monomer used in the amino fluorene polymer can be synthesized using a known synthesis method, and the structure of the monomer can also be confirmed using NMR and LC-MS.

The polymerization method of the amino fluorene polymer is not particularly limited, and known polymerization methods such as radical polymerization, anionic polymerization, and cationic polymerization may be used. As another example, it may be a radical polymerization reaction, but is not limited thereto.

The solvent used for polymerization of the amino fluorene polymer is, for example, toluene, xylene, diethyl ether, chloroform, ethyl acetate methylene chloride, tetrahydrofuran, acetone, acetonitrile, N, N-dimethylformamide, dimethyl It may be selected from sulfoxide, anisole, hexamethylphosphate triamide, and the like. As another example, the solvent may be selected from toluene and tetrahydrofuran. A solvent may be used individually by 1 type, and may use 2 or more types together. The monomer used for polymerization of the amino fluorene polymer according to an embodiment of the present invention has high solubility in the solvent.

The monomer concentration in the solvent (total monomers in the case of using a plurality of monomers) may be 5 to 90% by weight with respect to the entire reaction solution. Specifically, the monomer concentration in the solvent may be 10 to 80% by weight, but is not limited thereto.

Polymerization temperature may be 40 to 150 ℃ in terms of molecular weight control, but is not limited thereto.

The polymerization reaction may proceed for 30 minutes to 24 hours, but is not limited thereto.

The solvent to which the monomer is added may be degassed prior to addition of the polymerization initiator. For example, the deaeration treatment may be freeze deaeration or deaeration using an inert gas such as nitrogen gas, but is not limited thereto.

A known polymerization initiator may be used, and may be selected from, for example, benzophenone, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, and azobisisobutyronitrile, but is not limited thereto. The amount of the polymerization initiator added may be, for example, 0.0001 to 1 mole based on 1 mole of all monomers used in the preparation of the amino fluorene polymer, but is not limited thereto.

The main chain terminal of the aforementioned amino fluorene polymer may be appropriately defined depending on the type of material used, and may be, for example, a hydrogen atom, but is not limited thereto.

A method for synthesizing the amino fluorene polymer described above can be easily recognized by those skilled in the art by referring to the synthesis examples described later.

organic light emitting device

Hereinafter, an organic light emitting device according to an exemplary embodiment of the present invention will be described in detail with reference to FIG. 1 . 1 is a cross-sectional view of an organic light emitting diode 100 according to an exemplary embodiment of the present invention.

1 shows an organic light emitting device 100 comprising a substrate 110/a first electrode 120/a hole injection layer 130/a hole transport layer 140/a light emitting layer 150/an electron transport layer 160/an electron injection layer ( 170)/second electrode 180, but is not limited to this structure.

The organic light emitting device includes a first electrode/a single film having a hole injection function and a hole transport function/a light emitting layer/an electron transport layer/ a second electrode or a first electrode/a single film having a hole injection function and a hole transport function/a light emitting layer/an electron transport layer/ It may also have a structure such as an electron injection layer/second electrode.

The amino fluorene polymer may be included in at least one organic layer disposed between the first electrode 120 and the second electrode 180 . Specifically, from the viewpoint of long life and high efficiency of the organic light emitting device, the amino fluorene polymer may be included in the hole transport layer 140 .

The amino fluorene polymer may be more suitable for an organic light emitting device manufactured by a solution coating method.

The organic layer including the amino fluorene polymer may be formed by a solution coating method. Specifically, the organic layer containing the amino fluorene polymer is spin coat method, casting method, micro gravure coat method, gravure coat method, bar coat ) method, roll coat method, wire bar coat method, dip coat method, spray coat method, screen printing method, flexographic printing It is deposited using a solution coating method such as a printing method, an offset printing method, an ink jet printing method, or the like. Any solvent used in the solution coating method can be used as long as it can dissolve the amino fluorene polymer.

A method for forming a film of a layer other than the organic layer containing the amino fluorene polymer is not particularly limited. Layers other than the organic layer containing the amino fluorene polymer may be deposited by, for example, a vacuum deposition method or may be formed by a solution coating method.

As the substrate 110, a substrate used for a typical organic light emitting device may be used. For example, the substrate 110 may be a glass substrate, a semiconductor substrate, or a transparent plastic substrate.

The first electrode 120 is, for example, an anode. The first electrode 120 may be formed on the substrate 110 using a deposition method or a sputtering method. Specifically, the first electrode 120 may be formed of a material having a high work function among metals, alloys, conductive compounds, and the like. The first electrode 120 is, for example, indium tin oxide (In ₂ O ₃ -SnO ₂ : ITO), indium zinc oxide (In ₂ O ₃ -ZnO: IZO), tin oxide (SnO), which is transparent and has excellent conductivity. ₂ ), zinc oxide (ZnO), etc., and can be formed as a transmission type electrode. In addition, the first electrode 120 may be formed as a reflective electrode using magnesium (Mg), aluminum (Al), or the like.

A hole injection layer 130 is formed on the first electrode 120 . The hole injection layer 130 is a layer having a function of facilitating injection of holes from the first electrode 120, specifically about 10 nm to about 1000 nm, more specifically, about 10 nm to about 100 nm. It can be formed to a thickness of nm.

The hole injection layer 130 can be formed using a known material, for example, poly(ether ketone)-containg triphenylamine: TPAPEK, 4-isopropyl-4'. -Methyldiphenyliodonium tetrakis (pentafluorophenyl) borate (4-isopropyl-4'-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate: PPBI), N,N'-diphenyl-N,N'-bis-[4 -(phenyl-m-tolyl-amino)-phenyl]-biphenyl 4,4'-diamine (DNTPD), phthalocyanine compounds such as copper phthalocyanine, 4,4',4"-tris(3-methyl phenyl phenyl amino ) triphenyl amine (m-MTDATA), N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (NPB), 4,4',4"-tris{N,N-di Phenyl amino} triphenyl amine (TDATA), 4,4', 4"-tris (N, N-2-naphthylphenylamino) triphenyl amine (2-TNATA), PANI/DBSA (Polyaniline/Dodecylbenzenesulfonic acid: polyaniline /Dodecylbenzenesulfonic acid), PEDOT/PSS (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate): Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), PANI /CSA (Polyaniline/Camphor sulfonicacid: polyaniline/camphor sulfonic acid), PANI/PSS (Polyaniline)/Poly(4-styrenesulfonate): polyaniline)/poly(4-styrenesulfonate)), etc.

A hole transport layer 140 is formed on the hole injection layer 130 . The hole transport layer 140 is a layer including a hole transport material having a function of transporting holes, and may have a thickness of about 10 nm to about 150 nm.

The hole transport layer 140 may be formed by a solution coating method using the amino fluorene polymer. According to the solution application method, an amino fluorene polymer capable of improving the light emitting lifetime of the organic light emitting device 100 can be efficiently formed over a large area.

The hole transport layer 140 can be formed using a known material other than the above-mentioned amino fluorene polymer, for example, TAPC (1,1-bis [(di-4-tolylamino) phenyl] cyclohexane , 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane, N-phenylcarbazole, carbazole derivatives such as polyvinylcarbazole, TPD (N,N'-bis(3-methylphenyl)-N, N'-diphenyl-[1,1-biphenyl]-4,4'-diamine, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4 ,4'-diamine), TCTA (4,4',4"-tris(N-carbazolyl)triphenylamine, 4,4',4"-tris(N-carbazolyl)triphenylamine), NPB (N,N '-bis(naphthalen-2-yl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine), etc. can be formed using

A light emitting layer 150 is formed on the hole transport layer 140 . The light emitting layer 150 is a layer that emits light such as phosphorescence or fluorescence, and may be formed on the hole transport layer 140 using a vacuum deposition method, a spin coating method, an inkjet method, or the like. The light emitting layer 150 may have a thickness of about 10 nm to about 60 nm.

A known light emitting material can be used as the light emitting material of the light emitting layer 150 . However, the light emitting material included in the light emitting layer 150 is preferably a light emitting material capable of emitting light from triplet excitons (ie, phosphorescent light emission). In this case, the light emitting lifetime of the organic light emitting diode 100 may be further improved.

In addition, the light emitting layer 150 may include other host materials, for example, 1,3-bis (carbazole) benzene (mCP), Alq ₃ (tris (8-quinolinolate) aluminum), CBP ( 4,4'-N,N'-dicabazole-biphenyl, 4,4'-N,N'-dicabazole-biphenyl), PVK (poly(n-vinylcabazole), poly(n-vinylcarbazole)), ADN (9,10-di (naphthalene-2-yl) anthracene, 9,10-di (naphthalene-2-yl) anthracene), TCTA, TPBI (1,3,5-tris (N-phenylbenzimidazole-2-yl )benzene, 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene), TBADN(3-tert-butyl-9,10-di(naphth-2-yl) anthracene, 3-tert -Butyl-9,10-di(naphth-2-yl) anthracene), DSA(distyrylarylene, distyrylarylene), dmCBP(4.4'-bis(9-carbazol)-2,2'-dimethylbiphenyl, 4.4'-Bis(9-carbazole)-2,2'-dimethylbiphenyl), 2,4,6-tris(diphenylamino)-1,3,5-triazine, etc. can be used.

The light emitting layer 150 may be formed as a light emitting layer emitting light of a specific color. For example, the light emitting layer 150 may be formed as a red light emitting layer, a green light emitting layer, and a blue light emitting layer.

When the light emitting layer 150 is a blue light emitting layer, known materials can be used as the blue dopant, for example, perilene and its derivatives, bis[2-(4,6-difluorophenyl) pyridinate ] Iridium (Ir) complexes, such as picolinate iridium (III) (FIrpic), etc. can be used.

In addition, when the light emitting layer 150 is a red light emitting layer, a known material can be used as a red dopant, for example, rubrene and its derivatives, DCM (4-(Dicyanomethylene)-2-methyl-6-[ p-(dimethylamino)styryl]-4H-pyran, 4-(dicyanomethylene)-2-methyl-6-[p-(dimethylamino)styryl]-4H-pyran) and its derivatives, Ir(piq) ₂ An iridium complex such as (acac) (Bis(1-phenylisoquinoline)(acetylacetonate)iridium(III)), an osmium (Os) complex, a platinum complex, or the like may be used.

When the light emitting layer 150 is a green light emitting layer, known materials can be used as the green dopant, for example, coumarin and its derivatives, tris(2-phenylpyridine) iridium(III) (Ir(ppy) ₃ ) , iridium complexes such as tris(2-(3-p-xylyl)phenyl)pyridine iridium(III)(TEG), tris(acetylacetonato)iridium(III)(Ir(acac) ₃ ), etc. can be used. .

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

The electron transport layer 160 may be formed using a known electron transport material, for example, tris (8-quinolinato) aluminum: _Alq3 ) and nitrogen-containing -It may be a compound having an aromatic ring, and the like. Specific examples of the compound having a nitrogen-containing aromatic ring include, for example, 1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene (1,3,5-tri [(3 -pyridyl) -phen-3-yl] compounds containing a pyridine ring such as benzene), 2,4,6-tris(3 '-(pyridin-3-yl)biphenyl-3-yl)-1,3 Compounds containing a triazine ring such as ,5-triazine (2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine), 2 -(4-(N-phenylbenzoimidazolyl-1-yl-phenyl)-9,10-dinaphthylanthracene (2-(4-(N-phenylbenzoimidazolyl-1-yl-phenyl)-9,10- dinaphthylanthracene) can be formed using a compound containing an imidazole ring, etc. These materials for forming an electron transport layer may be commercially available products or synthetic products. Examples of commercial products are KLET-01 and KLET-02. , KLET-03, KLET-10, KLET-M1 (above, available from Chemipro Kasei), etc. These materials for forming an electron transport layer may be used alone or in combination of two or more.

An electron injection layer 170 is formed on the electron transport layer 160 . The electron injection layer 170 is a layer having a function of facilitating injection of electrons from the second electrode 180 and may be formed on the electron transport layer 160 using a vacuum deposition method or the like. The electron injection layer 170 may be formed to a thickness of about 0.3 nm to about 9 nm.

The electron injection layer 170 may be formed using a known electron injection material, for example, (8-quinolinato)lithium (Liq), lithium fluoride (LiF), or chloride. It can be formed using sodium (NaCl), cesium fluoride (CsF), lithium oxide (Li ₂ O), barium oxide (BaO), and the like.

A second electrode 180 is formed on the electron injection layer 170 . The second electrode 180 may be, for example, a cathode. Specifically, the second electrode 180 may be formed of a material having a low work function among metals, alloys, conductive compounds, and the like. The second electrode 180 may be, for example, a metal such as lithium (Li), magnesium (Mg), aluminum (Al), or calcium (Ca) or aluminum-lithium (Al-Li) or magnesium-indium (Mg-In). ), an alloy such as magnesium-silver (Mg-Ag), or the like, may be formed as a reflective electrode. In addition, the second electrode 180 may be formed as a transmissive electrode using indium tin oxide (ITO), indium zinc oxide (IZO), or the like of 20 nm or less.

The organic light emitting device 100 may be a top emission type or a bottom emission type.

In the above, an example of the structure of the organic light emitting device 100 related to one embodiment of the present invention has been described, but the structure of the organic light emitting device 100 related to one embodiment of the present invention is not limited to the above example. .

The organic light emitting device 100 related to an embodiment of the present invention may be formed using various other known organic light emitting device structures. For example, the organic light emitting diode 100 may not have at least one layer of the hole injection layer 130 , the hole transport layer 140 , the electron transport layer 160 , and the electron injection layer 170 . In addition, each layer of the organic light emitting device 100 may be formed as a single layer or may be formed as a plurality of layers.

The organic light emitting device 100 may include a hole blocking layer between the hole transport layer 140 and the light emitting layer 150 to prevent triplet excitons or holes from diffusing into the electron transport layer 160 . The hole blocking layer may be formed using, for example, an oxadiazole derivative, a triazole derivative, or a phenanthroline derivative.

In the present specification, the C ₁ -C ₂₀ alkyl group refers to a linear or branched aliphatic hydrocarbon monovalent group having 1 to 20 carbon atoms, and specific examples include methyl, ethyl, propyl, isobutyl, sec-butyl group, tert-butyl group, pentyl group, iso-amyl group, hexyl group and the like. In the present specification, a C ₁ -C ₂₀ alkylene group means a divalent group having the same structure as the C ₁ -C ₁₀ alkyl group.

In the present specification, the C ₁ -C ₂₀ alkoxy group refers to a monovalent group having a chemical formula of -OA ₁₀₁ (where A ₁₀₁ is the C ₁ -C ₂₀ alkyl group), and specific examples thereof include a methoxy group and an ethoxy group. , isopropyloxy groups, and the like.

In the present specification, a C ₁ -C ₂₀ oxyalkylene group means that some of the carbons constituting the C ₁ -C ₂₀ alkylene group are replaced with oxygen.

In the present specification, the C ₃ -C ₁₆ cycloalkyl group refers to a monovalent saturated hydrocarbon monocyclic group having 3 to 16 carbon atoms participating in ring formation, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group , cyclohexyl group, cycloheptyl group and the like are included. In the present specification, a C ₃ -C ₁₆ cycloalkylene group refers to a divalent group having the same structure as the C ₃ -C ₁₀ cycloalkyl group.

In the present specification, the C ₃ -C ₁₆ cycloalkoxy group refers to a monovalent group having a chemical formula of -OA ₁₀₂ (where A ₁₀₂ is the C ₃ -C ₁₆ cycloalkyl group), and specific examples thereof include cyclopropoxy A period, a cyclobutoxy group, a cyclopentoxy group, and the like are included.

In the present specification, a C _{3 -C 16 oxycycloalkylene group means that some of the carbons constituting the C 3 -C 16 cycloalkylene group} are replaced with oxygen.

In the present specification, a C ₆ -C ₃₀ aryl group refers to a monovalent group having a carbocyclic aromatic system having 6 to 30 carbon atoms participating in ring formation, and a C ₆ -C ₃₀ arylene group has 6 to 30 carbon atoms. It means a divalent group having 30 carbocyclic aromatic systems. Specific examples of the C ₆ -C ₃₀ aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a chrysenyl group, and the like. When the C ₆ -C ₃₀ aryl group and the C ₆ -C ₃₀ arylene group include two or more rings, the two or more rings may be condensed with each other.

In the present specification, a C ₆ -C ₃₀ aryloxy group refers to -OA ₁₀₃ (where A ₁₀₃ is the C ₆ -C ₃₀ aryl group).

In the present specification, the C ₆ -C ₃₀ oxyarylene group means that some of the carbons constituting the C ₆ -C ₃₀ arylene group are replaced with oxygen.

In the present specification, the C ₅ -C ₃₀ heteroaryl group includes at least one hetero atom selected from N, O, Si, P, and S as a ring-forming atom, and is a heterocyclic group having 5 to 30 carbon atoms participating in ring formation. It refers to a monovalent group having an aromatic system, and the C ₅ -C ₃₀ heteroarylene group contains at least one heteroatom selected from N, O, Si, P and S as a ring-forming atom and participates in ring formation. It refers to a divalent group having a heterocyclic aromatic system having 5 to 30 carbon atoms. Specific examples of the C ₅ -C ₃₀ heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, and the like. When the C ₅ -C ₃₀ heteroaryl group and the C ₅ -C ₃₀ heteroarylene group include two or more rings, the two or more rings may be condensed with each other.

In the present specification, a C ₇ -C ₄₀ aralkyl group refers to a monovalent group in which an aryl group is substituted for an alkyl group, and the sum of carbon atoms of the alkyl group and the aryl group constituting the group is 7 to 40. Specific examples of the C ₇ -C ₄₀ aralkyl group include a benzyl group, a phenylethyl group, a methylbenzyl group, a naphthylmethyl group, and the like.

In this specification, "halogen atom" may be selected from among fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

Hereinafter, synthesis examples and examples will be described in more detail with respect to the compound and the organic light emitting device according to one embodiment of the present invention. In the following synthesis example, in the expression "B was used instead of A", the molar equivalent of A and the molar equivalent of B are the same.

Hereinafter, for synthesis examples and examples, an amino fluorene polymer and an organic light emitting device according to an embodiment of the present invention will be described in more detail, but the present invention is not limited to the following synthesis examples and examples.

[Example]

Analysis was performed according to the method described later in the following Synthesis Example.

(1) Measurement of number average molecular weight, weight average molecular weight and degree of dispersion

Number average molecular weight (Mn), weight average molecular weight (Mw), and degree of dispersion (Mw/Mn) were measured under the following conditions by GPC (gel permeation chromatography) using polystyrene as a standard sample.

Analysis equipment: product of Shimadzu Corporation, trade name: Prominence

Column: Polymer Labs, PLgel MIXED-B

Column temperature: 40°C

Flow rate: 1.0 mL/min

Injection volume: 20μL

Solvent: tetrahydrofuran (THF) (concentration: about 0.05% by weight)

Detector: UV-VIS detector (manufactured by Shimadzu Corporation, trade name: SPD-10AV)

Standard Sample: Polystyrene

Synthesis Example 1: Synthesis of Compound 100

1) Synthesis of monomer A

Monomer A was synthesized according to the following reaction scheme.

2,7-dibromo-9,9-dioctylfluorene (2,7-dibromo-9,9-dioctylfluorene) (50.00g, 91.17mmol) was put in a 2L three-necked flask and filled with argon (purging). ). Tetrahydrofuran (750ml) was put into the flask, cooled to -75 °C in an acetone/dry ice bath, and stirred for 15 minutes. 1.6M of n-butyl lithium (n-BuLi) (36.12ml, 95.72mmol, hexane solution) was added dropwise to the flask and stirred for 1 hour. Triisopropyl borate (20.58ml, 109.40mmol) was added to the flask and stirred at room temperature for 3 hours. After completion of the reaction, water was added to the reaction mixture, extraction was performed using ethyl acetate, and the extracted organic layer was concentrated. Compound 1 was obtained by recrystallizing the solid obtained by concentrating the organic layer using chloroform and hexane.

The following is compound 1 (15.00g, 29.22mmol), iodobenzene (6.56g, 32.14mmol), tetrakis (triphenylphosphine) palladium (0) (tetrakis (triphenylphosphine) palladium ( 0)) (1.01 g, 0.88 mmol) and sodium carbonate (24.77 g, 233.75 mmol) were added, and argon was filled. Ethanol (15ml), water (100ml), and toluene (116ml) were put into the flask, and the mixture was stirred at 85° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and impurities were separated by filtration using Celite (registered trademark). After adding water to the filtrate, extraction was performed using toluene, and the extracted organic layer was concentrated. The concentrate was purified by column chromatography to obtain compound 2.

Compound 2 (15.00 g, 27.49 mmol), pinacol diborane (7.68 g, 30.24 mmol), 1,1'-bis (diphenylphosphino) ferrocene-palladium (II) were added to a 300 ml three-necked flask. Dichloride-dichloromethane complex (1,1'-Bis (diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex: Pd(dppf)Cl ₂ CH ₂ Cl ₂ ) (0.34g, 0.41mmol) and potassium acetate (0.34g, 0.41mmol) acetate) (8.09g, 82.47mmol) was added, and argon was filled. Anhydrous 1,4-dioxane (110ml) was added to the flask and the mixture was stirred at 100 °C for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, and impurities were separated by filtration using Celite. Activated carbon (10g) was added to the filtrate and stirred at 100° C. for 1 hour, then the activated carbon was removed using celite, and the filtrate was concentrated. The solid obtained by concentrating the filtrate was washed with acetonitrile (25ml) at room temperature to obtain compound 3.

Compound 3 (3.90 g, 6.59 mmol), N,N-bis(4-bromophenyl)-N,N-bis(4-methylphenyl)-9,9-dioctyl-9H-flu in a 500 ml three-necked flask Orene-2,7-diamine (N,N-bis(4-bromophenyl)-N, N-bis(4-methylphenyl)-9,9-dioctyl-9H-fluorene-2,7-diamine) (6.00g, 6.59mmol) and bis(triphenylphosphine)palladium(II) dichloride (0.23g, 0.33mmol) were added, and argon was filled. Tetraethyl ammonium hydroxide (3.88g, 26.35mmol) and anhydrous toluene (300ml) were added to the flask, and the mixture was stirred at 100 °C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and impurities were separated by filtration using Celite. After adding water to the filtrate, extraction was performed using toluene, and the extracted organic layer was concentrated. The concentrate was purified by column chromatography to obtain a light green solid. Compound 4 was obtained by recrystallizing the obtained solid using tetrahydrofuran and methanol.

Compound 4 (4.00 g, 3.08 mmol), 9,9-dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2 in a 50 ml three-neck flask -yl) -9H-fluorene-2-carboxyaldehyde (9,9-dioctyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-fluorene- 2-carboxaldehyde) (1.65g, 3.02mmol), Palladium (II) acetate (0.035g, 0.15mmol), tris(2-methoxyphenyl)phosphine ) (0.22 g, 0.62 mmol) was added, and argon was filled. Tetraethyl ammonium hydroxide (1.82g, 2.40mmol) and anhydrous toluene (10ml) were added to the flask, and the mixture was stirred at 100° C. for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and impurities were separated by filtration using Celite. Water was added to the filtrate, extraction was performed using toluene, and the extracted organic layer was concentrated. The concentrate was purified by column chromatography to obtain compound 5.

Compound 5 (3.80 g, 2.32 mmol) and methyltriphenylphosphonium iodide (1.31 g, 3.26 mmol) were placed in a 50 ml three-necked flask and filled with argon. Tetrahydrofuran (26ml) was added to the flask, cooled to 0° C. in an ice bath, potassium tert-butoxide (0.34g, 3.01mmol) was added, and the mixture was stirred. After completion of the reaction, water was added and extracted using toluene, and the extracted organic layer was concentrated. The concentrate was purified by column chromatography to obtain a pale yellow solid. After dissolving the obtained solid in tetrahydrofuran, it was re-precipitated with methanol to obtain monomer A.

The obtained monomer A was confirmed by H ¹ -NMR.

¹ H-NMR (300 MHz, CDCl ₃ ): σ 7.77-7.36 (m, 23H), 7.10-6.90 (m, 16H), 6.81 (dd, J = 17.4 Hz, 10.8 Hz, 1H), 5.80 (d, J = 17.4 Hz, 1H), 5.26 (d, J = 11.4 Hz, 1H), 2.35 (s, 6H), 2.06–1.96 (m, 8H), 1.83–1.77 (m, 2H), 1.53–1.06 (m , 60H), 0.88-0.71 (m, 30H)

2) Synthesis of monomer B

Monomer B was synthesized by the following reaction scheme.

Compound 6 (10.00 g, 19.03 mmol), pinacol diborane (5.80 g, 22.83 mmol), Pd(dppf)Cl ₂ CH ₂ Cl ₂ (0.56 g, 0.68 mmol) and potassium acetate ( 5.60 g, 57.09 mmol) was added, and argon was filled. Anhydrous 1,4-dioxane (100ml) was added to the flask and the mixture was stirred at 100 °C for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature and impurities were separated by filtration using Celite. Activated carbon (10 g) was added to the filtrate, stirred at 100 ° C. for 1 hour, and then activated carbon was removed using celite, and the filtrate was concentrated. The solid obtained by concentrating the filtrate was washed with acetonitrile (25ml) at room temperature to obtain compound 7.

In a 100 ml three-necked flask, compound 7 (0.95 g, 1.66 mmol), N,N-bis(4-bromophenyl)-N,N-bis(4-methylphenyl)-9,9-dioctyl-9H-flu Orene-2,7-diamine (1.51g, 1.66mmol) and bis(triphenylphosphine)palladium(II) dichloride (0.06g, 0.09mmol) were added, and argon was filled. Tetraethyl ammonium hydroxide (2.44g, 16.59mmol) and anhydrous toluene (47ml) were added to the flask, and the mixture was stirred at 100° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and impurities were separated by filtration using Celite. After adding water to the filtrate, extraction was performed using toluene, and the extracted organic layer was concentrated. The concentrate was purified by column chromatography to obtain a light green solid. Compound 8 was obtained by recrystallizing the obtained solid using tetrahydrofuran and methanol.

Compound 8 (1.00 g, 0.60 mmol), 9,9-dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2 in a 50 ml three-necked flask -yl) -9H-fluorene-2-carboxyaldehyde (0.33 g, 0.60 mmol), palladium (II) acetate (0.007 g, 0.03 mmol), tris (2-methoxyphenyl) phosphine (0.04 g 0.20 mmol) ), and filled with argon. Tetraethyl ammonium hydroxide (0.35g, 2.40mmol) and anhydrous toluene (10ml) were added to the flask, and the mixture was stirred at 100 °C for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and impurities were separated by filtration using Celite. Water was added to the filtrate, extraction was performed using toluene, and the extracted organic layer was concentrated. The concentrate was purified by column chromatography to obtain compound 9.

Compound 9 (0.73g, 0.45mmol) and methyltriphenylphosphonium iodide (0.25g, 0.63mmol) were placed in a 100ml three-necked flask and filled with argon. Tetrahydrofuran (50ml) was added to the flask, cooled to 0 °C in an ice bath, potassium tert-butoxide (0.06g, 0.59mmol) was added and the mixture was stirred. After completion of the reaction, water was added and extracted using toluene, and the extracted organic layer was concentrated. The concentrate was purified by column chromatography to obtain a pale yellow solid. After dissolving the obtained solid in tetrahydrofuran, it was re-precipitated with methanol to obtain monomer B.

The obtained monomer B was confirmed by H ¹ -NMR.

¹ H-NMR (300 MHz, CDCl ₃ ): σ 7.81-6.90 (m, 46H), 6.81 (dd, J = 17.4 Hz, 10.8 Hz, 1H), 5.80 (d, J = 17.4 Hz, 1H), 5.26 (d, J = 11.4 Hz, 1H), 3.09 (s, 8H), 2.35 (s, 6H), 2.01–1.96 (m, 4H), 1.80–1.75 (m, 4H), 1.25–1.05 (m, 42H) ), 0.87-0.69 (m, 12H)

3) Synthesis of compound 100

Compound 100 having the structure shown below was synthesized using the monomer A and monomer B synthesized above.

<Compound 100>

Monomer A (1000mg), Monomer B (105.0mg), azobisisobutyronitrile (2.0mg), and toluene (2.8ml) were added to a Schlenk flask, bubbled, and then frozen. After degassing, the mixture was heated and stirred at 80°C for 6.5 hours. After cooling the reaction mixture to room temperature, it was reprecipitated seven times using tetrahydrofuran as a good solvent and methanol/acetone as a bad solvent, and then the obtained precipitate was vacuum dried.

0.85 g of Compound 100, which is a random copolymer of monomer A and monomer B (provided that the ratio of structural unit Aa derived from monomer A to structural unit Bb derived from monomer B is Aa:Bb = 90:10) was obtained. Compound 100 had a number average molecular weight (Mn) of 35,800, a weight average molecular weight (Mw) of 74,600, and a degree of dispersion (Mw/Mn) of 2.08.

Synthesis Example 2: Synthesis of Compound 101

1) Synthesis of monomer C

Monomer C was synthesized by the following reaction scheme.

Compound 10 was synthesized in the same manner as in the synthesis of Compound 9, except that Compound 7 was used instead of Compound 8. Monomer C was synthesized in the same manner as in the synthesis of monomer B, except that compound 10 was used instead of compound 9.

The obtained monomer C was confirmed by H ¹ -NMR.

¹ H-NMR (300 MHz, CDCl ₃ ): σ 7.84 (d, J = 7.8, 2H), 7.71-7.50 (m, 10H), 7.44-7.20 (m, 9H), 6.70-6.93 (m, 2H) , 6.81 (dd, J = 17.4 Hz, 10.8 Hz, 1H), 5.80 (d, J = 18.0 Hz, 1H), 5.24 (d, J = 11.4 Hz, 1H), 3.09 (s, 8H), 2.00–1.95 (m, 4H), 1.21-1.05 (m, 20H), 0.82-0.66 (m, 10H)

2) Synthesis of Compound 101

Compound 101, which is a random copolymer of monomers A and C having the following structure, was synthesized in the same manner as in the synthesis of compound 100, except that monomer C was used instead of monomer B. The ratio of structural unit Aa derived from monomer A and structural unit Cc derived from monomer C was Aa:Cc=90:10. The compound 101 had a number average molecular weight (Mn) of 58,100, a weight average molecular weight (Mw) of 155,500, and a degree of dispersion (Mw/Mn) of 2.67.

<Compound 101>

Synthesis Example 3: Synthesis of Compound 102

1) Synthesis of monomer D

Monomer D was synthesized by the following reaction scheme.

Compound 12 was synthesized in the same manner as in the synthesis of Compound 8, except that Compound 11 was used instead of Compound 7. Compound 13 was synthesized in the same manner as in the synthesis of Compound 9, except that Compound 12 was used instead of Compound 8. Monomer D was synthesized in the same manner as in the synthesis of monomer B, except that Compound 13 was used instead of Compound 9.

The obtained monomer D was confirmed by H ¹ -NMR.

¹ H-NMR (300 MHz, CDCl ₃ ): σ 7.74-7.63 (m, 4H), 7.56-7.48 (m, 10H), 7.41-7.28 (m, 5H), 7.19-7.09 (m, 16H), 6.81 (dd, J = 17.4 Hz, 10.8 Hz, 1H), 5.80 (d, J = 17.4 Hz, 1H), 5.26 (d, J = 11.4 Hz, 1H), 2.35 (s, 6H), 2.01-1.96 (m) , 8H), 1.82-1.77 (m, 4H), 1.30-1.13 (m, 60H), 0.88-0.67 (m, 30H)

2) Synthesis of monomer E

Compound 15 was synthesized in the same manner as in the synthesis of Compound 7, except that Compound 14 was used instead of Compound 6. Compound 16 was synthesized in the same manner as in the synthesis of Compound 9, except that Compound 15 was used instead of Compound 8. Monomer E was synthesized in the same manner as in the synthesis of monomer B, except that Compound 16 was used instead of Compound 9.

The obtained monomer E was confirmed by H ¹ -NMR.

¹ H-NMR (300 MHz, CDCl ₃ ): σ 7.83-7.63 (m, 2H), 7.54-7.50 (m, 4H), 7.43-7.23 (m, 7H), 7.18-7.16 (m, 2H), 6.95 -6.91 (m, 4H), 6.81 (dd, J = 17.4 Hz, 10.8 Hz, 1H), 5.80 (d, J = 18.0 Hz, 1H), 5.24 (d, J = 11.4 Hz, 1H), 3.09 (s , 8H), 2.00-1.94 (m, 7H), 1.21-1.04 (m, 20H), 0.81-0.64 (m, 10H)

3) Synthesis of Compound 102

Compound 102, which is a random copolymer of monomers D and E, was synthesized in the same manner as in the synthesis of compound 100, except that monomers D and E were used instead of monomers A and B. The ratio of the structural unit Dd derived from monomer D to the structural unit Ee derived from monomer E was Dd : Ee = 90 : 10. Compound 102 had a number average molecular weight (Mn) of 74,000, a weight average molecular weight (Mw) of 195,000, and a degree of dispersion (Mw/Mn) of 2.60.

<Compound 102>

Synthesis Example 4: Synthesis of Compound 103

1) Synthesis of monomer F

Monomer F was synthesized by the following reaction scheme.

Compound 17 (1.66g, 2.79mmol), ditolylamine (0.50g, 2.53mmol), copper (I) iodide (CuI) (0.02g, 0.13mmol), trans-1, 2-cyclohexanediamine (0.06g, 0.51mmol) and sodium tert-butoxide (0.54g, 5.58mmol) were added and argon was filled. Anhydrous 1,4-dioxane (5ml) was added to the flask and the mixture was stirred at 100° C. for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and impurities were separated by filtration using Celite. After concentrating the filtrate, the concentrate was purified by column chromatography to obtain compound 18.

Compound 18 (1.00 g, 1.50 mmol), p-toluidine (0.21 g, 1.96 mmol), tris(dibenzylideneacetone) dipalladium (0) (tris(dibenzylideneacetone) dipalladium (0): Pd ₂ (dpa) ₃ ) (0.07g, 0.08mmol), 1,1'-bis (diphenylphosphino) ferrocene (1,1'-Bis (diphenylphosphino) ferrocene: dppf) (0.13g, 0.23mmol) and sodium tert-butoxide (0.29g, 3.01mmol), and argon was charged. Toluene (2ml) was added to the flask and the mixture was stirred at 100 °C for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and impurities were separated by filtration using Celite. After adding water to the filtrate, extraction was performed using toluene, and the extracted organic layer was concentrated. The concentrate was purified by column chromatography to obtain compound 19.

Compound 19 (10.00g, 14.50mmol), 1-bromo-4-iodobenzene (4.50g, 15.92mmol), copper (I) iodide (0.15g) in a 100ml three-necked flask , 0.80 mmol), trans-1,2-cyclohexanediamine (0.33 g, 2.89 mmol) and sodium tert-butoxide (2.78 g, 28.04 mmol), and argon was charged. Anhydrous 1,4-dioxane (14ml) was added to the flask, and the mixture was stirred at 100 °C for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and impurities were separated by filtration using Celite. After concentrating the filtrate, the concentrate was purified by column chromatography to obtain compound 20.

Compound 21 was synthesized in the same manner as in the synthesis of compound 9, except that compound 20 was used instead of compound 8. Monomer F was synthesized in the same manner as in the synthesis of monomer B, except that Compound 21 was used instead of Compound 9.

The obtained monomer F was confirmed by H ¹ -NMR.

1H ^- NMR (300 MHz, CDCl ₃ ): σ 7.71-7.37 (m, 10H), 7.28-7.04 (m, 18H), 6.81 (dd, J = 17.4 Hz, 10.8 Hz, 1H), 5.80 (d, J = 18.0 Hz, 1H), 5.24 (d, J = 11.4 Hz, 1H), 2.35 (s, 9H), 2.01–1.96 (m, 4H), 1.79–1.73 (m, 4H), 1.29–1.05 (m , 40H), 0.88-0.68 (m, 20H)

2) Synthesis of Compound 103

Compound 103 was synthesized in the same manner as in the synthesis of Compound 100, except that monomers E and F were used instead of monomers A and B. The ratio of structural unit Ee derived from monomer E and structural unit Ff derived from monomer F was Ee:Ff = 90:10. Compound 103 had a number average molecular weight (Mn) of 38,000, a weight average molecular weight (Mw) of 93,000, and a degree of dispersion (Mw/Mn) of 2.4.

<Compound 103>

Example 1

An organic light emitting device shown in FIG. 1 was manufactured according to a method described below.

A hole injection layer was formed by spin-coating with PEDOT/PSS (manufactured by Sigma-Aldrich) to a thickness of 30 nm after drying on an ITO glass substrate on which stripe-type ITO (thickness 150 nm) (anode) was disposed.

Then, compound 100 (1% by weight, xylene solution) was spin-coated on the hole injection layer under a nitrogen atmosphere, followed by heat treatment on a hot plate at 230 ° C. for 1 hour to form a hole transport layer having a thickness of 30 nm.

Then, 1,3-bis( N -carbazolyl)benzene (hereinafter mCP) and 4,4'-bis(carbazol-9-yl)biphenyl (hereinafter CBP) were mixed at a ratio of 7:3 (mass ratio). A host and a tris(2-(3-p-xylyl)phenyl)pyridine iridium(III) (hereinafter referred to as TEG) dopant mixed in a ratio are simultaneously deposited in a vacuum deposition apparatus to form a 30 nm thick light emitting layer (total mass of the light emitting layer). For , the dopant formed 10% by mass). TEG is a light emitting material capable of emitting light from triplet excitons (phosphorescence).

Subsequently, the substrate formed up to the light emitting layer was introduced into a vacuum evaporator, and Liq and KLET-03 were co-evaporated to form an electron transport layer having a thickness of 50 nm on the light emitting layer.

Subsequently, an electron injection material (LiF) was deposited to a thickness of 1 nm.

Subsequently, an organic light emitting device was manufactured by depositing aluminum on the electron injection layer to form a cathode (cathode) having a thickness of 100 nm.

Example 2

An organic light emitting device was manufactured in the same manner as in Example 1, except that Compound 101 was used instead of Compound 100.

Example 3

An organic light emitting device was manufactured in the same manner as in Example 1, except that Compound 102 was used instead of Compound 100.

Example 4

An organic light emitting device was manufactured in the same manner as in Example 1, except that Compound 103 was used instead of Compound 100.

Comparative Example 1

An organic light emitting device was manufactured in the same manner as in Example 1, except that Compound c1 was used instead of Compound 100. The following compound c1 is a random copolymer containing no repeating unit having a fluorene structure, and n and m are in a molar ratio of 90:10. The number average molecular weight (Mn) of compound c1 is 24,000, and the weight average molecular weight (Mw) is 64,000.

<Compound c1>

evaluation example

For the organic light emitting devices of Examples 1 to 4 and Comparative Example 1, current efficiency and light emitting lifetime were evaluated according to the following methods. The results are shown in Table 1 below. The current efficiency and luminous lifetime in Table 1 below are expressed as relative values for the current efficiency and luminous lifetime of Comparative Example 1, and represent relative values when the current efficiency and luminous lifetime of Comparative Example 1 are set to 100, respectively.

(1) Current efficiency

A predetermined voltage was applied to the organic light emitting element using a DC constant voltage power supply (for example, source meter manufactured by KEYENCE) to emit light from the organic light emitting element. A current applied to the organic light emitting device is gradually increased while measuring light emission of the organic light emitting device using a luminance measuring device (eg, SR-3: product of Topcom). When the luminance reached 1000 cd/m ² , the current was kept constant. Current efficiency (cd/A) was calculated by calculating the current value (current density) per unit area of the organic light emitting device and calculating the luminance (cd/m ² ) from the current density (A/m ₂ ). Current efficiency represents the efficiency of converting current into luminous energy, and the higher the current efficiency, the higher the performance of the organic light emitting device.

(2) Luminous lifetime

The time taken for the luminance value measured by the luminance measuring device to decrease and reach 80% of the initial luminance was referred to as "emission lifetime".

hole transport layer current efficiency luminous life Example 1 compound 100 120 1630 Example 2 compound 101 112 540 Example 3 compound 102 118 2000 Example 4 compound 103 110 910 Comparative Example 1 compound c1 100 100

Referring to the results of Table 1, it can be seen that Examples 1 to 4 have improved current efficiency and light emission lifetime compared to Comparative Example 1.

The amino fluorene polymer not only enables efficient film formation using a solution coating method, but also can improve the lifespan of an organic light emitting device.

100: organic light emitting element,
110: substrate
120: first electrode
130: hole injection layer
140: hole transport layer
150: light emitting layer
160: electron transport layer
170: electron injection layer
180: second electrode

Claims (20)

An amino fluorene polymer comprising a first repeating unit represented by Formula 1 below:
<Formula 1>

In Formula 1,
R ₁ to R ₃ may each independently represent a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group; is selected from;
m1 is an integer from 1 to 20;
F and F' are each independently selected from a substituted or unsubstituted azafluorenylene group and a substituted or unsubstituted fluorenylene group;
n1 and n2 are each independently selected from 1 and 2;
A is a group represented by the following formula (2);
R ₄ is a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, substituted or unsubstituted C ₆ -C ₃₀ aryloxy group, substituted or An unsubstituted C ₇ -C ₄₀ aralkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, -Si(Q ₁ )(Q ₂ )(Q ₃ ) and -N(Q ₁ )(Q ₂ ) is selected from;
<Formula 2>

In Formula 2,
L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkylene group, a substituted or unsubstituted C ₆ -C ₃₀ Arylene group, substituted or unsubstituted C ₁ -C ₂₀ oxyalkylene group, substituted or unsubstituted C ₃ -C ₁₆ oxycycloalkylene group, substituted or unsubstituted C ₆ -C ₃₀ oxyarylene group, substituted or unsubstituted selected from a C ₇ -C ₄₀ aralkylene group, a substituted or unsubstituted C ₅ -C ₃₀ heteroarylene group, -Si(Q ₄ )(Q ₅ )-, and -N(Q ₄ )-;
n3 and n4 are each independently selected from 1 and 2;
Ar ₁ is a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, substituted or unsubstituted C ₆ -C ₃₀ aryloxy group, substituted or unsubstituted C ₇ -C ₄₀ aralkyl group, substituted or It is selected from an unsubstituted C ₅ -C ₃₀ heteroaryl group and -N(Q ₆ )(Q ₇ );
Ar ₁ is optionally bonded to F, F', L ₁ or L ₂ to form a ring;
Q ₁ to Q ₇ are each independently selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group;
* is a binding site with a neighboring atom. According to claim 1,
R ₁ to R ₃ are each independently selected from a hydrogen atom, a methyl group, an ethyl group, an n-propyl group and an n-butyl group, an amino fluorene polymer. According to claim 1,
F and F' are, independently of each other, a group represented by the following formula (3), an amino fluorene polymer:
<Formula 3>

In Formula 3,
R ₅ to R ₈ are each independently a bonding site, a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, or a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group. , a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, a substituted or unsubstituted C ₆ - C ₃₀ aryloxy group, substituted or unsubstituted C ₇ -C ₄₀ aralkyl group, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, -Si(Q ₁ )(Q ₂ )(Q ₃ ) and -N (Q ₁ ) (Q ₂ );
Adjacent substituents among R ₅ to R ₈ are optionally bonded to each other to form a ring;
two substituents of R ₅ to R ₈ are binding sites;
Q ₁ to Q ₃ are each independently selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group;
a and b are each independently selected from 1, 2, 3 and 4;
Y ₁ to Y ₈ are each independently a carbon atom or a nitrogen atom. According to claim 3,
R ₅ to R ₈ are each independently a bonding site, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pen ethyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2 -Dimethyl butyl group, n-heptyl group, 1,4-dimethyl pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, 2-ethyl hexyl group, 3-methyl-1-isopropyl butyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methyl propyl group, n-nonyl group, 3,5,5- Trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group Decyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-eicosyl group, phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, pyridyl group, pyrimi a dil group, a pyrazinyl group, a triazinyl group, a furanyl group and a thiophenyl group;
-F, a methyl group, an ethyl group, and an n-propyl group, substituted with at least one selected from a phenyl group and a naphthyl group; and
methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-octyl group, phenyl group, naphthyl group, phenyl group substituted with methyl group, and tert- a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, a triazinyl group, a furanyl group, and a thiophenyl group, substituted with at least one selected from a phenyl group substituted with a butyl group; is selected from;
Adjacent substituents among R ₅ to R ₈ are optionally bonded to each other to form a ring;
An amino fluorene polymer, wherein two substituents of R ₅ to R ₈ are binding sites. According to claim 1,
F and F' are each independently selected from groups represented by the following formulas 4-1 to 4-58, an amino fluorene polymer:

In Formulas 4-1 to 4-58,
Two hydrogen atoms are replaced with binding sites. According to claim 1,
R ₄ is a hydrogen atom, a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₃₀ aryl group, a C ₁ -C ₂₀ alkoxy group, and -N(Q ₁ )(Q ₂ ); and
a C ₆ -C ₃₀ aryl group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₃₀ aryl group, and a C ₁ -C ₂₀ alkoxy group; is selected from;
Q ₁ and Q ₂ are each independently a hydrogen atom, a C ₆ -C ₃₀ aryl group; and
a C ₆ -C ₃₀ aryl group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group; An amino fluorene polymer selected from. According to claim 1,
R ₄ is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-phen ethyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2-dimethyl butyl group, n-heptyl group , 1,4-dimethyl pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, 2-ethyl hexyl group, 3-methyl -1-isopropyl butyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methyl-propyl group, phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group and -N(Q ₁ )(Q ₂ ); and
methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2-dimethyl butyl group, n-heptyl group, 1,4-dimethyl Pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, phenyl group, naphthyl group, methoxy group, ethoxy group, n-propoxy group group, isopropoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, phenyl group, naphthyl group, substituted with at least one selected from n-heptyloxy group and n-octyloxy group a tyl group, an anthracenyl group and a phenanthrenyl group; is selected from;
Q ₁ and Q ₂ are each independently a hydrogen atom, a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthrenyl group; and
methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group; a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthrenyl group, substituted with at least one selected from; An amino fluorene polymer selected from. According to claim 1,
L ₁ and L ₂ are each independently a single bond, a C ₁ -C ₂₀ alkylene group and a C ₆ -C ₃₀ arylene group; and
a C ₁ -C ₂₀ alkylene group and a C ₆ -C ₃₀ arylene group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group and a C ₆ -C ₃₀ aryl group; An amino fluorene polymer selected from. According to claim 1,
L ₁ and L ₂ are each independently a single bond, a methylene group and a phenylene group; and
a methylene group and a phenylene group substituted with at least one selected from a methyl group, an n-hexyl group and a phenyl group; An amino fluorene polymer selected from. According to claim 1,
Ar ₁ is a hydrogen atom, a C ₁ -C ₂₀ alkyl group and a C ₆ -C ₃₀ aryl group; and
a C ₆ -C ₃₀ aryl group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₃₀ aryl group, and a C ₁ -C ₂₀ alkoxy group; is selected from;
Ar ₁ is optionally (optionally), F, F', L ₁ or L ₂ bonded to form a ring, amino fluorene polymer. According to claim 1,
Ar ₁ is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-phen ethyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2-dimethyl butyl group, n-heptyl group , 1,4-dimethyl pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, 2-ethyl hexyl group, 3-methyl -1-isopropyl butyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methyl-propyl group, phenyl group, naphthyl group, anthracenyl group and phenanthrenyl group; and
methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethyl propyl group, n-hexyl group, isohexyl group, 1,3-dimethyl butyl group, 1-isopropyl propyl group, 1,2-dimethyl butyl group, n-heptyl group, 1,4-dimethyl Pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropyl propyl group, 1-ethyl-3-methyl butyl group, n-octyl group, phenyl group, naphthyl group, methoxy group, ethoxy group, n-propoxy group group, isopropoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, phenyl group, naphthyl group, substituted with at least one selected from n-heptyloxy group and n-octyloxy group a tyl group, an anthracenyl group and a phenanthrenyl group; is selected from;
Ar ₁ is optionally (optionally), F, F', L ₁ or L ₂ bonded to form a ring, amino fluorene polymer. According to claim 1,
The first repeating unit represented by Formula 1 is an amino fluorene polymer represented by Formula 1-1:
<Formula 1-1'>

In Chemical Formula 1-1,
R ₁ to R ₃ may each independently represent a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group; is selected from;
m1 is an integer from 1 to 20;
n1 and n2 are each independently selected from 1 and 2;
A is a group represented by the following formula (2);
R ₄ is a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, substituted or unsubstituted C ₆ -C ₃₀ aryloxy group, substituted or An unsubstituted C ₇ -C ₄₀ aralkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, -Si(Q ₁ )(Q ₂ )(Q ₃ ) and -N(Q ₁ )(Q ₂ ) is selected from;
<Formula 2>

In Formula 2,
L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkylene group, a substituted or unsubstituted C ₆ -C ₃₀ Arylene group, substituted or unsubstituted C ₁ -C ₂₀ oxyalkylene group, substituted or unsubstituted C ₃ -C ₁₆ oxycycloalkylene group, substituted or unsubstituted C ₆ -C ₃₀ oxyarylene group, substituted or unsubstituted selected from a C ₇ -C ₄₀ aralkylene group, a substituted or unsubstituted C ₅ -C ₃₀ heteroarylene group, -Si(Q ₄ )(Q ₅ )-, and -N(Q ₄ )-;
n3 and n4 are each independently selected from 1 and 2;
Ar ₁ is a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, substituted or unsubstituted C ₆ -C ₃₀ aryloxy group, substituted or unsubstituted C ₇ -C ₄₀ aralkyl group, substituted or It is selected from an unsubstituted C ₅ -C ₃₀ heteroaryl group and -N(Q ₆ )(Q ₇ );
Ar ₁ is optionally bonded to F, F', L ₁ or L ₂ to form a ring;
* is a binding site with a neighboring atom;
R ₅ to R ₈ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, or a substituted Or an unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkoxy group, a substituted or unsubstituted C ₆ -C ₃₀ An aryloxy group, a substituted or unsubstituted C ₇ -C ₄₀ aralkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, -Si(Q ₁ )(Q ₂ )(Q ₃ ) and -N(Q ₁ )(Q ₂ );
Adjacent substituents among R ₅ to R ₈ are optionally bonded to each other to form a ring;
a and b are each independently selected from 1, 2, 3 and 4;
Y ₁ to Y ₈ are each independently a carbon atom or a nitrogen atom;
Q ₁ to Q ₇ are each independently selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group. According to claim 1,
The first repeating unit represented by Formula 1 is an amino fluorene polymer selected from the following formulas:

In the above formulas, m is an integer from 1 to 10. According to claim 1,
An amino fluorene polymer further comprising a second repeating unit derived from a monomer containing at least one selected from crosslinking groups represented by Formulas 5-1 to 5-10:

In Chemical Formulas 5-1 to 5-10,
R ₁₀ to R ₁₆ are each independently a hydrogen atom or a substituted or unsubstituted C ₁ -C ₂₀ alkyl group;
p is an integer from 1 to 10;
* is a binding site with a neighboring atom. According to claim 14,
The second repeating unit is an amino fluorene polymer represented by Formula 6 below:
<Formula 6>

In Formula 6,
R ₁₇ to R ₁₉ are each independently a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, or a substituted or unsubstituted C ₆ -C ₃₀ aryl group;
R ₂₀ to R ₂₈ are each independently a crosslinking group, a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, or a substituted or unsubstituted C ₁ -C ₂₀ alkyl group represented by Formulas 5-1 to 5-10 below. , a substituted or unsubstituted C ₃ -C ₁₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, a substituted or unsubstituted C ₃ -C ₁₆ A cycloalkoxy group, a substituted or unsubstituted C ₆ -C ₃₀ aryloxy group, a substituted or unsubstituted C ₇ -C ₄₀ aralkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, -Si(Q ₁ ) (Q ₂ ) (Q ₃ ) and -N (Q ₁ ) (Q ₂ );
Adjacent substituents among R ₂₀ to R ₂₈ are optionally bonded to each other to form a ring;
at least one of R ₂₀ to R ₂₈ is selected from crosslinking groups represented by Formulas 5-1 to 5-10;
c, d, e and f are each independently selected from 1, 2 and 3;
A' is a single bond, a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₆ cycloalkylene group, a substituted or unsubstituted C ₆ -C ₃₀ arylene group, or a substituted or unsubstituted C 3 -C 16 cycloalkylene group. C ₁ -C ₂₀ oxyalkylene group, substituted or unsubstituted C ₃ -C ₁₆ oxycycloalkylene group, substituted or unsubstituted C ₆ -C ₃₀ oxyarylene group, substituted or unsubstituted C ₇ -C ₄₀ are It is selected from an alkylene group, a substituted or unsubstituted C ₅ -C ₃₀ heteroarylene group, -Si(Q ₄ )(Q ₅ )-, and -N(Q ₄ )-;
n5 is selected from 1, 2, 3, 4 and 5;
m2 is an integer from 0 to 20;
Q ₁ to Q ₅ are each independently selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, and a substituted or unsubstituted C ₆ -C ₃₀ aryl group;

In Chemical Formulas 5-1 to 5-10,
R ₁₀ to R ₁₆ are each independently a hydrogen atom or a substituted or unsubstituted C ₁ -C ₂₀ alkyl group;
p is an integer from 1 to 10;
* is a binding site with a neighboring atom. According to claim 15,
(A′) _n5 is a single bond, a C ₁ -C ₂₀ alkylene group, a C ₆ -C ₃₀ arylene group, and a group represented by the following formula (2); and
a C ₁ -C ₂₀ alkylene group and a C ₆ -C ₃₀ arylene group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group and a C ₆ -C ₃₀ aryl group; amino fluorene polymers, selected from:
<Formula 2>

In Formula 2,
L ₁ and L ₂ are each independently a single bond, a C ₁ -C ₂₀ alkylene group and a C ₆ -C ₃₀ arylene group; and
a C ₁ -C ₂₀ alkylene group and a C ₆ -C ₃₀ arylene group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group and a C ₆ -C ₃₀ aryl group; is selected from;
n3 and n4 are each independently selected from 1 and 2;
Ar ₁ is a hydrogen atom, a C ₁ -C ₂₀ alkyl group and a C ₆ -C ₃₀ aryl group; and
a C ₆ -C ₃₀ aryl group substituted with at least one selected from a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₃₀ aryl group, and a C ₁ -C ₂₀ alkoxy group; is selected from;
* is a binding site with a neighboring atom. According to claim 14,
wherein the second repeating unit is selected from the following structures:

Among the above chemical formulas,
n and m are independently of each other an integer from 1 to 10;
mn is an integer greater than or equal to 0; a first electrode; a second electrode; and an organic layer interposed between the first electrode and the second electrode;
The organic layer comprises an amino fluorene polymer according to any one of claims 1 to 17, an organic light emitting device. According to claim 18,
the organic layer includes a light emitting layer;
The light emitting layer includes a phosphorescent dopant, an organic light emitting device. According to claim 18,
the organic layer includes a hole transport layer;
The amino fluorene polymer is included in the hole transport layer, an organic light emitting device.

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