KR102436755B1 - Polymer, monomer, coating compositions comprising same, organic light emitting device using same and method of manufacturing of organic light emitting device using same - Google Patents

Abstract

The present specification relates to a polymer including a unit represented by Formula 1, a monomer represented by Formula 2, a coating composition including the same, an organic light emitting device formed using the same, and a method of manufacturing an organic light emitting device using the same.

Description

Polymer, monomer, coating composition containing same, organic light emitting device using same, and method for manufacturing organic light emitting device using same SAME}

The present specification relates to a polymer, a monomer, a coating composition comprising the same, an organic light emitting device formed using the same, and a method of manufacturing an organic light emitting device using the same.

This specification claims the benefit of the filing date of Korean Patent Application No. 10-2019-0115460 filed with the Korean Intellectual Property Office on September 19, 2019, the entire contents of which are incorporated herein by reference.

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

As materials used in organic light emitting devices, pure organic materials or complex compounds in which an organic material and a metal are complexed account for most, and depending on the use, a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. can be divided into Here, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material that is easily oxidized and has an electrochemically stable state upon oxidation is mainly used. On the other hand, as the electron injection material or the electron transport material, an organic material having an n-type property, that is, an organic material that is easily reduced and has an electrochemically stable state upon reduction is mainly used. As the light emitting material, a material having both p-type and n-type properties, that is, a material having a stable form in both oxidation and reduction states, is preferred, and a material with high luminous efficiency that converts excitons into light when formed desirable.

In addition to the above, it is preferable that the material used in the organic light emitting device additionally has the following properties.

이하의 값을 가지므로, 높은 전류를 필요로 하는 유기 발광 소자에는 사용하기 힘든 문제가 있다.First, it is preferable that the material used in the organic light emitting device has excellent thermal stability. This is because joule heating occurs due to the movement of electric charges in the organic light emitting diode. NPB (N,N'-Di(1-naphthyl)-N,N"-diphenyl-(1,1"-biphenyl)-4,4"-diamine), which is currently mainly used as a hole transport layer material, is free the transition temperature is 100

Since it has the following value, there is a problem in that it is difficult to use the organic light emitting device that requires a high current.

Second, in order to obtain a high-efficiency organic light-emitting device capable of low voltage driving, holes or electrons injected into the organic light-emitting device should be smoothly transferred to the light emitting layer, and the injected holes and electrons should be prevented from escaping out of the light emitting layer. To this end, a material used in the organic light emitting diode must have an appropriate band gap and a Highest Occupied Molecular Orbital (HOMO) or Lowest Unoccupied Molecular Orbital (LUMO) energy level. In the case of PEDOT:PSS (Poly(3,4-ethylenediocythiophene) doped:poly(styrenesulfonic acid)), which is currently used as a hole transport material in an organic light emitting device manufactured by a solution coating method, LUMO energy of an organic material used as a light emitting layer material Since the LUMO energy level is lower than the level, it is difficult to manufacture an organic light emitting device with high efficiency and long life.

In addition, the material used for the organic light emitting device must have excellent chemical stability, charge mobility, and interfacial properties with an electrode or an adjacent layer. That is, the material used for the organic light emitting diode should be less deformed by moisture or oxygen. In addition, by having appropriate hole or electron mobility, the density of holes and electrons in the light emitting layer of the organic light emitting device should be balanced to maximize exciton formation. In addition, for the stability of the device, it should be possible to improve the interface with the electrode including the metal or metal oxide.

In addition to the above, the material used in the organic light emitting device for the solution process should additionally have the following properties.

First, it must form a storable homogeneous solution. Commercially available materials for the deposition process have good crystallinity, so they do not dissolve well in a solution, or crystals are easily captured even when a solution is formed.

Second, the layers subjected to solution processing must be solvent and material resistant to other layers. For this, a curing group is introduced as in VNPB (N4,N4"-di(naphthalen-1-yl)-N4,N4"-bis(4-vinylphenyl)biphenyl-4,4"-diamine), and after solution application, heat treatment or A material capable of forming a self-crosslinked polymer on a substrate through UV (ultraviolet) irradiation or forming a polymer with sufficient resistance to the next process is preferable, and HATCN (Hexaazatriphenylene hexacarbonitrile) In the case of an arylamine-based monomolecule used in OLED (ORGANIC LIGHT EMITTING DEVICE), it does not have resistance to the solvent of the next process by itself, so An aryl amine-based monomolecular compound that can be used in OLEDs needs to introduce a curing group.

Therefore, there is a demand in the art to develop an organic material having the above requirements.

KR 10-2016-0129191 A

An object of the present specification is to provide a polymer, a monomer, a coating composition including the same, an organic light emitting device formed using the same, and a method of manufacturing an organic light emitting device using the same.

An exemplary embodiment of the present specification provides a polymer including a unit represented by the following formula (1).

[Formula 1]

In Formula 1,

L is a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

a is an integer of 0 to 3, and when a is 2 or more, L is the same as or different from each other,

Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; hydroxyl group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

r6 and r7 are the same as or different from each other and each independently an integer of 0 to 3, when r6 is 2 or more, R6 is the same as or different from each other, and when r7 is 2 or more, R7 is the same as or different from each other,

r4, r5 and r8 are the same as or different from each other and each independently an integer of 0 to 4, when r4 is 2 or more, R4 is the same as or different from each other, and when r5 is 2 or more, R5 is the same as or different from each other, and r8 is 2 or more, R8 is the same as or different from each other,

n is the repeating number of the unit, and is an integer from 2 to 10,000.

In addition, an exemplary embodiment of the present specification provides a monomer represented by the following formula (2).

[Formula 2]

In Formula 2,

L is a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

a is an integer of 0 to 3, and when a is 2 or more, L is the same as or different from each other,

Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; hydroxyl group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

r6 and r7 are the same as or different from each other and each independently an integer of 0 to 3, when r6 is 2 or more, R6 is the same as or different from each other, and when r7 is 2 or more, R7 is the same as or different from each other,

r4, r5 and r8 are the same as or different from each other and each independently an integer of 0 to 4, when r4 is 2 or more, R4 is the same as or different from each other, and when r5 is 2 or more, R5 is the same as or different from each other, and r8 is 2 In this case, R8 is the same as or different from each other.

Another embodiment of the present specification provides a coating composition comprising a polymer comprising a unit represented by the above-described formula (1).

Another embodiment of the present specification provides a coating composition comprising a monomer represented by Formula 2 above.

An exemplary embodiment of the present specification includes a first electrode; a second electrode; and an organic material layer provided between the first electrode and the second electrode, wherein the organic material layer includes a polymer including a unit represented by Chemical Formula 1 described above.

In addition, an exemplary embodiment of the present specification includes the steps of preparing a first electrode; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer,

The step of forming the at least one organic material layer is a step of forming an organic material layer using a coating composition comprising a polymer including a unit represented by Formula 1, or a coating composition comprising a monomer represented by Formula 2 described above. As a method of manufacturing an organic light emitting device comprising a,

Forming the organic material layer using the coating composition may include coating the coating composition on the first electrode; and heat-treating or light-treating the coated coating composition.

Since the organic material layer formed using the polymer including the unit represented by Formula 1 according to an exemplary embodiment of the present specification has very low solubility in some solvents, a lamination process through a solution process on the organic material layer formed using the polymer can be performed.

The polymer including the unit represented by Formula 1 according to an exemplary embodiment of the present specification has a high glass transition temperature due to the specificity of the spirobifluorene structure, as well as low π-π stacking and low crystallinity, , excellent solubility in solvents.

In addition, the polymer according to the exemplary embodiment of the present specification may be used as a material for the organic material layer of the organic light emitting device, thereby lowering the driving voltage of the organic light emitting device.

In addition, the polymer according to an exemplary embodiment of the present specification may be used as a material for an organic material layer of an organic light emitting device to improve light efficiency.

In addition, the polymer according to an exemplary embodiment of the present specification may be used as a material for an organic material layer of an organic light emitting device to improve lifespan characteristics of the device.

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

Hereinafter, the present specification will be described in more detail.

The present specification provides a polymer including a unit represented by the following formula (1).

In an exemplary embodiment of the present specification, the polymer including the unit represented by Formula 1 is a linear polymer. The linear polymer refers to a linear one-dimensional polymer polymerized by a monomer having only two functional groups and connected in a line. In one embodiment, the polymer including the unit represented by the formula (1) is a polymer in which the units represented by the formula (1) are arranged in a line.

In an exemplary embodiment of the present specification, the polymer including the unit represented by the formula (1) may include two or more types of the unit represented by the formula (1). In this case, the polymer including the unit represented by Formula 1 may be a random copolymer; or a block copolymer.

In an exemplary embodiment of the present specification, the polymer including the unit represented by Formula 1 may be a homopolymer. Here, the homopolymer means a polymer formed with only one type of monomer.

In the present specification, the polymer including the unit represented by the formula (1) is a polymer composed of 100 mol% of the unit represented by the formula (1).

As used herein, the term “unit” refers to a structure in which a monomer is included in a polymer and is repeated, and refers to a structure in which the monomer is bonded to the polymer by polymerization.

In the present specification, the meaning of “including a unit” means that the unit is included in the main chain in the polymer.

As used herein, the term “monomer” refers to a monomer or unit that is a unit constituting the polymer.

OLED materials used in solution processing require appropriate solubility in appropriate solvents. The compound in which spirobifluorene is connected through the main chain of the polymer and the p-phenylene group has a high polymerization rate during manufacture, and thus the molecular weight of the polymer increases, thereby reducing solubility in solvents and limiting usable solvents.

In an exemplary embodiment of the present specification, in the unit represented by Formula 1, spirobifluorene is connected to the main chain of the polymer through an m-phenylene group. The polymer according to an exemplary embodiment of the present invention has the effect of easily controlling the molecular weight of the polymer during the preparation of the polymer, and improving the solubility at the same molecular weight.

The polymer of the present invention in which spirobifluorene is linked to the backbone of the polymer through an m-phenylene group is more suitable for inkjet solvent screening than a polymer in which spirobifluorene is linked to the backbone of the polymer by a p-phenylene group.

Therefore, when the polymer including the unit represented by Formula 1 is used in a hole transport layer, a hole injection layer, or a layer that simultaneously transports and injects holes of an organic light emitting device, the prepared hole transport layer, hole injection layer, or hole transport layer And, since the uniformity and surface properties of the layer simultaneously injecting holes are also excellent, the performance and lifespan characteristics of the device can be improved.

In addition, the polymer including the unit represented by the formula (1) is easier to control the molecular weight compared to the monomolecular compound containing spirobifluorene, it is also easy to control the viscosity of the solution containing the same.

When the polymer according to an exemplary embodiment of the present specification is used, the organic material layer can be formed by a solution process. In one embodiment, a polymer comprising a unit represented by Formula 1 according to an embodiment of the present invention; Alternatively, the monomer represented by Formula 2 may be dissolved in a solvent such as tetrahydrofuran (THF), xylene, or toluene, but is not limited thereto. In addition, the solvent may be used alone or in combination of two or more.

An organic material layer comprising a polymer including a unit represented by Formula 1 according to an exemplary embodiment of the present specification is a cycloketone; cycloalkane; or solvent resistance to solvents such as dioxane.

In an exemplary embodiment, the solubility in cyclohexanone of the organic material layer including the polymer including the unit represented by Formula 1 is 0.05 wt% or less.

In one embodiment, the solubility in dioxane of the organic material layer including the polymer including the unit represented by Formula 1 is 0.05 wt% or less.

In an exemplary embodiment, the solubility in cyclohexane of the organic material layer including the polymer including the unit represented by Formula 1 is 0.05 wt% or less.

In one embodiment, cyclohexane of the organic material layer comprising the polymer including the unit represented by the formula (1); cyclohexanone; Or the solubility in dioxane is 0 wt% or more.

In one embodiment, whether the organic material layer is dissolved in a specific solvent, the difference in the UV absorption value of the organic material layer before and after exposure to the specific solvent by immersing the organic material layer in the solvent for which the solubility is to be measured and taking it out can be confirmed. . Here, the organic material layer exposed to the solvent may be in the form of a single organic material layer, or may be a laminate in which the organic material layer is provided in the outermost layer. The laminate of the form in which the organic material layer is provided in the outermost layer means a structure in which the organic material layer is provided in the last layer in the stacking direction of the layer in a laminate in which two or more layers are sequentially provided.

More specifically, when the UV absorption intensity at the maximum absorption wavelength before exposure to a specific solvent of the organic layer is a1, and the UV absorption intensity at the maximum absorption wavelength after exposure to the specific solvent of the organic layer is a2, a2/a1 If *100 is 97% or more and 100% or less, it may be understood as having solvent resistance to a specific solvent.

In an exemplary embodiment, the material constituting a specific organic material layer of the organic light emitting device may be analyzed through MS and NMR analysis by extracting the corresponding organic material layer from the organic light emitting device.

In one embodiment, a composition obtained by dissolving a polymer including a unit represented by Formula 1 in toluene at 2 wt % is spin-coated on a glass plate and heat-treated at 230° C. for 30 minutes to form an organic material layer having a thickness of 20 nm, the The solubility of the organic layer in cyclohexanone is 0.05 wt% or less.

In one embodiment, a composition obtained by dissolving a polymer including a unit represented by Formula 1 in toluene at 2 wt % is spin-coated on a glass plate and heat-treated at 230° C. for 30 minutes to form an organic material layer having a thickness of 20 nm, the The solubility of the organic layer in dioxane is 0.05 wt% or less.

In one embodiment, a composition obtained by dissolving a polymer including a unit represented by Formula 1 in toluene at 2 wt % is spin-coated on a glass plate and heat-treated at 230° C. for 30 minutes to form an organic material layer having a thickness of 20 nm, the The solubility of the organic layer in cyclohexane is 0.05 wt% or less.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In this specification,

refers to a site bonded to another substituent or a bonding group.

In the present specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

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

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

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

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; hydroxyl group; cyano group; an alkyl group; cycloalkyl group; alkenyl group; alkoxy group; aryloxy group; -N(Rm)(Rn); aryl group; And it means that it is substituted with one or more substituents selected from the group consisting of a heteroaryl group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents, and Rm and Rn are the same as or different from each other and each independently hydrogen; an alkyl group; aryl group; or a heteroaryl group. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two aryl groups are connected.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, iso Pentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentyl Methyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1 -Dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are limited thereto it is not

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include a vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1 -Butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but are not limited thereto .

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, neopentyloxy group, Isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, benzyloxy group, p - It may be a methylbenzyloxy group, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it is C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a triphenylenyl group, a pyrenyl group, a phenalenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, etc., but is not limited thereto. .

In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.

When the fluorenyl group is substituted, the substituted fluorenyl group may be, for example, any one selected from the following compounds, but is not limited thereto.

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

In the present specification, the heteroaryl group includes one or more heteroatoms other than carbon in the ring, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se and S. The number of carbon atoms of the heteroaryl group is not particularly limited, but it is preferably from 2 to 30 carbon atoms. The heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophenyl group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridinyl group, a bipyridinyl group, a pyrimidinyl group, a triazinyl group, Triazolyl group, acridinyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group group, isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophenyl group, dibenzothiophenyl group, benzofuranyl group, phenantri dinyl group (phenanthridine), phenanthroline group (phenanthroline), isoxazolyl group, thiadiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but is not limited thereto.

In the present specification, the aryl group in the aryloxy group is the same as the example of the aryl group described above. Specifically, the aryloxy group includes a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3- Biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthracenyloxy group , 2-anthracenyloxy group, 9-anthracenyloxy group, 1-phenanthrenyloxy group, 3-phenanthrenyloxy group, 9-phenanthrenyloxy group, and the like, but is not limited thereto.

In the present specification, specific examples of -N(Rm)(Rn) include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, and an anthracenyl group. Amine group, 9-methyl-anthracenylamine group, diphenylamine group, ditolylamine group, N,N-(phenyl)(tolyl)amine group, N,N-(phenyl)(biphenyl)amine group, N ,N- (phenyl) (naphthyl) amine group, N, N- (biphenyl) (naphthyl) amine group, N, N- (naphthyl) (fluorenyl) amine group, N, N- (phenyl) ) (phenanthrenyl) amine group, N, N- (biphenyl) (phenanthrenyl) amine group, N, N- (phenyl) (fluorenyl) amine group, N, N- (phenyl) (terphenyl) ) an amine group, an N,N-(phenanthrenyl)(fluorenyl)amine group, and a N,N-(biphenyl)(fluorenyl)amine group, but is not limited thereto.

In the present specification, the arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied.

In the present specification, the heteroarylene group means that the heteroaryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the heteroaryl group described above may be applied.

According to an exemplary embodiment of the present specification, Chemical Formulas 1 and 2 include a group represented by the following Chemical Formula A.

[Formula A]

In Formula A, the definitions of R5 to R8 and r5 to r8 are as defined in Formulas 1 and 2.

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

[Formula a-1]

In Formula (a-1), the definitions of R5 to R8 and r5 to r8 are as defined in Formula A.

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

[Formula a-2]

In Formula (a-2), the definitions of R5 to R8 and r5 to r8 are as defined in Formula A.

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

[Formula 1-1]

In Formula 1-1,

R1 to R8, L, Ar1, Ar2, r4 to r8, n and a are the same as defined in Formula 1.

According to an exemplary embodiment of the present specification, R1 is hydrogen; or an alkyl group.

According to an exemplary embodiment of the present specification, R1 is hydrogen; or a C _1-6 alkyl group.

According to an exemplary embodiment of the present specification, R1 is hydrogen; or a methyl group.

According to an exemplary embodiment of the present specification, R1 is hydrogen.

According to an exemplary embodiment of the present specification, R2 is hydrogen; or an alkyl group.

According to an exemplary embodiment of the present specification, R2 is hydrogen; or a C _1-6 alkyl group.

According to an exemplary embodiment of the present specification, R2 is hydrogen; or a methyl group.

According to an exemplary embodiment of the present specification, R2 is hydrogen.

According to an exemplary embodiment of the present specification, R3 is hydrogen; or an alkyl group.

According to an exemplary embodiment of the present specification, R3 is hydrogen; or a C _1-6 alkyl group.

According to an exemplary embodiment of the present specification, R3 is hydrogen; or a methyl group.

According to an exemplary embodiment of the present specification, R3 is hydrogen.

According to an exemplary embodiment of the present specification, R4 is hydrogen.

According to an exemplary embodiment of the present specification, R5 is hydrogen.

According to an exemplary embodiment of the present specification, R6 is hydrogen.

According to an exemplary embodiment of the present specification, R7 is hydrogen.

According to an exemplary embodiment of the present specification, R8 is hydrogen.

According to an exemplary embodiment of the present specification, L is a direct bond; or any one selected from the following structures.

In the above structure, R is an aryl group,

R' and R" are the same as or different from each other, and are each independently hydrogen; or an alkyl group;

The structure may be further substituted with an alkyl group.

According to an exemplary embodiment of the present specification, R is a phenyl group.

According to an exemplary embodiment of the present specification, R' and R" are the same as or different from each other, and are each independently hydrogen; or a C _1-10 alkyl group.

According to an exemplary embodiment of the present specification, R' and R" are the same as or different from each other, and are each independently hydrogen; or a C _1-6 alkyl group.

In one embodiment, when R' and R" are hydrogen, fluorene may react with oxygen to form a ketone, and when the ketone is formed, it may have a fatal effect on the device, so R' and R" are It is preferable that they are the same as or different from each other and each independently represent an alkyl group.

According to an exemplary embodiment of the present specification, R' and R" are the same as or different from each other, and each independently represents a hydrogen; a methyl group; or a butyl group.

According to an exemplary embodiment of the present specification, L is a direct bond; Or any one selected from the following structures, the following structures may be further substituted with an alkyl group.

According to an exemplary embodiment of the present specification, L is a direct bond; a phenylene group unsubstituted or substituted with a methyl group; naphthylene group; a divalent anthracenyl group; a divalent fluorenyl group unsubstituted or substituted with a methyl group or a butyl group; or a divalent carbazolyl group unsubstituted or substituted with a phenyl group.

According to an exemplary embodiment of the present specification, a is an integer of 0 to 3.

According to an exemplary embodiment of the present specification, a is an integer of 1 to 3.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently an aryl group unsubstituted or substituted with an aryl group; an aryl group substituted with a heteroaryl group; an aryl group substituted with an alkyl group; an aryl group substituted with an aryl group substituted with an alkyl group; an aryl group substituted with a heteroaryl group substituted with an aryl group; Or a heteroaryl group substituted or unsubstituted with an aryl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with an aryl group; biphenyl group; a phenyl group substituted with a heteroaryl group; a fluorenyl group substituted with an alkyl group; a phenyl group substituted with an aryl group substituted with an alkyl group; a phenyl group substituted with a heteroaryl group substituted with an aryl group; a carbazolyl group unsubstituted or substituted with an aryl group; or a spirobifluorenyl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a phenyl group; biphenyl group; a phenyl group substituted with a dibenzofuranyl group; a phenyl group substituted with a dimethyl fluorenyl group; a fluorenyl group substituted with a methyl group; a phenyl group substituted with a fluorenyl group substituted with a methyl group; a phenyl group substituted with a carbazolyl group substituted with a phenyl group; a carbazolyl group unsubstituted or substituted with a phenyl group; or a spirobifluorenyl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group; biphenyl group; 9,9-dimethyl fluorenyl group; 9-phenylcarbazolyl group; a phenyl group substituted with a 9-phenylcarbazolyl group; a phenyl group substituted with a dibenzofuranyl group; or a 9,9'-spirobifluorenyl group.

According to an exemplary embodiment of the present specification, the monomer represented by Formula 2 is any one selected from the following structures.

According to an exemplary embodiment of the present specification, the polymer including the unit represented by Formula 1 is any one selected from the following structures.

In the above structures, the definition of n is as defined in Formula 1.

In the present specification, the end group of the polymer may be hydrogen, but is not limited thereto.

In an exemplary embodiment of the present specification, the number average molecular weight of the polymer including the unit represented by Formula 1 is 5,000 g/mol to 1,000,000 g/mol, more preferably 10,000 g/mol to 300,000 g/mol . When the number average molecular weight of the polymer including the unit represented by Formula 1 is less than 5000 g/mol, it is difficult to implement the performance of the device desired in the present invention, and when it exceeds 1,000,000 g/mol, the solubility of the polymer in the solvent is Since there is a problem of lowering, it is preferable to have a molecular weight within the above range.

In an exemplary embodiment of the present specification, n is an integer of 4 to 200 as the number of repetitions.

In an exemplary embodiment of the present specification, n is an integer of 4 to 150 as the number of repetitions.

In an exemplary embodiment of the present specification, n is an integer of 4 to 100 as the number of repetitions.

In an exemplary embodiment of the present specification, the polymer may have a molecular weight distribution of 1 to 10. Preferably the polymer has a molecular weight distribution of 1 to 3.

In the present specification, the terms number average molecular weight (Mn) and weight average molecular weight (Mw) refer to molecular weights converted to standard polystyrene measured using Gel Permeation Chromatography (GPC). In the present specification, the molecular weight distribution refers to a value obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn), that is, the weight average molecular weight (Mw)/number average molecular weight (Mn).

The number average molecular weight (Mn) and molecular weight distribution can be measured as follows using gel permeation chromatography (GPC). First, put the analyte in a 5 mL vial, and dilute it in THF (tetrahydrofuran) to a concentration of about 1 mg/mL. After that, the standard sample for calibration and the sample to be analyzed are filtered through a syringe filter (pore size = 0.45 μm), and then GPC is measured. As the analysis program, ChemStation of Agilent technologies can be used, and the weight average molecular weight (Mw) and number average molecular weight (Mn) are obtained by comparing the elution time of the sample with the calibration curve, respectively, and the molecular weight distribution (Mw/Mn) PDI) can be calculated. GPC measurement conditions may be as follows.

Device: 1200 series by Agilent technologies

Column: Using 2 PL gel mixed B from Polymer laboratories

Solvent: THF

Column temperature: 40℃

Sample concentration: 1mg/mL, 100L injection

Standard sample: polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

The present specification provides a coating composition comprising the polymer.

According to an exemplary embodiment of the present specification, the coating composition may further include a solvent.

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

In one embodiment of the present specification, the solvent is, for example, a chlorine-based solvent such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene; ether solvents such as tetrahydrofuran and dioxane; aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Ketone solvents, such as acetone, methyl ethyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyvalents such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, and 1,2-hexanediol alcohols and derivatives thereof; alcohol solvents such as methanol, ethanol, propanol, isopropanol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; benzoate solvents such as methyl benzoate, butyl benzoate, and 3-phenoxy benzoate; And solvents such as tetralin are exemplified, but any solvent capable of dissolving or dispersing the compound according to an exemplary embodiment of the present specification is possible, and the present disclosure is not limited thereto.

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

In another exemplary embodiment, the viscosity of the single or mixed solvent is preferably 1 cP to 10 cP, more preferably 3 cP to 8 cP, but is not limited thereto.

In another exemplary embodiment, the content of the polymer including the unit represented by Formula 1 in the coating composition is preferably 0.1 wt/v% to 20 wt/v%, more preferably 0.5 wt/v% to 5 wt/v%, but is not limited thereto.

In another embodiment, the content of the monomer represented by Formula 2 in the coating composition is preferably 0.1 wt/v% to 20 wt/v%, more preferably 0.5 wt/v% to 5 wt/v %, but is not limited thereto.

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

The thermal polymerization initiator is methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide , bis-3,5,5-trimethyl hexanoyl peroxide, lauryl peroxide, benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-(t-butyloxy)-hexane, 1,3 -bis(t-butyl peroxy-isopropyl) benzene, t-butyl cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-(di-t-butyl peroxy) hexane , tris-(t-butyl peroxy) triazine, 1,1-dit-butyl peroxy-3,3,5-trimethyl cyclohexane, 1,1-dit-butyl peroxy cyclohexane, 2,2 -di(t-butyl peroxy)butane, 4,4-di-(t-butylperoxy)valeric acid n-butyl ester, 2,2-bis(4,4-t-butyl peroxycyclohexyl)propane , t-butylperoxyisobutylate, dit-butyl peroxyhexahydro terephthalate, t-butyl peroxy-3,5,5-trimethylhexaate, t-butylperoxybenzoate, dit-butyl peroxylate peroxides such as oxytrimethyl adipate, or azos such as azobisisobutylnitrile, azobisdimethylvaleronitrile, and azobiscyclohexylnitrile, but are not limited thereto.

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

In one embodiment, the coating composition may further include a photopolymerization accelerator. When a photoinitiator is used together with a photoinitiator, a polymerization reaction rate can be raised. The photopolymerization accelerator is, for example, triethanolamine, methyldiethanolamine, 4-dimethylaminoethyl benzoate, 4-dimethylaminobenzoate isoamyl, benzoic acid (2-dimethylamino)ethyl, 4,4'-dimethylaminobenzophenone and the like, but is not limited thereto.

An exemplary embodiment of the present specification provides a coating composition comprising a polymer including a unit represented by the formula (1).

Another embodiment of the present specification provides a coating composition comprising a monomer represented by Formula 2 above.

In one embodiment of the present specification, the coating composition may further include a p-doping material.

In one embodiment of the present specification, the p doping material is F ₄ TCNQ; and at least one selected from the group consisting of boron anions.

In an exemplary embodiment of the present specification, the boron anion includes a halogen group.

In one embodiment of the present specification, the boron anion includes F.

In an exemplary embodiment of the present specification, the p-doping material is one or two or more selected from the following structural formulas.

In an exemplary embodiment of the present specification, when the coating composition includes the p-doping material, the weight ratio of the polymer including the unit represented by Formula 1 to the p-doping material in the coating composition is 99:1 to 70: 30, and more preferably 90:10 to 70:30.

In one embodiment of the present specification, when the coating composition includes the p-doping material, the weight ratio of the monomer represented by Formula 2 to the p-doping material in the coating composition may be 99:1 to 70:30, and , more preferably 90:10 to 70:30.

The present specification also provides an organic light emitting device formed using the coating composition.

An exemplary embodiment of the present specification includes a first electrode; a second electrode; and an organic material layer provided between the first electrode and the second electrode, wherein the organic material layer includes a polymer including a unit represented by Chemical Formula 1 described above.

In the exemplary embodiment of the present specification, the first electrode is a cathode, and the second electrode is an anode.

In another exemplary embodiment, the first electrode is an anode, and the second electrode is a cathode.

In an exemplary embodiment of the present specification, the organic material layer including the polymer including the unit represented by Formula 1 may include an electron blocking layer; hole transport layer; hole injection layer; or a layer that simultaneously transports holes and injects holes.

In another exemplary embodiment of the present specification, the organic material layer including the polymer including the unit represented by Formula 1 may include a hole blocking layer; electron transport layer; electron injection layer; or a layer that simultaneously transports electrons and injects electrons.

In an exemplary embodiment of the present specification, the organic material layer includes a hole injection layer; hole transport layer; light emitting layer; electron transport layer; electron injection layer; electron blocking layer; And it may further include one or two or more layers selected from the group consisting of a hole blocking layer.

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

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

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

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

In FIG. 1 , a first electrode 201 , a hole injection layer 301 , a hole transport layer 401 , a light emitting layer 501 , a layer 601 for simultaneously transporting and injecting electrons 601 and a second The structure of the organic light emitting device in which the electrodes 701 are sequentially stacked is exemplified.

In one embodiment of the present specification, the hole injection layer 301 or the hole transport layer 401 of FIG. 1 is formed using a coating composition including a polymer including a unit represented by Formula 1, or It may be formed using a coating composition comprising a monomer represented by 2.

In an exemplary embodiment of the present specification, the hole injection layer 301 of FIG. 1 is formed using a coating composition including a polymer including a unit represented by Formula 1, or a monomer represented by Formula 2 It may be formed using a coating composition comprising.

In an exemplary embodiment of the present specification, the hole transport layer 401 of FIG. 1 is formed using a coating composition including a polymer including a unit represented by Formula 1, or includes a monomer represented by Formula 2 It can be formed using a coating composition that

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

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

The organic light emitting device of the present specification may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer is formed using a coating composition.

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

The present specification also provides a method of manufacturing an organic light emitting device formed using the coating composition. Here, the coating composition is a coating composition comprising a polymer including a unit represented by Formula 1; Or it means a coating composition comprising a monomer represented by the formula (2).

Specifically, in one embodiment of the present specification, the steps of preparing a first electrode; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer, wherein the forming of the at least one organic material layer is a coating composition comprising a polymer including a unit represented by Formula 1, or Formula 2 described above As a method of manufacturing an organic light emitting device comprising the step of forming an organic material layer using a coating composition comprising the indicated monomer, the step of forming the organic material layer using the coating composition is the coating composition on the first electrode coating the; and heat-treating or light-treating the coated coating composition.

In one embodiment of the present specification, the organic material layer formed using the coating composition is formed using spin coating or inkjet coating.

In another embodiment, the organic material layer formed using the coating composition is formed by a printing method.

In the present specification, the printing method includes, for example, inkjet printing, nozzle printing, offset printing, transfer printing, or screen printing, but is not limited thereto.

Since the coating composition according to an exemplary embodiment of the present specification is suitable for a solution process due to its structural characteristics, it can be formed by a printing method, thereby having an economical effect in terms of time and cost when manufacturing a device.

In one embodiment of the present specification, the step of forming an organic material layer using the coating composition comprises: coating the coating composition on the first electrode; and heat-treating or light-treating the coated coating composition.

In one embodiment of the present specification, in the heat treatment or light treatment step, the heat treatment time is preferably within 1 hour, more preferably within 30 minutes.

In the exemplary embodiment of the present specification, in the heat treatment or light treatment step, the heat treatment atmosphere is preferably an inert gas atmosphere such as argon or nitrogen.

In one embodiment, when using a coating composition comprising a polymer including a unit represented by Formula 1 as the coating composition, the step of heat-treating or light-treating the coated coating composition is a solvent from the coated coating composition. may be a step to remove

In one embodiment, when using a coating composition comprising a monomer represented by Formula 2 as the coating composition, the step of heat-treating or light-treating the coated coating composition includes the alkenyl group of the monomer represented by Formula 2 It may be a step in which the solvent is removed while participating in polymerization to form a polymer including the unit represented by Formula 1 above.

In the step of forming the organic material layer using the coating composition, the organic material layer formed through the heat treatment or light treatment step may have a structure in which the above-described coating composition is thinned. In this case, the organic material layer formed using the coating composition may not be dissolved, morphologically affected, or decomposed by the solvent of the organic material layer deposited on the surface.

Therefore, the organic layer formed using the coating composition has resistance to a specific solvent, and thus a multilayer can be formed by repeatedly performing a solution deposition method using the specific solvent. In addition, in this case, the stability of the organic material layer is increased to increase the lifespan characteristics of the device.

In an exemplary embodiment of the present specification, a polymer comprising a unit represented by Formula 1; Alternatively, the coating composition including the monomer represented by Formula 2 may further include a polymer binder.

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

In addition, the organic material layer according to an exemplary embodiment of the present specification may include the polymer including the unit represented by Chemical Formula 1 alone, but may further include other monomers or other polymers.

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

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

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

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

The electron blocking layer is a layer capable of improving the lifespan and efficiency of the device by preventing electrons injected from the electron injection layer from entering the hole injection layer through the emission layer, and, if necessary, using a known material to form the emission layer and the hole It may be formed in an appropriate portion between the injection layers.

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

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

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

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

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

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

In the present specification, as a material for the layer that simultaneously transports and injects electrons, the above-described materials for the electron injection layer and the electron transport layer may be used without limitation.

In the present specification, as a material for the layer for performing hole transport and hole injection at the same time, the materials of the hole injection layer and the hole transport layer described above may be used without limitation.

The hole blocking layer is a layer that blocks the holes from reaching the cathode, and the material of the hole blocking layer is specifically an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, an aluminum complex, etc., but is limited thereto. doesn't happen

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

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

Synthesis of Monomer 1

Synthesis of compound 3-A

50 g (105.4 mmol, 1eq) of compound 1-A and 31.2 g (211 mmol, 2eq) of compound 2-A were dissolved in 300 g of tetrahydrofuran (THF) and stirred in a silicone bath at 80° C. for 10 minutes. K ₂ CO ₃ 37.89g (274mmol, 2.6eq) was dissolved in 300mL of water and then added dropwise for 10 minutes. Pd catalyst 3.66g (3.2mmol, 0.03eq) was added under reflux. After stirring for 2 hours, the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After purification by column chromatography with n-hexane (n-Hex) and ethyl acetate (EA), it was recrystallized from tetrahydrofuran (THF) and ethanol to obtain compound 3-A as a white solid.

Synthesis of compound 6-A

Compound 4-A 17.24 g (47.7 mmol, 1.0 eq), Compound 5-A 19.07 g (57.26 mmol, 1.2 eq) NaOt-Bu 6.42 g (66.8 mmol, 1.4 eq) and 1,10-phenanthroline 1.72 g ( 9.54 mmol, 0.2 eq) was dissolved in 140 mL of DMF, and stirred in a silicone bath at 80° C. for 10 minutes. After adding CuI 0.91 g (4.77 mmol, 10 mol%), the mixture was stirred for 12 hours. The organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After MPLC (Medium Pressure Liquid Chromatography) purification using n-hexane (n-Hex) and ethyl acetate (EA), the compound 6-A was obtained by recrystallization from n-hexane (n-Hex).

Synthesis of compound 7-A

Compound 6-A 11.90g (21mmol, 1.0eq) and B ₂ Pin ₂ 13.3 g (52.4 mmol, 2.5 eq) was dissolved in 300 mL of 1,4-Dioxane, and stirred in a silicone bath at 80° C. for 10 minutes. KOAc 8.86g (90.3mmol, 4.3eq) and Pd(pddf)Cl ₂ ·DCM 1.38g (1.89mmol, 0.09eq) were added. After stirring for 12 hours in a silicone bath at 110° C., the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After MPLC (Medium Pressure Liquid Chromatography) purification using n-hexane (n-Hex) and dichloromethane (DCM), compound 7-A was obtained by recrystallization from n-hexane (n-Hex).

Synthesis of Monomer 1

Compound 3-A 2.49g (5mmol, 1eq) and Compound 7-A 3.68g (6mmol, 1.2eq) were dissolved in 20ml tetrahydrofuran (THF) and stirred in a silicone bath at 80° C. for 30 minutes. 5.1g (37mmol, 1.75eq) of K ₂ CO ₃ was dissolved in 40 mL of water and then added dropwise for 10 minutes while maintaining the internal temperature of the solution at 65°C. Pd catalyst 0.077g (0.15mmol, 0.03eq) was added under reflux. After stirring for 1 hour, the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After purification by column chromatography with n-hexane (n-Hex) and dichloromethane (DCM), 4.16 g of monomer 1 (MS: [M+H] ⁺ =903) was obtained by recrystallization from n-hexane (n-Hex). got it

Synthesis of monomer 2

Synthesis of compound 2-B

13.2 g (26.6 mmol, 1.0 eq) of compound 3-A and 4.58 g (29.3 mmol, 1.1 eq) of compound 1-B were dissolved in 100 mL of tetrahydrofuran (THF), and 10 in a silicone bath at 80 ° C. stirred for minutes. Cs ₂ CO ₃ 43.4 g (133 mmol, 5.0eq) was dissolved in 90 mL of water and then added dropwise for 10 minutes. 1.54 g (1.33 mol, 0.05 eq.) of Pd(PPh ₃ ) ₄ was added under reflux. After stirring for 12 hours in a silicone bath at 65° C., the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After MPLC (Medium Pressure Liquid Chromatography) purification using n-hexane (n-Hex) and ethyl acetate (EA), it was recrystallized from n-hexane (n-Hex) to obtain Compound 2-B.

Synthesis of monomer 2

Compound 2-B 3.6g (6mmol, 1eq) and Compound 3-B 4.49g (6.6mmol, 1.1eq) were dissolved in 36ml tetrahydrofuran (THF) and stirred in a silicone bath at 80° C. for 10 minutes. K ₂ CO ₃ 2.15 g (15 mmol, 2.6 eq) was dissolved in 30 mL of water and then added dropwise for 10 minutes. Pd catalyst 0.092g (0.18mmol, 0.03eq) was added under reflux. After stirring for 6 hours, the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After purification by column chromatography with n-hexane (n-Hex) and dichloromethane (DCM), recrystallization from n-hexane (n-Hex) as a white solid Monomer 2 (MS: [M+H] ⁺ = 1045) 4.5 g was obtained.

Synthesis of monomer 3

Synthesis of compound 3-C

Compound 1-C 19.93g (60.95mmol, 1.0eq) and Compound 2-C 37.65g (128mmol, 2.10eq) It was dissolved in 200 mL of tetrahydrofuran (THF) and stirred in a silicone bath at 80° C. for 10 minutes. K ₂ CO ₃ 21.9 g (158 mmol, 2.6eq) was dissolved in 87 mL of water and then added dropwise for 10 minutes. 2.11 g (1.8 mmol, 0.03 eq) of Pd catalyst was added under reflux. After stirring for 12 hours, the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After MPLC (Medium Pressure Liquid Chromatography) purification using n-hexane (n-Hex) and ethyl acetate (EA), it was recrystallized from n-hexane (n-Hex) to obtain compound 3-C.

Synthesis of monomer 3

3.01 g (6 mmol, 1eq) of compound 3-C and 3.28 g (6.6 mmol, 1.1 eq) of compound 3-A were dissolved in 15 g of anhydrous toluene and stirred in a silicone bath at 130° C. for 10 minutes. Sodium tert butoxide (NaOt-Bu) 1.45g (15mmol, 2.5eq) was added. Pd catalyst 0.077g (0.15mmol, 0.03eq) was added under reflux. After stirring for 1 hour, the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After purification by column chromatography with n-hexane (n-Hex) and dichloromethane (DCM), recrystallization from n-hexane (n-Hex) as a white solid monomer 3 (MS: [M+H] ⁺ = 917) 5.07 g was obtained.

Synthesis of Monomer 4

Synthesis of compound 2-D

13.2 g (26.6 mmol, 1.0 eq) of compound 3-A and 14.06 g (29.3 mmol, 1.1 eq) of compound 1-D were dissolved in 100 mL of tetrahydrofuran (THF), and 10 in a silicone bath at 80 ° C. stirred for minutes. Cs ₂ CO ₃ 43.4 g (133 mmol, 5.0eq) was dissolved in 90 mL of water and then added dropwise for 10 minutes. 1.54 g (1.33 mol, 0.05 eq.) of Pd(PPh ₃ ) ₄ was added under reflux. After stirring for 12 hours in a silicone bath at 65° C., the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After MPLC (Medium Pressure Liquid Chromatography) purification using n-hexane (n-Hex) and ethyl acetate (EA), it was recrystallized from n-hexane (n-Hex) to obtain Compound 2-D.

Synthesis of Monomer 4

Compound 3-D 2.5g (6mmol, 1eq) and Compound 2-D 5.08g (6.6mmol, 1.1eq) were dissolved in 36ml anhydrous toluene and stirred in a silicone bath at 130° C. for 10 minutes. Sodium tert butoxide (NaOt-Bu) 1.45g (15mmol, 2.5eq) was added. Pd catalyst 0.15g (0.3mmol, 0.05eq) was added under reflux. After stirring for 1 hour, the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After purification by column chromatography with n-hexane (n-Hex) and dichloromethane (DCM), recrystallization from n-hexane (n-Hex) as a white solid monomer 4 (MS: [M+H] ⁺ = 1143) 5.72 g was obtained.

Synthesis of monomer 5

Synthesis of compound 2-E

13.2 g (26.6 mmol, 1.0 eq) of compound 3-A and 9.42 g (29.3 mmol, 1.1 eq) of compound 1-E were dissolved in 100 mL of tetrahydrofuran (THF), and 10 in a silicone bath at 80 ° C. stirred for minutes. Cs ₂ CO ₃ 43.4 g (133 mmol, 5.0eq) was dissolved in 90 mL of water and then added dropwise for 10 minutes. 1.54 g (1.33 mol, 0.05 eq.) of Pd(PPh ₃ ) ₄ was added under reflux. After stirring for 12 hours in a silicone bath at 65° C., the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After MPLC (Medium Pressure Liquid Chromatography) purification using n-hexane (n-Hex) and ethyl acetate (EA), it was recrystallized from n-hexane (n-Hex) to obtain Compound 2-E.

Synthesis of monomer 5

Compound 2-E 3.47g (5mmol, 1eq) and Compound 3-E 3.10g (5.5mmol, 1.1eq) were dissolved in 20ml tetrahydrofuran (THF) and stirred in a silicone bath at 70° C. for 30 minutes. 5.1g (37mmol, 1.75eq) of K ₂ CO ₃ was dissolved in 40 mL of water and then added dropwise for 10 minutes while maintaining the internal temperature of the solution at 45° C. or higher. Pd catalyst 0.077g (0.15mmol, 0.03eq) was added under reflux. After stirring for 3 hours, the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After purification by column chromatography with n-hexane (n-Hex) and dichloromethane (DCM), 4.38 g of monomer 5 (MS: [M+H] ⁺ =1094) was obtained by recrystallization from n-hexane (n-Hex). got it

Synthesis of monomer 6

Synthesis of compound 3-A

50 g (105.4 mmol, 1eq) of compound 1-A and 31.2 g (211 mmol, 2eq) of compound 2-A were dissolved in 300 g of tetrahydrofuran (THF) and stirred in a silicone bath at 80° C. for 10 minutes. K ₂ CO ₃ 37.89g (274mmol, 2.6eq) was dissolved in 300mL of water and then added dropwise for 10 minutes. Pd catalyst 3.66g (3.2mmol, 0.03eq) was added under reflux. After stirring for 2 hours, the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After purification by column chromatography with n-hexane (n-Hex) and ethyl acetate (EA), it was recrystallized from tetrahydrofuran (THF) and ethanol to obtain compound 3-A as a white solid.

Synthesis of monomer 6

Monomer 3-A 2.49g (5mmol, 1eq) and Compound 1-F 3.38g (6mmol, 1.2eq) were dissolved in 20ml tetrahydrofuran (THF) and stirred in an oil bath at 80° C. for 30 minutes. 5.1g (37mmol, 1.75eq) of K ₂ CO ₃ was dissolved in 40 mL of water and then added dropwise for 10 minutes while maintaining the internal temperature of the solution at 65°C. Pd catalyst 0.077g (0.15mmol, 0.03eq) was added under reflux. After stirring for 1 hour, the organic layer was separated by washing with ethyl acetate (EA)/H ₂ O, and the solvent was dried in vacuo. After purification by column chromatography with n-hexane (n-Hex) and dichloromethane (DCM), 3.68 g of monomer 6 (MS: [M+H] ⁺ =853) was obtained by recrystallization from n-hexane (n-Hex). got it

Preparation of Polymer 1

The monomer 1 (0.48 g, 0.53 mmol) and AIBN (3.0 mg, 0.02 mmol) were placed in a Schlenk reaction flask and dissolved in THF (1.5 mL), followed by freeze-evacuate-thaw 3 This was repeated several times and stirred at 80 °C for 7 hours. Polymer 1 was prepared by dissolving unreacted monomers by adding ethyl acetate and precipitating the polymer.

Preparation of Polymers 2 to 6

Polymers 2 to 6 were prepared in the same manner as in the preparation method of Polymer 1, except that the monomers of Table 1 were used instead of Monomer 1.

Preparation of polymer P1

Polymer P1 was prepared in the same manner as in the preparation method of Polymer 1, except that the monomers of Table 1 were used instead of Monomer 1.

Preparation of polymers P3 to P5

Polymers P3 to P5 were prepared in the same manner as in the preparation method of Polymer 1, except that the monomers of Table 1 were used instead of Monomer 1.

polymer monomer Mn (g/mol) One One 21400 2 2 18600 3 3 31200 4 4 23600 5 5 22500 6 6 21900 P1 C1 48800 P3 C3 16600 P4 C4 51200 P5 C5 32500

Example One

A glass substrate coated with indium tin oxide (ITO) to a thickness of 150 nm was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl and acetone and dried. After washing the substrate for 5 minutes, the substrate was transported to a glove box.

On an ITO transparent electrode, a coating composition in which Compound A and Compound B (weight ratio of 8:2) were dissolved in cyclohexanone at 2wt/v% was spin-coated (4000rpm), and heat treated (cured) at 230°C for 30 minutes to 40 A hole injection layer having a thickness of nm was formed. A composition obtained by dissolving the polymer 1 in toluene at 2 wt % on the hole injection layer was spin-coated and heat-treated at 230° C. for 30 minutes to form a hole transport layer having a thickness of 20 nm. A coating composition in which the following compound C and the following compound D were dissolved in cyclohexanone of 2wt/v% in a weight ratio of 92:8 on the hole transport layer was spin-coated (4000rpm), and heat-treated at 150°C for 30 minutes to a thickness of 25 nm of the light emitting layer was formed. After transferring to a vacuum evaporator, the following compound E was vacuum-deposited to a thickness of 35 nm on the light emitting layer to form a layer that simultaneously transports electrons and injects electrons. A cathode was formed by sequentially depositing LiF with a thickness of 1 nm and aluminum with a thickness of 100 nm on the layer simultaneously performing the electron transport and electron injection.

In the above process, the deposition rate of organic materials was maintained at 0.04 nm/sec to 0.07 nm/sec, the deposition rate of LiF was maintained at 0.03 nm/sec, and the deposition rate of aluminum was maintained at 0.2 nm/sec, and the vacuum degree during deposition was 2 Х 10 ^{- 7} torr to 5 Х 10 ^-6 torr was maintained.

Example 2 to 6

Organic light emitting devices of Examples 2 to 6 were manufactured in the same manner as in Example 1, except that the polymer of Table 2 was used instead of Polymer 1.

comparative example 1 to 5

Organic light emitting devices of Comparative Examples 1 to 5 were prepared in the same manner as in Example 1, except that the polymer or compound of Table 2 was used instead of Polymer 1.

Compound P2 used in Comparative Example 2 is as follows.

device evaluation

The driving voltage, external quantum efficiency (EQE), luminance and lifetime were measured under a current density of 10 mA/cm ² for the organic light emitting devices prepared in Examples and Comparative Examples, and the results are shown in Table 2 below shown in The external quantum efficiency was calculated as (number of emitted photons)/(number of injected charge carriers). T90 denotes a time required for the luminance to decrease from the initial luminance (500 nit) to 90%.

compound Driving voltage (V) EQE (%) T90(hr) Example 1 Polymer 1 4.49 6.8 241 Example 2 Polymer 2 4.30 6.6 244 Example 3 Polymer 3 4.33 6.7 221 Example 4 Polymer 4 4.46 6.9 231 Example 5 polymer 5 4.26 6.6 233 Example 6 Polymer 6 4.39 6.8 242 Comparative Example 1 Polymer P1 4.74 6.1 211 Comparative Example 2 compound P2 not measurable not measurable not measurable Comparative Example 3 Polymer P3 4.55 6.7 121 Comparative Example 4 Polymer P4 4.27 6.1 209 Comparative Example 5 Polymer P5 4.41 6.2 211

The polymer according to an exemplary embodiment of the present specification has excellent solubility in an organic solvent, and is easy to prepare a coating composition. As a result of Table 2, it was confirmed that when the composition including the polymer of the present invention is used, a uniform coating layer can be formed, and the film stability is excellent, indicating excellent performance in an organic light emitting device.

In addition, from the device examples of Examples, it was confirmed that the organic material layer including the polymer including the unit of Formula 1 according to an exemplary embodiment of the present invention has resistance to the cyclohexanone solvent. That is, when the organic material layer is formed using the polymer including the unit of Formula 1 according to an exemplary embodiment of the present invention, there is an advantage in that another organic material layer can be formed on the organic material layer by using a solution process.

Comparing the above Example and Comparative Example 1, when spirobifluorene is connected to the main chain of the polymer through an m-phenylene group, the driving voltage of the device is lower than when phenylene is not bonded, and external quantum efficiency and lifespan It can be seen that the properties are improved.

In the device of Comparative Example 2, a hole transport layer was formed using a single molecule of compound P2. However, when the light emitting layer composition containing the cyclohexanone solvent was spin-coated on the hole transport layer formed using the compound P2, the compound P2 was dissolved in the cyclohexanone solvent, making it difficult to form the light emitting layer, and the device could not be manufactured . Accordingly, it was impossible to measure the characteristic value of the device of Comparative Example 2.

In the device of Comparative Example 3, the hole transport layer was formed using a polymer in which fluorene was bonded to the spirobifluorene position. Comparative Examples 4 and 5 use a polymer in which spirobifluorene is linked to the main chain of the polymer through phenylene-adamantane.

101: substrate
201: first electrode
301: hole injection layer
401: hole transport layer
501: light emitting layer
601: a layer that simultaneously transports electrons and injects electrons
701: second electrode

Claims (13)

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

In Formula 1,
L is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
a is an integer of 1 to 3, and when a is 2 or more, L is the same as or different from each other,
Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; hydroxyl group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
r6 and r7 are the same as or different from each other and each independently an integer of 0 to 3, when r6 is 2 or more, R6 is the same as or different from each other, and when r7 is 2 or more, R7 is the same as or different from each other,
r4, r5 and r8 are the same as or different from each other and each independently an integer of 0 to 4, when r4 is 2 or more, R4 is the same as or different from each other, and when r5 is 2 or more, R5 is the same as or different from each other, and r8 is 2 or more, R8 is the same as or different from each other,
n is the repeating number of the unit, and is an integer from 2 to 10,000. The method according to claim 1, wherein Chemical Formula 1 is a polymer represented by the following Chemical Formula 1-1:
[Formula 1-1]

In Formula 1-1,
R1 to R8, L, Ar1, Ar2, r4 to r8, n and a are the same as defined in Formula 1. The polymer of claim 1, wherein L is any one selected from the following structures:

In the above structure, R is an aryl group,
R' and R" are the same as or different from each other, and are each independently hydrogen; or an alkyl group;
The structure may be further substituted with an alkyl group. The method according to claim 1, wherein Ar1 and Ar2 are the same as or different from each other, and each independently an aryl group unsubstituted or substituted with an aryl group; an aryl group substituted with a heteroaryl group; an aryl group substituted with an alkyl group; an aryl group substituted with an aryl group substituted with an alkyl group; an aryl group substituted with a heteroaryl group substituted with an aryl group; Or a polymer that is a heteroaryl group unsubstituted or substituted with an aryl group. A monomer represented by the following formula (2):
[Formula 2]

In Formula 2,
L is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
a is an integer of 1 to 3, and when a is 2 or more, L is the same as or different from each other,
Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; hydroxyl group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
r6 and r7 are the same as or different from each other and each independently an integer of 0 to 3, when r6 is 2 or more, R6 is the same as or different from each other, and when r7 is 2 or more, R7 is the same as or different from each other,
r4, r5 and r8 are the same as or different from each other and each independently an integer of 0 to 4, when r4 is 2 or more, R4 is the same as or different from each other, and when r5 is 2 or more, R5 is the same as or different from each other, and r8 is 2 In this case, R8 is the same as or different from each other. A monomer that is any one selected from the following structures:

. A coating composition comprising a polymer according to any one of claims 1 to 4. A coating composition comprising the monomer according to claim 5 or 6. a first electrode;
a second electrode; and
An organic material layer provided between the first electrode and the second electrode,
The organic material layer is an organic light emitting device comprising the polymer according to any one of claims 1 to 4. The method according to claim 9, wherein the organic material layer comprising the polymer is an electron blocking layer; hole transport layer; hole injection layer; or an organic light-emitting device that is a layer that simultaneously transports holes and injects holes. The method according to claim 9, wherein the organic material layer containing the polymer is a hole blocking layer; electron transport layer; electron injection layer; or an organic light-emitting device that is a layer that simultaneously transports electrons and injects electrons. The organic light-emitting device according to claim 9, wherein the organic material layer including the polymer has a solubility in cyclohexanone of 0.05 wt% or less. preparing a first electrode; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer,
The step of forming the at least one organic material layer comprises the step of forming an organic material layer using the coating composition comprising the polymer according to any one of claims 1 to 4, or the coating composition comprising the monomer according to claim 5 or 6. As a method for manufacturing an organic light emitting device,
Forming the organic material layer using the coating composition may include coating the coating composition on the first electrode; and heat-treating or light-treating the coated coating composition.

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