KR20220138681A - Polymer and organic light emitting device using the same - Google Patents

Abstract

The present specification relates to a polymer and an organic light emitting device using the same. The polymer according to an exemplary embodiment of the present specification may be applied to a hole transport layer of the organic light emitting device to improve performance and/or lifetime characteristics of the device.

Description

Polymer and organic light emitting device using the same

The present specification relates to a polymer and an organic light emitting device formed using the same.

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, 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, an electron injection layer.

As materials used in organic light emitting devices, pure organic materials or complex compounds in which organic materials and metals are complexed occupy most of the materials. 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.

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 Since the transition temperature has a value of 100° C. or less, 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 device 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-ethylenedioxythiophene) 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, the interface with the electrode including the metal or metal oxide should be good.

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 like VNPB (N4,N4'-di(naphthalen-1-yl)-N4,N4'-bis(4-vinylphenyl)biphenyl-4,4'-diamine) to apply a solution and then heat treatment or A material capable of forming a self-cross-linked polymer on a substrate through UV (ultraviolet) irradiation or forming a polymer with sufficient resistance to the next process is preferable, such as HATCN (Hexaazatriphenylenehexacarbonitrile). Materials which can themselves have solvent resistance are also desirable.

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

Korean Patent Publication No. 10-2004-0028954

An object of the present specification is to provide a polymer and an organic light emitting device formed using the same.

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

[Formula 1]

In Formula 1,

A is represented by the following formula (2),

B is represented by the following formula (3),

C is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

E1 and E2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted siloxane group; crosslinking group; or a combination thereof,

a, b and c are each a mole fraction,

a is a real number 0 < a ≤ 1,

b is a real number of 0≤b<1,

c is a real number of 0≤c<1,

a+b+c is 1,

[Formula 2]

In Formula 2,

Ar1, Ar2, L1 and L2 are the same as or different from each other, and are each independently a substituted or unsubstituted arylene group,

R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; a substituted or unsubstituted arylamine group; Or a substituted or unsubstituted siloxane group,

n1 to n3 are each an integer of 1 to 4,

When each of n1 to n3 is 2 or more, the substituents in each parenthesis are the same as or different from each other,

* is the point of attachment in the polymer,

[Formula 3]

In Formula 3,

m is an integer of 3 or 4,

when m is 3, Z is CRa; SiRa; N; Or a trivalent substituted or unsubstituted aryl group,

when m is 4, Z is C; Si; Or a tetravalent substituted or unsubstituted aryl group,

Ra is hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

Y is a direct bond; a substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,

Y is a direct bond; Or in the case of a substituted or unsubstituted alkylene group, Z is a trivalent or tetravalent substituted or unsubstituted aryl group,

* is the point of attachment in the polymer.

Another exemplary embodiment of the present specification provides a polymer including a unit represented by the following formula (2) and a terminal group represented by the following formula (5).

[Formula 2]

[Formula 5]

In Formulas 2 and 5,

Ar1, Ar2, L1 and L2 are the same as or different from each other, and are each independently a substituted or unsubstituted arylene group,

R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; a substituted or unsubstituted arylamine group; Or a substituted or unsubstituted siloxane group,

n1 to n3 are each an integer of 1 to 4,

When each of n1 to n3 is 2 or more, the substituents in each parenthesis are the same as or different from each other,

E is hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted siloxane group; crosslinking group; or a combination thereof,

* is the point of attachment in the polymer.

Another embodiment of the present specification is a first electrode; a second electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the polymer.

The polymer according to an exemplary embodiment of the present specification includes a divalent benzofuran group. Accordingly, the energy level of the polymer is controlled, and intermolecular stacking is improved, thereby exhibiting the effect of improving hole mobility.

In addition, the polymer according to an exemplary embodiment of the present specification may be applied to a hole transport layer of an organic light emitting device to improve performance and/or lifespan characteristics of the device.

1 and 2 are diagrams illustrating the structure of an organic light emitting device according to some embodiments of the present specification.
3 is a view showing the film retention rate test results of the thin film formed with the coating composition 1 prepared in Experimental Example 3-1.
4 is a view showing the test results of the film retention rate of the thin film formed with the coating composition 2 prepared in Comparative Example 3-1.

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

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

[Formula 1]

In Formula 1,

A is represented by the following formula (2),

B is represented by the following formula (3),

C is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

E1 and E2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted siloxane group; crosslinking group; or a combination thereof,

a, b and c are each a mole fraction,

a is a real number 0 < a ≤ 1,

b is a real number of 0≤b<1,

c is a real number of 0≤c<1,

a+b+c is 1,

[Formula 2]

In Formula 2,

Ar1, Ar2, L1 and L2 are the same as or different from each other, and are each independently a substituted or unsubstituted arylene group,

R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; a substituted or unsubstituted arylamine group; Or a substituted or unsubstituted siloxane group,

n1 to n3 are each an integer of 1 to 4,

When each of n1 to n3 is 2 or more, the substituents in each parenthesis are the same as or different from each other,

* is the point of attachment in the polymer,

[Formula 3]

In Formula 3,

m is an integer of 3 or 4,

when m is 3, Z is CRa; SiRa; N; Or a trivalent substituted or unsubstituted aryl group,

when m is 4, Z is C; Si; Or a tetravalent substituted or unsubstituted aryl group,

Ra is hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

Y is a direct bond; a substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,

Y is a direct bond; Or in the case of a substituted or unsubstituted alkylene group, Z is a trivalent or tetravalent substituted or unsubstituted aryl group,

* is the point of attachment in the polymer.

In an exemplary embodiment of the present specification, Chemical Formula 2 included in the polymer includes a benzofuran group. Accordingly, the energy level of the polymer is controlled, and stacking between molecules is improved, so that hole mobility is improved.

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, is not limited, and when two or more are substituted , two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; an alkyl group; cycloalkyl group; alkoxy group; aryloxy group; amine group; aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, is substituted with a substituent to which two or more of the above exemplified substituents are connected, or does not have any substituents. 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 phenyl groups are connected.

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

In the present specification, examples of the halogen group include fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

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 60. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 30. Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like.

In this specification, although carbon number of a cycloalkyl group is not specifically limited, It is preferable that it is 3-60. According to an exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 30. Specific examples of the cycloalkyl group include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although the number of carbon atoms of the alkoxy group is not particularly limited, it is preferably from 1 to 30 carbon atoms. Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, iso pentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, and the like, but is not limited thereto.

In the present specification, the fluoroalkoxy group means an alkoxy group substituted with F.

In the present specification, the amine group is -NH ₂ ; an alkylamine group; an arylalkylamine group; arylamine group; an aryl heteroarylamine group; It may be selected from the group consisting of an alkylheteroarylamine group and a heteroarylamine group, but is not limited thereto. The number of carbon atoms of the amine group is not particularly limited, but is preferably 1 to 60.

In the present specification, the number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 to 60. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. In the exemplary embodiment of the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenyl group, a chrysenyl group, a fluorenyl group, and the like, 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, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group including two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the heterocyclic group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms of the heterocyclic group is not particularly limited, but preferably has 2 to 30 carbon atoms. In an exemplary embodiment of the present specification, the heterocyclic group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group, a triazole group, an acridine group. , pyridazine group, pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazine group, pyrido pyrimidine group, pyrido pyrazine group, pyrazino pyrazine group, isoquinoline group, indole group, carbazole group, benz Oxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, phenanthridine group, phenanthroline group, isoxazole group, thia There are a diazole group, a phenothiazine group, a dibenzofuran group, and the like, but is not limited thereto.

In the present specification, the divalent heterocycle may be monocyclic or polycyclic, meaning that there are two bonding positions in the heterocyclic group. For example, the divalent heterocyclic group includes, for example, a divalent thiophene group; a divalent carbazole group; divalent dibenzofuran group; and a divalent dibenzothiophene group, but is not limited thereto.

In the present specification, the aryloxy group is a group represented by -OR ₂₀₀ , and R ₂₀₀ is an aryl group. 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, benzyloxy, p-methylbenzyloxy, 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-naph tyloxy group, 1-anthryloxy group, 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, etc. It is not limited.

In the present specification, the silyl group is a group represented by -SiR ₂₀₁ R ₂₀₂ R ₂₀₃ , R ₂₀₁ , R ₂₀₂ and R ₂₀₃ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. The silyl group includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group and a phenylsilyl group, but is limited thereto. it is not

In the present specification, the siloxane group is -Si(R ₂₀₄ ) ₂ OSi(R ₂₀₅ ) ₃ Or a group represented by -OSi(R ₂₀₄ ) ₃ Si(R ₂₀₅ ) ₃ , wherein R ₂₀₄ and R ₂₀₅ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

In the present specification, the cross-linkable group may mean a reactive substituent that cross-links between compounds by exposure to heat, light and/or radiation. Crosslinking may be generated by connecting radicals generated while decomposing carbon-carbon multiple bonds and cyclic structures by heat treatment, light irradiation, and/or radiation irradiation.

In an exemplary embodiment of the present specification, the cross-linkable group is any one of the following structures.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In the structure,

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

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, in the ring formed by bonding adjacent groups to each other, "ring" is a substituted or unsubstituted hydrocarbon ring; Or it means a substituted or unsubstituted heterocyclic ring.

In the present specification, "mol fraction" means the ratio of the number of moles of a given component to the total number of moles of all components.

In the present specification, the combination of substituents means a substituent in which two or more substituents are connected among the exemplified substituents. For example, hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; crosslinkable group; Or in a combination thereof, 'combination' means a substituent in which two or more substituents among the above-exemplified substituents are connected. For example, it may be a structure in which an alkyl group and a crosslinking group are connected, or a structure in which an alkyl group and an aryl group are connected, but is not limited thereto.

In an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently an arylene group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a substituted or unsubstituted phenylene group; a substituted or unsubstituted biphenylene group; Or a substituted or unsubstituted terphenylene group.

In an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a phenylene group; biphenylene group; or a terphenylene group.

In an exemplary embodiment of the present specification, Chemical Formula 2 is represented by the following Chemical Formula 2-1.

[Formula 2-1]

In Formula 2-1,

R1 to R3, Ar1, Ar2, and n1 to n3 are the same as defined in Formula 2,

R4 and R5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; Or a substituted or unsubstituted alkyl group,

m1 and m2 are each an integer of 1 to 3,

When m1 and m2 are each 2 or more, the structures in each parenthesis are the same as or different from each other,

n4 and n5 are each an integer of 1 to 4,

When n4 and n5 are each 2 or more, the substituents in each parenthesis are the same as or different from each other,

* is the point of attachment in the polymer.

In the exemplary embodiment of the present specification, m1 and m2 are each 1.

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

[Formula 2-2]

In Formula 2-2,

R1 to R3, Ar1, Ar2, and n1 to n3 are the same as defined in Formula 2,

* is the point of attachment in the polymer.

In an exemplary embodiment of the present specification, Chemical Formula 2 is represented by the following Chemical Formula 2-3.

[Formula 2-3]

In Formula 2-3,

R1 to R3, Ar1, Ar2, and n1 to n3 are the same as defined in Formula 2,

R4 and R5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; Or a substituted or unsubstituted alkyl group,

m1 and m2 are each an integer of 1 to 3,

When m1 and m2 are each 2 or more, the structures in each parenthesis are the same as or different from each other,

n4 and n5 are each an integer of 1 to 4,

When n4 and n5 are each 2 or more, the substituents in each parenthesis are the same as or different from each other,

* is the point of attachment in the polymer.

In the exemplary embodiment of the present specification, Chemical Formula 2 is represented by the following Chemical Formula 2-4.

[Formula 2-4]

In Formula 2-4,

R1 to R3, Ar1, Ar2, and n1 to n3 are the same as defined in Formula 2,

* is the point of attachment in the polymer.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently represents a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently represents an arylene group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted phenylene group; a substituted or unsubstituted biphenylene group; Or a substituted or unsubstituted terphenylene group.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenylene group; biphenylene group; or a terphenylene group.

In an exemplary embodiment of the present specification, Chemical Formula 2 is represented by the following Chemical Formula 2-5.

[Formula 2-5]

In Formula 2-5,

R1 to R3 and n1 to n3 are the same as defined in Formula 2,

R4 to R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; Or a substituted or unsubstituted alkyl group,

n4 to n7 are each an integer of 1 to 4,

When n4 to n are each 2 or more, the substituents in each parenthesis are the same as or different from each other,

m1, m2, h1 and h2 are each an integer of 1 to 3,

When m1, m2, h1 and h2 are each 2 or more, the structures in each parenthesis are the same as or different from each other,

* is the point of attachment in the polymer.

In an exemplary embodiment of the present specification, Chemical Formula 2 is represented by the following Chemical Formula 2-6.

[Formula 2-6]

In Formula 2-6,

R1 to R3 and n1 to n3 are the same as defined in Formula 2,

R4 to R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; Or a substituted or unsubstituted alkyl group,

n4 to n7 are each an integer of 1 to 4,

When n4 to n are each 2 or more, the substituents in each parenthesis are the same as or different from each other,

m1, m2, h1 and h2 are each an integer of 1 to 3,

When m1, m2, h1 and h2 are each 2 or more, the structures in each parenthesis are the same as or different from each other,

* is the point of attachment in the polymer.

In an exemplary embodiment of the present specification, R1 to R3 are hydrogen; or a substituted or unsubstituted alkyl group.

In an exemplary embodiment of the present specification, R1 to R3 are hydrogen; or a substituted or unsubstituted C 1 to C 10 alkyl group.

In an exemplary embodiment of the present specification, R1 to R3 are hydrogen; or an alkyl group.

In an exemplary embodiment of the present specification, R1 to R3 are hydrogen; methyl group; or a hexyl group.

In an exemplary embodiment of the present specification, R1 and R3 are hydrogen; or a methyl group.

In an exemplary embodiment of the present specification, R2 is a hexyl group.

In an exemplary embodiment of the present specification, R4 and R5 are each hydrogen.

In the exemplary embodiment of the present specification, h1 and h2 are each 2.

In an exemplary embodiment of the present specification, R6 and R7 are each hydrogen.

In an exemplary embodiment of the present specification, Chemical Formula 2 has the following structure.

In the above structure, * is the point of attachment in the polymer.

In the exemplary embodiment of the present specification, a is a real number of 0<a≤1 as a mole fraction. That is, the polymer necessarily contains A.

In the exemplary embodiment of the present specification, b is a real number of 0≤b<1 as a mole fraction. That is, the polymer optionally comprises B.

In an exemplary embodiment of the present specification, B in Formula 1 is a unit represented by Formula 3.

In one embodiment of the present specification, B is a unit having three or four attachment points.

In an exemplary embodiment of the present specification, Y is a direct bond; or a substituted or unsubstituted arylene group.

In an exemplary embodiment of the present specification, Y is a direct bond; or a substituted or unsubstituted phenylene group.

In the exemplary embodiment of the present specification, Chemical Formula 3 is represented by any one of the following Chemical Formulas 3-1 to 3-4.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Formulas 3-1 to 3-4,

Z1 is CRa; SiRa; N; Or a trivalent substituted or unsubstituted aryl group,

Z2 and Z3 are the same as or different from each other, and each independently C; Si; Or a tetravalent substituted or unsubstituted aryl group,

L10 is a direct bond; Or a substituted or unsubstituted arylene group,

Ra is hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

R10 to R20 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; alkoxy group; aryloxy group; fluoroalkoxy group; siloxane group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; or a cross-linkable group, adjacent groups may combine with each other to form a ring,

k1 is an integer from 1 to 4,

k2 is an integer from 1 to 5,

When k1 is 2 or more, the substituents in parentheses are the same as or different from each other,

When k2 is 2 or more, the substituents in parentheses are the same as or different from each other,

* is the point of attachment in the polymer.

In the exemplary embodiment of the present specification, Chemical Formula 3 is represented by Chemical Formula 3-1.

In an exemplary embodiment of the present specification, Z1 is CH; SiH; N; or a substituted or unsubstituted trivalent aryl group.

In an exemplary embodiment of the present specification, Z1 is CH; SiH; N; or a substituted or unsubstituted trivalent phenyl group.

In one embodiment of the present specification, Z1 is N; or a trivalent phenyl group.

In an exemplary embodiment of the present specification, L10 is a direct bond; or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, L10 is a direct bond; or an arylene group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, L10 is a direct bond; or a phenylene group.

In an exemplary embodiment of the present specification, L10 is a direct bond.

In the exemplary embodiment of the present specification, Chemical Formula 3 is represented by Chemical Formula 3-2.

In an exemplary embodiment of the present specification, Z2 is C; or Si.

In an exemplary embodiment of the present specification, B is represented by Formula 3-3.

In one embodiment of the present specification, Z3 is C; or Si.

In an exemplary embodiment of the present specification, Chemical Formula 3 is represented by Chemical Formula 3-4.

In an exemplary embodiment of the present specification, Chemical Formula 3 is represented by any one of the following structures.

In the structure,

R10 to R20 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; alkoxy group; aryloxy group; fluoroalkoxy group; siloxane group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; or a cross-linkable group, adjacent groups may combine with each other to form a ring,

k1 is an integer from 1 to 4,

k2 is an integer from 1 to 5,

When k1 is 2 or more, the substituents in parentheses are the same as or different from each other,

When k2 is 2 or more, the substituents in parentheses are the same as or different from each other,

* is the point of attachment in the polymer.

In an exemplary embodiment of the present specification, R10 to R20 are each hydrogen.

Specifically, Chemical Formula 3 is represented by any one of the following structures.

In the above structure, * is the point of attachment in the polymer.

More specifically, Chemical Formula 3 is represented by any one of the following structures.

In the above structure, * is the point of attachment in the polymer.

More specifically, Chemical Formula 3 is represented by any one of the following structures.

In the above structure, * is the point of attachment in the polymer.

In the exemplary embodiment of the present specification, c is a real number of 0≤c<1 as a mole fraction. That is, the polymer optionally comprises C. Specifically, the polymer optionally comprises unit C.

In the exemplary embodiment of the present specification, C in Formula 1 is a unit having two attachment points.

In an exemplary embodiment of the present specification, C in Formula 1 is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group.

In an exemplary embodiment of the present specification, C in Formula 1 is an arylene group unsubstituted or substituted with deuterium or a crosslinking group; or a divalent heterocyclic group unsubstituted or substituted with deuterium or a crosslinking group.

In an exemplary embodiment of the present specification, C in Formula 1 is any one of the following structures.

In the structure,

Y1 is S, O or NR100;

R30 to R39 and R100 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a cross-linkable group,

k3 is an integer of 1 or 2,

k4 is an integer from 1 to 4,

k5 is an integer from 1 to 3,

k6 is an integer from 1 to 8,

When k3 to k6 are each 2 or more, the substituents in each parenthesis are the same as or different from each other,

* is the point of attachment in the polymer.

Specifically, C in Formula 1 is any one of the following structures.

In the structure,

Y1 is S, O or NR100;

R30 to R39 and R100 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a cross-linkable group,

k3 is an integer of 1 or 2,

k4 is an integer from 1 to 4,

k5 is an integer from 1 to 3,

k6 is an integer from 1 to 8,

When k3 to k6 are each 2 or more, the substituents in each parenthesis are the same as or different from each other,

* is the point of attachment in the polymer.

More specifically, C in Formula 1 is any one of the following structures.

In the above structure, * is the point of attachment in the polymer.

In an exemplary embodiment of the present specification, E1 and E2 are end-capping units of the polymer.

In the exemplary embodiment of the present specification, E1 and E2 are units having only one attachment point.

In an exemplary embodiment of the present specification, E1 and E2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; crosslinking group; or a combination thereof.

In an exemplary embodiment of the present specification, E1 and E2 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkyl group; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; crosslinking group; or a combination thereof.

In an exemplary embodiment of the present specification, E1 and E2 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 10 alkyl group; a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; crosslinking group; or a combination thereof.

In the exemplary embodiment of the present specification, each of E1 and E2 is any one of the following structures.

In the above structure, * is the point of attachment in the polymer.

More specifically, each of E1 and E2 has any one of the following structures.

In the above structure, * is the point of attachment in the polymer.

In an exemplary embodiment of the present specification, a, b and c are determined according to the equivalent ratio of the monomers used in the preparation of the polymer.

In one embodiment of the present specification, a is a real number of 0.4 or more.

In one embodiment of the present specification, a is a real number from 0.4 to 1.

In one embodiment of the present specification, a is a real number of 0.5 to 1.

In one embodiment of the present specification, a is a real number of 0.5 to 0.9.

In one embodiment of the present specification, a is a real number of 0.5 to 0.8.

In the exemplary embodiment of the present specification, b is a real number of 0 or more.

In one embodiment of the present specification, b is a real number of 0 to 0.5.

In one embodiment of the present specification, b is a real number of 0.1 to 0.4.

In one embodiment of the present specification, b is a real number of 0.1 to 0.3.

In one embodiment of the present specification, b is a real number of 0.1 to 0.3.

In one embodiment of the present specification, c is a real number of 0 to 0.2.

In one embodiment of the present specification, c is a real number from 0 to 0.1.

In one embodiment of the present specification, c is 0.

In one embodiment of the present specification, a is a real number from 0.4 to 1, b is a real number from 0 to 0.4, and c is a real number from 0 to 0.2.

In one embodiment of the present specification, a is a real number of 0.4 to 0.9, b is a real number of 0.1 to 0.4, and c is a real number of 0 to 0.2.

In an exemplary embodiment of the present specification, the molar ratio of (A+B):(E1+E2) is 40:60 to 98:2.

An exemplary embodiment of the present specification provides a polymer including a unit represented by the following formula (2) and a terminal group represented by the formula (5).

[Formula 2]

[Formula 5]

In Formulas 2 and 5,

Ar1, Ar2, L1 and L2 are the same as or different from each other, and are each independently a substituted or unsubstituted arylene group,

R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; a substituted or unsubstituted arylamine group; Or a substituted or unsubstituted siloxane group,

n1 to n3 are each an integer of 1 to 4,

When each of n1 to n3 is 2 or more, the substituents in each parenthesis are the same as or different from each other,

E is hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted siloxane group; crosslinking group; or a combination thereof,

* is the point of attachment in the polymer.

In an exemplary embodiment of the present specification, the polymer represented by Formula 1 may be represented by a polymer including a unit represented by Formula 2 and a terminal group represented by Formula 5. Specifically, when b and c in Formula 1 are 0, the polymer represented by Formula 1 may be represented as a polymer including a unit represented by Formula 2 and a terminal group represented by Formula 5.

In an exemplary embodiment of the present specification, the polymer including a unit represented by Formula 2 and a terminal group represented by Formula 5 further includes a unit represented by Formula 3 below.

[Formula 3]

In Formula 3,

m is an integer of 3 or 4,

when m is 3, Z is CRa; SiRa; N; Or a trivalent substituted or unsubstituted aryl group,

when m is 4, Z is C; Si; Or a tetravalent substituted or unsubstituted aryl group,

Ra is hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

Y is a direct bond; a substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,

Y is a direct bond; Or in the case of a substituted or unsubstituted alkylene group, Z is a trivalent or tetravalent substituted or unsubstituted aryl group,

* is the point of attachment in the polymer.

That is, an exemplary embodiment of the present specification provides a polymer including a unit represented by Formula 2, a unit represented by Formula 3, and a terminal group represented by Formula 5.

In this case, the polymer represented by Formula 1 may be represented by a polymer including a unit represented by Formula 2, a unit represented by Formula 3, and a terminal group represented by Formula 5.

Specifically, when b in Formula 1 is a real number greater than 0 and less than 1, and c is 0, the polymer represented by Formula 1 is a unit represented by Formula 2, a unit represented by Formula 3, and a unit represented by Formula 5 It can be expressed as a polymer comprising a terminal group.

In an exemplary embodiment of the present specification, the polymer including the unit represented by Formula 2 and the terminal group represented by Formula 5 further includes a unit represented by Formula 4 below.

[Formula 4]

In Formula 4,

C is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

* is the point of attachment in the polymer.

That is, an exemplary embodiment of the present specification provides a polymer including a unit represented by Formula 2, a unit represented by Formula 4, and a terminal group represented by Formula 5.

In this case, the polymer represented by Formula 1 may be represented by a polymer including a unit represented by Formula 2, a unit represented by Formula 4, and a terminal group represented by Formula 5.

Specifically, when b in Formula 1 is 0 and c is a real number greater than 0 and less than 1, the polymer represented by Formula 1 is a unit represented by Formula 2, a unit represented by Formula 4, and a unit represented by Formula 5 It can be expressed as a polymer comprising a terminal group.

In addition, an exemplary embodiment of the present specification provides a polymer including a unit represented by Formula 2, a unit represented by Formula 3, a unit represented by Formula 4, and a terminal group represented by Formula 5.

In this case, the polymer represented by Formula 1 may be represented by a polymer including a unit represented by Formula 2, a unit represented by Formula 3, a unit represented by Formula 4, and a terminal group represented by Formula 5.

Specifically, when b and c in Formula 1 are real numbers greater than 0 and less than 1, respectively, the polymer represented by Formula 1 is a unit represented by Formula 2, a unit represented by Formula 3, or a unit represented by Formula 4 and a polymer including a terminal group represented by Formula 5.

In an exemplary embodiment of the present specification, the description of Formula 2 of the polymer including the unit represented by Formula 2 and the terminal group represented by Formula 5 is equally applicable to the description of Formula 2 described above in Formula 1 . For example, in the polymer including the unit represented by Formula 2 and the terminal group represented by Formula 5, Formula 2 may be represented by Formula 2-1.

In the exemplary embodiment of the present specification, when the polymer including the unit represented by Formula 2 and the terminal group represented by Formula 5 further includes a unit represented by Formula 3, the description of Formula 3 is in Formula 1 The description of Formula 3 above applies equally. For example, in the polymer comprising a unit represented by Formula 2, a unit represented by Formula 3, and a terminal group represented by Formula 5, Formula 3 may be represented by any one of Formulas 3-1 to 3-4 have.

The descriptions of Chemical Formulas 2 and 3 are equally applied to a polymer including a unit represented by Formula 2, a unit represented by Formula 3, a unit represented by Formula 4, and a terminal group represented by Formula 5.

In the exemplary embodiment of the present specification, when the polymer including the unit represented by Formula 2 and the terminal group represented by Formula 5 further includes Formula 4, the description of C in Formula 4 is C defined in Formula 1 is equally applicable. For example, in the polymer including the unit represented by Formula 2, the unit represented by Formula 4, and the terminal group represented by Formula 5, C in Formula 4 is any one of the following structures.

The description of C is equally applied to a polymer including a unit represented by Formula 2, a unit represented by Formula 3, a unit represented by Formula 4, and a terminal group represented by Formula 5.

In an exemplary embodiment of the present specification, in the polymer including the unit represented by Formula 2 and the terminal group represented by Formula 5, the description of E1 of Formula 1 applies equally to E in Formula 5. For example, in the polymer including the unit represented by Formula 2 and the terminal group represented by Formula 5, E is an end-capping unit of the polymer, and may be represented by any one of the following structures.

The description of E is equally applicable to a polymer including a unit represented by Formula 2, a unit represented by Formula 3, and a terminal group represented by Formula 5. In addition, the description of E is equally applied to a polymer including a unit represented by Formula 2, a unit represented by Formula 3, a unit represented by Formula 4, and a terminal group represented by Formula 5.

In one embodiment of the present specification, the polymer is an alternating polymer, a block polymer, or a random polymer.

In an exemplary embodiment of the present specification, the weight average molecular weight (Mw) of the polymer is 10,000 g/mol to 2,000,000 g/mol. Specifically, from 10,000 g/mol to 1,000,000 g/mol. More specifically, from 10,000 g/mol to 500,000 g/mol.

When the weight average molecular weight of the polymer satisfies the above range, the viscosity is appropriate to exhibit an effect of facilitating the manufacture of an inkjet device and an organic light emitting device using fine pixels.

In an exemplary embodiment of the present specification, the unit represented by Formula 2, the unit represented by Formula 3, the unit represented by Formula 4, and the terminal group represented by Formula 5 may be distributed to optimize the properties of the polymer.

In an exemplary embodiment of the present specification, a1 is the mole fraction of the unit represented by Formula 2 in the polymer, b1 is the mole fraction of the unit represented by Formula 3, c1 is the mole fraction of the unit represented by Formula 4, and the unit represented by Formula 5. When the mole fraction of is e1, a1, b1, c1 and e1 are real numbers, respectively, 0<a1<1, 0≤b1<1, 0≤c1<1. 0<e1<1, and a1+b1+c1+e1=1.

In one embodiment of the present specification, a1 is a real number of 0.4 or more.

In an exemplary embodiment of the present specification, a1 is a real number of 0.4 or more and less than 1.

In one embodiment of the present specification, a1 is a real number of 0.4 to 0.9.

In one embodiment of the present specification, a1 is a real number of 0.4 to 0.8.

In the exemplary embodiment of the present specification, b1 is a real number of 0 or more.

In the exemplary embodiment of the present specification, b1 is a real number of 0 to 0.5.

In one embodiment of the present specification, b1 is a real number of 0.1 to 0.4.

In one embodiment of the present specification, b1 is a real number of 0.1 to 0.3.

In one embodiment of the present specification, c1 is a real number of 0 to 0.2.

In one embodiment of the present specification, c1 is a real number from 0 to 0.1.

In one embodiment of the present specification, c1 is 0.

In the exemplary embodiment of the present specification, e1 is a real number of 0.1 to 0.5.

In the exemplary embodiment of the present specification, e1 is a real number of 0.1 to 0.4.

In the exemplary embodiment of the present specification, e1 is a real number of 0.1 to 0.35.

In the exemplary embodiment of the present specification, a1 is a real number of 0.4 or more and less than 1, b1 is a real number of 0 to 0.5, c1 is a real number of 0 to 0.2, e1 is a real number of 0.1 to 0.5, a1+b1+ c1+e1=1.

In an exemplary embodiment of the present specification, a1 is a real number of 0.4 to 0.9, b1 is a real number of 0.1 to 0.4, c1 is a real number of 0 to 0.2, e1 is a real number of 0.1 to 0.5, a1+b1+c1 +e1=1.

In one embodiment of the present specification, a1 is a real number of 0.4 to 0.8, b1 is a real number of 0.1 to 0.3, c1 is a real number of 0 to 0.1, e1 is a real number of 0.1 to 0.35, a1+b1+c1 +e1=1.

In one embodiment of the present specification, the polymer is represented by any one of the following structures.

In the above structure, a1 is a real number of 0<a1<1, b1 is a real number of 0≤b1<1, e1 is a real number of 0<e1<1, and a1+b1+e1 is 1.

Specifically, in the above structure, a1 is a real number from 0.4 to 0.9, b1 is a real number from 0.1 to 0.4, e1 is a real number from 0.1 to 0.5, and a1+b1+e1 is 1.

More specifically, in the above structure, a1 is a real number from 0.4 to 0.8, b1 is a real number from 0.1 to 0.3, e1 is a real number from 0.1 to 0.35, and a1+b1+e1 is 1.

In the above structure, a1, b1, and e1 are determined according to the equivalent weight of the monomer added during the preparation of the polymer.

In one embodiment of the present specification, the polymer may be prepared using a known polymerization technique. For example, a preparation method such as Suzuki, Yamamoto, Stille, a C-N coupling reaction using a metal catalyst and an arylation reaction using a metal catalyst may be applied.

In one embodiment of the present specification, the polymer may be substituted with deuterium. In this case, deuterium may be substituted by applying a method using a precursor material. For example, deuterium can be displaced by treating undeuterated monomers and/or polymers with a deuterated solvent in the presence of a Lewis acid H/D exchange catalyst.

In one embodiment of the present specification, the molecular weight of the polymer can be controlled by adjusting the ratio of the monomers used. Also, in some embodiments, the molecular weight of the polymer may be controlled using a quenching reaction.

In one embodiment of the present specification, the polymer may be used as a hole transport material. For example, the polymer may be a 'hole transport polymer'.

In one embodiment of the present specification, the polymer may be formed into a layer through a solution process. The term 'layer' is used interchangeably with the terms 'film' or 'film' and refers to a coating covering a desired area. This term is not limited by size. The area can be as large as an entire device, as small as a specific functional area, such as a real visual display, or as small as a single sub-pixel. Layers and films can be formed by any conventional deposition technique, including vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot-die coating, spray coating, and continuous nozzle coating. Discontinuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing.

In an exemplary embodiment of the present specification, the polymer has an intrinsic viscosity of less than 60 mL/g. This is particularly useful for inkjet printing applications, where the lower viscosity can result in a thicker solution being sprayed. Specifically, the polymer has an intrinsic viscosity of less than 50 mL/g, more specifically less than 40 mL/g, and more specifically less than 30 mL/g.

In an exemplary embodiment of the present specification, the intrinsic viscosity of the polymer is 20 mL/g or more and less than 60 mL/g, specifically 20 mL/g to 50 mL/g, more specifically 20 mL/g to 40 mL /g.

An exemplary embodiment of the present specification provides a coating composition comprising the above-described polymer.

In one embodiment of the present specification, the coating composition further comprises a solvent. In one embodiment of the present specification, the coating composition includes the polymer and the 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, it is preferable that the solvent does not dissolve the material applied to the lower layer.

In one embodiment of the present specification, when the coating composition is applied to the organic material layer of the organic light emitting device, a solvent that does not dissolve the material of the lower layer is used. For example, when the coating composition is applied to the hole transport layer, a solvent that does not dissolve the material of the lower layer (first electrode, hole injection layer, etc.) is used. Accordingly, there is an advantage that the hole transport layer can be introduced through a solution process.

In one embodiment of the present specification, the coating composition has improved solvent resistance during heat treatment after coating.

For example, even if the coating composition is prepared using a solvent that dissolves the polymer and the layer is prepared by a solution process, it may have resistance to the same solvent after heat treatment.

Therefore, if an organic material layer is formed using the polymer and then undergoes a heat treatment process, a solution process is possible when applying another organic material layer.

In one embodiment of the present specification, the solvent included in the coating composition is, for example, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene, etc. chlorine-based solvents; ether solvents such as tetrahydrofuran and dioxane; aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; 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 polymer according to an exemplary embodiment of the present specification is possible, but is not limited thereto.

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

In an exemplary embodiment of the present specification, the boiling point of the solvent is preferably 40°C to 350°C, more preferably 80°C to 330°C, but is not limited thereto.

In one embodiment of the present specification, the concentration of the polymer in the coating composition is preferably 0.1 wt/v% to 20 wt/v%, more preferably 0.5 wt/v% to 10 wt/v%, but It is not limited.

An exemplary embodiment of the present specification is a first electrode; a second electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the polymer.

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

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

In an exemplary embodiment of the present specification, the organic light emitting device includes a first electrode; a second electrode; and a light emitting layer provided between the first electrode and the second electrode, and further comprising a single organic material layer between the light emitting layer and the first electrode, wherein the organic material layer includes the polymer.

In an exemplary embodiment of the present specification, the organic light emitting device includes a first electrode; a second electrode; and a light emitting layer provided between the first electrode and the second electrode, and further comprising a multi-layered organic material layer between the light emitting layer and the first electrode, wherein at least one of the organic material layers includes the polymer.

In an exemplary embodiment of the present specification, the organic material layer including the polymer is a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes.

In an exemplary embodiment of the present specification, the organic light emitting device includes a first electrode; a second electrode; and a light emitting layer provided between the first electrode and the second electrode, and further comprising at least one of a hole injection layer, a hole transport layer, and an electron blocking layer between the light emitting layer and the first electrode, the hole injection layer and the hole At least one of the transport layer and the electron blocking layer includes the polymer.

In an exemplary embodiment of the present specification, the organic light emitting device includes a first electrode; a second electrode; and a light emitting layer provided between the first electrode and the second electrode, and a hole injection layer and a hole transport layer between the first electrode and the light emitting layer, wherein at least one of the hole injection layer and the hole transport layer contains the polymer. include

In an exemplary embodiment of the present specification, the organic light emitting device includes a first electrode; hole injection layer; hole transport layer; light emitting layer; and a second electrode sequentially provided, wherein at least one of the hole injection layer and the hole transport layer includes the polymer.

In an exemplary embodiment of the present specification, the organic light emitting device includes a first electrode; hole injection layer; hole transport layer; light emitting layer; and a structure in which a second electrode is sequentially stacked, and the hole injection layer or the hole transport layer includes the polymer.

In an exemplary embodiment of the present specification, the organic light emitting device includes a first electrode; hole injection layer; hole transport layer; light emitting layer; and a structure in which a second electrode is sequentially stacked, and the hole transport layer includes the polymer.

In the exemplary embodiment of the present specification, an additional organic material layer may be further included between the light emitting layer and the second electrode.

In the exemplary embodiment of the present specification, a single organic material layer may be further included between the light emitting layer and the second electrode.

In an exemplary embodiment of the present specification, a multi-layered organic material layer may be further included between the light emitting layer and the second electrode. For example, at least one of a hole blocking layer, an electron injection layer, an electron transport layer, and a layer for simultaneously injecting and transporting electrons may be further included between the light emitting layer and the second electrode.

In an exemplary embodiment of the present specification, the organic light emitting device includes a first electrode; hole injection layer; hole transport layer; light emitting layer; electron injection and transport layer; and a structure in which a second electrode is sequentially stacked, and at least one of the hole injection layer and the hole transport layer includes the polymer.

In an exemplary embodiment of the present specification, the organic light emitting device includes a first electrode; hole injection layer; hole transport layer; light emitting layer; electron injection and transport layer; and a structure in which a second electrode is sequentially stacked, and the hole injection layer or the hole transport layer includes the polymer.

In an exemplary embodiment of the present specification, the organic light emitting device includes a first electrode; hole injection layer; hole transport layer; light emitting layer; electron injection and transport layer; and a structure in which a second electrode is sequentially stacked, and the hole transport layer includes the polymer.

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

1 illustrates a structure of an organic light emitting device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked.

2 is an organic light emitting device in which a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron injection and transport layer 7 and a cathode 4 are sequentially stacked. The structure of the device is illustrated.

1 and 2 illustrate an organic light emitting device, the structure of the organic light emitting device of the present invention is not limited thereto.

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

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 light emitting device of the present invention may be stacked in a structure as illustrated in the following example.

(1) Anode / hole transport layer / light emitting layer / cathode

(2) anode / hole injection layer / hole transport layer / light emitting layer / cathode

(3) anode / hole injection layer / hole buffer layer / hole transport layer / light emitting layer / cathode

(4) anode / hole transport layer / light emitting layer / electron transport layer / cathode

(5) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(6) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode

(7) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(8) anode / hole injection layer / hole buffer layer / hole transport layer / light emitting layer / electron transport layer / cathode

(9) anode / hole injection layer / hole buffer layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(10) anode / hole transport layer / electron suppression layer / light emitting layer / electron transport layer / cathode

(11) anode / hole transport layer / electron suppression layer / light emitting layer / electron transport layer / electron injection layer / cathode

(12) anode / hole injection layer / hole transport layer / electron suppression layer / light emitting layer / electron transport layer / cathode

(13) anode / hole injection layer / hole transport layer / electron suppression layer / light emitting layer / electron transport layer / electron injection layer / cathode

(14) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(15) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(16) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(17) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(18) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron injection layer and transport layer / cathode

In the above structure, “electron transport layer/electron injection layer” may be replaced with “electron injection and transport layer”.

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 prepared to include the polymer. Specifically, the organic light emitting device may be formed using a coating composition including the polymer at least one layer of the organic material layer.

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

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

Specifically, in one embodiment of the present specification, preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer, wherein at least one of the organic material layers is formed using the coating composition.

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

In another exemplary embodiment, the heat treatment time in the heat treatment step may be within 1 hour. Specifically, it may be within 30 minutes.

In an exemplary embodiment of the present specification, the atmosphere for heat-treating the organic material layer formed using the coating composition is preferably an inert gas atmosphere such as argon or nitrogen.

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

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

In the exemplary embodiment of the present specification, the cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the cathode material include metals such as 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.

In one embodiment of the present specification, the hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes, so that the hole injection effect at the anode, the light emitting layer or the light emitting material is excellent A compound having an injection effect, preventing the movement of excitons generated in the light emitting layer to the electron injection layer or the electron injection material, and excellent in the ability to form a thin film is preferred. In addition, the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include 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.

In an exemplary embodiment of the present specification, the hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer, and the hole transport material can transport holes from the anode or hole injection layer to the light emitting layer. As a material with high hole mobility, it is suitable. In an exemplary embodiment of the present specification, the hole transport layer includes the polymer.

In an exemplary embodiment of the present specification, the light emitting layer includes an organic compound. The organic compound 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-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene; Rubrene and the like, but are not limited thereto.

In one embodiment of the present specification, the light emitting 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. For example, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto. Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. For example, the aromatic amine derivative is a condensed aromatic ring derivative substituted with a substituted or unsubstituted arylamino group, and includes fluorene, benzofluorene, pyrene, anthracene, chrysene, periplanthene, etc. substituted with an arylamino group. The arylamine compound is a compound in which at least one arylvinyl group is substituted with a substituted or unsubstituted arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group substituted or unsubstituted. Specifically, the styrylamine compound includes, but is not limited to, styrylamine, styryldiamine, styryltriamine, and styryltetraamine. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

In an exemplary embodiment of the present specification, the host material is an anthracene derivative, and the dopant material is a benzofluorene-based compound substituted with an arylamine group. Specifically, the host material is a deuterated anthracene derivative, and the dopant material is a bis(diarylamino)benzophylluorene-based compound.

In an exemplary embodiment of the present specification, the light emitting layer includes quantum dots. For example, the light emitting layer may include a matrix resin and quantum dots, and the type and content of quantum dots may be those known in the art.

When quantum dots are included in the emission layer, the HOMO energy level is lower than when the organic compound is included in the emission layer, so the common layer must also exhibit a low HOMO energy level. Since the compound according to an exemplary embodiment of the present specification exhibits a low HOMO energy level by including a halogen group, it is possible to introduce quantum dots into the light emitting layer.

In an exemplary embodiment of the present specification, the common layer is a hole injection layer, a hole transport layer, a layer that simultaneously injects and transports holes, an electron injection layer, an electron transport layer, or a layer that simultaneously injects and transports electrons.

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

In one embodiment of the present specification, 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, has an excellent electron injection effect with respect to the light emitting layer or the light emitting material , a compound that prevents the movement of excitons generated in the light emitting layer to the hole injection layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, preorenylidene methane, anthrone, bathocuproine (BCP) and the like, and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

In an exemplary embodiment of the present specification, as the metal complex compound, 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, and 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., but is not limited thereto.

In the exemplary embodiment of the present specification, the hole blocking layer is a layer that blocks the holes from reaching the cathode, and may be formed under the same conditions as the hole injection layer in general. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but is not limited thereto.

In an exemplary embodiment of the present specification, the polymer represented by Formula 1; Alternatively, the layer adjacent to the organic material layer including the polymer including the unit represented by Formula 2 and the terminal group represented by Formula 5, for example, the bank layer, includes a compound having fluorine as a substituent.

For example, when the polymer represented by Formula 1 is included in the hole transport layer, at least one of the bank layer, the hole injection layer, and the light emitting layer adjacent to the hole transport layer contains fluorine.

Polymer represented by Formula 1 as described above; Alternatively, when the layer adjacent to the organic material layer including the polymer including the unit represented by Formula 2 and the end group represented by Formula 5 contains fluorine, the dipole moment is changed due to fluorine, so that a uniform layer can be formed there is

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 application is not to be construed as being limited to the embodiments described below. The embodiments of the present application are provided to more completely explain the present specification to those of ordinary skill in the art.

< Synthesis example >

Synthesis example 1. Preparation of Polymer 1-1

(1) Preparation of compound A-1

In a round flask equipped with a condenser were placed compound q-1 (50.0 g, 1.00 eq), compound q-2 (65.2 g, 1.35 eq), K ₂ CO ₃ (78.7 g, 2.5 eq) and bis(tri-tert-butyl). After phosphine) palladium (0) (1.74 g, 0.015 eq) was added, THF (500 mL) and distilled water (300 mL) were respectively injected, and the temperature was raised to 60° C. and stirred for 6 hours. After the reaction was terminated by injecting distilled water, the organic solvent was extracted and concentrated under reduced pressure to prepare a liquid compound A-1 (50.1 g).

(2) Preparation of compound B-1

In a round flask equipped with a condenser, compound A-2 (41.0 g, 1.00 eq) and the previously prepared compound A-1 (50.0 g, 3.0 eq) were dissolved in xylene (200 mL). When completely dissolved, sodium tert-butoxide (40.0 g, 5.00 eq) and bis (tri-tert-butylphosphine) palladium (0) (2.1 g, 0.05 eq) are added, and at 120 ° C. It was refluxed for 3 hours. After the reaction was terminated by injecting distilled water, the organic solvent was extracted with ethyl acetate and distilled water, and precipitated with toluene and hexane to obtain Compound B-1 as a white solid.

(3) Preparation of compound C-1

In a round flask equipped with a condenser, the previously prepared compound B-1 (15.1 g, 1.00 eq), 4-bromo-4'-iodo-1,1'-biphenyl (13.16 g, 2.50 eq) and sodium tert-butoxide (7.0 g, 5.00 eq) was dissolved in toluene (200 mL). When completely dissolved, tris (dibenzylideneacetone) dipalladium (0) (0.67 g, 0.05 eq) and 1,1'-bis (diphenylphosphino) ferrocene (0.81 g, 0.10 eq) are added, and at 90° C. It was refluxed for 8 hours. After the reaction was terminated by injecting distilled water, the organic solvent was extracted with ethyl acetate and distilled water, and compound C-1 having a purity of 99.7% was obtained through column chromatography.

(4) Preparation of compound D-1

In a round flask equipped with a condenser, 10.00 g (1.00 eq) of compound C-1, 14 g (2.00 eq) of Bis(pinacolato)diboron, and potassium tert-butoxide ) 1.60 g (3.00 eq) was dissolved in 200 mL of toluene. When completely dissolved, [1,1'-Bis (diphenylphosphino) ferrocene] dichloropalladium (II) 0.04 eq) was added and refluxed at 90° C. for 8 hours. After completion of the reaction through DI water, the organic solvent was extracted with ethyl acetate and distilled water, and 99.3% pure compound D-1 was obtained through column chromatography.

(5) Preparation of Polymer 1-1

Compound D-1 (0.765 mmol), 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl (0.158 mmol) and 4 -Bromo-4'-propyl-1,1'-biphenyl (0.369 mmol) was placed in a round flask and dissolved in toluene (11 mL) to prepare a first solution.

Bis (1,5-cyclooctadiene) nickel (0) (2.42 mmol) was added to a 50 mL Schlenk tube. 2,2'-dipyridyl (2.42 mmol) and 1,5-cyclooctadiene (2.42 mmol) were put into a scintillation vial, and then N,N'-dimethylformamide (5.5 mL) and toluene (11 mL) ) to prepare a second solution.

The second solution was put into a Schlenk tube and stirred at 50° C. for 30 minutes. The first solution was further added to a Schlenk tube and stirred at 50° C. for 3 hours. HCl and methanol (methanol:HCl = 95:5 (v:v)) were slowly added dropwise to terminate the reaction, followed by stirring for 45 minutes, and the resulting solid was filtered. The dried solid was dissolved in toluene (1% wt/v) and purified by passing through a column containing silica gel and basic aluminum oxide (6 g each). Polymer 1-1 was prepared by triturating the obtained toluene solution in acetone.

Synthesis example 2. Preparation of Polymer 2-1

In (5) of Synthesis Example 1, 3,3'' instead of 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl -Dibromo-5'-(3-bromophenyl)-1,1':3',1''-terphenyl was used in the same manner as in Synthesis Example 1, except that Polymer 2- 1 was prepared.

Synthesis example 3. Preparation of Polymer 3-1

In (5) of Synthesis Example 1, 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl instead of 1,3,5 - Polymer 3-1 was prepared in the same manner as in Synthesis Example 1, except that tribromobenzene was used.

Synthesis example 4: Preparation of Polymer 4-1

In (5) of Synthesis Example 1, 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl instead of tris(4-bro Polymer 4-1 was prepared in the same manner as in Synthesis Example 1, except that mophenyl) (phenyl) silane was used.

Synthesis example 5: Preparation of polymer 5-1

In (5) of Synthesis Example 1, 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl instead of tetrakis (4- Polymer 5-1 was prepared in the same manner as in Synthesis Example 1, except that bromophenyl)silane was used.

Synthesis example 6: Preparation of polymer 6-1

In (5) of Synthesis Example 1, 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl instead of tris(4-bro Polymer 6-1 was prepared in the same manner as in Synthesis Example 1, except that mophenyl)amine was used.

compare Synthesis example . Preparation of Comparative Polymer Q

Polymer Q was prepared in the same manner as in (5) of Synthesis Example 1, except that compound Q-1 was used instead of compound D-1 in (5) of Synthesis Example 1.

The polymers synthesized in Synthesis Examples 1 to 6 and Comparative Synthesis Examples were confirmed that the polymers were synthesized by measuring molecular weights through GPC.

< Experimental example 1> Energy level measurement

A coating composition was prepared by dissolving the compounds synthesized in Synthesis Examples 1 to 6 and Comparative Synthesis Examples at a concentration of 2wt% in toluene, respectively. The coating composition was spin-coated on an ITO substrate to form a thin film. Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) energy levels of the thin film formed to a thickness of about 100 nm were measured using AC3 equipment, and the results are shown in Table 1 below. Table 1 below lists the absolute values of HOMO and LUMO.

polymer
Q polymer
1-1 polymer
2-1 polymer
3-1 polymer
4-1 polymer
5-1 polymer
6-1 HOMO 5.60 5.65 5.64 5.63 5.65 5.64 5.62 LUMO 2.65 2.60 2.61 2.62 2.60 2.62 2.60 band gap 2.95 3.05 3.05 3.05 3.05 3.02 3.02

In the organic light emitting device, when holes move between the electrode, the hole injection layer, the hole transport layer, and the light emitting layer, if the HOMO gap between each layer is reduced, the holes can move smoothly, so the hole mobility is improved.

From Table 1 above, since the absolute HOMO values of polymers 1-1 to 6-1 are higher than the absolute HOMO values of the comparative polymers (that is, since the HOMO energy levels of polymers 1-1 to 6-1 are lower than those of the comparative polymers, ) and polymers 1-1 to 6-1, it can be seen that the HOMO gap with the electron injection layer will decrease compared to polymer Q.

That is, the polymer of the present invention exhibits a low HOMO energy level by including a benzofuran group, and thus it can be predicted that hole mobility will be improved when applied to a device.

< Experimental example 2> Molecular weight measurement

Experimental example 2-1.

Using GPC (Agilent, PLgel HFIPGEL column), the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (PDI) of polymer 1-1 prepared in Synthesis Example 1 were measured.

Experimental example 2-2 to 2-6.

Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (PDI) in the same manner as in Experimental Example 2-1 except that the polymer of Table 1 was used instead of Polymer 1-1 in Experimental Example 2-1. ) was measured.

comparative example 2-1.

Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (PDI) in the same manner as in Experimental Example 2-1 except that the polymer of Table 1 was used instead of Polymer 1-1 in Experimental Example 2-1. ) was measured.

The GPC results measured in Experimental Examples 2-1 to 2-6 and Comparative Example 2-1 are shown in Table 2 below.

polymer a:b1:e1
(molar ratio) Mn Mw PDI Experimental example
2-1 polymer
1-1 56.2:19.1:24.7 35,000 104,000 2.97 Experimental example
2-2 polymer
2-1 53.8:18.3:28 38,000 110,000 2.89 Experimental example
2-3 polymer
3-1 57:17.9:25.1 35,000 91,000 2.60 Experimental example
2-4 polymer
4-1 53.8:20.3:25.8 38,000 122,000 3.21 Experimental example
2-5 polymer
5-1 50.8:17.6:31.5 35,000 106,000 3.03 Experimental example
2-6 polymer
6-1 53.8:18.3:28 39,000 129,000 3.31 comparative example
2-1 polymer
Q 53.7:18.3:28.0 27,000 143,000 5.30

A large molecular weight distribution means that molecules of various molecular weights are distributed, which means that it is difficult to reproducibly synthesize polymers.

From Table 1, it can be seen that the PDI of Comparative Example 2-1 is larger than that of Experimental Examples 2-1 to 2-6. From this, it can be seen that in the polymer Q (Comparative Example 2-1), polymers of various molecular weights are distributed. That is, it can be seen that it is difficult to synthesize polymer Q reproducibly.

In short, in the case of the polymers (Examples 2-1 to 2-6) according to the exemplary embodiment of the present specification from Table 2, by including a benzofuran group, it shows a lower PDI than the polymer without it (Comparative Example 2-1) It can be confirmed that, from this, it can be seen that the polymer according to the exemplary embodiment of the present specification is capable of producing a homogeneous polymer.

<Experimental Example 3> Thin film retention measurement

Experimental Example 3-1.

Polymer 1-1 prepared in Synthesis Example 1 was dissolved in toluene at a concentration of 2 wt% to prepare a coating composition 1.

Comparative Example 3-1.

A coating composition 2 was prepared by dissolving the following compound C-1 prepared in (3) of Synthesis Example 1 in toluene at a concentration of 2 wt%.

The coating compositions 1 and 2 were respectively spin-coated on glass to form a thin film, and then UV-vis absorption was measured. Again, this thin film was immersed in cyclohexanone for 3 minutes, dried, and UV-vis absorption was measured. Thin film retention can be confirmed by comparing the size of the maximum peak of UV absorption before and after immersion.

3 is a view showing the test results of the film retention rate of the thin film formed of the coating composition 1.

4 is a view showing the test results of the film retention rate of the thin film formed of the coating composition 2.

3 and 4, (a) is the UV measurement result immediately after forming the thin film (before immersion in cyclohexanone for 3 minutes), and (b) is the UV measurement result after immersing the thin film in cyclohexanone for 3 minutes .

In the case of the thin film formed of the coating composition 1 through FIG. 3, it can be seen that the thin film retention rate is 100%. That is, it can be confirmed that the polymer according to an exemplary embodiment of the present specification has excellent solvent resistance.

On the other hand, in the case of the thin film formed of the coating composition 2 through FIG. 4, it can be seen that the thin film loss rate is large. That is, in the case of compound C-1 (monomer), it can be confirmed that there is no solvent resistance.

Experimental example 4. Fabrication of organic light emitting devices

Experimental example 4-1.

(1) Material

As the dopant, a bis(diarylamino)benzofluorene-based compound described in US 8,465,848B2 was used.

HIL used the material described in US 7,351,358B2. Specifically, a hole injection material prepared from an aqueous dispersion of an electrically conductive polymer and a polymeric fluorinated sulfonic acid was used.

The host used the deuterated anthracene compound described in WO2011-028216A1.

(2) device fabrication

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,500 Å 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 washing was performed with a solvent of isopropyl alcohol and acetone and dried, and then the substrate was washed for 5 minutes and then dried.

Immediately before device fabrication, cleaned and patterned ITO was treated with UV ozone for 10 min. After ozone treatment, an aqueous dispersion of HIL was spin-coated on the ITO surface, and the solvent was removed through heat treatment to form a hole injection layer with a thickness of about 40 nm. A toluene solution in which 1.5wt% of the polymer 1-1 prepared in Synthesis Example 1 was dissolved 1.5wt% was spin-coated on the hole injection layer formed above, and the solvent was removed through heat treatment to form a hole transport layer with a thickness of about 100 nm did. A methyl benzoate solution in which a host and a dopant (host:dopant=93:7(wt%)) were dissolved was spin-coated on the hole transport layer at a concentration of 2.0wt% to form a light emitting layer with a thickness of about 100nm. After transferring to a vacuum evaporator, BCP was vacuum-deposited to a thickness of 35 nm on the light emitting layer to form an electron injection and transport layer. A cathode was formed by sequentially depositing LiF to a thickness of 1 nm and aluminum to a thickness of 100 nm on the electron injection and transport layer.

In the above process, the deposition rate of lithium fluoride on the cathode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was maintained at 2 X 10 ^-7 torr to 5 X 10 ^-6 torr. did.

Experimental example 4-2 to 4-6.

An organic light emitting diode was manufactured in the same manner as in Experimental Example 4-1, except that the polymer of Table 3 below was used instead of Polymer 1-1 in Experimental Example 4-1.

comparative example 4-1.

An organic light emitting diode was manufactured in the same manner as in Experimental Example 4-1, except that the polymer of Table 3 below was used instead of Polymer 1-1 in Experimental Example 4-1.

For the organic light emitting diodes prepared in Experimental Examples 4-1 to 4-6 and Comparative Example 4-1, the results of performance measurements at a current density of 10 mA/cm ² are shown in Table 3 below.

The external quantum efficiency was calculated as (number of emitted photons)/(number of injected charge carriers), and the color coordinates are x and y coordinates according to the C.I.E chromaticity diagram (Commission Internationale de L'Eclairage, 1931), and CE/CIEy is the value obtained by dividing the luminous efficiency (cd/A) by the color coordinate (y) value.

hole
transport layer Driving
Voltage
(V) radiation
efficiency
(cd/A) power
efficiency
(lm/W) Out
quantum
efficiency
(QE)
(%) luminance
(cd/m ² ) color coordinates
(x) color coordinates
(y)

CE/CIEy Experimental example
3-1 polymer
1-1 4.44 4.66 3.29 5.69 465.97 0.138 0.103 45.43 Experimental example
3-2 polymer
2-1 4.37 4.58 3.29 5.58 458.01 0.139 0.103 44.48 Experimental example
3-3 polymer
3-1 4.54 4.69 3.25 5.82 469.09 0.139 0.100 46.81 Experimental example
3-4 polymer
4-1 4.67 4.68 3.15 6.17 467.68 0.141 0.092 51.04 Experimental example
3-5 polymer
5-1 4.24 4.59 3.40 6.03 458.51 0.140 0.092 49.84 Experimental example
3-6 polymer
6-1 4.25 4.23 3.13 5.57 422.55 0.141 0.091 46.34 comparative example
3-1 polymer
Q 7.81 1.21 0.49 1.41 121.05 0.150 0.107 11.31

From Table 3, it can be seen that Experimental Examples 3-1 to 3-6 exhibited lower driving voltage and excellent efficiency compared to Comparative Example 3-1. The fact that the polymers used in Experimental Examples 3-1 to 3-6 operate even at a lower voltage than the polymer used in Comparative Example 3-1 means that the hole mobility is excellent. Combining this with Tables 1 and 2, the polymer according to an exemplary embodiment of the present specification can prepare a homogeneous polymer by including a benzofuran group, and has a high absolute value of HOMO (that is, a low HOMO energy level and ) and high hole mobility, it can be seen that when applied to a device, it exhibits excellent performance.

Although the preferred embodiment (hole transport layer) of the present invention has been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and detailed description of the invention, and this belongs to the category of

1: substrate
2: Anode
3: light emitting layer
4: cathode
5: hole injection layer
6: hole transport layer
7: Electron injection and transport layer

Claims (10)

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

In Formula 1,
A is represented by the following formula (2),
B is represented by the following formula (3),
C is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,
E1 and E2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted siloxane group; crosslinking group; or a combination thereof,
a, b and c are each a mole fraction,
a is a real number 0 < a ≤ 1,
b is a real number of 0≤b<1,
c is a real number of 0≤c<1,
a+b+c is 1,
[Formula 2]

In Formula 2,
Ar1, Ar2, L1 and L2 are the same as or different from each other, and are each independently a substituted or unsubstituted arylene group,
R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; a substituted or unsubstituted arylamine group; Or a substituted or unsubstituted siloxane group,
n1 to n3 are each an integer of 1 to 4,
When each of n1 to n3 is 2 or more, the substituents in each parenthesis are the same as or different from each other,
* is the point of attachment in the polymer,
[Formula 3]

In Formula 3,
m is an integer of 3 or 4,
when m is 3, Z is CRa; SiRa; N; Or a trivalent substituted or unsubstituted aryl group,
when m is 4, Z is C; Si; Or a tetravalent substituted or unsubstituted aryl group,
Ra is hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,
Y is a direct bond; a substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,
Y is a direct bond; Or in the case of a substituted or unsubstituted alkylene group, Z is a trivalent or tetravalent substituted or unsubstituted aryl group,
* is the point of attachment in the polymer. The method according to claim 1,
E1 and E2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; crosslinking group; or a combination thereof. A polymer comprising a unit represented by the following formula (2) and a terminal group represented by the following formula (5):
[Formula 2]

[Formula 5]

In Formulas 2 and 5,
Ar1, Ar2, L1 and L2 are the same as or different from each other, and are each independently a substituted or unsubstituted arylene group,
R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; a substituted or unsubstituted arylamine group; Or a substituted or unsubstituted siloxane group,
n1 to n3 are each an integer of 1 to 4,
When each of n1 to n3 is 2 or more, the substituents in each parenthesis are the same as or different from each other,
E is hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted siloxane group; crosslinking group; or a combination thereof,
* is the point of attachment in the polymer. 4. The method of claim 3,
The polymer further comprises a unit represented by the following formula (3):
[Formula 3]

In Formula 3,
m is an integer of 3 or 4,
when m is 3, Z is CRa; SiRa; N; Or a trivalent substituted or unsubstituted aryl group,
when m is 4, Z is C; Si; Or a tetravalent substituted or unsubstituted aryl group,
Ra is hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,
Y is a direct bond; a substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,
Y is a direct bond; Or in the case of a substituted or unsubstituted alkylene group, Z is a trivalent or tetravalent substituted or unsubstituted aryl group,
* is the point of attachment in the polymer. 4. The method of claim 3,
The polymer further comprises a unit represented by the following formula (4):
[Formula 4]

In Formula 4,
C is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,
* is the point of attachment in the polymer. 6. The method according to any one of claims 1 to 5,
The above formula 2 is a polymer represented by the following formula 2-1:
[Formula 2-1]

In Formula 2-1,
R1 to R3, Ar1, Ar2, and n1 to n3 are the same as defined in Formula 2,
R4 and R5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; Or a substituted or unsubstituted alkyl group,
m1 and m2 are each an integer of 1 to 3,
When m1 and m2 are each 2 or more, the structures in each parenthesis are the same as or different from each other,
n4 and n5 are each an integer of 1 to 4,
When n4 and n5 are each 2 or more, the substituents in each parenthesis are the same as or different from each other,
* is the point of attachment in the polymer. 5. The method according to any one of claims 1, 2 and 4,
Chemical Formula 3 is a polymer represented by any one of the following Chemical Formulas 3-1 to 3-4:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Formulas 3-1 to 3-4,
Z1 is CRa; SiRa; N; Or a trivalent substituted or unsubstituted aryl group,
Z2 and Z3 are the same as or different from each other, and each independently C; Si; Or a tetravalent substituted or unsubstituted aryl group,
L10 is a direct bond; Or a substituted or unsubstituted arylene group,
Ra is hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,
R10 to R20 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; alkoxy group; aryloxy group; fluoroalkoxy group; siloxane group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; or a cross-linkable group, adjacent groups may combine with each other to form a ring,
k1 is an integer from 1 to 4,
k2 is an integer from 1 to 5,
When k1 is 2 or more, the substituents in parentheses are the same as or different from each other,
When k2 is 2 or more, the substituents in parentheses are the same as or different from each other,
* is the point of attachment in the polymer. 6. The method according to any one of claims 1 to 5,
The polymer has a weight average molecular weight of 10,000 g/mol to 2,000,000 g/mol. a first electrode;
a second electrode; and
At least one organic material layer provided between the first electrode and the second electrode,
At least one of the organic material layers is an organic light emitting device comprising the polymer according to any one of claims 1 to 5. 10. The method of claim 9,
The organic material layer including the polymer is an organic light emitting device that is a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes.

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