KR102481074B1 - Polymer, coating compositions comprising the same, and organic light emitting device using the same - Google Patents

Abstract

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

Description

Polymer, coating composition containing the same, and an organic light emitting device using the same

The present specification relates to a polymer, a coating composition including the same, 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 specific organic molecules. 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 light emitting device using this principle may generally be composed of a cathode, an anode, and an organic material layer disposed therebetween, such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an organic material layer including an electron injection layer.

Most of the materials used in organic light emitting devices are pure organic materials or complex compounds in which organic materials and metals are complexed. can be distinguished. 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 when oxidized is mainly used. On the other hand, as an electron injection material or 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 preferable, and a material with high luminous efficiency that converts excitons into light when formed is preferred. desirable.

In addition to the above, the material used in the organic light emitting device preferably additionally has the following properties.

First, the material used in the organic light emitting device preferably has excellent thermal stability. This is because Joule heating due to movement of charges occurs in the organic light emitting device. 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 ) has a glass transition temperature of 100° C. or less, so it is difficult to use in an organic light emitting device requiring a high current.

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

In addition, materials used in organic light emitting devices must have excellent chemical stability, charge mobility, and interface characteristics with electrodes or adjacent layers. That is, the material used in the organic light emitting device should be less deformed by moisture or oxygen. In addition, by having appropriate hole or electron mobility, the formation of excitons should be maximized by balancing the density of holes and electrons in the light emitting layer of the organic light emitting device. And, for the stability of the device, it should be possible to improve the interface with the electrode including metal or metal oxide.

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

First, it must form a storable, homogeneous solution. In the case of commercially available materials for the deposition process, because they have good crystallinity, they do not dissolve well in solutions, or even if they form a solution, the crystals are easily caught, so the concentration gradient of the solution varies depending on the storage period or there is a high possibility of forming defective devices.

Second, the layers subjected to solution processing must be solvent and material resistant to other layers. To this end, a solution is applied by introducing a curing group like VNPB (N4,N4′′-di(naphthalen-1-yl)-N4,N4′′-bis(4-vinylphenyl)biphenyl-4,4′′-diamine) Substances capable of forming self-crosslinked polymers on the substrate through post-heat treatment or UV (ultraviolet) irradiation or polymers with sufficient resistance to the next process are preferred, and HATCN (hexaazatriphenylene hexacarbonitrile: Hexaazatriphenylenehexacarbonitrile) is also preferred if it is capable of being solvent resistant by itself. In general, arylamine-based single molecules used in OLED (ORGANIC LIGHT EMITTING DEVICE) devices do not have resistance to solvents in the next process by themselves, so arylamine-based compounds that can be used in OLED devices for solution processing have a curing group. Solvent resistance must be secured in the form of a high molecular weight polymer.

Therefore, in the art, there is a demand for the development of organic materials meeting the above requirements.

Korean Patent Publication No. 10-2004-0028954

The present specification is intended to provide a polymer, a coating composition including the same, and an organic light emitting device formed using the same.

The present specification provides a polymer including a first unit represented by Formula 1 below.

[Formula 1]

In Formula 1,

L1 is -O-; A substituted or unsubstituted alkylene group; A substituted or unsubstituted divalent amine group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

L2 and L3 are the same as or different from each other, and are each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

a1 is an integer from 1 to 16;

When a1 is 2 or more, two or more L1s are the same as or different from each other,

Ar1 to Ar4 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or bonded to adjacent groups to form a ring;

R1 to R6 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

r1 is an integer from 1 to 4;

r2 and r3 are integers from 1 to 3;

When r1 to r3 are each 2 or more, two or more R1 to R3 are the same as or different from each other,

n1 is the repeating number of the unit, and is 10 to 10000.

In addition, the present specification provides a coating composition comprising the polymer.

In addition, the present specification is a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the coating composition or a cured product thereof. do.

Since the polymer consisting of only the first unit represented by Formula 1 according to an exemplary embodiment of the present specification includes units derived from monomers having high solubility in some solvents, solubility in some solvents is high, but it is not suitable for use in the solvent of the next step. resistance to the organic light emitting device, so that the compound is not washed away or the film properties are not changed, and thus a reproducible organic light emitting device can be manufactured. In addition, the organic layer formed using a polymer including a first unit represented by Chemical Formula 1 and a second unit represented by Chemical Formula 2 at the same time has excellent thermal and optical stability after curing through heat and light, and has excellent solubility in other solvents. Otherwise, a layered film formation process may be performed on the film formation through another solution process.

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

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

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

1 is a diagram illustrating an example of an organic light emitting device according to an exemplary embodiment of the present specification.
2 is a diagram showing GPC data of Compound 1.
3 is a diagram showing GPC data of compound 2.
4 is a diagram showing GPC data of compound 3.

Hereinafter, this specification will be described in more detail.

The present specification provides a polymer including a first unit represented by Formula 1 above.

In one embodiment of the present specification, the polymer including the first unit represented by Chemical Formula 1 is a random polymer or a block polymer.

In the present specification, a "unit" is a structure in which a monomer is included in a polymer and is repeated, and means a structure in which the monomer is bonded to the polymer by polymerization.

In this specification, the meaning of "including a unit" means included in the main chain in the polymer.

In the present specification, "monomer" means a monomer or a unit that is a unit constituting the polymer.

In one embodiment of the present specification, the first unit represented by Formula 1 includes an amine group that facilitates charge injection and transfer, and the amine group and the phenyl group of the core structure are connected in a non-linear form. contain the structure Therefore, a sufficient bandgap can be secured and the device can be smoothly driven.

In addition, the polymer including the first unit represented by Formula 1 has excellent solubility in organic solvents. Therefore, when the polymer represented by Chemical Formula 1 is used in the hole transport layer or hole injection layer of an organic light emitting device, it is easy to apply a solution process, and the hole transport layer or hole injection layer has excellent uniformity and surface properties. It is possible to improve the performance and life characteristics of

In addition, when the polymer including only the first unit represented by Formula 1 has a molecular weight of a certain level or more, or when it further includes the second unit represented by Formula 2, it has solvent resistance to a specific solvent. Layers can also be applied to the solution process.

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

In this specification, when a part is said to "include" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

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

는 연결되는 부위를 의미한다.In this specification,

indicates the connecting part.

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 hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same as or different from each other.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; nitrile group; an alkyl group; cycloalkyl group; amine group; silyl group; phosphine oxide group; aryl group; and N, O, S, Se, and a heteroaryl group containing at least one of Si atoms. It is substituted with one or two or more substituents selected from the group consisting of two or more substituents from among the substituents exemplified above. It means having no substituent.

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 50, more preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, more preferably 3 to 30 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3 ,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 50 carbon atoms, more preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, and the like, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it is 10-50 carbon atoms, and 10-30 are more preferable. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, triphenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may bond to each other to form a ring.

,

,

,

,

,

등이 될 수 있으나, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

,

etc., but is not limited thereto.

In the present specification, the heterocyclic group includes one or more of N, O, S, Si, and Se as heteroatoms, and the number of carbon atoms is not particularly limited, but preferably 2 to 60 carbon atoms, and more preferably 2 to 30 carbon atoms. Do. 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 triazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group, and an acridine group. , Pyridazine group, pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazine group, pteridine group, pyrido pyrimidine group, pyrido pyrazine group ), pyrazino pyrazine group, isoquinoline group, indole group, pyrido indole group, indeno pyrimidine group (5H-indeno pyrimidine), carbazole group, benzoxazole group, benzimidazole group, Benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, dibenzofuran group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group and thia diazolyl groups, etc., but are not limited thereto.

In the present specification, the heteroaryl group may be selected from examples of the heterocyclic group except for aromatic, but is not limited thereto.

In the present specification, the amine group is represented by -NR ₂₀₆ R ₂₀₇ , R ₂₀₆ and R ₂₀₇ are the same as or different from each other, and each independently hydrogen, deuterium, halogen group, alkyl group, alkenyl group, alkoxy group, cycloalkyl group, aryl It may be a substituent consisting of at least one of a group and a heterocyclic group. For example, -NH ₂ , monoalkylamine group, dialkylamine group, N-alkylarylamine group, monoarylamine group, diarylamine group, N-arylheteroarylamine group, N-alkylheteroarylamine group, mono It may be selected from the group consisting of a heteroarylamine group and a diheteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30, more preferably 1 to 20. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, and a 9-methyl-anthracenylamine group. , Diphenylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-biphenylnaphthylamine group, N- Naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine group, N-phenanthrenylflu There is an orenylamine group, N-biphenylfluorenylamine group, etc., but is not limited thereto.

In the present specification, the alkylene group means that there are two binding sites to the alkyl group, that is, a divalent group. The above description of the alkyl group can be applied except that each is a divalent group.

In the present specification, the arylene group means that the aryl group has two binding sites, that is, a divalent group. The description of the aryl group described above can be applied except that each is a divalent group.

In the present specification, the heteroarylene group means a heteroaryl group having two bonding sites, that is, a divalent group. The above description of the heteroaryl group may be applied except that each is a divalent group.

In one embodiment of the present specification, L1 is -O-; A substituted or unsubstituted alkylene group; A substituted or unsubstituted divalent amine group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

In one embodiment of the present specification, L1 is -O-.

In one embodiment of the present specification, L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

In one embodiment of the present specification, L1 is a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, or a substituted or unsubstituted pentylene group. , or a substituted or unsubstituted hexylene group.

In one embodiment of the present specification, L1 is a methylene group.

In one embodiment of the present specification, L1 is an ethylene group.

In one embodiment of the present specification, L1 is a heptylene group.

In one embodiment of the present specification, L1 is a hexylene group.

In one embodiment of the present specification, L1 is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L1 is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted terphenylene group. It is a cyclic fluorenylene group.

In one embodiment of the present specification, L1 is a phenylene group.

In one embodiment of the present specification, a1 is 1 to 16, and when a1 is 2 or more, two or more L1s are the same as or different from each other.

In one embodiment of the present specification, a1 is 1.

In one embodiment of the present specification, a1 is 3.

In one embodiment of the present specification, a1 is 5.

In one embodiment of the present specification, L2 and L3 are the same as or different from each other, and are each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

In one embodiment of the present specification, L2 and L3 are each a direct bond.

In one embodiment of the present specification, L2 and L3 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 one embodiment of the present specification, L2 and L3 are the same as or different from each other, and each independently represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, or a substituted Or an unsubstituted fluorenylene group.

In one embodiment of the present specification, L2 and L3 are each a phenylene group.

In one embodiment of the present specification, Ar1 to Ar4 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group; It is a substituted or unsubstituted heterocyclic group, or may be bonded to adjacent groups to form a ring.

In one embodiment of the present specification, Ar1 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, Ar1 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted triphenyl group, or a substituted or unsubstituted phenanthryl group , A substituted or unsubstituted naphthyl group, or a substituted or unsubstituted fluorenyl group.

In one embodiment of the present specification, Ar1 is a phenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar1 is a phenyl group unsubstituted or substituted with an amine group.

In one embodiment of the present specification, Ar1 is a phenyl group unsubstituted or substituted with an arylamine group.

In one embodiment of the present specification, Ar1 is a phenyl group unsubstituted or substituted with a diphenylamine group.

In one embodiment of the present specification, Ar1 is a phenyl group.

In one embodiment of the present specification, Ar1 is a biphenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar1 is a biphenyl group unsubstituted or substituted with an amine group.

In one embodiment of the present specification, Ar1 is a biphenyl group unsubstituted or substituted with an arylamine group.

In one embodiment of the present specification, Ar1 is a biphenyl group unsubstituted or substituted with a diphenylamine group.

In one embodiment of the present specification, Ar1 is a biphenyl group.

In one embodiment of the present specification, Ar1 is a fluorenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar1 is a fluorenyl group unsubstituted or substituted with a methyl group.

In one embodiment of the present specification, Ar1 is a dimethylfluorenyl group.

In one embodiment of the present specification, Ar2 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, Ar2 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted triphenyl group, or a substituted or unsubstituted phenanthryl group , A substituted or unsubstituted naphthyl group, or a substituted or unsubstituted fluorenyl group.

In one embodiment of the present specification, Ar2 is a phenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar2 is a phenyl group unsubstituted or substituted with an amine group.

In one embodiment of the present specification, Ar2 is a phenyl group unsubstituted or substituted with an arylamine group.

In one embodiment of the present specification, Ar2 is a phenyl group unsubstituted or substituted with a diphenylamine group.

In one embodiment of the present specification, Ar2 is a phenyl group.

In one embodiment of the present specification, Ar2 is a biphenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar2 is a biphenyl group unsubstituted or substituted with an amine group.

In one embodiment of the present specification, Ar2 is a biphenyl group unsubstituted or substituted with an arylamine group.

In one embodiment of the present specification, Ar2 is a biphenyl group unsubstituted or substituted with a diphenylamine group.

In one embodiment of the present specification, Ar2 is a biphenyl group.

In one embodiment of the present specification, Ar2 is a fluorenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar2 is a fluorenyl group unsubstituted or substituted with a methyl group.

In one embodiment of the present specification, Ar2 is a dimethylfluorenyl group.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted triphenyl group, or a substituted or unsubstituted phenanthryl group , A substituted or unsubstituted naphthyl group, or a substituted or unsubstituted fluorenyl group.

In one embodiment of the present specification, Ar3 is a phenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar3 is a phenyl group unsubstituted or substituted with an amine group.

In one embodiment of the present specification, Ar3 is a phenyl group unsubstituted or substituted with an arylamine group.

In one embodiment of the present specification, Ar3 is a phenyl group unsubstituted or substituted with a diphenylamine group.

In one embodiment of the present specification, Ar3 is a phenyl group.

In one embodiment of the present specification, Ar3 is a biphenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar3 is a biphenyl group unsubstituted or substituted with an amine group.

In one embodiment of the present specification, Ar3 is a biphenyl group unsubstituted or substituted with an arylamine group.

In one embodiment of the present specification, Ar3 is a biphenyl group unsubstituted or substituted with a diphenylamine group.

In one embodiment of the present specification, Ar3 is a biphenyl group.

In one embodiment of the present specification, Ar3 is a fluorenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar3 is a fluorenyl group unsubstituted or substituted with a methyl group.

In one embodiment of the present specification, Ar3 is a dimethylfluorenyl group.

In one embodiment of the present specification, Ar4 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, Ar4 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted triphenyl group, or a substituted or unsubstituted phenanthryl group. , A substituted or unsubstituted naphthyl group, or a substituted or unsubstituted fluorenyl group.

In one embodiment of the present specification, Ar4 is a phenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar4 is a phenyl group unsubstituted or substituted with an amine group.

In one embodiment of the present specification, Ar4 is a phenyl group unsubstituted or substituted with an arylamine group.

In one embodiment of the present specification, Ar4 is a phenyl group unsubstituted or substituted with a diphenylamine group.

In one embodiment of the present specification, Ar4 is a phenyl group.

In one embodiment of the present specification, Ar4 is a biphenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar4 is a biphenyl group unsubstituted or substituted with an amine group.

In one embodiment of the present specification, Ar4 is a biphenyl group unsubstituted or substituted with an arylamine group.

In one embodiment of the present specification, Ar4 is a biphenyl group unsubstituted or substituted with a diphenylamine group.

In one embodiment of the present specification, Ar4 is a biphenyl group.

In one embodiment of the present specification, Ar4 is a fluorenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar4 is a fluorenyl group unsubstituted or substituted with a methyl group.

In one embodiment of the present specification, Ar4 is a dimethylfluorenyl group.

In one embodiment of the present specification, Ar1 and Ar2 may combine with each other to form a substituted or unsubstituted ring.

In one embodiment of the present specification, Ar3 and Ar4 may combine with each other to form a substituted or unsubstituted ring.

In one embodiment of the present specification, R1 to R6 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present specification, R1 is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted isopropyl group, or a substituted or unsubstituted tert- It is a butyl group.

In one embodiment of the present specification, R1 is a methyl group.

In one embodiment of the present specification, R1 to R6 are each hydrogen.

In one embodiment of the present specification, r1 is an integer of 1 to 4, r2 and r3 are integers of 1 to 3, and when r1 to r3 are each 2 or more, two or more R1 to R3 are the same as or different from each other. Do.

According to an exemplary embodiment of the present specification, n1 is the number of repetitions of a unit, and may be 10 to 10000.

In one embodiment of the present specification, Formula 1 may be represented by Formula 3 below.

[Formula 3]

In Formula 3,

Definitions of L1 to L3, a1, Ar1 to Ar4, R1 to R6, r1 to r3, and n1 are the same as defined in Chemical Formula 1 above.

In one embodiment of the present specification, the first unit represented by Chemical Formula 1 is any one selected from the following structures.

In the above structure,

n1 is the repeating number of the unit, and is 10 to 10,000.

In one embodiment of the present specification, the polymer may further include a second unit represented by Formula 2 below.

[Formula 2]

In Formula 2,

X is a curing group;

L4 is a direct bond; -O-; A substituted or unsubstituted alkylene group; A substituted or unsubstituted divalent amine group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

a4 is an integer from 1 to 16;

When a4 is 2 or more, two or more L4s are the same or different from each other,

R7 to R9 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

n2 is the repeating number of the unit and is 1 to 10000.

In one embodiment of the present specification, X is a curing group.

In one embodiment of the present specification, X is a thermosetting group or a photocurable group.

In one embodiment of the present specification, X is any one selected from the following structures.

In one embodiment of the present specification, L11 is a direct bond; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group.

In one embodiment of the present specification, R11 to R16 are the same as or different from each other, and each independently represents an alkyl group having 1 to 5 carbon atoms.

In one embodiment of the present specification, L4 is a direct bond; -O-; A substituted or unsubstituted alkylene group; A substituted or unsubstituted divalent amine group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

In one embodiment of the present specification, L4 is a direct bond.

In one embodiment of the present specification, L4 is -O-.

In one embodiment of the present specification, L4 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

In one embodiment of the present specification, L4 is a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, or a substituted or unsubstituted pentylene group. , or a substituted or unsubstituted hexylene group.

In one embodiment of the present specification, L4 is a methylene group.

In one embodiment of the present specification, L4 is an ethylene group.

In one embodiment of the present specification, L4 is a heptylene group.

In one embodiment of the present specification, L4 is a hexylene group.

In one embodiment of the present specification, L4 is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L4 is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted terphenylene group. It is a cyclic fluorenylene group.

In one embodiment of the present specification, L4 is a phenylene group.

In one embodiment of the present specification, a4 is 1 to 16, and when a1 is 2 or more, two or more L4s are the same as or different from each other.

In one embodiment of the present specification, a4 is 1.

In one embodiment of the present specification, a4 is 3.

In one embodiment of the present specification, a4 is 5.

In one embodiment of the present specification, R7 to R9 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R7 to R9 are each hydrogen.

In one embodiment of the present specification, n2 is the number of repetitions of a unit, and is 1 to 10,000.

In one embodiment of the present specification, the second unit represented by Chemical Formula 2 is any one selected from the following structures.

In the above structure,

n2 is the repeating number of the unit and is 1 to 10,000.

In one embodiment of the present specification, the polymer is any one selected from the following structures.

In the above structure,

m1 is the mole fraction, 0 < m1 ≤ 1,

m2 is the mole fraction, 0 ≤ m2 < 1,

m1+m2≤1, and

n is the repeating number of the unit and is 10 to 10,000.

In one embodiment of the present specification, m1 preferably has 0.5 = m1 < 1, more preferably 0.8 = m1 < 1, and m2 preferably has 0 < m2 = 0.5, and more preferably 0 < m2 = 0.2. . When the above range is satisfied, the driving voltage of the device decreases and the efficiency and lifespan increase. When the above range is not satisfied, the solvent resistance of the cured product using the polymer decreases, making it difficult to manufacture the device.

In one embodiment of the present specification, the polymer is any one selected from the following structures.

In the above structure,

n is the repeating number of the unit and is 10 to 10,000.

In one embodiment of the present specification, the number average molecular weight of the polymer may be 5,000 g / mol to 1,000,000 g / mol. Specifically, it may be 5,000 g/mol to 300,000 g/mol.

In one embodiment of the present specification, the terminal group of the polymer is a substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted alkyl group, but is not limited thereto.

According to another exemplary embodiment, the end group of the polymer is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it may be a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, but is not limited thereto.

In another exemplary embodiment, the end group of the polymer is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or it may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, but is not limited thereto.

According to another exemplary embodiment, the terminal group of the polymer is an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with a nitrile group; Or it may be an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with a nitrile group, but is not limited thereto.

In another exemplary embodiment, the terminal group of the polymer is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted methyl group. It may be a substituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, and the like, but is not limited thereto.

In this specification, molecular weight analysis was analyzed through GPC equipment. The column used PL mixed Bx2, and tetrahydrofuran (THF) (filtered at 0.45 m) was used as the solvent. Measurements were made at a flow rate of 1.0 mL/min and a sample concentration of 1 mg/mL. 100 L of sample was injected, and the column temperature was set at 40°C. An Agilent RI detector was used as a detector, and PS (polystyrene) was set as a standard. Data processing was performed through the ChemStation program.

A polymer according to an exemplary embodiment of the present specification may be prepared by a manufacturing method described below. Representative examples are described in the preparation examples to be described later, but, if necessary, substituents may be added or excluded, and the position of the substituent may be changed. In addition, based on techniques known in the art, starting materials, reactants, reaction conditions, and the like can be changed.

For example, a polymer including a first unit represented by Formula 1 and a second unit represented by Formula 2 may have a core structure as shown in Scheme 1 below. Substituents may be combined by methods known in the art, and the type, position or number of substituents may be changed according to techniques known in the art. A substituent may be bonded as shown in Scheme 1 or Scheme 2 below, but is not limited thereto.

[Scheme 1]

[Scheme 2]

In Scheme 1, the definitions of L1 to L4, a1, a4, Ar1 to Ar4, R1 to R9, r1 to r3, X, n1 and n2 are the same as defined in Chemical Formulas 1 and 2 above.

The present specification provides a coating composition comprising the compound.

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

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

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

In another embodiment, the solvent may be used alone or in combination of two or more solvents.

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

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

In another embodiment, the concentration of the coating composition is preferably 0.1 wt/v% to 20 wt/v%, more preferably 0.5 wt/v% to 5 wt/v%, but is not limited thereto. .

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

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

The photopolymerization initiator is diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4-(2-hydroxyethoxy) Phenyl-(2-hydroxy-2-propyl)ketone,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1,2-hydroxy-2-methyl-1-phenyl Propan-1-one,2-methyl-2-morpholino(4-methylthiophenyl) Propan-1-one,1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime acetophenone-based or ketal-based photopolymerization initiators such as , benzoin, benzoin methyl ethyl, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, and the like Benzophenone-based photopolymerization initiators such as photopolymerization initiators, benzophenone, 4-hydroxybenzophenone, 2-benzoylnaphthalene, 4-benzoyl biphenyl, 4-benzoylphenyl ether, acrylated benzophenone, 1,4-benzoylbenzene, 2 - Thioxanthone-based photopolymerization initiators such as isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone , As other photopolymerization initiators, ethyl anthraquinone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide, bis(2,4,6-trimethylbenzoyl) Phenyl phosphine oxide, bis(2,4-dimethoxy benzoyl)-2,4,4-trimethyl pentylphosphine oxide, methylphenirgliooxyester, 9,10-phenanthrene, acridine-based compound, tria True compounds and imidazole compounds may be used, but are not limited thereto.

Moreover, you may use what has a photopolymerization accelerating effect individually or in combination with the said photoinitiator. Examples include triethanolamine, methyl diethanolamine, 4-dimethylamino ethyl benzoate, 4-dimethylamino isoamyl benzoate, (2-dimethylamino) ethyl benzoate, 4,4'-dimethylaminobenzophenone, etc. It is not limited.

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

In one embodiment of the present specification, the first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layers is formed using a coating composition containing the compound or a cured product thereof.

According to one embodiment of the present specification, the cured product of the coating composition is in a state in which the coating composition is cured by heat treatment or light treatment.

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

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

In one embodiment of the present specification, the organic material layer formed using the coating composition or a cured product thereof is a hole transport layer, a hole injection layer, or a layer that simultaneously transports and injects holes.

According to an exemplary embodiment of the present specification, the organic material layer formed using the coating composition or a cured product thereof is a light emitting layer.

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

In one embodiment of the present specification, the p-doped material is F ₄ TCNQ; or a boron anion.

In one embodiment of the present specification, the p-doped material is F ₄ TCNQ; or a boron anion, wherein the boron anion includes a halogen group.

In one embodiment of the present specification, the p-doped material is F ₄ TCNQ; or a boron anion, wherein the boron anion includes F.

In one embodiment of the present specification, the p-doped material may be selected from the following structures.

In one embodiment of the present specification, the organic light emitting device includes a hole injection layer and a hole transport layer. One layer or two or more layers selected from the group consisting of an electron transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer may be further included.

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 diode may be an inverted type organic light emitting diode in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.

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

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

1, the anode 201, the hole injection layer 301, the hole transport layer 401, the light emitting layer 501, the electron injection and electron transport layer 601 and the cathode 701 are formed on the substrate 101. A structure of an organic light emitting device in which are sequentially stacked is illustrated.

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

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

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

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

Specifically, in one embodiment of the present specification, preparing a substrate; forming a cathode or anode on the substrate; Forming one or more organic material layers on the cathode or anode; and forming an anode or cathode on the organic material layer, wherein the forming of the organic material layer includes forming one or more organic material layers using the coating composition. do.

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

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

In the state of 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 structural characteristics and can be formed by a printing method, there is an economical effect in terms of time and cost when manufacturing a device.

In one embodiment of the present specification, the forming of the organic material layer formed using the coating composition may include coating the coating composition on the cathode or anode; and heat-treating or light-treating the coated coating composition.

In one embodiment of the present specification, the heat treatment time for the organic material layer formed using the coating composition is preferably within 1 hour, more preferably within 30 minutes.

In one embodiment of the present specification, the temperature at which the organic material layer formed using the coating composition is heat-treated may be preferably 100 °C to 300 °C, more preferably 150 °C to 250 °C.

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

When the heat treatment or light treatment step is included in the step of forming the organic layer formed using the coating composition, a plurality of fluorene groups included in the coating composition may form cross-links to provide an organic layer having a thinned structure. In this case, it is possible to prevent the coating composition from being dissolved, morphologically affected or decomposed by the solvent deposited on the surface of the organic layer formed using the coating composition.

Therefore, when the organic layer formed using the coating composition is formed by including heat treatment or light treatment, the resistance to the solvent is increased, so that the solution deposition and crosslinking method can be repeatedly performed to form a multilayer, and the stability of the device is increased. life characteristics can be increased.

In one embodiment of the present specification, a coating composition containing the compound may be mixed and dispersed in a polymer binder.

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

In addition, the compound according to an exemplary embodiment of the present specification may be included alone in the organic material layer, or may be included as a copolymer using a coating composition mixed with other monomers. In addition, a copolymer or a mixture may be included using a coating composition mixed with other polymers.

As the anode material, a material having a high work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present specification include metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO:Al or SnO ₂ : A combination of a metal and an oxide such as 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.

The cathode material is preferably a material having a small work function so as 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; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer for injecting holes from an electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated in the light emitting layer A compound that prevents migration of excitons to the electron injection layer or electron injection material and has excellent thin film forming ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. The hole transport material is a material that can receive holes from the anode or the hole injection layer and transfer them to the light emitting layer, and has high hole mobility. material is suitable. Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

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

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

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamine group, such as pyrene, anthracene, chrysene, and periplanthene having an arylamine group. Examples of the styrylamine compound include substituted or unsubstituted A compound in which at least one arylvinyl group is substituted on an arylamine, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamine group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but is not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

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

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

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.

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

An organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double side emission type depending on materials used.

In one embodiment of the present specification, the compound may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

Hereinafter, examples will be described in detail in order to specifically describe the present specification. However, embodiments according to the present specification may be modified in many different forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present specification to those skilled in the art.

< manufacturing example >

< manufacturing example 1> - preparation of compound 1

1) Synthesis of Intermediate 1-1

4-(biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)phenyl boronic acid (12 g, 25 mmol), Pd(PPh ₃ ) ₄ (578 mg, 0 5 mmol) and K ₂ CO ₃ (6.9 g, 50 mmol) were put into a round-bottom flask, and then replaced with nitrogen. 1,3-dibromo-5-fluorobenzene [1,3-dibromo-5-fluorobenzene] (1.26 mL, 10 mmol), THF (Tetrahydrofuran, 40 mL) and H ₂ O (10 mL) were added Then, the mixture was stirred at 90° C. for 12 hours. After completion of the reaction, extraction was performed with ethyl acetate and water. After the organic layer was collected, the organic layer was dried using MgSO ₄ and filtered. After drying the filtrate in a vacuum rotary condenser to remove the organic solvent, the residue was purified by column to obtain 9.5 g of intermediate 1-1 (98% yield).

2) Synthesis of Intermediate 1-2

After putting NaH (60 wt%, 420 mg, 10.5 mmol) in a round bottom flask, nitrogen was purged. After adding NMP (N- Methylpyrrolidone, 8.8 mL), it was cooled to 0℃. A solution of 3-bromocarbazole (2.6 g, 10.5 mmol) in NMP (8.8 mL) was slowly added to the reaction mixture, followed by stirring at 0 °C for 30 minutes. A solution of Intermediate 1-1 (6.8 g, 7 mmol) in NMP (17 mL) was added to the reaction mixture, followed by stirring at 220 °C for 2 hours. After completion of the reaction, extraction was performed with ethyl acetate and water. After the organic layer was collected, the organic layer was dried using MgSO ₄ and filtered. After drying the filtrate in a vacuum rotary concentrator to remove the organic solvent, the residue was column-purified to obtain 5 g of Intermediate 1-2 (60% yield).

3) Synthesis of intermediates 1-3

Intermediate 1-2 (4 g, 3.35 mmol), 4-formylphenyl boronic acid (750 mg, 5 mmol), Pd(PPh ₃ ) ₄ (196 mg, 0.17 mmol) and K ₂ CO ₃ (1.4 g, 10 mmol) was put into a round bottom flask and replaced with nitrogen. After adding THF (13.4 mL) and H ₂ O (3.4 mL), the mixture was stirred at 90 °C for 4 hours. After completion of the reaction, extraction was performed with ethyl acetate and water. After the organic layer was collected, the organic layer was dried using MgSO ₄ and filtered. After drying the filtrate in a vacuum rotary concentrator to remove the organic solvent, the residue was purified by column to obtain 2.87 g of Intermediate 1-3 (70% yield).

4) Synthesis of intermediates 1-4

CH ₃ PPh ₃ Br (1.57g, 4.4 mmol) and THF (12 mL) were placed in a round bottom flask, purged with nitrogen, and cooled to 0°C. After KOtBu (494 mg, 4.4 mmol) was added to the reaction mixture, it was substituted with nitrogen and stirred at 0°C for 20 minutes. A solution of Intermediate 1-3 (2.68 g, 2.2 mmol) in THF (10 mL) was slowly added to the reaction mixture, followed by stirring at 0 °C for 40 minutes. After completion of the reaction, extraction was performed with ethyl acetate and water. After the organic layer was collected, the organic layer was dried using MgSO ₄ and filtered. After drying the filtrate in a vacuum rotary concentrator to remove the organic solvent, the residue was purified by column to obtain 2.25 g of Intermediate 1-4 (84% yield).

NMR measurement values of intermediates 1-4: ¹ H NMR (500 MHz, CD ₂ Cl ₂ ) δ 8.40 (s, 1H), 8.21 (d, 1H), 7.95 (s, 1H), 7.77 (s, 2H), 7.71 (d, 3H) 7.66 - 7.50 (m, 20H), 7.46 - 7.38 (m, 7H), 7.33 - 7.20 (m, 17H), 7.11 (d, 2H), 6.78 (dd, 1H), 5.80 (d , 1H), 5.26 (d, 2H), 1.41 (s, 12H)

5) Synthesis of Compound 1

Intermediate 1-4 (973 mg, 0.8 mmol) and azobisisobutyronitrile (1.3 mg, 0.008 mmol) were placed in a round bottom flask and dissolved in anhydrous toluene (1.6 mL) under a nitrogen atmosphere. Stirred at 70 °C for 6 hours. After completion of the reaction, the mixture was diluted with THF (5 mL) and added to ethyl acetate (70 mL). Filter the precipitate and wash with ethyl acetate. The obtained solid was dried to obtain 620 mg of Compound 1 (64% yield). (Mw=102591, Mn=45941)

The GPC data of Compound 1 is shown in FIG. 2 .

< manufacturing example 2> - preparation of compound 2

1) Synthesis of Compound 2

Intermediate 1-4 (973 mg, 0.8 mmol) and 3-(4-vinylphenyl)bicyclo[4.2.0]octa-1(6),2,4-triene (41 mg, 0.2 mmol), azoby After putting azobisisobutyronitrile (1.3 mg, 0.008 mmol) in a round bottom flask, it was dissolved in anhydrous toluene (1.6 mL) under a nitrogen atmosphere. Stirred at 70 °C for 6 hours. After completion of the reaction, the mixture was diluted with THF (5 mL) and added to ethyl acetate (70 mL). Filter the precipitate and wash with ethyl acetate. The obtained solid was dried to obtain 730 mg of Compound 2 (72% yield). (Mw=90410, Mn=48393)

The GPC data of the compound 2 is shown in FIG. 3 .

< manufacturing example 3> - preparation of compound 3

1) Synthesis of Intermediate 3-1

Intermediate 1-3 (2.44 g, 2 mmol) was put in a round bottom flask and dissolved in MeOH (5 mL) and THF (5 mL). While maintaining the reaction mixture at room temperature, sodium borohydride (227 mg, 6 mmol) was added little by little, and the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, extraction was performed with ethyl acetate and water. After the organic layer was collected, the organic layer was dried using MgSO ₄ and filtered. The filtrate was dried using a vacuum rotary condenser to obtain 2.1 g of intermediate 3-1 (86% yield).

2) Synthesis of Intermediate 3-2

After putting sodium hydride (60 wt%, 112 mg, 2.8 mmol) in a round bottom flask, the mixture was replaced with a nitrogen atmosphere. After adding anhydrous DMF (3.5 mL), the mixture was cooled to 0°C. A solution of Intermediate 3-1 (1.71 g, 1.4 mmol) in anhydrous DMF (3.5 mL) was slowly added to the reaction mixture, followed by stirring at 0 °C for 1 hour. After adding 4-vinylbenzyl chloride (0.39 mL, 2.8 mmol), the temperature was raised to 60 °C and stirred for 4 hours. After completion of the reaction, the mixture was extracted with ethyl acetate and water. After the organic layer was collected, the organic layer was dried using MgSO ₄ and filtered. The filtrate was dried using a vacuum rotary evaporator to blow off the organic solvent, and the residue was purified by column to obtain 1.22 g of Intermediate 3-2 (65% yield).

NMR measured values of intermediate 3-2: ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.40 (s, 1H), 8.21 (d, 1H), 7.95 (s, 1H), 7.77 (s, 2H), 7.71 ( d, 3H) 7.66 - 7.50 (m, 22H), 7.46 - 7.38 (m, 7H), 7.33 - 7.20 (m, 19H), 7.11 (d, 2H), 6.69 (dd, 1H), 5.73 (d, 1H) ), 5.21 (d, 1H), 4.50 (s, 2H), 4.48 (s, 2H), 1.41 (s, 12H)

3) Synthesis of Compound 3

Intermediate 3-2 (1.07 g, 0.8 mmol) and 3-(4-vinylphenyl)bicyclo[4.2.0]octa-1(6),2,4-triene (41 mg, 0.2 mmol), azoby After putting azobisisobutyronitrile (1.3 mg, 0.008 mmol) in a round bottom flask, it was dissolved in anhydrous toluene (1.6 mL) under a nitrogen atmosphere. Stirred at 70 °C for 6 hours. After completion of the reaction, the mixture was diluted with THF (5 mL) and added to ethyl acetate (70 mL). Filter the precipitate and wash with ethyl acetate. The obtained solid was dried to obtain 689 mg of Compound 3 (62% yield). (Mw=108187, Mn=78944)

The GPC data of the compound 3 is shown in FIG. 4 .

< manufacturing example 4> - preparation of comparative compound 1

After putting sodium hydride (60 wt%, 120 mg, 3 mmol) in a round bottom flask, nitrogen was purged. After adding NMP (5 mL), the mixture was cooled to 0°C. A solution of carbazole (502 mg, 3 mmol) in NMP (5 mL) was slowly added to the reaction mixture, followed by stirring at 0 °C for 30 minutes. A solution of Intermediate 1-1 (1.93 g, 2 mmol) in NMP (10 mL) was added to the reaction mixture, followed by stirring at 220°C for 2 hours. After completion of the reaction, extraction was performed with ethyl acetate and water. After the organic layer was collected, the organic layer was dried using MgSO ₄ and filtered. After drying the filtrate in a vacuum rotary concentrator to remove the organic solvent, the residue was purified by column to obtain 1.45 g of Comparative Compound 1 (65% yield).

< Example > - Manufacture of organic light emitting devices

[Preparation of ITO Substrate]

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,500 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered through a second filter of a product of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes.

After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl and acetone, and after drying, the substrate was cleaned for 5 minutes and transported to a glove box.

[ small example One]

On the ITO transparent electrode, 2 wt% cyclohexanone ink of the following compound A: the following p dopant (formula G) (weight ratio of 8: 2) was spin-coated (4000 rpm) on the ITO surface and heat-treated at 200 ° C. for 30 minutes to inject holes to a thickness of 40 nm layer was formed. Thereafter, Compound 1 was dissolved in toluene at 0.7 wt %, spin-coated on the hole injection layer to form a film of 20 nm, and heated at 200° C. for 30 minutes under a nitrogen atmosphere to form a hole transport layer.

Then, on the hole transport layer, cyclohexanone ink containing the following compound B and compound C at 8% concentration was spin-coated to form a light emitting layer having a thickness of 20 nm. An electron injection and transport layer was formed on the light emitting layer by vacuum depositing the following compound D to a thickness of 35 nm. 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 the organic material was maintained at 0.4 to 0.7 Å / sec, the deposition rate of LiF of the cathode was 0.3 Å / sec, and the deposition rate of aluminum was 2 Å / sec, and the vacuum degree during deposition was 2 X 10 ^-7 to 5 X 10 ^-8 torr.

[Compound A]

[Compound B]

[Compound C]

[Compound D]

[Formula G]

[ small example 2]

An organic light emitting device was manufactured in the same manner as in Device Example 1, except that 0.7 wt% toluene ink of Compound 2 was used instead of 0.7 wt% toluene ink of Compound 1 when forming the hole transport layer in the manufacturing process of Device Example 1. did

[ small example 3]

An organic light emitting device was manufactured in the same manner as in Device Example 1, except that 0.7 wt% toluene ink of Compound 3 was used instead of 0.7 wt% toluene ink of Compound 1 when forming the hole transport layer in the manufacturing process of Device Example 1. did

[compare small example One]

An organic light emitting device was prepared in the same manner as in Device Example 1, except that 0.7 wt% toluene ink of Comparative Compound 1 was used instead of 0.7 wt% toluene ink of Compound 1 when forming the hole transport layer in the manufacturing process of Device Example 1. manufactured.

[Comparative compound 1]

[compare small example 2]

An organic light emitting device was prepared in the same manner as in Device Example 1, except that 0.7 wt% toluene ink of Comparative Compound H was used instead of 0.7 wt% toluene ink of Compound 1 when forming the hole transport layer in the manufacturing process of Device Example 1. manufactured.

[Comparative compound H]

Driving voltage, external quantum efficiency, luminance and lifetime of the organic light emitting devices prepared in Device Example 1, Device Example 2, Comparative Device Example 1 and Comparative Device Example 2 at a current density of 10 mA/cm ² The measured results are shown in Table 1 below. The external quantum efficiency can be obtained as (number of photons emitted)/(number of charge carriers injected), and T95 is a measurement of the time required to reach 95% of the initial luminance at a current density of 10 mA/cm ² .

Volt(V) J (mA/cm ² ) EQE (%) Cd/ ^m2 T95@ 500 nits device example 1 4.21 10 6.2 98 66 device example 2 4.15 10 5.9 93 42 device example 3 4.03 10 5.3 98 47 Comparative device example 1 8.52 10 1.0 5.1 One Comparative device example 2 4.20 10 2.1 31 20

As shown in Table 1, Device Example 1 using a polymer comprising a first unit represented by Formula 1 and a polymer comprising a first unit represented by Formula 1 and a second unit represented by Formula 2 of the present specification It can be seen that the organic light emitting diodes of Device Examples 2 and 3 using , show high efficiency and long lifespan compared to Comparative Device Examples 1 and 2, and are applicable to organic light emitting devices.

Specifically, compared to Comparative Device Examples 1 and 2, Device Examples 1 to 3 have improved solubility and superior film stability to the solvent used in preparing the light emitting layer. In particular, in the case of Comparative Device Example 1, since solvent resistance was not secured, it could be seen that the hole transport layer was damaged during the manufacture of the light emitting layer, and thus the efficiency and lifespan decreased sharply.

Although the preferred embodiments of the present specification have been described above, the present invention is not limited thereto, and various modifications and implementations are possible within the scope of the claims and the detailed description of the invention, which also fall within the scope of the invention. belong

101: substrate
201 anode
301: hole injection layer
401: hole transport layer
501: light emitting layer
601: layer that simultaneously injects and transports electrons
701: cathode

Claims (14)

A polymer comprising a first unit represented by Formula 1 below:
[Formula 1]

In Formula 1,
L1 is -O-; A substituted or unsubstituted alkylene group; A substituted or unsubstituted divalent amine group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
L2 and L3 are the same as or different from each other, and are each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
a1 is an integer from 1 to 16;
When a1 is 2 or more, two or more L1s are the same as or different from each other,
Ar1 to Ar4 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or bonded to adjacent groups to form a ring;
R1 to R6 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
r1 is an integer from 1 to 4;
r2 and r3 are integers from 1 to 3;
When r1 to r3 are each 2 or more, two or more R1 to R3 are the same as or different from each other,
n1 is the repeating number of the unit, and is 10 to 10000. The polymer according to claim 1, wherein Chemical Formula 1 is represented by the following Chemical Formula 3:
[Formula 3]

In Formula 3,
Definitions of L1 to L3, a1, Ar1 to Ar4, R1 to R6, r1 to r3, and n1 are the same as defined in Chemical Formula 1 above. The method according to claim 1, wherein Ar1 to Ar4 are a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenyl group, Or a substituted or unsubstituted fluorenyl group of the polymer. The polymer according to claim 1, wherein the first unit represented by Formula 1 is any one selected from the following structures:

In the above structure,
n1 is the repeating number of the unit, and is 10 to 10,000. The polymer of claim 1, wherein the polymer further comprises a second unit represented by Formula 2 below:
[Formula 2]

In Formula 2,
X is a curing group;
L4 is a direct bond; -O-; A substituted or unsubstituted alkylene group; A substituted or unsubstituted divalent amine group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
a4 is an integer from 1 to 16;
When a4 is 2 or more, two or more L4s are the same or different from each other,
R7 to R9 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
n2 is the repeating number of the unit and is 1 to 10000. The polymer according to claim 5, wherein X is any one selected from the following structures:

In the above structure,
L11 is a direct bond; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,
R11 to R16 are the same as or different from each other, and are each independently an alkyl group having 1 to 5 carbon atoms. The polymer according to claim 5, wherein the second unit represented by Formula 2 is any one selected from the following structures:

In the above structure,
n2 is the repeating number of the unit and is 1 to 10,000. The polymer according to claim 1, wherein the polymer is any one selected from the following structures:

In the above structure,
m1 is the mole fraction, 0 < m1 ≤ 1,
m2 is the mole fraction, 0 ≤ m2 < 1,
m1+m2≤1, and
n is the repeating number of the unit and is 10 to 10,000. The polymer of claim 1, wherein the polymer has a number average molecular weight of 5,000 g/mol to 1,000,000 g/mol. A coating composition comprising the polymer according to any one of claims 1 to 9. a first electrode;
a second electrode provided to face the first electrode; and
Including one or more organic material layers provided between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic light emitting device comprising the coating composition of claim 10 or a cured product thereof. The organic light emitting device of claim 11, wherein the cured product of the coating composition is cured by heat treatment or light treatment of the coating composition. The organic light emitting device of claim 11, wherein the organic material layer including the coating composition or a cured product thereof is a hole transport layer, a hole injection layer, or a hole transport and hole injection layer simultaneously. The organic light emitting device of claim 11, wherein the organic material layer including the coating composition or a cured product thereof is a light emitting layer.

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