KR102500428B1 - Coating composition, method for manufacuring the same and, and organic light emitting device using the same - Google Patents

Abstract

The present invention relates to a coating composition, a method for manufacturing an organic light emitting device using the same, and an organic light emitting device using the same.

Description

Coating composition, method for manufacturing an organic light emitting device using the same, and organic light emitting device using the same

The present specification relates to a coating composition, a method for manufacturing an organic light emitting device using the same, and an organic light emitting device 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 an 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, and an organic material layer including an electron transport 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 as 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 material for the light emitting layer, a material having both p-type properties 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 occurs due to the movement of charges in the organic light emitting device. Since NPB, which is currently mainly used as a hole transport layer material, has a glass transition temperature of 100° C. or less, 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, materials used in organic light emitting devices must have appropriate band gaps and HOMO or LUMO energy levels. In the case of PEDOT:PSS, which is used as a hole transport material in organic light emitting devices manufactured by the current solution coating method, the LUMO energy level is lower than the LUMO energy level of organic materials used as light emitting layer materials. Therefore, organic light emitting devices with high efficiency and long lifespan can be manufactured. have difficulties with

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.

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

Korean Patent Publication No. 2012-0112277

The present specification provides a coating composition, a method for manufacturing an organic light emitting device using the same, and an organic light emitting device using the same.

The present specification provides a coating composition including an ionic compound containing an anionic group represented by Formula 1 or 2 below.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

At least one of R1 to R5 is -F, a cyano group, or a substituted or unsubstituted fluoroalkyl group,

At least one of the remaining R1 to R5 is -L-R,

The remaining R1 to R5 are the same as or different from each other, and each independently represents hydrogen,

L is a direct bond; -O-; -OC(=O)R11-; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted alkoxylene group,

R is a curing group,

R11 is a direct bond; Or a substituted or unsubstituted alkylene group,

R" is hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted fluoroalkyl group; or a substituted or unsubstituted aryl group.

Another exemplary embodiment of the present specification is 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 addition, the first electrode; a second electrode provided to face the first electrode; and

One or more organic material layers are included between the first electrode and the second electrode, and at least one layer of the organic material layers includes the coating composition or a cured product thereof.

The compound according to an exemplary embodiment of the present specification contains a functional group that is polymerized by heat or light, and thus, when sufficient heat or light is applied after film formation, the compound according to an exemplary embodiment of the present specification is resistant to a solvent for processing. It is possible to fabricate an organic light emitting device with reproducibility because the film properties are not changed by preventing the washing out or the movement of interlayer materials.

The compound according to an exemplary embodiment of the present specification may be dissolved in a solvent as an ionic single molecule and applied through a solution process to form a film through heat treatment or UV treatment. When cured, low driving voltage, high luminous efficiency and high lifespan characteristics can be provided.

1 illustrates an example of an organic light emitting device according to an exemplary embodiment of the present specification.
Figure 2 is a mass spectrum of anionic groups and cationic groups of Compound 1 according to Preparation Example 1 of the present specification.
3 is an NMR spectrum of Compound 1 according to Preparation Example 1 of the specification.
4 is an NMR spectrum of Compound 2 according to Preparation Example 2 of the specification.
5 is an NMR spectrum of Compound 3 according to Preparation Example 3 of the specification.

Hereinafter, this specification will be described in more detail.

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.

Throughout the present specification, the term "combination thereof" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, and the components It means including one or more selected from the group consisting of.

An exemplary embodiment of the present specification provides a coating composition including an ionic compound including an anionic group represented by Formula 1 or 2 above.

In an exemplary embodiment of the present specification, the coating composition is for coating an organic material layer of an organic light emitting device.

In an exemplary embodiment of the present specification, the ionic compound having an anionic group represented by Formula 1 or 2 is preferably a compound having solubility in an appropriate organic solvent.

In the present specification, "curing group" may mean a reactive substituent that crosslinks between compounds by exposure to heat and/or light. Crosslinking may be generated by linking radicals generated as carbon-carbon multiple bonds and cyclic structures are decomposed by heat treatment or light irradiation.

In one embodiment of the present specification, the curing group is selected from the following curing group.

[Lighter group]

In the curing group, L1 is a direct bond; O; S; A substituted or unsubstituted alkylene group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

k is an integer of 1 or 2, and when k is 2, the substituents in parentheses are the same as or different from each other;

R100 is a substituted or unsubstituted alkyl group.

Hereinafter, the substituents of the present specification will be described in detail below, but are not limited thereto.

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

Means a site to be bonded to another substituent or binding part.

In the present specification, 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 to a position where a hydrogen atom is substituted, that is, a position where a substituent can be substituted, and two or more When substituted, two or more substituents may be the same as or different from each other.

In this specification, the term “substituted or unsubstituted” means hydrogen; heavy hydrogen; halogen group; an alkyl group; cycloalkyl group; alkoxy group; aryloxy group; aryl group; amine group; Arylamine group; And substituted or unsubstituted with one or more substituents selected from the group consisting of curing groups, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above.

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

In the present specification, the alkyl group may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. 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, 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, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2- Propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but these not limited to

In the present specification, the alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It may be, but is not limited thereto.

The alkyl group may be substituted with an aryl group or a heterocyclic group to act as an arylalkyl group or a heteroarylalkyl group. The aryl group and heterocyclic group may be selected from examples of aryl groups and heterocyclic groups described below.

In the present specification, the length of the alkyl group does not affect the conjugation length of the compound, and may affect the application of the compound to an organic light emitting device, such as a vacuum deposition method or a solution coating method.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 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, etc., but are not limited thereto. don't

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably has 6 to 25 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 10-30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl 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.

The aryl group may be substituted with an alkyl group or an alkoxy group to function as an arylalkyl group or an aryloxy group. The alkyl group or alkoxy group may be selected from the examples described above.

In the present specification, the number of carbon atoms in the amine group is not particularly limited, but is preferably 1 to 30. The amine group may be substituted with the aforementioned alkyl group, aryl group, heterocyclic group, alkenyl group, cycloalkyl group, and combinations thereof, and specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, and diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group , triphenylamine group, etc., but is not limited thereto.

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. Specific examples of the arylamine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methyl-phenylamine, 4-methyl-naphthylamine, 2-methyl-biphenylamine, and 9-methyl-anthracenylamine. cenylamine, diphenyl amine, phenyl naphthyl amine, ditolyl amine, phenyl tolyl amine, carbazole and triphenyl amine, but are not limited thereto.

In the present specification, the heterocyclic group includes at least one atom or heteroatom other than carbon, and specifically, the heteroatom may include at least one atom selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furanyl group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazinyl group, tria Zolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, Examples include a phenanthroline group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

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, a divalent heterocyclic group means a heterocyclic group having two bonding sites, that is, a divalent group. The above description of the heterocyclic group can be applied except that each is a divalent group.

As used herein, "adjacent" refers to a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located sterically closest to the substituent, or another substituent substituted on the atom on which the substituent is substituted. can For example, two substituents substituted at ortho positions 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, a ring formed by bonding adjacent groups to each other may be monocyclic or polycyclic, may be an aliphatic, aromatic, or condensed ring of aliphatic and aromatic, and may form a hydrocarbon ring or a heterocyclic ring.

In one embodiment of the present specification, the anionic group represented by Chemical Formula 1 is represented by any one of Chemical Formulas 1-1 to 1-8.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

In Formulas 1-1 to 1-8, L and R are as defined in claim 1.

In one embodiment of the present specification, R" is -F; a cyano group; a substituted or unsubstituted fluoroalkyl group; and a phenyl group, a methyl group, an ethyl group, or a tricyclic group substituted with at least one of the substituents consisting of the group consisting of -L-R. A fluoromethyl group or a pentafluoroethyl group.

In one embodiment of the present specification, the anionic group represented by Chemical Formula 2 is represented by Chemical Formula 2-1 or 2-2 below.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2, at least one of R6 to R10 is F, a cyano group, or a substituted or unsubstituted fluoroalkyl group,

At least one of the remaining R6 to R10 is -L'-R',

The remaining R6 to R10 are hydrogen,

L' is a direct bond; -O-;-OC(=O)R12-; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted alkoxylene group,

R' is a curing group,

R12 is a direct bond; Or a substituted or unsubstituted alkylene group,

R101 is a substituted or unsubstituted alkyl group or a substituted or unsubstituted fluoroalkyl group.

In one embodiment of the present specification, at least one of R1 to R5 is -F, a cyano group, -CF ₃ , or -C ₂ F ₅ , and at least one of the remaining R1 to R5 is -LR.

In one embodiment of the present specification, R101 is a methyl group, an ethyl group, a trifluoromethyl group, or a pentafluoroethyl group.

In one embodiment of the present specification, the anionic group represented by Chemical Formula 2 is represented by any one of Chemical Formulas 2-3 to 2-10.

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

In Formulas 2-3 to 2-10, L and R are as defined in claim 1,

L' is a direct bond; -O-;-OC(=O)R12-; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted alkoxylene group,

R' is a curing group,

R12 is a direct bond; Or a substituted or unsubstituted alkylene group.

In one embodiment of the present specification, the -L-R is selected from the following structural formula.

In one embodiment of the present specification, the anionic group of Formula 1 or 2 is selected from the following structural formulas.

In one embodiment of the present specification, the ionic compound includes a cationic group, and the cationic group is an onium compound.

In the present specification, the onium compound refers to a compound formed by coordination bonding of hydrogen ions or other organic radicals to unshared electron pairs of iodine, oxygen, sulfur, nitrogen, phosphorus, and the like.

In one embodiment of the present specification, the ionic compound includes a cationic group, and the cationic group is selected from the following structural formulas.

In the above structural formula, X1 to X37 are the same as or different from each other, and each independently hydrogen; cyano group; nitro group; halogen group; -COOR ₁₀₀ ; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted fluoroalkyl group; Or a substituted or unsubstituted aryl group, or a curing group,

R ₁₀₀ is hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, the X1 to X37 are the same as or different from each other, and each independently hydrogen; cyano group; nitro group; F; Cl; -COOR ₁₀₀ ; methyl group; ethyl group; propyl group; butyl group; pentyl group; hexyl group; methoxy group; cyclopropyl group; ethoxyethoxy; phenyl group; naphthyl group; or a curing group, and R ₁₀₀ is a methyl group.

In one embodiment of the present specification, the ionic compound includes a cationic group, and the cationic group is selected from the following structural formulas.

In one embodiment of the present specification, in the ionic compound containing an anionic group represented by Formula 1, the anionic group represented by Formula 1 and the cationic group are included in an equivalent ratio of 1:5 to 5:1.

In an exemplary embodiment of the present specification, in the ionic compound including an anionic group represented by Chemical Formula 1, the anionic group represented by Chemical Formula 1 and the cationic group are included in an equivalent ratio of 1:1.

In one embodiment of the present specification, the coating composition is an arylamine compound having a curing group substituted; aniline oligomers in which a curing group is substituted; and at least one compound selected from the group consisting of thiophene oligomers in which a curing group is substituted.

In one embodiment of the present specification, the coating composition includes an arylamine compound in which the ionic compound and the curing group are substituted; aniline oligomers in which a curing group is substituted; And a weight ratio of at least one compound selected from the group consisting of a curing group substituted thiophene oligomer is 1: 10 to 1: 2.

In one embodiment of the present specification, the curing group-substituted arylamine compound may be represented by Formula A-1 or A-2 below.

[Formula A-1]

[Formula A-2]

In the above formulas A-1 and A-2,

Ar1 to Ar7 are aryl groups substituted or unsubstituted with curing groups, at least one of Ar1 to Ar3 and at least one of Ar4 to Ar6 are aryl groups substituted with curing groups,

L10 is a substituted or unsubstituted arylene group.

In one embodiment of the present specification, Ar1 to Ar7 are a phenyl group unsubstituted or substituted with a curing group; or a naphthyl group unsubstituted or substituted with a curing group.

In one embodiment of the present specification, Ar1 to Ar7 are a phenyl group unsubstituted or substituted with a vinyl group; Or a naphthyl group unsubstituted or substituted with a vinyl group.

In one embodiment of the present specification, Ar1 to Ar7 are a phenyl group unsubstituted or substituted with a vinyl group; or a naphthyl group.

In one embodiment of the present specification, at least one of Ar1 to Ar3 and at least one of Ar4 to Ar6 are phenyl groups substituted with curing groups.

In one embodiment of the present specification, at least one of Ar1 to Ar3 and at least one of Ar4 to Ar6 are a phenyl group substituted with a vinyl group.

In one embodiment of the present specification, at least one of Ar1 to Ar3 and at least one of Ar4 to Ar6 are a phenyl group substituted with a vinyl group, and the others are naphthyl groups.

In one embodiment of the present specification, L10 is a phenylene group; a biphenylylene group; or a naphthylene group.

In one embodiment of the present specification, L10 is a biphenylylene group.

In one embodiment of the present specification, the curing group-substituted aniline oligomer may be represented by Formula B below.

[Formula B]

In the formula B,

Ar8 is a substituted or unsubstituted aryl group,

L11 is a substituted or unsubstituted arylene group,

L12 is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

R200 is a curing group,

m is an integer from 1 to 30;

In one embodiment of the present specification, Ar8 is a substituted or unsubstituted phenyl group.

In one embodiment of the present specification, Ar8 is a phenyl group.

In one embodiment of the present specification, L11 is a substituted or unsubstituted phenylene group.

In one embodiment of the present specification, L11 is a phenylene group.

In one embodiment of the present specification, L12 is a substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthylene group; Or a substituted or unsubstituted divalent carbazole group.

In one embodiment of the present specification, L12 is a phenylene group; a biphenylylene group; naphthylene group; or a divalent carbazole group.

In one embodiment of the present specification, R200 is a vinyl group or a styrene group.

In one embodiment of the present specification, m is 2 or 3.

In one embodiment of the present specification, the curing group-substituted thiophene oligomer may be represented by a repeating unit of Formula C-1 or Formula C-2.

[Formula C-1]

[Formula C-2]

In the formulas C-1 and C-2,

R201 to R203 are curing groups,

R300 and R301 are hydrogen; or a substituted or unsubstituted alkyl group, or R300 and R301 may combine with each other to form a heterocycle, and have a total molecular weight of 1000 to 20000. n and o are ratios of repeating ends, respectively, and when n + o = 1, the ratio o of repeating ends including curing groups is 0.01 or more. The repeating units of n and o may be arranged randomly, alternately or in blocks.

이다. In one embodiment of the present specification, the R201 to R203

am.

In one embodiment of the present specification, R300 and R301 are the same as or different from each other, and each independently hydrogen; methyl group; ethyl group; proto-writing; butyl group; pentyl group; hexyl group; or a heptyl group, or bonded to each other to form a dioxane group.

In one embodiment of the present specification, R300 and R301 are the same as or different from each other, and each independently hydrogen; or a hexyl group, or bonded to each other to form a 1,4-dioxane group.

In one embodiment of the present specification, an arylamine compound in which the curing group is substituted; aniline oligomers in which a curing group is substituted; And at least one compound selected from the group consisting of a thiophene oligomer in which a curing group is substituted is selected from the following structural formulas or includes a repeating unit of the following structural formulas.

In the structural formula, the thiophene oligomer has a molecular weight of 1000 to 20000, and x and y are ratios of repeating groups in parentheses. y including the curing group is preferably 0.01 or more. The molecular weight of the oligomer is the Mw value measured through GPC.

The arylamine compound may form a crosslink to provide an organic material layer including 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.

In one embodiment of the 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 invention is sufficient and 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 to 10 CP, more preferably 3 to 8 CP, but is not limited thereto.

In another embodiment, the concentration of the coating composition is preferably 0.1 to 20 wt / v%, more preferably 0.5 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.

Examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, and 2,4-dichlorobenzoyl peroxide. oxide, 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- (dit-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-butyrpaoxyvaleric 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 peroxytrimethyl adipate, or azo systems such as azobis isobutylnitrile, azobisdimethylvaleronitrile, and azobis cyclohexyl nitrile, but are not limited thereto. .

As said photopolymerization initiator, diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4-(2-hydroxy ethoxy ) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone- 1,2-hydroxy-2-methyl-1- Phenyl propan-1-one, 2-methyl-2-morpholino (4-methyl thiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) acetophenone-based or ketal-based photopolymerization initiators such as oximes, benzoin such as benzoin, benzoin methyl ethyl, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ethyl ether, and the like Benzophenone-based photopolymerization initiators such as ether-based photopolymerization initiators, benzophenone, 4-hydroxybenzophenone, 2-benzoyl naphthalene, 4-benzoyl biphenyl, 4-benzoyl phenyl ether, acrylated benzophenone, 1,4-benzoyl benzene, and the like Photopolymerization of thioxanthone, such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, etc. Examples of the initiator and other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide, and 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 compounds, A triazine type compound and an imidazole type compound are mentioned. Moreover, you may use what has a photopolymerization accelerating effect individually or in combination with the said photoinitiator. Examples include triethanolamine, methyl diethanol amine, 4-dimethylamino ethyl benzoate, 4-dimethylamino isoamyl benzoate, (2-dimethylamino) ethyl benzoate, 4,4'-dimethylaminobenzophenone, etc. It is not limited to this.

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; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes an ionic compound containing an anionic group of Formula 1 or 2. is formed

In one embodiment of the present specification, the first electrode; a second 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 layer includes an ionic compound containing an anionic group of Formula 1 or 2, and a cured product of the coating composition. includes

In 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, when the organic layer including the cured product of the coating composition is formed by heat treatment or light treatment, the solvent resistance is increased and the solution deposition and crosslinking methods are repeatedly performed to form multilayers. And the stability can be increased to increase the lifespan characteristics of the device.

In one embodiment of the present specification, the organic material layer including the cured product of the coating composition is a hole injection layer.

In one embodiment of the present specification, the organic material layer including the cured product of the coating composition is a hole injection layer, and the ionic compound including an anionic group of Chemical Formula 1 or 2 is included as a dopant of the hole injection layer.

In one embodiment of the present specification, the organic material layer including the cured product of the coating composition is a low-hole injection layer.

In one embodiment of the present specification, the organic material layer including the cured product of the coating composition is a hole injection layer, and the ionic compound of the cured product of the coating composition is included as a p-doping material of the hole injection layer.

In one embodiment of the present specification, the organic material layer including the cured product of the coating composition is a hole injection layer, and the ionic compound including an anionic group of Chemical Formula 1 or 2 is included as a p-doping material of the hole injection layer.

In the present specification, the p-doped material means a material that allows the host material to have p-semiconductor characteristics. The p semiconductor property refers to the property of injecting or transporting holes at the highest occupied molecular orbital (HOMO) energy level, that is, the property of a material having high hole conductivity.

In one embodiment of the present specification, the organic material layer including the cured product of the coating composition is a hole transport layer, a hole injection layer, or a hole transport and hole injection layer at the same time.

In another embodiment, the organic material layer formed using the coating composition is a light emitting layer.

In one embodiment of the present specification, the organic light emitting device includes a hole injection layer and a hole transport layer. It further includes 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.

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

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

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 invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer 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, an organic light emitting device in which an anode 201, a hole injection layer 301, a hole transport layer 401, a light emitting layer 501, an electron transport layer 601, and a cathode 701 are sequentially stacked on a substrate 101. The structure of is illustrated.

In FIG. 1, the hole injection layer 301, the hole transport layer 401, and the light emitting layer 501 are formed using a coating composition containing a compound represented by Formula 1.

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 containing the compound.

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form an anode And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, 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 a cathode on the organic material layer, wherein at least one layer of the organic material layer 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 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 atmosphere for heat-treating the organic material layer formed using the coating composition is preferably an inert gas such as argon or nitrogen.

In addition, the composition according to one embodiment of the present specification may be thinned through heat treatment or light treatment, and 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 invention 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 injecting layer or electron injecting material and has excellent thin film formation 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 matter, anthraquinone, and 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, rubrene, etc., but are 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, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc. having an arylamino group, and styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, 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 arylamino 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 them 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; hydroxyflavone-metal complexes and the like, 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 an 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, BCP, 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.

<Example>

<Preparation Example 1 - Compound 1>

Tetrafluorophenol (150 mmol, 25 g) was put into a round flask and cooled to 0°C. 80ml of 20% fuming H ₂ SO ₄ was slowly added and stirred for 30 minutes. Then, after raising the temperature to 70 ° C., the mixture was stirred for 18 hours. 400 ml of sat. The NaCl solution was placed in a beaker and cooled to 0°C. The reaction solution in the flask was slowly put into a beaker containing NaCl solution to precipitate the material. After additional stirring for 1 hour, the precipitated material is filtered. The precipitated state was a white solid state. The solid crude material was dried in a vacuum oven to remove residual solvent. Then, the solid was put into 600 ml of boiled acetonitrile to dissolve the material. The dissolved material was filtered through a filter, cooled slowly to room temperature, and recrystallized for purification. 19.3 g of white solid a-1 was obtained. (Yield 48%) a-2 was obtained from a-1. A-1 (37.3 mmol, 10 g) was put in a round flask and dissolved in 30 ml of DMF and 450 ml of acetone. Then, methacrylic acid (45 mmol, 3.85 g) was added and stirred for 30 minutes. DCC (45 mmol, 9.3 g) was then added to the solution as a solid in one portion. It was stirred for 16 hours at room temperature. After 16 hours, a white solid was precipitated from the solution in the flask, which was filtered and washed with acetone to recover the material. The solvent was removed from the filtered solution using an evaporator. When the solution was reduced to about 30 ml, 500 ml of ethyl ether was added to precipitate. Thereafter, the precipitated solid was recovered by filtering to obtain 10 g of a white solid a-2. (Yield 80%) Compound 1 could be synthesized from a-2 obtained above. A-2 (1.48 mmol, 0.5 g) obtained above was dissolved in 5 ml of a 9:1 solution of DI water: acetone. Diphenyliodonium chloride (1.56 mmol, 0.49 g) pure water: dissolved in 5 ml of a 9:1 solution in acetone. When the mixture was slowly dropped and stirred into the solution of a-2, a white solid was precipitated while the solution was mixed. After this, the mixture was stirred at room temperature for 30 minutes. Solids were recovered by filtration. Thereafter, the mixture was washed with pure water and the solvent was removed in a vacuum oven for 24 hours to obtain Compound 1 as a white solid. 0.83 g (yield: 95%).

The mass spectrum of the anionic and cationic groups of Compound 1 is shown in FIG. 2 .

The NMR spectrum of Compound 1 is shown in FIG. 3 .

<Preparation Example 2-Compound 2>

Dissolve a-2 (1.48 mmol, 0.5 g) in 5 ml of a pure water: acetone 9:1 solution. p-tolyl(2,4,6-trimethoxyphenyl)iodonium bromide (1.56 mmol, 0.73 g) in pure: acetone 9:1 solution 5 dissolved in ml. When the mixture was slowly dropped and stirred into the solution of a-2, a white solid was precipitated while the solution was mixed. After this, the mixture was stirred at room temperature for 30 minutes. Solids were recovered by filtration. Thereafter, the mixture was washed with pure water and the solvent was removed in a vacuum oven for 24 hours to obtain Compound 2 as a white solid. 0.9 g (yield: 87%)

The NMR spectrum of the compound 2 is shown in FIG. 4 .

<Preparation Example 3-Compound 3>

A-1 (37.3 mmol, 10 g) was put into a round flask and dissolved in 30 ml of DMF and 450 ml of acetone. 4-Pentenoic acid (45 mmol, 4.5 g) was added and stirred for 30 minutes. DCC (45 mmol, 9.3 g) was then added to the solution as a solid in one portion. It was stirred for 16 hours at room temperature. After 16 hours, a white solid was precipitated from the solution in the flask, which was filtered and washed with acetone to recover the material. The solvent was removed from the filtered solution using an evaporator. When the solution was reduced to about 30 ml, 500 ml of ethyl ether was added to precipitate. Thereafter, when the precipitated solid was recovered by filtering, a-3 was obtained. Yield 9.8 g of white powder. (Yield 75%) Compound 3 was synthesized from a-3 above. Compound a-3 (1.43 mmol, 0.5 g) was dissolved in 5 ml of a 9:1 pure water:acetone solution. Diphenyliodonium chloride (1.56 mmol, 0.49 g) pure water: dissolved in 5 ml of a 9:1 solution in acetone. When the mixture was stirred while being slowly dropped into the solution of a-3, a white solid was precipitated while the solution was mixed. After this, the mixture was stirred at room temperature for 30 minutes. Solids were recovered by filtration. Thereafter, the mixture was washed with pure water and the solvent was removed in a vacuum oven for 24 hours to obtain Compound 3 as a white solid. 0.8 g (yield: 92%)

The NMR spectrum of the compound 3 is shown in FIG. 5 .

<Preparation Example 4- Compound 4>

A-2 (14.8 mmol, 5 g) was put into a round flask and dissolved in 50 ml of DMF. The flask was cooled to 0 °C. SOCl ₂ (148 mmol, 17.6 g) was added and stirred for 16 hours. In a cooled state, pure water was added and stirred for 30 minutes. Thereafter, extraction was performed with ethyl ether and the solvent was removed to obtain a-4 in a crude state of yellow oil. It was used without purification in subsequent reactions. a-5 could be synthesized from a-4. A-4 (6.0 mmol, 2.0 g) was added to 50 ml of aqueous ammonia solution and stirred at room temperature for 2 hours. Then, extraction was performed with ethyl ether and the solvent was removed to obtain a-5. Then, the sulfonimide anion was synthesized using a-4 and a-5. LiH (6.0 mmol, 48 mg) was put into a round flask and 10 ml of THF was added thereto. After putting a-4 (3.0 mmol, 1.0 g) and a-5 (3.0 mmol, 0.94 g) in a flask, the mixture was further stirred at room temperature for 12 hours. After the reaction, ethyl ether was added to the solution to precipitate and the solid was recovered. The recovered solid was washed with ethyl ether three times and the solvent was removed in a vacuum oven. The collected white powder was dissolved in 5 ml of a pure:acetone 9:1 solution. Diphenyliodonium chloride (3.12 mmol, 1.0 g) pure water: 5 ml of a 9:1 solution in acetone was prepared. When mixed slowly while stirring with the previously prepared solution, a white solid was precipitated. After this, the mixture was stirred at room temperature for 30 minutes. Solids were recovered by filtration. Thereafter, the mixture was washed with pure water and the solvent was removed in a vacuum oven for 24 hours to obtain Compound 4.

<Preparation Example 5- Compound 5>

The synthesis of sulfonimide anion was synthesized using trifluoromethanesulfonic acid and a-5, and was the same as the synthesis method of compound 4. LiH (6.0 mmol, 48 mg) was put into a round flask and 10 ml of THF was added thereto. Trifluoromethanesulfonic acid (3.0 mmol, 0.45 g) and a-5 (3.0 mmol, 0.94 g) were added to the flask and stirred at room temperature for an additional 12 hours. After the reaction, ethyl ether was added to the solution to precipitate and the solid was recovered. The recovered solid was washed with ethyl ether three times and the solvent was removed in a vacuum oven. The collected white powder was dissolved in 5 ml of pure: acetone 9:1 solution. Diphenyliodonium chloride (3.12 mmol, 1.0 g) pure water: 5 ml of a 9:1 solution in acetone was prepared. When mixed slowly while stirring with the previously prepared solution, a white solid was precipitated. After this, the mixture was stirred at room temperature for 30 minutes. The solid is recovered by filtering. Thereafter, the mixture was washed with pure water and the solvent was removed in a vacuum oven for 24 hours to obtain Compound 5. (Final yield: 1.6 g, yield: 73%)

<Preparation Example 6- Compound 6>

The synthesis of a-6 is the synthesis method of a-1, except that 2,6-bis (trifluoromethyl) phenol is used instead of tetrafluorophenol as the starting material. is the same as

The synthesis of a-7 and compound 6 is the same as the synthesis method of compound a-2 and compound 1 except that a-6 was used instead of a-1 as a starting material.

2,6-bis(trifluoromethyl)phenol (2,6-bis(trifluoromethyl)phenol) (150 mmol, 34.5 g) was put into a round flask and cooled to 0°C. 80ml of 20% fuming H ₂ SO ₄ was slowly added and stirred for 30 minutes. Then, after raising the temperature to 70 ° C., the mixture was stirred for 18 hours. 400 ml of sat. The NaCl solution was placed in a beaker and cooled to 0°C. The reaction solution in the flask was slowly put into a beaker containing NaCl solution to precipitate the material. After additional stirring for 1 hour, the precipitated material was filtered. The precipitated state was a white solid state. The solid crude material was dried in a vacuum oven to remove residual solvent. Then, the solid was put into 600 ml of boiled acetonitrile to dissolve the material. The dissolved material was filtered through a filter, cooled slowly to room temperature, and recrystallized for purification. 24 g of a white solid a-6 was obtained. (Yield 48%) a-7 was obtained from a-6.

A-6 (30.1 mmol, 10 g) was put in a round flask and dissolved in 30 ml of DMF and 450 ml of acetone. Then, methacrylic acid (36.2 mmol, 3.11 g) was added and stirred for 30 minutes. DCC (36.2 mmol, 7.5 g) was then added to the solution as a solid in one portion. It was stirred for 16 hours at room temperature. After 16 hours, a white solid precipitated from the solution in the flask, which was filtered and washed with acetone to recover the material. The solvent was removed from the filtered solution using an evaporator. When the solution was reduced to about 30 ml, 500 ml of ethyl ether was added to precipitate. Thereafter, when the precipitated solid was collected by filtering, a-7 was obtained. 9 g of a white solid was obtained. (75% yield)

A-7 (1.25 mmol, 0.5 g) obtained above was dissolved in 5 ml of a 9:1 solution of DI water: acetone. Diphenyliodonium chloride (1.25 mmol, 0.40 g) Pure water: Dissolve in 5 ml of a 9:1 solution in acetone. When the solution of a-7 was slowly dropped and stirred, a white solid was precipitated while the solution was mixed. After this, the mixture was stirred at room temperature for 30 minutes. Solids were recovered by filtration. Thereafter, the mixture was washed with pure water and the solvent was removed in a vacuum oven for 24 hours to obtain compound 6. 0.7 g (yield: 85%).

<Preparation Example 7- Compound 7>

A-1 (22 mmol, 5.9 g) was put into a round flask and a nitrogen atmosphere was created. 10 ml of pure water was added to dissolve the substance. Then, prepare a solution of 1-(4-bromobutyl)-4-vinylbenzene (20 mmol, 4.8 g) dissolved in 10 ml of acetone, and slowly add it to the flask. did After raising the temperature to 70 ℃ was stirred for 24 hours. The flask was cooled to room temperature and the precipitated solid was recovered. After washing with acetone three times and vacuum drying, a-8 was recovered. Yield 4.3 g of a white solid. (yield 53%)

A-8 (1.17 mmol, 0.5 g) obtained above was dissolved in 5 ml of a 9:1 solution of DI water: acetone. Diphenyliodonium chloride (1.17 mmol, 0.37 g) Pure water: Dissolve in 5 ml of a 9:1 solution in acetone. When the solution of a-8 was slowly dropped and stirred, a white solid was precipitated while the solution was mixed. After this, the mixture was stirred at room temperature for 30 minutes. Solids were recovered by filtration. Thereafter, the mixture was washed with pure water and the solvent was removed in a vacuum oven for 24 hours to obtain compound 7. 0.6 g (yield: 75%).

<Preparation Example 8- Compound 8>

A-1 (22 mmol, 5.9 g) was put into a round flask and a nitrogen atmosphere was created. 10 ml of pure water was added to dissolve the substance. Then 3-(4-bromobutoxy)bicyclo[4.2.0]octa-1(6),2,4-triene (3-(4-bromobutoxy)bicyclo[4.2.0]octa-1(6) A solution of ,2,4-triene) (20 mmol, 4.8 g) in 10 ml of acetone was prepared and slowly added to the flask. After raising the temperature to 70 ℃ was stirred for 24 hours. The flask was cooled to room temperature and the precipitated solid was recovered. After washing with acetone three times and vacuum drying, a-9 was recovered. 5.5 g of a white solid was obtained. (yield 64%)

A-9 (1.17 mmol, 0.5 g) obtained above was dissolved in 5 ml of a 9:1 solution of DI water: acetone. Diphenyliodonium chloride (1.17 mmol, 0.37 g) Pure water: Dissolve in 5 ml of a 9:1 solution in acetone. When the solution of a-9 was slowly dropped and stirred, a white solid was precipitated while the solution was mixed. After this, the mixture was stirred at room temperature for 30 minutes. Solids were recovered by filtration. Thereafter, the mixture was washed with pure water and the solvent was removed in a vacuum oven for 24 hours to obtain compound 8. 0.6 g (yield: 75%).

<Experimental Example 1>

[VNPB]

[NPB]

[Compound A]

[Compound B]

[Compound C]

The compound 1 prepared in Preparation Example 1; the VNPB; And an organic solvent (cyclohexanone: cyclohexanone) was mixed to prepare a coating composition. The ratio of VNPB: p-dopant (Compound 1) was mixed at 0.8: 0.2 by weight.

A glass substrate on which indium tin oxide (ITO) was deposited with a thickness of 1500 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After the distilled water washing was completed, the substrate was ultrasonically washed with solvents such as isopropyl alcohol and acetone for 30 minutes each, dried, and transported to a glove box. The coating composition was spin-coated on the prepared ITO transparent electrode to form a hole injection layer having a thickness of 300 Å, and the coating composition was cured on a hot plate under N ₂ atmosphere at 230° C. for 30 minutes.

Then, after transferring to a vacuum deposition machine, NPB, compound A and compound B (8% concentration, 300 Å), compound C (200 Å), LiF (12 Å), and Al (2000 Å) were sequentially applied on the hole injection layer. The device was fabricated by vapor deposition. 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 at the cathode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum level during deposition was 2×10 ^-7 ~ 5×10 ^-8 torr was maintained.

<Experimental Example 2>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that Compound 2 prepared in Preparation Example 2 was used instead of Compound 1 in Experimental Example 1.

<Experimental Example 3>

An organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that Compound 3 prepared in Preparation Example 3 was used instead of Compound 1 in Experimental Example 1.

<Experimental Example 4>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that Compound 4 prepared in Preparation Example 4 was used instead of Compound 1 in Experimental Example 1.

<Experimental Example 5>

An organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that Compound 5 prepared in Preparation Example 5 was used instead of Compound 1 in Experimental Example 1.

<Experimental Example 6>

An organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that Compound 6 prepared in Preparation Example 6 was used instead of Compound 1 in Experimental Example 1.

<Experimental Example 7>

An organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that Compound 7 prepared in Preparation Example 7 was used instead of Compound 1 in Experimental Example 1.

<Experimental Example 8>

An organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that Compound 8 prepared in Preparation Example 8 was used instead of Compound 1 in Experimental Example 1.

<Comparative Example 1>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the following compound ISS was used instead of Compound 1 in Experimental Example 1.

[ISS]

<Comparative Example 2>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the following compound ISI was used instead of Compound 1 in Experimental Example 1.

[ISI]

Table 1 shows the results of measuring driving voltage, current efficiency, power efficiency, and lifetime of the organic light emitting devices prepared in Experimental Examples 1 to 4 and Comparative Examples 1 and 2 at a current density of 10 mA/cm ² .

small example HIL Volt J(mA/cm ² ) Cd/A lm/W T _-90 Experimental example 1 Compound 1 + VNPB 4.70 10 5.70 3.81 43 Experimental Example 2 Compound 2 + VNPB 4.46 10 5.46 3.84 45 Experimental Example 3 compound 3 + VNPB 4.49 10 5.49 3.84 45 Experimental Example 4 Compound 4 + VNPB 4.22 10 5.52 4.11 51 Experimental Example 5 Compound 5 + VNPB 4.25 10 5.60 4.14 55 Experimental Example 6 Compound 6 + VNPB 4.68 10 5.68 3.81 40 Experimental Example 7 Compound 7 + VNPB 4.91 10 5.60 3.58 38 Experimental Example 8 Compound 8 + VNPB 4.95 10 5.71 3.62 35 Comparative Example 1 ISS + VNPB 9.12 10 4.86 1.67 <1 Comparative Example 2 ISI + VNPB 4.13 10 5.40 4.11 <1

As a result of Table 1, it can be seen that in the case of the dopant including the structure of Formula 1 or 2 of the present specification, it is superior in terms of power efficiency and lifespan to the compound (ISS) of Comparative Example 1 having only a curing, F It was found that the compound (ISI) of Comparative Example 1 having only an electron withdrawing group such as is superior in terms of lifetime. Therefore, when using a dopant containing a curing group and an electron withdrawing group such as F at the same time, it was confirmed that the curing group and the electron withdrawing group such as F are cured to prevent a decrease in lifespan due to interlayer flow, so that it can be applied to an organic light emitting device. .

101: substrate
201 anode
301: hole injection layer
401: hole transport layer
501: light emitting layer
601: electron transport layer
701: cathode

Claims (17)

Including an ionic compound containing an anionic group represented by Formula 1 or 2 below,
A coating composition further comprising at least one compound selected from the group consisting of Formula A-1, Formula A-2, Formula B, and Formula C-1:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
At least one of R1 to R5 is -F, a cyano group, or a fluoroalkyl group,
At least one of the remaining R1 to R5 is -LR,
The remaining R1 to R5 are hydrogen,
The -LR is any one selected from the following structural formulas,

R" is a fluoroalkyl group; or an aryl group substituted with at least one of the substituents consisting of -F and -LR,
[Formula A-1]

[Formula A-2]

In the above formulas A-1 and A-2,
Ar1 to Ar7 are a phenyl group unsubstituted or substituted with a vinyl group; Or a naphthyl group unsubstituted or substituted with a vinyl group,
L10 is a phenylene group; a biphenylylene group; Or a naphthylene group,
[Formula B]

In the formula B,
Ar8 is an aryl group,
L11 is an arylene group,
L12 is an arylene group or a divalent heterocyclic group;
R200 is a vinyl group or a styrene group,
m is an integer from 1 to 30;
[Formula C-1]

In the above formula C-1,
R201 is

ego,
R300 and R301 are each hydrogen or an alkyl group,
n and o are ratios of repeating stages, respectively, and when n+o is 1, o is 0.01 or more. The coating composition of claim 1, wherein the coating composition is for coating an organic material layer of an organic light emitting device. delete delete The coating composition according to claim 1, wherein the anionic group represented by Formula 2 is represented by Formula 2-1 or 2-2:
[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2, at least one of R6 to R10 is F,
At least one of the remaining R6 to R10 is -L'-R',
The remaining R6 to R10 are hydrogen,
The -L'-R' is any one selected from the following structural formulas,

R101 is a fluoroalkyl group. The coating composition of claim 1, wherein at least one of R1 to R5 is -F, a cyano group, -CF ₃ , or -C ₂ F ₅ , and at least one of the remaining R1 to R5 is -LR. The coating composition according to claim 1, wherein the anionic group represented by Formula 1 is represented by any one of Formulas 1-1 to 1-8:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

In Formulas 1-1 to 1-8, L and R are as defined in claim 1. The coating composition according to claim 1, wherein the anionic group represented by Formula 2 is represented by any one of Formulas 2-3, 2-4, 2-7 and 2-9:
[Formula 2-3]

[Formula 2-4]

[Formula 2-7]

[Formula 2-9]

In Formulas 2-3, 2-4, 2-7 and 2-9, L and R are as defined in claim 1,
The -L'-R' is any one selected from the following structural formulas.

delete The coating composition according to claim 1, wherein the anionic group of Formula 1 or 2 is selected from the following structural formulas:

. The coating composition of claim 1, wherein the ionic compound includes a cationic group, and the cationic group is selected from the following structural formulas:

delete The method according to claim 1, wherein the coating composition has a weight ratio of the ionic compound and at least one compound selected from the group consisting of Formula A-1, Formula A-2, Formula B and Formula C-1 of 1: 20 to 1: 2, the coating composition. 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 a cathode on the organic layer, wherein the forming of the organic layer is performed by using the coating composition according to any one of claims 1, 2, 5 to 8, 10, 11 and 13 A method of manufacturing an organic light emitting device comprising the step of forming one or more organic material layers. The method of claim 14 , wherein the forming of the organic layer formed using the coating composition comprises heat treatment or light treatment after applying the coating composition. a first electrode;
a second electrode provided to face the first electrode; and
Including one or more organic material layers between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic light emitting device comprising a cured product of the coating composition according to any one of claims 1, 2, 5 to 8, 10, 11 and 13. The organic light emitting device of claim 16, wherein the organic material layer is a hole injection layer.

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