KR20190077999A - 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 comprising an ionic compound including an anionic group represented by chemical formula (1) or chemical formula (2), to a production method of an organic light emitting device using the same, and to an organic light emitting device using the same which does not change film properties.

Description

TECHNICAL FIELD [0001] The present invention relates to a coating composition, a method of manufacturing an organic light emitting device using the same, and an organic light emitting device using the same. BACKGROUND ART [0002]

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

The organic light emission phenomenon is one example in which current is converted into visible light by an internal process of a specific organic molecule. The principle of organic luminescence phenomenon is as follows. When an organic layer is positioned between the anode and the cathode, electrons and holes are injected into the organic layer from the cathode and the anode, respectively, when an electric current is applied between the two electrodes. Electrons and holes injected into the organic layer are recombined to form an exciton, and the exciton falls back to the ground state to emit light. An organic light emitting device using such a principle may be generally composed of an organic material layer including a cathode, an anode and an organic material layer disposed therebetween, for example, a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer.

As a material used in an organic light emitting device, a pure organic material or a complex in which an organic material and a metal form a complex is mostly used. Depending on the application, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, . As the hole injecting material and the hole transporting material, an organic material having a p-type property, that is, an organic material that is easily oxidized and electrochemically stable at the time of oxidation is mainly used. On the other hand, as an electron injecting material or an electron transporting material, an organic material having an n-type property, that is, an organic material that is easily reduced and electrochemically stable when being reduced is mainly used. As the light emitting layer material, a material having both a p-type property and an n-type property, that is, a material having both a stable form in oxidation and in a reduced state is preferable, and a material having a high luminous efficiency for converting an exciton into light desirable.

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

First, the material used in the organic light emitting device is preferably excellent in thermal stability. This is because joule heating occurs due to the movement of charges in the organic light emitting device. NPB, which is mainly used as a hole transport layer material, has a glass transition temperature of 100 ° C or less, which is a problem that is difficult to use in an organic light emitting device requiring a high current.

Secondly, in order to obtain a highly efficient organic light emitting device capable of driving at a low voltage, holes or electrons injected into the organic light emitting element should be smoothly transferred to the light emitting layer, and injected holes and electrons should not escape from the light emitting layer. For this purpose, the material used in the organic light emitting device should have an appropriate band gap and a HOMO or LUMO energy level. In the case of PEDOT: PSS used as a hole transport material in the organic light emitting device manufactured by the solution coating method, since the LUMO energy level is lower than the LUMO energy level of the organic material used as the light emitting layer material, There is a difficulty in.

In addition, materials used in organic light emitting devices should 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 have little deformation of the material due to moisture or oxygen. In addition, by having appropriate hole or electron mobility, it is necessary to maximize the formation of excitons 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, the interface with the electrode including the metal or the metal oxide should be good.

Accordingly, there is a need in the art to develop organic materials having the above-mentioned requirements.

Korean Patent Laid-Open Publication No. 2012-0112277

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

The present invention provides a coating composition comprising an ionic compound comprising an anionic group represented by the following general formula (1) or (2).

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

At least one of R 1 to R 5 is -F, a cyano group, or a substituted or unsubstituted fluoroalkyl group,

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

And the remaining of R1 to R5 are the same or different and each independently hydrogen,

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

R is a curing agent,

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

R "is hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted fluoroalkyl group, or a substituted or unsubstituted aryl group.

Another embodiment of the present disclosure provides a method of manufacturing a semiconductor device, comprising: preparing a substrate; Forming a cathode or an anode on the substrate; Forming at least one organic material layer on the cathode or the anode; And forming an anode or a cathode on the organic material layer, wherein the forming the organic material layer includes forming one or more organic material layers using the coating composition. do.

A first electrode; A second electrode facing the first electrode; And

Wherein at least one layer of the organic compound layer includes at least one organic compound layer between the first electrode and the second electrode, and at least one of the organic compound layers includes the coating composition or a cured product thereof.

The compound according to one embodiment of the present invention includes a functional group polymerized by heat or light, and when sufficient heat or light is given after the film formation, resistance to the process solvent is generated, So that the film characteristics are not changed and the reproducible organic light emitting device can be manufactured.

The compound according to one embodiment of the present invention may be dissolved in a solvent as an ionic monomolecule, applied through a solution process, and then subjected to heat treatment or UV treatment to form a film. Particularly, When cured, it can provide low driving voltage, high luminous efficiency and high lifetime characteristics.

1 shows an example of an organic light emitting device according to an embodiment of the present invention.
2 is a mass spectrum of anion group and cation group 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, the present invention will be described in more detail.

When a member is referred to herein as being "on " another member, it includes not only a member in contact with another member but also another member between the two members.

Whenever a component is referred to as "comprising ", it is to be understood that the component may include other components as well, without departing from the scope of the present invention.

Throughout this specification, the term "combination thereof" included in the expression of the machine form means one or more combinations or combinations selected from the group consisting of the constituents described in the expression of the machine form, And the like.

One embodiment of the present invention provides a coating composition comprising an ionic compound having an anionic group represented by the above formula (1) or (2).

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

In one embodiment of the present invention, the ionic compound having an anionic group represented by the above formula (1) or (2) is preferably a compound having solubility in a suitable organic solvent.

As used herein, the term " hardener "may mean a reactive substituent which undergoes crosslinking between the compounds by exposure to heat and / or light. The crosslinking can be produced by heat treatment or light irradiation and connecting the radicals generated by the decomposition of the carbon-carbon multiple bond, cyclic structure.

In one embodiment of the present invention, the curing machine is selected from the group of the following curing machines.

[Curing group]

In the group of curing groups, 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 the parentheses are the same 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 the present invention is not limited thereto.

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

Quot; refers to a moiety bonded to another substituent or bond.

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

As used herein, the term "substituted or unsubstituted" heavy hydrogen; A halogen group; An alkyl group; A cycloalkyl group; An alkoxy group; An aryloxy group; An aryl group; An amine group; An arylamine group; And a hardening group, or a substituted or unsubstituted one in which at least two of the substituents exemplified above are connected to each other.

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

In the present specification, the alkyl group may be linear, 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- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, 3-methylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, Cyclohexyl, cycloheptyl, cyclooctyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2- Propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like. .

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, But is not limited thereto.

The alkyl group may be substituted with an aryl group or a heterocyclic group, and may function as an arylalkyl group or a heteroarylalkyl group. The aryl group and the heterocyclic group may be selected from the following examples of the aryl group or the heterocyclic group.

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 application method such as a vacuum deposition method or a solution application method.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, But are not limited to, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert- butylcyclohexyl, cycloheptyl, Do not.

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 25 carbon atoms. Specific examples of the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, and the like.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably 10 to 30 carbon atoms. Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl, klychenyl, fluorenyl, and the like.

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

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

In the present specification, the number of carbon atoms of the amine group is not particularly limited, but is preferably 1 to 30. The amine group may be substituted with the above-mentioned alkyl group, aryl group, heterocyclic group, alkenyl group, cycloalkyl group, and combinations thereof. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine A phenanthrene group, a phenylmethyl group, a phenylmethyl group, a phenylmethyl group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenylnaphthylamine group, , Triphenylamine group and the like, but are 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 having at least two aryl groups may contain 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-methylphenylamine, 4-methyl-naphthylamine, 2-methyl- But are not limited to, cenylamine, diphenylamine, phenylnaphthylamine, ditolylamine, phenyltolylamine, carbazole and triphenylamine groups.

In the present specification, the heterocyclic group includes at least one non-carbon atom or hetero atom, and specifically, the hetero atom may include at least one atom selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms is not particularly limited, but is preferably 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 pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, , An isoquinolinyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, Phenanthroline, isoxazolyl group, thiadiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but the present invention is not limited thereto.

In the present specification, an arylene group means a divalent group having two bonding positions in an aryl group. The description of the aryl group described above can be applied except that each of these is 2 groups.

In the present specification, a divalent heterocyclic group means a divalent group having two bonding positions in a heterocyclic group. The description of the above-mentioned heterocyclic group can be applied except that each of these is 2 groups.

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

In the present specification, the ring formed by bonding adjacent groups to each other may be monocyclic or polycyclic, and may be an aliphatic, aromatic, or aliphatic and aromatic condensed ring, and may form a hydrocarbon ring or a heterocyclic ring.

In one embodiment of the present invention, the anionic group represented by the formula (1) is represented by any one of the following formulas (1-1) to (1-8).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

In the above formulas 1-1 to 1-8, L and R are as defined in claim 1.

In one embodiment of the present specification, R "represents a phenyl group substituted with at least one of -F, cyano, substituted or unsubstituted fluoroalkyl, and -LR, a methyl group, A fluoromethyl group, or a pentafluoroethyl group.

In one embodiment of the present invention, the anionic group represented by the formula (2) is represented by the following formula (2-1) or (2-2).

[Formula 2-1]

[Formula 2-2]

In formulas (2-1) and (2-2), at least one of R 6 to R 10 is F, a cyano group, or a substituted or unsubstituted fluoroalkyl group,

At least one of the remaining R 6 to R 10 is -L'-R '

And the remaining R 6 to R 10 are hydrogen,

L 'is a direct bond; -O-; -OC (= O) R < 12 >-; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted alkoxysilyl group,

R 'is a curing agent,

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 R 1 to R 5 is -F, cyano group, -CF ₃ , or -C ₂ F ₅ , and at least one of the remaining R 1 to R 5 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 invention, the anionic group represented by the formula (2) is represented by any one of the following formulas (2-3) to (2-10).

[Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

[Chemical Formula 2-6]

[Chemical Formula 2-7]

[Chemical Formula 2-8]

[Chemical Formula 2-9]

[Chemical Formula 2-10]

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

L 'is a direct bond; -O-; -OC (= O) R < 12 >-; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted alkoxysilyl group,

R 'is a curing agent,

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

In one embodiment of the present disclosure, -L-R is selected from the following formulas.

In one embodiment of the present disclosure, the anion groups of Formula 1 or 2 are selected from the following formulas:

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

In the present specification, the onium compound means a compound produced by coordination bonding of a hydrogen ion or another organic radical to a non-covalent electron pair such as iodine, oxygen, sulfur, nitrogen, or phosphorus.

In one embodiment of the present disclosure, the ionic compound comprises a cationic group, and the cationic group is selected from the following formulas.

X1 to X37 in the structural formula are the same or different from each other, and each independently hydrogen; Cyano; A nitro group; A 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, X1 to X37 are the same or different from each other, and each independently hydrogen; Cyano; A nitro group; F; Cl; -COOR ₁₀₀ ; Methyl group; An ethyl group; Propyl group; Butyl group; Pentyl group; Hexyl group; Methoxy group; A cyclopropyl group; Ethoxyethoxy; A phenyl group; Naphthyl group; Or a hardener, and R ₁₀₀ is a methyl group.

In one embodiment of the present disclosure, the ionic compound comprises a cationic group, and the cationic group is selected from the following formulas.

In one embodiment of the present invention, in the ionic compound having an anionic group represented by the general formula (1), the anionic group and the cationic group represented by the general formula (1) are contained in an equivalent ratio of 1: 5 to 5: 1.

In one embodiment of the present disclosure, in an embodiment of the present invention, the anionic group and the cation group represented by the general formula (1) are contained in an equivalent ratio of 1: 1 in the ionic compound having an anionic group represented by the general formula (1).

In one embodiment of the present disclosure, the coating composition comprises an arylamine compound substituted with a curing agent; An anhydride-substituted aniline oligomer; And a thiophene oligomer substituted by a curing agent.

In one embodiment of the present disclosure, the coating composition comprises an arylamine compound substituted with the ionic compound and the curing agent; An anhydride-substituted aniline oligomer; And a thiophene oligomer substituted by a curing agent is in a weight ratio of 1:10 to 1: 2.

In one embodiment of the present invention, the arylamine compound substituted with the curing agent may be represented by the following formula (A-1) or (A-2).

[A-1]

[A-2]

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

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

L10 is a substituted or unsubstituted arylene group.

In one embodiment of the present invention, Ar1 to Ar7 each independently represent a phenyl group substituted or unsubstituted with a curing group; Or a naphthyl group substituted or unsubstituted by a hardening group.

In one embodiment of the present invention, Ar1 to Ar7 each independently represent a phenyl group substituted or unsubstituted with a vinyl group; Or a naphthyl group substituted or unsubstituted with a vinyl group.

In one embodiment of the present invention, Ar1 to Ar7 each independently represent a phenyl group substituted or unsubstituted with a vinyl group; Or a naphthyl group.

In one embodiment of the present invention, at least one of Ar1 to Ar3, and at least one of Ar4 to Ar6 is a phenyl group substituted with a curing group.

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

In one embodiment of the present invention, at least one of Ar1 to Ar3, at least one of Ar4 to Ar6 is a phenyl group substituted with a vinyl group, and the remainder is a naphthyl group.

In one embodiment of the present specification, L10 represents a phenylene group; Biphenyllylene groups; Or a naphthylene group.

In one embodiment of the present invention, L10 is a biphenylene group.

In one embodiment of the present invention, the aniline oligomer substituted with the curing agent may be represented by the following formula (B).

[Chemical Formula B]

In the above 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 unit,

and m is an integer of 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 invention, L11 is a substituted or unsubstituted phenylene group.

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

In one embodiment of the present invention, L12 is a substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene 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; Biphenyllylene groups; 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 disclosure, m is 2 or 3.

In one embodiment of the present invention, the thiophene oligomer substituted by the curing agent may be represented by the repeating unit represented by the following formula (C-1) or the formula (C-2).

[Chemical formula C-1]

[Chemical formula C-2]

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

R201 to R203 are curing units,

R300 and R301 are hydrogen; Or a substituted or unsubstituted alkyl group, or R < 300 > and R < 301 > may be bonded to each other to form a heterocyclic ring and have a total molecular weight of 1,000 to 20,000. When n + o = 1, the repeating unit ratio o including the curing unit is 0.01 or more. The repeating units repeating with n and o may be arranged randomly, alternately or in blocks.

이다. In one embodiment of the present disclosure, R201 through R203

to be.

In one embodiment of the present specification, R300 and R301 are the same or different and each independently hydrogen; Methyl group; An ethyl group; Writing; Butyl group; Pentyl group; Hexyl group; Or a heptyl group, or combine with each other to form a dioxane group.

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

In one embodiment of the present disclosure, the curing agent is a substituted arylamine compound; An anhydride-substituted aniline oligomer; And a thiophene oligomer substituted with a curing agent are selected from the following structural formulas or include repeating units of the following structural formulas.

In the above structural formulas, the thiophene oligomer has a molecular weight of 1000 to 20000, and x and y are the ratio of repeating units in parentheses. The value of y including the curing agent is preferably 0.01 or more. The molecular weight of the oligomer is the Mw value measured by GPC.

The arylamine compound may form an organic material layer including a structure formed by crosslinking. In this case, it can be prevented that it is 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 in a liquid phase. The "liquid phase" means that the liquid phase is at normal temperature and pressure.

In one embodiment of the present invention, the solvent includes, for example, chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; Ether solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene and mesitylene; Aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; Ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; Ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate; Examples of polyhydric alcohols such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, Alcohols and their derivatives; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; A sulfoxide-based solvent such as dimethylsulfoxide, an amide-based solvent such as N-methyl-2-pyrrolidone or N, N-dimethylformamide; Benzoate solvents such as methyl benzoate, butyl benzoate and 3-phenoxy benzoate; A solvent such as tetralin may be exemplified, but a solvent capable of dissolving or dispersing the compound according to one embodiment of the present invention is sufficient, and the solvent is not limited thereto.

In another embodiment, the solvents 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 invention, 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, methyl cyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide P-chlorobenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- (t-butylperoxy) -2,5-dimethylhexanoyl peroxide, lauryl peroxide, benzoyl peroxide, Butylperoxy) -hexane, 1,3-bis (t-butylperoxy-isopropyl) benzene, t-butyl cumyl peroxide, di- (T-butylperoxy) hexane-3, tris- (t-butylperoxy) triazine, 1,1-ditertiaryperoxy-3,3,5-trimethylcyclohexane, 1,1-di butylperoxycyclohexane, 2,2-di (t-butylperoxy) butane, 4,4-di-t-butoxypivalicylic acid n-butyl ester, 2,2-bis , 4-t-butyl perox Butyl peroxy isobutyrate, t-butyl peroxyhexahydroterephthalate, t-butyl peroxy-3,5,5-trimethyl hexaate, t-butyl peroxybenzoate, di and peroxides such as t-butyl peroxytrimethyl adipate, and azo compounds such as azobisisobutylnitrile, azobisdimethylvaleronitrile, and azobiscyclohexyl nitrile, but are not limited thereto.

Examples of the photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1 -hydroxy-cyclohexylphenyl-ketone, 4- (2-hydroxyethoxy (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedion-2- (o-ethoxycarbonyl) Oxime and the like, ketone-based photopolymerization initiators such as benzoin, benzoin methylurate, benzoin etchyrate, benzoin isobutyrate, benzoin isopropylacetal, etc., Based photopolymerization initiators such as benzophenone, 4-hydroxybenzophenone, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether, acrylated benzophenone and 1,4-benzoylbenzene, , 2-isopropylthioxanthone, 2- Examples of the photopolymerization initiator include thioxanthone photopolymerization initiators such as thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone, and other photopolymerization initiators include ethyl anthraquinone, 2 , 2,4,6-trimethylbenzoylphenyl ethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4- Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenyl glyoxycitester, 9,10-phenanthrene, acridine-based compounds, triazine-based compounds and imidazole-based compounds . The photopolymerization initiator having the photopolymerization promoting effect may be used alone or in combination with the photopolymerization initiator. Examples thereof include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid (2-dimethylamino) ethyl and 4,4'-dimethylaminobenzophenone, It is not limited thereto.

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

In one embodiment of the present disclosure, 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 of the organic material layers comprises an ionic compound having an anionic group of the formula 1 or 2 .

In one embodiment of the present disclosure, the first electrode; A second electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers is a cured product of a coating composition comprising an ionic compound having an anion group of Formula 1 or Formula 2 .

In one embodiment of the present disclosure, the cured product of the coating composition is in a cured state by heat treatment or light treatment.

In one embodiment of the present invention, when the organic material layer including the cured product of the coating composition is formed by the heat treatment or the light treatment step, the resistance to the solvent is increased and the multi-layer is formed by repeating the solution deposition and crosslinking methods And the stability can be increased, thereby increasing the lifetime characteristics of the device.

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

In one embodiment of the present invention, the organic compound layer including the cured product of the coating composition is a hole injection layer, and the ionic compound having an anion group of Formula 1 or 2 is included as a dopant in the hole injection layer.

In one embodiment of the present disclosure, the organic layer comprising the cured product of the coating composition is a low-purity injection layer.

In one embodiment of the present invention, the organic 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-doped material in the hole injection layer.

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

In this specification, the p-doped material means a material that has a p-type semiconductor property as a host material. p semiconductor property means a property of injecting or transporting holes at a highest occupied molecular orbital (HOMO) energy level, that is, a material having a high conductivity of holes.

In one embodiment of the present invention, the organic material layer including the cured product of the coating composition is a hole transporting layer, a hole injecting layer, or a layer simultaneously transporting holes and injecting holes.

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

In one embodiment of the present invention, the organic light emitting element is a hole injection layer, a hole transport layer, An electron transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer.

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

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

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

 In another embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, at least one organic layer, and an anode are sequentially stacked on a substrate.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer 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 injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

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

1 shows an organic light emitting device in which an anode 201, a hole injecting layer 301, a hole transporting layer 401, a light emitting layer 501, an electron transporting layer 601 and a cathode 701 are sequentially stacked on a substrate 101 Are illustrated.

1, the hole injecting layer 301, the hole transporting layer 401, and the light emitting layer 501 are formed using a coating composition comprising a compound represented by Chemical Formula (1).

FIG. 1 illustrates an organic light emitting device and is not limited thereto.

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

The organic light emitting device of the present invention can be manufactured by materials and methods known in the art, except that one or more of the organic layers are formed using a coating composition comprising the compound.

For example, the organic light emitting device of the present specification can be manufactured by sequentially laminating an anode, an organic layer, and a cathode on a substrate. At this time, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate by a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form an anode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and then depositing a material usable as a cathode thereon. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

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

Specifically, in one embodiment of the present disclosure, there is provided a method comprising: preparing a substrate; Forming a cathode or an anode on the substrate; Forming at least one organic material layer on the cathode or the anode; And forming an anode or a cathode on the organic material layer, wherein at least one of the organic material layers is formed using the coating composition.

In one embodiment of the present invention, the organic 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, but is not limited to, ink jet printing, nozzle printing, offset printing, transfer printing, or screen printing.

Since the coating composition according to one embodiment of the present invention has a structural characteristic and is suitable for a solution process, the coating composition can be formed by a printing method, so that there is an economical effect in time and cost in manufacturing a device.

In one embodiment of the present disclosure, the step of forming an organic layer formed using the coating composition comprises: coating the coating composition on the cathode or the anode; And heat treating or light treating the coated coating composition.

In one embodiment of the present invention, the time for heat-treating 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 invention, the atmosphere for heat-treating the organic compound 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 invention may be thinned through heat treatment or light treatment, or may be incorporated as a copolymer using a coating composition mixed with other monomers. Also, copolymers, or mixtures thereof, may be included using coating compositions mixed with other polymers.

As the anode material, a material having a large work function is preferably used so that injection of holes into the organic material layer is smooth. 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.

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

The hole injecting layer is a layer for injecting holes from the electrode. The hole injecting layer has a hole injecting effect for hole injecting effect on the anode, a hole injecting effect for the light emitting layer or the light emitting material due to its ability to transport holes to the hole injecting material, A compound which prevents the migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the thin film forming ability is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer and transports holes from the anode or the hole injection layer to the light emitting layer as the hole transport material. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

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

The electron injection layer is a layer for injecting electrons from an electrode and has an ability to transport electrons and has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, 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- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The hole blocking layer is a layer which prevents the cathode from reaching the hole, and can be generally formed under the same conditions as the hole injecting layer. Specific examples thereof include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes and the like.

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

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

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

<Examples>

&Lt; Preparation Example 1 - Compound 1 >

Tetrafluorophenol (150 mmol, 25 g) was added to the round flask and cooled to 0 占 폚. 80 ml of 20% fuming H ₂ SO ₄ was slowly added thereto, followed by stirring for 30 minutes. Thereafter, the mixture was heated to 70 DEG C and stirred for 18 hours. 400 ml sat. The NaCl solution was added to the beaker and cooled to 0 ° C. The reaction solution of the flask was slowly poured into a beaker containing the NaCl solution to precipitate the substance. After further stirring for 1 hour, the precipitated substance is filtered. The precipitated state was a white solid state. The solid crude material was dried in a baking oven to remove residual solvent. The solids were then dissolved in 600 ml of boiled acetonitrile. The dissolved material was filtered through a filter and slowly cooled to room temperature to be purified by recrystallization. 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 dissolved in 30 ml of DMF and 450 ml of acetone in a round flask. 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 in a solid state at once. The mixture was stirred at room temperature for 16 hours. 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 filtered solution was evaporated to remove the solvent. When the amount of the solution was reduced to about 30 ml, 500 ml of ethyl ether was added to precipitate the solution. The precipitated solid was then filtered to recover 10 g of white solid a-2. (Yield: 80%) Compound 1 could be synthesized from a-2 obtained above. The above obtained a-2 (1.48 mmol, 0.5 g) was dissolved in 5 ml of a DI water: acetone 9: 1 solution. Diphenyliodonium chloride (1.56 mmol, 0.49 g) was dissolved in 5 ml of a 9: 1 solution of pure water: acetone. The solution was slowly added dropwise to the solution of a-2, and the mixture was stirred to precipitate a white solid. Thereafter, the mixture was stirred at room temperature for 30 minutes. The solids were collected by filtration. Then, the solution 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 anion group and the cation group of the compound 1 is shown in Fig.

The NMR spectrum of Compound 1 is shown in Fig.

&Lt; Preparation Example 2 - Compound 2 >

a-2 (1.48 mmol, 0.5 g) is dissolved in 5 ml of a 9: 1 solution of pure: acetone. A solution of p-tolyl (2,4,6-trimethoxyphenyl) iodonium bromide (1.56 mmol, 0.73 g) in pure water: acetone 9: 1 ml. The solution was slowly added dropwise to the solution of a-2, and the mixture was stirred to precipitate a white solid. Thereafter, the mixture was stirred at room temperature for 30 minutes. The solids were collected by filtration. This was followed by washing with pure water and removing the solvent 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.

&Lt; Preparation Example 3 - Compound 3 >

A-1 (37.3 mmol, 10 g) was added to a round flask and dissolved using 30 ml of DMF and 450 ml of acetone. 4-Pentenoic acid (45 mmol, 4.5 g) was added thereto, followed by stirring for 30 minutes. DCC (45 mmol, 9.3 g) was then added to the solution in a solid state at once. The mixture was stirred at room temperature for 16 hours. After 16 hours, a white solid precipitated from the solution in the flask, which was filtered and rinsed with acetone to recover the material. The filtered solution was stripped of solvent with an evaporator. When the amount of the solution was reduced to about 30 ml, 500 ml of ethyl ether was added to precipitate the solution. Thereafter, the precipitated solid was collected by filtration to obtain a-3. 9.8 g of white powder was obtained. (Yield: 75%) Compound 3 was synthesized from a-3 in the above. Compound a-3 (1.43 mmol, 0.5 g) was dissolved in 5 ml of a 9: 1 solution of pure: acetone. Diphenyliodonium chloride (1.56 mmol, 0.49 g) was dissolved in 5 ml of a pure 9: 1 acetone solution. The solution was slowly added dropwise to the solution of a-3, and the mixture was stirred to precipitate a white solid. Thereafter, the mixture was stirred at room temperature for 30 minutes. The solids were collected by filtration. Then, the solution 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.

&Lt; Preparation Example 4 - Compound 4 >

A-2 (14.8 mmol, 5 g) was added to a round flask and dissolved in 50 ml of DMF. The flask was cooled to 0 &lt; 0 &gt; C. SOCl ₂ (148 mmol, 17.6 g) was added and stirred for 16 hours. Pure water was added in the cooled state and stirred for 30 minutes. Then, the mixture was extracted with ethyl ether and the solvent was removed to obtain crude a-4 in the form of yellow oil. The reaction was then used without purification. a-5 could be synthesized from a-4. a-4 (6.0 mmol, 2.0 g) was added to 50 ml of an aqueous ammonia solution and stirred at room temperature for 2 hours. Then extracted with ethyl ether and the solvent removed to give a-5. The sulfonimide anions were then synthesized using a-4 and a-5. LiH (6.0 mmol, 48 mg) was added to a round flask, and 10 ml of THF was added. a-4 (3.0 mmol, 1.0 g) and a-5 (3.0 mmol, 0.94 g) were placed in a 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 three times with ethyl ether 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) and 5 ml of a 9: 1 solution of pure water and acetone were prepared. The white solid was precipitated by stirring slowly with the previously prepared solution. Thereafter, the mixture was stirred at room temperature for 30 minutes. The solids were collected by filtration. Then, the solution was washed with pure water, and the solvent was removed in a vacuum oven for 24 hours to obtain Compound 4. [

&Lt; Production Example 5 - Compound 5 >

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

&Lt; Preparation Example 6-Compound 6 >

Synthesis of a-6 was carried out in the same manner as in the synthesis of a-1 except that 2,6-bis (trifluoromethyl) phenol was used instead of tetrafluorophenol as the starting material .

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

2,6-bis (trifluoromethyl) phenol (150 mmol, 34.5 g) was added to a round flask and cooled to 0 占 폚. 80 ml of 20% fuming H ₂ SO ₄ was slowly added thereto, followed by stirring for 30 minutes. Thereafter, the mixture was heated to 70 DEG C and stirred for 18 hours. 400 ml sat. The NaCl solution was added to the beaker and cooled to 0 ° C. The reaction solution of the flask was slowly poured into a beaker containing the NaCl solution to precipitate the substance. After further stirring for 1 hour, the precipitated substance was filtered. The precipitated state was a white solid state. The solid crude material was dried in a baking oven to remove residual solvent. The solids were then dissolved in 600 ml of boiled acetonitrile. The dissolved material was filtered through a filter and slowly cooled to room temperature to be purified by recrystallization. 24 g of white solid a-6 was obtained. (Yield: 48%) a-7 was obtained from a-6.

a-6 (30.1 mmol, 10 g) was dissolved in 30 ml of DMF and 450 ml of acetone in a round flask. Then, methacrylic acid (36.2 mmol, 3.11 g) was added thereto and stirred for 30 minutes. DCC (36.2 mmol, 7.5 g) was then added to the solution in a solid state at once. The mixture was stirred at room temperature for 16 hours. After 16 hours, a white solid precipitated from the solution in the flask, which was filtered and rinsed with acetone to recover the material. The filtered solution was evaporated to remove the solvent. When the amount of the solution was reduced to about 30 ml, 500 ml of ethyl ether was added to precipitate the solution. The precipitated solid was then filtered and recovered to obtain a-7. 9 g of white solid was obtained. (Yield: 75%)

The above a-7 (1.25 mmol, 0.5 g) obtained above was dissolved in 5 ml of a DI water: acetone 9: 1 solution. Diphenyliodonium chloride (1.25 mmol, 0.40 g) is dissolved in 5 ml of a 9: 1 solution of pure water: acetone. The solution was slowly added dropwise to the solution of a-7, and the mixture was stirred to precipitate a white solid. Thereafter, the mixture was stirred at room temperature for 30 minutes. The solids were collected by filtration. Then, the solution 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%).

&Lt; Preparation 7 - Compound 7 >

A-1 (22 mmol, 5.9 g) was placed in a round flask and made into a nitrogen atmosphere. 10 ml of pure water was added to dissolve the material. Then, a solution prepared by dissolving 1- (4-bromobutyl) -4-vinylbenzene (20 mmol, 4.8 g) in acetone (10 ml) was added to the flask, Respectively. Thereafter, the mixture was heated to 70 DEG C and stirred for 24 hours. The flask was cooled to room temperature and the precipitated solid was collected. Washed three times with acetone and dried to give a-8. 4.3 g of white solid was obtained. (Yield: 53%)

A-8 (1.17 mmol, 0.5 g) obtained above was dissolved in 5 ml of a DI water: acetone 9: 1 solution. Diphenyliodonium chloride (1.17 mmol, 0.37 g) is dissolved in 5 ml of a 9: 1 solution of pure water: acetone. The solution was slowly added dropwise to the solution of a-8, and the solution was stirred to precipitate a white solid. Thereafter, the mixture was stirred at room temperature for 30 minutes. The solids were collected by filtration. Thereafter, the mixture was washed with pure water, and the solvent was removed in a vacuum oven for 24 hours to obtain a compound 7. 0.6 g (Yield: 75%).

&Lt; Preparation Example 8 - Compound 8 >

A-1 (22 mmol, 5.9 g) was placed in a round flask and made into a nitrogen atmosphere. 10 ml of pure water was added to dissolve the material. (4-bromobutoxy) bicyclo [4.2.0] octa-1 (6), 2,4-triene (3- , 2,4-triene) (20 mmol, 4.8 g) was dissolved in acetone (10 ml), and the solution was slowly added to the flask. Thereafter, the mixture was heated to 70 DEG C and stirred for 24 hours. The flask was cooled to room temperature and the precipitated solid was collected. Washed three times with acetone and dried to give a-9. 5.5 g of a white solid was obtained. (Yield 64%)

 The above a-9 (1.17 mmol, 0.5 g) obtained above was dissolved in 5 ml of a DI water: acetone 9: 1 solution. Diphenyliodonium chloride (1.17 mmol, 0.37 g) is dissolved in 5 ml of a 9: 1 solution of pure water: acetone. The solution was slowly added dropwise to the solution of a-9, and the mixture was stirred to precipitate a white solid. Thereafter, the mixture was stirred at room temperature for 30 minutes. The solids were collected by filtration. This was followed by washing with pure water and removing the solvent 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) were mixed to prepare a coating composition. The ratio of VNPB: p-dopant (compound 1) was mixed at a weight ratio of 0.8: 0.2.

The glass substrate on which ITO (indium tin oxide) was deposited to a thickness of 1500 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing was performed with a solvent of isopropyl alcohol and acetone for 30 minutes each, and the substrate was transported to a glove box. The coating composition was spin-coated on the prepared ITO transparent electrode to form a 300 Å thick hole injection layer, and the coating composition was cured on a hot plate at 230 ° C. for 30 minutes under an N ₂ atmosphere.

Then, NPB, compound A and compound B (8% concentration, 300 Å), compound C (200 Å), LiF (12 Å) and Al (2000 Å) were successively deposited on the hole injection layer To fabricate a device. Was the deposition rate of the organic material in the above process, maintaining the 0.4 ~ 0.7Å / sec, LiF of the cathode was 0.3 Å / sec, aluminum were deposited at speeds of 2 Å / sec, During the deposition, a vacuum 2 × 10 ^-7 To 5 x 10 &lt; ^-8 &gt; torr.

<Experimental Example 2>

An organic light emitting device was prepared 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 prepared 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 prepared 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 prepared 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 prepared 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 prepared 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 prepared 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.

&Lt; Comparative Example 1 &

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

[ISS]

&Lt; Comparative Example 2 &

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

[ISI]

The results of measuring the driving voltage, current efficiency, power efficiency and lifetime of the organic light emitting device manufactured in Experimental Examples 1 to 4 and Comparative Examples 1 and 2 at a current density of 10 mA / cm ² are shown in Table 1 below.

Device 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 the above Table 1, it can be seen that the dopant containing the structure of the formula (1) or (2) of the present invention is superior to the compound (ISS) of Comparative Example 1 having only a curing agent in terms of power efficiency and life, (ISI) of Comparative Example 1 having only an electron withdrawing group as shown in Table 1. Therefore, in the case of using a dopant including an electron withdrawing group such as a hardening unit and F at the same time, it is confirmed that the electron withdrawing unit such as a hardening unit and F is cured to prevent a reduction in lifetime due to interlayer interfacial inflow, .

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

Claims (17)

A coating composition comprising an ionic compound comprising an anionic group represented by the following formula (1) or (2):
[Chemical Formula 1]

(2)

In the above formulas (1) and (2)
At least one of R 1 to R 5 is -F, a cyano group, or a substituted or unsubstituted fluoroalkyl group,
At least one of the remaining R1 to R5 is -LR,
And the other of R1 to R5 is hydrogen,
L is a direct bond; -O-; -OC (= O) R &lt; 11 &gt;-; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted alkoxysilyl group,
R is a curing agent,
R11 is a direct bond; Or a substituted or unsubstituted alkylene group,
R "is hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted fluoroalkyl group, or a substituted or unsubstituted aryl group. The coating composition of claim 1, wherein the coating composition is for coating an organic layer of an organic light emitting device. The coating composition of claim 1, wherein the curing machine is selected from the group of curing machines:
[Curing group]

In the group of curing groups, 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 the parentheses are the same or different from each other,
R100 is a substituted or unsubstituted alkyl group. The compound according to claim 1, wherein R "is a phenyl group substituted with at least one of -F, cyano, substituted or unsubstituted fluoroalkyl, and -LR, a methyl, ethyl, trifluoromethyl, Or a pentafluoroethyl group. The coating composition according to claim 1, wherein the anionic group represented by the formula (2) is represented by the following formula (2-1) or (2-2):
[Formula 2-1]

[Formula 2-2]

In formulas (2-1) and (2-2), at least one of R 6 to R 10 is F, a cyano group, or a substituted or unsubstituted fluoroalkyl group,
At least one of the remaining R 6 to R 10 is -L'-R '
And the remaining R 6 to R 10 are hydrogen,
L 'is a direct bond; -O-; -OC (= O) R &lt; 12 &gt;-; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted alkoxysilyl group,
R 'is a curing agent,
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. The coating composition of claim 1, wherein at least one of R 1 to R 5 is -F, cyano, -CF ₃ , or -C ₂ F ₅ , and at least one of R 1 to R 5 is -LR. The coating composition according to claim 1, wherein the anionic group represented by the formula (1) is represented by any one of the following formulas 1-1 to 1-8:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

In the above 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 the formula (2) is represented by any one of the following formulas (2-3) to (2-10)
[Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

[Chemical Formula 2-6]

[Chemical Formula 2-7]

[Chemical Formula 2-8]

[Chemical Formula 2-9]

[Chemical Formula 2-10]

In Formulas 2-3 to 2-10, L and R are the same as defined in Claim 1,
L 'is a direct bond; -O-; -OC (= O) R &lt; 12 &gt;-; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted alkoxysilyl group,
R 'is a curing agent,
R12 is a direct bond; Or a substituted or unsubstituted alkylene group. The coating composition of claim 1, wherein the -LR is selected from the following formulas:

The coating composition of 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 comprises a cationic group and the cationic group is selected from the following formulas:

The coating composition of claim 1, wherein the coating composition comprises an arylamine compound substituted with a curing agent; An anhydride-substituted aniline oligomer; And a thiophene oligomer wherein the curing agent is substituted. &Lt; Desc / Clms Page number 19 &gt; The coating composition of claim 12, wherein the coating composition comprises an arylamine compound substituted with the ionic compound and the curing agent; An anhydride-substituted aniline oligomer; Wherein the weight ratio of the at least one compound selected from the group consisting of substituted thiophene oligomers and curing agent substituted thiophene oligomers is from 1:20 to 1: Preparing a substrate;
Forming a cathode or an anode on the substrate;
Forming at least one organic material layer on the cathode or the anode; And forming an anode or a 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 according to any one of claims 1 to 13 Wherein the organic light-emitting layer is formed on the substrate. [16] The method of claim 14, wherein the step of forming the organic material layer using the coating composition comprises a step of applying heat treatment or light treatment after the coating composition is applied. A first electrode;
A second electrode facing the first electrode; And
And at least one organic layer between the first electrode and the second electrode,
Wherein at least one of the organic layers comprises a cured product of the coating composition according to any one of claims 1 to 13. 17. The organic light emitting device according to claim 16, wherein the organic material layer is a hole injection layer.

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