KR102496107B1 - Ionic compound, coating composition comprising the same and organic light emitting device - Google Patents

Abstract

The present invention relates to an ionic compound containing an anionic group of Chemical Formula 1, a coating composition containing the same, and an organic light emitting device.

Description

Ionic compound, coating composition and organic light emitting device containing the same

The present specification relates to an ionic compound, a coating composition including the same, and an organic light emitting device.

The organic light emitting phenomenon is one example in which electric current is converted into visible light by an internal process of specific organic molecules. The principle of the organic light emitting phenomenon is as follows. When the organic material layer is placed between the anode and the cathode, when a current is applied between the two electrodes, electrons and holes are injected into the organic material layer from the cathode and the anode, respectively. Electrons and holes injected into the organic material layer recombine to form excitons, and the excitons fall back to the ground state and emit light. An organic light emitting device using this principle may generally be composed of a cathode, an anode, and an organic material layer disposed therebetween, such as a hole injection layer, a hole transport layer, a light emitting layer, and 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 heat is generated by 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 the organic light emitting device must have an appropriate band gap and an energy level of HOMO (Highest Occupied Molecular Orbital) or LUMO (Lowest Unoccupied Molecular Orbital). In the case of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) used as a hole transport material in organic light emitting devices manufactured by the solution coating method However, since the LUMO energy level is lower than the LUMO energy level of the organic material used as the light emitting layer material, it is difficult to manufacture an organic light emitting device with high efficiency and long lifespan.

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 an ionic compound, a coating composition and an organic light emitting device including the same.

The present specification provides an ionic compound containing an anionic group represented by Formula 1 below.

[Formula 1]

In Formula 1,

At least one of R1 to R20 is F, a cyano group, or a substituted or unsubstituted fluoroalkyl group,

At least one of the remaining R1 to R20 is a curing group,

The remaining R1 to R20 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; nitro group; -C(O)R ₁₀₀ ; -OR ₁₀₁ ; -SR ₁₀₂ ; -SO ₃ R ₁₀₃ ; -COOR ₁₀₄ ; -OC(O)R ₁₀₅ ; -C(O)NR ₁₀₆ R ₁₀₇ ; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R ₁₀₀ to R ₁₀₇ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group.

The present specification provides a coating composition comprising the aforementioned ionic compound.

The present specification is a 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 a cured product of the aforementioned coating composition.

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 MS data of compound 2 according to an exemplary embodiment of the present specification.
Figure 3 is DSC data of compound 2 according to an exemplary embodiment of the present specification.
4 is film retention rate data of coating composition 5 according to an exemplary embodiment of the present 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 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 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, L 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 or different;

R21 is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, the curing group may use various curing groups as long as the curing group is capable of curing, and is not limited to the group of curing groups.

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 oxygen, sulfur, nitrogen, phosphorus, and the like.

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

In the present specification, the alkynyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include alkynyl groups such as ethynyl, propynyl, 2-methyl-2propynyl, 2-butynyl, and 2-pentynyl, but are not limited thereto.

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but 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.

,

및

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

,

and

etc. However, it is not limited thereto.

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, 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.

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.

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, when there is no curing group in the anionic group represented by Formula 1, curing is not performed, so the characteristics of the device are reduced due to movement between the cationic group and the anionic group of the present specification between electrode layers. In addition, when the number of curing groups increases, the curing rate of the coating composition increases and the film retention rate improves.

In one embodiment of the present specification, 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 a curing group,

The remaining R1 to R5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; nitro group; -C(O)R ₁₀₀ ; -OR ₁₀₁ ; -SR ₁₀₂ ; -SO ₃ R ₁₀₃ ; -COOR ₁₀₄ ; -OC(O)R ₁₀₅ ; -C(O)NR ₁₀₆ R ₁₀₇ ; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R ₁₀₀ to R ₁₀₇ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group,

The R6 to R20 are the same as or different from each other, and each independently a curing group; F; cyano group; A substituted or unsubstituted fluoroalkyl group; hydrogen; heavy hydrogen; nitro group; -C(O)R ₁₀₀ ; -OR ₁₀₁ ; -SR ₁₀₂ ; -SO ₃ R ₁₀₃ ; -COOR ₁₀₄ ; -OC(O)R ₁₀₅ ; -C(O)NR ₁₀₆ R ₁₀₇ ; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R ₁₀₀ to R ₁₀₇ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, at least one of R1 to R20 is F or CF ₃ .

In one embodiment of the present specification, the curing group of Chemical Formula 1 is selected from the following structural formula.

또는

이다.In one embodiment of the present specification, the curing group of Formula 1

or

am.

이다. In one embodiment of the present specification, the curing group of Formula 1

am.

In one embodiment of the present specification, the anionic group of Chemical Formula 1 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 selected from a monovalent cationic group, an onium compound, or the following structural formulas.

In one embodiment of the present specification, the monovalent cation group may be an alkali metal cation, and the alkali metal cation includes Na ⁺ , Li ⁺ , K ⁺ , but is not limited thereto.

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

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

X ₁ to X ₇₆ in the above structural formula are the same as or different from each other, and each independently hydrogen; cyano group; nitro group; halogen group; -COOR ₁₀₄ ; 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 selected from the curing group,

R ₁₀₄ is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group,

p is an integer from 0 to 10;

a is 1 or 2, b is 0 or 1, a+b=2,

X ₇₇ to X ₇₉ are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or groups adjacent to each other bond to each other to form a ring.

In one embodiment of the present specification, the cationic group is any one selected from the following structural formulas.

In one embodiment of the present specification, the ionic compound is selected from the following structural formulas.

In one embodiment of the present specification, a coating composition including an ionic compound containing an anionic group of Formula 1 is provided.

In one embodiment of the present specification, the coating composition containing the ionic compound is a coating composition for an organic light emitting device.

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

In one embodiment of the present specification, the solvent is, for example, chlorine-based solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene; ether solvents such as tetrahydrofuran and dioxane; aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; aliphatic hydrocarbon-based solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Ketone solvents, such as acetone, methyl ethyl ketone, and cyclohexanone; Ester solvents, such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, etc. alcohol and its derivatives; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; benzoate-based solvents such as methyl benzoate, butyl benzoate, and 3-phenoxy benzoate; And solvents such as tetralin are exemplified, but any solvent capable of dissolving or dispersing the compound according to an exemplary embodiment of the present 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 is formed using a coating composition containing an ionic compound containing an anionic group of Formula 1 .

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 layers includes a cured product of a coating composition containing an ionic compound containing an anionic group of Formula 1. do.

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, 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 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 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 hole injection layer, and the ionic compound including an anionic group of Chemical Formula 1 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 means the property of injecting or transporting holes at the highest occupied molecular orbital (HOMO) energy level, that is, the property of a material with high hole conductivity.

In one embodiment of the present specification, the organic material layer formed using the coating composition is a hole injection layer, the ionic compound containing an anionic group of Formula 1 is a dopant of the hole injection layer, and arylamine as a host of the hole injection layer contains a compound

In one embodiment of the present specification, the arylamine compound is a single molecule or a polymer.

In one embodiment of the present specification, a monomolecular or polymeric arylamine compound is further included as a host of the hole injection layer.

In one embodiment of the present specification, the arylamine compound includes one of curing groups having the following structure.

[Lighter group]

In the curing group, L 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 or different;

R21 is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, the host of the hole injection layer has a HOMO level of 4.8eV to 5.8eV.

The HOMO level in this specification is measured using electrochemical cyclic voltammetry (CV). The onset potential (E _onset ) at which oxidation of the host material starts is measured, and the potential (E _{1/2 ( Fc )} ) of ferrocene is measured under the same conditions. The potential of ferrocene is set to be 4.8 eV compared to the vacuum energy level and calculated by the following equation.

HOMO (eV) = 4.8 + (E _onset - E _{1/2( Fc )} )

The arylamine group compound may form a bridge 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.

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

In one embodiment of the present specification, the organic material layer formed using 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, strylamine 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 (Bathocuproine), 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_Preparation of Compound 2>

[Compound 1] [Compound 2] Put the starting material (2000 mg, 8.8885 mmol) in a round flask and add 30 ml of anhydrous THF. The flask was cooled to -78°C, and n-BuLi (9.3329 mmol, 3.73 mL) was slowly added by dropping. After stirring for 30 minutes, gallium chloride (2.0444 mmol, 4.09 mL, 0.5 M in pentane) was slowly added dropwise at -78°C. Stir 15 hours at room temperature (RT). 15 mL of water was slowly added dropwise to terminate the reaction. After extracting the organic solvent using ethyl acetate (EA), the solvent was removed to obtain compound 1 (lithium tetrakis(2,3,5,6-tetrafluoro-4-vinylphenyl) gallate).

Put the compound 1 obtained above into a 50 mL round flask and dissolve in 20 ml of a 1:1 solution of methylene chloride (MC): water. Diphenyliodonium chloride (731 mg, 2.3110 mmol) was put into a round bottom flask and vigorously stirred at room temperature for 30 minutes. After extracting the organic layer, 902 mg of compound 2 could be obtained through dean-stark. (Yield: 42%)

The MS date and NMR date of tetrakis(2,3,5,6-tetrafluoro-4-vinylphenyl) gallate, which is an anion of Compounds 1 and 2, are shown in FIGS. 2 and 3, respectively.

<Preparation Example 2_Preparation of Compound 4>

[Starting Material 1] [Starting Material 2] [Compound 3] [Compound 4]

Put starting material 1 (1097 mg, 4.4443 mmol) in round flask 1 and add 15 ml of anhydrous THF. The flask was cooled to -78 °C, and n-BuLi (4.6665 mmol, 1.87 mL) was slowly added by dropping. Put starting material 2 (1133 mg, 4.4443 mmol) in round flask 2 and add 15 mL of tetrahydrofuran (THF). The flask was cooled to -78 ° C, and n-BuLi (4.6665 mmol, 1.87 mL) was slowly added by dropping. After stirring for 30 minutes, gallium chloride (2.0444 mmol, 4.09 mL, 0.5 M in pentane) was slowly added dropwise to the round flask 1 at -78°C. Stir 15 hours at room temperature (RT). After lowering the temperature to -78℃ again, the solution in round flask 2 is slowly added dropwise to round flask 1 using a 2-way needle. After raising the temperature to room temperature, the mixture was stirred for 15 hours. 15 mL of water is added dropwise to terminate the reaction. After extracting the organic solvent using ethyl acetate (EA), the solvent was removed to obtain Compound 3.

Put the compound 3 obtained above into a 50 mL round flask and dissolve in 20 ml of a 1:1 solution of methylene chloride (MC): water. Diphenyliodonium chloride (731 mg, 2.3110 mmol) was put into a round bottom flask and vigorously stirred at room temperature for 30 minutes. After extracting the organic layer, 640 mg of compound 4 could be obtained through dean-stark. (Yield: 30%)

<Preparation Example 3_Preparation of Compound 6>

[Compound 5] [Compound 6]

4-Chloro-trifluoromethyl-styrene (1000 mg, 3.6418 mmol) (J. Am. Chem. Soc. 72, 9, 4053-4055) was added to a round flask and 12 ml of anhydrous THF was added. put in The flask was cooled to -78 °C, and n-BuLi (3.6418 mmol, 2.5 mL) was slowly added by dropping. After stirring for 30 minutes, gallium chloride (0.8376 mmol, 1.68 mL, 0.5 M in pentane) was slowly added dropwise to the round flask at minus 78°C. Stir 15 hours at room temperature (RT). 12 mL of water is added dropwise to terminate the reaction. After extracting the organic solvent using ethyl acetate (EA), the solvent was removed to obtain Compound 5.

Put the compound 5 obtained above into a 50 mL round flask and dissolve in 20 ml of a 1:1 solution of methylene chloride (MC): water. Para-tolyl (2,4,6-trimethoxyphenyl) iodonium bromide (506 mg, 1.0888 mmol) was added to a round bottom flask and 30 Stir vigorously at room temperature for a minute. After extracting the organic layer, 307 mg of compound 6 could be obtained through dean-stark. (Yield: 26%)

<Preparation Example 4_Preparation of Compound 8>

[Compound 7] [Compound 8]

1-bromo-2,3,5,6-tetrafluoro-4-(1,2,2-trifluorovinyl)benzene (1-bromo-2,3,5,6-tetrafluoro- 4-(1,2,2-trifluorovinyl)benzene) (1000 mg, 3.2365 mmol) was added and 11 ml of anhydrous THF was added. The flask was cooled to -78 °C, and n-BuLi (3.2365 mmol, 1.29 mL) was slowly added by dropping. After stirring for 30 minutes, gallium chloride (0.7444 mmol, 1.49 mL, 0.5 M in pentane) was slowly added dropwise to the round flask at minus 78°C. Stir 15 hours at room temperature (RT). 12 mL of water is added dropwise to terminate the reaction. After extracting the organic solvent using ethyl acetate (EA), the solvent was removed to obtain compound 7.

Put the compound 7 obtained above into a 50 mL round flask and dissolve in 20 ml of a 1:1 solution of methylene chloride (MC):water. Para-tolyl(2,4,6-trimethoxyphenyl)iodonium bromide (450 mg, 0.9677 mmol) was added to a round bottom flask and 30 Stir vigorously at room temperature for a minute. After extracting the organic layer, 235 mg of compound 8 could be obtained through dean-stark. (Yield: 23%)

Experimental example 1-1. Formation of a coating layer using a coating composition

The coating composition was a mixture of the coating composition as described in Table 1 below. Specifically, coating composition 1 is a p doping material represented by Compound 2 of the present invention, the host compound [Compound A], and an organic solvent (cyclohexanone: cyclohexanone), and specifically, the weight ratio of the compound 2, chemical A, and organic solvent was mixed at a weight ratio of 2: 8: 490 to create a coating composition, and the coating composition 1 was spin-coated to form a coating layer Formed, the film was fired at 250 ℃ or less.

Coating composition 2 was prepared in the same manner as the coating composition 1 except for using compound 4 instead of compound 2 in Experimental Example 1-1, and a coating layer was formed by spin coating the coating composition 2, and the film was formed at 250 ° C. or less. was fired in

Coating composition 3 was prepared in the same manner as the coating composition 1, except that Comparative Compound 1 was used instead of Compound 2 in Experimental Example 1-1, and a coating layer was formed by spin coating the coating composition 3, and the film was formed at 250 ° C. It was fired below.

Coating composition 4 was prepared in the same manner as the coating composition 1, except that Comparative Compound 2 was used instead of Compound 2 in Experimental Example 1-1, and a coating layer was formed by spin coating the coating composition 4, and the film was formed at 250 ° C It was fired below.

Coating composition 5 was prepared in the same manner as the coating composition 1, except that Comparative Compound 3 was used instead of Compound 2 in Experimental Example 1-1, and a coating layer was formed by spin coating the coating composition 5, and the film was formed at 250 ° C. It was fired below.

Coating composition 6 was prepared in the same manner as the coating composition 1, except that Comparative Compound 4 was used instead of Compound 2 in Experimental Example 1-1, and a coating layer was formed by spin coating the coating composition 6, and the film was formed at 250 ° C. It was fired below.

Coating composition 7 was prepared in the same manner as the coating composition 1, except that compound 6 was used instead of compound 2 in Experimental Example 1-1, and a coating layer was formed by spin coating the coating composition 7, and the film was formed at 250 ° C. or less. was fired in

Coating composition 8 was prepared in the same manner as the coating composition 1, except that compound 8 was used instead of compound 2 in Experimental Example 1-1, and a coating layer was formed by spin coating the coating composition 8, and the film was formed at 250 ° C. or less. was fired in

coating
composition host p-doping material Spin speed (rpm)
/time(s) Firing temperature ( ^o C)
/time (min) One compound A compound 2 1000/60 230/30 2 compound A compound 4 1000/60 230/30 3 compound A comparative compound 1 1000/60 230/30 4 compound A comparative compound 2 1000/60 230/30 5 compound A comparative compound 3 1000/60 230/30 6 compound A comparative compound 4 1000/60 230/30 7 compound A compound 6 1000/60 230/30 8 compound A compound 8 1000/60 230/30

[Compound A]

[Comparative compound 1]

[Comparative compound 2]

[Comparative Compound 3]

[Comparative compound 4]

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.

Coating composition 1 described in Table below 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 for 30 minutes on a hot plate under N ₂ atmosphere. Thereafter, after transferring to a vacuum evaporator, the compound D was vacuum deposited on the hole injection layer to form a hole transport layer.

Subsequently, a light emitting layer was formed by vacuum depositing compound F at a concentration of 8% with respect to compound E on the hole transport layer to a thickness of 300 Å. An electron injection and transport layer was formed by vacuum depositing the compound G on the light emitting layer to a thickness of 200 Å. A cathode was formed by sequentially depositing LiF to a thickness of 12 Å and aluminum to a thickness of 2000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7Å/sec, the deposition rate of LiF of the cathode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum level during deposition was 2x10 ^-7 to 5x10 ^{- 8} torr was maintained.

Example 2

An organic light emitting device was manufactured in the same manner as in Example 1, except that Coating Composition 2 was used instead of Coating Composition 1 as the hole injection layer in Example 1.

comparative example One

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Coating Composition 3 was used instead of Coating Composition 1 as the hole injection layer in Example 1.

comparative example 2

An organic light emitting device was manufactured in the same manner as in Example 1, except that Coating Composition 4 was used instead of Coating Composition 1 as the hole injection layer in Example 1.

comparative example 3

In order to check the film retention rate of the coating layer formed using the coating composition 5, toluene solvent was spin-treated on top of the film and washed.

comparative example 4

An organic light emitting device was manufactured in the same manner as in Example 1, except that Coating Composition 6 was used instead of Coating Composition 1 as the hole injection layer in Example 1.

The film retention rate data was obtained by comparing the degree of ultraviolet light absorption before and after the above-described film formation process.

4 is film retention rate data of coating composition 5 according to an exemplary embodiment of the present specification.

The film retention data of FIG. 4 has a difference in absorbance, which means that there is a difference in the effect of forming a film due to the difference. Specifically, it was confirmed from the data of FIG. .

Example Driving voltage (V) Current Efficiency (cd/A) Power Efficiency (lm/W) Life time
(95%,h) Example 1 5.1 7.73 4.76 51 Example 2 5.3 8.22 4.87 86 Comparative Example 1 9.9 4.44 1.41 One Comparative Example 2 4.8 3.83 2.49 20 Comparative Example 4 5.2 3.45 5.25 37

As a result of Table 2, the dopant having the structure of Formula 1 of the present specification has excellent solubility in organic solvents compared to commonly used dopants, so it is suitable for a solution process, and it is easy to prepare a coating composition, It was confirmed that a uniform coating layer can be formed using the coating composition, and unlike conventional dopants, since a curing group exists to prevent a decrease in lifetime due to inflow between layers, 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 (13)

An ionic compound comprising an anionic group represented by Formula 1, an alkali metal cation, and a cationic group selected from the following structural formulas:
[Formula 1]

In Formula 1,
At least one of R1 to R20 is F, a cyano group, or a substituted or unsubstituted fluoroalkyl group,
At least one of the remaining R1 to R20 is a curing group,
The remaining R1 to R20 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; nitro group; -C(O)R ₁₀₀ ; -OR ₁₀₁ ; -SR ₁₀₂ ; -SO ₃ R ₁₀₃ ; -COOR ₁₀₄ ; -OC(O)R ₁₀₅ ; -C(O)NR ₁₀₆ R ₁₀₇ ; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R ₁₀₀ to R ₁₀₇ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group,

X ₁ to X ₇₆ in the above structural formula are the same as or different from each other, and each independently hydrogen; cyano group; nitro group; halogen group; -COOR ₁₀₄ ; 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 selected from the curing group,
R ₁₀₄ is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group,
p is an integer from 0 to 10;
a is 1 or 2, b is 0 or 1, a+b=2,
X ₇₇ to X ₇₉ are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or groups adjacent to each other bond to each other to form a ring. The ionic compound according to claim 1, wherein the curing group is selected from the following group of curing groups:
[Lighter group]

In the curing group, L 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;
R21 is a substituted or unsubstituted alkyl group. The method according to claim 1, wherein 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 a curing group,
The remaining R1 to R5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; nitro group; -C(O)R ₁₀₀ ; -OR ₁₀₁ ; -SR ₁₀₂ ; -SO ₃ R ₁₀₃ ; -COOR ₁₀₄ ; -OC(O)R ₁₀₅ ; -C(O)NR ₁₀₆ R ₁₀₇ ; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R ₁₀₀ to R ₁₀₇ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group,
The R6 to R20 are the same as or different from each other, and each independently a curing group; F; cyano group; A substituted or unsubstituted fluoroalkyl group; hydrogen; heavy hydrogen; nitro group; -C(O)R ₁₀₀ ; -OR ₁₀₁ ; -SR ₁₀₂ ; -SO ₃ R ₁₀₃ ; -COOR ₁₀₄ ; -OC(O)R ₁₀₅ ; -C(O)NR ₁₀₆ R ₁₀₇ ; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R ₁₀₀ to R ₁₀₇ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or an ionic compound that is a substituted or unsubstituted alkyl group. The ionic compound according to claim 1, wherein the anionic group of Formula 1 is any one selected from the following structural formulas:

delete The ionic compound according to claim 1, wherein the cationic group is any one selected from the following structural formulas:

The ionic compound of claim 1, wherein the ionic compound is selected from the following structural formulas:

A coating composition comprising the ionic compound according to any one of claims 1 to 4, 6 and 7. The method of claim 8,
The coating composition is a coating composition for an organic light emitting device. The coating composition of claim 8 , wherein the coating composition further comprises a monomolecular or polymeric arylamine compound. a first electrode; a second electrode provided to face the first electrode; and
Including one or more organic material layers provided between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic light emitting device comprising a cured product of the coating composition of claim 8. The organic light emitting device of claim 11, wherein the cured product of the coating composition is cured by heat treatment or light treatment of the coating composition. The organic light emitting device of claim 12, wherein 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.

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