KR102123720B1 - Coating compositions, organic light emitting device manufactured by using the same and method of manufacturing the same - Google Patents

Abstract

The present specification is a compound containing a cation or a cationic radical and a monovalent anion of the compound represented by Formula 1; And it relates to a coating composition comprising an arylamine compound of Formula 2, an organic light emitting device formed using the same, and a method for manufacturing the same.

Description

Coating composition, organic light emitting device manufactured using the same, and manufacturing method thereof {COATING COMPOSITIONS, ORGANIC LIGHT EMITTING DEVICE MANUFACTURED BY USING THE SAME AND METHOD OF MANUFACTURING THE SAME}

The present specification is a compound containing a cation or a cationic radical and a monovalent anion; And an arylamine compound, an organic light-emitting device formed using the coating composition, and a method for manufacturing the same.

The organic light emission phenomenon is an example in which current is converted into visible light by an internal process of a specific organic molecule. The principle of the organic light emission phenomenon is as follows. When an organic layer is placed between the anode and the cathode, when an electric current is applied between the two electrodes, electrons and holes are injected into the organic layer from the cathode and the anode, respectively. Electrons and holes introduced into the organic material layer recombine to form excitons, and the excitons fall back to the ground state to emit light. An organic light emitting device using this principle may be generally composed of a cathode, an anode, and an organic material layer disposed therebetween, such as a hole injection layer, a hole transport layer, an emission layer, and an organic material layer including an electron transport layer.

As a material used in the organic light emitting device, a pure organic material or a complex compound in which an organic material and a metal are complex occupies most, and depending on the purpose, a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. Can be divided into. Here, as a hole injection material or a 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 during oxidation is mainly used. On the other hand, as an electron injection material or an electron transport material, an organic material having n-type properties, that is, an organic material that is easily reduced and has an electrochemically stable state during reduction, is mainly used. The light-emitting layer material is preferably a material having both p-type and n-type properties, that is, a material having a stable form in both the oxidation and reduction states, and a material having high luminous efficiency that converts it to light when excitons are formed. desirable.

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

First, it is preferable that the material used in the organic light emitting device has excellent thermal stability. This is because joule heating is caused by the movement of electric charges in the organic light emitting device. Currently, NPB, which is mainly used as a hole transport layer material, has a glass transition temperature of 100° C. or less, and thus is difficult to use in an organic light emitting device requiring high current.

Secondly, in order to obtain a high-efficiency organic light-emitting device capable of driving a low voltage, holes or electrons injected into the organic light-emitting device must be smoothly transferred to the light-emitting layer, and at the same time, injected holes and electrons must be prevented from exiting the light-emitting layer. To this end, the material used in the organic light emitting device should have an appropriate band gap and HOMO or LUMO energy level. In the case of PEDOT:PSS, which is used as a hole transport material in the organic light emitting device manufactured by the current solution coating method, the LUMO energy level is lower than the LUMO energy level of the organic material used as the light emitting layer material. Have difficulty.

In addition, the material used in the organic light emitting device should have excellent chemical stability, charge mobility, and interface properties with an electrode or an adjacent layer. That is, the material used in the organic light emitting device should be less deformed by moisture or oxygen. In addition, it should be possible to maximize exciton formation by having a hole or electron mobility to balance 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 containing metal or metal oxide.

Recently, an organic light-emitting device has been developed by using a solution process, particularly an inkjet process, in place of the existing deposition process. In this way, the process cost of the organic light emitting device can be drastically reduced. In the early days, all organic light-emitting device layers were coated with a solution process to develop an organic light-emitting device, but there are limitations in the current technology, so there are limitations in the form of a hole injection layer (HIL), hole transport layer (HTL), and light emitting layer (EML) A hybrid process that proceeds with the bay as a solution process and utilizes an existing deposition process in the future is being studied. In addition, in the early days, a lot of organic light-emitting materials having a polymer form were used in order to increase the coating property, but there is a problem of change and purity due to batch-batch intrinsic to the polymer.

In addition, in the past, an attempt was made to improve the performance and life of the organic light emitting device by mixing a hole transporting compound and an electron-accepting compound, but the hole transporting compound uses an inorganic material capable of solution processing or uses an organic material having semiconductor properties. In the case of PEDOT:PSS, which has been used and is currently used as a hole transport compound in an organic light emitting device manufactured by a solution coating method, the LUMO energy level is lower than the LUMO energy level of the organic material used as a light-emitting layer material, so that high-efficiency and long-life organic There is a difficulty in manufacturing a light emitting device.

In addition, the electron-accepting compound refers to a material that allows the host material to have p-semiconductor properties, and the p-semiconductor property is a property in which holes are injected or transported at a high occupied molecular orbital (HOMO) energy level, that is, the hole conductivity is large. It means the properties of a substance. The electron-accepting compound may receive electrons from all or part of the host material and promote the conversion of the host material to a cation or a cationic radical, thereby helping to smoothly polymerize the host material in a heat treatment or photo-treatment process after coating.

The electron-accepting compound may have the following structure, but is not limited thereto.

The above structures are added together with an arylamine compound used as a hole transporting compound to oxidize the hole transporting compound to convert it into a cation or a cationic radical, and the converted hole transporting compound becomes a counter ion of an anion and exists as an ionic pair. The cation of the existing electron-accepting compound that oxidizes the transportable compound is modified or reduced to exist in the hole injection layer. The modified or reduced existing cations may act as impurities in the hole injection layer, and are preferably removed during the process, but it is difficult to remove the existing cations that have been modified or reduced in the process currently used. Indeed, 4-isopropyl-4'-methyldiphenyl iodonium tetrakis(pentafluorofluorophenyl)borate in the above structure is 5% weight loss in TGA measurement. (weight loss) is observed at 235℃ and 4-isopropyl-4'-methyldiphenyliodonium ion or a substance modified from this ion is an electroluminescent device for general solution processing It can be assumed that it remains in the hole injection layer during the production process.

Korea Patent Publication No. 2012-0112277

An object of the present specification is to provide a coating composition for manufacturing an organic material layer of an organic light emitting device, an organic light emitting device including the same, and a manufacturing method thereof.

The specification is Z ⁺ X ^- or Z ^+. X ^- a compound represented by; And an arylamine compound represented by the following Chemical Formula 2, wherein Z is a compound represented by the following Chemical Formula 1, and X ⁻ is a monovalent anion.

[Formula 1]

In Chemical Formula 1,

L1 and L2 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

X1 and X2 are the same as or different from each other, and each independently hydrogen; Or a functional group crosslinkable by heat or light, at least one of X1 being a functional group crosslinkable by heat or light,

Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted arylamine group; Or it may be a substituted or unsubstituted heteroaryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,

a is an integer from 1 to 5,

b is an integer from 0 to 5,

m and n are each an integer from 0 to 4,

When m, n, a, and b are each 2 or more, the substituents in parentheses are the same or different from each other,

[Formula 2]

In Chemical Formula 2,

L3 to L6 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted alkylene group; A substituted or unsubstituted cycloalkylene group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted ester group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Ar3 is the same as or different from each other, and each independently substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Or a substituted or unsubstituted aryl group,

Y1 and Y2 are the same as or different from each other, and each independently hydrogen; Or a functional group capable of crosslinking by heat or light,

A is hydrogen; Or NRR',

R and R'are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

p is an integer from 0 to 4,

q is an integer from 0 to 3,

When p and q are each 2 or more, the substituents in parentheses are the same or different from each other.

The specification also includes a cathode; Anode; And one or more organic material layers provided between the cathode and the anode, and at least one layer of the organic material layer provides an organic light emitting device formed using the coating composition.

Finally, the present specification includes 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 forming the organic material layer includes forming one or more organic material layers using the coating composition. do.

A compound containing a cation and/or a cation radical and a monovalent anion according to an exemplary embodiment of the present specification increases the charge mobility and increases the number of charges, thereby acting as an efficient hole transporting material, and is a modified or reduced existing electron-accepting material Since no impurities such as cations are present, performance, life and reproducibility of the EL device can be improved.

When a coating composition comprising a compound containing a cation and/or cation radical and a monovalent anion according to an exemplary embodiment of the present specification and an arylamine compound having a curing temperature of 230° C. or less is used as a hole transport material, the upper layer is coated When doing so, it has the advantage of minimizing membrane washing and maximizing membrane retention.

The coating composition according to an exemplary embodiment of the present specification may be used as an organic material layer material of an organic light emitting device, and may provide low driving voltage, high luminous efficiency, and high lifespan characteristics.

1 shows an example of an organic light emitting device according to an exemplary embodiment of the present specification.
2 is a diagram showing an MS spectrum of a cation and an anion of Formula 3-1.
3 is a diagram showing an MS spectrum of Formula 1-1.
4 is a diagram showing an MS spectrum of Formula 1-5.

Hereinafter, the present specification will be described in detail.

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

In the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

In the present specification, the term “combination of these” included in the expression of the marki form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the marki form, the component It means to include one or more selected from the group consisting of.

One embodiment of the present invention relates to a coating composition, Z ⁺ X ^- or Z ^+. X ^- a compound represented by; And an arylamine compound represented by Chemical Formula 2 having a curing temperature of 230° C. or less. One embodiment described above relates to a coating composition capable of forming an organic material layer of an organic light emitting device by a solution process, Z ⁺ X ^- or Z ^+. The compound represented by X ^- has both electron-accepting properties as well as hole-transporting properties, and is therefore efficient because it does not require a process such as mixing two different materials.

In addition, attempts have been made to improve the performance and life of the organic light emitting device by mixing an electron-accepting compound and a hole-transporting compound, but the mixing of two different materials may cause a change in ratio and additional process problems. Became.

A hole transporting compound and an electron-accepting material are mixed in a specific ratio to prepare a solution for a hole transporting layer, but when the solution is prepared, the ratio of the two materials may vary depending on the batch, and if this ratio is different, the number and charge transfer of the generated charges Since the degree may vary, it may cause a batch-to-batch change problem in the electroluminescent device, and a film coated with a solution prepared by mixing the hole-transporting compound and the conventional electron-accepting material is a solvent for the next process solvent. Although there is a problem in that the electron-accepting material, which is not resistant and has not reacted by the solvent, is washed out and the hole mobility is reduced or the film properties are deteriorated, the device properties are deteriorated, but the present invention has electron-accepting properties together with hole-transport properties. The above problem can be solved by using a compound.

In addition, the present invention is Z ⁺ X ^- or Z ^+. By mixing the arylamine compound having the structure of Formula 2 having a curing temperature of 230° C. or less to the compound represented by X ⁻ , the coating composition is coated or jetted during the organic light emitting device process, and then thermally cured to form a film. At this time, it is possible to optimize the curing temperature and improve the performance and fairness of the organic light emitting device.

In the present specification, Z is an arylamine derivative represented by Chemical Formula 1, and Z+ is a cationic compound, Z ^+. Means a compound which is both a cation and a radical.

In the present specification, the cationic compound means a compound having a positive net charge because the number of protons is greater than the number of electrons. In addition, a radical compound means a compound having an unpaired electron, and depending on the type of the compound, a compound which is both a cation and a radical may exist. Generally, a π-radical compound is known to be unstable, but a cationic radical material may stably exist when it has an appropriate structure such as a π-conjugated system or an alkyl substituent. (Org. Biomol. Chem., 2005, 3, 561-569) In the present invention, the anion of the electron-accepting material is combined with the hole-transporting material, and the modified or reduced cationic material is removed through purification to remove the cation or cation of the hole-transporting layer compound. To generate radicals.

In one embodiment of the present specification, the compounds represented by Chemical Formula 1 and Chemical Formula 2 include a crosslinkable functional group, thereby curing after deposition.

As used herein, “crosslinkable functional group” may mean a reactive substituent that polymerizes between compounds by exposure to heat and/or light. Polymerization may be generated by heat treatment or irradiation with light, carbon-carbon multiple bonds, and radicals formed as the cyclic structures are decomposed and connected.

As in the exemplary embodiment of the present specification, in the case of a compound containing a crosslinkable functional group, an organic light-emitting device can be manufactured by a solution coating method, which is economical in time and cost.

In addition, by controlling the substituents of the compound represented by Chemical Formula 1 or 2 according to an exemplary embodiment of the present specification, it is possible to finely adjust an appropriate energy level and a band gap, and improve the interfacial properties between organic materials, resulting in low driving voltage and It is possible to provide an organic light emitting device having high luminous efficiency.

In addition, the compound represented by Formula 1 or 2 according to the exemplary embodiment of the present specification has one or more crosslinkable functional groups, which causes crosslinking during polymerization to extremely lower solubility in various solvents, and thus a solution containing the present compound In addition, a solution process is possible on the crosslinked film after the film formation process.

Since the compound represented by Chemical Formula 1 or 2 according to an exemplary embodiment of the present specification has excellent thermal stability after crosslinking, it is possible to induce driving stability and lifetime characteristics of the device.

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

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

Means a site that is attached to another substituent or linkage.

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 the hydrogen atom is substituted, that is, a position where the substituent is replaceable, and is 2 or more. When substituted, two or more substituents may be the same or different from each other.

The term "substituted or unsubstituted" as used herein refers to hydrogen; heavy hydrogen; Halogen group; Alkyl groups; Cycloalkyl group; Silyl group; Alkoxy groups; Alkenyl group; Ester groups; Aryl group; Amine group; Arylamine group; And substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups, or substituted or unsubstituted with two or more substituents among the exemplified substituents.

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

In the present specification, the alkyl group may be a straight chain, a branched chain, or a cyclic chain, and carbon number is not particularly limited, but is preferably 1 to 50. Specific examples are 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, 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, and the like, but are not limited to these.

The alkyl group is substituted with an aryl group or a heteroaryl group, and may function as an arylalkyl group or a heteroarylalkyl group. The aryl group or heterocyclic group may be selected from examples of an aryl group or heterocyclic group described later.

In the present specification, the length of the alkyl group does not affect the conjugate length of the compound, and may affect the method of applying the organic light-emitting device of the compound, for example, 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, and the like, but is not limited thereto. Does not.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 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 to this.

The alkoxy group is substituted with an aryl group or a heteroaryl group, and may function as an aryloxy group or a heteroaryloxy group. The aryl group or heterocyclic group may be selected from examples of an aryl group or heterocyclic group described later.

In the present specification, the alkenyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. 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, styrenyl group, styrenyl group, and the like, but are not limited thereto.

The alkenyl group is substituted with an aryl group or a heteroaryl group, and may function as an arylalkenyl group or a heteroaryl alkenyl group. The aryl group or heterocyclic group may be selected from examples of an aryl group or heterocyclic group described later.

In this specification, the number of carbon atoms of the ester group is not particularly limited, but is preferably 1 to 50 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or a quarterphenyl group, 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 has 10 to 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, etc., but is not limited thereto.

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

,

및

(스피로비 플루오렌),

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

,

And

(Spirobi fluorene),

It can be back. However, it is not limited thereto.

The aryl group is substituted with an alkyl group, and may function as an alkylaryl group. The alkyl group may be selected from the examples described above.

In the present specification, the heterocyclic group includes one or more non-carbon atoms and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, pyridyl group, bipyridyl group, naphthyl group, pyrimidyl group, triazine group, triazole group, Acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, Isooxazolyl groups, oxadiazolyl groups, thiadiazolyl groups, benzothiazolyl groups, phenothiazinyl groups, and dibenzofuranyl groups, but are not limited thereto.

The heterocyclic group may be monocyclic or polycyclic, and may be aromatic, aliphatic or condensed ring of aromatic and aliphatic.

In this 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 are 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, and the like, but are not limited to these.

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 can 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-anthra Senilamine, diphenyl amine group, dibiphenyl amine group, phenyl naphthyl amine group, ditolyl amine group, phenyl tolyl amine group, and triphenyl amine group, but are not limited thereto.

In the present specification, the arylene group means that the aryl group has two bonding positions, that is, a divalent group. These may be applied to the description of the aryl group described above, except that each is a divalent group.

In the present specification, the heteroarylene group means that the heteroaryl group has two bonding positions, that is, a divalent group. These may be applied to the description of the heteroaryl group described above, except that each is a divalent group.

In the present specification, the alkylene group means that the alkyl group has two bonding positions, that is, a divalent group. The description of the alkyl group described above can be applied, except that it is a divalent group.

In the present specification, a cycloalkylene group means a bivalent group having two binding positions on an alkyl group. The description of the cycloalkyl group described above may be applied, except that it is a divalent group.

In the present specification, the “adjacent” group refers to a substituent substituted on an atom directly connected to an atom in which the substituent is substituted, a substituent positioned closest to the substituent and the other substituent substituted on the atom in which the substituent is substituted. Can be. For example, two substituents substituted in the ortho position on the benzene ring 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 condensed ring of aliphatic and aromatic, and may form a hydrocarbon ring or a heterocycle.

The hydrocarbon ring may be selected from examples of the cycloalkyl group or aryl group, except that the monovalent group is not. The heterocyclic ring may be an aliphatic, aromatic or aliphatic and aromatic condensed ring, and may be selected from examples of the heterocyclic group, except that it is not a monovalent group.

In one embodiment of the present specification, Z ⁺ X ^- or Z ^+. X ^- a compound represented by; And it provides a coating composition comprising an arylamine compound represented by the formula (2).

In one embodiment of the present specification, Z is a compound represented by Formula 1 below, and has a cation or cation radical form.

In the present specification, the functional group capable of crosslinking by heat or light is any one of the following structures.

In the above structure,

R3 is hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

In one embodiment of the present specification, Chemical Formula 1 is as follows.

[Formula 1]

In Chemical Formula 1,

L1 and L2 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

X1 and X2 are the same as or different from each other, and each independently hydrogen; Or a functional group crosslinkable by heat or light, at least one of X1 being a functional group crosslinkable by heat or light,

Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted arylamine group; Or it may be a substituted or unsubstituted heteroaryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,

a is an integer from 1 to 5,

b is an integer from 0 to 5,

m and n are each an integer from 0 to 4,

When m, n, a and b are each 2 or more, the substituents in parentheses are the same or different from each other.

In one embodiment of the present specification, X1 and X2 are the same as or different from each other, and each independently hydrogen; Or a functional group crosslinkable by heat or light, and at least one of X1 is a functional group crosslinkable by heat or light.

In another exemplary embodiment, a is an integer from 1 to 5, and b is an integer from 0 to 5.

In another exemplary embodiment, a is an integer from 1 to 5, and b is an integer from 1 to 5.

According to another exemplary embodiment, a is an integer from 1 to 5, b is an integer from 1 to 5, at least one of X1 is a functional group capable of crosslinking by heat or light, and at least one of X2 is thermal Or a functional group capable of crosslinking by light.

According to the exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 4 to 30 carbon atoms.

According to one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In another exemplary embodiment, L1 and L2 are the same as or different from each other, and each independently a direct bond; It is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted fluorenylene group.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group.

According to another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

According to another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group having 6 to 13 carbon atoms.

In another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted phenyl group; Or a substituted or unsubstituted fluorenyl group.

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

[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,

X1, X2, a, b, m and n are the same as defined in Formula 1,

R4 and R5 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or may combine with an adjacent group to form a substituted or unsubstituted ring,

R11, R12, R21 and R22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted arylamine group; Or it may be a substituted or unsubstituted heteroaryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,

p2, q1 and q2 are each an integer from 0 to 5,

p1 is an integer from 0 to 7,

When p1, p2, q1 and q2 are each 2 or more, the substituents in parentheses are the same or different from each other.

In one embodiment of the present specification, R4 and R5 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; It is a substituted or unsubstituted aryl group, or combines with an adjacent group to form a substituted or unsubstituted ring.

In another exemplary embodiment, R4 and R5 are the same as or different from each other, and each independently substituted or an alkyl group having 1 to 30 carbon atoms; It is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or combines with an adjacent group to form a substituted or unsubstituted ring.

In another exemplary embodiment, R4 and R5 are the same as or different from each other, and each independently substituted or an alkyl group having 1 to 20 carbon atoms; It is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or combines with an adjacent group to form a substituted or unsubstituted ring.

In another exemplary embodiment, R4 and R5 are the same as or different from each other, and each independently substituted or an alkyl group having 1 to 12 carbon atoms; It is a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or combines with an adjacent group to form a substituted or unsubstituted ring.

In another exemplary embodiment, R4 and R5 are the same as or different from each other, and each independently a methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, phenyl group, Combined with a biphenyl group, a terphenyl group, a naphthyl group or an adjacent group to form spirobifluorene.

In one embodiment of the present specification, R11 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; Or a substituted or unsubstituted aryl group.

In another exemplary embodiment, R11 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In another exemplary embodiment, R11 is hydrogen; heavy hydrogen; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with an alkyl group or an aryl group; An alkoxy group having 1 to 20 carbon atoms unsubstituted or substituted with an alkyl group or an aryl group; Or an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with an alkyl group or an aryl group.

In another exemplary embodiment, R11 is hydrogen; heavy hydrogen; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a methyl group or a phenyl group; An alkoxy group having 1 to 20 carbon atoms unsubstituted or substituted with a methyl group or a phenyl group; It is an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a methyl group or a phenyl group.

According to another exemplary embodiment, R11 is hydrogen; heavy hydrogen; Methyl group; Ethyl group; Propyl group; Isopropyl group; Phenyl group; Biphenyl group; Or a naphthyl group.

In one embodiment of the present specification, p1 is 0.

In one embodiment of the present specification, p1 is 1.

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

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

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

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

In one embodiment of the present specification, q1 is 0.

In one embodiment of the present specification, q1 is 1.

In one embodiment of the present specification, R21 is hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to another exemplary embodiment, R21 is hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

According to another exemplary embodiment, R21 is hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms.

In another exemplary embodiment, R21 is hydrogen; heavy hydrogen; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted carbazole group.

According to another exemplary embodiment, R21 is hydrogen; heavy hydrogen; A phenyl group unsubstituted or substituted with an alkyl group, an aryl group, or a silyl group; A biphenyl group unsubstituted or substituted with an alkyl group, an aryl group, or a silyl group; Or a carbazole group unsubstituted or substituted with an alkyl group, an aryl group or a silyl group.

According to another exemplary embodiment, R21 is hydrogen; heavy hydrogen; a phenyl group unsubstituted or substituted with a t-butyl group, a phenyl group or a trimethylsilyl group; a biphenyl group unsubstituted or substituted with a t-butyl group, a phenyl group, or a trimethylsilyl group; Or a carbazole group unsubstituted or substituted with a t-butyl group, a phenyl group or a trimethylsilyl group.

In another exemplary embodiment, R21 is hydrogen; Phenyl group; It is a carbazole group unsubstituted or substituted with a phenyl group, trimethylsilyl group, or t-butyl group.

In another exemplary embodiment, R21 is hydrogen; Phenyl group; N-phenylcarbazole group; Or a carbazole group substituted with a trimethylsilyl group or a t-butyl group.

In one embodiment of the present specification, p2 is 0.

In one embodiment of the present specification, p2 is 1.

In one embodiment of the present specification, p2 is 2.

In one embodiment of the present specification, q2 is 0.

In one embodiment of the present specification, q2 is 1.

In one embodiment of the present specification, q2 is 2.

According to an exemplary embodiment of the present specification, R12 and R22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; A substituted or unsubstituted arylamine group; Or a substituted or unsubstituted heteroaryl group, or combine with an adjacent group to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, R12 and R22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted arylamine group; Or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or combine with adjacent groups to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, R12 and R22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; A substituted or unsubstituted arylamine group; Or a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, or combine with adjacent groups to form a substituted or unsubstituted ring.

In another exemplary embodiment, R12 and R22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted phenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted thiophene group; A substituted or unsubstituted dibenzofuran group; Or a substituted or unsubstituted carbazole group, or combine with an adjacent group to form a substituted or unsubstituted fluorenyl group.

According to another exemplary embodiment, R12 and R22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Phenyl group; A phenyl group substituted with a diphenylamine group; A phenyl group substituted with a dibiphenylamine group; A phenyl group substituted with a naphthyl group; 9,9-dimethylfluorenyl group; Diphenylamine group; Thiophene group; Dibenzofuran group; Carbazole; A carbazole group substituted with a phenyl group; A carbazole group substituted with a phenyl group substituted with a silyl group or an alkyl group; A carbazole group substituted with a substituted or unsubstituted alkoxy group; Or a carbazole group substituted with a substituted or unsubstituted alkyl group, or in combination with an adjacent group, a 9,9-dimethylfluorenyl group; Or 9,9-dihexylfluorenyl group.

In one embodiment of the present specification, Z may be any one selected from the following Chemical Formulas 1-1 to 1-52.

In one embodiment of the present specification, X ^- may be any one selected from the following Chemical Formulas 2-1 to 2-12.

In one embodiment of the present specification, Z ⁺ X ^- or Z ^+. The compound represented by X ^- may be any one selected from the following Chemical Formulas 3-1 to 3-60.

In one embodiment of the present specification, the arylamine compound represented by Chemical Formula 2 is as follows.

[Formula 2]

In Chemical Formula 2,

L3 to L6 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted alkylene group; A substituted or unsubstituted cycloalkylene group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted ester group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Ar3 is the same as or different from each other, and each independently substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Or a substituted or unsubstituted aryl group,

Y1 and Y2 are the same as or different from each other, and each independently hydrogen; Or a functional group capable of crosslinking by heat or light,

A is hydrogen; Or NRR',

R and R'are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

p is an integer from 0 to 4,

q is an integer from 0 to 3,

When p and q are each 2 or more, the substituents in parentheses are the same or different from each other.

In one embodiment of the present specification, Chemical Formula 2 may be represented by the following Chemical Formula 2-A.

In one embodiment of the present specification, A in Chemical Formula 2 is hydrogen; Or NRR', R and R'are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In one embodiment of the present specification, Chemical Formula 2 may be represented by the following Chemical Formula 2-A or 2-B.

[Formula 2-A]

[Formula 2-B]

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

R1, R2, p, q, L3 to L6, Ar3, Y1 and Y2 are the same as defined in Formula 2,

Ar4 and Ar5 are the same as or different from each other, and each independently an substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In one embodiment of the present specification, L5 is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

According to an exemplary embodiment of the present specification, L5 is a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

In another exemplary embodiment, L5 is a direct bond; An arylene group having 6 to 60 carbon atoms; Or a heteroarylene group having 2 to 60 carbon atoms.

According to another exemplary embodiment, L5 is a direct bond; It is an arylene group having 6 to 20 carbon atoms.

In one embodiment of the present specification, L5 is a phenylene group.

In another exemplary embodiment, L5 is a direct bond.

In one embodiment of the present specification, Chemical Formula 2 may be represented by Chemical Formula 2-C or Chemical Formula 2-D.

[Formula 2-C]

[Formula 2-D]

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

R1, R2, p, q, L3, L4, L6, Ar3, Y1 and Y2 are the same as defined in Formula 2,

R3 is hydrogen; heavy hydrogen; Silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted ester group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

s is an integer from 0 to 4.

According to one embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

According to another exemplary embodiment, R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 40 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group having 1 to 20 carbon atoms; Or an aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, R1 to R3 are hydrogen.

In one embodiment of the present specification, L3 and L4 are the same as or different from each other, and each independently an substituted or unsubstituted alkylene group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

According to an exemplary embodiment of the present specification, L3 and L4 are the same as or different from each other, and each independently substituted or unsubstituted alkylene group having 1 to 40 carbon atoms; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

According to another exemplary embodiment, L3 and L4 are the same as or different from each other, and each independently an alkylene group having 1 to 40 carbon atoms; An arylene group having 6 to 60 carbon atoms; Or a heteroarylene group having 2 to 60 carbon atoms.

In another exemplary embodiment, L3 and L4 are the same as or different from each other, and each independently an alkylene group having 1 to 20 carbon atoms; An arylene group having 6 to 20 carbon atoms; Or a heteroarylene group having 2 to 20 carbon atoms.

According to one embodiment of the present specification, L3 and L4 are the same as or different from each other, and each independently an arylene group having 6 to 20 carbon atoms.

According to another exemplary embodiment, L3 and L4 are phenylene groups.

In one embodiment of the present specification, L3 and L4 are the same as or different from each other, and each independently an alkylene group having 1 to 20 carbon atoms.

In another exemplary embodiment, L3 and L4 are a methylene group, an ethylene group, or a propylene group.

In another exemplary embodiment, L3 and L4 are methylene groups.

In one embodiment of the present specification, Y1 and Y2 are the same as or different from each other, and each independently a thermosetting group or a photosetting group.

In one embodiment of the present specification, L6 is a substituted or unsubstituted arylene group having 6 to 60 carbon atoms.

According to an exemplary embodiment of the present specification, L6 is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

In another exemplary embodiment, L6 is an arylene group having 6 to 20 carbon atoms.

In another exemplary embodiment, L6 is a phenylene group; Biphenylene group; Terphenylene group; Naphthylene group; Or a substituted or unsubstituted fluorenylene group.

According to another exemplary embodiment, L6 is a phenylene group; Or a biphenylene group.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, Ar3 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

In another exemplary embodiment, Ar3 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In another exemplary embodiment, Ar3 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthyl group; Or a substituted or unsubstituted fluorenyl group.

According to another exemplary embodiment, Ar3 is a phenyl group unsubstituted or substituted with an alkyl group, an arylamine group, or a heteroaryl group; A biphenyl group unsubstituted or substituted with an alkyl group, an arylamine group, or a heteroaryl group; A naphthyl group unsubstituted or substituted with an alkyl group, an arylamine group, or a heteroaryl group; Or a fluorenyl group unsubstituted or substituted with an alkyl group, an arylamine group, or a heteroaryl group.

According to another exemplary embodiment, Ar3 is a phenyl group substituted with a phenyl group, a biphenyl group, a naphthyl group, a 9,9-dimethylfluorenyl group, a diphenylamine group, or a phenyl group substituted with a carbazole group.

In one embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

In another exemplary embodiment, Ar4 and Ar5 are the same as or different from each other, and each independently substituted or unsubstituted phenyl group, substituted or unsubstituted, biphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted It is a substituted fluorenyl group, a substituted or unsubstituted dibenzofuran group, a substituted or unsubstituted dibenzothiophene group, or a substituted or unsubstituted carbazole group.

In another exemplary embodiment, Ar4 and Ar5 are the same as or different from each other, and each independently a phenyl group, a phenyl group substituted with a vinyl group, a phenyl group substituted with an isopropenylphenylamine group, or a phenyl group substituted with a phenylpyridylamine group, Phenyl group substituted with diphenylamine group, phenyl group substituted with carbazole group, biphenyl group, biphenyl group substituted with diphenylamine group, biphenyl group substituted with 9,9-dimethylfluorenylphenylamine group, naphthyl group, dibenzofuran group , Dibenzothiophene group, N-phenylcarbazole group, N-ethylcarbazole group, or 9,9-dimethylfluorenyl group.

According to an exemplary embodiment of the present invention, the compound of Formula 2 may be represented by any one of the following structural formulas.

The compound according to an exemplary embodiment of the present specification may be prepared by a manufacturing method described later.

For example, the compound of Formula 1 may be prepared as in the following scheme. Substituents can be combined by methods known in the art, and the type, location, or number of substituents can be varied according to techniques known in the art.

<Synthesis example>

Synthesis Example 1. Synthesis Example of Formula 1

Synthesis of 2,2'-(5'-chloro-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(1,3-dioxolane) (Compound 2)

[Scheme 1]

1,3-dibromo-5-chlorobenzene (10g, 36.98mmol) and (4-formylphenyl)boronic acid[() in a 1L round bottom flask (RBF) 4-formylphenyl)boronic acid] (11.4g, 75.8mmol), potassium carbonate (15.33g, 110.09mmol) was added, and 200ml of toluene, 100ml of ethanol, and 100ml of water were added and dissolved while stirring to 80°C. When the reactants were completely dissolved in the solvent, tetrakis(triphenylphosphine)palladium (2.14g, 1.849mmol) was added and reacted for 24 hours. After lowering the temperature and extracting with EA and water, the residual water was removed with MgSO ₄ , stirred in charcoal, passed through silica gel, the solvent was removed, and white crystals were obtained using THF and methanol. (Yield: 62%)

5'-chloro-[1,1':3',1''-terphenyl]-4,4''-dicarbaldehyde obtained above (5'-chloro-[1,1':3',1''-terphenyl]-4,4''-dicarbaldehyde) (Compound 1) (7.35 g, 22.91 mmol) was added to 250 mL RBF, 100 ml of toluene was added, and TsOH (0.04 g, 0.23 mmol) and ethylene glycol (5.1 ml, 91.64) mmol) was added and dean-stark was installed to react for 24 hours while draining water at high temperature. After quenching with NaHCO ₃ and work-up with EA and Brine, residual water was removed with MgSO ₄ , filtered and the solvent was removed. Column with EA:Hex=1:5, precipitated with EA and Hex, and filtered to obtain a white solid. (Yield: 53%) H-NMR results of compound 2 synthesis are shown in FIG. 3.

[Scheme 2]

N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (N-([1,1'-biphenyl]-4-yl)- 9,9-dimethyl-9H-fluoren-2-amine) (6.5g, 17.98mmol), compound 2 (7.0g, 17.12mmol), NaOtBu (6.58g, 68.48mmol) was added to 250mL RBF for N ₂ purging. After 60 ml of toluene bubbling with Nitrogen was added and heated to 90°C to dissolve the starting materials, Pd(PtBu ₃ ) ₂ (0.437g, 0.86mmol) was added, heated to 120°C, stirred for 2 hours, and then temperature Lowered to work-up with EA and water. The residual water was removed with MgSO ₄ and stirred on a charcoal, passed through a silica gel pad, and then the solvent was removed and column with EA:Hex=1:5 to obtain a white solid (Compound 3). (Yield 84%)

Compound 3 (7.5 g, 10.19 mmol) was dissolved in 100 ml of THF, 10 ml of water and 1N HCl (1.3 ml, 1.01 mmol) were added and stirred for 3 hours while refluxing at 70°C. As the reaction progressed, it was observed that a fluorescent yellow solid precipitated, the temperature was lowered, and the fluorescent yellow solid was immediately filtered with THF to dry in a vacuum oven at 50°C for 24 hours to obtain a compound 4 of 99.9% purity. (Yield: 86%)

Weigh CH ₃ PPh ₃ Br (10.96 g, 30.68 mmol) vacuum dried at 50°C in 500 mL RBF, purify N ₂ , inject 350 ml of distilled THF, and 2.5M n-BuLi (11.2 ml, 27.9) in an ice bath. mmol) was dropped and stirred for about 30 minutes to produce a product. The temperature of the bath was again set to 0°C, and compound 4 was added to carry out the olefination reaction. At this time, Compound 4 was put in a solid state because the solubility is not very good, and the reaction time was extended overnight. After confirming that the reaction was over, it was terminated with water to work-up with EA and Brine, and the residue was removed with Na ₂ SO ₄ and the solvent was blown to add TEA to deactivation silica gel and load it as a solid to EA:Hex=1:250. Flash column. After removal of the solvent, recrystallization using MC and EA gave a white solid (Formula 1-1). (Yield: 27%)

Formula 1-5 could also be obtained in the same manner using the starting material.

The MS spectra for confirming Chemical Formulas 1-1 and 1-5 are shown in FIGS. 3 and 4, respectively.

The compound (Z) of Formula 1 is converted into a cation (Z ⁺ ) or a cation radical (Z ^+. ) by the electron-accepting compound. In this process, the compound of Formula 1 may be entirely cationized or cationic radicalized. In addition, in the above process, some of the compounds of Formula 1 may be converted into a cation or a cationic radical, and some may remain in the form of a compound (Z) of Formula 1.

In addition, this specification is Z ⁺ X ^- or Z ^+. It provides a coating composition comprising a compound represented by X ^- .

In another exemplary embodiment, the coating composition may include a compound (Z) of Formula 1 that is not cationized or cation radicalized in the process of preparing a cation (Z ⁺ ) or a cation radical (Z ^+. ) ^. have.

According to an exemplary embodiment of the present specification, the coating composition is Z ⁺ X ^- or Z ^+. X ^- a compound represented by; And an arylamine compound represented by Formula 2, wherein the weight ratio of the compound and the arylamine compound is 90:10 to 50:50, and may be 85:15 to 60:40, and 80:20 to 70:30. Can be

In one embodiment of the present specification, the coating composition further includes a solvent.

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

In one embodiment of the present specification, the solvent includes, for example, chlorine-based solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, and o-dichlorobenzene; Ether-based solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon-based 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; Polyvalent values of 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 derivatives thereof; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; Sulfoxide-based solvents such as dimethyl sulfoxide; and amide-based solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; Benzoate solvents such as methyl benzoate, butyl benzoate, and 3-phenoxy benzoate; A solvent such as tetralin is exemplified, but a 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 exemplary embodiment, the solvent may be used alone or as a mixture of two or more solvents.

In another exemplary 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 exemplary 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 exemplary 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 photo polymerization initiator.

As the thermal polymerization initiator, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl per Oxide, bis-3,5,5-trimethyl hexanoyl peroxide, lauryl peroxide, benzoyl peroxide, p-crol 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-dit-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-butyroxycybareric acid n-butyl ester, 2,2-bis(4 ,4-t-butyl peroxy cyclohexyl)propane, t-butylperoxyisobutylate, dit-butyl peroxy hexahydro terephthalate, t-butyl peroxy-3,5,5-trimethylhexaate, t -Peroxides such as butyl peroxybenzoate and dit-butyl peroxy trimethyl adipate, or azo systems such as azobis isobutylnitrile, azobisdimethylvaleronitrile, and azobis cyclohexyl nitrile, but are not limited thereto. .

Examples of the photopolymerization initiator include diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one,1-hydroxy-cyclohexyl-phenyl-ketone,4-(2-hydroxyethoxy ) Phenyl-(2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone- 1,2-hydroxy-2-methyl-1- Phenyl propan-1-one,2-methyl-2-morpholino(4-methyl thiophenyl) propan-1-one,1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) Acetophenone-based or ketal-based photopolymerization initiators such as oxime, benzoin, benzoin methyl ether, benzoin ether ether, benzoin isobutyl ether, benzoin isopropierate, benzoin, etc. Ether-based photopolymerization initiators, benzophenone-based photopolymerization initiators such as benzophenone, 4-hydroxybenzophenone, 2-benzoyl naphthalene, 4-benzoyl biphenyl, 4-benzoyl phenyl ether, acrylate benzophenone, 1,4-benzoyl benzene, and the like. Thioxanthone-based photopolymerization such as, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, etc. As an initiator and other photoinitiators, ethyl anthraquinone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide, bis(2,4,6-trimethylbenzoyl ) Phenyl phosphine oxide, bis(2,4-dimethoxy benzoyl)-2,4,4-trimethyl pentylphosphine oxide, methyl phenyl glyciokistelyl, 9,10-phenanthrene, acridine compound, And triazine-based compounds and imidazole-based compounds. Moreover, what has a photopolymerization promoting effect can also be used individually or in combination with the said photoinitiator. Examples include triethanolamine, methyl diethanol amine, ethyl 4-dimethylamino benzoate, isoamyl 4-dimethylamino benzoate, ethyl benzoate (2-dimethylamino), 4,4'-dimethylaminobenzophenone, and the like, It is not limited.

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

In one embodiment of the present specification, the cathode; Anode; And one or more organic material layers provided between the cathode and the anode, and one or more layers of the organic material layers are formed using the coating composition.

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 layer that simultaneously performs hole transport and hole injection.

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

In another exemplary embodiment, the organic material layer formed using the coating composition is a light-emitting layer, and the light-emitting layer includes a compound containing cations and/or cation radicals and monovalent anions of the arylamine derivative as a host of the light-emitting layer.

In one embodiment of the present specification, the organic light emitting device is a hole injection layer, a hole transport layer. It further includes at least 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 another exemplary embodiment, the organic light emitting device may be an organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

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

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

For example, the structure of the organic light emitting device according to the 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 Figure 1, the hole injection layer 301, the hole transport layer 401, the light emitting layer 501 is a coating composition comprising a compound containing a cation and / or cation radical and monovalent anion of the arylamine derivative represented by the formula (1) It is formed using.

1 illustrates an organic light emitting device and 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 is in the art except that at least one layer of the organic material layer is formed using a coating composition comprising a compound containing a cation and/or a cationic radical and a monovalent anion of the arylamine derivative. It can be made from known materials and methods.

For example, the organic light emitting device of the present specification can be manufactured by sequentially laminating an anode, an organic material layer, and a cathode on a substrate. At this time, an anode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. And, it can be prepared by forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be formed 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 exemplary embodiment, the organic material 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 one embodiment of the present specification has a structural property, a solution process is suitable and can be formed by a printing method, and thus has an economical effect in time and cost when manufacturing the device.

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

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

In the case of including the heat treatment or the light treatment step in the step of forming the organic layer formed using the coating composition, a plurality of arylamine derivatives included in the coating composition may form a crosslink to provide an organic layer having a thinned structure. . In this case, it can be prevented 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 material layer formed using the coating composition is formed by including a heat treatment or photo-treatment step, resistance to a solvent is increased, and a solution deposition and crosslinking method can be repeatedly performed to form a multi-layer, and stability is increased to increase the Life characteristics can be increased.

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

In one embodiment of the present specification, as the polymer binder, it is preferred that the charge transport is not extremely inhibited, and that the absorption of visible light is not strong is preferably used. Examples of the polymer binder include poly(N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly(p-phenylenevinylene) and derivatives thereof, poly(2,5-thienylenevinylene), and And derivatives thereof, polycarbonate, polyacrylate, polymethylacrylate, polymethylmethacrylate, polystyrene, polyvinyl chloride, polysiloxane, and the like.

In addition, the compound according to an exemplary embodiment of the present specification may include an amine group, the compound alone may be included in the organic material layer, or the coating composition containing the compound may be thinned through heat treatment or light treatment, and mixed with other monomers. One coating composition can be used as a copolymer. In addition, a copolymer or a mixture may be included using a coating composition mixed with other polymers.

The anode material is preferably a material having a large work function so that hole injection 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, 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 : Combination of metal and 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 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 is a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

The hole injection layer is a layer for injecting holes from an electrode, and has the ability to transport holes as a hole injection material, has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is generated in the light emitting layer A compound that prevents migration of the excitons to the electron injection layer or the electron injection 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 material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic matter, hexanitrile hexaazatriphenylene-based organic matter, quinacridone-based organic matter, and perylene-based , Organic 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 holes from the hole injection layer to the light emitting layer. As the hole transport material, the hole is transported from the anode or the hole injection layer and transported to the light emitting layer. 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, but are not limited thereto.

As the light-emitting material, a material capable of emitting light in the visible region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material 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-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly(p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more 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. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. Further, examples of the metal complex include an iridium complex, a platinum complex, and the like, but are not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. Do. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including 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 that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, 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, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.

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

The organic light emitting device according to the present specification may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.

Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

< Manufacturing example >

Manufacturing example 1. Preparation of Chemical Formula 3-1

[Formula 1-1] [Formula 3-1]

Add Formula 1-1 (160mg, 0.25mmol) to 100mL RBF and add 50mL of Dichlorooromethane and stir. After the formula 1-1 is sufficiently dissolved, 4-isopropyl-4'-methyl diphenyl iodonium tetrakis(pentafluorophenyl) borate (40mg, 0.04mmol) is added and refluxed and heated to 50°C. After stirring for 40 hours, after cooling to room temperature, the solvent is concentrated and removed by vacuum. 10 mL of dichloromethane was added to completely dissolve the mixture, followed by stirring, 50 mL of methanol was added, and after stirring for 1 hour, the residue was recovered by filtration to obtain an off-white solid (84 mg) containing Formula 3-1. Got.

2 is a diagram showing an MS spectrum of a cation and an anion of Formula 3-1.

Manufacturing example 2. Preparation of Chemical Formula 3-43

[Formula 1-25] [Formula 3-43]

Add formula 1-25 (160mg, 0.23mmol) to 100mL RBF and add 50mL of dichlorooromethane and stir. After the formula 1-25 is sufficiently dissolved, 4-isopropyl-4'-methyl diphenyl iodonium tetrakis(pentafluorophenyl) borate (40mg, 0.04mmol) is added and refluxed and heated to 50°C. After stirring for 24 hours, after cooling to room temperature, the solvent is concentrated and removed by vacuum. 15 mL of dichloromethane was added to completely dissolve the mixture, followed by stirring, 70 mL of methanol was added, and after stirring for 1 hour, the residue was recovered by filtration to obtain a green powder solid (78 mg) containing the formula 3-43. Got.

Manufacturing example 3. Preparation of Formula 3-12

[Formula 1-5] [Formula 3-12]

Add formula 1-5 (400mg, 0.47mmol) to 100mL RBF and add 100mL of dichlorooromethane and stir. After the formula 1-5 is sufficiently dissolved, silver hexafluoroantimonate (100 mg, 0.29 mmol) is added and refluxed and heated to 50°C. After stirring for 24 hours, the mixture was cooled to room temperature, passed through a celite pad, and vacuum-dried dichloromethane in an evaporator to obtain a black red powder (375 mg) containing 3-12.

Manufacturing example 4. Concrete compound of formula (2) Synthetic example

[Formula 2-A-1]

2-bromo-9H-fluorene (5g, 20.4mmol) was dissolved in tetrahydrofuran (200ml), sodium hydroxide (sodium hydroxide, 1.67g, 41.8mmol), benzyl trimethyl ammonium chloride (465mg, 2.04mmol) Put it, stir at room temperature for 1 hour, add 1-(chloromethyl)-4-vinylbenzene (8.29g, 48.9mmol) at 0°C, raise to room temperature, and stir for 16 hours under a nitrogen atmosphere. The reaction is terminated by adding 1N HCl (10 ml). After extracting the organic layer using methylene chloride, the column was separated with a solvent of normal-hexane/ethyl acetate=1:20 and dried under vacuum to obtain the formula 2-A-1. (7,2g, yield 74%)

MS: [M+H] ⁺ =477

[Formula 2-A-2]

2-Bromo-9H-fluorene (20g, 1eq, 81.592mmol) (4-chlorophenyl)boronic acid (15.31g, 97.910mmol), Pd(PPh ₃ ) ₄ (0.942g, 0.816mmol), K ₂ After adding 500 ml of tetrahydrofuran (THF) to CO ₃ (33.83 g, 244.776 mmol), the mixture was refluxed at 80° C. for 16 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted using methylene chloride (MC). Recrystallization using methylene chloride and ethanol to prepare an intermediate of Formula 2-A-2. (18 g, 80% yield) MS: [M+H] ⁺ =277

NaOH (2.96g, 74.071mmol) and benzyltrimethylammonium chloride (820mg, 3.613mmol) were dissolved in 400ml of tetrahydrofuran (THF) in this intermediate (10g, 36.132mmol), and 4-chloromethylstyrene (14.09g, 3.613mmol) ) Was added and stirred at room temperature for 16 hours, and then 1N HCl (10 ml) was added to terminate the reaction. After extracting the organic layer using methylene chloride, the column was separated with a solvent of normal-hexane/ethyl acetate-1:25, followed by vacuum drying to obtain the formula 2-A-2 (10 g, yield 54%).

MS: [M+H] ⁺ =509

[Formula 2-A-1] [Formula 1-1-1]

Formula 2-A-1 (4g, 8.378mmol), (4-(diphenylamino)phenyl)boronic acid (2.9g, 10.054mmol) was dissolved in tetrahydrofuran (THF) (200ml), followed by potassium carbonate (3.48 g, 25.134mmol), Pd(PPh ₃ ) ₄ (986mg, 0.838mmol) was added and refluxed at 80°C for 17 hours. The organic layer was extracted using methylene chloride. The reaction solution was concentrated, dissolved in methylene chloride (MC), and recrystallized with ethyl alcohol (EtOH) to obtain Chemical Formula 1-1-1 (3 g, yield 56%). MS: [M+H] ⁺ = 642

Example 1. Preparation of coating composition

Example 1-1.

The coating composition, as described in Table 1, Z ⁺ of the present invention satisfying the p-doping role and the host role at the same time ^. X ^- type compound of formula 3-1; Formula 1-1-1 compound for improving coating properties; And organic solvents (cyclohexanone). In addition, the prepared coating composition was formed by spin coating as described in Table 1, and the film was fired at 250°C or lower.

Example 1-2.

The coating composition, as described in Table 1, Z ⁺ of the present invention satisfying the p-doping role and the host role at the same time ^. X ^- type compound of formula 3-43; Formula 1-1-1 compound for improving coating properties; And organic solvents (cyclohexanone). In addition, the prepared coating composition was formed by spin coating as described in Table 1, and the film was fired at 250°C or lower.

Example 1-3

The coating composition, as described in Table 1, Z ⁺ of the present invention satisfying the p-doping role and the host role at the same time ^. X ^- type compound of formula 3-12; Formula 1-1-1 compound for improving coating properties; And organic solvents (cyclohexanone). In addition, the prepared coating composition was formed by spin coating as described in Table 1, and the film was fired at 250°C or lower.

Comparative example 1-1.

In Example 1-1, the compound of Formula 1-1-1 for improving coating properties was not used, and only the compound of Formula 3-1 was used.

Example Compound 1 Compound 2 Compound 1
: Compound 2 Spin speed (rpm)/
Time(s) Firing temperature
(℃) Example 1-1 Formula 3-1 Chemical formula
1-1-1 80:20 1000/ 60 230/ 30 Example 1-2 Formula 3-43 Chemical formula
1-1-1 80:20 1000/ 60 230/ 30 Example 1-3 Formula 3-12 Chemical formula
1-1-1 90:10 1000/ 60 230/ 30 Comparative Example 1-1 Formula 3-1 - 100:0 1000/ 60 230/ 30

Example 2. Thin film maintenance experiment

The coating composition of Example 1-1 was spin-coated at a spin speed of 1000 rpm for 60 seconds, and then heat-sintered on a hot plate at 230° C. for 30 minutes to form a thin film.

Thereafter, after soaking for 10 minutes in toluene, the result was measured by UV-Visible spectoscopy, confirming that the film retention rate was 100%.

Example 3. Manufacturing of organic light emitting device

Example 3-1.

A glass substrate on which ITO (indium tin oxide) was thinned to 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 washing was repeated for 10 minutes by repeating it twice with distilled water. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol and acetone for 30 minutes each, and after drying, the substrate was transferred to a glove box.

The coating composition of Example 1-1 described in the table below was spin coated on the prepared ITO transparent electrode to form a hole injection layer having a thickness of 300 mm 3, and the coating composition was cured for 30 minutes on a hot plate under an N ₂ atmosphere. Thereafter, after transferring to a vacuum evaporator, the following compound A was vacuum-deposited on the hole injection layer to form a hole transport layer.

[Compound A] [Compound B]

[Compound C] [Compound D]

Subsequently, on the hole transport layer, Compound B and Compound C were vacuum-deposited to a thickness of 300 Pa at a concentration of 8% to form a light emitting layer. The compound D was vacuum-deposited to a thickness of 200 Pa on the light emitting layer to form an electron injection and transport layer. A cathode was formed by sequentially depositing aluminum with a thickness of 12 MPa and a thickness of 2000 MPa on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å/sec, the LiF of the cathode was maintained at a deposition rate of 0.3 알루미늄/sec, and the aluminum was 2 2/sec, and the vacuum degree during deposition was 2x10 ^-7 to 5x10. ^-6 torr was maintained.

Example 3-2.

An organic light emitting device was manufactured in the same manner as in Example 3-1, except that the hole injection layer in Example 3-1 was used instead of the coating composition of Example 1-2 instead of the coating composition of Example 1-1. .

Example 3-3.

An organic light emitting device was manufactured in the same manner as in Example 3-1, except that the hole injection layer in Example 3-1 was used instead of the coating composition of Example 1-3 in Example 1-1. .

Comparative example 3-1.

An organic light emitting device was manufactured in the same manner as in Example 3-1, except that the hole injection layer in Example 3-1 was used instead of the coating composition of Example 1-1 and the coating composition of Comparative Example 1-1.

Table 2 shows the results of measuring the driving voltage and the luminous efficiency of the organic light-emitting device manufactured by the above-described method at a current density of 10 mA/cm ² .

Device structure Driving voltage (V) Driving current
(mA/ cm ² ) Current efficiency
(cd/ A) Example 3-1 5.19 10 4.34 Example 3-2 5.23 10 4.25 Example 3-3 4.99 10 4.32 Comparative Example 3-1 5.87 10 3.01

As a result of Table 2, a compound comprising a cation or a cationic radical and a monovalent anion of the compound represented by Formula 1 according to an exemplary embodiment of the present specification; And an arylamine compound represented by Chemical Formula 2, excellent solubility in an organic solvent, and easy to prepare a coating composition, thereby forming a uniform coating layer when applied to an organic light emitting device, and having excellent film retention Was confirmed.

In addition, a compound containing a cation or a cationic radical and a monovalent anion of the compound represented by Formula 1; And when manufacturing an organic light emitting device with a coating composition comprising an arylamine compound represented by the formula (2), it was confirmed that the current efficiency is low because the film properties are not better than Comparative Example 3-1 does not include the compound corresponding to the formula (2) Can be.

The present invention is not limited to this, and it is possible to carry out various modifications within the scope of the claims and detailed description of the invention, and this also belongs to the scope of the invention.

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

Claims (11)

Z ⁺ X ^- or Z ^+. X ^- a compound represented by; And a coating composition comprising an arylamine compound represented by the formula (2),
Z is a compound represented by Formula 1 below,
The X ^- is a monovalent anion coating composition:
[Formula 1]

In Chemical Formula 1,
L1 and L2 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
X1 and X2 are the same as or different from each other, and each independently hydrogen; Or a functional group crosslinkable by heat or light, at least one of X1 being a functional group crosslinkable by heat or light,
Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted arylamine group; Or it may be a substituted or unsubstituted heteroaryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,
a is an integer from 1 to 5,
b is an integer from 0 to 5,
m and n are each an integer from 0 to 4,
When m, n, a, and b are each 2 or more, the substituents in parentheses are the same or different from each other,
[Formula 2]

In Chemical Formula 2,
L3 to L6 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted alkylene group; A substituted or unsubstituted cycloalkylene group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted ester group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Ar3 is the same as or different from each other, and each independently substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Or a substituted or unsubstituted aryl group,
Y1 and Y2 are the same as or different from each other, and each independently hydrogen; Or a functional group capable of crosslinking by heat or light,
A is hydrogen; Or NRR',
R and R'are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
p is an integer from 0 to 4,
q is an integer from 0 to 3,
When p and q are each 2 or more, the substituents in parentheses are the same or different from each other. The method according to claim 1,
The formula 1 is a coating composition represented by any one of the following formulas 3 and 4:
[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,
X1, X2, a, b, m and n are the same as defined in Formula 1,
R4 and R5 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or may combine with an adjacent group to form a substituted or unsubstituted ring,
R11, R12, R21 and R22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted arylamine group; Or it may be a substituted or unsubstituted heteroaryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,
p2, q1 and q2 are each an integer from 0 to 5,
p1 is an integer from 0 to 7,
When p1, p2, q1 and q2 are each 2 or more, the substituents in parentheses are the same or different from each other. The method according to claim 1,
The coating composition capable of crosslinking by heat or light is one of the following structures:

In the above structure,
R3 is hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. The method according to claim 1,
The Z is a coating composition that is any one selected from the following formulas 1-1 to 1-52:

The method according to claim 1,
The X ^- is a coating composition that is any one selected from the following formulas 2-1 to 2-12:

The method according to claim 1,
Z ⁺ X ^- or Z ^+. The compound represented by X ^- is any one selected from the following Chemical Formulas 3-1 to 3-60:

Cathode;
An anode provided to face the cathode; And
It includes at least one organic material layer provided between the cathode and the anode,
At least one layer of the organic layer comprises an organic light-emitting device comprising a cured product of the coating composition of claim 1. The method according to claim 7,
The cured product of the coating composition is an organic light emitting device in which the coating composition is cured by heat treatment or light treatment. The method according to claim 7,
The organic material layer containing the cured product of the coating composition is a hole transport layer, a hole injection layer or an organic light emitting device that is a layer that simultaneously transports holes and holes. 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,
The step of forming the organic material layer comprises forming one or more organic material layers using the coating composition of claim 1. The method according to claim 10,
The step of forming an organic material layer formed using the coating composition is
Coating the coating composition on the cathode or anode; And
A method of manufacturing an organic light emitting device comprising the step of heat-treating or photo-treating the coated coating composition.

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