KR102166014B1 - Compound, coating compositions comprising the same, and organic light emitting device using the same - Google Patents

Abstract

The present invention relates to a compound of Formula 1, a coating composition comprising the compound, and an organic light emitting device formed using the compound.

Description

A compound, a coating composition containing the same, and an organic light-emitting device using the same {COMPOUND, COATING COMPOSITIONS COMPRISING THE SAME, AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME}

The present specification relates to a compound, a coating composition including the compound, and an organic light emitting device formed using the compound. This specification claims the benefit of the filing date of No. 10-2017-0018789 filed with the Korean Intellectual Property Office on February 10, 2017, all of the contents of which are incorporated herein.

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 material layer is placed between the anode and the cathode, when current is applied between the two electrodes, electrons and holes are injected into the organic material layer from the cathode and the anode, respectively. The electrons and holes injected 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 generally be composed of an organic material layer including a cathode and an anode, and an organic material layer positioned therebetween, for example, a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.

Materials used in organic light-emitting devices are pure organic materials or complex compounds in which organic materials and metals form a complex, and depending on the use, hole injection materials, hole transport materials, light-emitting materials, electron transport materials, electron injection materials, etc. Can be divided into Here, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material that is easily oxidized and has an electrochemically stable state upon oxidation is mainly used. Meanwhile, as an electron injection material or an electron transport material, an organic material having an n-type property, that is, an organic material that is easily reduced and has an electrochemically stable state upon reduction is mainly used. As the light-emitting layer material, a material having both p-type and n-type properties, that is, a material having a stable form in both oxidation and reduction states, is preferable, and a material with high luminous efficiency that converts excitons to light when formed is preferred. desirable.

In addition to the above-mentioned, 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 occurs due to the movement of electric charges in the organic light-emitting device. NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine), which is currently mainly used as a material for the hole transport layer, is free Since the transition temperature has a value of 100°C or less, there is a problem that it is difficult to use in an organic light-emitting device requiring a high current.

Second, in order to obtain a high-efficiency organic light-emitting device capable of low voltage driving, holes or electrons injected into the organic light-emitting device must be smoothly transferred to the light-emitting layer, and holes and electrons injected into the light-emitting layer must not escape out of the light-emitting layer. For this, the material used in the organic light emitting device must have an appropriate band gap and an HOMO (Highest Occupied Molecular Orbita) or LUMO (Lowest Unoccupied Molecular Orbital) energy level. In the case of PEDOT:PSS (poly(3,4-ethylenedioxydiophene) polystyrene sulfonate) used as a hole transport material in an organic light emitting device manufactured by the current solution coating method, the LUMO energy level of the organic material used as the light emitting layer material Compared to the LUMO energy level is low, it is difficult to manufacture a high-efficiency, long-life organic light-emitting device.

In addition, materials used in organic light-emitting devices should have excellent chemical stability, charge mobility, and interfacial properties with electrodes or adjacent layers. That is, the material used in the organic light-emitting device should be less deformed by moisture or oxygen. In addition, by having an appropriate hole or electron mobility, the density of holes and electrons in the emission layer of the organic light-emitting device should be balanced to maximize the formation of excitons. In addition, for the stability of the device, the interface with the electrode including metal or metal oxide must be improved.

Therefore, in the technical field, the development of organic materials having the above requirements is required.

Korean Patent Publication No. 2012-0112277

The present specification provides a compound, a coating composition including the same, and an organic light emitting device formed using the compound.

The present specification provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1, X1 and X2 are the same as or different from each other, and each independently, a direct bond; -O-; Or an arylene group,

Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group,

Ar3 to Ar5 are the same as or different from each other, and each independently, is a substituted or unsubstituted aryl group, Ar6 is a direct bond or a substituted or unsubstituted arylene group,

m is 1 or 2,

When m is 1, n is 0 or 1, when m is 2, n is 0,

When m is 1, Ar7 is hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted arylamine group, and when m is 2, Ar7 is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent arylamine group,

When Ar6 is a direct bond, Ar7 is not hydrogen or a direct bond,

Ar3 and Ar4 can be combined to form a ring, Ar5 and Ar6 can be combined to form a ring,

R2 to R5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

o and p are each an integer of 0 to 4, r is an integer of 0 to 3,

When n is 0, q is an integer of 0 to 4, when n is 1, q is an integer of 0 to 3, and when o, p, q, or r is 2 or more, the substituents in parentheses are the same or different, and .

Y1 and Y2 are each independently selected from the following structural formula,

In the above structural formula, R1 is hydrogen or a substituted or unsubstituted alkyl group.

In addition, the present specification provides a coating composition comprising the compound described above.

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

The compound according to an exemplary embodiment of the present specification contains a functional group that is polymerized by heat or light, and when sufficient heat or light is applied after film formation, the solubility in the solvent for the process is lowered, and the exemplary embodiment of the present specification The organic light emitting device with reproducibility can be manufactured because the compound according to the method is not washed away or the film properties are not changed.

The compound according to an exemplary embodiment of the present specification is an ionic single molecule, which is dissolved in a solvent and applied through a solution process, and then heat treatment or UV (ultraviolet) treatment may be used to form a film.In particular, the compound according to the present specification is 200 When cured before and after °C, low driving voltage, high luminous efficiency, and high lifespan characteristics can be provided.

1 shows an example of an organic light-emitting device according to an exemplary embodiment of the present specification.
2 shows HPLC (high performance liquid chromatography) data and MS (mass spectrum) data of Compound 1.
3 is HPLC data and MS data of Compound 3.
4 shows HPLC data and MS data of Compound 4.
5 shows HPLC data and MS data of Compound 5.
6 is DSC (Differential Scanning Calorimetry) data of Compound 3.
7 is DSC data of Compound 4.
8 is DSC data of Compound 5.
9 is an NMR (nuclear magnetic resonance) spectrum of Compound 3.
10 is data of the film retention rate of Comparative Compound 2.

Hereinafter, the present specification will be described in more detail.

When a member is referred to herein as being “on” another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In the entire specification of the present application, the term "combination of these" included in the expression of the Makushi format refers to one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Makushi format, and the component It means to include one or more selected from the group consisting of.

An exemplary embodiment of the present specification provides a compound represented by Chemical Formula 1.

In an exemplary embodiment of the present specification, the compound of Formula 1 is preferably a compound having solubility in a suitable organic solvent.

In the present specification, the term "curing group" may mean a reactive substituent that crosslinks compounds by exposure to heat and/or light. Crosslinking may be generated by linking the radicals generated by decomposition of a carbon-carbon multiple bond or cyclic structure by heat treatment or light irradiation.

In an exemplary embodiment of the present specification, the curing group has any one of the following structures.

In the above structural formula, R1 is hydrogen or a substituted or unsubstituted alkyl group.

In an exemplary embodiment of the present specification, R1 is hydrogen or an alkyl group.

In an exemplary embodiment of the present specification, R1 is hydrogen, a methyl group, or an ethyl group.

In an exemplary embodiment of the present specification, R1 is hydrogen or a methyl group.

In an exemplary embodiment of the present specification, a compound in which a curing group is substituted in a structure in which a linker is substituted with fluorene has an increase in reactivity of the elapsed period due to the linker, and orthogonality through post polymerization Can be secured.

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

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

Means a site bonded to another substituent or a bonding portion.

In the present specification, the term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent can be substituted, and 2 or more When substituted, two or more substituents may be the same or different from each other.

In the present specification, the term "substituted or unsubstituted" refers to hydrogen; heavy hydrogen; Halogen group; Alkyl group; Cycloalkyl group; Aryl group; Amine group; And a substituted or unsubstituted with one or more substituents selected from the group consisting of an arylamine group, or substituted or unsubstituted with two or more substituents connected among the aforementioned 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, branched chain or cyclic chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3- Dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2- Propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but these Is not limited to

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

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

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

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but it 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, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

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

및

,

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

And

,

Etc. However, it is not limited thereto.

The aryl group may be substituted with an alkyl group and may function as an arylalkyl group. The alkyl group may be selected from the above examples.

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

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above. Specific examples of the arylamine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methyl-phenylamine, 4-methyl-naphthylamine, 2-methyl-biphenylamine, 9-methyl-anthra There are senylamine, diphenyl amine group, phenyl naphthyl amine group, ditolyl amine group, phenyl tolyl amine group, carbazole, and triphenyl amine group, but are not limited thereto.

In the present specification, the heteroaryl group includes one or more atoms and heteroatoms other than carbon, and specifically, the heteroatom may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include thiophene group, furanyl group, pyrrolyl group, imidazolyl group, oxazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, triazolyl group, acridyl group, pyrida Genyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinolinyl group, indolyl group, Carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl Group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, phenothiazinyl group, benzoquinazolinyl group, indolofluorenyl group, indolocarbazolyl group, dibenzocarbazolyl group, benzoquinolinyl group, Benzonaphthofuranyl group, benzonaphthothiophene group, dibenzofuranyl group, phenoxazinyl group, and the like, but are not limited thereto.

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

In the present specification, the "adjacent" group means a substituent substituted on an atom directly connected to the atom where the corresponding substituent is substituted, a substituent positioned three-dimensionally closest to the corresponding substituent, or another substituent substituted on the atom where the corresponding substituent is substituted. I can. For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups to each other.

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

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 2 to 4.

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4, X1, X2, Y1, Y2, Ar1 to Ar7, R2 to R5 o, p, q, and r are the same as defined in Formula 1,

Ar8 is the same as the definition of Ar6 when m in Formula 1 is 2,

Ar9 is the same as the definition of Ar5 in Formula 1,

Ar10 is the same as the definition of Ar2 in Formula 1,

R6 to R9 are the same as the definition of R2 to R5 in Formula 1,

s is an integer of 0 to 3, t, u and v are each an integer of 0 to 3,

When s, t, u and v are 2 or more, the substituents in parentheses are the same as or different from each other,

X3 and X4 are the same as the definitions of X1 and X2 in Formula 1,

Y3 and Y4 are the same as the definitions of Y1 and Y2 in Chemical Formula 1.

In the exemplary embodiment of the present specification, Formula 1 is represented by any one of the following Formulas 2-1, 3-1, and 4-1.

[Formula 2-1]

[Formula 3-1]

[Formula 4-1]

In Formulas 2-1, 3-1 and 4-1, X1, X2, Y1, Y2, Ar1, Ar2, Ar5, and R2 to R5 are the same as defined in Formula 1,

q', r'and s'are each an integer of 0 to 3, q" and t'are each an integer of 0 to 4, and when q',q", r', s', t'are 2 or more, parentheses Substituents are the same as or different from each other, Ar13 to Ar18 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group,

Ar9 is the same as the definition of Ar5 in Formula 1,

Ar10 is the same as the definition of Ar2 in Formula 1,

Ar20 to Ar29 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group.

In the exemplary embodiment of the present specification, Ar13 to Ar18 are the same as or different from each other, and each independently an arylene group.

In the exemplary embodiment of the present specification, Ar13 to Ar18 are the same as or different from each other, and each independently a phenylene group.

In the exemplary embodiment of the present specification, Ar20 to Ar29 are the same as or different from each other, and each independently an aryl group.

In the exemplary embodiment of the present specification, Ar20 to Ar29 are the same as or different from each other, and each independently a phenyl group.

In the exemplary embodiment of the present specification, R6 to R9 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

In the exemplary embodiment of the present specification, X3 and X4 are the same as or different from each other, and each independently, a direct bond; -O-; Or an arylene group.

In an exemplary embodiment of the present specification, Y3 and Y4 are each independently selected from the following structural formula,

In the above structural formula, R10 is hydrogen or a substituted or unsubstituted alkyl group.

In the exemplary embodiment of the present specification, R10 is hydrogen or an alkyl group.

In the exemplary embodiment of the present specification, R10 is hydrogen, a methyl group, or an ethyl group.

In the exemplary embodiment of the present specification, R10 is hydrogen or a methyl group.

In the exemplary embodiment of the present specification, Ar8 is a direct bond or a substituted or unsubstituted arylene group.

In the exemplary embodiment of the present specification, Ar9 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted arylamine group.

In the exemplary embodiment of the present specification, Ar10 is a substituted or unsubstituted arylene group.

In the exemplary embodiment of the present specification, X1 and X2 are a direct bond or -O-.

In the exemplary embodiment of the present specification, X1 and X2 are direct bonds.

In the exemplary embodiment of the present specification, X1 and X2 are -O-.

또는

이다.In the exemplary embodiment of the present specification, Y1 and Y2 are

or

to be.

이다.In the exemplary embodiment of the present specification, Y1 and Y2 are

to be.

이다.In the exemplary embodiment of the present specification, Y1 and Y2 are

to be.

또는

이다. In the exemplary embodiment of the present specification, X1 and X2 are a direct bond or -O-, and Y1 and Y2 are

or

to be.

In the exemplary embodiment of the present specification, Ar3 to Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In the exemplary embodiment of the present specification, Ar3 to Ar5 are the same as or different from each other, and each independently is an aryl group unsubstituted or substituted with an arylamine group.

In the exemplary embodiment of the present specification, Ar3 to Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; Or a substituted or unsubstituted biphenyl group.

In the exemplary embodiment of the present specification, Ar3 to Ar5 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with an arylamine group; Or a biphenyl group unsubstituted or substituted with an arylamine group.

In the exemplary embodiment of the present specification, Ar3 to Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group with a substituted or unsubstituted arylamine group; Or a substituted or unsubstituted biphenyl group unsubstituted or substituted with a substituted or unsubstituted arylamine group.

In the exemplary embodiment of the present specification, Ar3 to Ar5 are the same as or different from each other, and each independently a diphenylamine group, a diphenylamine group substituted with a diphenylamine group, and a diphenylamine group substituted with a diphenylamine group. A phenyl group unsubstituted or substituted with a diphenylamine group; Or a diphenylamine group, a diphenylamine group substituted with a diphenylamine group, a diphenylamine group substituted with a diphenylamine group, or a biphenyl group unsubstituted with an arylamine group substituted or unsubstituted with a diphenylamine group.

In the exemplary embodiment of the present specification, Ar6 is a direct bond. Or a substituted or unsubstituted C 6 to C 30 arylene group.

In the exemplary embodiment of the present specification, Ar6 is a direct bond, or an arylene group unsubstituted or substituted with an arylamine group.

In the exemplary embodiment of the present specification, Ar6 is a direct bond; A substituted or unsubstituted phenylene group; Or a substituted or unsubstituted biphenylylene group.

In the exemplary embodiment of the present specification, Ar6 is a direct bond; A phenylene group unsubstituted or substituted with an arylamine group; Or a biphenylene group unsubstituted or substituted with an arylamine group.

In the exemplary embodiment of the present specification, Ar6 is a direct bond; A phenylene group unsubstituted or substituted with a substituted or unsubstituted arylamine group; Or a substituted or unsubstituted biphenylylene group with a substituted or unsubstituted arylamine group.

In the exemplary embodiment of the present specification, Ar6 is a direct bond; A phenylene group unsubstituted or substituted with a diphenylamine group, a diphenylamine group substituted with a diphenylamine group, and a diphenylamine group substituted with a diphenylamine group; Or a diphenylamine group substituted with a diphenylamine group, a diphenylamine group substituted with a diphenylamine group, or a biphenylylene group unsubstituted or substituted with an arylamine group substituted or unsubstituted with a diphenylamine group substituted with a diphenylamine group to be.

In the exemplary embodiment of the present specification, when m is 1, Ar7 is hydrogen; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, and when m is 2, a direct bond; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or a substituted or unsubstituted C6-C30 divalent arylamine group.

In the exemplary embodiment of the present specification, when m is 1, Ar7 is hydrogen; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted diphenylamine group, and when m is 2, a direct bond; A substituted or unsubstituted phenylene group; Or a substituted or unsubstituted biphenylylene group; Or a substituted or unsubstituted divalent diphenylamine group.

In the exemplary embodiment of the present specification, when m is 1, Ar7 is hydrogen; A phenyl group unsubstituted or substituted with an arylamine group; A biphenyl group unsubstituted or substituted with an arylamine group; Or a diphenylamine group unsubstituted or substituted with an arylamine group, and when m is 2, a direct bond; A phenylene group unsubstituted or substituted with an arylamine group; A biphenylylene group unsubstituted or substituted with an arylamine group; Or a divalent diphenylamine group unsubstituted or substituted with an arylamine group.

In the exemplary embodiment of the present specification, when m is 1, Ar7 is hydrogen; A phenyl group unsubstituted or substituted with a diphenylamine group, a diphenylamine group substituted with a diphenylamine group, and a diphenylamine group substituted with a diphenylamine group; A diphenylamine group, a diphenylamine group substituted with a diphenylamine group, a biphenyl group unsubstituted or substituted with a diphenylamine group substituted with a diphenylamine group; Or a diphenylamine group, a diphenylamine group substituted with a diphenylamine group, a diphenylamine group unsubstituted or substituted with a diphenylamine group substituted with a diphenylamine group, and m is 2, Direct bond; A phenylene group unsubstituted or substituted with a diphenylamine group, a diphenylamine group substituted with a diphenylamine group, and a diphenylamine group substituted with a diphenylamine group; A diphenylamine group, a diphenylamine group substituted with a diphenylamine group, a biphenylylene group unsubstituted or substituted with a diphenylamine group substituted with a diphenylamine group substituted with a diphenylamine group; Or a diphenylamine group, a diphenylamine group substituted with a diphenylamine group, or a divalent diphenylamine group unsubstituted or substituted with a diphenylamine group substituted with a diphenylamine group substituted with a diphenylamine group.

In an exemplary embodiment of the present specification, Formula 1 is represented by any one of the following structural formulas.

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

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

In an exemplary embodiment of the present specification, the solvent is, for example, a chlorine-based solvent such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, and o-dichlorobenzene; Ether solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; Aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; Ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyvalents such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, etc. Alcohol and its derivatives; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; Sulfoxide solvents such as dimethyl sulfoxide; and amide 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 any solvent capable of dissolving or dispersing the compound according to an exemplary embodiment of the present invention is not sufficient, and these are not limited.

In another exemplary embodiment, the solvent may be used alone or in combination 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 embodiment, the viscosity of the single or mixed solvent is preferably 1 to 10 CP, more preferably 3 to 8 CP, but is not limited thereto.

In another embodiment, the concentration of the compound of Formula 1 in 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 the exemplary embodiment of the present specification, the coating composition may further include a p-doped material, and the p-doped material is a p-type dopant in the form of an organic compound or an ionic p-type dopant, and may be represented by the following structural formula. However, it is not limited thereto.

In one embodiment of the present specification, the coating composition further includes a p-doped material, a solvent, or a mixture thereof.

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

Examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide. Oxide, bis-3,5,5-trimethyl hexanoyl peroxide, lauryl peroxide, benzoyl peroxide, p-crole benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-(t- Butyloxy)-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-butyric acid vareric 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 -There are peroxides such as butyl peroxybenzoate and dit-butyl peroxy trimethyl adipate, or azo systems such as azobis isobutyl nitrile, azobisdimethylvaleronitrile, and azobis cyclohexyl nitrile, but are not limited thereto. .

As the photoinitiator, diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4-(2-hydroxy ethoxy ) Phenyl-(2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone- 1,2-hydroxy-2-methyl-1- Phenyl propan-1-one,2-methyl-2-morpholino(4-methylthiophenyl)propan-1-one,1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) Acetophenone-based or ketal-based photopolymerization initiators such as oxime, benzoin, benzoin methylate, benzoin ethylate, benzoin isobylate, benzoin isopropyrate, and benzoin Benzophenone photopolymerization initiators such as ether photoinitiators, benzophenone, 4-hydroxybenzophenone, 2-benzoyl naphthalene, 4-benzoyl biphenyl, 4-benzoyl phenyl ether, acrylated benzophenone, and 1,4-benzoyl benzene ,2-isopropyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, etc. Thioxanthone photopolymerization 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) ) Phenylphosphine oxide, bis(2,4-dimethoxybenzoyl)-2,4,4-trimethyl pentylphosphine oxide, methylphenirgryoxystel, 9,10-phenanthrene, acridine compounds, Triazine-based compounds, imidazole-based compounds, and the like. Moreover, what has a photopolymerization accelerating effect can also be used individually or in combination with the said photoinitiator. For example, triethanolamine, methyl diethanol amine, 4-dimethylamino benzoate ethyl, 4-dimethylamino benzoate isoamyl, benzoic acid (2-dimethylamino) ethyl, 4,4'-dimethylaminobenzophenone, etc. It is not limited to this.

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

In one embodiment of the present specification, the first electrode; A second electrode; And at least one organic material layer provided between the first electrode and the second electrode, and at least one of the organic material layers is formed by using a coating composition containing the compound of Formula 1.

In the exemplary embodiment of the present specification, the thickness of the organic material layer including Formula 1 is 10nm to 100nm, more preferably 20nm to 50nm.

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

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

In another exemplary embodiment, the organic material layer formed by using the coating composition is an emission layer, and the emission layer includes the compound as a host of the emission layer.

In the exemplary embodiment of the present specification, the organic light emitting device is a hole injection layer and a hole transport layer. It further includes one 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 an exemplary embodiment of the present specification, the first electrode is a cathode, and the second electrode is an anode.

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

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

In another exemplary embodiment, the organic light-emitting device may be an organic light-emitting device of an inverted type 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 multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

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

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

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

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 may be manufactured by materials and methods known in the art, except that at least one of the organic material layers is formed using a coating composition including the compound.

For example, the organic light emitting device of the present specification may be manufactured by sequentially laminating an anode, an organic material layer, and a cathode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, an anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be produced by depositing a material that can be used as a cathode thereon. In addition to such a method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

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

Specifically, in the exemplary embodiment of the present specification, the step of preparing a substrate; Forming a cathode or an anode on the substrate; Forming one or more organic material layers on the cathode or anode; And forming an anode or a cathode on the organic material layer, wherein at least one layer of the organic material layer is formed using the coating composition.

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

In another embodiment, the organic material layer formed by 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.

The coating composition according to an exemplary embodiment of the present specification has structural characteristics and is suitable for a solution process and can be formed by a printing method, so that there is an economic effect in terms of time and cost when manufacturing a device.

In an exemplary embodiment of the present specification, the forming of the organic material layer formed by using the coating composition includes coating the coating composition on the cathode or anode; And heat treatment or light treatment of the coated coating composition.

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

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

In the case of including the heat treatment or light treatment step in the step of forming the organic material layer formed using the coating composition, a plurality of fluorene groups included in the coating composition may form crosslinks, thereby providing an organic material layer having a thinned structure. In this case, it is possible to prevent dissolution, morphological influence, or decomposition by a solvent deposited on the surface of the organic material layer formed using the coating composition.

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

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

In one embodiment of the present specification, as the polymeric binder, those that do not extremely inhibit charge transport, and those that do not have strong absorption of visible light are preferably used. As the polymeric binder, poly(N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly(p-phenylenevinylene) and derivatives thereof, poly(2,5-thienylenevinylene) and Derivatives thereof, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane, and the like are exemplified.

In addition, the compound according to an exemplary embodiment of the present specification may include a compound alone in the organic material layer by including a carbazole and an amine group, and a coating composition including the compound may be thinned through heat treatment or light treatment. It can be included as a copolymer by using a coating composition mixed with a monomer. In addition, a copolymer or a mixture may be included by using a coating composition mixed with another polymer.

As the anode material, a material having a large work function is preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO:Al or SnO ₂ :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

The cathode material is generally 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 are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer that injects holes from an electrode, and has the ability to transport holes as a hole injection material, and thus has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated from the light emitting layer. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) 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 hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the emission layer.The hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission layer, and has high mobility for holes. The material is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

The light-emitting material is a material capable of emitting light in a visible light region by transporting and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene; And rubrene, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials 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, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted A compound in which at least one arylvinyl group is substituted on the arylamine, and one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer.As an electron transport material, a material capable of receiving electrons from the cathode and transferring them to the emission layer, and a material having high mobility for electrons is suitable. Do. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron 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 layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

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

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, 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)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

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

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

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

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

<Example>

<Production Example 1 _ Preparation of compound 1>

[Compound 1-a]

Add 2,7-dibromofluorene (20.0 g, 59.172 mmol), phenol (55.686 g, 591.72 mmol) and methanesulfonic acid (0.7 M, 84 mL) to a 250 mL round bottom flask (RBF) and add 50 to 12 hours. It was stirred. The reaction solution was added to cold water at room temperature. The precipitate was filtered and washed several times with water. After dissolving the obtained solid in tetrahydrofuran (THF), 16.8 g of compound 1-a was obtained as a precipitate using petroleum ether. (Yield: 55%)

[Compound 1-a] [Compound 1-b]

Compound 1-a (3.00 g, 5.9031 mmol) and N-([1,1'-biphenyl]-4-yl)-N-(4-(4,) in a 250 mL round bottom flask (RBF) under nitrogen atmosphere 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'-biphenyl]-4-amine (6489 mg, 12.3965 mmol), Pd( PPh ₃ ) ₄ (341 mg, 0.2952 mmol), K ₂ CO ₃ (15.0 mmol, 2 M), and 34 mL of toluene were added, followed by stirring at 115 for 14 hours. 40 mL of water was added to the reaction solution at room temperature to terminate the reaction, and the organic layer was extracted using ethyl acetate (EA, Ethyl acetate) (10 mL X 3). The residual water was removed with MgSO ₄ and filtered to remove the organic solvent. By column with MC:Hex = 5:1, 3.960 g of compound 1-b could be obtained. (Yield: 59%)

[Compound 1-c] [Compound 1-d]

Compound 1-c (2.0 g, 4.6586 mmol) and K ₂ CO ₃ (23.0 mL, 2 M, 46.0 mmol), N1,N1'-(1,4-phenyl) in a 250 mL round bottom flask (RBF) under nitrogen atmosphere. Ren)bis(N1,N4-diphenyl-N4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzene-1,4 -Diamine) (2115 mg, 2.1175 mmol), Pd(PPh ₃ ) ₄ (269 mg, 0.2329 mmol), 45.0 mL of toluene was added and stirred at 125°C for 16 hours. The reaction was terminated by adding 40 mL of saturated aqueous NaHCO ₃ solution to the stirred solution. The solution after the reaction was terminated was extracted with an organic layer using CH ₂ Cl ₂ (30 mL × 3). Water was removed from the extracted organic solution using MgSO ₄ . The organic solution was filtered with Celite and the solvent was removed. The obtained solution was subjected to silica gel column chromatography EA:Hex = 1:9 to obtain 1.05 g of compound 1-d. (Yield: 34%)

[Compound 1-d] [Compound 1]

Compound 1-d (1.00 g, 0.6926 mmol) and 7.0 mL of dimethylformamide were added to a 25 mL round bottom flask (RBF) under a nitrogen atmosphere, and stirred at 0 °C for 15 minutes. NaH (144 mg, 3.6015 mmol) was added at 0° C. and the reaction solution was stirred for 30 minutes. To this solution, 4-vinylbenzyl chloride (507 mg, 0.47 mL, 3.3245 mmol) was added at 0°C and stirred for 2 hours. 5 mL of water was added to the stirred solution to terminate the reaction. The solution at which the reaction was terminated was obtained by extracting the organic layer using CH ₂ Cl ₂ (3 mL × 3). Water was removed from the extracted organic solution using MgSO ₄ . The organic solution was filtered with Celite and the solvent was removed. The obtained solution was subjected to silica gel column chromatography (CH ₂ Cl ₂ ) to obtain 938 mg of compound 1. (Yield: 71%)

<Production Example 2_ Preparation of Compound 2>

[Compound 1-a] [Compound 2-b]

Compound 1-a (4.00 g, 7.8708 mmol) and (4-(bis(4-(diphenylamino)phenyl)amino)phenyl)boronic acid (10307 mg, 16.5286) in a 250 mL round bottom flask (RBF) under nitrogen atmosphere mmol), Pd(PPh ₃ ) ₄ (455 mg, 0.3935 mmol), K ₂ CO ₃ (40.0 mmol, 2 M), and 40 mL of toluene were added, followed by stirring at 125°C for 16 hours. 40 mL of water was added to the reaction solution at room temperature to terminate the reaction, and then the organic layer was extracted using dichloromethane (MC, Dicholro methane) (30 mL × 3). The residual water was removed with MgSO4, filtered, and the organic solvent was removed. By column with MC:Hex = 6:1, 6.4 g of compound 2-b could be obtained. (Yield: 54%)

[Compound 2-b] [Compound 2]

Compound 2-b] (2.00 g, 1.3281 mmol) and 10.0 mL of dimethylformamide were added to a 25 mL round bottom flask (RBF) under a nitrogen atmosphere, and stirred at 0 °C for 15 minutes. NaH (159 mg, 3.9843 mmol) was added at 0° C. and the reaction solution was stirred for 30 minutes. To this solution, 4-vinylbenzyl chloride (486 mg, 0.45 mL, 3.1874 mmol) was added at 0°C and stirred for 2 hours. 8 mL of water was added to the stirred solution to terminate the reaction. The solution at which the reaction was terminated was obtained by extracting the organic layer using CH ₂ Cl ₂ (4 mL × 3). Water was removed from the extracted organic solution using MgSO ₄ . The organic solution was filtered with Celite and the solvent was removed. The obtained solution was subjected to silica gel column chromatography (CH ₂ Cl ₂ ) to obtain 1085 mg of compound 2. (Yield: 47%)

<Preparation Example 3_Preparation of Compound 3>

[Compound 1-b] [Compound 3]

Compound 1-b (1.50 g, 1.3141 mmol) and 10.0 mL of dimethylformamide were added to a 50 mL round bottom flask (RBF) under a nitrogen atmosphere, and stirred at 0° C. for 15 minutes. NaH (158 mg, 3.9424 mmol) was added at 0° C. and the reaction solution was stirred for 30 minutes. To this solution, 4-vinylbenzyl chloride (481mg, 0.44 mL, 3.1538 mmol) was added at 0°C and stirred for 2 hours. 10 mL of water was added to the stirred solution to terminate the reaction. The solution at which the reaction was terminated was subjected to extraction of the organic layer using CH ₂ Cl ₂ (5 mL × 3). Water was removed from the extracted organic solution using MgSO ₄ . The organic solution was filtered with Celite and the solvent was removed. The obtained solution was subjected to silica gel column chromatography (CH ₂ Cl ₂ ) to obtain 1.487 g of compound 3. (Yield: 82%)

<Production Example 4_Preparation of Compound 4>

[Compound 1-b] [Compound 4-c]

Compound 1-b (1.00 g, 0.8761 mmol) and perfluorobutane sulfonate (1.588 g, 0.94 mL 5.2566 mmol), K ₂ CO ₃ (727 mg, 5.2577 mmol) in a 10 mL round bottom flask (RBF) under nitrogen atmosphere. ), 5.0 mL of acetone and 3.0 mL of H ₂ O were added and stirred at 50° C. for 6 hours. The reaction was terminated by adding 10 mL of saturated aqueous NaHCO ₃ solution to the stirred solution. The solution at which the reaction was terminated was subjected to extraction of the organic layer using CH ₂ Cl ₂ (5 mL × 3). Water was removed from the extracted organic solution using Na ₂ SO ₄ . The organic solution was filtered with Celite and the solvent was removed. The obtained solution was subjected to silica gel column chromatography EA:Hex = 1:9 to obtain 1.5 g of compound 4-c. (Yield: 100%)

[Compound 4-c] [Compound 4]

Compound 4-c (1.60 g, 0.9346 mmol) and K ₂ CO ₃ (517 mg, 3.7383 mmol), 4-vinylphenylboronic acid in a 50 mL round bottom flask (RBF) under nitrogen atmosphere. (415 mg, 2.8038 mmol), Pd(PPh ₃ ) ₄ (65 mg, 0.0561 mmol), 15 mL of tetrahydrofuran (THF), and 4.0 mL of H ₂ O were added and stirred at 85° C. for 16 hours. The reaction was terminated by adding 10 mL of saturated aqueous NaHCO ₃ solution to the stirred solution. The solution after the reaction was terminated was extracted with an organic layer using CH ₂ Cl ₂ (5 mL 3). Water was removed from the extracted organic solution using MgSO ₄ . The organic solution was filtered with Celite and the solvent was removed. The obtained solution was subjected to silica gel column chromatography EA:Hex = 2:8 to obtain 433 mg of compound 4. (Yield: 35%)

<Production Example 5_Preparation of compound 5>

[Compound 1-c]

To a 250 mL round bottom flask (RBF), add 2-bromofluorene (20.0 g, 77.190 mmol), phenol (72.644 g, 771.90 mmol) and methanesulfonic acid (0.7 M, 110 mL) and stir at 50°C for 12 hours. gave. The reaction solution was added to cold water at room temperature. The precipitate was filtered and washed several times with water. After dissolving the obtained solid in tetrahydrofuran (THF), 31.3 g of compound 1-c was obtained as a precipitate using petroleum ether. (Yield: 95%)

[Compound 1-c] [Compound 5-d]

Compound 1-c (3.00 g, 6.9880 mmol) and N-([1,1'-biphenyl]-4-yl)-N-(4-(4,) in a 100 mL round bottom flask (RBF) under nitrogen atmosphere. 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'-biphenyl]-4-amine (4024 mg, 7.6868 mmol), Pd( PPh ₃ ) ₄ (444 mg, 0.3843 mmol), K ₂ CO ₃ (15.0 mL, 2 M), 56 mL of toluene was added and stirred at 115° C. for 14 hours. After adding 40 mL of water to the reaction solution at room temperature to terminate the reaction, the organic layer was extracted using EA (40 mL × 3). After removing residual water with MgSO ₄ and filtering, the organic solvent was removed. By column with EA:Hex = 3:7, 4.0 g of compound 5-d could be obtained. (Yield: 38%)

[Compound 5-d] [Compound 5]

Compound 5-d (1.00 g, 1.3406 mmol) and 10.0 mL of dimethylformamide were added to a 50 mL round bottom flask (RBF) under a nitrogen atmosphere, and stirred at 0°C for 15 minutes. NaH (161 mg, 4.0219 mmol) was added at 0° C. and the reaction solution was stirred for 30 minutes. To this solution, 4-vinylbenzyl chloride (491mg, 0.45 mL, 3.2374 mmol) was added at 0°C and stirred for 2 hours. 10 mL of water was added to the stirred solution to terminate the reaction. The solution at which the reaction was terminated was subjected to extraction of the organic layer using CH ₂ Cl ₂ (5 mL × 3). Water was removed from the extracted organic solution using MgSO ₄ . The organic solution was filtered with Celite and the solvent was removed. The obtained solution was subjected to silica gel column chromatography (CH ₂ Cl ₂ ) to obtain 1.0 g of compound 5. (Yield: 61%)

<Production Example 6_Preparation of Comparative Compound 2>

[Comparative compound 2]

In a 250 mL round bottom flask (RBF) under nitrogen atmosphere, 2,7-dibromo-9,9-diphenylfluorene (5.00 g, 10.4996 mmol) and N-([1,1'-biphenyl]-4- Yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'-biphenyl]-4- Amine (11542 mg, 7.6868 mmol), Pd(PPh ₃ ) ₄ (1213 mg, 1.0500 mmol), K ₂ CO ₃ (20.0 mL, 2 M), 52 mL of toluene was added and stirred at 115° C. for 14 hours. . After adding 40 mL of water to the reaction solution at room temperature to terminate the reaction, the organic layer was extracted using EA (40 mL × 3). After removing residual water with MgSO ₄ and filtering, the organic solvent was removed. By column with EA:Hex = 3:7, 6.0 g of [Comparative Compound 2] could be obtained. (Yield: 52%)

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

The coating composition may be a compound represented by Compound 1, Compound 2, Comparative Compound 1, or Comparative Compound 2 of the present invention, as described in Table 1 below; p doping material; And an organic solvent (cyclohexanone). In addition, the prepared coating composition was spin-coated as shown in Table 1 to form a coating layer having a thickness of 30 nm, and the film was fired at 250°C or less.

[Comparative compound 2]

The following p-doped materials are p dopants in the form of organic compounds of compound 2-1, or ionic p dopants of compound 3-1, but are not limited thereto.

coating
Composition compound p-doped substance Spin speed (rpm)
/Hour(s) Firing temperature ( ^o C)
/Hour(min) One Compound 1 Compound 2-1 1000/60 230/30 2 Compound 1 Compound 3-1 1000/60 230/30 3 Compound 2 Compound 2-1 1000/60 230/30 4 Compound 2 Compound 3-1 1000/60 230/30 5 Comparative compound 1 Compound 2-1 1000/60 230/30 6 Comparative compound 2 Compound 2-1 1000/60 230/30

When the film was fired with the coating composition 6 including Comparative Compound 2, the film film was not maintained, so that device data could not be obtained. Therefore, it is judged that Comparative Compound 2 is not suitable for the solution process. The film retention data of Comparative Compound 2 is attached to [Fig. 10].

Experimental example 1-2. Film retention rate test of coating layer

In order to check the film retention rate of the coating layer using the coating composition of Table 1, a toluene solvent was spin-treated on top of the film and washed.

The films formed using the coating compositions 1 to 4 included a fullerene derivative containing a functional group capable of crosslinking with respect to toluene, and the crosslinkable functional group formed crosslinking, so that chemical resistance and film retention were high.

Example One

A glass substrate on which ITO (indium tin oxide) was deposited with a thickness of 1500Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating 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, followed by drying, and the substrate was transported to a glove box.

The coating composition 1 described in the following table was spin-coated on the thus prepared ITO transparent electrode to form a hole injection layer having a thickness of 300 Å, and the coating composition was cured on a hot plate in an N ₂ atmosphere for 30 minutes. Thereafter, after being transferred to a vacuum evaporator, the following Compound A was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 400 Å.

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

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7Å/sec, the deposition rate of LiF of the cathode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum degree during deposition was 2×10 ^-7 ~ 5×10 ^-8 torr was maintained.

Example 2

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

Example 3

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

Example 4

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

Comparative example One

An organic light-emitting device was manufactured in the same manner as in Example 1, except that coating composition 5 was used instead of coating composition 1 for the hole injection layer in Example 1.

Comparative example 2

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

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

Example Driving voltage (V) Current efficiency (cd/A) Power efficiency (lm/W) Example 1 5.3 3.24 5.14 Example 2 6.3 2.68 7.38 Example 3 4.9 2.89 5.32 Example 4 6.1 3.73 5.14 Comparative Example 1 7.5 4.20 4.78

As a result of Table 2, the derivative of Formula 1 according to an exemplary embodiment of the present specification has excellent solubility in an organic solvent, and it is easy to prepare a coating composition, so that a uniform coating layer can be formed using the coating composition. And it was confirmed that it can be applied to organic light emitting devices.

In addition, in the case of the present invention in which an aryl group is directly bonded to fluorene than in Comparative Example 1 in which an amine group other than an aryl group is directly bonded, better device performance is shown.

In the case of Comparative Example 2, the film retention rate was not satisfied, so device data could not be obtained.

Experimental example 2-1. Formation of coating layer using coating composition

The coating composition was prepared by mixing in a substance represented by the following compounds 3 to 5 of the present invention and an organic solvent (cyclohexanone) as described in Table 3 below. In addition, the prepared coating composition was spin-coated as shown in Table 3 to form a coating layer having a thickness of 30 nm, and the film was fired at 250°C or less.

Materials of the following formula were used as the material for the hole transport layer, but the material is not limited thereto.

coating
Composition Hole transport layer Spin speed (rpm)
/Hour(s) Firing temperature ( ^o C)
/Hour(min) 7 Compound 3 1000/60 230/30 8 Compound 4 1000/60 230/30 9 Compound 5 1000/60 230/30

Experimental example 2-2. Film retention rate test of coating layer

In order to check the film retention rate of the coating layer using the coating composition of Table 3, a toluene solvent was spin-treated on the top of the film and washed.

The film formed using the coating compositions 7 to 9 contained a carbazole derivative containing a functional group capable of crosslinking with respect to toluene, and the crosslinkable functional group formed a crosslink, so that chemical resistance and film retention were high.

Example 5

A glass substrate on which ITO (indium tin oxide) was deposited with a thickness of 1500Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating 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, followed by drying, and the substrate was transported to a glove box.

The hole injection layer was spin-coated on the prepared ITO transparent electrode to form a hole injection layer having a thickness of 300 Å, and cured on a hot plate for 30 minutes in an N ₂ atmosphere.

Thereafter, the coating composition 7 was spin-coated at a spin speed of 1000 rpm for 60 seconds, and then heated and baked at 230 on a hot plate for 30 minutes to form a thin film.

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

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7Å/sec, the deposition rate of LiF of the cathode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum degree during deposition was 2×10 ^-7 ~ 5×10 ^-8 torr was maintained.

Example 6

An organic light-emitting device was manufactured in the same manner as in Example 5, except that coating composition 8 was used instead of coating composition 7 for the hole injection layer in Example 5.

Example 7

An organic light-emitting device was manufactured in the same manner as in Example 5, except that coating composition 9 was used instead of coating composition 7 for the hole injection layer in Example 5.

Comparative example 3

An organic light-emitting device was manufactured in the same manner as in Example 5, except that Comparative Compound 3 was used instead of the coating composition 7 for the hole injection layer in Example 5.

Comparative example 4

An organic light-emitting device was manufactured in the same manner as in Example 5, except that Comparative Compound 4 was used instead of the coating composition 7 for the hole injection layer in Example 5.

[Comparative compound 3] [Comparative compound 4]

Table 4 shows the results of measuring the driving voltage and luminous efficiency at a current density of 10 mA/cm ² for the organic light emitting device manufactured by the above method.

Example Driving voltage (V) Current efficiency (cd/A) Power efficiency (lm/W) Membrane retention
(%) Life time
(95%,h) Example 5 5.4 3.23 5.25 95 70 Example 6 5.6 3.34 5.26 97 86 Example 7 6.5 3.26 6.26 97 67 Comparative Example 3 7.2 5.28 4.28 94 13 Comparative Example 4 7.1 5.12 4.35 86 23

As a result of Table 4, the hole transport layer having the structures of [Compound 3], [Compound 4] and [Compound 5] of the present specification has excellent solubility in an organic solvent, and it is easy to prepare a coating composition, so that the coating It was confirmed that a uniform coating layer can be formed by using the composition, and since it has excellent solubility compared to the existing hole transport layer, it is easy to maintain the film properties and prevents a reduction in lifespan, so it can be applied to an organic light emitting device.

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

Claims (12)

In the coating composition comprising a compound represented by the following formula (1),
The coating composition further comprises a p-doped material, and the p-doped material is selected from the following p-type dopants:
[Formula 1]

In Formula 1, X1 and X2 are the same as or different from each other, and each independently, a direct bond; -O-; Or an arylene group,
Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group,
Ar3 to Ar5 are the same as or different from each other, and each independently, is a substituted or unsubstituted aryl group, Ar6 is a direct bond or a substituted or unsubstituted arylene group,
m is 1 or 2,
When m is 1, n is 0 or 1, when m is 2, n is 0,
When m is 1, Ar7 is hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted arylamine group, and when m is 2, Ar7 is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent arylamine group,
When Ar6 is a direct bond, Ar7 is not hydrogen or a direct bond,
Ar3 and Ar4 can be combined to form a ring, Ar5 and Ar6 can be combined to form a ring,
R2 to R5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,
o and p are each an integer of 0 to 4, r is an integer of 0 to 3,
When n is 0, q is an integer of 0 to 4, when n is 1, q is an integer of 0 to 3, and when o, p, q, or r is 2 or more, the substituents in parentheses are the same or different .
Y1 and Y2 are each independently selected from the following structural formula,

In the above structural formula, R1 is hydrogen or a substituted or unsubstituted alkyl group.
[p-type dopant]

. The coating composition of claim 1, wherein the formula 1 is represented by any one of the following formulas 2 to 4:
[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4, X1, X2, Y1, Y2, Ar1 to Ar7, o, p, q and r are the same as defined in Formula 1,
Ar8 is the same as the definition of Ar6 when m in Formula 1 is 2,
Ar9 is the same as the definition of Ar5 in Formula 1,
Ar10 is the same as the definition of Ar2 in Formula 1,
R6 to R9 are the same as the definition of R2 to R5 in Formula 1,
s is an integer of 0 to 3, t, u and v are each an integer of 0 to 3,
When s, t, u and v are 2 or more, the substituents in parentheses are the same as or different from each other,
X3 and X4 are the same as the definitions of X1 and X2 in Formula 1,
Y3 and Y4 are the same as the definitions of Y1 and Y2 in Chemical Formula 1. The method according to claim 1, wherein X1 and X2 are a direct bond or -O-,
Y1 and Y2 are

or

Phosphorus coating composition. The method according to claim 1,
Ar3 to Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; Or a substituted or unsubstituted biphenyl group coating composition. The method according to claim 1, wherein when m is 1, Ar7 is hydrogen or a substituted or unsubstituted diphenylamine group, and when m is 2, Ar7 is a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylylene group; Or a substituted or unsubstituted divalent diphenylamine group coating composition. The coating composition of claim 1, wherein Formula 1 is represented by any one of the following structural formulas:

delete The method according to claim 1,
The coating composition is a coating composition for an organic light emitting device. The method according to claim 1,
The coating composition is a coating composition that further comprises a solvent. A first electrode; A second electrode provided to face the first electrode; And
It includes at least one organic material layer provided between the first electrode and the second electrode,
At least one of the organic material layers is an organic light-emitting device comprising a cured product of the coating composition according to any one of claims 1 to 6, 8 and 9. The organic light-emitting device of claim 10, wherein the cured product of the coating composition is cured by heat treatment or light treatment of the coating composition. The organic light emitting device of claim 10, wherein the organic material layer including the cured product of the coating composition is a light emitting layer.

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