KR102127006B1 - Monomer compounds comprising uracil group, Organic layers comprising the cross-linked of the monomer compounds, and Organic electronic device comprising the organic layers - Google Patents

Abstract

In the present invention, a monomolecular compound containing a pyrimidine-based functional group represented by the following formula (I) is provided as an organic material layer material of an organic electronic device, and the compound can be formed into an organic material layer in a short time by photocuring at room temperature:
[Formula I]
Ar-(R ₁ -R ₂ -Py)n
In the formula (I),
n is 2 to 10,
Ar is a substituted or unsubstituted C ₆ -C ₆₀ aryl group having an n-order linking group or a substituted or unsubstituted C ₃ -C ₆₀ heteroaryl group,
R ₁ and R ₂ are each independently a simple bond, -O-, a substituted or unsubstituted C ₆ -C ₃₀ arylene group, a substituted or unsubstituted C ₃ -C ₃₀ heteroarylene group, a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₁ -C ₁₀ alkoxy group, a substituted or unsubstituted amide group, or a substituted or unsubstituted amine group,
Py is a monovalent linking group derived from a pyrimidine-based functional group.

Description

A monomolecular compound containing a pyrimidine-based functional group, an organic compound layer including the photo-crosslinked product of the compound, and an organic electronic device comprising the same {Monomer compounds comprising uracil group, Organic layers comprising the cross-linked of the monomer compounds, and Organic electronic device comprising the organic layers}

The present invention relates to a monomolecular compound containing a pyrimidine-based functional group, an organic material layer containing a photocrosslinked product of the compound, and an organic electronic device including the same.

In general, permanent materials such as resist materials for forming ITO electrodes, such as liquid crystal displays (LCDs), organic EL displays, interlayer insulating films, circuit protection films, colored pigment dispersion resists for color filter production of liquid crystal displays, and bulkheads for organic EL displays A photocurable resin composition is widely used as a film-forming material. Such a resin composition was applied to an organic light-emitting diode (OLED), which is an example of an organic electronic device by a conventional deposition method, but it is difficult to manufacture a large display by this deposition method and expensive equipment is used. There is a problem.

Accordingly, recently, a method of using a solution process such as inkjet has emerged for the production of a large display. But. In the case of an OLED display using a solution process, it is difficult to form a multi-layer thin film, and thus there is a problem that the efficiency of the device is low. In order to solve this problem, studies have been conducted to synthesize materials having functional groups capable of curing such as epoxy and acrylate and use them as materials for organic electronic devices, but materials having such functional groups require high temperature for curing or It has a problem of forming a byproduct in the curing process.

The present invention has been made to solve the above-mentioned problems, and an object thereof is to provide an organic layer containing a compound capable of forming a polymer film by photocuring at room temperature and a photocured product of the compound.

Another object of the present invention is to provide an organic electronic device including the organic material layer.

According to the first aspect of the present invention, there is provided a monomolecular compound containing a pyrimidine-based functional group represented by the following formula (I):

[Formula I]

Ar-(R ₁ -R ₂ -Py)n

In the formula (I),

n is 2 to 10,

Ar is a substituted or unsubstituted C ₆ -C ₃₀ aryl group having an n-order linking group or a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group,

R ₁ and R ₂ are each independently -O-, a substituted or unsubstituted C ₆ -C ₃₀ arylene group, a substituted or unsubstituted C ₃ -C ₃₀ heteroarylene group, a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₁ -C ₁₀ alkoxy group, a substituted or unsubstituted amide group, or a substituted or unsubstituted amine group,

The substitution is C ₆ -C ₃₀ aryl, C ₃ -C ₃₀ heteroaryl or C1 at least one hydrogen atom bonded to a carbon atom of the arylene group, heteroarylene group, alkylene group, alkoxyl group, amide group or amine group. -C10 may be substituted with an alkyl group,

Py is a monovalent linking group derived from a pyrimidine-based functional group.

According to the second aspect of the present invention, in the first aspect, there is provided a monomolecular compound containing a pyrimidine-based functional group wherein the pyrimidine-based functional group is a pyrimidine group, a uracil group or a thymine group.

According to the third aspect of the present invention, in the first aspect or the second aspect, a monomolecular compound containing a pyrimidine-based functional group wherein n is preferably 2 to 6 is provided.

According to a fourth aspect of the present invention, in any one of the first to third aspects, Ar is benzene, triphenylamine, triazole, carbazole, triphenylbenzene, tetraphenylsilane, pentarene, indene , Naphthylene, fluorene, phenarene, azulene, heptalene, indacene, acenaphthylene, fluorene, pheneneene, Phenanthrene, perylene, pentaphene, hexacene, thiophene, pyrrole, pyrazole, pyrazolidine, imidazole A group containing a pyrimidine-based functional group that is a linking group derived from (imidazole), imidazoline, pyrazine, pyrimidine, indolye, benzimidazole, or quinoline Molecular compounds are provided.

According to the fifth aspect of the present invention, in the aspect of any one of the first to fourth aspects, the pyrimidine-based functional group-containing monomolecular compound is any of the following compounds 1 to 7: This is provided:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

According to the fifth aspect of the present invention, there is provided a photocurable composition comprising a monomolecular compound containing a pyrimidine-based functional group of any one of the first aspect to the fourth aspect.

According to a sixth aspect of the present invention, a first electrode; A second electrode; And an organic material layer including a photocured product of a monomolecular compound containing a pyrimidine functional group according to any one of the first to fourth aspects between the first electrode and the second electrode.

According to a seventh aspect of the present invention, in the sixth aspect, an organic electronic device is provided in which the organic material layer is a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron injection layer, an electron transport layer, or two or more of them.

According to an eighth aspect of the present invention, there is provided a first substrate; A driving thin film transistor positioned on the first substrate; A light-emitting diode located on the first substrate and connected to the driving thin film transistor, wherein the photocured product of a monomolecular compound containing a pyrimidine functional group of any one of the first to fourth aspects is included in at least one organic layer An organic electronic device; A display device including a second substrate covering the organic electronic device and bonding to the first substrate is provided.

The photocurable composition comprising a monomolecular compound containing a pyrimidine-based functional group according to the present invention has the advantage of being cured in a short time at room temperature and photocured to form an organic layer.

In addition, unlike conventional catalysts such as benzophenone, AIBN, and EDMAB, when the polymer compound is crosslinked and cured, the photocurable composition according to the present invention is cured without using a catalyst, so the catalyst remaining after curing is an impurity It is unlikely or will decrease.

In addition, unlike the conventional polymer compound crosslinked and cured, the organic layer formed by swelling with a solvent was poor in form stability, whereas the organic layer formed from the photocurable composition according to the present invention was insoluble in not being soluble in the solvent at all. And it is possible to form an elaborate pattern.

Figure 1a shows the structure of a polymer compound containing a conventional pyrimidine-based functional group, Figure 1b is a monomolecular compound containing the pyrimidine-based functional group according to the present invention (left) and the compound is crosslinked by photocuring (Right).
2 is a graph showing the UV spectrum of the photocurable composition of Example 9 over time.
3 to 5 are graphs showing the curing degree of the photocurable compositions of Examples 10 to 12 over time.
6 is a graph showing the voltage-current characteristics of the OLED device of Example 13 manufactured according to the present invention.
7 is a graph showing the current density-current efficiency characteristics of the OLED device of Example 13 manufactured according to the present invention.

All technical and scientific terms used in this specification, unless defined otherwise, have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this 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.

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

According to the present invention, a monomolecular compound containing a pyrimidine-based functional group represented by the following formula (I) is provided:

[Formula I]

Ar-(R ₁ -R ₂ -Py) _n

In the formula (I),

n is 2 to 10,

Ar is a substituted or unsubstituted C ₆ -C ₃₀ aryl group having an n-order linking group or a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group,

R ₁ and R ₂ are each independently -O-, a substituted or unsubstituted C ₆ -C ₃₀ arylene group, a substituted or unsubstituted C ₃ -C ₃₀ heteroarylene group, a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₁ -C ₁₀ alkoxy group, a substituted or unsubstituted amide group, or a substituted or unsubstituted amine group,

Py is a monovalent linking group derived from a pyrimidine-based functional group.

The substitution is at least one hydrogen atom bonded to the carbon atom of the arylene group, heteroarylene group, alkylene group, alkoxyl group, or amide group is C ₆ -C ₃₀ aryl, C ₃ -C ₃₀ heteroaryl or C1-C10 It may be substituted with an alkyl group, one or more hydrogen atoms bonded to a nitrogen atom of an amide group or an amine group may be substituted with a C ₆ -C ₃₀ aryl, a C ₃ -C ₃₀ heteroaryl or a C1-C10 alkyl group, Further, at least one of the arylene group, heteroarylene group, alkylene group, alkoxyl group, carbon atom of the amide group, or nitrogen atom of the amide group or amine group may be substituted with oxygen.

In addition, the arylene group or heteroarylene group is a single benzene ring structure (first structure), or a structure in which two or more benzene rings are connected to each other by a simple bond (second structure), fused structure (third structure), nitrogen atom Or, it may be a structure (fourth structure) in which two or more benzene rings are connected to a silicon atom. Also, at least two or more of the first to fourth structures may be mixed and connected.

In the above, n is preferably 2 to 10, more preferably 2 to 6.

Wherein Ar is benzene, triphenylamine, triazole, carbazole, triphenylbenzene, tetraphenylsilane, pentarene, indene, naphthylene, fluorene, phenarene, azulene, heptane ( heptalene, indacene, acenaphthylene, fluorene, phenalene, phenanthrene, perylene, pentaphene, hexacene ), thiophene, pyrrole, pyrazole, pyrazolidine, imidazole, imidazoline, pyrazine, pyrimidine , It is a linking group derived from indolye, benzimidazole or quinoline.

More preferably, Ar is benzene, triphenylamine, triazole, carbazole, triphenylbenzene or tetraphenylsilane.

In the above, R ₁ or R ₂ may be each independently phenyl.

Py is a pyrimidine group, uracil group or thymine group.

In the above, the hetero atom may be O or N.

In one embodiment of the present invention, a non-limiting example of the pyrimidine-based functional group-containing monomolecular compound includes a uracil group-containing monomolecular compound of any one of the following compounds 1 to 7, but is not limited thereto.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

The pyrimidine-based functional group-containing monomolecular compound of Formula I is included in the photocurable composition for forming an organic layer.

The solvent used in the photocurable composition is not particularly limited as long as it can dissolve the pyrimidine-based functional group-containing monomolecular compound. As specific examples, chlorobenzene, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N,N-diethylacetamide, gamma-butyro Lactone, gamma-valerolactone, m-cresol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate , Propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether, Propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether, Propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether, Propylene glycol monobutyl Ether acetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl tyl ether, propylene glycol dibutyl ether, ethyl lactate, butyl lactate, cyclohexanone and cyclopentanone. Can be used.

It is preferable that the photocurable composition uses 2 to 60 parts by weight of a solvent based on 100 parts by weight of a monomolecular compound containing a pyrimidine-based functional group. When the content of the solvent satisfies the above range, it becomes an appropriate viscosity to obtain a smooth surface when coated, it is easy to implement a desired thickness, and it is possible to form an even mixture in the crude liquid, thereby realizing physical properties for fine pattern formation. It is possible, the adhesion to the substrate is improved, and a uniform coating property and a desired film thickness can be obtained.

In one embodiment, the photocurable composition may further include a photoinitiator, an acrylic polymer, and other additives commonly used in the art.

When the photoinitiator is included in the photocurable composition of the present invention, the photoinitiator may be included in an amount of 0. to 10 parts by weight based on 100 parts by weight of the photocurable composition of the present invention. When the photoinitiator is included in the above content, a satisfactory effect can be expected in terms of photocuring time. Non-limiting examples of photoinitiators that can be used include phenylbiphenylketone, thioxanthone, isopropylthioxanthone, diethylthioxanthone, benzophenone, 1-benzyl-1-dimethylamino-1-(4-morpholino -Benzoyl)propane, 1-hydroxy-1-benzoylcyclohexane, 2-morpholinyl-2-(4-methylmercapto) benzoylpropane, ethyl anthraquinone, 4-benzoyl-4-methyldiphenylsulfide, benzoin Butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4-isopropyl)benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, diphenyl-2, 4,6-trimethylbenzoylphosphine oxide, methyl benzoyl formate, 1,7-bis(9-acridinyl)heptane, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2- Phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl-4,6-bis(trichloromethyl)-s-triazine, 1-[9-ethyl-6-(2 -Methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime), 1-(o-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl )-9H-carbazol-3-yl]ethanone and 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione. Can.

The photocurable composition according to an embodiment of the present invention may further include an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in a side chain in order to impart thin film properties such as control of pattern characteristics and heat resistance. When the acrylic polymer is included in the photocurable composition of the present invention, the acrylic polymer may be included in an amount of 5 to 70 parts by weight based on 100 parts by weight of the photocurable composition of the present invention. When the acrylic polymer is included in the above content, a satisfactory effect can be expected in terms of photocuring time. Acrylic polymers that can be used are copolymers of monomers including the monomers described below. Examples of the monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate, Hexyl (meth)acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate and hexadecyl (meth)acrylate, isobornyl (meth) )Acrylate, damantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, Acrylic acid, methacrylic acid, styrene, acetoxystyrene, glycidyl acrylate, glycidyl methacrylate, itaconic acid, maleic anhydride, maleic acid monoalkyl ester, monoalkyl fumarate, 3,4-epoxybutyl ( Meth)acrylate,2,3-epoxycyclohexyl(meth)acrylate,3,4-epoxycyclohexylmethyl(meth)acrylate, 3-ethyloxetane-3-methyl(meth)acrylate, N-methyl Maleimide, N-butyl maleimide, N-phenyl maleimide, (meth)acrylamide, etc. are mentioned, These can be used individually or by polymerizing 2 or more types.

The photocurable composition according to an embodiment of the present invention may further include at least one colorant pigment selected from the group consisting of red, green, blue, and black, if necessary.

At this time, the content of the color colorant pigment added may be appropriately selected according to the conditions of use of the organic layer, for example, 1 to 50 parts by weight based on 100 parts by weight of the photocurable composition, more preferably 1 to 20 parts by weight . When the content of the colorant pigment satisfies this range, the color purity and luminance characteristics of the obtained color filter may be very excellent.

The photocurable composition according to the present invention may be coated using a conventional solution processing method such as spin coating, slit spin coating, roll coating, die coating, curtain coating on a substrate such as a glass substrate. Subsequently, the coating may be formed into a film after exposure to UV light and through a development process.

In the exposure process, ultraviolet light, for example, ultraviolet light in a wavelength range of 250 nm to 400 nm, may be used as the light source irradiated by the light irradiation means. Further, as a method of irradiating the light source, a known means such as a high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, cold cathode tube for copier, LED, semiconductor laser, etc. can be used, but is not limited thereto. The light irradiation may be performed at room temperature, preferably 20 to 25 ℃ for 5 minutes to 120 minutes, preferably 5 minutes to 50 minutes. When the light irradiation time is in the above range, a satisfactory effect can be expected in light curing.

The developing process is a process of forming a pattern by removing an exposed area from a photocurable film that has been subjected to an exposure process using a developer. Examples of the developer used therein are hydroxides, carbonates, hydrogen carbonates and ammonia water of alkali metals or alkaline earth metals. A basic aqueous solution such as a quaternary ammonium salt can be used. Particularly preferred is an aqueous ammonia quaternary ammonium solution, such as an aqueous tetramethyl ammonium solution.

The overall process of one embodiment according to the present invention comprises the steps of coating a photocurable composition comprising a monomolecular compound containing a pyrimidine-based functional group of the present invention by a solution process; And irradiating ultraviolet light; afterwards, optionally, a post-treatment may be performed at 70 to 200° C. for about 30 minutes to 2 hours through a development process.

The organic material layer formed from the above can be used in an organic electronic device.

The monomolecular compound containing a pyrimidine-based functional group provided in the present invention is compared with a pyrimidine-based functional group-containing high molecular compound:

(1) A pyrimidine-based functional group-containing polymer compound is a substance that dissolves well in an organic solvent, but cannot be manufactured with an accurate molecular weight, and it is difficult to remove impurities such as catalysts in the manufacturing process. It is a material that is difficult to commercialize due to the reduced lifespan of the device as well as difficulties. In particular, when a pyrimidine-based functional group is bonded to a side branch of the polymer, a problem with solvent resistance occurs after photocrosslinking.

(2) Monomolecules are known to be insoluble in a conventional solvent and therefore cannot be used for the production of a multi-layer thin film by a solution process, but according to the present invention, the monomole containing a pyrimidine-based functional group is added to the monomolecule to dissolve in the solvent. If possible, it can be used in solution processing. In addition, after the pyrimidine-based functional group is crosslinked by photocrosslinking, it does not dissolve in the solvent.

(3) In addition, the pyrimidine-based functional group-containing polymer compound and the pyrimidine-based functional group-containing monomolecular compound have a difference in the structure forming a thin film after formation of the thin film, and the pyrimidine-based functional group-containing polymer compound is shown in FIG. 1A. Although it has a simple structure that maintains the main chain structure, the monomolecular compound containing a pyrimidine-based functional group has a form in which the main chain itself forms a bond after binding as shown in FIG. 1B, so that the structure of the thin film is completely different. In addition, when a monomolecular compound containing a pyrimidine-based functional group is used, the structure of the thin film can be made in a variety of forms from linear to radial depending on the number of pyrimidine groups included.

(4) In addition, even if the pyrimidine-based functional group-containing polymer compound is dissolved in an organic solvent, it has a high molecular weight and maintains a high viscosity, making it difficult to use in processes such as inkjet, while the pyrimidine-based functional group-containing polymer compound has a low viscosity. Forming has the advantage of being advantageous for use in processes such as inkjet.

An organic electronic device according to an aspect of the present invention, the first electrode; A second electrode; And the organic material layer between the first electrode and the second electrode.

In one embodiment of the present invention, the organic electronic device is an organic light emitting device (OLED), an organic solar cell, an organic photodiode (OPD), an optical sensor, an organic photoreceptor (OPC), and an organic transistor (OTFT). It can be selected from the group consisting.

The organic material layer may be an electron transport layer. Meanwhile, the organic electronic device may further include at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and the organic material layer according to the present invention is a hole injection layer , A hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

More specifically, one embodiment of the organic electronic device according to the present invention has a structure of a first electrode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/second electrode. Alternatively, the organic electronic device according to the present invention has a structure consisting of a first electrode/hole injection layer/light emitting layer/electron transport layer/electron injection layer/second electrode, or a first electrode/hole injection layer/hole transport layer/light emitting layer/ A hole blocking layer/electron transport layer/electron injection layer/second electrode may have a structure, but is not limited thereto.

The light emitting layer of the organic electronic device according to the present invention may include a phosphorescent or fluorescent dopant including red, green, blue or white. Among them, the phosphorescent dopant may be an organometallic compound containing one or more elements selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb and Tm.

In addition, in the present invention, the first substrate; A driving thin film transistor positioned on the first substrate; An organic electronic device positioned on the first substrate and connected to the driving thin film transistor, the organic electronic device including a photocured product of a pyrimidine-based functional group-containing monomolecular compound in at least one organic material layer; A display device including a second substrate covering the organic electronic device and bonding to the first substrate is provided.

Hereinafter, an embodiment of a method for manufacturing an organic electronic device will be described.

First, a first electrode having a high work function is formed on a substrate by a vapor deposition method or a sputtering method to form a first electrode.

The first electrode may be an anode or a cathode. Here, as a substrate, a substrate used in a conventional organic electronic device is used. A glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, handling ease, and waterproof property is preferable.

As the material for the first electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), Al, Mg, Ag, etc. having excellent conductivity may be used. It does not work. The first electrode may be provided as a transparent electrode, a translucent electrode, or a reflective electrode.

Next, a hole injection layer (HIL) may be formed on the first electrode. The hole injection layer may be an organic material layer formed by coating the photocurable composition according to the present invention by a solution process.

The hole injection layer may have a thickness of about 100 mm to 10000 mm, preferably 100 mm to 1000 mm. This is because when the thickness of the hole injection layer is less than 100 mA, hole injection characteristics may be deteriorated, and when the thickness of the hole injection layer exceeds 10000 MPa, the driving voltage may increase.

Next, a hole transport layer (HTL) may be formed on the hole injection layer. The hole transport layer may be an organic material layer formed by coating the photocurable composition according to the present invention by a solution process.

The hole transport layer may have a thickness of about 50 mm2 to 1000 mm2, preferably 100 mm2 to 600 mm2. This is because when the thickness of the hole transport layer is less than 50 Å, hole transport characteristics may be deteriorated, and when the thickness of the hole transport layer exceeds 1000 Å, the driving voltage may increase.

Next, an emission layer (EML) may be formed on the hole transport layer. The light emitting layer can be formed using various known light emitting materials. Meanwhile, the light emitting layer may be formed using a known host and dopant, and in the case of a dopant, both a known fluorescent dopant and a known phosphorescent dopant may be used.

For example, Alq3, CBP (4,4'-N,N'-dicarbazole-biphenyl), PVK (poly(n-vinylcarbazole)) or DSA (distyryl arylene) can be used as the host. However, it is not limited thereto.

For dopants, Ir(ppy)3 (ppy is an abbreviation for phenylpyridine) (green), (4,6-F2ppy)2Irpic, PtOEP(platinum(II)octaethylporphyrin), compound having the following structural formula, Firpric, TBPe, etc. It can be used, but is not limited thereto.

The content of the dopant is preferably 0.1 to 20 parts by weight, particularly 0.5 to 12 parts by weight, based on 100 parts by weight of the light emitting layer forming material (that is, the total weight of the host and the dopant is 100 parts by weight). If the content of the dopant is less than 0.1 part by weight, the effect of adding dopant is insignificant, and if it exceeds 20 parts by weight, concentration quenching such as phosphorescent or fluorescence is unfavorable.

The thickness of the light emitting layer may be about 100 mm 2 to 1000 mm 2, preferably 200 mm 2 to 600 mm 2. This is because when the thickness of the light emitting layer is less than 100 mV, light emission characteristics may be deteriorated, and when the thickness of the light emitting layer exceeds 1000 mV, the driving voltage may increase.

When the light emitting layer includes a phosphorescent dopant, a hole blocking layer (HBL) may be formed on the light emitting layer to prevent the triplet excitons or holes from diffusing into the electron transport layer. The hole blocking layer material that can be used at this time may be an organic material layer formed by coating the photocurable composition according to the present invention by a solution process.

The hole blocking layer may have a thickness of about 50 mm2 to 1000 mm2, preferably 100 mm2 to 300 mm2. This is because when the thickness of the hole blocking layer is less than 50 mV, hole blocking characteristics may be deteriorated, and when the thickness of the hole blocking layer exceeds 1000 mV, the driving voltage may increase.

Next, an electron transport layer (ETL) is formed. The electron transport layer may be an organic material layer formed by coating the photocurable composition according to the present invention by a solution process.

The thickness of the electron transport layer may be about 100 mm 2 to 1000 mm 2, preferably 100 mm 2 to 500 mm 2. This is because when the thickness of the electron transport layer is less than 100 Å, electron transport characteristics may be deteriorated, and when the thickness of the electron transport layer exceeds 1000 Å, the driving voltage may increase.

In addition, an electron injection layer (EIL), which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer.

As the electron injection layer, any material known as an electron injection layer forming material such as LiF, NaCl, CsF, Li2O, BaO, or the like can be used. The deposition conditions and the coating conditions of the electron injection layer vary depending on the compound used, but are generally selected from the same condition ranges as the formation of the hole injection layer.

The thickness of the electron injection layer may be about 1 mm to 100 mm, preferably 5 mm to 90 mm. This is because when the thickness of the electron injection layer is less than 1 Å, the electron injection characteristics may be deteriorated, and when the thickness of the electron injection layer exceeds 100 구동, the driving voltage may increase.

Finally, a second electrode may be formed on the electron injection layer using a method such as a vacuum deposition method or a sputtering method.

The second electrode may be used as a cathode or anode. As the metal for forming the second electrode, a metal having low work function, an alloy, an electrically conductive compound, and a mixture thereof may be used. Specific examples include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). Can be lifted. In addition, a transparent cathode using ITO and IZO may be used to obtain a front light emitting device.

The present invention will be described in more detail based on examples as follows. However, the present invention is not limited to this.

Example 1: Compound of Formula 1

Preparation of compound 1

Sodium hydride (0.4 g, 0.016 mol) was added to a 250 mL two-neck flask under a nitrogen atmosphere and stirred for 1 hour. Uracil (0.9 g, 0.008 mol) was dissolved in dimethyl sulfoxide (DMSO) (50 ml) in a reaction flask, and then slowly added, followed by 4-bromodiphenylamine (2 g, 0.008 mol). It was added after dissolving in DMSO (50 mL). The reaction was allowed to proceed at room temperature for 48 hours. After completion of the reaction, quenching was performed and all the organic solvent was removed under reduced pressure. The mixture in the solid state was purified by column chromatography (ethyl acetate:hexane = 1:7 volume ratio) to obtain Compound 1, and the yield and NMR data of Compound 1 are described below.

Yield: 1.7 g (77%)

1H NMR (DMSO, 300 MHz); δ = 11 (s, -NH-), 9.2 (d, -H), 7.3~7.22 (m, -CH-), 7.02 (t,-CH-), 6.83 (t, -CH-), 6.6 ( d, -CH-), 5.73 (d, -H), 4.0 (s, -NH-)

Preparation of compound of formula 1

In a 1-neck flask, compound 1 (1 g, 0.00367 mol), tris(4-bromophenyl)amine (0.6 g, 0.0012 mol), copper iodide (0.07 g, 0.000367 mol) prepared as above ), potassium phosphate (2 g, 0.0147 mol), 1,2-trans-cyclohexane diamine (0.4 mL, 0.00367 mol) was added, and 1,4-dioxane (100 mL) was added and stirred. The reaction was allowed to proceed at 110°C for 48 hours. After completion of the reaction, the mixture was cooled at room temperature, and the organic layer was separated by work-up with methylene chloride and distilled water. Subsequently, all of the solvent of the organic layer was evaporated and subjected to column chromatography (methylene chloride:hexane = 1:10 volume ratio) to obtain the final compound of formula (1). The yield and NMR data of the obtained compound of Formula 1 are described below.

Yield: 1 g (77%)

1H NMR (DMSO, 300 MHz); δ = 11 (s, -NH-), 9.25 (d, -H), 7.0 to 6.61 (m, -CH-), 5.67 (d, -H)

Example 2: Compound of Formula 2

Preparation of compound 2-1

Sodium hydride (0.2 g, 0.008 mol) was added to a 2-neck flask under a nitrogen atmosphere and stirred for 1 hour. Uracil (3 g, 0.027 mol) was dissolved in DMSO (50 mL) in the reaction flask, and then slowly added dropwise. After adding all of uracil, 3-bromo-1-propanol (3.8 mL, 0.027 mol) was dissolved in DMSO (50 ml) and then slowly added. The reaction was allowed to proceed for 48 hours at room temperature. After the reaction was completed, ?? and the organic solvent were all removed under reduced pressure. The solid mixture was washed with (ethyl acetate:hexane = 1:4 volume ratio) to obtain compound 2-1. The yield and NMR data of Compound 2-1 are as follows.

Yield: 1.8 g (39%)

1H NMR (DMSO, 300 MHz); δ = 11 (s, -NH-), 9.95 (d, -H), 5.7 (d, -H) 4.99 (d, -CH-), 4.5 (m, -CH2-), 3.6 (s, -OH ), 3.5(m, -CH2-), 1.99 (s, -CH ₂ -)

Preparation of compound 2-2

Sodium hydride (0.1 g, 0.04 mol) was added to a 100 mL 2-neck flask under a nitrogen atmosphere and stirred for 1 hour. Compound 2-1 (1.5 g, 0.0088 mol) was added thereto, dissolved in DMSO (50 mL), and slowly added dropwise. After adding compound 2-1, 2-bromocarbazole (2.2 g, 0.0088 mol) was dissolved in DMSO (50 ml) and added. The reaction was allowed to proceed at room temperature for 72 hours. After completion of the reaction, the precipitate was filtered, and the filtrate was received to remove the solvent under reduced pressure. The crude mixture was purified by column chromatography (ethyl acetate:hexane = 1: 20) to give compound 2-2. The yield and NMR data of Compound 2-2 are as follows.

Yield: 2 g (68%)

1H NMR (DMSO, 300 MHz); δ = 11 (d, -NH-), 9.95 (d, -H), 8.12 (m, -CH-), 8.01 to 6.9 (m, -CH-), 5.7 (d, -H), 4.5 (m ,-CH2-), 1.99 (m, -CH2-)

Preparation of compound of formula 2

Compound 2-2 (2 g, 0.006 mol), tris(4-bromophenyl)amine (1 g, 0.002 mol), potassium phosphate (5 g, 0.024 mol), CuI in a 250 mL 1-neck flask under nitrogen atmosphere (0.2 g, 0.0015 mol), trans-1,2-diaminocyclohexane (0.68 mL, 0.006 mol), 1,4-dioxane (100 mL) was added. The reaction was allowed to proceed at 80° C. for 48 hours. After completion of the reaction, ?? and the organic solvent was removed under reduced pressure. The mixture in the solid state was purified by column chromatography (methylene chloride:hexane = 1:7 volume ratio) to obtain the final compound of Formula 2. Yield and NMR data of the compound of Formula 2 are as follows.

Yield: 0.8 g (32%)

1H NMR (DMSO, 300 MHz); δ = 11 (d, -NH-), 9.95 (d, -H), 7.98 to 7.13 (m, -CH-), 5.7 (d, -H), 4.5 (m, -CH ₂ -), 1.99 ( m, -CH ₂ -)

Example 3: Compound of Formula 3

Preparation of compound 3-1

In a 500 mL round bottom flask under nitrogen atmosphere, 1,3,5-tribromobenzene (7 g, 0.022 mol), bis(pinacolato)diboron (11.3 g, 0.044 mol), potassium acetate (6.4 g, 0.066 mol), Pd(pph ₃ ) ₄ (0.2 g, 0.0002 mol) was added and 1,4-dioxane (200 mL) was added and stirred. The reaction was conducted by refluxing at 110° C. for 24 hours. After the reaction was completed, it was cooled to room temperature and washed with ethyl acetate. After receiving the filtrate and blowing off all of the solvent, compound 3-1 was obtained by column chromatography (ethyl acetate: hexane=1:20 volume ratio). The yield and NMR data of compound 3-1 were as follows.

Yield: 6.8 g (76%)

1H NMR (CDCl ₃ , 300 MHz); δ = 7.8 (s, -CH-), 7.45 (s, -CH-), 1.8 (s, -CH ₃ )

Preparation of compound 3-2

In a 250 mL 2-neck flask under nitrogen atmosphere, compound 3-1 (5 g, 0.012 mol), 1,4-dibromobenzene (5.8 g, 0.024 mol), Pd(pph ₃ ) ₄ (0.6 g, 0.0001 mol ) And THF (100 mL) was added and stirred. Potassium carbonate solution (2N, 100 mL) was added to the flask when the material was all dissolved. The reaction was conducted by refluxing at 80° C. for 12 hours. After the reaction, the organic layer was separated by cooling at room temperature and extracting with ethyl acetate/distilled water. After washing off the solvent of the separated organic layer, purification was performed by column chromatography (ethyl acetate: hexane = 1:8 volume ratio) to obtain compound 3-2. The yield and NMR data of compound 3-2 are as follows.

Yield: 3.4 g (61%)

1H NMR (CDCl ₃ , 300 MHz); δ = 7.86 (m, -CH-), 7.6 (d, -CH-), 7.54 (s, -CH-)

Preparation of compound 3-3

Nitrogen purging was performed in a 250 mL 2-neck flask, sodium hydride (2.2 g, 0.09 mol) was added, and the mixture was stirred for 1 hour to maintain a nitrogen atmosphere. After sufficiently purging with nitrogen, uracil (3 g, 0.027 mol) was dissolved in DMSO (50 mL) in a reaction flask and then added slowly, and compound 3-2 (6.2 g, 0.013 mol) was dissolved in DMSO (50 mL). Was added. The reaction proceeded at room temperature for 48 hours. After the completion of the reaction, the organic solvent was removed under reduced pressure, and then purified by column chromatography (methylene chloride:hexane = 1: 5 volume ratio) to obtain compound 3-3. The yield and NMR data of compound 3-3 are as follows.

Yield: 2.8 g (54%)

1H NMR (DMSO, 300 MHz); δ = 11 (s, -NH-) 9.2 (d, -H), 8.4 to 7.58 (d, -CH-), 7.5 to 7.36 (d, -CH-), 5.5 (d, -H)

Preparation of compound 3-4

3,6-dibromocarbazole (5 g, 0.015 mol), bromobenzene (2.4 g, 0.015 mol), cuprous iodide (0.57 g, 0.003 mol), potassium phosphate in a 250 mL round-bottom flask under nitrogen atmosphere ( 6.4 g, 0.03), trans-1,2-cyclohexane diamine (1.7 mL, 0.015 mol) was added and 1,4-dioxane (200 mL) was added and stirred. The reaction was conducted by refluxing at 110° C. for 19 hours. After completion of the reaction, after cooling at room temperature, the organic layer was separated by extraction with methylene chloride/distilled water. The solvent in the organic layer was blown off and washed with ethyl acetate. After receiving the filtrate and removing ethyl acetate under reduced pressure, compound (a) is obtained by column chromatography (methylene chloride:hexane = 1: 10 volume ratio). The yield and NMR data of compound 3-4 are as follows.

Yield: 5.8 g (78%)

1H NMR (CDCl ₃ , 300 MHz); δ = 8.0~7.8 (d, -CH-), 7.64~7.4 (m, -CH-), 7.32 (d,-CH-)

Preparation of compound 3-5

In a 250 mL round bottom flask under nitrogen atmosphere, compound 3-4 (2 g, 0.005 mol), bis(pinacolato)diboron (2.5 g, 0.01 mol), potassium acetate (0.5 g, 0.015 mol), Pd ( pph ₃ ) ₄ (0.34 g, 0.0005 mol) was added and 1,4-dioxane (100 mL) was added and stirred.

The reaction was conducted by refluxing at 110° C. for 24 hours. After the reaction, the mixture was cooled to room temperature and washed with ethyl acetate. After receiving the filtrate and blowing off all of the solvent, column chromatography (ethyl acetate: hexane = 1:10 volume ratio) to obtain compound 3-5. Yield and NMR data for Compound 3-5 are as follows.

Yield: 1.73 g (68%)

1H NMR (CDCl ₃ , 300 MHz); δ = 8.0 (m, -CH-), 7.6 to 7.55 (m, -CH-), 1.8 (s, -CH ₃ )

Preparation of compound of formula 3

In a 500 mL 2-neck flask under nitrogen atmosphere, add compound 3-5 (1 g, 0.002 mol), compound 3-3 (2.1 g, 0.004 mol), Pd(pph ₃ ) ₄ (0.2 g, 0.0002 mol) , Tetrahydrofuran (THF) (100 mL) was added and stirred. When all the substances in the flask were dissolved, a potassium carbonate solution (2N, 100 mL) was added. The reaction was conducted by refluxing at 80° C. for 12 hours. After the reaction, the organic layer was separated by cooling at room temperature and extracting with ethyl acetate/distilled water. After the solvent of the separated organic layer was all blown off, purification was performed by column chromatography (methylene chloride:hexane = 1:4 volume ratio) to obtain the final compound of formula (3). Yield and NMR data of the compound of Formula 3 are as follows.

Yield: 0.7 g (32%)

1H NMR (DMSO, 300 MHz); δ = 11 (s, -NH-), 9.23 (d, -CH-), 8.1 to 7.66 (m, -CH-), 7.55 to 7.32 (m, -CH-), 5.5 (d, -H)

Example 4: Preparation of compound of formula 4

Potassium phosphate (0.8 g, 0.006 mol) and reactant 4-1 (0.3 g, 0.0017 mol) were added to a 2-neck flask under a nitrogen atmosphere and stirred with DMSO (80 mL). After the mixture was stirred for about 1 hour, reactant 4-2 (0.4 g, 0.0009 mol) was dissolved in DMSO (30 ml) and added. Subsequently, the reaction was allowed to proceed for 72 hours at room temperature. After the reaction was completed, the precipitate was filtered, and the filtrate was collected to remove the solvent under reduced pressure. The crude mixture was purified by column chromatography (methylene chloride:hexane = 1: 10 volume ratio) to obtain the final compound of formula 4 (0.32 g).

Example 5: compound of formula 5

Preparation of compound 5-1

3-pyridineboronic acid pinacol ester (10 g, 0.048 mol), 1,3,5-tribromobenzene (15 g, 0.024 mol), Pd (pph ₃ ) ₄ ( 2.7 g, 0.0024 mol) was added and THF (200 mL) was added and stirred. When all the substances in the flask were dissolved, potassium carbonate solution (2N, 200 mL) was added and stirred together. The reaction was conducted by refluxing at 80° C. for 12 hours. After completion of the reaction, column chromatography (ethyl acetate: hexane = 1:20 volume ratio) yields pure compound 5-1. The yield and NMR data of compound 5-1 are as follows.

Yield: 5.6 g (37%)

1H NMR (CDCl3, 300 MHz); δ = 9.2 (d, -CH-), 8.77 (d, -CH-), 8.48 (t, -CH-), 8.0 (s,-CH-), 7.62 (m,-CH-), 7.35 (s , -CH-)

Preparation of compound 5-2

To a 1000 mL round bottom flask under nitrogen atmosphere, 1,3,5-tribromobenzene (15 g, 0.047 mol), bis(pinacolato)diboron (36 g, 0.14 mol), potassium acetate (13 g, 0.14 mol), Pd(pph ₃ ) ₄ (2.7 g, 0.0023 mol) was added, and 1,4-dioxane (500 mL) was added and stirred. The reaction was conducted by refluxing at 110° C. for 24 hours. After the reaction, the mixture was cooled to room temperature and washed with ethyl acetate. After receiving the filtrate and blowing off all of the solvent, column chromatography (methylene chloride:hexane = 1:15 volume ratio) gave compound 5-2. The yield and NMR data of compound 5-2 are as follows.

Yield: 6.8 g (30%)

1H NMR (CDCl ₃ , 300 MHz); δ = 7.48 (s, -CH-), 1.25(s,-CH ₃ )

Preparation of compound 5-3

In a 500 mL 2-neck flask under nitrogen atmosphere, add compound 5-2 (2 g, 0.004 mol), compound 5-1 (4.2 g, 0.013 mol), Pd(pph ₃ ) ₄ (0.23 g, 0.0002 mol) , THF (80 mL) was added and stirred. Potassium carbonate solution (2N, 80 mL) was added when all the materials in the flask were dissolved. The reaction was conducted by refluxing at 80° C. for 12 hours. After the reaction was completed, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After the solvent of the separated organic layer was blown away, it was purified by column chromatography (ethyl acetate: hexane = 1:20 volume ratio) to obtain compound 5-3. The yield and NMR data of compound 5-3 are as follows.

Yield: 1.8 g (52.6 %)

1H NMR (CDCl3, 300 MHz); δ = 9.2 (d, -CH-), 8.77 (d, -CH-), 8.48 (t, -CH-), 7.7 to 7.35 (m, -CH-)

Preparation of compound 5-4

To a 250 mL 2-neck flask under a nitrogen atmosphere, compound 5-3 (1.5 g, 0.002 mol), 3-aminopyridine-5-boronic acid pinacol ester (1.3 g, 0.006 mol), Pd(pph ₃ ) ₄ ( 0.42 g, 0.00005 mol) was added, and THF (50 mL) was added and stirred. Potassium carbonate solution (2N, 50 mL) was added when all the materials in the flask were dissolved. The reaction was conducted by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with methylene chloride/distilled water to separate the organic layer. After the solvent of the separated organic layer was blown off, purification was performed by column chromatography (methylene chloride:hexane = 1: 15 volume ratio) to obtain compound 5-4. The yield and NMR data of compound 5-4 are as follows.

Yield: 1 g (67%)

1H NMR (CDCl ₃ , 300 MHz); δ = 9.2(d, -CH-), 8.9 (s, -CH-), 8.75 (d, -CH-), 8.42 (t, -CH-), 8.02 (s, -CH-), 7.05-6.95 (m, -CH-), 6.25 (s, -NH ₂ )

Preparation of compound of formula 5

Sodium hydride (0.4 g, 0.0016 mol) was added to a 1.250 mL 2-neck flask, and the nitrogen atmosphere was maintained while stirring for 1 hour. Orotic acid (1.85 g, 0.012 mol) was dissolved in DMSO (50 ml) and then slowly added to the reaction flask. After adding all, the mixture was stirred for 30 minutes. To the reaction flask, compound 5-4 (1 g, 0.004 mol) was dissolved in DMSO (10 ml) and then slowly added. After reacting at room temperature for 6 hours, the reaction was performed at 40°C for 12 hours. After the completion of the reaction, ?? was called, and the organic solvent layer was received to remove all of the solvent under reduced pressure. After washing with ethyl acetate, the crude material was purified by column chromatography (ethyl acetate:hexane = 1: 20 volume ratio) to obtain the final compound of formula (5). Yield and NMR data of the compound of Formula 5 are as follows.

Yield: 0.9 g (20%)

1H NMR (DMSO, 300 MHz); δ = 11.48 (s, -NH-), 11.0 (s, -NH-), 8.33 (d, -CH-), 7.9 (s, -CH-), 7.75 to 7.22 (m, -CH-), 6.81 (d, -CH-), 6.25 (s, -NH-)

Example 6: Compound of Formula 6

Preparation of compound 6-1

Sodium hydride (0.2 g, 0.008 mol) was added to a 2-neck flask under a nitrogen atmosphere and stirred for 1 hour. Uracil (3 g, 0.027 mol) was dissolved in DMSO (50 mL) in a reaction flask, and then slowly added dropwise. After adding uracil, 3-bromo-1-propanol (3.8 mL, 0.027 mol) was dissolved in DMSO (50 ml) and then slowly added. The reaction was allowed to proceed for 48 hours at room temperature. After the completion of the reaction, ?? and the organic solvent were all removed under reduced pressure. The solid mixture was washed with (ethyl acetate:hexane = 1:4 volume ratio) to give compound 6-1. Yield and NMR data of the compound of Formula 6-1 are as follows.

Yield: 1.8 g (39%)

1H NMR (DMSO, 300 MHz); δ = 11 (s, -NH-), 8.97 (d, -CH-), 4.99 (d, -CH-), 4.5 (t,-CH2-), 3.6 (s, -OH), 1.99 (s, -CH ₃ )

Preparation of compound 6-2

To a 250 mL 1-neck flask under a nitrogen atmosphere, 1-(4-bromophenyl)2-phenylbenzimidazole (5 g, 0.014 mol), Bis (Pinacolato)diboron (3.6 g, 0.014 mol), potassium acetate (4.1 g, 0.042 mol ), Pd(pph ₃ ) ₄ (0.8 g, 0.0007 mol) is added and 1,4-dioxane (100 mL) is added and stirred. The reaction was conducted by refluxing at 110° C. for 24 hours. After the reaction was completed, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After removing the solvent of the separated organic layer under reduced pressure, column chromatography (ethyl acetate:hexane = 1:20 volume ratio) to obtain compound 6-2. Yield and NMR data of the compound of Formula 6-2 are as follows.

Yield: 4.3 g (78%)

1H NMR (DMSO, 300 MHz); δ = 7.68 (d, -CH-), 7.52 (d, -CH-), 7.43~7.13 (m, -CH-), 1.25 (s, -CH ₃ )

Preparation of compound 6-3

In a 200 mL 2-neck flask under nitrogen atmosphere, compound 6-2 (4.3 g, 0.011 mol), 9,10-dibromoanthracene (3.7 g, 0.011 mol), Pd(pph ₃ ) ₄ (0.6 g, 0.0005 mol ) And THF (100 mL) was added and stirred. When all the substances in the flask were dissolved, a potassium carbonate solution (2N, 100 mL) was added. The reaction was conducted by refluxing at 80° C. for 12 hours. After the reaction was completed, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After washing off the solvent of the separated organic layer, the compound was purified by column chromatography (methylene chloride:hexane = 1:5 volume ratio) to obtain compound 6-3. Yield and NMR data of the compound of Formula 6-3 are as follows.

Yield: 5.5 g (95%)

1H NMR (DMSO, 300 MHz); δ = 7.68 (d, -CH-), 7.52 (d, -CH-), 7.48 (t, -CH-), 7.43~7.13 (m, -CH-)

Preparation of compound 6-4

In a 250 mL 1-neck flask under a nitrogen atmosphere, purified compound 6-3 (5 g, 0.0095 mol), bis(pinacolato)diboron (2.4 g, 0.0095 mol), potassium acetate (2.7 g, 0.028 mol) , Pd(pph ₃ ) ₄ (0.5 g, 0.00048 mol) was added and 1,4-dioxane (100 mL) was added and stirred. The reaction was conducted by refluxing at 110° C. for 24 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with MC/distilled water to separate the organic layer. The solvent of the separated organic layer was removed under reduced pressure, and then subjected to column chromatography (ethyl acetate:hexane = 1:7 volume ratio) to obtain compound 6-4. Yield and NMR data of the compound of Formula 6-4 are as follows.

Yield: 4.3 g (80%)

1H NMR (DMSO, 300 MHz); δ = 7.68 (d, -CH-), 7.52 (d, -CH-), 7.48 (t, -CH-), 7.43 to 7.13 (m, -CH-), 1.25 (s, -CH ₃ )

Preparation of compound 6-5

In a 500 mL 2-neck flask under nitrogen atmosphere, compound 6-4 (4 g, 0.0052 mol), 1,3,5-tribromobenzene (1.6 g, 0.0052 mol), Pd(pph ₃ ) ₄ (0.4 g , 0.00026 mol) and THF (80 mL) was added and stirred. Potassium carbonate solution (2N, 80 mL) was added to the flask when all of the material was dissolved. The reaction was conducted by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with methylene chloride/distilled water to separate the organic layer. After the solvent of all the separated organic layers was blown off, purification was performed by column chromatography (methylene chloride:hexane = 1:4 volume ratio) to obtain compound 6-5. Yield and NMR data of the compound of Formula 6-5 are as follows.

Yield: 1.1 g (31%)

1H NMR (DMSO, 300 MHz); δ = 7.68 (d, -CH-), 7.52 (d, -CH-), 7.48 (t, -CH-), 7.43~7.13 (m, -CH-)

Preparation of compound of formula 6

Sodium hydride (0.1 g, 0.04 mol) was added to a 100 mL 2-neck flask under a nitrogen atmosphere and stirred for 1 hour. Compound 6-1 (0.5 g, 0.003 mol) was added, dissolved in DMSO (50 mL), and slowly added dropwise. After adding compound 6-1, compound 6-5) (1 g, 0.0015 mol) was dissolved in DMSO (50 ml) and added. The reaction was allowed to proceed at room temperature for 72 hours. After the reaction was completed, the precipitate was filtered, and the filtrate was received to remove the solvent under reduced pressure. The crude mixture was purified by column chromatography (ethyl acetate: hexane = 1: 20 volume ratio) to obtain the final compound of formula (6). Yield: 0.65 g (51%)

1H NMR (DMSO, 300 MHz); δ = δ = 11 (s, -NH-), 8.97 (d, -CH-), 7.52 (d, -CH-), 7.48 (t, -CH-), 7.43~7.13 (m, -CH-) , 4.99 (d, -CH-), 4.5 (t,-CH2-), 3.6 (s, -OH), 1.99 (s, -CH ₃ )

Example 7: Compound of Formula 7

Preparation of compound 7-1

Dissolve 1,3-dibromo-5-hexylbenzene (5 g, 15.6 mmol) in dehydrated diethyl ether (20 mL), and then flow nitrogen. After adding n-butyl lithium (10.75mL, 17.2mmol) at 0°C, the reaction was performed for about 3 hours. After 2 hours, dichlorodiphenylsilane (1.97 g, 7.8 mmol) was added, and reaction was continued at room temperature for 12 hours. After completion of the reaction by adding water, extraction was performed with diethyl ether. Purified by column chromatography using hexane. The NMR of the obtained compound 7-1 is as follows.

1H NMR (300 MHz, CDCl3) δ7.55 (d, 4H, J = 6.0 Hz), 7.40-7.49 (m, 10H), 7.30 (s, 2H), 2.57 (t, 4H J = 7.5 Hz), 1.58 (t, 4H, J = 6 Hz), 1.30 (m, 12H), 0.90 (t, 6H, J = 6 Hz).

Preparation of compound 7-2

Compound 7-11. (1) (3.9 g, 5.9 mmol) was dissolved in THF (25 mL), followed by 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-2 -Add amine (3g, 135.mmol). After that, 4M K2CO3 aqueous solution and ethanol were added and Pd(PPh ₃ ) ₄ (0.54g, 0.47mmol) was finally added while sufficiently flowing nitrogen. The reaction was run at 80°C for 12 hours, and after the reaction was completed, it was extracted with water and methylene chloride. Then, ethyl acetate and hexane were purified by column chromatography using a 1:8 volume ratio. The NMR of the obtained compound 7-2 is as follows.

1H NMR (300 MHz, CDCl3) δ8.25 (d, 2H, J = 3.0 Hz), 7.58-7.66 (m, 6H), 7.54 (d, 2H, J = 3.0 Hz), 7.38-7.46 (m, 10H ,), 6.53 (d, 2H, J = 9.0 Hz), 5.54 (s, 4H), 2.65 (t, 4H J = 7.5 Hz), 1.63 (t, 4H, J = 7.5 Hz), 1.29-1.37 (m , 12H,), 0.89 (t, 6H, J = 6 Hz).

Preparation of compound of formula 7

2.2 g of compound 7-2 was dissolved in 50 ml of DMF. To this was added a mixture of 1.5 g orotic acid, 2 g 1-hydroxybenzothiazole hydrate (HOBt) and 0.5 g N,N-dicyclohexylcarbodiimide (DCC). After flowing nitrogen, the mixture was reacted at room temperature for 12 hours, and after completion of the reaction, water:methylene chloride 1:1 was extracted at a volume ratio. It was purified by column chromatography using 1:5 volume ratio of ethyl acetate and hexane. The obtained compound of Formula 7 had the following NMR data.

1H NMR (300 MHz, CDCl3) δ10.00 (s, 2H), δ8.40 (d, 2H, J = 3.9 Hz), 8.26 (d, 2H, J = 8.4 Hz), 8.02 (s, 2H), 7.84 (d, 2H, J = 6.3 Hz), 7.62-7.66 (m, 4H), 7.57 (d, 2H, J = 3.0 Hz), 7.40-7.50 (m, 12H), 6.01 (s, 2H), 2.65 (t, 4H J = 7.5 Hz), 1.63 (t, 4H, J = 7.5 Hz), 1.29-1.37 (m, 12H,), 0.89 (t, 6H, J = 6 Hz).

Example 8: Compound of Formula 8

Preparation of compound 8-1

Sodium hydride (0.2 g, 0.008 mol) was added to a 2-neck flask under a nitrogen atmosphere and stirred for 1 hour. Uracil (3 g, 0.027 mol) was dissolved in DMSO (50 mL) in a reaction flask, and then slowly added dropwise. After adding all of uracil, 3-bromo-1-propanol (3.8 mL, 0.027 mol) was dissolved in DMSO (50 ml) and then slowly added. The reaction was allowed to proceed for 48 hours at room temperature. After the completion of the reaction, ?? and the organic solvent were all removed under reduced pressure. The solid mixture was washed with a 1:4 volume ratio of ethyl acetate:hexane to give compound 8-1.

Preparation of compound 8-2

Sodium hydride (0.1 g, 0.04 mol) was added to a 100 mL 2-neck flask under a nitrogen atmosphere and stirred for 1 hour. Compound 8-1 (1.5 g, 0.0088 mol) was added, dissolved in DMSO (50 mL), and slowly added dropwise. After all of compound 8-1 was added, 1,4-dibromobenzene (2.1 g, 0.0088 mol) was dissolved in DMSO (50 ml) and added. The reaction was allowed to proceed at room temperature for 72 hours. After the reaction was completed, the precipitate was filtered, and the filtrate was received to remove the solvent under reduced pressure. The crude mixture was purified by column chromatography using 1:20 volume ratio of ethyl acetate:hexane to give compound 8-2.

Preparation of compound 8-3

Compound 8-2 (2 g, 0.006 mol), bis(4-bromophenyl)amine (1.97 g, 0.006 mol), potassium phosphate (1.8 g, 0.018 mol), CuI in a 250 mL 1-neck flask under nitrogen atmosphere (0.1 g, 0.0006 mol), trans-1,2-diaminocyclohexane (0.68 mL, 0.006 mol), 1,4-dioxane (50 mL) was added. The reaction was carried out at 80°C for 48 hours. After completion of the reaction, ?? and the organic solvent was removed under reduced pressure. The solid mixture was purified by column chromatography using a 1:7 volume ratio of methylene chloride:hexane to obtain compound 8-3.

Preparation of compound of formula 8

Compound 8-3 (1.5 g, 0.0026 mol), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2 in a 250 mL 1-neck flask under a nitrogen atmosphere -Yl)-9,9-di-n-octylfluorene (1.7 g, 0.0026 mol), potassium phosphate (0.9 g, 0.0091 mol), CuI (0.05 g, 0.00026 mol), trans-1,2-diamino Cyclohexane (0.72 mL, 0.0026 mol), 1,4-dioxane (30 mL) was added. The reaction was carried out at 80°C for 48 hours. After completion of the reaction, ?? and the organic solvent was removed under reduced pressure. The solid mixture was purified by column chromatography using 1:10 volume ratio of methylene chloride:hexane to obtain the final compound of formula (8). The NMR of the obtained compound of Formula 8 is as follows.

1H NMR (CDCl ₃ , 300 MHz); δ = 10 (s, -NH-), 9.62 (d, -H), 7.93 (d, -CH-), 7.15 (d, -CH-), 7.63~7.15 (m,-CH-), 7.18( d, -CH-), 6.98 (d,-CH-), 6.87~6.74 (m,-CH-), 5.76 (d,-H), 4.06~4.08 (t, -CH ₂ -), 2.34(s , -CH ₃ ), 1.87 (d, -CH ₂ -), 1.29 (s, -CH ₂ -), 0.88 (t, -CH ₃ )

Example 9: Photocurable Preparation of composition 1

Photocurable composition 1 was prepared by adding 0.5 g of the compound of formula 1 obtained in Example 1 to 2 ml of solvent chlorobenzene.

Example 10: Photocurable Preparation of composition 2

A photocurable composition 2 was prepared in the same manner as in the preparation of the photocurable composition 1, except that the compound of formula 2 obtained in Example 2 was used.

Example 11: Photocurable Preparation of composition 3

Photocurable composition 3 was prepared in the same manner as in preparation of photocurable composition 1, except that the compound of formula 3 obtained in Example 3 was used.

Example 12: Photocurable Preparation of composition 4

Photocurable composition 4 was prepared in the same manner as in the preparation of photocurable composition 1, except that the compound of formula 5 obtained in Example 5 was used.

Evaluation example One: Solubility evaluation for solvents

In order to evaluate the solubility resistance to the solvent, the photocurable composition 1 was coated with a material of ITO to a thickness of about 40 nm by spin coating. An example in which UV photocuring was not performed after coating was described as a reference, and the coated thin film was soaked in chlorobenze, a solvent used after light irradiation for 5 minutes, 10 minutes, 20 minutes, 30 minutes, and 60 minutes for about 1 minute, and then again. The UV spectrum was measured and compared to the initial reference spectrum, and shown in FIG. 2. It can be seen from the comparison of the UV spectrum of FIG. 2 that the photocuring has progressed completely after irradiating the UV light source for about 60 minutes or more.

Example 13: organic light emitting device ( OLED ) Production

PEDOT:PSS was coated on ITO to form a hole injection layer. On top of that, the compound of Formula 1 prepared in Example 1 was dissolved in chlorobenzene and coated by a spin method, followed by photocuring for 60 minutes under UV light in a wavelength range of 375 nm to form a hole transporting layer (HTL). On HTL, Ir(mppy)3 was mixed with a compound of Formula 3 prepared in Example 3 and a dopant, dissolved in chlorobenzene, coated with a spin coating method, and photocured for 60 minutes to form a light emitting layer. In addition, after preparing the photocurable composition 5 containing the compound of formula 5 prepared in Example 5 on the light emitting layer, and coated with a spin coating method and photocured to form an electron transport layer. LiF and Al were vacuum-deposited on the ETL layer to form electrodes, and an organic light emitting device was fabricated.

Evaluation example : Device driving

Current density (I), voltage (V), and luminescence intensity (L) were measured by Keithley 236 source measurement. As a result, graphs of FIGS. 6 and 7 were obtained. The voltage-current density characteristics can be confirmed from the graph of FIG. 6, and the device efficiency can be confirmed from the graph of FIG. 7, confirming that the organic light emitting device of the present invention operates normally, from which each organic material layer in the organic light emitting device You can see that it is performing this role properly.

Claims (9)

A photocured product of a monomolecular compound containing a pyrimidine-based functional group represented by the following formula (I):
[Formula I]
Ar-(R ₁ -R ₂ -Py)n
In the formula (I),
n is 2 to 10,
Ar is a substituted or unsubstituted C ₆ -C ₆₀ aryl group having an n-order linking group or a substituted or unsubstituted C ₃ -C ₆₀ heteroaryl group,
R ₁ and R ₂ are each independently a simple bond, -O-, a substituted or unsubstituted C ₆ -C ₃₀ arylene group, a substituted or unsubstituted C ₃ -C ₃₀ heteroarylene group, a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₁ -C ₁₀ alkoxy group, a substituted or unsubstituted amide group, or a substituted or unsubstituted amine group,
Py is a pyrimidine group, a uryl group, or a thymine group.
delete According to claim 1,
The n is a photocured product of a monomolecular compound containing a pyrimidine-based functional group of 2 to 6.
According to claim 1,
The Ar is benzene, triphenylamine, triazole, carbazole, triphenylbenzene, tetraphenylsilane, pentarene, indene, naphthylene, fluorene, phenarene, azulene, heptalene ), indacene, acenaphthylene, fluorene, phenalene, phenanthrene, perylene, pentaphene, hexacene , Thiophene, pyrrole, pyrazole, pyrazolidine, imidazole, imidazoline, pyrazine, pyrimimidine, A photocured product of a monomolecular compound containing a pyrimidine-based functional group, which is a linking group derived from indolye, benzimidazole or quinoline.
According to claim 1,
A photocured product of a pyrimidine-based functional group-containing monomolecular compound represented by any one of the formulas 1 to 7 below.
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

delete A first electrode; A second electrode; And an organic material layer including a photocured product of a monomolecular compound containing a pyrimidine functional group according to any one of claims 1 and 3 to 5, between the first electrode and the second electrode.
The method of claim 7,
An organic electronic device wherein the organic material layer is a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron injection layer, an electron transport layer, or two or more of them.
A first substrate;
A driving thin film transistor positioned on the first substrate;
A light-emitting diode located on the first substrate and connected to the driving thin film transistor, wherein the photocured product of the monomolecular compound containing the pyrimidine-based functional group of any one of claims 1 and 3 to 5 is at least one organic layer. An organic electronic device included in the;
A display device comprising a second substrate covering the organic electronic device and bonding to the first substrate.

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