KR20210156733A - Organic light-emitting compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel compound having excellent light emitting ability and an organic electroluminescent device comprising the same, and the compound according to the present invention is an organic layer material of an organic electroluminescent device, preferably an electron transport layer material and an electron transport auxiliary layer material. It is possible to improve the luminous efficiency, driving voltage, lifespan, and the like of the organic electroluminescent device.

Description

Organic light emitting compound and organic electroluminescent device using same

The present invention relates to a novel organic light emitting compound and an organic electroluminescent device using the same, and more particularly, to a compound having excellent electron transport ability and an organic compound having improved characteristics such as luminous efficiency, driving voltage, and lifespan by including the compound in one or more organic material layers. It relates to an electroluminescent device.

A study on organic electroluminescent (EL) devices (hereinafter simply referred to as 'organic EL devices') that led to blue electroluminescence using anthracene single crystals in 1965, starting with Bernanose's observation of organic thin film emission in the 1950s, began in 1987. (Tang) presented an organic EL device having a stacked structure divided into a functional layer of a hole layer and a light emitting layer. Since then, in order to make a high-efficiency, long-life organic EL device, it has been developed in the form of introducing each characteristic organic material layer in the device, leading to the development of a specialized material used for this.

When a voltage is applied between the two electrodes of the organic electroluminescent device, holes are injected from the anode, and electrons are injected into the organic material layer from the cathode. When the injected holes and electrons meet, an exciton is formed, and when the exciton falls to the ground state, light is emitted. In this case, the material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.

The material for forming the light emitting layer of the organic EL device may be classified into blue, green, and red light emitting materials according to the emission color. In addition, yellow and orange light emitting materials are also used as light emitting materials for realizing better natural colors. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. The development of such a phosphorescent material can theoretically improve luminous efficiency up to four times compared to fluorescence, and thus, attention is focused on phosphorescent host materials as well as phosphorescent dopants.

Until now, hole injection layer, hole transport layer. As the hole blocking layer and the electron transporting layer, NPB, BCP, Alq _3, etc. represented by the following chemical formulas are widely known, and anthracene derivatives have been reported as fluorescent dopant/host materials as light emitting materials. In particular, among the light emitting materials, as a phosphorescent material having a great advantage in terms of efficiency improvement _{, a metal complex compound containing Ir such as Firpic, Ir(ppy) 3} , (acac)Ir(btp) _{2 ,} etc. is a blue, green, and red dopant material. is being used as So far, CBP has shown excellent properties as a phosphorescent host material.

However, although the existing materials have advantages in terms of luminescent properties, they are not satisfactory in terms of lifespan in organic EL devices due to their low glass transition temperature and very poor thermal stability.

Republic of Korea Patent Publication No. 10-2015-0033082 (published date: 04. 01, 2015)

In the present invention, a specific heterocyclic compound can be applied to an organic electroluminescent device, and the specific heterocyclic compound is used as an electron transport layer (ETL) material, which is a common layer of an organic electroluminescent device. An object of the present invention is to provide a novel organic compound.

In addition, the present invention includes a material for an electron transport layer with improved lifespan and improved electron injection and transport ability, a hole transport layer material with improved hole injection and transport ability, and a material for the hole transport layer including the novel organic compound, which exhibits low driving voltage and high luminous efficiency, and includes the same Another object of the present invention is to provide an organic electroluminescent device.

In order to achieve the above object, the present invention provides a compound represented by the following formula (1) or (2).

[Formula 1]

[Formula 2]

In Formula 1,

R _{1 To} R _{4 Are} the same as or different from each other, and each independently a C1~ C40 alkyl group, or a C6~ C60 aryl group, or combine with each other to form a condensed ring,

L is a single bond, or _{is selected from the group consisting of a C 6} ~ C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms,

n is an integer from 0 to 3,

A is a substituent represented by the following formula (3),

[Formula 3]

* is the part where the bond is made,

A plurality of Xs are the same as or different from each other, and each independently C (R) or N, but at least one is N,

R is hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, nucleus A heterocycloalkyl group having 3 to 40 atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, C ₃ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₆₀ Aryl boron group, C ₆ ~ C ₆₀ Aryl phosphine group, C ₆ ~ C ₆₀ Mono or diarylphosphinyl group and C ₆ ~ C ₆₀ Selected from the group consisting of an arylamine group, and forms a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with adjacent groups or spiro bond can achieve,

R of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, a cycloalkyl group, a heterocycloalkyl group, an arylamine group, an alkylsilyl group, an alkylboron group, an arylboron group, an aryl group Phosphine group, mono or diarylphosphinyl group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryl Amine group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkylboron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C substituted with at least ₆₀ of the aryl phosphine group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ selected from the group consisting arylsilyl of C ₆₀ one kind of substituent or being unsubstituted , when substituted with a plurality of substituents, they may be the same or different from each other,

m is an integer from 1 to 3,

When Ar1 is plural, the same or different from each other, and each independently is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, It is a substituted or unsubstituted heteroaryl group, and may form a condensed ring with adjacent X.

In addition, the present invention includes an anode, a cathode, and one or more organic material layers interposed between the positive and negative electrodes, wherein at least one of the one or more organic layers includes a compound represented by Formula 1 above. A light emitting device is provided.

Here, at least one of the one or more organic material layers including the compound represented by Formula 1 may be selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron transport auxiliary layer, and an electron injection layer, It is preferably a transport layer, an electron transport auxiliary layer and/or a light emitting layer. In this case, the compound represented by Formula 1 is an electron transport layer material, an electron transport auxiliary layer material, and/or a light emitting layer material.

Since the compound of the present invention has excellent luminous efficiency, driving voltage, lifespan, etc., it can be usefully applied as an organic material layer material of an organic electroluminescent device. , life, efficiency, etc. are greatly improved, so that it can be effectively applied to a full-color display panel.

1 is a cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention. 2 is a cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

1. Organic compounds

The present invention provides a novel fluorene-based compound excellent in luminous efficiency, driving voltage, lifespan, and the like.

Specifically, the novel organic compound according to the present invention adopts a fused fluorene as a core, and an electron withdrawing group (EWG) having excellent electron transport ability is combined with the core structure, so that the basic make up the skeleton

The compound represented by Formula 1 or Formula 2 of this structure forms a substituent through a condensed bond of alkyl and aryl to fused fluorene, so it is electrochemically compared to the previously known 6-membered heterocyclic structure. It is stable and has excellent electron mobility as well as high glass transition temperature and thermal stability. In addition, in order to improve the electron transfer rate, it has a flat form and has high triplet energy according to a short conjugation length so that excitons generated in the light emitting layer are adjacent electrons. Diffusion (migration) to the transport layer or the hole transport layer can be prevented. Therefore, when the number of excitons contributing to light emission in the light emitting layer is increased and the compound of Formula 1 or Formula 2 of the present invention is used in an organic electroluminescent device, excellent thermal stability and carrier transport ability (especially, electron transport ability and light emitting ability) Not only can it be expected, but also the driving voltage, efficiency, and lifespan of the device can be improved, and the high triplet energy can show excellent efficiency increase due to the triplet-triplet fusion (TTF) effect as the latest ETL material.

In addition, the compounds represented by Formula 2 or Formula 3 of the present invention can easily control the HOMO and LUMO energy levels depending on the direction or position of the substituent, and thus can exhibit high electron transport properties in an organic electroluminescent device using these compounds.

In addition, in the present invention, a dibenzo-based moiety [eg, dibenzofuran (DBF) or dibenzothiophene (DBT)] having an amphoteric physicochemical property for a hole and an electron is added to the fused fluorene core at least It may include more than one. It can be applied as a green phosphorescent material with excellent luminous efficiency through the combination of such a dibenzo-based moiety and a nitrogen-containing aromatic ring (eg, pyridine, pyrazine, triazine), which is a strong electron-withdrawing group (EWG). In addition, it is possible to drive at a low voltage, thereby exhibiting an effect of increasing the lifespan, and has excellent device characteristics due to thermal stability, high glass transition temperature characteristics, and uniform morphology.

As described above, the compound represented by Formula 1 or Formula 2 of the present invention is an organic material layer material of an organic electroluminescent device, preferably a light emitting layer material (a phosphorescent host material of blue, green and/or red), an electron transport layer/injection layer When applied as a material, an electron transport auxiliary layer material, a hole transport layer/injection layer material, a light emitting auxiliary layer material, and a life improvement layer material, the performance and lifespan characteristics of the organic electroluminescent device can be greatly improved. As a result, such an organic electroluminescent device can maximize the performance of a full color organic light emitting panel.

In the compound represented by Formula 1 or Formula 2, R ₁ to R ₄ are the same as or different from each other, and each independently is a C1~ C40 alkyl group, or a C6~ C60 aryl group, or combine with each other to form a condensed ring do.

L is a single bond, or _{is selected from the group consisting of a C 6} ~ C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms, and n is an integer of 0 to 3.

In Formula 3, * is a bonding moiety, a plurality of Xs are the same as or different from each other, and each independently C(R) or N, but at least one or more is N, and R is hydrogen, deuterium, halogen, cya. No group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms , C ₆ ~ C ₆₀ Aryl group, a heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₃ ~ C ₄₀ Alkylsilyl group , C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₆₀ Aryl boron group, C ₆ ~ C ₆₀ Arylphosphine group, C ₆ ~ C ₆₀ Mono or dia It is selected from the group consisting of a rilphosphinyl group and a C ₆ ~ C ₆₀ arylamine group, and may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with adjacent groups or form a spiro bond.

R of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, a cycloalkyl group, a heterocycloalkyl group, an arylamine group, an alkylsilyl group, an alkylboron group, an arylboron group, an aryl group Phosphine group, mono or diarylphosphinyl group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryl Amine group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkylboron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C substituted with at least ₆₀ of the aryl phosphine group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ selected from the group consisting arylsilyl of C ₆₀ one kind of substituent or being unsubstituted , when substituted with a plurality of substituents, they may be the same or different from each other, m is an integer from 1 to 3, and when Ar1 is a plurality, they are the same or different from each other, and are each independently substituted or unsubstituted alkyl, A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, which may form a condensed ring with adjacent X.

Specifically, the compound represented by Formula 3 may be represented by any one of Formulas 4 to 8.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 4 to 8, * is a moiety to which a bond is formed, Y is N, O, or S;

X and Ar1 are each as defined in Formula 1;

In addition, the compound represented by Formula 4 may be represented by any one of Formula 9 or Formula 10 below.

[Formula 9]

[Formula 10]

In Formula 9 or Formula 10, * is a portion where a bond is formed, and Ar1 is as defined in Formula 1.

Specifically, Chemical Formula 5 may be embodied as Chemical Formula 11 below.

[Formula 11]

In Chemical Formula 11, * is a moiety to which a bond is formed, and Ar1 is as defined in Chemical Formula 1.

The L may be a single bond or a linker selected from the following L-1 to L-3.

In L-1 to L-3, * is a portion where a bond is formed, and Z is N, O or S.

The compound represented by Formula 1 or Formula 2 according to an example of the present invention described above may be further specified as a compound represented by any one selected from the group consisting of the compounds exemplified below. However, the compound represented by Formula 1 of the present invention is not limited by those exemplified below.

In the present invention, "alkyl" refers to a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.

In the present invention, “alkenyl” refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

In the present invention, "alkynyl" refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.

In the present invention, "aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms in which a single ring or two or more rings are combined. In addition, two or more rings may be simply attached to each other (pendant) or condensed form may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.

In the present invention, "heteroaryl" refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. In this case, one or more carbons in the ring, preferably 1 to 3 carbons, are substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are simply attached to each other or condensed may be included, and further, a form condensed with an aryl group may be included. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl), purinyl, quinolyl, benzothiazole, and carbazolyl, and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but is not limited thereto.

In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.

In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R' means an alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure. may include Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, and the like.

In the present invention, "arylamine" refers to an amine substituted with an aryl having 6 to 40 carbon atoms.

In the present invention, "cycloalkyl" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S or a hetero atom such as Se. Examples of such heterocycloalkyl include, but are not limited to, morpholine and piperazine.

In the present invention, "alkylsilyl" refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" refers to silyl substituted with aryl having 5 to 40 carbon atoms.

In the present invention, "condensed ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

2. Electron transport layer

According to the present invention, the compound represented by Formula 1 or Formula 2 employs fused fluorene as a core, and an electron withdrawing group (EWG) having excellent electron transport ability is bonded to a phenyl group of the core structure. When the compound of Formula 1 is applied as an electron transport layer because it has a strong property of receiving electrons, it can easily receive electrons from the cathode, thereby smoothly transferring electrons to the light emitting layer. Therefore, the present invention can be used as the compound for the electron transport layer represented by the formula (1).

The electron transport layer (ETL) serves to receive electrons from the cathode and move the electrons to the light emitting layer. Accordingly, the stronger the material used for the electron transport layer, the more suitable it is to move electrons.

Specifically, the electron transport layer (ETL) serves to move electrons injected from the cathode to an adjacent layer, specifically, a light emitting layer, and the compound represented by Formula 1 may be used alone as an electron transport layer (ETL) material. , or may be mixed with an electron transport layer material known in the art.

The electron transport layer material that can be mixed with the compound of Formula 1 includes an electron transport material commonly known in the art, and non-limiting examples of the electron transport material that can be used include an oxazole-based compound, an isoxazole-based compound, and a tria. Sol-based compounds, isothiazole-based compounds, oxadiazole-based compounds, thiadiazole-based compounds, perylene-based compounds, aluminum complexes (eg, Alq3 (tris(8-quinolinolato)) -aluminum (tris(8-quinolinolato)-aluminium) BAlq, SAlq, Almq3, gallium complex (eg Gaq'2OPiv, Gaq'2OAc, 2(Gaq'2)), etc. These may be used alone or in two types more can be mixed.

In the present invention, when the compound of Formula 1 and the electron transport layer material are mixed, their mixing ratio is not particularly limited and may be appropriately adjusted within a range known in the art.

3. Organic electroluminescent device

Meanwhile, another aspect of the present invention relates to an organic electroluminescent device (organic EL device) including the compound represented by Formula 1 according to the present invention.

Specifically, the present invention is an organic electroluminescent device comprising an anode, a cathode, and one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is and a compound represented by Formula 1 above. In this case, the compound may be used alone or in mixture of two or more.

The one or more organic material layers may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, a light emission auxiliary layer, an electron transport layer, an electron transport auxiliary layer, and an electron injection layer, and at least one organic material layer is represented by Formula 1 including compounds. Specifically, it is preferable that the organic material layer including the compound of Formula 1 is a light emitting layer, an electron transport layer, and an electron transport auxiliary layer.

The light emitting layer of the organic electroluminescent device according to the present invention includes a host material and a dopant material, and in this case, the compound of Formula 1 may be included as the host material. In addition, the light emitting layer of the present invention may include a known compound in the art other than the compound of Formula 1 as a host.

When the compound represented by Formula 1 is included as a light emitting layer material of an organic electroluminescent device, preferably a blue, green, or red phosphorescent host material, since the bonding force between holes and electrons in the light emitting layer is increased, the efficiency of the organic electroluminescent device (luminous efficiency and power efficiency), lifespan, luminance, and driving voltage can be improved. Specifically, the compound represented by Formula 1 is preferably included in the organic electroluminescent device as a green and/or red phosphorescent host, a fluorescent host, or a dopant material. In particular, the compound represented by Formula 1 of the present invention is preferably a green phosphorescent exciplex N-type host material of the light emitting layer having high efficiency.

The structure of the organic electroluminescent device of the present invention is not particularly limited, but may be a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer and a cathode are sequentially stacked. At this time, at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer may include the compound represented by Formula 1, preferably the light emitting layer, more preferably a phosphorescent host may include a compound represented by Formula 1 above. Meanwhile, an electron injection layer may be additionally stacked on the electron transport layer.

The structure of the organic electroluminescent device of the present invention may be a structure in which an insulating layer or an adhesive layer is inserted at the interface between the electrode and the organic material layer.

The organic electroluminescent device of the present invention can be manufactured by forming an organic material layer and an electrode using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Formula 1 above. have.

The organic material layer may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer method.

The substrate used in manufacturing the organic electroluminescent device of the present invention is not particularly limited, and for example, a silicon wafer, quartz, a glass plate, a metal plate, a plastic film, and a sheet may be used.

In addition, as the cathode material, a cathode material known in the art may be used without limitation. For example, 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); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDT), polypyrrole or polyaniline; and carbon black, but is not limited thereto.

In addition, as the negative electrode material, any negative electrode material known in the art may be used without limitation. For example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or an alloy thereof; and a multilayer structure material such as LiF/Al or LiO2/Al, but is not limited thereto.

In addition, the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer are not particularly limited, and conventional materials known in the art may be used without limitation.

Hereinafter, the present invention will be described in detail through examples. However, the following examples only illustrate the present invention, and the present invention is not limited by the following examples.

[Preparation Example 1] Synthesis of methyl 5-chloro-2-(spiro[cyclohexane-1,9'-fluoren]-2'-yl)benzoate

4,4,5,5-tetramethyl-2-(spiro[cyclohexane-1,9'-fluoren]-2'-yl)-1,3,2-dioxaborolane (50.0 g, 138.77 mmol), methyl 2-bromo -5-chlorobenzoate (34.62 g, 138.77 mmol) and Pd(PPh ₃ ) ₄ (8.02 g, 6.94 mmol), K ₂ CO ₃ (38.36 g, 277.55 mmol) were added to 1,4-Dioxane and heated to reflux for 12 hours. did After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound, methyl 5-chloro-2-(spiro[cyclohexane-1,9'-fluoren]-2'-yl)benzoate (40.26 g, yield 72%), was used by column chromatography. ) was obtained.

¹ H-NMR: δ 1.46(s, 1H), 1.44(s, 1H), 1.53(s, 2H), 1.43(s, 2H), 2.15(s, 2H), 1.90(s, 2H), 7.55( d, 1H), 7.28(t, 1H), 7.38(t, 1H), 7.90(d, 1H), 8.09(d, 1H), 7.78(d, 1H), 7.89(s, 1H), 7.82(d) , 1H), 7.74 (d, 1H), 8.15 (s, 1H), 3.90 (s, 3H)

[LCMS]: 402

[Preparation Example 2] Synthesis of 2-(5-chloro-2-(spiro[cyclohexane-1,9'-fluoren]-2'-yl)phenyl)propan-2-ol

Methyl 5-chloro-2-(spiro[cyclohexane-1,9'-fluoren]-2'-yl)benzoate (50.0 g, 124.08 mmol), methylmagnesiumbromide (44.39g, 372.25 mmol) was added to 1000ml of THF for 12 hours. It was heated to reflux. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound, 2-(5-chloro-2-(spiro[cyclohexane-1,9'-fluoren]-2'-yl)phenyl)propan-2- ol (36 g, yield 72%) was obtained.

¹ H-NMR: δ 1.46(s, 1H), 1.44(s, 1H), 1.53(s, 2H), 1.43(s, 2H), 2.15(s, 2H), 1.90(s, 2H), 7.55( d, 1H), 7.28(t, 1H), 7.38(t, 1H), 7.90(d, 1H), 8.09(d, 1H), 7.78(d, 1H), 7.89(s, 1H), 7.82(d) , 1H), 7.74 (d, 1H), 8.15 (s, 1H), 5.1 (s, 1H), 1.35 (m, 6H)

[LCMS]: 402

[Preparation Example 3] 2'-chloro-12',12'-dimethyl-12'H-spiro[cyclohexane-1,6'-indeno[1,2-b]fluorene], 2'-chloro-12', Synthesis of 12'-dimethyl-12'H-spiro[cyclohexane-1,11'-indeno[2,1-a]fluorene]

2-(5-chloro-2-(spiro[cyclohexane-1,9'-fluoren]-2'-yl)phenyl)propan-2-ol (50.0 g, 124.08 mmol) was dissolved in 1000ml of Acetic acid and 1mL of Sulfuric acid. and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound 2'-chloro-12',12'-dimethyl-12'H-spiro[cyclohexane-1,6'-indeno[1,2-b ]fluorene], (17g, yield 36%) was converted to 2'-chloro-12',12'-dimethyl-12'H-spiro[cyclohexane-1,11'-indeno[2,1-a]fluorene] (8g , yield 17%) was obtained.

2'-chloro-12',12'-dimethyl-12'H-spiro[cyclohexane-1,6'-indeno[1,2-b]fluorene]

¹ H-NMR: δ 1.46(s, 1H), 1.44(s, 1H), 1.53(s, 2H), 1.43(s, 2H), 2.15(s, 2H), 1.90(s, 2H), 7.55( d, 1H), 7.28(t, 1H), 7.38(t, 1H), 7.90(d, 1H), 8.09(d, 1H), 7.78(d, 1H), 7.89(s, 1H), 7.82(d) , 1H), 7.74 (d, 1H), 8.15 (s, 1H), 1.34 (m, 6H)

2'-chloro-12',12'-dimethyl-12'H-spiro[cyclohexane-1,11'-indeno[2,1-a]fluorene]

¹ H-NMR: δ 1.46(s, 1H), 1.44(s, 1H), 1.53(s, 2H), 1.43(s, 2H), 2.15(s, 2H), 1.90(s, 2H), 7.55( d, 1H), 7.28 (t, 1H), 7.38 (t, 1H), 7.95 (d, 1H), 8.08 (d, 1H), 7.78 (d, 1H), 7.89 (s, 1H), 7.82 (d) , 1H), 7.74 (d, 1H), 8.15 (s, 1H), 1.34 (m, 6H)

[LCMS]: 384

[Preparation Example 4] 2-(12',12'-dimethyl-12'H-spiro[cyclohexane-1,6'-indeno[1,2-b]fluoren]-2'-yl)-4,4, Synthesis of 5,5-tetramethyl-1,3,2-dioxaborolane

2'-chloro-12',12'-dimethyl-12'H-spiro[cyclohexane-1,6'-indeno[1,2-b]fluorene] (50.0 g, 130.21 mmol), bis(pinacolato)diboron ( 39.68 g, 156.25 mmol) and Pd(OAc) 2 (0.88 g, 3.91 mmol), Pd(dppf)Cl ₂ (3.19 g, 3.91 mmol), KOA _c (25.56 g, 260.42 mmol), XPhos (6.21 g, 13.02) mmol) was added to 1000 ml of 1,4-dioxane and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound, 2-(12',12'-dimethyl-12'H-spiro[cyclohexane-1,6'-indeno[1,2-b]fluoren), was used by column chromatography. ]-2'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50.87 g, yield 82%) was obtained.

¹ H-NMR: δ 1.46(s, 1H), 1.44(s, 1H), 1.53(s, 2H), 1.43(s, 2H), 2.15(s, 2H), 1.90(s, 2H), 7.55( d, 1H), 7.28(t, 1H), 7.38(t, 1H), 7.90(d, 1H), 8.09(d, 1H), 7.78(d, 1H), 7.89(s, 1H), 7.82(d) , 1H), 7.74 (d, 1H), 8.15 (s, 1H), 1.34 (m, 6H), 1.28 (m, 12H)

[LCMS]: 476

[Preparation Example 5] 2-(12',12'-dimethyl-12'H-spiro[cyclohexane-1,11'-indeno[2,1-a]fluoren]-2'-yl)-4,4, Synthesis of 5,5-tetramethyl-1,3,2-dioxaborolane

2'-chloro-12',12'-dimethyl-12'H-spiro[cyclohexane-1,11'-indeno[2,1-a]fluorene] (50.0 g, 130.21 mmol), bis(pinacolato)diboron ( 39.68 g, 156.25 mmol) and Pd(OAc) 2 (0.88 g, 3.91 mmol), Pd(dppf)Cl ₂ (3.19 g, 3.91 mmol), KOA _c (25.56 g, 260.42 mmol), XPhos (6.21 g, 13.02) mmol) was added to 1000 ml of 1,4-dioxane and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, column chromatography was used to obtain the target compound 2-(12',12'-dimethyl-12'H-spiro[cyclohexane-1,11'-indeno[2,1-a]fluoren). ]-2'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50.87 g, yield 82%) was obtained.

¹ H-NMR: δ 1.46(s, 1H), 1.44(s, 1H), 1.53(s, 2H), 1.43(s, 2H), 2.15(s, 2H), 1.90(s, 2H), 7.55( d, 1H), 7.28 (t, 1H), 7.38 (t, 1H), 7.95 (d, 1H), 8.08 (d, 1H), 7.78 (d, 1H), 7.89 (s, 1H), 7.82 (d) , 1H), 7.74 (d, 1H), 8.15 (s, 1H), 1.26 (m, 6H)

[LCMS]: 476

[Preparation Example 6] Synthesis of 2'-chlorodispiro[cyclohexane-1,6'-indeno[1,2-b]fluorene-12',1''-cyclohexane]

2'-chloro-12'H-spiro[cyclohexane-1,6'-indeno[1,2-b]fluorene] (50.0 g, 140.1 mmol), 1,5-dibromopentane (32.21 g, 140.1 mmol) and t -BuOk (57.6 g, 0.509 mmol) was added to 1000 ml of THF and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound 2'-chlorodispiro[cyclohexane-1,6'-indeno[1,2-b]fluorene-12',1''-cyclohexane] (41g) using column chromatography , yield 71%) was obtained.

¹ H-NMR: δ 1.46(s, 1H), 1.44(s, 1H), 1.53(s, 2H), 1.43(s, 2H), 2.15(s, 2H), 1.90(s, 2H), 7.55( d, 1H), 7.28 (t, 1H), 7.38 (t, 1H), 7.95 (d, 1H), 8.08 (d, 1H), 7.78 (d, 1H), 7.89 (s, 1H), 7.82 (d) , 1H), 7.74 (d, 1H), 8.15 (s, 1H), 1.22 (m, 8H), 1.26 (m, 2H)

[LCMS]: 425

[Preparation Example 7] Preparation Example Conversion Compound Synthesis According to Substituent Position Conversion

In [Preparation Example 1], instead of methyl 2-bromo-5-chlorobenzoate, using methyl 2-bromo-4-chlorobenzoate or, methyl 2-bromo-3-chlorobenzoate or methyl 2-bromo-6-chlorobenzoate, Preparation Example 2 Using the same method from to 5, the following compounds can be synthesized.

In addition, instead of 4,4,5,5-tetramethyl-2-(spiro[cyclohexane-1,9'-fluoren]-2'-yl)-1,3,2-dioxaborolane in [Preparation Example 1], 2- (9,9-dimethyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane with methyl 2-bromo-5-chlorobenzoate or methyl 2-bromo- Using the same method as in Preparation Examples 2 to 5 using 4-chlorobenzoate or methyl 2-bromo-3-chlorobenzoate or methyl 2-bromo-6-chlorobenzoate, the following compound can be synthesized.

In addition, 1-bromo-4-chloro-2-(methoxymethyl)benzene in [Preparation Example 1]

Instead, use 2-bromo-4-chloro-1-(methoxymethyl)benzene or 1-bromo-3-chloro-2-(methoxymethyl)benzene or 2-bromo-1-chloro-3-(methoxymethyl)benzene. The following compounds can be synthesized using the synthesis method shown in [Preparation Example 6].

In addition, instead of 4,4,5,5-tetramethyl-2-(spiro[cyclohexane-1,9'-fluoren]-2'-yl)-1,3,2-dioxaborolane in [Preparation Example 1], 2- (9,9-dimethyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, instead of 2-bromo-4-chloro-1-(methoxymethyl)benzene Alternatively, 1-bromo-3-chloro-2-(methoxymethyl)benzene or 2-bromo-1-chloro-3-(methoxymethyl)benzene is used and using the synthesis method shown in [Preparation Example 6], the following compounds can be synthesized.

* Synthesis example

[Synthesis Example 1] Synthesis of compound A-5

The target compound of the preparation example (10g, 20.98mmol) and 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine (8.81 g, 20.98 mmol) and Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (5.8 g, 41.96 mmol) were added to 200 ml of Toluene, 50 ml of EtOH, 50 ml of H ₂ O, and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-5 (11.09 g, yield 72%) was obtained by column chromatography.

[LCMS] : 733

In the same way, B-5 using the target compounds of Preparation Example and 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine , C-5, D-5, E-5, F-5, G-5, H-5, I-5, J-5, K-5, L-5 can be obtained.

[Synthesis Example 2] Synthesis of compound A-3

The target compound of preparation (10g, 20.98mmol) and 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (7.21 g, 20.98 mmol) and Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (5.8 g, 41.96 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-3 (11.09 g, yield 72%) was obtained by column chromatography.

[LCMS]: 657

In the same way, B-3, C-3, D-3, E-3, F using the target compounds of Preparation Example and 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine The target compound such as -3, G-3, H-3, I-3, J-3, K-3, and L-3 can be obtained.

[Synthesis Example 3] Synthesis of compound A-54

The target compound of the preparation example (10g, 20.98mmol) and 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine (9.42 g, 20.98 mmol) and Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (5.8 g, 41.96 mmol) were placed in 200 ml of Toluene, 50 ml of EtOH, 50 ml of H ₂ O and heated for 12 hours. refluxed. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-54 (11.53 g, yield 72%) was obtained by column chromatography.

[LCMS] : 763

In the same way, use the target compounds of Preparation Example and 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-4-phenylbenzo[4,5]thieno[2,3-d]pyrimidine to obtain the desired compound such as B-54, C-54, D-54, E-54, F-54, G-54, H-54, I-54, J-54, K-54, L-54 can

[Synthesis Example 4] Synthesis of compound A-70

The target compound of the preparation example (10g, 20.98mmol) and 4-(3'-chloro-[1,1'-biphenyl]-3-yl)-2-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (9.42 g, 20.98 mmol) and Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (5.8 g, 41.96 mmol) were placed in 200 ml of Toluene, 50 ml of EtOH, 50 ml of H ₂ O and heated for 12 hours. refluxed. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-70 (11.53 g, yield 72%) was obtained by column chromatography.

[LCMS] : 763

In the same way, use the target compounds of Preparation Example and 4-(3'-chloro-[1,1'-biphenyl]-3-yl)-2-phenylbenzo[4,5]thieno[3,2-d]pyrimidine to obtain the desired compound such as B-70, C-70, D-70, E-70, F-70, G-70, H-70, I-70, J-70, K-70, L-70 can

[Synthesis Example 5] Synthesis of compound M-173

The target compound of the preparation example (10g, 20.98mmol) and 2-(3''-chloro-[1,1':3',1''-terphenyl]-3-yl)-4,6-diphenyl-1,3 ,5-triazine (10.41 g, 20.98 mmol) and Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (5.8 g, 41.96 mmol) were added to 200 ml of Toluene, 50 ml of EtOH, 50 ml of H ₂ O It was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound M-173 (12.24 g, yield 72%) was obtained by column chromatography.

[LCMS]: 810

In the same way, 2-(3''-chloro-[1,1':3',1''-terphenyl]-3-yl)-4,6-diphenyl-1,3,5 -triazine can be used to obtain the target compound such as M-174.

[Synthesis Example 6] Synthesis of compound M-175

The target compound of the preparation example (10g, 20.98mmol) and 4-(3''-chloro-[1,1':3',1''-terphenyl]-3-yl)-2-phenylbenzo[4,5]thieno [3,2-d]pyrimidine (11.02 g, 20.98 mmol) and Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (5.8 g, 41.96 mmol) were mixed with 200 ml of Toluene, 50 ml of EtOH, H ₂ O 50ml, and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound M-175 (12.67 g, yield 72%) was obtained by column chromatography.

[LCMS] : 839

In the same way, 4-(3''-chloro-[1,1':3',1''-terphenyl]-3-yl)-2-phenylbenzo[4,5]thieno[3 By using ,2-d]pyrimidine, a target compound such as M-176 can be obtained.

[Synthesis Example 7] Synthesis of compound A-1

The target compound of preparation (10g, 20.98mmol) and 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (7.21 g, 20.98 mmol) and Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (5.8 g, 41.96 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-1 (9.94 g, yield 72%) was obtained by column chromatography.

[LCMS]: 657

In the same way, B-1, C-1, D-1, E-1, F using the target compounds of Preparation Example and 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine Object compounds such as -1, G-1, H-1, I-1, J-1, K-1, and L-1 can be obtained.

[Synthesis Example 8] Synthesis of compound A-3

The target compound of preparation (10g, 20.98mmol) and 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (7.21 g, 20.98 mmol) and Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (5.8 g, 41.96 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-3 (9.94 g, yield 72%) was obtained by column chromatography.

[LCMS]: 657

In the same way, B-3, C-3, D-3, E-3, F using the target compounds of Preparation Example and 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine The target compound such as -3, G-3, H-3, I-3, J-3, K-3, and L-3 can be obtained.

[Synthesis Example 9] Synthesis of compound A-18

The target compound of the preparation example (10g, 20.98mmol) and 4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-2-phenylpyrimidine (8.79 g, 20.98 mmol) and Pd(PPh) ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (5.8 g, 41.96 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-18 (11.07 g, yield 72%) was obtained by column chromatography.

[LCMS] : 732

In the same way, using the target compounds of Preparation Example and 4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-2-phenylpyrimidine, B-18, C-18, D- 18, E-18, F-18, G-18, H-18, I-18, J-18, K-18, L-18 can be obtained.

[Synthesis Example 10] Synthesis of compound A-2

The target compound of the preparation example (10g, 20.98mmol) and 2-([1,1'-biphenyl]-4-yl)-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine (8.81 g , 20.98 mmol) and Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (5.8 g, 41.96 mmol) were placed in 200 ml of Toluene, 50 ml of EtOH, 50 ml of H ₂ O, and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-2 (11.07 g, yield 72%) was obtained by column chromatography.

[LCMS] : 733

In the same way, using the target compounds of Preparation Example and 2-([1,1'-biphenyl]-4-yl)-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine, B- 2, C-2, D-2, E-2, F-2, G-2, H-2, I-2, J-2, K-2, L-2 can be obtained.

[Synthesis Example 11] Synthesis of compound A-34

The target compound of preparation (10g, 20.98mmol) and 2-(4-chlorophenyl)-3,5,6-triphenylpyrazine (8.79 g, 20.98 mmol) and Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (5.8 g, 41.96 mmol) was added to 200 ml of Toluene, 50 ml of EtOH, and 50 ml of H ₂ O, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-34 (11.07 g, yield 72%) was obtained by column chromatography.

[LCMS] : 732

In the same way, B-34, C-34, D-34, E-34, F-34, G-34 using the target compounds of Preparation Example and 2-(4-chlorophenyl)-3,5,6-triphenylpyrazine , H-34, I-34, J-34, K-34, and the target compound such as L-34 can be obtained.

[Synthesis Example 12] Synthesis of compound A-13

The target compound of the preparation example (10g, 20.98mmol) and 4-(3''-chloro-[1,1':3',1''-terphenyl]-3-yl)-2-phenylbenzo[4,5]thieno [3,2-d]pyrimidine (11.02 g, 20.98 mmol) and Pd(PPh ₃ ) ₄ (1.21 g, 1.05 mmol), K ₂ CO ₃ (5.8 g, 41.96 mmol) were mixed with 200 ml of Toluene, 50 ml of EtOH, H ₂ O 50ml, and heated to reflux for 12 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound A-13 (12.67 g, yield 72%) was obtained by column chromatography.

[LCMS] : 839

In the same way, 4-(3''-chloro-[1,1':3',1''-terphenyl]-3-yl)-2-phenylbenzo[4,5]thieno[3 B-13, C-13, D-13, E-13, F-13, G-13, H-13, I-13, J-13, K-13, L with ,2-d]pyrimidine A target compound such as -13 can be obtained.

* Device example (device evaluation result)

[Examples 1 to 6] Preparation of green organic EL device

Compounds A-3, B-3, C-3, D-3, E-3, F-3, G-3, H-3, I-3, J-3, K-3, L-3 are conventional After high-purity sublimation purification by a known method, a green organic EL device was manufactured according to the following procedure.

두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV OZONE 세정기 (Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.First, ITO (Indium tin oxide) is 1500

The thin film-coated glass substrate was washed with distilled water and ultrasonic waves. After washing with distilled water, it is ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, transferred to a UV OZONE cleaner (Power sonic 405, Hwashin Tech), and then the substrate is cleaned using UV for 5 minutes and vacuum evaporator The substrate was transferred to

m-MTDATA (60 nm)/TCTA (80 nm)/ A-3, B-3, C-3, D-3, E-3, F-3, G-3, H- on the prepared ITO transparent electrode 3, each compound of I-3, J-3, K-3, L-3 + 10% Ir(ppy) ₃ (30 nm)/BCP (10 nm)/Alq ₃ (30 nm)/LiF (1 nm )/Al (200 nm) were stacked in the order to fabricate an organic EL device.

The structures of m-MTDATA, TCTA, Ir(ppy) ₃ , CBP and BCP are as follows.

[Comparative Example 1] Preparation of green organic EL device

A green organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound A-3 as a light emitting host material when the light emitting layer was formed.

[Evaluation Example 1]

For each of the green organic EL devices manufactured in Examples 1 to 12 and Comparative Example 1, the driving voltage, current efficiency, and emission peak at a current density of (10) mA/cm 2 were measured, and the results are shown in Table 1 below. it was

Sample host Driving voltage (V) EL peak (nm) Current efficiency (cd/A) Example 1 B-3 5.43 515 44.2 Example 2 B-3 5.52 516 42.2 Example 3 B-3 5.44 516 49.2 Example 4 B-3 5.54 517 44.7 Example 5 B-3 5.34 518 45.2 Example 6 B-3 5.69 516 43.5 Example 7 B-3 5.43 515 44.2 Example 8 B-3 5.55 517 42.3 Example 9 B-3 5.44 518 49.1 Example 10 B-3 5.53 517 44.8 Example 11 B-3 5.35 517 45.4 Example 12 B-3 5.69 516 43.6 Comparative Example 1 CBP 6.52 516 38.2

As shown in Table 1 above, compounds A-3, B-3, C-3, D-3, E-3, F-3, G-3, H-3, I-3, J according to the present invention When -3, K-3, and L-3 were used as the light emitting layer of the green organic EL device (Examples 1 to 12), compared to the green organic EL device using the conventional CBP (Comparative Example 1), efficiency and driving voltage It can be seen that the better performance is shown in

[Examples 13 to 72] Fabrication of blue organic electroluminescent device

Compounds A-1 to 34, B-1 to 34, C-1 to 34, D-1 to 34, E-1 to 34, F-1 to 34, G-1 to 34, H- synthesized in Synthesis Example After high-purity sublimation purification of 1 to 34, I-1 to 34, J-1 to 34, K-1 to 34, L-1 to 34, and M-137 to 158 by a commonly known method, blue as follows An organic electroluminescent device was fabricated.

두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면, 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후, UV OZONE 세정기(Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.First, ITO (Indium tin oxide) is 1500

The thin film-coated glass substrate was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. The substrate was transferred to a vacuum evaporator.

On the ITO transparent electrode prepared as above, DS-205 (Doosan Electronics, 80 nm)/NPB (15 nm)/ADN + 5 % DS-405 (Doosan Electronics, 30 nm)/Compounds A-1 to 34, B -1 to 34, C-1 to 34, D-1 to 34, E-1 to 34, F-1 to 34, G-1 to 34, H-1 to 34, I-1 to 34, J-1 ~ 34, K-1 ~ 34, L-1 ~ 34, M-137 ~ 158 Each compound (30 nm) / LiF (1 nm) / Al (200 nm) was laminated in order to fabricate an organic electroluminescent device. .

[Comparative Example 2] Fabrication of a blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 13, except that Alq3 was used instead of Compound A-1 as the electron transport layer material.

[Comparative Example 3] Fabrication of a blue organic electroluminescent device

A blue organic electroluminescent device was manufactured in the same manner as in Example 13, except that Compound A-1 was not used as the electron transport layer material.

The structures of NPB, AND, and Alq3 used in Examples 13 to 72 and Comparative Examples 2 and 3 are as follows.

[Evaluation Example 2]

For each of the blue organic electroluminescent devices manufactured in Examples 13 to 72 and Comparative Examples 2 and 3, the driving voltage, current efficiency, and emission peak at a current density (10) mA/cm 2 were measured, and the results are shown in the table below 2 is shown.

Sample material Driving voltage (V) EL peak (nm) Current efficiency (cd/A) Example 13 A-1 3.6 456 6.6 Example 14 A-2 3.7 456 6.5 Example 15 A-3 3.7 458 6.6 Example 16 A-18 4.1 453 6.5 Example 17 A-34 3.8 456 6.8 Example 18 B-1 4.0 457 6.6 Example 19 B-2 3.6 456 6.6 Example 20 B-3 3.6 456 6.6 Example 21 B-18 3.7 456 6.5 Example 22 B-34 3.6 458 6.6 Example 23 C-1 4.1 453 6.5 Example 24 C-2 3.8 456 6.8 Example 25 C-3 3.6 456 6.6 Example 26 C-18 3.7 456 6.5 Example 27 C-34 4.1 453 6.5 Example 28 D-1 3.8 456 6.8 Example 29 D-2 4.0 457 6.6 Example 30 D-3 3.6 456 6.6 Example 31 D-18 3.6 456 6.6 Example 32 D-34 3.7 456 6.5 Example 33 E-1 3.7 458 6.6 Example 34 E-2 4.1 453 6.5 Example 35 E-3 3.8 456 6.8 Example 36 E-18 3.6 456 6.6 Example 37 E-34 3.7 456 6.5 Example 38 F-1 3.7 458 6.6 Example 39 F-2 4.1 453 6.5 Example 40 F-3 3.8 456 6.8 Example 41 F-18 3.8 456 6.8 Example 42 F-34 4.0 457 6.6 Example 43 G-1 4.0 457 6.6 Example 44 G-2 4.1 453 6.5 Example 45 G-3 3.8 456 6.8 Example 46 G-18 4.0 457 6.6 Example 47 G-34 3.6 456 6.6 Example 48 H-1 3.8 456 6.8 Example 49 H-2 4.0 457 6.6 Example 50 H-3 3.6 456 6.6 Example 51 H-18 3.7 456 6.5 Example 52 H-34 3.7 458 6.6 Example 53 I-1 4.1 453 6.5 Example 54 I-2 4.1 453 6.5 Example 55 I-3 3.8 456 6.8 Example 56 I-18 4.0 457 6.6 Example 57 I-34 3.7 456 6.5 Example 58 J-1 3.7 458 6.6 Example 59 J-2 4.1 453 6.5 Example 60 J-3 4.1 453 6.5 Example 61 J-18 3.8 456 6.8 Example 62 J-34 4.0 457 6.6 Example 63 K-1 3.6 456 6.6 Example 64 K-2 4.1 453 6.5 Example 65 K-3 3.8 456 6.8 Example 66 K-18 4.0 457 6.6 Example 67 K-34 3.7 456 6.5 Example 68 L-1 3.7 458 6.6 Example 69 L-2 4.1 453 6.5 Example 70 L-3 3.8 456 6.8 Example 71 L-18 4.0 457 6.6 Example 72 L-34 4.0 457 6.6 Example 73 M-137 3.7 458 6.6 Example 74 M-138 4.1 453 6.5 Example 75 M-139 3.8 456 6.8 Example 76 M-140 4.0 457 6.6 Example 78 M-148 3.6 456 6.6 Example 79 M-149 3.7 456 6.5 Example 80 M-152 3.7 458 6.6 Example 81 M-154 4.1 453 6.5 Example 82 M-155 3.8 456 6.8 Example 83 M-156 4.0 457 6.6 Example 84 M-157 3.7 458 6.6 Example 85 M-158 4.1 453 6.5 Comparative Example 2 Alq ₃ 4.7 459 5.6 Comparative Example 3 - 4.8 460 6.2

As shown in Table 2 above, the compound of the present invention was used in the electron transport layer.

The blue organic electroluminescent device (Examples 13 to 85) has a driving voltage compared to the conventional blue organic electroluminescent device using Alq3 for the electron transport layer (Comparative Example 2) and the blue organic electroluminescent device without the electron transport layer (Comparative Example 3) , it was found that it showed excellent performance in terms of emission peak and current efficiency.

[Examples 86 to 177] Preparation of blue organic electroluminescent device

Synthesis Examples A-3 to 78, B-3 to 70, C-3 to 70, D-3 to 70, E-3 to 78, F-3 to 70, G-3 to 70, H-3 to 70, After high-purity sublimation purification of the compounds synthesized in I-3~70, J-3~70, K-3~70, L-3~70, and M-173~176 by a commonly known method, in the following process Accordingly, a blue organic electroluminescent device was manufactured.

두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면, 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후, UV OZONE 세정기(Power sonic 405, 화신테크)로 이송시킨 다음, UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.ITO (Indium tin oxide) is 1500

The thin film-coated glass substrate was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. and transferred the substrate to a vacuum evaporator.

On the ITO transparent electrode prepared as above, DS-205 (80 nm) / NPB (15 nm) / ADN + 5 % DS-405 (Doosan Electronics, 30 nm) / A-3~78, B-3~70, C-3~70, D-3~70, E-3~78, F-3~70, G-3~70, H-3~70, I-3~70, J-3~70, K- 3-70, L-3~70, M-173-176 (5 nm) / Alq3 (25 nm) / LiF (1 nm) / Al (200 nm) were stacked in the order to prepare an organic electroluminescent device.

The structures of NPB, ADN and Alq ₃ used at this time are as follows.

[Comparative Example 4] Preparation of blue organic electroluminescent device

In Example 86, the same procedure as in Example 86 was carried out, except that Compound A-3 used as an electron transport auxiliary layer material was not used, and Alq3, an electron transport layer material, was deposited at 30 nm instead of 25 nm. An electroluminescent device was fabricated.

[Evaluation Example 3]

For the organic electroluminescent devices prepared in Examples 86 to 177 and Comparative Example 4, respectively, the driving voltage, emission wavelength, current efficiency, and emission wavelength at a current density of 10 mA/cm 2 were measured, and the results are shown in Table 3 below. indicated.

Sample electron transport auxiliary layer Driving voltage (V) Emission peak (nm) Current efficiency (cd/A) Example 86 A-3 3.6 456 6.6 Example 87 A-5 3.7 456 6.5 Example 88 A-13 3.7 458 6.6 Example 89 A-19 3.6 456 6.6 Example 90 A-20 3.7 456 6.5 Example 91 A-21 3.7 458 6.6 Example 92 A-22 3.6 456 6.6 Example 93 A-36 3.6 456 6.6 Example 94 A-37 3.7 456 6.5 Example 95 A-38 3.7 458 6.6 Example 96 A-52 4.1 453 6.5 Example 97 A-54 3.7 458 6.6 Example 98 A-56 3.7 458 6.6 Example 99 A-58 4.1 453 6.5 Example 100 A-62 3.8 456 6.8 Example 101 A-68 3.7 456 6.5 Example 102 A-70 3.8 456 6.8 Example 103 A-74 3.8 456 6.8 Example 104 A-78 3.8 456 6.8 Example 105 B-3 3.6 456 6.6 Example 106 B-5 3.7 456 6.5 Example 107 B-13 3.7 458 6.6 Example 108 B-54 4.1 453 6.5 Example 109 B-70 3.8 456 6.8 Example 110 C-3 3.7 458 6.6 Example 111 C-5 4.1 453 6.5 Example 112 C-13 3.8 456 6.8 Example 113 C-54 3.6 456 6.6 Example 114 C-70 3.8 456 6.8 Example 115 D-3 3.6 456 6.6 Example 116 D-5 3.7 456 6.5 Example 117 D-13 4.1 453 6.5 Example 118 D-54 3.8 456 6.8 Example 119 D-70 3.6 456 6.6 Example 120 E-3 3.6 456 6.6 Example 121 E-5 3.7 456 6.5 Example 122 E-13 3.7 458 6.6 Example 123 E-19 3.6 456 6.6 Example 124 E-20 3.6 456 6.6 Example 125 E-21 3.7 456 6.5 Example 126 E-22 3.7 458 6.6 Example 127 E-36 4.1 453 6.5 Example 128 E-37 3.7 458 6.6 Example 129 E-38 3.7 458 6.6 Example 130 E-52 4.1 453 6.5 Example 131 E-54 4.1 453 6.5 Example 132 E-56 4.1 453 6.5 Example 133 E-58 4.1 453 6.5 Example 134 E-62 3.8 456 6.8 Example 135 E-68 3.7 456 6.5 Example 136 E-70 3.8 456 6.8 Example 137 E-74 3.6 456 6.6 Example 138 E-78 3.7 456 6.5 Example 139 F-3 3.6 456 6.6 Example 140 F-5 3.7 456 6.5 Example 141 F-13 3.7 458 6.6 Example 142 F-54 4.1 453 6.5 Example 143 F-70 3.8 456 6.8 Example 144 G-3 3.6 456 6.6 Example 145 G-5 3.7 456 6.5 Example 146 G-13 3.7 458 6.6 Example 147 G-54 3.6 456 6.6 Example 148 G-70 3.6 456 6.6 Example 149 H-3 3.7 456 6.5 Example 150 H-5 3.7 458 6.6 Example 151 H-13 4.1 453 6.5 Example 152 H-54 3.7 458 6.6 Example 153 H-70 4.1 453 6.5 Example 154 I-3 4.1 453 6.5 Example 155 I-5 3.8 456 6.8 Example 156 I-13 3.6 456 6.6 Example 157 I-54 4.1 453 6.5 Example 158 I-70 3.8 456 6.8 Example 159 J-3 3.6 456 6.6 Example 160 J-5 3.7 456 6.5 Example 161 J-13 3.7 458 6.6 Example 162 J-54 4.1 453 6.5 Example 163 J-70 3.8 456 6.8 Example 164 K-3 3.7 456 6.5 Example 165 K-5 3.7 458 6.6 Example 166 K-13 4.1 453 6.5 Example 167 K-54 4.1 453 6.5 Example 168 K-70 3.8 456 6.8 Example 169 L-3 3.7 456 6.5 Example 170 L-5 3.7 458 6.6 Example 171 L-13 4.1 453 6.5 Example 172 L-54 4.1 453 6.5 Example 173 L-70 3.8 456 6.8 Example 174 M-173 3.7 456 6.5 Example 175 M-174 3.7 458 6.6 Example 176 M-175 4.1 453 6.5 Example 177 M-176 3.8 456 6.8 Comparative Example 4 - 4.8 457 5.8

As shown in Table 3, the blue organic electroluminescent device of Examples 86 to 177 including an electron transport auxiliary layer formed of the compound according to the present invention is Comparative Example 4 comprising an electron transport layer made of Alq3 without an electron transport auxiliary layer It was found that the organic electroluminescent device exhibited superior performance in terms of current efficiency and driving voltage.

10: positive electrode 20: negative electrode 30: organic layer 31: hole transport layer 32: light emitting layer 33: hole transport auxiliary layer 34: electron transport layer 35: electron transport auxiliary layer 36: electron injection layer 37: hole injection layer

Claims (8)

A compound represented by Formula 1 or Formula 2: [Formula 1]

[Formula 2]

In Formula 1, R _{1 To} R _{4 Are} the same or different from each other, and each independently is a C1~ C40 alkyl group, or a C6~ C60 aryl group, or combine with each other to form a condensed ring, and L is a single bond, Or C ₆ ~ C ₁₈ selected from the group consisting of an arylene group and a heteroarylene group having 5 to 18 nuclear atoms, n is an integer of 0 to 3, wherein A is a substituent represented by the following formula (3), [Formula 3]

* is a portion where a bond is formed, a plurality of Xs are the same or different from each other, and each independently C (R) or N, but at least one is N, and R is hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ Alkyl group, C ₂ ~ C ₄₀ Alkenyl group, C ₂ ~ C ₄₀ Alkynyl group, C ₃ ~ C ₄₀ A cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, C ₆ ~ C ₆₀ of an aryl group, a heteroaryl group of 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₃ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C aryl silyl group of _60, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C group ₆₀ arylboronic of, C ₆ ~ mono or diaryl phosphine of C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ of blood groups and C ₆ ~ C _{60 It} is selected from the group consisting of an arylamine group, and may form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with adjacent groups or form a spiro bond, and an alkyl group of R, an alkenyl group, an alky Nyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkylboron group, arylboron group, arylphosphine group, mono or diarylphosphi The nyl group and the arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₆₀ Aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₆ ~ C ₆₀ Aryloxy group, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Arylamine group, C ₃ ~ C ₄₀ Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₆₀ Aryl boron group, C ₆ ~ C ₆₀ Arylphosphine group, C ₆ ~ C ₆₀ Mono or diaryl phosphinyl group and C ₆ ~ C _{60 From} the group consisting of an arylsilyl group When substituted with one or more selected substituents or unsubstituted, and substituted with a plurality of substituents, they may be the same or different from each other, m is an integer from 1 to 3, and when Ar1 is a plurality, they are the same or different from each other, Each independently represents a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and adjacent X and can form a condensed ring. The compound according to claim 1, wherein Chemical Formula 3 is selected from the group consisting of Chemical Formulas 4 to 8: [Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 4 to 8, * is a portion to which a bond is formed, Y is N, O, or S, and X and Ar1 are each as defined in Formula 1; The compound according to claim 2, wherein Chemical Formula 4 is the following Chemical Formula 9 or Chemical Formula 10: [Formula 9]

[Formula 10]

In Formula 9 or Formula 10, * is a portion where a bond is formed, and Ar1 is as defined in Formula 1. The compound according to claim 2, wherein Chemical Formula 5 is the following Chemical Formula 11: [Formula 11]

In Formula 11, * is a portion to which a bond is formed, and Ar1 is as defined in Formula 1. The compound of claim 1, wherein L is a single bond or a linker selected from the following L-1 to L-3:

In L-1 to L-3, * is a moiety to which a bond is formed, and Z is N, O or S. The compound according to claim 1, wherein the compound is selected from the group consisting of the following compounds:

An organic electroluminescent device comprising (i) an anode, (ii) a cathode, and (iii) one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is represented by Formula 1 of claim 1 An organic electroluminescent device comprising the compound represented. The organic electroluminescent device according to claim 7, wherein the organic material layer comprises one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron transport layer, an electron transport auxiliary layer, and a light emitting layer.

Images