KR102467071B1 - Compound for organic electronic element having benzocyclobutene functional group for cross-linked bond, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and is characterized in that it includes at least one benzocyclobutene group at its terminal.

Description

Compounds for organic electric devices having a cross-linkable benzocyclobutene group, organic electric devices using the same, and electronic devices thereof THEREOF}

The present invention relates to an organic chemical composition for use in OLED applications, and more particularly, to a compound for an organic electric device having a crosslinkable benzocyclobutene group, an organic electric device using the same, and an electronic device thereof.

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as organic layers in organic electric devices may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions.

The term 'organic electric device' used in the present invention includes an organic integrated circuit (OIC), an organic field-effect transistor (OFET), an organic thin film transistor (OTFT), an organic light emitting transistor (OLET), an organic solar cell (OSC), Organic photodetectors, organic photoreceptors, organic field-quench devices (OFQDs), organic light emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs), and the like are defined.

In the present invention, we are particularly interested in providing novel organic compounds used in organic electric devices referred to as OLEDs. The general structure of OLEDs and their functional principles are well known to the person skilled in the art and are described in particular in US Pat. No. 4,539,507, US Pat. No. 5,151,629, EP 0676461 and WO 1998/27136.

OLED (organic photoelectric device), which is attracting attention as a next-generation display device, forms an organic light emitting layer between a substrate coated with a transparent anode material such as ITO and a cathode, and when a predetermined voltage is applied to the electrode, holes injected from the anode and holes injected from the cathode It is a device using the principle of emitting light by combining electrons in the organic light emitting layer. OLEDs are increasingly gaining attention as they are applied to electronic devices such as flat panel displays, lighting and backlighting. OLED technology is described in Geffroy et al., “Organic Light Emitting Diode (OLED) Technology: Materials Device and Display Technology,” Polym, Int., 55:572-582 (2006), U.S. Pat. Nos. 5,844,363, 6,303,238 and 5,707,745 is described in several OLED materials and constructions, all of which are incorporated herein by reference.

The organic electroluminescent device (OLED) has a multi-layer structure including a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and a charge blocking layer according to the characteristics of the light emitting layer in addition to the organic light emitting layer to realize industrially applicable performance. is made with

In the prior art, each layer constituting an organic electric device (in particular, an OLED) is generally formed by a vacuum deposition process. Japanese Patent Laid-Open No. 2006-156847 (Patent Document 1) discloses an organic compound and a technique for manufacturing an organic electric device including a single-layered organic film by depositing the same on a substrate by a vacuum deposition method. The vacuum deposition method is a principle of forming a thin film by applying heat to a sample in a high vacuum atmosphere of 10 ^-4 Torr or less to sublimate it, and the sublimated sample grows into a solid on a substrate at a relatively low temperature. However, the vacuum deposition method has a large deposition device and is not easy to install, requires a vacuum to be maintained during the process, a high process temperature, and in particular, because a mask is used for the pattern, the material consumption rate is high, so the productivity is low and the manufacturing cost is high. Therefore, it is difficult to manufacture an organic electric element in a large area.

In order to solve this problem, research to form an organic thin film through a low-cost solution process has been steadily progressing. The solution process has the disadvantage of not having high resolution compared to the vacuum deposition process, but it does not require a separate vacuum device because it can be manufactured at atmospheric pressure and temperature. Its advantage is that it can be scaled to a large area.

Types of such solution processes include spin coating, inkjet coating, screen printing, spray coating, roll-to-roll coating, and blade coating. Specific examples of a method for manufacturing a large-area organic thin film based on a solution process and a device therefor include Korean Patent Publication No. 2016-0069799, Korean Patent Registration No. 10-1618395, Korean Patent Publication No. 2017-0066703, Korean Patent Registration No. 10-1618395, Korean Patent Publication No. 2016-0141127 and Korean Patent Publication No. 2016-0138845 are detailed. Thermal printing techniques and devices that can also be used are described in, for example, published US patent applications US 2008/0311307 A1, US 2008/0308037 A1, US2006/0115585 A1, US 2010/0188457 A1, US 2011/0008541 A1, US 2010/ 0171780 A1, and US 2010/0201749 A1, which are incorporated herein by reference in their entirety.

However, when coating a multilayer organic film for an organic electric device using a solution process, there is a problem in that the organic thin film of the lower layer is damaged by the organic solvent included in the organic compound of the upper layer, making it difficult to form the multilayer thin film. In order to solve this problem, an organic compound having a crosslinkable functional group must be used, and known crosslinking groups include styrene, acrylate, oxetane, and the like. However, since these crosslinking groups require a high crosslinking temperature for the crosslinking reaction, it is difficult to use a plastic substrate. In addition, in the case of UV crosslinking, there is a disadvantage in that a photoinitiator is used or a byproduct is generated, causing problems in the lifespan and efficiency of the organic electric device.

On the other hand, the benzocyclobutene (BCB: Benzocyclobutene) group is an example of a part that undergoes thermally activated dimerization, typically above 200 ° C., in this case, formed by cleavage of one of the C-C bonds of cyclobutene, A dibenzocyclooctadiene ring is formed, followed by irreversible cyclization. In this cyclobutene ring, it is documented in the published literature (Dobish, JN; Hamilton, SK; Harth, EPolymer Chemistry 2012, 3, 857-860) that substitution of the oxygen-based donor has a dramatic effect on the ring-opening temperature of the BCB. It is recorded. However, this phenomenon has not yet been exploited for OLED applications.

OLED에서 벤조시클로부텐(BCB) 화학 및 그의 용도는 하기 공개 문헌들에서 기재된다: US20040004433, US20080315757, US20080309229, US20100133566, US20110095278, US20110065222, US20110198573, US20110042661, JP2010062120, US7893160, US20110089411, US20070181874, US20070096082, CN102329411, US20120003790 , WO2012052704, WO2012175975, WO2013007966, international application PCT/CN14/084918 (filed on 8/21/14), US provisional application 62/039935 (filed on 8/21/14)

In particular, Korean Patent Publication No. 2017-0043557 (Patent Document 2) provides a composition comprising a crosslinkable BCB-functionalized material for use in OLED applications. The composition of Patent Document 2 can be used to form a hole-transporting material for use in an electroluminescent device. In particular, Patent Document 2 provides a composition containing at least one compound selected from [Structure A] below. That is, a composition containing at least one compound selected from [Structure A] below may be a composition containing carbazole substituted with benzocyclobutene.

[Structure A]

However, there is still a need for new and novel compounds for organic electronics for use in OLED applications that include crosslinkable BCB-functionalized materials. These needs are met by the present invention.

JP 2006-156847 A KR 2017-0043557 A

"Organic Light Emitting Diode (OLED) Technology: Material Device and Display Technology", Polym, Int., 55:572-582(2006) Dobish, JN; Hamilton, SK; Harth, EP Polymer Chemistry 2012, 3, 857-860

The technical problem to be achieved by the present invention is to provide a new and novel compound for an organic electric device comprising a crosslinkable BCB-functionalized material suitable for use in OLED applications.

In addition, the present invention is to provide a novel compound for an organic electric device that can be crosslinked at a low temperature of 120° C. or less, does not generate byproducts, and has excellent efficiency and lifespan characteristics, and a method for preparing the compound.

In particular, another object of the present invention is to provide an organic thin film for an organic electric device in which crosslinking occurs through heating at a low temperature of about 120° C., and thus is insoluble in an organic solvent.

Another object of the present invention is to provide an organic electric device including an OLED formed by laminating such organic thin films in multiple layers, and an electronic device including the organic electric device.

The technical problem to be achieved by the present invention is not limited to the above-mentioned technical problem, and other technical problems not mentioned can be clearly understood by those skilled in the art from the description below. There will be.

A first aspect of the present invention for achieving the above technical problem is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, the organic compound is, the following [structural formula A] Characterized in that it comprises at least one compound selected from.

[Structural Formula A]

In [Formula A], R ₁ , R ₂ , R ₃ , R ₄ are the same as or different from each other, and each independently hydrogen, an alkyl group, a substituted alkyl group, a heterocyclic group ), a substituted heterocyclic group, an aryl group, a substituted aryl group, an amine group, a pyridine group, a pyrimidine group, It is selected from a triazole group, a triazine group, a phosphine group, a silole group, an arylamine group, a carbazole group, or a substituted carbazole group, ;

At least two or more selected from among R ₁ , R ₂ , R ₃ , and R ₄ , a benzocyclobutene group of [Structural Formula B] below is directly applied, or hydrogen, an alkyl group, or a substituted alkyl group ), a heterocyclic group, a substituted heterocyclic group, an aryl group, a substituted aryl group, and an amine group below [Formula B] of benzo A derivative substituted with a cyclobutene group (benzocyclobutene) is applied;

[Structural Formula B]

In [Structural Formula B], Y is hydrogen or a hydrocarbon, in particular, an alkyl group having a carbon chain of C ₁ to C ₁₃ or a substituted alkyl group, hydrogen, an amine or an alkyl group having a halogen, X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ are the same as or different from each other, and are each independently selected from hydrogen, hydrocarbon, substituted hydrocarbon, halogen, cyano, nitro, hydroxyl, alkoxy, amine or substituted amine, and carbonyl.

Another second aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric element, characterized in that it has the following chemical formula.

Another third aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric element, characterized in that it has the following chemical formula.

Another fourth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric element, characterized in that it has the following chemical formula.

Another fifth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric element, characterized in that it has the following chemical formula.

Another sixth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric element, characterized in that it has the following chemical formula.

Another seventh aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric element, characterized in that it has the following chemical formula.

The organic compound is at least one selected from the group consisting of a light emitting layer material, a hole injection layer material, a hole transport layer material, an electron injection layer material, an electron transport layer material, an electron blocking layer material, and a hole blocking layer material among organic thin film materials for an organic electric device. Characterized in that it is used for a purpose.

Another eighth aspect of the present invention is an ink composition for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric element, wherein the ink composition is any one selected from the first to seventh aspects Characterized in that it contains an organic compound of.

The ink composition is characterized in that it is a solution or suspension further containing a solvent. In addition, the ink composition may further include a pigment or dye.

The ink composition may further include a phosphorescent dopant or a fluorescent dopant.

Another ninth aspect of the present invention is an organic electric device in which an organic thin film layer comprising one or a plurality of layers including at least a light emitting layer is sandwiched between a cathode and an anode, wherein the organic compound for forming the organic thin film layer is It is characterized by including the organic compound of any one selected from the first aspect to the seventh aspect.

Cross-linking is formed between benzocyclobutene groups at the ends of organic compounds forming the organic thin film layer.

The organic thin film layer is at least one selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer, and an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, It has a structure in which an electron injection layer and a cathode are stacked in this order.

In addition, the organic thin film layer is characterized in that it is prepared by coating the ink composition containing the organic compound by a solution process and drying it to form a film.

Another tenth aspect of the present invention relates to an electronic device including the organic electric element according to the ninth aspect.

According to one embodiment of the present invention, the solubility of low molecular organic compounds having low solubility can be improved by providing a BCB-crosslinking substituent in the compound for an organic electric device, and as the solubility is improved, it is applied to a solution process with high productivity. The first effect is that, when an organic compound is provided with at least two or more BCB-crosslinkable substituents, a stable organic thin film is formed by cross-linking of the BCB-crosslinkable substituents at a relatively low temperature (below 150°C). The second effect that it is possible to manufacture a device with a stable multi-layer structure without the phenomenon of dissolving the adjacent layer by the solution even if a multi-layer organic thin film layer is formed through the solution process, the third effect that the organic device has a large area and low cost It has the fourth effect that anger is possible.

The organic compound according to the present invention may have improved solubility in various solvents by having a BCB substituent capable of crosslinking. In addition, in the prior art, organic thin films were formed mainly through a deposition process due to low solubility of low molecular organic compounds, but the organic compound according to the present invention can provide characteristics suitable for various solution processes by improving solubility.

In addition, in the prior art, even if an organic thin film is formed through a solution process, there is a problem in that it must be performed under high temperature conditions in order to form a stable organic thin film. However, the organic compound according to the present invention not only has excellent solubility in solvents, but also can form a heat-stable thin film even at a low temperature due to crosslinking between BCB substituents provided in the compound, so that mass production and large-area organic devices can be formed. And cost reduction is possible.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the configuration of the invention described in the claims.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention may be embodied in many different forms and, therefore, is not limited to the embodiments described herein.

Throughout the specification, when a part is said to be "connected (connected, contacted, combined)" with another part, this is not only "directly connected", but also "indirectly connected" with another member in between. "Including cases where In addition, when a part "includes" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

Terms used in this specification are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "include" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

Terms used in the specification are only used to describe specific embodiments (aspects, configurations, aspects) (or embodiments), and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, terms such as ~comprising~ or ~consisting of are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

Hereinafter, embodiments of the present invention will be described in detail with reference to structured chemical formulas and the like.

Crosslinkable BCB-functionalized materials have also been found in conventional OLED applications. In the present invention, by substituting various functional groups (eg, oxygen donor, hydroxyl group, amino group, etc.) on the ring of the benzocyclobutene compound, the temperature of ring opening is 150 ° C. or less, particularly 120 ° C. or less It was found that it can be lowered to a low temperature, thereby sufficiently satisfying the solution-processing conditions in OLED applications. In particular, substitution of the oxygen donor can significantly reduce the ring-opening temperature of the benzocyclobutene compound to 100 to 120° C., thereby providing significant process advantages.

Specifically, the present invention relates to an organic compound containing at least two or more benzocyclobutene crosslinkable derivatives at the ends of a core material forming an organic thin film for OLED application. In particular, the organic compound according to the present invention provides a composition comprising at least one compound selected from [Structural Formula 1] below.

[Structural Formula 1]

In [Formula 1], R ₁ , R ₂ , R ₃ , R ₄ are the same as or different from each other, and each independently hydrogen, an alkyl group, a substituted alkyl group, a heterocyclic group ), a substituted heterocyclic group, an aryl group, a substituted aryl group, an amine group, a pyridine group, a pyrimidine group, It is selected from a triazole group, a triazine group, a phosphine group, a silole group, an arylamine group, a carbazole group, or a substituted carbazole group. .

At least two or more selected from among R ₁ , R ₂ , R ₃ , and R ₄ , a benzocyclobutene group of [Structural Formula 2] below is directly applied, or hydrogen, an alkyl group, or a substituted alkyl group ), a heterocyclic group, a substituted heterocyclic group, an aryl group, a substituted aryl group, an amine group, etc. Benzo of [Formula 2] below A derivative substituted with a cyclobutene group (benzocyclobutene) is applied.

[Structural Formula 2]

In [Formula 2], Y is hydrogen or hydrocarbon, in particular, an alkyl group having a carbon chain of C ₁ to C ₁₃ or a substituted alkyl group, hydrogen, an amine or an alkyl group having a halogen, X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ are the same as or different from each other, and are each independently selected from hydrogen, hydrocarbon, substituted hydrocarbon, halogen, cyano, nitro, hydroxyl, alkoxy, amine or substituted amine, and carbonyl.

Examples of the heterocyclic group applicable in the present invention include tetrahyrofuran, thiophene, pyridine, pyrimidine, benzothiophene, benzofuran ( benzofuran), dibenzofuran, and the like.

In addition, examples of the aryl group applicable in the present invention include phenyl, naphthyl, phenanthryl, pyrenyl, fluorenyl, carbazoyl ( cabazolyl), spirobifluorene, tetraphenylsilane, tetraphenylmethane, and the like.

In addition, examples of the amine group applicable in the present invention include diphenylamine, triphenylamine, and the like.

The organic compound represented by [Structural Formula 1] according to the present invention is a light emitting layer (EML) material and a hole injection layer (HIL) material for forming various organic thin films disposed between the first electrode and the second electrode of an organic electric device. , a hole transport layer (HTL) material, an electron injection layer (EIL) material, an electron transport layer (ETL) material, an electron blocking layer (EBL) material, and a hole blocking layer (HBL) material.

When the organic compound according to the present invention is heated at a low temperature of about 120° C., cross-linking occurs between the benzocyclobutene groups of [Structural Formula 2] through a thermal isomerization reaction.

For this reason, in the case of the organic thin film made of the organic compound according to the present invention, since it is not dissolved in the organic solvent of the adjacent organic thin film layer, the thin film is not damaged even when multi-layered thin films are stacked through the solution process. is optimized for making

In one embodiment of the present invention, specific examples of the organic compound of the present invention represented by [Structural Formula 1] may be selected from [Formula 1] to [Formula 6] below.

In another embodiment of the present invention, an ink composition comprising an organic compound according to [Structural Formula 1], in particular, an organic compound represented by [Formula 1] to [Formula 6] according to the present invention is provided.

The ink composition may be a solution or suspension containing a solvent, and the solvent is, for example, anisole, dimethyl anisole, xylene, o-xylene, m-xylene, p-xylene, toluene, mesitylene, methyl Benzoate, dioxane, tetrahydrofuran, methyl tetrahydrofuran, tetrahydropyran, tetralin, veratrol, chlorobenzene, N-methyl pyrrolidone, N,N-dimethylformamide, dimethylsulfoxide and combinations thereof It may include one selected from the group consisting of.

An organic thin film layer may be formed by applying the ink composition and then removing the solvent to form a film. The ink composition may further include a pigment or dye. The ink composition may further include a phosphorescent dopant or a fluorescent dopant.

In another embodiment of the present invention, in an organic electric device in which a plurality of organic thin film layers including one or a plurality of layers including at least a light emitting layer are stacked between a cathode and an anode, at least one of the organic thin film layers has the [structural formula 1], in particular, it provides an organic electric device characterized in that it contains the organic compounds of [Chemical Formula 1] to [Chemical Formula 6]. In particular, the organic electric device is preferably an organic light emitting device (OLED).

The organic thin film layer may be prepared by forming a film through a solution process using the above-described ink composition containing the organic compound according to the present invention. The solution process includes any one method selected from the group consisting of spin coating, gravure offset printing, reverse offset printing, screen printing, roll-to-roll printing, slot die coating, dip coating, spray coating, doctor blade coating, and inkjet coating. do.

The organic thin film layer is a layer formed of the organic compound including at least one selected from the group consisting of a light emitting layer material, a hole injection layer material, a hole transport layer material, an electron injection layer material, an electron transport layer material, an electron blocking layer material, and a hole blocking layer material. can include The emission layer material may be a phosphorescent or fluorescent host and a phosphorescent dopant or fluorescent dopant material.

In particular, the organic light emitting device (OLED) may have a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are stacked in this order. The light emitting layer may include a phosphorescent dopant or a fluorescent dopant including red, green, blue or white, together with the organic compound according to the present invention. For example, the phosphorescent dopant may be an organometallic compound including one or more elements selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, and Tm.

The hole transport layer, the hole injection layer, the hole blocking layer, the electron injection transport layer, the electron transport layer, the electron injection layer, and the electron blocking layer may include the above-described organic compound according to the present invention.

Hereinafter, an organic electroluminescent device as an organic electric device according to the present invention will be described as an example. The organic light emitting device of the present invention may have a structure in which an anode (hole injection electrode), a hole injection layer (HIL) and/or a hole transport layer (HTL), a light emitting layer (EML), and a cathode (electron injection electrode) are sequentially stacked. Preferably, an electron blocking layer (EBL) may be further included between the anode and the light emitting layer, and an electron transport layer (ETL), an electron injection layer (EIL) or a hole blocking layer (HBL) may be further included between the cathode and the light emitting layer. have.

In the manufacturing method of the organic light emitting device according to the present invention, first, an anode is formed by coating a substrate surface with a material for an anode in a conventional manner. At this time, the substrate used is preferably a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and water resistance. In addition, as the material for the anode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, may be used.

Next, a hole injection layer (HIL) material is spin-coated on the surface of the anode to form a hole injection layer, and a hole transport layer (HTL) material is spin-coated on the surface of the hole injection layer to form a hole transport layer. A light emitting layer (EML) material is spin-coated on the surface to form the light emitting layer, and an electron transport layer is formed by spin coating an electron transport layer (ETL) material on the surface of the light emitting layer.

At this time, it is possible to selectively prevent diffusion of triplet excitons or holes into the electron transport layer by additionally forming a hole blocking layer (HBL) between the light emitting layer and the electron transport layer and using a phosphorescent dopant in the light emitting layer together. Formation of the hole blocking layer may be performed by spin-coating the hole blocking layer material, and in the case of the hole blocking layer material, the organic compound of the present invention may be used.

An electron injection layer is formed by spin-coating an electron injection layer (EIL) material on the surface of the electron transport layer. Finally, a negative electrode is formed by vacuum thermal evaporation of a negative electrode material on the surface of the electron injection layer in a conventional manner. At this time, the negative electrode material used is lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and the like may be used. In addition, in the case of a top-emitting organic light emitting device, a transparent cathode through which light can pass may be formed using indium tin oxide (ITO) or indium zinc oxide (IZO).

The organic electroluminescent device according to the present invention may be manufactured in the order described above, that is, in the order of anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode, or vice versa, cathode/hole injection layer/cathode. It may be prepared in the order of electron injection layer/electron transport layer/hole blocking layer/light emitting layer/hole transport layer/hole injection layer/anode.

In another embodiment of the present invention, an electronic device (or electronic device) including the organic light emitting device is provided.

Hereinafter, a method for synthesizing organic compounds according to the present invention will be described below through representative examples. However, the synthesis method of the organic compounds of the present invention is not limited to the methods exemplified below, and the organic compounds of the present invention may be prepared by the methods exemplified below and methods known in the art.

<Synthesis of intermediates >

Intermediates for preparing the organic compound according to the present invention were synthesized through the following process.

(1) Intermediate (a)

Referring to the above reaction scheme, in a 250mL round bottom flask under a nitrogen atmosphere, 3-bromo-7-butoxybicyclo[4.2.0]octa-1(6),2,4-triene (2.5g, 0.01mol), Bis (Pinacolato ) Add diboron (2.5g, 0.01mol), potassium acetate (0.5g, 0.015mol), Pd (pph ₃ ) ₄ (0.34g, 0.5mmol), add 1,4-dioxane (100mL) and stir. The reaction proceeds by refluxing at 110 ° C. for 24 hours. After completion of the reaction, the temperature was lowered to room temperature and washed with ethyl acetate. After receiving the filtrate and removing all the solvent, it is purified by column chromatography to obtain the intermediate (a) below.

Intermediate (a)

(2) Intermediate (b)

Referring to the above reaction scheme, in a 500mL two-neck flask under a nitrogen atmosphere, 4-bromo-N-phenylaniline (0.5g, 2mmol), the intermediate (a) (0.6g, 2mmol), Pd (pph ₃ ) ₄ (0.2 g, 0.0002 mol) was added, and THF (100 mL) was added and stirred. When all substances in the flask are dissolved, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80 ° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate an organic layer. After removing all the solvent of the separated organic layer, it is purified by column chromatography (methylene chloride: hexane = 1:4) to obtain the intermediate (b) below.

Intermediate (b)

(3) Intermediate (c)

Referring to the reaction scheme, in a 500mL two-neck flask under a nitrogen atmosphere, bis (4-bromophenyl)amine (0.5g, 2mmol), the intermediate (a) (0.6g, 2mmol), Pd (pph ₃ ) ₄ (0.2 g, 0.0002 mol) was added, and THF (100 mL) was added and stirred. When all substances in the flask are dissolved, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80 ° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate an organic layer. After removing all the solvent from the separated organic layer, it is purified by column chromatography (methylene chloride: hexane = 1:4) to obtain the intermediate (c) below.

Intermediate (c)

(4) Intermediate (d)

Referring to the above reaction scheme, in a 500mL two-neck flask under a nitrogen atmosphere, N- (4-bromophenyl) naphthalen-2-amine (0.5g, 2mmol), the intermediate (a) (0.6g, 2mmol), Pd (pph ₃ ) Add ₄ (0.2g, 0.0002mol), add THF (100mL) and stir. When all substances in the flask are dissolved, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80 ° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate an organic layer. After removing all the solvent from the separated organic layer, it is purified by column chromatography (methylene chloride: hexane = 1:4) to obtain the intermediate (d) below.

Intermediate (d)

(5) Intermediate (e)

Referring to the above reaction scheme, in a 500 mL two-neck flask under a nitrogen atmosphere, 2,2'-dibromo-9,9'-spirobi [fluorene] (0.5 g, 2 mmol), 9,10-bis (4,4,5 After adding ,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anthracene (0.6g, 2mmol) and Pd(pph ₃ ) ₄ (0.2g, 0.0002mol), add THF (100mL) and stir. When all substances in the flask are dissolved, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80 ° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate an organic layer. After removing all the solvent from the separated organic layer, it is purified by column chromatography (methylene chloride: hexane = 1:4) to obtain the intermediate (e) below.

intermediate (e)

(6) Intermediate (f)

Referring to the above reaction formula, 9,10-dibromoanthracene (0.5 g, 2 mmol), 2,2'-bis (4,4,5,5-tetramethyl-1,3,2 in a 500 mL two-neck flask under a nitrogen atmosphere After adding -dioxaborolan-2-yl)-9,9'-spirobi[fluorene] (0.6g, 2mmol) and Pd(pph ₃ ) ₄ (0.2g, 0.0002mol), add THF (100mL) and stir. When all substances in the flask are dissolved, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80 ° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate an organic layer. After removing all the solvent from the separated organic layer, it is purified by column chromatography (methylene chloride: hexane = 1:4) to obtain the intermediate (f) below.

intermediate (f)

(7) Intermediate (g)

Referring to the above reaction scheme, 3,3'-(5-bromo-1,3-phenylene)bis(7-butoxybicyclo[4.2.0]octa-1(6),2 was added to a 500mL two-neck flask under a nitrogen atmosphere. ,4-triene)(0.5g, 2mmol), 1,3,5-tris(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene(0.6g, 2mmol), After adding Pd(pph ₃ ) ₄ (0.2g, 0.0002mol), add THF (100mL) and stir. When all substances in the flask are dissolved, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80 ° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate an organic layer. After removing all the solvent from the separated organic layer, it is purified by column chromatography (methylene chloride: hexane = 1:4) to obtain the intermediate (g) below.

Intermediate (g)

<Example 1>

The organic compound of [Formula 1] was synthesized through the following reaction scheme.

In a one-neck flask, the intermediate (b) (0.96g, 2.8mmol), 2,2',7,7'-tetrabromo-9,9'-spirobi [fluorene] (0.40g, 0.63mmol), copper iodide ( 0.07g, 0.367mol), potassium phosphate (2g, 0.0147mol), 1,2-trans-cyclohexane diamine (0.4mL, 3.67mmol) were added, and 1,4-dioxane (100mL) was added and stirred. The reaction proceeds at 110 ° C. for 48 hours. After completion of the reaction, it was cooled at room temperature and worked up with MC and distilled water to separate an organic layer. The solvent of the organic layer is removed and purified by column chromatography to obtain an organic compound represented by the following [Formula 1].

[Formula 1]

<Example 2>

The organic compound of [Formula 2] was synthesized through the following reaction scheme.

In a one-neck flask, the above intermediate (c) (1.5g, 2.88mmol), 2,2'-dibromo-9,9'-spirobi [fluorene] (0.44g, 0.92mmol), copper iodide (0.07g, 0.367mol) ), potassium phosphate (2g, 0.0147mol), 1,2-trans-cyclohexane diamine (0.4mL, 3.67mmol), and 1,4-dioxane (100mL) were added and stirred. The reaction proceeds at 110 ° C. for 48 hours. After completion of the reaction, it was cooled at room temperature and worked up with MC and distilled water to separate an organic layer. The solvent of the organic layer is removed and purified by column chromatography to obtain an organic compound represented by Chemical Formula 2 below.

[Formula 2]

<Example 3>

The organic compound of [Formula 3] was synthesized through the following reaction scheme.

In a one-neck flask, the above intermediate (d) (1.5g, 2.88mmol), 2,7-dibromo-9,9'-spirobi [fluorene] (0.44g, 0.92mmol), copper iodide (0.07g, 0.367mol) , potassium phosphate (2g, 0.0147mol), 1,2-trans-cyclohexane diamine (0.4mL, 3.67mmol) were added, and 1,4-dioxane (100mL) was added and stirred. The reaction proceeds at 110 ° C. for 48 hours. After completion of the reaction, it was cooled at room temperature and worked up with MC and distilled water to separate an organic layer. The solvent of the organic layer was removed and purified by column chromatography to obtain an organic compound represented by Formula 3 below.

[Formula 3]

<Example 4>

The organic compound of [Formula 4] was synthesized through the following reaction scheme.

In a one-neck flask, the intermediate (e) (1.5g, 2.88mmol), 9,10-bis (2'-bromo-9,9'-spirobi [fluoren] -2-yl) anthracene (0.44g, 0.92mmol) ), copper iodide (0.07g, 0.367mol), potassium phosphate (2g, 0.0147mol), 1,2-trans-cyclohexane diamine (0.4mL, 3.67mmol), add 1,4-dioxane (100mL) and stir let it The reaction proceeds at 110 ° C. for 48 hours. After completion of the reaction, it was cooled at room temperature and worked up with MC and distilled water to separate an organic layer. The solvent of the organic layer is removed and purified by column chromatography to obtain an organic compound represented by the following [Chemical Formula 4].

[Formula 4]

<Example 5>

The organic compound of [Chemical Formula 5] was synthesized through the following reaction scheme.

In a one-neck flask, the intermediate (f) (1.5g, 2.88mmol), the intermediate (g) (0.44g, 0.92mmol), copper iodide (0.07g, 0.367mol), potassium phosphate (2g, 0.0147mol), After adding 1,2-trans-cyclohexane diamine (0.4mL, 3.67mmol), add 1,4-dioxane (100mL) and stir. The reaction proceeds at 110 ° C. for 48 hours. After completion of the reaction, it was cooled at room temperature and worked up with MC and distilled water to separate an organic layer. The solvent of the organic layer is removed and purified by column chromatography to obtain an organic compound represented by Formula 5 below.

[Formula 5]

<Example 6>

The organic compound of [Chemical Formula 6] was synthesized through the following reaction scheme.

In a one-neck flask, the intermediate (f) (1.5g, 2.88mmol), the intermediate (c) (0.44g, 0.92mmol), copper iodide (0.07g, 0.367mol), potassium phosphate (2g, 0.0147mol), After adding 1,2-trans-cyclohexane diamine (0.4mL, 3.67mmol), add 1,4-dioxane (100mL) and stir. The reaction proceeds at 110 ° C. for 48 hours. After completion of the reaction, it was cooled at room temperature and worked up with MC and distilled water to separate an organic layer. The solvent of the organic layer is removed and purified by column chromatography to obtain an organic compound represented by the following [Chemical Formula 6].

[Formula 6]

Claims (18)

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric element,
The organic compound is an organic compound, characterized in that it comprises at least one compound selected from the following [Structural Formula A].
[Structural Formula A]

In [Formula A], R ₁ , R ₂ , R ₃ , R ₄ are the same as or different from each other, and each independently hydrogen, an alkyl group, a substituted alkyl group, a heterocyclic group ), a substituted heterocyclic group, an aryl group, a substituted aryl group, an amine group, a pyridine group, a pyrimidine group, It is selected from a triazole group, a triazine group, a phosphine group, a silole group, an arylamine group, a carbazole group, or a substituted carbazole group;
At least two or more selected from among R ₁ , R ₂ , R ₃ , and R ₄ , a benzocyclobutene group of [Structural Formula B] below is directly applied, or hydrogen, an alkyl group, or a substituted alkyl group ), a heterocyclic group, a substituted heterocyclic group, an aryl group, a substituted aryl group, and an amine group below [Formula B] of benzo A derivative substituted with a cyclobutene group (benzocyclobutene) is applied;
[Structural Formula B]

In [Structural Formula B], Y is hydrogen or a hydrocarbon, an alkyl group having a carbon chain of C ₁ to C ₁₃ or a substituted alkyl group, hydrogen, an amine or an alkyl group having a halogen, X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are the same as or different from each other, and are each independently selected from hydrogen, hydrocarbon, substituted hydrocarbon, halogen, cyano, nitro, hydroxyl, alkoxy, amine or substituted amine, and carbonyl. As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric element,
The organic compound is an organic compound, characterized in that it has the following chemical formula.

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric element,
The organic compound is an organic compound, characterized in that it has the following chemical formula.

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric element,
The organic compound is an organic compound, characterized in that it has the following chemical formula.

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric element,
The organic compound is an organic compound, characterized in that it has the following chemical formula.

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric element,
The organic compound is an organic compound, characterized in that it has the following chemical formula.

As an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric element,
The organic compound is an organic compound, characterized in that it has the following chemical formula.

According to any one of claims 1 to 7,
The organic compound is at least one selected from the group consisting of a light emitting layer material, a hole injection layer material, a hole transport layer material, an electron injection layer material, an electron transport layer material, an electron blocking layer material, and a hole blocking layer material among organic thin film materials for an organic electric device. An organic compound characterized in that it is used for a purpose. An ink composition for forming an organic thin film disposed between a first electrode and a second electrode of an organic electric element,
The ink composition characterized in that the ink composition comprises the organic compound of any one selected from claims 1 to 7. According to claim 9,
The ink composition, characterized in that the ink composition is a solution or suspension further containing a solvent. According to claim 9,
The ink composition, characterized in that the ink composition further comprises a pigment or dye. According to claim 9,
The ink composition further comprises a phosphorescent dopant or a fluorescent dopant. In an organic electric device in which an organic thin film layer comprising one or a plurality of layers including at least a light emitting layer is sandwiched between a cathode and an anode,
An organic electric device characterized in that the organic compound for forming the organic thin film layer includes any one organic compound selected from claims 1 to 7. According to claim 13,
An organic electric device, characterized in that a crosslink is formed between benzocyclobutene groups at the ends of organic compounds forming the organic thin film layer. 15. The method of claim 14,
The organic electric device, characterized in that the organic thin film layer is at least one selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer and a hole blocking layer. According to claim 15,
An organic electric device characterized in that it has a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode are stacked in this order. 17. The method of claim 16,
The organic thin film layer is an organic electric device, characterized in that manufactured by coating the ink composition containing the organic compound by a solution process and drying to form a film. An electronic device comprising the organic electric element according to claim 13.