KR20100094415A - Cycloaralkyl derivatives and organoelectroluminescent device using the same - Google Patents

Abstract

PURPOSE: Cycloalkyl derivatives are provided to have superior color purity, power efficiency, and luminous efficiency and to obtain an organic electroluminescent device having a lifespan which is remarkably improved. CONSTITUTION: Cycloalkyl derivatives are marked by chemical formula 1. The organic electroluminescent device comprises an anode, a cathode, and a layer which is placed between the anode and the cathode and includes the cycloalkyl derivatives. The cycloalkyl derivatives are included in an electroluminescent layer between the anode and the cathode. The thickness of the electroluminescent layer is 50-2,000 angstroms.

Description

Cycloaralkyl derivative and organic electroluminescent device using same {CYCLOARALKYL DERIVATIVES AND ORGANOELECTROLUMINESCENT DEVICE USING THE SAME}

The present invention relates to a cycloaralkyl derivative and an organic electroluminescent device employing the cycloaralkyl derivative. More particularly, when used in an organic electroluminescent device, color purity, power efficiency and luminous efficiency are improved, and a long lifetime is achieved. It relates to a cycloaralkyl derivative having an organic light emitting device comprising the cycloaralkyl derivative. The invention also relates to the field of display elements, flat panel displays, backlights, lighting, interiors, signs, signs, electrophotographic cameras, optical signal generators, MP3 players or mobile phones that can convert electrical energy into light. The present invention relates to a light emitting device that can be used.

Recently, as the size of the display device increases, the demand for a flat display device having less space is increasing. A liquid crystal display, which is a typical flat display device, has an advantage of being lighter than a conventional CRT. However, the viewing angle is limited and the rear surface is limited. There were disadvantages such as the need for back light. On the contrary, organic light emitting diodes (OLEDs), which are new flat display devices, are displays using self-luminous phenomena, and have a large viewing angle, are thinner and shorter than liquid crystal displays, and have fast response speeds. It has a vertex.

Currently, organic light emitting diodes have excellent characteristics such as low driving voltage (eg, 10V or less), wide viewing angle, high-speed response, and high contrast compared to plasma display panel (PDP) or inorganic electroluminescent display. It can be used as a pixel of a graphic display, a pixel of a television image display or a surface light source. The device can be formed on a flexible transparent substrate, can be made very thin and light, and has good color, which is emerging as a device suitable for the next generation flat panel display (FPD).

Such an organic light emitting device has a hole from the anode and a cathode in an organic light emitting layer formed between a first electrode (anode), which is a hole injection electrode (anode), and a second electrode (cathode, cathode), which is an electron injection electrode. When electrons are injected, electrons and holes combine to form an exciton in the excited state as a pair, and the exciton in the excited state falls to the ground state and disappears and emits light. In recent years, full color ) Application to display is expected.

Representative organic electroluminescent devices of the early days have a single layer structure known by Gurnee in 1969 (US Patent No. 3,172,862 and US Patent No. 3,173,050), and are practically used because they require excessive driving voltage of 100 V or more. There was a problem that it is difficult to be. Therefore, in order to solve this problem, a multi-layer organic electroluminescent device having a significantly low driving voltage of about 6 to 14V was developed by Tang of Eastman Kodak co. In 1987 (Applied Physics Letters, 51, 913 (1987); Journal of Applied Physics, 65, 3610 (1989); U.S. Patent No. 4,356,429, currently organic with various functional stacking structures such as hole injection layer, hole transport layer, electron transport layer and electron injection layer Electroluminescent devices are continuously being developed.

As a light emitting material using a triplet of organic light emitting materials, several phosphorescent materials using iridium or platinum metal compounds have been published by Princeton University and the University of Southern California (Inorganic Chemistry, 40, 1704-1711, 2001 and Journal of the American Chemical). Society, 123, 4304-4312, 2001) Recently, due to the need for high-efficiency and long-life materials required for large screens, the development of phosphorescent materials and devices using the same have been increasing.

In general, a host and a dopant system are used to improve luminous efficiency in a light emitting layer using fluorescence or phosphorescence. CBP (4, 4'-N, N'-dicarbazolbipheny) is the most commonly used host material as a phosphorescent material. It is widely used. Carbazole, which is used as a main skeleton constituting CBP, has a relatively large triplet band gap and is widely used for phosphorescent host materials and hole blocking layers. Therefore, recently, various materials have been developed by fusing an aryl group to carbazole or introducing various substituents (Japanese Patent Laid-Open Publication No. 2008-0214244, Japanese Patent Laid-Open Publication 2003-0133075). Organic field devices having sufficient performance in terms of voltage, luminous efficiency, current efficiency, device life, power efficiency and external quantum efficiency have not yet been obtained.

Prior to the present invention, attempts have been made to link aryl groups by rings, but the substance used in the present invention is different from those intended in the present invention, such as being different from the basic structure or used in medicine. (Japanese Patent Publication No. 1994-0078316, Japanese Patent Publication 2005-0539088)

The material secured by the present invention is not limited to the light emitting layer, but may be used in various layers of the light emitting device such as a hole transport layer, an electron transport layer, and a hole blocking layer.

Accordingly, a first object of the present invention is to provide a cycloaralkyl derivative which improves color purity, power efficiency, and luminous efficiency of an organic light emitting diode and has a long lifetime.

In addition, a second technical problem to be achieved by the present invention is to provide an organic electroluminescent device comprising the cycloaralkyl derivative.

The present invention provides a cycloaralkyl derivative of the formula (1) to achieve the first object.

                 (One)

In the above formula

R ₁ to R ₄ may be the same or different, and each independently represent a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 10 to 60 Condensed aromatic ring, substituted or unsubstituted condensed aromatic heterocycle having 10 to 60 carbon atoms, substituted or unsubstituted styryl group, substituted or unsubstituted amino group, substituted or unsubstituted carbonyl group, substituted or unsubstituted carboxyl group, substituted or unsubstituted aryl value Or substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, substituted or unsubstituted cycloalkenyl group having 3 to 40 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted alkylsilyl having 1 to 40 carbon atoms Group, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, substituted or unsubstituted straight chain, pulverized or cyclic alkyl group having 1 to 60 carbon atoms, substituted or unsubstituted From the group consisting of a cyclic group having 6 to 60 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted hetero aralkyl group having 3 to 40 carbon atoms Is optional,

Y ₁ and Y ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted hetero group having 5 to 40 carbon atoms It may be selected from the group consisting of an aralkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms.

According to one embodiment of the present invention, the substituents of R ₁ to R ₄ , Y ₁ and Y ₂ are a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an alkylsilyl group having 1 to 10 carbon atoms, and 1 carbon atom. An alkyl group of 40, an alkoxy group of 1-40 carbon atoms, an alkylamino group of 1-40 carbon atoms, an aryl group of 6-30 carbon atoms, an aryloxy group of 6-30 carbon atoms, an arylamino group of 6-30 carbon atoms, and 6-30 carbon atoms One or more may be selected from the group consisting of an arylsilyl group, a heteroaryl group having 3 to 40 carbon atoms.

According to another embodiment of the present invention, R ₁ to R ₄ may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, the ring is preferably a 5-membered wheel to 8-membered wheel, It is preferable that the substituted saturated or unsaturated ring substituent is a C3-C40 cycloalkyl group. The substituents of the saturated or unsaturated rings may also be attached or fused together in a pendant manner.

The cycloaralkyl derivative according to the present invention may be, for example, any one compound selected from the group represented by the following formulas (2) to (4):

                             (2)

                             (3)

                                (4)

In the formula, R ₅ to R ₂₆ may be the same or different, and each independently hydrogen atom, deuterium atom, halogen atom, hydroxy group, cyano group, nitro group, alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon number 10 60 condensed aromatic rings, substituted or unsubstituted condensed aromatic heterocycles having 10 to 60 carbon atoms, substituted or unsubstituted styryl groups, substituted or unsubstituted amino groups, substituted or unsubstituted carbonyl groups, substituted or unsubstituted carboxyl groups, substituted or unsubstituted An aryl group, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon group having 1 to 30 carbon atoms Silyl groups, substituted or unsubstituted straight chain, crushed or cyclic alkyl groups having 1 to 60 carbon atoms, substituted or unsubstituted aryl groups having 6 to 60 carbon atoms, substituted Is unsubstituted C6-heterocycloalkyl is selected from an aralkyl group of 40 - 60 aralkyl group, a substituted or unsubstituted 3-40 membered heteroaryl group, a substituted or unsubstituted 3

Substituents of R ₅ to R ₂₆ include a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an alkylsilyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, and a carbon atom 1 A group consisting of an alkylamino group of 40, an aryl group of 6 to 30 carbon atoms, an aryloxy group of 6 to 30 carbon atoms, an arylamino group of 6 to 30 carbon atoms, an arylsilyl group of 6 to 30 carbon atoms, and a heteroaryl group of 3 to 40 carbon atoms One or more selected from

Y ₁ and Y ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted hetero group having 5 to 40 carbon atoms It is selected from the group consisting of an aralkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms,

The substituents of Y ₁ and Y ₂ are a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an alkylsilyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, and a carbon atom 1 A group consisting of an alkylamino group of 40, an aryl group of 6 to 30 carbon atoms, an aryloxy group of 6 to 30 carbon atoms, an arylamino group of 6 to 30 carbon atoms, an arylsilyl group of 6 to 30 carbon atoms, and a heteroaryl group of 3 to 40 carbon atoms At least one substituent selected from.

The present invention also provides an organic electroluminescent device having a layer comprising an anode cathode and a cycloaralkyl derivative represented by Formula 1 interposed between the anode and the cathode in order to achieve the second technical problem. . In this case, the cycloaralkyl derivative according to the present invention is preferably included in the light emitting layer between the anode and the cathode. According to an embodiment of the present invention, the anode and the cathode may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer. .

According to an embodiment of the present invention, the thickness of the light emitting layer is 50 to 2,000 mm 3.

According to an embodiment of the present invention, one or more layers selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer may be formed by a single molecule deposition method or a solution process. And is preferably used for display elements, display elements and monochromatic or white illumination elements.

By using the cycloaralkyl derivative according to the present invention, it is possible to provide an organic light emitting device excellent in color purity, power efficiency and luminous efficiency.

1A to 1F are cross-sectional views illustrating a laminated structure of organic light emitting diodes according to an exemplary embodiment of the present invention.

The present invention provides a derivative having a basic skeleton of cycloaralkyl represented by Chemical Formula 1, and the paracyclo derivative is designed to maintain a flat form and to facilitate the transport of holes or electrons in a specific layer. The material secured by the present invention can be effectively used in all layers of the organic field device, but in particular, it can be used as a host of the light emitting layer to transfer holes or electrons introduced from both electrodes to the dopant to facilitate the formation of excitons.

Cycloaralkyl derivatives according to the present invention is characterized by the following formula (1).

                 (One)

In the above formula, R ₁ to R ₄ may be the same or different, and each independently hydrogen atom, deuterium atom, halogen atom, hydroxy group, cyano group, nitro group, alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted Condensed aromatic ring having 10 to 60 carbon atoms, substituted or unsubstituted condensed aromatic heterocycle having 10 to 60 carbon atoms, substituted or unsubstituted styryl group, substituted or unsubstituted amino group, substituted or unsubstituted carbonyl group, substituted or unsubstituted carboxyl group, substituted or Unsubstituted aryl, substituted or unsubstituted C3-C40 cycloalkyl group, substituted or unsubstituted C3-C40 cycloalkenyl group, substituted or unsubstituted C1-C60 alkoxy group, substituted or unsubstituted C1-C1 40 alkylsilyl groups, substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms, substituted or unsubstituted straight chain, pulverized or cyclic alkyl having 1 to 60 carbon atoms A group, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted heteroalkyl having 3 to 40 carbon atoms An alkyl group,

Y ₁ and Y ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted hetero group having 5 to 40 carbon atoms It may be selected from the group consisting of an aralkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms.

According to one embodiment of the present invention, the substituents of R ₁ to R ₄ , Y ₁ and Y ₂ are a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an alkylsilyl group having 1 to 10 carbon atoms, and 1 carbon atom. An alkyl group of 40, an alkoxy group of 1-40 carbon atoms, an alkylamino group of 1-40 carbon atoms, an aryl group of 6-30 carbon atoms, an aryloxy group of 6-30 carbon atoms, an arylamino group of 6-30 carbon atoms, and 6-30 carbon atoms One or more may be selected from the group consisting of an arylsilyl group, a heteroaryl group having 3 to 40 carbon atoms.

According to another embodiment of the present invention, R ₁ to R ₄ may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, the ring is preferably a 5-membered wheel to 8-membered wheel, It is preferable that the substituted saturated or unsaturated ring substituent is a C3-C40 cycloalkyl group. The substituents of the saturated or unsaturated rings may also be attached or fused together in a pendant manner.

The cycloaralkyl derivative according to the present invention may be, for example, any one compound selected from the group represented by the following formulas (2) to (4):

                             (2)

                             (3)

                                (4)

In the formula, R ₅ to R ₂₆ may be the same or different, and each independently hydrogen atom, deuterium atom, halogen atom, hydroxy group, cyano group, nitro group, alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon number 10 60 condensed aromatic rings, substituted or unsubstituted condensed aromatic heterocycles having 10 to 60 carbon atoms, substituted or unsubstituted styryl groups, substituted or unsubstituted amino groups, substituted or unsubstituted carbonyl groups, substituted or unsubstituted carboxyl groups, substituted or unsubstituted An aryl group, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon group having 1 to 30 carbon atoms Silyl groups, substituted or unsubstituted straight chain, crushed or cyclic alkyl groups having 1 to 60 carbon atoms, substituted or unsubstituted aryl groups having 6 to 60 carbon atoms, substituted Is unsubstituted, having 6 - 40, and heteroaralkyl of the alkyl group, - an aralkyl group of 60, a substituted or unsubstituted 3-heteroaryl group 40, a substituted or unsubstituted 3

Substituents of R ₅ to R ₂₆ include a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an alkylsilyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, and a carbon atom 1 A group consisting of an alkylamino group of 40, an aryl group of 6 to 30 carbon atoms, an aryloxy group of 6 to 30 carbon atoms, an arylamino group of 6 to 30 carbon atoms, an arylsilyl group of 6 to 30 carbon atoms, and a heteroaryl group of 3 to 40 carbon atoms One or more selected from

Y ₁ and Y ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted hetero group having 5 to 40 carbon atoms A divalent linking group consisting of an aralkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms,

The substituents of Y ₁ and Y ₂ are a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an alkylsilyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, and a carbon atom 1 A group consisting of an alkylamino group of 40, an aryl group of 6 to 30 carbon atoms, an aryloxy group of 6 to 30 carbon atoms, an arylamino group of 6 to 30 carbon atoms, an arylsilyl group of 6 to 30 carbon atoms, and a heteroaryl group of 3 to 40 carbon atoms At least one substituent selected from.

The cycloaralkyl derivative according to an embodiment of the present invention may be any one compound selected from the group represented by the following Chemical Formulas 5 to 79, but is not limited to these exemplary compounds.

       (5) (6) (7)

(8) (9) (10)

(11) (12) (13)

(14) (15) (16)

(17) (18) (19)

(20) (21) (22)

       (23) (24) (25)

      (26) (27) (28)

(29) (30) (31)

(32) (33) (34)

(35) (36) (37)

(38) (39) (40)

(41) (42) (43)

(44) (45) (46)

(47) (48) (49)

(50) (51) (52)

(53) (54) (55)

(56) (57) (58)

(59) (60)

(61) (62)

(63) (64)

(65) (66)

(67) (68)

(69) (70)

(71) (72)

(73) (74)

(75) (76)

(78) (79)

In addition, the organic light emitting device according to the present invention is an anode; Cathode; And a layer comprising a cycloaralkyl derivative represented by Formula 1 interposed between the anode and the cathode. In this case, the cycloaralkyl derivative according to the present invention is preferably included in the light emitting layer between the anode and the cathode. According to an embodiment of the present invention, the anode and the cathode may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer. .

According to an embodiment of the present invention, the thickness of the light emitting layer is 50 to 2,000 mm 3.

According to an embodiment of the present invention, one or more layers selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer may be formed by a single molecule deposition method or a solution process. And is preferably used for display elements, display elements and monochromatic or white illumination elements.

Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like. Halogen atom, hydroxy group, nitro group, cyano group, silyl group (in this case referred to as "alkylsilyl group"), substituted or unsubstituted amino group (-NH ₂ , -NH (R), -N (R ') (R ''), R 'and R "are independently of each other an alkyl group having 1 to 10 carbon atoms, in this case," alkylamino group "), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, 1 carbon atom An alkyl group of 20 to 20 carbon atoms, a halogenated alkyl group of 1 to 20 carbon atoms, an alkenyl group of 1 to 20 carbon atoms, an alkynyl group of 1 to 20 carbon atoms, a heteroalkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, and 6 to 20 carbon atoms An aralkyl group, a heteroaryl group having 6 to 20 carbon atoms, or having 6 carbon atoms It may be substituted with hetero-aralkyl group of 20.

Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like. At least one hydrogen atom of the alkoxy group may be substituted with the same substituent as in the alkyl group.

The aryl group, which is a substituent used in the compound of the present invention, means an aromatic system including one or more rings, and the rings may be attached or fused together by a pendant method. Specific examples of the aryl group include aromatic groups such as phenyl, naphthyl, tetrahydronaphthyl and the like, and one or more hydrogen atoms of the aryl group may be substituted with the same substituents as in the case of the alkyl group (for example, When substituted with an amino group, an "arylamino group", when substituted with a silyl group, an "arylsilyl group", and when substituted with an oxy group, "aryloxy group".

Heteroaryl group which is a substituent used in the compound of the present invention, N, O, P means a ring aromatic system having 3 to 30 carbon atoms containing 1, 2 or 3 hetero atoms selected from S, and the remaining ring atoms are carbon, The rings may be attached or fused together in a pendant manner. At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the alkyl group.

The cycloaralkyl compound according to the present invention may have a structure represented by the above formula. However, the above structural formulas merely show an example of the cycloaralkyl compound according to the present invention and in no way limit the present invention.

Referring to the organic light emitting device according to the present invention in more detail, the organic light emitting device further comprises at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer and an electron injection layer between the anode and the cathode. In some embodiments, the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer effectively transfer holes or electrons to the light emitting layer, thereby increasing the probability of light emission coupling in the light emitting layer.

The hole injection layer and the hole transport layer are laminated to facilitate the injection of holes from the anode and the transport of the injected holes. As the material for the hole transport layer, electron donor molecules having small ionization potential are used. Diamine, triamine or tetraamine derivatives based on amines are frequently used. In the present invention, as a material of the hole transport layer, as long as it is commonly used in the art, various materials can be used without limitation, for example, N, N' -bis (3-methylphenyl) -N, N' -diphenyl- [1,1-biphenyl] -4,4'-diamine (TPD) or N, N' -di (naphthalen-1-yl) -N, N' -diphenyl benzidine (α- NPD) and the like can be used. In addition, a hole injection layer (HIL) may be further stacked below the hole transport layer, and the hole injection layer material may also be used without particular limitation as long as it is commonly used in the art. For example, CuPc or Starburst type amines such as TCTA, m-MTDATA, IDE406 (manufactured by Idemitsu Corp.) and the like can be used.

                 CuPc TCTA

            m-MTDATA

An organic light emitting layer is stacked on the hole transport layer, and the organic light emitting layer may be made of a single material or may be made of a host / dopant.

In general, when the compound is used as a single material, a host / dopant-based light emitting layer is preferable, because an intermolecular interaction generates a mound peak at long wavelengths, resulting in poor color purity, and low efficiency due to a light emission decay effect. The cycloaralkyl derivative may be used as a host material in the host / dopant light emitting layer. The dopant material in the host / dopant light emitting layer is not particularly limited as long as it is generally used in the art. The electron transport layer serves to increase the chance of recombination in the light emitting layer by smoothly transporting electrons supplied from the cathode to the light emitting layer and suppressing movement of holes that are not bonded in the light emitting layer. Such electron transport layer material is not particularly limited as long as it is a material used in the art, for example, tri-8-hydroxyquinoline aluminum (Alq 3), PBD (2- (4-biphenylyl) -5- ( 4-t-butylphenyl) -1,3,4-oxadiazole), TNF (2,4,7-trinitro fluorenone), BMD, BND and the like can be used.

Meanwhile, an electron injection layer (EIL), which facilitates electron injection from the cathode and ultimately improves power efficiency, may be further stacked on the electron transport layer. Also commonly used in the art may be used without particular limitation, for example, it may be used a material such as LiF, NaCl, CsF, Li ₂ O, BaO.

Furthermore, in addition to the above-described hole injection layer, hole transport layer, electron transport layer, and electron injection layer, the organic light emitting device according to the present invention may further include additional functional laminated structures such as a hole blocking layer or an electron blocking layer. . At this time, the hole blocking layer serves to prevent such a problem by using a material having a very low HOMO level because the life and efficiency of the device is reduced when holes are introduced into the cathode through the organic light emitting layer. The material constituting the hole blocking layer is not particularly limited, but must have an ionization potential higher than that of the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, and the like may be used.

More specifically, FIGS. 1A to 1F illustrate organic light emitting diodes having various types of stacked structures. Referring to this, the organic light emitting diode of FIG. 1A includes an anode / hole injection layer / light emitting layer / cathode. The organic electroluminescent device of FIG. 1B has a structure consisting of an anode / hole injection layer / light emitting layer / electron injection layer / cathode. In addition, the organic light emitting display device of FIG. 1c has a structure of an anode / hole injection layer / hole transporting layer / light emitting layer / cathode, and the organic light emitting device shown in FIG. 1d includes an anode / hole injection layer / hole transporting layer / light emitting layer / electron injection. The organic electroluminescent device of FIG. 1E has a structure of a layer / cathode, and has an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode. Finally, the organic electroluminescent device of FIG. 1F is an anode. It has a structure of / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

The organic electroluminescent device according to the present invention may include the cycloaralkyl derivative in various laminated structures interposed between the anode and the cathode. Preferably, the cycloaralkyl derivative is a host in the light emitting layer between the anode and the cathode. Can be used as a material.

In addition, the thickness of the light emitting layer including the cycloaralkyl derivative may be 50 to 2,000 kPa, but when the thickness is less than 50 kPa, the luminous efficiency is lowered, and when it exceeds 2,000 kPa, the driving voltage is uneconomical. .

A method of manufacturing an organic light emitting display device according to the present invention will be described with reference to FIGS. 1A to 1F.

First, an anode material is coated on the substrate. As the substrate, a substrate used in a conventional light emitting device is used. A glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness is preferable. In addition, as the anode material, materials commonly used in the art, such as transparent and conductive indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), or zinc oxide (ZnO), may be used. have. The hole injection layer is selectively stacked on the anode by vacuum thermal deposition or spin coating, and then the hole transport layer is formed on the hole injection layer by vacuum thermal deposition or spin coating. .

Next, after the light emitting layer is laminated on the hole transport layer, a hole blocking layer is selectively formed thereon by vacuum thermal evaporation or spin coating. Finally, the electron transport layer is deposited on the hole blocking layer by vacuum thermal deposition or spin coating, and then an electron injection layer is selectively formed, and the cathode forming metal is vacuum-deposited on the electron injection layer. The organic electroluminescent device according to the present invention can be manufactured. On the other hand, as the cathode forming metal, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) or the like, and a transmissive cathode using ITO or IZO may be used to obtain a front light emitting device.

Synthesis Example 1 Synthesis of Chemical Formula 31

Synthesis Example 1-1. Synthesis of Chlorodiphenyl Triazine.

In a 100 ml round bottom flask, 24.3 g (1 mol) of magnesium and 2 g of iodine are added to 40 ml of tetrahydrofuran and refluxed for 2 hours. After lowering to room temperature, the reactor is slowly added at 0 ° C. by diluting 157 g (3 mol) of bromobenzene in 200 ml of tetrahydrofuran. When the drop is completed, reflux for 2 hours. 61.4 g (0.33 mol) of cyanuric chloride is added to a 1000 ml round bottom flask, and it is dissolved in 210 ml of tetrahydrofuran and maintained at 0 to 10 ° C. The green yard reagent prepared above is cooled to room temperature and then added dropwise to the reactor. When the reaction was completed, the reaction was terminated by slowly dropwise addition of 300 ml of 2 M aqueous hydrochloric acid solution. After completion of the dropwise addition, the reaction solution was concentrated under reduced pressure and extracted with 300 ml of toluene and 400 ml of water. Repeat three times. The organic layer was concentrated under reduced pressure and separated by column chromatography with ethyl acetate: hexane = 1: 5 to give 42 g (47.5%) of chlorodiphenyl triazine.

Synthesis Example 1-2. Synthesis of Formula 31.

Into a 250 ml round bottom flask was placed 5 g (0.013 mol) of 4,16-dibromo [2,2] paracycloclophan and 50 ml of tetrahydrofuran was added. The reactor is lowered to −78 ° C. and then stirred for 10 minutes. After stirring, 24.3 ml (0.03 mol) of 1.6 M normal butyllithium was slowly added dropwise while maintaining the temperature. When the dropping is completed, the temperature is raised to room temperature over 1 hour. After the temperature was raised, the mixture was stirred for 30 minutes, lowered to -78 ° C, and then rapidly added dropwise to 10.7 g (0.04 mol) of chlorodiphenyltriazine made in 1-1). The reaction is completed by raising the temperature to room temperature. After the reaction is completed, distilled water is added to terminate the reaction, and the organic layer is concentrated under reduced pressure. Separated by column chromatography with ethyl acetate: hexane = 1: 4, and recrystallized with methylene chloride and hexane to obtain the formula (31). (2.5 g, 29%)

MS (MALDI-TOF): m / z 670 [M] ⁺

Synthesis Example 2 Synthesis of Chemical Formula 5

Synthesis Example 2-1. Synthesis of Dichlorophenyltriazine

 In a 250 ml round bottom flask, 11.6 g (0.477 mol) of magnesium and 2 g of iodine were added to 50 ml of tetrahydrofuran and refluxed for 2 hours. After bringing down to room temperature, the reactor is slowly added by diluting 50 g (0.318 mol) of bromobenzene in 100 ml of tetrahydrofuran at 0 ° C. When the drop is completed, reflux for 2 hours. Add 53.38 g (0.289 mol) of cyanuric chloride to a 500 ml round bottom flask, dissolve in 150 ml of tetrahydrofuran, and keep it at 0 to 10 ° C. The green yard reagent prepared above is cooled to room temperature and then added dropwise to the reactor. When the reaction was completed, the reaction was terminated by slowly dropwise adding 50 ml of 2 M aqueous hydrochloric acid solution. After completion of the dropwise addition, the reaction solution was concentrated under reduced pressure and extracted with 200 ml of toluene and 300 ml of water. Repeat three times. The organic layer was concentrated under reduced pressure, separated by column chromatography with ethyl acetate: hexane = 1: 5 to obtain 48.5 g (75%) of dichlorophenyltriazine.

Synthesis Example 2-2. Synthesis of N-phenyl [2,3-a] indolo carbazole.

    48.5 g (0.189 mol) of indolo [2,3-a] carbazole in a 1 L round bottom flask,

42.5 g (0.208 mol) of iodobenzene, 19.4 g (0.378 mol) of copper powder, 15 g (0.057 mol) of 18-crown-6, 104.5 g (0.756 mol) of potassium carbonate are added in this order, 480 ml of ortho-dichlorobenzene After the addition, the mixture was refluxed at 180 ° C. for 2 days. After the reaction was completed, the mixture was extracted using 500 ml of methylene chloride and 400 ml of distilled water. The extraction is repeated twice. The organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane as a developing solvent to remove ortho-dichlorobenzene. After the solvent is removed, the solid obtained by the addition of excess methylene chloride is column chromatographed with methylene chloride: hexane = 1: 10 to give 17.9 g (28%) of the pure product.

Synthesis Example 2-3. Synthesis of N-3-chloro-4-phenyltriazine-N'-phenylindolo [2,3-a] carbazole.

   Put 0.9 g (0.0225 mol) of NaH (60% mineral oil) and 30 ml of DMF into a 250 ml round bottom flask and stir at room temperature for 10 minutes. 5 g (0.015 mol) of N-phenylindolo [2,3-a] carbazole is dissolved in 50 ml of DMF and slowly added dropwise, and stirred at room temperature for 1 hour. After falling to 0 ° C., 4.4 g (0.0195 mol) of dichlorophenyltriazine are dissolved in 50 ml of DMF and added dropwise. Raise to room temperature, and when the reaction is completed, attach the reaction liquid to excess water and filter the solid.

The filtered solid is column chromatographed with ethyl acetate: hexane = 1: 5 to obtain 4.6 g (60%) of pure product.

Synthesis Example 2-4. Synthesis of Formula 5.

 Synthesis Example 1-2. 2.3 g (68 g) of compound 5 in the same manner, except that 4.6 g (0.009 mol) of [2,3-a] carbazole was used as N-chlorophenyl triazine-N'-phenylindolo instead of chlorodiphenyltriazine in %) Was obtained.

MS (MALDI-TOF): m / z 1178 [M] ⁺

Synthesis Example 3 Synthesis of Chemical Formula 8

Synthesis Example 3-1. Synthesis of Dichloro- (4-cyanophenyl) triazine

20 g (58%) of the product was obtained in the same manner as in Synthesis Example 2-1, except that 25 g (0.137 mol) of 4-bromocyanobenzene was used instead of 4-bromobenzene.

Synthesis Example 3-2. Synthesis of N-3-chloro-5- (4-cyanophenyl) triazine-N'-phenylindolo [2,3-a] carbazole.

  3.8 g (46.6%) of the product was obtained by the same method as in Synthesis Example 2-3, except that dittro- (4-cyanophenyl) triazine was used instead of dichlorophenyltriazine.

Synthesis Example 3-3. Synthesis of Formula 5.

  3.8 g (0.007 mol) of N-3-chloro- (4-cyanophenyl) triazine-N-phenylindolo [2,3-a] carbazole was used in Synthesis Example 1-2 instead of chloro diphenyl triazine. 1.5 g (52%) of Formula 5 were obtained in the same manner except that.

MS (MALDI-TOF): m / z 1228 [M] ⁺

Synthesis Example 4 Synthesis of Chemical Formula 40

Using Synthesis Example 1, 3g (34%) was synthesized in the same manner as in Synthesis Example 1, except that chloro ditolyl triazine was used instead of chloro diphenyl triazine.

MS (MALDI-TOF): m / z 726 [M] ⁺

Synthesis Example 5 Synthesis of Chemical Formula 13

  3.4 g (61%) of Chemical Formula 13 was synthesized in the same manner as in Synthesis Example 2, except that 4-trimethylsilylbenzene was used instead of bromobenzene in Synthesis Example 2-1.

MS (MALDI-TOF): m / z 1322 [M] ⁺

Example

Fabrication of Organic Light Emitting Diode

The light emitting area of the ITO glass was patterned to a size of 2 mm x mm, and then washed. After mounting the substrate in a vacuum chamber, the base pressure was 1x10 ^-6 torr, and the organic material was placed on the ITO, DNTPD (700 kPa), NPD (300 kPa). ), The compound prepared according to the present invention + Ir (ppy) ₃ (10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å), Al (1,000 Å) was formed in the order of, the measurement at 0.4 mA It was.

Comparative example

The organic light emitting diode device for the comparative example was manufactured in the same manner except for using CBP instead of the compound prepared by the invention in the device structure of the above example.

division Host Dopant Doping concentration% ETL V Cd / A CIEx CIEy Comparative Example 1 CBP Ir (ppy) 3 10 Alq3 8.20 38.81 0.29 0.62 Example 1 Compound 5 Ir (ppy) 3 10 Alq3 5.18 48 0.32 0.61 Example 2 Compound8 Ir (ppy) 3 10 Alq3 5.75 50.38 0.29 0.62 Example 3 Compound 13 Ir (ppy) 3 10 Alq3 6.07 48.9 0.34 0.62 Example 4 Compound 31 Ir (ppy) 3 10 Alq3 5.03 47.74 0.35 0.60 Example 5 Compound 40 Ir (ppy) 3 10 Alq3 4.92 52.41 0.31 0.61

As shown in the above table, the organic compound secured by the present invention has a low driving voltage and excellent luminous efficiency as compared to CBP which is widely used as a phosphorescent material. In addition, the performance of the organic field device using the compound according to the present invention is shown in the figure.

Claims (12)

Cycloaralkyl derivatives represented by the following general formula (1):

(One)
In the above formulas,
R ₁ to R ₄ may be the same or different, and each independently represent a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 10 to 60 Condensed aromatic ring, substituted or unsubstituted condensed aromatic heterocycle having 10 to 60 carbon atoms, substituted or unsubstituted styryl group, substituted or unsubstituted amino group, substituted or unsubstituted carbonyl group, substituted or unsubstituted carboxyl group, substituted or unsubstituted aryl value Or substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, substituted or unsubstituted cycloalkenyl group having 3 to 40 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted alkylsilyl having 1 to 40 carbon atoms Group, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, substituted or unsubstituted straight chain, pulverized or cyclic alkyl group having 1 to 60 carbon atoms, substituted or unsubstituted From the group consisting of a cyclic group having 6 to 60 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted hetero aralkyl group having 3 to 40 carbon atoms Selected,
Y ₁ and Y ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted hetero group having 5 to 40 carbon atoms Selected from the group consisting of an aralkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms) The method of claim 1,
The substituents of R ₁ to R ₄ , Y ₁ and Y ₂ are hydrogen atom, deuterium atom, halogen atom, cyano group, nitro group, C1-C10 alkylsilyl group, C1-C40 alkyl group, C1-C40 Alkoxy group, alkylamino group of 1 to 40 carbon atoms, aryl group of 6 to 30 carbon atoms, aryloxy group of 6 to 30 carbon atoms, arylamino group of 6 to 30 carbon atoms, arylsilyl group of 6 to 30 carbon atoms, 3 to 40 carbon atoms Cycloaralkyl derivatives, characterized in that at least one selected from the group consisting of heteroaryl groups. The method of claim 1,
R ₁ to R ₄ may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, wherein the ring is 5 to 8 membered wheel, and the substituted saturated or unsaturated ring may have 3 to 3 carbon atoms. A cycloaralkyl derivative, which is a cycloalkyl group of 40. The method of claim 3,
Cycloaralkyl derivative, characterized in that the substituent of the saturated or unsaturated ring is attached or fused together in a pendant method. The method of claim 1,
A cycloaralkyl derivative, which is any one compound selected from the group represented by formulas (2) to (4):

(2)

(3)

(4)
In the formula, R ₅ to R ₂₆ may be the same or different, and each independently hydrogen atom, deuterium atom, halogen atom, hydroxy group, cyano group, nitro group, alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon number 10 60 condensed aromatic rings, substituted or unsubstituted condensed aromatic heterocycles having 10 to 60 carbon atoms, substituted or unsubstituted styryl groups, substituted or unsubstituted amino groups, substituted or unsubstituted carbonyl groups, substituted or unsubstituted carboxyl groups, substituted or unsubstituted An aryl group, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon group having 1 to 30 carbon atoms Silyl groups, substituted or unsubstituted straight chain, crushed or cyclic alkyl groups having 1 to 60 carbon atoms, substituted or unsubstituted aryl groups having 6 to 60 carbon atoms, substituted Is an unsubstituted C 6 - is selected from the group consisting of hetero-aralkyl group of 40 - 60 aralkyl group, a substituted or unsubstituted 3-to 40 membered heteroaryl group, a substituted or unsubstituted 3
Substituents of R ₅ to R ₂₆ include a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an alkylsilyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, and a carbon atom 1 A group consisting of an alkylamino group of 40, an aryl group of 6 to 30 carbon atoms, an aryloxy group of 6 to 30 carbon atoms, an arylamino group of 6 to 30 carbon atoms, an arylsilyl group of 6 to 30 carbon atoms, and a heteroaryl group of 3 to 40 carbon atoms One or more selected from
Y ₁ and Y ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted hetero group having 5 to 40 carbon atoms It is selected from the group consisting of an aralkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms,
The substituents of Y ₁ and Y ₂ are a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an alkylsilyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, and a carbon atom 1 A group consisting of an alkylamino group of 40, an aryl group of 6 to 30 carbon atoms, an aryloxy group of 6 to 30 carbon atoms, an arylamino group of 6 to 30 carbon atoms, an arylsilyl group of 6 to 30 carbon atoms, and a heteroaryl group of 3 to 40 carbon atoms At least one selected from) The method of claim 1,
A cycloalkyl derivative characterized in that the compound of any one selected from the group represented by the formula 5 to 79:

(5) (6) (7)

(8) (9) (10)

(11) (12) (13)

(14) (15) (16)

(17) (18) (19)

(20) (21) (22)

(23) (24) (25)

(26) (27) (28)

(29) (30) (31)

(32) (33) (34)

(35) (36) (37)

(38) (39) (40)

(41) (42) (43)

(44) (45) (46)

(47) (48) (49)

(50) (51) (52)

(53) (54) (55)

(56) (57) (58)

(59) (60)

(61) (62)

(63) (64)

(65) (66)

(67) (68)

(69) (70)

(71) (72)

(73) (74)

(75) (76)

(78) (79) Anode; Cathode; And a layer comprising a cycloaralkyl derivative according to any one of claims 1 to 6 interposed between the anode and the cathode. The method of claim 7, wherein
The cycloaralkyl derivative is an organic light emitting device, characterized in that contained in the light emitting layer between the anode and the cathode. The method of claim 8,
The thickness of the light emitting layer is an organic light emitting device, characterized in that 50 to 2,000 kPa. The method of claim 8,
An organic electroluminescent device further comprising at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer between the anode and the cathode. The method of claim 10,
At least one layer selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer is formed by a single molecule deposition method or a solution process. The method of claim 7, wherein
An organic light emitting display device, which is used for display devices, display devices, and monochrome or white lighting devices.

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