JP2020055779A - Organic compound and organic light emitting element - Google Patents

Abstract

To provide an organic compound that outputs red light emission of long wavelength.SOLUTION: The present invention provides an organic compound represented by general formula (1) [In formula (1), Rto Rare independently selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to 10 alkyl group, a substituted or unsubstituted C1 to 10 alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted C6 to 18 aryl group, a substituted or unsubstituted C3 to 15 heterocyclic group, a substituted or unsubstituted aryloxy group, silyl group and cyano group].SELECTED DRAWING: None

Description

  The present invention relates to an organic compound and an organic luminous element using the same.

An organic light emitting element (organic electroluminescence element (organic EL element)) is an electronic element having a pair of electrodes and an organic compound layer disposed between these electrodes. By injecting electrons and holes from the pair of electrodes, an exciton of the light-emitting organic compound in the organic compound layer is generated, and when the exciton returns to the ground state, the organic light-emitting element emits light. .
Recent advances in organic light-emitting devices have been remarkable, and include low drive voltage, various emission wavelengths, high-speed response, and the ability to make light-emitting devices thinner and lighter.
In addition, as a color reproduction range used for a display, standards of sRGB and Adobe RGB are used, and materials for reproducing the same have been demanded. Recently, BT-2020 has been cited as a standard for further expanding the color reproduction range.
By the way, luminescent organic compounds have been actively created to date. This is because, in providing a high-performance organic light-emitting device, it is important to create a compound having excellent light-emitting characteristics.
Compounds created so far include the following compound 1-A described as a basic skeleton in Patent Document 1 and the following compound 1-B described as a basic skeleton in Patent Document 2.

JP 2000-34234 A JP 2013-139426 A

Compound 1-A and compound 1-B emit red light as described later, as determined by the present inventors.
However, the organic light-emitting devices using the compounds described in Patent Documents 1 and 2 have difficulty in reproducing the red chromaticity coordinates in the color reproduction range of BT-2020, and compounds that emit red light at a longer wavelength. Is required.
The present invention has been made to solve the above problems, and an object of the present invention is to provide an organic compound which emits red light of longer wavelength emission. Another object of the present invention is to provide an organic light emitting device having excellent luminous efficiency and driving durability.

  The organic compound of the present invention is represented by the following general formula (1).

［式（１）において、Ｒ₁乃至Ｒ₂₄は、水素原子、ハロゲン原子、置換あるいは無置換の炭素原子数１乃至１０のアルキル基、置換あるいは無置換の炭素原子数１乃至１０のアルコキシ基、置換あるいは無置換のアミノ基、置換あるいは無置換の炭素原子数６乃至１８のアリール基、置換あるいは無置換の炭素原子数３乃至１５の複素環基、置換あるいは無置換のアリールオキシ基、シリル基及びシアノ基からそれぞれ独立に選ばれる。］

[In the formula (1), R _{1 to} R ₂₄ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, A substituted or unsubstituted amino group, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 15 carbon atoms, a substituted or unsubstituted aryloxy group, a silyl group And a cyano group. ]

  The organic compound according to the present invention can emit red light with high color purity. Further, since the organic compound according to the present invention has sublimability, it can be highly purified, and can provide an organic light-emitting element having high luminous efficiency and excellent driving durability.

It is a cross section showing an example of the display concerning this embodiment. FIG. 1 is a schematic diagram illustrating an example of a display device according to an embodiment. FIG. 1 is a schematic diagram illustrating an example of a display device according to an embodiment. FIG. 1 is a schematic diagram illustrating an example of an imaging device according to an embodiment. It is a schematic diagram showing an example of the portable device according to the present embodiment. It is a schematic diagram which shows an example of the lighting device which concerns on this embodiment. It is a schematic diagram which shows an example of the moving body concerning this embodiment and others.

≪Organic compounds≫
First, the organic compound according to the present embodiment will be described. The organic compound according to the present embodiment is represented by the following general formula (1).

In the formula (1), R _{1 to} R ₂₄ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, Or an unsubstituted amino group, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 15 carbon atoms, a substituted or unsubstituted aryloxy group, a silyl group, Each is independently selected from cyano groups. R _{1 to} R ₂₄ are preferably each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. R _{1 to} R ₂₄ are more preferably independently selected from a hydrogen atom and a substituted or unsubstituted aryl group having 6 to 18 carbon atoms.

In this specification, the basic skeleton is a skeleton in which all of R _{1 to} R _{24 of the} compound represented by the general formula (1) are hydrogen atoms.

Examples of the halogen atom represented by R _{1 to} R ₂₄ include, but are not limited to, fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R _{1 to} R ₂₄ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a secondary butyl group, an octyl group, and a cyclohexyl. Groups, 1-adamantyl group, 2-adamantyl group, and the like, but are not limited thereto. Preferably, it is an alkyl group having 1 to 4 carbon atoms.

Examples of the alkoxy group having 1 to 8 carbon atoms represented by R _{1 to} R ₂₄ include a methoxy group, an ethoxy group, a propoxy group, a 2-ethyl-hexyloxy group, and a benzyloxy group, but are not limited thereto. Not something.

As the amino group represented by R _{1 to} R ₂₄ , N-methylamino group, N-ethylamino group, N, N-dimethylamino group, N, N-diethylamino group, N-methyl-N-ethylamino group, N-benzylamino group, N-methyl-N-benzylamino group, N, N-dibenzylamino group, anilino group, N, N-diphenylamino group, N, N-dinaphthylamino group, N, N-diflur Olenylamino group, N-phenyl-N-tolylamino group, N, N-ditolylamino group, N-methyl-N-phenylamino group, N, N-dianisolylamino group, N-mesityl-N-phenylamino group , N, N-dimesitylamino group, N-phenyl-N- (4-tert-butylphenyl) amino group, N-phenyl-N- (4-trifluoromethylphenyl) amino group, N-piper Le group and the like, but not limited thereto.

Examples of the aryl group having 6 to 18 carbon atoms represented by R _{1 to} R ₂₄ include a phenyl group, a naphthyl group, an indenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a phenanthryl group, and a triphenylenyl group. It is not limited to these.

As a heterocyclic group having 3 to 15 carbon atoms represented by R _{1 to} R ₂₄ , a pyridyl group, an oxazolyl group, an oxadiazolyl group, a thiazolyl group, a thiadiazolyl group, a carbazolyl group, an acridinyl group, a phenanthrolyl group, a dibenzofuranyl group, Examples include, but are not limited to, dibenzothiophenyl groups.

Examples of the aryloxy group represented by R _{1 to} R ₂₄ include, but are not limited to, a phenoxy group and a thienyloxy group.

Examples of the silyl group represented by R _{1 to} R ₂₄ include, but are not limited to, a trimethylsilyl group and a triphenylsilyl group.

  Examples of the substituent which the alkyl group, alkoxy group, amino group, aryl group, heterocyclic group and aryloxy group may further have include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group and a tertiary group. Alkyl group such as butyl group, aralkyl group such as benzyl group, aryl group such as phenyl group and biphenyl group, heterocyclic group such as pyridyl group and pyrrolyl group, dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group An amino group such as a ditolylamino group, a methoxy group, an ethoxy group, an alkoxy group such as a propoxy group, an aryloxy group such as a phenoxy group, fluorine, chlorine, bromine, a halogen atom such as iodine, and a cyano group. However, the present invention is not limited to this. Preferably, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 9 carbon atoms. Group, a cyano group.

  By the way, in the organic compound according to this embodiment, the basic skeleton has a group other than a hydrogen atom, that is, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted aryl group having 6 to 18 carbon atoms, substituted or unsubstituted heterocyclic group having 3 to 15 carbon atoms, substituted or unsubstituted aryloxy group When a silyl group or a cyano group is introduced, concentration quenching can be suppressed, and a compound having improved sublimability during sublimation and improved solvent solubility when used for coating can be obtained.

  Next, a method for synthesizing the organic compound according to the present embodiment will be described. The organic compound according to this embodiment is synthesized, for example, according to the following reaction scheme.

As shown in the above synthesis scheme, the organic compound according to the present embodiment is synthesized using the compounds shown in the following (a) to (d) as raw materials.
(A) Acenaphthenequinone derivative (D1)
(B) Dibenzyl ketone derivative (D2)
(C) Benzofluoranthene derivative (D3)
(D) Naphthalene derivative (D4)

Here, by appropriately introducing a substituent into the compounds shown in the above (a) to (d), any _one of R _{1 to} R _{24 in} the general formula (1) may be a hydrogen atom to a predetermined group other than a hydrogen atom. Will be replaced by In the above synthesis scheme, various organic compounds can be synthesized by changing D1 to D4, respectively.

Next, since the organic compound according to the present embodiment has the following characteristics, it becomes a stable compound exhibiting red emission with high color purity, and further, by using this organic compound, the luminous efficiency is high and the device durability is high. An excellent organic light emitting device can be provided. Since the basic skeleton of the organic compound according to this embodiment has an electron-deficient π-conjugate, HOMO and LUMO are low, and electron acceptability is high.
(1) The emission wavelength of the basic skeleton itself is in the red region with high color purity. (2) Since the transition dipole moment is high, the quantum yield is high. (3) Since there is no highly reactive SP2 carbon, High thermal stability

  Hereinafter, these features will be described.

  The following molecular orbital calculations were used for the calculated values of the S1 (singlet excited state) wavelength, oscillator strength, and dihedral angle of the molecular structures shown in Tables 2 and 3.

  As a calculation method of the molecular orbital calculation method, a density functional theory (DFT) which is widely used at present is used. The functional was B3LYP, and the basis function was 6-31G *. The molecular orbital calculation method is based on Gaussian 09 (Gaussian 09, Revision C.01, MJ. Frisch, GW Trucks, HB Schlegel, GE Scuseria, MA) which is currently widely used. Robb, JR Cheeseman, G. Scalmani, V. Barone, B. Mennucci, GA Petersson, H. Nakatsuji, M. Caricato, X. Li, HP Hratchian, A. F. Izmaylov. J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, JA Montgomery, Jr., JE Peralta, F. Ogliaro, M. Bearpark, JJ Heyd, E. Brothers, KN Kudin, V. N. Starovov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, JC Burant, SS Iyengar, J. Tomasi, M. Regis, N. Regis. M. Millam, M. Klenx, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomberts, R. E. Stratmann, O. Yazyev, A. J. Austi , R. Cami, C. Pomerli, JW Ochterski, RL Martin, K. Morokuma, VG Zakrzewski, GA Voth, P. Salvador, J. J. Dannenberg, S. Daprich. , AD Daniels, O. Farkas, JB Foresman, JV Ortiz, J. Cioslowski, and DJ J. Fox, Gaussian, Inc., Wallingford CT, 2010.).

(1) The emission wavelength of the basic skeleton itself is in the red region having high color purity. The present inventors paid attention to the basic skeleton itself when inventing the organic compound represented by the formula (1). Specifically, an attempt was made to provide one in which the emission wavelength of a molecule having only the basic skeleton falls within a desired emission wavelength region. In the present embodiment, the desired emission wavelength region is a red region having high color purity, and specifically, a maximum emission wavelength within a band of 595 nm to 630 nm in a dilute solution.

Next, the nature of the basic skeleton of the organic compound according to the present invention will be described while comparing and comparing a comparative compound having a structure similar to the organic compound of the present invention. Specifically, compounds represented by the following formulas (2) and (3) are mentioned as comparative compounds. On the other hand, as one of the organic compounds according to the present invention, R _{1 to} R ₇ , R _{9 to} R ₂₂ , and R ₂₄ have a basic skeleton represented by the formula (1), and R ₂₄ is a hydrogen atom, and R ₈ and R ₂₃ are phenyl. Exemplary compound A2 which is a group.

  The present inventors compared the measured maximum emission wavelengths of the comparative compound (2) and the comparative compound (3) with the exemplary compound A2 of the present invention. Table 1 shows the results. The emission wavelength was measured by photoluminescence measurement of a diluted toluene solution at an excitation wavelength of 350 nm at room temperature using Hitachi F-4500.

  From Table 1, the maximum emission wavelengths of the comparative compounds (2) and (3) are not within the desired band. On the other hand, since the exemplary compound A1 has a maximum emission wavelength in a desired band, it exhibits an emission color suitable for a display standard of red. The same applies to Exemplified Compound A1, which is the basic skeleton itself. Therefore, the basic skeleton of the present invention can emit red light with high color purity. The red chromaticity coordinates will be described in detail in Examples.

(2) High quantum yield due to high transition dipole moment Generally, when the molecular weight of the basic skeleton increases, the sublimation temperature increases and approaches the decomposition temperature, so that decomposition is likely to occur. Therefore, it was necessary to increase the emission wavelength without increasing the molecular weight as much as possible. Also, there is a vibrator strength as a parameter related to luminous efficiency. In order to have high luminous efficiency, high oscillator strength is required. Therefore, it was necessary to increase the number of condensed rings in order to increase the emission wavelength by conjugation expansion of the basic skeleton. However, the present inventors focused on the extended position of the condensed rings.

  The S1 (singlet excited state) wavelength and the oscillator strength of the comparative compounds a to c and the exemplary compound A2 of the present invention were compared using molecular orbital calculation. Table 2 shows the results. Since the S1 wavelength and the oscillator strength of the comparative compounds (2) and (3) were 580 nm, 1.3, 576 nm, and 1.3, respectively, the S1 wavelength was 580 nm or more. Regarding the oscillator strength, 1.3 or more was evaluated as Δ, and less than 1.3 was evaluated as ×.

  According to Table 2, when benzene is condensed in the longest direction with respect to the molecular axis, as in the case of Exemplified Compound A2 and Comparative Compound a, the effect of increasing the wavelength is large and the oscillator strength that affects the quantum yield is also high. I understood. The skeleton of the present invention has a transition dipole moment in the longest direction with respect to the molecular axis, and when benzene is condensed, extending in this direction has a large effect of increasing the transition dipole moment. it is conceivable that.

(3) Since it does not have highly reactive SP ² carbon, it has high thermal stability. As shown in Table 2, a comparative compound a and an exemplary compound A2 satisfying the S1 wavelength and the oscillator strength are synthesized and purified by sublimation. As a result, Comparative Compound a partially decomposed before and after sublimation purification, whereas Exemplified Compound A2 was not decomposed. The presence or absence of decomposition was determined by liquid chromatography analysis. This result indicates that the comparative compound a has low thermal stability, because it has a highly reactive SP ² carbon in the anthracene structure contained in the basic skeleton. On the other hand, Exemplified Compound A2 of the present invention has high thermal stability because it does not have a highly reactive SP ² carbon in the basic skeleton. Stable sublimation purification that does not cause decomposition enables the purification of materials and the production of organic light-emitting devices by vapor deposition. Thereby, impurities contained in the organic electroluminescent element can be reduced, and it is possible to prevent the reduction in luminous efficiency and the driving durability due to the impurities.

  As described above, the compound according to the present invention is an invention having a longer emission wavelength, high efficiency, and sublimation stability. By using these in an organic electroluminescent device, high color purity, high efficiency red light emission characteristics, and excellent driving durability can be obtained. Further, for example, when used as a display, a deep red color can be reproduced.

Hereinafter, the characteristics of the preferred embodiment of the compound according to the present invention will be further described.
(4) R ₇ , R ₈ , R ₁₃ , R ₁₈ , R ₂₃ , and R ₂₄ each have a group other than a hydrogen atom. (5) A group that covers the molecular plane is described below.

_{(4) R 7, R 8} , R 13, R 18, R 23, the organic compound according to the present invention having any one in the group other than a hydrogen atom of R ₂₄ is a group other than a hydrogen atom in R ₁ to R ₂₄ By introducing, it is possible to suppress the crystallinity of the molecule itself due to the overlap between the molecules to some extent. Suppressing crystallinity leads to suppression of concentration quenching between molecules and improvement in sublimability. The organic compound according to the present invention has a high flatness due to a longer wavelength, and when R _{1 to} R ₂₄ are all hydrogen atoms, the molecules tend to overlap. Therefore, the replacement position that can be effectively suppressed will be described.

Table 3 shows the dihedral angle between the phenyl group and the basic skeleton when each of R _{1 to} R ₂₄ is a phenyl group, that is, the degree of twist. In the case of substitution positions R ₇ , R ₈ , R ₁₃ , R ₁₈ , R ₂₃ , and R ₂₄ , the dihedral angle is large because the steric repulsion between the ortho-position hydrogen of the phenyl group and the hydrogen of the basic skeleton is large. Therefore, the planarity of the whole molecule is lost. This effect prevents overlap between molecules, suppresses crystallinity, suppresses concentration quenching between molecules, and improves sublimability.

Therefore, at least one selected from R ₇ , R ₈ , R ₁₃ , R ₁₈ , R ₂₃ and R ₂₄ , preferably one of R ₇ and R ₈ , and one of R ₂₃ and R ₂₄ has hydrogen It is preferable to introduce a group other than an atom, preferably a group having a bulky group or a bulky substituent. The group other than a hydrogen atom includes a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a substituted or unsubstituted amino group. A substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 15 carbon atoms, a substituted or unsubstituted aryloxy group, a silyl group or a cyano group, Is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms.

(5) Having a group covering the molecular plane Specific examples of the group other than a hydrogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group in the case of an alkyl group having 1 to 10 carbon atoms. Octyl group, etc., and particularly preferably a sterically large isopropyl group or tertiary butyl group. In the case of an aryl group having 6 to 18 carbon atoms, an aryl group such as a phenyl group or a naphthyl group is preferable, but a phenyl group having a small molecular weight is preferable from the viewpoint of sublimation, and a substituent such as a methyl group, an isopropyl group, or a tertiary butyl group is preferable. An aryl group such as a phenyl group having In addition, a group other than a hydrogen atom is also preferably a fluorine atom or an aryl group having a fluorine atom. In addition, it is preferable to introduce a group other than a hydrogen atom, since it leads to an improvement in film properties when it is used in a method in which it is contained in a liquid and placed (applied) at a predetermined position and the solvent is subsequently removed.

Furthermore, as an effect of improvement, the present inventors have tried to introduce a group that blocks a π-conjugate plane. As a result, as shown in Table 4, an ortho-tolyl derivative having a methyl group at the ortho-position of the phenyl group introduced as at least one selected from R ₇ , R ₈ , R ₁₃ , R ₁₈ , R ₂₃ and R _24. It has been found that an aryl group having a substituent at the ortho position, such as an orthobiphenyl derivative having a phenyl group or a phenyl group, covers the π-conjugated plane of the basic skeleton and can suppress the overlap between molecules. The effect is that the phenyl group shields the π-conjugated plane more than the methyl group, but can suppress the overlap between molecules.

  As described above, when the condition (5) is satisfied, the organic compound according to the present invention has a wide difference between the sublimation temperature and the thermal decomposition temperature and is excellent in sublimability.

  As described above, since the organic compound according to the present invention is a compound having the properties described in (1) to (3) above, the emission wavelength of the basic skeleton itself is red and the sublimability is lower than that of the comparative compound. It becomes the maintained organic compound. Furthermore, by becoming a compound having the properties of (4) and (5), it becomes a compound capable of suppressing overlap between molecules, improving sublimability and suppressing concentration quenching. By using this, it is possible to obtain an organic light-emitting element that emits red light with high color purity and high efficiency and high element durability.

  Specific examples of the organic compound according to the present invention are shown below. However, the present invention is not limited to these.

Among the above-exemplified compounds, A1 to A11, C1 to compound of C12, the whole molecule is composed only of carbon and hydrogen SP ² hybrid orbital. Here, a compound composed of only carbon and hydrogen in an SP ² hybrid orbital generally has a low HOMO energy level. Therefore, the compounds A1 to A11 and C1 to C12 are compounds having a low oxidation potential, that is, compounds that are stable against oxidation. Therefore, among the compounds according to the present embodiment, organic compounds composed of only carbon and hydrogen in SP ² hybrid orbitals, that is, compounds A1 to A11 and C1 to C12 are preferable because of high molecular stability. In short, the compounds A1 to A11 and C1 to C12 can also be used in the light-emitting layer host material, the transport layer, and the injection layer.

Among the above-exemplified compounds, A12 to A18, B group, as a substituent group of the R ₁ to R ₂₄ or as a R ₁ to R ₂₄ are those belonging to the C13 to C21, alkyl group, fluorine, an alkoxy group, an amino group, a carbon This is an example in which a heterocyclic group having a number of 7 or more, a nitrogen-containing heterocyclic group, an aryloxy group, a silyl group, or a cyano group is introduced. When the compound into which the alkyl group or fluorine is introduced avoids intermolecular stacking, the sublimation or deposition start temperature is lowered, and when used as a guest material of the light emitting layer, concentration quenching can be suppressed. Further, since the solubility of the compound is improved, it can be used as a material for coating. A compound into which an alkoxy group, an aryloxy group, or a silyl group is introduced has an effect of similarly suppressing concentration quenching, and can be used as a coating material. Compounds in which a nitrogen-containing heterocyclic group or cyano group is introduced have an effect of attracting electrons to the basic skeleton, and among the compounds according to the present invention, compounds having a low HOMO energy level and being more stable to oxidation It is. The compound having an amino group introduced therein has an effect of donating electrons to the basic skeleton, the band gap becomes narrower, and the compound emits light of a longer wavelength. A compound into which a heterocyclic group having 7 or more carbon atoms is introduced has a higher glass transition temperature than a compound into which a phenyl group is introduced, and when used as a light emitting layer host material or a transport layer, forms a thermally stable amorphous film.

Among the above exemplified compounds, those belonging to Group B and C21 have an aryl group such as a phenyl group or a pyridyl group as R _{1 to} R ₂₄ , and further have an alkyl group, a fluorine, an alkoxy group, and a cyano group at the ortho position of the aryl group. This is an example of introducing. By having a substituent at the ortho position of the aryl group, the aryl group is twisted with respect to the basic skeleton, and the substituent at the ortho position covers the π-conjugated plane of the basic skeleton and suppresses molecular packing. Further, stacking between molecules is avoided, and the sublimation or deposition start temperature is lowered. In addition, when used as a guest material in the light-emitting layer, concentration quenching can be suppressed.

Among the above exemplified compounds, those belonging to Group C are examples in which a phenyl group is contained as R _{1 to} R ₂₄ , and a phenyl group is further introduced at the ortho position of the phenyl group. Since the effect of covering the π-conjugated plane of the basic skeleton is larger than that of the group B, the molecular packing is further suppressed, so that stacking between molecules is further avoided than in the case of the group B, and the sublimation or deposition start temperature is lowered.

  The organic compound according to the present invention is a compound that emits light suitable for emitting red light. Therefore, by using the organic compound according to the present invention as a constituent material of an organic light emitting device, an organic light emitting device having good light emitting characteristics and excellent durability characteristics can be obtained.

≪Organic light emitting device≫
Next, the organic light emitting device of the present embodiment will be described. The organic light emitting device of the present embodiment has at least an anode and a cathode, which are a pair of electrodes, and an organic compound layer disposed between these electrodes. In the organic light-emitting device of the present embodiment, the organic compound layer may be a single layer as long as it has a light-emitting layer, or may be a laminate including a plurality of layers. Here, when the organic compound layer is a laminate composed of a plurality of layers, the organic compound layer is, in addition to the light emitting layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole / exciton blocking layer, an electron transport layer, and an electron transport layer. It may have an injection layer or the like. The light-emitting layer may be a single layer or a stacked body including a plurality of layers.

  In the organic light emitting device of the present embodiment, at least one of the organic compound layers contains the organic compound according to the present embodiment. Specifically, the organic compound according to the present embodiment may be any of the above-described light emitting layer, hole injection layer, hole transport layer, electron blocking layer, light emitting layer, hole / exciton blocking layer, electron transport layer, electron injection layer, etc. Crab included. The organic compound according to the present embodiment is preferably contained in the light emitting layer.

  In the organic light emitting device of the present embodiment, when the organic compound according to the present embodiment is included in the light emitting layer, the light emitting layer may be a layer composed of only the organic compound according to the present embodiment, A layer composed of such an organic compound and another compound may be used. Here, when the light emitting layer is a layer composed of the organic compound according to the present embodiment and another compound, the organic compound according to the present embodiment may be used as a host of the light emitting layer or used as a guest. You may. Further, it may be used as an assist material that can be included in the light emitting layer. Here, the host is a compound having the largest mass ratio among the compounds constituting the light emitting layer. The guest is a compound having a smaller mass ratio than that of the host among the compounds constituting the light-emitting layer, and is a compound responsible for main light emission. In addition, the assist material is a compound that has a smaller mass ratio than the host among the compounds forming the light emitting layer and assists the light emission of the guest. Note that the assist material is also called a second host.

  When the organic compound according to this embodiment is used as a guest of the light emitting layer, the concentration of the guest is preferably 0.01% by mass or more and 20% by mass or less, and preferably 0.1% by mass or more and 5% by mass or less based on the whole light emitting layer. It is more preferable that the content is not more than mass%.

  When the organic compound according to this embodiment is used as a guest of a light-emitting layer, a material having a higher LUMO than the organic compound according to this embodiment (a material whose LUMO is closer to a vacuum level) is preferably used as a host. This is because the organic compound according to the present embodiment has a low LUMO. By using a material having a higher LUMO than the organic compound according to the present embodiment as a host, electrons supplied to the host of the light-emitting layer can be used in the present embodiment. This is because such an organic compound can be more received.

  The present inventors have conducted various studies, the organic compound according to the present embodiment as a host or guest of the light-emitting layer, especially when used as a guest of the light-emitting layer, exhibits a high-efficiency and high-luminance light output, and It has been found that an element having extremely high durability can be obtained. The light-emitting layer may be a single layer or a multi-layer, or can include a light-emitting material having another light-emitting color to be mixed with red light, which is the light-emitting color of this embodiment. The multilayer means a state in which a light emitting layer and another light emitting layer are stacked. In this case, the emission color of the organic light emitting element is not limited to red. More specifically, the color may be white or an intermediate color. In the case of white, another light emitting layer emits a color other than red, that is, blue or green. In addition, a film is formed by vapor deposition or coating. This will be described in detail in an embodiment described later.

  The organic compound according to the present embodiment can be used as a constituent material of an organic compound layer other than the light emitting layer constituting the organic light emitting device of the present embodiment. Specifically, it may be used as a constituent material of an electron transport layer, an electron injection layer, a hole transport layer, a hole injection layer, a hole blocking layer, and the like. In this case, the emission color of the organic light emitting element is not limited to red. More specifically, the color may be white or an intermediate color.

  Here, in addition to the organic compound according to the present embodiment, if necessary, conventionally known low-molecular and high-molecular hole-injecting compounds or hole-transporting compounds, compounds serving as hosts, luminescent compounds, and electron-injecting compounds Compounds or electron transporting compounds can be used together. Examples of these compounds will be described below.

  As the hole injecting / transporting material, a material having high hole mobility is preferable so that holes can be easily injected from the anode and the injected holes can be transported to the light emitting layer. Further, in order to suppress deterioration of film quality such as crystallization in the organic light emitting device, a material having a high glass transition temperature is preferable. Examples of low-molecular and high-molecular materials having hole injecting and transporting performance include triarylamine derivatives, arylcarbazole derivatives, phenylenediamine derivatives, stilbene derivatives, phthalocyanine derivatives, porphyrin derivatives, poly (vinylcarbazole), poly (thiophene), and others. Conductive polymers can be used. Further, the above-described hole injecting and transporting material is also suitably used for an electron blocking layer. Hereinafter, specific examples of the compound used as the hole injecting and transporting material are shown, but are not limited thereto.

  The light-emitting materials mainly related to the light-emitting function include, in addition to the organic compounds represented by the general formula (1), fused ring compounds (for example, fluorene derivatives, naphthalene derivatives, pyrene derivatives, perylene derivatives, tetracene derivatives, anthracene derivatives, rubrene, etc.) ), Quinacridone derivatives, coumarin derivatives, stilbene derivatives, organoaluminum complexes such as aluminum tris (8-quinolinolato), iridium complexes, platinum complexes, rhenium complexes, copper complexes, europium complexes, ruthenium complexes, and poly (phenylenevinylene) derivatives, Polymer derivatives such as a poly (fluorene) derivative and a poly (phenylene) derivative are exemplified.

  Since the organic compound of the present invention is a compound having a narrow band gap and a low HOMO / LUMO energy, when a mixed layer with another light emitting material is formed or when a light emitting layer is laminated, another light emitting material is used. It is also preferable that the HOMO / LUMO energy is similarly low. This is because when the HOMO / LUMO energy is high, there is a possibility that a quench component or a trap level, such as formation of an exciplex with the organic compound of the present invention, may be formed.

  Hereinafter, specific examples of the compound used as the light emitting material are shown, but are not limited thereto.

  Examples of the light emitting layer host or light emitting assisting material contained in the light emitting layer include aromatic hydrocarbon compounds or derivatives thereof, carbazole derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, organic aluminum complexes such as tris (8-quinolinolate) aluminum, and organic compounds. Beryllium complex and the like.

  Since the organic compound of the present invention is a compound having a narrow band gap and a low HOMO / LUMO energy, it is preferable that the host material is also formed of a hydrocarbon and the HOMO / LUMO energy is low. This is because, when the host material contains a hetero atom such as a nitrogen atom, the HOMO / LUMO energy becomes high, and there is a possibility that a quenching component or a trap level such as formation of an exciplex with the organic compound of the present invention may be formed. It is.

  Particularly preferably, the host material preferably has an anthracene, tetracene, perylene, or pyrene skeleton in a molecular skeleton. This is because, in addition to being composed of hydrocarbon as described above, the organic compound of the present invention has S1 energy capable of causing sufficient energy transfer.

  Hereinafter, specific examples of the compound used as the light emitting layer host or the light emitting assisting material included in the light emitting layer are shown, but are not limited thereto.

  The electron transporting material can be arbitrarily selected from those capable of transporting electrons injected from the cathode to the light emitting layer, and is selected in consideration of the balance with the hole mobility of the hole transporting material and the like. . Examples of the material having an electron-transporting property include oxadiazole derivatives, oxazole derivatives, pyrazine derivatives, triazole derivatives, triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, organic aluminum complexes, and condensed compounds (for example, fluorene derivatives, naphthalene derivatives, Chrysene derivatives, anthracene derivatives, etc.). Furthermore, the above-mentioned electron transporting material is also suitably used for a hole blocking layer. Hereinafter, specific examples of the compound used as the electron-transporting material are shown, but are not limited thereto.

  Hereinafter, constituent members other than the organic compound layer that constitute the organic light emitting device of the present embodiment will be described.

  The organic light emitting device of the present embodiment may have a substrate. As the substrate, any material such as quartz, glass, silicon wafer, resin, and metal may be used. Further, a switching element such as a transistor and a wiring may be provided over the substrate, and an insulating layer may be provided thereover. As the insulating layer, any material may be used as long as a contact hole can be formed in order to secure conduction between the anode and the wiring and insulation between the anode and the unconnected wiring can be ensured. For example, a resin such as polyimide, silicon oxide, silicon nitride, or the like can be used.

  As a constituent material of the anode, a material having a work function as large as possible is preferable. For example, simple metals such as gold, platinum, silver, copper, nickel, palladium, cobalt, selenium, vanadium, and tungsten, and mixtures containing these, or alloys thereof, tin oxide, zinc oxide, indium oxide, and tin oxide Metal oxides such as indium (ITO) and indium zinc oxide can be used. Also, conductive polymers such as polyaniline, polypyrrole, and polythiophene can be used. One of these electrode substances may be used alone, or two or more thereof may be used in combination. Further, the anode may be composed of one layer, or may be composed of a plurality of layers. When used as a reflective electrode, for example, chromium, aluminum, silver, titanium, tungsten, molybdenum, an alloy thereof, a layered material thereof, or the like can be used. When used as a transparent electrode, an oxide transparent conductive layer of indium tin oxide (ITO), indium zinc oxide, or the like can be used, but it is not limited thereto. Photolithography technology can be used for forming the anode.

  On the other hand, the constituent material of the cathode preferably has a small work function. For example, an alkali metal such as lithium, an alkaline earth metal such as calcium, a simple metal such as aluminum, titanium, manganese, silver, lead, and chromium, or a mixture containing these can be used. Alternatively, an alloy obtained by combining these metals alone can also be used. For example, magnesium-silver, aluminum-lithium, aluminum-magnesium, silver-copper, zinc-silver and the like can be used. It is also possible to use a metal oxide such as indium tin oxide (ITO). One of these electrode substances may be used alone, or two or more thereof may be used in combination. The cathode may have a single-layer structure or a multilayer structure.

  The cathode may be a top emission element using an oxide conductive layer such as ITO, or a bottom emission element using a reflective electrode such as aluminum (Al), and is not particularly limited. Although there is no particular limitation on the method for forming the cathode, it is more preferable to use a direct current or alternating current sputtering method because the film has good coverage and resistance can be easily reduced.

  After forming the cathode, a sealing member may be provided. For example, by adhering a glass provided with a hygroscopic agent on the cathode, intrusion of water or the like into the organic compound layer can be suppressed, and occurrence of display defects can be suppressed. Further, as another embodiment, a passivation film such as silicon nitride may be provided on the cathode to suppress entry of water or the like into the organic compound layer. For example, the sealing film may be formed by transporting the cathode to another chamber without breaking the vacuum after forming the cathode and forming a silicon nitride film having a thickness of 2 μm by a CVD method.

  Further, a color filter may be provided for each pixel. For example, a color filter according to the size of a pixel may be provided on another substrate, which may be attached to a substrate provided with an organic light-emitting element, or may be formed on a sealing film such as silicon oxide by using a photolithography technique. Alternatively, the color filter may be patterned.

  The organic compound layers (the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer, the electron injection layer, etc.) constituting the organic light emitting device according to the present embodiment are as follows. It is formed by the method shown. That is, a dry process such as vacuum evaporation, ionization evaporation, sputtering, or plasma can be used for forming the organic compound layer. Instead of the dry process, a wet process of forming a layer by a known coating method (for example, spin coating, dipping, casting, LB method, inkjet method, etc.) by dissolving in a suitable solvent can also be used. Here, when a layer is formed by a vacuum evaporation method, a solution coating method, or the like, crystallization or the like hardly occurs, and the stability with time is excellent. When the film is formed by a coating method, the film can be formed in combination with an appropriate binder resin. Examples of the binder resin include, but are not limited to, polyvinyl carbazole resin, polycarbonate resin, polyester resin, ABS resin, acrylic resin, polyimide resin, phenol resin, epoxy resin, silicon resin, and urea resin. Further, as the binder resin, one type may be used alone as a homopolymer or a copolymer, or two or more types may be mixed and used. If necessary, known additives such as a plasticizer, an antioxidant, and an ultraviolet absorber may be used in combination.

≫Apparatus using organic light emitting element 素 子
The organic light emitting device according to the present embodiment can be used as a constituent member of a display device or a lighting device. There are also other uses such as an exposure light source for an electrophotographic image forming apparatus, a backlight for a liquid crystal display device, and a light emitting device having a color filter for a white light source. Examples of the color filter include a filter that transmits any one of three colors of red, green, and blue.

  The display device according to the present embodiment includes a plurality of pixels, and at least one of the pixels includes the organic light-emitting element according to the present embodiment. The pixel has the organic light emitting device according to the present embodiment and an active device. The active element includes a switching element or an amplifying element, and specifically includes a transistor. An anode or a cathode of the organic light emitting device is electrically connected to a drain electrode or a source electrode of the transistor. The transistor may include an oxide semiconductor in its active region. The oxide semiconductor may be amorphous, crystalline, or a mixture of both. The crystal may be a single crystal, a microcrystal, or a crystal in which a specific axis such as the C axis is oriented, or a mixture of at least two of them.

  The organic light emitting device having such a switching element may be used as an image display device in which each organic light emitting element is provided as a pixel, or may be used as a lighting device. Further, it may be used as an exposure light source for exposing a photosensitive member of an electrophotographic image forming apparatus such as a laser beam printer and a copying machine.

  Here, the display device can be used as an image display device such as a PC. Examples of the transistor include a TFT element, which is provided, for example, on an insulating surface of a substrate. The display device has an image input unit for inputting image information from an area CCD, a linear CCD, a memory card, etc., has an information processing unit for processing the input information, and displays the input image on the display unit. An image information processing apparatus that performs the processing may be used. Further, the display unit included in the imaging device or the inkjet printer may have a touch panel function. The driving method of the touch panel function may be an infrared method, a capacitance method, a resistive film method, or an electromagnetic induction method, and is not particularly limited. The display device may be used for a display unit of a multifunction printer.

  The lighting device is, for example, a device that illuminates a room. The lighting device may emit any color of white to white (color temperature of 4200K), neutral white (color temperature of 5000K), and other colors from blue to red. Any of the organic light emitting elements included in the lighting device may be the organic light emitting element of the present invention. The lighting device according to the present embodiment includes the organic light emitting device according to the present embodiment and an AC / DC converter connected to the organic light emitting device. An AC / DC converter is a circuit that converts an AC voltage into a DC voltage. This converter is a circuit for supplying a drive voltage to the organic light emitting device. Note that the lighting device may further include a color filter. In addition, the lighting device according to the present embodiment may include a heat radiating unit. The heat radiating section is for radiating heat inside the apparatus to the outside of the apparatus, and examples thereof include a metal having a high specific heat and liquid silicon.

  In the organic light emitting element according to the present embodiment, the light emission luminance is controlled by a TFT which is an example of a switching element, and an image can be displayed with each light emission luminance by providing the organic light emitting element in a plurality of planes. The switching element according to the present embodiment is not limited to a TFT, and may be a transistor, an MIM element, or an active matrix driver formed on a substrate such as a Si substrate. On the substrate can also be referred to as within the substrate. This is selected depending on the definition. For example, in the case of a definition of about 1 inch and QVGA, it is preferable to provide an organic light emitting element on a Si substrate. By driving the display device using the organic light emitting device according to the present embodiment, stable display can be performed with good image quality and long-time display.

<Display device>
FIG. 1 is a schematic cross-sectional view illustrating an example of a display device according to the embodiment, and is a diagram illustrating an example of a display device including an organic light emitting element and a TFT element connected to the organic light emitting element. A TFT element is an example of an active element. The display device according to the present embodiment may include a color filter having red, green, and blue colors. In the color filters, the red, green, and blue colors may be arranged in a delta arrangement.

  The display device 10 shown in FIG. 1 includes a substrate 11 made of glass or the like, and a moisture-proof film 12 for protecting the TFT element 18 or the organic compound layer 22 on the substrate 11. The TFT element 18 has a metal gate electrode 13, a gate insulating film 14, a semiconductor layer 15, a drain electrode 16, and a source electrode 17. An insulating film 19 is provided on the TFT element 18. The anode 21 and the source electrode 17 constituting the organic light emitting device are connected via the contact hole 20. The method of electrical connection between the electrodes (the anode 21 and the cathode 23) included in the organic light emitting element and the electrodes (the source electrode 17 and the drain electrode 16) included in the TFT is not limited to the mode shown in FIG. Absent. That is, any one of the anode 21 and the cathode 23 may be electrically connected to one of the source electrode 17 and the drain electrode 16 of the TFT element. Although the organic compound layer 22 is illustrated as one layer in the display device 10 of FIG. 1, the organic compound layer 22 may be a plurality of layers. On the cathode 23, a first protective layer 24 and a second protective layer 25 for suppressing the deterioration of the organic light emitting element are provided.

  Although the display device 10 of FIG. 1 uses a transistor as a switching element, an MIM element may be used as a switching element instead. The transistor used in the display device 10 of FIG. 1 is not limited to a transistor using a single crystal silicon wafer, but may be a thin film transistor having an active layer on an insulating surface of a substrate. Examples of the active layer include non-single-crystal silicon such as single-crystal silicon, amorphous silicon, and microcrystalline silicon; and non-single-crystal oxide semiconductors such as indium zinc oxide and indium gallium zinc oxide. Note that the thin film transistor is also called a TFT element. The transistor included in the display device 10 of FIG. 1 may be formed in a substrate such as a Si substrate. Here, being formed in a substrate means that a transistor is manufactured by processing a substrate itself such as a Si substrate. That is, having a transistor in a substrate can be regarded as a case where the substrate and the transistor are formed integrally. Whether a transistor is provided in a substrate is selected depending on definition. For example, in the case of 1 inch and a definition of about QVGA, it is preferable to provide a transistor in a Si substrate.

  FIG. 2 is a schematic diagram illustrating an example of the display device according to the present embodiment. The display device 1000 may include a touch panel 1003, a display panel 1005, a frame 1006, a circuit board 1007, and a battery 1008 between the upper cover 1001 and the lower cover 1009. The touch panel 1003 and the display panel 1005 are connected to flexible printed circuits FPCs 1002 and 1004. The organic light-emitting device according to this embodiment may be used for the display panel 1005. Transistors are printed on the circuit board 1007. The battery 1008 need not be provided if the display device is not a portable device, and need not be provided at this position even if the display device is a portable device.

  FIG. 3 is a schematic diagram illustrating an example of the display device according to the present embodiment. FIG. 3A shows a display device such as a television monitor or a PC monitor. The display device 1300 has a frame 1301 and a display portion 1302. The organic light emitting element according to the embodiment may be used for the display unit 1302. In addition, the display device 1300 includes a frame 1301 and a base 1303 that supports the display unit 1302. The base 1303 is not limited to the form shown in FIG. The lower side of the frame 1301 may also serve as a base. Further, the frame 1301 and the display unit 1302 may be curved. The radius of curvature may be 5000 mm or more and 6000 mm or less. The display device 1310 in FIG. 3B is configured to be bendable, and is a so-called folderable display device. The display device 1310 includes a first display portion 1311, a second display portion 1312, a housing 1313, and a bending point 1314. The first display unit 1311 and the second display unit 1312 may include the organic light emitting device according to the embodiment. The first display unit 1311 and the second display unit 1312 may be one seamless display device. The first display unit 1311 and the second display unit 1312 can be separated by a bending point. The first display unit 1311 and the second display unit 1312 may display different images, respectively, or may display one image with the first and second display units.

<Imaging device>
The display device according to the present embodiment may be used for a display unit of an imaging device that includes an optical unit having a plurality of lenses and an image sensor that receives light passing through the optical unit. The imaging device may include a display unit that displays information acquired by the imaging device. Further, the display unit may be a display unit exposed to the outside of the imaging device or a display unit arranged in a viewfinder. The imaging device may be a digital camera or a digital video camera.

  FIG. 4 is a schematic diagram illustrating an example of the imaging device according to the present embodiment. The imaging device 1100 may include a viewfinder 1101, a rear display 1102, a housing 1103, and an operation unit 1104. The viewfinder 1101 may include the display device according to the present embodiment. In that case, the display device may display not only the image to be captured but also environment information, an imaging instruction, and the like. The environmental information may include the intensity of the external light, the direction of the external light, the moving speed of the subject, the possibility that the subject is blocked by a blocking object, and the like. Since the timing suitable for imaging is a short time, it is better to display information as soon as possible. Therefore, it is preferable to use a display device using the organic light emitting device of the present invention. This is because the organic light emitting device has a high response speed. A display device using an organic light emitting element can be more suitably used in a device requiring a display speed than a liquid crystal display device. The imaging device 1100 has an optical unit (not shown). The optical unit has a plurality of lenses, and forms an image on an imaging element housed in the housing 1103. The focus of the plurality of lenses can be adjusted by adjusting their relative positions. This operation can be performed automatically.

<Electronic equipment>
The display device according to the present embodiment may be used for a display unit of an electronic device such as a mobile terminal. In that case, both the display function and the operation function may be provided. Examples of the mobile terminal include a mobile phone such as a smartphone, a tablet, and a head-mounted display.

  FIG. 5 is a schematic diagram illustrating an example of the mobile device according to the present embodiment. The mobile device 1200 includes a display unit 1201, an operation unit 1202, and a housing 1203. The housing 1203 may include a circuit, a printed circuit board including the circuit, a battery, and a communication unit. The operation unit 1202 may be a button or a touch panel type reaction unit. The operation unit may be a biometric recognition unit that recognizes a fingerprint and unlocks the lock. A portable device having a communication unit can also be called a communication device.

<Lighting device>
FIG. 6 is a schematic diagram illustrating an example of the lighting device according to the present embodiment. The lighting device 1400 may include a housing 1401, a light source 1402, a circuit board 1403, an optical filter 1404, and a light diffusion unit 1405. The light source 1402 may include the organic light emitting device according to the embodiment. The optical filter 1404 may be a filter that improves the color rendering of the light source 1402. The light diffusing unit 1405 can effectively diffuse the light of the light source 1402 such as light-up and deliver the light to a wide range. If necessary, a cover may be provided on the outermost side.

  The lighting device is, for example, a device that illuminates a room. The lighting device may emit white, neutral white, or any other color from blue to red. It may have a dimming circuit for dimming them. The lighting device may include the organic light emitting device of the present invention and a power supply circuit connected thereto. The power supply circuit is a circuit that converts an AC voltage into a DC voltage. White has a color temperature of 4200K and neutral white has a color temperature of 5000K. The lighting device may have a color filter.

  In addition, the lighting device according to the present embodiment may include a heat radiating unit. The heat radiating section is for radiating heat inside the apparatus to the outside of the apparatus, and examples thereof include a metal having a high specific heat and liquid silicon.

<Mobile>
The moving body according to the present embodiment and others has a body and a lamp provided on the body. FIG. 7 is a schematic diagram illustrating an example of a moving body according to the present embodiment and the like, and is a diagram illustrating an automobile having a tail lamp, which is an example of a vehicular lamp. The vehicle 1500 as a body may have a tail lamp 1501 and turn on the tail lamp 1501 when a brake operation or the like is performed. The tail lamp 1501 may include the organic light emitting device according to the embodiment. The tail lamp 1501 may have a protection member for protecting the organic light emitting device. The material of the protective member is not limited as long as it has a certain high strength and is transparent, but is preferably made of polycarbonate or the like. A polycarbonate may be mixed with a furandicarboxylic acid derivative, an acrylonitrile derivative, or the like. Automobile 1500 may have a body 1503 and a window 1502 attached thereto. The window 1502 may be a transparent display as long as it is not a window for confirming the front and rear of the automobile 1500. The transparent display may include the organic light emitting device according to the embodiment. In this case, a constituent material such as an electrode included in the organic light emitting element is formed of a transparent member.

Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to these.
Example 1 (Synthesis of Exemplified Compound A2)

(1) Synthesis of Compound E3 The following reagents and solvents were charged into a 200-ml eggplant flask.
Compound E1: 2.00 g (4.59 mmol)
Compound E2: 1.79 g (4.73 mmol)
Pd (PPh ₃ ) ₄ : 159 mg (0.14 mmol)
Toluene: 45 ml
Ethanol: 20ml
10% aqueous sodium carbonate solution: 25 ml
Next, the reaction solution was heated to 90 ° C. under a nitrogen stream, and stirred at this temperature (90 ° C.) for 5 hours. After completion of the reaction, the mixture was extracted with toluene and water, concentrated, purified by silica gel column chromatography (heptane: toluene = 2: 1), and dispersed and washed with heptane / ethanol to give a dark green color. 2.01 g (yield: 72%) of Compound E3 was obtained.

(2) Synthesis of Compound E5 The following reagents and solvents were charged into a 100 ml eggplant flask.
Compound E3: 2.00 g (3.30 mmol)
Compound E4: 991 mg (4.00 mmol)
Isoamyl nitrite: 0.66 ml (4.95 mmol)
Toluene: 35ml
Next, the reaction solution was heated to 105 ° C. under a nitrogen stream and stirred at this temperature (105 ° C.) for 2 hours. Furthermore, 330 mg (1.32 mmol) of compound E4 and 0.18 ml (1.32 mmol) of isoamyl nitrite were added, and the mixture was stirred for 2 hours. After completion of the reaction, the reaction mixture was extracted with toluene and water, concentrated, purified by silica gel column chromatography (heptane: toluene = 4: 1), and dispersed and washed with heptane / ethanol to obtain a yellow compound. 1.82 g (yield: 77%) of E5 was obtained.

(3) Synthesis of Compound E7 The following reagents and solvents were charged into a 100-ml eggplant flask.
Compound E5: 1.80 g (2.51 mmol)
Compound E6: 474 mg (2.76 mmol)
Pd (PPh ₃ ) ₄ : 87 mg (0.075 mmol)
Cesium carbonate: 3.27 g (10.0 mmol)
Toluene: 25 ml
Ethanol: 10ml
Water: 15ml
Next, the reaction solution was heated to 90 ° C. under a nitrogen stream and stirred at this temperature (90 ° C.) for 4 hours. After completion of the reaction, the mixture was extracted with toluene and water, concentrated, purified by silica gel column chromatography (heptane: toluene = 4: 1), and dispersed and washed with heptane / ethanol to obtain a yellowish color. 1.82 g (yield: 89%) of compound E7 was obtained.

(5) Synthesis of Compound E8 The following reagents and solvent were charged into a 20 ml eggplant flask.
Compound E7: 1.80 g (2.21 mmol)
Pd (dba) ₂ : 381 mg (0.66 mmol)
P (Cy) ₃ (tricyclohexylphosphine): 384 mg (1.37 mmol)
DBU (diazabicycloundecene): 1.32 ml (8.83 mmol)
DMAc: 30 ml
Next, the reaction solution was heated to 170 ° C. under a nitrogen stream and stirred at this temperature (170 ° C.) for 5 hours. After completion of the reaction, methanol was added to precipitate crystals. The crystals were separated by filtration, and dispersed and washed sequentially with water, methanol, ethanol, and heptane. Next, the obtained yellow crystals were purified by silica gel column chromatography (heptane: chloroform = 2: 1), and then dispersed and washed with heptane / ethanol to obtain 1.43 g of a yellow compound E8 (yield: 83%).

(6) Synthesis of Exemplified Compound A2 The following reagents and solvents were charged into a 20 ml eggplant flask.
Compound E8: 300 mg (0.385 mmol)
t-BuOK: 1.73 g (15.4 mmol)
DBU (diazabicycloundecene): 4.61 ml (30.8 mmol)
Diethylene glycol dimethyl ether: 18 ml
Next, the reaction solution was heated to 180 ° C. under a nitrogen stream and stirred at this temperature (180 ° C.) for 10 hours. After completion of the reaction, water was added to precipitate crystals, and the crystals were separated by filtration and dispersed and washed with water, methanol, ethanol, and heptane sequentially. Next, the obtained dark purple solid was dissolved in chlorobenzene at 130 ° C., alumina was added thereto, and a heat adsorption treatment was performed. This was filtered while hot, concentrated and dispersed and washed with acetone / heptane to obtain 233 mg (yield: 78%) of dark purple example compound A2.

The emission spectrum of the toluene solution of Exemplified Compound A2 at 1 × 10 ⁻⁵ mol / L was measured by photoluminescence at an excitation wavelength of 360 nm using Hitachi F-4500, and as a result, the spectrum having the maximum intensity at 603 nm was obtained. I got

The exemplary compound A2 was subjected to mass spectrometry using MALDI-TOF-MS (Autoflex LRF manufactured by Bruker).
[MALDI-TOF-MS]
Found: m / z = 777 Calculated: C ₆₂ H ₃₂ = 776

[Examples 2 to 22 (Synthesis of exemplified compounds)]
With respect to the exemplified compounds shown in Tables 5 to 7, the exemplified compounds were synthesized in the same manner as in Example 1 except that the raw materials E1, E2, and E6 of Example 1 were changed to the raw materials 1, 2, and 3, respectively. The measured value of the mass spectrometry result measured in the same manner as in Example 1 is shown as m / z.

[Example 23]
An organic light emitting device having a bottom emission structure in which an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode are sequentially formed on a substrate. Was prepared.

First, an ITO film was formed on a glass substrate, and a desired patterning process was performed to form an ITO electrode (anode). At this time, the thickness of the ITO electrode was set to 100 nm. The substrate on which the ITO electrode was formed as described above was used as an ITO substrate in the following steps. Next, vacuum deposition was performed by resistance heating in a vacuum chamber of 1.33 × 10 ⁻⁴ Pa to continuously form an organic compound layer and an electrode layer shown in Table 8 on the ITO substrate. At this time, the electrode area of the facing electrode (metal electrode layer, cathode) was set to 3 mm ² .

The characteristics of the obtained device were measured and evaluated. The maximum emission wavelength of the light emitting device is 622 nm, the maximum external quantum efficiency (EQE) is 5.5%, and the chromaticity is (X, Y) = (0.67, 0.33) red emission. Was obtained. Further, a continuous driving test was performed at a current density of 100 mA / cm ² , and the time when the luminance deterioration rate reached 5% was measured. Specifically, the measurement device measured the current-voltage characteristics with a microammeter 4140B manufactured by Hewlett-Packard Company, and the emission luminance was measured with BM7 manufactured by Topcon Corporation.

[Examples 24 and 37, Comparative Examples 1 and 2]
An organic light-emitting device was manufactured in the same manner as in Example 23 except that the compounds shown in Table 9 were appropriately changed. The characteristics of the obtained device were measured and evaluated in the same manner as in Example 23. Table 9 shows the measurement results.

  From Table 9, the chromaticity coordinates of Comparative Example 1 and Comparative Example 2 are (0.66, 0.35) and (0.65, 0.34), respectively, and the Example has an sRGB color reproduction range. It can be seen that the color reproduction range is further expanded. This is because the compound of the present invention emits red light at a longer wavelength.

[Example 38]
Top emission in which an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a first light emitting layer, a second light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode are sequentially formed on a substrate An organic light emitting device having a mold structure was manufactured.

A 40 nm Ti film was formed on a glass substrate by a sputtering method, and was patterned using a photolithography technique to form an anode. At this time, the electrode area of the facing electrode (metal electrode layer, cathode) was set to 3 mm ² . Subsequently, the substrate and the material formed up to the cleaned electrode were attached to a vacuum evaporation apparatus (manufactured by ULVAC, Inc.), and after evacuation to 1.33 × 10 ⁻⁴ Pa (1 × 10 ⁻⁶ Torr), UV / ozone was applied. Washing was performed. Thereafter, each layer was formed with the layer configuration shown in Table 10, and finally, sealing was performed in a nitrogen atmosphere.

  The characteristics of the obtained device were measured and evaluated. The obtained device showed good white light emission. The chromaticity coordinates of red after passing through the RGB color filter were estimated from the obtained white emission spectrum, and the chromaticity coordinates of red in sRGB were (0.68, 0.32).

[Examples 39 and 27, Comparative Examples 3 and 4]
An organic light-emitting device was manufactured in the same manner as in Example 38 except that the compounds shown in Table 11 were appropriately changed. The characteristics of the obtained device were measured and evaluated in the same manner as in Example 38. Table 11 shows the measurement results.

  From Table 11, the red chromaticity coordinates of Comparative Example 3 and Comparative Example 4 are (0.67, 0.35) and (0.65, 0.34), respectively. It can be seen that the direction is to extend the color reproduction range more than the color reproduction range. This is because the compound of the present invention emits red light at a longer wavelength.

10: display device, 11: substrate, 12: moisture-proof film, 13: gate electrode, 14: gate insulating film, 15: semiconductor layer, 16: drain electrode, 17: source electrode, 18: TFT, 19: insulating film, 20 : Contact hole, 21: anode, 22: organic compound layer, 23: cathode, 24: first protective layer, 25: second protective layer

Claims (21)

An organic compound represented by the following general formula (1).

[In the formula (1), R _{1 to} R ₂₄ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, A substituted or unsubstituted amino group, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 15 carbon atoms, a substituted or unsubstituted aryloxy group, a silyl group And a cyano group. ] R _{1 to} R ₂₄ are each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. The organic compound according to claim 1, At least one selected from R ₇ , R ₈ , R ₁₃ , R ₁₈ , R ₂₃ and R ₂₄ is a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon group. An alkoxy group having 1 to 10 atoms, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 15 carbon atoms, The organic compound according to claim 1, wherein the organic compound is independently selected from an unsubstituted aryloxy group, a silyl group, and a cyano group. At least one selected from R ₇ , R ₈ , R ₁₃ , R ₁₈ , R ₂₃ and R ₂₄ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted carbon group having 6 carbon atoms. The organic compound according to any one of claims 1 to 3, wherein the organic compound is independently selected from the aryl groups of 1 to 18. 2. The method according to claim 1, wherein at least one selected from the group consisting of R ₇ , R ₈ , R ₁₃ , R ₁₈ , R ₂₃ and R ₂₄ is a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. The organic compound according to any one of claims 1 to 4.   The organic compound according to claim 5, wherein the aryl group has a substituent at an ortho position. 5. The method according to claim 1, wherein at least one selected from the group consisting of R ₇ , R ₈ , R ₁₃ , R ₁₈ , R ₂₃ and R ₂₄ is a substituted or unsubstituted phenyl group. 6. The organic compound according to the above. At least one selected from the group consisting of R ₇ , R ₈ , R ₁₃ , R ₁₈ , R ₂₃ and R ₂₄ is one of R ₇ and R ₈ and one of R ₂₃ and R _24. The organic compound according to any one of claims 3 to 7, wherein   An anode and a cathode, having an organic compound layer disposed between the anode and the cathode, wherein the organic compound layer contains the organic compound according to any one of claims 1 to 8. An organic light-emitting device comprising a layer.   The organic light emitting device according to claim 9, wherein the layer containing the organic compound is a light emitting layer.   The organic light emitting device according to claim 10, wherein the organic light emitting device emits red light.   The light-emitting layer according to claim 10, further comprising another light-emitting layer disposed so as to be stacked with the light-emitting layer, wherein the another light-emitting layer emits a color different from a color emitted by the light-emitting layer. Organic light-emitting device.   The organic light emitting device according to claim 12, wherein the organic light emitting device emits white light.   A display device, comprising: a plurality of pixels, each of the pixels comprising: the organic light emitting device according to claim 9; and an active device connected to the organic light emitting device. .   The display device according to claim 14, further comprising a color filter. An input unit for inputting image information, and a display unit for outputting an image,
An image display device comprising: the display unit according to claim 14. An optical unit having a plurality of lenses, an image sensor that receives light passing through the optical unit, and a display unit,
An imaging device, wherein the display unit is a display unit that displays information captured by the imaging device, and the display unit includes the display device according to claim 14. A housing, a communication unit that communicates with the outside, and a display unit,
An electronic device, wherein the display unit is the display device according to claim 14. A lighting device having a light source and a light diffusion unit or an optical filter,
A lighting device, comprising: the organic light emitting device according to claim 9.   A lighting device, comprising: the organic light-emitting device according to claim 9; and a power supply circuit connected to the organic light-emitting device. Having a body and a lamp provided on the body,
A moving body, comprising: the organic light emitting device according to claim 9.

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