Carbazole derivative

Abstract

To provide a light-emitting element having high luminous efficiency by providing a novel carbazole derivative. Further, it is another object of the present invention to provide a light-emitting device and an electronic device with low power consumption and low driving voltage.SOLUTION: The carbazole derivative is represented by general formula (1). In the formula, α 1, α 2, α 3, and α 4 each represent an arylene group having 13 or less carbon atoms in a ring, Ar1 and Ar2 each represent an aryl group having 13 or less carbon atoms in a ring, R1 represents any of hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted phenyl groups, and substituted or unsubstituted biphenyl groups, and R2 represents any of alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted phenyl groups, and substituted or unsubstituted biphenyl groups. L, m, and n are each independently 0 or 1. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a carbazole derivative, a light-emitting element using the carbazole derivative, a light-emitting device, and and electronic devices. [Background technology]

[0002] In recent years, electroluminescence has been used The basic structure of these light-emitting devices is a pair of A layer containing a light-emitting substance is sandwiched between the electrodes. This allows light emission from the luminescent substance to be obtained.

[0003] These light-emitting elements are self-luminous, so the pixels are more visible than those of LCDs. It has the advantage of being simple and does not require a backlight, making it suitable for use as a flat panel display element. Furthermore, such a light-emitting element can be manufactured to be thin and lightweight. Another major advantage is that it has an extremely fast response time.

[0004] These light-emitting elements can be formed in a film shape, making it possible to form elements with a large area. By forming this, it is possible to easily obtain a surface light emission. This is a feature that is difficult to obtain with point light sources such as D or linear light sources such as fluorescent lamps. It is also highly useful as a surface light source that can be applied to lighting, etc.

[0005] The light-emitting element that utilizes electroluminescence uses an organic compound as the light-emitting substance. They can be broadly classified according to whether they are organic or inorganic compounds, but when organic compounds are used as luminescent materials, In this case, when a voltage is applied to the light emitting element, electrons and holes are emitted from the pair of electrodes. The current flows through the layer containing the photo-active organic compound, and the carriers (electrons and The recombination of electrons (electrons and holes) causes the light-emitting organic compound to form an excited state, and the excited state Light is emitted when the state returns to the ground state.

[0006] Due to this mechanism, such a light-emitting element is called a current-excited light-emitting element. The types of excited states that organic compounds form are singlet excited states and triplet excited states. Light emitted from the singlet excited state is called fluorescence, and light emitted from the triplet excited state is called phosphorescence. It's been discovered.

[0007] Regarding such light-emitting devices, there are material-dependent issues in improving the device characteristics. To overcome these problems, improvements to device structures and material development are being carried out. , Non-Patent Document 1) [Prior art documents] [Non-patent literature]

[0008] [Non-Patent Document 1] Meng-Huan Ho, Yao-Shan Wu and Chin H. Chen, 2005 SID International Symposium Digest of Technical Papers, Vol.XXXVI. p802-805

[0009] In the light-emitting device described in Non-Patent Document 1, a layer in contact with the light-emitting layer is a 4,4'-bis[N- (1-naphthyl)-N-phenylamino]biphenyl (NPB) is used. However, NPB has a low singlet excitation energy, and the energy transfer from the excited state emitting material is In particular, in the case of light-emitting materials that emit blue light, which is a short wavelength, excitation Since the energy level of the excited state is high, there is a greater possibility of energy transfer to NPB. If energy is transferred to NPB, the luminous efficiency of the light-emitting element will decrease. There was a problem. Summary of the Invention [Problem to be solved by the invention]

[0010] Therefore, the present invention provides a novel carbazole derivative, which can improve the luminous efficiency. Furthermore, it is an object of the present invention to provide a light-emitting element that consumes less power and is driven at a low voltage. The present invention aims to provide an optical device and an electronic device. [Means for solving the problem]

[0011] One aspect of the present invention is a carbazole derivative represented by the following general formula (1). [ka] (In the formula, α 1 , α 2 , α 3 , α 4 represents an arylene group having 13 or less carbon atoms forming a ring. And Ar 1 , Ar 2 represents an aryl group having 13 or less carbon atoms forming a ring, and R 1 is water a nitrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, R represents either a phenyl group or a 2 is an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted fluorocarbon In addition, l, m, and n represent either a phenyl group or a substituted or unsubstituted biphenyl group. Each is independently 0 or 1.)

[0012] In the above structure, α in general formula (1) 1 ~α 4 is represented by the following general formula (2-1) It is characterized by being any one of the compounds represented by general formula (2-12). [ka] (In the formula, R 11 ~R 16 , R 21 ~R 30 , R 31 ~R 38 , R 41 ~R 45 Yes, respectively represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a biphenyl group. .R 46 , R 47 represents either an alkyl group having 1 to 6 carbon atoms or a phenyl group. Also, R 46 and R 47 may be bonded to each other to form a ring. 48 is a hydrogen atom , an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a biphenyl group.)

[0013] In the above structure, Ar 1 and Ar 2 is represented by the general formula (3-1) -It is characterized in that it is any one of the compounds represented by general formula (3-6). [ka] (In the formula, R 51 ~R 56 , R 61 ~R 70 , R 71 ~R 78 , R 81 ~R 85 Yes, respectively represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a biphenyl group. .R 86 , R 87 represents either an alkyl group having 1 to 6 carbon atoms or a phenyl group. Also, R 86 and R 87 may be bonded to each other to form a ring. 88 , R 89 teeth, It represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a biphenyl group.

[0014] Furthermore, in the above structure, R 1 is the general formula (4-1) ~ general formula (4-9), and R 2 Formula (4-2) to Formula (4-9) The present invention is characterized in that the formula is any one of the formulas shown below. It is characterized in that: [ka] (In the formula, R 51 ~R 70 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a biphenyl group, represents either a hydroxyl group or a hydroxyl group.)

[0015] Furthermore, one aspect of the present invention is characterized in that it is any one of the following structural formulas (5) to (8): It is a sign.

[0016] [ka]

[0017] [ka]

[0018] [ka]

[0019] [ka]

[0020] Another aspect of the present invention is a light-emitting element having an EL layer between a pair of electrodes, has at least a light-emitting layer and a hole-transporting layer, and at least one of the light-emitting layer and the hole-transporting layer is The present invention is characterized by containing the carbazole derivative described above.

[0021] Furthermore, another aspect of the present invention is a light-emitting device having an EL layer between an anode and a cathode, The EL layer has at least a light-emitting layer, a hole-transporting layer, and a hole-injecting layer, and the hole-injecting layer At least one of the light-emitting layer, the hole-transporting layer, and the hole-injecting layer is formed in contact with the anode, and The present invention is characterized in that it contains a carbazole derivative of the formula:

[0022] In the above structure, the hole injection layer is a compound of the above carbazole derivative and the carbazole The inorganic compound may also contain an inorganic compound that exhibits electron accepting properties with respect to the sol derivative. As the inorganic compound, oxides of transition metals can be used. Titanium oxide, vanadium oxide, molybdenum oxide, tungsten oxide, rhenium oxide Ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, One or more of tantalum oxide and silver oxide can be used.

[0023] Furthermore, another configuration of the present invention is characterized in that it is formed using the light-emitting element described above. The present invention also provides an electronic device formed using a light-emitting device. do.

[0024] The present invention also provides a light-emitting device having the above-described light-emitting element and an electronic device having the light-emitting device. The light-emitting device in this specification includes image display devices, light-emitting devices, and the like. It refers to a device or light source (including lighting equipment). Also, a light-emitting device with a connector, e.g. FPC (Flexible printed circuit) or TAB (Tap Automated Bonding (ATB) tape or TCP (Tape Carrier) Modules with a TAB tape or TCP attached, A module with a printed wiring board or a light emitting element with COG (Chip On Glass) All modules in which ICs (integrated circuits) are directly mounted using the OLED (LED) method are also included in the category of light-emitting devices. It shall be. [Effects of the Invention]

[0025] The carbazole derivative of the present invention exhibits high hole transport properties and is therefore useful mainly for the EL element of a light-emitting element. The carbazole derivative of the present invention can be used in a hole transport layer constituting a hole transport layer. By forming a light emitting element using the hole transport layer, a light emitting element with high luminous efficiency can be formed. This can be done.

[0026] Furthermore, by using this light-emitting element, a light-emitting device with low power consumption and low driving voltage can be realized. , and electronic devices can be obtained. [Brief explanation of the drawings]

[0027] [Figure 1] 10A and 10B illustrate a stacked structure of a light-emitting element according to Embodiment 2. [Figure 2] 10A and 10B illustrate light-emitting modes of a light-emitting element according to Embodiment 2. [Figure 3]10A and 10B illustrate a stacked structure of a light-emitting element according to Embodiment 3. [Figure 4] FIG. 10 illustrates an active matrix light-emitting device according to Embodiment 4. [Figure 5] FIG. 10 illustrates a passive matrix light-emitting device according to Embodiment 4. [Figure 6] 10A to 10C are diagrams illustrating electronic devices according to Embodiment 5. [Figure 7] FIG. 10 is a diagram showing a liquid crystal display device using a light-emitting device of the present invention as a backlight. [Figure 8] 10A and 10B are diagrams showing a desk lamp using a light-emitting device of the present invention. [Figure 9] 1 is a diagram showing an indoor lighting device using a light-emitting device of the present invention. [Figure 10] A diagram showing the 1H NMR chart of PCBA1BP (abbreviation). [Figure 11] FIG. 1 shows the absorption spectrum and emission spectrum of PCBA1BP (abbreviation). [Figure 12] A diagram showing the 1H NMR chart of PCBBi1BP (abbreviation). [Figure 13] FIG. 1 shows the absorption spectrum and emission spectrum of PCBBi1BP (abbreviation). [Figure 14] A diagram showing the 1H NMR chart of PCBAF (abbreviation). [Figure 15] 1 shows the absorption spectrum and emission spectrum of PCBAF (abbreviation). [Figure 16] A diagram showing the 1H NMR chart of PCBASF (abbreviation). [Figure 17] 1 shows the absorption spectrum and emission spectrum of PCBASF (abbreviation). [Figure 18] FIG. 10 is a diagram showing the element structure of a light-emitting element in Example 5. [Figure 19] FIG. 10 shows current density-luminance characteristics of Light-emitting Elements 1 and 2. [Figure 20] FIG. 10 shows voltage-luminance characteristics of Light-emitting Elements 1 and 2. [Figure 21] FIG. 10 shows luminance-current efficiency characteristics of Light-emitting Elements 1 and 2. [Figure 22] 10 is a graph showing voltage-current characteristics of Light-emitting Elements 1 and 2. FIG. [Figure 23] FIG. 2 shows emission spectra of Light-Emitting Element 1 and Light-Emitting Element 2. [Figure 24] 10A and 10B are graphs showing the results of a continuous lighting test of the light-emitting element 1 and the light-emitting element 2 driven by a constant current. [Figure 25] FIG. 10 shows current density-luminance characteristics of Light-emitting Elements 1 and 3. [Figure 26] FIG. 10 shows voltage-luminance characteristics of Light-emitting Elements 1 and 3. [Figure 27] FIG. 10 shows luminance-current efficiency characteristics of Light-Emitting Element 1 and Light-Emitting Element 3. [Figure 28] FIG. 10 shows voltage-current characteristics of Light-emitting Elements 1 and 3. [Figure 29] FIG. 2 shows emission spectra of Light-Emitting Elements 1 and 3. [Figure 30] FIG. 10 shows current density-luminance characteristics of Light-emitting Elements 1 and 4. [Figure 31] FIG. 10 shows voltage-luminance characteristics of Light-emitting Elements 1 and 4. [Figure 32] FIG. 10 shows luminance-current efficiency characteristics of Light-emitting Elements 1 and 4. [Figure 33] 10 is a graph showing voltage-current characteristics of Light-emitting Elements 1 and 4. FIG. [Figure 34] FIG. 10 shows emission spectra of Light-Emitting Element 1 and Light-Emitting Element 4. [Figure 35] 10 is a graph showing the results of a continuous lighting test of the light-emitting element 1 and the light-emitting element 4 driven by a constant current. [Figure 36] FIG. 10 shows current density-luminance characteristics of Light-emitting Elements 1 and 5. [Figure 37] FIG. 10 shows voltage-luminance characteristics of Light-emitting Elements 1 and 5. [Figure 38] FIG. 10 shows luminance-current efficiency characteristics of Light-emitting Elements 1 and 5. [Figure 39] FIG. 10 is a graph showing voltage-current characteristics of the light-emitting element 1 and the light-emitting element 5. [Figure 40]FIG. 10 shows emission spectra of the light-emitting elements 1 and 5. [Figure 41] Graph showing the CV characteristics of PCBA1BP (abbreviation). [Figure 42] Graph showing the CV characteristics of PCBBi1BP (abbreviation). [Figure 43] Graph showing the CV characteristics of PCBAF (abbreviation). [Figure 44] Graph showing the CV characteristics of PCBASF (abbreviation). [Figure 45] A diagram showing the 1H NMR chart of PCTA1BP (abbreviation). [Figure 46] A diagram showing the 1H NMR chart of PCTBi1BP (abbreviation). [Figure 47] 1H NMR chart of PCBANB (abbreviation). [Figure 48] 1H NMR chart of PCBNBB (abbreviation). [Figure 49] Figure showing the 1H NMR chart of PCBBiNB (abbreviation). [Figure 50] A diagram showing the 1H NMR chart of PCBANT (abbreviation). [Figure 51] A diagram showing the 1H NMR chart of BCBA1BP (abbreviation). [Figure 52] 1H NMR chart of BCBANB (abbreviation). [Figure 53] A diagram showing the 1H NMR chart of BCBBiNB (abbreviation). [Figure 54] A diagram showing the 1H NMR chart of NBCBA1BP (abbreviation). [Figure 55] A diagram showing the 1H NMR chart of NCBA1BP (abbreviation). [Figure 56] FIG. 10 is a graph showing voltage-luminance characteristics of Light-emitting element 1 and Light-emitting elements 6 to 8. [Figure 57] FIG. 10 shows luminance-current efficiency characteristics of Light-Emitting Element 1 and Light-Emitting Elements 6 to 8. [Figure 58] 10 is a graph showing voltage-current characteristics of the light-emitting element 1 and the light-emitting elements 6 to 8. FIG. [Figure 59]FIG. 1 shows emission spectra of the light-emitting element 1 and the light-emitting elements 6 to 8. [Figure 60] 10 is a graph showing the results of a continuous lighting test of light-emitting elements 6 to 8 driven at a constant current. FIG. [Figure 61] A diagram showing the 1H NMR chart of PCBBi1BPIII (abbreviation). [Figure 62] A diagram showing the 1H NMR chart of PCBA1BPIV (abbreviation). [Figure 63] 1H NMR chart of PCBNBBβ (abbreviation). [Figure 64] A diagram showing the 1H NMR chart of PCBBiFLP (abbreviation). DETAILED DESCRIPTION OF THE INVENTION

[0028] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The present invention is not limited to the above description, and the embodiments and details thereof may be modified without departing from the spirit and scope of the present invention. Therefore, the present invention is not limited to the embodiments described below. It is not to be construed as being limited to the content.

[0029] (Embodiment 1) In the first embodiment, a carbazole derivative of the present invention will be described.

[0030] The carbazole derivative of the present invention is represented by general formula (1).

[0031] [ka]

[0032] (In the formula, α 1 , α 2 , α 3 , α 4 represents an arylene group having 13 or less carbon atoms forming a ring. Represents Ar 1 , Ar2 represents an aryl group having 13 or less carbon atoms forming a ring, and R 1 teeth, A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, and R 2 represents an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted represents a phenyl group, or a substituted or unsubstituted biphenyl group. are independently 0 or 1.)

[0033] In the general formula (1), α1 to α4 are each an aryl group having 13 or less carbon atoms forming a ring. Specifically, the substituents shown in structural formulas (2-1) to (2-12) are exemplified. It can be obtained.

[0034] [ka] (In the formula, R 11 ~R 16 , R 21 ~R 30 , R 31 ~R 38 , R 41 ~R 45 Is that Each of them represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a biphenyl group. R 46 , R 47 represents either an alkyl group having 1 to 6 carbon atoms or a phenyl group. Also, R 46 and R 47 may be bonded to each other to form a ring. 48 is a hydrogen atom represents a phenyl group, an alkyl group having 1 to 6 carbon atoms, a biphenyl group, or a phenyl group.

[0035] In the general formula (1), Ar1 and Ar2 each represent a ring having 13 or less carbon atoms. It represents an aryl group. Specifically, the substituents shown in structural formulas (3-1) to (3-6) are exemplified. It can be obtained.

[0036] [ka] (In the formula, R 51 ~R 56 , R 61 ~R 70 , R 71 ~R 78 , R 81 ~R 85 Yes, respectively represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a biphenyl group. .R 86 , R 87 represents either an alkyl group having 1 to 6 carbon atoms or a phenyl group. Also, R 86 and R 87 may be bonded to each other to form a ring. 88 , R 89 teeth, It represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a biphenyl group.

[0037] In general formula (1), R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group, represents a substituted phenyl group or a substituted or unsubstituted biphenyl group, and R 2 is the number of carbon atoms 1 to 6 alkyl groups, substituted or unsubstituted phenyl groups, substituted or unsubstituted biphenyl groups Specifically, R 1 The structural formulas (4-1) to (4-9) are shown in Substituent, R 2 Examples of the substituents include those shown in structural formulas (4-2) to (4-9).

[0038] [ka] (In the formula, R 51 ~R 70 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a biphenyl group, represents either a hydroxyl group or a hydroxyl group.)

[0039] Specific examples of the carbazole derivative of the present invention represented by general formula (1) include those represented by structural formula (9): The carbazole derivative represented by the structural formula (421) can be mentioned. are not limited to these.

[0040] [ka]

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[0127] The carbazole derivative of the present invention represented by the general formula (1) can be prepared by the following synthetic scheme: Synthetic Scheme (A-1) to Synthetic Scheme (A-7), Synthetic Scheme (B-1), Synthetic Scheme (C- 1) to (C-2).

[0128] [Synthesis of halogenated secondary arylamine (compound A)] The halogenated secondary arylamine represented by the general formula (Compound A) can be synthesized by the following synthesis scheme: A-1) can be synthesized as follows: First, a secondary arylamine (compound A-1) Substance A1) is halogenated with a halogenating agent to give a halogenated secondary arylamine ( Compound A) can be obtained. As a halogenating agent, N-bromosuccinimide can be used. N-iodosuccinimide (NBS), N-iodosuccinimide (NIS), bromine, iodine, potassium iodide, etc. can be used. Also, X 1Each represents a halogen group, preferably a bromo group or or an iodo group.

[0129] [ka]

[0130] [Synthesis of halogenated carbazole derivatives (compound B2)] The halogenated carbazole derivative represented by the general formula (Compound B2) can be synthesized by the following synthesis scheme: It can be synthesized as shown in (A-2). That is, first, a carbazole derivative ( Compound B1) is halogenated with a halogenating agent to obtain a halogenated carbazole derivative (Compound B2) can be obtained. Note that N-bromosuccine can be used as a halogenating agent. Imide (NBS), N-iodosuccinimide (NIS), bromine, iodine, potassium iodide Also, X 2 each represents a halogen group, preferably bromo group or an iodo group.

[0131] [ka]

[0132] [9H-carbazole-3-boronic acid or 9H-carbazole in which the 3-position is substituted with an organic boron] Synthesis of the substituted compound (Compound B) The 3-position of the 9H-carbazole represented by the general formula (Compound B) is boronic acid or organic boron. The compound substituted with can be synthesized according to the following synthesis scheme (A-3). That is, a halogenated carbazole derivative (compound B2) is reacted with an alkyllithium reagent and 9H-Carbazoles can be obtained by boronation or organoboration using uranyl reagents. The compound (Compound B) can be obtained by substituting boronic acid or organic boron at the 3-position of .

[0133] In addition, R in Scheme (A-3) 99 represents an alkyl group having 1 to 6 carbon atoms. 98 represents an alkyl group having 1 to 6 carbon atoms. 100 , R 101 are hydrogen or R represents an alkyl group having 1 to 6 carbon atoms. 102 and R 103 are bonded to each other to form a ring In addition, examples of alkyllithium reagents include n-butyllithium and methyllithium. Examples of boron reagents that can be used include trimethyl borate and isopropyl borate. can be used.

[0134] [ka]

[0135] [Synthesis of secondary arylamine (compound C3)] The secondary arylamine represented by the general formula (compound C3) can be synthesized by the following synthesis scheme (A-4): That is, the aryl halide (compound C1) and 1 and a triarylamine (compound C2) are coupled with the compound C1 using a metal catalyst in the presence of a base. By this reaction, a secondary arylamine (compound C3) can be obtained.

[0136] [ka]

[0137] In the synthesis scheme (A-4), when the Hartwig-Buchwald reaction is carried out, Palladium catalysts that can be used include bis(dibenzylideneacetone)palladium. (0), palladium(II) acetate, etc., but the catalysts that can be used are Palladium compounds that can be used in the synthesis scheme (A-4) include, but are not limited to: The catalyst ligands include tri(tert-butyl)phosphine and tri(n-hexyl) Examples of suitable coordination groups include phosphine and tricyclohexylphosphine. Children are not limited to these.

[0138] Examples of bases that can be used in the synthesis scheme (A-4) include sodium te Examples of the base include organic bases such as rt-butoxide and inorganic bases such as potassium carbonate. The bases that can be used are not limited to these. Examples of solvents that can be used in this process include toluene, xylene, benzene, tetrahydrofuran, and the like. However, the solvents that can be used are not limited to these. .

[0139] In addition, in the synthesis scheme (A-4), the Ullmann reaction will be described. In the synthetic scheme (A-4), R 104 and R 105 are halogen and acetylene, respectively. The halogens include chlorine, bromine, and iodine. 104 Gayo Copper(I) iodide, or R 105 is an acetyl group, copper(II) acetate is preferred. The copper compounds used in the reaction are not limited to these. In the synthesis scheme (A-4), the base that can be used is Examples of the base that can be used include inorganic bases such as potassium carbonate. It is not something that can be done.

[0140] In the synthesis scheme (A-4), the solvent that can be used is 1,3-dimethyl dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone (DMPU), toluene, Examples of solvents that can be used include xylene and benzene. In the Ullmann reaction, a reaction temperature of 100°C or higher results in a shorter time and higher yield. It is preferable to use DMPU or xylene, which have high boiling points, because the product obtained is The temperature is more preferably 150°C or higher, and therefore, DMPU is more preferably used. do.

[0141] [Synthesis of tertiary arylamine (compound C5)] The tertiary arylamine represented by the general formula (compound C5) can be synthesized by the following synthesis scheme (A-5): That is, a secondary arylamine (compound C3) and a halogen atom can be synthesized as follows. and an aryl halide (compound C4) are coupled with the compound C4 using a metal catalyst in the presence of a base. By this reaction, a tertiary arylamine (compound C5) can be obtained.

[0142] [ka]

[0143] In the synthesis scheme (A-5), when the Hartwig-Buchwald reaction is carried out, Palladium catalysts that can be used include bis(dibenzylideneacetone)palladium. (0), palladium(II) acetate, etc., but the catalysts that can be used are Palladium compounds that can be used in the synthesis scheme (A-5) include, but are not limited to: The catalyst ligands include tri(tert-butyl)phosphine and tri(n-hexyl) Examples of suitable coordination groups include phosphine and tricyclohexylphosphine. Children are not limited to these.

[0144] The base that can be used in the synthesis scheme (A-5) is sodium te Examples of the base include organic bases such as rt-butoxide and inorganic bases such as potassium carbonate. The bases that can be used are not limited to these. Examples of solvents that can be used in this process include toluene, xylene, benzene, tetrahydrofuran, and the like. However, the solvents that can be used are not limited to these. .

[0145] In addition, in the synthesis scheme (A-5), the Ullmann reaction will be described. In the synthetic scheme (A-5), R 104 and R 105 are halogen and acetylene, respectively. The halogens include chlorine, bromine, and iodine. 104 Gayo Copper(I) iodide, or R 105 is an acetyl group, copper(II) acetate is preferred. The copper compounds used in the reaction are not limited to these. In the synthesis scheme (A-5), the base that can be used is Examples of the base that can be used include inorganic bases such as potassium carbonate. It is not something that can be done.

[0146] In the synthesis scheme (A-5), the solvent that can be used is 1,3-dimethyl dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone (DMPU), toluene, Examples of solvents that can be used include xylene and benzene. In the Ullmann reaction, a reaction temperature of 100°C or higher results in a shorter time and higher yield. It is preferable to use DMPU or xylene, which have high boiling points, because the product obtained is The temperature is more preferably 150°C or higher, and therefore, DMPU is more preferably used. do.

[0147] [Synthesis of tertiary arylamine (compound C5)] The tertiary arylamine represented by the general formula (compound C5) can be synthesized by the following synthesis scheme (A-6): That is, a primary arylamine (compound C2) and a halogen atom can be synthesized as follows. The aryl halide (compounds C1 and C4) is coupled with the aryl halide using a metal catalyst in the presence of a base. By carrying out the reaction, a tertiary arylamine (compound C5) can be obtained. Ar 1 and Ar 2 are the same and β 1 , β 2 are the same and l and m are the same. However, compound C5 can be obtained in good yield.

[0148] [ka]

[0149] In the synthesis scheme (A-6), when the Hartwig-Buchwald reaction is carried out, Palladium catalysts that can be used include bis(dibenzylideneacetone)palladium. (0), palladium(II) acetate, etc., but the catalysts that can be used are Palladium compounds that can be used in the synthesis scheme (A-6) include, but are not limited to: The catalyst ligands include tri(tert-butyl)phosphine and tri(n-hexyl) Examples of suitable coordination groups include phosphine and tricyclohexylphosphine. Children are not limited to these.

[0150] The base that can be used in the synthesis scheme (A-6) is sodium te Examples of the base include organic bases such as rt-butoxide and inorganic bases such as potassium carbonate. The bases that can be used are not limited to these. Examples of solvents that can be used in this process include toluene, xylene, benzene, tetrahydrofuran, and the like. However, the solvents that can be used are not limited to these. .

[0151] In addition, in the synthesis scheme (A-6), the Ullmann reaction will be described. In the synthetic scheme (A-6), R 104 and R 105 are halogen and acetylene, respectively. The halogens include chlorine, bromine, and iodine. 104 Gayo Copper(I) iodide, or R 105 is an acetyl group, copper(II) acetate is preferred. The copper compounds used in the reaction are not limited to these. In the synthesis scheme (A-6), the base that can be used is Examples of the base that can be used include inorganic bases such as potassium carbonate. It is not something that can be done.

[0152] In the synthesis scheme (A-6), the solvent that can be used is 1,3-dimethyl dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone (DMPU), toluene, Examples of solvents that can be used include xylene and benzene. In the Ullmann reaction, a reaction temperature of 100°C or higher results in a shorter time and higher yield. It is preferable to use DMPU or xylene, which have high boiling points, because the product obtained is The temperature is more preferably 150°C or higher, and therefore, DMPU is more preferably used. do.

[0153] [Synthesis of halogenated tertiary arylamine derivatives (compound C)] The halogenated tertiary amine represented by the general formula (Compound C) can be synthesized by the following synthesis scheme (A-7): That is, first, a tertiary arylamine (compound C5) is halogenated with a halogenating agent to obtain a halogenated tertiary arylamine (compound C ) can be obtained. As a halogenating agent, N-bromosuccinimide (NB S), N-iodosuccinimide (NIS), bromine, iodine, potassium iodide, etc. Also, X 3 Each represents a halogen group, preferably a bromo group or an iodine group. It is a do-based group.

[0154] [ka]

[0155] [Synthesis of secondary arylamine (compound D)] The secondary arylamine having a carbazole represented by the general formula (Compound D) can be synthesized by the following synthesis: It can be synthesized as shown in scheme (B-1). Substitution of boronic acid or organic boron at the 3-position of 9H-carbazole and 9H-carbazole (compound A) and coupling the resulting compound (compound B) with the compound (compound B) in the presence of a base using a metal catalyst. This gives a carbazole-containing secondary arylamine (compound D). It is possible.

[0156] [ka]

[0157] In the above scheme, we will explain the case where the Suzuki-Miyaura reaction is used. Examples of palladium catalysts that can be used include palladium(II) acetate, tetrakis( (triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium Examples of the ligand for the palladium catalyst include thiamin (II) dichloride. tri(ortho-tolyl)phosphine, triphenylphosphine, tricyclohexylphosphine, Examples of the base that can be used include sodium te Examples of suitable bases include organic bases such as rt-butoxide and inorganic bases such as potassium carbonate. Examples of solvents that can be used include a mixture of toluene and water, and an alcoholic solvent such as toluene and ethanol. Coal and water mixed solvent, xylene and water mixed solvent, xylene and alcohol such as ethanol and water mixed solvents, benzene and water mixed solvents, benzene and alcohol such as ethanol and water mixed solvents Examples of suitable solvents include mixed solvents of ethers such as ethylene glycol dimethyl ether and water. can be done.

[0158] However, the catalysts and their ligands, bases, and solvents that can be used are not limited to these. It is not something that can be done.

[0159] In the above scheme, other than arylboronic acids, organoaluminum compounds can also be used as substrates. Cross-coupling using organozirconium, organozinc, and organotin compounds is also possible. Good, but not limited to these.

[0160] [Synthesis of carbazole-containing tertiary arylamine (compound E)] The tertiary arylamine having a carbazole represented by the general formula (Compound E) can be synthesized by the following synthesis: It can be synthesized as shown in scheme (C-1). The secondary arylamine (compound D) and the aryl halide (compound C4) were reacted in the presence of a base. Metal-catalyzed coupling under conditions as described above gives the final product, carbazole. A tertiary arylamine having a hydroxyl group (compound E) can be obtained.

[0161] [ka]

[0162] [Synthesis of carbazole-containing tertiary arylamine (compound E) by other synthetic methods] The tertiary arylamine having a carbazole represented by the general formula (Compound E) can be synthesized by the following synthesis: It can be synthesized as shown in the scheme (Reaction Formula C-2). The 3-position of the 9H-carbazole is substituted with a boronic acid or organic boronic acid. The iodine-substituted compound (compound B) is coupled with the compound B using a metal catalyst in the presence of a base. By carrying out the reaction, the final product, a carbazole-containing tertiary arylamine (chemical Compound E) can be obtained.

[0163] [ka]

[0164] (Embodiment 2) In the second embodiment, the carbazole derivative of the present invention described in the first embodiment is used as a hole transport A light-emitting element formed using the layer will be described.

[0165] The light-emitting element according to the first embodiment has a first electrode functioning as an anode and a second electrode functioning as a cathode. a second electrode connected to the first electrode and an EL layer provided between the first electrode and the second electrode. In the light emitting element according to the second embodiment, the first electrode is thicker than the second electrode. When a voltage is applied to each of them so that the potential is also high, light emission is obtained. .

[0166] In addition, the EL layer of the light-emitting element in the second embodiment is formed by a first layer (hole injection layer), the second layer (hole transport layer), the third layer (light emitting layer), the fourth layer (electron transport layer), The structure includes the layer 5 (electron injection layer).

[0167] The structure of the light-emitting device in the first embodiment will be described with reference to FIG. The substrate 101 is used as a support for the element. For example, glass, quartz, plastic, etc. etc. can be used.

[0168] The substrate 101 is a light emitting device or an electronic device that uses the light emitting element of the present invention. It may remain in the child device, but it will not remain in the final product and will be used as a support in the manufacturing process of the light emitting element. It may have only physical functions.

[0169] The first electrode 102 formed on the substrate 101 is made of a material having a large work function (specifically, 4. 0 eV or more) metals, alloys, electrically conductive compounds, and mixtures thereof can be used. Specifically, for example, indium oxide-tin oxide (ITO) is preferable. in Oxide), indium oxide-tin oxide containing silicon or silicon oxide, oxide Indium zinc oxide (IZO), tungsten oxide Indium oxide containing zinc oxide and indium oxide are also included. (Pt), Nickel (Ni), Tungsten (W), Chromium (Cr), Molybdenum (Mo ), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium (Ti) or nitrides of metal materials (for example, titanium nitride), etc. In this case, the first layer 111 of the EL layer 103 formed in contact with the first electrode 102 is The first electrode 102 is made of a composite material that is easy to inject holes into regardless of the work function. Therefore, the electrode material can be made of a material such as a metal, an alloy, an electrically conductive compound, or and mixtures thereof, including other elements belonging to Groups 1 and 2 of the Periodic Table Any known material can be used.

[0170] These materials are usually deposited by sputtering. Zinc oxide (IZO) is a target material that contains 1 to 20 wt% zinc oxide added to indium oxide. Indium oxide containing tungsten oxide and zinc oxide is The target contains 0.5 to 5 wt% of tungsten oxide and 0.1 to 1 wt% of zinc oxide. By using a nozzle, it can be formed by sputtering. It may be prepared by a coating method, an ink jet method, a spin coating method, or the like.

[0171] In addition, in the EL layer 103 formed on the first electrode 102, the When a layer containing a composite material, which will be described later, is used as the material for the first layer 111 formed by In this case, the material used for the first electrode 102 may be any of various metals and alloys, regardless of the magnitude of the work function. Gold, electrically conductive compounds, and mixtures thereof can be used. Aluminum (Al), silver (Ag), and alloys containing aluminum (AlSi) can also be used. can.

[0172] In addition, materials with a small work function, such as elements belonging to Group 1 or 2 of the periodic table, That is, alkali metals such as lithium (Li) and cesium (Cs), and magnesium ( Alkaline earth metals such as Mg, calcium (Ca), and strontium (Sr), and Alloys containing these metals (MgAg, AlLi), europium (Eu), ytterbium (Yb ) and alloys containing these may also be used.

[0173] The first electrode is made of an alkali metal, an alkaline earth metal, or an alloy containing these metals. When forming the layer 102, a vacuum deposition method or a sputtering method can be used. In addition, when using silver paste, the coating method or inkjet method can be used. Cut.

[0174] The EL layer 103 formed on the first electrode 102 can be made of a known material. Both low molecular weight compounds and high molecular weight compounds can be used. The substances that form 3 include not only those that consist of organic compounds but also those that contain inorganic compounds. This also includes configurations that include:

[0175] The EL layer 103 is a hole injection layer containing a substance with high hole injection properties, a material with high hole transport properties, and a a hole transport layer comprising a material having high electron transport properties; a light emitting layer comprising a light emitting material; and an electron injection layer containing a material with high electron injection properties. It is formed by laminating.

[0176] The EL layer 103 shown in FIG. 1A is formed by a hole injection layer from the first electrode 102 side to the first layer (hole injection layer). layer) 111, a second layer (hole transport layer) 112, a third layer (light emitting layer) 113, a fourth layer (electrode A fifth layer (electron transport layer) 114 and a fifth layer (electron injection layer) 115 are laminated in this order.

[0177] The first layer 111, which is a hole-injecting layer, is a hole-injecting layer containing a substance with a high hole-injecting property. Materials with high hole injection properties include molybdenum oxide, titanium oxide, vanadium oxide, Rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide oxide, tantalum oxide, silver oxide, tungsten oxide, manganese oxide, etc. Other low molecular weight organic compounds include phthalocyanine (abbreviated as HPc), Copper (II) phthalocyanine (abbreviation: CuPc), vanadyl phthalocyanine (abbreviation: VOP c) Phthalocyanine compounds such as

[0178] In addition, the low molecular weight organic compound 4,4',4''-tris(N,N-diphenylamine) N-(3-)triphenylamine (abbreviation: TDATA), 4,4',4''-tris[N-(3- Methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), 4,4'-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl Nyl (abbreviation: DPAB), 4,4'-bis(N-{4-[N'-(3-methylphenyl) -N'-phenylamino]phenyl}-N-phenylamino)biphenyl (abbreviation: DNT PD), 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenyla 3-[N-(9-phenylcarbazole-3-ylamino]benzene (abbreviation: DPA3B), [N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1), 3 ,6-bis[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9 -phenylcarbazole (abbreviation: PCzPCA2), 3-[N-(1-naphthyl)-N- (9-phenylcarbazol-3-yl)amino]-9-phenylcarbazole (abbreviation: Also included are aromatic amine compounds such as PCzPCN1). The carbazole derivatives of the present invention can be used in the same manner.

[0179] Furthermore, polymeric compounds (oligomers, dendrimers, polymers, etc.) can also be used. For example, poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltriazole) phenylamine) (abbreviation: PVTPA), poly[N-(4-{N'-[4-(4-diphenyl N-(Nylamino)phenyl]phenyl-N'-phenylamino}phenyl)methacrylamide ] (abbreviation: PTPDMA) poly[N,N'-bis(4-butylphenyl)- ... Examples include polymer compounds such as [poly(phenyl)benzidine] (abbreviation: Poly-TPD). In addition, poly(3,4-ethylenedioxythiophene) / poly(styrenesulfonic acid) (PEDOT / PSS), polyaniline / poly(styrene sulfonate) (PAni / PS It is also possible to use a polymer compound to which an acid such as methyl methyl stearate is added.

[0180] In addition, the first layer 111 may be formed by adding an acceptor substance to a substance having a high hole transporting property. A composite material having a high hole transporting property and an acceptor substance can be used. By using a material containing such a material, the material for forming the electrode can be selected regardless of the work function of the electrode. That is, the first electrode 102 can be made of a material having not only a large work function but also a material having a low work function. These composite materials can be used as materials with high hole transport properties. It can be formed by co-evaporating the acceptor material with the ion beam. In this context, composite does not simply mean mixing two materials, but mixing multiple materials. This means that materials can transfer electric charges between them.

[0181] The organic compounds used in the composite materials include aromatic amine compounds, carbazole derivatives, aromatic Aromatic hydrocarbons, polymer compounds (oligomers, dendrimers, polymers, etc.), and various chemical compounds As the organic compound used for the composite material, a hole transporting compound having It is preferable that the organic compound has a high molecular weight. -6 cm 2 / Vs or more However, it is preferable that the material has a higher hole transporting property than an electron transporting property. Other organic materials that can be used in the composite material are listed below. The compounds are specifically listed below.

[0182] Examples of organic compounds that can be used in composite materials include MTDATA and TDAT. A, DPAB, DNTPD, DPA3B, PCzPCA1, PCzPCA2, PCzPC N1,4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation N,N'-bis(3-methylphenyl)-N,N'-diphenyl Aromatic alkyl amines such as phenyl-[1,1'-biphenyl]-4,4'-diamine (abbreviation: TPD) amine compounds, 4,4'-di(N-carbazolyl)biphenyl (abbreviation: CBP), 1,3 ,5-tris[4-(N-carbazolyl)phenyl]benzene (abbreviation: TCPB), 9- [4-(N-carbazolyl)]phenyl-10-phenylanthracene (abbreviation: CzPA ), 1,4-bis[4-(N-carbazolyl)phenyl]-2,3,5,6-tetraphenyl Examples of the carbazole derivatives include carbazole derivatives such as phenylbenzene. The carbazole derivative of the present invention can also be used in a composite material.

[0183] In addition, 2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t -BuDNA), 2-tert-butyl-9,10-di(1-naphthyl)anthracene, 9,10-bis(3,5-diphenylphenyl)anthracene (abbreviation: DPPA), 2- tert-Butyl-9,10-bis(4-phenylphenyl)anthracene (abbreviation: t- BuDBA), 9,10-di(2-naphthyl)anthracene (abbreviation: DNA), 9,10 -Diphenylanthracene (abbreviation: DPAnth), 2-tert-butylanthracene (abbreviation: t-BuAnth), 9,10-bis(4-methyl-1-naphthyl)anthracene DMNA, 9,10-bis[2-(1-naphthyl)phenyl]-2-tert-butyl ether t-Butyl-anthracene, 9,10-bis[2-(1-naphthyl)phenyl]anthracene 2,3,6,7-tetramethyl-9,10-di(1-naphthyl)anthracene, etc. Aromatic hydrocarbon compounds can be mentioned.

[0184] Furthermore, 2,3,6,7-tetramethyl-9,10-di(2-naphthyl)anthracene , 9,9'-bianthryl, 10,10'-diphenyl-9,9'-bianthryl, 10 ,10'-bis(2-phenylphenyl)-9,9'-bianthryl, 10,10'-bi bis[(2,3,4,5,6-pentaphenyl)phenyl]-9,9'-bianthryl, tetracene, rubrene, perylene, 2,5,8,11-tetra(tert- butyl)perylene, pentacene, coronene, 4,4'-bis(2,2-diphenylvinyl ) biphenyl (abbreviation: DPVBi), 9,10-bis[4-(2,2-diphenylvinyl )phenyl]anthracene (abbreviation: DPVPA) and other aromatic hydrocarbon compounds. can be done.

[0185] As an acceptor substance, 7,7,8,8-tetracyano-2,3,5,6 -Tetrafluoroquinodimethane (abbreviation: F4-TCNQ), chloranil and other organic compounds In addition, oxides of transition metals in Groups 4 to 8 of the periodic table can be used. Examples of oxides of metals belonging to the group include vanadium oxide, niobium oxide, Tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, lenium oxide Molybdenum oxide is particularly stable in the atmosphere. It is preferable because it has low hygroscopicity and is easy to handle.

[0186] In addition, the polymer compounds such as PVK, PVTPA, PTPDMA, and Poly-TPD mentioned above A composite material is formed using the above-mentioned acceptor material and used for the first layer 111. The carbazole derivative of the present invention shown in Embodiment 1 may also be used in the above-mentioned acceptor. The first layer 111 can be formed from a composite material by combining it with a conductive material.

[0187] The second layer 112, which is a hole transport layer, is a layer containing a substance with a high hole transport property. The second layer 112 in the second embodiment is made of the carbazole of the present invention described in the first embodiment. A fluorine derivative will be used.

[0188] In addition, the carbon nanotube of the present invention described in the first embodiment is used for both the first layer 111 and the second layer 112. A rubazole derivative can also be used. In this case, the device can be easily fabricated, and the material utilization is low. In addition, the energy density of the first layer 111 and the second layer 112 can be improved. Since the diagrams are the same or close to each other, the difference between the first layer 111 and the second layer 112 This allows for easy movement of the carrier.

[0189] The third layer 113 is a light-emitting layer containing a highly light-emitting substance. The following low molecular weight organic compounds can be used.

[0190] As a blue emitting material, N,N'-bis[4-(9H-carbazol-9-yl) Phenyl]-N,N'-diphenylstilbene-4,4'-diamine (abbreviation: YGA2S ), 4-(9H-carbazol-9-yl)-4'-(10-phenyl-9-anthryl ) triphenylamine (abbreviated as YGAPA), etc.

[0191] Green luminescent materials include N-(9,10-diphenyl-2-anthryl)-N,9 -diphenyl-9H-carbazol-3-amine (abbreviation: 2PCAPA), N-[9,1 0-Bis(1,1'-biphenyl-2-yl)-2-anthryl]-N,9-diphenyl -9H-carbazol-3-amine (abbreviation: 2PCABPhA), N-(9,10-difluoromethyl) (phenyl-2-anthryl)-N,N',N'-triphenyl-1,4-phenylenediamine N-[9,10-bis(1,1'-biphenyl-2-yl)] (abbreviation: 2DPAPA) -2-anthryl]-N,N',N'-triphenyl-1,4-phenylenediamine (abbreviation Name: 2DPABPhA), 9,10-bis(1,1'-biphenyl-2-yl)-N-[ 4-(9H-carbazol-9-yl)phenyl]-N-phenylanthracene-2-a amine (abbreviation: 2YGABPhA), N,N,9-triphenylanthracene-9-amine (abbreviation: DPhAPhA) and others.

[0192] Yellow luminescent materials include rubrene, 5,12-bis(1,1'-biphenyl-4- (yl)-6,11-diphenyltetracene (abbreviation: BPT), etc. As a red luminescent material, N,N,N',N'-tetrakis(4-methylphenyl)tetrakis Helical-5,11-diamine (abbreviation: p-mPhTD), 7,13-diphenyl-N,N ,N',N'-Tetrakis(4-methylphenyl)acenaphtho[1,2-a]fluoran Examples include phen-3,10-diamine (abbreviation: p-mPhAFD).

[0193] The third layer 113 has a structure in which the above-described highly light-emitting substance is dispersed in another substance. In addition, when dispersing, the concentration of the dispersed substance must be 20% by mass of the total. It is preferable that the following conditions are satisfied. Although it is possible to use conventional materials, the lowest unoccupied molecular orbital (LUMO) level is lower than that of luminescent materials. The highest occupied molecular orbital (HOMO) level is shallow (absolute value is small). It is preferable to use a material (i).

[0194] Specifically, tris(8-quinolinolato)aluminum(III) (abbreviation: Alq), Tris(4-methyl-8-quinolinolato)aluminum(III) (Almq3) , bis(10-hydroxybenzo[h]quinolinato)beryllium(II) (abbreviation: BeB q2), bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum zinc(III) (abbreviation: BAlq), bis(8-quinolinolato)zinc(II) (abbreviation: Zn q), bis[2-(2-benzoxazolyl)phenolato]zinc(II) (abbreviation: ZnP BO), bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnB Metal complexes such as TZ can be used.

[0195] Also, 2-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-1, 3,4-Oxadiazole (abbreviation: PBD), 1,3-bis[5-(p-tert-butyl) phenyl)-1,3,4-oxadiazol-2-yl]benzene (abbreviation: OXD-7 ), 3-(biphenyl-4-yl)-4-phenyl-5-(4-tert-butylphenyl) 2,2',2''-(1,3,5-triazole)-1,2,4-triazole (abbreviation: TAZ), Benzenetriyl)tris(1-phenyl-1H-benzimidazole) (abbreviation: TPB I), bathophenanthroline (abbreviated as BPhen), bathocuproine (abbreviated as BCP) Heterocyclic compounds such as the following can be used.

[0196] Others include 9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazo CzPA, 3,6-diphenyl-9-[4-(10-phenyl-9-anthracene] tolyl)phenyl]-9H-carbazole (abbreviation: DPCzPA), 9,10-bis(3 ,5-diphenylphenyl)anthracene (abbreviation: DPPA), 9,10-di(2-naphthyl)anthracene 2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: DNA), t-BuDNA), 9,9'-Bianthryl (BAN T), 9,9'-(stilbene-3,3'-diyl)diphenanthrene (abbreviation: DPNS ), 9,9'-(stilbene-4,4'-diyl)diphenanthrene (abbreviation: DPNS2 ), 3,3',3''-(benzene-1,3,5-triyl)tripylene (abbreviation: TPB Condensed aromatic compounds such as 3) can also be used.

[0197] In addition, a plurality of materials can be used to disperse the light-emitting material. In order to suppress crystallization, a substance that suppresses crystallization, such as rubrene, may be further added. In order to transfer energy to the luminescent material more efficiently, NPB or Alq In this way, a highly luminescent substance may be dispersed in another substance. This can suppress the crystallization of the third layer 113. Concentration quenching due to high concentration can be suppressed.

[0198] In addition, among the above-mentioned substances, a light-emitting substance is dispersed using a substance with electron transport properties. It is more preferable to form the third layer 113. Specifically, the above-mentioned metal complexes, heterocycles, etc. compounds, condensed aromatic compounds CzPA, DNA, t-BuDNA, and later The polymer compound shown in the table below can be used for the fourth layer 114. It is also possible.

[0199] The third layer 113 may also be made of the following polymer compounds.

[0200] Blue light-emitting materials include poly(9,9-dioctylfluorene-2,7-diyl) ) (abbreviation: PFO), poly[(9,9-dioctylfluorene-2,7-diyl)-co -(2,5-dimethoxybenzene-1,4-diyl)] (abbreviation: PF-DMOP), poly {(9,9-dioctylfluorene-2,7-diyl)-co-[N,N'-di-(p- butylphenyl-1,4-diaminobenzene]} (abbreviation: TAB-PFH) can be done.

[0201] Green light-emitting materials include poly(p-phenylene vinylene) (abbreviated as PPV), poly [(9,9-dihexylfluorene-2,7-diyl)-alt-co-(benzo[2, 1,3]thiadiazole-4,7-diyl)] (abbreviation: PFBT), poly[(9,9-di Octyl-2,7-divinylenefluorenylene)-alt-co-(2-methoxy-5- (2-ethylhexyloxy)-1,4-phenylene)].

[0202] Orange to red luminescent materials include poly[2-methoxy-5-(2'-ethylhexyl) (II)-1,4-phenylene vinylene] (abbreviation: MEH-PPV), poly(3-butylthio) phen-2,5-diyl) (abbreviation: R4-PAT), poly{[9,9-dihexyl-2, 7-bis(1-cyanovinylene)fluorenylene]-alt-co-[2,5-bis(N ,N'-diphenylamino)-1,4-phenylene]}, poly{[2-methoxy-5-( 2-ethylhexyloxy)-1,4-bis(1-cyanovinylenephenylene)]-alt -co-[2,5-bis(N,N'-diphenylamino)-1,4-phenylene]}(abbreviation Examples include CN-PPV-DPD.

[0203] The fourth layer 114 is an electron transport layer containing a substance with a high electron transport property. For example, low molecular weight organic compounds include Alq, Almq3, BeBq2, BAlq, Metal complexes such as Znq, ZnPBO, and ZnBTZ can be used. In addition to the benzodiazepines, heterocyclic compounds such as PBD, OXD-7, TAZ, TPBI, BPhen, and BCP are also The substances mentioned here are mainly 10 -6 cm 2 / Vs or more It should be noted that if a substance has a higher electron transporting property than a hole transporting property, The electron transport layer may be formed of a single layer or a multilayer structure. Alternatively, two or more layers made of the above materials may be laminated.

[0204] A polymer compound can also be used for the fourth layer 114. For example, poly[(9,9- dihexylfluorene-2,7-diyl)-co-(pyridine-3,5-diyl)](abbreviation Name: PF-Py), poly[(9,9-dioctylfluorene-2,7-diyl)-co- (2,2'-bipyridine-6,6'-diyl)] (abbreviation: PF-BPy) This can be done.

[0205] The fifth layer 115 is an electron injection layer containing a substance with high electron injection properties. 15 includes lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride ( Use alkali metals, alkaline earth metals, or their compounds such as CaF2 In addition, the substance having an electron transport property may be an alkali metal, an alkaline earth metal, or or compounds thereof, specifically magnesium (Mg) in Alq In this case, electron injection from the second electrode 104 may be performed. can be done more efficiently.

[0206] The second electrode 104 is made of a metal, alloy, or The cathode material may be an electrically conductive compound or a mixture thereof. A specific example of this is an element belonging to group 1 or 2 of the periodic table, namely lithium ( Alkali metals such as Li and cesium (Cs), as well as magnesium (Mg) and calcium Alkaline earth metals such as (Ca), strontium (Sr), and alloys containing these (M Rare earth metals such as Ag, Al, Li, europium (Eu), ytterbium (Yb) and and alloys containing these.

[0207] The second electrode 104 may be made of an alkali metal, an alkaline earth metal, or an alloy containing these metals. When forming the silver foil, a vacuum deposition method or a sputtering method can be used. When paste or the like is used, a coating method, an ink jet method, or the like can be used.

[0208] By providing the fifth layer 115, it is possible to use Al, Ag, Various conductive materials such as ITO, indium tin oxide containing silicon or silicon oxide The second electrode 104 can be formed using these conductive materials. The film can be formed by a coating method, an ink jet method, a spin coating method, or the like.

[0209] The first layer (hole injection layer) 111, the second layer (hole transport layer) 112, the third layer (light emitting layer) a fourth layer (electron transport layer) 114, and a fifth layer (electron injection layer) 115 are arranged in this order. The EL layer 103 formed by subsequent lamination can be produced by various methods, whether dry or wet. For example, a vacuum deposition method, an ink jet method, or a spin coating method can be used. It is also possible to use a different film formation method for each layer. .

[0210] The second electrode 104 can be formed by not only a dry method such as a sputtering method or a vacuum deposition method, but also a The metal layer can be formed by a wet method such as a sol-gel method using a paste of a metal material.

[0211] In the light-emitting device of the present invention described above, the voltage generated between the first electrode 102 and the second electrode 104 is The potential difference causes a current to flow, and the holes and electrons recombine in the EL layer 103, causing light to be emitted. This light emission is transmitted to either the first electrode 102 or the second electrode 104. Therefore, the electric current is taken out through the first electrode 102 or the second electrode 10 Either one or both of the electrodes 4 is a light-transmitting electrode.

[0212] In addition, when only the first electrode 102 is a light-transmitting electrode, In this way, light emitted from the EL layer 103 passes through the first electrode 102 and is extracted from the substrate 101 side. In addition, when only the second electrode 104 is a light-transmitting electrode, As shown in FIG. 1, light emitted from the EL layer 103 is emitted to the opposite side of the substrate 101 through the second electrode 104. Furthermore, both the first electrode 102 and the second electrode 104 are transparent. In the case of an electrode having the same structure, as shown in FIG. 2(C), light emitted from the EL layer 103 is through the first electrode 102 and the second electrode 104, are taken from both.

[0213] The structure of the layers provided between the first electrode 102 and the second electrode 104 is the same as that described above. The second layer 112 is a hole transport layer, and the light emitting layer is a light emitting layer. As long as it has a configuration including the third layer 113, other configurations than those described above may also be used.

[0214] As shown in FIG. 1B, a second electrode 104 functioning as a cathode is formed on the substrate 101. The first electrode 102 may be formed by laminating an EL layer 103 and a first electrode 102 that functions as an anode in this order. In this case, the EL layer 103 is formed by forming a fifth layer 115 on the second electrode 104 and a fourth layer 114, the third layer 113, the second layer 112, the first layer 111, and the first electrode 102 are stacked in this order. It has a layered structure.

[0215] By using the light-emitting element of the present invention, a passive matrix light-emitting device or a thin film transistor Active matrix light emitting device in which the driving of light emitting elements is controlled by thin film transistors (TFTs) Optical devices can be fabricated.

[0216] In the case of manufacturing an active matrix type light emitting device, the structure of the TFT is For example, a staggered or inverted staggered TFT may be used as appropriate. In addition, the driving circuit formed on the TFT substrate is also made up of N-type and P-type TFTs. Alternatively, the TFT may be composed of only one of N-type TFTs or P-type TFTs. Furthermore, there is no particular limitation on the crystallinity of the semiconductor film used in the TFT. An amorphous semiconductor film or a crystalline semiconductor film may be used.

[0217] In the light-emitting element shown in this embodiment mode 2, the second layer (hole transport layer) 112 is a carbon nanotube of the present invention. Since it is formed using a rubazole derivative, it not only improves the device efficiency but also reduces the driving voltage. The rise can be minimized.

[0218] In the second embodiment, the configurations shown in the first embodiment are used in appropriate combination. It is possible to do so.

[0219] (Embodiment 3) In this embodiment mode 3, a light emitting element having a plurality of EL layers of the light emitting element shown in embodiment mode 2 ( The stacked light emitting device (hereinafter referred to as a stacked light emitting device) will be described with reference to FIG. 3. This light emitting device comprises a first A plurality of EL layers (first EL layer 303, second EL layer 304, In the third embodiment, the EL layer is a stacked light emitting device having two EL layers. Although the case of one layer is shown, three or more layers may also be used.

[0220] In the third embodiment, the first electrode 301 is an electrode that functions as an anode, and the second electrode 302 is an electrode that functions as an anode. The electrode 302 functions as a cathode. The electrode 302 can have the same structure as that of the second embodiment. The first EL layer 303 and the second EL layer 304 are the same as the EL layer shown in the second embodiment. The first EL layer 303 and the second EL layer 304 may be made of the same material. The configuration may be the same as that of the second embodiment. It is possible.

[0221] In addition, a charge generation layer is formed between the plurality of EL layers (the first EL layer 303 and the second EL layer 304). The charge generating layer 305 is provided between the first electrode 301 and the second electrode 302. When a voltage is applied to the EL layer, electrons are injected into one EL layer and holes are injected into the other EL layer. In the third embodiment, the first electrode 301 has a function of forming a conductive film. When a voltage is applied so that the potential becomes high, electricity is transferred from the charge generating layer 305 to the first EL layer 303. Electrons are injected into the second EL layer 304 and holes are injected into the second EL layer 304.

[0222] It is preferable that the charge generating layer 305 be light-transmitting from the viewpoint of light extraction efficiency. In addition, the charge generating layer 305 has a lower conductivity than the first electrode 301 and the second electrode 302. It still works.

[0223] The charge generation layer 305 is formed by adding an acceptor to a material with high hole transporting properties. sexIn a composition where substances are added Alternatively, a structure in which a donor substance is added to a substance with a high electron-transporting property may be used. Alternatively, both of these structures may be stacked.

[0224] Acceptor in a material with high hole transport properties sex In the case where a substance is added, As a material with high hole transport properties, for example, 4,4'-bis[N-(1-naphthyl)-N-phenyl] N,N'-bis(3-phenylamino)biphenyl (abbreviation: NPB or α-NPD) (1,1'-diphenyl)-N,N'-diphenyl-[1,1'-biphenyl]-4,4'-diamino (abbreviation: TPD), 4,4',4''-tris(N,N-diphenylamino)triphenylphosphine Nylamine (abbreviation: TDATA), 4,4',4''-tris[N-(3-methylphenyl) (methyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), 4,4'-biphenyl Su[N-(spiro-9,9'-bifluoren-2-yl)-N-phenylamino]-1, Aromatic amine compounds such as 1'-biphenyl (abbreviation: BSPB) can be used. The substances mentioned here are mainly 10 -6 cm 2 / Vs or more. However, other substances may be used as long as they have a higher hole transporting property than electron transporting property. stomach.

[0225] As an acceptor substance, 7,7,8,8-tetracyano-2,3,5,6 -tetrafluoroquinodimethane (abbreviation: F4-TCNQ), chloranil, etc. Also, transition metal oxides can be used. Examples of oxides of metals belonging to Groups 1 to 8 include vanadium oxide, vanadium oxide, Niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide Molybdenum oxide and rhenium oxide are preferred because they have high electron-accepting properties. Among these, it is preferred because it is stable, has low hygroscopicity, and is easy to handle.

[0226] On the other hand, in the case of a structure in which a donor substance is added to a substance with high electron transport properties, As a substance with high electron transport properties, for example, tris(8-quinolinolato)aluminum (II I) (abbreviation: Alq), tris(4-methyl-8-quinolinolato)aluminum (III ) (abbreviation: Almq3), bis(10-hydroxybenzo[h]quinolinato)beryllium (II) (abbreviation: BeBq2), bis(2-methyl-8-quinolinolato)(4-phenyl phenolato)aluminum(III) (abbreviation: BAlq), etc. Metal complexes having a bis[2-(2 '-hydroxyphenyl)benzoxazolato]zinc(II) (abbreviation: Zn(BOX)2 ), bis[2-(2'-hydroxyphenyl)benzothiazolato]zinc(II) (abbreviation: Metal complexes with oxazole and thiazole ligands, such as Zn(BTZ)2, are also available. In addition to metal complexes, 2-(biphenyl-4-yl)-5- (4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD) , 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazo [2-yl]benzene (abbreviation: OXD-7), 3-(biphenyl-4-yl)-4-furan Phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (abbreviation: T AZ), bathophenanthroline (abbreviated as BPhen), bathocuproine (abbreviated as BCP) ) can also be used. The substances mentioned here are mainly 10 -6 cm 2 / Vs or more It should be noted that if a substance has a higher electron transporting property than a hole transporting property, Other materials may also be used.

[0227] The donor substance may be an alkali metal, an alkaline earth metal, or a rare earth metal. Or, metals belonging to Group 13 of the periodic table and their oxides and carbonates Specifically, lithium (Li), cesium (Cs), magnesium (Mg), Calcium (Ca), ytterbium (Yb), indium (In), lithium oxide, carbon It is preferable to use cesium phosphate or the like. The substance may be used as a donor substance.

[0228] By forming the charge generating layer 305 using the above-mentioned materials, an EL layer is laminated. When the voltage is increased, the increase in the driving voltage can be suppressed.

[0229] In the third embodiment, the light emitting device having two EL layers has been described. The present invention can be similarly applied to a light-emitting device in which two or more EL layers are stacked. As in the light-emitting device according to the third embodiment, a plurality of EL layers are separated by charge generating layers between a pair of electrodes. By arranging the elements in this way, it is possible to realize a long-life element in the high-brightness region while keeping the current density low. In addition, when applied to lighting, the voltage drop due to the resistance of the electrode material can be reduced. This allows for uniform light emission over a large area. This can be achieved.

[0230] In addition, by making the luminescent color of each EL layer different, the desired luminescence color can be obtained as a whole. For example, in a light-emitting element having two EL layers, the first By making the luminous color of the first EL layer and the luminous color of the second EL layer complementary to each other, It is also possible to obtain a light-emitting element that emits white light as a whole. In other words, the color that becomes achromatic when it is made of a substance that emits complementary colors. The resulting light can be mixed to produce white light.

[0231] The same applies to a light-emitting element having three EL layers. For example, The luminescent color of the first EL layer is red, the luminescent color of the second EL layer is green, and the luminescent color of the third EL layer is blue. In this case, the light emitting element as a whole can emit white light.

[0232] In the third embodiment, the configurations shown in the first and second embodiments are appropriately combined. They may be used in combination.

[0233] (Fourth embodiment) In this embodiment mode 4, a light emitting device having a light emitting element of the present invention in a pixel portion will be described with reference to FIG. 4A is a top view of the light-emitting device, and FIG. 4B is a cross-sectional view of FIG. 4A. Cross-sectional views taken along lines -A' and BB'.

[0234] In FIG. 4A, 401 indicated by a dotted line is a driving circuit section (source side driving circuit), 40 2 is a pixel section, 403 is a driving circuit section (gate side driving circuit), and 404 is a sealing substrate. , 405 is a sealing material, and the inside surrounded by the sealing material 405 is a space 407. .

[0235] The lead wiring 408 is connected to the source side driver circuit 401 and the gate side driver circuit 403. The wiring is for transmitting the input signal, and the FPC (flexible printed circuit board) is the external input terminal. Video signal, clock signal, start signal, reset signal from Lint Circuit 409 Although only the FPC is shown here, this FPC has a printed circuit board. A printed wiring board (PWB) may be attached. This includes not only the light-emitting device itself, but also the state in which an FPC or PWB is attached to it. It shall be.

[0236] Next, the cross-sectional structure will be described with reference to FIG. A source side driver circuit 401, which is a driver circuit section, is formed in this example. 4 shows one pixel in the pixel section 402. The source side driver circuit 401 is an N-channel A CMOS circuit is formed by combining a P-channel TFT423 and a P-channel TFT424. The driving circuit can be a variety of CMOS circuits, PMOS circuits, or NMOS circuits. In this embodiment, a driver integrated type in which a driver circuit is formed on a substrate is shown. However, this is not necessarily required, and the drive circuit can be formed externally rather than on the substrate.

[0237] The pixel section 402 includes a switching TFT 411, a current control TFT 412, and The pixel is formed by a plurality of pixels including a first electrode 413 electrically connected to the drain. An insulator 414 is formed to cover the edge of the first electrode 413 .

[0238] In order to improve the covering property, the upper end or the lower end of the insulator 414 is provided with a curvature. For example, the material of the insulator 414 is a positive electrode. By using a photosensitive acrylic mold, the radius of curvature (0.2 μm) was set only at the top end of the insulator 414. In addition, the insulating material 414 can be used to provide a curved surface having a thickness of about 3 μm. Negative type that becomes insoluble in etchant by irradiation with light, or Any positive photosensitive material that is soluble can be used.

[0239] An EL layer 416 and a second electrode 417 are formed on the first electrode 413. Here, the material used for the first electrode 413 may be various metals, alloys, electrically conductive materials, The following compounds and mixtures thereof can be used: The materials shown in the second embodiment as usable for the first electrode can be used. It shall be possible.

[0240] The EL layer 416 can be formed by a deposition method using a deposition mask, an inkjet method, or a spin coating method. The EL layer 416 has the structure shown in Embodiment 2. Other materials constituting the EL layer 416 include low molecular weight compounds or high molecular weight compounds. The material used for the EL layer may be a polymer compound (including an oligomer and a dendrimer). As the material, not only organic compounds but also inorganic compounds may be used.

[0241] The second electrode 417 may be made of various metals, alloys, or electrically conductive materials. The second electrode 417 is used as a cathode. In this case, metals, alloys, and electrodes with small work functions (work functions of 3.8 eV or less) are used. It is preferable to use a conductive compound and a mixture thereof. Elements belonging to Group 1 or 2 of the table, such as lithium (Li) and cesium (Cs) Alkali metals, as well as magnesium (Mg), calcium (Ca), strontium ( Examples include alkaline earth metals such as Sr, and alloys containing these metals (MgAg, AlLi). can be done.

[0242] In addition, in the case where the light generated in the EL layer 416 is transmitted through the second electrode 417, The electrode 417 of the second electrode is a thin metal film and a transparent conductive film (indium oxide-oxide). Tin oxide (ITO), indium oxide containing silicon or silicon oxide, indium tin oxide, Indium-zinc oxide (IZO), indium oxide containing tungsten oxide and zinc oxide It is also possible to use a laminate with a material such as a polyimide.

[0243] Furthermore, by bonding the sealing substrate 404 to the element substrate 410 with the sealing material 405, The light is emitted into a space 407 surrounded by the element substrate 410, the sealing substrate 404, and the sealant 405. The structure is provided with an element 418. The space 407 is filled with a filler. In addition to being filled with an inert gas (nitrogen, argon, etc.), it is also possible to fill it with a sealing material 405. In some cases, this may be the case.

[0244] It is preferable to use an epoxy resin for the sealing material 405. It is desirable that the sealing substrate 404 be made of a material that is as impermeable to moisture and oxygen as possible. Materials used for this include glass substrates, quartz substrates, and FRP (Fiberglass-Reinforced Plastics). Enforced Plastics), PVF (Polyvinyl Fluoride), Polyester Alternatively, a plastic substrate made of acrylic or the like can be used.

[0245] In this manner, an active matrix light emitting device having the light emitting element of the present invention is obtained. It is possible.

[0246] The light-emitting element of the present invention can be used not only in the above-mentioned active matrix light-emitting device but also in a panel light-emitting device. The light-emitting element of the present invention can also be used in a passive matrix light-emitting device. 5A and 5B show a perspective view and a cross-sectional view of a passive matrix light-emitting device. 5(B) is a cross-sectional view of FIG. 5(A) taken along the XY line.

[0247] In FIG. 5, an EL layer is disposed between a first electrode 502 and a second electrode 503 on a substrate 501. The end of the first electrode 502 is covered with an insulating layer 505. A partition layer 506 is provided on the insulating layer 505. The sidewalls of the partition layer 506 are in contact with the substrate surface. As the distance between the side walls approaches , the distance between the side walls becomes narrower. That is, the cross section of the partition layer 506 in the short side direction is trapezoidal, and the bottom side (the surface direction of the insulating layer 505) The side that faces the same direction as the insulating layer 505) faces the upper side (the side that faces the same direction as the insulating layer 505). The side of the partition wall layer 506 is oriented in the same direction as the insulating layer 505 and is shorter than the side of the partition wall layer 506 that is not in contact with the insulating layer 505. By providing the protective film, defects in the light-emitting element due to static electricity or the like can be prevented.

[0248] As a result, a passive matrix light emitting device having the light emitting element of the present invention can be obtained. can.

[0249] Note that the light-emitting device (active matrix type, passive matrix type) shown in this embodiment mode Since both of the above types are formed using the light-emitting element of the present invention with high luminous efficiency, the power consumption is low. A light emitting device with reduced forces can be obtained.

[0250] In the fourth embodiment, the configurations shown in the first to third embodiments are appropriately combined. It may be used.

[0251] (Embodiment 5) In the fifth embodiment, an electronic device includes the light emitting device of the present invention shown in the fourth embodiment. The electronic devices include cameras such as video cameras and digital cameras, Gloupe type displays, navigation systems, sound reproduction devices (car audio, audio audio components, computers, game devices, personal digital assistants (mobile computers, mobile mobile phones, portable game consoles, electronic books, etc.), image playback devices equipped with recording media (specifically plays recording media such as Digital Versatile Disc (DVD), (Devices equipped with a display device capable of displaying the image) An example is shown in Figure 6.

[0252] FIG. 6A shows a television device according to the present invention, which includes a housing 611, a support base 612, a display unit 61, and a display section 61. 3, a speaker unit 614, a video input terminal 615, etc. The light emitting device of the present invention can be applied to the display unit 613. Since the light emitting device of the present invention has the characteristic of being able to obtain high luminous efficiency, Thus, a television set with reduced power consumption can be obtained.

[0253] FIG. 6B shows a computer according to the present invention, which includes a main body 621, a housing 622, a display unit 62 3. Includes a keyboard 624, an external connection port 625, a pointing device 626, etc. In this computer, the light emitting device of the present invention can be applied to the display unit 623. The light emitting device of the present invention has the feature of being able to obtain high light emitting efficiency. By applying the light emitting device of the present invention, a computer with reduced power consumption can be obtained. do.

[0254] FIG. 6C shows a mobile phone according to the present invention, which includes a main body 631, a housing 632, a display unit 633, An audio input unit 634, an audio output unit 635, an operation key 636, an external connection port 637, an antenna In this mobile phone, the light emitting device of the present invention is applied to the display unit 633. The light emitting device of the present invention is characterized in that it can obtain high light emitting efficiency. Therefore, by applying the light emitting device of the present invention, a mobile phone with reduced power consumption can be obtained. This can be done.

[0255] FIG. 6D shows a camera according to the present invention, which includes a main body 641, a display unit 642, a housing 643, an external connection port 644, remote control receiver 645, image receiver 646, battery 647, audio input The camera includes a display unit 648, operation keys 649, and an eyepiece unit 650. The light emitting device of the present invention can be applied to the above-mentioned luminous efficiency. Therefore, by applying the light emitting device of the present invention, A camera with reduced forces can be obtained.

[0256] As described above, the light emitting device of the present invention has a very wide range of applications, and can be used in a variety of fields. By using the light emitting device of the present invention, it is possible to reduce power consumption. Reduced force electronics can be obtained.

[0257] The light emitting device of the present invention can also be used as a lighting device. This is an example of a liquid crystal display device using a light source as a backlight. The device has a housing 701, a liquid crystal layer 702, a backlight 703, and a housing 704. 2 is connected to a driver IC 705. The backlight 703 is a light emitting device according to the present invention. An optical device is used and electrical current is supplied by terminal 706 .

[0258] In this way, by using the light emitting device of the present invention as a backlight for a liquid crystal display device, A backlight with low power consumption can be obtained. In addition, the light emitting device of the present invention is a surface-emitting lighting device. Since the area can be increased, the backlight area can also be increased. It is possible to obtain a liquid crystal display device with a large area.

[0259] FIG. 8 shows an example in which a light emitting device to which the present invention is applied is used as a desk lamp, which is a lighting device. The desk lamp shown in FIG. 8 has a housing 801 and a light source 802. The light emitting device of the present invention is used in the above-described light emitting device. Therefore, it can be used as a low-power desk lamp.

[0260] FIG. 9 shows an example in which a light emitting device to which the present invention is applied is used as an indoor lighting device 901. The light emitting device of the present invention can be made large in area, and therefore can be used as a large-area lighting device. In addition, the light emitting device of the present invention has a light emitting element with high light emitting efficiency, and therefore consumes low power. In this way, the light emitting device to which the present invention is applied can be used as a lighting device with a high power. In the room used as the indoor lighting device 901, the lighting device according to the present invention as described with reference to FIG. 6(A) was installed. A television set 902 can be installed to watch public broadcasts and movies.

[0261] In addition, in the fifth embodiment, the same as in the first to fifth embodiments 4 By appropriately combining the configurations shown in It may be used. [Example]

[0262] In this Example 1, a carbazole derivative of the present invention, 4-phenanthroline, represented by structural formula (5), was used. Nyl-4'-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation The synthesis method of PCBA1BP will be specifically explained.

[0263] [ka]

[0264] [Step 1: Synthesis of 4-bromodiphenylamine]

[0265] The synthesis scheme of 4-bromodiphenylamine in Step 1 is shown below (D-1). vinegar.

[0266] [ka]

[0267] 51g (0.3mol) of diphenylamine was dissolved in 700ml of ethyl acetate in a 1L Erlenmeyer flask. After dissolving in 0.3 mL, add 54 g (0.3 mL) of N-bromosuccinimide (abbreviation: NBS) to the solution. After about 300 hours, the mixture was washed with water, and then magnesium sulfate was added. The mixture was filtered and the filtrate was concentrated and recovered. The yield was 70 g and the yield was 94%. [Step 2-1: Synthesis of 3-bromo-9-phenyl-9H-carbazole]

[0268] Step 2-1 Synthesis of 3-bromo-9-phenyl-9H-carbazole The system is shown below (D-2-1).

[0269] [ka]

[0270] In a 1000 mL Erlenmeyer flask, add 24 g (10 0 mmol), 18 g (100 mmol) of N-bromosuccinimide, 450 g of toluene 200 mL of ethyl acetate was added and stirred at room temperature for 45 hours. After washing, magnesium sulfate was added to remove water. The filtrate was concentrated and dried to obtain the caramel-like target product, 3-bromo-9-phenyl-9 The amount of H-carbazole obtained was 32 g, and the yield was 99%. [Step 2-2: Synthesis of 9-phenyl-9H-carbazole-3-boronic acid]

[0271] Step 2-2: Synthesis of 9-phenyl-9H-carbazole-3-boronic acid The team is shown below (D-2-2).

[0272] [ka]

[0273] In a 500 mL three-neck flask, 2 9g (90mmol) of tetrahydrofuran (abbreviation: THF) in 200mL, After stirring to form a solution, n-butyllithium (1.57 mol / L hexane solution) was added. 110 mL (69 mmol) of boric acid was added dropwise and stirred at the same temperature for 2 hours. 13 mL (140 mmol) of trimethylsilane was added, and the mixture was stirred at room temperature for 24 hours.

[0274] After the reaction was completed, 200 mL of 1.0 mol / L hydrochloric acid was added thereto, and the mixture was stirred at room temperature for 1 hour. This was washed with water, sodium hydroxide solution, and water in that order, and magnesium sulfate was added to remove moisture. The suspension was filtered, and the resulting filtrate was concentrated and diluted with chloroform and hexane. After applying ultrasonic waves, recrystallization was carried out. The amount of carbazole-3-boronic acid obtained was 21 g, and the yield was 80%.

[0275] Step 3: 4-(9-phenyl-9H-carbazol-3-yl)diphenylamine Synthesis of PCBA

[0276] 4-(9-phenyl-9H-carbazol-3-yl)diphenyl in Step 3 The synthesis scheme of the amine (abbreviation: PCBA) is shown in (D-3) below.

[0277] [ka]

[0278] 4-Bromodiphenylamine 6.5g (26mmol), 9-phenyl-9H-carba 7.5g (26mmol) of zole-3-boronic acid, tri(o-tolyl)phosphine 400 mg (1.3 mmol) was placed in a 500 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. To this mixture, 100 mL of toluene, 50 mL of ethanol, and an aqueous solution of potassium carbonate (0.2 m The mixture was degassed under reduced pressure with stirring. 67 mg (30 mmol) of palladium(II) acid was added.

[0279] The mixture was refluxed at 100°C for 10 hours. After refluxing, the aqueous layer of the mixture was extracted with toluene. The extract and the organic layer were combined and washed with saturated saline. After removing the water, the mixture was gravity filtered and the filtrate was concentrated to give a pale brown solid. This oil was purified by silica gel column chromatography (eluent: hexane). The white solid obtained after purification was dissolved in dichloromethane / hexane (hexane:toluene = 4:6). The target product was obtained as a white solid by recrystallization from hexane. The yield was 4.9 g and the product yield was 45%. %. [Step 4: 4-phenyl-4'-(9-phenyl-9H-carbazol-3-yl) ) Synthesis of triphenylamine (abbreviation: PCBA1BP)

[0280] Step 4: 4-phenyl-4'-(9-phenyl-9H-carbazole-3- The synthesis scheme of PCBA1BP is shown in (D-4) below. show.

[0281] [ka]

[0282] 4-(9-phenyl-9H-carbazol-3-yl)diphenylamine 2.0g (4 0.9mmol), 4-bromobiphenyl 1.1g (4.9mmol), sodium te Place 2.0 g (20 mmol) of rt-butoxide into a 100 mL three-neck flask. The atmosphere was replaced with nitrogen. To this mixture, 50 mL of toluene and tri(tert-butyl)phosphine were added. 0.30 mL of vin (10 wt % hexane solution) was added.

[0283] This mixture was degassed under reduced pressure while stirring, and after degassing, bis(dibenzylideneacetone) 0.10 g of palladium(0) was added. Then, the mixture was heated and stirred at 80° C. for 5 hours. After the reaction, toluene was added to the reaction mixture, and the resulting suspension was passed through a pad of celite and aluminum. The filtrate was filtered through Florisil and saturated sodium carbonate solution was added. The organic layer was washed with the solution and saturated saline in that order. Magnesium sulfate was added to the organic layer to dry it. After drying, The mixture was suction filtered to remove magnesium sulfate and obtain a filtrate.

[0284] The obtained filtrate was concentrated and purified by silica gel column chromatography. Silica gel column chromatography is first developed using a mixed solvent of toluene:hexane = 1:9. A mixture of toluene and hexane (3:7) is used as the developing solvent. The obtained fraction was concentrated, and the solid was extracted with chloroform and hexane. The yield of the white powdery solid was 2.3 g, and the yield was 84%. there were.

[0285] The resulting white solid (1.2 g) was purified by train sublimation. The purification was carried out at 280°C for 20 hours under a reduced pressure of 7.0 Pa with an argon flow rate of 3 mL / min. The yield was 1.1 g, or 89%.

[0286] The compound obtained in step 4 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The H NMR charts are shown in Figures 10(a) and 10(b). From the results, it is clear that the carbazole derivative of the present invention, 4-phenyl, represented by the above structural formula (5), 4'-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation :PCBA1BP) was obtained.

[0287] 1 H NMR (DMSO- d 6,300MHz):δ(ppm)=7.05-7.20 (m,7H),7.28-7.78(m,21H),8.34(d,J=7.8Hz,1 H),8.57(s,1H).

[0288] The absorption spectrum of PCBA1BP (abbreviation) in toluene is shown in Figure 11(a). The absorption spectrum of the thin film of PCBA1BP (abbreviation) is shown in Figure 11(b). The spectrum of the solution was measured using an ultraviolet-visible spectrophotometer (V550 model, manufactured by JASCO Corporation). was measured in a quartz cell. The thin film sample was prepared by depositing PCBA1BP (abbreviation) on a quartz substrate. The absorption spectrum of quartz was subtracted from the measured spectrum of the sample. The obtained absorption spectra are shown in Figures 11(a) and 11(b).

[0289] In Figure 11(a) and Figure 11(b), the horizontal axis is wavelength (nm) and the vertical axis is absorption intensity (arbitrary In the case of a toluene solution, an absorption peak is observed around 335 nm, and in the case of a thin film, In the case of PCBA1BP (abbreviation), an absorption peak was observed around 341 nm. The emission spectrum of the PCBA solution (excitation wavelength 346 nm) is shown in Figure 11(a). The emission spectrum of a thin film of 1BP (abbreviation) (excitation wavelength 386 nm) is shown in Figure 11(b). In Figures 11(a) and 11(b), the horizontal axis represents wavelength (nm) and the vertical axis represents emission intensity (arbitrary unit). The maximum emission wavelength is 391 nm (excitation wavelength 346 nm) in the case of a toluene solution. In the case of thin films, it was 416 nm (excitation wavelength 386 nm).

[0290] In addition, the redox reaction characteristics of PCBA1BP (abbreviation) were analyzed by cyclic voltammetry (C The measurements were carried out using an electrochemical analyzer (manufactured by BAS Co., Ltd.). ALS model 600A or 600C was used.

[0291] The solution used in the CV measurement was dehydrated dimethylformamide (DMF) (Asahi Chemical Industries, Ltd.). The supporting electrolyte was 0.1% sucrose (manufactured by Rudrich, 99.8%, catalog number: 22705-6). Tetra-n-butylammonium perchlorate (n-Bu4NClO4) (Tokyo Chemical Industry Co., Ltd.) (Cat. No. T0836) was dissolved to a concentration of 100 mmol / L, and The measurement target was dissolved in the solution to a concentration of 2 mmol / L. The electrode was a platinum electrode (PTE platinum electrode, manufactured by BAS Co., Ltd.), and the auxiliary electrode was a platinum electrode. A gold electrode (Pt counter electrode (5 cm) for VC-3, manufactured by BAS Co., Ltd.) was used as a reference. The reference electrode is Ag / Ag + Electrode (manufactured by BAS Co., Ltd., RE7 non-aqueous solvent reference electrode) The measurements were carried out at room temperature (20-25°C). The scan rate was standardized to 0.1 V / sec.

[0292] (Calculation of potential energy relative to the vacuum level of the reference electrode) First, the reference electrode (Ag / Ag + potential of the electrode relative to the vacuum level The electron energy (eV) was calculated. + The Fermi level of the electrode was calculated. The redox potential of ferrocene in methanol is +0.61 vs. the standard hydrogen electrode. 0 [V vs. SHE] (references; Christian R.Goldsmith et al., J.Am.Chem.Soc., Vol. 124, No.1, 83-96, 2002). On the other hand, the reference electrode used in this example The oxidation-reduction potential of ferrocene in methanol was found to be +0.11 V[ vs. Ag / Ag + Therefore, the potential of the reference electrode used in this Example 4 The energy of the electrode was found to be 0.50 eV lower than that of the standard hydrogen electrode. .

[0293] Here, the potential energy of the standard hydrogen electrode from the vacuum level is -4.44 eV. It is known that (Reference: Toshihiro Onishi and Tamami Koyama, Polymer EL Materials (Kyoritsu Shuppan) , pp.64-67). From the above, the potential of the reference electrode used in this example relative to the vacuum level The potential energy can be calculated as -4.44-0.50=-4.94[eV]. Ta.

[0294] The CV measurement results of the oxidation reaction characteristics are shown in Figure 41. The oxidation reaction characteristics were measured using a reference electrode. The potential of the working electrode relative to the It was scanned down to .07V.

[0295] First, we will explain in detail the calculation of the HOMO level from the CV measurement of PCBA1BP (abbreviation). As shown in Figure 41, the oxidation peak potential E pa The voltage was 0.536V. Arc potential E pc The half-wave potential (E pa and E pc Between This means that PCBA1BP (abbreviation) is 0.49[ V vs. Ag / Ag + ] is oxidized by the electrical energy of As described above, the reference voltage used in Example 1 is The potential energy of the pole relative to the vacuum level is -4.94 eV, so PC The HOMO level of BA1BP (abbreviation) is -4.94-0.49=-5.43[eV]. It was also found that the oxidation peak remained at the same value even after 100 cycles. This indicates that the compound exhibits good properties in repeating oxidation-reduction cycles between the oxidized and neutral states. . [Example]

[0296] In this Example 2, the carbazole derivative of the present invention, 4,4', represented by structural formula (6), -diphenyl-4''-(9-phenyl-9-H-carbazol-3-yl)triphenyl A method for synthesizing PCBBi1BP will be specifically described.

[0297] [ka]

[0298] [Step 1-1: Synthesis of 4-phenyl-diphenylamine]

[0299] The synthesis scheme of 4-phenyl-diphenylamine in Step 1-1 is shown below (E- 1-1).

[0300] [ka]

[0301] In a three-neck flask, 20.0 g (85.8 mmol) of 4-bromobiphenyl and aniline 16.0 g (172 mmol) of methylparaben, 0.19 g (0.86 mmol) of palladium(II) acetate l), 23.7 g (172 mmol) of potassium carbonate suspended in 150 mL of dehydrated xylene Tri-tert-butylphosphine (10 wt% hexane solution) 5.2 g (2.5 mm The mixture was refluxed at 120°C for 10 hours under a nitrogen atmosphere. The reaction mixture was washed with water, separated into an organic layer and an aqueous layer, and the aqueous layer was extracted with toluene.

[0302] The obtained toluene layer and the organic layer were combined, washed with saturated saline, and then extracted with magnesium sulfate. The water in the organic layer was removed by adding ammonium hydroxide. The filtrate was concentrated, and the resulting residue was purified by silica gel column chromatography (developing solvent: The resulting solution was concentrated to give 4-phenyl-diphenyl The amount of the amine obtained as a white solid was 13.5 g, and the yield was 64%. [Step 1-2: Synthesis of 4,4'-diphenyltriphenylamine]

[0303] The synthesis scheme of 4,4'-diphenyltriphenylamine in steps 1-2 is shown below. The details are shown in (E-1-2).

[0304] [ka]

[0305] 3.7g (15mmol) of 4-phenyl-diphenylamine, 4-bromobiphenyl 3.5g (15mmol) of sodium tert-butoxide and 2.5g (25mmol) of sodium tert-butoxide. ol), bis(dibenzylideneacetone)palladium(0) 10 mg (0.02 mmo l) was placed in a 100 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. 40 mL of xylene was added. The mixture was degassed under reduced pressure while stirring. Tri(tert-butyl)phosphine (10 wt% hexane solution) 0.2 mL (60 mm l) was added.

[0306] Next, this mixture was heated and stirred at 120°C for 5 hours to react. Toluene was added, and the suspension was suction filtered through Celite, alumina, and Florisil. The filtrate was washed with saturated aqueous sodium carbonate solution and saturated saline solution in this order. Magnesium sulfate was added to the organic layer to remove moisture. The mixture was filtered through Lumina and Florisil under suction, and the filtrate was concentrated. After adding toluene and methanol and applying ultrasonic waves, the product was recrystallized to give a white powdery solid. Obtained 5.4 g, 92% yield. [Step 1': Synthesis of 4,4'-diphenyltriphenylamine]

[0307] In addition to the synthesis method according to Step 1-1 and Step 1-2 described above, 4,4'-Diphenyltriphenylamine can also be synthesized using synthetic methods. The synthesis scheme of 4,4'-diphenyltriphenylamine in step 1' is shown below. Shown in (E-1').

[0308] [ka]

[0309] 1.9 g (20 mmol) of aniline and 9.3 g (40 mmol) of 4-bromobiphenyl l), sodium tert-butoxide 4.5g (45mmol), palladium acetate 0.4 g (2.0 mmol), 1,1-bis(diphenylphosphino)ferrocene (abbreviated 1.1 g (2.0 mmol) of DPPF (designated DPPF) was placed in a 200 mL three-neck flask. The atmosphere was replaced with nitrogen. 70 mL of dehydrated xylene was added to this mixture. The mixture was degassed under pressure while stirring, and then heated and stirred at 110°C for 3 hours to allow the reaction to proceed. Toluene was added to the mixture, and the suspension was suction filtered through Celite, alumina, and Florisil. The filtrate was washed with saturated aqueous sodium carbonate and saturated saline in this order. Magnesium sulfate was added to the obtained organic layer to remove moisture. The mixture was filtered through alumina and Florisil under suction, and the filtrate was concentrated. After adding acetone and hexane and applying ultrasonic waves, the mixture was recrystallized, yielding a white powdery solid. The amount was 5.4 g, with a yield of 67%. Step 2: Synthesis of 4-bromo-4',4''-diphenyltriphenylamine

[0310] The above-mentioned steps (1-1) and (1-2), or the case shown in step 1' 4,4'-Diphenyltriphenylamine was synthesized using the synthetic method. ',4''-Diphenyltriphenylamine is synthesized. The synthesis scheme of bromo-4',4''-diphenyltriphenylamine is shown below (E-2). Shown below.

[0311] [ka]

[0312] 4.0 g (10 mmol) of 4,4'-diphenyltriphenylamine was placed in an Erlenmeyer flask. After dissolving in a mixed solvent of 50 mL of toluene and 50 mL of ethyl acetate, Succinimide (abbreviation: NBS) was added and the mixture was stirred at room temperature for 120 hours. The mixture was washed with water, and magnesium sulfate was added to remove water. The mixture was filtered. The obtained filtrate was concentrated and recrystallized. The yield of the target white powder was 4.5 g, and the yield was 95%. Step 3: 4,4'-diphenyl-4''-(9-phenyl-9-H-carbazol-2-yl) Synthesis of PCBBi1BP

[0313] Step 3: 4,4'-diphenyl-4''-(9-phenyl-9-H-carba The synthesis scheme of PCBBi1BP is shown below. This is shown in (E-3).

[0314] [ka]

[0315] 4-Bromo-4',4''-diphenyltriphenylamine 1.5g (3.1mmol ), 9-phenyl-9H-carbazole-3-boronic acid 0.9g (3.1mmol), vinegar Palladium(II) acid 50 mg (0.023 mmol), tri(o-tolyl)phosphine Put 0.050g (0.17mmol) into a 100mL three-neck flask and purify the flask with nitrogen. The synthesis of 9-phenyl-9H-carbazole-3-boronic acid is Since this is the same as the method described in Example 1, we refer to that method. To this mixture, 30% ethylene glycol dimethyl ether (DME) was added. 15 mL of 2 mol / L aqueous potassium carbonate solution was added. The mixture was stirred under reduced pressure. After degassing, the mixture was heated and stirred at 90°C for 5 hours to allow the reaction to proceed.

[0316] After the reaction, ethyl acetate was added to the reaction mixture, and the suspension was diluted with saturated aqueous sodium bicarbonate solution. The organic layer was dried by adding magnesium sulfate. The mixture was suction filtered to remove magnesium sulfate, and the filtrate was obtained. The solid obtained was dissolved in toluene and suctioned through Celite, alumina, and Florisil. The filtrate was concentrated and purified by silica gel column chromatography. Silica gel column chromatography was first carried out using a toluene:hexane=1 A mixed solvent of toluene:hexane = 3:7 was used as the developing solvent. The reaction was carried out by using the solution as a developing solvent.

[0317] The obtained fraction was concentrated and the solid obtained was reconstituted with a mixed solvent of dichloromethane and hexane. Upon crystallization, the target white solid was obtained in an amount of 1.3 g and a yield of 66%. Sublimation purification of 1.1 g of the compound was carried out by train sublimation. When the reaction was carried out under reduced pressure at 305°C for 15 hours with an argon flow rate of 4 mL / min, The yield was 840 mg, and the yield was 76%.

[0318] The compound obtained in step 4 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The H NMR charts are shown in Figures 12(a) and 12(b). From the results, it is clear that the carbazole derivative of the present invention, 4,4'- Diphenyl-4''-(9-phenyl-9-H-carbazol-3-yl)triphenyl It was found that the amine (abbreviation: PCBBi1BP) was obtained.

[0319] 1 H NMR(CDCl3,300MHz):δ(ppm)=7.25-7.69(m ,32H),8.19(d,J=7.3Hz,1H),8.35(s,1H).

[0320] The absorption spectrum of PCBBi1BP (abbreviation) in toluene solution is shown in Figure 13(a). The absorption spectrum of the thin film of PCBBi1BP (abbreviation) is shown in Figure 13(b). A UV-visible spectrophotometer (V550 model, manufactured by JASCO Corporation) was used for the measurement. The torr was measured in a quartz cell. The thin film sample was made by evaporating PCBBi1BP (abbreviation) onto a quartz substrate. The absorption spectrum of quartz was subtracted from the measured spectrum of the sample. The absorption spectra obtained by subtraction are shown in Figure 13(a) and Figure 13(b). ) and Fig. 13(b), the horizontal axis represents wavelength (nm) and the vertical axis represents absorption intensity (arbitrary units). In the case of the toluene solution, an absorption peak is observed around 347 nm, and in the case of the thin film, it is observed around 350 An absorption peak was observed around nm. The emission spectrum of PCBBi1BP (at a wavelength of 358 nm) is shown in Figure 13(a). The emission spectrum of a thin film (excitation wavelength 366 nm) of ZnO (abbreviation) is shown in Figure 13(b). In Figure 13(a) and Figure 13(b), the horizontal axis represents wavelength (nm) and the vertical axis represents emission intensity (arbitrary units). The maximum emission wavelength is 399 nm (excitation wavelength 358 nm) in the case of a toluene solution, and In the case of the IR spectrum, the wavelength was 417 nm (excitation wavelength 366 nm).

[0321] In addition, the redox reaction properties of PCBBi1BP (abbreviation) were analyzed by cyclic voltammetry ( The measurement method was the same as in Example 1, so the explanation will be omitted. do.

[0322] The CV measurement results of the oxidation reaction characteristics are shown in Figure 42. As shown in Figure 42, the oxidation peak potential E pa is 0.521V, reduction peak potential E pc can be read as +0.431V Therefore, the half-wave potential (the potential between Epc and Epa) can be calculated as +0.48V. By the same calculation as in Example 1, the HOMO level of PCBBi1BP (abbreviation) is = -5.4 2 eV. The oxidation peak remained at the same value even after 100 cycles. It was found that the compound exhibited good properties in repeating oxidation-reduction cycles between the oxidized and neutral states. .

[0323] In addition, the thin film was measured in air by photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of CBBi1BP (abbreviation) was -5.34 eV. The Tauc plot of the absorption edge was 3.15 eV. Therefore, the solid-state energy The gap is estimated to be 3.15 eV, which corresponds to the LUMO This means that the level is -2.19 eV.

[0324] In addition, the glass transition temperature of PCBBi1BP (abbreviation) was measured using a differential scanning calorimeter ( DSC:Differential Scanning Calorimetry The measurement was carried out using a Kin-Elmer Pyris1 DSC. The transition temperature was found to be 123°C. It exhibits a high glass transition temperature and good heat resistance. It was found that no crystallization occurred and that the substance was difficult to crystallize. [Example]

[0325] In Example 2, the carbazole derivative of the present invention, 9,9- Dimethyl-N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl) Specific methods for synthesizing [phenyl]-fluoren-2-amine (abbreviation: PCBAF) explain.

[0326] [ka]

[0327] [Step 1: Synthesis of 2-bromo-9,9-dimethylfluorene]

[0328] The synthesis scheme of 2-bromo-9,9-dimethylfluorene in Step 1 is shown below ( F-1).

[0329] [ka]

[0330] 2-Bromofluorene 12.5 g (51 mmol), potassium iodide 8.5 g (51 m mol), potassium hydroxide 14.3g (0.50mol), dimethyl sulfoxide 250 The mixture was stirred for 30 minutes in a 500 mL Erlenmeyer flask. The mixture was stirred at room temperature for 48 hours. After the reaction, 400 ml of L of chloroform was added and stirred. This solution was diluted with 1N hydrochloric acid, saturated aqueous sodium carbonate, The organic layer was washed with saturated saline, and then magnesium sulfate was added to remove water. Ta.

[0331] The mixture was suction filtered and concentrated, and the residue was purified by silica gel column chromatography. Silica gel column chromatography was first carried out using hexane as a developing solvent. Then, a mixed solvent of ethyl acetate and hexane (1:5) was used as the developing solvent. The fractions were concentrated and dried to give a brown oil, 12 g, 97% yield. .

[0332] [Step 2: 9,9-dimethyl-N-phenyl-N-[4-(9-phenyl-9H- Carbazol-3-yl)phenyl]-fluoren-2-amine (abbreviation: PCBAF) Synthesis]

[0333] Step 2: 9,9-dimethyl-N-phenyl-N-[4-(9-phenyl-9 H-carbazol-3-yl)phenyl]-fluoren-2-amine (abbreviation: PCBAF The synthesis scheme of (F-2) is shown below.

[0334] [ka]

[0335] 4-(9-phenyl-9H-carbazol-3-yl)diphenylamine (abbreviation: PC BA) 2.0 g (4.9 mmol), 2-bromo-9,9-dimethylfluorene 1.3 g (4.9 mmol), sodium tert-butoxide 2.0 g (20 mmol) The mixture was placed in a 00 mL three-neck flask and the atmosphere in the flask was replaced with nitrogen. The method for producing the ion beam is the same as that described in Example 2, so please refer to that method. The mixture was added to 50 mL of toluene and 10 mL of tri(tert-butyl) 0.30 mL of ethyl phosphine (10 wt % hexane solution) was added. Degass the mixture while stirring under pressure. After degassing, bis(dibenzylideneacetone)palladium(0) 0.10 g of methylcellulose was added. Then, the mixture was heated and stirred at 80°C for 5 hours to react. After the reaction, toluene was added to the reaction mixture, and the suspension was passed through Celite, alumina, and Florisil. The mixture was then filtered under suction to obtain a filtrate.

[0336] The obtained filtrate was concentrated and purified by silica gel column chromatography. Silica gel column chromatography is first developed using a mixed solvent of toluene:hexane = 1:9. A mixture of toluene and hexane (3:7) is used as the developing solvent. The obtained fraction was concentrated, and the solid was extracted with chloroform and hexane. The target compound was recrystallized from the mixed solvent of 1.3 g and the yield was 44%. It was.

[0337] The resulting pale yellow solid (1.3 g) was purified by train sublimation. The sublimation purification was carried out under reduced pressure of 7.0 Pa with an argon flow rate of 3 mL / min at 270°C for 20 min. The yield was 1.0 g and the yield was 77%.

[0338] The compound obtained in step 2 above was analyzed by nuclear magnetic resonance spectroscopy ( 1 1 H NMR was measured. The measurement data is shown below. 1 The H NMR chart is shown in Figure 14. The carbazole derivative of the present invention, 9,9-dimethyl-N- Phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]- It was found that fluoren-2-amine (abbreviation: PCBAF) was obtained.

[0339] 1 H NMR(DMSO-d,300MHz):δ(ppm)=1.39(s,6H) 6.98-7.82(m,26H),8.35(d,J=6.8Hz,1H),8.57 (s,1H).

[0340] The absorption spectrum of PCBAF (abbreviation) in toluene is shown in Figure 15(a). The absorption spectrum of a thin film of PCBAF (abbreviation) is shown in Figure 15(b). A spectrophotometer (V550 model, manufactured by JASCO Corporation) was used. The thin film sample was prepared by evaporating PCBAF (abbreviation) onto a quartz substrate. The absorption spectrum obtained by subtracting the absorption spectrum of quartz from the spectrum of the measured sample was The spectra are shown in Figures 15(a) and 15(b). ), the horizontal axis represents wavelength (nm) and the vertical axis represents absorption intensity (arbitrary units). In the case of the thin film, an absorption peak is observed around 339 nm, and in the case of the thin film, an absorption peak is observed around 345 nm. In addition, the emission of PCBAF (abbreviation) in toluene solution (excitation wavelength 347 nm) The spectrum is shown in Figure 15(a). The emission spectrum of m) is shown in Figure 15(b). The horizontal axis represents wavelength (nm) and the vertical axis represents emission intensity (arbitrary units). In the case of a thin film, the excitation wavelength is 394 nm (excitation wavelength 347 nm), and in the case of a thin film, the excitation wavelength is 404 nm (excitation wavelength 37 0 nm).

[0341] In addition, the redox reaction characteristics of PCBAF (abbreviation) were analyzed by cyclic voltammetry (CV). The measurement method was the same as in Example 1, so the explanation will be omitted.

[0342] The CV measurement results of the oxidation reaction characteristics are shown in Figure 43. As shown in Figure 43, the oxidation peak potential E pa is 0.481V, reduction peak potential E pc can be read as +0.393V Therefore, the half-wave potential (E pc and E pa The intermediate potential between these two can be calculated as +0.44V. By the same calculation as in Example 1, the HOMO level of PCBAF (abbreviation) is = -5.38 [e V]. Furthermore, the oxidation peak remained at the same value even after 100 cycles. This indicates that it exhibits good properties in repeating oxidation-reduction between the oxidized and neutral states. Understood. [Example]

[0343] In Example 4, N-phenylenediamine, a carbazole derivative of the present invention represented by structural formula (8), N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-spiro Specific methods for synthesizing 9,9'-bifluorene-2-amine (abbreviation: PCBASF) Explain in a concrete manner.

[0344] [ka]

[0345] [Step 1-1: 9-(biphenyl-2-yl)-2-bromofluoren-9-ol Synthesis of 9-(biphenyl-2-yl)-2-bromofluorene-9- The synthesis scheme of ol is shown below (G-1-1).

[0346] [ka]

[0347] In a 100 mL three-neck flask equipped with a dropping funnel and a Dimroth, add 1.2 mL of magnesium The system was placed under vacuum and heated and stirred for 30 minutes to obtain magnesium. After cooling to room temperature, the system was placed under a nitrogen stream, and 5 mL of diethyl ether and A few drops of dibromoethane were added, and 2- 11.65g (0.050mol) of bromobiphenyl was slowly added dropwise, and after 3 hours The mixture was refluxed for 1 hour to form a Grignard reagent.

[0348] A 200 mL three-neck flask equipped with a dropping funnel and a Dimroth was charged with 2-bromo-9-fluoro- 11.7 g (0.045 mol) of oleone and 40 mL of diethyl ether were added to this reaction mixture. The Grignard reagent synthesized was slowly added dropwise to the reaction solution using a dropping funnel. After the addition, the reaction solution was left for 2 hours. The mixture was refluxed and further stirred at room temperature overnight. After the reaction was completed, the solution was washed twice with saturated aqueous ammonium chloride. The resulting aqueous layer was extracted twice with ethyl acetate. The solution and the resulting organic layer were combined and washed with saturated saline. After removing the solvent, the mixture was filtered by suction and concentrated to give 9-(biphenyl-2-yl)-2-bromo A solid of mo-9-fluorenol was obtained in an amount of 18.76 g and a yield of 90%. [Step 1-2: Synthesis of 2-bromo-spiro-9,9'-bifluorene]

[0349] Synthesis scheme of 2-bromo-spiro-9,9'-bifluorene in step 1-2 is shown below (G-1-2).

[0350] [ka]

[0351] In a 200 mL three-neck flask, add the synthesized 9-(biphenyl-2-yl)-2-bromo-9 -Add 18.76g (0.045mol) of fluorenol and 100mL of glacial acetic acid, and After the reaction was completed, the mixture was collected by suction filtration and saturated sodium bicarbonate was added. The brown solid was recrystallized from ethanol. As a result, a light brown powdery solid was obtained in an amount of 10.24 g, with a yield of 57%.

[0352] [Step 2: N-phenyl-N-[4-(9-phenyl-9H-carbazole-3- yl)phenyl]-spiro-9,9'-bifluoren-2-amine (abbreviation: PCBASF ) synthesis]

[0353] Step 2: N-phenyl-N-[4-(9-phenyl-9H-carbazole- 3-yl)phenyl]-spiro-9,9'-bifluoren-2-amine (abbreviation: PCBA The synthesis scheme of SF) is shown in (G-2) below.

[0354] [ka]

[0355] 4-(9-phenyl-9H-carbazol-3-yl)diphenylamine (abbreviation: PC BA) 2.0 g (4.9 mmol), 2-bromo-spiro-9,9'-bifluorene 1. 9g (4.9mmol), sodium tert-butoxide 2.0g (20mmol) The mixture was placed in a 100 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. 50 mL, tri(tert-butyl)phosphine (10 wt% hexane solution) 0.30 m The mixture was degassed under reduced pressure while stirring. After degassing, bis(dibenzylidene) 0.10 g of palladium(0) in dichloroacetone was added.

[0356] Next, this mixture was heated and stirred at 80°C for 5 hours to react. Toluene was added, and the suspension was suction filtered through Celite, alumina, and Florisil. The obtained filtrate was washed with saturated aqueous sodium carbonate solution and saturated saline solution in this order. Magnesium sulfate was added to the layer to remove moisture, and the mixture was then suction filtered and the magnesium sulfate The filtrate was concentrated and the solid was dissolved in chloroform and hexane. The product was recrystallized from a mixed solvent of 1,000 mg of PEG-1000, yielding 3.4 g of a white powdery solid with a 94% yield. The resulting white solid (2.3 g) was purified by train sublimation. The sublimation purification was carried out under reduced pressure of 7.0 Pa with an argon flow rate of 3 mL / min at 310°C for 2 min. The reaction was carried out for 0 hours. The yield was 1.7 g, and the yield was 74%.

[0357] The compound obtained in step 2 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The H NMR chart is shown in Figure 16. The carbazole derivative of the present invention, N-phenyl-N-[4 -(9-phenyl-9H-carbazol-3-yl)phenyl]-spiro-9,9'-bi It was found that fluorene-2-amine (abbreviation: PCBASF) was obtained.

[0358] 1 H NMR(CDCl3,300MHz):δ(ppm)=6.61-6.70(m ,2H),6.83(d,J=8.3Hz,2H),6.88-7.79(m,30H) ,8.16(d,J=8.3Hz,1H),8.26(s,1H).

[0359] The absorption spectrum of a toluene solution of PCBASF (abbreviation) is shown in FIG. 17(a). The absorption spectrum of a thin film of PCBASF (abbreviation) is shown in Figure 17(b). An infrared-visible spectrophotometer (V550 model, manufactured by JASCO Corporation) was used. The thin film sample was prepared by evaporating PCBASF (abbreviation) onto a quartz substrate. The absorption spectrum of quartz was subtracted from the spectrum of the measured sample. The absorption spectra are shown in Figures 17(a) and 17(b). In 7(b), the horizontal axis represents wavelength (nm) and the vertical axis represents absorption intensity (arbitrary units). In the case of the liquid, an absorption peak is observed around 338 nm, and in the case of the thin film, an absorption peak is observed around 345 nm. In addition, a toluene solution of PCBASF (abbreviation) (excitation wavelength 352 nm) The emission spectrum of PCBASF (abbreviation) is shown in Figure 17(a). The emission spectrum of the ion beam (371 nm) is shown in Figure 17(b). ), the horizontal axis represents wavelength (nm) and the vertical axis represents emission intensity (arbitrary units). In the case of the toluene solution, the excitation wavelength was 396 nm (352 nm), and in the case of the thin film, the excitation wavelength was 427 nm ( The excitation wavelength was 371 nm.

[0360] In addition, the oxidation-reduction reaction characteristics of PCBASF (abbreviation) were analyzed by cyclic voltammetry (CV The measurement method was the same as in Example 1, so the explanation will be omitted. .

[0361] The CV measurement results of the oxidation reaction characteristics are shown in Figure 44. As shown in Figure 44, the oxidation peak potential E pa is 0.52 V, reduction peak potential E pc can be read as +0.428V. Therefore, the half-wave potential (E pc and E pa The intermediate potential between the two can be calculated as +0.47V. By the same calculation as in Example 1, the HOMO level of PCBASF (abbreviation) is = -5.41 [e V]. Furthermore, the oxidation peak remained at the same value even after 100 cycles. This indicates that it exhibits good properties in repeating oxidation-reduction between the oxidized and neutral states. Understood. [Example]

[0362] In this Example 5, the carbazole derivative 4 of the present invention synthesized in Examples 1 to 4 was -phenyl-4'-(9-phenyl-9H-carbazol-3-yl)triphenylamine A light-emitting element 2,4,4'-diphenyl-4' '-(9-phenyl-9-H-carbazol-3-yl)triphenylamine (abbreviation: P Light-emitting device 3 formed using CBBi1BP) [4-(9-phenyl-9H-carbazol-3-yl)phenyl]-fluorene-2- The light-emitting element 4 formed using amine (abbreviation: PCBAF) and N-phenyl-N-[ 4-(9-phenyl-9H-carbazol-3-yl)phenyl]-spiro-9,9'- Method for manufacturing light-emitting element 5 formed using bifluorene-2-amine (abbreviation: PCBASF) The method and the measurement results of the device characteristics are shown below.

[0363] The element structure of the light-emitting element in this example is the structure shown in FIG. 18, and the hole transport layer 1512 was formed using the carbazole derivative of the present invention described above. The light-emitting element 1, which is a comparative light-emitting element, has a hole-transporting layer 1512 containing 4,4′-bis[N-(1-naphthalene)-2-(2-methylphenyl)-2-propanol]. (N-phenylamino)biphenyl (abbreviation: NPB) was used to form the compound. In order to align them, the light emitting elements 2 to 5 are formed on the same substrate. The element 1 was formed and compared with the light-emitting elements 2 to 5. The structural formula of the compound is shown below.

[0364] [ka]

[0365] First, on the substrate 1501, which is a glass substrate, indium oxide-tin oxide containing silicon oxide is formed. The first electrode 1502 was formed by sputtering. The thickness was set to 0 nm and the electrode area was set to 2 mm x 2 mm.

[0366] Next, an EL layer 1503 in which a plurality of layers are stacked is formed on the first electrode 1502. In the example, the EL layer 1503 comprises a first layer 1511 which is a hole injection layer, a second layer 1512 which is a hole transport layer, and a third layer 1513 which is a hole transport layer. The second layer 1512 is a light-emitting layer, the third layer 1513 is a light-emitting layer, and the fourth layer 1514 is an electron transport layer. 4 and a fifth layer 1515, which is an electron injection layer, are laminated in this order.

[0367] The first electrode 1502 is formed so that the surface on which the first electrode 1502 is formed faces downward. The substrate was fixed to a substrate holder installed in a vacuum deposition apparatus, and -4 Reduced to about Pa After the pressure application, 4,4′-bis[N-(1-naphthyl)-N-phenylene] is deposited on the first electrode 1502. co-evaporation of [nylamino]biphenyl (abbreviation: NPB) and molybdenum (VI) oxide The first layer 1511, which is a hole injection layer, was formed by the above method. The weight ratio of B to molybdenum (VI) oxide is 4:1 (NPB: molybdenum oxide). The deposition rate was adjusted so that the deposition rate was 100%. This is a deposition method in which deposition is carried out simultaneously from

[0368] Next, a hole transporting material is deposited on the first layer 1511 by a deposition method using resistance heating. The second layer 1512 was formed as a hole transport layer. When forming the optical element 1, 4,4'-bis[N-(1-naphthyl)-N-phenylalanine] When the light-emitting element 2 is formed using 4-phenylaminobiphenyl (abbreviation: NPB), 4'-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation When the light-emitting element 3 is formed using 4,4'-diphenyl-4 ''-(9-phenyl-9-H-carbazol-3-yl)triphenylamine (abbreviation: When the light emitting element 4 is formed using PCBBi1BP, 9,9-dimethyl-N-phenyl Phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]- When the light-emitting element 5 is formed using olefin-2-amine (abbreviation: PCBAF), N- Phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-s Using pyro-9,9'-bifluorene-2-amine (abbreviation: PCBASF), Successful.

[0369] Next, a third layer (a light-emitting layer) is formed on the second layer 1512 by a vapor deposition method using resistance heating. Formation of 1513: 9-[4-(10-phenyl-9-anthryl)phenyl]-9H -carbazole (abbreviation: CzPA) and 4-(10-phenyl-9-anthryl)-4'- (9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBA The third layer 1513 was formed to a thickness of 30 nm by co-evaporation with PA. The weight ratio of CzPA to PCBAPA was 1:0.10 (=CzPA:PCBAPA). The deposition rate was adjusted so that

[0370] Furthermore, tris(8-quinolinol) was deposited on the third layer 1513 by using a vapor deposition method using resistance heating. A 10 nm layer of (tetrato)aluminum(III) (abbreviation: Alq) was deposited on it, and bathophenanthro Phosphorus (abbreviation: BPhen) was formed to a thickness of 20 nm, and the fourth electron transport layer was formed. A layer 1514 was formed.

[0371] On the fourth layer 1514, a lithium fluoride (LiF) film is formed to a thickness of 1 nm. In this way, a fifth layer 1515 serving as an electron injection layer was formed.

[0372] Finally, aluminum was evaporated to a thickness of 200 nm using resistance heating. By forming a film, a second electrode 1504 was formed, and light-emitting elements 1 to 5 were fabricated. .

[0373] The light-emitting devices 1 to 5 obtained above were placed in a glove box with a nitrogen atmosphere. After sealing the light emitting elements so that they are not exposed to the atmosphere, The operating characteristics were measured. The measurements were carried out at room temperature (an atmosphere maintained at 25°C). .

[0374] FIG. 19 shows the current density-luminance characteristics of Light-emitting Elements 1 and 2. The characteristics are shown in FIG. 20, the luminance-current efficiency characteristics are shown in FIG. 21, and the voltage-current characteristics are shown in FIG.

[0375] Light-emitting element 2 has a luminance of 1277 cd / m when the driving voltage is 3.4 V. 2 , the current value is 0.7 The current consumption was 9 mA. The light-emitting element 2 using PCBA1BP (abbreviation) for 1512 exhibits a low driving voltage. Furthermore, the current efficiency was found to be high.

[0376] In addition, in the light-emitting element 2, the emission spectrum shown in FIG. 23 indicates that the blue light-emitting material PCB The emission wavelength originating from APA was observed, but the emission wavelength originating from the hole transport material was not observed. Therefore, the light emitting element 2 using PCBA1BP (abbreviation) of the present invention has a good structure. It was found that they achieved a good career balance.

[0377] Regarding the light-emitting element 2, the initial luminance is set to 1000 cd / m 2 As a result, continuous constant current drive The results of the continuous lighting test are shown in Figure 24 (the vertical axis is 1000 cd / m 2 was set to 100% The results in FIG. 24 show that Light-emitting element 3 maintained 90% of its initial luminance even after 160 hours. The luminance of the light-emitting element was 2% of that of the light-emitting element 1, and it was found that the light-emitting element had a longer life than the light-emitting element 1. By applying PCBA1BP (abbreviation) of the present invention, a long-life light-emitting element can be obtained. .

[0378] FIG. 25 shows current density-luminance characteristics of Light-emitting Elements 1 and 3. The characteristics are shown in FIG. 26, the luminance-current efficiency characteristics are shown in FIG. 27, and the voltage-current characteristics are shown in FIG.

[0379] The light-emitting element 3 has a luminance of 1328 cd / m when the driving voltage is 3.4 V. 2 , the current value is 0.7 The current consumption was 8 mA. The light-emitting element 3 using PCBBi1BP (abbreviation) for 1512 exhibits a low driving voltage. Furthermore, it was found that the current efficiency was high.

[0380] In addition, in the light-emitting element 3, the emission spectrum shown in FIG. 29 indicates that PCB, which is a blue light-emitting material, The emission wavelength originating from APA was observed, but the emission wavelength originating from the hole transport material was not observed. Therefore, the light-emitting element 3 using PCBBi1BP (abbreviation) of the present invention has a good structure. I found that I had achieved a good career balance.

[0381] FIG. 30 shows current density-luminance characteristics of Light-emitting Elements 1 and 4. The characteristics are shown in FIG. 31, the luminance-current efficiency characteristics are shown in FIG. 32, and the voltage-current characteristics are shown in FIG.

[0382] The light-emitting element 4 has a luminance of 1328 cd / m when the driving voltage is 3.8 V. 2 , the current value is 1.0 The current consumption was 8 mA. It was found that the light-emitting element 4 using PCBAF (abbreviation) for 1512 exhibited a low driving voltage. It was.

[0383] In addition, in the light-emitting element 4, the emission spectrum shown in FIG. 34 indicates that the blue light-emitting material PCB The emission wavelength originating from APA was observed, but the emission wavelength originating from the hole transport material was not observed. Therefore, the light-emitting element 4 using PCBAF (abbreviation) of the present invention has a good crystal structure. It was found that this achieved carrier balance.

[0384] Regarding the light-emitting element 4, the initial luminance is set to 1000 cd / m 2 As a result, continuous constant current drive The results of the continuous lighting test are shown in Figure 35 (the vertical axis is 1000 cd / m 2 was set to 100% The results in FIG. 35 show that Light-emitting element 3 maintained 90% of its initial luminance even after 160 hours. The luminance of the light-emitting element was 2% of that of the light-emitting element 1, and it was found that the light-emitting element had a longer life than the light-emitting element 1. By applying the PCBAF (abbreviation) of the present invention, a light emitting element with a long life can be obtained.

[0385] FIG. 36 shows current density-luminance characteristics of Light-emitting Elements 1 and 5. The characteristics are shown in FIG. 37, the luminance-current efficiency characteristics are shown in FIG. 38, and the voltage-current characteristics are shown in FIG.

[0386] The light-emitting element 5 has a luminance of 1398 cd / m when the driving voltage is 3.8 V. 2 , the current value is 1.1 The current consumption was 1 mA. The light-emitting element 5 using PCBASF (abbreviation) as 1512 exhibits a low driving voltage. Furthermore, we found that the current efficiency was high.

[0387] In addition, in the light-emitting element 5, the emission spectrum shown in FIG. 40 indicates that the blue light-emitting material PCB The emission wavelength originating from APA was observed, but the emission wavelength originating from the hole transport material was not observed. Therefore, the light-emitting element 5 using PCBASF (abbreviation) of the present invention has a good structure. I found that I achieved career balance.

[0388] As described above, the light-emitting elements 2 to 5 formed using the carbazole derivative of the present invention are It was found that the efficiency was at the same level as that of the optical element 1. Therefore, by applying the present invention, It was found that a highly efficient light-emitting element could be obtained.

[0389] In the structure of the light-emitting element 1 shown in this example, when the first layer 1511 is formed, Instead of NPB (abbreviation), PCBA1BP (abbreviation) was used, and molybdenum (VI) oxide was The efficiency of the light-emitting element in which the first layer 1511 was formed by co-evaporation with 2 Inoke The driving voltage and reliability were measured using NPB and molybdenum (VI) oxide in Example 10. Light emitting device formed by using a vapor-deposited film as the hole injection layer and PCBBiNB (abbreviation) as the hole transport layer. A good value equivalent to that of Device 8 was obtained (luminance 949 cd / m when the driving voltage was 3.8 V). 2 The current value was 0.65mA, and the brightness remained at 64% of the initial brightness after 1500 hours of operation. Ta).

[0390] In this way, PCBA1BP (abbreviation) is also a good material for hole injection. It was also found that good characteristics were obtained when a co-evaporated film with molybdenum oxide was used as the hole injection layer. I found that it can be obtained.

[0391] Furthermore, in the structure of the light-emitting element 2 shown in this example, when the first layer 1511 is formed, Instead of NPB (abbreviation) used in the previous study, PCBA1BP (abbreviation) was used, and molybdenum oxide (VI The efficiency of the light-emitting element in which the first layer 1511 was formed by co-evaporation with ZnO) was about 1000 cd / m 2 To In Example 10, the driving voltage and reliability of the NPB and molybdenum (VI) oxide were The co-evaporated film was used as the hole injection layer and PCBBiNB (abbreviation) was used as the hole transport layer. A good value equivalent to that of optical element 8 was obtained (luminance 843 cd / m when the driving voltage was 3.6 V). 2 The current value was 0.53mA, and the brightness remained at 65% of the initial brightness after 1500 hours of operation. there was).

[0392] In this way, PCBA1BP (abbreviation) has a first layer 1511 which is a hole injection layer and a It is a good material that can be used simultaneously for both the second layer 1512, which is a hole transport layer. This has made it easier to fabricate the device and improved the efficiency of material utilization. This was possible. [Example]

[0393] In Example 6, the carbazole derivative of the present invention represented by structural formula (15) (bifuran) was used. (phenyl-4-yl)(phenyl)[4'-(9-phenyl-9H-carbazole-3-yl) We will explain the synthesis method of PCTA1BP. will be explained.

[0394] [ka]

[0395] Step 1: 4-[N-(biphenyl-4-yl)-N-phenyl]aminophenylborate Synthesis of uronic acid]

[0396] 4-[N-(biphenyl-4-yl)-N-phenyl]aminophenyl in Step 1 The synthesis scheme of ylboronic acid is shown below in (H-1).

[0397] [ka]

[0398] 7.0 g (18 mmol) of 4-bromo-4'-phenyltriphenylamine, 300 The flask was purged with nitrogen, and then tetrahydrofuran (abbreviated 80 mL of THF was added and stirred at -78°C for 10 minutes. 13 mL (21 mmol) of n-butyllithium hexane solution was added dropwise using a syringe. The mixture was stirred at −78° C. for 1 hour. After stirring, 3.5 mL (31 mL) of trimethyl borate was added to the reaction mixture. After the reaction, 1 mmol was added to the reaction solution, and the mixture was stirred at -78°C for 1 hour and at room temperature for 24 hours. 100 mL of M diluted hydrochloric acid was added and stirred at room temperature for 1 hour. After stirring, the solution was extracted with ethyl acetate. The organic layer was washed with saturated saline, and then magnesium sulfate was added to the organic layer to dry it. After drying, the magnesium sulfate was removed by suction filtration to obtain a filtrate. After concentrating and recrystallizing with a mixed solvent of chloroform and hexane, the target product was obtained in a yield of 3.6 g. , was obtained in a yield of 56%.

[0399] [Step 2: (biphenyl-4-yl)(phenyl)[4'-(9-phenyl-9H- Synthesis of [carbazol-3-yl]biphenyl-4-yl]amine (abbreviation: PCTA1BP) ]

[0400] Step 2: (biphenyl-4-yl)(phenyl)[4'-(9-phenyl- The synthesis scheme of 9H-carbazol-3-yl)biphenyl-4-yl]amine is shown below ( H-2).

[0401] [ka]

[0402] 4-[N-(biphenyl-4-yl)-N-phenyl]aminophenylboronic acid 2. 2g (5.5mmol), 3-(4-bromophenyl)-9-phenyl-9H-carbazo 2.0 g (5.5 mmol) of palladium(II) acetate and 10 mg (0.045 mmol) of palladium(II) acetate were added. mol), 0.69 g (0.23 mmol) of tri(o-tolyl)phosphine, 100 m Place in a 100 mL three-neck flask, add 10 mL of 2.0 mol / L potassium carbonate solution, and diethylene glycol. 20 mL of dimethyl ether (DME) was added to the mixture, and the mixture was stirred under reduced pressure. The mixture was degassed while stirring, and the atmosphere in the flask was replaced with nitrogen. The mixture was heated and stirred at 90°C for 5 hours. After stirring, toluene was added to the reaction mixture and heated to 90°C.

[0403] After heating, the suspension was separated into an organic layer and an aqueous layer. The organic layer was washed with an aqueous solution of ammonium chloride and saturated brine, and dried over magnesium sulfate. This mixture was suction filtered through Celite, alumina, and Florisil to obtain a filtrate. The filtrate was concentrated to give a solid. The solid was dissolved and purified by silica gel column chromatography. The silica gel column chromatography was first carried out by toluene:hexane. A mixture of toluene and hexane (1:9) was used as the developing solvent, followed by a mixture of toluene and hexane (2:3). The obtained fraction was concentrated, and the solid was extracted with chloroform. The mixture was dissolved in chloroform and subjected to high performance liquid chromatography (HPLC) (eluent: chloroform). The obtained fraction was concentrated, and the solid was purified by chloroform and hexane. The desired white solid was obtained in an amount of 1.7 g and a yield of 48%. Ta.

[0404] The resulting white solid (1.0 g) was purified by train sublimation. The purification was carried out at 300°C for 15 hours under a reduced pressure of 7.0 Pa with an argon flow rate of 4 mL / min. After 2 hours of stirring, the yield was 0.62 g, 62%.

[0405] The compound obtained in step 2 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The 1 H NMR chart is shown in Figure 45. PCTA1BP (abbreviation), which is a carbazole derivative of the present invention represented by the above-mentioned structural formula 15, It was found that it was obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm) = 7.02-7.79(m,32H), 8.19(d,J=7.3Hz,1H), 8.39 (s,1H).

[0406] Also, the absorption spectrum of PCTA1BP (abbreviation) (measurement range 200nm to 800nm) The absorption peak on the long wavelength side was observed around 349 nm in the case of the toluene solution. In the case of thin films, it was observed around 357 nm.

[0407] Also, the emission spectrum of PCTA1BP (abbreviation) (measurement range 370nm to 550nm) The maximum emission wavelength was 405 nm (excitation wavelength 320 nm) in the case of a toluene solution. In the case of the thin film, it was 420 nm (excitation wavelength 284 nm). The method for measuring the emission spectrum is the same as in Example 1, and therefore the explanation will be omitted.

[0408] In addition, the thin film was measured in air by photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of CTA1BP (abbreviation) was -5.49 eV. The Tauc plot showed that the absorption edge was 3.10 eV. The gap is estimated to be 3.10 eV, which means that the LUMO level of PCTA1BP (abbreviation) is This means that the energy is -2.39 eV.

[0409] In addition, the redox reaction characteristics of PCTA1BP (abbreviation) were analyzed by cyclic voltammetry (C V) Measurement was carried out. The measurement method was the same as in Example 1, so the explanation will be omitted. By calculation similar to that in Example 1, the HOMO level of PCTA1BP (abbreviation) is = -5. The oxidation peak was found to be 48 eV. Even after 100 cycles, the oxidation peak remained at the same value. This indicates that the compound exhibits good properties in the repeated oxidation-reduction between the oxidized and neutral states. I found that.

[0410] In addition, the glass transition temperature of PCTA1BP (abbreviation) was measured using a differential scanning calorimeter (D SC:Differential Scanning Calorimetry The measurement was carried out using a KinElmer Pyris1 DSC. The transition temperature was found to be 118°C. It exhibits a low glass transition temperature and good heat resistance. It was found that the substance was difficult to crystallize.

[0411] In addition, similarly to Example 5, PCTA1BP (abbreviation) synthesized in Example 6 was used as the hole transport layer. The efficiency of the light-emitting device formed using this material was 1000 cd / m 2 The driving voltage and reliability at , and the same good results as the light-emitting element 8 formed using PCBBiNB (abbreviation) in Example 10. A luminance of 1044 cd / m was obtained when the driving voltage was 3.6 V. 2 , the current value is 0.6 7mA, and maintained 52% of the initial brightness after 1100 hours of operation). [Example]

[0412] In Example 7, a bis(2-methyl-2-phenylpropanol) compound, which is a carbazole derivative of the present invention represented by structural formula (190), was used. (biphenyl-4-yl)[4'-(9-phenyl-9H-carbazol-3-yl)biphenyl-4-yl] This section explains in detail how to synthesize [phenyl-4-yl]amine (abbreviation: PCTBi1BP). Reveal.

[0413] [ka]

[0414] Step 1: Synthesis of 4-[bis(biphenyl-4-yl)amino]phenylboronic acid

[0415] Step 1: 4-[bis(biphenyl-4-yl)amino]phenylboronic acid The synthesis scheme is shown below in (I-1).

[0416] [ka]

[0417] 6.0 g (13 mmol) of 4-bromo-4',4''-diphenyltriphenylamine ) was placed in a 300 mL three-neck flask, the atmosphere in the flask was replaced with nitrogen, and then tetrahydrofuran was added. 80 mL of furan (abbreviation: THF) was added and stirred at -78°C for 10 minutes. 10 mL of 3 mol / L n-butyllithium hexane solution was added dropwise using a syringe, and the temperature was adjusted to -7 The mixture was stirred at 8° C. for 1 hour. After stirring, 2.8 mL (25 mmol) of trimethyl borate was added to the reaction mixture. l) was added, and the mixture was stirred at -78°C for 1 hour, and then stirred at room temperature for a further 24 hours. Approximately 50 mL of dilute hydrochloric acid was added to the mixture, and the mixture was stirred at room temperature for 30 minutes. After extraction, the organic layer was washed with saturated saline and magnesium sulfate was added to the organic layer. After drying, the mixture was subjected to suction filtration to obtain a filtrate. After concentrating and recrystallizing with a mixed solvent of chloroform and hexane, the target substance was obtained as a white powdery solid. The compound was obtained in an amount of 4.8 g and a yield of 86%.

[0418] Step 2: Bis(biphenyl-4-yl)[4'-(9-phenyl-9H-carbazo] Synthesis of [(3-yl)biphenyl-4-yl]amine (abbreviation: PCTBi1BP)

[0419] Step 2: Bis(biphenyl-4-yl)[4'-(9-phenyl-9H-carboxylate] The synthesis scheme of [(1-1)-biphenyl-4-yl]-benzol-3-yl-biphenyl-4-ylamine is shown below (I-2). Shown below.

[0420] [ka]

[0421] 2.0 g (4.5 m) of 4-[bis(biphenyl-4-yl)amino]phenylboronic acid mol), 1.8 g of 3-(4-bromophenyl)-9-phenyl-9H-carbazole (4.5 mmol), palladium(II) acetate 10 mg (0.045 mmol), tri 0.69 g (0.23 mmol) of (o-tolyl)phosphine was placed in a 100 mL three-neck flask. Add 10 mL of 2.0 mol / L potassium carbonate solution, ethylene glycol dimethyl ether, and 20 mL of diethyl ether (DME) was added to the mixture, which was then degassed under reduced pressure while stirring. The atmosphere in the flask was replaced with nitrogen. The mixture was heated and stirred at 90°C for 5 hours. After stirring, the reaction Toluene was added to the mixture and heated at 90°C.

[0422] After heating, the suspension was separated into an organic layer and an aqueous layer. The organic layer was washed with an aqueous solution of ammonium chloride and saturated brine, and dried over magnesium sulfate. This mixture was suction filtered through Celite, alumina, and Florisil to obtain a filtrate. The filtrate was concentrated to give a solid. The solid was dissolved in toluene and purified by silica gel column chromatography. The silica gel column chromatography was carried out using toluene. The resulting fraction was concentrated to give a solid. Recrystallization from a mixed solvent of toluene and hexane yielded the desired white solid in an amount of 2.4 g. The rate was 74%.

[0423] The obtained white solid was purified by train sublimation. The reaction was carried out at 340°C for 20 hours under a reduced pressure of 7 Pa with an argon flow rate of 3 mL / min. The amount added was 1.5 g, and the yield was 0.70 g, giving a yield of 46%.

[0424] The compound obtained in step 2 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The 1 H NMR chart is shown in Figure 46. PCTBi1BP (abbreviation: PCTBi1BP), a carbazole derivative of the present invention represented by the above structural formula 190, ) was found to be obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm )=7.18-7.83(m,36H), 8.21(d,J=7.3Hz,1H), 8. 40(s,1H).

[0425] In addition, the absorption spectrum of PCTBi1BP (abbreviation) (measurement range: 200 nm to 800 nm) The absorption peak on the long wavelength side was observed around 350 nm in the case of the toluene solution. In the case of the thin film, it was observed around 357 nm.

[0426] In addition, the emission spectrum of PCTBi1BP (abbreviation) (measurement range: 370 nm to 550 nm) The maximum emission wavelength was 410 nm (excitation wavelength 320 nm) in the case of a toluene solution. ), and in the case of a thin film, it was 447 nm (excitation wavelength 340 nm). The method for measuring the emission spectrum is the same as in Example 1, and therefore the explanation will be omitted.

[0427] In addition, the thin film was measured in air by photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of CTBi1BP (abbreviation) was -5.50 eV. The Tauc plot of the absorption edge was 3.14 eV. Therefore, the energy of the solid state The gap is estimated to be 3.14 eV, which corresponds to the LUMO level of PCTBiBP (abbreviation). This means that the potential is -2.36 eV.

[0428] In addition, the redox reaction properties of PCTBi1BP (abbreviation) were analyzed by cyclic voltammetry ( The measurement method was the same as in Example 1, so the explanation will be omitted. do.

[0429] Using the same calculation as in Example 1, the HOMO level of PCTBiBP (abbreviation) is = -5. The oxidation peak was found to be 46 eV. Even after 100 cycles, the oxidation peak remained at the same value. This indicates that the compound exhibits good properties in the repeated oxidation-reduction between the oxidized and neutral states. I found that.

[0430] In addition, the glass transition temperature of PCTBi1BP (abbreviation) was measured using a differential scanning calorimeter ( DSC:Differential Scanning Calorimetry The measurement was carried out using a Kin-Elmer Pyris1 DSC. The transition temperature was found to be 133°C. exhibits a high glass transition temperature and has good heat resistance. No peak was observed, indicating that the substance was difficult to crystallize.

[0431] In the same manner as in Example 5, PCTBi1BP (abbreviation) synthesized in Example 7 was used as a hole transport layer. The efficiency of the light-emitting device formed using 2 Drive voltage and reliability The result is as good as that of the light-emitting element 8 formed using PCBBiNB (abbreviation) in Example 10. A good value was obtained (luminance 873 cd / m when the driving voltage was 3.6 V). 2 , the current value is 0.5 6mA, and maintained 80% of the initial brightness after 110 hours of operation). [Example]

[0432] In Example 8, a carbazole derivative of the present invention, 4- (1-Naphthyl)-4'-(9-phenyl-9H-carbazol-3-yl)-triphenyl The synthesis method of PCBANB (abbreviated as PCBANB) will be specifically explained.

[0433] [ka]

[0434] Step 1: Synthesis of 3-(4-bromophenyl)-9-phenyl-9H-carbazole ]

[0435] 3-(4-bromophenyl)-9-phenyl-9H-carbazole in Step 1 The synthesis scheme is shown in (J-1) below.

[0436] [ka]

[0437] 3-Iodo-9-phenyl-9H-carbazole 3.7g (9.9mmol), 4- Bromophenylboronic acid 2.0 g (9.9 mmol), tri(o-tolyl)phosphine 0.61 g (2.0 mmol) of the above was placed in a 200 mL three-neck flask, and 5 0 mL of ethylene glycol dimethyl ether (abbreviated as DME) and 2 mol / L carbonate 10 mL of an aqueous sodium solution was added to the mixture, which was then degassed under reduced pressure while being stirred. The atmosphere in the flask was replaced with nitrogen.

[0438] To this mixture was added 0.11 g (0.50 mmol) of palladium(II) acetate. The mixture was stirred at 80° C. for 9.5 hours. After stirring, the mixture was cooled to room temperature. The resulting aqueous layer was extracted twice with toluene, and the extract and the organic layer were combined. The organic layer was dried over magnesium sulfate, and the mixture was subjected to gravity filtration. The filtrate was then concentrated.

[0439] The obtained oil was dissolved in about 20 mL of toluene, and the solution was poured onto a silica gel column containing Celite, alumina, and fluorine. The filtrate was concentrated and the solid was filtered through a silica gel column. The compound was purified by column chromatography (developing solvent: toluene:hexane = 1:4). As a result, 1.9 g of the target white powdery solid was obtained in a yield of 49%.

[0440] [Step 2: Synthesis of 4-(1-naphthyl)diphenylamine]

[0441] The synthesis scheme of 4-(1-naphthyl)diphenylamine in Step 2 is shown below (J -2).

[0442] [ka]

[0443] 12 g (50 mmol) of 4-bromodiphenylamine and 8 g of 1-naphthaleneboronic acid 0.6g (50mmol), palladium(II) acetate 22mg (0.1mmol), tri 60 mg (0.2 mmol) of (o-tolyl)phosphine was placed in a 200 mL three-neck flask. To this mixture, 50 mL of toluene, 20 mL of ethanol, and 2 mol / L potassium carbonate were added. 35 mL of aqueous solution was added, and the mixture was degassed under reduced pressure with stirring, and then reconstituted under a nitrogen atmosphere. The mixture was heated and stirred at 90°C under atmospheric pressure for 2 hours to allow the reaction to proceed.

[0444] After the reaction, 100 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added to reduce the moisture content. The suspension was concentrated and purified by silica gel column chromatography (developing solvent: The resulting fractions were purified with a solvent mixture of toluene, hexane, and ethyl acetate (1:8:1). The ethanol was concentrated, methanol was added, and ultrasonic waves were applied. After recrystallization, the desired white A powder was obtained in an amount of 3.0 g and a yield of 20%.

[0445] [Step 3: 4(1-naphthyl)-4'(9-phenyl-9H-carbazole-3-yl) Synthesis of PCBANB

[0446] Step 3: 4(1-naphthyl)-4'(9-phenyl-9H-carbazole- The synthesis scheme of (3-yl)-triphenylamine is shown in (J-3) below.

[0447] [ka]

[0448] 1.2 g (3.0 g) of 3-(4-bromophenyl)-9-phenyl-9H-carbazole 0.9g (3.0mmol), 4-(1-naphthyl)diphenylamine, 0.5 g (5.0 mmol) of thorium tert-butoxide, bis(dibenzylidene (acetone) palladium(0), 6.0 mg (0.01 mmol), 50 mL three-neck flask 15 mL of dehydrated xylene was added to the mixture. The mixture was stirred under reduced pressure. After degassing, tri(tert-butyl)phosphine (10 wt% hexane solution) 0.06 mL (0.03 mmol) of HCl was added to the mixture, and the mixture was heated at 120° C. under a nitrogen atmosphere. The mixture was heated and stirred at room temperature for 4.5 hours to carry out the reaction.

[0449] After the reaction, 250 mL of toluene was added to the reaction mixture, and the suspension was The resulting filtrate was washed with water and filtered through silica gel, alumina, and celite. The suspension was then washed with Florisil, alumina, and silica gel. The filtrate was concentrated and mixed with acetone and methanol. After adding the compound and applying ultrasonic waves, recrystallization was performed to obtain the target white powder with a yield of 1.5 g. The rate was 82%.

[0450] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.34, 3-(4-bromophenyl)-9-phenyl -9H-carbazole is 0.46, and 4-(1-naphthyl)diphenylamine is 0.25 It was.

[0451] The compound obtained in step 3 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The 1 H NMR chart is shown in Figure 47. The carbazole derivative of the present invention, PCBANB (abbreviation: PCBANB), represented by the above structural formula (343), ) was found to be obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm )=7.07 (t, J=6.6Hz, 1H), 7.25-7.67 (m, 2 6H), 7.84 (d, J=7.8Hz, 1H), 7.89-7.92 (m , 1H), 8.03-8.07 (m, 1H), 8.18 (d, J=7.8 Hz, 1H), 8.35 (d, J=0.9Hz, 1H).

[0452] In addition, the absorption spectrum of PCBANB (abbreviation) (measurement range 200nm to 800nm) The absorption peak on the long wavelength side was observed around 335 nm in the case of the toluene solution, In the case of thin films, it was observed around 341 nm.

[0453] In addition, the emission spectrum of PCBANB (abbreviation) (measurement range 370nm to 550nm) The maximum emission wavelength was 410 nm (excitation wavelength 345 nm) in the case of a toluene solution. In the case of the thin film, it was 433 nm (excitation wavelength 341 nm).

[0454] The methods for measuring the absorption spectrum and emission spectrum are the same as those in Example 1, so the explanation will be omitted. will be omitted.

[0455] In addition, the thin film was measured in air by photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of CBANB (abbreviation) was -5.44 eV. The Tauc plot showed that the absorption edge was 3.25 eV. The gap is estimated to be 3.25 eV, which means that the PCBANB (abbreviation) LUMO level is - This means that the electron energy is 2.19 eV.

[0456] In addition, the oxidation-reduction reaction characteristics of PCBANB (abbreviation) were analyzed by cyclic voltammetry (CV The measurement method was the same as in Example 1, so the explanation will be omitted. .

[0457] By the same calculation as in Example 1, the HOMO level of PCBANB (abbreviation) is = -5.44 It was also found that the oxidation peak was at a similar value even after 100 cycles. This indicates that the compound exhibits good properties in the repeated oxidation-reduction cycle between the oxidized and neutral states. I found out that...

[0458] In addition, the glass transition temperature of PCBANB (abbreviation) was measured using a differential scanning calorimeter (DS C:Differential Scanning Calorimetry) The measurement was carried out using a Pyris1 DSC (manufactured by Nelmer). The transition temperature was found to be 115°C. Thus, PCBANB (abbreviation) has a high The crystal transition temperature is high and the material has good heat resistance. It was found that the substance does not exist and is difficult to crystallize.

[0459] In addition, similarly to Example 5, the carbazole derivative P of the present invention synthesized in Example 8 was FIG. 1 shows the measurement results of the device characteristics of a light-emitting element 6 formed using CBANB (abbreviation) as a hole transport layer. 56, 57, 58, and 59. Compared with the NPB of the light-emitting element 1, It was found that the hole transport material of the present invention of Example 6 exhibited a low driving voltage. The light-emitting element 1 was formed by dissolving 4,4'-bis[ Formed using N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB) did.

[0460] In addition, in the light-emitting element 6, the emission spectrum shown in FIG. 59 indicates that the blue light-emitting material PCB The emission wavelength originating from APA was observed, but the emission wavelength originating from the hole transport material was not observed. Therefore, the hole transport material of the present invention has a good carrier balance in the structure of the light-emitting element 6. It was found that this was achieved.

[0461] Regarding the light-emitting element 6, the initial luminance is set to 1000 cd / m 2 As a result, continuous constant current drive The results of the continuous lighting test are shown in Figure 60 (the vertical axis is 1000 cd / m 2 was set to 100% The results in Figure 60 show that the light-emitting element has a longer life than Light-emitting element 1. Therefore, by applying the present invention, a light emitting element with a long life can be obtained. [Example]

[0462] In Example 9, 4, which is a carbazole derivative of the present invention represented by structural formula (229), 4'-Di(1-naphthyl)-4''-(9-phenyl-9H-carbazol-3-yl) A method for synthesizing triphenylamine (abbreviated as PCBNBB) will be specifically described.

[0463] [ka] Step 1: Synthesis of 4,4'-dibromotriphenylamine

[0464] The synthesis scheme of 4,4'-dibromotriphenylamine in Step 1 is shown below (K -1).

[0465] [ka] 12 g (50 mmol) of triphenylamine was dissolved in acetic acid in a 500 mL Erlenmeyer flask. After dissolving in 250 mL of a mixed solvent, N-bromosuccinimide (NB 18 g (100 mmol) of HCl was added and stirred at room temperature for 24 hours. The mixture was washed with water, and magnesium sulfate was added to remove moisture. The mixture was filtered. The obtained filtrate was concentrated to dryness to obtain 20 g of a white solid, which was the target substance, in a yield of 99%.

[0466] [Step 2: Synthesis of 4,4'-di(1-naphthyl)triphenylamine]

[0467] Step 2: Synthesis of 4,4'-di(1-naphthyl)triphenylamine is shown below in (K-2).

[0468] [ka]

[0469] 4,4'-Dibromotriphenylamine 6.0g (15mmol), 1-naphthalene 5.2 g (30 mmol) of boronic acid and 2.0 mg (0.01 mmol), tri(o-tolyl)phosphine 6.0 mg (0.02 mmol), 100 To this mixture, add 20 mL of toluene, 5 mL of ethanol, and 2 mL of 20 mL of 1 / L potassium carbonate aqueous solution was added, and the mixture was degassed under reduced pressure while stirring. Thereafter, the mixture was heated and stirred at 90°C for 4.5 hours under a nitrogen atmosphere to allow the reaction to proceed.

[0470] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added to reduce the moisture content. The suspension was filtered through Florisil, alumina, silica gel, and Celite. The filtrate was concentrated, methanol was added, and the mixture was sonicated. Upon crystallization, 6.4 g of the target white powder was obtained in a yield of 86%.

[0471] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.53, and 4,4'-dibromotriphenylamine was 0. It was .69.

[0472] Step 3: Synthesis of 4-bromo-4',4''-di(1-naphthyl)triphenylamine ]

[0473] 4-Bromo-4',4''-di(1-naphthyl)triphenylamine in Step 3 The synthesis scheme of the compound is shown in (K-3) below.

[0474] [ka]

[0475] 6.4 g (13 mmol) of 4,4'-di-(1-naphthyl)triphenylamine was added to 3 After dissolving in 150 mL of ethyl acetate in a 0.0 mL Erlenmeyer flask, N-bromo 2.3 g (13 mmol) of NBS was added and stirred at room temperature for 24 hours. After the reaction was completed, the mixture was washed with water, and magnesium sulfate was added to remove moisture. This mixture was filtered, and the resulting filtrate was concentrated. Methanol was added to the filtrate, and the mixture was then sonicated. After that, the mixture was recrystallized and then purified by silica gel column chromatography (developing solvent: toluene). The target product was purified with a solvent (hexane = 1:5) to give a white powder in an amount of 1.6 g and a yield of 22. Obtained in %.

[0476] [Step 4: 4,4'-di(1-naphthyl)-4''-(9-phenyl-9H-carbamoyl) Synthesis of PCBNBB

[0477] Step 4: 4,4'-di(1-naphthyl)-4''-(9-phenyl-9H- The synthesis scheme of (carbazol-3-yl)triphenylamine is shown in (K-4) below.

[0478] [ka]

[0479] 1.4 g (2. 5mmol), 0.7g (2 0.5 mmol), palladium(II) acetate 4.0 mg (0.02 mmol), tri(o 6.0 mg (0.02 mmol) of 2-tolylphosphine was placed in a 50 mL three-neck flask. To this mixture, 20 mL of toluene, 5 mL of ethanol, and 2 mol / L aqueous potassium carbonate solution were added. The mixture was degassed under reduced pressure while stirring, and then placed under a nitrogen atmosphere. The mixture was heated and stirred at 90°C for 6.5 hours to react.

[0480] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added to reduce the moisture content. The suspension was filtered through Florisil, alumina, silica gel, and Celite. The filtrate was concentrated and purified by silica gel column chromatography (developing solvent). The solvent was toluene:hexane (1:4). The obtained fraction was concentrated. After adding methanol and applying ultrasonic waves, the product was recrystallized to obtain a white powder. Obtained 0.04g, 22% yield.

[0481] The compound obtained in step 4 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The 1 H NMR chart is shown in Figure 48. The carbazole derivative of the present invention, PCBNBB (abbreviation: ) was found to be obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm )=7.28-7.72 (m, 30H), 7.85 (d, J=7.8Hz, 2H), 7.90-7.93 (m, 2H), 8.06-8.09 (m, 2H) ), 8.19 (d, J=7.5Hz, 1H), 8.38 (d, J=1.5 Hz, 1H).

[0482] In addition, the absorption spectrum (measurement range 200nm to 800nm) of PCBNBB (abbreviation) The absorption peak on the long wavelength side was observed around 345 nm in the case of the toluene solution, In the case of thin films, it was observed around 355 nm.

[0483] In addition, the emission spectrum of PCBNBB (abbreviation) (measurement range 370nm to 550nm) The maximum emission wavelength was 413 nm (excitation wavelength 355 nm) in the case of toluene solution. In the case of the thin film, it was 428 nm (excitation wavelength 370 nm).

[0484] The methods for measuring the absorption spectrum and emission spectrum are the same as those in Example 1, so the explanation will be omitted. will be omitted.

[0485] In addition, the thin film was measured in air by photoelectron spectroscopy (Riken Keiki, AC-2). The CBNBB (abbreviation) HOMO level was -5.46 eV. From the auc plot, the absorption edge was 3.15 eV. The LUMO level of PCBNBB (abbreviation) is estimated to be 3.15 eV, which means that the LUMO level of PCBNBB (abbreviation) is -2 This means that the energy is 0.31eV.

[0486] In addition, the oxidation-reduction reaction characteristics of PCBNBB (abbreviation) were analyzed by cyclic voltammetry (CV The measurement method was the same as in Example 1, so the explanation will be omitted. By the same calculation as in Example 1, the HOMO level of PCBNBB (abbreviation) is = -5.43 It was also found that the oxidation peak was at a similar value even after 100 cycles. This indicates that the compound exhibits good properties in the repeated oxidation-reduction cycle between the oxidized and neutral states. I found out that...

[0487] In addition, the glass transition temperature of PCBNBB (abbreviation) was measured using a differential scanning calorimeter (DS C:Differential Scanning Calorimetry) The measurement was carried out using a Pyris1 DSC (manufactured by Nelmer). The transition temperature was found to be 136°C. Thus, PCBNBB (abbreviation) has a high gas The crystal transition temperature is high and the material has good heat resistance. It was found that the substance does not exist and is difficult to crystallize.

[0488] In addition, similarly to Example 5, the carbazole derivative P of the present invention synthesized in Example 9 was FIG. 1 shows the measurement results of the device characteristics of light-emitting element 7 formed using CBNBB (abbreviation) in the hole transport layer. 56 to 59. Compared with the NPB of the light-emitting element 1, the hole transport of the light-emitting element 7 according to the present invention is It was found that the light-emitting material exhibited a low driving voltage. 1 was formed on the hole transport layer 1512 in the same manner as in Example 5 by using 4,4'-bis[N-(1-naphthyl)- N-phenylamino]biphenyl (abbreviation: NPB).

[0489] In addition, in the light-emitting element 7, the emission spectrum shown in FIG. 59 indicates that PCB, which is a blue light-emitting material, The emission wavelength originating from APA was observed, but the emission wavelength originating from the hole transport material was not observed. Therefore, the hole transport material of the present invention has a good carrier balance in the structure of the light-emitting element 7. It was found that this was achieved.

[0490] Regarding the light-emitting element 7, the initial luminance is set to 1000 cd / m 2 As a result, continuous constant current drive The results of the continuous lighting test are shown in Figure 60 (the vertical axis is 1000 cd / m 2 was set to 100% The results in Figure 60 show that the light-emitting element has a longer life than Light-emitting element 1. Therefore, by applying the present invention, a light emitting element with a long life can be obtained. [Example]

[0491] In this Example 10, the carbazole derivative of the present invention represented by the structural formula (220) 4 -(1-naphthyl)-4'-phenyl-4''-(9-phenyl-9H-carbazole- This article explains in detail how to synthesize PCBBiNB. Reveal.

[0492] [ka] [Step 1: Synthesis of 4-phenyltriphenylamine]

[0493] The synthesis scheme of 4-phenyltriphenylamine in Step 1 is shown below (L-1). Shown below.

[0494] [ka]

[0495] 9.3 g (40 mmol) of 4-bromobiphenyl and 6.8 g (4 0mmol), sodium tert-butoxide 5.0g (50mol), bis(di 10 mg of (benzylideneacetone)palladium(0) was placed in a 300 mL three-neck flask. The atmosphere in the flask was replaced with nitrogen. 100 mL of xylene and tri(tert-butyl) 0.6 mL of t-butyl)phosphine (10 wt % hexane solution) was added.

[0496] This mixture was degassed under reduced pressure while stirring, and the atmosphere was replaced with nitrogen. After that, it was heated at 130°C for 3.5 hours. After stirring, 250 mL of toluene was added to the reaction mixture, and the suspension was passed through a pad of Celite, The resulting filtrate was washed with water and filtered through alumina and Florisil. The mixture was filtered through Celite, alumina, and Florisil. The filtrate was concentrated, and recrystallization was carried out by adding methanol and applying ultrasonic waves. The target white powder was obtained in an amount of 11 g and a yield of 89%.

[0497] Step 2: Synthesis of 4-bromo-4'-phenyltriphenylamine

[0498] Step 2: Synthesis of 4-bromo-4'-phenyltriphenylamine Shown below in (L-2).

[0499] [ka]

[0500] 6.4 g (20 mmol) of 4-phenyltriphenylamine and 250 ml of ethyl acetate 150 mL of toluene was added to a 500 mL Erlenmeyer flask and stirred. 3.6 g (20 mmol) of succinimide (NBS) was added and the mixture was stirred for 27.5 hours. The resulting suspension was washed with water and then dehydrated with magnesium sulfate. The mixture was concentrated to dryness to obtain 7.7 g of the target white powder in a yield of 96%.

[0501] Step 3: Synthesis of 4-(1-naphthyl)-4'-phenyltriphenylamine

[0502] Step 3: Synthesis of 4-(1-naphthyl)-4'-phenyltriphenylamine The scheme is shown below (L-3).

[0503] [ka]

[0504] 8.0 g (20 mmol) of 4-bromo-4'-phenyltriphenylamine, 1-naphthalene 3.4 g (20 mmol) of phthaleneboronic acid and 44 mg (0 0.2 mmol), tri(o-tolyl)phosphine 60 mg (0.4 mmol), 100 To this mixture, add 20 mL of toluene, 10 mL of ethanol, and 2 mL of 15 mL of 0.5% ethanol / L aqueous potassium carbonate solution was added. The mixture was degassed under reduced pressure with stirring. After evaporating, the mixture was heated and stirred at 90°C for 2.5 hours under a nitrogen atmosphere to allow the reaction to proceed.

[0505] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added. The suspension was then mixed with Florisil, alumina, silica gel, and Celite to remove water. The filtrate was concentrated, methanol was added, and the mixture was sonicated. Thereafter, recrystallization was carried out to obtain 8.6 g of the target white powder in a yield of 97%.

[0506] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.43, 4-bromo-4'-phenyltriphenylamine. Min was 0.50.

[0507] [Step 4: 4-Bromo-4'-(1-naphthyl)-4''-phenyl-triphenyl Synthesis of amines]

[0508] Step 4: 4-Bromo-4'-(1-naphthyl)-4''-phenyl-trifluoromethyl The synthesis scheme of phenylamine is shown below (L-4).

[0509] [ka]

[0510] 8.6 g (19 mmol) of 4-(1-naphthyl)-4'-phenyltriphenylamine ) was dissolved in 150 mL of ethyl acetate in a 300 mL Erlenmeyer flask, and then N-bromo Add 3.4 g (19 mmol) of NBS (Non-Succinimide) and leave at room temperature for 24 hours. After the reaction was completed, the mixture was washed with water and magnesium sulfate was added to remove moisture. The mixture was filtered, and the resulting filtrate was concentrated and purified by silica gel column chromatography. The resulting fraction was purified by elution with a developing solvent of toluene and hexane (1:4). The solution was concentrated, methanol was added, and the mixture was subjected to ultrasonic waves. When the solution was recrystallized, the target white A colored powder was obtained in an amount of 8.1 g and a yield of 80%.

[0511] [Step 5: 4-(1-naphthyl)-4'-phenyl-4''-(9-phenyl-9H Synthesis of (-carbazol-3-yl)triphenylamine (abbreviation: PCBBiNB)

[0512] Step 5: 4-(1-naphthyl)-4'-phenyl-4''-(9-phenyl The synthesis scheme of (9H-carbazol-3-yl)triphenylamine is shown below (L-5). Shown below.

[0513] [ka]

[0514] 4-Bromo-4'-(1-naphthyl)-4' '-phenyl-triphenylamine 0.6g (3.0mmol) 9-phenyl-9H-carbazol-3-yl-boronic acid 0.9 g (3.0 mmol) of palladium(II) acetate, 12 mg (0.06 mmol) 36 mg (0.12 mmol) of tri(o-tolyl)phosphine was added to a 50 mL three-neck flask. Add 15 mL of toluene, 15 mL of ethanol, and 2 mol / L calcium carbonate to this mixture. 3 mL of an aqueous sodium solution was added. The mixture was degassed under reduced pressure while stirring, and then The mixture was heated and stirred at 90°C under atmospheric pressure for 2 hours to allow the reaction to proceed.

[0515] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added. The suspension was then mixed with Florisil, alumina, silica gel, and Celite to remove water. The filtrate was concentrated and purified by silica gel column chromatography. The resulting fraction was purified by elution with a developing solvent of toluene and hexane (1:4). The solution was concentrated, acetone and methanol were added, and the mixture was sonicated. The target product, a white powder, was obtained in an amount of 0.9 g and a yield of 44%.

[0516] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.26, 4-bromo-4'-(1-naphthyl)-4' '-Phenyltriphenylamine was 0.45.

[0517] The compound obtained in step 5 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1The 1 H NMR chart is shown in Figure 49. PCBBiNB (abbreviated as PCBBiNB), a carbazole derivative of the present invention represented by the above structural formula (220), It was found that the name was obtained. 1 H NMR (CDCl3, 300 MHz): δ (pp m)=7.27-7.69 (m, 31H), 7.84 (d, J=7.8Hz, 1H), 7.89-7.92 (m, 1H), 8.04-8.08 (m, 1 H), 8.18 (d, J=7.8Hz, 1H), 8.36 (d, J=1. 5Hz 1H).

[0518] Also, the absorption spectrum of PCBBiNB (abbreviation) (measurement range 200nm to 800nm) The absorption peak on the long wavelength side was observed around 342 nm in the case of the toluene solution. In the case of thin films, it was observed around 351 nm.

[0519] Also, the emission spectrum of PCBBiNB (abbreviation) (measurement range 370nm to 550nm) The maximum emission wavelength was 409 nm (excitation wavelength 355 nm) in the case of a toluene solution. In the case of the thin film, it was 433 nm (excitation wavelength 336 nm).

[0520] The methods for measuring the absorption spectrum and emission spectrum are the same as those in Example 1, so the explanation will be omitted. will be omitted.

[0521] In addition, the thin film was measured in air by photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of CBBiNB (abbreviation) was -5.35 eV. The Tauc plot showed that the absorption edge was 3.18 eV. The gap is estimated to be 3.18 eV, which means that the LUMO level of PCBBiNB (abbreviation) is This means that the energy is -2.17 eV.

[0522] In addition, the redox reaction properties of PCBBiNB (abbreviation) were investigated by cyclic voltammetry (C V) Measurement was carried out. The measurement method was the same as in Example 1, so the explanation will be omitted. do.

[0523] By the same calculation as in Example 1, the HOMO level of PCBBiNB (abbreviation) is = -5.4 2 eV. The oxidation peak remained at the same value even after 100 cycles. This indicates that the compound exhibits good properties in the repeated oxidation-reduction cycle between the oxidized and neutral states. I found out that...

[0524] In addition, the glass transition temperature of PCBBiNB (abbreviation) was measured using a differential scanning calorimeter (D SC:Differential Scanning Calorimetry The measurement was carried out using a KinElmer Pyris1 DSC. The transition temperature was found to be 143°C. Thus, PCBBiNB (abbreviation) has a high It exhibits a low glass transition temperature and good heat resistance. It was found that the substance was difficult to crystallize.

[0525] In addition, similarly to Example 5, the carbazole derivative of the present invention synthesized in Example 10 The device characteristics of light-emitting device 8 formed using PCBBiNB (abbreviation) as the hole transport layer were measured. The results are shown in FIGS. 56 to 59. It was found that the hole transport material of the present invention exhibits a low driving voltage. The light-emitting element 1 was formed by the same method as in Example 5, except that the hole transport layer 1512 was formed of 4,4'-bis[N-(1 -naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB).

[0526] In addition, in the light-emitting element 8, the emission spectrum shown in FIG. 59 indicates that the blue light-emitting material PCB The emission wavelength originating from APA was observed, but the emission wavelength originating from the hole transport material was not observed. Therefore, the hole transport material of the present invention has a good carrier balance in the structure of the light-emitting element 8. It was found that this was achieved.

[0527] Regarding the light-emitting element 8, the initial luminance is set to 1000 cd / m 2 As a result, continuous constant current drive The results of the continuous lighting test are shown in Figure 60 (the vertical axis is 1000 cd / m 2 was set to 100% The results in Figure 60 show that the light-emitting element has a longer life than Light-emitting element 1. Therefore, by applying the present invention, a light emitting element with a long life can be obtained.

[0528] Furthermore, in the structure of the light-emitting element 8 shown in this example, when the first layer 1511 is formed, Instead of NPB (abbreviation) used in the previous study, PCBBiNB (abbreviation) was used, and molybdenum oxide (VI The efficiency of the light-emitting element in which the first layer 1511 was formed by co-evaporation with ZnO) was about 1000 cd / m 2 To In Example 10, the driving voltage and reliability of the NPB and molybdenum (VI) oxide were The co-evaporated film was used as the hole injection layer and PCBBiNB (abbreviation) was used as the hole transport layer. A good value equivalent to that of optical element 8 was obtained (luminance 1062 cd / at a driving voltage of 4.2 V). m 2 The current value was 0.75mA, and the brightness remained at 81% of the initial brightness after 350 hours of operation. there was).

[0529] In this way, PCBBiNB (abbreviation) is composed of a first layer 1511 which is a hole injection layer and a It is a good material that can be used simultaneously for both the second layer 1512, which is a hole transport layer. This has made it easier to fabricate the device and improved the efficiency of material utilization. This was possible. [Example]

[0530] In this Example 11, a carbazole derivative of the present invention represented by structural formula (355) [ 4'-(1-naphthyl)biphenyl-4-yl](phenyl)[4-(9-phenyl-9 Regarding the synthesis of H-carbazol-3-ylphenyl]amine (abbreviation: PCBANT) This will be explained in detail.

[0531] [ka]

[0532] Step 1: Synthesis of 4-(4-bromophenyl)-4'-phenyl-triphenylamine ]

[0533] 4-(4-bromophenyl)-4'-phenyl-triphenylamine in Step 1 The synthesis scheme of the compound is shown in (M-1) below.

[0534] [ka]

[0535] 22 g (70 mmol) of 4,4'-dibromobiphenyl and 8.5 g of diphenylamine g (50 mmol), 1.9 g (10 mmol) of copper(I) iodide, 18-crown-6 - 2.6g (10mmol) of ether, 6.9g (50mmol) of potassium carbonate, 1 ,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (abbreviation: D MPU) was placed in 50 mL and 500 mL three-neck flasks and heated at 180°C for 37 hours under a nitrogen atmosphere. The mixture was stirred for a while.

[0536] After the reaction, 500 mL of toluene was added to the reaction mixture, and the suspension was filtered with Florisil, The mixture was filtered through silica gel and Celite. The filtrate was washed with water and added magnesium sulfate. The suspension was then washed with Florisil, alumina, silica gel, and Celite. The filtrate was concentrated and purified by silica gel column chromatography. The resulting fraction was purified using a developing solvent of toluene and hexane (1:4). The solution was concentrated, hexane and methanol were added, and after ultrasonic treatment, recrystallization was achieved. The target substance, a white powder, was obtained in an amount of 5.3 g and a yield of 27%.

[0537] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The yield of the target compound was 0.5 and that of 4,4'-dibromobiphenyl was 0.59. Ta.

[0538] Step 2: Synthesis of [4'-(1-naphthyl)biphenyl-4-yl]diphenylamine ]

[0539] [4'-(1-naphthyl)biphenyl-4-yl]diphenylamine in Step 2 The synthesis scheme of the compound is shown in (M-2) below.

[0540] [ka]

[0541] 4.0 g (10 1.7 g (10 mmol) of 1-naphthaleneboronic acid, palladium acetate (I I) 11 mg (0.05 mmol), tri(o-tolyl)phosphine 15 mg (0. 05mmol) into a 100mL three-neck flask, and add 20mL of toluene and ethanol to the mixture. 5 mL of ethanol and 10 mL of 2 mol / L potassium carbonate aqueous solution were added. After degassing while stirring under pressure, the mixture was heated and stirred at 90°C for 7 hours under a nitrogen atmosphere to allow the reaction to proceed. Ta.

[0542] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The resulting filtrate was washed with water and magnesium sulfate was added. The suspension was filtered through silica gel, alumina, and celite. The obtained filtrate was concentrated, methanol was added, and the mixture was subjected to ultrasonic irradiation, followed by recrystallization. As a result, 3.6 g of the target white powder was obtained in a yield of 80%.

[0543] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.58, 4-bromophenyl-4'-phenyl-trimethyl-4-methyl-2-propanol. Phenylamine was 0.65.

[0544] [Step 3: (4-Bromophenyl)[4'-(1-naphthyl)biphenyl-4-yl ]Synthesis of phenylamine]

[0545] Step 3: (4-bromophenyl)[4'-(1-naphthyl)biphenyl-4 The synthesis scheme of [-yl]phenylamine is shown below in (M-3).

[0546] [ka]

[0547] 3.6 g (8. 0 mmol) was dissolved in 100 mL of ethyl acetate in a 200 mL Erlenmeyer flask, and then Add 1.4 g (8.0 mmol) of N-bromosuccinimide (abbreviation: NBS) to the After the reaction was completed, the mixture was washed with water and magnesium sulfate was added. The mixture was filtered, and the filtrate was concentrated. After adding the compound and applying ultrasonic waves, recrystallization was performed to obtain the target white powder with a yield of 3.9 g. The success rate was 93%.

[0548] [Step 4: [4'-(1-naphthyl)biphenyl-4-yl](phenyl)[4-( 9-phenyl-9H-carbazol-3-yl)phenyl]amine (abbreviation; PCBANT) ) synthesis]

[0549] In step 4, [4'-(1-naphthyl)biphenyl-4-yl](phenyl)[ Synthesis scheme of 4-(9-phenyl-9H-carbazol-3-yl)phenyl]amine is shown below in (M-4).

[0550] [ka]

[0551] (4-Bromophenyl)[4'-(1-naphthyl)biphenyl-4-yl]phenyl 1.6 g (3 mmol) of amine and 0 g of 9-phenyl-9H-carbazole-3-boronic acid 0.8g (3mmol), palladium(II) acetate 6.0mg (0.03mmol), 18 mg (0.03 mmol) of tri(o-tolyl)phosphine in a 100 mL three-neck flask To this mixture, add 20 mL of toluene, 5 mL of ethanol, and 2 mol / L potassium carbonate. The mixture was degassed under reduced pressure while stirring, and then resuspended in a nitrogen atmosphere. The mixture was heated and stirred at 80°C under atmospheric pressure for 6.5 hours to allow the reaction to proceed.

[0552] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added. The suspension was filtered through Florisil, alumina, and celite. The filtrate was concentrated and purified by silica gel column chromatography (developing solvent). The solvent was toluene:hexane (1:4). The obtained fraction was concentrated. After adding methanol and applying ultrasonic waves, the product was recrystallized to obtain a white powder. Obtained 1.2 g, 60% yield.

[0553] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.28, (4-bromophenyl) [4'-(1-naphthyl)-2-methyl-2-propanol]. The α-tolyl)biphenyl-4-yl]phenylamine was 0.42.

[0554] The compound obtained in step 4 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The H NMR chart is shown in Figure 50. The carbazole derivative of the present invention, PCBANT (abbreviation: PCBANT), represented by the above structural formula (355), ) was found to be obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm )=7.08 (t, J=7.5Hz, 1H), 7.20-7.73 (m, 3 0H), 7.87 (d, J=8.1Hz, 1H), 7.92 (d, J=7 .2Hz, 1H), 8.00 (d, J=8.4Hz, 1H), 8.19 ( d, J=7.8Hz, 1H), 8.35 (d, J=1.8Hz, 1H).

[0555] The molecular weight of the above compound was measured using a TOF-MS detector (Waters Microwave Oscilloscope, manufactured by Waters Corporation). The measurement was carried out using a 0.1% acetonitrile and 0.1% A mixture of formic acid and water (mixing ratio 80 / 20 vol / vol) was used as the solvent. The main peak at molecular weight 689.30 (mode ES+) was detected, and the target P It was confirmed that CBANT (abbreviation) was obtained.

[0556] In addition, the absorption spectrum of PCBANT (abbreviation) (measurement range 200nm to 800nm) The absorption peak on the long wavelength side was observed around 342 nm in the case of the toluene solution, In the case of thin films, it was observed around 351 nm.

[0557] In addition, the emission spectrum of PCBANT (abbreviation) (measurement range 370nm to 550nm) The maximum emission wavelength was 414 nm (excitation wavelength 355 nm) in the case of a toluene solution. In the case of the thin film, it was 342 nm (excitation wavelength 365 nm). The methods for measuring the absorption spectrum and emission spectrum are the same as those in Example 1, so the explanation will be omitted. will be omitted.

[0558] In addition, the thin film was measured in air by photoelectron spectroscopy (Riken Keiki, AC-2). The CBANT (abbreviation) HOMO level was -5.38 eV. From the auc plot, the absorption edge was 3.11 eV. The LUMO level of PCBANT is estimated to be 3.11 eV, which means that the LUMO level of PCBANT is -2 This means that the energy is 0.27eV.

[0559] In addition, the oxidation-reduction reaction characteristics of PCBANT (abbreviation) were investigated by cyclic voltammetry (CV The measurement method was the same as in Example 1, so the explanation will be omitted. .

[0560] By the same calculation as in Example 1, the HOMO level of PCBANT (abbreviation) is = -5.43 It was also found that the oxidation peak was at a similar value even after 100 cycles. This indicates that the compound exhibits good properties in the repeated oxidation-reduction cycle between the oxidized and neutral states. I found out that...

[0561] In addition, the glass transition temperature of PCBANT (abbreviation) was measured using a differential scanning calorimeter (DS C:Differential Scanning Calorimetry) The measurement was carried out using a Pyris1 DSC (manufactured by Nelmer). The transition temperature was found to be 131°C. Thus, PCBANT (abbreviation) is a high The crystal transition temperature is high and the material has good heat resistance. It was found that the substance does not exist and is difficult to crystallize.

[0562] As in Example 5, PCBANT (abbreviation) synthesized in Example 11 was used as the hole transport layer. The efficiency of the light-emitting device formed using 2 The driving voltage in Example In 10, a good value equivalent to that of the light-emitting element 8 formed using PCBBiNB (abbreviation) was obtained. (When the driving voltage is 4.0V, the luminance is 1186cd / m 2 , the current value is 0.73mA After 180 hours of operation, the brightness remained at 65% of the initial brightness. [Example]

[0563] In this Example 12, a carbazole derivative of the present invention, 4- [9-(biphenyl-4-yl)-9H-carbazol-3-yl]-4'-phenyl- A method for synthesizing triphenylamine (abbreviation: BCBA1BP) will be specifically described.

[0564] [ka]

[0565] Step 1: Synthesis of 9-(biphenyl-4-yl)-9H-carbazole

[0566] Step 1: Synthesis of 9-(biphenyl-4-yl)-9H-carbazole The system is shown below (N-1).

[0567] [ka] 12 g (50 mmol) of 4-bromobiphenyl and 8.4 g (50 mmol) of carbazole ol), 230 mg (1 mmol) of palladium acetate (abbreviation: Pd(OAc)(II)) 1.8 g (3 0mmol), 13g (180mmol) of sodium tert-butoxide in 20 The mixture was placed in a 0 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. 80 mL of silane was added, and the mixture was degassed under reduced pressure with stirring, and then heated under a nitrogen atmosphere. The mixture was heated and stirred at 120°C for 7.5 hours to carry out the reaction.

[0568] After the reaction was completed, about 600 mL of warm toluene was added to the suspension, and the mixture was separated into Florisil, The filtrate was filtered twice through alumina and celite. In addition, recrystallization was carried out, and the target substance, a white powder, was obtained in an amount of 14 g and a yield of 87%.

[0569] Step 2: Synthesis of 9-(biphenyl-4-yl)-3-bromo-9H-carbazole Law]

[0570] 9-(biphenyl-4-yl)-3-bromo-9H-carbazole in Step 2 The synthesis scheme is shown in (N-2) below.

[0571] [ka] 3.1 g (10 mmol) of 9-(biphenyl-4-yl)-9H-carbazole, 2 In a 100 mL Erlenmeyer flask, dissolve 100 mL of chloroform, then add N-bromo Add 1.8 g (10 mmol) of succinimide (abbreviation: NBS) and leave at room temperature for 24 hours. After the reaction was completed, the mixture was washed with water and magnesium sulfate was added to remove moisture. This mixture was filtered, and the resulting filtrate was concentrated to dryness, yielding the target white powder. The compound was obtained in an amount of 3.7 g and a yield of 95%.

[0572] Step 3: [9-(biphenyl-4-yl)-9H-carbazol-3-yl]boro Synthesis of phosphate

[0573] Step 3: [9-(biphenyl-4-yl)-9H-carbazol-3-yl] The synthesis scheme of boronic acid is shown below in (N-3).

[0574] [ka]

[0575] 8.0 g (20 mmol) of 9-(4-biphenyl)-3-bromo-9H-carbazole ), and place it in a 500 mL three-neck flask. After replacing the atmosphere in the flask with nitrogen, add tetrahydrofuran. 200 mL of THF was added and the temperature was adjusted to -78°C. 16 mL (24 mmol) of 1 / L n-butyllithium hexane solution was added dropwise and the mixture was stirred for 2 hours. To this mixture was added 4.0 mL (40 mmol) of trimethyl borate, and the mixture was heated to -78°C. The mixture was stirred at room temperature for 2 hours and then at room temperature for 18 hours. After the reaction, 50 mL of 1 M diluted hydrochloric acid was added to the reaction solution. The mixture was stirred for 3 hours, extracted with toluene, and the resulting organic layer was washed with saturated saline. After washing, magnesium sulfate was added to the organic layer to remove water. The filtrate was concentrated, hexane was added, and ultrasonic waves were applied to it. After recrystallization, the target compound was obtained. A white powder was obtained in an amount of 6.6 g and a yield of 91%.

[0576] [Step 4: 4-[9-(biphenyl-4-yl)-9H-carbazol-3-yl] Synthesis of 4'-phenyl-triphenylamine (abbreviation: BCBA1BP)

[0577] Step 4: 4-[9-(biphenyl-4-yl)-9H-carbazole-3- The synthesis scheme of [4'-phenyl-1yl]-4'-phenyl-triphenylamine is shown below in (N-4).

[0578] [ka]

[0579] 1.2 g (3.0 mmol) of 4-bromo-4'-phenyl-triphenylamine, [ 1.1 g (9-(biphenyl-4-yl)-9H-carbazol-3-yl)boronic acid 3.0 mmol), palladium(II) acetate 6.0 mg (0.03 mmol), tri( 18 mg (0.06 mmol) of o-tolylphosphine was placed in a 50 mL three-neck flask. To this mixture, 20 mL of toluene, 5 mL of ethanol, and 2 mol / L aqueous potassium carbonate solution were added. The mixture was degassed under reduced pressure while stirring, and then heated under a nitrogen atmosphere. The mixture was heated and stirred at 90°C for 6.5 hours to carry out the reaction.

[0580] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added to reduce the moisture content. The suspension was filtered through Florisil, alumina, silica gel, and Celite. The filtrate was concentrated, and acetone and methanol were added and the mixture was sonicated. After that, recrystallization gave 1.5 g of the target white powder in a yield of 79%.

[0581] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.45, 4-bromo-4'-phenyl-triphenyl Amin was 0.68.

[0582] The compound obtained in step 4 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The 1 H NMR chart is shown in Figure 51. BCBA1BP (abbreviation), which is a carbazole derivative of the present invention represented by the above structural formula 63, It was found that it was obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm) = 7.06 (t, J=7.2Hz, 1H), 7.20-7.72 (m, 29H ), 7.83 (d, J=8.4Hz, 2H), 8.19 (d, J=7.8 Hz, 1H), 8.35 (s, 1H).

[0583] The molecular weight of the above compound was measured using a TOF-MS detector (Waters Microwave Oscilloscope, manufactured by Waters Corporation). The measurement was carried out using a 0.1% acetonitrile and 0.1% A mixture of formic acid and water (mixing ratio 80 / 20 vol / vol) was used as the solvent. The main peak at molecular weight 638.27 (mode ES+) was detected, and the target compound B It was confirmed that CBA1BP (abbreviation) was obtained.

[0584] Also, the absorption spectrum of BCBA1BP (abbreviation) (measurement range 200nm to 800nm) The absorption peak on the long wavelength side was observed around 336 nm in the case of the toluene solution. In the case of thin films, it was observed around 342 nm.

[0585] Also, the emission spectrum of BCBA1BP (abbreviation) (measurement range 370nm to 550nm) The maximum emission wavelength was 394 nm (excitation wavelength 350 nm) in the case of a toluene solution. In the case of thin films, it was 408 nm (excitation wavelength 301 nm). The methods for measuring the absorption spectrum and emission spectrum are the same as those in Example 1, so the explanation will be omitted. will be omitted.

[0586] In addition, the thin film was measured in air using photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of CBA1BP (abbreviation) was -5.48 eV. The Tauc plot showed that the absorption edge was 3.19 eV. The gap is estimated to be 3.19 eV, which means that the LUMO level of BCBA1BP (abbreviation) is This means that the energy is -2.29 eV.

[0587] In addition, the redox reaction characteristics of BCBA1BP (abbreviation) were analyzed by cyclic voltammetry (C V) Measurement was carried out. The measurement method was the same as in Example 1, so the explanation will be omitted. do.

[0588] By the same calculation as in Example 1, the HOMO level of BCBA1BP (abbreviation) is = -5.4 3 eV. The oxidation peak remained at the same value even after 100 cycles. This indicates that the compound exhibits good properties in the repeated oxidation-reduction cycle between the oxidized and neutral states. I found out that...

[0589] In addition, the glass transition temperature of BCBA1BP (abbreviation) was measured using a differential scanning calorimeter (D SC:Differential Scanning Calorimetry The measurement was carried out using a KinElmer Pyris1 DSC. The transition temperature was found to be 122°C. It exhibits a low glass transition temperature and good heat resistance. It was found that the substance was difficult to crystallize.

[0590] In the same manner as in Example 5, BCBA1BP (abbreviation) synthesized in Example 12 was used as a hole transport layer. The efficiency of the light-emitting device formed using 2 Drive voltage and reliability The result is as good as that of the light-emitting element 8 formed using PCBBiNB (abbreviation) in Example 10. A good value was obtained (luminance 1031 cd / m when the driving voltage was 4.0 V). 2 , the current value is 0. 72mA, and maintained 89% of the initial brightness after 180 hours of operation). [Example]

[0591] In this Example 13, a carbazole derivative of the present invention represented by structural formula (364) was prepared using 4-[ 9-(biphenyl-4-yl)-9H-carbazol-3-yl]-4'-(1-naphthyl) A method for synthesizing BCBANB (C1)triphenylamine (abbreviation: BCBANB) will be specifically described.

[0592] [ka]

[0593] [Step 1: Synthesis of 4-bromotriphenylamine]

[0594] The synthesis scheme of 4-bromotriphenylamine in Step 1 is shown below (O-1). show.

[0595] [ka]

[0596] In a 1.5 L ethyl acetate solution of 54.0 g (220 mmol) of triphenylamine, 35.6 g (200 mmol) of bromosuccinimide (NBS) was added and stirred for 24 hours. The resulting suspension was concentrated to 1 L and then washed with 1 L of a 5% aqueous sodium acetate solution. After washing, the solution was further concentrated to about 50 mL and methanol was added to precipitate the product. The resulting precipitate was collected by filtration and dried to obtain 46.5 g of the target white powder in a yield of 73%. .

[0597] [Step 2: Synthesis of 4-(1-naphthyl)triphenylamine]

[0598] The synthesis scheme of 4-(1-naphthyl)triphenylamine in Step 2 is shown below ( O-2).

[0599] [ka]

[0600] 9.7 g (30 mmol) of 4-bromotriphenylamine, 1-naphthaleneboronic acid 5.7 g (33 mmol), 67 mg (0.3 mmol) of palladium (II) acetate, Add 91 g (0.3 mmol) of tri(o-tolyl)phosphine to a 200 mL three-neck flask. To this mixture, add 50 mL of toluene, 20 mL of ethanol, and 2 mol / L potassium carbonate. 20 mL of an aqueous solution of ethanol was added to the mixture. The mixture was degassed under reduced pressure while stirring, and then heated under a nitrogen atmosphere. The mixture was heated and stirred at 90°C for 2 hours to carry out the reaction.

[0601] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was filtered through silica gel and celite. After drying, the suspension was washed with water, dried with magnesium sulfate, and The filtrate was obtained by filtering through lumina, silica gel, and celite. The obtained filtrate was concentrated and dried. The target pale yellow solid was obtained in an amount of 11 g and a yield of 99%.

[0602] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.48 and 4-bromotriphenylamine was 0.55. It was. The compound obtained in step 2 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data are shown below. From the measurement results, it is confirmed that the compound of the present invention represented by the above structural formula 364 It was found that it was obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm) = 7.07 (t, J=7.5Hz, 1H), 7.22-7.61 (m, 21H ), 7.83 (d, J=7.8Hz, 1H), 7.88-7.91 (m, 1H), 8.02-8.05 (m, 1H).

[0603] [Step 3: Synthesis of 4-bromo-4'-(1-naphthyl)triphenylamine]

[0604] Step 3: Synthesis of 4-bromo-4'-(1-naphthyl)triphenylamine The scheme is shown below (O-3).

[0605] [ka]

[0606] 11g (30mmol) of 4-(1-naphthyl)triphenylamine, 500mL After dissolving it in 300 mL of ethyl acetate in a flask, N-bromosuccinimide ( 5.3 g (30 mmol) of NBS was added and the mixture was stirred at room temperature for 168 hours. After completion of the reaction, the mixture was washed with water and magnesium sulfate was added to remove the moisture. The liquid was filtered, and the resulting filtrate was concentrated and purified by silica gel column chromatography (developing solvent The resulting fraction was concentrated and purified with toluene:hexane (1:4). After adding ethanol and applying ultrasound, recrystallization was performed to obtain the desired white powder in a yield of 7. 8 g was obtained in 43% yield.

[0607] [Step 4: 4-[9-(biphenyl-4-yl)-9H-carbazol-3-yl] Synthesis of 4'-(1-naphthyl)triphenylamine (abbreviation: BCBANB)

[0608] Step 4: 4-[9-(biphenyl-4-yl)-9H-carbazole-3- The synthesis scheme of [4'-(1-naphthyl)-yl]triphenylamine is shown below in (O-4). show.

[0609] [ka]

[0610] 1.35 g (3.0 mmol) of 4-bromo-4'-(1-naphthyl)triphenylamine l), [9-(biphenyl-4-yl)-9H-carbazol-3-yl]boronic acid 1 0.1g (3.0mmol), 6.0mg (0.02mmol) of palladium(II) acetate , tri(o-tolyl)phosphine 9.0 mg (0.06 mmol), 100 mL three-neck Add 20 mL of toluene, 5 mL of ethanol, and 2 mol / L carbonate to the mixture. 3 mL of an aqueous potassium solution was added, and the mixture was degassed under reduced pressure with stirring, and then The mixture was heated and stirred at 90°C for 3 hours under nitrogen atmosphere to cause a reaction.

[0611] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added. The suspension was then mixed with Florisil, alumina, silica gel, and Celite to remove water. The filtrate was concentrated and purified by silica gel column chromatography. The resulting fraction was purified by elution with a developing solvent of toluene and hexane (1:4). The solution was concentrated, acetone and methanol were added, and the mixture was sonicated. The target product, a white powder, was obtained in an amount of 1.0 g and a yield of 50%.

[0612] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.45, 4-bromo-4'-(1-naphthyl)trifluoromethylpropional. Phenylamine was 0.66.

[0613] The compound obtained in step 4 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The 1 H NMR chart is shown in Figure 52. BCBANB (abbreviation), which is a carbazole derivative of the present invention represented by the above structural formula 364, It was found that it was obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm) = 7.08 (t, J=6.9Hz, 1H), 7.28-7.71 (m, 28H ), 7.82-7.86 (m, 3H), 7.89-7.92 (m, 1H), 8.04-8.07 (m, 1H), 8.20 (d, J=7.8Hz, 1H ), 8.37 (d, J=1.2Hz, 1H).

[0614] The molecular weight of the above compound was measured using a TOF-MS detector (Waters Microwave Oscilloscope, manufactured by Waters Corporation). The measurement was carried out using a 0.1% acetonitrile and 0.1% A mixture of formic acid and water (mixing ratio 80 / 20 vol / vol) was used as the solvent. The main peak at molecular weight 556.52 (mode ES+) was detected, and the target compound B It was confirmed that CBANB (abbreviation) was obtained.

[0615] In addition, the absorption spectrum of BCBANB (abbreviation) (measurement range 200nm to 800nm) The absorption peak on the long wavelength side was observed around 335 nm in the case of the toluene solution, In the case of thin films, it was observed around 344 nm.

[0616] In addition, the emission spectrum of BCBANB (abbreviation) (measurement range 370nm to 550nm) The maximum emission wavelength was 410 nm (excitation wavelength 345 nm) in the case of a toluene solution. In the case of the thin film, it was 422 nm (excitation wavelength 328 nm).

[0617] The methods for measuring the absorption spectrum and emission spectrum are the same as those in Example 1, so the explanation will be omitted. will be omitted.

[0618] In addition, the thin film was measured in air using photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of CBANB (abbreviation) was -5.42 eV. From the auc plot, the absorption edge was 3.19 eV. The LUMO level of BCBANB is estimated to be 3.19 eV, which means that the LUMO level of BCBANB is -2 This means that the energy is 0.23eV.

[0619] In addition, the redox reaction characteristics of BCBANB (abbreviation) were analyzed by cyclic voltammetry (CV The measurement method was the same as in Example 1, so the explanation will be omitted. .

[0620] By the same calculation as in Example 1, the HOMO level of BCBANB (abbreviation) is = -5.45 It was also found that the oxidation peak was at a similar value even after 100 cycles. This indicates that the compound exhibits good properties in the repeated oxidation-reduction cycle between the oxidized and neutral states. I found out that...

[0621] In addition, the glass transition temperature of BCBANB (abbreviation) was measured using a differential scanning calorimeter (DS C:Differential Scanning Calorimetry) The measurement was carried out using a Pyris1 DSC (manufactured by Nelmer). The transition temperature was found to be 130°C. The crystal transition temperature is high and the material has good heat resistance. It was found that the substance does not exist and is difficult to crystallize.

[0622] As in Example 5, BCBANB (abbreviation) synthesized in Example 13 was used as the hole transport layer. The efficiency of the light-emitting device formed using 2 The driving voltage in Example In 10, a good value equivalent to that of the light-emitting element 8 formed using PCBBiNB (abbreviation) was obtained. (When the driving voltage is 4.0V, the brightness is 848cd / m 2The current value is 0.52mA. (That was it.) [Example]

[0623] In this Example 14, a carbazole derivative of the present invention represented by structural formula (366) was prepared. 9-(biphenyl-4-yl)-9H-carbazol-3-yl]-4'-(1-naphthyl) Regarding the synthesis of 4''-phenyl-triphenylamine (abbreviation: BCBBiNB) This will be explained in detail.

[0624] [ka]

[0625] [Step 1: 4-[9-(biphenyl-4-yl)-9H-carbazol-3-yl] -4'-(1-naphthyl)4''-phenyl-triphenylamine (abbreviated as BCBBiN Synthesis of B)

[0626] Step 1: 4-[9-(biphenyl-4-yl)-9H-carbazole-3- Synthesis scheme of [4'-(1-naphthyl)4''-phenyl-triphenylamine is shown below (P-1).

[0627] [ka]

[0628] 4-Bromo-4'-(1-naphthyl)-4' '-phenyl-triphenylamine 0.6g (3.0mmol), [9-(biphenyl-4-yl)-9H-carbazole-3 -yl]boronic acid 1.1 g (3.0 mmol), palladium (II) acetate 6.0 mg (0.03 mmol), tri(o-tolyl)phosphine 18 mg (0.03 mmol) , put into a 100 mL three-neck flask, and add 20 mL of toluene and 5 mL of ethanol to this mixture. Then, 3 mL of a 2 mol / L aqueous solution of potassium carbonate was added. The mixture was stirred under reduced pressure. After degassing, the mixture was heated and stirred at 90°C for 6.5 hours under a nitrogen atmosphere to allow the reaction to proceed.

[0629] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added. The suspension was then mixed with Florisil, alumina, silica gel, and Celite to remove water. The filtrate was concentrated and purified by silica gel column chromatography. The resulting fraction was purified by elution with a developing solvent of toluene and hexane (1:4). The solution was concentrated, acetone and methanol were added, and the mixture was sonicated. The target product, a white powder, was obtained in an amount of 1.4 g and a yield of 60%.

[0630] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.26, 4-bromo-4'-(1-naphthyl)-4' '-phenyl-triphenylamine was 0.46.

[0631] The compound obtained in step 1 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The 1 H NMR chart is shown in Figure 53. BCBBiNB (abbreviation), which is a carbazole derivative of the present invention represented by the above structural formula 366 It was found that the following was obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm) =7.30-7.71 (m, 33H), 7.82-7.86 (m, 3H), 7.90-7.93 (m, 1H), 8.05-8.08 (m,1H), 8.2 0 (d, J=7.8Hz, 1H), 8.38 (d, J=1.5Hz, 1H ).

[0632] The molecular weight of the above compound was measured using a TOF-MS detector (Waters Microwave Oscilloscope, manufactured by Waters Corporation). The measurement was carried out using a 0.1% acetonitrile and 0.1% A mixture of formic acid and water (mixing ratio 80 / 20 vol / vol) was used as the solvent. The main peak at molecular weight 765.32 (mode ES+) was detected, and the target compound B It was confirmed that CBBiNB (abbreviation) was obtained.

[0633] Also, the absorption spectrum of BCBBiNB (abbreviation) (measurement range 200nm to 800nm) The absorption peak on the long wavelength side was observed around 342 nm in the case of the toluene solution. In the case of thin films, it was observed around 351 nm.

[0634] Also, the emission spectrum of BCBBiNB (abbreviation) (measurement range 370nm to 550nm) The maximum emission wavelength was 409 nm (excitation wavelength 355 nm) in the case of a toluene solution. In the case of the thin film, it was 433 nm (excitation wavelength 336 nm).

[0635] The methods for measuring the absorption spectrum and emission spectrum are the same as those in Example 1, so the explanation will be omitted. will be omitted.

[0636] In addition, the thin film was measured in air using photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of CBBiNB (abbreviation) was -5.35 eV. The Tauc plot showed that the absorption edge was 3.18 eV. The gap is estimated to be 3.18 eV, which means that the BCBBiNB (abbreviation) LUMO level is This means that the energy is -2.17 eV.

[0637] In addition, the redox reaction characteristics of BCBBiNB (abbreviation) were investigated by cyclic voltammetry (C V) Measurement was carried out. The measurement method was the same as in Example 1, so the explanation will be omitted. do.

[0638] By the same calculation as in Example 1, the HOMO level of BCBBiNB (abbreviation) is = -5.4 2 eV. The oxidation peak remained at the same value even after 100 cycles. This indicates that the compound exhibits good properties in the repeated oxidation-reduction cycle between the oxidized and neutral states. I found out that...

[0639] In addition, the glass transition temperature of BCBBiNB (abbreviation) was measured using a differential scanning calorimeter (D SC:Differential Scanning Calorimetry The measurement was carried out using a KinElmer Pyris1 DSC. The transition temperature was found to be 143°C. It exhibits a low glass transition temperature and good heat resistance. It was found that the substance was difficult to crystallize.

[0640] In the same manner as in Example 5, BCBBiNB (abbreviation) synthesized in Example 14 was used as a hole transport layer. The efficiency of the light-emitting device formed using 2 Drive voltage and reliability The result is as good as that of the light-emitting element 8 formed using PCBBiNB (abbreviation) in Example 10. A good value was obtained (luminance 996 cd / m when the driving voltage was 4.0 V). 2 , the current value is 0.5 9mA, and maintained 84% of the initial brightness after 180 hours of operation. [Example]

[0641] In this Example 15, a carbazole derivative of the present invention represented by structural formula (386) was prepared. 9-[4-(1-naphthyl)phenyl]-9H-carbazol-3-yl}-4'-phenyl A detailed explanation of the synthesis method of 1-nyl-triphenylamine (abbreviation: NBCBA1BP) do.

[0642] [ka]

[0643] Step 1: Synthesis of 9-(4-bromophenyl)-9H-carbazole

[0644] Step 1: Synthesis scheme of 9-(4-bromophenyl)-9H-carbazole is shown in (Q-1) below.

[0645] [ka]

[0646] 56 g (240 mmol) of 1,4-dibromobenzene and 31 g of 9H-carbazole (180 mmol), 4.6 g (24 mmol) of copper(I) iodide, 18-crown-6 - 2.1 g (8.0 mmol) of ether, 66 g (480 mmol) of potassium carbonate, 1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (abbreviation: 8 mL of DMPU) was placed in a 300 mL three-neck flask and heated at 180°C for 6 hours under a nitrogen atmosphere. Stirred.

[0647] After the reaction, the suspension was filtered, and the filtrate was diluted with dilute hydrochloric acid, saturated aqueous sodium bicarbonate, saturated aqueous sodium chloride, and The suspension was washed with brine, and then with magnesium sulfate to remove the water. The filtrate was concentrated and purified by silica gel column chromatography (eluent: hexane / acetic acid) The resulting fraction was concentrated and purified with chloroform and Hexane was added and recrystallization was performed to obtain the target pale brown plate-like crystals in a yield of 21 g. Got it at 35%.

[0648] Step 2: Synthesis of 9-[4-(1-naphthyl)phenyl]-9H-carbazole

[0649] Synthesis of 9-[4-(1-naphthyl)phenyl]-9H-carbazole in Step 2 The synthesis scheme is shown below (Q-2).

[0650] [ka]

[0651] 4.8 g (15 mmol) of 9-(4-bromophenyl)-9H-carbazole, 1- 2.6 g (15 mmol) of naphthaleneboronic acid, 2.0 mg of palladium(II) acetate (0.01 mmol), tri(o-tolyl)phosphine 6.0 mg (0.02 mmol ), and place in a 100 mL three-neck flask. Add 20 mL of toluene and 10 mL of ethanol to this mixture. 10 mL of 2 mol / L aqueous potassium carbonate solution was added. The mixture was stirred under reduced pressure. After degassing, the mixture was heated and stirred at 90°C for 9 hours under a nitrogen atmosphere to allow the reaction to proceed.

[0652] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added to reduce the moisture content. The suspension was filtered through Florisil, alumina, silica gel, and Celite. The filtrate was concentrated, and acetone and methanol were added and the mixture was sonicated. After that, recrystallization gave 5.0 g of the target white powder in a yield of 90%.

[0653] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.46, 9-(4-bromophenyl)-9H-carbamoyl Zoll was 0.54.

[0654] [Step 3: 3-Bromo-9-[4-(1-naphthyl)phenyl]-9H-carbazole Synthesis of

[0655] 3-Bromo-9-[4-(1-naphthyl)phenyl]-9H-carbamoyl in Step 3 The synthesis scheme of bazole is shown below (Q-3).

[0656] [ka]

[0657] 5.0 g (14 mmo) of 9-[4-(1-naphthyl)phenyl]-9H-carbazole l) In a 300 mL Erlenmeyer flask, a mixture of 50 mL of toluene and 250 mL of ethyl acetate was added. After dissolving in the solvent, 2.5 g (14 mm) of N-bromosuccinimide (abbreviation: NBS) was added. After the reaction was completed, the mixture was washed with Florisil and CeO After filtering through a light, the filtrate was washed with water, magnesium sulfate was added, and the mixture was diluted with water. The mixture was filtered, and the resulting filtrate was concentrated. Hexane was added to the mixture. After applying ultrasonic waves, the target white powder was obtained in an amount of 6.1 g and a yield of 99%. Obtained in %.

[0658] [Step 4: 9-[4-(1-naphthyl)phenyl]-9H-carbazole-3-boro Synthesis of phosphate

[0659] Step 4: 9-[4-(1-naphthyl)phenyl]-9H-carbazole-3 The synthesis scheme of -boronic acid is shown below in (Q-4).

[0660] [ka]

[0661] 5.0 g of 3-bromo-9-[4-(1-naphthyl)phenyl]-9H-carbazole (14 mmol) was placed in a 500 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. Then, 200 mL of tetrahydrofuran (abbreviation: THF) was added and the mixture was cooled to -78°C. Add 11 mL (17 mmol) of 1.6 mol / L n-butyllithium hexane solution to the mixture. The mixture was added dropwise and stirred for 4 hours. The mixture was stirred at -78°C for 2 hours and at room temperature for 16 hours. 50 mL of the mixture was added and stirred for 4 hours. This was extracted with toluene, and the resulting organic layer was diluted with saturated sodium chloride. After washing, magnesium sulfate was added to the organic layer to remove water. The liquid was filtered, and the resulting filtrate was concentrated, and chloroform and hexane were added, and the mixture was sonicated. The resulting mixture was recrystallized to give 3.5 g of a white powder, in a yield of 63%.

[0662] [Step 5: 4-{9-[4(1-naphthyl)phenyl]-9H-carbazole-3- Synthesis of {4'-phenyl-4'-yl}-4'-phenyl-triphenylamine (abbreviation: NBCBA1BP)

[0663] Step 5: 4-{9-[4(1-naphthyl)phenyl]-9H-carbazole The synthesis scheme of {-3-yl}-4'-phenyl-triphenylamine is shown below (Q-5). show.

[0664] [ka]

[0665] 1.0 g (2.5 mmol) of 4-bromo-4'-phenyl-triphenylamine, 9 1.0 g ( 2.5 mmol), palladium(II) acetate 4.0 mg (0.02 mmol), tri( 6.0 mg (0.02 mmol) of o-tolylphosphine was placed in a 50 mL three-neck flask. To this mixture, 20 mL of toluene, 5 mL of ethanol, and 2 mol / L potassium carbonate water were added. The mixture was degassed under reduced pressure with stirring, and then reconstituted under a nitrogen atmosphere. The mixture was heated and stirred at 90°C under atmospheric pressure for 13 hours to carry out the reaction.

[0666] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added. The suspension was then mixed with Florisil, alumina, silica gel, and Celite to remove water. The filtrate was concentrated, and acetone and methanol were added to the concentrate. After sonication, recrystallization yielded 1.2 g of the desired white powder in 70% yield. Got it.

[0667] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.41, 4-bromo-4'-phenyl-triphenyl Amin was 0.62.

[0668] The compound obtained in step 5 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The H NMR chart is shown in Figure 54. The carbazole derivative of the present invention, NBCBA1BP (abbreviation: NBCBA1BP), is represented by the above structural formula 386. ) was found to be obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm )=7.06 (t, J=6.6Hz, 1H), 7.21-7.77 (m, 3 0H), 7.92-7.98 (m, 2H), 8.04-8.08 (m, 1H) ), 8.22 (d, J=7.8Hz, 1H), 8.37 (d, J=1.5 Hz, 1H).

[0669] In addition, the absorption spectrum of NBCBA1BP (abbreviation) (measurement range: 200 nm to 800 nm) The absorption peak on the long wavelength side was observed around 333 nm in the case of the toluene solution. In the case of the thin film, it was observed around 340 nm.

[0670] In addition, the emission spectrum of NBCBA1BP (abbreviation) (measurement range: 370 nm to 550 nm) The maximum emission wavelength was 393 nm (excitation wavelength 350 nm) in the case of a toluene solution. ), and 488 nm (excitation wavelength 302 nm) for the thin film.

[0671] The methods for measuring the absorption spectrum and emission spectrum are the same as those in Example 1, so the explanation will be omitted. will be omitted.

[0672] In addition, the thin film was measured in air by photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of BCBA1BP (abbreviation) was -5.53 eV. The Tauc plot of the absorption edge was 3.22 eV. The gap is estimated to be 3.22 eV, which corresponds to the LUMO level of NBCBA1BP (abbreviation). This means that the potential is -2.31 eV.

[0673] In addition, the redox reaction properties of NBCBA1BP (abbreviation) were analyzed by cyclic voltammetry ( The measurement method was the same as in Example 1, so the explanation will be omitted. do.

[0674] By the same calculation as in Example 1, the HOMO level of NBCBA1BP (abbreviation) is = -5.4 3 eV. The oxidation peak remained at the same value even after 100 cycles. This indicates that the compound exhibits good properties in the repeated oxidation-reduction cycle between the oxidized and neutral states. I found out that...

[0675] In addition, the glass transition temperature of NBCBA1BP (abbreviation) was measured using a differential scanning calorimeter ( DSC:Differential Scanning Calorimetry The measurement was carried out using a Kin-Elmer Pyris1 DSC. The transition temperature was found to be 132°C. It exhibits a high glass transition temperature and good heat resistance. It was found that no crystallization occurred and that the substance was difficult to crystallize.

[0676] As in Example 5, NBCBA1BP (abbreviation) synthesized in Example 15 was used as a hole transport The efficiency of the light-emitting device formed using the layer and the 2 The driving voltage in In Example 10, the light-emitting element 8 was formed using PCBBiNB (abbreviation). was obtained (when the driving voltage was 3.6V, the luminance was 773cd / m 2 , current value is 0.47mA was). [Example]

[0677] In this Example 16, a carbazole derivative of the present invention represented by structural formula (395) was prepared. 9-(1-naphthyl)-9H-carbazol-3-yl]-4'-phenyl-triphenyl A method for synthesizing methylaminobenzoate (abbreviation: NCBA1BP) will be specifically described.

[0678] [ka]

[0679] [Step 1: Synthesis of 9-(1-naphthyl)-9H-carbazole]

[0680] The synthesis scheme of 9-(1-naphthyl)-9H-carbazole in Step 1 is shown below. (R-1) shows the results.

[0681] [ka]

[0682] 21 g (100 mmol) of 1-bromonaphthalene and 17 g (100 mmol) of carbazole mol), 0.1 g (5.0 mmol) of copper(I) iodide, 18-crown-6-ether 0.7g (2.5mmol) of ethanol, 33g (240mmol) of potassium carbonate, 1,3- Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (abbreviation: DMPU 80 mL of the above was placed in a 500 mL three-neck flask and stirred at 170°C for 6 hours under a nitrogen atmosphere. To this reaction mixture, 10 g (50 mmol) of 1-bromonaphthalene and copper iodide were added. 2.0 g (10 mmol) of (I) and 2.6 g (10 mmol) of 18-crown-6-ether mol) was added and the mixture was stirred at 170°C for 7.5 hours. 10 g (50 mmol) of bromonaphthalene was added, and the mixture was further stirred at 180° C. for 6 hours.

[0683] After the reaction, about 200 mL of toluene and about 100 mL of 1 mol / L hydrochloric acid were added to the reaction mixture. The resulting filtrate was filtered through Florisil and Celite. The obtained filtrate was separated into an organic layer and an aqueous layer, and the organic layer was washed with 1 mol / L hydrochloric acid and water, in that order. After washing, magnesium sulfate was added to remove water. The filtrate was concentrated to give an oily substance, to which hexane was added. After applying ultrasonic waves to the mixture and recrystallizing, the target white powder was obtained in an amount of 22 g and a yield of 75%. I got it.

[0684] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.61, 1-bromonaphthalene was 0.74, and carbazoline was 0.61. The rule was 0.24.

[0685] Step 2: Synthesis of 3-bromo-9-(1-naphthyl)-9H-carbazole

[0686] Step 2: Synthesis of 3-bromo-9-(1-naphthyl)-9H-carbazole The scheme is shown below (R-2).

[0687] [ka]

[0688] 5.9 g (20 mmol) of 9-(1-naphthyl)-9H-carbazole, 500 mL After dissolving it in a mixed solvent of 50 mL of toluene and 50 mL of ethyl acetate in an Erlenmeyer flask, Add 3.6 g (20 mmol) of N-bromosuccinimide (abbreviation: NBS) to this and stir for 17 minutes. After the reaction was completed, the mixture was washed with water and magnesium sulfate was added. The mixture was filtered, and the filtrate was concentrated to dryness to obtain the target white A colored powder was obtained in an amount of 7.4 g and a yield of 99%.

[0689] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.43, and 9-(1-naphthyl)9H-carbazole was It was 0.35.

[0690] Step 3: Synthesis of 9-(1-naphthyl)9H-carbazole-3-boronic acid

[0691] Step 3: Synthesis of 9-(1-naphthyl)9H-carbazole-3-boronic acid The scheme is shown below (R-3).

[0692] [ka]

[0693] 3.7 g (10 mmol) of 9-(1-naphthyl)9H-carbazole, 500 mL The atmosphere in the flask was replaced with nitrogen, and then tetrahydrofuran (abbreviated 200 mL of (THF) was added and the temperature was set at -78°C. 7 mL (13 mmol) of a hexane solution of ethyl lithium was added dropwise, and the mixture was stirred for 2 hours. Add 2 mL (20 mmol) of trimethyl borate to the mixture and incubate at -78°C for 3 hours and at room temperature for 16 hours. After the reaction, 50 mL of 1 M diluted hydrochloric acid was added to the reaction solution and stirred for 4 hours. The organic layer was extracted with ethyl acetate, and the resulting organic layer was washed with saturated saline. Magnesium was added to remove water. The suspension was filtered, and the obtained filtrate was concentrated. After adding chloroform and hexane and applying ultrasonic waves, the product was recrystallized to obtain the desired yellow powder. The product was obtained in an amount of 2.6 g and a yield of 78%.

[0694] [Step 4: 4-[9-(1-naphthyl)-9H-carbazol-3-yl]-4'- Synthesis of phenyl-triphenylamine (abbreviation: NCBA1BP)

[0695] Step 4: 4-[9-(1-naphthyl)-9H-carbazol-3-yl]- The synthesis scheme of 4'-phenyl-triphenylamine is shown below (R-4).

[0696] [ka]

[0697] 1.2 g (3.0 mmol) of 4-bromo-4'-phenyl-triphenylamine, 9 -(1-naphthyl)9H-carbazole-3-boronic acid 1.0 g (3.0 mmol), Palladium(II) acetate 6.0 mg (0.03 mmol), tri(o-tolyl)phosphite 0.03 mg (18 mmol) of acetone was placed in a 50 mL three-neck flask, and the mixture was 15 mL of benzene, 5 mL of ethanol, and 3 mL of a 2 mol / L aqueous potassium carbonate solution were added. The mixture was degassed under reduced pressure while stirring, and then heated at 90°C for 6.5 hours under a nitrogen atmosphere. The mixture was heated and stirred to react.

[0698] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added. The suspension was then mixed with Florisil, alumina, silica gel, and Celite to remove water. The filtrate was concentrated and purified by silica gel column chromatography. The resulting fraction was purified by elution with a developing solvent of toluene and hexane (1:3). The solution was concentrated, methanol was added, and the mixture was subjected to ultrasonic waves. When the solution was recrystallized, the target white A colored powder was obtained in an amount of 0.5 g and a yield of 25%.

[0699] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.34, 4-bromo-4'-phenyl-triphenyl Amin was 0.54.

[0700] The compound obtained in step 4 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The 1 H NMR chart is shown in Figure 55. NCBA1BP (abbreviation), which is a carbazole derivative of the present invention represented by the above structural formula 395 It was found that the following was obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm) =7.00-7.07 (m, 3H), 7.19-8.00 (m, 25H), 8.03-8.07 (m, 2H), 8.22-8.25 (m, 1H), 8. 40 (d, J=1.5, 1H).

[0701] Also, the absorption spectrum of NCBA1BP (abbreviation) (measurement range 200nm to 800nm) The absorption peak on the long wavelength side was observed around 333 nm in the case of the toluene solution. In the case of thin films, it was observed around 340 nm.

[0702] Also, the emission spectrum of NCBA1BP (abbreviation) (measurement range 370nm to 550nm) The maximum emission wavelength was 392 nm (excitation wavelength 345 nm) in the case of a toluene solution. In the case of the thin film, it was 426 nm (excitation wavelength 328 nm). The method for measuring the emission spectrum is the same as in Example 1, and therefore the explanation will be omitted.

[0703] In addition, the thin film was measured in air by photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of CBA1BP (abbreviation) was -5.44 eV. The Tauc plot showed that the absorption edge was 3.19 eV. The gap is estimated to be 3.19 eV, which means that the NCBA1BP (abbreviation) LUMO level is This means that the energy is -2.25 eV.

[0704] In addition, the redox reaction characteristics of NCBA1BP (abbreviation) were analyzed by cyclic voltammetry (C V) Measurement was carried out. The measurement method was the same as in Example 1, so the explanation will be omitted. By calculation similar to that in Example 1, the HOMO level of NCBA1BP (abbreviation) is = -5. The oxidation peak was found to be 43 eV. Even after 100 cycles, the oxidation peak remained at the same value. This indicates that the compound exhibits good properties in the repeated oxidation-reduction between the oxidized and neutral states. I found that.

[0705] In addition, the glass transition temperature of NCBA1BP (abbreviation) was measured using a differential scanning calorimeter (D SC:Differential Scanning Calorimetry The measurement was carried out using a KinElmer Pyris1 DSC. The transition temperature was found to be 128°C. It exhibits a low glass transition temperature and good heat resistance. It was found that the substance was difficult to crystallize.

[0706] In the same manner as in Example 5, NCBA1BP (abbreviation) synthesized in Example 16 was used as a hole transport layer. The efficiency of the light-emitting element formed using 2 The driving voltage in In Example 10, a good value equivalent to that of the light-emitting element 8 formed using PCBBiNB (abbreviation) was obtained. The obtained brightness was 1198 cd / m when the driving voltage was 4.0 V. 2 , the current value is 0.82mA was). [Example]

[0707] In this Example 17, the carbazole derivative of the present invention represented by the structural formula (422) was used. '-Diphenyl-4''-(6,9-diphenyl-9H-carbazol-3-yl)trimethylsilyl This section explains in detail how to synthesize phenylamine (abbreviated as PCBBi1BPIII). .

[0708] [ka]

[0709] Step 1: Synthesis of 3-bromo-6,9-diphenyl-9H-carbazole

[0710] Step 1: Synthesis of 3-bromo-6,9-diphenyl-9H-carbazole The team is shown below (S-1).

[0711] [ka]

[0712] 4.8 g (15 mmol) of 3,9-diphenyl-9H-carbazole was added to 300 mL of A Lenmeyer flask was placed in which 250 ml of a mixed solvent of ethyl acetate and toluene (4:1) was added. The solution was added with N-bromosuccinimide (abbreviation: NBS) 2. 7 g (15 mmol) was added in small portions and stirred at room temperature for 48 hours.

[0713] After stirring, the mixture was washed with a saturated aqueous solution of sodium bicarbonate and then with saturated saline. After washing, the obtained organic layer was dehydrated with magnesium sulfate, and the mixture was then suctioned. The filtrate was filtered to obtain a filtrate. The filtrate was concentrated to obtain an oily substance, to which a small amount of methanol was added. When ultrasonic waves were applied, a solid precipitated. The precipitated solid was collected by suction filtration. A white powdery solid was obtained in an amount of 5.4 g and a yield of 90%.

[0714] [Step 2: 4,4'-diphenyl-4''-(6,9-diphenyl-9H-carbazoline) Synthesis of PCBBi1BPIII

[0715] Step 2: 4,4'-diphenyl-4''-(6,9-diphenyl-9H-carboxylate) The synthesis scheme of (rubazol-3-yl)triphenylamine is shown below in (S-2).

[0716] [ka]

[0717] N,N-bis(biphenyl-4-yl)aminophenyl-4-boronic acid 1.7 g (3. 8mmol), 3-bromo-6,9-diphenyl-9H-carbazole 1.5g (3.8 mmol), palladium(II) acetate 8.4 mg (0.038 mmol), tri(ortho 0.080 g (0.26 mmol) of (-tolyl)phosphine was placed in a 100 mL three-neck flask. To this mixture, 10 mL of toluene, 2 mL of ethanol, and 10 mL of 2M aqueous potassium carbonate solution were added. After adding 1 mL of HCl, the mixture was degassed under reduced pressure, and the atmosphere in the flask was replaced with nitrogen. The mixture was heated and stirred at 100° C. for 3 hours.

[0718] After stirring, toluene was added to the mixture, and the mixture was heated to 50°C and stirred. After the suspension was returned to room temperature, the organic layer and the aqueous layer were separated. After washing, magnesium sulfate was added to the obtained organic layer. The mixture was filtered under suction to obtain a filtrate. (Wako Pure Chemical Industries, Ltd., Catalog No.: 531-16855), Florisil (Wako Junyaku Kogyo Co., Ltd., Catalog No. 540-00135), and suction filtered through alumina. The filtrate was concentrated and purified by silica gel column chromatography. Silica gel column chromatography was performed using a mixture of toluene and hexane (1:4). The combined solvent was used as the developing solvent, followed by a 1:1 mixture of toluene and hexane. The obtained fraction was concentrated, and the solid was dissolved in chloroform. The product was recrystallized from a mixed solvent of ethanol and hexane to give a white powdery solid (2.3 g, yield 87%). Obtained in %.

[0719] The resulting white solid (2.3 g) was purified by train sublimation. The purification was carried out at 320°C for 18 hours under a reduced pressure of 7.0 Pa with an argon flow rate of 4 mL / min. The yield was 1.8 g, which was 78%.

[0720] The compound obtained in step 2 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The 1 H NMR chart is shown in Figure 61. PCBBi1BPI is a carbazole derivative of the present invention represented by the above structural formula (422). It was found that II (abbreviation) was obtained. 1 H NMR (CDCl3, 300 MHz) :δ(ppm)=7.22-7.77(m,36H),8.38-8.42(m,2H) .

[0721] The molecular weight of the above compound was measured using a TOF-MS detector (Waters Microwave Oscilloscope, manufactured by Waters Corporation). The measurement was carried out using a 0.1% acetonitrile and 0.1% A mixture of formic acid and water (mixing ratio 80 / 20 vol / vol) was used as the solvent. The main peak at molecular weight 714.30 (mode ES+) was detected, and the target P It was confirmed that CBBi1BPIII (abbreviation) was obtained.

[0722] In addition, various physical properties of PCBBi1BPIII (abbreviation) were measured as follows: .

[0723] Absorption spectrum of PCBBi1BPIII (abbreviation) (measurement range: 200nm to 800nm) The absorption peak on the long wavelength side was observed around 348 nm in the case of the toluene solution. In the case of the thin film, the emission spectrum (measurement range 390 nm to The maximum emission wavelength was 397 nm (excitation wavelength 550 nm) in the case of the toluene solution. 358 nm) and 439 nm (excitation wavelength 369 nm) for thin films.

[0724] The thin film was measured in air using photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of i1BPIII (abbreviation) was -5.46 eV. The Tauc plot of the absorption edge was 3.21 eV. The energy gap is estimated to be 3.21 eV, which corresponds to a LUMO level of -2.25 eV. This means that

[0725] The redox reaction characteristics of PCBBi1BPIII (abbreviation) were investigated by cyclic voltammetry ( The measurement method was the same as in Example 1, so the explanation will be omitted. By the same calculation as in Example 1, the HOMO level of PCBBi1BPIII (abbreviation) is , = -41 [eV]. In addition, the oxidation peak was the same even after 100 cycles. This indicates that the oxidized and neutral states are repetitively oxidized and reduced. It was found to show sexuality.

[0726] The glass transition temperature of PCBBi1BPIII (abbreviation) was measured using a differential scanning calorimeter ( The glass transition temperature was measured using DSC (differential scanning calorimetry). In addition, PCBBi1BPIII (abbreviation) exhibits a high glass transition temperature and good heat resistance. Furthermore, there was no peak indicating crystallization, indicating that the substance is difficult to crystallize. I found out that...

[0727] As in Example 5, PCBBi1BPIII (abbreviation) synthesized in this Example 17 was used. The efficiency of the light-emitting device formed using this as a hole transport layer was approximately 1000 cd / m 2 The driving voltage at The reliability and durability were evaluated using a film formed in Example 10 using PCBBiNB (abbreviation) as the hole transport layer. A good value equivalent to that of the light-emitting element 8 was obtained (a luminance of 1070c when the driving voltage was 4.2V). d / m 2 The current value is 0.75mA, and the brightness is maintained at 74% of the initial brightness after 360 hours of operation. (It was.) [Example]

[0728] In this Example 18, a carbazole derivative of the present invention represented by structural formula (423) was used. '-Dimethyl-4' '-phenyl-4-(9-phenyl-9H-carbazole-3-yl) This paper explains in detail the synthesis method of PCBA1BPIV. Reveal.

[0729] [ka]

[0730] Step 1: Synthesis of 3,3'-dimethyl-4''-phenyl-triphenylamine

[0731] Synthesis of 3,3'-dimethyl-4''-phenyl-triphenylamine in Step 1 The synthesis scheme is shown below (T-1).

[0732] [ka]

[0733] 5.8 g (25 mmol) of 4-bromobiphenyl and 4. 9g (25mmol), sodium tert-butoxide 3.0g (30mmol) , bis(dibenzylideneacetone)palladium(0) 140 mg (0.25 mmol) The mixture was placed in a 100 mL three-neck flask, and the atmosphere in the flask was replaced with nitrogen. 50 mL of dehydrated xylene was added, and the mixture was degassed under reduced pressure while stirring. Tri(tert-butyl)phosphine (10 wt% hexane solution) 1.0 mL (0.5 m The mixture was heated and stirred at 130°C for 1.5 hours under a nitrogen atmosphere. I made him respond.

[0734] After the reaction, 80 mL of toluene and 420 mL of hexane were added to the reaction mixture, and the suspension was The mixture was filtered through Florisil, silica gel, and Celite. The filtrate was washed with water. Magnesium sulfate was added to remove water. The suspension was passed through Florisil and Celite. The filtrate was concentrated, methanol was added, and the mixture was sonicated. Then, recrystallization gave 8.5 g of a white powder, which was the target substance, in a yield of 97%.

[0735] The compound obtained in step 1 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). 1 H NMR(CDCl3,300MHz):δ(ppm)=2.28 (s, 6H) , 6.85 (d, J=6.9, 2H), 6.91-6.95 (m, 4H) , 7.09-7.18 (m, 4H), 7.29 (t, J=7.5, 1H) , 7.38-7.48 (m, 4H), 7.56-7.59 (m, 2H).

[0736] Step 2: 4-Bromo-3,3'-dimethyl-4''-phenyl-triphenylamine Synthesis of

[0737] Step 2: 4-bromo-3,3'-dimethyl-4''-phenyl-triphenyl The synthesis scheme of diamine is shown below (T-2).

[0738] [ka]

[0739] 2.5 g (24 mmol) of 3,3'-dimethyl-4''-phenyl-triphenylamine l) was dissolved in 200 mL of ethyl acetate in a 200 mL Erlenmeyer flask, and then N-bromo Add 4.3 g (24 mmol) of bromo succinimide (abbreviation: NBS) and leave at room temperature for 48 hours. After the reaction was completed, the mixture was washed with water and magnesium sulfate was added to remove moisture. The mixture was filtered, and the filtrate was concentrated and dried. A molten solid was obtained in an amount of 9.1 g and a yield of 88%.

[0740] Step 3: 3,3'-dimethyl-4''-phenyl-4-(9-phenyl-9H-carboxylate) Synthesis of PCBA1BPIV

[0741] Step 3: 3,3'-dimethyl-4''-phenyl-4-(9-phenyl-9 The synthesis scheme of (H-carbazol-3-yl)-triphenylamine is shown below (T-3). show.

[0742] [ka]

[0743] 4-Bromo-3,3'-dimethyl-4' '-phenyl-triphenylamine 1.7 g (4.0 mmol), 1.4 g ( 5.0 mmol), palladium(II) acetate 5.0 mg (0.02 mmol), tri( 6.0 mg (0.02 mmol) of o-tolylphosphine was added to a 300 mL round-bottom flask. Add 30 mL of toluene, 5 mL of ethanol, and 2 mol / L potassium carbonate to this mixture. 3.5 mL of aqueous solution was added, and the mixture was degassed under reduced pressure with stirring, and then The mixture was heated and stirred at 90°C under atmospheric pressure for 3 hours to carry out the reaction.

[0744] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added to reduce the moisture content. The suspension was filtered through Florisil, alumina, silica gel, and Celite. The filtrate was concentrated and purified by silica gel column chromatography (developing solvent). The solvent was toluene:hexane (1:4). The obtained fraction was concentrated. After adding hexane and acetone and applying ultrasonic waves, the desired white powder was obtained by recrystallization. The powder was obtained in an amount of 1.0 g and a yield of 42%.

[0745] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.51, 4-bromo-3,3'-dimethyl-4' -phenyl-triphenylamine was 0.62.

[0746] The compound obtained in step 3 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The H NMR chart is shown in Figure 62. The carbazole derivative of the present invention, PCBA1BPIV, represented by the above structural formula (423), It was found that (abbreviation) was obtained. 1 H NMR (CDCl3, 300 MHz): δ( ppm)=2.26 (s, 3H), 2.30 (s, 3H), 6.86 (d , J=7.8, 1H), 6.99-7.59 (m, 25H), 8.09-8 .13 (m, 2H).

[0747] The molecular weight of the above compound was measured using a TOF-MS detector (Waters Microwave Oscilloscope, manufactured by Waters Corporation). The measurement was carried out using a 0.1% acetonitrile and 0.1% A mixture of formic acid and water (mixing ratio 80 / 20 vol / vol) was used as the solvent. The main peak at molecular weight 591.28 (mode ES+) was detected, and the target P It was confirmed that CBA1BPIV (abbreviation) was obtained.

[0748] In addition, various physical properties of PCBA1BPIV (abbreviation) were measured as follows.

[0749] Absorption spectrum of PCBA1BPIV (abbreviation) (measurement range 200nm~800nm) The absorption peak on the long wavelength side was observed around 325 nm in the case of the toluene solution, In the case of thin films, the emission spectrum was observed around 329 nm. The maximum emission wavelength was 393 nm (excitation wavelength 330 nm) in the case of the toluene solution. 0 nm) and 422 nm (excitation wavelength 357 nm) for the thin film.

[0750] The thin film was measured in air using photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of 1BPIV (abbreviation) was -5.57 eV. The Tauc plot showed that the absorption edge was 3.36 eV. The gap is estimated to be 3.36 eV, which corresponds to the LUMO This means that the level is -2.21 eV.

[0751] The glass transition temperature was investigated using a differential scanning calorimeter (DSC). Therefore, the glass transition temperature was 105°C. Furthermore, there was no peak indicating crystallization, indicating that the material was difficult to crystallize. It was found to be a valuable substance.

[0752] In addition, PCBA1BPIV (abbreviation) synthesized in this Example 18 was used as a hole transporter in the same manner as in Example 5. The efficiency of the light-emitting device formed using the transmission layer is approximately 1000 cd / m 2 The driving voltage in The same as the light-emitting element 8 formed in Example 10 using PCBBiNB (abbreviation) for the hole transport layer. A good value of 924 cd / m was obtained (when the driving voltage was 4.0 V, the luminance was 924 cd / m 2 , the current value is 0 (It was 0.61mA). [Example]

[0753] In this Example 19, a carbazole derivative of the present invention represented by structural formula (345) was used. '-Di(2-naphthyl)-4''-(9-phenyl-9H-carbazol-3-yl)- A method for synthesizing triphenylamine (abbreviation: PCBNBBβ) will be specifically described.

[0754] [ka]

[0755] [Step 1: Synthesis of 4,4'-di(2-naphthyl)-triphenylamine]

[0756] Step 1: Synthesis of 4,4'-di(2-naphthyl)-triphenylamine The system is shown below (U-1).

[0757] [ka]

[0758] 6.0 g (15 mmol) of 4,4'-dibromotriphenylamine, 2-naphthalene 6.2 g (36 mmol) of boronic acid and 16 mg (0.1 mm) of palladium(II) acetate were used. ol), tri(o-tolyl)phosphine 21 mg (0.1 mmol), 300 mL three-neck Put into a flask and add 50 mL of toluene, 20 mL of ethanol, and 2 mol / L 20 mL of an aqueous solution of potassium carbonate was added, and the mixture was degassed under reduced pressure while stirring. The mixture was then heated and stirred at 90°C for 4.5 hours under a nitrogen atmosphere to allow the reaction to proceed.

[0759] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added. The suspension was then mixed with Florisil, alumina, silica gel, and Celite to remove water. The filtrate was concentrated, hexane was added, and the mixture was subjected to ultrasonic treatment. After that, recrystallization gave 5.6 g of the target white powder in a yield of 75%.

[0760] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.53, and 4,4'-dibromotriphenylamine was 0. It was .78.

[0761] Step 2: 4-Bromo-4',4''-di(2-naphthyl)-triphenylamine Synthesis]

[0762] 4-Bromo-4',4''-di(2-naphthyl)-triphenylamine in Step 2 The synthesis scheme of Mine is shown below (U-2).

[0763] [ka]

[0764] 4.0 g (8.0 mmol) of 4,4'-di(2-naphthyl)-triphenylamine, In a 500 mL Erlenmeyer flask, add 200 mL of toluene and 250 mL of ethyl acetate to a mixed solvent. After dissolving, add 1.4 g (8 mmol) of N-bromosuccinimide (abbreviation: NBS) After the reaction was completed, the mixture was washed with water and The suspension was filtered through Florisil and Celite. The obtained filtrate was concentrated and purified by silica gel column chromatography (developing solvent: toluene). The resulting fraction was concentrated and purified with acetone and hexane (1:4). After adding hexane and applying ultrasound, recrystallization resulted in the desired white powder being obtained in a yield of 3. 4 g was obtained in 61% yield.

[0765] The compound obtained in step 2 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 H NMR (CDCl3, 300 MHz): δ (ppm) = 7.09 (d, J=8.4, 2H), 7.24 (d, J=7.8, 4H) , 7.40 (d, J=8.4, 2H), 7.47-7.51 (m, 4H) , 7.66 (d, J=8.1, 4H), 7.73-7.76 (m, 2H) , 7.85-7.93 (m, 6H), 8.03 (s, 2H).

[0766] [Step 3: 4,4'-di(2-naphthyl)-4''(9-phenyl-9H-carbazo Synthesis of PCBNBBβ

[0767] Step 3: 4,4'-di(2-naphthyl)-4''(9-phenyl-9H-carboxylate) The synthesis scheme of (rubazol-3-yl)-triphenylamine is shown below in (U-3).

[0768] [ka]

[0769] 1.0 g (1 0.7 mmol), 0.6 g (2.0 mmol) of 9-phenyl-9H-carbazole-3-boronic acid mmol), palladium(II) acetate 2.2 mg (10 μmol), tri(o-tolyl ) 3.0 mg (10 μmol) of phosphine was placed in a 50 mL three-neck flask, and this mixture 20 mL of toluene, 3 mL of ethanol, 2.0 mL of 2 mol / L potassium carbonate aqueous solution The mixture was degassed under reduced pressure while stirring, and then heated at 90°C under a nitrogen atmosphere. The mixture was heated and stirred for 14 hours to react.

[0770] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The resulting filtrate was concentrated and filtered through silica gel, alumina, and celite. Purification was performed by column chromatography (developing solvent toluene:hexane = 1:4). The obtained fraction was concentrated and purified by adding methanol, chloroform, acetone, and hexane. After adding the mixture and applying ultrasonic waves, recrystallization was performed, and the target pale yellow powder was obtained in a yield of 1.5 g. I got it at 95%.

[0771] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.31, 4-bromo-4',4''-di-2-naphthyl The α-triphenylamine was 0.56.

[0772] The compound obtained in step 3 above was analyzed by nuclear magnetic resonance ( 1 1 H NMR). The measurement data is shown below. 1 The H NMR chart is shown in Figure 63. PCBNBBβ (abbreviation), which is a carbazole derivative of the present invention represented by the above structural formula 345 It was found that the following was obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm )=7.29-7.90 (m, 34H), 8.03 (s, 2H), 8.16 (d, J=7.2, 1H), 8.34 (d, J=1.5, 1H).

[0773] The molecular weight of the above compound was measured using a TOF-MS detector (Waters Microwave Oscilloscope, manufactured by Waters Corporation). The measurement was carried out using a 0.1% acetonitrile and 0.1% A mixture of formic acid and water (mixing ratio 80 / 20 vol / vol) was used as the solvent. The main peak at molecular weight 739.32 (mode ES+) was detected, and the target P It was confirmed that CBNBBβ (abbreviation) was obtained.

[0774] In addition, various physical properties of PCBNBBβ (abbreviation) were measured as follows.

[0775] Measure the absorption spectrum (measurement range 200nm to 800nm) of PCBNBBβ (abbreviation) The absorption peak on the long wavelength side was observed around 357 nm in the case of the toluene solution, and In the case of PCBNBBβ, the emission spectrum (measured) was observed around 366 nm. The maximum emission wavelength was 41 nm in the case of the toluene solution. 5 nm (excitation wavelength 360 nm) for thin films, and 449 nm (excitation wavelength 376 nm) for thin films. It was.

[0776] The thin film was measured in air using photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of BBβ (abbreviation) was -5.36 eV. The absorption edge was 3.06 eV from the uc plot. The LUMO level of PCBNBBβ (abbreviation) is estimated to be 3.06 eV. This means that the electron energy is 2.30 eV.

[0777] The oxidation-reduction reaction characteristics of PCBNBBβ (abbreviation) were measured by cyclic voltammetry (CV). The measurement method was the same as in Example 1, so the explanation will be omitted. By the same calculation as in Example 1, the HOMO level of PCBNBBβ (abbreviation) is = -5.41[ eV]. Furthermore, the oxidation peak remained at a similar value even after 100 cycles. This indicates that the compound exhibits good properties in the repeated oxidation-reduction cycle between the oxidized and neutral states. I found out.

[0778] The glass transition temperature of PCBNBBβ (abbreviation) was measured using a differential scanning calorimeter (DSC) The measurement results showed that the glass transition temperature was 129°C. BNBBβ (abbreviation) is known to have a high glass transition temperature and good heat resistance. Furthermore, there was no peak indicating crystallization, indicating that the substance is difficult to crystallize.

[0779] In the same manner as in Example 5, PCBNBBβ (abbreviation) synthesized in Example 19 was used as a hole transport layer. The efficiency of the light-emitting element formed using the method, the driving voltage at about 1000 cd / m2, and the signal The reliability was measured using the light-emitting diode formed in Example 10 using PCBBiNB (abbreviation) as the hole transport layer. A good value equivalent to that of Device 8 was obtained (luminance 1104 cd / m when the driving voltage was 4.4 V). 2 The current value was 0.74mA, and the brightness remained at 75% of the initial brightness after 650 hours of operation. Ta). [Example]

[0780] In this Example 20, a carbazole derivative of the present invention represented by structural formula (424) was prepared. Phenyl-4'-(9-phenyl-9H-carbazol-3-yl)-4''-(9-phenyl Synthesis of PCBBiFLP The method will be specifically described below. (The compound is a carbazoline compound represented by the general formula (1).) R of the hydroxyl derivative 1 is hydrogen, R 2 is a phenyl group, l is 0, m is 1, n is 0, α 2 is 1,4 -phenylene group, α 4 is a 1,4-phenylene group, Ar1 is a biphenyl-4-yl group, Ar 2 is a fluoren-9-yl group, and the 9-position of the fluoren-9-yl group is a phenyl group. It is replaced.)

[0781] [ka]

[0782] Step 1: Synthesis of 4-bromo-4'-phenyl-diphenylamine

[0783] Step 1: Synthesis of 4-bromo-4'-phenyl-diphenylamine Shown below in (V-1).

[0784] [ka]

[0785] 37 g (150 mmol) of 4-phenyl-diphenylamine was added to a 1000 mL Erlenmeyer flask. After dissolving it in 400 mL of ethyl acetate in a scooperate, N-bromosuccinimide (abbreviated 27 g (150 mmol) of NBS was added and the mixture was stirred at room temperature for 24 hours.

[0786] After the reaction was completed, the mixture was washed with water, and magnesium sulfate was added to remove moisture. The mixture was filtered through Florisil, silica gel, alumina, and Celite. The filtrate was concentrated, and after adding toluene and hexane and applying ultrasonic waves, it was recrystallized. The desired white powder was obtained in a yield of 4.0 g. Purification by gel column chromatography (developing solvent: toluene:hexane = 1:4) The obtained fraction was concentrated, methanol was added, and the mixture was sonicated. Upon crystallization, 4.5 g of the target white powder was obtained. Obtained 8.5 g, 73% yield.

[0787] [Step 2: 4-phenyl-4'-(9-phenyl-9H-carbazol-3-yl) -Synthesis of diphenylamine]

[0788] Step 2: 4-phenyl-4'-(9-phenyl-9H-carbazole-3- The synthesis scheme of (V-1)-diphenylamine is shown in (V-2) below.

[0789] [ka]

[0790] 16 g (50 mmol) of 4-bromo-4'-phenyl-diphenylamine, 9-phenyl 16 g (55 mmol) of 9H-carbazole-3-boronic acid and palladium acetate ( II) 110 mg (0.4 mmol), tri(o-tolyl)phosphine 150 mg ( 0.4mmol) into a 200mL three-neck flask, and add 70mL of toluene to this mixture. 5 mL of ethanol and 23 mL of a 2 mol / L aqueous potassium carbonate solution were added to the mixture. After degassing while stirring under reduced pressure, the mixture was heated and stirred at 90°C for 7.5 hours under a nitrogen atmosphere. I made him respond.

[0791] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added. The suspension was then mixed with Florisil, alumina, silica gel, and Celite to remove water. The filtrate was concentrated and purified by silica gel column chromatography. The resulting fraction was purified by elution with a developing solvent of toluene and hexane (1:4). The solution was concentrated, chloroform and methanol were added, and the mixture was sonicated and recrystallized. As a result, 10 g of the target pale yellow powder was obtained in a yield of 41%.

[0792] Step 3: Synthesis of 9-(4-bromophenyl)-9-phenylfluorene

[0793] Step 3: Synthesis of 9-(4-bromophenyl)-9-phenylfluorene The format is shown in (V-3) below.

[0794] [ka]

[0795] Place 1.2 g (50 mmol) of magnesium in a 100 mL three-neck flask and reduce the temperature to 3 The mixture was heated and stirred for 10 minutes to activate the magnesium. The mixture was then cooled to room temperature and placed in a nitrogen atmosphere. After that, a few drops of dibromoethane were added and it was confirmed that foaming and heat were generated. 12 g (50 mmol) of 2-bromobiphenyl dissolved in 10 mL of water was slowly added dropwise. Thereafter, the mixture was heated under reflux and stirred for 2.5 hours to form a Grignard reagent.

[0796] 10 g (40 mmol) of 4-bromobenzophenone and 100 mL of diethyl ether The Grignard reagent synthesized earlier was slowly added to the 500 mL three-neck flask. After the dropwise addition, the mixture was heated under reflux and stirred for 9 hours.

[0797] After the reaction, the mixture was filtered to obtain a residue. The residue was dissolved in 150 mL of ethyl acetate. However, 1N hydrochloric acid was added and stirred for 2 hours. The organic layer of this liquid was washed with water and Magnesium carbonate was added to remove water. The suspension was filtered, and the obtained filtrate was concentrated. A candy-like substance was obtained.

[0798] Add this syrup, 50 mL of glacial acetic acid, and 1.0 mL of hydrochloric acid to a 500 mL flask. The mixture was heated and stirred at 130°C for 1.5 hours under a nitrogen atmosphere to cause a reaction. The mixture was filtered to obtain a residue, which was then washed with water, sodium hydroxide solution, water, and methanol. The target substance, a white powder, was obtained in an amount of 11 g and a yield of 69%.

[0799] [Step 4: 4-phenyl-4'-(9-phenyl-9H-carbazol-3-yl) -4''-(9-phenylfluoren-9-yl)-triphenylamine (abbreviated as PCB Synthesis of BiFLP]

[0800] Step 4: 4-phenyl-4'-(9-phenyl-9H-carbazole-3- Synthesis of (4''-(9-phenylfluoren-9-yl)-triphenylamine The scheme is shown below (V-4).

[0801] [ka]

[0802] 1.2 g (3.0 mmol) of 9-(4-bromophenyl)-9-phenylfluorene , 4-phenyl-4'-(9-phenyl-9H-carbazol-3-yl)-diphenyl 1.5 g (3.0 mmol) of amine and 0.4 g ( 4.0 mmol), bis(dibenzylideneacetone)palladium(0) 17 mg (0. 03 mmol) was placed in a 100 mL three-neck flask, and the atmosphere inside the flask was replaced with nitrogen. To this mixture, 20 mL of dehydrated xylene was added. The mixture was dehydrated under reduced pressure with stirring. After degassing, 0.2g of tri(tert-butyl)phosphine (10wt% hexane solution) was added. The mixture was heated at 130°C for 5.5 hours under a nitrogen atmosphere. The mixture was heated and stirred to react.

[0803] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The resulting filtrate was concentrated and purified by silica gel column chromatography. The resulting fraction was purified using a developing solvent of toluene:hexane = 1:4. The concentrate was added with acetone and methanol, and after ultrasonic treatment, the desired product was recrystallized. The product was obtained as a white powder in an amount of 1.8 g and a yield of 76%.

[0804] Rf values ​​in silica gel thin layer chromatography (TLC) (eluent: ethyl acetate:hexane) The target compound was 0.35, 9-(4-bromophenyl)-9-phenyl Fluorene 0.65, 4-phenyl-4'-(9-phenyl-9H-carbazole-3 -yl)-diphenylamine was 0.19.

[0805] The compound obtained in step 4 above was measured by nuclear magnetic resonance (NMR). The constant data is shown. 1 The 1 H NMR chart is shown in Figure 64. From the measurement results, it is clear that the above structure PCBBiFLP (abbreviation), a carbazole derivative of the present invention represented by formula (424), It was found that the following was obtained. 1 H NMR (CDCl3, 300 MHz): δ (ppm )=7.02 (d,J=8.7,2H), 7.12 (d,J=8.7,2H), 7.17-7.64 (m, 36H), 7.77 (d, J=6.9, 2H).

[0806] In addition, various physical properties of PCBBiFLP (abbreviation) were measured as follows.

[0807] The absorption spectrum (measurement range 200 nm to 800 nm) of PCBBiFLP (abbreviation) was measured. The absorption peak on the long wavelength side was observed around 337 nm in the case of the toluene solution, and In the case of the film, it was observed around 339 nm. The measurement range was 390 nm to 550 nm. The maximum emission wavelength was 395 nm (excitation wavelength 343 nm), 425 nm (excitation wavelength 361 nm) for thin films It was.

[0808] The thin film was measured in air using photoelectron spectroscopy (Riken Keiki, AC-2). The HOMO level of iFLP (abbreviation) was -5.53 eV. From the auc plot, the absorption edge was 3.28 eV. The LUMO level of PCBBiFLP (abbreviation) is estimated to be 3.28 eV. This means that the electron density is -2.25 eV.

[0809] The redox reaction characteristics of PCBBiFLP (abbreviation) were analyzed by cyclic voltammetry (CV) The measurement method was the same as in Example 1, so the explanation will be omitted. By the same calculation as in Example 1, the HOMO level of PCBBiFLP (abbreviation) is = -5.4 2 eV. The oxidation peak remained at the same value even after 100 cycles. This indicates that the compound exhibits good properties in the repeated oxidation-reduction cycle between the oxidized and neutral states. I found out that...

[0810] The glass transition temperature of PCBBiFLP (abbreviation) was measured using a differential scanning calorimeter (DSC The measurement results showed that the glass transition temperature was 156°C. CBBiFLP (abbreviation) is known to have a high glass transition temperature and good heat resistance. In addition, there was no peak indicating crystallization, indicating that the substance is difficult to crystallize. .

[0811] In addition, PCBBiFLP (abbreviation) synthesized in this Example 20 was used as a hole transporting The efficiency of the light-emitting device formed using this layer is approximately 1000 cd / m 2 the driving voltage at The reliability was evaluated using the device formed in Example 10 using PCBBiNB (abbreviation) as the hole transport layer. A good value equivalent to that of optical element 8 was obtained (luminance 1104 cd / at a driving voltage of 4.4 V). m 2 The current value was 0.74mA, and the brightness remained at 75% of the initial brightness after 650 hours of operation. there was).

[0812] In addition, PCBBiFLP (abbreviation) synthesized in this Example 20 was used as a hole transporting The efficiency of the light-emitting device formed using this layer is approximately 1000 cd / m 2 the driving voltage at The reliability was evaluated using the device formed in Example 10 using PCBBiNB (abbreviation) as the hole transport layer. A good value equivalent to that of optical element 8 was obtained (luminance 1171 cd / at a driving voltage of 4.0 V). m 2 The current value was 0.65mA, and the brightness remained at 74% of the initial brightness after 360 hours of operation. there was). [Example]

[0813] In this Example 21, 4, a carbazole derivative of the present invention represented by structural formula (343), -(1-naphthyl)-4'-(9-phenyl-9H-carbazol-3-yl)-triphenyl This section explains in detail a synthesis method for phenylamine (abbreviation: PCBANB) different from that in Example 8. Reveal.

[0814] [ka]

[0815] Step 1: Synthesis of 1-(4-bromophenyl)-naphthalene

[0816] The synthesis scheme of 1-(4-bromophenyl)-naphthalene in Step 1 is shown below ( W-1).

[0817] [ka]

[0818] 46 g (160 mmol) of 4-bromoiodobenzene and 2 g of 1-naphthaleneboronic acid 4g (140mmol), 45mg (0.2mmol) of palladium(II) acetate, tri 60 mg (0.2 mmol) of tri(o-tolyl)phosphine was placed in a 500 mL three-neck flask. Add 100 mL of toluene, 20 mL of ethanol, and 2 mol / L potassium carbonate to this mixture. 11 mL of aqueous ammonium hydroxide solution was added. The mixture was degassed under reduced pressure while stirring, and then The mixture was heated and stirred at 90°C under atmospheric pressure for 4 hours to carry out the reaction.

[0819] After the reaction, 500 mL of toluene was added to the reaction mixture, and the suspension was The filtrate was washed with water and magnesium sulfate was added to reduce the moisture content. The suspension was filtered through Florisil and Celite to obtain a filtrate. The filtrate was concentrated and purified by silica gel column chromatography (eluent: hexane). The obtained fraction was concentrated, and the target product, a colorless transparent liquid, was obtained in a yield of 25%. g in a yield of 62%.

[0820] The Rf value in silica gel thin layer chromatography (TLC) (developing solvent: hexane) is: The target substance was 0.38 and 4-bromoiodobenzene was 0.57.

[0821] [Step 2: 4-(1-naphthyl)-4'-(9-phenyl-9H-carbazole-3 Synthesis of (-yl)-triphenylamine (abbreviation: PCBANB)

[0822] Step 2: 4-(1-naphthyl)-4'-(9-phenyl-9H-carbazole) The synthesis scheme of (phenyl-3-yl)-triphenylamine is shown in (W-2) below.

[0823] [ka]

[0824] 2.8 g (10 mmol) of 1-(4-bromophenyl)-naphthalene, 4-(9- 4.1 g (10 mmol) of (phenyl-9H-carbazol-3-yl)-diphenylamine ), sodium tert-butoxide 1.2g (12mmol), bis(dibenzyl 11 mg (0.02 mmol) of palladium(0) (deceneacetone) was added to a 100 mL three-neck flask. The mixture was placed in a flask and the atmosphere inside the flask was replaced with nitrogen. 30 mL of dehydrated xylene was added to the mixture. The mixture was degassed under reduced pressure while stirring, and after degassing, tri(tert-butyl) 0.1 mL (0.06 mmol) of methyltrimethylphosphine (10 wt % hexane solution) was added. The mixture was heated and stirred at 110° C. for 6 hours under a nitrogen atmosphere to allow the reaction to proceed.

[0825] After the reaction, 150 mL of toluene was added to the reaction mixture, and the suspension was The resulting filtrate was concentrated and purified by silica gel column chromatography. The resulting product was purified by HPLC (developing solvent: toluene:hexane = 1:4). The fractions were concentrated, and recrystallized after adding acetone and methanol and applying ultrasound. As a result, 5.2 g of the target white powder was obtained in a yield of 85%.

[0826] Unless otherwise specified, Florisil described in each synthesis method in the examples of the present invention is Wako Pure Chemical Industries, Ltd., Catalog Number: 540-00135. The material used is from Wako Pure Chemical Industries, Ltd., catalog number: 531-16855. . [Explanation of symbols]

[0827] 101 Substrate 102 first electrode 103 EL layer 104 Second electrode 111 First layer (hole injection layer) 112 Second layer (hole transport layer) 113 Third layer (light-emitting layer) 114 Fourth layer (electron transport layer) 115 Fifth layer (electron injection layer) 301 First electrode 302 Second electrode 303 First EL layer 304 Second EL layer 305 Charge generation layer 401 Drive circuit section (source side drive circuit) 402 Pixel section 404 Sealing substrate 405 Sealing material 407 Space 408 Wiring 409 FPC (Flexible Printed Circuit) 410 Element substrate 411 Switching TFT 412 Current control TFT 413 First electrode 414 Insulators 416 EL layer 417 Second Electrode 418 Light-emitting element 423 N-channel TFT 424 P-channel TFT 501 PCB 502 first electrode 503 Second electrode 504 EL layer 505 Insulation Layer 506 Partition layer 611 Case 612 Support stand 613 Display section 614 Speaker section 615 Video input terminal 621 Main Unit 622 Case 623 Display section 624 keyboard 625 External connection port 626 Pointing Device 631 Main Unit 632 Case 633 Display section 634 Audio Input Unit 635 Audio output section 636 Operation Key 637 External connection port 638 Antenna 641 Main Unit 642 Display section 643 Case 644 external connection port 645 Remote control receiver 646 Image receiving unit 647 Battery 648 Audio Input Unit 649 Operation Key 650 Eyepiece 701 Case 702 Liquid crystal layer 703 Backlight 704 Case 705 Driver IC 706 terminal 801 Case 802 light source 901 Lighting equipment 902 Television equipment 1501 Circuit Board 1502 First electrode 1503 EL layer 1504 Second electrode 1511 First Layer 1512 Second Layer 1513 Third Layer 1514 Fourth Layer 1515 Fifth Layer

Claims

[Claim 1] A carbazole derivative represented by general formula (1): 【Chemistry 1】 (In the formula, α １ , α ２ , α ３ , α ４ represents an arylene group having 13 or less carbon atoms forming a ring, Ar １ , Ar ２ represents an aryl group having 13 or less carbon atoms forming a ring, and R １ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group; R ２ represents an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group; and l, m, and n each independently represent 0 or 1.

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