Polycyclic aromatic compounds

Abstract

To provide a novel polycyclic aromatic compound having a plurality of aromatic rings linked by a boron atom, a nitrogen atom, and the like, and a material for an organic electroluminescent device comprising the compound.SOLUTION: The present invention provides a polycyclic aromatic compound represented by formula (1) (where A ring, B ring, C ring and D ring independently represent a substituted / unsubstituted aryl ring or heteroaryl ring, Y is B (boron), X1, X2, X3 and X4 independently represent >O, >N-R, >S or >Se, and Z1 and Z2 independently represent a substituted / unsubstituted aryl, a substituted / unsubstituted heteroaryl or the like).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycyclic aromatic compound, an organic electroluminescent device using the same, and an organic field-effect transistor. Used in organic devices such as transistors and organic thin-film solar cells, as well as display devices and lighting devices Regarding. [Background technology]

[0002] Conventionally, display devices using electroluminescent light-emitting elements have been developed to be energy-efficient and thin. Various researches have been conducted, and organic electroluminescent devices made of organic materials are easy to make lighter and larger. In particular, the luminescence properties of blue, one of the three primary colors of light, have been actively investigated. Development of organic materials with charge transport capabilities (holes, electrons, etc.) (potential to become semiconductors or superconductors) Regarding the development of organic materials with the potential for It has been actively researched to date.

[0003] The organic EL element comprises a pair of electrodes consisting of an anode and a cathode, and a light-emitting element disposed between the pair of electrodes. The layer containing the organic compound has a structure consisting of one or more layers. The layers include a light-emitting layer and a charge transport / injection layer that transports or injects charges such as holes and electrons. However, a variety of organic materials suitable for these layers have been developed.

[0004] As a material for the light-emitting layer, for example, benzofluorene-based compounds have been developed (International (Publication No. 2004 / 061047) Examples of hole transport materials include triphenylamine. Compounds based on ZnO have been developed (Japanese Patent Application Laid-Open No. 2001-172232). For example, anthracene-based compounds have been developed (Japanese Patent Laid-Open Publication No. 2005-170911).

[0005] In recent years, triphenylamine has been used as a material for organic EL elements and organic thin-film solar cells. Materials that have been improved from amine derivatives have also been reported (WO 2012 / 118164). The starting material was N,N'-diphenyl-N,N'-bis(3-methylphenyl) )-1,1'-biphenyl-4,4'-diamine (TPD) as a reference A material characterized by its enhanced planarity due to the linking of aromatic rings that make up the amine. In this document, for example, the charge transport properties of an NO-linked compound (compound 1 on page 63) However, there is no description of the manufacturing method of materials other than NO-linked compounds. In addition, if the linked elements are different, the electronic state of the entire compound will be different. Therefore, NO-linked compounds The properties that can be obtained from materials other than these are not yet known. For example, the triplet exciton energy (T1) is Compounds with large conjugated structures can emit phosphorescence at shorter wavelengths, resulting in blue light. In addition, it is useful as an electron transport material or a hole transport material sandwiching the light emitting layer. Therefore, there is a demand for compounds with novel conjugated structures that have large T1.

[0006] The host material for organic EL devices is generally an existing aromatic ring such as benzene or carbazole. It is a molecule in which multiple atoms are connected by single bonds or phosphorus or silicon atoms. By connecting many small aromatic rings, the large HOMO-LUMINUM required for the host material can be obtained. This is because the O gap (band gap Eg in the thin film) is guaranteed. The host materials for organic EL devices using materials and thermally activated delayed fluorescence (TADF) materials have high Triplet excitation energy (E T ) is also required, but the molecule must have donor or acceptor properties. By connecting aromatic rings and substituents, the SOMO1 and SOM of the triplet excited state (T1) can be By localizing O2 and reducing the exchange interaction between the two orbitals, the triplet excitation energy (E T However, small aromatic rings in the conjugated system can cause redox reactions. The stability was insufficient, so molecules made by linking existing aromatic rings were used as the host material. On the other hand, polycyclic aromatic compounds with extended π-conjugated systems generally have the following characteristics: Although the redox stability is excellent, the HOMO-LUMO gap (band gap in thin films) cap (Eg) and triplet excitation energy (E T ) is low, so it is considered unsuitable as a host material. It has been coming.

[0007] In recent years, compounds in which multiple aromatic rings are condensed with a central atom such as boron have also been reported. In this document, a dopant material for the light-emitting layer is The organic EL device evaluation using the compound in which the plurality of aromatic rings are condensed has been carried out. The document discloses a large number of compounds, among which the following are particularly well-known: It is beneficial to consider compounds with excellent organic electroluminescence properties.

[0008] In addition to the vacuum deposition method, wet film formation is also used as a method for forming the organic layers that make up the organic EL element. For the development of materials for the wet film formation method, the hole injection layer, hole transport layer and The development of inks for forming the hole injection layer and the light emitting layer is being actively pursued. The inks for the layer and the hole transport layer were formed by a wet film formation method using these inks. The properties of each layer have reached a practical level. The development of inks for red and green emitting layers is progressing towards improving their properties, but the ink for blue emitting layer is Ink is generally made of polycyclic aromatic compounds such as anthracene and styryl derivatives. Although development of compositions using conductors etc. has been carried out, they have not yet reached practical properties. However, currently, ink for blue light-emitting layers with high color purity has not been developed. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication No. 2004 / 061047 [Patent Document 2] Japanese Patent Application Laid-Open No. 2001-172232 [Patent Document 3] Japanese Patent Application Laid-Open No. 2005-170911 [Patent Document 4] International Publication No. 2012 / 118164 [Patent Document 5] International Publication No. 2011 / 107186 [Patent Document 6] International Publication No. 2015 / 102118 [Patent Document 7] International Publication No. 2001 / 072673 [Patent Document 8] International Publication No. 2012 / 102333 [Patent Document 9] Japanese Patent Application Laid-Open No. 2006-045503 [Patent Document 10] Japanese Patent Application Laid-Open No. 2013-168411 [Patent Document 11] Japanese Patent Application Laid-Open No. 2013-247179 [Patent Document 12] U.S. Patent Application Publication No. 2013 / 214259 Summary of the Invention [Problem to be solved by the invention]

[0010] As mentioned above, various materials have been developed for use in organic EL devices. However, it is necessary to further improve organic EL characteristics such as light-emitting properties and to select organic EL materials such as materials for the light-emitting layer. In order to increase options, it is desirable to develop compounds that have not been specifically known so far. [Means for solving the problem]

[0011] As a result of extensive research to solve the above problems, the present inventors have found that a boron atom and a nitrogen atom or is a polycyclic aromatic compound that has a specific structure, consisting of multiple aromatic rings linked by oxygen atoms. By using such a compound, it was found that an excellent organic EL device can be obtained, and the present invention was completed. That is, the present invention provides the following polycyclic aromatic compounds, and further the following polycyclic aromatic compounds. We provide organic device materials containing aromatic ring compounds.

[0012] Section 1. A polycyclic aromatic compound represented by the following general formula (1): [ka] (In the above formula (1), Ring A, ring B, ring C and ring D are each independently an aryl ring or a heteroaryl ring. rings, at least one hydrogen atom in these rings may be substituted; Y is B (boron), X 1 , X 2 , X 3 and X 4 are each independently >O, >NR, >S or >S e, and R of the >NR is an optionally substituted aryl, an optionally substituted R in the >NR is heteroaryl or optionally substituted alkyl. It may be bonded to the ring A, ring B, ring C and / or ring D via a linking group or a single bond. Ku, R 1 and R 2 are each independently hydrogen, alkyl having 1 to 6 carbon atoms, aryl having 2 to 15 carbon atoms, heteroaryl having 2 to 15 carbon atoms, or diarylamino (wherein aryl is aryl is an aryl having 6 to 12 carbon atoms; Z 1 and Z 2 each independently represents an optionally substituted aryl, a substituted optionally substituted heteroaryl, optionally substituted diarylamino, optionally substituted optionally substituted arylheteroarylamino; optionally substituted arylheteroarylamino; optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted arylthio or optionally substituted heteroarylthio; Z 1 is a linking group or may be bonded to the ring A via a single bond, and Z 2 is bonded to the ring C via a linking group or a single bond Well, and At least one hydrogen atom in the compound represented by formula (1) is cyano, halogen, or heavy. may be substituted with hydrogen.

[0013] Section 2. Ring A, ring B, ring C and ring D are each independently an aryl ring or a heteroaryl ring. rings, and at least one hydrogen atom in these rings is replaced by an aryl, heteroaryl, diaryl, arylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy, arylthio, may be substituted with heteroarylthio or alkyl-substituted silyl, At least one hydrogen may be replaced by an aryl, heteroaryl, or alkyl. The A and B rings may also be Y, X 1 and X 2 The fused two-ring structure on the left of the above formula is The C and D rings have a 5- or 6-membered ring that shares a bond with the structure, and the Y and X rings 3 and X 4 mosquito a 5- or 6-membered ring that shares a bond with the fused bicyclic structure of the right formula above, Y is B (boron), X 1 , X 2 , X 3 and X 4 are each independently >O, >NR, >S or >S e, wherein R of the >NR is aryl, heteroaryl, or alkyl, and R At least one hydrogen atom in the alkyl group is selected from the group consisting of aryl, heteroaryl, diarylamino, diethylamino, and diethylamino. arylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy oxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio or may be substituted with alkyl-substituted silyl, and R in the >NR may be -O-, - and ring A, ring B, ring C and / or ring D via S-, -C(-R)2- or a single bond. R in the -C(-R)2- may be hydrogen or alkyl; R 1 and R 2 are each independently hydrogen, alkyl having 1 to 6 carbon atoms, aryl having 2 to 15 carbon atoms, heteroaryl having 2 to 15 carbon atoms, or diarylamino (wherein aryl is aryl is an aryl having 6 to 12 carbon atoms; Z 1 and Z 2 are each independently an aryl, heteroaryl, or diarylamino group. , diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl , aryloxy, heteroaryloxy, arylthio or heteroarylthio At least one hydrogen atom in these groups is selected from aryl, heteroaryl, diaryla, and amino, alkyl, cycloalkyl, alkoxy, aryloxy or alkyl substituted silyl may be substituted with Z 1 is -O-, -S-, -C(-R)2- or a single bond may be bonded to the ring A via Z 2 is -O-, -S-, -C(-R)2- or It may be bonded to the ring C via a single bond, and R in the -C(-R)2- is hydrogen or alkyl. It was Lukil, and, At least one hydrogen atom in the compound represented by formula (1) is cyano, halogen, or heavy. optionally substituted with hydrogen; Item 1. The polycyclic aromatic compound according to item 1.

[0014] Section 3. Item 1. The polycyclic aromatic compound according to item 1, which is represented by the following general formula (2): [ka] (In the above formula (2), R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12Yes, respectively independently hydrogen, aryl, heteroaryl, diarylamino, diheteroaryl amino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryl aryloxy, heteroaryloxy, arylthio, heteroarylthio or alkyl and substituted silyl, in which at least one hydrogen is aryl, heteroaryl or or alkyl, and R 5 ~R 7 and R 10 ~R 12 Of Adjacent groups are bonded to form an aryl or heteroaryl ring together with ring b and / or ring d. At least one hydrogen atom in the formed ring may be substituted with an aryl, Heteroaryl, diarylamino, diheteroarylamino, arylheteroaryl Amino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy substituted with silyl, arylthio, heteroarylthio, or alkyl-substituted silyl. At least one hydrogen atom in these groups is an aryl, heteroaryl, or alkyl. may be substituted with Y is B (boron), X 1 , X 2 , X 3 and X 4 are each independently >O, >NR, >S or >S e, and R in the >NR is an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or R in the >NR is -O-, -S -, -C(-R)2- or a single bond to the ring a, ring b, ring c and / or ring d R in the -C(-R)2- is hydrogen or alkyl having 1 to 6 carbon atoms. the law of nature, R 1 and R 2 are each independently hydrogen, alkyl having 1 to 6 carbon atoms, or alkyl having 6 carbon atoms. is an aryl of 12 or less, Z 1 and Z 2 are each independently an aryl, heteroaryl, or diarylamino group. , diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl , aryloxy, heteroaryloxy, arylthio or heteroarylthio At least one hydrogen atom in these groups is selected from aryl, heteroaryl, alkyl, or may be substituted with alkyl-substituted silyl; Z 1 -O-, -S-, -C(-R) may be bonded to the ring a via a double bond or a single bond, Z 2 -O-, -S-, -C(- R of said -C(-R)2- may be bonded to said ring c by a single bond, and R of said -C(-R)2- may be hydrogen. is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and At least one hydrogen atom in the compound represented by formula (2) is cyano, halogen, or heavy. may be substituted with hydrogen.

[0015] Section 4. R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Yes, respectively each independently represents hydrogen, an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, or a diaryl Arylamino (where aryl is aryl with 6 to 12 carbon atoms), alkyl with 1 to 6 carbon atoms , aryloxy having 6 to 12 carbon atoms, or arylthio having 6 to 12 carbon atoms, At least one hydrogen atom in the formula (I) is selected from aryl having 6 to 12 carbon atoms or aryl having 1 to 6 carbon atoms. may be replaced by kill, or R 5 ~R 7 and R 10 ~R 12 Adjacent of The groups are bonded to each other to form an aryl ring or carbon atom having 9 to 16 carbon atoms together with the b ring and / or the d ring. A heteroaryl ring having 6 to 15 rings may be formed, and at least One hydrogen is substituted with an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 6 carbon atoms. It is okay to Y is B (boron), X 1 , X 2 , X 3 and X 4 are each independently >O or >NR, R in NR is an aryl having 6 to 10 carbon atoms or an alkyl having 1 to 4 carbon atoms, R 1 and R 2 are each independently hydrogen, alkyl having 1 to 6 carbon atoms, or alkyl having 6 carbon atoms. is an aryl of 12 or less, Z 1 and Z 2 are each independently an aryl having 6 to 30 carbon atoms, an aryl having 2 to 30 carbon atoms, Heteroaryl, diarylamino (where aryl has 6 to 12 carbon atoms), carbon Alkyl with 1 to 12 prime numbers, cycloalkyl with 3 to 12 carbon atoms, aryl with 6 to 30 carbon atoms oxy, heteroaryloxy having 2 to 30 carbon atoms, arylthio having 6 to 30 carbon atoms, or heteroarylthio having 2 to 30 carbon atoms, in which at least one hydrogen atom is Aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 12 carbon atoms silyl or trialkyl-substituted silyl (wherein the alkyl has 1 to 6 carbon atoms) and At least one hydrogen atom in the compound represented by formula (2) is cyano, halogen, or heavy. optionally substituted with hydrogen; Item 3. The polycyclic aromatic compound according to item 3.

[0016] Section 5. R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Yes, respectively are independently hydrogen, aryl having 6 to 10 carbon atoms, or alkyl having 1 to 6 carbon atoms; Y is B (boron), X 1 , X 2 , X 3 and X 4 are each independently >O or >NR, R in NR is an aryl having 6 to 10 carbon atoms or an alkyl having 1 to 4 carbon atoms, R 1 and R 2 are each independently hydrogen, alkyl having 1 to 6 carbon atoms, or alkyl having 6 carbon atoms. is an aryl of 12 or less, Z 1 and Z 2 are each independently an aryl having 6 to 16 carbon atoms, an aryl having 2 to 15 carbon atoms, Heteroaryl, diarylamino (where aryl has 6 to 10 carbon atoms), carbon Alkyl with 1 to 6 prime numbers, cycloalkyl with 3 to 10 carbon atoms, aryl alkyl with 6 to 12 carbon atoms arylthio or arylthio having 6 to 12 carbon atoms, may be substituted with an aryl having 6 to 10 carbon atoms or an alkyl having 1 to 6 carbon atoms, do, At least one hydrogen atom in the compound represented by formula (2) is cyano, halogen, or heavy. optionally substituted with hydrogen; Item 3. The polycyclic aromatic compound according to item 3.

[0017] Section 6. Item 1. The polycyclic aromatic compound according to item 1, which is represented by any one of the following formulas: [ka] [ka] [ka] [ka] [ka] (At least one hydrogen atom in the compounds represented by the above formulas is an alkyl group having 1 to 6 carbon atoms.) , which may be substituted with an aryl having 6 to 10 carbon atoms, cyano, halogen or deuterium, In the formula, each R is independently an alkyl having 1 to 6 carbon atoms or an aryl having 6 to 10 carbon atoms. Yes, R 100 are each independently an aryl having 6 to 10 carbon atoms, a carbazolyl, or a diaryl Arylamino (where aryl is aryl with 6 to 10 carbon atoms), alkyl with 1 to 6 carbon atoms , cycloalkyl having 3 to 10 carbon atoms, or aryloxy having 6 to 10 carbon atoms; The aryl may be substituted with alkyl having 1 to 6 carbon atoms, and the carbazolyl may be substituted with carbon atoms. It may be substituted with an aryl having 6 to 10 carbon atoms or an alkyl having 1 to 6 carbon atoms.

[0018] Section 7. A material for an organic device containing the polycyclic aromatic compound according to any one of items 1 to 6. .

[0019] Section 8. The organic device material includes a material for an organic electroluminescent element and a material for an organic field effect transistor. Item 8. The material for organic devices according to Item 7, which is a material for organic thin-film solar cells.

[0020] Section 9. Item 9. The organic device material according to Item 8, wherein the material for organic electroluminescent elements is a material for a light-emitting layer. Fee.

[0021] Section 10. A composition for forming a light-emitting layer for forming a light-emitting layer of an organic electroluminescent device by coating, comprising: As a first component, at least one polycyclic aromatic compound described in any one of items 1 to 6 , as a second component, at least one host material; As a third component, at least one organic solvent; A composition for forming a light-emitting layer comprising:

[0022] Section 11. A pair of electrodes consisting of an anode and a cathode, and a generator described in item 9, which is disposed between the pair of electrodes. and a light-emitting layer containing a material for the light-emitting layer.

[0023] Section 12. A pair of electrodes consisting of an anode and a cathode, and a device described in item 10, which is disposed between the pair of electrodes. and a light-emitting layer formed by applying and drying a composition for forming a light-emitting layer.

[0024] Section 13. The light-emitting layer further comprises a compound represented by the following general formula (3) and / or a compound represented by the following general formula (4): Item 13. The organic electroluminescent device according to item 11 or 12, comprising a compound represented by the formula: [ka] (In the above formula (3), L 1 is an arylene having 6 to 24 carbon atoms, In the above formula (4), L 2 and L 3 are each independently an aryl having 6 to 30 carbon atoms or or heteroaryl having 2 to 30 carbon atoms, At least one hydrogen atom in the compounds represented by the above formulas is replaced by an alkyl group having 1 to 6 carbon atoms. , cyano, halogen or deuterium.

[0025] Section 14. Any of items 11 to 13, wherein the light-emitting layer further contains a compound represented by the following general formula (5): The organic electroluminescent device according to any one of claims 1 to 4. [ka] (In the above formula (5), R 1 ~R 11 are each independently hydrogen, aryl, heteroaryl, diaryla amino, diheteroarylamino, arylheteroarylamino or alkyl; At least one hydrogen atom in these may be further selected from aryl, heteroaryl, diaryla, may be substituted with amino or alkyl, R 1 ~R 11 Adjacent groups among these are bonded to form an aryl ring together with the a, b or c ring. A ring or heteroaryl ring may be formed, and at least one of the rings formed The hydrogen of the aryl, heteroaryl, diarylamino, diheteroarylamino, The alkyl group may be substituted with aryl, heteroaryl, amino or alkyl, and at least one of these may be substituted with aryl, heteroaryl, amino or alkyl. At least one hydrogen may further be aryl, heteroaryl, diarylamino, or alkyl. may be substituted with methyl; At least one hydrogen atom in the compound represented by formula (5) is independently selected from the group consisting of halo, It may be substituted with hydrogen or deuterium.

[0026] Section 15. an electron transport layer and / or an electron injection layer disposed between the cathode and the light-emitting layer; At least one of the electron transport layer and the electron injection layer is formed using a compound selected from the group consisting of borane derivatives, pyridine derivatives, fluorine derivatives, and the like. Fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, Sphingoxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives , benzimidazole derivatives, phenanthroline derivatives and quinolinol-based metal complexes 15. The method according to any one of items 11 to 14, comprising at least one selected from the group consisting of: Organic electroluminescent device.

[0027] Section 16. The electron transport layer and / or the electron injection layer may further comprise an alkali metal, an alkaline earth metal, or metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metals oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals genides, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals Item 16. The organic electroluminescent device according to item 15, comprising at least one selected from the group consisting of organic complexes. Optical element.

[0028] Section 17. A display device or a lighting device comprising the organic electroluminescent device according to any one of items 11 to 16. . [Effects of the Invention]

[0029] According to a preferred embodiment of the present invention, a previously unknown compound represented by formula (1) is The polycyclic aromatic compounds further enhance organic EL properties such as light-emitting properties, and are also useful as materials for the light-emitting layer. This will increase the options for organic EL materials such as [Brief explanation of the drawings]

[0030] [Figure 1] 1 is a schematic cross-sectional view showing an organic EL element according to an embodiment of the present invention. [Figure 2] 1 shows the absorption, fluorescence, and phosphorescence spectra of compound (1-1). [Figure 3] 1 shows the absorption, fluorescence, and phosphorescence spectra of compound (1-201). [Figure 4] 1 shows the absorption, fluorescence, and phosphorescence spectra of compound (1-101). [Figure 5] 1 shows the absorption, fluorescence, and phosphorescence spectra of compound (1-9). [Figure 6] FIG. 1 is a diagram showing the organic EL characteristics (luminance) of compound (1-1). [Figure 7] FIG. 1 is a diagram showing the organic electroluminescence characteristics (external quantum efficiency) of compound (1-1). [Figure 8] FIG. 2 is a diagram showing the organic electroluminescence characteristics (emission spectrum) of compound (1-1). [Figure 9] FIG. 1 is a diagram illustrating a method for producing an organic EL element on a substrate having a bank by using an inkjet method. DETAILED DESCRIPTION OF THE INVENTION

[0031] 1. Polycyclic aromatic compounds represented by formula (1) The polycyclic aromatic compound represented by the general formula (1) is preferably represented by the following general formula (2): It is a polycyclic aromatic compound. [ka]

[0032] For example, light-emitting materials for organic EL displays include fluorescent materials, phosphorescent materials, and thermally activated materials. Three types of delayed fluorescence (TADF) materials are used, but fluorescent materials have low luminous efficiency. On the other hand, phosphorescent materials and TADF materials have a luminous efficiency of 1. Although it may reach 0.00%, the color purity is low (the width of the emission spectrum is wide). In displays, the three primary colors of light, red, green, and blue, are mixed together. However, if the purity of each color is low, some colors cannot be reproduced. This causes the image quality of the display to drop significantly. By removing unwanted colors from the emission spectrum with optical filters, color purity is improved. Therefore, the original spectral width is If the area is wide, the removal rate increases, so even if the luminous efficiency is high, the actual efficiency will be significantly lower. For example, the half-width of the blue light emission spectrum of a commercially available smartphone is approximately 20 The half-width of a typical fluorescent material is about 40-60 nm, while that of a typical phosphorescent material is about 25 nm. For fluorescent materials, it is about 60 to 90 nm, and for TADF materials it is about 70 to 100 nm. In the case of phosphorescent materials, the half-width is relatively narrow, so it is sufficient to remove only a part of the unwanted color. When using TADF materials, more than half of the light must be removed. There has been a demand for the development of luminescent materials that combine both high efficiency and color purity.

[0033] Generally, TADF materials consist of electron-donating substituents called donors and acceptors. By using electron-accepting substituents with the ability to localize the HOMO and LUMO in a molecule, efficient reverse It is designed to allow reverse intersystem crossing to occur, but The use of a valence atom or an acceptor increases the structural relaxation in the excited state (in some molecules, Since the stable structures of the ground state and excited state are different, external stimuli can cause the ground state to transition to the excited state. After this conversion, the structure changes to the stable structure in the excited state), and the color purity is This results in a low and broad emission spectrum.

[0034] Therefore, in Patent Document 6 (International Publication No. 2015 / 102118), the color purity of TADF materials is The paper proposes a new molecular design that dramatically improves the In (1-401), the multiple resonance effect of boron (electron donating) and nitrogen (electron withdrawing) is utilized. By doing so, the HOMO is located at three carbon atoms (black circles) on the benzene ring, which consists of six carbon atoms, and the remaining The LUMO is successfully localized on the three carbon atoms (white circles) of the Due to the crossover, the luminescence efficiency of the compound reaches up to 100%. The boron and nitrogen atoms in 401 not only localize the HOMO and LUMO, but also The fused Zene ring maintains a robust planar structure and suppresses structural relaxation in the excited state. As a result, the Stokes shift of the absorption and emission peaks is small. In this case, they have also succeeded in obtaining an emission spectrum with high color purity. The half-width is 28 nm, which is a level of color that surpasses even the high color purity of fluorescent materials currently in practical use. In addition, in a dimer compound such as formula (1-422), two boron atoms and The two nitrogen atoms bond to the central benzene ring, creating multiple bonds in the central benzene ring. This enhances the resonance effect, resulting in emission with an extremely narrow emission peak width. It is. [ka]

[0035] On the other hand, in the dimer compound such as formula (1-422), the molecular planarity is high and the resonance is broad. The emission wavelength is longer and farther from the practical blue wavelength. This may be due to the intermolecular stacking induced by the ZnO-based ZnO nanoparticles, and the efficiency of the light-emitting device is also satisfactory. The issue also arose that this was not the case.

[0036] Therefore, as a result of our intensive research, we have introduced substituents at appropriate positions to adjust the multiple resonance effect. This has made it possible to shorten the wavelength of light emitted and to achieve high device efficiency. The polycyclic aromatic compound represented by formula (1) is a compound having two Z (Z 1 and Z 2 ) as Z. All electron-withdrawing or electron-donating functional groups allow the entire molecule to be oriented through the resonance of the A and C rings. Affecting the resonance structure and / or multiple resonance effects of the molecule. For example, introducing electron-withdrawing groups By doing so, the electron density of the LUMO can be reduced, shortening the emission wavelength. Regardless of donor nature, the introduction of a substituent at Z allows the molecule to exist on the same plane. The ratio of the structure is reduced, which reduces the stacking between molecules. The light wavelength was significantly shortened, and in addition, intermolecular stacking was reduced by introducing substituents. However, the polycyclic aromatic compound of the present invention The effect of is not limited to the above principle.

[0037] In general formula (1), ring A, ring B, ring C and ring D are each independently an aryl ring. or heteroaryl ring, and at least one hydrogen atom in these rings is replaced by a substituent. The substituent may be a substituted or unsubstituted aryl, a substituted or unsubstituted Heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroaryl arylamino, substituted or unsubstituted arylheteroarylamino (aryl and heteroaryl an amino group having an alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted aryloxy represents unsubstituted heteroaryloxy, substituted or unsubstituted arylthio, substituted or unsubstituted Heteroarylthio or alkyl-substituted silyl are preferred. When present, the substituents include aryl, heteroaryl, or alkyl.

[0038] In addition, the A and B rings are "Y", "X" 1 " and "X 2 " The above formula (1) It has a 5- or 6-membered ring that shares a bond with the fused 2-ring structure on the left, and the C and D rings are "Y" , "X 3 " and "X 4 " and the fused two-ring structure of the formula (1) on the right. It is preferred that the ring has a five- or six-membered ring.

[0039] Here, the "fused bicyclic structure" refers to the "Y" and "X" shown on the left side of general formula (1). 1 "oh Call "X 2 " means a structure in which two saturated hydrocarbon rings are fused together. The same applies to the fused bicyclic structure on the right side of general formula (1). The "six-membered ring sharing a bond" refers to, for example, a fused two-ring structure as shown in the above general formula (2). Also, "(A ring) aryl ring or "The heteroaryl ring has this six-membered ring" means that the A ring is formed only by this six-membered ring. Or, other rings are condensed to this six-membered ring to form ring A. In other words, the "6-membered ring (A ring)" "Heteroaryl ring or heteroaryl ring" means that the 6-membered ring constituting all or part of ring A is fused. This means that the ring is fused to a two-ring structure. The same explanation applies to "(d ring)" and "5-membered ring."

[0040] The ring A (or ring B, ring C, or ring D) in the general formula (1) is the ring a in the general formula (2). and its substituent R 3 and R 4 (or ring b and its substituent R 5 ~R 7 , ring c and its substituent R 8 and R 9 , d ring and its substituent R 10 ~R 12 ) That is, it corresponds to the general formula (2) corresponds to a formula in which "rings A to D having a 6-membered ring" is selected as rings A to D in general formula (1). In this sense, each ring in general formula (2) is represented by a lower case letter a to d.

[0041] R in general formula (2) 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 oh Yobi R 12are each independently hydrogen, aryl, heteroaryl, diarylamino , diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl , alkoxy, aryloxy, heteroaryloxy, arylthio, heteroaryl thio or alkyl-substituted silyl, in which at least one hydrogen is aryl. The group may be substituted with aryl, heteroaryl or alkyl.

[0042] In the general formula (2), the substituent R 5 ~R 7 and / or the substituent R of the d ring 10 ~R 1 2 Adjacent groups among these are bonded to form an aryl ring or a heterocyclic ring together with ring b and / or ring d. A heteroaryl ring may be formed, and at least one hydrogen atom in the ring formed may be an aryl group. Aryl, heteroaryl, diarylamino, diheteroarylamino, arylhetero Arylamino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryl substituted with aryloxy, arylthio, heteroarylthio or alkyl-substituted silyl At least one hydrogen atom in these groups may be aryl, heteroaryl, or aryl. Therefore, the compound represented by the general formula (2) may be substituted with a ring b and Depending on the mutual bonding form of the substituents in the d ring and the d ring, the compound can be formed as shown in the following formula (2-1). The ring structures constituting the compound change. ) respectively correspond to the B ring and the D ring. The definitions of each symbol in formula (2-1) are as follows: The symbols are the same as those in general formula (2).

[0043] [ka]

[0044] The rings B′ and D′ in the above formula (2-1) are, as explained in the general formula (2), the substituents R 5 ~R 7 and R 10 ~R 12 Adjacent groups of the The aryl or heteroaryl ring formed with the ring (the b or d ring has another ring structure) (It can also be said that the ring structure is condensed.) Also, as can be seen from the above formula (2-1), b Ring R 7 and d-ring R 12 are not considered to be "adjacent groups" and are not bonded to each other. In other words, "adjacent groups" means groups adjacent to each other on the same ring. 1 is concatenated It may be bonded to ring A (ring a) via a group or a single bond, and Z 2 is a linking group or a single bond, C It may be bonded to the ring (ring c), and when bonded, it forms a ring structure similar to the ring B' and ring D' described above. will change.

[0045] The compound represented by the above formula (2-1) can be, for example, a compound represented by the formula (2-1) listed below as a specific compound. (1-5) That is, for example, in the b ring (or d ring), Some benzene rings are benzene rings, others are indole rings, pyrrole rings, benzofurano rings It has a B' ring (or D' ring) formed by condensation of a benzothiophene ring or a benzothiophene ring. The fused ring B' (or fused ring D') formed is a naphthalene ring, In addition to the above, a carbazole ring, an indole ring, a dibenzofuran ring, or a dibenzothiophene ring And so on.

[0046] Y is B (boron).

[0047] X in general formula (1) 1 , X 2 , X 3 and X 4 are independently >O, >N -R, >S or >Se, wherein R of said >NR is optionally substituted aryl; optionally substituted heteroaryl or optionally substituted alkyl; R of the >NR is a linking group or a single bond to the ring A, ring B, ring C and / or ring D The linking group may be -O-, -S- or -C(-R)2-. It is preferable that R in the above "-C(-R)2-" is hydrogen or alkyl. X in general formula (2) 1 , X 2 , X 3 and X 4 But it's the same.

[0048] In the general formula (1), R in >NR is a linking group or a single bond that binds to the ring A, The definition of "bonded to ring B, ring C and / or ring D" means ">N- R in R is -O-, -S-, -C(-R)2-, or a single bond between the ring a, ring b, and ring c. and / or bonded to the d ring."

[0049] This rule is expressed by the following formula (2-3), X 1 or X 3 is fused ring B' and fused ring D' That is, for example, in the general formula (2), X for the b-ring (or d-ring) benzene ring in 1 (or X 3 ) to incorporate It is a compound having a ring B' (or ring D') formed by condensing another ring to the ring B'. The compound is, for example, a compound represented by formula (1-11) listed below as a specific compound. The fused ring B' (or fused ring D') formed corresponds to the compound, for example, a carbazole. Other examples include a phenoxazine ring, a phenothiazine ring, and an acridine ring. The definitions of the symbols in formula (2-3) are the same as those in general formula (2).

[0050] [ka]

[0051] In equation (2-3), X 1 or X 3 is incorporated into fused ring B' and fused ring D'. However, X 2 or X 4 Similarly, R in >NR can be bonded to the a-ring or c-ring, When the ring is bonded to the ring, the ring structure changes in the same manner as the ring B' and ring D' described above.

[0052] In addition, the substituent Z in the general formula (2) 1 and Z 2 The substitution positions of The para position of the ring A in the general formula (1) is limited to the position where Y (boron) is bonded. The C ring is not limited to a benzene ring but may be various aryl rings or heteroaryl rings. Substituent Z on the ring 1 and Z 2 The substitution position of is not limited, but as in the general formula (2), It is preferable to substitute at a position relatively far from the position where the nucleotide is to be bound. For example, when the ring A is a naphthalene ring or a fluorene ring, , this Z 1 (and Z2 Preferred substitution positions of the aryl group are shown below. The symbols have the same definition as those in formula (2). A is >CR2, >NR2, >O or > S, and R is hydrogen, alkyl (preferably alkyl having 1 to 4 carbon atoms), or phenyl. be. [ka]

[0053] R in general formula (1) or general formula (2) 1 and R 2 are each independently hydrogen , alkyl having 1 to 6 carbon atoms, aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms and aryl or diarylamino (wherein aryl has 6 to 12 carbon atoms).

[0054] Z in general formula (1) or general formula (2) 1 and Z 2 are independently aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroaryl arylamino, alkyl, aryloxy, heteroaryloxy, arylthio or heteroarylthio, in which at least one hydrogen atom is selected from aryl, heteroaryl, Aryl, diarylamino, alkyl, cycloalkyl, alkoxy, aryloxy or alkyl-substituted silyl, Z 1 is a linking group or a single bond, and may be bonded to ring (a ring), Z 2 is bonded to the C ring (c ring) via a linking group or a single bond Examples of the linking group include -O-, -S-, and -C(-R)2-. In the formula -C(-R)2-, R is hydrogen or alkyl.

[0055] Examples of the "aryl rings" which are rings A, B, C and D in general formula (1) include: Examples of the aryl ring include an aryl ring having 6 to 30 carbon atoms, and an aryl ring having 6 to 16 carbon atoms is preferred. An aryl ring having 6 to 12 carbon atoms is more preferred, and an aryl ring having 6 to 10 carbon atoms is particularly preferred. In addition, this "aryl ring" is "R 5 ~R 7 and R 10 ~R 12 adjacent groups are bonded to each other to form an aryl group together with ring b and / or ring d. The b ring (or d ring) is already composed of a benzene ring with six carbon atoms. Therefore, the total number of carbon atoms in the fused ring formed by fusing this with a 5-membered ring is 9, which is the lower limit of the number of carbon atoms. Z 1 is bonded to ring A (ring a) via a linking group or single bond to form an aryl ring, or Z 2 Garen The same applies to an aryl ring formed by bonding to the C ring (c ring) via a bond or single bond.

[0056] Specific examples of the "aryl ring" include a monocyclic benzene ring and a bicyclic biphenyl ring. ring, a fused bicyclic ring, a naphthalene ring, a tricyclic ring, a terphenyl ring (m-terphenyl, o-Terphenyl, p-Terphenyl), fused tricyclic ring system, acenaphthylene ring, fluoro phenylene ring, phenalene ring, phenanthrene ring, triphenylene ring which is a fused tetracyclic ring system, pyrene ring, naphthacene ring, and fused five-ring system perylene ring and pentacene ring.

[0057] Examples of the "heteroaryl ring" which is ring A, ring B, ring C and ring D in general formula (1) include: Examples include heteroaryl rings having 2 to 30 carbon atoms, and heteroaryl rings having 2 to 25 carbon atoms. A heteroaryl ring having 2 to 20 carbon atoms is preferred, a heteroaryl ring having 2 to 15 carbon atoms is more preferred. Heteroaryl rings are more preferred, and heteroaryl rings having 2 to 10 carbon atoms are particularly preferred. Furthermore, examples of "heteroaryl rings" include rings in which oxygen, sulfur, and the like are present in addition to carbon atoms. and heterocycles containing 1 to 5 heteroatoms selected from nitrogen. The "heteroaryl ring" is defined as "R 5 ~R 7 and R 10 ~ R 12 Adjacent groups among these are bonded to form a heterocycle together with ring b and / or ring d. The b ring (or d ring) already consists of a benzene ring with 6 carbon atoms. Therefore, the total number of carbon atoms in the fused ring formed by condensing this with a 5-membered ring is 6, which is the lower limit. Also, Z 1 is bonded to ring A (ring a) via a linking group or single bond to form a heteroaryl Ring and Z 2 A heteroaryl ring formed by bonding to the C ring (c ring) via a linking group or a single bond is also The same is true.

[0058] Specific examples of the "heteroaryl ring" include a pyrrole ring, an oxazole ring, an isoaryl ring, and an aryl ring. Oxazole ring, thiazole ring, isothiazole ring, imidazole ring, oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, Pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole 1H-indazole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, Azole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring , quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridin ring ring, carbazole ring, acridine ring, phenoxathiin ring, phenoxazine ring, phenon Thiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring Ran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring , a furazan ring, an oxadiazole ring, a thianthrene ring, and the like.

[0059] At least one hydrogen atom in the above "aryl ring" or "heteroaryl ring" is 1, a substituted or unsubstituted "aryl", a substituted or unsubstituted "heteroaryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteroaryl" substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "alkyl", substituted or unsubstituted "cycloalkyl", substituted or unsubstituted "alkoxy", "aryloxy", substituted or unsubstituted "heteroaryloxy", substituted or unsubstituted "aryloxy", substituted or unsubstituted "arylthio", substituted or unsubstituted "heteroaryl The first substituent may be substituted with methyl silyl or alkyl-substituted silyl. "aryl", "heteroaryl", "diarylamino" aryl, "diheteroaryl" The heteroaryl in "arylamino" and the aryl and heteroaryl in "arylheteroarylamino" The aryl in "aryloxy" and the heteroaryl in "heteroaryloxy" The aryl of "arylthio" and the heteroaryl of "heteroarylthio" are listed above. Examples thereof include the monovalent groups of the aforementioned "aryl ring" or "heteroaryl ring".

[0060] The "alkyl" as the first substituent may be either a straight chain or a branched chain. Examples of the alkyl group include linear alkyl groups having 1 to 24 carbon atoms and branched alkyl groups having 3 to 24 carbon atoms. Alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms) is preferred, Alkyl groups having 1 to 12 prime numbers (branched alkyl groups having 3 to 12 carbon atoms) are more preferred, and alkyl groups having 1 to 12 prime numbers (branched alkyl groups having 3 to 12 carbon atoms) are more preferred. Alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms) is more preferred, and alkyl having 1 to 4 carbon atoms is more preferred. Alkyl (branched alkyl having 3 to 4 carbon atoms) is particularly preferred.

[0061] Specific examples of alkyl include methyl, ethyl, n-propyl, isopropyl, and n-butyl. butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl , t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl , n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5, 5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n -hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, etc. do.

[0062] Furthermore, examples of the "cycloalkyl" as the first substituent include cycloalkyl having 3 to 12 carbon atoms. Preferred cycloalkyls include cycloalkyls having 3 to 10 carbon atoms. More preferred cycloalkyl is cycloalkyl having 3 to 8 carbon atoms. The most preferred cycloalkyl is cycloalkyl having 3 to 6 carbon atoms.

[0063] Specific cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, Cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclo dimethylcyclohexyl, dimethylcyclohexyl, and adamantyl.

[0064] Furthermore, the "alkoxy" as the first substituent includes, for example, straight chain or alkyl groups having 1 to 24 carbon atoms. or branched alkoxy having 3 to 24 carbon atoms. Branched alkoxy having 3 to 18 carbon atoms is preferred, and alkoxy having 1 to 12 carbon atoms (carbon Alkoxy having 1 to 6 carbon atoms (branched alkoxy having 3 to 12 carbon atoms) is more preferred, and alkoxy having 1 to 6 carbon atoms (branched alkoxy having 3 to 12 carbon atoms) is more preferred. Alkoxy having 1 to 4 carbon atoms (branched alkoxy having 3 to 6 carbon atoms) is more preferred, and alkoxy having 1 to 4 carbon atoms (branched alkoxy having 3 to 6 carbon atoms) is more preferred. Particularly preferred are alkoxy groups having up to 4 branched chains.

[0065] Specific examples of alkoxy include methoxy, ethoxy, propoxy, isopropoxy, and butyl. butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy , heptyloxy, octyloxy, and the like.

[0066] The "alkyl-substituted silyl" as the first substituent includes trialkyl-substituted silyl. The alkyl to be substituted is preferably the same as the "alkyl" as the first substituent described above. You can refer to the description.

[0067] The first substituent is a substituted or unsubstituted "aryl", a substituted or unsubstituted "hetero aryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "dihetero arylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "arylheteroarylamino", Unsubstituted "alkyl", substituted or unsubstituted "cycloalkyl", substituted or unsubstituted " "alkoxy", "substituted or unsubstituted aryloxy", "substituted or unsubstituted heteroaryl" substituted or unsubstituted "aryloxy", substituted or unsubstituted "arylthio", substituted or unsubstituted "heteroaryl" "Reilchio" is described as substituted or unsubstituted, and at least One hydrogen atom may be substituted with a second substituent, such as , aryl, heteroaryl or alkyl, and specific examples thereof are those described above in " A monovalent group of an "aryl ring" or "heteroaryl ring", and an "aryl" as a first substituent The explanation of "aryl" can be found in the following. In addition, the aryl and heteroaryl groups as the second substituents are Aryl groups include those in which at least one hydrogen atom is replaced by an aryl such as phenyl (examples are Groups substituted with alkyl (specific examples of which are the groups listed above) or methyl (specific examples of which are the groups listed above) can also be used as the second substituent. The substituents aryl and heteroaryl include, for example, In the case of a carbazolyl group, at least one hydrogen atom at the 9-position is an aryl group such as phenyl. Carbazolyl groups substituted with alkyl groups such as methyl and methyl are also suitable as heteroaryl groups. Included in the reel.

[0068] R in general formula (2) 3 ~R 12 Aryl, heteroaryl, diarylamino aryl, diheteroarylamino, heteroaryl, arylheteroarylamino aryl and heteroaryl of aryloxy, aryl of heteroaryloxy, heteroaryl of heteroaryloxy Examples of the heteroaryl, aryl in arylthio, and heteroaryl in heteroarylthio include: Examples include the monovalent groups of the "aryl ring" or "heteroaryl ring" explained in the general formula (1). Also, R 3 ~R 12 Alkyl, cycloalkyl, alkoxy or alkyl The alkyl-substituted silyl includes the alkyl group as the first substituent in the description of the general formula (1). "Alkyl," "cycloalkyl," "alkoxy," or "alkyl-substituted silyl" Further, aryl and heteroaryl groups as substituents on these groups can be used. The same applies to aryl or alkyl. 5 ~R 7 and R 10 ~R 12 Adjacent of The groups bond together to form an aryl ring or heteroaryl ring together with ring b or ring d. In the case where the substituents on these rings are aryl, heteroaryl, diarylamino, di Heteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, a Alkoxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio or alkyl-substituted silyl, and further substituents aryl, heteroaryl or The same applies to alkyl.

[0069] X in general formula (1) 1 , X 2 , X 3 and X 4 In NR, R is aryl, hetero aryl or alkyl, and at least one hydrogen atom in these is aryl, hetero Diaryl, diarylamino, diheteroarylamino, arylheteroarylamino alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy, It may be substituted with arylthio, heteroarylthio or alkyl-substituted silyl. Examples of these groups and the substituents that substitute thereon include the examples described above. 0 aryl (e.g., phenyl, naphthyl, etc.), heteroaryl having 2 to 15 carbon atoms (e.g., carbazolyl, etc.), and alkyl having 1 to 4 carbon atoms (for example, methyl, ethyl, etc.). This explanation is based on X in general formula (2). 1 , X 2 , X 3 and X 4 But it's the same.

[0070] In the general formula (1), R in the linking group "-C(-R)2-" is hydrogen or alkyl. The alkyl group may be any of the groups described above. Alkyl groups with 1 to 4 prime numbers (e.g., methyl, ethyl, etc.) are preferred. This explanation is based on the general formula (2 The same applies to the linking group "-C(-R)2-" in

[0071] R in general formula (1) or general formula (2) 1 and R 2 Alkyl having 1 to 6 carbon atoms aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, or diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms) Description of "alkyl", "aryl", "heteroaryl" or "diarylamino" can be referred to.

[0072] Z in general formula (1) or general formula (2) 1 and Z 2In the aryl, heteroaryl aryl, diarylamino, diheteroarylamino, arylheteroarylamino, aryl alkyl, cycloalkyl, aryloxy, heteroaryloxy, arylthio or heteroaryloxy aryl, heteroaryl, diaryl, and arylthio as substituents thereon; alkyl, cycloalkyl, alkoxy, aryloxy or alkyl group The substituted silyl groups are also the same as those described above for "aryl," "heteroaryl," and "diarylamino." "," "diheteroarylamino," "arylheteroarylamino," "arylox "arylthio", "heteroaryloxy", "arylthio", "aryl See the explanation for "alkyl," "cycloalkyl," "alkoxy," or "alkyl-substituted silyl." The preferred Z 1 and Z 2 is, for example, diarylamino, alkyl , cycloalkyl, aryloxy, heteroaryl such as carbazole.

[0073] In addition, all or part of the hydrogen atoms in the compound represented by the general formula (1) or (2) are It may be substituted with cyano, halogen or deuterium. For example, in formula (1): Ring A, ring B, ring C, ring D (rings A to D are aryl or heteroaryl rings), The substituent, X 1 ~X 4 In NR, R (=aryl, heteroaryl, alkyl) ), R 1 , R 2 , Z 1 and Z 2 where hydrogen is replaced by cyano, halogen or deuterium. Among these, all or some of the hydrogen atoms in the aryl and heteroaryl groups can be substituted with silyl groups. Examples of the halogen include fluorine, chlorine, and the like. , bromine or iodine, preferably fluorine, chlorine or bromine, more preferably chlorine. be.

[0074] Specific examples of the polycyclic aromatic compound represented by formula (1) include compounds represented by the following structural formula: Examples of compounds that can be used include: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (At least one hydrogen atom in the compounds represented by the above formulas is an alkyl group having 1 to 6 carbon atoms.) , which may be substituted with an aryl having 6 to 10 carbon atoms, cyano, halogen or deuterium, In the formula, each R is independently an alkyl having 1 to 6 carbon atoms or an aryl having 6 to 10 carbon atoms. and preferably phenyl, methyl, or t-butyl.

[0075] Further specific examples of the polycyclic aromatic compound represented by formula (1) include those having the following structure: Examples of compounds include compounds represented by the formula: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0076] At least one hydrogen atom in the compounds represented by the above formulas is replaced by an alkyl group having 1 to 6 carbon atoms. , which may be substituted with an aryl having 6 to 10 carbon atoms, cyano, halogen or deuterium, R in the formula 100 are each independently an aryl having 6 to 10 carbon atoms, a carbazolyl, or a diaryl Arylamino (where aryl is aryl with 6 to 10 carbon atoms), alkyl with 1 to 6 carbon atoms , cycloalkyl having 3 to 10 carbon atoms, or aryloxy having 6 to 10 carbon atoms; The above "aryl", "aryl" in "diarylamino", "aryl" in "aryloxy" The "aryl" may be substituted with alkyl having 1 to 6 carbon atoms, and the carbazolyl is It may be substituted with an aryl having 6 to 10 carbon atoms or an alkyl having 1 to 6 carbon atoms.

[0077] R 100 Tuning the emission wavelength by the steric hindrance, electron donating and electron withdrawing properties of the structure It is preferably a group represented by the following formula, more preferably methyl, t-butyl Tolyl, phenyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5-xylyl, 2, 6-xylyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis (p-(t-butyl)phenyl)amino, carbazolyl, 3,6-dimethylcarbazolyl , 3,6-di-t-butylcarbazolyl and phenoxy, more preferably methyl butyl, t-butyl, phenyl, o-tolyl, 2,6-xylyl, 2,4,6-mesityl, Diphenylamino, di-p-tolylamino, bis(p-(t-butyl)phenyl)amino , carbazolyl, 3,6-dimethylcarbazolyl and 3,6-di-t-butylcarbazolyl From the viewpoint of ease of synthesis, a larger steric hindrance is preferred for selective synthesis. Preferably, specifically, t-butyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5 -xylyl, 2,6-xylyl, 2,4,6-mesityl, di-p-tolylamino, bis( p-(t-butyl)phenyl)amino, 3,6-dimethylcarbazolyl and 3,6-di -t-butylcarbazolyl is preferred.

[0078] [ka]

[0079] From the viewpoint of synthetic difficulty, highly symmetric structures and / or p-type structures are preferred for the N-binding site. Preferred are structures having a substituent at the position, specifically, those represented by the formula (1-5000-R100), the formula (1-5010-R100), Formula (1-5020-R100), Formula (1-5100-R100), Formula (1-5110-R100), Formula (1-5120-R100), Formula (1-7000-R1 00), formula (1-7010-R100), formula (1-7020-R100), formula (1-7100-R100), formula (1-7110-R100), formula (1-71 20-R100), formula (1-7200-R100), formula (1-7210-R100), formula (1-7220-R100), formula (1-7400-R100), formula (1-7410-R100), the formula (1-7420-R100) and the formula (1-9000-R100) are preferred, and the formula (1-5000-R100), Formula (1-5010-R100), Formula (1-5020-R100), Formula (1-5100-R100), Formula (1-5110-R100) and Formula (1-512 0-R100) is more preferred.

[0080] In addition, from the viewpoint of blue emission and / or high luminous efficiency, it is desirable to use a compound having many N-aryl groups. A structure having many carbazolyl structures and / or a structure having many carbazolyl structures is preferred, and specifically, (1-5000-R100), formula (1-5010-R100), formula (1-5020-R100), formula (1-5100-R100), formula (1-5110-R100) ), formula (1-5120-R100), formula (1-6000-R100), formula (1-6010-R100), formula (1-6020-R100), formula (1-6200 -R100), Formula (1-6210-R100), Formula (1-6220-R100), Formula (1-7400-R100), Formula (1-7410-R100) and The formula (1-7420-R100) is preferred.

[0081] In addition, from the viewpoint of enhancing the multiple resonance effect, it is preferable that more N atoms are bonded to the central aromatic ring. are preferred, and specifically, the formula (1-5000-R100), the formula (1-5010-R100), the formula (1-5020-R100), the formula (1- 5100-R100), formula (1-5110-R100), formula (1-5120-R100), formula (1-6100-R100), formula (1-6110-R100), Formula (1-6120-R100), Formula (1-6500-R100), Formula (1-6510-R100), Formula (1-6520-R100), Formula (1-7100-R1 00), formula (1-7110-R100) and formula (1-7120-R100) are preferred.

[0082] More specific examples of the polycyclic aromatic compound represented by formula (1) include the following compounds (1) In addition to compounds represented by structural formulas starting with the formula (1-1), In the structural formula, compounds in which the t-butyl group is replaced by a methyl group are also included. , R in general formula (1) 1 and R 2 In the structural formula where the moiety corresponding to R is a phenyl group, 1 and R 2 A compound of the structural formula R 1Phenyl The group is replaced by hydrogen and R 2 Compounds with the structural formula R 2 The phenyl group of Replaced by element R 1 Compounds with the structural formula R 1 The phenyl group is replaced with a methyl group. is replaced by R 2 and compounds of the structural formula R 1 Feni The aryl group is replaced by hydrogen and R 2 This also includes compounds with the structural formula in which the phenyl group is replaced with a methyl group. For example, the structural formula of formula (1-2) and the structural formula of formula (1-6) are as follows: In each formula, "Me" represents a methyl group, t "Bu" stands for t-butyl group, and "Ph" stands for phenyl. It is a hydroxyl group.

[0083] [ka]

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[0208] 2. Method for producing polycyclic aromatic compounds Polycyclic aromatic compounds represented by general formula (1) or (2) basically consist of the respective ring structures. The intermediate is produced by bonding the ring structures together (first reaction), and then the ring structures are bonded to each other. The final product can be produced by bonding with the iodine atom (Reaction 2). So, for example, nucleophilic substitution reactions, common etherification reactions such as the Ullmann reaction, and the Buchmann reaction Common amination reactions such as the Barth-Hartwig reaction can be used. In the second reaction, the tandem hetero-Friedel-Crafts reaction (sequential electrophilic aromatic substitution, The symbols in the structural formulas in the following schemes represent the general formula (1 ) or the same definition as those in general formula (2).

[0209] The second reaction is carried out by reacting the boron atoms that connect the ring structures together as shown in the following scheme (1). This is a reaction that introduces a child. First, X 1 and X 2 Between and X 3 and X 4 The hydrogen atoms between n- Orthometalates such as butyllithium, sec-butyllithium, or t-butyllithium Next, boron trichloride or boron tribromide is added to cause lithium-boron metal exchange. After this, a Bronsted base such as N,N-diisopropylethylamine is added. This allows for a tandem Bola-Friedel-Crafts reaction to yield the desired product. In order to promote the reaction, a Lewis acid such as aluminum trichloride may be added. [ka]

[0210] In scheme (1), lithium was introduced to the desired position by orthometalation. As shown in the following scheme (2), a halogen atom (Hal) is previously introduced at the position where lithium is to be introduced. Lithium can also be introduced into the desired position by halogen-metal exchange. This method allows the desired reaction to be achieved even in cases where ortho-metallation is not possible due to the influence of substituents. It is useful because it allows you to synthesize things. [ka]

[0211] By appropriately selecting the above synthesis method and the raw materials to be used, it is possible to obtain a substituent at the desired position. wherein Y is boron and X 1 , X 2 , X 3 and X 4 However, independently, >O, >N- Polycyclic aromatic compounds can be synthesized that are R, >S, or >Se.

[0212] In addition, the rotation of the amino group in the intermediate may result in a tandem boron-Friedel-Crafts reaction. Since the reaction may occur at different locations, by-products may be produced. In such cases, the desired polycyclic aromatic compounds can be extracted from these mixtures by chromatography or recrystallization. The compound can be isolated.

[0213] Examples of orthometalation reagents used in the above scheme include methyllithium, n- Alkyl lithium such as butyl lithium, sec-butyl lithium, and t-butyl lithium , lithium diisopropylamide, lithium tetramethylpiperidide, lithium hexame Examples include organic alkali compounds such as ethyl disilazide and potassium hexamethyl disilazide. do.

[0214] The metal exchange reagent for metal-Y (boron) used in the above scheme is a boron trifluoride. Boron halides such as fluoride, trichloride, tribromide, triiodide, CIPN(NEt 2) Aminated halides of Y, alkoxylated Y, and aryloxylated Y, such as 2 Examples include:

[0215] The Bronsted base used in the above scheme is N,N-diisopropylethyl Amines, triethylamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6 ,6-Pentamethylpiperidine, N,N-Dimethylaniline, N,N-Dimethyltoluidine 2,6-Lutidine, Sodium Tetraphenylborate, Potassium Tetraphenylborate Ar, triphenylborane, tetraphenylsilane, Ar4BNa, Ar4BK, Ar3B , Ar4Si (wherein Ar is an aryl such as phenyl), etc.

[0216] The Lewis acids used in the above scheme include AlCl3, AlBr3, AlF3, and BF 3·OEt2, BCl3, BBr3, GaCl3, GaBr3, InCl3, InBr3 , In(OTf)3, SnCl4, SnBr4, AgOTf, ScCl3, Sc(OTf )3, ZnCl2, ZnBr2, Zn(OTf)2, MgCl2, MgBr2, Mg(O Tf)2, LiOTf, NaOTf, KOTf, Me3SiOTf, Cu(OTf)2, CuCl2, YCl3, Y(OTf)3, TiCl4, TiBr4, ZrCl4, ZrB Examples include r4, FeCl3, FeBr3, CoCl3, and CoBr3.

[0217] In the above scheme, Brönstein was used to promote the tandem hetero-Friedel-Crafts reaction. A Lewis base or Lewis acid may be used, except for boron trifluoride, trichloride, and trichloride. When boron halides such as bromide and triiodide are used, the aromatic electrophilic substitution reaction As the process progresses, acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide are produced. The use of a Bronsted base to capture the acid is effective. When using boron alkoxides and boron hydrides, the aromatic electrophilic substitution reaction proceeds. In order to generate amines and alcohols, Bronsted bases are often used. However, since the amino group and alkoxy group have low elimination ability, Lewis acid that promotes their elimination is The use of benzoic acid is effective.

[0218] In addition, the polycyclic aromatic compounds represented by the general formula (1) or (2) contain at least a part Compounds in which hydrogen atoms are replaced by cyano, halogen, or deuterium are also included, but such compounds For such compounds, the desired sites should be cyanated, halogenated, or deuterated. can be synthesized in the same manner as above.

[0219] 3. Organic Devices The polycyclic aromatic compound according to the present invention can be used as a material for an organic device. Examples of the organic device include an organic electroluminescent device, an organic field effect transistor, or an organic Examples include thin-film solar cells.

[0220] 3-1. Organic electroluminescent device The polycyclic aromatic compound according to the present invention can be used, for example, as a material for an organic electroluminescent device. The organic EL element according to this embodiment will be described in detail below with reference to the drawings. 1 is a schematic cross-sectional view showing an organic EL element according to this embodiment.

[0221] <Structure of organic electroluminescent device> The organic electroluminescent device 100 shown in FIG. 1 includes a substrate 101 and a An anode 102, a hole injection layer 103 provided on the anode 102, and a layer a hole transport layer 104 provided on the hole transport layer 104; and a light emitting layer 105 provided on the hole transport layer 104. An electron transport layer 106 provided on the light-emitting layer 105 and a The device has an electron injection layer 107 and a cathode 108 provided on the electron injection layer 107 .

[0222] The organic electroluminescent device 100 can be fabricated in the reverse order, for example, by fabricating the substrate 101 and the substrate a cathode 108 provided on the cathode 101, and an electron injection layer 107 provided on the cathode 108; An electron transport layer 106 is provided on the electron injection layer 107, and a a light-emitting layer 105 formed on the light-emitting layer 105; a hole transport layer 104 formed on the light-emitting layer 105; A hole injection layer 103 is provided on the cathode 104, and an anode 10 is provided on the hole injection layer 103. 2 may also be included.

[0223] Not all of the above layers are necessary, but the minimum structural unit is the anode 102 and the light-emitting layer. The cathode 108 is made up of a hole injection layer 103, a hole transport layer 104, an electron The transport layer 106 and the electron injection layer 107 are layers that are optionally provided. Each of them may consist of a single layer or multiple layers.

[0224] The layer configuration of the organic electroluminescent device may be the above-mentioned "substrate / anode / hole injection layer / In addition to the "hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode" configuration, there is also the "substrate / anode" configuration. / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole injection layer / Light-emitting layer / electron transport layer / electron injection layer / cathode," "substrate / anode / hole injection layer / hole transport layer / light-emitting layer" Light layer / electron injection layer / cathode," "substrate / anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / cathode", "substrate / anode / light-emitting layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole transport layer / light emitting layer / electron injection layer / cathode," "substrate / anode / hole transport layer / light emitting layer / electron transport "Transmission layer / cathode", "Substrate / anode / hole injection layer / light-emitting layer / electron injection layer / cathode", "Substrate / anode / hole injection layer / light-emitting layer / electron transport layer / cathode", "substrate / anode / light-emitting layer / electron transport layer / cathode" or "substrate / anode / light-emitting layer / electron injection layer / cathode".

[0225] <Substrate in organic electroluminescent device> The substrate 101 is a support for the organic electroluminescent device 100 and is usually made of quartz, glass, metal, The substrate 101 may be in the form of a plate, a film, or the like depending on the purpose. It is formed into a sheet shape, for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic Among them, glass plates, polyester, polymer A transparent synthetic resin plate such as acrylate, polycarbonate, or polysulfone is preferred. For glass substrates, soda lime glass or alkali-free glass is used. The thickness should be sufficient to maintain mechanical strength, for example, 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. The glass material should be alkali-free, since the less ions dissolved from the glass, the better. is preferred, but soda lime glass coated with a barrier coating such as SiO2 is also commercially available. In addition, the substrate 101 has a gas barrier property. For this purpose, a gas barrier film such as a dense silicon oxide film may be provided on at least one surface. A synthetic resin plate, film or sheet having a low gas barrier property is used as the substrate 101. In this case, it is preferable to provide a gas barrier film.

[0226] <Anode in organic electroluminescent device> The anode 102 serves to inject holes into the light-emitting layer 105. When the hole injection layer 103 and / or the hole transport layer 104 are provided between the layer 105 In this case, holes are injected into the light-emitting layer 105 via these.

[0227] Materials for forming the anode 102 include inorganic and organic compounds. Examples of compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (I TO), indium zinc oxide (IZO), etc.), metal halides (copper iodide, etc.), Examples include copper sulfide, carbon black, ITO glass, and Nesa glass. Examples of such polythiophenes include poly(3-methylthiophene), polypyrrole, Conductive polymers such as polyaniline are also used. The substance can be appropriately selected from those used as the base material.

[0228] The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for the light emitting element to emit light. However, from the viewpoint of power consumption of the light emitting element, low resistance is desirable. For example, 300Ω / ITO substrates with a resistance of 10Ω / □ or less can function as device electrodes, but currently, substrates with a resistance of about 10Ω / □ are required. Therefore, for example, 100 to 5Ω / □, preferably 50 to 5Ω / □ It is especially desirable to use a low resistance product. The thickness of the ITO can be selected arbitrarily according to the resistance value. Although it is possible to increase the thickness, it is usually used in the range of 50 to 300 nm.

[0229] <Hole injection layer and hole transport layer in organic electroluminescent device> The hole injection layer 103 efficiently injects holes moving from the anode 102 into the light emitting layer 105. The hole transport layer 104 serves to inject electrons from the anode 102 into the hole transport layer 104. The injected holes or holes injected from the anode 102 through the hole injection layer 103 are efficiently The hole injection layer 103 and the hole transport layer 104 serve to transport electrons to the light-emitting layer 105. , respectively, one or more kinds of hole injection and transport materials are laminated or mixed, or hole injection and It is formed by a mixture of a transport material and a polymer binder. Also, iron chloride is used as the hole injection / transport material. An inorganic salt such as (III) may be added to form a layer.

[0230] As a hole injection / transport material, it efficiently transports holes from the positive electrode between electrodes with an applied electric field. It is necessary to have good hole injection and transport efficiency, and to have high hole injection efficiency and efficient transport of injected holes. To achieve this, it is necessary to have a small ionization potential and a high hole mobility. It is large and has excellent stability, making it difficult for impurities to be trapped during manufacturing and use. It is preferable that the material is a non-ionic surfactant.

[0231] The hole injection layer 103 and the hole transport layer 104 are made of a photoconductive material. The compounds that have been conventionally used as charge transport materials for holes, p-type semiconductors, organic electroluminescent devices, Any compound selected from known compounds used in the hole injection layer and hole transport layer of optical elements. You can select and use things.

[0232] Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, carbazole, bis(N-arylcarbazole) or bis(N-alkylcarbazole) biscarbazole derivatives such as triarylamine derivatives (aromatic tertiary amino Polymers with 1,1-bis(4-di-p-tolylaminophenyl) in the main chain or side chain Cyclohexane, N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4 '-Diaminobiphenyl, N,N'-diphenyl-N,N'-dinaphthyl-4,4'-di Aminobiphenyl, N,N'-diphenyl-N,N'-di(3-methylphenyl)-4, 4'-Diphenyl-1,1'-diamine, N,N'-dinaphthyl-N,N'-diphenyl -4,4'-diphenyl-1,1'-diamine, N 4 ,N 4’ -diphenyl-N 4 ,N 4 ’ -Bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl] -4,4'-diamine, N 4 ,N 4,N 4’ ,N 4’ -tetra[1,1'-biphenyl] -4-yl)-[1,1'-biphenyl]-4,4'-diamine, 4,4',4"-tri triphenylamine, such as bis(3-methylphenyl(phenyl)amino)triphenylamine amine derivatives, starburst amine derivatives, stilbene derivatives, phthalocyanine derivatives, etc. Conductors (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzoates Zofuran derivatives, thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (e.g. For example, 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10, 11-hexacarbonitrile, heterocyclic compounds such as porphyrin derivatives, polysilanes, In the polymer system, polycarbonate and styrene derivatives having the above-mentioned monomers in the side chain are used. Conductors, polyvinylcarbazole and polysilane are preferred, but If a compound can form the necessary thin film, inject holes from the anode, and transport holes, There is no particular limitation.

[0233] It is also known that the conductivity of organic semiconductors is strongly affected by their doping. Such organic semiconductor matrix materials are compounds with good electron donating properties, or , and is composed of compounds with good electron-accepting properties. For doping with electron-donating substances, Tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetrafluoroethane Strong electron acceptors such as cyano-1,4-benzoquinone dimethane (F4TCNQ) are known. (For example, see the reference "M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(22), 32 02-3204(1998)" and the document "J. Blochwitz, M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(6), 729-731(1998)). These are electron-donating base materials (hole-transporting materials) ) generates so-called holes by an electron transfer process. The conductivity of the base material changes considerably depending on the Examples of the oxidizing agent include benzidine derivatives (such as TPD) or starburst amine. derivatives (such as TDATA) or certain metal phthalocyanines (especially zinc phthalocyanine) (ZnPc, etc.) are known (Japanese Patent Laid-Open Publication No. 2005-167175).

[0234] <Light-emitting layer in organic electroluminescent device> The light-emitting layer 105 reacts with holes injected from the anode 102 between the electrodes to which an electric field is applied. The layer emits light by recombining with the electrons injected from the cathode 108. The material for forming 105 is a compound that emits light when excited by the recombination of holes and electrons. Any substance (luminescent compound) can be used, and it can be formed into a stable thin film shape and can be used in a solid state. In the present invention, the material for the light-emitting layer is preferably a compound that exhibits strong luminescence (fluorescence) efficiency in the light-emitting state. As the material, a polycyclic aromatic compound represented by the above general formula (1) can be used.

[0235] The light-emitting layer may be a single layer or a multi-layer. The host material and the dopant material are The dopant material may be one kind or a combination of two or more kinds. It may be contained entirely or partially in the stock material. The doping method can be a co-evaporation method with the host material. The host material is mixed with the organic solvent and then vapor-deposited. Alternatively, a film may be formed by a wet film forming method.

[0236] The amount of the host material used varies depending on the type of host material, and should be adjusted to suit the properties of the host material. The amount of the host material to be used is preferably 50 to 100% of the total amount of the materials for the light-emitting layer. 99.999% by weight, more preferably 80 to 99.95% by weight, and even more preferably The content is preferably 90 to 99.9% by weight.

[0237] The amount of dopant material used varies depending on the type of dopant material. The amount of dopant used should preferably be determined according to the characteristics of the light-emitting layer material. It is 0.001 to 50% by weight of the total, more preferably 0.05 to 20% by weight, and even more preferably It is more preferably 0.1 to 10% by weight. Within the above range, for example, concentration quenching phenomenon can be prevented. This is preferable in that it can prevent the above.

[0238] On the other hand, in organic electroluminescent devices using thermally activated delayed fluorescent dopant materials, The amount of the absorbing agent used is preferably low in order to prevent the concentration quenching phenomenon. A high concentration of the dopant material is preferable in terms of the efficiency of the thermally activated delayed fluorescence mechanism. Furthermore, the present invention relates to an organic electroluminescent device using a thermally activated delayed fluorescence assist dopant material. In terms of the efficiency of the thermally activated delayed fluorescence mechanism of the assist dopant material, It is preferable that the amount of dopant material used is low in comparison with the amount of dopant material used.

[0239] When an assist dopant material is used, the host material and the assist dopant The amount of the materials and dopant materials used should be 40 to 99% of the total amount of materials for the light-emitting layer. 0.999% by weight, 59 to 1% by weight, and 20 to 0.001% by weight, and preferably The amounts are 60 to 99.99% by weight, 39 to 5% by weight, and 10 to 0.01% by weight, respectively. More preferably, the content is 70 to 99.95% by weight, 29 to 10% by weight, and 5 to 0.05% by weight. The compound according to the present invention and its polymer compound can also be used as an assist dopant material. You can also do this.

[0240] As the host material, anthracene and pyrene, which have been known as light emitters for a long time, Fused ring derivatives, bisstyryl anthracene derivatives, distyrylbenzene derivatives, etc. Styryl derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, fluoro fluorene derivatives, benzofluorene derivatives, etc.

[0241] The T1 energy of the host material is considered to promote rather than inhibit the generation of TADF in the emitting layer. From this point of view, the dopant or assisted dopant with the highest T1 energy in the light-emitting layer It is preferable that the T1 energy is higher than that of the host. The energy is preferably 0.01 eV or more, more preferably 0.03 eV or more, and more preferably 0.1 eV or more. The above is more preferable. A TADF-active compound may also be used as the host material.

[0242] Examples of the host material include a compound represented by the following general formula (3) and a compound represented by the following general formula ( 4) is a compound represented by the formula: [ka] In the above formula (3), L 1 is an arylene having 6 to 24 carbon atoms, and is an arylene having 6 to 16 carbon atoms. Arylene having 6 to 12 carbon atoms is preferred, and arylene having 6 to 10 carbon atoms is more preferred. Particularly preferred are benzene rings, biphenyl rings, naphthalene rings, terphenyl rings, and the like. nyl ring, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, triphenylene ring Examples of divalent groups include an nylene ring, a pyrene ring, a naphthacene ring, a perylene ring, and a pentacene ring. It can be obtained. In the above formula (4), L 2 and L 3 are each independently an aryl having 6 to 30 carbon atoms or or heteroaryl having 2 to 30 carbon atoms. The aryl is an aryl having 6 to 24 carbon atoms. An aryl having 6 to 16 carbon atoms is preferred, an aryl having 6 to 12 carbon atoms is more preferred. is more preferred, and an aryl having 6 to 10 carbon atoms is particularly preferred. Specifically, a benzene ring , biphenyl ring, naphthalene ring, terphenyl ring, acenaphthylene ring, fluorene ring, Phenalene ring, phenanthrene ring, triphenylene ring, pyrene ring, naphthacene ring, perylene Examples of heteroaryl include monovalent groups such as a 2-carbon ring and a pentacene ring. Heteroaryl having from 1 to 25 carbon atoms is preferred, and heteroaryl having from 2 to 20 carbon atoms is more preferred. Heteroaryl having 2 to 15 carbon atoms is more preferred, and heteroaryl having 2 to 10 carbon atoms is Particularly preferred are pyrrole ring, oxazole ring, isoxazole ring, thiazo an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, Triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine Indole ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzophenone ring, Isotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring, quinoxazoline ring Sarin ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, Acridine ring, phenoxathiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazan ring, oxadienyl ring Examples include monovalent groups such as an azole ring and a thianthrene ring. At least one hydrogen atom in the compound represented by formula (3) or formula (4) is a 1-carbon atom hydrogen atom. It may be substituted with up to 6 alkyl, cyano, halogen or deuterium.

[0243] Examples of the host material include compounds represented by the following general formula (5): . [ka] (In the above formula (5), R 1 ~R 11 are each independently hydrogen, aryl, heteroaryl, diaryla amino, diheteroarylamino, arylheteroarylamino or alkyl (the above, (first substituent), and at least one hydrogen atom in these groups may be further selected from aryl, heteroaryl, and optionally substituted with aryl, diarylamino, or alkyl (the second substituent). , R 1 ~R 11 Adjacent groups among these are bonded to form an aryl ring together with the a, b or c ring. A ring or heteroaryl ring may be formed, and at least one of the rings formed The hydrogen of the aryl, heteroaryl, diarylamino, diheteroarylamino, and optionally substituted with aryl, heteroaryl, amino, or alkyl (the first substituent). In these, at least one hydrogen atom may be further substituted with an aryl, heteroaryl, diaryl, or and optionally substituted with methylamino or alkyl (these are second substituents), At least one hydrogen atom in the compound represented by formula (5) is independently selected from the group consisting of halo, It may be substituted with hydrogen or deuterium.

[0244] Preferably, in the above formula (5), R 1 ~R 11 are each independently hydrogen, an aryl having 6 to 30 carbon atoms, an aryl having 2 to 3 carbon atoms, 0 heteroaryl, diarylamino (where aryl has 6 to 12 carbon atoms) or alkyl having 1 to 12 carbon atoms, wherein at least one hydrogen atom is further Aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (only The aryl is substituted with an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 12 carbon atoms. It's okay to be there, R 1 ~R 11 Adjacent groups among these are bonded to each other and together with the a, b or c ring have 9 carbon atoms. An aryl ring having 6 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms may be formed. At least one hydrogen atom in the resulting ring is substituted by an aryl having 6 to 30 carbon atoms, an aryl having 2 to 3 carbon atoms, 0 heteroaryl, diarylamino (where aryl has 6 to 12 carbon atoms) or may be substituted with alkyl having 1 to 12 carbon atoms, and at least one of these The other hydrogen atom can be further selected from aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diaryl. arylamino (wherein aryl is aryl having 6 to 12 carbon atoms) or aryl having 1 to 12 carbon atoms May be replaced by kill.

[0245] More preferably, in the above formula (5), R 1 ~R 11 are each independently hydrogen, an aryl having 6 to 16 carbon atoms, an aryl having 2 to 1 carbon atoms, 5 heteroaryl, diarylamino (wherein aryl has 6 to 10 carbon atoms) or alkyl having 1 to 6 carbon atoms, in which at least one hydrogen atom is further replaced by a carbon atom. Aryl having 6 to 16 prime numbers, heteroaryl having 2 to 15 carbon atoms, diarylamino (however, Aryl is substituted with aryl having 6 to 10 carbon atoms or alkyl having 1 to 6 carbon atoms. Also, R 1 ~R 11 Adjacent groups among these are bonded to each other and together with the a, b or c ring have 9 carbon atoms. may form an aryl ring having 6 to 12 carbon atoms or a heteroaryl ring having 6 to 12 carbon atoms, At least one hydrogen atom in the resulting ring is substituted by an aryl having 6 to 16 carbon atoms, an aryl having 2 to 1 carbon atoms, 5 heteroaryl, diarylamino (wherein aryl has 6 to 10 carbon atoms) or alkyl having 1 to 6 carbon atoms, and at least one of these The hydrogen atom in the formula (I) can be further selected from aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diarylaryl, and aryl. arylamino (wherein aryl is aryl having 6 to 10 carbon atoms) or alkyl having 1 to 6 carbon atoms may be substituted with.

[0246] In the first and second substituents, aryl, heteroaryl, diaryla "Aryl" in amino, diheteroarylamino, arylheteroarylamino, Examples of "heteroaryl" include the following.

[0247] Specific examples of "aryl" include aryls having 6 to 30 carbon atoms. An aryl having 6 to 24 carbon atoms is preferred, an aryl having 6 to 20 carbon atoms is more preferred, and an aryl having 6 to 24 carbon atoms is more preferred. Aryl having 6 to 16 carbon atoms is more preferred, and aryl having 6 to 12 carbon atoms is particularly preferred. Aryl having 6 to 10 carbon atoms is most preferred. For example, phenyl, which is a monocyclic aryl, aryl (2-, 3-, 4-) biphenylyl; fused bicyclic aryl (1-, 2 -) naphthyl, tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-Terphenyl-4'-yl, m-Terphenyl-5'-yl, o-Terphenyl-3'-yl '-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terf m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl- o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p -terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl ), fused tricyclic aryls, acenaphthylene-(1-, 3-, 4-, 5-)yl, phenyl Fluoren-(1-, 2-, 3-, 4-, 9-)yl, phenalen-(1-, 2-)yl, (1-, 2-, 3-, 4-, 9-)phenanthryl, tetracyclic aryl quaterphenone 5'-phenyl-m-terphenyl-2-yl m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenyl aryl), fused tetracyclic aryls such as triphenylene-(1-,2-)yl, pyrene-(1- , 2-, 4-)yl, naphthacene-(1-, 2-, 5-)yl, fused pentacyclic aryl Perylene-(1-, 2-, 3-)yl, pentacene-(1-, 2-, 5-, 6-)yl Examples include:

[0248] Specific examples of "heteroaryl" include heteroaryls having 2 to 30 carbon atoms. Heteroaryl having 2 to 25 carbon atoms is preferable, and heteroaryl having 2 to 20 carbon atoms is preferable. Heteroaryl having 2 to 15 carbon atoms is more preferred, and heteroaryl having 2 to 10 carbon atoms is even more preferred. Heteroaryl is particularly preferred, for example, furyl, thienyl, pyrrolyl, oxazolyl, Isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxazolyl Azolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridyl Imidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzo[b]thienyl Zoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, Quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, na Phthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl phenyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indole Examples include ginyl.

[0249] In the first and second substituents, the "alkyl" includes straight and branched chain alkyls. For example, a linear alkyl group having 1 to 24 carbon atoms or a branched alkyl group having 3 to 24 carbon atoms may be used. alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms) is preferred, and alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms) is more preferred. Preferably, the alkyl has 1 to 6 carbon atoms (branched alkyl has 3 to 6 carbon atoms). Alkyl having 1 to 4 prime numbers (branched alkyl having 3 to 4 carbon atoms) is particularly preferred, and methyl is the most preferred. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl butyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl ethyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethyl butyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t- Octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethyl ethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-thiazolinone 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecy Examples of aryl include n-heptadecyl, n-octadecyl, and n-eicosyl.

[0250] When the first substituent is aryl, the substitution position is R 1 , R 3 , R 4 , R 5 , R 10 and R 11 is preferred, for example, R 1 and R 3 Substitution to R 5 and R 10 Substitution to R 4 oh Yobi R 11 The aryl is preferably a phenyl group.

[0251] When the first substituent is heteroaryl, the substitution position is R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 9 , R 10 and R 11 is preferred, for example, R 1 Substitution to R 2 Substitution to R 3 Substitution to R 1 and R 3 Substitution to R 4 and R 11 Substitution to R 5 and R 10 to Replacement, R 6 and R 9 The heteroaryl is preferably a carbazolyl group. The heteroaryl (for example, carbazolyl) is substituted at the above position via a phenylene group. It may be replaced.

[0252] Specific examples of the compound represented by formula (5) include compounds represented by the following structural formula: In the formula, "Me" is a methyl group.

[0253] [ka]

[0254] The compound represented by formula (5) is first prepared by bonding rings a to c with a bonding group (—O—). The intermediate compound is produced (first reaction), and then the a-c rings are bonded with B (boron) to produce the final product. In the first reaction, for example, nucleophilic substitution or urea can be produced (second reaction). In the second reaction, a tandem etherification reaction can be used. The Friedel-Crafts reaction (sequential aromatic electrophilic substitution) can be used. For details of the second reaction, please refer to the description in International Publication No. WO 2015 / 102118. It can be made into.

[0255] Regarding the host material, another example is, for example, Advanced Materials, 2017, 29, 1 605444, Journal of Material Chemistry C,2016,4,11355-11381, Chemical Science, 20 16, 7, 3355-3363, Thin Solid Films, 2016, 619, 120-124, etc. In addition, TADF organic EL devices can be used with a host material in the emitting layer that has a high T1 energy. In order to require ghee, phosphorus as described in Chemistry Society Reviews, 2011, 40, 2943-2970 The host material for photo-organic EL devices can also be used as a host material for TADF OLED devices. This can be done.

[0256] More specifically, the host compound is selected from the group of partial structures (HA) represented by the following formula: A compound having at least one structure represented by the formula (I) and each structure in the group of partial structures (HA) At least one hydrogen atom in the group (HA) or the group (HB) In these structures, at least one water atom may be substituted. The elements are deuterium, halogen, cyano, alkyl with 1 to 4 carbon atoms (e.g., methyl and t-butyl). ), trimethylsilyl or phenyl.

[0257] [ka]

[0258] [ka]

[0259] The host compound is preferably a compound represented by any one of the structural formulas listed below. Among these, a structure selected from the above partial structure (HA) group is more preferred. and one structure selected from the partial structure (HB) group. and more preferably, a compound having a carbazole group as the partial structure (HA) group. Particularly preferred are compounds represented by the following formulas (3-201), (3-202), and (3-203): , formula (3-204), formula (3-212), formula (3-221), formula (3-222), formula (3 -261) or a compound represented by formula (3-262). In the formula, at least one hydrogen atom is replaced by a halogen atom, a cyano atom, an alkyl group having 1 to 4 carbon atoms ( It may be substituted with, for example, methyl or t-butyl, phenyl or naphthyl.

[0260] [ka]

[0261] [ka]

[0262] [ka]

[0263] [ka]

[0264] [ka]

[0265] The following polymer host materials can also be used. [ka] In formula (B-6), MU is independently selected from the general formulae (B-1) to (B-5): and in MU, at least one selected from the group consisting of divalent groups of compounds represented by Two hydrogens are replaced with EC or MU, and EC is each independently hydrogen, aryl, Heteroaryl, diarylamino, diheteroarylamino, arylheteroaryl amino or aryloxy, wherein at least one hydrogen atom is further substituted with aryl. and k is 2 to 500. k is preferably an integer of 100 to 40,000, and more preferably an integer of 500 to 25 More preferably, it is the integer 000.

[0266] Here, the compounds represented by general formulae (B-1) to (B-5) are as follows: [ka]

[0267] In formula (B-1) to formula (B-4), each Ar is independently hydrogen, aryl, Heteroaryl, diarylamino, diheteroarylamino, arylheteroaryl amino or aryloxy, wherein at least one hydrogen atom is further substituted with aryl. Ar may be substituted with aryl, heteroaryl or diarylamino, and the adjacent Adjacent groups are bonded to form an anthracene ring, a pyrene ring, a fluorene ring, or a carbene ring. may form an aryl ring or a heteroaryl ring together with the base skeleton of the benzol ring, At least one hydrogen atom in the formed ring is substituted by an aryl, heteroaryl, diaryl Amino, diheteroarylamino, arylheteroarylamino or aryloxy The specific explanation of each group is given in the general formula (1) and the general formula (2) above. In each formula, n is an integer of 1 to 6, An integer of 1 to 4 is preferred, an integer of 1 to 2 is more preferred, and 1 is particularly preferred.

[0268] In the formulae (B-1) to (B-4), specific examples of "Ar" include the following: Examples include monovalent groups of the structural formulas shown below or groups that are combinations of the structures shown below.

[0269] [ka]

[0270] In formula (B-5), R 1 ~R 11 are each independently hydrogen, aryl, or hetero Aryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, wherein at least one hydrogen atom is further substituted with an aryl, optionally substituted with heteroaryl or diarylamino; R 1 ~R 11 Adjacent groups among these are bonded to form an aryl ring together with the a, b or c ring. A ring or heteroaryl ring may be formed, and at least one of the rings formed The hydrogen of the aryl, heteroaryl, diarylamino, diheteroarylamino, and the aryl group may be substituted with arylheteroarylamino or aryloxy. At least one hydrogen atom in the alkyl group may be further selected from aryl, heteroaryl, or diarylamino. It may be substituted. Specific explanations of each group are given in the polycyclic aromatic compounds of the above general formula (1) and general formula (2). The explanations given can be cited.

[0271] At least one hydrogen atom in the compounds represented by formula (B-1) to formula (B-5) is a group represented by formula (FG-1), a group represented by formula (FG-2) described later, or a group having a carbon number may be substituted with 1 to 24 alkyl, halogen or deuterium, and further Any -CH2- in the group may be replaced by -O- or -Si(CH3)2-. Preferably, the alkyl is directly bonded to the compounds represented by the above formulas (B-1) to (B-5). Any -CH2- except for the -CH2- in the formula is substituted with an arylene having 6 to 24 carbon atoms. Any hydrogen in the alkyl may be substituted with fluorine.

[0272] At least one hydrogen atom in EC in formula (B-6) is represented by the following general formula (FG-1): a group represented by the following general formula (FG-2), an alkyl group having 1 to 24 carbon atoms, a halogen atom, or deuterium, and any —CH2— in the alkyl may be substituted. may be substituted with -O- or -Si(CH3)2-, and the formula in said alkyl Any -CH2- other than the -CH2- directly bonded to EC in (B-6) has 6 to 24 carbon atoms. and any hydrogen in the alkyl may be substituted with fluorine. It may be done. [ka] (In the above formula (FG-1), R is independently fluorine, trimethylsilyl, trifluoromethyl, or a group having 1 carbon atom. alkyl having 3 to 24 carbon atoms or cycloalkyl having 3 to 24 carbon atoms, Any -CH2- may be replaced by -O-, and the phenyl or Any -CH2- except for -CH2- directly bonded to phenylene has 6 to 24 carbon atoms. At least one hydrogen in the cycloalkyl may be substituted with a carbon atom. may be substituted with alkyl having 1 to 24 carbon atoms or aryl having 6 to 12 carbon atoms, When two adjacent R's are alkyl or cycloalkyl, they are bonded to form a ring. It may be formed, Each m is independently an integer of 0 to 4, n is an integer of 0 to 5, and p is an integer of 1 to 5. It is a number.) [ka] (In the above formula (FG-2), R is independently fluorine, trimethylsilyl, trifluoromethyl, or a group having 1 carbon atom. alkyl having 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, or aryl having 6 to 12 carbon atoms Any —CH2— in the alkyl may be replaced with —O—, Any -CH2- except for -CH2- directly attached to phenyl or phenylene in alkyl 2- may be substituted with an arylene having 6 to 24 carbon atoms, At least one hydrogen atom is an alkyl having 1 to 24 carbon atoms or an aryl having 6 to 12 carbon atoms. At least one hydrogen atom in the aryl may be substituted with a C1 to C24 aryl. may be substituted with alkyl, When two adjacent R's are alkyl or cycloalkyl, they are bonded to form a ring. It may be formed, m is an integer of 0 to 4, and each n is independently an integer of 0 to 5.

[0273] Examples of MU include those represented by the following general formulae (MU-1-1) to (MU-1-12), General formula (MU-2-1) ~ formula (MU-2-202), general formula (MU-3-1) ~ formula (M U-3-201), the following general formulas (MU-4-1) to (MU-4-122) and the following Examples include divalent groups represented by general formulas (MU-5-1) to (MU-5-12). In addition, EC includes, for example, groups represented by the following general formulae (EC-1) to (EC-29). In these, MU binds to MU or EC at *, and EC binds to It binds to MU.

[0274] Furthermore, the compound represented by formula (B-6) has a structure in which the compound represented by formula (B-6) is present in the molecule from the viewpoint of charge transport. It is preferable that the compound has at least one divalent group represented by the formula (B-6-X 1) in an amount of 10% or more relative to the molecular weight of the compound represented by formula (B-6). Here, it is more preferable that the divalent group represented by formula (B-6-X1) is Binds to MU or EC.

[0275] [ka]

[0276] [ka]

[0277] [ka]

[0278] [ka]

[0279] [ka]

[0280] [ka]

[0281] [ka]

[0282] The compound represented by formula (B-6) has a MU in the molecule from the viewpoint of solubility and film-forming properties. It is preferable that 10 to 100% of the total number (n) of MUs have alkyl groups having 1 to 24 carbon atoms. , 30-100% of the total number of MUs (n) in the molecule are alkyl (carbon number 1-18) It is more preferable that the total number of MUs (n) in the molecule is 5 or more. 0-100% of MU is alkyl with 1-12 carbon atoms (branched alkyl with 3-12 carbon atoms). On the other hand, from the viewpoint of in-plane orientation and charge transport, it is more preferable that It is preferred that 10 to 100% of the total number of MUs (n) have alkyl groups having 7 to 24 carbon atoms. The total number of MUs in the molecule (n) is 30-100% of the MUs. It is more preferable that the alkyl group has a branched chain alkyl group having a prime number of 7 to 24.

[0283] The dopant material is not particularly limited, and known compounds can be used. A variety of materials can be selected depending on the desired luminescent color. Phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene fused ring derivatives such as benzoxazole, dibenzopyrene, rubrene and chrysene; derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives Conductors, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole Derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives Conductors, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives , bisstyryl derivatives such as bisstyryl anthracene derivatives and distyrylbenzene derivatives compounds (JP-A-1-245087), bisstyryl arylene derivatives (JP-A-2-24 7278), diazaindacene derivatives, furan derivatives, benzofuran derivatives, phenanthracene derivatives, Nylisobenzofuran, Dimesitylisobenzofuran, Di(2-methylphenyl)isobenzofuran Di(2-trifluoromethylphenyl)isobenzofuran, phenylisobenzofuran Isobenzofuran derivatives such as benzofuran, dibenzofuran derivatives, 7-dialkylamino 7-Hydroxycoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, -Methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazolylcoumarin Phosphorus derivatives, 3-benzimidazolyl coumarin derivatives, 3-benzoxazolyl coumarin Coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyrane derivatives, etc. Orchid derivatives, polymethine derivatives, cyanine derivatives, oxobenzoanthracene derivatives, chiral Santhene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbo Styryl derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2,5-Thiadiazolopyrene derivatives, pyrromethene derivatives, perinone derivatives, pyrrolopyr rol derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acrylonitrile derivatives, Lidone derivatives, deazaflavin derivatives, fluorene derivatives and benzofluorene derivatives Examples include:

[0284] As examples of dopant materials for blue to blue-green light, naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, Aromatic hydrocarbon compounds such as ricene and their derivatives, furan, pyrrole, thiophene, cyclohexyl 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, dibenzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, Phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxane Aromatic heterocyclic compounds such as benzene and their derivatives, distyrylbenzene derivatives, tetraphenyl butadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazoline azole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, Azole derivatives such as triazole and their metal complexes and N,N'-diphenyl-N ,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine Examples of suitable aromatic amine derivatives include:

[0285] In addition, green to yellow dopant materials include coumarin derivatives, phthalimide derivatives, naphthyl phthalimide derivatives, and naphthyl phthalimide derivatives. thalimid derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives acridone derivatives, quinacridone derivatives, and naphthacene derivatives such as rubrene. Further, the compounds exemplified as the blue to blue-green dopant materials include aryl, hexafluorophenyl ... Introduce substituents such as aryl, arylvinyl, amino, and cyano that enable longer wavelengths Compounds such as these are also suitable examples.

[0286] Furthermore, as an orange to red dopant material, bis(diisopropylphenyl)perylene Naphthalimide derivatives such as tetracarboxylic acid imides, perinone derivatives, acetylacetonates Rare earth complexes such as Eu complexes with ligands such as benzoylacetone and phenanthroline. 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4 H-pyran and its analogues, magnesium phthalocyanine, aluminum chlorophthalocyanine metal phthalocyanine derivatives such as phthalocyanine, rhodamine compounds, deazaflavin derivatives, coumadin Phosphorus derivatives, quinacridone derivatives, phenoxazine derivatives, oxazine derivatives, quinazolidinone derivatives, pyrrolopyridine derivatives, squarylium derivatives, violanthrone derivatives, phenanthroline derivatives, nadine derivatives, phenoxazone derivatives and thiadiazolopyrene derivatives. Further, the compounds exemplified as the blue to blue-green and green to yellow dopant materials include aryl, Substituents such as heteroaryl, arylvinyl, amino, and cyano are introduced to enable longer wavelengths. Compounds containing the above are also suitable examples.

[0287] Other dopants include those listed in the Chemical Industry, June 2004 issue, p. 13, and The compounds can be appropriately selected from compounds described in the references cited above.

[0288] Among the above-mentioned dopant materials, amines having a stilbene structure and perylene derivatives are particularly preferred. compounds, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives or pyrene derivatives A conductor is preferred.

[0289] The amine having a stilbene structure is represented by, for example, the following formula: [ka] In the formula, Ar 1 is an m-valent group derived from an aryl having 6 to 30 carbon atoms, and Ar 2 Oh and Ar 3 are each independently an aryl having 6 to 30 carbon atoms, and Ar 1 ~Ar 3 few At least one has a stilbene structure, and Ar 1 ~Ar 3 is an aryl, heteroaryl, Alkyl, trisubstituted silyl (aryl and / or alkyl trisubstituted silyl) or may be substituted with cyano, and m is an integer of 1 to 4.

[0290] The amine having a stilbene structure is more preferably diaminostilbene represented by the following formula: stomach. [ka] In the formula, Ar 2 and Ar 3 are each independently an aryl having 6 to 30 carbon atoms, , Ar 2 and Ar3 is an aryl, heteroaryl, alkyl, trisubstituted silyl (aryl silyl (also trisubstituted with alkyl and / or alkyl) or cyano-substituted good.

[0291] Specific examples of the aryl having 6 to 30 carbon atoms include phenyl, naphthyl, acenaphthylenyl, fluoro. Olenyl, phenalenyl, phenanthrenyl, anthryl, fluoranthenyl, triphenyl Nylenyl, pyrenyl, chrysenyl, naphthacenyl, perylenyl, stilbenyl, distyryl distyrylphenyl, distyrylbiphenylyl, distyrylfluorenyl, and the like.

[0292] A specific example of an amine having a stilbene structure is N,N,N',N'-tetra(4-biphenyl). N,N,N',N'-tetra(1-naphthyl)-4,4'-diaminostilbene )-4,4'-diaminostilbene, N,N,N',N'-tetra(2-naphthyl)-4 ,4'-Diaminostilbene, N,N'-di(2-naphthyl)-N,N'-diphenyl- 4,4'-Diaminostilbene, N,N'-di(9-phenanthryl)-N,N'-diphenyl Phenyl-4,4'-diaminostilbene, 4,4'-bis[4"-bis(diphenylamino) 1,4-bis[4'-bis(diphenylamino)styryl]-biphenyl ]-benzene, 2,7-bis[4'-bis(diphenylamino)styryl]-9,9-di Methylfluorene, 4,4'-bis(9-ethyl-3-carbazovinylene)-biphenyl , 4,4'-bis(9-phenyl-3-carbazovinylene)-biphenyl, etc. do. Further, stills described in Japanese Patent Laid-Open No. 2003-347056 and Japanese Patent Laid-Open No. 2001-307884 are An amine having a phenyl structure may also be used.

[0293] Examples of perylene derivatives include 3,10-bis(2,6-dimethylphenyl)perimethylenediamine. perylene, 3,10-bis(2,4,6-trimethylphenyl)perylene, 3,10-diphenyl 3,4-diphenylperylene, 2,5,8,11-tetra-t-butylperylene Rylene, 3,4,9,10-tetraphenylperylene, 3-(1'-pyrenyl)-8,1 1-Di(t-butyl)perylene, 3-(9'-anthryl)-8,11-di(t-butyl) ) perylene, 3,3'-bis(8,11-di(t-butyl)perylenyl), etc. do. Also, Japanese Patent Application Laid-Open Nos. 11-97178, 2000-133457, 2000-26324, and 2000-2 JP 001-267079 A, ​​JP 2001-267078 A, JP 2001-267076 A, JP 2000-34234 A perylenes described in JP-A-2001-267075, JP-A-2001-217077, etc. Derivatives may also be used.

[0294] Examples of borane derivatives include 1,8-diphenyl-10-(dimesitylboryl)aryl. anthracene, 9-phenyl-10-(dimesitylboryl)anthracene, 4-(9'- Dimesitylborylnaphthalene, 4-(10'-phenyl-9'-anthryl) Dimesitylborylnaphthalene, 9-(dimesitylboryl)anthracene, 9-(4'-biphenyl) phenylyl)-10-(dimesitylboryl)anthracene, 9-(4'-(N-carbazo (phenyl)-10-(dimesitylboryl)anthracene. In addition, borane derivatives described in WO 2000 / 40586 and the like can also be used. good.

[0295] The aromatic amine derivative is represented by, for example, the following formula: [ka] In the formula, Ar 4 is an n-valent group derived from an aryl having 6 to 30 carbon atoms, and Ar 5 Oh and Ar 6 are each independently an aryl having 6 to 30 carbon atoms, and Ar 4 ~Ar 6 Yes, Ali aryl, heteroaryl, alkyl, trisubstituted silyl (aryl and / or alkyl) and n is an integer from 1 to 4, and n may be substituted with methyl, ... It's a number.

[0296] In particular, Ar 4 is anthracene, chrysene, fluorene, benzofluorene or pyrene is a divalent group derived from Ar 5 and Ar 6 are each independently an alkyl group having 6 to 30 carbon atoms Reel and Ar 4 ~Ar 6 is an aryl, heteroaryl, alkyl, trisubstituted silyl aryl (aryl and / or alkyl trisubstituted silyl) or cyano substituted and n is 2.

[0297] Specific examples of the aryl having 6 to 30 carbon atoms include phenyl, naphthyl, acenaphthylenyl, fluoro. Olenyl, phenalenyl, phenanthrenyl, anthryl, fluoranthenyl, triphenyl Examples include nylenyl, pyrenyl, chrysenyl, naphthacenyl, perylenyl, and pentacenyl. can be done.

[0298] As the aromatic amine derivative, for example, N,N,N',N'-tetramethyl amine is used as the chrysene derivative. Tetraphenylchrysene-6,12-diamine, N,N,N',N'-tetra(p-tolyl) ) Chrysene-6,12-diamine, N,N,N',N'-tetra(m-tolyl)chrysene -6,12-diamine, N,N,N',N'-tetrakis(4-isopropylphenyl) Chrysene-6,12-diamine, N,N,N',N'-tetra(naphthalen-2-yl) Chrysene-6,12-diamine, N,N'-diphenyl-N,N'-di(p-tolyl) chrysene Ricen-6,12-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl) N,N'-diphenyl-N,N'-bis(4-isopropyl)chrysene-6,12-diamine N,N'-isopropylphenyl)chrysene-6,12-diamine, N,N'-diphenyl-N,N' -bis(4-t-butylphenyl)chrysene-6,12-diamine, N,N'-bis(4 -isopropylphenyl)-N,N'-di(p-tolyl)chrysene-6,12-diamine Examples include:

[0299] Examples of pyrene-based compounds include N,N,N',N'-tetraphenylpyrene-1, 6-diamine, N,N,N',N'-tetra(p-tolyl)pyrene-1,6-diamine, N,N,N',N'-tetra(m-tolyl)pyrene-1,6-diamine, N,N,N', N'-Tetrakis(4-isopropylphenyl)pyrene-1,6-diamine, N,N,N ',N'-Tetrakis(3,4-dimethylphenyl)pyrene-1,6-diamine, N,N '-Diphenyl-N,N'-di(p-tolyl)pyrene-1,6-diamine, N,N'-di Phenyl-N,N'-bis(4-ethylphenyl)pyrene-1,6-diamine, N,N' -Diphenyl-N,N'-bis(4-isopropylphenyl)pyrene-1,6-diamine , N,N'-diphenyl-N,N'-bis(4-t-butylphenyl)pyrene-1,6- Diamine, N,N'-bis(4-isopropylphenyl)-N,N'-di(p-tolyl) Pyrene-1,6-diamine, N,N,N',N'-tetrakis(3,4-dimethylphenyl) N,N,N,N-tetraphenyl Pyrene-1,8-diamine, N,N'-bis(biphenyl-4-yl)-N,N'-diphenyl Phenylpyrene-1,8-diamine, N 1 ,N 6 -diphenyl-N 1 ,N 6 -Bis-(4- trimethylsilanyl-phenyl)-1H,8H-pyrene-1,6-diamine. can be.

[0300] As an anthracene-based compound, for example, N,N,N,N-tetraphenylanthracene is N,N,N',N'-tetra(p-tolyl)anthracene-9,10-diamine ,10-diamine, N,N,N',N'-tetra(m-tolyl)anthracene-9,10 -diamine, N,N,N',N'-tetrakis(4-isopropylphenyl)anthracene N,N'-diphenyl-N,N'-di(p-tolyl)anthracene sen-9,10-diamine, N,N'-diphenyl-N,N'-di(m-tolyl) amine Helical-9,10-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl) N,N'-diphenyl-N,N'-bis(4 -isopropylphenyl)anthracene-9,10-diamine, N,N'-diphenyl- N,N'-bis(4-t-butylphenyl)anthracene-9,10-diamine, N,N '-Bis(4-isopropylphenyl)-N,N'-di(p-tolyl)anthracene-9 ,10-diamine, 2,6-di-t-butyl-N,N,N',N'-tetra(p-tolyl ) Anthracene-9,10-diamine, 2,6-di-t-butyl-N,N'-diphenyl -N,N'-bis(4-isopropylphenyl)anthracene-9,10-diamine, 2 ,6-di-t-butyl-N,N'-bis(4-isopropylphenyl)-N,N'-di( p-Tolyl)anthracene-9,10-diamine, 2,6-dicyclohexyl-N,N' -bis(4-isopropylphenyl)-N,N'-di(p-tolyl)anthracene-9, 10-diamine, 2,6-dicyclohexyl-N,N'-bis(4-isopropylphenyl) N,N'-bis(4-t-butylphenyl)anthracene-9,10-diamine, 9,10-bis(4-diphenylamino-phenyl)anthracene, 9,10-bis(4 -di(1-naphthylamino)phenyl)anthracene, 9,10-bis(4-di(2-naphthylamino)phenyl)anthracene 10-di-p-tolylamino-9-(4-di- p-Tolylamino-1-naphthyl)anthracene, 10-diphenylamino-9-(4- Diphenylamino-1-naphthyl)anthracene, 10-diphenylamino-9-(6- diphenylamino-2-naphthyl)anthracene.

[0301] Also, [4-(4-diphenylamino-phenyl)naphthalen-1-yl]- Diphenylamine, [6-(4-diphenylamino-phenyl)naphthalen-2-yl] -Diphenylamine, 4,4'-bis[4-diphenylaminonaphthalen-1-yl]biphenylamine phenyl, 4,4'-bis[6-diphenylaminonaphthalen-2-yl]biphenyl, 4,4"-bis[4-diphenylaminonaphthalen-1-yl]-p-terphenyl, 4 ,4"-bis[6-diphenylaminonaphthalen-2-yl]-p-terphenyl, etc. Examples include: Alternatively, aromatic amine derivatives such as those described in JP-A-2006-156888 may be used.

[0302] Coumarin derivatives include coumarin-6 and coumarin-334. Also, Japanese Patent Application Laid-Open No. 2004-43646, Japanese Patent Application Laid-Open No. 2001-76876, and Japanese Patent Application Laid-Open No. 6-298758 Coumarin derivatives described elsewhere may also be used.

[0303] Examples of pyran derivatives include DCM and DCJTB shown below. [ka] Also, Japanese Patent Application Laid-Open Nos. 2005-126399, 2005-097283, 2002-234892, The inventions described in Japanese Patent Laid-Open No. 2001-220577, Japanese Patent Laid-Open No. 2001-081090, and Japanese Patent Laid-Open No. 2001-052869, etc. The pyran derivatives described above may also be used.

[0304] The polycyclic aromatic compound represented by the general formula (1) can be used together with an organic solvent to form a composition for forming a light-emitting layer. The composition may also be used as a first component. a second component comprising at least one host material; and a third component comprising at least one The first component is a dopant component for the light-emitting layer obtained from the composition. The second component functions as a host component for the light-emitting layer, and the third component functions as a light-emitting layer host component for the first component in the composition. It acts as a solvent to dissolve the second and third components, and allows the controlled evaporation of the third component itself upon application. The speed gives a smooth and uniform surface profile.

[0305] <Organic solvents> The composition for forming a light-emitting layer contains at least one organic solvent as a third component. By controlling the evaporation rate of the organic solvent, it is possible to control the film forming property, the presence or absence of defects in the coating, the surface roughness, The smoothness can be controlled and improved. Controls meniscus stability at pinholes in inkjet heads, controlling and improving ejection performance In addition, by controlling the drying rate of the film and the orientation of the derivative molecules, The electrical characteristics, luminous characteristics and efficiency of an organic EL device having a luminescent layer obtained from a composition for forming a luminescent layer are The efficiency and lifespan can be improved.

[0306] (1) Physical properties of organic solvents In the third component, the boiling point of at least one organic solvent is 130°C to 300°C, The boiling point is more preferably 140°C to 270°C, and even more preferably 150°C to 250°C. If the boiling point is higher than 0°C, it is preferable from the viewpoint of inkjet ejection properties. A lower value is preferable from the viewpoint of defects in the coating film, surface roughness, residual solvent, and smoothness. The components are selected from the viewpoints of good inkjet ejection properties, film forming properties, smoothness, and low residual solvent. It is more preferable to use two or more organic solvents. In consideration of this, the composition is made into a solid state by removing the solvent from the composition for forming the light-emitting layer. That's fine.

[0307] Furthermore, the third component acts as a good solvent (GS) and a poor solvent (PS) for the host material of the second component. The boiling point (BP) of the good solvent (GS) is GS ) is the boiling point (BP) of the poor solvent (PS) PS ) than A low, configuration is particularly preferred. By adding a poor solvent with a high boiling point, the good solvent with a low boiling point volatilizes first during film formation, and the content of the composition The concentration of the solvent and the concentration of the poor solvent increase, promoting rapid film formation. A coating film with low surface roughness and high smoothness can be obtained.

[0308] Difference in solubility (S GS -S PS ) is preferably 1% or more, and more preferably 3% or more. The difference in boiling point (BP) is more preferably 5% or more, and even more preferably 5% or more. PS -BP G S ) is preferably 10°C or higher, more preferably 30°C or higher, and ° C. or higher is more preferable.

[0309] After film formation, the organic solvent is removed from the coating by a drying process using vacuum, reduced pressure, or heat. When heating, from the viewpoint of improving coating film forming properties, the glass transition temperature (Tg) of the first component + It is preferable to carry out the process at 30°C or less. From the viewpoint of reducing residual solvent, the glass of the first component is It is preferable to heat the solution at a temperature higher than the boiling point of the organic solvent (Tg) minus 30°C. Even if the temperature is lower than this, the organic solvent is sufficiently removed because the film is thin. Drying may be performed, or a plurality of drying methods may be used in combination.

[0310] (2) Specific examples of organic solvents The organic solvent used in the composition for forming the light-emitting layer includes alkylbenzene solvents, phenyl alkyl ether solvents, alkyl ether solvents, cyclic ketone solvents, aliphatic ketone solvents, Examples include monocyclic ketone solvents, solvents having a diester skeleton, and fluorine-containing solvents. Specific examples include pentanol, hexanol, heptanol, octanol, and nonanol. decanol, undecanol, dodecanol, tetradecanol, hexane-2-ol ol, heptan-2-ol, octan-2-ol, decan-2-ol, dodecane- 2-ol, cyclohexanol, α-terpineol, β-terpineol, γ-terpineol Pineol, δ-terpineol, terpineol (mixture), ethylene glycol mono Methyl ether acetate, propylene glycol monomethyl ether acetate, diene ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene Diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether dipropylene glycol monomethyl ether, diethylene glycol diethyl ether Diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, p-xylene, m-xylene , o-xylene, 2,6-lutidine, 2-fluoro-m-xylene, 3-fluoro-o- Xylene, 2-chlorobenzotrifluoride, cumene, toluene, 2-chloro-6-fluoro Toluene, 2-fluoroanisole, anisole, 2,3-dimethylpyrazine, bromobenzyl Benzene, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethylanisole Nisole, mesitylene, 1,2,4-trimethylbenzene, t-butylbenzene, 2-methyl Chilanisole, Phenetole, Benzodioxole, 4-Methylanisole, s-Butylanisole Benzene, 3-methylanisole, 4-fluoro-3-methylanisole, cymene, 1 ,2,3-trimethylbenzene, 1,2-dichlorobenzene, 2-fluorobenzonitrile 4-Fluoroveratrol, 2,6-dimethylanisole, n-butylbenzene, 3 -Fluorobenzonitrile, Decalin (Decahydronaphthalene), Neopentylbenzene , 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3,5 -Dimethylanisole, diphenyl ether, 1-fluoro-3,5-dimethoxybenzene Benzene, methyl benzoate, isopentylbenzene, 3,4-dimethylanisole, o-toluni Tolyl, n-amylbenzene, veratrole, 1,2,3,4-tetrahydronaphthalene , ethyl benzoate, n-hexylbenzene, propyl benzoate, cyclohexylbenzene , 1-methylnaphthalene, butyl benzoate, 2-methylbiphenyl, 3-phenoxyethanol ene, 2,2'-bitolyl, dodecylbenzene, dipentylbenzene, tetramethylbenzene benzene, trimethoxybenzene, trimethoxytoluene, 2,3-dihydrobenzofuran, 1-methyl-4-(propoxymethyl)benzene, 1-methyl-4-(butyloxymethyl)benzene benzene, 1-methyl-4-(pentyloxymethyl)benzene, 1-methyl-4-(hexyloxymethyl)benzene 1-Methyl-4-(heptyloxymethyl)benzenebenzylbutyl ether, benzyl pentyl ether, benzyl hexyl ether, benzyl heptyl ether, benzyl octyl ether, etc., but are not limited thereto. The solvent may be used alone or in combination.

[0311] <Optional ingredients> The composition for forming a light-emitting layer may contain optional components to the extent that the properties of the composition are not impaired. Optional components include a binder and a surfactant.

[0312] (1) Binder The composition for forming a light-emitting layer may contain a binder. A film is formed, and the obtained film is bonded to a substrate. It serves to dissolve, disperse and bind the other ingredients.

[0313] Examples of binders used in the composition for forming a light-emitting layer include acrylic resins, polyesters, and the like. Ethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer Polymer, acrylonitrile-ethylene-styrene copolymer (AES) resin, ionomer , chlorinated polyether, diallyl phthalate resin, unsaturated polyester resin, polyethylene Polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate Nyl, Teflon, acrylonitrile-butadiene-styrene copolymer (ABS) resin, Acrylonitrile-styrene copolymer (AS) resin, phenolic resin, epoxy resin, amine resins, urea resins, alkyd resins, polyurethanes, and the like, as well as the above resins and polymers. Copolymers, but are not limited to these.

[0314] The binder used in the composition for forming the light-emitting layer may be one type or a mixture of multiple types. It may also be used as such.

[0315] (2) Surfactants The composition for forming a light-emitting layer is, for example, a composition for forming a light-emitting layer having a uniform film surface, a solvent affinity on the film surface, and the like. A surfactant may be contained to control the liquid repellency. They are classified into ionic and nonionic types based on their structure, and further into alkyl and nonionic types based on the structure of their hydrophobic groups. They are classified into silicon-based and fluorine-based. Also, due to the molecular structure, the molecular weight is relatively small. Simple monomolecular systems and large polymer systems with side chains and branches In addition, based on the composition, they are classified into a single system, a mixture of two or more surfactants and base materials, and The surfactants that can be used in the composition for forming the light-emitting layer include all of the following: Any type of surfactant can be used.

[0316] Examples of surfactants include Polyflow No. 45, Polyflow KL-245, Poly Flow No. 75, Polyflow No. 90, Polyflow No. 95 (product names, Kyoeisha Chemical Co., Ltd.) Disperbyk 161, Disperbyk 1 62, Disperbake 163, Disperbake 164, Disperbake 166, De Disperbake 170, Disperbake 180, Disperbake 181, Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK33 0, BYK342, BYK344, BYK346 (trade name, BYK Japan Co., Ltd.) ), KP-341, KP-358, KP-368, KF-96-50CS, KF-5 0-100CS (product name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflo KH-40 (product name, manufactured by Seimi Chemical Co., Ltd.), Futergent 222F, Futerji Fent 251, FTX-218 (product name, manufactured by Neos Co., Ltd.), EFTOP EF-351 , EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (product name, manufactured by Mitsubishi Materials Corporation), Megafac F-47 0, Megafuck F-471, Megafuck F-475, Megafuck R-08, Megaf F-477, Megafuck F-479, Megafuck F-553, Megafuck F -554 (trade name, manufactured by DIC Corporation), fluoroalkylbenzene sulfonate, fluoro Fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl Ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate , diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoro Alkyltrimethylammonium salts, fluoroalkylaminosulfonates, polyoxy Ethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, poly Oxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene Oleate, Polyoxyethylene Stearate, Polyoxyethylene Laurylamine, Sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, poly Oxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, Polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, arsenic alkylbenzene sulfonates and alkyldiphenyl ether disulfonates. This can be done.

[0317] The surfactant may be used alone or in combination of two or more.

[0318] <Composition and Properties of the Composition for Forming the Light-Emitting Layer> The content of each component in the composition for forming a light-emitting layer is determined based on the desired properties of each component in the composition for forming a light-emitting layer. The composition for forming a light-emitting layer has excellent solubility, storage stability and film-forming property, and a coating film obtained from the composition for forming a light-emitting layer. The composition has good film quality, good ejection properties when using an ink jet method, and The organic EL device having the prepared light-emitting layer has good electrical characteristics, light-emitting characteristics, efficiency, and lifespan. From this viewpoint, the first component is preferably 0.0001% by weight to 2.0% by weight based on the total weight of the composition for forming the light-emitting layer. % by weight, and the second component is 0.0999% by weight to 8.0% by weight based on the total weight of the composition for forming the light-emitting layer. % by weight, and the third component is 90.0% by weight to 99.9% by weight based on the total weight of the composition for forming the light-emitting layer. Amount % is preferred.

[0319] More preferably, the first component is 0.005% by weight based on the total weight of the composition for forming a light-emitting layer. and the second component is 0.095% by weight or more relative to the total weight of the composition for forming the light-emitting layer. 4.0% by weight, and the third component is 95.0% by weight to 99.0% by weight based on the total weight of the composition for forming the light-emitting layer. More preferably, the first component is 0.9% by weight based on the total weight of the composition for forming the light-emitting layer. , 0.05 wt % to 0.5 wt %, and the second component is 0 0.25% by weight to 2.5% by weight, and the third component is 97. It is 0% by weight to 99.7% by weight.

[0320] The composition for forming a light-emitting layer can be prepared by stirring, mixing, heating, cooling, dissolving, etc., the above-mentioned components in a known manner. After preparation, the mixture can be produced by appropriately selecting and performing the steps of filtration, degassing ( (also called degassing), ion exchange treatment, and inert gas replacement / filling treatment are selected appropriately. It is also possible.

[0321] The higher the viscosity of the composition for forming the light-emitting layer, the better the film-forming properties and ink-jet printing properties. On the other hand, low viscosity makes it easier to form a thin film. From this, it is understood that the viscosity of the composition for forming a light-emitting layer is 0.3 mPa at 25°C. It is preferable that the value is 1 mPa·s to 3 mPa·s, and more preferably 1 mPa·s to 3 mPa·s. In the present invention, the viscosity is measured using a cone-plate type rotational viscometer. The values ​​were measured using a

[0322] The lower the surface tension of the composition for forming the light-emitting layer, the better the film-forming properties and the more defect-free the coating film. On the other hand, the higher the value, the better the inkjet ejection properties. The viscosity of the composition for forming the light-emitting layer is such that the surface tension at 25°C is 20 mN / m to 40 mN / m. It is preferable that the resistance is in the range of 20 mN / m to 30 mN / m. In the above, the surface tension is a value measured using the pendant drop method.

[0323] <Electron injection layer and electron transport layer in organic electroluminescent device> The electron injection layer 107 efficiently injects electrons moving from the cathode 108 into the light-emitting layer 105. The electron transport layer 106 serves to inject electrons from the cathode 108 into the electron transport layer 106. The injected electrons or the electrons injected from the cathode 108 through the electron injection layer 107 are efficiently The electron transport layer 106 and the electron injection layer 107 serve to transport electrons to the light-emitting layer 105. , respectively, one or more kinds of electron transporting and injecting materials are laminated or mixed, or electron transporting and It is formed by a mixture of an injectable material and a polymeric binder.

[0324] The electron injection / transport layer is a layer that injects electrons from the cathode and transports them. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. To achieve this, the electron affinity must be large, the electron mobility must be large, and the stability and tracking ability must be excellent. It is preferable that the material be one that is unlikely to generate impurities that can become a problem during production and use. However, when considering the balance of hole and electron transport, the holes from the anode do not recombine and are transported to the cathode. If the electron transport capacity is not so high, the electron transport capacity will be Even if the electron transporting ability is not high, the effect of improving the luminous efficiency is equivalent to that of a material with high electron transporting ability. Therefore, the electron injection / transport layer in this embodiment is a layer that can efficiently block the movement of holes. Functions may also be included.

[0325] The material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107 is: Compounds that have been conventionally used as electron transport compounds in photoconductive materials, organic EL devices The compound is arbitrarily selected from known compounds used in the electron injection layer and electron transport layer. You can be there.

[0326] The materials used for the electron transport layer or the electron injection layer include carbon, hydrogen, oxygen, sulfur, ketone, and the like. Aromatic rings or heteroaromatic rings consisting of one or more atoms selected from silicon and phosphorus Compounds consisting of aromatic rings, pyrrole derivatives and their fused ring derivatives, and compounds having electron-accepting nitrogen It is preferable that the metal complex contains at least one selected from the following metal complexes. Condensed ring aromatic derivatives such as naphthalene and anthracene, 4,4'-bis(diphenyl Styryl aromatic ring derivatives, such as ethenylbiphenyl, perinone derivatives, and kumari quinone derivatives such as quinone derivatives, naphthalimide derivatives, anthraquinone and diphenoquinone , phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes having an electron-accepting nitrogen include hydroxyphenyloxazole. Complexes such as hydroxyazole complexes, azomethine complexes, tropolone metal complexes, flavonoid complexes, These materials can be used alone or in combination with other materials. However, it is acceptable to use a mixture of different materials.

[0327] Specific examples of other electron transport compounds include pyridine derivatives, naphthalene derivatives, and ammonium salts. Thracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalene Imide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives , perylene derivatives, oxadiazole derivatives (1,3-bis[(4-t-butylphenyl )1,3,4-oxadiazolyl]phenylene, etc.), thiophene derivatives, triazoles Derivatives (e.g., N-naphthyl-2,5-diphenyl-1,3,4-triazole), thiazides Azole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives Conductors, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazoles perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzophenone derivatives, benzoquinoline derivative (2,2'-bis(benzo[h]quinolin-2-yl)-9,9'-s pyrobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole Derivatives (such as tris(N-phenylbenzimidazol-2-yl)benzene), benzo Oxazole derivatives, benzothiazole derivatives, quinoline derivatives, terpyridines, etc. Polypyridine derivatives, bipyridine derivatives, terpyridine derivatives (1,3-bis(4'-( 2,2':6'2"-terpyridinyl))benzene, etc.), naphthyridine derivatives (bis( 1-Naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide aldazine derivatives, carbazole derivatives, indole derivatives, phosphorus oxide derivatives, bisstyryl derivatives, etc.

[0328] Metal complexes having an electron-accepting nitrogen atom can also be used, for example, quinolinol-based Metal complexes, hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomes tin complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. Examples include:

[0329] The above-mentioned materials may be used alone or in combination with other materials.

[0330] Among the above-mentioned materials, borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives , pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives The compounds, phenanthroline derivatives, and quinolinol-based metal complexes are preferred.

[0331] <Borane derivatives> The borane derivative is, for example, a compound represented by the following general formula (ETM-1), and in detail This is disclosed in Japanese Patent Application Laid-Open No. 2007-27587. [ka] In the above formula (ETM-1), R 11 and R 12 are each independently hydrogen, alkyl, , optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing at least one of a heterocyclic ring, a cyclic ring, or a cyano group; and R 13 ~R 16 are each independently , optionally substituted alkyl, or optionally substituted aryl; and X is Y is an optionally substituted arylene having 16 or less carbon atoms. aryl, substituted boryl, or optionally substituted carbazolyl; and n's are each independently an integer of 0 to 3.

[0332] Among the compounds represented by the above general formula (ETM-1), the compound represented by the following general formula (ETM-1-1) and compounds represented by the following general formula (ETM-1-2) are preferred. [ka] In formula (ETM-1-1), R 11 and R 12 are each independently hydrogen, alkyl, , optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing at least one of a heterocyclic ring, a cyclic ring, or a cyano group; and R 13 ~R 16 are each independently , optionally substituted alkyl, or optionally substituted aryl; R 21 and R 22 each independently represents hydrogen, alkyl, or optionally substituted aryl, At least one of substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano There is also one X 1 represents an optionally substituted arylene having 20 or less carbon atoms, and n represents Each m is independently an integer of 0 to 3, and each m is independently an integer of 0 to 4. do. [ka] In formula (ETM-1-2), R 11 and R 12 are each independently hydrogen, alkyl, , optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing at least one of a heterocyclic ring, a cyclic ring, or a cyano group; and R 13 ~R 16 are each independently , optionally substituted alkyl, or optionally substituted aryl; and X 1 teeth , an optionally substituted arylene having 20 or less carbon atoms, and each n is independently and is an integer between 0 and 3.

[0333] X 1 Specific examples of the divalent groups include those represented by the following formulae (X-1) to (X-9). It can be obtained. [ka] (In each formula, R aare each independently an alkyl group or an optionally substituted phenyl group. )

[0334] Specific examples of the borane derivative include the following compounds: [ka]

[0335] This borane derivative can be produced using known raw materials and known synthesis methods.

[0336] <Pyridine derivatives> The pyridine derivative is, for example, a compound represented by the following formula (ETM-2), and preferably The compound is represented by formula (ETM-2-1) or formula (ETM-2-2). [ka]

[0337] φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or trifluorene ring phenylene ring), and n is an integer of 1 to 4.

[0338] In the above formula (ETM-2-1), R 11 ~R 18 are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably alkyl having 3 to 4 carbon atoms), cycloalkyl having 6 to 12 carbon atoms) or aryl (preferably aryl having 6 to 30 carbon atoms). do.

[0339] In the above formula (ETM-2-2), R 11 and R 12 are each independently hydrogen , alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably aryl having 6 to 30 carbon atoms) and R 11 and R 12 may be bonded to form a ring.

[0340] In each formula, the "pyridine-based substituent" is any one of the following formulae (Py-1) to (Py-15): The pyridine-based substituents are each independently substituted with alkyl having 1 to 4 carbon atoms. In addition, the pyridine-based substituent may be connected in each formula via a phenylene group or a naphthylene group. The φ in the formula (I) may be bonded to an anthracene ring or a fluorene ring.

[0341] [ka]

[0342] The pyridine-based substituent is any one of the above formulas (Py-1) to (Py-15). Among these, any one of the following formulas (Py-21) to (Py-44) is preferred. stomach. [ka]

[0343] At least one hydrogen atom in each pyridine derivative may be replaced by deuterium. In addition, the two "pyridine-based compounds" in the above formula (ETM-2-1) and formula (ETM-2-2) One of the "substituents" may be replaced by an aryl.

[0344] R 11 ~R 18 The "alkyl" in the formula (I) may be either a straight chain or a branched chain. For example, a linear alkyl group having 1 to 24 carbon atoms or a branched alkyl group having 3 to 24 carbon atoms can be mentioned. Preferred "alkyl" is alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms). More preferred "alkyl" is alkyl having 1 to 12 carbon atoms (alkyl having 3 to 12 carbon atoms). A more preferred "alkyl" is an alkyl having 1 to 6 carbon atoms. Particularly preferred "alkyl" is a branched alkyl having 1 to 6 carbon atoms. 4 alkyl (branched alkyl having 3 to 4 carbon atoms).

[0345] Specific examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n- Butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n- Octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl ethyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3, 5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-do Decyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl , n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, etc. can be done.

[0346] The alkyl having 1 to 4 carbon atoms that is substituted on the pyridine-based substituent is the same as the alkyl described above. It can be cited.

[0347] R 11 ~R 18The "cycloalkyl" in the above formula includes, for example, cycloalkyl having 3 to 12 carbon atoms. Preferred "cycloalkyl" is a cycloalkyl having 3 to 10 carbon atoms. A more preferred "cycloalkyl" is a cycloalkyl having 3 to 8 carbon atoms. More preferred "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms. Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, and cyclopentyl. cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, Examples include cyclooctyl and dimethylcyclohexyl.

[0348] R 11 ~R 18 As for the "aryl" in the above, preferred aryl is an aryl having 6 to 30 carbon atoms. Aryl is more preferably an aryl having 6 to 18 carbon atoms, and even more preferably Preferably, it is an aryl having 6 to 14 carbon atoms, and particularly preferably an aryl having 6 to 12 carbon atoms. do.

[0349] Specific examples of "aryl having 6 to 30 carbon atoms" include monocyclic aryl such as phenyl, condensed aryl, and the like. (1-,2-)naphthyl is a fused bicyclic aryl; acenaphthyl is a fused tricyclic aryl; ethylene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9 -)yl, phenalen-(1-,2-)yl, (1-,2-,3-,4-,9-)phenalen triphenylene-(1-,2-)yl, pyrene-( 1-, 2-, 4-)yl, naphthacene-(1-, 2-, 5-)yl, fused pentacyclic aryl Perylene-(1-, 2-, 3-)yl, pentacene-(1-, 2-, 5-, 6-) Examples include Iru.

[0350] Preferred examples of the "aryl having 6 to 30 carbon atoms" include phenyl, naphthyl, phenanthryl, and chlorine. phenyl, 1-naphthyl, and the like are preferred. Particularly preferred are phenyl, 1-naphthyl and phenanthryl. Examples of the alkyl radical include 2-naphthyl and 2-naphthyl.

[0351] R in the above formula (ETM-2-2) 11 and R 12 Even if they bond to form a ring, As a result, the five-membered ring of the fluorene skeleton is often cyclobutane, cyclopentane, cyclopentane, Pentene, cyclopentadiene, cyclohexane, fluorene, or indene are spin It may be bonded to the

[0352] Specific examples of the pyridine derivative include the following compounds: [ka]

[0353] This pyridine derivative can be produced using known raw materials and known synthesis methods.

[0354] <Fluoranthene derivatives> The fluoranthene derivative is, for example, a compound represented by the following general formula (ETM-3): Details are disclosed in International Publication No. 2010 / 134352. [ka]

[0355] In the above formula (ETM-3), X 12 ~X 21 is hydrogen, halogen, straight chain, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0356] Specific examples of this fluoranthene derivative include, for example, the following compounds. [Chemical formula]

[0357] [BO-based derivative] The BO-based derivative is, for example, a polycyclic aromatic compound represented by the following formula (ETM-4), or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (ETM-4). [Chemical formula]

[0358] R 1 ~R 11 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, alkoxy or aryloxy, and at least one hydrogen in these may be substituted with aryl, hetero aryl or alkyl.

[0359] Also, adjacent groups among R 1 ~R 11 may combine with each other to form an aryl ring or a heteroaryl ring together with the a-ring, b-ring or c-ring, and at least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, alkoxy or aryloxy, and at least one hydrogen in these may be substituted with aryl, heteroaryl or substituted with alkyl, alkoxy or aryloxy, and at least one hydrogen in these may be substituted with aryl, heteroaryl or alkyl. may be substituted with alkyl.

[0360] In addition, at least one hydrogen atom in the compound or structure represented by formula (ETM-4) It may be substituted with halogen or deuterium.

[0361] The substituents and ring formation forms in formula (ETM-4), and the structure of formula (ETM-4) The explanation of the multimers that are formed by combining them is given in the chemical formulas (1) and (1') above. The description of the compound and its multimers can be cited.

[0362] Specific examples of the BO derivative include the following compounds: [ka]

[0363] This BO derivative can be produced using known raw materials and known synthesis methods.

[0364] <Anthracene derivatives> One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-1): do. [ka]

[0365] Ar are each independently a divalent benzene or naphthalene; R 1 ~R 4 teeth, Each independently represents hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or or an aryl having 6 to 20 carbon atoms.

[0366] Ar may be independently selected from divalent benzene or naphthalene. The two Ar groups may be different or the same, but the synthesis of anthracene derivatives From the viewpoint of easiness, it is preferable that they are the same. Ar is bonded to pyridine, and and a pyridine moiety" is formed, and this moiety is, for example, represented by the following formula (Py-1) to formula ( Py-12) is bonded to anthracene.

[0367] [ka]

[0368] Among these groups, the group represented by any one of the above formulas (Py-1) to (Py-9) A group represented by any one of the above formulae (Py-1) to (Py-6) is more preferred. The two "Ar and pyridine moieties" that bind to anthracene have the same structure. However, from the viewpoint of ease of synthesis of the anthracene derivative, it is preferable to use the same However, from the viewpoint of device characteristics, it is preferable that the two "Ar and pyrimidine" structures are the same. The structures of the "sin-containing moieties" may be the same or different.

[0369] R 1 ~R 4 The alkyl group having 1 to 6 carbon atoms can be either straight or branched. That is, it is a linear alkyl having 1 to 6 carbon atoms or a branched alkyl having 3 to 6 carbon atoms. More preferably, it is an alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. butyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl ethyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethyl methyl, ethyl, n-propyl, 2-ethylbutyl, etc. isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl is preferred, and methyl More preferred are butyl, ethyl, or t-butyl.

[0370] R 1 ~R 4 Specific examples of the cycloalkyl having 3 to 6 carbon atoms include cyclopropyl , cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl cyclohexyl, methylcyclohexyl, cyclooctyl, or dimethylcyclohexyl. can be done.

[0371] R 1 ~R 4 For aryls having 6 to 20 carbon atoms, aryls having 6 to 16 carbon atoms is preferred, aryl having 6 to 12 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred. Preferred.

[0372] Specific examples of "aryl having 6 to 20 carbon atoms" include monocyclic aryl such as phenyl, ( o-,m-,p-)tolyl, (2,3-,2,4-,2,5-,2,6-,3,4-,3 ,5-)xylyl, mesityl (2,4,6-trimethylphenyl), (o-, m-, p- ) cumenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, fused bicyclic aryl (1-,2-)naphthyl, a tricyclic aryl; terphenylyl (m-terphenyl); m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-Terphenyl-3'-yl, o-Terphenyl-4'-yl, p-Terphenyl-2 '-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terpheny o-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terfenyl p-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, ... phenyl-4-yl), fused tricyclic aryl anthracene-(1-, 2-, 9-phenyl-4-yl), -)yl, acenaphthylene-(1-,3-,4-,5-)yl, fluorene-(1-,2 -,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-,2-,3-, 4-, 9-)phenanthryl, fused tetracyclic aryl triphenylene-(1-, 2- )yl, pyrene-(1-, 2-, 4-)yl, tetracene-(1-, 2-, 5-)yl, Examples include perylene-(1-, 2-, 3-)yl, which is a fused pentacyclic aryl.

[0373] Preferred "aryl having 6 to 20 carbon atoms" are phenyl, biphenylyl, and terphenylyl. or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2- naphthyl or m-terphenyl-5'-yl, more preferably phenyl, biphenyl It is preferably phenylyl, 1-naphthyl or 2-naphthyl, and most preferably phenyl.

[0374] One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-2): do. [ka]

[0375] Ar 1 are each independently a single bond, a divalent benzene, a divalent naphthalene, an anthracene, fluorene or phenalene.

[0376] Ar 2are each independently an aryl having 6 to 20 carbon atoms, and The same explanation as for "aryl having 6 to 20 carbon atoms" in -1) can be cited. An aryl having 6 to 16 carbon atoms is preferred, an aryl having 6 to 12 carbon atoms is more preferred, and an aryl having 6 to 16 carbon atoms is more preferred. Particularly preferred is an aryl having a carbon number of 10 or less. Specific examples include phenyl, biphenylyl, and naphthyl. , terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, Examples include phenanthryl, triphenylenyl, pyrenyl, tetracenyl, and perylenyl. can be.

[0377] R 1 ~R 4 are each independently hydrogen, alkyl having 1 to 6 carbon atoms, is a cycloalkyl or an aryl having 6 to 20 carbon atoms, and in the above formula (ETM-5-1), The explanations given can be cited.

[0378] Specific examples of these anthracene derivatives include the following compounds: [ka]

[0379] These anthracene derivatives can be produced using known raw materials and known synthesis methods. Cut.

[0380] <Benzofluorene derivatives> The benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6). [ka]

[0381] Ar 1 are each independently an aryl having 6 to 20 carbon atoms, and The same explanation as for "aryl having 6 to 20 carbon atoms" in -1) can be cited. An aryl having 6 to 16 carbon atoms is preferred, an aryl having 6 to 12 carbon atoms is more preferred, and an aryl having 6 to 16 carbon atoms is more preferred. Particularly preferred is an aryl having a carbon number of 10 or less. Specific examples include phenyl, biphenylyl, and naphthyl. , terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, Examples include phenanthryl, triphenylenyl, pyrenyl, tetracenyl, and perylenyl. can be.

[0382] Ar 2 are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), ), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably Preferably, it is an aryl having 6 to 30 carbon atoms, and two Ar 2 are bonded to form a ring Good too.

[0383] Ar 2 The "alkyl" in the above may be either a straight chain or a branched chain, and examples thereof include: Examples of the alkyl group include linear alkyl groups having 1 to 24 carbon atoms and branched alkyl groups having 3 to 24 carbon atoms. Preferred "alkyl" is alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms). More preferred "alkyl" is alkyl having 1 to 12 carbon atoms (e.g., alkyl having 3 to 12 carbon atoms). A more preferred "alkyl" is an alkyl having 1 to 6 carbon atoms (a branched alkyl). Particularly preferred "alkyl" is alkyl having 1 to 4 carbon atoms. alkyl (branched alkyl with 3-4 carbon atoms). Specific examples of "alkyl" include methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl ethyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1- Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl Examples include ethyl, n-heptyl, and 1-methylhexyl.

[0384] Ar 2 The "cycloalkyl" in the above formula includes, for example, cycloalkyl having 3 to 12 carbon atoms. Preferred "cycloalkyl" is cycloalkyl having 3 to 10 carbon atoms. More preferred "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. Preferred "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms. Examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl or or dimethylcyclohexyl.

[0385] Ar 2 As for the "aryl" in the above, preferred aryl is an aryl having 6 to 30 carbon atoms. The aryl is more preferably an aryl having 6 to 18 carbon atoms, and further preferably an aryl having 6 to 18 carbon atoms. It is an aryl having 6 to 14 carbon atoms, and particularly preferably an aryl having 6 to 12 carbon atoms.

[0386] Specific examples of "aryl having 6 to 30 carbon atoms" include phenyl, naphthyl, and acenaphthyl. nyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, na Examples include phthalocenyl, perylenyl, and pentacenyl.

[0387] Two Ar 2 may be bonded to form a ring, resulting in a five-membered ring of the fluorene skeleton. These include cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, and cyclohexene. The oxane, fluorene, or indene may be spiro-linked.

[0388] Specific examples of the benzofluorene derivative include the following compounds: [ka]

[0389] This benzofluorene derivative can be produced using known raw materials and known synthesis methods. Cut.

[0390] <Phosphine oxide derivatives> The phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1): The details are also described in International Publication No. 2013 / 079217. [ka] R 5 is a substituted or unsubstituted alkyl having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. or a heteroaryl having 5 to 20 carbon atoms, R 6 is CN, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, Tetraalkyl, aryl with 6 to 20 carbon atoms, heteroaryl with 5 to 20 carbon atoms, is an alkoxy having 6 to 20 carbon atoms or an aryloxy having 6 to 20 carbon atoms; R 7 and R 8 are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. aryl or heteroaryl having 5 to 20 carbon atoms, R 9 is oxygen or sulfur, j is 0 or 1, k is 0 or 1, r is an integer of 0 to 4, and q is an integer of 1 to 3. is an integer.

[0391] The phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-2): Good too. [ka]

[0392] R 1 ~R 3 may be the same or different and are hydrogen, an alkyl group, a cycloalkyl group, Aralkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, alkoxy groups, alkoxy groups, A arylthio group, an aryl ether group, an arylthioether group, an aryl group, a heterocyclic group, a halo group, Aldehyde, cyano, aldehyde, carbonyl, carboxyl, amino, nitro , a silyl group, and a fused ring formed between adjacent substituents.

[0393] Ar 1 may be the same or different and are arylene or heteroarylene groups. Ri, Ar 2 may be the same or different and are aryl or heteroaryl groups However, Ar 1 and Ar 2 At least one of the groups has a substituent, or the adjacent groups A condensed ring is formed between the substituted and unsaturated groups. n is an integer of 0 to 3. When n is 0, the unsaturated group is When n is 3, R 1 does not exist.

[0394] Among these substituents, the alkyl group includes, for example, a methyl group, an ethyl group, a propyl group, a bromine group, and the like. refers to a saturated aliphatic hydrocarbon group, such as a methyl group, which may be unsubstituted or substituted. If substituted, the substituent is not particularly limited, and examples thereof include alkyl groups and aryl groups. and heterocyclic groups, which are also included in the following description. The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of availability and cost, it is usually 1 to 20. It is a range.

[0395] The cycloalkyl group includes, for example, cyclopropyl, cyclohexyl, norbornyl, It refers to saturated alicyclic hydrocarbon groups such as benzoyl, benzoyl, and adamantyl, which can be unsubstituted or substituted. The number of carbon atoms in the alkyl group is not particularly limited, but is usually in the range of 3 to 20. be.

[0396] The aralkyl group is an aliphatic hydrocarbon group such as a benzyl group or a phenylethyl group. It indicates an aromatic hydrocarbon group mediated by a substituent, and both aliphatic and aromatic hydrocarbons are unsubstituted. The number of carbon atoms in the aliphatic moiety is not particularly limited, but it is usually 1. The range is ~20.

[0397] The alkenyl group is a double bonded group such as a vinyl group, an allyl group, or a butadienyl group. represents an unsaturated aliphatic hydrocarbon group containing a bond, which may be unsubstituted or substituted. The number of carbon atoms in the alkenyl group is not particularly limited, but is usually in the range of 2 to 20.

[0398] The cycloalkenyl group includes, for example, a cyclopentenyl group, a cyclopentadienyl group, and the like. It refers to an unsaturated alicyclic hydrocarbon group containing a double bond, such as a cyclohexene group or a cyclohexene group. It doesn't matter if it's a substitution or a replacement.

[0399] The alkynyl group is an unsaturated aliphatic group containing a triple bond, such as an acetylenyl group. represents a hydrocarbon group, which may be unsubstituted or substituted. The number is not particularly limited, but is usually in the range of 2 to 20.

[0400] The alkoxy group is an aliphatic carbonized group via an ether bond, such as a methoxy group. represents a hydrogen group, and the aliphatic hydrocarbon group may be unsubstituted or substituted. The number of carbon atoms in the group is not particularly limited, but is usually in the range of 1-20.

[0401] An alkylthio group is a group in which the oxygen atom of the ether bond of an alkoxy group is replaced with a sulfur atom. It is a group that has been

[0402] The aryl ether group is an aromatic group formed via an ether bond, such as a phenoxy group. The aromatic hydrocarbon group may be unsubstituted or substituted. The number of carbon atoms in the aryl ether group is not particularly limited, but is usually in the range of 6 to 40.

[0403] In addition, an aryl thioether group is a group in which the oxygen atom of the ether bond of the aryl ether group is It is a group substituted with a sulfur atom.

[0404] The aryl group includes, for example, a phenyl group, a naphthyl group, a biphenylyl group, a phenanthyl group, and the like. The aryl group is an aromatic hydrocarbon group such as a tolyl group, a terphenyl group, or a pyrenyl group. The number of carbon atoms in the aryl group is not particularly limited, but is usually It is usually in the range of 6 to 40.

[0405] The heterocyclic group includes, for example, a furanyl group, a thiophenyl group, an oxazolyl group, a pyridinyl group, and the like. a cyclic structural group having atoms other than carbon, such as a quinolinyl group, a carbazolyl group, The heterocyclic group may be unsubstituted or substituted. The number of carbon atoms in the heterocyclic group is not particularly limited. , usually in the range of 2 to 30.

[0406] Halogen refers to fluorine, chlorine, bromine, and iodine.

[0407] Aldehyde groups, carbonyl groups, and amino groups are used in aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. It may also include groups substituted with aromatic hydrocarbons, heterocycles, etc.

[0408] In addition, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocyclic rings may be unsubstituted or substituted. It doesn't matter if it's broken.

[0409] The silyl group refers to a silicon compound group such as a trimethylsilyl group, which is an unsubstituted silyl group. The number of carbon atoms in the silyl group is not particularly limited, but is usually 3. The silicon number is usually in the range of 1 to 20.

[0410] The fused ring formed between adjacent substituents is, for example, Ar 1 and R 2 , Ar 1 and R 3 , A r 2 and R 2 , Ar 2 and R 3 , R 2 and R 3 , Ar 1 and Ar 2 Conjugates formed between is a non-conjugated fused ring. Here, when n is 1, two R 1 Conjugate or non-conjugate with each other These fused rings may contain nitrogen, oxygen, or sulfur atoms in the ring structure. Alternatively, it may be condensed with another ring.

[0411] Specific examples of the phosphine oxide derivative include the following compounds: . [ka]

[0412] This phosphine oxide derivative can be produced using known raw materials and known synthesis methods. can be done.

[0413] <Pyrimidine derivatives> The pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), and is preferably is a compound represented by the following formula (ETM-8-1). This is also described in Publication No. 1689. [ka]

[0414] Ar each independently represents an optionally substituted aryl or an optionally substituted n is an integer of 1 to 4, preferably an integer of 1 to 3, More preferably, it is 2 or 3.

[0415] The "aryl" in the "optionally substituted aryl" includes, for example, an aryl having 6 to 30 carbon atoms. The aryl having 6 to 24 carbon atoms is preferable, and the aryl having 6 to 24 carbon atoms is more preferable. The aryl group preferably has from 1 to 20 carbon atoms, and more preferably has from 6 to 12 carbon atoms.

[0416] Specific examples of "aryl" include phenyl, which is a monocyclic aryl, and phenyl, which is a bicyclic aryl. (2-, 3-, 4-) biphenylyl, fused bicyclic aryl, (1-, 2-) naphthyl tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terf phenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), fused triphenyl Aryl ring systems, such as acenaphthylene-(1-, 3-, 4-, 5-)yl, fluorene- (1-,2-,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-,2 -, 3-, 4-, 9-)phenanthryl, tetracyclic aryl quaterphenylyl (5 '-Phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3- yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensed Tetracyclic aryls such as triphenylen-(1-,2-)yl and pyrene-(1-,2-,4 -)yl, naphthacene-(1-, 2-, 5-)yl, and perylene, a fused pentacyclic aryl. -(1-, 2-, 3-)yl, pentacene-(1-, 2-, 5-, 6-)yl, etc. can be done.

[0417] The "heteroaryl" in "optionally substituted heteroaryl" includes, for example, carbonyl groups. Heteroaryl having 2 to 30 carbon atoms is preferred, and heteroaryl having 2 to 25 carbon atoms is preferred. Heteroaryl having 2 to 20 carbon atoms is more preferred, and heteroaryl having 2 to 15 carbon atoms is preferred. Heteroaryl having 2 to 10 carbon atoms is more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Examples of the ring-constituting atom include a hetero atom selected from oxygen, sulfur, and nitrogen in addition to carbon. and heterocycles containing 1 to 5 aryl atoms.

[0418] Specific examples of heteroaryl include furyl, thienyl, pyrrolyl, and oxazolidinyl. isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxazolyl thiadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, Pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzo Furanyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl , naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, fenoxa dinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, in Examples include dolizinyl.

[0419] The aryl and heteroaryl may be substituted, and may each be, for example, any of the above. The aryl and heteroaryl may be substituted.

[0420] Specific examples of the pyrimidine derivative include the following compounds: [ka]

[0421] This pyrimidine derivative can be produced using known raw materials and known synthesis methods.

[0422] <Carbazole derivatives> The carbazole derivative is, for example, a compound represented by the following formula (ETM-9), or It is a polymer formed by multiple bonds such as single bonds. For details, see U.S. Patent Publication 2014 / 0197386 This is described in publication no. [ka]

[0423] Ar each independently represents an optionally substituted aryl or an optionally substituted n is independently an integer of 0 to 4, preferably an integer of 0 to 3. and more preferably 0 or 1.

[0424] The "aryl" in the "optionally substituted aryl" includes, for example, an aryl having 6 to 30 carbon atoms. The aryl having 6 to 24 carbon atoms is preferable, and the aryl having 6 to 24 carbon atoms is more preferable. The aryl group preferably has from 1 to 20 carbon atoms, and more preferably has from 6 to 12 carbon atoms.

[0425] Specific examples of "aryl" include phenyl, which is a monocyclic aryl, and phenyl, which is a bicyclic aryl. (2-, 3-, 4-) biphenylyl, fused bicyclic aryl, (1-, 2-) naphthyl tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terf phenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), fused triphenyl Aryl ring systems, such as acenaphthylene-(1-, 3-, 4-, 5-)yl, fluorene- (1-,2-,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-,2 -, 3-, 4-, 9-)phenanthryl, tetracyclic aryl quaterphenylyl (5 '-Phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3- yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensed Tetracyclic aryls such as triphenylen-(1-,2-)yl and pyrene-(1-,2-,4 -)yl, naphthacene-(1-, 2-, 5-)yl, and perylene, a fused pentacyclic aryl. -(1-, 2-, 3-)yl, pentacene-(1-, 2-, 5-, 6-)yl, etc. can be done.

[0426] The "heteroaryl" in "optionally substituted heteroaryl" includes, for example, carbonyl groups. Heteroaryl having 2 to 30 carbon atoms is preferred, and heteroaryl having 2 to 25 carbon atoms is preferred. Heteroaryl having 2 to 20 carbon atoms is more preferred, and heteroaryl having 2 to 15 carbon atoms is preferred. Heteroaryl having 2 to 10 carbon atoms is more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Examples of the ring-constituting atom include a hetero atom selected from oxygen, sulfur, and nitrogen in addition to carbon. and heterocycles containing 1 to 5 aryl atoms.

[0427] Specific examples of heteroaryl include furyl, thienyl, pyrrolyl, and oxazolidinyl. isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxazolyl thiadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, Pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzo Furanyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl , naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, fenoxa dinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, in Examples include dolizinyl.

[0428] The aryl and heteroaryl may be substituted, and may each be, for example, any of the above. The aryl and heteroaryl may be substituted.

[0429] The carbazole derivative is a compound represented by the above formula (ETM-9) that is bonded by multiple bonds such as single bonds. In this case, in addition to the single bond, an aryl ring (preferably a polyvalent Benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phen The rings may be bonded together via a naphthylene ring, a naphthylene ring, a phenanthrene ring, or a triphenylene ring).

[0430] Specific examples of the carbazole derivative include the following compounds. [ka]

[0431] This carbazole derivative can be produced using known raw materials and known synthesis methods. .

[0432] <Triazine derivatives> The triazine derivative is, for example, a compound represented by the following formula (ETM-10), and is preferably The compound is represented by the following formula (ETM-10-1). This is described in Publication No. / 0156013. [ka]

[0433] Ar each independently represents an optionally substituted aryl or an optionally substituted n is an integer of 1 to 4, preferably an integer of 1 to 3, More preferably, it is 2 or 3.

[0434] The "aryl" in the "optionally substituted aryl" includes, for example, an aryl having 6 to 30 carbon atoms. The aryl having 6 to 24 carbon atoms is preferable, and the aryl having 6 to 24 carbon atoms is more preferable. The aryl group preferably has from 1 to 20 carbon atoms, and more preferably has from 6 to 12 carbon atoms.

[0435] Specific examples of "aryl" include phenyl, which is a monocyclic aryl, and phenyl, which is a bicyclic aryl. (2-, 3-, 4-) biphenylyl, fused bicyclic aryl, (1-, 2-) naphthyl tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terf phenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), fused triphenyl Aryl ring systems, such as acenaphthylene-(1-, 3-, 4-, 5-)yl, fluorene- (1-,2-,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-,2 -, 3-, 4-, 9-)phenanthryl, tetracyclic aryl quaterphenylyl (5 '-Phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3- yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensed Tetracyclic aryls such as triphenylen-(1-,2-)yl and pyrene-(1-,2-,4 -)yl, naphthacene-(1-, 2-, 5-)yl, and perylene, a fused pentacyclic aryl. -(1-, 2-, 3-)yl, pentacene-(1-, 2-, 5-, 6-)yl, etc. can be done.

[0436] The "heteroaryl" in "optionally substituted heteroaryl" includes, for example, carbonyl groups. Heteroaryl having 2 to 30 carbon atoms is preferred, and heteroaryl having 2 to 25 carbon atoms is preferred. Heteroaryl having 2 to 20 carbon atoms is more preferred, and heteroaryl having 2 to 15 carbon atoms is preferred. Heteroaryl having 2 to 10 carbon atoms is more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Examples of the ring-constituting atom include a hetero atom selected from oxygen, sulfur, and nitrogen in addition to carbon. and heterocycles containing 1 to 5 aryl atoms.

[0437] Specific examples of heteroaryl include furyl, thienyl, pyrrolyl, and oxazolidinyl. isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxazolyl thiadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, Pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzo Furanyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl , naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, fenoxa dinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, in Examples include dolizinyl.

[0438] The aryl and heteroaryl may be substituted, and may each be, for example, any of the above. The aryl and heteroaryl may be substituted.

[0439] Specific examples of the triazine derivative include the following compounds: [ka]

[0440] This triazine derivative can be produced using known raw materials and known synthesis methods.

[0441] <Benzimidazole derivatives> The benzimidazole derivative is, for example, a compound represented by the following formula (ETM-11): . [ka]

[0442] φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or trifluorene ring a phenylene ring), n is an integer of 1 to 4, and the "benzimidazole-based substituent" is The "pyriferous" in formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) It is a substituent in which the pyridyl group in the "pyridyl-based substituent" is replaced with a benzimidazole group, At least one hydrogen atom in the benzimidazole derivative may be replaced by deuterium. stomach. [ka]

[0443] R in the benzimidazole group 11 is hydrogen, alkyl with 1 to 24 carbon atoms, carbon cycloalkyl having 3 to 12 carbon atoms or aryl having 6 to 30 carbon atoms, 2-1) and R in Equation (ETM-2-2) 11 The explanation can be cited.

[0444] φ is preferably an anthracene ring or a fluorene ring, and in this case, The structure can be explained by referring to the explanation of the above formula (ETM-2-1) or formula (ETM-2-2). R in each formula 11 ~R 18 is the above formula (ETM-2-1) or formula (ETM-2-2) The explanation in the above formula (ETM-2-1) or formula (ETM- 2-2) is explained as a form in which two pyridine-based substituents are bonded, but these are When replacing both pyridine-based substituents with benzimidazole-based substituents, It may be replaced by an azole-based substituent (i.e., n=2), or any one of the pyridine-based substituents. The substituent is replaced with a benzimidazole-based substituent and the other pyridine-based substituent is replaced with R 11 ~R 1 8 (i.e., n=1). Furthermore, for example, in the above formula (ETM-2-1), R in 11 ~R 18 At least one of the groups is replaced with a benzimidazole-based substituent to form a "pi Lysine-based substituents" R11 ~R 18 may be replaced with .

[0445] Specific examples of the benzimidazole derivative include 1-phenyl-2-(4-( 10-Phenylanthracen-9-yl)phenyl)-1H-benzo[d]imidazole , 2-(4-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)- 1-phenyl-1H-benzo[d]imidazole, 2-(3-(10-(naphthalene-2 -yl)anthracen-9-yl)phenyl)-1-phenyl-1H-benzo[d]imide dazole, 5-(10-(naphthalen-2-yl)anthracen-9-yl)-1,2- Diphenyl-1H-benzo[d]imidazole, 1-(4-(10-(naphthalene-2- (yl)anthracen-9-yl)phenyl)-2-phenyl-1H-benzo[d]imida 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)azole phenyl)-1-phenyl-1H-benzo[d]imidazole, 1-(4-(9,10- Di(naphthalen-2-yl)anthracen-2-yl)phenyl)-2-phenyl-1H -benzo[d]imidazole, 5-(9,10-di(naphthalen-2-yl)anthracene) (2-phenyl-1H-benzo[d]imidazole) do. [ka]

[0446] This benzimidazole derivative can be produced using known raw materials and known synthesis methods. can.

[0447] <Phenanthroline derivatives> The phenanthroline derivative is, for example, a compound represented by the following formula (ETM-12) or the formula (ETM-12- 1). Details are described in International Publication No. 2006 / 021982. are. [ka]

[0448] φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or trifluorene ring phenylene ring), and n is an integer of 1 to 4.

[0449] R in each formula 11 ~R 18 are each independently hydrogen, alkyl (preferably having 1 to 10 carbon atoms), 24 alkyl), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or is an aryl (preferably an aryl having 6 to 30 carbon atoms). 2-1) R 11 ~R 18 Either of these bonds to φ, an aryl ring.

[0450] At least one hydrogen atom in each phenanthroline derivative is replaced with a deuterium atom. good.

[0451] R 11 ~R 18 The alkyl, cycloalkyl and aryl in the formula ( R in ETM-2 11 ~R 18 The explanation of the above can be cited. In addition to the above examples, the following structural formulas are also included: Independently, hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, It is preferably phenylyl, 2-naphthyl, biphenylyl or terphenylyl. [ka]

[0452] Specific examples of the phenanthroline derivative include 4,7-diphenyl-1,10 -phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Phosphorus, 9,10-di(1,10-phenanthrolin-2-yl)anthracene, 2,6- Di(1,10-phenanthrolin-5-yl)pyridine, 1,3,5-tri(1,10- phenanthrolin-5-yl)benzene, 9,9'-difluoro-bis(1,10-phenanthrolin-5-yl)benzene anthroline-5-yl), bathocuproine, and 1,3-bis(2-phenyl-1,10- phenanthroline-9-yl)benzene and the like. [ka]

[0453] This phenanthroline derivative can be produced using known raw materials and known synthesis methods. Cut.

[0454] <Quinolinol-based metal complexes> The quinolinol metal complex is, for example, a compound represented by the following general formula (ETM-13): do. [ka] In the formula, R 1 ~R 6 is hydrogen or a substituent, and M is Li, Al, Ga, Be, or Zn and n is an integer of 1 to 3.

[0455] Specific examples of quinolinol-based metal complexes include 8-quinolinol lithium and tris(8- Tris(4-methyl-8-quinolinolato)aluminum, Tris(4-methyl-8-quinolinolato)aluminum aluminum, tris(5-methyl-8-quinolinolato)aluminum, tris(3,4-dimethyl Tris(4,5-dimethyl-8-quinolinolate)aluminum, tris(4,5-dimethyl-8-quinolinolate)aluminum tris(4,6-dimethyl-8-quinolinolato)aluminum, tris(4,6-dimethyl-8-quinolinolato)aluminum, Bis(2-methyl-8-quinolinolato)(phenolato)aluminum, bis(2-methyl Bis(2-methyl-8-quinolinolato)(2-methylphenolato)aluminum -8-quinolinolato)(3-methylphenolato)aluminum, bis(2-methyl- 8-quinolinolato)(4-methylphenolato)aluminum, bis(2-methyl-8 -quinolinolato)(2-phenylphenolato)aluminum, bis(2-methyl-8 -quinolinolato)(3-phenylphenolato)aluminum, bis(2-methyl-8 -quinolinolato)(4-phenylphenolato)aluminum, bis(2-methyl-8 -quinolinolato)(2,3-dimethylphenolato)aluminum, bis(2-methyl -8-quinolinolato)(2,6-dimethylphenolato)aluminum, bis(2-methyl- bis(2-methyl-8-quinolinolato)(3,4-dimethylphenolato)aluminum -methyl-8-quinolinolato)(3,5-dimethylphenolato)aluminum, bis (2-methyl-8-quinolinolate)(3,5-di-t-butylphenolate)aluminium ammonium, bis(2-methyl-8-quinolinolato)(2,6-diphenylphenolato)a Aluminum, bis(2-methyl-8-quinolinolato)(2,4,6-triphenylphenyl) Aluminum bis(2-methyl-8-quinolinolate)(2,4,6-trimethyl-8-quinolinolate) Methylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(2,4 ,5,6-tetramethylphenolate)aluminum, bis(2-methyl-8-quinolinol) bis(2-methyl-8-quinolinolate)(1-naphtholate)aluminum, bis(2-methyl-8-quinolinolate) (2-naphtholato)aluminum, bis(2,4-dimethyl-8-quinolinolato)( 2-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinol) bis(2,4-dimethyl-8-quinolinyl)aluminum(triphenylphenolate) bis(2,4-dimethyl-8-)(4-phenylphenolate)aluminum Quinolinolato)(3,5-dimethylphenolato)aluminum, bis(2,4-dimethylphenolato)aluminum (3,5-di-t-butylphenolate)aluminum, bis(methyl-8-quinolinolato) Bis(2-methyl-8-quinolinolato)aluminum-μ-oxo-bis(2-methyl- 8-quinolinolato)aluminum, bis(2,4-dimethyl-8-quinolinolato)aluminum Aluminum-μ-oxo-bis(2,4-dimethyl-8-quinolinolato)aluminum , bis(2-methyl-4-ethyl-8-quinolinolato)aluminum-μ-oxo-bi Bis(2-methyl-4-ethyl-8-quinolinolato)aluminum, Bis(2-methyl- 4-Methoxy-8-quinolinolato)aluminum-μ-oxo-bis(2-methyl-4 -Methoxy-8-quinolinolato)aluminum, bis(2-methyl-5-cyano-8- Quinolinolato)aluminum-μ-oxo-bis(2-methyl-5-cyano-8-quino Aluminum linoleate, bis(2-methyl-5-trifluoromethyl-8-quinolinol) bis(2-methyl-5-trifluoromethyl-8-methyl-2-oxo-2-methyl-5-trifluoromethyl-4-methyl-2-methyl-2-oxo ... Quinolinolate)aluminum, Bis(10-hydroxybenzo[h]quinoline)beryl Examples include Um.

[0456] This quinolinol-based metal complex can be produced using known raw materials and known synthesis methods. Cut.

[0457] <Thiazole Derivatives and Benzothiazole Derivatives> The thiazole derivative is, for example, a compound represented by the following formula (ETM-14-1). [ka] The benzothiazole derivative is, for example, a compound represented by the following formula (ETM-14-2): do. [ka]

[0458] In each formula, φ represents an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, a helical ring, a fluorene ring, a benzofluorene ring, a phenalene ring, a phenanthrene ring, or triphenylene ring), and n is an integer of 1 to 4. The "zothiazole-based substituent" is a group represented by the above formula (ETM-2), formula (ETM-2-1) and formula (E In TM-2-2), the pyridyl group in the "pyridine-based substituent" is a thiazole group or a benzo It is a substituent substituted for the thiazole group, and is used in thiazole derivatives and benzothiazole derivatives. At least one hydrogen in the conductor may be substituted with deuterium. [ka]

[0459] φ is preferably an anthracene ring or a fluorene ring, and in this case, The structure can be explained by referring to the explanation of the above formula (ETM-2-1) or formula (ETM-2-2). R in each formula 11 ~R 18 is the above formula (ETM-2-1) or formula (ETM-2-2) The explanation in the above formula (ETM-2-1) or formula (ETM- 2-2) is explained as a form in which two pyridine-based substituents are bonded, but these are When replacing with an azole-based substituent (or a benzothiazole-based substituent), both pyridines Even if the thiazole-based substituent is replaced with a thiazole-based substituent (or a benzothiazole-based substituent), (i.e., n=2), any one of the pyridine-based substituents may be replaced with a thiazole-based substituent (or or benzothiazole-based substituent) and the other pyridine-based substituent is replaced by R 11 ~R 18 (i.e., n=1). Furthermore, for example, in the above formula (ETM-2-1), KerR 11 ~R 18 At least one of the following is a thiazole-based substituent (or a benzothiazole-based substituent) Substituent) and replace "pyridine-based substituent" with R 11 ~R 18 may be replaced with .

[0460] These thiazole derivatives or benzothiazole derivatives are synthesized using known raw materials and known synthesis methods. It can be produced using the method.

[0461] The electron transport layer or the electron injection layer may further include a material for forming the electron transport layer or the electron injection layer. The reducing agent may contain a substance capable of reducing the feedstock. If so, various substances can be used, such as alkali metals, alkaline earth metals, and rare earth metals. alkali metal oxides, alkali metal halides, alkaline earth metal oxides, Alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, Organic complexes of alkaline metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals. At least one selected from the following group can be suitably used.

[0462] Preferred reducing substances include Na (work function 2.36 eV) and K (work function 2.28 eV). , alkali metals such as Rb (2.16 eV) or Cs (1.95 eV), and Ca ( 2.9 eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV) Alkali earth metals are preferred, and substances with a work function of 2.9 eV or less are particularly preferred. Among them, the more preferred reducing substance is an alkali metal such as K, Rb or Cs, and even more preferred Preferably, Rb or Cs, and most preferably Cs. These alkali metals are In particular, it has a high reducing ability and is useful when added in a relatively small amount to a material forming an electron transport layer or an electron injection layer. By adding the above, the luminance of the organic EL element can be improved and the life span can be extended. As a reducing substance having a valence of 2.9 eV or less, a combination of two or more of these alkali metals is also preferred. Preferably, combinations containing Cs, such as Cs and Na, Cs and K, Cs and Rb, Alternatively, a combination of Cs, Na and K is preferred. By including Cs, the reduction ability is effectively improved. By adding it to the material that forms the electron transport layer or the electron injection layer, This will improve the luminance and extend the life of organic EL elements.

[0463] <Cathode in organic electroluminescent device> The cathode 108 supplies electricity to the light-emitting layer 105 via the electron injection layer 107 and the electron transport layer 106 . It plays a role in injecting the offspring.

[0464] The material for forming the cathode 108 can be any material that can efficiently inject electrons into the organic layer. Although not particularly limited, the same material as that forming the anode 102 can be used. However, tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold , platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium, etc. metals or their alloys (magnesium-silver alloy, magnesium-indium alloy, Aluminum-lithium alloys such as lithium fluoride / aluminum are preferred. In order to increase the electron injection efficiency and improve the device characteristics, lithium, sodium, and potassium Cesium, calcium, magnesium, or alloys containing these low work function metals are effective. However, these low work function metals are generally unstable in the atmosphere. To improve this, for example, trace amounts of lithium, cesium, or magnesium are added to the organic layer. A method is known in which highly stable electrodes are obtained by doping with other dopants. Examples include lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide. However, it is not limited to these.

[0465] In addition, platinum, gold, silver, copper, iron, tin, aluminum and indium are used to protect the electrodes. Metals such as titanium, or alloys using these metals, as well as silica, titania and silicon nitride Inorganic materials such as silicon dioxide, polyvinyl alcohol, vinyl chloride, hydrocarbon polymer compounds, etc. The method for producing these electrodes is also known by resistance heating, electron Beam evaporation, sputtering, ion plating and coating, etc. There are no particular limitations as long as it can be done.

[0466] <Binders that may be used in each layer> The materials used in the hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer are Each layer can be formed using a single material, but polyvinyl chloride, polycarbonate, etc. can be used as a polymer binder. Carbonate, polystyrene, poly(N-vinylcarbazole), polymethyl methacrylate Polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide Polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl Solvent-soluble resins such as cellulose, vinyl acetate resin, ABS resin, and polyurethane resin, Phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester Dispersed in curable resins such as terephthalate resin, alkyd resin, epoxy resin, and silicone resin. It is also possible to use them together.

[0467] <Method for producing organic electroluminescent device> Each layer constituting the organic electroluminescent device is formed by depositing the material for each layer using a deposition method, resistance heating deposition, Electron beam evaporation, sputtering, molecular layer deposition, printing, spin coating or casting It can be formed by forming a thin film using a method such as a coating method. There are no particular limitations on the thickness of each layer formed in this way, and it can be set appropriately depending on the properties of the material. The film thickness is usually in the range of 2 nm to 5000 nm. The thickness can be measured using a film thickness measuring device. When using a vapor deposition method to make a thin film, the vapor deposition conditions depend on the material. The deposition conditions vary depending on the type of material, the desired crystal structure and association structure of the film, etc. , heating temperature of evaporation crucible +50~+400℃, vacuum degree 10 -6 ~10 -3 Pa, deposition rate Degree 0.01 to 50 nm / sec, substrate temperature -150 to +300°C, film thickness range 2 nm to 5 μm It is preferable to set it appropriately.

[0468] Next, as an example of a method for producing an organic electroluminescent device, a method for forming an anode / hole injection layer / hole transport layer / Emitting layer consisting of host material and dopant material / Electron transport layer / Electron injection layer / Cathode A method for producing an organic electroluminescent device will be described.

[0469] <Vapor deposition method> A thin film of anode material is formed on a suitable substrate by vapor deposition or the like to create an anode. A thin film of a hole injection layer and a hole transport layer is formed on the anode. The light-emitting layer is formed by co-evaporating a phototransport material and a thin film. An injection layer is formed, and then a thin film made of a cathode material is formed by vapor deposition or the like to form a cathode. By doing so, the desired organic electroluminescent device can be obtained. In the fabrication, the fabrication order is reversed, with the cathode, electron injection layer, electron transport layer, light-emitting layer, and hole transport layer. It is also possible to fabricate the transport layer, the hole injection layer and the anode in this order.

[0470] <Wet film formation method> In the case of the composition for forming a light-emitting layer, a film is formed by using a wet film-forming method.

[0471] The wet film formation method generally includes a coating step of coating a substrate with a composition for forming a light-emitting layer and a coating step of A coating film is formed by a drying step in which the solvent is removed from the composition for forming a light-emitting layer. Depending on the fabric process, the method using a spin coater is called the spin coat method, and the slit coater slit coating method using a plate, gravure using a plate, offset, reverse offset, Lexo printing, a method using an inkjet printer, is an inkjet method, spraying in a mist The method of drying is called the spray method. There are several drying methods, such as air drying, heating, and vacuum drying. The drying step may be carried out only once, or may be carried out multiple times using different methods and conditions. Also, different methods may be used in combination, such as calcination under reduced pressure.

[0472] The wet film formation method is a film formation method using a solution, for example, some printing methods (inkjet method ), spin coating or casting, coating, etc. Wet film formation methods include vacuum evaporation. Unlike conventional deposition methods, there is no need to use expensive vacuum deposition equipment, and films can be formed under atmospheric pressure. In addition, the wet film formation method allows for large-area and continuous production, which leads to reduced manufacturing costs. .

[0473] On the other hand, compared to the vacuum deposition method, the wet film formation method is difficult to laminate. When a laminated film is produced using a solubility-reducing agent, it is necessary to prevent the dissolution of the lower layer by the composition of the upper layer. Controlled composition, underlying crosslinking and orthogonal solvent (mutually soluble However, even with these techniques, the coating of all films is difficult. It can be difficult to use wet deposition methods for this purpose.

[0474] Therefore, in general, only some layers are formed by wet deposition, and the rest are formed by vacuum deposition. A method of fabricating an L element is adopted.

[0475] For example, the procedure for producing an organic EL element by partially applying a wet film formation method is shown below. (Step 1) Formation of the anode by vacuum deposition (Step 2) Formation of the hole injection layer using the wet film formation method (Step 3) Formation of the hole transport layer using the wet film formation method (Step 4) Formation of a composition for forming an emitting layer containing a host material and a dopant material by a wet film formation method film (Step 5) Formation of the electron transport layer by vacuum deposition (Step 6) Formation of the electron injection layer by vacuum deposition (Step 7) Cathode deposition by vacuum evaporation By going through this procedure, the anode / hole injection layer / hole transport layer / host material and dopant material An organic EL element comprising a light-emitting layer / electron transport layer / electron injection layer / cathode is obtained.

[0476] <Other film formation methods> The composition for forming the light-emitting layer can be formed into a film by laser thermal imaging (LITI). LITI is a method of heating and vapor-depositing a compound attached to a substrate with a laser. The material to be applied can be a composition for forming a light-emitting layer.

[0477] <Optional process> Before and after each film-forming step, appropriate treatment steps, cleaning steps, and drying steps may be inserted as appropriate. Examples of the treatment process include exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, Examples of such treatments include washing with an appropriate solvent and heating. A series of steps can also be mentioned.

[0478] The bank can be fabricated using photolithography. Positive resist materials and negative resist materials can be used as bank materials. In addition, inkjet printing, gravure offset printing, reverse offset printing, Printing methods that allow for patterns, such as printing and screen printing, can also be used. A permanent resist material may also be used.

[0479] Materials used for the bank include polysaccharides and their derivatives, hydroxyl-containing enzymes, and Homopolymers and copolymers of ethylenic monomers, biopolymers, polyacryloylation Compounds, polyester, polystyrene, polyimide, polyamideimide, polyetherimide Polysulfide, polysulfone, polyphenylene, polyphenyl ether, polyurethane Tan, epoxy (meth)acrylate, melamine (meth)acrylate, polyolefin , cyclic polyolefin, acrylonitrile-butadiene-styrene copolymer (AB S), silicone resin, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, Polyacetate, polynorbornene, synthetic rubber, polyfluorovinylidene, polytetrafluoroethylene Fluorinated polymers such as fluoroethylene and polyhexafluoropropylene, fluoroolefins Examples of the copolymer include olefin-hydrocarbon olefin copolymers and fluorocarbon polymers. However, it is not limited to this.

[0480] Referring to Figure 9, an organic EL element was fabricated on a substrate with a bank using the inkjet method. First, the bank (200) is formed by the electrode (120) on the substrate (110). In this case, ink is discharged from the inkjet head (300) to the bank (200 ) and drying to form a coating film (130). This process is repeated to form the next coating film (140) and then the light-emitting layer (150). By forming an electron transport layer, an electron injection layer, and an electrode using a vacuum deposition method, the light-emitting portion can be formed using a bank material. It is possible to fabricate organic EL devices with separated regions.

[0481] When a DC voltage is applied to the organic electroluminescent device obtained in this way, the anode is connected to +, The cathode should be negative, and when a voltage of 2 to 40 V is applied, the transparent or semi-transparent Light emission can be observed from the transparent electrode side (anode or cathode, or both). The field light emitting element also emits light when a pulse current or an alternating current is applied. The waveform of may be any.

[0482] <Application examples of organic electroluminescent devices> The present invention also provides a display device including an organic electroluminescent device or a display device including an organic electroluminescent device. It can also be applied to lighting devices, etc. A display device or a lighting device equipped with an organic electroluminescent device may be the organic electroluminescent device according to this embodiment. It can be manufactured by a known method, such as connecting an optical element to a known driving device, and The liquid crystal display device can be driven by appropriately using a known driving method such as pulse driving or AC driving.

[0483] The display device may be, for example, a panel display such as a color flat panel display. flexible displays such as flexible color organic electroluminescent (EL) displays (For example, Japanese Patent Application Laid-Open No. 10-335066, Japanese Patent Application Laid-Open No. 2003-321546, (See, for example, Japanese Patent Application Laid-Open Publication No. 2004-281086.) In addition, the display method may be, for example, The matrix and segment display methods are also available. The display may coexist in the same panel.

[0484] In a matrix, the pixels for display are arranged two-dimensionally, such as in a grid or mosaic pattern. A set of pixels is used to display characters and images. The shape and size of the pixels are determined by the application. For example, images and text displayed on computers, monitors, and televisions usually have a side length of 300 μm or more. The square pixels below are used, and in the case of large displays such as display panels, In the case of monochrome display, pixels of the same color are arranged. In the case of a color display, red, green, and blue pixels are displayed side by side. In this case, there are typically delta type and stripe type. The method may be either a line sequential driving method or an active matrix method. has the advantage of being simpler in structure, but when considering the operating characteristics, the active matrix There are cases where Ricks is superior, so it is necessary to use it depending on the purpose. .

[0485] In the segment type, patterns are formed to display predetermined information. For example, the time on a digital clock or thermometer is Time and temperature displays, operating status displays for audio equipment and induction cookers, and automobile panel displays Examples include:

[0486] Examples of lighting devices include lighting devices for indoor lighting, backlights for liquid crystal display devices, etc. (For example, Japanese Patent Application Laid-Open No. 2003-257621, Japanese Patent Application Laid-Open No. 2003-277741, Japanese Patent Application Laid-Open No. 2004-1 (See, for example, Patent Publication No. 19211.) Backlights are primarily used to improve the visibility of non-self-luminous display devices. It is used for the purpose of displaying images, and is used in LCD displays, clocks, audio equipment, automobile panels, display boards, and They are used in LCD displays, especially in personal computers, where thinning is an issue. Backlights for LCD screens have traditionally been made using fluorescent lamps and light guide plates, making them thinner. Considering the difficulty of this, the backlight using the light-emitting element according to this embodiment is thin and lightweight. Quantity is a feature.

[0487] 3-2. Other organic devices The polycyclic aromatic compound according to the present invention can be used in organic electroluminescent devices as well as in organic field effect transistors. It can be used to manufacture transistors or organic thin-film solar cells.

[0488] Organic field-effect transistors control current flow by generating an electric field through voltage input. A transistor that has a gate electrode in addition to a source electrode and a drain electrode. When a voltage is applied to the gate electrode, an electric field is generated, and a current flows between the source electrode and the drain electrode. A transistor that can control the current by arbitrarily blocking the flow of electrons (or holes). A field effect transistor is a simple transistor (bipolar transistor). It is easier to miniaturize than silicon dioxide, and is often used as an element that makes up integrated circuits.

[0489] The structure of an organic field effect transistor is usually formed using the polycyclic aromatic compound according to the present invention. A source electrode and a drain electrode are provided in contact with the organic semiconductor active layer formed thereon. Furthermore, a gate electrode is provided sandwiching an insulating layer (dielectric layer) in contact with the organic semiconductor active layer. The element structure may be, for example, as follows: (1) Substrate / gate electrode / insulating layer / source and drain electrodes / organic semiconductor active layer (2) Substrate / gate electrode / insulating layer / organic semiconductor active layer / source electrode / drain electrode (3) Substrate / organic semiconductor active layer / source electrode / drain electrode / insulator layer / gate electrode (4) Substrate / source electrode / drain electrode / organic semiconductor active layer / insulator layer / gate electrode The organic field-effect transistor configured in this way is an active matrix driving system. Pixel driving switching for liquid crystal displays and organic electroluminescence displays It can be used as a sensing element.

[0490] Organic thin-film solar cells are made up of an anode such as ITO, a hole transport layer, and a photovoltaic cell on a transparent substrate such as glass. It has a laminated structure of a photoelectric conversion layer, an electron transport layer, and a cathode. The photoelectric conversion layer has a p-type semiconductor on the anode side. The polycyclic aromatic compound according to the present invention has an n-type semiconductor layer on the cathode side. Depending on the physical properties of the material, it can be used as a material for the hole transport layer, p-type semiconductor layer, n-type semiconductor layer, and electron transport layer. The polycyclic aromatic compound according to the present invention can be used in an organic thin-film solar cell. They can function as hole transport materials or electron transport materials. The layer may be provided with a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, etc. For the organic thin-film solar cell, known materials used for organic thin-film solar cells may be appropriately selected. can be selected and used in combination. [Example]

[0491] The present invention will be described in detail below with reference to examples. The following compounds were synthesized in the examples, but are not limited thereto.

[0492] Synthesis example (1) Compound (1-1):N 7 ,N 7 ,N 13 ,N 13 ,5,9,11,15-octapheny 5,9,11,15-tetrahydro-5,9,11,15-tetraaza-19b,2 0b-diborazinenaphtho[3,2,1-de:1',2',3'-jk]pentacene-7, Synthesis of 13-diamines [ka]

[0493] [1st stage] Under a nitrogen atmosphere, 1,3-dibromobenzene (25.0 g, 106 mmol), aniline (20.3 ml, 223 mmol), tris(dibenzylideneacetone)dipalladium ( 0)(Pd2(dba)3)(971 mg, 1.06 mmol), 2,2'-bis(difluoromethyl) (phenylphosphino)-1,1'-binaphthyl (BINAP: 1.98 g, 3.18 mmol) 1), NaOtBu (25.5 g, 265 mmol) and toluene (400 ml) The flask was heated to 110°C and stirred for 18 hours. The reaction mixture was cooled to room temperature and added to silica gel. The mixture was filtered through gel (eluent: toluene), and the solvent was removed by distillation under reduced pressure to obtain a crude product. The crude product was dissolved in toluene, and then an appropriate amount was evaporated under reduced pressure, and hexane was added to reprecipitate. By doing so, N 1 ,N 3 -Diphenylbenzene-1,3-diamine (16.5 g, yield 60 %) as a white solid. [ka]

[0494] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=5.63(s,2H), 6.60(d d,2H), 6.74(t,1H), 6.90(t,2H), 7.06(d,4H), 7 .12(t,1H), 7.24(dt,4H).

[0495] [Second stage] Under a nitrogen atmosphere, 1,3-dibromo-5-chlorobenzene (8.11 g, 30 mmol) , diphenylamine (10.1 g, 60 mmol), Pd2(dba)3 (550 mg, 0.6mmol), 2-dicyclohexylphenylphosphino-2',6'-dimethoxy Diphenyl (SPhos: 0.493 g, 1.2 mmol), NaOtBu (8.60 g A flask containing 1,2-dimethyl-3-propanol (90 mmol) and toluene (300 ml) was heated to 80°C. The reaction mixture was stirred for 5 hours, cooled to room temperature, and filtered through silica gel (eluent: toluene). The solvent was distilled off under reduced pressure to obtain a crude product. The crude product was dissolved in toluene and The saturated solution was prepared by distilling off the chloroform under reduced pressure, and hexane was added to reprecipitate the chloroform. Lo-N 1 ,N 1 ,N 3 ,N 3 -Tetraphenylbenzene-1,3-diamine (5.66g (43% yield) was obtained as a white solid. [ka]

[0496] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=6.56(d,2H), 6.64(t ,1H), 7.00(t,4H), 7.05(d,8H), 7.21(dd,8H).

[0497] [3rd stage] Under a nitrogen atmosphere, N synthesized in the first stage 1 ,N 3 -Diphenylbenzene-1,3-diamine (1.34 g, 5.1 mmol), 5-chloro-N synthesized in the second step 1 ,N 1 ,N 3 ,N 3 -Tetraphenylbenzene-1,3-diamine (4.80 g, 11 mmol), Pd2 (dba)3 (0.140 g, 0.15 mmol), tri-tert-butylphosphine (60.7 mg, 0.30 mmol), NaOtBu (1.47 g, 15 mmol) and The flask containing the reaction mixture and toluene (200 ml) was heated to 110°C and stirred for 8 hours. The solution was cooled to room temperature, filtered through silica gel (eluent: toluene), and the solvent was evaporated under reduced pressure. The crude product was washed with hexane and then with methanol to give a crude product. N 1 ,N 1 '-(1,3-phenylene)bis(N 1 ,N 3 ,N 3 ,N 5 ,N 5 -Pentuff Phenylbenzene-1,3,5-triamine (4.80 g, 87% yield) as a white solid Got it. [ka]

[0498] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=6.38(d,4H), 6.41(t ,2H), 6.58(dd,2H), 6.70(t,1H), 6.88-6.90(m, 14H), 6.85(t,1H), 6.99(d,16H), 7.08-7.15(m, 20H).

[0499] [4th stage] N 1 ,N 1 '-(1,3-phenylene)bis(N 1 ,N 3 ,N 3 ,N 5 ,N 5 -Penta Phenylbenzene-1,3,5-triamine (3.24 g, 3.0 mmol) and ol In a flask containing 400 ml of dichlorobenzene, the tribromide was heated at room temperature under a nitrogen atmosphere. After the dropwise addition, the temperature was raised to 180°C and the mixture was stirred for 2 The mixture was stirred for 10 hours. After that, it was cooled to room temperature again and N-diisopropylethylamine (7 The mixture was stirred until the heat generation subsided. The reaction solution was evaporated to give a crude product. The mixture was washed with toluene and then silica gel column chromatography (eluent: toluene). After purifying with 1×10 -4 mmHg Purification by sublimation was carried out at 440° C. under reduced pressure, thereby obtaining 1.17 g of compound (1-1). [ka]

[0500] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=5.72(s,2H), 5.74(s ,2H), 5.86(s,1H), 6.83(d,2H), 6.88-6.93(m,1 2H), 7.05(t,8H), 7.12-7.19(m,6H), 7.24-7.26 (m,4H), 7.05(d,4H), 7.12(dd,8H), 7.12-7.19( m,6H), 7.32(d,4H), 7.38(dd,2H), 7.42(t,2H), 7.46(dd,2H), 7.47(dd,4H), 9.30(d,2H), 10.5( s,1H).

[0501] 13 C-NMR (101MHz, CDCl3):99.5(2C+2C), 103.4(1 C), 116.8(2C), 120.0(2C), 123.1(4C), 125.3(8C) ), 127.1(2C), 127.6(2C), 128.5(8C), 129.6(4C), 129.8(4C), 130.2(4C+2C), 130.3(4C), 135.0(2C) , 142.1(2C), 142.5(2C), 143.3(1C), 146.8(4C) , 147.9(2C+2C), 148.0(2C), 150.1(2C), 151.1(2 C).

[0502] Synthesis example (2) Compound (1-201):N 7 ,N 7 ,N 13 ,N 13 ,5,15-Hexaphenyl-5 ,15-Dihydro-5,15-diaza-9,11-diox-19b,20b-diborazine of pentacene-7,13-diamine synthesis [ka]

[0503] [1st stage] Under a nitrogen atmosphere, 1,3-dibromo-5-fluorobenzene (15.5 g, 61 mmol) ), resorcinol (3.10 g, 29 mmol), potassium carbonate (10.0 g, 73 m A flask containing 1000 mol) and N-methyl-2-pyrrolidone (NMP: 300 ml) was placed in the flask. The reaction mixture was heated to 140°C and stirred for 13 hours. The reaction mixture was cooled to room temperature, and NMP was distilled off under reduced pressure. After that, water and toluene were added and the mixture was separated. Then, the mixture was filtered using silica gel (eluent: The solvent was removed by distillation under reduced pressure to obtain a crude product. The crude product was washed with hexane. By this, 1,3-bis(3,5-dibromophenoxy)benzene (14.9 g, yield 8 9%). [ka]

[0504] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=7.41(t,2H), 7.37(t ,1H), 7.10(d,4H), 6.82(dd,2H), 6.70(t,1H).

[0505] [Second stage] Under a nitrogen atmosphere, 1,3-bis(3,5-dibromophenoxy)benzene (8.00 g, 14 mmol), diphenylamine (10.0 g, 59 mmol), Pd2(dba)3 (0.256 g, 0.28 mmol), tri-tert-butylphosphine (0.113 g, 0.56 mmol), NaOtBu (6.70 g, 70 mmol) and toluene ( The flask containing the 300 ml of ethanol was heated to 110°C and stirred for 6 hours. After cooling, the mixture was filtered through silica gel (eluent: toluene), and the solvent was removed under reduced pressure to obtain a crude product. The crude product was washed with hexane to obtain 5,5'-(1,3-phenylenediamine). Nbis(oxy)bis(N 1 ,N 1 ,N 3 ,N 3 -Tetraphenylbenzene-1,3- The diamine (11.2 g, 86% yield) was obtained as a white solid. [ka]

[0506] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=7.24-7.28(m,1H), 7 .18(dd,16H), 7.05(d,16H), 6.94(t,8H), 6.57( t,2H), 6.54(d,1H), 6.51(d,2H), 6.29(d,4H).

[0507] [3rd stage] 5,5'-(1,3-phenylenebis(oxy))bis(N 1 ,N 1 ,N 3 ,N 3 -Te tetraphenylbenzene-1,3-diamine (2.03 g, 2.2 mmol) and ortho In a flask containing xylene (500 ml), boron tribromide (0 After the dropwise addition was completed, the temperature was raised to 150°C and the mixture was stirred for 24 hours. After stirring, the mixture was cooled to room temperature again and N,N-diisopropylethylamine (5.6 0 ml, 33 mmol) was added and stirred until the heat generation subsided. Then, the mixture was filtered using silica gel (eluent: toluene), and the solvent was removed by distillation under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography (eluent: toluene). The mixture was filtered using a solvent mixture of ethanol and hexane (volume ratio: 1 / 2), and the solvent was distilled off under reduced pressure to obtain a crude product. After washing with toluene, compound (1-201) was obtained (50.0 mg, yield 2.4 %). [ka]

[0508] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=5.79(d,2H), 6.70(d ,2H), 6.80(d,2H), 7.07(t,4H), 7.12(t,8H), 7. 21-7.28(m,12H), 7.31(s,1H), 7.35(dd,2H), 7. 40(t,2H), 7.44-7.51(m,6H), 9.12(d,2H), 10.2 (s,1H).

[0509] 13 C-NMR (101MHz, CDCl3): 98.6 (2C), 100.8 (2C), 104.9(1C), 117.4(2C), 120.1(2C), 124.1(4C), 12 6.0(8C), 128.4(2C), 129.2(8C), 130.0(4C), 130. 7(4C), 131.3(2C), 134.9(2C), 141.6(2C), 142.3( 1C), 146.6(4C), 147.1(2C), 148.1(2C), 152.6( 2C), 159.1(2C), 163.0(2C).

[0510] Synthesis example (3) Compound (1-9): 2,18-dimethyl-N 7 ,N7 ,N 13 ,N 13 ,9,11-He Xaparatril-5,9,11,15-tetrahydro-5,9,11,15-tetraaza -19b,20b-diborazinenaphtho[3,2,1-de:1',2',3'-jk]penta Synthesis of sen-7,13-diamine [ka]

[0511] [1st stage] Under a nitrogen atmosphere, 1,3-dibromobenzene (10.8 g, 1.9 mmol) and paratol Idine (20.3 g, 190 mmol), Pd2(dba)3 (1.60 g, 1.8 mm ol), tri-tert-butylphosphine (0.728 g, 3.6 mmol), NaO A flask containing tBu (25.9 g, 270 mmol) and toluene (500 ml) The mixture was stirred at room temperature for 10 hours. The reaction mixture was filtered through silica gel (eluent: toluene). The solvent was evaporated under reduced pressure to obtain a crude product. The obtained crude product was washed with methanol to obtain N 1 ,N 3 -Diparatolylbenzene-1,3-diamine (19.3 g, 74% yield) Obtained as a coloured solid. [ka]

[0512] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=7.06-7.11(m,5H), 6 .99(d,4H), 6.64(t,1H), 6.52(dd,2H), 5.54(s, 2H), 2.29(s,6H).

[0513] [Second stage] Under a nitrogen atmosphere, 1,3-dibromo-5-chlorobenzene (13.5 g, 50 mmol) , paraditolylamine (19.7 g, 0.10 mol), Pd2(dba)3 (1.15 g, 2.0 mmol), 2-dicyclohexylphenylphosphino-2',6'-dimeth Diphenyl ether (0.986 g, 2.4 mmol), NaOtBu (14.5 g, 0.1 A flask containing 5 mol of toluene (200 ml) was heated to 80°C and left for 15 hours. The reaction mixture was filtered through silica gel (eluent: toluene), and the solvent was evaporated under reduced pressure. The crude product was washed with methanol and then hexane to give 5 -chloro-N 1 ,N 1 ,N 3 ,N 3 -Tetraparatolylbenzene-1,3-diamine (2 1.7 g, 86% yield, was obtained as a white solid. [ka]

[0514] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=7.01(d,8H), 6.92(d ,8H), 7.00(t,4H), 6.51(t,1H), 6.45(sd,2H), 2 .28(s,12H).

[0515] [3rd stage] Under a nitrogen atmosphere, N synthesized in the first stage 1 ,N 3 -Diparatolylbenzene-1,3-diamine 5-chloro-N-(2-chloro-N-methyl ... 1,N 1 ,N 3 ,N 3 -Tetra-para-tolylbenzene-1,3-diamine (11.2 g, 22 mmol), Pd2 (dba)3 (0.503 g, 0.55 mmol), tri-tert-butylphosphine (0.223 g, 1.1 mmol), NaOtBu (3.20 g, 33 mmol) and The flask containing toluene (300 ml) was heated to 110°C and stirred for 18 hours. The liquid was filtered through silica gel (eluent: toluene), and the solvent was removed by distillation under reduced pressure to obtain the crude product. The obtained crude product was washed with methanol and then toluene to remove N 1 ,N 1 '-( 1,3-phenylene)bis(N 1 ,N 3 ,N 3 ,N 5 ,N 5 -Pentaparatolylbenzene -1,3,5-triamine (11.4 g, 85% yield) was obtained as a white solid. [ka]

[0516] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=6.86-6.93(m,37H), 6.80(d,4H), 6.74(t,1H), 6.44(dd,2H), 6.30(d ,4H), 6.29(t,2H), 2.23(s,6H), 2.20(s,24H).

[0517] [4th stage] N 1 ,N 1 '-(1,3-phenylene)bis(N 1 ,N 3 ,N 3 ,N5 ,N 5 -Penta para-Tolylbenzene-1,3,5-triamine (0.661 g, 0.5 mmol) and A flask containing o-dichlorobenzene (10 ml) was heated at room temperature under a nitrogen atmosphere with three odorants. After the dropwise addition, the temperature was raised to 180°C. The mixture was stirred for 24 hours, and then cooled to room temperature again. The mixture was stirred until the heat generation subsided. The reaction solution was evaporated under reduced pressure at 0°C. Then, the residue was filtered through silica gel (eluent: toluene). The solvent was distilled off under reduced pressure to obtain a crude product. The crude product was washed with toluene. As a result, compound (1-9) was obtained (0.365 g, yield 59%). [ka]

[0518] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=δ=2.32(s,12H), 2. 39(s,6H), 2.47(s,6H), 2.59(s,6H), 5.47-5.51 (m,4H), 5.97(s,1H), 6.80(d,2H), 6.87-6.94(m ,20H), 7.05(d,4H), 7.18(d,4H), 7.27(d,2H), 7 .31(d,4H), 9.00(s,2H), 10.5(s,1H).

[0519] 13 C-NMR(126MHz,(CDCl2)2):=20.4(4C), 20.6(2 C), 20.7(2C), 21.0(2C), 97.8(2C), 97.9(2C), 103 .5(1C), 116.7(2C), 125.7(8C), 128.1(2C), 129.0 (8C), 129.5(4C), 130.0(4C), 130.1(4C), 130.7(4 C), 131.2(2C), 132.6(4C), 134.7(2C), 136.5(2 C), 137.3(2C), 139.6(2C), 140.1(2C), 143.0(1 C), 144.1(4C), 146.1(2C), 147.9(2C+2C), 150. 1(2C), 151.1(2C).

[0520] Synthesis example (4) Compound (1-101): 7,13-diphenoxy-5,9,11,15-tetrapheny 5,9,11,15-tetrahydro-5,9,11,15-tetraaza-19b,2 Synthesis of 0b-diborazinenaphtho[3,2,1-de:1',2',3'-jk]pentacene [ka]

[0521] [1st stage] Under a nitrogen atmosphere, 1-bromo-3-chloro-5-fluorobenzene (5.50 ml, 45 mmol), phenol (4.40 g, 47 mmol), potassium carbonate (9.30 g, 6 A flask containing 8 mmol) and NMP (300 ml) was heated to 150°C and The reaction mixture was cooled to room temperature, and NMP was distilled off under reduced pressure. The mixture was then filtered using silica gel (eluent: toluene), and the solvent was removed by distillation under reduced pressure. After removal of the solvent, 1-bromo-3-chloro-5-phenoxybenzene (12.2 g, yield 98%) was obtained. Got it. [ka]

[0522] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=7.37(m,2H), 7.16-7 .21(m,2H), 7.00-7.03(m,3H), 6.90(t,1H).

[0523] [Second stage] Under a nitrogen atmosphere, 1-bromo-3-chloro-5-phenoxybenzene (5.30 ml, 2 7 mmol), diphenylamine (4.80 g, 28 mmol), Pd2(dba)3( 0.247g, 0.27mmol), tri-tert-butylphosphine (109mg, 0.54 mmol), NaOtBu (3.90 g, 41 mmol) and toluene (30 The flask containing 100 ml of ethanol was heated to 80°C and stirred for 14 hours. The mixture was filtered using a solvent (eluent: toluene), and the solvent was evaporated under reduced pressure to give 3-chloro-5-phenylenediamine. N,N-diphenylaniline (8.30 g, 83% yield) was obtained as a white solid. . [ka]

[0524] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=7.24-7.28(m,1H), 7 .18(dd,16H), 7.05(d,16H), 6.94(t,8H), 6.57( t,2H), 6.54(d,1H), 6.51(d,2H), 6.29(d,4H).

[0525] [3rd stage] Under nitrogen atmosphere, N 1 ,N 3 -Diphenylbenzene-1,3-diamine (1.56g, 6 .0mmol), 3-chloro-5-phenoxy-N,N-diphenylaniline (4.69 g, 13 mmol), Pd2(dba)3 (0.110 g, 0.12 mmol), tri- tert-Butylphosphine (49.0 mg, 0.24 mmol), NaOtBu (1. A flask containing 44 g (15 mmol) and toluene (200 ml) was heated to 110°C. The reaction mixture was filtered through silica gel (eluent: toluene) and the eluate was The solvent was removed by distillation under reduced pressure to obtain a crude product. The crude product was washed with methanol to obtain a crude product. 1 ,N 1 '-(1,3-phenylene)bis(5-phenoxy-N 1 ,N 3 ,N 3 -Trif Phenylbenzene-1,3-diamine (4.9 g, 87% yield) was obtained as a white solid. [ka]

[0526] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=6.88-7.27(m,41H), 6.79(t,1H), 6.65(dd,2H), 6.51(t,1H), 6.30-6 .32(m,4H).

[0527] [4th stage] N 1 ,N 1 '-(1,3-phenylene)bis(5-phenoxy-N 1 ,N 3 ,N 3 -to Triphenylbenzene-1,3-diamine (0.559 g, 0.60 mmol) and ol In a flask containing 10 ml of dichlorobenzene, phosphate tribromide was added at room temperature under a nitrogen atmosphere. After the dropwise addition, the temperature was raised to 180°C. The mixture was stirred for 24 hours, then cooled to room temperature again, and N,N-diisopropylethylamine was added. (1.5 ml, 9 mmol) was added and stirred until the heat generation subsided. After that, the mixture was heated at 60°C under reduced pressure. The reaction solution was evaporated under reduced pressure. Then, the mixture was filtered using silica gel (eluent: toluene). The solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography. The mixture was filtered using a solvent (eluent: toluene / hexane = 1 / 2 (volume ratio)), and the solvent was evaporated under reduced pressure. By removing the solvent, compound (1-101) was obtained (57.3 mg, yield 10%). [ka]

[0528] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=5.71-5.74(m,5H), 6 .79(d,2H), 6.82(d,4H), 6.96(t,2H), 7.09(d,4 H), 7.15(dd,4H), 7.28-7.38(m,12H), 7.45-7.5 2(m,4H), 7.61(t,4H), 9.24(d,2H), 10.5(s,1H) .

[0529] 13 C-NMR (101MHz, CDCl3): δ=96.1(2C), 96.2(2C) , 103.4(1C), 117.1(2C), 119.1(4C), 120.3(2C), 1 23.2(2C), 128.0(2C), 128.5(8C), 129.3(4C), 129 .8(4C), 130.3(4C), 130.6(4C), 130.8(2C), 131.0 (4C), 135.2(2C), 141.6(2C), 142.0(2C), 143.8 (1C), 147.7(2C), 148.4(2C), 148.6(2C), 150.0 (2C), 156.0(2C), 160.6(2C).

[0530] Synthesis example (5): Compound (1-2001):N 7 ,N 7 ,N 13 ,N 13 ,5,9,15-tetrahydro -5,9,15-triaza-11-oxa-19b,20b-diborazine [3,2, Synthesis of 1-de:1',2',3'-jk]pentacene-7,13-diamine [ka]

[0531] Under a nitrogen atmosphere, 1,3-dibromo-5-fluorobenzene (25.4 g, 0.10 mo l), m-chlorophenol (16.7 g, 0.13 mol), cesium carbonate (40.1 g, 0.12 mol) and N-methylpiperidone (NMP, 300 ml) The flask was heated to 120°C and stirred for 20 hours. The reaction solution was cooled to room temperature, and NMP was removed under reduced pressure. After distillation, the mixture was filtered using a silica gel short-path column (eluent: hexane) and the solvent The crude product was obtained by distilling off under reduced pressure. -4 8 mmHg vacuum Purification by sublimation at 0°C yields 1,3-dibromo-5-(3-chlorophenoxy)benzene The compound (27.7 g, yield 77%) was obtained. [ka]

[0532] The structure of the compound obtained was confirmed by NMR measurement. 1 H-NMR (400MHz, CDCl3): δ=6.90(d,1H), 7.02(s ,1H), 7.07(s,2H), 7.15(d,1H), 7.29(t,1H), 7. 41(s,1H).

[0533] Under a nitrogen atmosphere, 1,3-dibromo-5-(3-chlorophenoxy)benzene (10.2 g, 28 mmol), diphenylamine (10.6 g, 62 mmol), Pd2 (dba )3 (131 mg, 0.14 mmol), tri-tert-butylphosphine (56.7 mg, 0.28 mmol), NaO t Bu (6.37 g, 70 mmol) and toluene The flask containing the 300 ml of ethanol was heated to 80°C and stirred for 30 minutes. The mixture was cooled to RT, filtered using a Florisil short-path column (eluent: toluene), and the solvent was removed. The crude product was obtained by distillation under reduced pressure. The obtained crude product was washed with methanol to give 5-( 3-Chlorophenoxy)N 1 ,N 1 ,N 3 ,N 3 -Tetraphenylbenzene-1,3-di The amine (12.6 g, 83% yield) was obtained as a white solid. [ka]

[0534] The structure of the compound obtained was confirmed by NMR measurement. 1H-NMR (400MHz, CDCl3): δ=6.28(d,2H), 6.56(t ,1H), 6.82(dd,1H), 6.91(t,1H), 6.95-6.99(m, 5H)7.07(d,8H), 7.15(t,1H), 7.21(t,8H).

[0535] Under nitrogen atmosphere, 5-(3-chlorophenoxy)N 1 ,N 1 ,N 3 ,N 3 -Tetrapheny Benzene-1,3-diamine (10.2 g, 18 mmol), aniline (3.35 g, 36mmol), Pd2(dba)3(0.330g, 0.36mmol), 2-disic 2,6-dimethoxybiphenyl (0.296 g, 0.72 m mol), NaO t Bu (5.19 g, 54 mmol) and toluene (200 ml) The flask containing the reaction mixture was heated to 110°C and stirred for 2 hours. The mixture was filtered using a Lysil short-path column (eluent: toluene), and the solvent was removed by distillation under reduced pressure to obtain a crude product. The crude product was washed with hexane and then with methanol to obtain a product. 1 , N 1 ,N 3 ,N 3 -Tetraphenyl 5-(3-(phenylamino)phenoxy)benzene The resulting 1,3-diamine (9.49 g, 89% yield) was obtained as a white solid. [ka]

[0536] The structure of the compound obtained was confirmed by NMR measurement. 1 H-NMR (400MHz, CDCl3): δ=5.65(s,1H), 6.34(t ,2H), 6.47(d,1H), 6.55(dd,1H), 6.65(dd,2H), 6.94-6.98(m,5H), 7.03-7.08(m,10H), 7.10(t, 1H), 7.19(t,8H), 7.27(t,2H).

[0537] Under nitrogen atmosphere, N 1 ,N 1 ,N 3 ,N 3 -tetraphenyl 5-(3-(phenylamino) )phenoxy)benzene-1,3-diamine (4.29 g, 7.2 mmol), 5-chloro Lo-N 1 ,N 1 ,N 3 ,N 3 -Tetraphenylbenzene-1,3-diamine (2.67g , 6.0 mmol), Pd2(dba)3 (0.165 g, 0.18 mmol), tri- tert-Butylphosphine (72.8 mg, 0.36 mmol), NaO t Bu(1. A flask containing 15 g of benzophenone (12 mmol) and toluene (200 ml) was heated to 110°C. The reaction solution was cooled to room temperature and then loaded onto a Florisil short-path column ( The mixture was filtered using toluene (eluent), and the solvent was removed by distillation under reduced pressure to obtain a crude product. The product was washed with acetonitrile to remove N 1 -(3-(3,5-bis)diphenylamine N)phenoxy)phenol-(N 1 ,N 3 ,N 3 ,N 5 ,N 5 -Pentaphenylbenzene The resulting product was 1,3,5-triamine (4.93 g, 82% yield) as a white solid. [ka]

[0538] The structure of the compound obtained was confirmed by NMR measurement. 1 H-NMR(500MHz,(CDCl2)2):δ=6.28(d,2H), 6.3 8(d,2H), 6.40-6.42(m,2H), 6.52(s,1H), 6.58- 6.60(m,2H), 6.86(t,4H), 6.92-7.07(m,24H), 7 .11-7.20(m,18H).

[0539] N 1 -(3-(3,5-bis)diphenylamino)phenoxy)phenol-(N 1 , N 3 ,N 3 ,N 5 ,N 5 -Pentaphenylbenzene-1,3,5-triamine (1.05 g, 1.0 mmol) and chlorobenzene (50 ml) in a flask under a nitrogen atmosphere. Boron tribromide (0.569 ml, 6.0 mmol) was added at room temperature under atmospheric pressure. The temperature was raised to 140°C and stirred for 24 hours. After that, the mixture was cooled to room temperature again and N-diisopropyl alcohol was added. Add propylethylamine (3.13 ml, 18 mmol) and stir until the heat generation subsides. The reaction solution was then distilled off under reduced pressure at 60°C to obtain a crude product. After washing with heptane, compound (1-2001) was obtained (0.251 g, 24% yield). ). [ka]

[0540] The structure of the compound obtained was confirmed by NMR measurement. 1 H-NMR(500MHz,(CDCl2)2):δ=5.67(s,1H), 5.6 8(s,1H), 5.75(d,1H), 6.51(d,1H), 6.58(s,1H) ,6.77(m,2H),6.92-7.12(m,18H),7.18-7.51(m ,21H), 9.17(m,2H), 10.3(s,1H). 13 C-NMR(126MHz,(CDCl2)2):98.5(1C), 98.9(1 C), 99.0(1C), 100.6(1C), 103.3(1C), 117.0(1C ), 117.3(1C), 120.0(1C), 120.1(1C), 123.5(2C ), 124.0(2C), 124.4(1C), 125.6(4C), 126.0(4C ), 128.1(1C), 128.3(2C), 128.8(4C), 129.0(1C ), 129.1(4C), 130.0(2C), 130.2(2C), 130.5(1C ), 130.6(2C), 130.7(2C), 130.8(2C), 131.2(1C ), 135.0(1C), 135.1(1C), 141.7(1C), 141.8(1C ), 142.1(1C), 143.0(1C), 146.5(2C), 146.7(2C ), 147.1(1C), 146.8(1C), 147.8(1C), 147.9(1C ), 148.0(1C), 151.1(1C), 151.2(1C), 152.3(1C ), 159.2 (1C), 161.9 (1C).

[0541] Synthesis example (6): Compound (1-31):2,18-ジメチル-N 7 N 7 N 13 N 13 ,9,11- ヘキサパトリル-5,9,11,15-テトラヒドロ-5,9,11,15-テトラア The-19b,20b-diborazinenaphtho[3,2,1-de:1',2',3'-jk]pen Synthesis of thacene-7,13-diamine [ka]

[0542] [1st stage] Under a nitrogen atmosphere, 1,3-dibromo-5-chlorobenzene (13.7 g, 51 mmol) , methaditolylamine (19.8 g, 0.10 mol), Pd2(dba)3 (0.93 g, 1.0 mmol), 2-dicyclohexylphenylphosphino-2',6'-dimeth Diphenyl ether (SPhos: 0.838 g, 2.0 mmol), NaOtBu (14. A flask containing 640 ml of toluene and 6 g of benzophenone (0.15 mol) was heated to 80°C. The mixture was stirred for 1.5 hours. Water was added to stop the reaction, and then extraction was carried out using toluene. The crude product obtained by distilling off the solvent was then passed through a silica gel column (eluent: heptane:toluene = 6:4 (volume By purifying using 5-chloro-N 1 ,N 1 ,N 3 ,N 3 -Tetrametat Il-benzene-1,3-diamine (27.0 g, 84% yield) was obtained as a white paste. . [ka]

[0543] [Second stage] Under nitrogen atmosphere, N 1 ,N 3 -Diphenylbenzene-1,3-diamine (4.22g, 1 6mmol), 5-chloro-N 1 ,N 1 ,N 3 ,N 3-Tetramethatrilbenzene-1, 3-diamine (21.5 g, 43 mmol), Pd-132 (0.12 g, 0.17 mmol), ol), NaOtBu (3.89 g, 40 mmol) and toluene (80 ml) The flask was heated to 110°C and stirred for 2 hours. Water was added to stop the reaction, and then toluene was used to The crude product obtained by distilling off the solvent was extracted with a silica gel column (eluent: toluene). ) and the resulting crude product was reprecipitated with heptane to obtain N 1 ,N 1 '-( 1,3-phenylene)bis(N 1 -phenyl-N 3 ,N 3 ,N 5 ,N 5 -Tetrametatri Benzene-1,3,5-triamine (19.9 g, 80% yield) was obtained as a white solid. . [ka]

[0544] [3rd stage] N 1 ,N 1 '-(1,3-phenylene)bis(N 1 -phenyl-N 3 ,N 3 ,N 5 ,N 5 -Tetramethatrilbenzene-1,3,5-triamine (0.661 g, 0.5 mmol) A flask containing 10 ml of chloroform and o-dichlorobenzene was placed in a nitrogen atmosphere. Boron tribromide (0.819 ml, 2.0 mmol) was added at 180°C. The mixture was heated to rt and stirred for 24 hours. Ethylamine (1.28 ml, 7.5 mmol) was added and the mixture was stirred until the heat generation subsided. After that, the reaction solution was distilled off under reduced pressure at 60°C. Then, the reaction solution was filtered using silica gel (elution The solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was washed with toluene. Compound (1-31) was obtained by purification (0.365 g, 59% yield). [ka]

[0545] The structure of the compound obtained was confirmed by NMR spectroscopy. 1 H-NMR (400MHz, CDCl3): δ=2.32(s,12H), 2.39 (s,6H), 2.47(s,6H), 2.59(s,6H), 5.47-5.51(m ,4H), 5.97(s,1H), 6.80(d,2H), 6.87-6.94(m,2 0H), 7.05(d,4H), 7.18(d,4H), 7.27(d,2H), 7.3 1(d,4H), 9.00(s,2H), 10.5(s,1H). 13 C-NMR (101MHz, CDCl3): 20.4 (4C), 20.6 (2C), 20.7(1C), 21.0(2C), 97.8(2C), 97.9(2C), 103.5( 1C), 116.7(2C), 125.7(8C), 128.1(2C), 129.0(8C ), 129.5(4C), 130.0(4C), 130.1(4C), 130.7(4C), 131.2(2C), 132.6(4C), 134.7(2C), 136.5(2C), 137.3(2C), 139.6(2C), 140.1(2C), 143.0(1C), 144.1(4C), 146.1(2C), 147.9(2C+2C), 150.1(2 C), 151.1(2C).

[0546] By appropriately changing the raw material compounds, other compounds of the present invention can be obtained by the method similar to the synthesis example described above. The compound can be synthesized.

[0547] Next, we evaluated the basic properties of the compound of the present invention and fabricated an organic EL device using the compound of the present invention. and evaluation will be described.

[0548] <Evaluation of basic physical properties> Sample preparation When evaluating the absorption and emission characteristics (fluorescence and phosphorescence) of a compound, The compound may be dissolved in a solvent and evaluated in the solvent, or in a thin film state. When evaluating in a thin film state, the evaluation should be carried out according to the mode of use of the compound to be evaluated in the organic EL device. There are two ways to evaluate the compound: by forming a thin film of only the compound to be evaluated, or by forming the compound into an appropriate matrix. In some cases, the material is dispersed in a thin film and evaluated.

[0549] As the matrix material, commercially available PMMA (polymethyl methacrylate) etc. is used. For example, a thin film sample dispersed in PMMA can be obtained by separating the PMMA and the compound to be evaluated. The compound was dissolved in toluene and then spin-coated onto a transparent quartz support substrate ( It can be fabricated by forming a thin film on a substrate (10mm x 10mm).

[0550] The method for preparing a thin film sample when the matrix material is the host material is described below. A transparent support substrate made of quartz (10 mm × 10 mm × 1.0 mm) was prepared using a commercially available deposition system (Showa A molybdenum evaporation boat containing the host material was fixed to a substrate holder (manufactured by Shinku Co., Ltd.). Next, a molybdenum evaporation boat containing the dopant material is installed. 0 -4The pressure was reduced to 100 Pa, and the deposition boat containing the host material and the deposition boat containing the dopant material were The host material and dopant material are deposited by simultaneously heating the boat and depositing them to an appropriate film thickness. The deposition rate is controlled according to the set weight ratio of the host material and the dopant material. Control.

[0551] Absorption and emission properties The absorption spectrum of the sample was measured using an ultraviolet-visible-near infrared spectrophotometer (Shimadzu Corporation). The fluorescence spectrum or phosphorescence of the sample was also measured. The spectra were measured using a spectrofluorometer (Hitachi High-Tech, F-7000). went.

[0552] For measuring the fluorescence spectrum, photoluminescence was measured at room temperature using an appropriate excitation wavelength. For the measurement of phosphorescence spectrum, the attached cooling unit was used. The sample was immersed in liquid nitrogen (temperature 77K) and the measurement was performed. Therefore, an optical chopper was used to adjust the delay time from irradiation of the excitation light to the start of measurement. The pull was excited with an appropriate excitation wavelength and photoluminescence was measured.

[0553] In addition, an absolute PL quantum yield measurement device (Hamamatsu Photonics, C9920-02G) was used. The fluorescence quantum yield is measured using

[0554] Evaluation of fluorescence lifetime (delayed fluorescence) A fluorescence lifetime measurement device (Hamamatsu Photonics, C11367-01) was used at 300K. The fluorescence lifetime is measured at the maximum emission wavelength measured at an appropriate excitation wavelength. Observe the fast and slow components. Fluorescence of a typical organic electroluminescent material at room temperature. In lifetime measurements, the triplet component originating from phosphorescence is involved due to thermal quenching of the triplet component. Slow components are rarely observed. Slow components are rarely observed in the compounds being evaluated. When the triplet energy is converted to singlet energy by thermal activation, the triplet energy with a long excited lifetime is transferred to singlet energy. This indicates that the fluorescence was observed as delayed fluorescence.

[0555] Calculation of energy gap (Eg) From the long wavelength end A (nm) of the absorption spectrum obtained by the above method, Eg = 1240 / A It is calculated as follows.

[0556] E S 、E T and calculation of ΔEST Singlet excitation energy (E S ) is the maximum emission wavelength B (nm) to E (nm) of the fluorescence spectrum. S = 1240 / B. The triplet excitation energy (E T ) is the phosphorescence spectrum Maximum emission wavelength C (nm) to E T =1240 / C.

[0557] ΔEST is E S and E T The energy difference is ΔEST=E S -E T It is also defined as , ΔEST is, for example, "Purely organic electroluminescent material realizing 100% "conversion from electricity to light", H. Kaji, H. Suzuki, T. Fukushima, K. Shi zu, K. Katsuaki, S. Kubo,T. Komino, H. Oiwa, F. Suzuki, A. Wakamiya, Y. Murata, It can also be calculated by the method described in C. Adachi, Nat. Commun. 2015, 6, 8476.

[0558] Evaluation of the basic physical properties of compound (1-1) [Absorption characteristics] A thin film formed on a quartz substrate in which compound (1-1) was dispersed in PMMA at a concentration of 1 wt% was prepared. The absorption spectrum was measured using a sample prepared for this purpose (Figure 2). As a result, the maximum absorption wavelength in the visible light region was 4 In addition, a thin film formed on a substrate consisting of only compound (1-1) was prepared, and the absorption spectrum was As a result of measuring the spectrum, the long wavelength absorption edge of the absorption spectrum was 477 nm, with Eg = 2. The calculated energy gap was 60 eV, which was found to be an appropriate value.

[0559] [Light Emitting Properties] The fluorescence spectrum was measured using a thin film of compound (1-1) dispersed in PMMA at a concentration of 1 wt.%. A film-forming substrate (made of quartz) was prepared, and photoluminescence was detected by excitation at an excitation wavelength of 340 nm. The maximum emission wavelength was measured (Fig. 2). S is 2 The calculated value is 0.66 eV. The same substrate is also prepared and excited with an excitation wavelength of 340 nm. The quantum yield was measured and found to be as high as 92%.

[0560] The phosphorescence spectrum was measured using a thin film of compound (1-1) dispersed in PMMA at a concentration of 1 wt.%. A film-forming substrate (made of quartz) was prepared, and photoluminescence was detected by excitation at an excitation wavelength of 340 nm. As a result, the maximum emission wavelength was 470 nm. T is 2 The value was found to be high at 0.64 eV.

[0561] The calculated ΔEST was 0.02 eV.

[0562] From the above, it was confirmed that compound (1-1) is a material that can achieve high efficiency and a deep blue color. In particular, since it has a small ΔEST, it is expected to be a thermally activated delayed fluorescence material. do.

[0563] Comparative compound 1 The compound of formula (1-2676) disclosed in WO 2015 / 102118 is a comparative compound. The compound (1-1) was used except that the compound (1-1) of the present invention was replaced with the comparative compound 1. The ΔEST was calculated in the same manner as in Example 1. The maximum emission wavelength of the fluorescence spectrum was 469 nm. The maximum emission wavelength of the phosphorescence spectrum is 502 nm, and ΔEST is calculated to be 0.17 eV. This ΔEST value is small enough to obtain thermally activated delayed fluorescence, but The thermally activated delayed fluorescence is larger than that of the compound (1-1), and is suitable for the organic EL device configuration. Therefore, the external quantum efficiency is expected to be lower than that of the compound (1-1). [ka]

[0564] Comparative compound 2 The compound of formula (1-422) disclosed in WO 2015 / 102118 is comparative compound 2. The compound (1-1) was used in the present invention except that the compound (1-1) was replaced with the comparative compound 2. The evaluation was carried out in the same manner as in Example 1. As a result, the maximum emission wavelength of the fluorescence spectrum was 477 nm, which is an emission wavelength 10 nm longer than that of compound (1-1), and emits a deep blue light. It was a result that was not achieved. [ka]

[0565] From the above, compound (1-1) has an appropriate energy gap and high triplet excitation energy. In particular, it has a small ΔEST, making it an ideal material for the light-emitting layer. It is also expected to be used as a thermally activated delayed fluorescent material for optical layers.

[0566] Evaluation of the basic properties of compound (1-201) A thin film-forming base prepared by dispersing compound (1-201) in PMMA under the same conditions as compound (1-1). The plate was prepared and the absorption and emission spectra were measured (Fig. 3). The excitation wavelength during spectrum measurement was 375 nm. The wavelength was 438 nm. The same substrate was also prepared and excited with an excitation wavelength of 375 nm to measure fluorescence. The quantum yield was measured and found to be a high value of 87%. The length was 466 nm. T is 2.66 eV, which is a high value. The calculated ΔEST was 0.17 eV.

[0567] From the above, compound (1-201) is a material that can achieve a deep blue color with high efficiency. In particular, it is expected to be a thermally activated delayed fluorescence material because it has a small ΔEST. can.

[0568] Evaluation of the basic properties of compound (1-101) A thin film-forming base prepared by dispersing compound (1-101) in PMMA under the same conditions as compound (1-1). The plate was prepared and the absorption and emission spectra were measured (Fig. 4). The excitation wavelength during spectrum measurement was 407 nm. The wavelength was 457 nm. The same substrate was also prepared and excited with an excitation wavelength of 407 nm to measure fluorescence. The quantum yield was measured and found to be as high as 91%. The length was 461 nm. T is 2.69 eV, which is a high value. The calculated ΔEST was 0.02 eV.

[0569] From the above, compound (1-101) is a material that can achieve a deep blue color with high efficiency. In particular, it is expected to be a thermally activated delayed fluorescence material because it has a small ΔEST. can.

[0570] Evaluation of the basic physical properties of compound (1-9) Compound (1-9) was dispersed in PMMA under the same conditions as compound (1-1) to form a thin film on the substrate. The absorption spectrum and emission spectrum were measured (Fig. 5). The excitation wavelength for the fluorescence spectrum measurement was 374 nm. The fluorescence quantum yield was 473 nm. The yield was measured and found to be as high as 89%. Furthermore, the maximum emission wavelength of the phosphorescence spectrum was 477 nm. T is 2.60 eV, which is a high value. The calculated ΔEST was 0.02 eV.

[0571] From the above, it was confirmed that compound (1-9) is a material that can achieve high efficiency and a deep blue color. In particular, since it has a small ΔEST, it is expected to be a thermally activated delayed fluorescence material. do.

[0572] <Evaluation of organic EL elements> As described above, the compound of the present invention has an appropriate energy gap (Eg), a high triplet excitation, and Electromotive energy (E T) and a small ΔEST, The application of the compound to a charge transport layer is expected, and the application to a light-emitting layer is particularly expected.

[0573] Evaluation items and evaluation methods The evaluation items are driving voltage (V), emission wavelength (nm), CIE chromaticity (x, y), external These include quantum efficiency (%), maximum wavelength (nm) and half-width (nm) of the emission spectrum. For these evaluation items, values ​​at appropriate luminance can be used.

[0574] The quantum efficiency of a light-emitting element is divided into internal quantum efficiency and external quantum efficiency. The internal quantum efficiency is External energy injected into the light-emitting layer of a light-emitting device as electrons (or holes) is converted purely into photons. On the other hand, the external quantum efficiency indicates the rate at which these photons are converted outside the light-emitting element. The amount of photons emitted from the light-emitting layer is calculated based on the amount of photons emitted from the light-emitting element. The light is absorbed or reflected inside the light emitting element and is not emitted to the outside. Therefore, the external quantum efficiency is lower than the internal quantum efficiency.

[0575] The spectral radiance (emission spectrum) and external quantum efficiency were measured as follows. The element is generated by applying voltage using the voltage / current generator R6144 manufactured by Intest. Using a TOPCON SR-3AR spectroradiometer, The spectral radiance of the visible light region was measured from the direction. Assuming that the light-emitting surface is a perfectly diffusing surface, The measured spectral radiance value of each wavelength component is divided by the wavelength energy and multiplied by π. Next, the number of photons is integrated over the entire wavelength range observed, and the The value obtained by dividing the applied current value by the elementary charge injected into the element was used as the total number of photons emitted from the The number of carriers is calculated by dividing the total number of photons emitted from the element by the number of carriers injected into the element. The value obtained is the external quantum efficiency. The width between the upper and lower wavelengths where the intensity is 50% is calculated.

[0576] Fabrication of organic EL devices Organic EL elements according to the examples and comparative examples were prepared, and voltage was applied to measure the current density, brightness, and color. The organic EL device was fabricated with the following configuration: A (Tables 1 and 3), B (Table 2), C (Table 4) and D (Table 5). The structures A, C, and D are suitable for thermally activated delayed fluorescence materials. Configuration B is the more common configuration. Configuration A is described in the literature (Adv. Mater. 2016, 28, 2777-2 This is the device configuration that can be expected to achieve high efficiency as shown in the literature (Scientific Report 781). rts, 6, 2016, 22463) is a material that can be expected to have relatively high efficiency and long-term driving stability. Configuration D is the same as the configuration shown in the literature (Thin Solid Films, 619, 2016, 120-124). This is a device configuration that uses a host material different from that of Compositions A and C. The application is not limited to these structures, and the thickness and constituent materials of each layer may vary depending on the basic physical properties of the compound of the present invention. The amount of the saturation can be appropriately changed by

[0577] [Table 1]

[0578] In Table 1, "HI" represents N,N'-diphenyl-N,N'-dinaphthyl-4,4'- diaminobiphenyl, and "HT" is 4,4',4"-tris(N-carbazolyl)triphenyl phenylamine, and "EB" is 1,3-bis(N-carbazolyl)benzene. "EMH1" is 3,3'-bis(N-carbazolyl)-1,1'-biphenyl; "ET" is diphenyl[4-(triphenylsilyl)phenyl]phosphine oxide The chemical structure is shown below along with that of comparative compound 1.

[0579] [ka]

[0580] [Table 2]

[0581] In Table 2, "HI-1" is N 4 ,N 4’ -diphenyl-N 4 ,N 4’ -Bis(9- Phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4,4'-di amine, and "HAT-CN" is 1,4,5,8,9,12-hexaazatriphenyl and "HT-1" is N-([1,1'-biphenyl]-4- yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl) )phenyl)-9H-fluoren-2-amine, and "HT-2" is N,N-bis(4 -(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1"-tert-butyl]phenyl phenyl]-4-amine, and "EMH2" is 9-phenyl-10-(4-phenylamine). phthalen-1-yl)anthracene, and "ET-1" is 4,6,8,10-tetrafluoroethane. phenyl[1,4]benzoxaborinino[2,3,4-kl]phenoxaborinine, "ET-2" is 3,3'-((2-phenylanthracene-9,10-diyl)bis(4 ,1-phenylene))bis(4-methylpyridine), and the chemical formula below is "Liq". The structure is shown.

[0582] [ka]

[0583] Example 1 <Configuration A: Device using compound (1-1) as a dopant> ITO film formed by sputtering to a thickness of 200 nm was polished to 150 nm. Transparent support for a 26mm x 28mm x 0.7mm glass substrate (manufactured by Optoscience Co., Ltd.) This transparent support substrate was placed on a substrate holder of a commercially available deposition device (manufactured by Showa Vacuum Co., Ltd.). HI, HT, EB, EMH1, compound (1-1), ET, and LiF were fixed, respectively. Molybdenum evaporation boat containing aluminum, and tungsten evaporation boat containing aluminum. I put it on.

[0584] The following layers were formed in order on the ITO film of the transparent support substrate. -4 Pa The pressure is reduced to 100 psi, and HI is heated and evaporated to a thickness of 40 nm to form a hole injection layer. Next, HT was heated and evaporated to a thickness of 15 nm to form a hole transport layer. Next, the electron blocking layer was formed by heating the EB and depositing the material to a thickness of 15 nm. EMH1 and compound (1-1) were heated simultaneously and evaporated to a thickness of 20 nm to form an emitting layer. The deposition rate was adjusted so that the weight ratio of EMH1 to compound (1-1) was approximately 99:1. Next, ET was heated and evaporated to a thickness of 40 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / sec.

[0585] After that, LiF was heated and evaporated at a rate of 0.01 to 0.1 nm / sec to a film thickness of 1 nm. Then, aluminum was evaporated by heating to a thickness of 100 nm to form a cathode. The aluminum deposition rate was 1 nm to 10 nm. It was adjusted to be / sec.

[0586] The ITO electrode was used as the anode and the aluminum electrode as the cathode, and a DC voltage was applied to measure the brightness, chromaticity, and The luminance and external quantum efficiency were measured. The results are shown in Figures 6 and 7. When 7 V was applied, the luminance was 59. 1cd / m 2 Achieves high brightness of 250cd / m 2 The emission spectrum at half maximum (F WHM) 19nm, peak wavelength 473nm, chromaticity is CIE chromaticity (x,y) = (0. 118,0.104), a deep blue emission of 50 cd / m 2 , 100cd / m 2 Oh and 250cd / m 2 The external quantum efficiencies during light emission were 16.8%, 15.7%, and The result was a high value of 14.3% and a small roll-off.

[0587] <Comparative Example 1> <Configuration A: Device using Comparative Compound 1 as a dopant> An EL device was obtained using the same procedure and configuration as in Example 1, except that the dopant was changed. The results are shown in Figures 6 and 7. The luminance at 7 V was 322 cd / m 2 250c d / m 2 The chromaticity when emitting light is CIE chromaticity (x, y) = (0.126, 0.108), which is 5 0 cd / m 2 , 100cd / m 2 and 250 cd / m 2 The external quantum efficiency of light emission is The luminances achieved were 14.0%, 12.0%, and 9.0%, respectively. The results showed low external quantum efficiency and large roll-off.

[0588] <Example 2> <Configuration B: Device using compound (1-1) as a dopant> An EL device having the structure B was obtained by the same procedure as that of the structure A, except that EMH2 and compound (1-1) The deposition rate was adjusted so that the weight ratio of 100 0 cd / m 2 The applied voltage during light emission was 4.1 V, the external quantum efficiency was 6.7%, and the emission spectrum ( Figure 8) has a maximum emission wavelength of 471 nm, a half-width of 18 nm, and a CIE chromaticity (x, y) of In particular, the half-width of the emission spectrum is small and the color is deep blue. Such a narrow half-width allows for deep blue chromaticity and cuts off the low wavelength region. This makes it possible to achieve these goals simultaneously, and also allows for the design of devices that are gentle on the eyes and biological rhythms. become.

[0589] <Comparative Example 2> <Configuration B: Device using Comparative Compound 1 as a dopant> An EL device was obtained using the same procedure and configuration as in Example 2, except that the dopant was changed. As a result, 1000 cd / m 2 The applied voltage during light emission was 4.1 V, the external quantum efficiency was 6.6%, and the The optical spectrum (Fig. 8) has a maximum emission wavelength of 468 nm and a half-width of 26 nm, conforming to the CIE standard. The degree (x, y) was (0.124, 0.111). Although the pressure and external quantum efficiency were comparable, the half-width was wider.

[0590] The above compounds (1-201), (1-101) and (1-9) are compounds As in (1-1), organic EL devices can be fabricated and evaluated using the configurations A and B.

[0591] [Table 3]

[0592] <Comparative Example 3> <Configuration A: Device using Comparative Compound 2 as a dopant> ITO film formed by sputtering to a thickness of 200 nm was polished to 150 nm. Transparent support for a 26mm x 28mm x 0.7mm glass substrate (manufactured by Optoscience Co., Ltd.) This transparent support substrate was placed on a substrate holder of a commercially available deposition device (manufactured by Showa Vacuum Co., Ltd.). Fix the cells and place HI, HT, EB, EMH1, comparative compound 2, ET, and LiF. A molybdenum evaporation boat containing aluminum and a tungsten evaporation boat containing aluminum were installed. did.

[0593] The following layers were formed in order on the ITO film of the transparent support substrate. -4 Pa The pressure is reduced to 100 psi, and HI is heated and evaporated to a thickness of 40 nm to form a hole injection layer. Next, HT was heated and evaporated to a thickness of 15 nm to form a hole transport layer 1. Next, the EB was heated to vapor-deposit the layer to a thickness of 15 nm to form a hole transport layer 2. Then, EMH1 and comparative compound 2 were simultaneously heated and evaporated to a thickness of 20 nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of EMH1 to comparative compound 2 was approximately 99:1. Next, ET was heated and evaporated to a thickness of 40 nm to form an electron transport layer. The deposition rate for each layer was 0.01 to 1 nm / sec. After that, LiF was heated to a thickness of 1 Then, aluminum was evaporated at a deposition rate of 0.01 to 0.1 nm / sec to a thickness of 1 nm. The cathode was formed by heating and vapor deposition to a thickness of 100 nm, and an organic EL device was obtained. At this time, the deposition rate of aluminum was adjusted to 1 nm to 10 nm / sec.

[0594] The ITO electrode was used as the anode and the aluminum electrode as the cathode, and a DC voltage was applied to measure the brightness, chromaticity, and The external quantum efficiency was measured. 2 , 100cd / m 2 and 250 cd / m 2 The emission spectrum during emission has a full width at half maximum (FWHM) of 18 nm and a peak wavelength of 480 nm. Although a very narrow emission was observed, the peak wavelength was long, so the chromaticity was CIE chromaticity (x, y) = (0.092, 0.224), which was a pale blue. 2 Departure The external quantum efficiency under light was 4.9%.

[0595] Example 3 <Configuration A: Device using compound (1-9) as a dopant> An EL device was obtained using the same procedure and configuration as in Comparative Example 3, except that the dopant was changed. 00cd / m 2 The emission spectrum has a full width at half maximum (FWHM) of 21 nm and a peak wavelength of 47 3nm, and a very thin emission is observed, and the chromaticity is CIE chromaticity (x,y) = (0.105,0 210), which was a slightly deeper blue than Comparative Example 3. 2 Illumination The external quantum efficiency was 19.0%, which was higher than that of Comparative Example 3.

[0596] Example 4 <Configuration A: Device using compound (1-31) as a dopant> An EL device can be obtained using the same procedure and configuration as in Comparative Example 3, except that the dopant was changed. .

[0597] <Example 5> <Configuration A: Device using compound (1-2001) as a dopant> An EL device was obtained using the same procedure and configuration as in Comparative Example 3, except that the dopant was changed. 00cd / m 2 The emission spectrum has a full width at half maximum (FWHM) of 22 nm and a peak wavelength of 46 The wavelength is 4 nm, and a very thin emission is observed. The chromaticity is CIE chromaticity (x, y) = (0.132, 0 079), which was a much deeper blue than Comparative Example 3. 2 Illumination The external quantum efficiency at this time was 14.0%, which was higher than that of Comparative Example 3.

[0598] [Table 4]

[0599] In Table 4, "HAT-CN" is 1,4,5,8,9,12-hexaazatripheny Tris-PCz is 9,9',9"-triphenylhexacarbonitrile. 3-9H,9H',9H"-3,3',6',3"-tert-carbazole, " is 2,4,6-tri[[1,1'-biphenyl]-3-yl]-1,3,5-triazine "BPy-TP2" is 2,7-di([2,2'-bipyridin]-5-yl)trimethylsilyl It is phenylene. The chemical structure is shown below.

[0600] [ka]

[0601] Example 6 <Configuration C: Device using compound (1-1) as a dopant> ITO film formed by sputtering was polished to 50nm. A 0.7 mm glass substrate (Optoscience Co., Ltd.) was used as a transparent support substrate. The substrate was fixed to the substrate holder of a commercially available deposition device (Choshu Sangyo Co., Ltd.), and HAT-CN, T ris-PCz, EMH1, compound (1-1), T2T, BPy-TP2, and LiF Tantalum evaporation crucibles containing aluminum and aluminum nitride. A crucible for vapor deposition is attached.

[0602] The following layers are formed in order on the ITO film of the transparent support substrate. -4 The pressure was reduced to 100 Pa, and first, HAT-CN was heated and evaporated to a thickness of 10 nm. Then, Tris-PCz is heated and evaporated to a thickness of 30 nm to form a two-layer film. Next, EMH1 and compound (1-1) were simultaneously heated to form a hole layer with a thickness of 30 nm. The light-emitting layer is formed by vapor deposition so that the weight ratio of EMH1 to compound (1-1) is approximately 9. Adjust the deposition rate so that the ratio is 0 to 10. Next, heat T2T until the film thickness becomes 10 nm. BPy-TP2 was evaporated to a thickness of 30 nm to form a two-layer electron transport layer. The deposition rate of each layer is 0.01 to 1 nm / sec. After that, LiF is heated to form a The film was evaporated at a deposition rate of 0.01 to 0.1 nm / sec to a thickness of 1 nm, and then aluminum The aluminum is heated and evaporated at a deposition rate of 0.1 nm to 2 nm / sec to a thickness of 100 nm. By forming a cathode using the organic EL element, an organic EL element can be obtained.

[0603] [Table 5]

[0604] Example 7 <Configuration D: Device using compound (1-1) as a dopant> ITO film formed by sputtering was polished to 50nm. A 0.7 mm glass substrate (Optoscience Co., Ltd.) was used as a transparent support substrate. The substrate was fixed to the substrate holder of a commercially available deposition device (Choshu Sangyo Co., Ltd.), and HAT-CN, T ris-PCz, EB, compound (3-262), compound (1-1), BPy-TP2 and The tantalum evaporation crucibles were filled with LiF and LiF, and the aluminum nitride crucible was filled with aluminum. An aluminum evaporation crucible is installed.

[0605] The following layers are formed in order on the ITO film of the transparent support substrate. -4 The pressure was reduced to 100 Pa, and first, HAT-CN was heated and evaporated to a thickness of 10 nm. Then, Tris-PCz was heated and evaporated to a thickness of 25 nm, and then the EB was heated. Then, a hole layer consisting of three layers is formed by depositing the compound (3-262) and compound (1-1) were simultaneously heated and evaporated to a thickness of 30 nm. The light-emitting layer is formed by mixing the compound (3-262) and the compound (1-1) in a weight ratio of about 90:1. The deposition rate is adjusted so that the film thickness becomes 100 nm. BPy-TP2 was evaporated to a thickness of 40 nm, and BPy-TP2 was evaporated to a thickness of 40 nm. The deposition rate of each layer is 0.01 to 1 nm / sec. Heat the film and deposit it at a deposition rate of 0.01 to 0.1 nm / sec until the film thickness reaches 1 nm. The aluminum was heated at a deposition rate of 0.1 nm to 2 nm / sec to achieve a film thickness of 100 nm. By forming a cathode by vapor deposition at a high rate, an organic EL device can be obtained.

[0606] [Table 6]

[0607] In Table 6, compound (5-102) is 3,11-di-o-tolyl-5,9-dioxa -13b-boranaphtho[3,2,1-de]anthracene, compound (5-201) is 9- (5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracen-7-yl )-9H-carbazole. The chemical structure is shown below. [ka]

[0608] Example 8 <Configuration A: Device using compound (1-1) as a dopant and compound (5-201) as a host> ITO film formed by sputtering to a thickness of 200 nm was polished to 150 nm. Transparent support for a 26mm x 28mm x 0.7mm glass substrate (manufactured by Optoscience Co., Ltd.) This transparent support substrate was placed on a substrate holder of a commercially available deposition device (manufactured by Choshu Sangyo Co., Ltd.). The mixture was fixed, and HI, HT, EB, compound (5-201), compound (1-1), and ET were added. Tantalum evaporation boats containing LiF and aluminum, respectively. An aluminum evaporation boat was installed.

[0609] The following layers were formed in order on the ITO film of the transparent support substrate. -4 Pa The pressure was reduced to 100 MPa, and HI was first heated to deposit a film thickness of 40 nm. The EB is heated and evaporated to a thickness of 15 nm, forming three layers. Next, compound (5-201) and compound (1-1) were simultaneously added. The compound (5-201) was heated and evaporated to a thickness of 20 nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of the mixture (1-1) to the ET was approximately 99:1. The electron transport layer was formed by heating and vapor deposition to a thickness of 40 nm. The rate was 0.01 to 1 nm / sec. After that, the LiF was heated for 0. The aluminum was then heated to a thickness of 100 nm. The cathode was formed by vapor deposition so that the thickness of the aluminum film was 100 nm, and an organic EL device was obtained. The deposition rate was adjusted to 1 nm to 10 nm / sec.

[0610] The ITO electrode was used as the anode and the aluminum electrode as the cathode, and a DC voltage was applied to measure the brightness, chromaticity, and The external quantum efficiency was measured. 2 The emission spectrum at the time of emission is M) 21 nm, the peak wavelength is 473 nm, and emission with very high color purity is observed, with a chromaticity of The CIE chromaticity (x, y) was (0.116, 0.199), which was a slightly deep blue. , 100cd / m 2 The external quantum efficiency during light emission was 33.6%, which is extremely high. was made.

[0611] Example 9 <Configuration A: Device using compound (1-1) as a dopant and compound (5-102) as a host> The same procedure and configuration as in Example 8 were used except that the host was changed to compound (5-102). An EL device was obtained. 100 cd / m 2 The emission spectrum has a full width at half maximum (FWHM) of 21n The peak wavelength is 471 nm at 1000 nm, and emission with extremely high color purity is observed. The chromaticity is CIE chromaticity ( x, y) = (0.118, 0.137), which was a deep blue. 2 The external quantum efficiency during light emission was 28.0%, which was extremely high.

[0612] <Comparative Example 4> <Configuration A: Device using Comparative Compound 1 as a dopant and Compound (5-102) as a host> Example 8 except that the dopant was changed to comparative compound 1 and the host was changed to compound (5-102). An EL device was obtained using the same procedure and configuration as in Example 1. 2 Emission spectrum during emission The full width at half maximum (FWHM) was 28 nm and the peak wavelength was 465 nm, which was more color-correcting than Examples 8 and 9. The emission is of poor purity, and the chromaticity is CIE chromaticity (x,y) = (0.128,0.124). On the other hand, 100 cd / m 2 The external quantum efficiency during light emission was 15.4%. The quantum efficiency was lower than that of 9. [Table 7]

[0613] Example 10 <Configuration A: Device using compound (1-1) as a dopant and compound (5-102) as a host> ITO film formed by sputtering to a thickness of 200 nm was polished to 150 nm. Transparent support for a 26mm x 28mm x 0.7mm glass substrate (manufactured by Optoscience Co., Ltd.) This transparent support substrate was placed on a substrate holder of a commercially available deposition device (manufactured by Choshu Sangyo Co., Ltd.). The mixture was fixed, and HI, HT, EB, compound (5-102), compound (1-1), and ET were added. Tantalum evaporation boats containing LiF and aluminum, respectively. An aluminum evaporation boat was installed.

[0614] The following layers were formed in order on the ITO film of the transparent support substrate. -4 Pa The pressure was reduced to 100 MPa, and HI was first heated to deposit a film thickness of 40 nm. The EB is heated and evaporated to a thickness of 15 nm, forming three layers. Next, compound (5-102) and compound (1-1) were simultaneously added. The compound (5-102) was heated and evaporated to a thickness of 20 nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of the mixture (1-1) to the ET was approximately 99:1. The electron transport layer was formed by heating and vapor deposition to a thickness of 30 nm. The rate was 0.01 to 1 nm / sec. After that, the LiF was heated for 0. The aluminum was then heated to a thickness of 100 nm. The cathode was formed by vapor deposition so that the thickness of the aluminum film was 100 nm, and an organic EL device was obtained. The deposition rate was adjusted to 1 nm to 10 nm / sec.

[0615] The ITO electrode was used as the anode and the aluminum electrode as the cathode, and a DC voltage was applied to measure the brightness, chromaticity, and The external quantum efficiency was measured. 2 The emission spectrum at the time of emission is M) 17 nm, the peak wavelength is 470 nm, and emission with very high color purity is observed, with a chromaticity of C The IE chromaticity (x, y) was (0.119, 0.122), which was a deep blue. 0 cd / m 2 The external quantum efficiency during light emission was 30.1%, which was extremely high. . [Industrial Applicability]

[0616] The present invention provides novel polycyclic aromatic compounds, which can be used as materials for organic EL devices. Furthermore, the novel polycyclic aromatic compounds can be used as materials for organic electroluminescent devices. By using the organic EL element, an excellent organic EL element, a display device including the organic EL element, and a lighting device including the organic EL element etc. can be provided. [Explanation of symbols]

[0617] 100 Organic electroluminescent device 101 Substrate 102 Anode 103 Hole injection layer 104 Hole transport layer 105 Light-emitting layer 106 Electron transport layer 107 Electron injection layer 108 Cathode

Claims

1. A polycyclic aromatic compound represented by the following general formula (1): 【Chemistry 1】 (In the above formula (1), ring A and ring C are each independently a benzene ring or a naphthalene ring, and at least one hydrogen atom in these rings may be substituted with alkyl having 1 to 6 carbon atoms; Ring B and ring D are each independently an aryl ring having 6 to 12 carbon atoms or a heteroaryl ring having 2 to 15 carbon atoms, and at least one hydrogen atom in these rings may be substituted with an aryl ring having 6 to 12 carbon atoms, a heteroaryl ring having 2 to 15 carbon atoms, or an alkyl ring having 1 to 6 carbon atoms, and at least one hydrogen atom in these rings may be substituted with an aryl ring having 6 to 12 carbon atoms. Ring B is also preferably a ring having Y, X １ and X ２ and the ring D has a 5-membered or 6-membered ring that shares a bond with the fused bicyclic structure of the left side of the formula ３ and X ４ a 5- or 6-membered ring sharing a bond with the fused bicyclic structure of the right formula Y is B (boron), X １ , X ２ , X ３ and X ４ are each independently >O, >N-R, >S or >Se, R in the >N-R is an aryl having 6 to 30 carbon atoms or a heteroaryl having 2 to 15 carbon atoms, and at least one hydrogen atom in R is optionally substituted with an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 6 carbon atoms; The X １ R in >N-R is -O-, -S-, -C(-R) ２ or may be bonded to ring B via a single bond, ３ R in >N-R is -O-, -S-, -C(-R) ２ - or may be bonded to the ring D via a single bond, and the -C(-R) ２ R in - is hydrogen or alkyl having 1 to 6 carbon atoms; R １ and R ２ are each independently hydrogen, an aryl having 6 to 12 carbon atoms, or an alkyl having 1 to 6 carbon atoms; Z １ and Z ２ are each independently an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 20 carbon atoms, a diarylamino (wherein the aryl has 6 to 30 carbon atoms), an alkyl having 1 to 6 carbon atoms, or an aryloxy having 6 to 12 carbon atoms, in which at least one hydrogen atom is optionally substituted by an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 6 carbon atoms, Z １ and Z ２ are each independently bonded to a position represented by any one of the following formulae on the benzene ring or naphthalene ring, which is ring A or ring C, and 【Chemistry 2】 At least one hydrogen atom in the polycyclic aromatic compound represented by formula (1) may be substituted with cyano, halogen, or deuterium. However, polycyclic aromatic compounds excluding compounds represented by the following general formula (1'): 【Chemistry 1X】 (In the above formula (1'), ring A and ring C are each independently a benzene ring or a naphthalene ring, and at least one hydrogen atom in these rings may be substituted with alkyl having 1 to 6 carbon atoms; ring B and ring D are each independently an aryl ring having 6 to 12 carbon atoms or a heteroaryl ring having 2 to 15 carbon atoms, in which at least one hydrogen atom in these rings may be substituted by alkyl having 1 to 6 carbon atoms, ring B is a 5- or 6-membered ring that shares a bond with the fused bicyclic structure shown on the left of the above formula, which is composed of Y, X 1 and X 2, and ring D is a 5- or 6-membered ring that shares a bond with the fused bicyclic structure shown on the right of the above formula, which is composed of Y, X 3 and X 4; Y is B (boron), X 1 , X 2 , X 3 and X 4 each independently represent >O, >N—R, >S or >Se, in which R in the >N—R represents an aryl having 6 to 12 carbon atoms or a heteroaryl having 2 to 15 carbon atoms, and at least one hydrogen atom in R may be substituted with an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 6 carbon atoms; R 1 and R 2 are each independently hydrogen or alkyl having 1 to 6 carbon atoms; Z 1 and Z 2 are each independently an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 20 carbon atoms, a diarylamino (wherein the aryl has 6 to 12 carbon atoms), an alkyl having 1 to 6 carbon atoms, or an aryloxy having 6 to 12 carbon atoms, in which at least one hydrogen atom may be substituted by an alkyl having 1 to 6 carbon atoms; Z 1 and Z 2 are each independently bonded to a position represented by any of the following formulae on the benzene ring or naphthalene ring, which is ring A or ring C, and 【Chemical 2X】 At least one hydrogen atom in the compound represented by formula (1') may be substituted with cyano, halogen, or deuterium.

2. A polycyclic aromatic compound represented by the following general formula (2): 【Transformation 3】 (In the above formula (2), R ３ , R ４ , R ８ , and R ９ are each independently hydrogen or alkyl having 1 to 6 carbon atoms; R ５ , R ６ , R ７ , R １０ , R １１ and R １２ are each independently hydrogen, an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or an alkyl having 1 to 6 carbon atoms, in which at least one hydrogen atom may be substituted with an aryl having 6 to 12 carbon atoms; and R ５ ~R ７ and R １０ ~R １２ adjacent groups among these may be bonded to each other to form, together with ring b and / or ring d, an aryl ring having 9 to 12 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms, and at least one hydrogen atom in the formed ring may be substituted with an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and at least one hydrogen atom in these rings may be substituted with an aryl group having 6 to 12 carbon atoms, Y is B (boron), X １ , X ２ , X ３ and X ４ are each independently >O, >N—R, >S, or >Se, and R in the >N—R is an aryl having 6 to 30 carbon atoms or a heteroaryl having 2 to 15 carbon atoms, and at least one hydrogen atom in R is optionally substituted by an alkyl having 1 to 6 carbon atoms; The X １ R in >N-R is -O-, -S-, -C(-R) ２ or may be bonded to the ring b via a single bond, ３ R in >N-R is -O-, -S-, -C(-R) ２ or may be bonded to the d ring via a single bond, and the -C(-R) ２ R in - is hydrogen or alkyl having 1 to 6 carbon atoms; R １ and R ２ are each independently hydrogen, an aryl having 6 to 12 carbon atoms, or an alkyl having 1 to 6 carbon atoms; Z １ and Z ２ are each independently an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 20 carbon atoms, a diarylamino (wherein the aryl has 6 to 30 carbon atoms), an alkyl having 1 to 6 carbon atoms, or an aryloxy having 6 to 12 carbon atoms, in which at least one hydrogen atom may be substituted by an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 6 carbon atoms, and At least one hydrogen atom in the polycyclic aromatic compound represented by formula (2) may be substituted with cyano, halogen, or deuterium. However, polycyclic aromatic compounds excluding compounds represented by the following general formula (2'): 【3X】 (In the above formula (2'), R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen or alkyl having 1 to 6 carbon atoms, and adjacent groups among R 5 to R 7 and R 10 to R 12 may be bonded to each other to form an aryl ring having 9 to 12 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with ring b and / or ring d, and at least one hydrogen atom in the formed ring may be substituted with alkyl having 1 to 6 carbon atoms; Y is B (boron), X 1 , X 2 , X 3 and X 4 each independently represent >O, >N—R, >S or >Se, and R in the >N—R represents an aryl having 6 to 12 carbon atoms or a heteroaryl having 2 to 15 carbon atoms; R 1 and R 2 are each independently hydrogen or alkyl having 1 to 6 carbon atoms; Z 1 and Z 2 are each independently an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 20 carbon atoms, a diarylamino (wherein the aryl has 6 to 12 carbon atoms), an alkyl having 1 to 6 carbon atoms, or an aryloxy having 6 to 12 carbon atoms, in which at least one hydrogen atom may be substituted with an alkyl having 1 to 6 carbon atoms, and At least one hydrogen atom in the compound represented by formula (2') may be substituted with cyano, halogen, or deuterium.

3. In formula (2), R ３ , R ４ , R ８ , and R ９ are each independently hydrogen or alkyl having 1 to 6 carbon atoms; R ５ , R ６ , R ７ , R １０ , R １１ and R １２ are each independently hydrogen, an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or an alkyl having 1 to 6 carbon atoms, in which at least one hydrogen atom may be substituted with an aryl having 6 to 12 carbon atoms; and R ５ ~R ７ and R １０ ~R １２ adjacent groups among these may be bonded to each other to form, together with ring b and / or ring d, an aryl ring having 9 to 12 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms, and at least one hydrogen atom in the formed ring may be substituted with an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and at least one hydrogen atom in these rings may be substituted with an aryl group having 6 to 12 carbon atoms, Y is B (boron), X １ , X ２ , X ３ and X ４ are each independently >O or >N—R, R of the >N—R is an aryl having 6 to 30 carbon atoms, and at least one hydrogen atom in R may be substituted by an alkyl having 1 to 6 carbon atoms; The X １ R in >N-R may be bonded to the ring b via a single bond, and ３ R in >N—R may be bonded to the d ring via a single bond, R １ and R ２ are each independently hydrogen, an aryl having 6 to 12 carbon atoms, or an alkyl having 1 to 6 carbon atoms; Z １ and Z ２ are each independently an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 20 carbon atoms, a diarylamino (wherein the aryl has 6 to 30 carbon atoms), an alkyl having 1 to 6 carbon atoms, or an aryloxy having 6 to 12 carbon atoms, in which at least one hydrogen atom may be substituted by an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 6 carbon atoms, and At least one hydrogen atom in the polycyclic aromatic compound represented by formula (2) may be substituted with cyano, halogen, or deuterium. The polycyclic aromatic compound according to claim 2.

4. In formula (2), R ３ , R ４ , R ８ , and R ９ are each independently hydrogen or alkyl having 1 to 6 carbon atoms; R ５ , R ６ , R ７ , R １０ , R １１ and R １２ are each independently a hydrogen atom, an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or an alkyl having 1 to 6 carbon atoms, in which at least one hydrogen atom is optionally substituted by an aryl having 6 to 12 carbon atoms; Y is B (boron), X １ , X ２ , X ３ and X ４ are each independently >O or >N—R, R of the >N—R is an aryl having 6 to 30 carbon atoms, and at least one hydrogen atom in R may be substituted by an alkyl having 1 to 6 carbon atoms; R １ and R ２ are each independently hydrogen, an aryl having 6 to 12 carbon atoms, or an alkyl having 1 to 6 carbon atoms; Z １ and Z ２ are each independently an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, a diarylamino (wherein the aryl has 6 to 30 carbon atoms), an alkyl having 1 to 6 carbon atoms, or an aryloxy having 6 to 12 carbon atoms, in which at least one hydrogen atom may be substituted by an aryl having 6 to 12 carbon atoms or an alkyl having 1 to 6 carbon atoms, and At least one hydrogen atom in the polycyclic aromatic compound represented by formula (2) may be substituted with cyano, halogen, or deuterium. The polycyclic aromatic compound according to claim 2.

5. A material for organic devices, comprising the polycyclic aromatic compound according to any one of claims 1 to 4.

6. The material for an organic device according to claim 5 , wherein the material for an organic device is a material for an organic electroluminescent element, a material for an organic field effect transistor, or a material for an organic thin-film solar cell.

7. The material for an organic device according to claim 6 , wherein the material for an organic electroluminescent device is a material for a light-emitting layer.

8. A composition for forming a light-emitting layer for forming a light-emitting layer of an organic electroluminescent device by coating, comprising: As a first component, at least one polycyclic aromatic compound according to any one of claims 1 to 4; as a second component, at least one host material; as a third component, at least one organic solvent; A composition for forming a light-emitting layer comprising:

9. 8. An organic electroluminescent device comprising a pair of electrodes consisting of an anode and a cathode, and a light-emitting layer disposed between the pair of electrodes and containing the material for a light-emitting layer according to claim 7.

10. 10. An organic electroluminescent device comprising a pair of electrodes consisting of an anode and a cathode, and a light-emitting layer disposed between the pair of electrodes and formed by applying and drying the composition for forming a light-emitting layer according to claim 8.

11. The organic electroluminescent device according to claim 9 or 10, wherein the light-emitting layer further contains a compound represented by the following general formula (3) and / or a compound represented by the following general formula (4): 【Transformation 8】 (In the above formula (3), L １ is an arylene having 6 to 24 carbon atoms, In the above formula (4), L ２ and L ３ are each independently an aryl having 6 to 30 carbon atoms or a heteroaryl having 2 to 30 carbon atoms, At least one hydrogen atom in the compounds represented by the above formulas may be substituted with alkyl having 1 to 6 carbon atoms, cyano, halogen, or deuterium.

12. The organic electroluminescent device according to any one of claims 9 to 11, wherein the light-emitting layer further contains a compound represented by the following general formula (5): 【Chemistry 9】 (In the above formula (5), R １ ~R １１ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, or alkyl, in which at least one hydrogen may be further substituted with aryl, heteroaryl, diarylamino, or alkyl; R １ ~R １１ adjacent groups among At least one hydrogen atom in the compound represented by formula (5) may be independently substituted with a halogen atom or deuterium atom.

13. 13. The organic electroluminescent device according to claim 9, further comprising an electron transport layer and / or an electron injection layer disposed between the cathode and the light-emitting layer, wherein at least one of the electron transport layer and the electron injection layer contains at least one selected from the group consisting of borane derivatives, pyridine derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol-based metal complexes.

14. 14. The organic electroluminescent device according to claim 13, wherein the electron transport layer and / or the electron injection layer further contains at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals.

15. A display device or a lighting device comprising the organic electroluminescent device according to any one of claims 9 to 14.

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