Polycyclic aromatic compound

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, and an organic electroluminescent device and an organic field-effect transistor using the same. Used in organic devices such as organic 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 designed to be energy-efficient and thin. Various research has been conducted, and organic electroluminescent devices made of organic materials can be easily made lighter and larger. In particular, the luminescence properties of blue, one of the three primary colors of light, have been investigated. Development of organic materials with charge transport capabilities (such as holes and electrons) that can become semiconductors or superconductors Regarding the development of organic materials with the potential to It has been actively researched to date.

[0003] The organic EL element is composed of a pair of electrodes consisting of an anode and a cathode, and a light-emitting diode (LED) disposed between the pair of electrodes. The layer containing the organic compound has a structure consisting of one or more layers. These 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 suitable organic materials have been developed for these layers.

[0004] As materials for the light-emitting layer, for example, benzofluorene-based compounds have been developed (International (Publication No. 2004 / 061047) As the hole transport material, for example, triphenylamine Compounds based on the above have been developed (JP Patent Publication 2001-172232 A). For example, anthracene-based compounds have been developed (JP Patent Publication No. 2005-170911).

[0005] In recent years, triphenylamine has been used as a material in organic electroluminescence (EL) elements and organic thin-film solar cells. Materials that improve amine derivatives have also been reported (WO 2012 / 118164). The 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 improved planarity due to the linking of aromatic rings constituting the amine. In this document, for example, the charge transport properties of an NO-linked compound (compound 1 on page 63) are However, there is no description of the production method of materials other than NO-linked compounds. In addition, the electronic state of the entire compound differs depending on the linked elements, so 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 larger conjugated structures can emit shorter wavelength phosphorescence, resulting in blue light. In addition, it is useful as an electron transport material or hole transport material sandwiching the light emitting layer. Therefore, there is a demand for compounds having novel conjugated structures with large T1.

[0006] The host material for organic electroluminescence devices is generally a compound that contains existing aromatic rings such as benzene and carbazole. It is a molecule in which multiple units are linked together by single bonds or phosphorus or silicon atoms. By connecting many small aromatic rings, the large HOMO-LUM 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 electroluminescence (EL) devices using 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 triplet excited state (T1) SOMO1 and SOM 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 have a high redox potential. The stability was insufficient, so molecules that linked existing aromatic rings were used as the host material. On the other hand, polycyclic aromatic compounds with extended π-conjugated systems generally have Although the redox stability is excellent, the HOMO-LUMO gap (band gap in thin films) Chapping Eg and triplet excitation energy (E T ) is low, so it is considered unsuitable as a host material. It has come.

[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 multiple aromatic rings are condensed has been carried out. The document discloses a very large number of compounds, among which the luminescence properties, etc. It is beneficial to consider compounds with excellent organic electroluminescence properties.

[0008] In addition, as a method for forming the organic layers constituting the organic EL element, in addition to the vacuum deposition method, wet film formation is also available. For the development of materials for the wet film formation method, in particular, hole injection layers, hole transport layers, 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. In addition, the ink used to form the light-emitting layer Development of inks for red and green emitting layers is progressing toward improving the characteristics, but inks for blue emitting layers are not yet available. Ink is generally made of polycyclic aromatic compounds such as anthracene and styryl derivatives. Although the development of compositions using conductors, etc. has been carried out, they have not yet reached a level of practical properties. However, currently, it has not been possible to develop ink for the blue light-emitting layer with high color purity. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication No. 2004 / 061047 [Patent Document 2] JP 2001-172232 A [Patent Document 3] JP 2005-170911 A [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] JP 2006-045503 A [Patent Document 10] JP 2013-168411 A [Patent Document 11] JP 2013-247179 A [Patent Document 12] US Patent 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, the light-emitting properties of organic EL devices are being improved, and the selection of organic EL materials such as light-emitting layer materials is being improved. 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 intensive research to solve the above problems, the present inventors have found that a boron atom and a nitrogen atom or It is a polycyclic aromatic compound that has a specific structure, in which multiple aromatic rings are linked by oxygen atoms. By using such a compound, it has been found that an excellent organic EL device can be obtained, and the present invention has been completed. That is, the present invention relates to the following polycyclic aromatic compounds, and further to the following polycyclic aromatic compounds. The present invention provides 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 the rings may be replaced; 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 >NR is heteroaryl or optionally substituted alkyl. It may be bonded to the A ring, B ring, C ring and / or D ring 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, 2 aryl, heteroaryl or diarylamino having 2 to 15 carbon atoms (wherein aryl is an aryl having 6 to 12 carbon atoms; Z 1 and Z 2 each independently represents an optionally substituted aryl, optionally substituted heteroaryl, optionally substituted diarylamino, optionally substituted 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, 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, at least one hydrogen in these rings is selected from 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 are preferably Y, X 1 and X 2 The fused two-ring structure shown on the left in the above formula is The rings C and D are connected to each other by Y and X. 3 and X 4 mosquito and a 5- or 6-membered ring sharing a bond with the fused bicyclic structure of the above formula (R), Y is B (boron), X 1 , X 2 , X 3 and X 4 are each independently >O, >NR, >S or >S e, R of the >NR is aryl, heteroaryl or alkyl, and R At least one hydrogen atom in the formula (I) is selected from the group consisting of aryl, heteroaryl, diarylamino, diheteroaryl, and diphenyl. arylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy oxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio or may be substituted with alkyl-substituted silyl, and R in >NR is -O-, - and connected to ring A, ring B, ring C and / or ring D via S-, -C(-R)2- or a single bond. R of -C(-R)2- may be hydrogen or alkyl; R 1 and R 2 are each independently hydrogen, alkyl having 1 to 6 carbon atoms, 2 aryl, heteroaryl or diarylamino having 2 to 15 carbon atoms (wherein aryl is an aryl having 6 to 12 carbon atoms; Z 1 and Z 2 each independently represents an aryl, heteroaryl, or diarylamino group; , diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl , aryloxy, heteroaryloxy, arylthio or heteroarylthio. At least one hydrogen atom in these is an aryl, heteroaryl, diaryla 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 C ring through a single bond, and R in the -C(-R)2- is hydrogen or a Rukill, and, At least one hydrogen atom in the compound represented by formula (1) is cyano, halogen or heavy. may be substituted with hydrogen; Item 1. The polycyclic aromatic compound according to item 1.

[0014] Section 3. Item 3. 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 12Each Each independently is 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 an aryl, heteroaryl or or alkyl; and R 5 ~R 7 and R 10 ~R 12 Of Adjacent groups are bonded to each other to form an aryl or heteroaryl ring together with ring b and / or ring d. At least one hydrogen atom in the ring formed may be substituted with an aryl ring. Heteroaryl, diarylamino, diheteroarylamino, arylheteroaryl Amino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy arylthio, heteroarylthio or alkyl-substituted silyl. At least one hydrogen atom in these is an aryl, heteroaryl or alkyl group. 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 R of the >NR is an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, R in >NR is -O-, -S -, -C(-R)2- or a single bond to said 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 is an aryl of 12 to 12; Z 1 and Z 2 each independently represents an aryl, heteroaryl, or diarylamino group; , diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl , aryloxy, heteroaryloxy, arylthio or heteroarylthio. At least one hydrogen atom in these is selected from the group consisting of aryl, heteroaryl, alkyl, and aryl. may be substituted with alkyl-substituted silyl; Z 1 -O-, -S-, -C(-R) may be bonded to the a ring via a 2- or single bond; Z 2 -O-, -S-, -C(- R)2- or a single bond may be bonded to the ring c, and R of the -C(-R)2- is hydrogen. or an alkyl group having 1 to 6 carbon atoms, 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 Each Each independently is selected from hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diaryl, Arylamino (wherein aryl is aryl having 6 to 12 carbon atoms), alkyl having 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 an aryl group having 6 to 12 carbon atoms or an aryl group having 1 to 6 carbon atoms. It 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 ring members may be formed, and at least One hydrogen is replaced by 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 is an aryl of 12 to 12; Z 1 and Z 2 each independently represents an aryl having 6 to 30 carbon atoms, Heteroaryl, diarylamino (wherein 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 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. may be 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 Each each independently represents hydrogen, an aryl having 6 to 10 carbon atoms, or an 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 is an aryl of 12 to 12; Z 1 and Z 2 each independently represents an aryl having 6 to 16 carbon atoms, Heteroaryl, diarylamino (wherein aryl has 6 to 10 carbon atoms), 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. may be substituted with hydrogen; Item 3. The polycyclic aromatic compound according to item 3.

[0017] Section 6. Item 2. The polycyclic aromatic compound according to item 1, 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 group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Yes, R 100 each independently represents an aryl having 6 to 10 carbon atoms, a carbazolyl, or a diaryl Arylamino (wherein aryl is aryl having 6 to 10 carbon atoms), alkyl having 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 an alkyl having 1 to 6 carbon atoms, and the carbazolyl may be substituted with a carbon atom. 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, comprising 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 according to 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 the above compound.

[0022] Section 11. A pair of electrodes consisting of an anode and a cathode, and a generator according to 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 electroluminescence 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 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 the preceding claims. [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 each other to form an aryl ring together with the a, b or c ring. A ring or a heteroaryl ring may be formed, and at least one of the rings formed may be The hydrogen of is an aryl, heteroaryl, diarylamino, diheteroarylamino, a The alkyl group may be substituted with aryl, heteroaryl, amino or alkyl. At least one hydrogen may further be an aryl, heteroaryl, diarylamino or alkyl group. may be substituted with At least one hydrogen atom in the compound represented by formula (5) is independently a 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 borane derivative, a pyridine derivative, a fluorine derivative, or a fluorine derivative. 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, further 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 further comprises an alkali metal, an alkaline earth metal, metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metals oxides of rare earth metals, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides genides, organic complexes of alkali metals, organic complexes of alkaline earth metals and 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. . Effect 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 can be used to further improve the organic electroluminescence properties such as light emission properties, and can also be used as materials for the light-emitting layer. This will increase the options for organic EL materials such as these. [Brief description of the drawings]

[0030] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an organic EL element according to an embodiment of the present invention. [Diagram 2] The absorption, fluorescence, and phosphorescence spectra of compound (1-1). [Diagram 3] The absorption, fluorescence, and phosphorescence spectra of compound (1-201). [Figure 4] 4 shows the absorption, fluorescence, and phosphorescence spectra of compound (1-101). [Diagram 5] 4 shows the absorption, fluorescence and phosphorescence spectra of compound (1-9). [Figure 6] FIG. 1 is a diagram showing the organic electroluminescence characteristics (luminance) of compound (1-1). [Figure 7] FIG. 2 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 PREFERRED EMBODIMENTS

[0031] 1. Polycyclic aromatic compound 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 electroluminescence (EL) displays include fluorescent materials, phosphorescent materials, and thermally activated Three types of delayed fluorescence (TADF) materials are used, but the fluorescent materials have low luminous efficiency. On the other hand, phosphorescent and TADF materials have a luminous efficiency of 1 In some cases, the color purity reaches 0.00%, but in all cases, the color purity is low (the emission spectrum is wide). In displays, the three primary colors of light, red, green, and blue, are mixed together. However, if the color purity of each is low, some colors cannot be reproduced. This causes the image quality of the display to deteriorate significantly. By removing unwanted colors from the emission spectrum using optical filters, color purity is increased. Therefore, the original spectral width is If the width is large, the removal rate increases, so even if the luminous efficiency is high, the actual efficiency is significantly lower. For example, the half-width of the blue emission spectrum of a commercially available smartphone is approximately 20 The half-width of typical fluorescent materials is about 40 to 60 nm, while that of typical phosphorescent materials is about 25 nm. For fluorescent materials, the wavelength 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 was a need to develop a luminescent material that combined both high efficiency and color purity.

[0033] In general, TADF materials consist of electron-donating substituents called donors and acceptors. By using electron-accepting substituents that can 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 or acceptor increases the structural relaxation in the excited state (in some molecules, Since the stable structures of the ground and excited states are different, external stimuli can cause the ground state to change 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 WO 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 set to the three carbons (black circles) on the six-carbon benzene ring, and the remaining The LUMO is successfully localized on the three carbons (white circles) of the Due to the crossover between the two, the luminescence efficiency of the compound reaches up to 100%. The boron and nitrogen in 401) not only localize the HOMO and LUMO, but also The condensation of the Zene rings 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 that of fluorescent materials with high color purity currently in practical use. The purity is shown. In addition, in a dimer compound such as formula (1-422), two boron and The two nitrogen atoms are attached to the central benzene ring, forming multiple rings. The resonance effect is enhanced, 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. The efficiency of the light-emitting device was satisfactory, probably due to the intermolecular stacking induced by the The issue also arose that this was not the case.

[0036] As a result of intensive research, we have been trying to introduce substituents at appropriate positions to adjust the multiple resonance effect. As a result, the emission wavelength can be shortened and high device efficiency can be achieved. The polycyclic aromatic compound represented by formula (1) is a compound having two Z (Z 1 and Z 2 ) as Z. The electron-withdrawing or electron-donating functional groups in all the rings allow the entire molecule to be coupled through the resonance of the A and C rings. Influence the resonance structure and / or multiple resonance effects of the molecule. For example, by 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 results in the molecule existing on the same plane. The ratio of structures is reduced, so that the stacking between molecules can be reduced. 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 can increase the efficiency of the device. The effect of is not limited to the above principle.

[0037] In the general formula (1), the ring A, the ring B, the ring C and the ring D are each independently an aryl ring. or a heteroaryl ring, and at least one hydrogen atom in the ring is replaced by a substituent. The substituents are substituted or unsubstituted aryl, substituted or unsubstituted Heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroaryl arylamino, substituted or unsubstituted arylheteroarylamino (aryl and heteroaryl aryl amino group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted aryloxy, is unsubstituted heteroaryloxy, substituted or unsubstituted arylthio, substituted or unsubstituted Preferred are heteroarylthio and alkyl-substituted silyl. Substituents, when present, 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 " The fused two-ring structure of the above formula (1) is composed of the following two rings. It is preferred that the aryl group has a 5- or 6-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 and "X 2 " means a structure in which two saturated hydrocarbon rings are condensed together. The same applies to the fused bicyclic structure on the right side of the general formula (1). The bond-sharing six-membered ring refers to a fused two-ring structure, for example, 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, this six-membered ring is condensed with another ring to form ring A. In other words, the 6-membered (A-ring) aryl group mentioned here is "Heteroaryl ring or heteroaryl ring" refers to a 6-membered ring constituting all or part of ring A that is fused This means that the ring is fused to a two-ring structure. "B ring (b ring)", "C ring (c ring)", "D ring" 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 the formula (1) in which "rings A to D having 6 members" are selected as rings A to D. For this reason, each ring in the 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 YobiR 12each independently represents 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 an aryl It 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 on the d ring 10 ~R 1 2 Adjacent groups among these may be bonded to each other to form an aryl ring or a hexacyclic ring together with ring b and / or ring d. A heteroaryl ring may be formed, and at least one hydrogen in the ring formed is 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 a Therefore, the compound represented by the general formula (2) may be substituted with ring b and Depending on the mutual bonding form of the substituents in the rings d and d, the compounds can be formed as shown in the following formula (2-1). The ring structure constituting the compound changes. The ring B' and ring D' in the formula (2-1) are represented by the general formula (1 In addition, 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 B′ ring and the D′ ring in the above formula (2-1) are each independently a substituent R 5 ~R 7 and R 10 ~R 12 Adjacent groups among The aryl or heteroaryl ring formed with the ring (the b or d ring may have 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 adjacent groups on the same ring. 1 is concatenated It may be bonded to the A ring (a ring) through 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 has 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 listed below as a specific compound. (1-5) corresponds to the compound represented by the formula (1-5). That is, for example, in the b ring (or d ring), For some benzene rings, benzene rings, for others, indole rings, pyrrole rings, benzofurano rings It has a ring B' (or ring D') formed by condensation of a benzothiophene ring or a benzothiophene ring. The compound is a fused ring B' (or fused ring D') formed by the reaction. 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, and R of >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-. In addition, R in the above-mentioned "-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 to the ring A, The definition of "bonded to ring B, ring C and / or ring D" means ">N- R of R is -O-, -S-, -C(-R)2- or a single bond to the ring a, ring b or ring c. and / or bonded to the d ring."

[0049] This provision 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) of the benzene ring in 1 (or X 3 ) to be included. The compound has 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 as a specific compound described later. The fused ring B' (or fused ring D') formed corresponds to the compound, for example, a carbazole. and others include a phenoxazine ring, a phenothiazine ring, or an acridine ring. The definitions of each symbol in formula (2-3) are the same as those in general formula (2).

[0050] [ka]

[0051] In formula (2-3), X 1 Or X 3 The ring structure shown is incorporated into fused rings B' and D'. However, X 2 Or X 4 Similarly, R in >NR as a ring can be bonded to the a 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 are in the a and c rings. 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 any of a variety of aryl and heteroaryl rings. Substituent Z on the ring 1 and Z 2 The substitution position of is not limited, but Y is preferably a bond as in the general formula (2). It is preferable to substitute at a position relatively far from the position where the nucleotide matches, and it is preferable to substitute at the furthest position. For example, when the A ring is a naphthalene ring or a fluorene ring, , this Z 1 (and Z2 Preferred substitution positions of 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 diaryl or diarylamino (wherein aryl is an aryl having 6 to 12 carbon atoms).

[0054] Z in general formula (1) or general formula (2) 1 and Z 2 are independent of each other, Aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroaryl arylamino, alkyl, aryloxy, heteroaryloxy, arylthio or heteroarylthio, in which at least one hydrogen is an aryl, hetero Aryl, diarylamino, alkyl, cycloalkyl, alkoxy, aryloxy or alkyl-substituted silyl; Z 1 is a linking group or a single bond, 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 ring" which is ring A, ring B, ring C and ring 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 preferable. 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 among these are bonded to each other to form an aryl group together with the b ring and / or the d ring. The b ring (or d ring) corresponds to a benzene ring with six carbon atoms. Therefore, the total number of carbon atoms in the fused ring formed by condensing the 5-membered ring is 9, which is the lower limit of the number of carbon atoms. Z 1 is bonded to the A ring (a ring) via a linking group or single bond to form an aryl ring, or Z 2 Gas The same applies to an aryl ring formed by bonding to a 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 condensed bicyclic ring, a naphthalene ring, a tricyclic 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 condensed tetracyclic ring system, pyrene ring, naphthacene ring, a perylene ring which is a condensed five-ring system, a pentacene ring, and the like.

[0057] Examples of the "heteroaryl ring" which is the ring A, ring B, ring C and ring D of the general formula (1) include Examples of the heteroaryl 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 preferable, and a heteroaryl ring having 2 to 15 carbon atoms is more preferable. A heteroaryl ring is more preferred, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferred. In addition, examples of the "heteroaryl ring" include ring-constituting atoms such as oxygen, sulfur, and 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 the above are bonded to each other to form a heterocycle together with the b ring and / or the d ring. Also, the b ring (or the d ring) is already composed of a benzene ring having six carbon atoms. Therefore, the total number of carbon atoms in the fused ring formed by condensing the 5-membered ring to this 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 Same here.

[0058] Specific examples of the "heteroaryl ring" include a pyrrole ring, an oxazole ring, and an isoaryl 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 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, pteridinyl ring ring, carbazole ring, acridine ring, phenoxathiin ring, phenoxazine ring, phenon Thiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran 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-mentioned "aryl ring" or "heteroaryl ring" is 1, substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl" aryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteroaryl arylamino”, substituted or unsubstituted “arylheteroarylamino”, substituted or unsubstituted “arylheteroarylamino”, substituted or unsubstituted "alkyl", substituted or unsubstituted "cycloalkyl", substituted or unsubstituted "arylene" "aryloxy", substituted or unsubstituted "heteroaryloxy", "aryloxy", substituted or unsubstituted "arylthio", substituted or unsubstituted "heteroaryl The first substituent may be substituted with aryl, arylthio, or alkyl-substituted silyl. "aryl", "heteroaryl", and "diarylamino" Heteroaryl in "arylamino" and aryl and heteroaryl in "arylheteroarylamino" The aryl in "aryloxy" and the heteroaryl in "heteroaryloxy" The aryl, aryl of "arylthio", and heteroaryl of "heteroarylthio" are listed above. Examples of the monovalent "aryl ring" or "heteroaryl ring" include the above-mentioned "aryl ring" or "heteroaryl ring".

[0060] The "alkyl" as the first substituent 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. 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. More preferably, the alkyl group has from 1 to 6 carbon atoms (branched alkyl group having from 3 to 6 carbon atoms). 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 ethyl, 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] The "cycloalkyl" as the first substituent is, for example, a 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 Examples of the alkyl groups include dialkyl aryl, ...

[0064] Furthermore, the "alkoxy" as the first substituent is, for example, a straight-chain or alkoxy group 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. 1 to 4 branched alkoxy) is particularly preferred.

[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 is, for example, trialkyl-substituted silyl. The alkyl to be substituted is preferably the same as the first substituent "alkyl" described above. You can refer to the explanation.

[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" "aryloxy", substituted or unsubstituted "arylthio", substituted or unsubstituted "heteroaryl "Reilthio" is described as substituted or unsubstituted, and at least One hydrogen may be replaced by a second substituent, such as, for example, , aryl, heteroaryl or alkyl, specific examples of which are as described above in " A monovalent radical of an "aryl ring" or "heteroaryl ring", and an "aryl" as a first substituent The explanation of "aryl" can be referred to. In addition, aryl and heteroaryl as the second substituent The alkyl groups include those in which at least one hydrogen atom is an aryl, such as phenyl (examples include Groups substituted with alkyl (specific examples of which are the groups listed above) or methyl (specific examples of which are the groups listed above) may 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 at the 9-position is an aryl group such as phenyl. Carbazolyl groups substituted with alkyl groups such as aryl and methyl are also suitable as heteroaryl groups as the second substituent. 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, heteroaryl of heteroaryloxy Examples of the heteroaryl in the heteroarylthio group include: Examples of the monovalent "aryl ring" or "heteroaryl ring" described in the general formula (1) include Also, R 3 ~R 12 In the formula (I), the alkyl, cycloalkyl, alkoxy or alkyl The alkyl-substituted silyl includes the alkyl group as the first substituent in the above description of the general formula (1). Please explain the meaning of "alkyl", "cycloalkyl", "alkoxy" or "alkyl-substituted silyl". In addition, aryl, heteroaryl, and aryl groups as substituents for these groups can be used. The same is true for aryl or alkyl. 5 ~R 7 and R 10 ~R 12 Adjacent of The groups bonded to each other to form an aryl ring or a heteroaryl ring together with the b ring or the d ring In the case where the substituents on these rings are aryl, heteroaryl, diarylamino, diaryl Heteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, a Alkoxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio or alkyl-substituted silyl, and further substituted aryl, heteroaryl or The same is true for alkyl.

[0069] X in general formula (1) 1 , X 2 , X 3 and X 4 In the formula, R is aryl, hetero aryl or alkyl, in which at least one hydrogen is aryl, Diaryl, diarylamino, diheteroarylamino, arylheteroarylamino No, 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 with 2 to 15 carbon atoms (e.g., and alkyl having 1 to 4 carbon atoms (e.g., 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 having 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 an 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 heptaryloxy. aryl, heteroaryl, diaryl, and arylthio as substituents on these; arylamino, alkyl, cycloalkyl, alkoxy, aryloxy or alkyl group The substituted silyl groups are the same as those described above for "aryl", "heteroaryl" and "diarylamino". ", "diheteroarylamino", "arylheteroarylamino", "aryloxy "Heteroaryloxy", "arylthio", "heteroarylthio", "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 a part of the hydrogen atoms in the compound represented by the general formula (1) or (2) It may be substituted with cyano, halogen or deuterium. For example, in formula (1), A ring, B ring, C ring, D ring (A to D rings are aryl or heteroaryl rings), A to D rings The substituent, X 1 ~X 4 In NR, R (=aryl, heteroaryl, alkyl) ), R 1 , R 2 , Z 1 and Z 2 Hydrogen in 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. The halogen is fluorine, chlorine or deuterium. , 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 those 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 group having 1 to 6 carbon atoms or an aryl group 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 the compound include those 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 each independently represents an aryl having 6 to 10 carbon atoms, a carbazolyl, or a diaryl Arylamino (wherein aryl is aryl having 6 to 10 carbon atoms), alkyl having 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", and "aryloxy" in "aryl" The aryl may be substituted with an alkyl group 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 The alkyl group is preferably a group represented by the following formula, and 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 tolyl, 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. More 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 for the N binding site are Preferred are structures having a substituent at the position, specifically, structures 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] From the viewpoint of blue emission and / or high luminous efficiency, it is desirable to use a compound having many N-aryl groups. and / or a structure having many carbazolyl structures, 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 to have more N atoms bonded to the central aromatic ring. 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 the compounds represented by the structural formula starting with (1-1), In the structural formula, the t-butyl group is replaced by a methyl group. 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 having 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 water Replaced by the element R 1 Compounds with the structural formula R 1 The phenyl group is a methyl group. Replaced by R 2 A compound having the structural formula: 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 by a methyl group. For example, the structural formulas of formula (1-2) and formula (1-6) are as follows: In the formulas, "Me" stands for methyl group, t "Bu" is a t-butyl group, and "Ph" is a phenyl group. It is a nyl 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) are basically compounds having the respective ring structures The intermediate is produced by bonding the rings together (first reaction), and then each ring structure is bonded to the holocarbon. The final product can be produced by bonding with an iodine atom (Reaction 2). For example, let us consider the common etherification reactions such as nucleophilic substitution reactions, 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 reactions, 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 link the ring structures together as shown in the following scheme (1). This is a reaction that introduces an ion. 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. The second reaction can be carried out in a tandem boron-Friedel-Crafts reaction to obtain the desired product. In the above reaction, a Lewis acid such as aluminum trichloride may be added to promote the reaction. [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 added to 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 product to be obtained even in cases where ortho-metallation is not possible due to the influence of substituents. It is useful for synthesizing 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. Y is boron, X 1 , X 2 , X 3 and X 4 However, independently, >O, >N- Polycyclic aromatic compounds can be synthesized where R, >S or >Se.

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

[0213] The orthometalation reagent used in the above scheme is, for example, methyllithium, n- Alkyl lithium such as butyl lithium, sec-butyl lithium, and t-butyl lithium , lithium diisopropylamide, lithium tetramethylpiperidide, lithium hexame Examples of organic alkali compounds include potassium hexamethyldisilazide and potassium hexamethyldisilazide. do.

[0214] The metal exchange reagent for metal-Y (boron) used in the above scheme is 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 etc.

[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-Dimethyltoluidin 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 are 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, trisodium nitrate, and trisodium nitrate. 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. In this case, the use of a Bronsted base to capture the acid is effective. When boron alkoxides and boron hydrides are used, the aromatic electrophilic substitution reaction proceeds. In order to produce amines and alcohols, Bronsted bases are often used. It is not necessary to use a Lewis acid that promotes the removal of amino and alkoxy groups because they have low ability to be removed. The use of sulphuric acid is effective.

[0218] In addition, the polycyclic aromatic compound represented by the general formula (1) or (2) contains at least one Also included are compounds in which hydrogen atoms are replaced by cyano, halogen, or deuterium. 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 Thin-film solar cells and the like.

[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 electroluminescence 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 is provided on the light emitting layer 105, and a The device includes an electron injection layer 107 and a cathode 108 provided on the electron injection layer 107 .

[0222] The organic electroluminescence 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, and a hole transport layer 105 formed on the hole transport layer 104. 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 structure is composed 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 be made up of a single layer or multiple layers.

[0224] The layer configuration of the organic electroluminescence device may be the above-mentioned "substrate / anode / hole injection layer / In addition to the configuration of "hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode," there is also the configuration of "substrate / anode / Hole transport layer / Emitting layer / Electron transport layer / Electron injection layer / Cathode", "Substrate / Anode / Hole injection layer / "Emitting layer / electron transport layer / electron injection layer / cathode" or "substrate / anode / hole injection layer / hole transport layer / 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 injection layer" "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 a configuration of "substrate / anode / light-emitting layer / electron injection layer / cathode."

[0225] <Substrate for organic electroluminescence device> The substrate 101 is a support for the organic electroluminescent device 100 and is usually made of quartz, glass, metal, or 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, etc. are used. A transparent synthetic resin plate such as acrylate, polycarbonate, or polysulfone is preferred. For glass substrates, soda lime glass or non-alkali 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 fewer ions dissolved from the glass, the better. is preferred, but soda lime glass with a barrier coating such as SiO2 is also commercially available. In addition, the substrate 101 is provided with a material having a high 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 of the substrate. A synthetic resin plate, film or sheet having a low gas barrier property is used as the substrate 101. In such cases, 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.) etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (I TO), indium zinc oxide (IZO), metal halides (copper iodide, etc.), Examples include copper sulfide, carbon black, ITO glass, and Nesa glass. Organic compounds and Examples of such polythiophenes include poly(3-methylthiophene), polypyrrole, Conductive polymers such as polyaniline are also included. Other examples include the anode of an organic electroluminescent device. 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 to light the light emitting element. However, from the viewpoint of power consumption of the light-emitting element, it is desirable to have a low resistance. For example, 300 Ω / ITO substrates with a resistance of 10Ω / □ or less can function as element electrodes, but currently, substrates with a resistance of about 10Ω / □ are required. For example, 100 to 5Ω / □, preferably 50 to 5Ω / □, can be provided. It is especially desirable to use a low resistance product such as ITO. The thickness of ITO can be selected according to the resistance value. Although it is possible to achieve a thickness of up to 50 to 300 nm, it is usually used at a thickness of between 50 and 300 nm.

[0229] <Hole injection layer and hole transport layer in organic electroluminescence 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 the 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 the electrons to the light emitting layer 105. , respectively, one or more kinds of hole injection / transport materials are laminated or mixed, or hole injection / transport materials are laminated or mixed, respectively, It is formed by a mixture of a transport material and a polymer binder. In addition, iron chloride is used as a 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 is used to efficiently transport holes from the positive electrode between electrodes in which an electric field is applied. It is necessary to have good hole injection and transport efficiency, and to have high hole injection efficiency and efficient transport of injected holes. For this purpose, it is necessary to have a small ionization potential and a large hole mobility. Larger, more stable, and less likely to trap impurities during manufacturing and use. It is preferable that the material be a non-aqueous material.

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

[0232] Specific examples of such compounds include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.). carbazole, bis(N-arylcarbazole, etc.), bis(N-alkylcarbazole, etc.) 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, benzoxazoles, etc. 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, porphyrin derivatives and other heterocyclic compounds, polysilanes In the polymer system, polycarbonate and styrene derivatives having the above monomers in the side chains are Conductors, polyvinylcarbazole and polysilane are preferred, but the materials required for the fabrication of light-emitting elements are If a compound can form the necessary thin film, inject holes from the anode, and transport the holes, There is no particular limitation.

[0233] It is also known that the electrical conductivity of organic semiconductors is strongly affected by their doping. Such organic semiconductor matrix materials are compounds with good electron donating properties, or , which is composed of compounds with good electron-accepting properties. For doping with electron-donating substances, Tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetra 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 donor base materials (hole transport materials ) generates so-called holes. Number and mobility of holes The conductivity of the base material changes considerably depending on the material. Examples of the amines include benzidine derivatives (TPD, etc.) and starburst amines. derivatives (such as TDATA) or certain metal phthalocyanines (especially zinc phthalocyanine) (ZnPc, etc.) are known (JP Patent Publication No. 2005-167175).

[0234] <Light-emitting layer in organic electroluminescent device> The light-emitting layer 105 is formed between the electrodes to which an electric field is applied, and the positive holes injected from the anode 102 and the 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 material (luminescent compound) that can form a stable thin film and can be used in a solid state is acceptable. 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 type or a combination of multiple types. 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 evaporated at the same time. Alternatively, the 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 characteristics 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, more preferably 0.05 to 20% by weight, based on the total weight. More preferably, the content is 0.1 to 10% by weight. Within the above range, for example, the concentration quenching phenomenon can be prevented. This is preferable in that it can prevent the above.

[0238] On the other hand, in an organic electroluminescent device using a thermally activated delayed fluorescent dopant material, 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 electroluminescence 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 preferred that the amount of the dopant material used is low compared to the amount of the dopant material used.

[0239] When an assist dopant material is used, the host material, the assist dopant The amount of the dopant and the material to be used is approximately 40 to 99% of the total amount of the light-emitting layer material. 0.999% by weight, 59 to 1% by weight, and 20 to 0.001% by weight, and preferably The respective amounts are 60 to 99.99% by weight, 39 to 5% by weight, and 10 to 0.01% by weight. 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. It is also possible.

[0240] As host materials, anthracene and pyrene, which have long been known as light emitters, Fused ring derivatives, bisstyryl anthracene derivatives, distyrylbenzene derivatives, and other bis 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 light-emitting layer. From this viewpoint, the dopant or assisted dopant having the highest T1 energy in the light-emitting layer is 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. In addition, a TADF active compound may 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 an example of 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 preferable, and arylene having 6 to 10 carbon atoms is more preferable. Particularly preferred are benzene rings, biphenyl rings, naphthalene rings, terphenyl rings, etc. nyl ring, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, triphenyl ring Examples of divalent groups include an nylene ring, a pyrene ring, a naphthacene ring, a perylene ring, and a pentacene ring. 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 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 preferable, and an aryl having 6 to 12 carbon atoms is more preferable. is more preferable, and an aryl having 6 to 10 carbon atoms is particularly preferable. 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 cyclic ring and a pentacene ring. Heteroaryl having from 1 to 25 carbon atoms is preferable, and heteroaryl having from 2 to 20 carbon atoms is more preferable. Heteroaryl having 2 to 15 carbon atoms is more preferred, and heteroaryl having 2 to 10 carbon atoms is preferred. Particularly preferred are a pyrrole ring, an oxazole ring, an isoxazole ring, a 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-benzo quinazoline 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, oxadiazine ring Examples of such monovalent groups include 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 a compound 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 (above, (first substituent), wherein at least one hydrogen atom is further selected from aryl, heteroaryl, may be substituted with aryl, diarylamino or alkyl (the second substituent) , R 1 ~R 11 Adjacent groups among these are bonded to each other to form an aryl ring together with the a, b or c ring. A ring or a heteroaryl ring may be formed, and at least one of the rings formed may be The hydrogen of is an aryl, heteroaryl, diarylamino, diheteroarylamino, a aryl, heteroaryl, amino, or alkyl (the first substituent) At least one hydrogen atom in these groups may be further selected from aryl, heteroaryl, diaryl, and and optionally substituted with arylamino or alkyl (the second substituents); At least one hydrogen atom in the compound represented by formula (5) is independently a 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, 0 heteroaryl, diarylamino (wherein aryl has 6 to 12 carbon atoms) or alkyl having 1 to 12 carbon atoms, in which 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 to form a ring having 9 carbon atoms together with the a, b or c ring. may form an aryl ring having 6 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms, At least one hydrogen atom in the ring is an aryl having 6 to 30 carbon atoms, an aryl having 2 to 3 carbon atoms, 0 heteroaryl, diarylamino (wherein aryl has 6 to 12 carbon atoms) or an alkyl group having 1 to 12 carbon atoms, The hydrogen atom is furthermore an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, or a 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, 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 Aryl having 6 to 16 prime numbers, heteroaryl having 2 to 15 carbon atoms, diarylamino (but 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 to form a ring having 9 carbon atoms together with the a, b or c ring. 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 an aryl having 6 to 16 carbon atoms, an aryl having 2 to 1 5 heteroaryl, diarylamino (wherein aryl has 6 to 10 carbon atoms) or an alkyl group having 1 to 6 carbon atoms, The hydrogen atom of the formula (I) can be further selected from aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diaryl 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 above first and second substituents, aryl, heteroaryl, diaryla The "aryl" in amino, diheteroarylamino, and arylheteroarylamino Examples of "heteroaryl" include the following.

[0247] Specific examples of "aryl" include aryl having 6 to 30 carbon atoms. An aryl having 6 to 24 carbon atoms is preferable, an aryl having 6 to 20 carbon atoms is more preferable, and an aryl having 6 Aryl having 6 to 12 carbon atoms is more preferred, and the number of 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-terphenyl m-Terphenyl-2-yl, m-Terphenyl-3-yl, m-Terphenyl-4-yl, o-Terphenyl-2-yl 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, Luoren-(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, 5'-phenyl-m-terphenyl-2-yl m-terphenylyl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl aryl), triphenylene-(1-,2-)yl, pyrene-(1- , 2-, 4-)yl, naphthacene-(1-, 2-, 5-)yl, fused five-ring aryl. Perylene-(1-,2-,3-)yl, pentacene-(1-,2-,5-,6-)yl etc.

[0248] Specific examples of "heteroaryl" include heteroaryl 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 Midinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl nyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, Zoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, Quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, na Phthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl phenyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolyl Examples include ginyl.

[0249] In the above first and second substituents, the "alkyl" includes straight and branched chains. 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. and branched alkyls having 1 to 18 carbon atoms (branched alkyls having 3 to 18 carbon atoms). is preferred, and an alkyl group having 1 to 12 carbon atoms (branched alkyl group having 3 to 12 carbon atoms) is more preferred. Preferably, the alkyl group has 1 to 6 carbon atoms (branched alkyl group has 3 to 6 carbon atoms). Particularly preferred is alkyl having 1 to 4 prime numbers (branched alkyl having 3 to 4 carbon atoms), and most preferred is methyl. 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 n-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-tridecyl 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 an 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 YobiR 11 The substitution with is more preferred, and the aryl is preferably a phenyl group.

[0251] When the first substituent is a 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 (e.g., 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 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 reactions or urethane In the second reaction, a tandem etherification reaction can be used. The Friedel-Crafts reaction (sequential aromatic electrophilic substitution reaction) can be used. For details of the second reaction, please refer to the description in International Publication No. WO 2015 / 102118. It can be.

[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 use a host material with high T1 energy in the emitting layer. 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 (1) and each structure in the group of partial structures (HA) is At least one hydrogen atom in the (HA) or (HB) group In addition, at least one water atom in these structures 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 preferable. and one structure selected from the partial structure (HB) group. and more preferably, the partial structure (HA) group is a compound having a carbazole group. Particularly preferred are 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 ( For example, it may be substituted with methyl, t-butyl, phenyl or naphthyl.

[0260] [ka]

[0261] [ka]

[0262] [ka]

[0263] [ka]

[0264] [ka]

[0265] In addition, the following polymer host materials can also be used. [ka] In the formula (B-6), MU is each 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 by EC or MU, and EC is each independently hydrogen, aryl, Heteroaryl, diarylamino, diheteroarylamino, arylheteroaryl amino or aryloxy, in which at least one hydrogen atom is further aryl, heteroaryl or diarylamino; 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 the following compounds. [ka]

[0267] In formulae (B-1) to (B-4), each Ar is independently hydrogen, aryl, Heteroaryl, diarylamino, diheteroarylamino, arylheteroaryl amino or aryloxy, in which at least one hydrogen atom is further Ar may be substituted with aryl, heteroaryl or diarylamino; Adjacent groups are bonded to form an anthracene ring, a pyrene ring, a fluorene ring, or a carbene ring. may form an aryl or heteroaryl ring together with the base skeleton of the azol ring, At least one hydrogen atom in the ring formed is an aryl, heteroaryl, diaryl Amino, diheteroarylamino, arylheteroarylamino or aryloxy Each group may be substituted with the following. Specific explanations of each group are given in the above general formula (1) and general formula (2). 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 heterocyclic. Aryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy, wherein at least one hydrogen is further aryl, optionally substituted with heteroaryl or diarylamino; R 1 ~R 11 Adjacent groups among these are bonded to each other to form an aryl ring together with the a, b or c ring. A ring or a heteroaryl ring may be formed, and at least one of the rings formed may be The hydrogen of is an aryl, heteroaryl, diarylamino, diheteroarylamino, a aryl, heteroaryl, amino or aryloxy; At least one hydrogen in the alkyl group is further selected from the group consisting of aryl, heteroaryl, and diarylamino. It may be substituted. The specific explanation of each group is given in the polycyclic aromatic compound of the above-mentioned general formula (1) or general formula (2). The explanation given can be cited.

[0271] At least one hydrogen atom in the compounds represented by formulae (B-1) to (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; Any -CH2- in the alkyl group may be replaced with -O- or -Si(CH3)2-. Preferably, the alkyl is directly bonded to the compound represented by the above formula (B-1) to formula (B-5). Any -CH2- except for -CH2- is replaced with arylene having 6 to 24 carbon atoms. Any hydrogen in the alkyl may be substituted by 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 the alkyl Any -CH2- other than the -CH2- directly bonded to EC in (B-6) has 6 to 24 carbon atoms. Any hydrogen in the alkyl may be substituted with fluorine. It may be possible. [ka] (In the above formula (FG-1), R is independently fluorine, trimethylsilyl, trifluoromethyl, or a group having 1 carbon atom. is an alkyl having 3 to 24 carbon atoms or a cycloalkyl having 3 to 24 carbon atoms, Any -CH2- may be replaced by -O-, and the phenyl or Any -CH2- except -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, 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. ~24 alkyl, 3-24 carbon cycloalkyl or 6-12 carbon aryl Any -CH2- in the alkyl may be replaced with -O-; Any -CH2- bonded directly to the 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 group having 1 to 24 carbon atoms or an aryl group having 6 to 12 carbon atoms. At least one hydrogen atom in the aryl may be substituted with an aryl having 1 to 24 carbon atoms. 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 formulae (MU-4-1) to (MU-4-122) and the following Divalent groups represented by the general formulae (MU-5-1) to (MU-5-12) are included. In addition, EC may be, for example, a group represented by the following general formula (EC-1) to formula (EC-29). In these, MU binds to MU or EC at *, and EC binds to *. It binds to MU.

[0274] Furthermore, from the viewpoint of charge transport, the compound represented by formula (B-6) has a structure represented by the formula (B-6 It is preferable that the compound has at least one divalent group represented by the formula (B-6-X 1) is present in an amount of 10% or more based on the molecular weight of the compound represented by formula (B-6). It is more preferable that the divalent group represented by the 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 coating film-forming property. It is preferable that 10 to 100% of the total number (n) of MU has alkyl having 1 to 24 carbon atoms. 30-100% of the total number of MU in the molecule (n) is alkyl with 1-18 carbon atoms (carbon number It is more preferable that the total number of MUs (n) in the molecule is 5 to 18. 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 alignment and charge transport, It is preferred that 10 to 100% of the total number of MUs (n) have alkyl groups having 7 to 24 carbon atoms. Of the total number of MU in the molecule (n), 30-100% is alkyl (carbon number 7-24). 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 any known compound can be used. A variety of materials can be selected depending on the desired emission color. Phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphtha fused ring derivatives such as benzoxazolidine, 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 aryl derivatives (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)isobe Di(2-trifluoromethylphenyl)isobenzofuran, phenylisobenzofuran Isobenzofuran derivatives such as benzofuran, dibenzofuran derivatives, 7-dialkylamines 7-Hydroxycoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, -Methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazolyl coumarin derivatives Phosphorus derivatives, 3-benzimidazolyl coumarin derivatives, 3-benzoxazolyl coumarin Derivatives such as coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, Oran derivatives, polymethine derivatives, cyanine derivatives, oxobenzoanthracene derivatives, Santen 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, pyrrolopyridine derivatives rol derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acrylonitrile derivatives, Lidone derivatives, deazaflavin derivatives, fluorene derivatives and benzofluorene derivatives etc.

[0284] As examples of dopant materials for blue to blue-green light, naphthalene, anthracene, Cene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, Aromatic hydrocarbon compounds such as ricin and their derivatives, furan, pyrrole, thiophene, cyclohexyl 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, Phenothroline, 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, imidazo 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 the aromatic amine derivatives include aromatic amine derivatives.

[0285] In addition, the green to yellow dopant materials include coumarin derivatives, phthalimide derivatives, naphtha derivatives, and the like. Talimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives , acridone derivatives, quinacridone derivatives, and naphthacene derivatives such as rubrene. 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 the above 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, derivatives, pyrrolopyridine derivatives, squarylium derivatives, violanthrone derivatives, phenanthroline derivatives, nadine derivatives, phenoxazone derivatives and thiadiazolopyrene derivatives. In addition to the compounds exemplified as the blue to blue-green and green to yellow dopant materials, aryl, Substituents such as heteroaryl, arylvinyl, amino, and cyano are introduced to enable longer wavelengths. Compounds containing the above-mentioned amines are also suitable examples.

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

[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, for example, by 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, 1 ~Ar 3 Few At least one has a stilbene structure, and Ar 1 ~Ar 3 is an aryl, heteroaryl, Alkyl, tri-substituted silyl (aryl and / or alkyl tri-substituted silyl) or cyano, and m is an integer of 1 to 4.

[0290] The amine having a stilbene structure is preferably a 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 aryl and / or alkyl trisubstituted silyl) or cyano substituted good.

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

[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, the stills described in Japanese Patent Application Laid-Open No. 2003-347056 and Japanese Patent Application 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)perimidine. Perylene, 3,10-bis(2,4,6-trimethylphenyl)perylene, 3,10-diphenyl Nylperylene, 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 No. 11-97178, Japanese Patent Application Laid-Open No. 2000-133457, Japanese Patent Application Laid-Open No. 2000-26324, Japanese Patent Application Laid-Open No. 2000-26324, JP 001-267079 A, ​​JP 2001-267078 A, JP 2001-267076 A, JP 2000-34234 A Perylenes described in JP-A-2001-267075 and JP-A-2001-217077, etc. Derivatives may also be used.

[0294] The borane derivatives include, for example, 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'-bi phenylyl)-10-(dimesitylboryl)anthracene, 9-(4'-(N-carbazo (aryl)phenyl)-10-(dimesitylboryl)anthracene and the like. In addition, borane derivatives described in International Publication No. 2000 / 40586 can also be used. good.

[0295] The aromatic amine derivative is represented, for example, by 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, ants aryl, heteroaryl, alkyl, trisubstituted silyl (aryl and / or alkyl) trisubstituted silyl) or cyano, and n is an integer from 1 to 4. It is 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 Each independently has 6 to 30 carbon atoms Reel, 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, and 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'-tetramethylphenylamine is a 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-phenyl)chrysene-6,12-diamine N,N'-diphenyl-N,N'-isopropylphenyl)chrysene-6,12-diamine -Bis(4-t-butylphenyl)chrysene-6,12-diamine, N,N'-bis(4 -isopropylphenyl)-N,N'-di(p-tolyl)chrysene-6,12-diamine etc.

[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, etc. can be.

[0300] As an anthracene-based compound, for example, N,N,N,N-tetraphenylanthracene is used. 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)naphthalene-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-diphenylaminonaphthalene-2-yl]-p-terphenyl, etc. Some examples include: Furthermore, aromatic amine derivatives described in, for example, JP-A-2006-156888 may also 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 The coumarin derivatives described in any of the above may be used.

[0303] Examples of the pyran derivative include DCM and DCJTB shown below. [ka] Also, JP 2005-126399 A, JP 2005-097283 A, JP 2002-234892 A, The following are described in Japanese Patent Application Laid-Open No. 2001-220577, Japanese Patent Application Laid-Open No. 2001-081090, and Japanese Patent Application 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) is 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 third component functions as a first component in the composition, and the second component functions as a host component in the light-emitting layer. 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 solvent> The composition for forming a light-emitting layer includes at least one organic solvent as a third component. By controlling the evaporation rate of the organic solvent, the film forming property, the presence or absence of defects in the coating, the surface roughness, The smoothness can be controlled and improved. In addition, when forming a film using the inkjet method, Controls meniscus stability at the pinhole of the inkjet head, and controls and improves ejection performance In addition, the drying rate of the film and the orientation of the derivative molecules can be controlled. The electrical characteristics, luminescence characteristics, and efficiency of an organic EL device having a luminescent layer obtained from the composition for forming a luminescent layer are The rate and life of the battery 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 temperature 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. If it is lower, it 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 the above, the composition for forming the light-emitting layer is made into a solid state by removing the solvent from the composition. This is also 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 PS ) than The 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 concentration of the solvent and the concentration of the poor solvent increase, promoting rapid film formation. This results in fewer defects and 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. More preferably, the difference in boiling point (BP) is 5% or more. PS -BP G S ) is preferably 10°C or higher, more preferably 30°C or higher, and It is more preferable that the temperature is 0.4 ° C. or higher.

[0309] After deposition, 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 the coating film forming property, 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 melt transition point (Tg) -30°C. Even if the temperature is lower than 100°C, 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 is an alkylbenzene solvent, a phenyl ether solvents, alkyl ether solvents, cyclic ketone solvents, aliphatic ketone solvents, Examples of the solvent 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 Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol 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 butyl methyl ether, triethylene glycol, polyethylene glycol 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, bromophenyl benzene, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethylanisole Nisole, mesitylene, 1,2,4-trimethylbenzene, t-butylbenzene, 2-methylbenzene Chilanisole, Phenetole, Benzodioxole, 4-Methylanisole, s-Butyran Fluorobenzene, 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-toluidine Tolyl, n-amylbenzene, veratrole, 1,2,3,4-tetrahydronaphthalene , Ethyl benzoate, n-Hexylbenzene, Propyl benzoate, Cyclohexylbenzene , 1-methylnaphthalene, butyl benzoate, 2-methylbiphenyl, 3-phenoxytolu 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)benzenebenzylbutyrate benzyl pentyl ether, benzyl hexyl ether, benzyl heptyl ether, benzyl octyl ether, and the like, but are not limited thereto. The solvent may be used alone or in admixture.

[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 the 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 the binder used in the composition for forming the light-emitting layer include acrylic resin, polyethylene resin, 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, mer amine resins, urea resins, alkyd resins, polyurethanes, and 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 of 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, suitable for uniformity of the film surface of the composition for forming a light-emitting layer, affinity for the solvent on the film surface, etc. A surfactant may be contained to control the liquid repellency. The surfactant is a compound having a hydrophilic group structure. Based on the structure, they are classified as ionic or nonionic, and further, based on the structure of the hydrophobic group, they are classified as alkyl or nonionic. They are classified into silicon-based and fluorine-based. In addition, due to the molecular structure, the molecular weight is relatively small. Simple monomolecular systems and polymeric systems with large molecular weights and side chains or branches In addition, based on the composition, they are classified into a single system, a mixture of two or more types of surfactants and base materials. 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 name, Kyoeisha Chemical Industrial 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 (product 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 (product name, manufactured by DIC Corporation), fluoroalkylbenzene sulfonate, fluoro Fluoroalkyl carboxylates, fluoroalkyl polyoxyethylene ethers, fluoroalkyl Quilammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate , diglycerol 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, ar alkylbenzene sulfonates and alkyldiphenyl ether disulfonates. This can be done.

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

[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 preferable 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 a good film quality, good ejection properties when an ink-jet method is used, 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. A volume percentage is preferred.

[0319] More preferably, the first component is 0.005% by weight based on the total weight of the composition for forming the light-emitting layer. 0.095% by weight or more of the second component 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% by weight to 0.5% by weight, and the second component is 0. .25% by weight to 2.5% by weight, and the third component is 97. It is 0% to 99.7% by weight.

[0320] The composition for forming the 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 filtered, degassed ( Degassing, ion exchange, and inert gas replacement / filling are appropriately selected. It is also possible.

[0321] The higher the viscosity of the composition for forming the light-emitting layer, the better the film-forming property and the ink-jet printing property. On the other hand, a low viscosity makes it easier to form a thin film. From this, it is considered that the viscosity of the composition for forming a light-emitting layer is 0.3 mPa at 25° C. It is preferable that the viscosity is from 1 mPa·s to 3 mPa·s, and more preferably from 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 concentration, 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 hanging drop method.

[0323] <Electron injection layer and electron transport layer in organic electroluminescence device> The electron injection layer 107 efficiently injects electrons moving from the cathode 108 into the light emitting layer 105. or into the electron transport layer 106. The electron transport layer 106 serves to inject electrons from the cathode 108. 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 efficiency of electron injection is high and the injected electrons are transported efficiently. In order to achieve this, the compound must have a large electron affinity, a large electron mobility, excellent stability, and a high tracking ability. It is preferable that the material be one that is unlikely to generate any harmful impurities during manufacture or 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 is not so high. Even if the material does not have a high electron transporting ability, it has the effect of improving the luminous efficiency as well as a material with a 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 electroluminescence (EL) elements The compound is selected from the known compounds used in the electron injection layer and the electron transport layer. There can be.

[0326] Materials used in the electron transport layer or the electron injection layer include carbon, hydrogen, oxygen, sulfur, and ketone. Aromatic ring or heteroaromatic ring composed of one or more atoms selected from among nitrogen and phosphorus Compounds having aromatic rings, pyrrole derivatives and condensed ring derivatives thereof, 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 ethenyl)biphenyl, perinone derivatives, and kumari quinone derivatives, naphthalimide derivatives, anthraquinone and diphenoquinone derivatives , 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, etc. These materials can be used alone. However, it may be mixed with different materials.

[0327] Specific examples of other electron transport compounds include pyridine derivatives, naphthalene derivatives, and aryl groups. Thracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalene derivatives 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), thiadiazole Azole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives Conductors, quinoxaline derivative polymers, benzazole compounds, gallium complexes, pyrazolidine perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoyl derivatives, 2,2'-bis(benzo[h]quinolin-2-yl)-9,9'-s pyrobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole Derivatives (e.g. tris(N-phenylbenzimidazol-2-yl)benzene), benzo Oxazole derivatives, benzothiazole derivatives, quinoline derivatives, terpyridine, 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. Some examples include:

[0329] The above-mentioned materials may be used alone or in combination with different 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 quinolinol-based metal complexes, 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 more specifically, This is disclosed in JP 2007-27587 A. [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 or cyano, and R 13 ~R 16 are each independently , optionally substituted alkyl, or optionally substituted aryl; and X is arylene which may be substituted, and Y is an arylene having 16 or less carbon atoms which may be substituted. aryl, substituted boryl, or optionally substituted carbazolyl; and each n is 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 a compound 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 or cyano, 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 is an optionally substituted arylene having 20 or less carbon atoms, and n is 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 or cyano, and R 13 ~R 16 are each independently , optionally substituted alkyl, or optionally substituted aryl; 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 group include the divalent groups represented by the following formulae (X-1) to (X-9). Can be obtained. [ka] (In each formula, R aeach independently represents an alkyl group or an optionally substituted phenyl group It is.)

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

[0335] The 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, a alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably alkyl having 3 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). Each pyridine-based substituent is independently substituted with an alkyl group having 1 to 4 carbon atoms. In addition, the pyridine-based substituent may be substituted in each formula via a phenylene group or a naphthylene group. In the above, φ may be bonded to the anthracene ring or the 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 preferable. stomach. [ka]

[0343] At least one hydrogen atom in each pyridine derivative may be replaced by deuterium atom. 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 an 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). More preferably, the "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, and n- Butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl ethyl, 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 Nonyl, 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, and n-eicosyl. can be done.

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

[0347] R 11 ~R 18In the above, the "cycloalkyl" is, for example, a 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, more preferably aryl having 6 to 18 carbon atoms, and further 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 the "aryl having 6 to 30 carbon atoms" include monocyclic aryl such as phenyl and condensed aryl. The fused bicyclic aryl is (1-,2-)naphthyl, the fused tricyclic aryl is acenaphthyl, Fluorene-(1-,2-,3-,4-,9-)yl -)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 five-ring aryl Perylene-(1-,2-,3-)yl, pentacene-(1-,2-,5-,6-) Examples include Ile.

[0350] Preferred "aryl having 6 to 30 carbon atoms" are phenyl, naphthyl, phenanthryl, chlorine, More preferably, phenyl, 1-naphthalene, 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 are bonded to form a ring, As a result, the five-membered ring of the fluorene skeleton is often cyclobutane, 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): More details are disclosed in International Publication No. 2010 / 134352. [ka]

[0355] In the above formula (ETM-3), X 12 ~X 21 is hydrogen, halogen, linear, 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) is 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) may be multiple The explanation of the multimers that are formed by combining them is given in the above general formula (1) and formula (1'). Descriptions of the compounds and their multimers can be found in the following references.

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

[0363] The 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 is 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] Each Ar may be independently selected from divalent benzene or naphthalene. The two Ar may be different or the same, but in 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, 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 groups represented by any one of the above formulas (Py-1) to (Py-9) are A group represented by any one of the above formulae (Py-1) to (Py-6) is preferable. The two "Ar and pyridine moieties" that bind to anthracene have the same structure. From the viewpoint of ease of synthesis of the anthracene derivative, however, the same However, from the viewpoint of device characteristics, it is preferable to use two “Ar and pyrimidine” structures. It is preferred that the structures of the "sin-containing moieties" are the same or different.

[0369] R 1 ~R 4 The alkyl group having 1 to 6 carbon atoms may be either straight or branched. That is, it is preferably a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms. More preferably, it is an alkyl group having 1 to 4 carbon atoms (branched alkyl group having 3 to 4 carbon atoms). Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutene. butyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl ethyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethyl butyl, or 2-ethylbutyl; methyl, ethyl, n-propyl, iridium, n-butyl, isobutyl, s-butyl or t-butyl are 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 the aryl having 6 to 20 carbon atoms, is preferable, an aryl having 6 to 12 carbon atoms is more preferable, and an aryl having 6 to 10 carbon atoms is particularly preferable. 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 the tricyclic aryl, (1-,2-)naphthyl; the tricyclic aryl, terphenylyl (m-terphenylyl); 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-terphenyl o-Terphenyl-4-yl, o-Terphenyl-2-yl, o-Terphenyl-3-yl, o-Terf p-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, anthracene-(1-,2-,9-phenyl-4-yl), fused tricyclic aryl -)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 five-ring 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 each independently represents a single bond, a divalent benzene, a divalent naphthalene, anthracene, fluorene, or phenalene.

[0376] Ar 2are each independently an aryl having 6 to 20 carbon atoms, 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 preferable, an aryl having 6 to 12 carbon atoms is more preferable, and an aryl having 6 Particularly preferred is aryl having a carbon number of 10 to 10. 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, Cycloalkyl or aryl having 6 to 20 carbon atoms, The explanation 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, 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 preferable, an aryl having 6 to 12 carbon atoms is more preferable, and an aryl having 6 Particularly preferred is aryl having a carbon number of 10 to 10. 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, for example, 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 (carbon Particularly preferred "alkyl" is an alkyl group having 1 to 4 carbon atoms. alkyl (branched alkyl with 3 to 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 of alkoxy groups include ethyl, n-heptyl, and 1-methylhexyl.

[0384] Ar 2 In the above, the "cycloalkyl" is, for example, a cycloalkyl having 3 to 12 carbon atoms. Preferred "cycloalkyl" is a cycloalkyl having 3 to 10 carbon atoms. More preferred "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. The preferred "cycloalkyl" is a cycloalkyl having 3 to 6 carbon atoms. Examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. cyclopentyl, 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. More preferably, the aryl has 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, 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 bond may be spiro-linked, such as xane, fluorene or indene.

[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. WO 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 heterocyclic group, an aryl ether group, an arylthioether group, an aryl group, a heterocyclic 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 an arylene group or a heteroarylene group. 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 adjacent substituent. n is an integer from 0 to 3. When n is 0, the unsaturated When there is no structural part and 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. In the case where the group is substituted, the substituent is not particularly limited, and examples of the substituent include an alkyl group and an aryl group. , heterocyclic groups, etc., which are also included in the following description. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 to 20 in terms of availability and cost. The range is.

[0395] The cycloalkyl group includes, for example, cyclopropyl, cyclohexyl, norbornyl, It refers to a saturated alicyclic hydrocarbon group such as cyclohexyl, ... 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 such as a benzyl group or a phenylethyl group. The aromatic hydrocarbon group is an aromatic hydrocarbon group mediated by an atom. Both the aliphatic and aromatic hydrocarbons are unsubstituted. The number of carbon atoms in the aliphatic portion is not particularly limited, but is usually 1. The range is ~20.

[0397] The alkenyl group is, for example, a double bonded alkyl group such as a vinyl group, an allyl group, or a butadienyl group. It refers to 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, It refers to an unsaturated alicyclic hydrocarbon group containing a double bond, such as a cyclohexene group or a cyclohexene group. It does not matter whether it is replaced or substituted.

[0399] The alkynyl group is an unsaturated aliphatic group containing a triple bond, such as an acetylenyl group. The carbon atom of an alkynyl 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, for example, an aliphatic carbonized group via an ether bond such as a methoxy group. It 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] In addition, 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 ring structure 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 6-40.

[0403] In addition, an aryl thioether group is an aryl ether group in which the oxygen atom of the ether bond 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 an atom other than carbon, such as a cyclic group, a quinolinyl group, or 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 also involved in aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. It may also include groups substituted with aromatic hydrocarbons, heterocycles, and the like.

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

[0409] The silyl group refers to a silicon compound group such as a trimethylsilyl group, which is an unsubstituted 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 condensed 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, the two R 1 Conjugated or non-conjugated 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 preferably is a compound represented by the following formula (ETM-8-1). For details, see International Publication No. 2011 / 02 This is also described in Publication No. 1689. [ka]

[0414] Each Ar is independently 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" is, 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 The aryl group is preferably an aryl having from 6 to 20 carbon atoms, and more preferably an aryl having from 6 to 12 carbon atoms.

[0416] Specific examples of "aryl" include monocyclic aryl, phenyl, bicyclic aryl, and aryl. (2-, 3-, 4-) biphenylyl, (1-, 2-) naphthyl, fused bicyclic aryl and 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), condensed 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- m-terphenylyl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensation Tetracyclic aryls such as triphenylene-(1-,2-)yl and pyrene-(1-,2-,4 -)yl, naphthacene-(1-, 2-, 5-)yl, and perylene, a fused five-ring aryl system. -(1-,2-,3-)yl, pentacene-(1-,2-,5-,6-)yl, etc. can be done.

[0417] The "heteroaryl" in the "optionally substituted heteroaryl" includes, for example, carbonyl, Heteroaryl having 2 to 30 carbon atoms is preferable, and heteroaryl having 2 to 25 carbon atoms is preferable. Heteroaryl having 2 to 20 carbon atoms is more preferable, and heteroaryl having 2 to 15 carbon atoms is preferable. 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 Sadiazolyl, 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 doliginyl.

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

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

[0421] The 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): It is a polymer formed by multiple bonds such as single bonds. For details, see US Patent Publication 2014 / 0197386 This is described in publication no. [ka]

[0423] Each Ar is independently 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" is, 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 The aryl group is preferably an aryl having from 6 to 20 carbon atoms, and more preferably an aryl having from 6 to 12 carbon atoms.

[0425] Specific examples of "aryl" include monocyclic aryl, phenyl, bicyclic aryl, and aryl. (2-, 3-, 4-) biphenylyl, (1-, 2-) naphthyl, fused bicyclic aryl and 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), condensed 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- m-terphenylyl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensation Tetracyclic aryls such as triphenylene-(1-,2-)yl and pyrene-(1-,2-,4 -)yl, naphthacene-(1-, 2-, 5-)yl, and perylene, a fused five-ring aryl system. -(1-,2-,3-)yl, pentacene-(1-,2-,5-,6-)yl, etc. can be done.

[0426] The "heteroaryl" in the "optionally substituted heteroaryl" includes, for example, carbonyl, Heteroaryl having 2 to 30 carbon atoms is preferable, and heteroaryl having 2 to 25 carbon atoms is preferable. Heteroaryl having 2 to 20 carbon atoms is more preferable, and heteroaryl having 2 to 15 carbon atoms is preferable. 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 Sadiazolyl, 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 doliginyl.

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

[0429] Carbazole derivatives are compounds represented by the above formula (ETM-9) that are 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, phenanthracene ring, The ring may be bonded to the ring 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. 2001 / 0156013. [ka]

[0433] Each Ar is independently 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" is, 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 The aryl group is preferably an aryl having from 6 to 20 carbon atoms, and more preferably an aryl having from 6 to 12 carbon atoms.

[0435] Specific examples of "aryl" include monocyclic aryl, phenyl, bicyclic aryl, and aryl. (2-, 3-, 4-) biphenylyl, (1-, 2-) naphthyl, fused bicyclic aryl and 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), condensed 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- m-terphenylyl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensation Tetracyclic aryls such as triphenylene-(1-,2-)yl and pyrene-(1-,2-,4 -)yl, naphthacene-(1-, 2-, 5-)yl, and perylene, a fused five-ring aryl system. -(1-,2-,3-)yl, pentacene-(1-,2-,5-,6-)yl, etc. can be done.

[0436] The "heteroaryl" in the "optionally substituted heteroaryl" includes, for example, carbonyl, Heteroaryl having 2 to 30 carbon atoms is preferable, and heteroaryl having 2 to 25 carbon atoms is preferable. Heteroaryl having 2 to 20 carbon atoms is more preferable, and heteroaryl having 2 to 15 carbon atoms is preferable. 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 Sadiazolyl, 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 doliginyl.

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

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

[0440] The 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 phenylene ring), n is an integer of 1 to 4, and the "benzoimidazole-based substituent" is The "pyrifos" in formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) The pyridyl group in the "pyridyl-based substituents" 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 and the above formula (ETM- 2-1) and R in formula (ETM-2-2) 11 The explanation can be cited.

[0444] φ is preferably an anthracene ring or a fluorene ring. The structure can be referenced to the explanation in 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- In 2-2), two pyridine-based substituents are bonded together, but these are When replacing the pyridine substituent with a benzoimidazole substituent, both pyridine substituents are replaced with benzimidazoles. may be replaced by an azole-based substituent (i.e., n=2), or any one of the pyridine-based substituents may be replaced by an aryl-based substituent (i.e., n=2). 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 11 ~R 18 At least one of the substituents is replaced with a benzimidazole-based substituent to form a "pi Lysine-based Substituents" R11 ~R 18 may be substituted.

[0445] Specific examples of the benzimidazole derivative include 1-phenyl-2-(4-( 10-Phenylanthracen-9-yl)phenyl)-1H-benzo[d]imidazole , 2-(4-(10-(naphthalene-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- 2-phenyl-1H-benzo[d]imidazo[3-yl]anthracen-9-yl 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl) 1-(4-(9,10-phenyl)-1-phenyl-1H-benzo[d]imidazole Di(naphthalene-2-yl)anthracen-2-yl)phenyl)-2-phenyl-1H -Benz[d]imidazole, 5-(9,10-di(naphthalen-2-yl)anthracene 1,2-diphenyl-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 following formula (ETM-12- 1). Details are described in International Publication No. 2006 / 021982. is. [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 of 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 aryl (preferably aryl having 6 to 30 carbon atoms). In 2-1) R 11 ~R 18 Either one of the rings is bonded to φ, which is an aryl ring.

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

[0451] R 11 ~R 18 The alkyl, cycloalkyl and aryl in the above 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. In the structural formulas below, R is Independently, hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthalene, 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-phenanthroline-2-yl)anthracene, 2,6- Di(1,10-phenanthroline-5-yl)pyridine, 1,3,5-tri(1,10- Phenanthroline-5-yl)benzene, 9,9'-difluoro-bis(1,10-phenanthroline 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 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 where n is an integer from 1 to 3.

[0455] Specific examples of quinolinol-based metal complexes include 8-quinolinol lithium, 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 Aluminum tris(4,5-dimethyl-8-quinolinolato) Tris(4,6-dimethyl-8-quinolinolato)aluminum, Bis(2-methyl-8-quinolinolato)(phenolato)aluminum, bis(2-methyl Aluminum bis(2-methyl-8-quinolinolato)(2-methylphenolato) -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 Aluminum bis(2-ethyl-8-quinolinolato)(3,4-dimethylphenolato) -Methyl-8-quinolinolato)(3,5-dimethylphenolato)aluminum, bis (2-methyl-8-quinolinolate)(3,5-di-t-butylphenolate)aluminium , 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- Methylphenolate)aluminum, bis(2-methyl-8-quinolinate)(2,4 ,5,6-tetramethylphenolate)aluminum, bis(2-methyl-8-quinolinate) bis(2-methyl-8-quinolinolate)aluminum (1-naphtholate) (2-naphtholato)aluminum, bis(2,4-dimethyl-8-quinolinolato)( 2-Phenylphenolate)aluminum, Bis(2,4-dimethyl-8-quinolinol) (3-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinyl) Nolate)(4-phenylphenolate)aluminum, bis(2,4-dimethyl-8- Quinolinolato)(3,5-dimethylphenolato)aluminum, Bis(2,4-dimethyl (3,5-di-t-butylphenolate)aluminum, 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-quinoline Aluminum linoleate, bis(2-methyl-5-trifluoromethyl-8-quinolinol) 2-methyl-5-trifluoromethyl-8-(2-oxo-bis(2-methyl-5-trifluoromethyl-8-hydroxyethyl)aluminum Quinolinolato)aluminum, Bis(10-hydroxybenzo[h]quinoline)beryllium 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, an aryl ring, A helical ring, a fluorene ring, a benzofluorene ring, a phenalene ring, a phenanthrene ring, or triphenylene ring), n is an integer from 1 to 4, and is not a "thiazole-based substituent" or a "benzoxazole-based substituent". The "zothiazole-based substituent" is 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 replaced with deuterium. [ka]

[0459] φ is preferably an anthracene ring or a fluorene ring. The structure can be referenced to the explanation in 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- In 2-2), two pyridine-based substituents are bonded together, but these are not shown. When replacing with an azole-based substituent (or a benzothiazole-based substituent), both pyridines Even if the thiazole-based substituent is replaced with a benzothiazole-based substituent, or (i.e. n=2), any one of the pyridine-based substituents may be replaced by 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), R 11 ~R 18 At least one of the following is a thiazole-based substituent (or a benzothiazole-based Substituent) to make "pyridine-based substituent" R 11 ~R 18 may be substituted.

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

[0461] The electron transport layer or the electron injection layer further includes 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, rare earth metals, etc. group, alkali metal oxides, alkali metal halides, alkaline earth metal oxides, Alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, The organic complexes of alkaline metals, alkaline earth metals and rare earth metals are At least one selected from the following group can be suitably used.

[0462] Preferred reducing substances are Na (work function 2.36 eV) and K (work function 2.28 eV). , Rb (2.16 eV) or Cs (1.95 eV), and other alkali metals, Ca ( 2.9 eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV) Alkaline 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. A combination of two or more of these alkali metals is also preferred as a reducing substance with an energy of 2.9 eV or less. 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 forming 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 the role of injecting the child.

[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, a material similar to the material 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 air. To improve this, for example, trace amounts of lithium, cesium, or magnesium are added to the organic layer. A method is known in which a highly stable electrode is produced by doping with other dopants. Examples of fluoride include lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide. Other suitable inorganic salts may also be used, including, but not limited to, the following:

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

[0466] <Binding agents that may be used in each layer> Materials used in the hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer Each layer can be formed by using only one 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 terephthalic acid resin, alkyd resin, epoxy resin, and silicone resin. It is also possible to use them in combination.

[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, a resistance heating deposition method, or a method for forming a thin film. Electron beam deposition, sputtering, molecular deposition, printing, spin coating or casting The film can be formed by forming it into a thin film using a method such as a coating method. There is no particular limitation on the thickness of each layer formed in this manner, and it can be set appropriately depending on the properties of the material. The thickness can be adjusted to 2 to 5000 nm, but is usually in the range of 2 nm to 5000 nm. The thickness can be measured with a film thickness measuring device. When using a deposition method to make a thin film, the 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 0.01~50nm / sec, substrate temperature -150~+300℃, film thickness range 2nm~5μm 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 the organic electroluminescent device will now be described.

[0469] <Vapor deposition method> A thin film of anode material is formed on a suitable substrate by deposition or other method to create an anode. A thin film of a hole injection layer and a hole transport layer is formed on the anode. A thin film of the photo-emitting layer is formed by co-evaporating the photo-emitting material, and an electron transport layer and an electron An injection layer is formed, and then a thin film made of a cathode material is formed by a deposition method or the like to form a cathode. By this, the desired organic electroluminescence device can be obtained. In the fabrication, the order of fabrication is reversed: cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer. It is also possible to fabricate the transport layer, the hole injection layer, and the anode in that 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 The solvent is removed from the composition for forming a light-emitting layer through a drying process to form a coating film. Depending on the fabric process, the method using a spin coater is called the spin coat method, the slit coater method, etc. slit coating method using a plate, gravure using a plate, offset, reverse offset, Lexo printing, a method using an inkjet printer, is used in the inkjet method, which sprays the material in a mist. The method of drying is called the spray method. There are several methods for the drying process, such as air drying, heating, and vacuum drying. The drying step may be carried out once or may be carried out multiple times using different methods and conditions. Also, different methods may be used in combination, for example 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 method, casting method, coating method, etc. Wet film formation method is vacuum evaporation. Unlike 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 prepared using the above-mentioned composition, it is necessary to prevent the dissolution of the lower layer by the composition of the upper layer. Controlled composition, crosslinking of the underlayer and orthogonal solvent (mutually soluble However, even with these techniques, the coating of all films is However, 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 will be described below. (Step 1) Formation of the anode by vacuum deposition (Step 2) Formation of the hole injection layer using a wet film formation method (Step 3) Formation of the hole transport layer using a 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 forming 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 deposition Through this procedure, the anode / hole injection layer / hole transport layer / host material and dopant material An organic EL element consisting of 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 using the laser thermal imaging (LITI) method. LITI is a method of heating and evaporating a compound attached to a substrate with a laser. The material to be applied may 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 suitable methods include washing with a suitable solvent and heating. Also included are a series of steps.

[0478] The bank can be fabricated by photolithography. The bank material that can be used is a positive resist material or a negative resist material. In addition, it can be used in inkjet printing, gravure offset printing, reverse offset printing, etc. 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 Fluoropolymers such as polyfluoroethylene and polyhexafluoropropylene, fluoroolefins, etc. Examples of the copolymer include olefin-hydrocarbon olefin copolymers and fluorocarbon polymers. However, this is not limited to this.

[0480] Referring to Figure 9, an organic EL element was created on a substrate with a bank using the inkjet method. First, the bank (200) is formed by bonding the electrode (120) on the substrate (110). In this case, the ink jet head (300) is provided on the bank (200 A droplet of ink (310) is dropped between the electrodes and dried to form a coating film (130). This process is repeated to produce the next coating film (140) and then the light-emitting layer (150). By forming an electron transport layer, an electron injection layer, and electrodes using a vacuum deposition method, a light-emitting portion can be formed using a bank material. It is possible to fabricate a site-separated organic EL device.

[0481] When applying a DC voltage to the organic electroluminescence device thus obtained, the anode is connected to +, The negative polarity is simply applied to the cathode, and when a voltage of 2 to 40 V is applied, the film becomes transparent or semi-transparent. Light emission can be observed from the transparent electrode side (anode or cathode, or both). The field-emitting element also emits light when a pulse current or an alternating current is applied. The waveform of may be arbitrary.

[0482] <Applications of organic electroluminescent devices> The present invention also relates to 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 including an organic electroluminescent device may include 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 can be used to The liquid crystal display device can be driven by appropriately using a known driving method such as direct current driving, 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 Plays and the like can be mentioned (for example, JP-A-10-335066, JP-A-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 a pixel are determined by its purpose. For example, images and characters displayed on computers, monitors, and televisions usually have a side length of 300 μm or more. The square pixels shown below are used, and in the case of a large display such as a display panel, In the case of monochrome display, pixels of the same color are arranged However, in the case of a color display, red, green, and blue pixels are displayed side by side. In this case, there are typically delta and stripe types. 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 In some cases, Ricks may be superior, so it is necessary to use them according to the purpose. .

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

[0486] Examples of the lighting device include lighting devices for indoor lighting, backlights for liquid crystal display devices, etc. (For example, JP-A-2003-257621, JP-A-2003-277741, JP-A-2004-1 (See, for example, 19211.) Backlights are primarily used to improve the visibility of non-self-luminous display devices. They are used for the purpose of displaying images, and are used in liquid crystal display devices, clocks, audio equipment, automobile panels, display boards, and They are used in displays and signs. In particular, liquid crystal displays, especially personal computers, where thinning is an issue, are becoming more and more popular. Backlights for smartphones 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 the feature.

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

[0488] Organic field-effect transistors control the current flow by generating an electric field through a 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 semiconductors than semiconductors, and they are often used as elements in 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 on the semiconductor substrate. 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, the following structure. (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 and 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, etc.

[0490] Organic thin-film solar cells are made up of a transparent substrate such as glass, an anode such as ITO, a hole transport layer, and a photoconductor. It has a laminated structure of an electric 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, 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. In addition to the above, organic thin-film solar cells can function as hole transport materials or electron transport materials. The layer is 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, a known material used for the organic thin-film solar cell may be appropriately selected. can be selected and used in combination. EXAMPLES

[0491] The present invention will be described in detail below with reference to examples. The following are compounds 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 Leu-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 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(difluoro (phenylphosphino)-1,1'-binaphthyl (BINAP: 1.98g, 3.18mmol 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 a gel (eluent: toluene) and the solvent was removed under reduced pressure to obtain a crude product. The crude product was dissolved in toluene, and then a suitable amount was distilled off 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 spectrum. 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 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-dichlorophenyl ether (90 mmol) and toluene (300 ml) was heated to 80°C. The mixture was stirred for 5 hours. The reaction mixture was cooled to room temperature and filtered using silica gel (eluent: toluene). The solvent was removed under reduced pressure to obtain a crude product. The crude product was dissolved in toluene and then The saturated solution was prepared by distilling under reduced pressure, and hexane was added to reprecipitate the 5-chloroformate. Lo-N 1 ,N 1 ,N 3 ,N 3 -Tetraphenylbenzene-1,3-diamine (5.66g (43% yield) as a white solid. [ka]

[0496] The structure of the compound obtained was confirmed by NMR spectrum. 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 nitrogen atmosphere, N synthesized in the first stage 1 ,N 3 -Diphenylbenzene-1,3-diamine (1.34 g, 5.1 mmol), 5-chloro-N 1 ,N 1 ,N 3 ,N 3 -Tetraphenylbenzene-1,3-diamine (4.80g, 11mmol), 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 liquid was cooled to room temperature, filtered through silica gel (eluent: toluene), and the solvent was removed under reduced pressure. The crude product was washed with hexane and then with methanol to obtain 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 spectrum. 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 trichlorobenzene, the tribromide was heated at room temperature under a nitrogen atmosphere. Boron (1.13 ml, 12 mmol) was added. After the dropwise addition was completed, the temperature was raised to 180°C and 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. After that, the pressure was reduced at 60°C. The reaction solution was distilled off to obtain a crude product. The crude product was dissolved in acetonitrile and methanol. The mixture was washed with toluene and then silica gel column chromatography (eluent: toluene). After purifying with 1×10, the crude product was recrystallized twice from o-dichlorobenzene. -4 mmHg Purification by sublimation at 440° C. under reduced pressure was performed to obtain 1.17 g of compound (1-1). [ka]

[0500] The structure of the compound obtained was confirmed by NMR spectrum. 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-dioxy-19b,20b-diborazine Futo[3,2,1-de:1',2',3'-jk]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 mmol), A flask containing 100 mol) and N-methyl-2-pyrrolidone (NMP: 300 ml) was placed in the flask. The mixture was heated to 140° C. and stirred for 13 hours. The reaction mixture was cooled to room temperature, and NMP was removed by distillation 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 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 spectrum. 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, 14mmol), diphenylamine (10.0g, 59mmol), Pd2(dba)3 (0.256g, 0.28mmol), tri-tert-butylphosphine (0.113 g, 0.56 mmol), NaOtBu (6.70 g, 70 mmol) and toluene ( The flask containing 300 ml of ethanol was heated to 110°C and stirred for 6 hours. The reaction mixture was allowed to cool to room temperature. Cool, filter through silica gel (eluent: toluene), and remove the solvent under reduced pressure to obtain a crude product. The crude product was washed with hexane to obtain 5,5'-(1,3-phenylenediamine). Bis(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 spectrum. 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. The mixture was then 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 reaction solution was distilled off. Then, the mixture was filtered using silica gel (eluent: toluene), and the solvent was removed under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (eluent: toluene). The mixture was filtered using hexane / hexane = 1 / 2 (volume ratio), 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 spectrum. 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-H 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 were 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 removed under reduced pressure to obtain a crude product. The 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 spectrum. 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(0.986g, 2.4mmol), NaOtBu(14.5g, 0.1 A flask containing 5 mol) and toluene (200 ml) was heated to 80°C and incubated for 15 hours. The reaction mixture was filtered through silica gel (eluent: toluene), and the solvent was removed 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 Obtained 1.7 g, 86% yield, as a white solid. [ka]

[0514] The structure of the compound obtained was confirmed by NMR spectrum. 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 nitrogen atmosphere, N synthesized in the first stage 1 ,N 3 -Diparatolylbenzene-1,3-diamine 5-Chloro-N (3.1 g, 11 mmol) synthesized in the second step 1,N 1 ,N 3 ,N 3 -Tetraparatolylbenzene-1,3-diamine (11.2g, 22mmol), 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 under reduced pressure to obtain the crude product. The crude product was washed with methanol and then with toluene to obtain 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 spectrum. 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 p-Tolylbenzene-1,3,5-triamine (0.661 g, 0.5 mmol) and In a flask containing orthodichlorobenzene (10 ml), three odorants were added at room temperature under a nitrogen atmosphere. Boron chloride (0.819 ml, 2.0 mmol) was added. After the dropwise addition was completed, the temperature was raised to 180°C. The mixture was stirred for 24 hours at room temperature. Add 60 ml of dimethylamine (1.28 ml, 7.5 mmol) and stir until the heat generation subsided. The reaction solution was distilled off under reduced pressure at 0° C., and then filtered using silica gel (eluent: toluene). The solvent was removed 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 spectrum. 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-tetraphenyl Leu-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, NMP was distilled off under reduced pressure, and water and toluene were then added. 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 spectrum. 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 7mmol), diphenylamine (4.80g, 28mmol), 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 ethyl acetate was heated to 80°C and stirred for 14 hours. The mixture was filtered using a toluene distillation solvent (eluent), and the solvent was removed 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 spectrum. 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 (1.56 g, 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 dissolved in toluene. The solvent was removed under reduced pressure to obtain a crude product. The crude product was washed with methanol to obtain N 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 spectrum. 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, 10 ml of bromotribromide 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 the mixture was stirred until the heat generation subsided. After that, the mixture was cooled to 60°C and the pressure was reduced. The reaction solution was then distilled off. The mixture was then filtered through silica gel (eluent: toluene) and the eluate was 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 filtration solvent (eluent: toluene / hexane = 1 / 2 (volume ratio)), and the solvent was distilled off 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 spectrum. 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-diborazinenaphtho[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-pass column (eluent: hexane) and the solvent was removed. The crude product was obtained by distilling off under reduced pressure. -4 Under reduced pressure of 8 mmHg By sublimation purification at 0℃, 1,3-dibromo-5-(3-chlorophenoxy)benzene was obtained. The compound (27.7 g, 77% yield) was obtained. [ka]

[0532] The structure of the obtained compound 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 300 ml of ethanol was heated to 80°C and stirred for 30 minutes. The mixture was cooled at 40° C., 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 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 obtained compound 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 reaction mixture was cooled to room temperature and The mixture was filtered using a Lysil short-pass column (eluent: toluene), and the solvent was removed under reduced pressure to obtain a crude product. The crude product was washed with hexane and then with methanol to obtain the product. 1 , N 1 ,N 3 ,N 3 -Tetraphenyl 5-(3-(phenylamino)phenoxy)benzene The -1,3-diamine (9.49 g, 89% yield) was obtained as a white solid. [ka]

[0536] The structure of the obtained compound 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 (4.29g, 7.2mmol), 5-chloro Lo-N 1 ,N 1 ,N 3 ,N 3 -Tetraphenylbenzene-1,3-diamine (2.67g , 6.0mmol), Pd2(dba)3(0.165g, 0.18mmol), tri- tert-Butylphosphine (72.8 mg, 0.36 mmol), NaO t Bu (1. A flask containing 15 g of toluene (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 under reduced pressure to obtain a crude product. The product was washed with acetonitrile to remove N 1 -(3-(3,5-bis)diphenylamine Phenoxyphenol-(N 1 ,N 3 ,N 3 ,N 5 ,N 5 -Pentaphenylbenzene The resulting mixture was treated with hexane-1,3,5-triamine (4.93 g, 82% yield) as a white solid. [ka]

[0538] The structure of the obtained compound 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) were placed in a flask under a nitrogen atmosphere. Boron tribromide (0.569 ml, 6.0 mmol) was added at room temperature under atmospheric pressure. The mixture was heated to 140° C. and stirred for 24 hours. After that, the mixture was cooled to room temperature again and N-diiso 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, yield 24%). ). [ka]

[0540] The structure of the obtained compound 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]pentane 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 xydiphenyl (SPhos: 0.838 g, 2.0 mmol), NaOtBu (14. A flask containing 6 g (0.15 mol) and toluene (640 ml) was heated to 80°C. The mixture was stirred for 1.5 hours. Water was added to stop the reaction, and the mixture was extracted with toluene. Solvent The crude product obtained by distilling off the solvent was eluted on a silica gel column (eluent: heptane:toluene = 6:4 (volume By purifying using 5-chloro-N 1 ,N 1 ,N 3 ,N 3 -Tetramet Arylbenzene-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 (4.22 g, 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 mm 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). The crude product was purified using 1,2-dichlorophenyl ether (1,2-dichlorophenyl ether) and 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 Triphenylbenzene-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 -Tetramethatriylbenzene-1,3,5-triamine (0.661g, 0.5mmol A flask containing 10 ml of 10 ... Boron tribromide (0.819 ml, 2.0 mmol) was added at 180°C. The mixture was heated to 35° C. and stirred for 24 hours. After that, it was cooled to room temperature again and N,N-diisopropyl 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 mixture was filtered using silica gel (elution The crude product was washed with toluene and the solvent was removed under reduced pressure. Purification afforded compound (1-31) (0.365 g, 59% yield). [ka]

[0545] The structure of the compound obtained was confirmed by NMR spectrum. 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 above synthesis examples. It is possible to synthesize a compound of the formula:

[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 the 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 performed according to the mode of use of the compound to be evaluated in the organic EL device. In one case, the target compound is thin-filmed and evaluated, and in the other case, the target compound is thin-filmed and evaluated. In some cases, the material may be dispersed in a thin film and evaluated.

[0549] The matrix material used is commercially available PMMA (polymethyl methacrylate). A thin film sample dispersed in PMMA can be used to measure the amount of PMMA and the chemical compound to be evaluated. The mixture was dissolved in toluene and then coated on a transparent quartz support substrate ( It can be produced by forming a thin film on a substrate (10 mm x 10 mm).

[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 placed on a commercially available deposition device (Showa A molybdenum evaporation boat containing the host material was fixed to a substrate holder manufactured by Shinku Co., Ltd. Then, a molybdenum evaporation boat containing the dopant material is installed. Next, the vacuum chamber is opened to 5×1 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 the dopant material are deposited by simultaneously heating the boat and evaporating to an appropriate thickness. The deposition rate is controlled according to the set weight ratio of the host material and the dopant material. To control.

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

[0552] For the measurement of fluorescence spectra, photoluminescence was measured at room temperature with excitation at an appropriate excitation wavelength. For the measurement of phosphorescence spectrum, the above-mentioned 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 the irradiation of the excitation light to the start of the 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 to measure the fluorescence at 300 K. 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 deactivation of the triplet component. Slow components are rarely observed. Slow components are rarely observed in the compounds under evaluation. In this case, the triplet energy, which has a long excited life, is transferred to the singlet energy by thermal activation. 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 between 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 basic physical properties of compound (1-1) [Absorption characteristics] A thin film formed on a substrate (made of quartz) in which compound (1-1) was dispersed in PMMA at a concentration of 1 wt% was prepared. The absorption spectrum was measured (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 made of only compound (1-1) was prepared, and the absorption spectrum As a result of measuring the spectrum, the long wavelength absorption edge of the absorption spectrum was 477 nm, and 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% by weight. A film-forming substrate (made of quartz) was prepared, and photoluminescence was observed by exciting the substrate at an excitation wavelength of 340 nm. As a result, the maximum emission wavelength was 467 nm. 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 to obtain fluorescence. The quantum yield was measured and found to be high at 92%.

[0560] The phosphorescence spectrum was measured using a thin film of compound (1-1) dispersed in PMMA at a concentration of 1% by weight. A film-forming substrate (made of quartz) was prepared, and photoluminescence was observed by exciting the substrate 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 .64 eV.

[0561] The calculated ΔEST was 0.02 eV.

[0562] From the above, it was confirmed that compound (1-1) is a material capable of achieving a deep blue color with high efficiency. 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. 1. Compound (1-1) except that the compound (1-1) of the present invention was changed to comparative compound 1. The ΔEST was calculated in the same manner as in the previous example. The maximum emission wavelength of the fluorescence spectrum was 469 nm. m, the maximum emission wavelength of the phosphorescence spectrum is 502 nm, and ΔEST is calculated to be 0.17 eV. This value of ΔEST is small enough to obtain thermally activated delayed fluorescence, but This is larger than that of the compound (1-1) and is suitable for the construction of an organic electroluminescence device that exhibits thermally activated delayed fluorescence. Therefore, the external quantum efficiency is expected to be lower than that of the compound (1-1). [ka]

[0564] Comparative compound 2 Comparative compound 2 is the compound of formula (1-422) disclosed in WO 2015 / 102118. The compound (1-1) was used as the comparative compound 2, except that the compound (1-1) of the present invention was replaced with the comparative compound 2. The evaluation was carried out in the same manner as in the example. As a result, the maximum emission wavelength of the fluorescence spectrum was 477 nm, which is an emission wavelength 10 nm larger 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 promising as a thermally activated delayed fluorescent material for optical layers.

[0566] Evaluation of 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 spectrum and emission spectrum were measured (Figure 3). The excitation wavelength for the spectrum measurement was 375 nm. As a result, the maximum emission of the fluorescence spectrum The wavelength was 438 nm. The same substrate was also prepared and excited with an excitation wavelength of 375 nm to obtain fluorescence. The quantum yield was measured and found to be high at 87%. The length was 466 nm. T The value is 2.66 eV, which is a high value. The calculated ΔEST was 0.17 eV.

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

[0568] Evaluation of 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 spectrum and emission spectrum were measured (Figure 4). The excitation wavelength for the spectrum measurement was 407 nm. As a result, the maximum emission of the fluorescence spectrum 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 high at 91%. The length was 461 nm. T The value is 2.69 eV, which is a high value. The calculated ΔEST was 0.02 eV.

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

[0570] Evaluation of 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 and emission spectra were measured (Figure 5). The excitation wavelength for the spectrum measurement was 374 nm. The fluorescence quantum yield was 473 nm. The yield was measured and found to be high at 89%. Furthermore, the maximum emission wavelength of the phosphorescence spectrum was 477 nm. From this, E 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 capable of achieving a deep blue color with high efficiency. 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), high triplet excitation, and Electromotive energy (E T) and a small ΔEST. The application of the compound to a charge transport layer is also expected, and the application to a light emitting layer is particularly expected.

[0573] Evaluation items and evaluation methods The evaluation items were 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 classified 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 ratio of these photons to the light emitted from the light-emitting element. The amount of photons emitted is calculated based on the amount of photons emitted from the light-emitting layer. Because it continues to be absorbed or reflected inside the light emitting element and is not emitted to the outside of the light emitting element, Therefore, the external quantum efficiency is lower than the internal quantum efficiency.

[0575] The measurement methods for spectral radiance (emission spectrum) and external quantum efficiency are as follows. The element is generated by applying a voltage using the voltage / current generator R6144 manufactured by Intest. The SR-3AR spectroradiometer manufactured by TOPCON was used to measure the brightness perpendicular to the light-emitting surface. The spectral radiance of the visible light region was measured from the direction. Assuming that the light-emitting surface is a perfect diffuser, The measured spectral radiance value of each wavelength component is divided by the wavelength energy and multiplied by π to obtain the value for each wavelength. The number of photons is then integrated over the entire wavelength range observed. The total number of photons emitted from the device was calculated by dividing the applied current by the elementary charge injected into the device. 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 by dividing the total number of the emission spectrum by the maximum emission wavelength is the external quantum efficiency. It is calculated as the width between the upper and lower wavelengths where the intensity is 50%.

[0576] Fabrication of organic electroluminescence devices Organic EL elements according to the examples and comparative examples were prepared, and voltage was applied to measure the current density, luminance, 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 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 of the present invention is not limited to these compositions, and the thickness and material of each layer may vary depending on the basic physical properties of the compound of the present invention. The amount of the change can be appropriately changed.

[0577] [Table 1]

[0578] In Table 1, "HI" is 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- 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]-4-amine, and "EMH2" is 9-phenyl-10-(4-phenylamine phthalen-1-yl)anthracene, and "ET-1" is 4,6,8,10-tetrafluoroethylene. 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 is as follows: The structure is shown.

[0582] [ka]

[0583] <Example 1> <Configuration A: Device using compound (1-1) as a dopant> The ITO film was deposited to a thickness of 200 nm by sputtering and polished to a thickness of 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 the substrate holder of a commercially available deposition device (Showa Vacuum Co., Ltd.). Then, HI, HT, EB, EMH1, compound (1-1), ET and LiF were fixed. A molybdenum evaporation boat containing aluminum and a tungsten evaporation boat containing molybdenum and 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 was reduced to 100 MPa, and HI was 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 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 / s until the film thickness reached 1 nm. Then, aluminum was heated and evaporated to a thickness of 100 nm to form a cathode. The deposition rate of aluminum was 1 nm to 10 nm. It was adjusted to be / sec.

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

[0587] <Comparative Example 1> <Configuration A: Device using Comparative Compound 1 as a dopant> An EL device was obtained in the same manner and with the same structure 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 of the light emitted 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 during light emission is The luminance achieved in Example 1 was 14.0%, 12.0%, and 9.0%, respectively. The results showed low external quantum efficiency and large roll-off.

[0588] <Example 2> <Configuration B: Element using compound (1-1) as a dopant> An EL device having the structure B was obtained in the same manner as in the structure A, except that EMH2 and compound (1-1) The deposition rate was adjusted so that the weight ratio of the two was approximately 98:2. 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 (0.118, 0.106). In particular, the half-width of the emission spectrum is narrow 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 both at the same time, and also enables device design that is kind to 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 in the same manner and with the same structure as in Example 2, except that the dopant was changed. The result is 1000cd / m 2 The applied voltage during light emission was 4.1 V, the external quantum efficiency was 6.6%, and the The optical spectrum (Figure 8) has a maximum emission wavelength of 468 nm and a half-width of 26 nm, which is in line with the CIE standard. The degree (x, y) was (0.124, 0.111). The pressure and external quantum efficiency were comparable, but the half-width was broad.

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

[0591] [Table 3]

[0592] <Comparative Example 3> <Configuration A: Device using Comparative Compound 2 as a dopant> The ITO film was deposited to a thickness of 200 nm by sputtering and polished to a thickness of 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 the substrate holder of a commercially available deposition device (Showa Vacuum Co., Ltd.). Fix and place HI, HT, EB, EMH1, comparison compound 2, ET and LiF, respectively. A molybdenum evaporation boat containing aluminum was installed. did.

[0593] 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 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 deposit a film having a thickness of 15 nm to form a hole transport layer 2. Then, EMH1 and the comparative compound 2 were heated at the same time 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 of each layer was 0.01 to 1 nm / sec. LiF was then 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. During this process, the deposition rate of aluminum was adjusted to 1 nm to 10 nm / sec.

[0594] The ITO electrode is the anode and the aluminum electrode is the cathode, and a DC voltage is 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 has a full width at half maximum (FWHM) of 18 nm and a peak wavelength of 480 nm. Although a very thin 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 color. 2 Departure The external quantum efficiency during light irradiation 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 The wavelength is 3 nm and a very thin emission is observed. The chromaticity is CIE chromaticity (x,y) = (0.105,0 .210), which was a slightly deeper blue than Comparative Example 3. Also, at 100 cd / m 2 Illumination The external quantum efficiency at this time 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 element 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-hexaazatriphenylphosphine Tris-PCz is 9,9',9”-triphenylhexacarbonitrile. 3,3',6',3"-tert-9H,9H',9H"- " is 2,4,6-tri[[1,1'-biphenyl]-3-yl]-1,3,5-triazinyl BPy-TP2 is 2,7-di([2,2'-bipyridine]-5-yl)tetrahydrofuran. 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 50 nm. A 0.7 mm glass substrate (Optoscience, Inc.) was used as the transparent support substrate. The substrate was fixed to the substrate holder of a commercially available deposition device (Choshu Sangyo Co., Ltd.) and ris-PCz, EMH1, compound (1-1), T2T, BPy-TP2 and LiF Tantalum evaporation crucibles with aluminum in them, and aluminum nitride crucibles with aluminum in them 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 10 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 30 nm to form a two-layered film. Next, EMH1 and compound (1-1) were heated simultaneously 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. Then, 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. Then, LiF is heated to form The deposition rate was 0.01 to 0.1 nm / sec to give a film thickness of 1 nm. Then, aluminum was 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 50 nm. A 0.7 mm glass substrate (Optoscience, Inc.) was used as the transparent support substrate. The substrate was fixed to the substrate holder of a commercially available deposition device (Choshu Sangyo Co., Ltd.) and ris-PCz, EB, compound (3-262), compound (1-1), BPy-TP2 and The tantalum crucibles were filled with LiF and LiF, respectively, and the aluminum nitride crucible was filled with aluminum. An aluminum evaporation crucible is attached.

[0605] The following layers are formed in order on the ITO film of the transparent support substrate. -4 The pressure was reduced to 10 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 the EB was then heated. Then, a hole layer consisting of three layers is formed by depositing the compound (3-262) and compound (1-1) were heated simultaneously and evaporated to a thickness of 30 nm. A light-emitting layer is formed. The weight ratio of compound (3-262) to compound (1-1) is about 90:1. The deposition rate is adjusted so that the film thickness becomes 10n. 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. Then, LiF is Heat the film and deposit it at a deposition rate of 0.01 to 0.1 nm / sec until the film thickness becomes 1 nm. Aluminum was 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 by vapor deposition at a high temperature, an organic EL element 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> The ITO film was deposited to a thickness of 200 nm by sputtering and polished to a thickness of 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 the substrate holder of a commercially available deposition device (manufactured by Choshu Sangyo Co., Ltd.). Then, 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. HT was then heated to deposit a film thickness of 40 nm. The EB is heated to deposit a film of 15 nm thickness, and three layers are formed. Next, compound (5-201) and compound (1-1) were added simultaneously. The compound (5-201) was 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) was approximately 99:1. The electron transport layer was formed by heating and depositing the material to a thickness of 40 nm. The deposition rate of each layer was 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 layer was 1 nm, and an organic EL device was obtained. The deposition rate was adjusted to 1 nm to 10 nm / sec.

[0610] The ITO electrode is the anode and the aluminum electrode is the cathode, and a DC voltage is applied to measure the brightness, chromaticity, and The external quantum efficiency was measured. 2 The emission spectrum at the time of emission is the half width (FWH M) 21 nm, the peak wavelength is 473 nm, and emission with extremely 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 an extremely high quantum efficiency. It was made.

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

[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 100 cd / m 2 Emission spectrum during emission The full width at half maximum (FWHM) was 28 nm and the peak wavelength was 465 nm, which is more color-matched than Examples 8 and 9. The emission is of poor purity, with a CIE chromaticity of (x,y)=(0.128,0.124). On the other hand, 100cd / 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> The ITO film was deposited to a thickness of 200 nm by sputtering and polished to a thickness of 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 the substrate holder of a commercially available deposition device (manufactured by Choshu Sangyo Co., Ltd.). Then, 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. HT was then heated to deposit a film thickness of 40 nm. The EB is heated to deposit a film of 15 nm thickness, and three layers are formed. Next, compound (5-102) and compound (1-1) were added simultaneously. The compound (5-102) was 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) was approximately 99:1. The electron transport layer was formed by heating and depositing the material to a thickness of 30 nm. The deposition rate of each layer was 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 layer was 1 nm, and an organic EL device was obtained. The deposition rate was adjusted to 1 nm to 10 nm / sec.

[0615] The ITO electrode is the anode and the aluminum electrode is the cathode, and a DC voltage is applied to measure the brightness, chromaticity, and The external quantum efficiency was measured. 2 The emission spectrum at the time of emission is the half width (FWH M) 17 nm, the peak wavelength is 470 nm, and emission with extremely 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 color. 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 a novel polycyclic aromatic compound, which expands the range of materials for organic EL devices. In addition, the novel polycyclic aromatic compound can be used as a material for an organic electroluminescence device. 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, ring B, ring C and ring D are each independently an aryl ring or a heteroaryl ring. rings, at least one hydrogen atom in the rings may be replaced; Y is B (boron), X １ , X ２ , X ３ and X ４ are each independently >O, >N-R, >S or >S e, and R in the >N--R is an optionally substituted aryl, an optionally substituted R in the >N-R 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, or diarylamino (wherein aryl is an aryl having 6 to 12 carbon atoms; Z １ and Z ２ each independently represents an optionally substituted aryl, optionally substituted heteroaryl, optionally substituted diarylamino, optionally substituted 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; 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.)

2. Ring A, ring B, ring C and ring D are each independently an aryl ring or a heteroaryl ring. rings, at least one hydrogen in these rings is selected from the group consisting of 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. Preferably, the A ring and the B ring are each independently selected from Y, X １ and X ２ The fused two-ring structure shown on the left in the above formula The ring C and the ring D are each a 5-membered ring or a 6-membered ring sharing a bond with the ring structure, and the rings C and D are each a Y, X ３ and X ４ mosquito a 5- or 6-membered ring sharing a bond with the fused bicyclic structure of the above formula (R), Y is B (boron), X １ , X ２ , X ３ and X ４ are each independently >O, >N-R, >S or >S e, R of the >N-R is aryl, heteroaryl or alkyl, and R At least one hydrogen atom in the formula (I) is selected from the group consisting of aryl, heteroaryl, diarylamino, diheteroaryl, and the like. arylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy oxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio or may be substituted with an alkyl-substituted silyl; and R in the >N-R may be -O-, - S-, -C(-R) ２ or a single bond between said ring A, ring B, ring C and / or ring D may be bonded, and the -C(-R) ２ R in - is 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, or diarylamino (wherein aryl is an aryl having 6 to 12 carbon atoms; Z １ and Z ２ each independently represents an aryl, heteroaryl, or diarylamino group; , diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl , aryloxy, heteroaryloxy, arylthio or heteroarylthio. At least one hydrogen atom in these is an aryl, heteroaryl, diaryla Amino, alkyl, cycloalkyl, alkoxy, aryloxy or alkyl substituted silyl Z may be substituted with １ is -O-, -S-, -C(-R) ２ - or single bond may be bonded to the ring A via Z ２ is -O-, -S-, -C(-R) ２ -or may be bonded to the ring C via a single bond, and the -C(-R) ２ -R is hydrogen or a Rukill, and, At least one hydrogen atom in the compound represented by formula (1) is cyano, halogen or heavy. may be substituted with hydrogen; The polycyclic aromatic compound according to claim 1.

3. The polycyclic aromatic compound according to claim 1, which is represented by the following general formula (2): 【Chemistry 2】 (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 Each Each independently is 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 an aryl, heteroaryl or or alkyl; and R ５ ~R ７ and R １０ ~R １２ Of Adjacent groups are bonded to each other 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 replaced by an aryl ring. Heteroaryl, diarylamino, diheteroarylamino, arylheteroaryl Amino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy arylthio, heteroarylthio or alkyl-substituted silyl. At least one hydrogen atom in these is an aryl, heteroaryl or alkyl group. may be substituted with Y is B (boron), X １ , X ２ , X ３ and X ４ are each independently >O, >N-R, >S or >S R of the >N-R is an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, R in the >N-R is -O-, -S -, -C(-R) ２ or bonded to the ring a, ring b, ring c and / or ring d by a single bond; may be bonded to said -C(-R) ２ R in - is hydrogen or alkyl having 1 to 6 carbon atoms. the law of nature, R １ and R ２ each independently represents hydrogen, alkyl having 1 to 6 carbon atoms, or is an aryl of from 1 to 12; Z １ and Z ２ each independently represents an aryl, heteroaryl, or diarylamino group; , diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl , aryloxy, heteroaryloxy, arylthio or heteroarylthio. At least one hydrogen atom in these is selected from the group consisting of aryl, heteroaryl, alkyl, and aryl. may be substituted with alkyl-substituted silyl; Z １ is -O-, -S-, -C(-R) ２ may be bonded to the ring a via a single bond, Z ２ is -O-, -S-, -C(- R) ２ may be bonded to the ring c via a single bond, and the -C(-R) ２ -R is water or an alkyl group having 1 to 6 carbon atoms, At least one hydrogen atom in the compound represented by formula (2) is cyano, halogen or heavy. may be substituted with hydrogen.)

4. R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ Each each independently being hydrogen, an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, Arylamino (wherein aryl is aryl having 6 to 12 carbon atoms), alkyl having 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 an aryl group having 6 to 12 carbon atoms or an aryl group having 1 to 6 carbon atoms. may be substituted with aryl; 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 ring members may be formed, and at least one of the ring members may be One hydrogen is replaced by 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 >N-R, R in >N-R is an aryl having 6 to 10 carbon atoms or an alkyl having 1 to 4 carbon atoms, R １ and R ２ each independently represents hydrogen, alkyl having 1 to 6 carbon atoms, or is an aryl of from 1 to 12; Z １ and Z ２ each independently represents an aryl having 6 to 30 carbon atoms, Heteroaryl, diarylamino (wherein aryl has 6 to 12 carbon atoms), carbon Alkyl having 1 to 12 prime numbers, cycloalkyl having 3 to 12 carbon atoms, aryl having 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 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. may be substituted with hydrogen; The polycyclic aromatic compound according to claim 3.

5. R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ Each each independently represents hydrogen, an aryl having 6 to 10 carbon atoms, or an 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 >N-R, R in >N-R is an aryl having 6 to 10 carbon atoms or an alkyl having 1 to 4 carbon atoms, R １ and R ２ each independently represents hydrogen, alkyl having 1 to 6 carbon atoms, or is an aryl of from 1 to 12; Z １ and Z ２ each independently represents an aryl having 6 to 16 carbon atoms, Heteroaryl, diarylamino (wherein aryl has 6 to 10 carbon atoms), carbon Alkyl having 1 to 6 prime numbers, cycloalkyl having 3 to 10 carbon atoms, aryl alkyl having 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. may be substituted with hydrogen; The polycyclic aromatic compound according to claim 3.

6. The polycyclic aromatic compound according to claim 1 , which is represented by any one of the following formulas: 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 (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 group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Yes, R １００ each independently represents an aryl having 6 to 10 carbon atoms, a carbazolyl, or a dialkylamino group. Arylamino (wherein aryl is aryl having 6 to 10 carbon atoms), alkyl having 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 an alkyl having 1 to 6 carbon atoms, and the carbazolyl may be substituted with a carbon atom. It may be substituted with an aryl having 6 to 10 carbon atoms or an alkyl having 1 to 6 carbon atoms.

7. A material for organic devices, comprising the polycyclic aromatic compound according to any one of claims 1 to 6. 。

8. The organic device material includes a material for an organic electroluminescent element and a material for an organic field effect transistor. The material for an organic device according to claim 7 , which is a material for an organic thin-film solar cell.

9. 9. The organic device according to claim 8, wherein the material for an organic electroluminescent element is a material for a light-emitting layer. Materials for use.

10. A composition for forming a light-emitting layer for forming a light-emitting layer of an organic electroluminescent device by coating, comprising: As the first component, at least one polycyclic aromatic compound according to any one of claims 1 to 6 is Things and 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 the above compound.

11. A pair of electrodes consisting of an anode and a cathode, and the device according to claim 9, which is disposed between the pair of electrodes. and a light-emitting layer containing a material for a light-emitting layer.

12. A pair of electrodes consisting of an anode and a cathode, and the liquid crystal display device according to claim 10, which is disposed between the pair of electrodes. and a light-emitting layer formed by applying and drying the light-emitting layer-forming composition. 。

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) 13. The organic electroluminescence device according to claim 11, comprising a compound represented by the formula: 【Chemistry 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 heteroaryl having 2 to 30 carbon atoms, At least one hydrogen atom in the compounds represented by the above formulas is an alkyl group having 1 to 6 carbon atoms. , cyano, halogen or deuterium.

14. The light-emitting layer further contains a compound represented by the following general formula (5):

13. The organic electroluminescent device according to claim 12, 【Chemistry 9】 (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 each other to form an aryl ring together with the a, b or c ring. A ring or a heteroaryl ring may be formed, and at least one of the rings formed may be The hydrogen of is an aryl, heteroaryl, diarylamino, diheteroarylamino, a The alkyl group may be substituted with aryl, heteroaryl, amino or alkyl. At least one hydrogen may further be an aryl, heteroaryl, diarylamino or alkyl group. may be substituted with At least one hydrogen atom in the compound represented by formula (5) is independently a halo. It may be substituted with hydrogen or deuterium.

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 borane derivative, a pyridine derivative, a fluorine derivative, or a fluorine derivative. 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 The composition according to any one of claims 11 to 14, comprising at least one selected from the group consisting of: An organic electroluminescent device.

16. The electron transport layer and / or the electron injection layer may further comprise an alkali metal, an alkaline earth metal, metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metals oxides of rare earth metals, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides genides, organic complexes of alkali metals, organic complexes of alkaline earth metals and rare earth metals The organic electrochemical device according to claim 15, comprising at least one selected from the group consisting of organic electrochemical complexes. Field light emitting element.

17. A display device or lighting device comprising the organic electroluminescent device according to any one of claims 11 to 16. Device.

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