JP2020147563A - Polycyclic aromatic compound and polymer thereof - Google Patents

Abstract

To provide a polycyclic aromatic compound excellent as an organic electroluminescent element material, and an organic electroluminescent element employing the same.SOLUTION: A novel polycyclic aromatic compound represented by general formula (1) is a polycyclic aromatic compound in which multiple aromatic rings are connected through, e.g., a boron atom and a nitrogen atom or an oxygen atom, and pyridine nitrogen is introduced into the aromatic rings. In the formula, Y1 to Y6 are each independently =C(-R)- or =N-, where at least one of them is =N- (pyridine nitrogen); R1 to R5 are hydrogen, aryl, or the like; and X1 and X2 are oxygen or the like.SELECTED DRAWING: None

Description

In the present invention, a polycyclic aromatic compound and a multimer thereof (hereinafter, these are collectively simply referred to as "polycyclic aromatic compound"), an organic electroluminescent device, an organic field effect transistor, and an organic thin film solar using the same. It relates to organic devices such as batteries, as well as display devices and lighting devices.

Conventionally, display devices using electroluminescent elements have been studied in various ways because they can be reduced in power consumption and thickness. Furthermore, organic electroluminescent elements made of organic materials can be easily reduced in weight and size. Therefore, it has been actively examined. In particular, the development of organic materials having emission characteristics such as blue, which is one of the three primary colors of light, and the development of organic materials having charge transporting ability such as holes and electrons (which have the potential to become semiconductors and superconductors). Development has been actively studied for both high molecular weight compounds and low molecular weight compounds.

The organic EL element has a structure composed of a pair of electrodes composed of an anode and a cathode, and one layer or a plurality of layers containing an organic compound, which is arranged between the pair of electrodes. Layers containing organic compounds include light emitting layers and charge transport / injection layers that transport or inject charges such as holes and electrons, and various organic materials suitable for these layers have been developed.

As a material for a light emitting layer, for example, a benzofluorene compound or the like has been developed (International Publication No. 2004/061047). Further, as a hole transport material, for example, a triphenylamine-based compound has been developed (Japanese Patent Laid-Open No. 2001-172232). Further, as an electron transport material, for example, an anthracene compound and the like have been developed (Japanese Patent Laid-Open No. 2005-170911).

Further, in recent years, a material obtained by improving a triphenylamine derivative has been reported as a material used for an organic EL element or an organic thin-film solar cell (International Publication No. 2012/118164). This material was prepared with reference to N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine (TPD), which had already been put into practical use. It is a material characterized in that its flatness is enhanced by connecting aromatic rings constituting triphenylamine to each other. In this document, for example, the charge transport property of a NO-linking compound (Compound 1 on page 63) is evaluated, but a method for producing a material other than the NO-linking compound is not described, and the element to be linked is not described. Since the electronic states of the entire compound are different if they are different, the properties obtained from materials other than the NO-linking compound are not yet known. Other examples of such compounds can be found (International Publication No. 2011/107186). For example, a compound having a conjugated structure having a large triplet exciton energy (T1) is useful as a material for a blue light emitting layer because it can emit phosphorescence having a shorter wavelength. Further, as an electron transport material or a hole transport material that sandwiches the light emitting layer, a compound having a novel conjugated structure having a large T1 is required.

The host material of the organic EL element is generally a molecule in which a plurality of existing aromatic rings such as benzene and carbazole are linked by a single bond or a phosphorus atom or a silicon atom. This is because the large HOMO-LUMO gap (bandgap Eg in the thin film) required for the host material is secured by connecting a large number of relatively small aromatic rings of the conjugated system. In addition, the host material of the organic EL element using a phosphorescent material or a heat activated delayed fluorescence (TADF) material, high triplet excitation energy (E _T) is also required, the donor or acceptor properties of aromatic in the molecule by connecting the ring or substituent, to localize the SOMO1 and SOMO2 triplet excited state (T1), by reducing the exchange interaction between the two trajectories, improve triplet excitation energy (E _T) It becomes possible to make it. However, the redox stability of the small aromatic ring of the conjugated system is not sufficient, and the lifetime of the device using the molecule in which the existing aromatic ring is linked as the host material is not sufficient. On the other hand, polycyclic aromatic compounds having an extended π conjugated system, generally, but the redox stability is excellent, because HOMO-LUMO gap and triplet excitation energy (band gap Eg of the thin film) (E _T) is low, It has been considered unsuitable for host materials.

Further, in recent years, compounds in which a plurality of aromatic rings are condensed with boron or the like as a central atom have been reported (International Publication No. 2015/102118). In this document, an organic EL device evaluation using a compound obtained by condensing the plurality of aromatic rings as a dopant material of a light emitting layer is carried out, but the document discloses an extremely large number of compounds, among these. In particular, it is useful to study a compound having excellent organic EL properties such as light emission properties. The emission characteristics, emission spectrum of the narrow half width basically, high fluorescence quantum yield, a small delayed fluorescence lifetime, a large energy gap Eg, and a small Delta] E _ST, etc. is required, in these one or more properties It is desirable that it is excellent, and when it has overall excellent properties, it is expected to be used as a heat-activated delayed fluorescent material.

International Publication No. 2004/061047 Japanese Unexamined Patent Publication No. 2001-172232 Japanese Patent Application Laid-Open No. 2005-170911 International Publication No. 2012/118164 International Publication No. 2011/107186 International Publication No. 2015/102118

As described above, various materials have been developed as materials used for organic EL devices, but in order to further enhance organic EL characteristics such as light emitting characteristics and to increase the choices of organic EL materials such as materials for light emitting layers. In addition, the development of compounds that have not been specifically known in the past is desired.

As a result of diligent studies to solve the above problems, the present inventors have found that in a polycyclic aromatic compound in which a plurality of aromatic rings are linked by a boron atom and a nitrogen atom or an oxygen atom, pyridine nitrogen is attached to the aromatic ring. We have found that an excellent organic EL element can be obtained by introducing the above, and have completed the present invention. That is, the present invention provides the following polycyclic aromatic compounds, and further, organic device materials containing the following polycyclic aromatic compounds.

In addition, although the chemical structure and the substituent may be represented by the number of carbon atoms in the present specification, the number of carbon atoms in the case where the substituent is substituted in the chemical structure or the substituent is further substituted in the substituent is the chemical structure. It means the carbon number of each of the substituents and substituents, and does not mean the total carbon number of the chemical structure and the substituents or the total carbon number of the substituents and the substituents. For example, "substituent B of carbon number Y substituted with substituent A of carbon number X" means that "substituent A of carbon number X" is substituted with "substituent B of carbon number Y". However, the number of carbon atoms Y is not the total number of carbon atoms of the substituent A and the substituent B. Further, for example, "substituent B having a carbon number Y substituted with substituent A" means that "substituent A having no limitation on the number of carbon atoms" is substituted for "substituent B having a carbon number Y". However, the number of carbon atoms Y is not the total number of carbon atoms of the substituent A and the substituent B.

Item 1.
A multimer of a polycyclic aromatic compound represented by the following general formula (1) or a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1).
In the above formula (1),
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are single-bonded). (Or may be attached via a linking group), alkyl, cycloalkyl, alkoxy or aryloxy, at least one hydrogen in which is further substituted with aryl, heteroaryl, alkyl or cycloalkyl. Well,
X ¹ and X ² are independently>N-R,>O,> C (-R) ₂ ,> S or> Se, and both X ¹ and X ² are> C (-R) _2. Never become
The Rs in> N-R and> C (-R) ₂ are independent of hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, and diarylboryl (two aryls are simple). It may be attached via a bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy, in which at least one hydrogen is further substituted with aryl, heteroaryl, alkyl or cycloalkyl. The R of> N-R and> C (-R) ₂ may be independently bonded to at least one ring of the a ring, b ring and c ring by a linking group or a single bond, respectively. Often,
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ are independently = C (-R)-or = N-, and at least one is = N-.
R in = C (-R)-is independent of hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls have a single bond or a linking group). (May be bonded via), alkyl, cycloalkyl, alkoxy or aryloxy, wherein at least one hydrogen in these may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl.
Adjacent groups of R ¹ , R ² , R ³ , R ⁴ and R ⁵ , and = C (-R)-R as Y ^{1 to} Y ⁶ are bonded to each other to form a ring, b. An aryl ring or a heteroaryl ring may be formed together with at least one ring of the ring and the c ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, aryl hetero. Arylamino, diallylboryl (two aryls may be attached via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy may be substituted, in which at least one hydrogen is. , And may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, and
At least one hydrogen in the compound and structure represented by the general formula (1) may be substituted with cyano, halogen or deuterium.

Item 2.
In the above formula (1),
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen, aryl with 6 to 30 carbon atoms, heteroaryl with 2 to 30 carbon atoms, and diarylamino (however, each aryl has 6 carbon atoms). ~ 12 aryl), diarylboryl (where aryl is an aryl having 6-12 carbon atoms, and the two aryls may be bonded via a single bond or a linking group), an alkyl having 1 to 12 carbon atoms, It is a cycloalkyl having 3 to 16 carbon atoms, an alkoxy having 1 to 12 carbon atoms or an aryloxy having 6 to 30 carbon atoms, and at least one hydrogen in these is an aryl having 6 to 30 carbon atoms and 2 to 2 carbon atoms. It may be substituted with 30 heteroaryls, alkyls with 1-12 carbon atoms or cycloalkyls with 3-16 carbon atoms.
X ¹ and X ² are independently>N-R,>O,> C (-R) ₂ ,> S or> Se, and both X ¹ and X ² are> C (-R) _2. Never become
The R in> N-R and> C (-R) ₂ are independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, each aryl has carbon number of carbon). 6-12 aryls), diarylboryls (where aryls are 6-12 carbon atoms, and the two aryls may be attached via a single bond or a linking group), alkyls with 1-12 carbon atoms. , Cycloalkyl with 3 to 16 carbon atoms, alkoxy with 1 to 12 carbon atoms or aryloxy with 6 to 30 carbon atoms, in which at least one hydrogen is an aryl with 6 to 30 carbon atoms, 2 carbon atoms. It may be substituted with ~ 30 heteroaryl, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 16 carbon atoms, and the above-mentioned> N-R and> C (-R) ₂ R are independent of each other. Then, it may be bonded to at least one of the a ring, the b ring and the c ring by −O−, −S−, −C (−R) _2- or a single bond, and the −C (−C (−C). R) _2- R is hydrogen, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms.
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ are independently = C (-R)-or = N-, and at least one is = N-.
The Rs in = C (-R)-are independent of hydrogen, aryls having 6 to 30 carbon atoms, heteroaryls having 2 to 30 carbon atoms, and diarylaminos (however, each aryl has 6 to 12 carbon atoms). ), Diarylboryl (where aryl is an aryl having 6 to 12 carbon atoms, and the two aryls may be bonded via a single bond or a linking group), an alkyl having 1 to 12 carbon atoms, and 3 to 12 carbon atoms. 16 cycloalkyls, alkoxys with 1-12 carbon atoms or aryloxys with 6-30 carbon atoms, at least one of which is an aryl with 6-30 carbon atoms and a heteroaryl with 2-30 carbon atoms. , May be substituted with alkyls having 1-12 carbon atoms or cycloalkyls having 3-16 carbon atoms.
Adjacent groups of R ¹ , R ² , R ³ , R ⁴ and R ⁵ , and = C (-R)-R as Y ^{1 to} Y ⁶ are bonded to each other to form a ring, b. An aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms may be formed together with at least one ring of the ring and the c ring, and at least one hydrogen in the formed ring has 6 carbon atoms. ~ 30 aryls, 2-30 carbon heteroaryls, diarylaminos (where each aryl is 6-12 carbons), diarylboryl (where aryls are 6-12 carbons, and the two aryls are (May be bonded via a single bond or a linking group), alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, alkoxy having 1 to 12 carbon atoms, or aryloxy having 6 to 30 carbon atoms. At least one hydrogen in these may be substituted further, an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms or an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 16 carbon atoms. May be replaced with, and
At least one hydrogen in the compound and structure represented by the general formula (1) may be substituted with cyano, halogen or deuterium.
Item 2. The polycyclic aromatic compound according to Item 1 or a multimer thereof.

Item 3.
Item 2. The polycyclic aromatic compound or a multimer thereof according to Item 1 or 2, wherein X ¹ and X ² are independently> N-R or> O, respectively.

Item 4.
X ¹ and X ² are independently> N-R or> O, respectively.
Y ^{2, Y} 3, ^{Y 4} and ^{Y 5} are each independently, = C (-R) - and is, ^{Y 1} and ^{Y 6} are each independently, = C (-R) - or = N -And at least one = N-,
Item 3. The polycyclic aromatic compound according to any one of Items 1 to 3 or a multimer thereof.

Item 5.
Item 2. The polycyclic aromatic compound according to any one of Items 1 to 4, or a multimer thereof, which comprises a partial structure represented by any of the following formulas.

Item 6.
Item 2. The polycyclic aromatic compound or a multimer thereof represented by any of the following formulas.

Item 7.
Item 5. A reactive compound in which a polycyclic aromatic compound according to any one of Items 1 to 6 or a multimer thereof is substituted with a reactive substituent.

Item 8.
A polymer compound obtained by polymerizing the reactive compound according to Item 7 as a monomer, or a polymer crosslinked product obtained by further cross-linking the polymer compound.

Item 9.
A pendant type polymer compound in which a main chain type polymer is substituted with the reactive compound according to Item 7, or a pendant type polymer crosslinked product in which the pendant type polymer compound is further crosslinked.

Item 10.
A material for an organic device containing the polycyclic aromatic compound according to any one of Items 1 to 6 or a multimer thereof.

Item 11.
A material for an organic device containing the reactive compound according to Item 7.

Item 12.
A material for an organic device containing the polymer compound or polymer crosslinked product according to Item 8.

Item 13.
A material for an organic device containing the pendant type polymer compound or the pendant type polymer crosslinked body according to Item 9.

Item 14.
Item 2. The material for an organic device according to any one of Items 10 to 13, wherein the material for an organic device is a material for an organic electroluminescent device, a material for an organic field effect transistor, or a material for an organic thin film solar cell.

Item 15.
Item 2. The material for an organic device according to Item 14, wherein the material for the organic electroluminescent device is a material for a light emitting layer.

Item 16.
An ink composition containing the polycyclic aromatic compound according to any one of Items 1 to 6 or a multimer thereof, and an organic solvent.

Item 17.
An ink composition containing the reactive compound according to Item 7 and an organic solvent.

Item 18.
An ink composition containing a main chain polymer, the reactive compound according to Item 7, and an organic solvent.

Item 19.
An ink composition containing the polymer compound or polymer crosslinked product according to Item 8 and an organic solvent.

Item 20.
An ink composition containing the pendant-type polymer compound or the pendant-type polymer crosslinked product according to Item 9 and an organic solvent.

Item 21.
Item 8 is a polycyclic aromatic compound or a polymer thereof, which is arranged between a pair of electrodes composed of an anode and a cathode and the pair of electrodes, according to any one of Items 1 to 6, and a reactive compound according to Item 7. Item 2. An organic electroluminescent element having an organic layer containing the polymer compound or polymer crosslinked body according to Item 9 or the pendant type polymer compound or pendant type polymer crosslinked body according to Item 9.

Item 22.
Item 2. The organic electroluminescent device according to Item 21, wherein the organic layer is a light emitting layer.

Item 23.
The light emitting layer is further represented by a compound represented by the following general formula (H1), a compound represented by the following general formula (H2), a compound represented by the following general formula (H3), and a compound represented by the following general formula (H4). Item 22. The organic electroluminescent element according to Item 22, which comprises a compound containing the above-mentioned structure, a compound represented by the following general formula (H5), and at least one selected from the group consisting of TADF materials.
In the general formula (H1), ^{L 1} is a heteroarylene arylene or C2-30 6 to 30 carbon atoms,
In the above general formula (H2), L ² and L ³ are independently aryls having 6 to 30 carbon atoms or heteroaryls having 2 to 30 carbon atoms.
In the above general formula (H3), MU is a divalent group independently represented by removing any two hydrogen atoms from the aromatic compound, and EC is each independently an arbitrary hydrogen from the aromatic compound. It is a monovalent group represented excluding atoms, with two hydrogens in the MU replaced by EC or MU, where k is an integer of 2-50000.
In the general formula (H4), G is independently = C (−H) − or = N−, and H in the above = C (−H) − is a substituent or another formula (H4). It may be replaced by the structure represented
In the above general formula (H5),
R ^{1 to} R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl or cycloalkyl, wherein at least one hydrogen in these is an additional aryl, It may be substituted with heteroaryl, diarylamino, alkyl or cycloalkyl,
Adjacent groups of R ^{1 to} R ¹¹ may be bonded to 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 is It may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl, in which at least one hydrogen is further aryl, heteroaryl, diarylamino, alkyl or cycloalkyl. May be replaced with, and
At least one hydrogen in the compound or structure represented by each of the above formulas may be substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, cyano, halogen or deuterium.

Item 24.
It has at least one of an electron transporting layer and an electron injecting layer arranged between the cathode and the light emitting layer, and at least one of the electron transporting layer and the electron injecting layer is a borane derivative, a pyridine derivative, or a fluorantene derivative. , BO-based derivative, anthracene derivative, benzofluorene derivative, phosphine oxide derivative, pyrimidine derivative, carbazole derivative, triazine derivative, benzoimidazole derivative, phenanthroline derivative and quinolinol-based metal complex. Item 22 or 23. The organic electric field light emitting element.

Item 25.
At least one of the electron transport layer and the electron injection layer further comprises an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, and an alkaline earth metal. Contains at least one selected from the group consisting of halides, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals. 24. The organic electric field light emitting element.

Item 26.
At least one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer is a polymer compound obtained by polymerizing a low molecular compound capable of forming each layer as a monomer, or a polymer compound. , A polymer crosslinked product obtained by further cross-linking the polymer compound, or a pendant type polymer compound obtained by reacting a low molecular weight compound capable of forming each layer with a main chain type polymer, or the pendant type polymer compound. Item 2. The organic electric field light emitting element according to any one of Items 21 to 25, which comprises a pendant type polymer crosslinked body further crosslinked.

Item 27.
A display device or a lighting device including the organic electroluminescent element according to any one of Items 21 to 26.

According to a preferred embodiment of the present invention, a polycyclic aromatic compound represented by the general formula (1), which has not been specifically known in the past, can further enhance organic EL characteristics such as light emission characteristics, or can further enhance organic EL characteristics such as light emitting layer. The choice of organic EL materials such as materials for materials can be increased. As the light emission characteristics, in particular the half-value width of the emission spectrum, fluorescence quantum yield, delayed fluorescence lifetime, energy gap Eg and Delta] E _ST and the like, according to a preferred embodiment of the present invention, any of these or When excellent effects can be obtained in a plurality of properties and the overall excellent properties are provided, it can be expected to be used as a heat-activated delayed fluorescent material.

It is a schematic sectional drawing which shows the organic EL element which concerns on this embodiment.

1. 1. Polycyclic aromatic compound represented by the general formula (1) and its multimer The present invention is a polycyclic aromatic compound represented by the following general formula (1) or a structure represented by the following general formula (1). It is a multimer of a polycyclic aromatic compound having a plurality of.

(1) Outline of the present invention For example, as a light emitting material for an organic EL display, three types of a fluorescent material, a phosphorescent material, and a heat-activated delayed fluorescence (TADF) material are used. The fluorescent material has a luminous efficiency. Is low, about 25 to 62.5%. On the other hand, the phosphorescent material and the TADF material may reach 100% luminous efficiency, but both have a problem of low color purity (wide emission spectrum). In the display, various colors are expressed by mixing the three primary colors of light, red, green, and blue, but if the color purity of each is low, colors that cannot be reproduced will be produced, and the image quality of the display will be poor. It drops significantly. Therefore, in commercially available displays, unnecessary colors are removed from the emission spectrum with an optical filter to increase the color purity (after narrowing the spectrum width) before use. Therefore, if the original spectral width is wide, the rate of removal increases, so that even if the luminous efficiency is high, the substantial efficiency is greatly reduced. For example, the half width of the blue emission spectrum of a commercially available smartphone is about 20 to 25 nm, but the half width of a general fluorescent material is about 40 to 60 nm, the phosphorescent material is about 60 to 90 nm, and the TADF material. It is about 70 to 100 nm. When a fluorescent material is used, the half width is relatively narrow, so it is sufficient to remove a part of unnecessary colors, but when a phosphorescent material or a TADF material is used, it is necessary to remove more than half. Against this background, the development of a luminescent material having both luminous efficiency and color purity has been desired.

In general, TADF materials use electron-donating substituents called donors and electron-accepting substituents called acceptors to localize HOMO and LUMO in the molecule for efficient reverse intersystem. Although it is designed to cause crossing), the structural relaxation in the excited state becomes large when donors and acceptors are used (for some molecules, the stable structure differs between the ground state and the excited state, so the ground state is affected by an external stimulus. When the conversion from to the excited state occurs, the structure changes to a stable structure in the excited state), which gives a wide emission spectrum with low color purity.

Therefore, Patent Document 6 (International Publication No. 2015/102118) proposes a new molecular design that dramatically improves the color purity of TADF materials. For example, in the compound (1-401) disclosed in the document, three carbons on a benzene ring consisting of six carbons are used by utilizing the multiple resonance effect of boron (electron accepting) and nitrogen (electron donating). We have succeeded in localizing HOMO in (black circles) and LUMO in the remaining three carbons (white circles). Due to this efficient intersystem crossing, the luminous efficiency of the compound reaches up to 100%. Furthermore, the boron and nitrogen of compound (1-401) not only localize HOMO and LUMO, but also maintain a robust planar structure by condensing three benzene rings to relax the structure in the excited state. It also plays a role of suppressing, and as a result, it has succeeded in obtaining an emission spectrum having high color purity with a small Stokes shift of absorption and emission peaks. The half-value width of the emission spectrum is 28 nm, which is a level of color purity that surpasses even the high-color-purity fluorescent materials that have been put into practical use. Further, in the dimer compound (1-422), two borons and two nitrogens are bonded to the central benzene ring to further enhance the multiple resonance effect in the central benzene ring, and as a result, the multiple resonance effect is extremely enhanced. It is possible to emit light having a narrow emission peak width.

On the other hand, Compound (1-401) is Delta] E _ST and excited singlet energy is an energy difference between the triplet energy is relatively small, high spin-orbit interaction flatness (Spin-Orbit Coupling: SOC) is less Therefore, there is a problem that the delayed fluorescence lifetime (Tau (Delay)) is long, and the efficiency is low or the roll-off is large when used as a light emitting material of an organic electric field light emitting element using the thermoactive delayed fluorescence (TADF). was there.

Therefore, as a result of diligent research, (i) an element that enhances the multiple resonance effect is introduced at an appropriate position, (ii) the aromatic ring is cross-linked to increase the flatness of the molecule, and (iii) the molecule is distorted. By properly combining the three approaches of introducing substituents at appropriate positions to reduce flatness, the emission wavelength and half-value width of the emission spectrum can be adjusted and high emission can be achieved in polycyclic aromatic compounds. Achieved efficiency and short delayed fluorescence lifetime, and achieved a suitable emission wavelength and half-width of the emission spectrum, high element efficiency and small roll-off in the device.

Regarding (i) above, in order to enhance the multiple resonance effect, amine nitrogen, which is an electron donating element, and boron, which is an electron accepting element, are introduced at appropriate positions in the molecule. Specifically, the electron donating elements or the electron attracting elements are arranged at the meta position, and the electron donating elements and the electron attracting elements are arranged at the ortho position or the para position. In addition to boron, pyridine nitrogen is another electron-accepting element. Pyridine nitrogen is nitrogen substituted with carbon constituting the benzene ring. By arranging this pyridine nitrogen at the meta position with respect to boron (that is, the positional relationship between the central element B of the above formula (1) and Y ¹ to Y ⁶ ), electron acceptability is established between the pyridine nitrogen and boron. By strengthening each other, a stronger multiple resonance effect can be obtained. As a result, Delta] E _ST is reduced, it is possible to design higher efficiency, a long lifetime TADF dopant material. At the same time, by narrowing the half width, the light extraction efficiency can be further improved.

Further, when an electron donating substituent is bonded to a carbon in which LUMO is distributed (a carbon at the ortho or para position with respect to an existing electron accepting substituent), the electron orbital of the electron donating substituent is changed from HOMO to LUMO. Gives strong perturbation and greatly increases LUMO. As a result, the distance between the HOMO and the LUMO is widened, and the emission wavelength can be shortened.

Similarly, when an electron-accepting substituent is attached to a carbon in which HOMO is distributed (a carbon at the ortho or para position with respect to an existing electron-donating substituent), the electron orbital of the electron-accepting substituent becomes HOMO rather than LUMO. Gives a strong perturbation and greatly lowers HOMO. As a result, the distance between the HOMO and the LUMO is widened, and the emission wavelength can be shortened.

It exhibits shorter wavelength emission characteristics due to the multiple resonance effect by arranging pyridine nitrogen at the meta position with respect to boron and the multiple resonance effect by binding an electron donating / accepting substituent to a specific carbon. Dopant materials can be designed.

Regarding (ii) described above, specifically, the polycyclic aromatic compounds represented by the general formula (1) of the present invention are> N-R and> C (-R) as X ¹ and X ^2. The R of ₂ may be bonded to at least one ring of a ring, b ring and c ring by a linking group or a single bond. This linking structure extends conjugation and increases the flatness of the molecule. As a result, the overlap of the orbitals of the ground state and the excited state becomes large, the transition probability increases, and the luminous efficiency increases. On the other hand, the extension of conjugation leads to a longer emission wavelength. Further, the fused ring formed by this linking structure changes in flatness and flexibility depending on the type of linking group including a single bond, and if the flatness is high, the luminous efficiency is expected to be improved, while the emission wavelength is high. The wavelength may be lengthened, and if the flexibility is high, the intermolecular stacking can be reduced, but the half width of the emission spectrum may be widened.

Regarding the above (iii), specifically, to adjust the substituents ^{R 3} or ^{R 4.} The introduction of a particular substituent distorts the molecule, which in turn distorts both singlet and triplet orbitals. This orbital distortion leads to greater spin-orbit interaction, and the greater the spin-orbit interaction, the more likely TADF is to occur. The transition from triplet to singlet (or singlet to triplet) involves the reversal of electron spin, but the change in orbital angular momentum, which is the same as electron spin, between the orbits that transition according to the law of conservation of energy and the law of conservation of angular momentum. is necessary. Molecular and orbital strains induced by substituents lead to the generation of larger orbital angular momentum during the transition, which induces greater magnetic moments and greater spin-orbit interactions (also known as spin-orbit coupling). Occurs. In addition, since the flatness is lowered due to the large strain of the molecules, it also leads to the reduction of intermolecular stacking.

As a result of properly combining these approaches (i) to (iii), in the compound, the adjustment of the emission wavelength and the half width of the emission spectrum, the realization of high emission efficiency and the short delayed fluorescence lifetime, and the appropriate emission in the device. Half width of wavelength and emission spectrum, high device efficiency and small roll-off can be realized. However, the effect of the polycyclic aromatic compound of the present invention is not bound by the above principle.

(2) Explanation of General Formula (1) Representing the Compound of the Present Invention In the above general formula (1),
R ¹ , R ² , R ³ , R ⁴ and R ⁵ (hereinafter, also referred to as “R ¹ etc.”) are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroaryl. Amino, diallylboryl (two aryls may be attached via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy (above, first substituent), at least one of these. Hydrogen may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl (above, second substituent).
X ¹ and X ² are independently> N-R (amineous nitrogen),>O,> C (-R) ₂ ,> S or> Se, and both X ¹ and X ² are> C. (-R) It never becomes ₂ ,
The Rs in> N-R and> C (-R) ₂ are independent of hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, and diarylboryl (two aryls are simple). It may be attached via a bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy (above, the first substituent), in which at least one hydrogen is further aryl, heteroaryl,. It may be substituted with an alkyl or a cycloalkyl (above, a second substituent), and the R of> N-R and> C (-R) ₂ is independently a linking group or a single bond to form the a ring. It may be bonded to at least one ring of b ring and c ring.
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ (hereinafter, also referred to as “Y ¹ etc.”) are independently = C (-R)-or = N- (pyridine nitrogen). ), At least one = N- (pyridine nitrogen),
R in = C (-R)-is independent of hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls have a single bond or a linking group). It may be attached via an alkyl, cycloalkyl, alkoxy or aryloxy (above, first substituent), wherein at least one hydrogen in these is further aryl, heteroaryl, alkyl or cycloalkyl (above, first substituent). As described above, it may be substituted with the second substituent).
Adjacent groups of R ¹ , R ² , R ³ , R ⁴ and R ⁵ , and = C (-R)-R as Y ^{1 to} Y ⁶ are bonded to each other to form a ring, b. An aryl ring or a heteroaryl ring may be formed together with at least one ring of the ring and the c ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, aryl hetero. It may be substituted with arylamino, diarylboryl (two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy (above, the first substituent). , At least one hydrogen in these may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl (above, second substituent).
At least one hydrogen in the compound and structure represented by the general formula (1) may be substituted with cyano, halogen or deuterium.

^(2-1) Description Y ¹ such as combinations of Y 1 to Y ⁶ are each independently, = C (-R) - or = a N-, at least one = a N-. Any of Y ^{1 to} Y ⁶ may be = N−. Preferably, Y ¹ and Y ⁶ are = N- (a ring is a pyrimidine ring), Y ¹ or Y ⁶ is = N- (a ring is a pyridine ring), and Y ² and Y ⁵ are = N- (b ring and C ring is a pyridine ring), Y ³ and Y ⁴ are = N- (b ring and c ring are pyridine rings), Y ^{2 to} Y ⁵ are = N- (b ring and c ring are pyrimidine rings), Y ¹ , Y ³ , Y ⁴ and Y ⁶ are = N- (a ring is a pyrimidine ring, b and c rings are pyridine rings), Y ¹ , Y ² , Y ⁵ and Y ⁶ are = N- (a ring is a pyrimidine ring) , B and c rings are pyridine rings), Y ^{1 to} Y ⁶ are = N- (a ring, b and c rings are pyrimidine rings), and Y ² or Y ⁵ are = N- (b or c rings). Pyridine ring).

Further, in addition to the above-mentioned arrangement relationship of = N-, it is preferable that X ¹ and X ² are> O, and a polycyclic aromatic compound containing a partial structure represented by any of the following formulas is preferable.

In particular, the polycyclic aromatic compound containing a partial structure represented by the formula (1-1601-R) has a higher S1, a higher T1, and a smaller ΔE (ST) than a structure without N, and thus has a blue TADF assist. Promising as dopants, TADF hosts and phosphorescent hosts. It also has deep HOMO and deep LUMO, and is promising as a hole block material (hole blocking material) and an electron transport material.

Further, in addition to the above-mentioned arrangement relationship of = N-, it is preferable that X ¹ and X ² are> N-R (R = phenyl, pyridyl or pyrimidyl), and a partial structure represented by any of the following formulas. It is preferably a polycyclic aromatic compound containing the above or a multimer thereof.

Each of the above formulas represents a "partial structure" of a polycyclic aromatic compound or a multimer thereof. Accordingly, the general formula (1) ^{R 1} such as defined in; ^{Y 1} such as a = C (-R) - of ^{R; R} 1 ^{~R 5} and ^Y 1 to Y ⁶ as a = C (-R) - of aryl or heteroaryl ring adjacent groups of R can be formed by combining, substituent (first substituent and second substituent) to these; as X ¹ and X ^2> N- The second substituent of R to R and the linking group or single bond between the R and at least one ring of a ring, b ring and c ring; further, cyano, halogen or dehydrogen which can be substituted with a compound is omitted. There is.

From a synthetic point of view, the aromatic rings (rings b and c) that cause the Friedel-Crafts reaction on boron do not contain nitrogen and are not electron deficient. A polycyclic aromatic compound having a partial structure represented by 1-841-R), formula (1-1-R) or formula (1-381-R) is preferable, and the above formula (1-1601-R) or A polycyclic aromatic compound having a partial structure represented by the formula (1-381-R) is more preferable.

From a physical property point of view, the more nitrogen there is, the stronger the multiple resonance effect can be. Therefore, many have a partial structure represented by the above formula (1-601-R) in which all meta positions are replaced with nitrogen with respect to boron. Ring aromatic compounds are preferred.

The bulkier the alkyl substituent, the higher the photoluminescence quantum yield (PLQY), and the higher the external quantum efficiency when used as an element. For example, a methyl group is preferable, a t-butyl group is more preferable, and an adamantyl group is most preferable.

A compound containing nitrogen as an electron-accepting element has a low LUMO and tends to become an electron trap site when it is used as an element. Therefore, when the polycyclic aromatic compound of the above formula (1) is used as the dopant material, the host material is preferably a compound having a low LUMO as shown in the following structural formula, for example. "Me" in the formula is a methyl group.

(2-2) Description of R ^{1 to} R ⁵ The "aryl" (first substituent) such as R ¹ is, for example, an aryl having 6 to 30 carbon atoms, preferably an aryl having 6 to 20 carbon atoms, and carbon. Aryls having 6 to 16 carbon atoms are more preferable, aryls having 6 to 12 carbon atoms are further preferable, and aryls having 6 to 10 carbon atoms are particularly preferable.

Specific aryls include phenyl, which is a monocyclic system, biphenylyl, which is a bicyclic system, naphthyl, which is a condensed bicyclic system, terfenylyl (m-terphenylyl, o-terphenylyl, and p-terphenylyl), which is a tricyclic system, and condensation. Examples thereof include tricyclics such as acenaftyrenyl, fluorenyl, phenalenyl, phenanthrenyl, condensed tetracyclics triphenylenyl, pyrenyl, naphthalenyl, and condensed pentacyclics perylenel and pentasenyl.

The "heteroaryl" (first substituent) such as R ¹ is, for example, a heteroaryl having 2 to 30 carbon atoms, preferably a heteroaryl having 2 to 25 carbon atoms, and more preferably a heteroaryl having 2 to 20 carbon atoms. Preferably, a heteroaryl having 2 to 15 carbon atoms is more preferable, and a heteroaryl having 2 to 10 carbon atoms is particularly preferable. Further, the heteroaryl is, for example, a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific examples of the heteroaryl include pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyridadinyl, pyrazinyl, triazinyl, indrill, isoindrill, 1H-indazolyl, and so on. Benomidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyldinyl, prynyl, pteridinyl, carbazolyl, acridinyl, phenoxatinyl, phenoxadinyl, phenoxadinyl. Phenazacillinyl, indolidinyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, naphthobenzofuranyl, thiophenyl, benzothiophenyl, isobenzothiophenyl, dibenzothiophenyl, naphthobenzothiophenyl, benzophosphoyl, dibenzophosphole, benzophos Examples thereof include a monovalent group of the whole oxide ring, a monovalent group of the dibenzophosphole oxide ring, frazanyl, thiantranyl, indolocarbazolyl, benzoindrocarbazolyl and benzobenzoindorocarbazolyl.

"Aryl", "diheteroarylamino""heteroaryl" (first substituent) wherein "aryl heteroarylamino" (first substituent in "diarylamino" such as R ¹ (first substituent) ) In "aryl" and "heteroaryl", and as "aryl" in "aryloxy" (first substituent), the above description of aryl and heteroaryl can be cited.

The "alkyl" (first substituent) such as R ¹ may be either a straight chain or a branched chain, for example, a linear alkyl having 1 to 24 carbon atoms or a branched chain alkyl having 3 to 24 carbon atoms. Alkyl with 1 to 18 carbon atoms (branched chain alkyl with 3 to 18 carbon atoms) is preferable, alkyl with 1 to 12 carbon atoms (branched chain alkyl with 3 to 12 carbon atoms) is more preferable, and alkyl with 1 to 6 carbon atoms. (Branched chain alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 5 carbon atoms (branched chain alkyl having 3 to 5 carbon atoms) and alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms) are more preferable. Alkyl) is particularly preferred.

Specific alkyls include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl), n-. Hexyl, 1-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl (1,1,3,3-tetramethylbutyl), 1- Methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, Examples thereof include 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicosyl.
Also, for example, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1,1,4-trimethylpentyl, 1,1,2- Trimethylpropyl, 1,1-dimethyloctyl, 1,1-dimethylpentyl, 1,1-dimethylheptyl, 1,1,5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl-1,3- Dimethylbutyl, 1,1,2,2-tetramethylpropyl, 1-butyl-1-methylpentyl, 1,1-diethylbutyl, 1-ethyl-1-methylpentyl, 1,1,3-trimethylbutyl, 1 -Propyl-1-methylpentyl, 1,1,2-trimethylpropyl, 1-ethyl-1,2,2-trimethylpropyl, 1-propyl-1-methylbutyl, 1,1-dimethylhexyl and the like can also be mentioned.

Examples of the "cycloalkyl" (first substituent) such as R ¹ include cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, and 3 to 14 carbon atoms. Examples thereof include cycloalkyl, cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, and cycloalkyl having 5 carbon atoms.

Specific cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, alkyl (particularly methyl) substituents having 1 to 4 carbon atoms, norbornenyl, and bicyclo [1]. .0.1] Butyl, Bicyclo [1.1.1] Pentyl, Bicyclo [2.0.1] Pentyl, Bicyclo [1.2.1] Hexyl, Bicyclo [3.0.1] Hexyl, Bicyclo [2] .1.2] Heptyl, bicyclo [2.2.2] Octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.

The “alkoxy” (first substituent) such as R ¹ is, for example, an alkoxy having a linear chain having 1 to 24 carbon atoms or a branched chain having 3 to 24 carbon atoms. Alkoxy having 1 to 18 carbon atoms (alkoxy of branched chains having 3 to 18 carbon atoms) is preferable, and alkoxy having 1 to 12 carbon atoms (alkoxy of branched chains having 3 to 12 carbon atoms) is more preferable, and alkoxy having 1 to 6 carbon atoms. Alkoxy (alkoxy of branched chains having 3 to 6 carbon atoms) is more preferable, and alkoxy having 1 to 5 carbon atoms (alkoxy of branched chains having 3 to 5 carbon atoms) and alkoxy having 1 to 4 carbon atoms (alkoxy having 3 to 4 carbon atoms) are more preferable. Alkoxy of the branched chain of 4) is particularly preferable.

Specific alkoxys include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, t-amyloxy, n-pentyloxy, isopentyloxy, neopentyloxy, and t-pentyl. Oxy, n-hexyloxy, 1-methylpentyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-heptyloxy, 1-methylhexyloxy, n-octyloxy, t-octyloxy, 1-methylheptyl Oxy, 2-ethylhexyloxy, 2-propylpentyloxy, n-nonyloxy, 2,2-dimethylheptyloxy, 2,6-dimethyl-4-heptyloxy, 3,5,5-trimethylhexyloxy, n-decyloxy, n-undecyloxy, 1-methyldecyloxy, n-dodecyloxy, n-tridecyloxy, 1-hexylheptyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-hepta Examples thereof include decyloxy, n-octadecyloxy and n-eicosyloxy.

As "Jiariruboriru", "aryl" (first substituent) in such R ¹ can cite the description of the aryl described above. Further, the two aryls may be bonded via a single bond or a linking group (for example,> C (-R) ₂ ,>O,> S or> N-R). Here, R of> C (-R) ₂ and> N-R is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy (above, first). 1 Substituent), and the first substituent may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl (above, the second substituent), and specific examples of these groups are described above. The description of aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy as the first substituent can be cited.

As the aryl, heteroaryl, alkyl or cycloalkyl (above, the second substituent) further substituted with R ¹ or the like (first substituent), the above-mentioned aryl, heteroaryl, alkyl or cycloalkyl as the first substituent is used. You can quote the explanation of.

^(2-3) Y 1 to Y ⁶ Description Y ^1, etc. = C (-R) - in as R, aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, Jiariruboriru (2 One aryl may be attached via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy (above, first substituent), and further substitute for at least one hydrogen in these. aryl, heteroaryl, alkyl or cycloalkyl (more second substituent) as the aryl as described above R ¹ etc. (first substituent), heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino , Diarylboryl, alkyl, cycloalkyl, alkoxy or aryloxy can be cited.

^(2-4) The R 1 to R ⁵ and one embodiment specifically of ^Y 1 to Y ^{6, R 1} etc. (first substituent) and ^{Y 1} such as a = C (-R) - in R ( The emission wavelength can be adjusted by the steric hindrance, electron donating property and electron accepting property of the structure of the first substituent), and the group is preferably represented by the following structural formula. In the following structural formula, "Me" represents methyl, "tBu" represents t-butyl, "tAm" represents t-amyl, "tOct" represents t-octyl, and * represents the binding position.

More preferably, methyl, t-butyl, t-amyl, t-octyl, phenyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5-xsilyl, 2,6-xsilyl, 2,4. 6-Methylyl, diphenylamino, di-p-tolylamino, bis (p- (t-butyl) phenyl) amino, carbazolyl, 3,6-dimethylcarbazolyl, 3,6-di-t-butylcarbazolyl and Phenoxy, more preferably methyl, t-butyl, t-amyl, t-octyl, 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 preferable for selective synthesis, and specifically, t-butyl, t-amyl, t-octyl, o-tryl, p-trill, 2 , 4-xylyl, 2,5-xylyl, 2,6-xsilyl, 2,4,6-mesityl, di-p-tolylamino, bis (p- (t-butyl) phenyl) amino, 3,6-dimethylcarba Zolyl and 3,6-di-t-butylcarbazolyl are preferred.

(2-5) Adjustment of molecular strain by R ³ and R ⁴ By applying strain to the molecule, the spin-orbit interaction can be increased. As a result, the delayed fluorescence lifetime can be shortened, the TADF mechanism can be expressed, and the luminous efficiency of the device can be increased. For this purpose, the substituent group Z described below is introduced into at least one of R ³ and R ^{4 in} the general formula (1).

In the general formula (1), at least one of ^{R 3} and ^{R 4} is a Z, Z is halogen, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 14 carbon atoms, aryl having 6 to 10 carbon atoms or It is a heteroaryl having 2 to 10 carbon atoms, and specifically, the following partial structural formula (m), formula (e), formula (v), formula (t), formula (h), formula (p), formula. (Q), Expression (r), Expression (s), Expression (y), Expression (u), Expression (w), Expression (j), Expression (k), Expression (f), Expression (c), Expression. The groups of formula (b), formula (i) and formula (n) are preferable, and among these, the groups of formula (m), formula (t), formula (p), formula (f) and formula (n) are more preferable. , Formula (m) and formula (t) are more preferred. In the following structural formula, "Me" represents methyl, "Et" represents ethyl, "iPr" represents isopropyl, "tBu" represents t-butyl, "CN" represents cyano, and * represents the binding position.

It is preferable that both R ³ and R ⁴ are Z from the viewpoint of shortening the delayed fluorescence lifetime and expressing the TADF mechanism by giving strain to the molecule. From the viewpoint of obtaining high PLQY and the stability of the molecule, it is preferable that only one of R ³ and R ⁴ is Z.

From the viewpoint of ease of synthesis and stability, it is preferable that the substituent is small, and the above formulas (m), (e), formula (v), formula (t), formula (h), formula (p), Of the formulas (q), formulas (r), formulas (s), formulas (j), formulas (k), formulas (f), formulas (c), formulas (b), formulas (i) and formulas (n). Groups are preferred, and among these, groups of formula (m), formula (e), formula (v), formula (t), formula (p), formula (f) and formula (n) are more preferred, and formula (m). ) And the group of the formula (t) are more preferable, and the group of the formula (m) is the most preferable.

(2-6) Formation of Condensation Ring by Bonding Adjacent Groups In the general formula (1), R ^{1 to} R ⁵ and Y ^{1 to} Y ⁶ are adjacent to each other of = C (-R)-R. The groups may be bonded to each other to form an aryl ring or a heteroaryl ring together with at least one ring of a ring, b ring and c ring. Therefore, the polycyclic aromatic compound represented by the general formula (1) has the following formulas (1'-1) and (1'-) depending on the mutual bonding form of the substituents in the a ring, b ring and c ring. As shown in 2), the ring structure constituting the compound changes. The definitions of R ^{1 to} R ⁵ , Y ^{1 to} R ⁶ , a, b, c, X ¹ and X ² in each formula are the same as the definitions in the general formula (1).

The formula (1'-1) and a 'ring, b' of (1'-2) in the ring and c 'ring, the substituents ^R 1 to R ⁵ and ^Y 1 to Y ⁶ as a = C (- R)-Represents an aryl ring or a heteroaryl ring formed by bonding adjacent groups of R to each other together with a ring, b ring and c ring (a ring, b ring or c ring and another ring). It can also be said to be a fused ring formed by condensing the structure). Although not shown in the formula, there are some compounds in which all of the a ring, b ring and c ring are changed to a'ring, b'ring and c'ring.

Further, as can be seen from the above equations (1'-1) and (1'-2), for example, = C (-R)-R as Y ¹ in the a ring and Y ² as Y ² in the b ring. C (-R) -R, b ring R ³ and c ring R ⁴ , c ring Y ⁵ = C (-R) -R and a ring Y ⁶ = C (-R) )-Groups that straddle the ring, such as R, do not correspond to "adjacent groups", and they do not bond. It is possible to combine R ¹ in the a ring, R of = C (-R)-as Y ¹ in the a ring, R of = C (-R)-as Y ² in the b ring, and R in the b ring. ^2, b rings in as ^{Y 3} in ^{R 2} and b rings = C (-R) - for R, = C as ^{Y 3} in b ring (-R) - R and b ^R 3 in the ring, c ring = as ^{Y 4} in ^{R 4} and c ring in C (-R) - of R, as ^{Y 4} in c ring = C (-R) - with ^{R 5} in ^R 5, c ring in R and c rings There are only = C (-R) -R as Y ⁵ in the c ring, = C (-R) -R as Y ⁶ in the a ring, and R ¹ in the a ring. That is, the "adjacent group" means an adjacent group on the same ring.

The compound represented by the above formula (1'-1) or formula (1'-2) is, for example, a 6-membered ring (Y ¹ and Y ⁶ ) which is an a ring (or b ring or c ring) = C (-). In the case of R)-, it has an a'ring (or b'ring or c'ring) formed by condensing a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring, etc. with a benzene ring). It is a compound. The formed fused ring a'(or fused ring b'or fused ring c') is a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzofuran ring, respectively, when the a ring (or b ring or c ring) is a benzene ring. Such as the dibenzothiophene ring.
Moreover, even when it is (either = N- of Y ¹ and Y ⁶⁾ a ring (or b ring or c ring) pyridine ring, likewise benzene ring, indole ring, a pyrrole ring, a benzofuran ring or A benzothiophene ring or the like may be condensed. As described later, two Y (e.g. both Y ¹ and Y ⁶ of a ring) on one ring = If N- fused rings is not formed.

Only when Y ^{1 to} Y ⁶ are = C (-R)-can they combine with R ^{1 to} R ⁵ to form a fused ring, and when Y ^{1 to} Y ⁶ is = N-. A fused ring originating from this = N- is not formed. For example, as shown in the example of the structural formula below, when both Y ¹ and Y ⁶ of the a ring are = N−, the condensed ring a'is not formed, and at least one of Y ¹ and Y ⁶ is = C (. -R) -In some cases, a fused ring a'is formed.

Examples of the "aryl ring"(a'ring,b'ring or c'ring) formed in this manner include an aryl ring having 9 to 30 carbon atoms, an aryl ring having 9 to 16 carbon atoms, and 9 carbon atoms. Examples thereof include aryl rings having ~ 12 and aryl rings having 9 to 10 carbon atoms. The lower limit of the carbon number 9 of this aryl ring is a 5-membered ring with respect to a benzene ring having 6 carbon atoms (Y ^{1 to} Y ⁶ = C (-R)-). It corresponds to the total carbon number 9 of the fused ring formed by condensation of (carbon number 5).

Specific examples of the "aryl ring" include naphthalene ring, which is a fused dicyclic system, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, and triphenylene ring, pyrene ring, which are fused tricyclic systems. Examples thereof include a naphthalene ring, a perylene ring which is a condensed pentacyclic system, and a pentacene ring.

The formed "heteroaryl ring"(a'ring,b'ring or c'ring) includes, for example, a heteroaryl ring having 5 to 30 carbon atoms, a heteroaryl ring having 5 to 25 carbon atoms, and a carbon number of carbon atoms. Examples thereof include a heteroaryl ring having 5 to 20 carbon atoms, a heteroaryl ring having 5 to 15 carbon atoms, and a heteroaryl ring having 5 to 10 carbon atoms. Examples of the "heteroaryl ring" include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms. The lower limit of 5 carbon atoms of this heteroaryl ring is the lower limit when the a ring, b ring or c ring is a pyridine ring (assuming that one Y ¹ to Y ⁶ on each ring = N−). It is a value and corresponds to the total number of carbon atoms of the fused ring formed by condensing a 5-membered ring with a pyridine ring having 5 carbon atoms. Therefore, for example, for ring a, if both Y ¹ and Y ⁶ are = C (-R)-, the lower limit is changed to 6 (if both Y ¹ and Y ⁶ are = N-, the condensed ring is changed. Not formed).

Specific "heteroaryl rings" include indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, and the like. Kinazoline ring, quinoxaline ring, phthalazine ring, naphthylidine ring, carbazole ring, aclysine ring, phenoxatiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, benzothiophene ring, dibenzothiophene ring , Thiantole ring and the like.

Aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls are attached via a single bond or a linking group) that replace the formed aryl ring or heteroaryl ring. (May be), alkyl, cycloalkyl, alkoxy or aryloxy (above, first substituent), and aryl, heteroaryl, alkyl or cycloalkyl (above, second substitution) further substituting at least one hydrogen in these. the group), an aryl as above-mentioned R ^1, etc. (first substituent), heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, Jiariruboriru, alkyl, cycloalkyl, alkoxy or aryloxy description Can be quoted.

(2-7) ^{X 1} and described X ¹ and ^{X 2} of ^{X 2} are each independently,> N-R (amine nitrogen),>O,> C ( -R) 2,> S or> Se Therefore, both X ¹ and X ² do not have> C (-R) ₂ . Among these,>N-R,> O or> C (-R) ₂ is preferable, and> N-R or> O is preferable. Particularly preferably, both X ¹ and X ² are> N-R or> O, and most preferably both X ¹ and X ² are> N-R.

Aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl as R in> N-R and> C (-R) ₂ (two aryls via a single bond or linking group) Aryl, heteroaryl, alkyl or cycloalkyl (or higher) that are further substituted with (may be bonded), alkyl, cycloalkyl, alkoxy or aryloxy (or higher, first substituent), and at least one hydrogen in these. as the second substituent), aryl as above R ¹ etc. (first substituent), heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, Jiariruboriru, alkyl, cycloalkyl, alkoxy or The explanation of aryloxy can be quoted.

(2-8) Bonding of X ¹ and X ² to a ring, b ring and c ring "> N-R and> C (-R) ₂ (as X ¹ and X ² ) in the general formula (1) R is independently bonded to at least one ring of the a ring, b ring, and c ring by a linking group or a single bond. ”The following formula (1'-3) or formula (1) It can also be represented by a compound having a ring structure in which at least one of X ¹ and X ² represented by'-4) is incorporated into the fused ring a'. That is, for example, a'formed by condensing other rings so as to incorporate X ¹ (or X ² , or X ¹ and X ² ) with respect to the 6-membered ring which is the a ring in the general formula (1). It is a compound having a ring. More specifically, for example, R of> N-R or> C (-R) ₂ as X ¹ and R of = C (-R)-as Y ¹ are bonded by a linking group or a single bond. The embodiment to be used can be exemplified. The same applies to the coupling between X ² and Y ⁶ . The formed fused ring a'is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.
Further, the above specification can be expressed by a compound having a ring structure in which X ¹ and X ² are incorporated into the condensed ring b'and the condensed ring c', which are represented by the following formula (1'-5). That is, for example, X ¹ (or X ² , or X ¹ and X ² ) is incorporated into the 6-membered ring which is the b ring (or c ring, or b ring and c ring) in the general formula (1). It is a compound having a b'ring (or c'ring, or b'ring and c'ring) formed by condensing other rings. More specifically, for example, R of> N-R or> C (-R) ₂ as X ¹ and R of = C (-R)-as Y ² are bonded by a linking group or a single bond. The embodiment to be used can be exemplified. The same applies to the coupling between X ² and Y ⁵ . The formed fused ring b'(or fused ring c') is, for example, a phenoxazine ring, a phenothiazine ring, or an aclysine ring.
In addition, R ^{1 to} R ⁵ , Y ^{1 to} Y ⁶ , a, b, c, a', b in the following formulas (1'-3), formulas (1'-4) and formulas (1'-5). The definitions of', c', X ¹ and X ² are the same as the definitions in the general formula (1).

As the linking group, -O-, -S- or -C (-R) ₂ -is preferable. Note that the "-C (-R) 2 _-" R in is hydrogen, alkyl or cycloalkyl, more of these groups, alkyl or cycloalkyl as above R ¹ etc. (first substituent) You can quote the explanation of. In particular, alkyls having 1 to 4 carbon atoms (for example, methyl, ethyl, etc.) are preferable.

(2-9) Description of Multimer The present invention is a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (1). The multimer is preferably a 2-hexamer, more preferably a 2-3mer, and particularly preferably a dimer. The multimer may be in the form of having a plurality of the above unit structures in one compound. For example, the multimer has a single bond, an alkylene group having 1 to 3 carbon atoms (for example, a methylene group), a phenylene group, and a naphthylene group. In addition to the form in which a plurality of bonds are bonded by a linking group such as (linked multimer), any ring (a ring, b ring or c ring) contained in the above unit structure is bonded so as to be shared by the plurality of unit structures. It may be a form (ring-shared multimer), or a form in which arbitrary rings (a ring, b ring or c ring) included in the unit structure are bonded so as to condense (ring condensation type). It may be a multimer).

Examples of such a multimer include a multimer represented by the following general formula (1A) or formula (1B). The multimer represented by the following formula (1A) shares a 6-membered ring which is a c ring (a ring or b ring) according to the general formula (1), and a plurality of multimers (in the following structural formula). It is a multimer (ring-covalent multimer) having a unit structure represented by the general formula (1) of (2) in one compound. Further, the multimer represented by the following formula (1B) can be described by the general formula (1), for example, a 6-membered ring which is an a ring (b ring or c ring) of a certain unit structure and a certain unit structure. One compound has a plurality of unit structures represented by the general formula (1) (two in the following structural formula) so as to be condensed with a 6-membered ring which is an a ring (b ring or c ring). It is a multimer (ring-condensation type multimer). The definition of the code in each equation is the same as the definition of the general equation (1).

The multimer may be a multimer in which the quantified form represented by the formula (1A) and the quantified form represented by the formula (1B) are combined.

(2-9) Explanation of Other Substituents Hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (1) and its multimer is cyano, halogen or deuterium in whole or in part. It may be replaced. The halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.

(3) Specific Examples of Polycyclic Aromatic Compounds of the Present Invention Further specific examples of the polycyclic aromatic compounds of the present invention include compounds represented by the following structural formulas.

The polycyclic aromatic compound represented by the general formula (1) and its multimer according to the present invention are polymer compounds obtained by polymerizing a reactive compound in which a reactive substituent is substituted therein as a monomer (this high polymer compound). The monomer for obtaining a molecular compound has a polymerizable substituent) or a polymer crosslinked product obtained by further cross-linking the polymer compound (the polymer compound for obtaining this polymer crosslinked product has a crosslinkable substituent). (Having), or a pendant type polymer compound obtained by reacting a main chain type polymer with the above-mentioned reactive compound (the above-mentioned reactive compound for obtaining this pendant type polymer compound has a reactive substituent). Alternatively, the pendant type polymer crosslinked product obtained by further cross-linking the pendant type polymer compound (the pendant type polymer compound for obtaining this pendant type polymer crosslinked product has a crosslinkable substituent) can also be used for organic devices. It can be used as a material, for example, a material for an organic field light emitting element, a material for an organic field effect transistor, or a material for an organic thin film solar cell.

As the above-mentioned reactive substituent (including the polymerizable substituent, the crosslinkable substituent, and the reactive substituent for obtaining a pendant type polymer, hereinafter, also simply referred to as “reactive substituent”). , The substituent capable of increasing the molecular weight of the polycyclic aromatic compound or its multimer, the substituent capable of further cross-linking the polymer compound thus obtained, and the substituent capable of pendant reaction with the main chain type polymer. The group is not particularly limited as long as it is a group, but a substituent having the following structure is preferable. * In each structural formula indicates the bonding position.

L is a single bond, −O−, −S−,> C = O, −OC (= O) −, alkylene having 1 to 12 carbon atoms, and oxyalkylene having 1 to 12 carbon atoms, respectively. And a polyoxyalkylene having 1 to 12 carbon atoms. Among the above substituents, it is represented by the formula (XLS-1), the formula (XLS-2), the formula (XLS-3), the formula (XLS-9), the formula (XLS-10) or the formula (XLS-17). The group represented by the formula (XLS-1), the formula (XLS-3) or the formula (XLS-17) is more preferable.

Details of the uses of such polymer compounds, polymer crosslinked products, pendant type polymer compounds and pendant type polymer crosslinked products (hereinafter, also simply referred to as “polymer compounds and polymer crosslinked products”) will be described later.

2. 2. Method for Producing Polycyclic Aromatic Compound The polycyclic aromatic compound of the present invention and its multimer can be synthesized by applying, for example, the method disclosed in International Publication No. 2015/102118. That is, as in the following scheme, it is desired to synthesize an intermediate in which rings a to c are bonded and cyclize it by a tandem hetero-Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction). Polycyclic aromatic compounds and their multimers can be synthesized. In the scheme below, the definition of the code of each formula is the same as the definition described above.

The intermediate before cyclization in the above scheme can also be synthesized by the method shown in International Publication No. 2015/102118 and the like. That is, an intermediate having a desired substituent can be synthesized by appropriately combining a Buchwald-Hartwig reaction, a Suzuki coupling reaction, an etherification reaction by a nucleophilic substitution reaction, an Ullmann reaction, or the like.

The cyclization by the tandem hetero-Friedel-Crafts reaction shown in the above scheme is a reaction for introducing B (boron) that binds the a ring, the b ring, and the c ring. First, the hydrogen atom (-H) on the a ring between X ¹ and X ² is orthometalated with n-butyllithium, sec-butyllithium, t-butyllithium, or the like. Next, boron trichloride, boron tribromide, etc. are added, the metal of lithium-boron is exchanged, and then Bronsted bases such as N, N-diisopropylethylamine are added to cause a tandem Bora Friedel-Crafts reaction. You can get things. Here, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction.

Further, in addition to the method of introducing lithium to a desired position by orthometalation, a halogen such as a bromine atom can be introduced at a position where lithium is to be introduced, and lithium can be introduced to a desired position by halogen-metal exchange. it can.

3. 3. Organic device In the chemical structural formulas exemplified below, "Me" represents a methyl group and "tBu" represents a t-butyl group.
The polycyclic aromatic compound according to the present invention can be used as a material for organic devices. Examples of the organic device include an organic electroluminescent device, an organic field effect transistor, an organic thin film solar cell, and the like.

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. Hereinafter, the organic EL element according to the present embodiment will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an organic EL device according to the present embodiment.

<Structure of organic electroluminescent device>
The organic electroluminescent element 100 shown in FIG. 1 is above the substrate 101, the anode 102 provided on the substrate 101, the hole injection layer 103 provided on the anode 102, and the hole injection layer 103. The hole transport layer 104 provided in the hole transport layer 104, the light emitting layer 105 provided on the hole transport layer 104, the electron transport layer 106 provided on the light emitting layer 105, and the electron transport layer 106 provided on the electron transport layer 106. It has an electron injection layer 107 and a cathode 108 provided on the electron injection layer 107.

The organic electroluminescent element 100 is manufactured in the reverse order, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer. The electron transport layer 106 provided on the 107, the light emitting layer 105 provided on the electron transport layer 106, the hole transport layer 104 provided on the light emitting layer 105, and the hole transport layer 104. The structure may include a hole injection layer 103 provided above and an anode 102 provided above the hole injection layer 103.

Not all of the above layers are required, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection. The layer 107 is an arbitrarily provided layer. Further, each of the above layers may be composed of a single layer or a plurality of layers.

As the mode of the layer constituting the organic electric field light emitting element, in addition to the above-described "board / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode" configuration mode, "Substrate / anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode", "board / anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode", "board / Anofect / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode "," substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode "," substrate / Anofect / light emitting layer / electron transport layer / electron injection layer / cathode "," substrate / anode / hole transport layer / light emitting layer / electron injection layer / cathode "," substrate / anode / hole transport layer / light emitting layer / "Electron transport layer / cathode", "Substrate / anode / hole injection layer / light emitting layer / electron injection layer / cathode", "board / anode / hole injection layer / light emitting layer / electron transport layer / cathode", "board / substrate / The configuration may be "anode / light emitting layer / electron transport layer / cathode" or "substrate / anode / light emitting layer / electron injection layer / cathode".

<Substrate in organic electroluminescent device>
The substrate 101 is a support for the organic electroluminescent element 100, and usually quartz, glass, metal, plastic, or the like is used. The substrate 101 is formed in a plate shape, a film shape, or a sheet shape depending on the purpose, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Of these, a glass plate and a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable. As for the glass substrate, soda lime glass, non-alkali glass, or the like is used, and the thickness may be sufficient to maintain the mechanical strength. Therefore, for example, 0.2 mm or more may be used. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. As for the material of the glass, non-alkali glass is preferable because it is better that there are few elution ions from the glass, but soda lime glass with a barrier coat such as SiO ₂ is also commercially available, so it is possible to use this. it can. Further, in order to enhance the gas barrier property, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side, and a synthetic resin plate, film or sheet having a particularly low gas barrier property may be used as the substrate 101. When used, it is preferable to provide a gas barrier film.

<Anode in organic electroluminescent device>
The anode 102 serves to inject holes into the light emitting layer 105. When at least one layer of the hole injection layer 103 and the hole transport layer 104 is provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. It will be.

Examples of the material forming the anode 102 include an inorganic compound and an organic compound. Examples of the inorganic compound include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxidation, etc.). (IZO, etc.), metals halide (copper iodide, etc.), copper sulfide, carbon black, ITO glass, nesa glass, and the like. Examples of the organic compound include polythiophene such as poly (3-methylthiophene) and conductive polymers such as polypyrrole and polyaniline. In addition, it can be appropriately selected and used from the substances used as the anode of the organic electroluminescent device.

The resistance of the transparent electrode is not limited as long as a sufficient current can be supplied to emit light from the light emitting element, but it is desirable that the resistance is low from the viewpoint of power consumption of the light emitting element. For example, an ITO substrate of 300 Ω / □ or less functions as an element electrode, but since it is now possible to supply a substrate of about 10 Ω / □, for example, 100 to 5 Ω / □, preferably 50 to 5 Ω. It is especially desirable to use a low resistance product of / □. The thickness of ITO can be arbitrarily selected according to the resistance value, but it is usually used in the range of 50 to 300 nm.

<Hole injection layer and hole transport layer in organic electroluminescent devices>
The hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104. The hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 via the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are formed by laminating and mixing one or more of the hole injection / transport materials or a mixture of the hole injection / transport material and the polymer binder, respectively. Will be done. Further, an inorganic salt such as iron (III) chloride may be added to the hole injection / transport material to form a layer.

As a hole injection / transporting substance, it is necessary to efficiently inject / transport holes from the positive electrode between electrodes to which an electric field is applied, and the hole injection efficiency is high, and the injected holes are efficiently transported. It is desirable to do. For that purpose, it is preferable that the substance has a small ionization potential, a large hole mobility, excellent stability, and is less likely to generate trap impurities during production and use.

As a material for forming the hole injection layer 103 and the hole transport layer 104, in a photoconductive material, a compound conventionally used as a hole charge transport material, a p-type semiconductor, and a hole injection of an organic electric field light emitting element are used. Any compound can be selected and used from the known compounds used for the layer and the hole transport layer.

Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), and triarylamine derivatives (aromatic tertiary). Polymers with amino in the main or side chains, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4 , 4'-diaminobiphenyl, N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminobiphenyl, 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 "-tris (3-methylphenyl (phenyl) Triphenylamine derivatives such as amino) triphenylamine, starburstamine derivatives, etc.), stillben derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives , Kinoxalin derivatives (eg, 1,4,5,8,9,12-hexazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonate or styrene derivatives having the monomer in the side chain, polyvinylcarbazole, polysilane, etc. are preferable, but a thin film necessary for producing a light emitting element can be formed and holes can be injected from the anode. Further, the compound is not particularly limited as long as it can transport holes.

It is also known that the conductivity of organic semiconductors is strongly affected by its doping. Such an organic semiconductor matrix substance is composed of a compound having a good electron donating property or a compound having a good electron accepting property. Strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known for doping electron donors. (For example, the document "M.Pfeiffer, A.Beyer, T.Fritz, K.Leo, Appl.Phys.Lett., 73 (22), 3202-3204 (1998)" and the document "J. Blochwitz, M." See .Pheiffer, T.Fritz, K.Leo, Appl.Phys.Lett., 73 (6), 729-731 (1998) "). They generate so-called holes by an electron transfer process in an electron donating base material (hole transport material). Depending on the number of holes and the mobility, the conductivity of the base material changes considerably. As the matrix substance having hole transporting properties, for example, a benzidine derivative (TPD or the like) or a starburst amine derivative (TDATA or the like) or a specific metal phthalocyanine (particularly, zinc phthalocyanine (ZnPc) or the like) is known (Japanese Patent Laid-Open No. 2005-167 No. 175).

The above-mentioned materials for the hole injection layer and the material for the hole transport layer are polymer compounds obtained by polymerizing a reactive compound in which a reactive substituent is substituted as a monomer, or a polymer crosslinked product thereof, or a polymer crosslinked product thereof. A pendant type polymer compound obtained by reacting a main chain type polymer with the above-mentioned reactive compound, or a pendant type polymer crosslinked product thereof can also be used as a material for a hole layer. As the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited.
Details of the uses of such polymer compounds and crosslinked polymers will be described later.

<Light emitting layer in organic electroluminescent device>
The light emitting layer 105 is a layer that emits light by recombining the holes injected from the anode 102 and the electrons injected from the cathode 108 between the electrodes to which an electric field is applied. The material for forming the light emitting layer 105 may be a compound (light emitting compound) that is excited by recombination of holes and electrons to emit light, and can form a stable thin film shape and is in a solid state. It is preferable that the compound exhibits a strong emission (fluorescence) efficiency. In the present invention, a polycyclic aromatic compound represented by the above general formula (1) can be used as a material for the light emitting layer.

The light emitting layer may be either a single layer or a plurality of layers, and each is formed of a light emitting layer material (host material, dopant material). The host material and the dopant material may be one type or a plurality of combinations. The dopant material may be included entirely, partially, or partially in the host material. As a doping method, it can be formed by a co-evaporation method with a host material, but it can be produced by a wet film formation method after being mixed with the host material in advance and then vapor-deposited at the same time, or mixed with an organic solvent in advance with the host material. It may be filmed.

The amount of the host material used depends on the type of host material and may be determined according to the characteristics of the host material. The guideline for the amount of the host material used is preferably 50 to 99.99% by weight, more preferably 80 to 99.95% by weight, and further preferably 90 to 99.9% by weight of the entire light emitting layer material. Is.

The amount of the dopant material used varies depending on the type of the dopant material, and may be determined according to the characteristics of the dopant material. The guideline for the amount of the dopant used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, still more preferably 0.1 to 10% by weight of the entire light emitting layer material. is there. The above range is preferable in that, for example, the density quenching phenomenon can be prevented.

On the other hand, in an organic electroluminescent device using a heat-activated delayed fluorescence dopant material, it is preferable that the amount of the dopant material used is low in that the concentration quenching phenomenon can be prevented, but the amount of the dopant material used is high. The concentration is preferable from the viewpoint of the efficiency of the electroluminescence delayed fluorescence mechanism. Furthermore, in an organic electroluminescent device using a heat-activated delayed fluorescence assisted dopant material, the dopant material is more efficient than the amount of the assisted dopant material used in terms of the efficiency of the heat-activated delayed fluorescence mechanism of the assisted dopant material. It is preferable that the amount used is low.

When the assist dopant material is used, the guideline for the amount of the host material, the assist dopant material, and the dopant material used is 40 to 99.999% by weight, 59 to 1% by weight, and 20 to 20 to the total weight of the light emitting layer material, respectively. It is 0.001% by weight, preferably 60-99.99% by weight, 39-5% by weight and 10-0.01% by weight, respectively, more preferably 70-99.95% by weight, 29-10% by weight. %% 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.

Host materials include fused ring derivatives such as anthracene and pyrene, which have long been known as luminescent materials, bisstyryl derivatives such as bisstyryl anthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, and benzo. Examples include fluorene derivatives.

The T1 energy of the host material is preferably higher than the T1 energy of the dopant or assist dopant having the highest T1 energy in the light emitting layer from the viewpoint of promoting the generation of TADF in the light emitting layer without inhibiting it. Specifically, the T1 energy of the host is preferably 0.01 eV or more, more preferably 0.03 eV or more, and even more preferably 0.1 eV or more. Moreover, you may use a TADF active compound as a host material.

Examples of the host material include a compound represented by the following general formula (H1), a compound represented by the following general formula (H2), a compound represented by the following general formula (H3), and the following general formula (H4). Examples thereof include a compound containing the structure represented, a compound represented by the following general formula (H5), and a TADF material. It is preferably a compound represented by the general formula (H1).

<Compound represented by the general formula (H1)>
In the formula (H1), ^{L 1} is a heteroarylene arylene or C2-30 6 to 30 carbon atoms, preferably an arylene having 6 to 24 carbon atoms, more preferably an arylene having 6 to 16 carbon atoms, An arylene having 6 to 12 carbon atoms is more preferable, an arylene having 6 to 10 carbon atoms is particularly preferable, a heteroarylene having 2 to 25 carbon atoms is preferable, a heteroarylene having 2 to 20 carbon atoms is more preferable, and an arylene having 2 to 20 carbon atoms is more preferable. Heteroarylene of ~ 15 is more preferable, and heteroarylene having 2 to 10 carbon atoms is particularly preferable. Specifically, the arylene is divalent such as benzene ring, biphenyl ring, naphthalene ring, terphenyl ring, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, triphenylene ring, pyrene ring, naphthalene ring, perylene ring and pentacene ring. The basis of. Specific examples of the heteroarylene include a pyrrole ring, an oxazole ring, an isooxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxaziazole ring, a thiazazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, and a pyridine ring. Pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzoimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, synnoline ring , Kinazoline ring, quinoxaline ring, phthalazine ring, naphthylidine ring, purine ring, pteridine ring, carbazole ring, aclysine ring, phenoxatiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, phenazacillin ring, indridin ring, furan ring, Benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, frazane ring, oxazole ring, thiantolen ring, indolocarbazole ring, benzoindolobazole ring, benzobenzoindolobazole ring and naphthobenzofuran Bivalent groups such as rings can be mentioned.
At least one hydrogen in the compound represented by the formula (H1) may be substituted with an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, cyano, a halogen or deuterium.

<Compound represented by the general formula (H2)>
In the above formula (H2), L ² and L ³ are independently aryls having 6 to 30 carbon atoms or heteroaryls having 2 to 30 carbon atoms. As the aryl, an aryl having 6 to 24 carbon atoms is preferable, an aryl having 6 to 16 carbon atoms is more preferable, an aryl having 6 to 12 carbon atoms is further preferable, and an aryl having 6 to 10 carbon atoms is particularly preferable, specifically. Examples include monovalent groups such as a benzene ring, a biphenyl ring, a naphthalene ring, a terphenyl ring, an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a naphthalene ring, a perylene ring and a pentacene ring. .. As the heteroaryl, a heteroaryl having 2 to 25 carbon atoms is preferable, a heteroaryl having 2 to 20 carbon atoms is more preferable, a heteroaryl having 2 to 15 carbon atoms is further preferable, and a heteroaryl having 2 to 10 carbon atoms is particularly preferable. Preferably, specifically, a pyrrole ring, an oxazole ring, an isooxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxaziazole ring, a thiazylazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, Pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzoimidazolan ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring , Kinoxalin ring, phthalazine ring, naphthylidine ring, purine ring, pteridine ring, carbazole ring, aclysin ring, phenoxatiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, phenazacillin ring, indolidin ring, furan ring, benzofuran ring, Isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, frazane ring, oxadiazole ring, thiantolene ring, indolocarbazole ring, benzoindolobazole ring, benzobenzoindrocarbazole ring and naphthobenzofuran ring, etc. There is a monovalent group.
At least one hydrogen in the compound represented by the formula (H2) may be substituted with an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, cyano, a halogen or deuterium.

<Compound represented by the general formula (H3)>

In formula (H3)
MU is a divalent group independently represented by removing any two hydrogen atoms from an aromatic compound, and EC is independently represented by removing any one hydrogen atom from an aromatic compound1 A valence group, two hydrogens in the MU are replaced by EC or MU, where k is an integer of 2-50000.

More specifically
The MUs are arylene, heteroarylene, dialylene arylamino, dialylene arylboryl, oxaborin-diyl, and azaborin-diyl, respectively.
ECs are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino or aryloxy.
At least one hydrogen in MU and EC may be further substituted with aryl, heteroaryl, diarylamino, alkyl and cycloalkyl.
k is an integer of 2 to 50,000.
k is preferably an integer of 20,000 to 50,000, more preferably an integer of 100 to 50,000.

At least one hydrogen in MU and EC in the formula (H3) may be substituted with an alkyl having 1 to 24 carbon atoms, a cycloalkyl having 3 to 24 carbon atoms, a halogen or deuterium, and further in the alkyl. arbitrary -CH ₂ - -O- or -Si _{(CH 3) 2} - in may be substituted, -CH ₂ connected directly to the EC in the formula (H3) in the alkyl - any except -CH 2 _- may be substituted arylene of 6 to 24 carbon atoms, arbitrary hydrogen in the alkyl may be substituted by fluorine.

Examples of the MU include a divalent group represented by removing any two hydrogen atoms from any of the following compounds.

More specifically, a divalent group represented by any of the following structures can be mentioned. In these, the MU binds to another MU or EC at *.

Further, as the EC, for example, a monovalent group represented by any of the following structures can be mentioned. In these, EC binds to MU at *.

From the viewpoint of solubility and coating film-forming property, the compound represented by the formula (H3) preferably has an alkyl having 1 to 24 carbon atoms in which 10 to 100% of the total number of MUs (k) in the molecule has an alkyl having 1 to 24 carbon atoms. It is more preferable that 30 to 100% of the total number of MUs (k) in the molecule has an alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms), and the total number of MUs in the molecule (k). It is more preferable that 50 to 100% of the MUs have an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms). On the other hand, from the viewpoint of in-plane orientation and charge transport, it is preferable that 10 to 100% of the total number of MUs (k) in the molecule has an alkyl having 7 to 24 carbon atoms, and the total number of MUs in the molecule (k). ), It is more preferable that 30 to 100% of the MU has an alkyl having 7 to 24 carbon atoms (branched chain alkyl having 7 to 24 carbon atoms).

<Compound containing a structure represented by the general formula (H4)>
The compound is a compound containing a structure represented by the following formula (H4), and has a plurality of such structures, preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, most preferably. Is included, and when a plurality of the structures are contained, the structures are directly bonded to each other by a single bond or bonded by a specific linking group.

In the general formula (H4), G is "= C (-H)-" or "= N-", and H in the "= C (-H)-" is a substituent or another formula (H4). ) May be replaced with the structure represented by.

As the compound containing the structure represented by the general formula (H4), for example, the compounds described in International Publication No. 2012/153780 and International Publication No. 2013/038650 can be used, and the methods described in the above-mentioned documents can be used. Can be manufactured according to.

Examples of substituents when H in "= C (-H)-" which is G is substituted are as follows, but are not limited to these.

Specific examples of the "aryl group" as a substituent include phenyl, tolyl, xylyl, naphthyl, phenanthryl, pyrenyl, chrysenyl, benzo [c] phenanthryl, benzo [g] chrysenyl, benzoanthril, triphenylenyl, fluorenyl, 9, Examples thereof include 9-dimethylfluorenyl, benzofluorenyl, dibenzofluorenyl, biphenylyl, terphenylyl, quaterphenylyl, fluoranthenyl and the like, preferably phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, triphenylenyl and the like. And fluorenyl and the like. Examples of the aryl group having a substituent include tolyl, xsilyl and 9,9-dimethylfluorenyl. As specific examples show, aryl groups include both condensed aryl groups and non-condensed aryl groups.

Specific examples of the "heteroaryl group" as a substituent include pyrrolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridadinyl, pyridyl, triazinyl, indolyl, isoindrill, imidazolyl, benzimidazolyl, indazolyl, imidazolyl [1,2-a] pyridinyl, Frill, benzofuranyl, isobenzofuranyl, dibenzofuranyl, azadibenzofuranyl, thiophenyl, benzothienyl, dibenzothienyl, azadibenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, naphthilidinyl, carbazolyl, azacarbazolyl, phenanthridinyl, acridinyl , Phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxadinyl, oxazolyl, oxadiazolyl, frazanyl, benzoxazolyl, thienyl, thiazolyl, thiadiazolyl, benzthiazolyl, triazolyl, tetrazolyl and the like, preferably dibenzofuranyl, dibenzothienyl, etc. Examples thereof include carbazolyl, pyridyl, pyrimidinyl, triazinyl, azadibenzofuranyl and azadibenzothienyl. Dibenzofuranyl, dibenzothienyl, azadibenzofuranyl or azadibenzothienyl are more preferred.

The substituent "substituted silyl group" is a group selected from the group consisting of a substituted or unsubstituted trialkylsilyl group, a substituted or unsubstituted arylalkylsilyl group, and a substituted or unsubstituted triarylsilyl group. It is also preferable to have.

Specific examples of the substituted or unsubstituted trialkylsilyl group include trimethylsilyl and triethylsilyl. Specific examples of the substituted or unsubstituted arylalkylsilyl group include diphenylmethylsilyl, ditrilmethylsilyl, phenyldimethylsilyl and the like. Specific examples of the substituted or unsubstituted triarylsilyl group include triphenylsilyl and tritrylsilyl.

The "substituted phosphine oxide group" which is a substituent is also preferably a substituted or unsubstituted diarylphosphine oxide group. Specific examples of the substituted or unsubstituted diarylphosphine oxide group include diphenylphosphine oxide and ditrilphosphine oxide.

Examples of the "substituted carboxy group" which is a substituent include benzoyloxy and the like.

Examples of the linking group that binds a plurality of structures represented by the formula (H4) include the above-mentioned 2-4-valent, 2-3-valent, or divalent derivatives of aryl and heteroaryl.

Specific examples of the compound containing the structure represented by the general formula (H4) are shown below.

<Compound represented by the general formula (H5)>
In the above formula (H5)
R ^{1 to} R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl or cycloalkyl (all of which are the first substituents). At least one hydrogen may be further substituted with aryl, heteroaryl, diarylamino, alkyl or cycloalkyl (above, second substituent).
Adjacent groups of R ^{1 to} R ¹¹ may be bonded to 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 is It may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl or cycloalkyl (above, first substituent), in which at least one hydrogen is further aryl, heteroaryl. , Diarylamino, alkyl or cycloalkyl (above, second substituent).
At least one hydrogen in the compound represented by the formula (H5) may be independently substituted with halogen or deuterium.

Preferably, in the above formula (H5),
R ^{1 to} R ¹¹ are independently hydrogen, aryl with 6 to 30 carbon atoms, heteroaryl with 2 to 30 carbon atoms, diarylamino (where aryl is aryl with 6 to 12 carbon atoms), and 1 to 1 carbon atoms. It is an alkyl of 12 or a cycloalkyl of 3 to 16 carbon atoms, in which at least one hydrogen is an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, and a diarylamino (where aryl is 6 to 16 carbon atoms). 12 aryl), may be substituted with alkyl having 1-12 carbon atoms or cycloalkyl having 3-16 carbon atoms.
Adjacent groups of R ^{1 to} R ¹¹ may be bonded to each other to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a ring, b ring or c ring. , At least one hydrogen in the formed ring is aryl with 6 to 30 carbon atoms, heteroaryl with 2 to 30 carbon atoms, diarylamino (where aryl is aryl with 6 to 12 carbon atoms), and 1 to 12 carbon atoms. It may be substituted with alkyl or cycloalkyl having 3 to 16 carbon atoms, in which at least one hydrogen is an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, and a diarylamino (where aryl is a carbon). It may be substituted with an aryl of number 6 to 12), an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 16 carbon atoms.

More preferably, in the above formula (H5),
R ^{1 to} R ¹¹ are independently hydrogen, aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, diarylamino (where aryl is aryl with 6 to 10 carbon atoms), and 1 to 1 carbon atoms. It is an alkyl of 6 or a cycloalkyl of 3 to 14 carbon atoms, in which at least one hydrogen is an aryl having 6 to 16 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, and a diarylamino (where aryl has 6 to 15 carbon atoms). 10 aryl), may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms.
Adjacent groups of R ^{1 to} R ¹¹ may be bonded to each other to form an aryl ring having 9 to 12 carbon atoms or a heteroaryl ring having 6 to 12 carbon atoms together with the a ring, b ring or c ring. , At least one hydrogen in the formed ring is an aryl having 6 to 16 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, a diarylamino (where the aryl is an aryl having 6 to 10 carbon atoms), and an aryl having 6 to 6 carbon atoms. It may be substituted with alkyl or cycloalkyl having 3 to 14 carbon atoms, in which at least one hydrogen is an aryl having 6 to 16 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, and a diarylamino (where aryl is a carbon). It may be substituted with an alkyl having the number 6 to 10), an alkyl having 1 to 6 carbon atoms, or a cycloalkyl having 3 to 14 carbon atoms.

Examples of "aryl" and "heteroaryl" in aryl, heteroaryl, diarylamino, diheteroarylamino, and aryl heteroarylamino in the first and second substituents include the following examples.

Specific examples of the "aryl" include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, more preferably aryls having 6 to 20 carbon atoms, and aryls having 6 to 16 carbon atoms. Is more preferable, aryl having 6 to 12 carbon atoms is particularly preferable, and aryl having 6 to 10 carbon atoms is most preferable. For example, phenyl which is a monocyclic aryl, (2-, 3-, 4-) biphenylyl which is a bicyclic aryl, (1-, 2-) naphthyl which is a condensed bicyclic aryl, and tricyclic aryl. Terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'- Il, 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-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), fused tricyclic aryl Yes, acenaftylene- (1-, 3-, 4-, 5-) yl, fluoren- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) Phenantril, quaterphenyl-2-yl, a tetracyclic aryl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-) Terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene- (1-, 2-) yl, which is a fused tetracyclic aryl, pyrene- ( 1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-) yl, which is a fused pentacyclic aryl, pentacene- (1) -, 2-, 5-, 6-) Il and the like.

Specific examples of the "heteroaryl" include heteroaryls having 2 to 30 carbon atoms, preferably heteroaryls having 2 to 25 carbon atoms, more preferably heteroaryls having 2 to 20 carbon atoms, and 2 carbon atoms. Heteroaryl of ~ 15 is more preferable, and heteroaryl having 2 to 10 carbon atoms is particularly preferable. For example, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyridadinyl, pyrazinyl, triazinyl, indrill, isoindryl, 1H-indazolyl, benzoimidazolyl, benzoimidazolyl , 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyldinyl, prynyl, pteridinyl, carbazolyl, acridinyl, phenoxatinyl, phenoxadinyl, phenothiazinyl, phenazinyl, phenylazacillinyl, indolinyl Isobenzofuranyl, dibenzofuranyl, naphthobenzofuranyl, thiophenyl, benzothiophenyl, isobenzothiophenyl, dibenzothiophenyl, naphthobenzothiophenyl, benzophosphoryl, dibenzophosphoyl, monovalent group of benzophosphole oxide ring , The monovalent group of the dibenzophosphole oxide ring, flazanyl, thianthrenyl, indolocarbazolyl, benzoindrocarbazolyl and benzobenzoindorocarbazolyl and the like.

In the first substituent and the second substituent, the "alkyl" may be either a straight chain or a branched chain, and for example, a straight chain alkyl having 1 to 24 carbon atoms or a branched chain alkyl having 3 to 24 carbon atoms may be used. Alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms) is preferable, alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms) is more preferable, and alkyl having 1 to 12 carbon atoms is more preferable. Alkyl of 6 (branched chain alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 5 carbon atoms (branched chain alkyl having 3 to 5 carbon atoms) and alkyl having 1 to 4 carbon atoms (3 to 4 carbon atoms) are more preferable. (Branched chain alkyl) is particularly preferable, and methyl is most preferable. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl), n-hexyl, 1-methyl. Pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl (1,1,3,3-tetramethylbutyl), 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 and the like can be mentioned. Also, for example, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1,1,4-trimethylpentyl, 1,1,2- Trimethylpropyl, 1,1-dimethyloctyl, 1,1-dimethylpentyl, 1,1-dimethylheptyl, 1,1,5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl-1,3- Dimethylbutyl, 1,1,2,2-tetramethylpropyl, 1-butyl-1-methylpentyl, 1,1-diethylbutyl, 1-ethyl-1-methylpentyl, 1,1,3-trimethylbutyl, 1 -Propyl-1-methylpentyl, 1,1,2-trimethylpropyl, 1-ethyl-1,2,2-trimethylpropyl, 1-propyl-1-methylbutyl, 1,1-dimethylhexyl and the like can also be mentioned.

In the first substituent and the second substituent, the "cycloalkyl" includes cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, and 3 to 3 carbon atoms. Examples thereof include 14 cycloalkyl, 5 to 10 carbon number cycloalkyl, 5 to 8 carbon number cycloalkyl, 5 to 6 carbon number cycloalkyl, and 5 carbon number cycloalkyl. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (particularly methyl) substituents thereof having 1 to 4 carbon atoms, and bicyclo [1.0.1] butyl, bicyclo. [1.1.1] Pentyl, Bicyclo [2.0.1] Pentyl, Bicyclo [1.2.1] Hexyl, Bicyclo [3.0.1] Hexyl, Bicyclo [2.1.2] Heptyl, Bicyclo [2.2.2] Examples thereof include octyl, adamantyl, diamantyl, decahydronaphthalenyl, and decahydroazurenyl.

When the first substituent is aryl, the substitution positions are preferably R ¹ , R ³ , R ⁴ , R ⁵ , R ¹⁰ and R ¹¹ , for example, substitution with R ¹ and R ^3, to R ⁵ and R ¹⁰ . substitutions, more preferably substitution of R ⁴ and R ^11, aryl is preferably a phenyl group.

When the first substituent is heteroaryl, the substitution positions are preferably R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹¹ , for example, substitution with R ¹ . , R ² substitution, R ³ substitution, R ¹ and R ³ substitution, R ⁴ and R ¹¹ substitution, R ⁵ and R ¹⁰ substitution, R ⁶ and R ⁹ substitution. Preferably, the heteroaryl is preferably a carbazolyl group. This heteroaryl (eg, carbazolyl) may be substituted at the above position via a phenylene group.

Specific examples of the compound represented by the formula (H5) include a compound represented by the following structural formula. In addition, "Me" in the formula is a methyl group.

For the compound represented by the formula (H5), an intermediate is first produced by binding the a to c rings with a binding group (−O−) (first reaction), and then the a to c rings are B (1). The final product can be produced by bonding with boron) (second reaction). In the first reaction, general etherification reactions such as nucleophilic substitution reaction and Ullmann reaction can be used. Further, in the second reaction, a tandem hetero-Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction) can be used. For details of the first and second reactions, the explanation described in International Publication No. 2015/102118 can be referred to.

<TADF material>
By reducing the energy difference between the excited singlet state and the excited triplet state, the reverse energy transfer from the excited triplet state, which normally has a low transition probability, to the excited singlet state can be generated with high efficiency, from the singlet. (Thermal activation delayed fluorescence, TADF) is expressed. In normal fluorescence emission, 75% of triplet excitons generated by current excitation cannot be taken as fluorescence because they pass through the heat deactivation path. On the other hand, in TADF, all excitons can be used for fluorescence emission, and a highly efficient organic EL device can be realized.

Examples of the TADF material that can be used for such a purpose include a compound represented by the following general formula (H6) or a compound having the following general formula (H6) as a partial structure.
In formula (H6), ED is an electron donating group, Ln is a binding group, and EA is an electron accepting group, which is triplet with the singlet energy (S ¹ ) of the compound represented by the formula (H6). The energy difference (ΔS ¹ T ¹ ) of the term energy (T ¹ ) is 0.2 eV or less (Hiroki Uoyama, Kenichi Goushi, Katsuyuki Shizu, Hiroko Nomura, Chihaya Adachi, Nature, 492, 234-238 (2012)). The energy difference (ΔS ¹ T ¹ ) is preferably 0.15 eV or less, more preferably 0.10 eV or less, and further preferably 0.08 eV or less.

TADF materials use electron-donating substituents called donors and electron-accepting substituents called acceptors to localize intramolecular HOMO and LUMO for efficient reverse intersystem crossing. ) Is preferably a donor-acceptor type TADF compound (DA type TADF compound) designed so as to occur.

Here, in the present specification, the "electron-donating substituent" (donor) means a substituent and a partial structure in which the LUMO orbital is localized in the TADF compound molecule, and "electron acceptor substitution". The "group" (acceptor) is meant to mean a substituent and a partial structure in which the HOMO orbital is localized in the TADF compound molecule.

In general, TADF compounds using donors and acceptors have a large spin-orbit coupling (SOC) due to their structure, a small exchange interaction between HOMO and LUMO, and a small ΔE (ST). In addition, a very fast intersystem crossing speed is obtained. On the other hand, TADF compounds using donors and acceptors have greater structural relaxation in the excited state (for some molecules, the stable structure differs between the ground state and the excited state, so conversion from the ground state to the excited state by an external stimulus is performed. After that, the structure changes to a stable structure in the excited state), and since it gives a wide emission spectrum, it may reduce the color purity when used as a light emitting material.

When the color purity is lowered by the TADF material, a fluorescent compound may be added to the light emitting layer or a layer adjacent to the light emitting layer as another component. The TADF material acts as an assisting dopand and the other components act as an emerging dopant. The other component may be a compound in which the absorption spectrum of the compound overlaps at least partly with the emission peak of the assisting dopant.

As the donor and acceptor structures used in the TADF material, for example, the structures described in Chemistry of Materials, 2017, 29, 1946-1963 can be used. Examples of the ED include functional groups containing sp ³ nitrogen, and more specifically, carbazole, dimethylcarbazole, di-tbutylcarbazole, dimethoxycarbazole, tetramethylcarbazole, benzofluorocarbazole, and benzothienocarbazole. , Phenyldihydroindrocarbazole, phenylbicarbazole, bicarbazole, turcarbazole, diphenylcarbazolylamine, tetraphenylcarbazolyldiamine, phenoxazine, dihydrophenazine, phenothiazine, dimethyldihydroacrine, diphenylamine, bis (tbutyl) phenyl) Examples include groups derived from amines, (diphenylamino) phenyl) diphenylbenzenediamine, dimethyltetraphenyldihydroacrididinediamine, tetramethyl-dihydro-indenoaclydin and diphenyl-dihydrodibenzoazacillin. Examples of EA include sp ^2- nitrogen-containing aromatic rings, CN-substituted aromatic rings, ketone-containing rings and cyano groups, and more specifically, sulfonyldibenzene, benzophenone, and phenylenebis (phenylmethanone). Benzonitrile, isonicotinonitrile, phthalonitrile, isophthalonitrile, paraphthalonitrile, triazole, oxazole, thiadiazol, benzothiazole, benzobis (thiazole), benzoxazole, benzobis (oxazole), quinoline, benzoimidazole, dibenzoquinoxalin, hepta Azaphenalene, thioxanthone dioxide, dimethylanthracenone, anthracendione, pyridine, cycloheptabipyridine, benzenetricarbonitrile, fullorange carbonitrile, pyrazine dicarbonitrile, pyridinedicarbonitrile, dibenzoquinoxalin dicarbonitrile, pyrimidine, phenyl Examples thereof include groups derived from pyrimidine, methylpyrimidine, triazine, triphenyltriazine, bis (phenylsulfonyl) benzene, dimethylthioxanthendioxide, thianthrenetetraoxide and tris (dimethylphenyl) borane. Examples of Ln include single bond and arylene, and more specifically, phenylene, biphenylene, naphthylene and the like. Further, hydrogen may be substituted with alkyl, cycloalkyl and aryl in any structure. In particular, as a partial structure, at least one selected from carbazole, phenoxazine, aclysine, triazine, pyrimidine, pyrazine, thioxanthene, benzonitrile, phthalonitrile, isophthalonitrile, diphenylsulfone, triazole, oxadiazole, thiadiazole and benzophenone. It is preferable that the compound has one.

More specifically, the compound represented by the general formula (H6) is a compound represented by any of the following general formulas (H6-1), formula (H6-2) and formula (H6-3). ..

In the general formula (H6-1), formula (H6-2) and formula (H6-3),
M are independently single-bonded, -O-,> N-Ar or> C (-Ar) ₂ , respectively, and the HOMO depth and excited singlet energy level and excited triplet of the substructure to be formed. From the point of view of the height of the energy level, it is preferably a single bond, −O− or> N—Ar.
J is a spacer structure that separates the donor substructure and the acceptor substructure, each of which is an arylene having 6 to 18 carbon atoms, and is a conjugate that exudes from the donor substructure and the acceptor substructure. From the viewpoint of the size of the above, an arylene having 6 to 12 carbon atoms is preferable, and more specific examples thereof include phenylene, methylphenylene and dimethylphenylene.
Q is independently = C (-H)-or = N-, and is a viewpoint of the shallowness of LUMO and the height of the excited singlet energy level and the excited triplet energy level of the formed partial structure. Therefore, preferably = N-,
Ar is independently hydrogen, an aryl having 6 to 24 carbon atoms, a heteroaryl having 2 to 24 carbon atoms, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 18 carbon atoms, and forms a partial structure. From the viewpoint of the depth of HOMO and the height of the excited single-term energy level and the excited triple-term energy level, hydrogen, an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 14 carbon atoms, and a carbon number of carbon atoms are preferable. It is an alkyl of 1 to 4 or a cycloalkyl of 6 to 10 carbon atoms, more preferably hydrogen, phenyl, trill, xylyl, mesityl, biphenyl, pyridyl, bipyridyl, triazil, carbazolyl, dimethylcarbazolyl, di-tbutyl. Carbazolyl, benzoimidazole or phenylbenzoimidazole, more preferably hydrogen, phenyl or carbazolyl.
m is 1 or 2
n is an integer of 2 to (6-m), and is preferably an integer of 4 to (6-m) from the viewpoint of steric hindrance.
Further, at least one hydrogen in the compound represented by each of the above formulas may be substituted with halogen or deuterium.

Examples of the compound represented by the formula (H6) include a compound represented by the following structure. In the structural formula, * indicates a bond position, “Me” indicates a methyl group, and “tBu” indicates a t-butyl group.

Among the above-mentioned specific compounds, the compound represented by the general formula (H6) includes 4CzBN, 4CzBN-Ph, 5CzBN, 3Cz2DPhCzBN, 4CzIPN, 2PXZ-TAZ, Cz-TRZ3, BDPCC-TPTA, MA-TA, PA. -TA, FA-TA, PXZ-TRZ, DMAC-TRZ, BCzT, DCzTrz, DDCzTrz, spiroAC-TRZ, Ac-HPM, Ac-PPM, Ac-MPM, TCzTrz, TmCzTrz and DCzmCzTrz are preferable.

Further, the dopant material is not particularly limited, and a known compound can be used, and it can be selected from various materials according to a desired emission color. Specifically, for example, fused ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene, rubrene and chrysen, benzoxazole derivatives, benzothiazole derivatives, benzoimidazole derivatives, benzotriazole derivatives, oxazoles. Bistylyl derivatives such as derivatives, oxadiazol derivatives, thiazole derivatives, imidazole derivatives, thiadiazol derivatives, triazole derivatives, pyrazoline derivatives, stillben derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives and distyrylbenzene derivatives. (Japanese Patent Laid-Open No. 1-245087), bisstyrylallylene derivative (Japanese Patent Laid-Open No. 2-247278), diazaindacene derivative, furan derivative, benzofuran derivative, phenylisobenzofuran, dimesitylisobenzofuran, di (2-methylphenyl) Isobenzofuran derivatives such as isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, phenylisobenzofuran, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7- Cumarin derivatives such as methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazolylcoumarin derivatives, 3-benzoimidazolylcoumarin derivatives, 3-benzoxazolylcoumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine Derivatives, cyanine derivatives, oxobenzoanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyryl derivatives, acrydin derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrolopyridine derivatives, flopyridine derivatives, Examples thereof include 1,2,5-thiadiazolopylene derivatives, pyromethene derivatives, perinone derivatives, pyrolopyrrole derivatives, squarylium derivatives, biolantron derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives and benzofluorene derivatives.

For example, as blue to blue-green dopant materials for each coloring light, aromatic hydrocarbon compounds such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, inden, and chrysen and their derivatives, furan, pyrrole, thiophene, etc. Aromatic complexes such as silol, 9-silafluolene, 9,9'-spirobicilafluorene, benzothiophene, benzofuran, indol, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthylidine, quinoxalin, pyrolopyridine, thioxanthene Ring compounds and their derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stillben derivatives, aldazine derivatives, coumarin derivatives, imidazole, thiazole, thiadiazol, carbazole, oxazole, oxadiazol, triazole and other azole derivatives and their metal complexes and N , N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diphenyl-1,1'-diamine and other aromatic amine derivatives.

Examples of the green to yellow dopant material include a coumarin derivative, a phthalimide derivative, a naphthalimide derivative, a perinone derivative, a pyrolopyrrole derivative, a cyclopentadiene derivative, an acrydone derivative, a quinacridone derivative, a naphthacene derivative such as rubrene, and the like. A preferable example is a compound in which a substituent capable of lengthening the wavelength, such as aryl, heteroaryl, arylvinyl, amino, and cyano, is introduced into the compound exemplified as the blue-green dopant material.

Further, as the orange to red dopant material, naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic acid imide, perinone derivatives, rare earth complexes such as Eu complex having acetylacetone, benzoylacetone and phenanthroline as ligands, 4 -(Dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinacridone Derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrolopyridine derivatives, squarylium derivatives, biolantron derivatives, phenazine derivatives, phenoxazone derivatives, thiadiazolopyrene derivatives, etc. are mentioned, and further exemplified as the above-mentioned blue-blue-green and green-yellow dopant materials. A preferable example is a compound in which a substituent capable of lengthening the wavelength, such as aryl, heteroaryl, arylvinyl, amino, and cyano, is introduced into the above-mentioned compound.

In addition, as the dopant, it can be appropriately selected and used from the compounds described in the June 2004 issue of Chemical Industry, page 13, and the references listed therein.

Among the above-mentioned dopant materials, amines, perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyrane derivatives or pyrene derivatives having a stillben structure are particularly preferable.

An amine having a stilbene structure is represented by, for example, the following formula.
In the formula, Ar ¹ is an m-valent group derived from an aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ are independently aryls having 6 to 30 carbon atoms, but Ar ^{1 to} Ar. ^At least one of ³ has a stilben structure, and Ar ^{1 to} Ar ³ are aryl, heteroaryl, alkyl, cycloalkyl, tri-substituted silyl (silyl substituted with at least one of aryl, alkyl and cycloalkyl). Alternatively, it may be substituted with cyano, and m is an integer of 1 to 4.

The amine having a stilbene structure is more preferably diaminostilbene represented by the following formula.
In the formula, Ar ² and Ar ³ are independently aryls having 6 to 30 carbon atoms, and Ar ² and Ar ³ are aryls, heteroaryls, alkyls, cycloalkyls, and trisubstituted silyls (aryls, alkyls and). It may be tri-substituted with at least one of the cycloalkyl) or cyano.

Specific examples of aryls having 6 to 30 carbon atoms are phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, perylenel, stillbenyl, distyrylphenyl, distyrylbiphenylyl. , Distylyl fluorenyl, etc.

Specific examples of amines having a stilbene structure are N, N, N', N'-tetra (4-biphenylyl) -4,4'-diaminostilbene, N, N, N', N'-tetra (1-naphthyl). ) -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-4,4'-diaminostilbene, 4,4'-bis [4 "-bis (Diphenylamino) stilbene] -biphenyl, 1,4-bis [4'-bis (diphenylamino) stilbene] -benzene, 2,7-bis [4'-bis (diphenylamino) stilbene] -9,9-dimethyl Examples thereof include fluorene, 4,4'-bis (9-ethyl-3-carbazobinylene) -biphenyl, 4,4'-bis (9-phenyl-3-carbazovinylene) -biphenyl and the like.
Further, amines having a stilbene structure described in JP-A-2003-347056 and JP-A-2001-307884 may be used.

Examples of the perylene derivative include 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene, 3,10-diphenylperylene, and 3,4-. Diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3- (1'-pyrenyl) -8,11-di (t-butyl) perylene , 3- (9'-anthryl) -8,11-di (t-butyl) perylene, 3,3'-bis (8,11-di (t-butyl) perylenel) and the like.
In addition, JP-A-11-97178, JP-A-2000-133457, JP-A-2000-26324, JP-A-2001-267079, JP-A-2001-267078, JP-A-2001-267076, Perylene derivatives described in JP-A-2000-34234, JP-A-2001-267075, JP-A-2001-217077, and the like may be used.

Examples of the borane derivative include 1,8-diphenyl-10- (dimethylboryl) anthracene, 9-phenyl-10- (dimethylboryl) anthracene, 4- (9'-anthril) dimethylborylnaphthalene, 4- (10'). -Phenyl-9'-anthryl) dimesitylborylnaphthalene, 9- (dimesitylboryl) anthracene, 9- (4'-biphenylyl) -10- (dimesitylboryl) anthracene, 9- (4'-(N-carbazolyl) phenyl) -10- (Dimethylboryl) anthracene and the like can be mentioned.
Further, the borane derivative described in International Publication No. 2000/40586 pamphlet or the like may be used.

The aromatic amine derivative is represented by, for example, the following formula.
In the formula, Ar ⁴ is an n-valent group derived from a aryl having 6 to 30 carbon atoms, Ar ⁵ and Ar ⁶ are each independently an aryl having 6 to 30 carbon ^atoms, Ar 4 to Ar ⁶ is , Aryl, heteroaryl, alkyl, cycloalkyl, tri-substituted silyl (silyl substituted with at least one of aryl, alkyl and cycloalkyl) or cyano, and n is 1-4. It is an integer.

In particular, a divalent group Ar ⁴ is derived from anthracene, chrysene, fluorene, benzo fluorene or pyrene, Ar ⁵ and Ar ⁶ are each independently an aryl having 6 to 30 carbon ^atoms, Ar 4 to Ar ⁶ May be substituted with aryl, heteroaryl, alkyl, cycloalkyl, tri-substituted silyl (silyl substituted with at least one of aryl, alkyl and cycloalkyl) or cyano, and n is 2. , Aromatic amine derivatives are more preferred.

Specific examples of aryls having 6 to 30 carbon atoms include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, naphthalenyl, perylenyl, pentasenyl and the like.

As the aromatic amine derivative, as a chrysen system, for example, N, N, N', N'-tetraphenylcrisen-6,12-diamine, N, N, N', N'-tetra (p-tolyl) Chrysen-6,12-diamine, N, N, N', N'-tetra (m-tolyl) Chrysen-6,12-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) chrysen -6,12-diamine, N, N, N', N'-tetra (naphthalen-2-yl) chrysen-6,12-diamine, N, N'-diphenyl-N, N'-di (p-tolyl) ) Chrysen-6,12-diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) Chrysen-6,12-diamine, N, N'-diphenyl-N, N'-bis ( 4-isopropylphenyl) chrysene-6,12-diamine, N, N'-diphenyl-N, N'-bis (4-t-butylphenyl) chrysen-6,12-diamine, N, N'-bis (4) -Isopropylphenyl) -N, N'-di (p-tolyl) chrysen-6,12-diamine and the like.

As the pyrene system, for example, 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'-diphenyl-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) -3,8-diphenylpyrene-1,6 -Diamine, N, N, N, N-Tetraphenylpyrene-1,8-diamine, N, N'-bis (biphenyl-4-yl) -N, N'-diphenylpyrene-1,8-diamine, N ¹ , N ⁶ -diphenyl-N ¹ , N ⁶ -bis- (4-trimethylsilanyl-phenyl) -1H, 8H-pyrene-1,6-diamine and the like can be mentioned.

The anthracene system includes, for example, N, N, N, N-tetraphenylanthracene-9,10-diamine, N, N, N', N'-tetra (p-tolyl) anthracene-9,10-diamine. , N, N, N', N'-tetra (m-tolyl) anthracene-9,10-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-di (p-tolyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-di (m-tolyl) anthracene-9,10- Diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) anthracene-9,10-diamine, 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 and the like can be mentioned.

In addition, [4- (4-diphenylamino-phenyl) naphthalene-1-yl] -diphenylamine, [6- (4-diphenylamino-phenyl) naphthalene-2-yl] -diphenylamine, 4,4'. -Bis [4-diphenylaminonaphthalene-1-yl] biphenyl, 4,4'-bis [6-diphenylaminonaphthalen-2-yl] biphenyl, 4,4 "-bis [4-diphenylaminonaphthalen-1-yl] ] -P-Terphenyl, 4,4 "-bis [6-diphenylaminonaphthalen-2-yl] -p-terphenyl and the like.
Further, the aromatic amine derivative described in JP-A-2006-156888 may be used.

Examples of the coumarin derivative include coumarin-6 and coumarin-334.
Further, the coumarin derivatives described in JP-A-2004-43646, JP-A-2001-76876, JP-A-6-298758 and the like may be used.

Examples of the pyran derivative include the following DCM, DCJTB and the like.
Further, JP-A-2005-126399, JP-A-2005-097283, JP-A-2002-234892, JP-A-2001-220577, JP-A-2001-081090, and JP-A-2001-052869. The pyran derivative described in the above may be used.

The above-mentioned materials for the light emitting layer (host material and dopant material) are polymer compounds obtained by polymerizing a reactive compound in which a reactive substituent is substituted as a monomer, or a polymer crosslinked product thereof, or a main chain. A pendant type polymer compound obtained by reacting a type polymer with the reactive compound, or a pendant type polymer crosslinked product thereof can also be used as a material for a light emitting layer. As the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited.
Details of the uses of such polymer compounds and crosslinked polymers will be described later.

<Electronic injection layer and electron transport layer in organic electroluminescent device>
The electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106. The electron transport layer 106 plays a role of efficiently transporting the electrons injected from the cathode 108 or the electrons injected from the cathode 108 via the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are formed by laminating and mixing one or more kinds of electron transport / injection materials or a mixture of the electron transport / injection material and the polymer binder, respectively.

The electron injection / transport layer is a layer in which electrons are injected from the cathode and further transports the electrons, and it is desirable that the electron injection efficiency is high and the injected electrons are efficiently transported. For that purpose, it is preferable that the substance has a large electron affinity, a high electron mobility, excellent stability, and is less likely to generate impurities as traps during production and use. However, when considering the transport balance between holes and electrons, the electron transport capacity is so high when it mainly plays a role of efficiently blocking the holes from the anode from flowing to the cathode side without recombination. Even if it is not high, it has the same effect of improving luminous efficiency as a material having high electron transport capacity. Therefore, the electron injection / transport layer in the present embodiment may also include the function of a layer capable of efficiently blocking the movement of holes.

As the material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107, it is used as a compound conventionally used as an electron transfer compound in a photoconductive material, an electron injection layer and an electron transport layer of an organic EL element. It can be arbitrarily selected and used from the known compounds known.

The material used for the electron transport layer or the electron injection layer is a compound composed of an aromatic ring or a complex aromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus. It preferably contains at least one selected from a pyrrole derivative, a condensed ring derivative thereof, and a metal complex having an electron-accepting nitrogen. Specifically, fused ring-based aromatic ring derivatives such as naphthalene and anthracene, styryl-based aromatic ring derivatives typified by 4,4'-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives. , Quinone derivatives such as anthraquinone and diphenoquinone, phosphoroxide derivatives, carbazole derivatives and indol derivatives and the like. Examples of the metal complex having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes and benzoquinoline metal complexes. These materials may be used alone, but may be mixed with different materials.

Specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, and oxadiazol. Derivatives (1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4- Triazole, etc.), thiazazole derivatives, oxine derivative metal complexes, quinolinol-based metal complexes, quinoxalin derivatives, quinoxalin derivative polymers, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorophenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinolins Derivatives (2,2'-bis (benzo [h] quinoline-2-yl) -9,9'-spirobifluorene, etc.), imidazole pyridine derivatives, borane derivatives, benzoimidazole derivatives (tris (N-phenylbenzoimidazole-) 2-yl) benzene, etc.), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as telpyridine, bipyridine derivatives, telpyridine derivatives (1,3-bis (4'-(2,2': 6'2)) "-Terpyridinyl)) benzene, etc.), naphthylidine derivatives (bis (1-naphthyl) -4- (1,8-naphthylidine-2-yl) phenylphosphine oxide, etc.), aldazine derivatives, carbazole derivatives, indol derivatives, phosphoroxide derivatives , Bistylyl derivatives and the like.

Further, a metal complex having electron-accepting nitrogen can also be used. For example, hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes and benzoquinoline metal complexes can be used. Can be mentioned.

The above-mentioned materials may be used alone, but may be mixed with different materials.

Among the above-mentioned materials, borane derivatives, pyridine derivatives, fluorantene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzoimidazole derivatives, phenanthroline derivatives, and quinolinol metals Derivatives are preferred.

<Borane derivative>
The borane derivative is, for example, a compound represented by the following general formula (ETM-1), and is disclosed in detail in JP-A-2007-27587.
In the above formula (ETM-1), R ¹¹ and R ¹² each independently contain hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, and optionally substituted nitrogen. At least one of the heterocycle or cyano, R ^{13 to} R ¹⁶ are independently optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl, respectively. , X are optionally substituted arylene, Y is optionally substituted aryl having 16 or less carbon atoms, substituted boron, or optionally substituted carbazolyl, and n. Are independently integers from 0 to 3. In addition, examples of the substituent in the case of "may be substituted" or "substituted" include aryl, heteroaryl, alkyl, cycloalkyl and the like.

Among the compounds represented by the above general formula (ETM-1), the compound represented by the following general formula (ETM-1-1) and the compound represented by the following general formula (ETM-1-2) are preferable.
In formula (ETM-1-1), R ¹¹ and R ¹² are independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen, respectively. At least one of the containing heterocycles, or cyano, R ^{13 to} R ¹⁶ are independently optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl, respectively. Yes, R ²¹ and R ²² are independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or at least cyano. One, X ¹ is an arylene having 20 or less carbon atoms which may be substituted, n is an integer of 0 to 3 independently, and m is an integer of 0 to 4 independently. It is an integer. In addition, examples of the substituent in the case of "may be substituted" or "substituted" include aryl, heteroaryl, alkyl, cycloalkyl and the like.
In formula (ETM-1-2), R ¹¹ and R ¹² are independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen, respectively. Containing heterocycles, or at least one of cyano, R ^{13 to} R ¹⁶ are independently optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl, respectively. Yes, X ¹ is an arylene having 20 or less carbon atoms which may be substituted, and n is an independently integer of 0 to 3. In addition, examples of the substituent in the case of "may be substituted" or "substituted" include aryl, heteroaryl, alkyl, cycloalkyl and the like.

Specific examples of X ¹ include divalent groups represented by any of the following formulas (X-1) to (X-9). * In each structural formula represents the bonding position.
(In each formula, ^Ra is an alkyl group, a cycloalkyl group, or a optionally substituted phenyl group, respectively.)

Specific examples of this borane derivative include the following compounds.

This borane derivative can be produced by using a known raw material and a known synthesis method.

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

φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. is there.

In the above formula (ETM-2-1), R ^{11 to} R ¹⁸ are independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), and cycloalkyl (preferably cyclo having 3 to 12 carbon atoms). Alkyl) or aryl (preferably aryl with 6 to 30 carbon atoms).

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

In each formula, the "pyridine-based substituent" is any of the following formulas (Py-1) to (Py-15), and the pyridine-based substituents are independently alkyl or carbon having 1 to 4 carbon atoms. It may be substituted with the number 5 to 10 of cycloalkyl. Further, the pyridine-based substituent may be bonded to φ, anthracene ring or fluorene ring in each formula via a phenylene group or a naphthylene group. * In each structural formula represents the bonding position.

The pyridine-based substituent is any of the above formulas (Py-1) to (Py-15), and among these, any of the following formulas (Py-21) to (Py-44). Is preferable. * In each structural formula represents the bonding position.

At least one hydrogen in each pyridine derivative may be substituted with deuterium, and of the two "pyridine-based substituents" in the above formula (ETM-2-1) and (ETM-2-2). One may be replaced with aryl.

The "alkyl" in R ^{11 to} R ¹⁸ may be either a straight chain or a branched chain, and examples thereof include a straight chain alkyl having 1 to 24 carbon atoms and a branched chain alkyl having 3 to 24 carbon atoms. A preferred "alkyl" is an alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms). A more preferred "alkyl" is an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms). A more preferable "alkyl" is an alkyl having 1 to 6 carbon atoms (branched chain alkyl having 3 to 6 carbon atoms). A particularly preferable "alkyl" is an alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms).

Specific "alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl), and the like. n-hexyl, 1-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl (1,1,3,3-tetramethylbutyl), 1-Methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n- Examples thereof include undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicosyl.
Also, for example, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1,1,4-trimethylpentyl, 1,1,2- Trimethylpropyl, 1,1-dimethyloctyl, 1,1-dimethylpentyl, 1,1-dimethylheptyl, 1,1,5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl-1,3- Dimethylbutyl, 1,1,2,2-tetramethylpropyl, 1-butyl-1-methylpentyl, 1,1-diethylbutyl, 1-ethyl-1-methylpentyl, 1,1,3-trimethylbutyl, 1 -Propyl-1-methylpentyl, 1,1,2-trimethylpropyl, 1-ethyl-1,2,2-trimethylpropyl, 1-propyl-1-methylbutyl, 1,1-dimethylhexyl and the like can also be mentioned.

As the alkyl having 1 to 4 carbon atoms to be substituted with the pyridine-based substituent, the above description of the alkyl can be cited.

Examples of the "cycloalkyl" in R ^{11 to} R ¹⁸ include cycloalkyl having 3 to 12 carbon atoms. A preferred "cycloalkyl" is a cycloalkyl having 3 to 10 carbon atoms. A more preferable "cycloalkyl" is a cycloalkyl having 3 to 8 carbon atoms. A more preferable "cycloalkyl" is a cycloalkyl having 3 to 6 carbon atoms.
Specific examples of the "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.

As the cycloalkyl having 5 to 10 carbon atoms to be substituted with the pyridine-based substituent, the above description of cycloalkyl can be cited.

As the "aryl" in R ^{11 to} R ¹⁸ , the preferred aryl is an aryl having 6 to 30 carbon atoms, the more preferable aryl is an aryl having 6 to 18 carbon atoms, and more preferably an aryl having 6 to 14 carbon atoms. Yes, particularly preferably an aryl having 6 to 12 carbon atoms.

Specific examples of the "aryl having 6 to 30 carbon atoms" include phenyl, which is a monocyclic aryl, (1-, 2-) naphthyl, which is a fused dicyclic aryl, and acenaphthylene- (which is a condensed tricyclic aryl). 1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1-, 2-) yl, (1-, 2) -, 3-, 4-, 9-) Phenantril, fused tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-) , 2-, 5-) yl, perylene- (1-, 2-, 3-) yl which is a fused pentacyclic aryl, pentacene- (1-, 2-, 5-, 6-) yl and the like. ..

Preferred "aryls having 6 to 30 carbon atoms" include phenyl, naphthyl, phenanthryl, chrysenyl or triphenylenyl, and more preferably phenyl, 1-naphthyl, 2-naphthyl or phenanthryl, and particularly preferably phenyl, 1 −naphthyl or 2-naphthyl can be mentioned.

R ¹¹ and R ¹² in the above formula (ETM-2-2) may be combined to form a ring, and as a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, etc. are formed on the 5-membered ring of the fluorene skeleton. Cyclohexane, fluorene, indene and the like may be spiro-bonded.

Specific examples of this pyridine derivative include the following compounds.

This pyridine derivative can be produced by using a known raw material and a known synthesis method.

<Fluoranthene derivative>
The fluoranthene derivative is, for example, a compound represented by the following general formula (ETM-3), and is disclosed in detail in International Publication No. 2010/134352.

In the above formula (ETM-3), X ^{12 to} X ²¹ are hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted. Represents a heteroaryl. Here, examples of the substituent when substituted include aryl, heteroarylalkyl, cycloalkyl and the like.

Specific examples of this fluoranthene derivative include the following compounds.

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

R ^{1 to} R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these. May be substituted with aryl, heteroaryl, alkyl or cycloalkyl.

Further, adjacent groups of R ^{1 to} R ¹¹ may be bonded to 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, aryl heteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, in which at least one hydrogen is aryl, heteroaryl, alkyl or It may be substituted with cycloalkyl.

Further, at least one hydrogen in the compound or structure represented by the formula (ETM-4) may be substituted with halogen or deuterium.

For the explanation of the form of substituents and ring formation in the formula (ETM-4) and the multimer formed by combining a plurality of structures of the formula (ETM-4), the compound represented by the above general formula (1) and its large amount You can quote the description of the body.

Specific examples of this BO-based derivative include the following compounds.

This BO-based derivative can be produced by using a known raw material and a known synthesis method.

<Anthracene derivative>
One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-1).

Ar is independently divalent benzene or naphthalene, and R ^{1 to} R ⁴ are independently hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or carbon number of carbon atoms. 6 to 20 aryls.

Ar can be independently selected from divalent benzene or naphthalene, and the two Ars may be different or the same, but they are the same from the viewpoint of ease of synthesis of the anthracene derivative. Is preferable. Ar binds to pyridine to form a "site consisting of Ar and pyridine", and this site is anthracene as a group represented by any of the following formulas (Py-1) to (Py-12), for example. Is bound to. * In each structural formula represents the bonding position.

Among these groups, the group represented by any of the above formulas (Py-1) to (Py-9) is preferable, and the group represented by any of the above formulas (Py-1) to (Py-6) is represented. Is more preferred. The two "sites composed of Ar and pyridine" that bind to anthracene may have the same or different structures, but are preferably the same structure from the viewpoint of ease of synthesis of the anthracene derivative. However, from the viewpoint of device characteristics, it is preferable that the structures of the two "sites composed of Ar and pyridine" are the same or different.

The alkyl having 1 to 6 carbon atoms in R ^{1 to} R ⁴ may be either a straight chain or a branched chain. That is, it is a straight chain alkyl having 1 to 6 carbon atoms or a branched chain alkyl having 3 to 6 carbon atoms. More preferably, it is an alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl), n-hexyl, and so on. Examples thereof include 1-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc., preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl, and methyl, Ethyl or t-butyl is more preferred.

Specific examples of cycloalkyl having 3 to 6 carbon atoms in R ^{1 to} R ⁴ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl or dimethylcyclohexyl.

Regarding the aryl having 6 to 20 carbon atoms in R ^{1 to} R ^4, the aryl having 6 to 16 carbon atoms is preferable, the aryl having 6 to 12 carbon atoms is more preferable, and the aryl having 6 to 10 carbon atoms is particularly preferable.

Specific examples of the "aryl having 6 to 20 carbon atoms" include phenyl, which is a monocyclic aryl, (o-, m-, p-) trill, and (2,3-,2,4-,2,5-). , 2,6-, 3,4-, 3,5-) xsilyl, mesityl (2,4,6-trimethylphenyl), (o-, m-, p-) cumenyl, bicyclic aryl (2) -, 3-, 4-) Biphenylyl, fused bicyclic aryl (1-, 2-) naphthyl, tricyclic aryl terphenyl (m-terphenyl-2'-yl, m-terphenyl-4) '-Il, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -Il, m-terphenyl-3-yl, m-terphenyl-4-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 aryl, anthracene- (1-, 2-, 9-) yl, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluoren- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1-, 2-) 2-, 3-, 4-, 9-) phenanthryl, fused tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, tetracene- (1) -, 2-, 5-) yl, perylene- (1-, 2-, 3-) yl, which is a fused pentacyclic aryl, and the like can be mentioned.

Preferred "aryl of 6-20 carbons" are phenyl, biphenylyl, terphenylyl or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2-naphthyl or m-terphenyl-5'-yl. More preferably, it is phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, and most preferably phenyl.

One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-2).

Ar ¹ is independently a single bond, divalent benzene, naphthalene, anthracene, fluorene, or phenalene.

Ar ² is an aryl having 6 to 20 carbon atoms independently, and the same explanation as “aryl having 6 to 20 carbon atoms” in the above formula (ETM-5-1) can be quoted. Aryl having 6 to 16 carbon atoms is preferable, aryl having 6 to 12 carbon atoms is more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphtylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetrasenyl, perylenyl and the like.

R ^{1 to} R ⁴ are independently hydrogen, an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, or an aryl having 6 to 20 carbon atoms, respectively, according to the above formula (ETM-5-1). The explanation in can be quoted.

Specific examples of these anthracene derivatives include the following compounds.

These anthracene derivatives can be produced using known raw materials and known synthetic methods.

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

Ar ¹ is an aryl having 6 to 20 carbon atoms independently, and the same explanation as “aryl having 6 to 20 carbon atoms” in the above formula (ETM-5-1) can be quoted. Aryl having 6 to 16 carbon atoms is preferable, aryl having 6 to 12 carbon atoms is more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphtylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetrasenyl, perylenyl and the like.

Ar ² is 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 the two Ar ² may form a ring.

The "alkyl" in Ar ² may be either a straight chain or a branched chain, and examples thereof include a linear alkyl having 1 to 24 carbon atoms and a branched chain alkyl having 3 to 24 carbon atoms. A preferred "alkyl" is an alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms). A more preferred "alkyl" is an alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms). A more preferable "alkyl" is an alkyl having 1 to 6 carbon atoms (branched chain alkyl having 3 to 6 carbon atoms). A particularly preferable "alkyl" is an alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms). Specific "alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl), and the like. Examples thereof include n-hexyl, 1-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like.

Examples of the "cycloalkyl" in Ar ² include cycloalkyl having 3 to 12 carbon atoms. A preferred "cycloalkyl" is a cycloalkyl having 3 to 10 carbon atoms. A more preferable "cycloalkyl" is a cycloalkyl having 3 to 8 carbon atoms. A more preferable "cycloalkyl" is a cycloalkyl having 3 to 6 carbon atoms. Specific examples of the "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.

As the "aryl" in Ar ² , the preferred aryl is an aryl having 6 to 30 carbon atoms, the more preferable aryl is an aryl having 6 to 18 carbon atoms, and more preferably an aryl having 6 to 14 carbon atoms, particularly. It is preferably an aryl having 6 to 12 carbon atoms.

Specific examples of the "aryl having 6 to 30 carbon atoms" include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, naphthacenyl, perylenyl, pentasenyl and the like.

Two Ar ² may form a ring, as a result, the 5-membered ring of the fluorene skeleton, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene or indene are spiro-linked You may.

Specific examples of this benzofluorene derivative include the following compounds.

This benzofluorene derivative can be produced by using a known raw material and a known synthetic method.

<Phosphine oxide derivative>
The phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1). Details are also described in International Publication No. 2013/07927.
R ⁵ is a substituted or unsubstituted alkyl having 1 to 20 carbon atoms, heteroaryl cycloalkyl, aryl, or 5 to 20 carbon atoms of 6 to 20 carbon atoms having 3 to 20 carbon atoms,
R ⁶ is CN, substituted or unsubstituted, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, and 5 to 5 carbon atoms. 20 heteroaryl, alkoxy with 1 to 20 carbons or aryloxy with 6 to 20 carbons.
R ⁷ and R ⁸ are independently substituted or unsubstituted aryls having 6 to 20 carbon atoms or heteroaryls having 5 to 20 carbon atoms, respectively.
R ⁹ is oxygen or sulfur
j is 0 or 1, k is 0 or 1, r is an integer from 0 to 4, and q is an integer from 1 to 3.
Here, examples of the substituent when substituted include aryl, heteroaryl, alkyl, cycloalkyl and the like.

The phosphine oxide derivative may be, for example, a compound represented by the following formula (ETM-7-2).

R ^{1 to} R ³ may be the same or different, and may be the same or different, hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, alkylthio group, cycloalkylthio group, arylether group. , Arylthioether group, aryl group, heterocyclic group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, amino group, nitro group, silyl group, and in the fused ring formed between adjacent substituents. Is selected from.

Ar ¹ may be the same or different and is an arylene or heteroarylene group, and Ar ² may be the same or different and is an aryl or heteroaryl group. However, at least one of Ar ¹ and Ar ² has a substituent or forms a condensed ring with an adjacent substituent. n is an integer from 0 to 3, and when n is 0, the unsaturated structure portion does not exist, and when n is 3, R ¹ does not exist.

Among these substituents, the alkyl group indicates a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, which may be unsubstituted or substituted. The substituent when substituted is not particularly limited, and examples thereof include an alkyl group, an aryl group, and a heterocyclic group, and this point is also common to the following description. The number of carbon atoms of the alkyl group is not particularly limited, but is usually in the range of 1 to 20 from the viewpoint of availability and cost.

Further, the cycloalkyl group means, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, adamantyl, etc., which may be unsubstituted or substituted. The number of carbon atoms in the alkyl group moiety is not particularly limited, but is usually in the range of 3 to 20.

Further, the aralkyl group indicates an aromatic hydrocarbon group mediated by an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group, and both the aliphatic hydrocarbon and the aromatic hydrocarbon are substituted without substitution. It doesn't matter. The carbon number of the aliphatic portion is not particularly limited, but is usually in the range of 1 to 20.

Further, the alkenyl group indicates, for example, an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, which may be unsubstituted or substituted. The carbon number of the alkenyl group is not particularly limited, but is usually in the range of 2 to 20.

Further, the cycloalkenyl group indicates, for example, an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, a cyclohexene group, and this may be substituted or substituted. It doesn't matter.

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

Further, the alkoxy group indicates, for example, an aliphatic hydrocarbon group via an ether bond such as a methoxy group, and the aliphatic hydrocarbon group may be unsubstituted or substituted. The number of carbon atoms of the alkoxy group is not particularly limited, but is usually in the range of 1 to 20.

The alkylthio group is a group in which the oxygen atom of the ether bond of the alkoxy group is replaced with a sulfur atom.

The cycloalkylthio group is a group in which the oxygen atom of the ether bond of the cycloalkoxy group is replaced with a sulfur atom.

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

The arylthioether group is a group in which the oxygen atom of the ether bond of the arylether group is replaced with a sulfur atom.

Further, the aryl group indicates, for example, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenylyl group, a phenanthryl group, a terphenyl group and a pyrenyl group. The aryl group may be unsubstituted or substituted. The number of carbon atoms of the aryl group is not particularly limited, but is usually in the range of 6 to 40.

Further, the heterocyclic group refers to a cyclic structural group having an atom other than carbon such as a furanyl group, a thiophenyl group, an oxazolyl group, a pyridyl group, a quinolinyl group and a carbazolyl group, which are substituted even if they are not substituted. It doesn't matter. The number of carbon atoms of the heterocyclic group is not particularly limited, but is usually in the range of 2 to 30.

Halogen refers to fluorine, chlorine, bromine, and iodine.

The aldehyde group, carbonyl group, and amino group can also include groups substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocycles, and the like.

In addition, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocycles may be substituted or substituted.

The silyl group refers to a silicon compound group such as a trimethylsilyl group, which may be unsubstituted or substituted. The carbon number of the silyl group is not particularly limited, but is usually in the range of 3 to 20. The number of silicon is usually 1 to 6.

The condensed rings formed between the adjacent substituents are, for example, Ar ¹ and R ² , Ar ¹ and R ³ , Ar ² and R ² , Ar ² and R ³ , R ² and R ³ , and Ar ¹ . It is a conjugated or non-conjugated fused ring formed between Ar ² and the like. Here, when n is 1, may be formed conjugated or non-conjugated fused ring with two of R ¹ each other. These fused rings may contain nitrogen, oxygen, and sulfur atoms in the ring structure, or may be fused with another ring.

Specific examples of this phosphine oxide derivative include the following compounds.

This phosphine oxide derivative can be produced by using a known raw material and a known synthetic method.

<Pyrimidine derivative>
The pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), and preferably a compound represented by the following formula (ETM-8-1). Details are also described in International Publication No. 2011/021689.

Ar is an aryl which may be substituted or a heteroaryl which may be substituted independently of each other. n is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2 or 3.

Examples of the "aryl" of the "optionally substituted aryl" include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, and more preferably aryls having 6 to 20 carbon atoms. More preferably, it is an aryl having 6 to 12 carbon atoms.

Specific examples of "aryl" include phenyl, which is a monocyclic aryl, biphenylyl (2-, 3-, 4-) biphenylyl, and (1-, 2-) naphthyl, which is a fused bicyclic aryl. , Terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-3'-yl, tricyclic aryl -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-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , Condensed tricyclic aryls, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1) -, 2-) Il, (1-, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene- (1-, 2), a fused tetracyclic aryl -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-), which is a fused pentacyclic aryl ) Il, pentasen- (1-, 2-, 5-, 6-) il and the like.

Examples of the "heteroaryl" of the "optionally substituted heteroaryl" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferable, heteroaryl having 2 to 15 carbon atoms is further preferable, and heteroaryl having 2 to 10 carbon atoms is particularly preferable. Examples of the heteroaryl include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific heteroaryls include, for example, frills, thienyl, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, frazayl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridadinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indrill, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, synnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthylidine, prynyl , Pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazinyl, phenazinyl, phenoxatiinyl, thiantranyl, indridinyl and the like.

Further, the above-mentioned aryl and heteroaryl may be substituted, and for example, the above-mentioned aryl and heteroaryl may be substituted, respectively.

Specific examples of this pyrimidine derivative include the following compounds.

This pyrimidine derivative can be produced by using a known raw material and a known synthetic method.

<Carbazole derivative>
The carbazole derivative is, for example, a compound represented by the following formula (ETM-9) or a multimer in which a plurality of the compounds are bound by a single bond or the like. Details are described in US Publication No. 2014/0197386.

Ar is an aryl which may be substituted or a heteroaryl which may be substituted independently of each other. n is an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably 0 or 1, respectively.

Examples of the "aryl" of the "optionally substituted aryl" include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, and more preferably aryls having 6 to 20 carbon atoms. More preferably, it is an aryl having 6 to 12 carbon atoms.

Specific examples of "aryl" include phenyl, which is a monocyclic aryl, biphenylyl (2-, 3-, 4-) biphenylyl, and (1-, 2-) naphthyl, which is a fused bicyclic aryl. , Terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-3'-yl, tricyclic aryl -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-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , Condensed tricyclic aryls, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1) -, 2-) Il, (1-, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene- (1-, 2), a fused tetracyclic aryl -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-), which is a fused pentacyclic aryl ) Il, pentasen- (1-, 2-, 5-, 6-) il and the like.

Examples of the "heteroaryl" of the "optionally substituted heteroaryl" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferable, heteroaryl having 2 to 15 carbon atoms is further preferable, and heteroaryl having 2 to 10 carbon atoms is particularly preferable. Examples of the heteroaryl include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific heteroaryls include, for example, frills, thienyl, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, frazayl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridadinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indrill, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, synnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthylidine, prynyl , Pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazinyl, phenazinyl, phenoxatiinyl, thiantranyl, indridinyl and the like.

Further, the above-mentioned aryl and heteroaryl may be substituted, and for example, the above-mentioned aryl and heteroaryl may be substituted, respectively.

The carbazole derivative may be a multimer in which a plurality of compounds represented by the above formula (ETM-9) are bonded by a single bond or the like. 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, phenalene ring, phenanthrene ring or triphenylene ring) may be bonded.

Specific examples of this carbazole derivative include the following compounds.

This carbazole derivative can be produced by using a known raw material and a known synthetic method.

<Triazine derivative>
The triazine derivative is, for example, a compound represented by the following formula (ETM-10), preferably a compound represented by the following formula (ETM-10-1). Details are described in US Publication No. 2011/015601.

Ar is an aryl which may be substituted or a heteroaryl which may be substituted independently of each other. n is an integer of 1-3, preferably 2 or 3.

Examples of the "aryl" of the "optionally substituted aryl" include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, and more preferably aryls having 6 to 20 carbon atoms. More preferably, it is an aryl having 6 to 12 carbon atoms.

Specific examples of "aryl" include phenyl, which is a monocyclic aryl, biphenylyl (2-, 3-, 4-) biphenylyl, and (1-, 2-) naphthyl, which is a fused bicyclic aryl. , Terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-3'-yl, tricyclic aryl -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-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , Condensed tricyclic aryls, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1) -, 2-) Il, (1-, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, which is a tetracyclic aryl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene- (1-, 2), a fused tetracyclic aryl -) Ill, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-), which is a fused pentacyclic aryl ) Il, pentasen- (1-, 2-, 5-, 6-) il and the like.

Examples of the "heteroaryl" of the "optionally substituted heteroaryl" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferable, heteroaryl having 2 to 15 carbon atoms is further preferable, and heteroaryl having 2 to 10 carbon atoms is particularly preferable. Examples of the heteroaryl include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

Specific heteroaryls include, for example, frills, thienyl, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, frazayl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridadinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indrill, isoindrill, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, synnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthylidine, prynyl , Pteridinyl, carbazolyl, acridinyl, phenoxadinyl, phenothiazinyl, phenazinyl, phenoxatiinyl, thiantranyl, indridinyl and the like.

Further, the above-mentioned aryl and heteroaryl may be substituted, and for example, the above-mentioned aryl and heteroaryl may be substituted, respectively.

Specific examples of this triazine derivative include the following compounds.

This triazine derivative can be produced by using a known raw material and a known synthetic method.

<Benzimidazole derivative>
The benzimidazole derivative is, for example, a compound represented by the following formula (ETM-11).

φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzfluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. Yes, in the "benzimidazole-based substituent", the pyridyl group in the "pyridine-based substituent" in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) is benzo. It is a substituent that replaces the imidazole group, and at least one hydrogen in the benzimidazole derivative may be substituted with dehydrogen. * In the following structural formula represents the bonding position.

R ¹¹ in the benzimidazole group is hydrogen, an alkyl having 1 to 24 carbon atoms, a cycloalkyl having 3 to 12 carbon atoms, or an aryl having 6 to 30 carbon atoms, and is the above formula (ETM-2-1) and the formula (ETM-2-1). It may be cited to the description of ^{R 11} in ETM-2-2).

φ is further preferably an anthracene ring or a fluorene ring, and the structure in this case can be quoted from the above formula (ETM-2-1) or the above formula (ETM-2-2). For R ^{11 to} R ¹⁸ in the formula, the description in the above formula (ETM-2-1) or the formula (ETM-2-2) can be cited. Further, in the above formula (ETM-2-1) or formula (ETM-2-2), two pyridine-based substituents are described in a bonded form, but when these are replaced with benzoimidazole-based substituents, both are used. The pyridine-based substituent of the above may be replaced with a benzoimidazole-based substituent (that is, n = 2), any one of the pyridine-based substituents may be replaced with a benzoimidazole-based substituent, and the other pyridine-based substituent may be replaced with R ^11. It may be replaced with ~ R ¹⁸ (that is, n = 1). Further, for example, at least one of R ^{11 to} R ¹⁸ in the above formula (ETM-2-1) may be replaced with a benzimidazole-based substituent, and the “pyridine-based substituent” may be replaced with R ^{11 to} R ¹⁸ .

Specific examples of this benzoimidazole derivative include 1-phenyl-2- (4- (10-phenylanthracene-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- (10-). Naphthalen-2-yl) anthracene-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracene-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 5- (10- (naphthalen-2-yl) anthracene-9-yl) -1,2-diphenyl-1H-benzo [d] imidazole, 1- (4) -(10- (Naphthalen-2-yl) anthracene-9-yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 2- (4- (9,10-di (naphthalen-2-yl)) Anthracene-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 1-(4- (9,10-di (naphthalen-2-yl) anthracene-2-yl) phenyl) -2- Examples thereof include phenyl-1H-benzo [d] imidazole and 5- (9,10-di (naphthalen-2-yl) anthracene-2-yl) -1,2-diphenyl-1H-benzo [d] imidazole.

This benzimidazole derivative can be produced by using a known raw material and a known synthetic method.

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

φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. is there.

R ^{11 to} R ¹⁸ of each formula are independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably carbon number 3 to 12). The number 6 to 30 aryl). Further, in the above formula (ETM-12-1), any one of R ^{11 to} R ¹⁸ is bonded to φ which is an aryl ring.

At least one hydrogen in each phenanthroline derivative may be substituted with deuterium.

Alkyl in R ¹¹ to R ^18, cycloalkyl and aryl may be cited to the description of ^R 11 ^{to R 18} in the formula (ETM-2). Further, for φ, in addition to the above-mentioned example, for example, the following structural formula can be mentioned. In addition, R in the following structural formula is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl. In addition, * in each structural formula represents the bonding position.

Specific examples of this phenanthroline derivative include, for example, 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 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' Examples thereof include −difluol-bis (1,10-phenanthroline-5-yl), vasocproin and 1,3-bis (2-phenyl-1,10-phenanthroline-9-yl) benzene.

This phenanthroline derivative can be produced by using a known raw material and a known synthetic method.

<Kinolinol-based metal complex>
The quinolinol-based metal complex is, for example, a compound represented by the following general formula (ETM-13).
In the formula, R ^{1 to} R ⁶ are independently hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy or aryl, and M is Li, Al, Ga, Be or Zn. n is an integer of 1-3.

Specific examples of the quinolinol-based metal complex include 8-quinolinol lithium, tris (8-quinolinolate) aluminum, tris (4-methyl-8-quinolinolate) aluminum, tris (5-methyl-8-quinolinolate) aluminum, and tris (3). , 4-Dimethyl-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, bis (2-methyl-8-quinolinolate) ( Phenolate) Aluminum, bis (2-methyl-8-quinolinolate) (2-methylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-methylphenorate) aluminum, bis (2-methyl-8- Kinolinolate) (4-methylphenorate) aluminum, bis (2-methyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-phenylphenolate) aluminum, bis (2-Methyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) ( 2,6-Dimethylphenolate) Aluminum, bis (2-methyl-8-quinolinolate) (3,4-dimethylphenolate) Aluminum, bis (2-methyl-8-quinolinolate) (3,5-dimethylphenolate) Aluminum, bis (2-methyl-8-quinolinolate) (3,5-di-t-butylphenolate) Aluminum, bis (2-methyl-8-quinolinolate) (2,6-diphenylphenolate) Aluminum, bis ( 2-Methyl-8-quinolinolate) (2,4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl -8-quinolinolate) (2,4,5,6-tetramethylphenorate) aluminum, bis (2-methyl-8-quinolinolate) (1-naphtholate) aluminum, bis (2-methyl-8-quinolinolate) (2) -Naftrat) Aluminum, bis (2,4-dimethyl-8-quinolinolate) (2-phenylphenylate) Aluminum, bis (2,4-dimethyl-8-quinolinolate) ) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-dimethylphenolate) Lat) Aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-di-t-butylphenolate) aluminum, bis (2-methyl-8-quinolinolate) aluminum-μ-oxo-bis (2) -Methyl-8-quinolinolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolate) aluminum, bis (2-methyl-4-ethyl) -8-Kinolinolate) Aluminum-μ-oxo-bis (2-methyl-4-ethyl-8-quinolinolate) Aluminum, bis (2-methyl-4-methoxy-8-quinolinolate) Aluminum-μ-oxo-bis (2) -Methyl-4-methoxy-8-quinolinolate) aluminum, bis (2-methyl-5-cyano-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolate) aluminum, bis (2-Methyl-5-trifluoromethyl-8-quinolinolate) Aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolate) Aluminum, bis (10-hydroxybenzo [h] quinolinate) Berylium and the like can be mentioned.

This quinolinol-based metal complex can be produced by using a known raw material and a known synthesis method.

<Thiazole derivative and benzothiazole derivative>
The thiazole derivative is, for example, a compound represented by the following formula (ETM-14-1).
The benzothiazole derivative is, for example, a compound represented by the following formula (ETM-14-2).

Φ of each formula is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is 1 to 4 The "thiazole-based substituent" and "benzothiazole-based substituent" are the "pyridine-based" in the above formulas (ETM-2), (ETM-2-1) and (ETM-2-2). The pyridyl group in the "substituent" is a substituent in which the thiazole group or the benzothiazole group is replaced, and at least one hydrogen in the thiazole derivative and the benzothiazole derivative may be substituted with dehydrogen. * In the following structural formula represents the bonding position.

φ is further preferably an anthracene ring or a fluorene ring, and the structure in this case can be quoted from the above formula (ETM-2-1) or the above formula (ETM-2-2). For R ^{11 to} R ¹⁸ in the formula, the description in the above formula (ETM-2-1) or the formula (ETM-2-2) can be cited. Further, in the above formula (ETM-2-1) or formula (ETM-2-2), two pyridine-based substituents are described in a bonded form, but these are described as thiazole-based substituents (or benzothiazole-based substituents). When substituting with (group), both pyridine-based substituents may be replaced with thiazole-based substituents (or benzothiazole-based substituents) (that is, n = 2), or any one of the pyridine-based substituents may be replaced with thiazole-based substituents. It may be replaced with a group (or a benzothiazole-based substituent) and the other pyridine-based substituent may be replaced with R ^{11 to} R ¹⁸ (that is, n = 1). Further, for example, at least one of R ^{11 to} R ¹⁸ in the above formula (ETM-2-1) is replaced with a thiazole-based substituent (or a benzothiazole-based substituent) to replace the "pyridine-based substituent" with R ^{11 to} R ^18. May be replaced with.

These thiazole derivatives or benzothiazole derivatives can be produced by using known raw materials and known synthetic methods.

The electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As this reducing substance, various substances are used as long as they have a certain reducing property. For example, alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkali. From the group consisting of oxides of earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals. At least one selected can be preferably used.

Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2.95 eV). Examples thereof include alkaline earth metals such as 9 eV), Sr (2.0 to 2.5 eV) and Ba (2.52 eV), and a substance having a work function of 2.9 eV or less is particularly preferable. Of these, the more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have a particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the emission brightness and the life of the organic EL device can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of these two or more kinds of alkali metals is also preferable, and in particular, a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by adding to the material forming the electron transport layer or the electron injection layer, the emission brightness and the life of the organic EL device can be improved.

The above-mentioned materials for the electron injection layer and the material for the electron transport layer are polymer compounds obtained by polymerizing a reactive compound in which a reactive substituent is substituted as a monomer, or a polymer crosslinked product thereof, or a main chain. A pendant type polymer compound obtained by reacting the type polymer with the reactive compound, or a pendant type polymer crosslinked product thereof can also be used as a material for an electron layer. As the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited.
Details of the uses of such polymer compounds and crosslinked polymers will be described later.

<Cathode in organic electroluminescent device>
The cathode 108 serves to inject electrons into the light emitting layer 105 via the electron injecting layer 107 and the electron transporting layer 106.

The material for forming the cathode 108 is not particularly limited as long as it is a substance capable of efficiently injecting electrons into the organic layer, but a substance similar to the material for forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or their alloys (magnesium-silver alloy, magnesium). -Indium alloys, aluminum-lithium alloys such as lithium fluoride / aluminum, etc.) are preferred. Alloys containing lithium, sodium, potassium, cesium, calcium, magnesium or these low work function metals are effective for increasing electron injection efficiency and improving device characteristics. However, these low work function metals are generally often unstable in the atmosphere. In order to improve this point, for example, a method of doping an organic layer with a trace amount of lithium, cesium or magnesium and using a highly stable electrode is known. Inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide and cesium oxide can also be used as other dopants. However, it is not limited to these.

In addition, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium for electrode protection, or alloys using these metals, and inorganic substances such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride. , Laminating a hydrocarbon-based polymer compound or the like is given as a preferable example. The method for producing these electrodes is also not particularly limited as long as conduction can be obtained, such as resistance heating, electron beam deposition, sputtering, ion plating and coating.

<Binder that may be used in each layer>
The materials used for the above-mentioned hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can form each layer independently, but as a polymer binder, polyvinyl chloride, polycarbonate, etc. Polystyrene, poly (N-vinylcarbazole), polymethylmethacrylate, polybutylmethacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin It is also possible to disperse and use it in solvent-soluble resins such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, and curable resin such as silicone resin. is there.

<Method of manufacturing organic electroluminescent device>
For each layer constituting the organic electroluminescent device, the material to be composed of each layer is subjected to a thin-film deposition method, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method or casting method, coating method, or the like. It can be formed by forming a thin film. The film thickness of each layer formed in this manner is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like. When a thin film is formed by using a thin film deposition method, the vapor deposition conditions differ depending on the type of material, the target crystal structure and association structure of the film, and the like. The vapor deposition conditions are generally: heating temperature of the crucible for vapor deposition + 50 to + 400 ° C., vacuum degree ^10-6 to ^10-3 Pa, vapor deposition rate 0.01 to 50 nm / sec, substrate temperature -150 to + 300 ° C., film thickness 2 nm. It is preferable to set it appropriately in the range of ~ 5 μm.

When a DC voltage is applied to the organic EL element thus obtained, the anode may be applied with a positive polarity and the cathode may be applied with a negative polarity, and when a voltage of about 2 to 40 V is applied, a transparent or translucent electrode is applied. Emission can be observed from the side (anode or cathode, or both). The organic EL element also emits light when a pulse current or an alternating current is applied. The waveform of the applied alternating current may be arbitrary.

Next, as an example of a method for manufacturing an organic EL device, an organic EL device composed of an anode / hole injection layer / hole transport layer / light emitting layer composed of a host material and a dopant material / electron transport layer / electron injection layer / cathode. The manufacturing method of the above will be described.

<Thin-film deposition method>
A thin film of an anode material is formed on an appropriate substrate by a vapor deposition method or the like to prepare an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-deposited on this to form a thin film to form a light emitting layer, an electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by a vapor deposition method or the like. By forming it into a cathode, the desired organic EL element can be obtained. In the above-mentioned production of the organic EL device, it is also possible to reverse the production order and manufacture the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. Is.

<Wet film formation method>
The wet film forming method is carried out by preparing a low molecular weight compound capable of forming each organic layer of an organic EL device as a liquid organic layer forming composition and using the same. If there is no suitable organic solvent to dissolve this low molecular weight compound, it is high together with other monomers having a soluble function as a reactive compound in which the low molecular weight compound is substituted with a reactive substituent and a main chain type polymer. A composition for forming an organic layer may be prepared from a molecularized polymer compound or the like.

In the wet film forming method, a coating film is generally formed by undergoing a coating step of applying an organic layer forming composition to a substrate and a drying step of removing a solvent from the applied organic layer forming composition. When the polymer compound has a crosslinkable substituent (also referred to as a crosslinkable polymer compound), it is further crosslinked by this drying step to form a crosslinked polymer. Depending on the difference in the coating process, the method using a spin coater is the spin coating method, the method using the slit coater is the slit coating method, the method using the plate is gravure, offset, reverse offset, the flexographic printing method, and the method using the inkjet printer is the inkjet method. , The method of spraying in a mist form is called the spray method. The drying step includes methods such as air drying, heating, and vacuum drying. The drying step may be performed only once, or may be performed a plurality of times using different methods and conditions. Further, different methods may be used in combination, for example, firing under reduced pressure.

The wet film forming method is a film forming method using a solution, and is, for example, a partial printing method (injection method), a spin coating method or a casting method, a coating method, or the like. Unlike the vacuum vapor deposition method, the wet film deposition method does not require the use of an expensive vacuum vapor deposition apparatus and can form a film under atmospheric pressure. In addition, the wet film formation method enables a large area and continuous production, leading to a reduction in manufacturing cost.

On the other hand, when compared with the vacuum vapor deposition method, the wet film deposition method may be difficult to stack. When the laminated film is prepared by the wet film formation method, it is necessary to prevent the dissolution of the lower layer by the composition of the upper layer, and the composition having controlled solubility, the cross-linking of the lower layer and the orthogonal solvent (Orthogonal solvent) dissolve each other. No solvent) etc. are used. However, even if these techniques are used, it may be difficult to use the wet film forming method for coating all the films.

Therefore, in general, a method is adopted in which an organic EL device is produced by using a wet film forming method for only a few layers and a vacuum vapor deposition method for the rest.

For example, the procedure for manufacturing an organic EL device by partially applying the wet film forming method is shown below.
(Procedure 1) Film formation by vacuum vapor deposition method of anode (Procedure 2) Film formation by wet film formation method of composition for forming hole injection layer containing material for hole injection layer (Procedure 3) Material for hole transport layer Formation of a composition for forming a hole transport layer containing (Procedure 4) Formation of a composition for forming a light emitting layer containing a host material and a dopant material by a wet film formation method (Procedure 5) Electron transport layer (Procedure 6) Film formation by vacuum vapor deposition method of electron injection layer (Procedure 7) Film formation by vacuum vapor deposition method of cathode By going through this procedure, anode / hole injection layer / hole transport An organic EL element including a light emitting layer / electron transport layer / electron injection layer / cathode composed of a layer / host material and a dopant material can be obtained.
Of course, there is a means for preventing the dissolution of the light emitting layer of the lower layer, or by using a means for forming a film from the cathode side contrary to the above procedure, a layer including a material for an electron transport layer and a material for an electron injection layer is formed. They can be prepared as compositions for use and deposited by a wet film forming method.

<Other film formation methods>
A laser heating drawing method (LITI) can be used to form a film of the composition for forming an organic layer. LITI is a method in which a compound adhered to a substrate is heated and vapor-deposited by a laser, and an organic layer forming composition can be used as a material to be applied to the substrate.

<Arbitrary process>
Appropriate treatment steps, cleaning steps, and drying steps may be appropriately added before and after each step of film formation. Examples of the treatment step include exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, cleaning treatment using an appropriate solvent, heat treatment and the like. Further, a series of steps for producing a bank can be mentioned.

Photolithography technology can be used to create the bank. As the bank material that can be used for photolithography, a positive resist material and a negative resist material can be used. In addition, patternable printing methods such as an inkjet method, gravure offset printing, reverse offset printing, and screen printing can also be used. In that case, a permanent resist material can also be used. Further, the bank may be formed by using one material or may be formed by combining a plurality of structures using a plurality of materials.

Materials used for banks include inorganic materials such as silicon oxide, silicon dioxide, silicon nitride and silicon nitride, polysaccharides and derivatives thereof, homopolymers and copolymers of ethylenic monomers having hydroxyls, and biopolymer compounds. , Polyacryloyl compound, polyester, polystyrene, polyimide, polyamideimide, polyetherimide, polysulfide, polysulfone, polyphenylene, polyphenyl ether, polyurethane, epoxy (meth) acrylate, melamine (meth) acrylate, polyolefin, cyclic polyolefin, acrylonitrile-butadiene -Fluorine such as styrene copolymer polymer (ABS), silicone resin, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyacetate, polynorbornene, synthetic rubber, polyfluorovinylidene, polytetrafluoroethylene, polyhexafluoropropylene, etc. Polymers, fluoroolefin-hydrocarbon olefin copolymers, and fluorocarbon polymers include, but are not limited to.

<Composition for forming an organic layer used in a wet film formation method>
The composition for forming an organic layer is obtained by dissolving a low molecular weight compound capable of forming each organic layer of an organic EL element or a high molecular weight compound obtained by polymerizing the low molecular weight compound in an organic solvent. For example, the composition for forming a light emitting layer includes a polycyclic aromatic compound (or a polymer compound thereof) which is at least one type of dopant material as a first component, at least one kind of host material as a second component, and a third component. It contains at least one organic solvent as a component. The first component functions as a dopant component of the light emitting layer obtained from the composition, and the second component functions as a host component of the light emitting layer. The third component functions as a solvent that dissolves the first component and the second component in the composition, and at the time of application, the third component itself gives a smooth and uniform surface shape by the controlled evaporation rate of the third component itself.

<Organic solvent>
The composition for forming an organic layer contains at least one kind of organic solvent. By controlling the evaporation rate of the organic solvent at the time of film formation, it is possible to control and improve the film forming property, the presence or absence of defects in the coating film, the surface roughness, and the smoothness. Further, when the film is formed by using the inkjet method, the meniscus stability at the pinhole of the inkjet head can be controlled, and the ejection property can be controlled and improved. In addition, by controlling the drying rate of the film and the orientation of the derivative molecules, the electrical characteristics, light emission characteristics, efficiency, and life of the organic EL device having the organic layer obtained from the composition for forming the organic layer can be improved. Can be done.

(1) Physical Properties of Organic Solvent The boiling point of at least one organic solvent is 130 ° C. to 300 ° C., more preferably 140 ° C. to 270 ° C., and even more preferably 150 ° C. to 250 ° C. When the boiling point is higher than 130 ° C., it is preferable from the viewpoint of ejection property of the inkjet. Further, when the boiling point is lower than 300 ° C., it is preferable from the viewpoint of coating film defects, surface roughness, residual solvent and smoothness. The organic solvent is more preferably configured to contain two or more kinds of organic solvents from the viewpoint of good inkjet ejection property, film forming property, smoothness and low residual solvent. On the other hand, in some cases, the composition may be in a solid state by removing the solvent from the composition for forming an organic layer in consideration of transportability and the like.

Further, the organic solvent contains a good solvent (GS) and a poor solvent (PS) for at least one of the solutes, and the boiling point (BP _GS ) of the good solvent (GS) is higher than the boiling point (BP _PS ) of the poor solvent (PS). Also low, configuration is particularly preferred.
By adding the poor solvent having a high boiling point, the good solvent having a low boiling point volatilizes first at the time of film formation, and the concentration of the content in the composition and the concentration of the poor solvent increase to promote rapid film formation. As a result, a coating film having few defects, a small surface roughness, and high smoothness can be obtained.

Differential solubility _(S GS _{-S PS)} is preferably 1% or more, more preferably 3% or more, more preferably 5% or more. The difference in boiling points (BP _PS- BP _GS ) is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and even more preferably 50 ° C. or higher.

After the film formation, the organic solvent is removed from the coating film by a drying step such as vacuum, reduced pressure, and heating. When heating is performed, it is preferable to perform heating at a glass transition temperature (Tg) of at least one kind of solute + 30 ° C. or less from the viewpoint of improving the coating film-forming property. From the viewpoint of reducing the residual solvent, it is preferable to heat the solute at at least one glass transition point (Tg) of −30 ° C. or higher. Even if the heating temperature is lower than the boiling point of the organic solvent, the organic solvent is sufficiently removed because the film is thin. Further, the drying may be performed a plurality of times at different temperatures, or a plurality of drying methods may be used in combination.

(2) Specific Examples of Organic Solvents Examples of the organic solvent used in the composition for forming an organic layer include an alkylbenzene solvent, a phenyl ether solvent, an alkyl ether solvent, a cyclic ketone solvent, an aliphatic ketone solvent, and a monocyclic solvent. Examples thereof include a ketone solvent, a solvent having a diester skeleton, and a fluorine-containing solvent. Specific examples thereof include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexane-2-ol, and the like. Heptane-2-ol, octane-2-ol, decan-2-ol, dodecane-2-ol, cyclohexanol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, terpineol (mixture), ethylene glycol Monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, 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, tripropylene glycol Dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, p-xylene, m-xylene , O-xylene, 2,6-lutidine, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 2-chlorobenzotrifluoride, cumene, toluene, 2-chloro-6-fluorotoluene, 2-fluoro Anisol, anisole, 2,3-dimethylpyrazine, bromobenzene, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethylanisole, mecitylene, 1,2,4-trimethylbenzene, t-butylbenzene, 2-methyl Anisole, phenetol, benzodioxol, 4-methylanisole, s-butylbenzene, 3-methylanisole, 4-fluoro-3-methyl Anisole, Simene, 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, benzoic acid Methyl, isopentylbenzene, 3,4-dimethylanisole, o-tornitrile, n-amylbenzene, veratrol, 1,2,3,4-tetrahydronaphthalene, ethyl benzoate, n-hexylbenzene, propyl benzoate, cyclohexylbenzene , 1-Methylnaphthalene, butyl benzoate, 2-methylbiphenyl, 3-phenoxytoluene, 2,2'-vitril, dodecylbenzene, dipentylbenzene, tetramethylbenzene, trimethoxybenzene, trimethoxytoluene, 2,3-dihydro Benzofuran, 1-methyl-4- (propoxymethyl) benzene, 1-methyl-4- (butyloxymethyl) benzene, 1-methyl-4- (pentyloxymethyl) benzene, 1-methyl-4- (hexyloxymethyl) ) Benzene, 1-methyl-4- (heptyloxymethyl) benzene, benzylbutyl ether, benzylpentyl ether, benzylhexyl ether, benzylheptyl ether, benzyloctyl ether and the like, but are not limited thereto. Moreover, the solvent may be used alone or may be mixed.

<Arbitrary ingredient>
The composition for forming an organic layer may contain an arbitrary component as long as its properties are not impaired. Examples of the optional component include a binder, a surfactant and the like.

(1) Binder The composition for forming an organic layer may contain a binder. The binder forms a film at the time of film formation and joins the obtained film to the substrate. It also plays a role in dissolving, dispersing and binding other components in the composition for forming an organic layer.

Examples of the binder used in the composition for forming an organic layer include acrylic resin, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, acrylonitrile-ethylene-styrene copolymer (AES) resin, and the like. Ionomer, chlorinated polyether, diallyl phthalate resin, unsaturated polyester resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, Teflon, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile -Styrene copolymer (AS) resin, phenol resin, epoxy resin, melamine resin, urea resin, alkyd resin, polyurethane, and copolymers of the above resins and polymers, but are not limited thereto.

The binder used in the composition for forming an organic layer may be only one kind or a mixture of a plurality of kinds may be used.

(2) Surfactant The composition for forming an organic layer contains, for example, a surfactant for controlling the film surface uniformity, the solvent-like property and the liquid repellency of the film surface of the composition for forming an organic layer. May be good. Surfactants are classified into ionic and nonionic based on the structure of hydrophilic groups, and further classified into alkyl-based, silicon-based and fluorine-based based on the structure of hydrophobic groups. Further, from the molecular structure, it is classified into a monomolecular system having a relatively small molecular weight and a simple structure and a polymer system having a large molecular weight and having side chains and branches. Further, it is classified into a single system and a mixed system in which two or more kinds of surfactants and a base material are mixed according to the composition. As the surfactant that can be used in the composition for forming an organic layer, all kinds of surfactants can be used.

Examples of the surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181 and Disper. Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, manufactured by Big Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF -50-100CS (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Futagent 222F, Futergent 251 and FTX-218 (trade name) Product name, Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (Product name, manufactured by Mitsubishi Materials Co., Ltd.), Megafuck F- 470, Megafuck F-471, Megafuck F-475, Megafuck R-08, Megafuck F-477, Megafuck F-479, Megafuck F-553, Megafuck F-554 (trade name, DIC Co., Ltd.) ), Fluoroalkylbenzene sulfonate, Fluoralkyl carboxylate, Fluoroalkyl polyoxyethylene ether, Fluoroalkyl ammonium iodide, Fluoroalkyl betaine, Fluoroalkyl sulfonate, Diglycerin tetrakis (Fluoroalkyl polyoxyethylene ether) ), Fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene 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, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, Polyoxyethylene sorbitan oleate, polyo Examples thereof include xyethylene naphthyl ether, alkylbenzene sulfonate and alkyldiphenyl ether disulfonate.

Further, the surfactant may be used alone or in combination of two or more.

<Composition and physical properties of composition for forming organic layer>
The content of each component in the composition for forming an organic layer is obtained from the good solubility, storage stability and film forming property of each component in the composition for forming an organic layer, and the composition for forming an organic layer. Good film quality of the coating film, good ejection property when the inkjet method is used, and good electrical characteristics, light emission characteristics, efficiency, and life of the organic EL device having an organic layer produced by using the composition. It is decided in consideration of the viewpoint of. For example, in the case of a composition for forming a light emitting layer, the first component is 0.0001% by weight to 2.0% by weight based on the total weight of the composition for forming a light emitting layer, and the second component is for forming a light emitting layer. 0.0999% by weight to 8.0% by weight based on the total weight of the composition, and 90.0% by weight to 99.9% by weight of the third component based on the total weight of the composition for forming a light emitting layer. preferable.

More preferably, the first component is 0.005% by weight to 1.0% by weight based on the total weight of the light emitting layer forming composition, and the second component is based on the total weight of the light emitting layer forming composition. The third component is 0.095% by weight to 4.0% by weight, and the third component is 95.0% by weight to 99.9% by weight based on the total weight of the composition for forming a light emitting layer. More preferably, the first component is 0.05% by weight to 0.5% by weight based on the total weight of the light emitting layer forming composition, and the second component is based on the total weight of the light emitting layer forming composition. 0.25% by weight to 2.5% by weight, and the third component is 97.0% by weight to 99.7% by weight based on the total weight of the composition for forming a light emitting layer.

The composition for forming an organic layer can be produced by appropriately selecting the above-mentioned components by a known method such as stirring, mixing, heating, cooling, dissolving, and dispersing. Further, after the preparation, filtration, degassing (also referred to as degas), ion exchange treatment, inert gas replacement / encapsulation treatment and the like may be appropriately selected.

As the viscosity of the composition for forming an organic layer, the higher the viscosity, the better the film forming property and the good ejection property when the inkjet method is used. On the other hand, the lower the viscosity, the easier it is to form a thin film. From this, the viscosity of the composition for forming an organic layer is preferably 0.3 to 3 mPa · s at 25 ° C., and more preferably 1 to 3 mPa · s. In the present invention, the viscosity is a value measured using a conical flat plate type rotational viscometer (cone plate type).

The lower the surface tension of the composition for forming an organic layer, the better the film-forming property and the coating film without defects. On the other hand, the higher the value, the better the inkjet ejection property. From this, the organic layer forming composition preferably has a surface tension of 20 to 40 mN / m at 25 ° C., and more preferably 20 to 30 mN / m. In the present invention, the surface tension is a value measured by using the suspension method.

<Crosslinkable polymer compound: Compound represented by the general formula (XLP-1)>
Next, a case where the above-mentioned polymer compound has a crosslinkable substituent will be described. Such a crosslinkable polymer compound is, for example, a compound represented by the following general formula (XLP-1).
In formula (XLP-1)
MUx, ECx and k have the same definition as MU, EC and k in the above formula (H3), except that the compound represented by the formula (XLP-1) has at least one crosslinkable substituent (XLS). The content of the monovalent or divalent aromatic compound having a crosslinkable substituent is preferably 0.1 to 80% by weight in the molecule.

The content of the monovalent or divalent aromatic compound having a crosslinkable substituent is preferably 0.5 to 50% by weight, more preferably 1 to 20% by weight.

The crosslinkable substituent (XLS) is not particularly limited as long as it is a group capable of further crosslinking the above-mentioned polymer compound, but a substituent having the following structure is preferable. * In each structural formula indicates the bonding position.

L is a single bond, −O−, −S−,> C = O, −OC (= O) −, alkylene having 1 to 12 carbon atoms, and oxyalkylene having 1 to 12 carbon atoms, respectively. And a polyoxyalkylene having 1 to 12 carbon atoms. Among the above substituents, it is represented by the formula (XLS-1), the formula (XLS-2), the formula (XLS-3), the formula (XLS-9), the formula (XLS-10) or the formula (XLS-17). The group represented by the formula (XLS-1), the formula (XLS-3) or the formula (XLS-17) is more preferable.

Examples of the divalent aromatic compound having a crosslinkable substituent include a compound having the following partial structure. * In the following structural formula represents the bonding position.

<Manufacturing method of polymer compound and crosslinkable polymer compound>
The method for producing the polymer compound and the crosslinkable polymer compound will be described by taking the compound represented by the above formula (H3) and the compound represented by (XLP-1) as examples. These compounds can be synthesized by appropriately combining known production methods.

Examples of the solvent used in the reaction include aromatic solvents, saturated / unsaturated hydrocarbon solvents, alcohol solvents, ether solvents and the like, and examples thereof include dimethoxyethane, 2- (2-methoxyethoxy) ethane, and 2- (2). -Ethoxyethoxy) ethane and the like.

Moreover, the reaction may be carried out in a two-phase system. When the reaction is carried out in a two-phase system, a phase transfer catalyst such as a quaternary ammonium salt may be added, if necessary.

When the compound of the formula (H3) and the compound of (XLP-1) are produced, they may be produced in one step or in multiple steps. Further, it may be carried out by a batch polymerization method in which the reaction is started after all the raw materials are placed in the reaction vessel, or it may be carried out by a dropping polymerization method in which the raw materials are added dropwise to the reaction vessel, and the product advances the reaction. It may be carried out by a precipitation polymerization method in which precipitation is accompanied, and these can be combined and synthesized as appropriate. For example, when the compound represented by the formula (H3) is synthesized in one step, the desired product is obtained by carrying out the reaction with the monomer unit (MU) and the end cap unit (EC) added to the reaction vessel. Further, when the compound represented by the formula (H3) is synthesized in multiple stages, the target product is obtained by polymerizing the monomer unit (MU) to the target molecular weight and then adding the end cap unit (EC) to react. .. By adding different types of monomer units (MUs) in multiple stages and carrying out the reaction, a polymer having a concentration gradient in the structure of the monomer units can be produced. In addition, after preparing the precursor polymer, the target polymer can be obtained by a post-reaction.

Moreover, the primary structure of the polymer can be controlled by selecting the polymerizable group of the monomer unit (MU). For example, as shown in 1 to 3 of the synthesis scheme, it is possible to synthesize a polymer having a random primary structure (synthesis scheme 1), a polymer having a regular primary structure (synthesis schemes 2 and 3), and the like. Therefore, it can be used in combination as appropriate according to the target product. Furthermore, hyperbranched polymers and dendrimers can be synthesized by using a monomer unit having three or more polymerizable groups.

Examples of the monomer unit that can be used in the present invention include JP-A-2010-189630, International Publication No. 2012/086671, International Publication No. 2013/191088, International Publication No. 2002/045184, and International Publication No. 2011/049241. No., International Publication No. 2013/146806, International Publication No. 2005/049546, International Publication No. 2015/145871, Japanese Patent Application Laid-Open No. 2010-215886, Japanese Patent Application Laid-Open No. 2008-106241, Japanese Patent Application Laid-Open No. 2010-215886, International Publication No. It can be synthesized according to the methods described in Publication No. 2016/031639, Japanese Patent Application Laid-Open No. 2011-174062, International Publication No. 2016/031639, International Publication No. 2016/031639, and International Publication No. 2002/045184. ..

Regarding specific polymer synthesis procedures, Japanese Patent Application Laid-Open No. 2012-036388, International Publication No. 2015/008851, Japanese Patent Application Laid-Open No. 2012-36381, Japanese Patent Application Laid-Open No. 2012-144722, International Publication No. 2015/194448 , International Publication No. 2013/146806, International Publication No. 2015/145871, International Publication No. 2016/031639, International Publication No. 2016/125560, International Publication No. 2016/031639, International Publication No. 2016/031639, International It can be synthesized according to the method described in Publication No. 2016/125560, International Publication No. 2015/145871, International Publication No. 2011/049241 and Japanese Patent Application Laid-Open No. 2012-144722.

<Application example of organic electroluminescent device>
The present invention can also be applied to a display device provided with an organic electroluminescent element, a lighting device provided with an organic electroluminescent element, and the like.
A display device or a lighting device provided with an organic electroluminescent element can be manufactured by a known method such as connecting an organic electroluminescent element according to the present embodiment to a known driving device, and can be manufactured by a known method such as direct current driving, pulse driving, or alternating current. It can be driven by appropriately using a known driving method such as driving.

Examples of the display device include a panel display such as a color flat panel display and a flexible display such as a flexible color organic electroluminescent (EL) display (for example, JP-A-10-335066, JP-A-2003-321546). See Japanese Patent Application Laid-Open No. 2004-281086, etc.). In addition, examples of the display method of the display include a matrix method and a segment method. The matrix display and the segment display may coexist in the same panel.

In the matrix, pixels for display are arranged two-dimensionally in a grid pattern or a mosaic pattern, and characters and images are displayed as a set of pixels. The shape and size of the pixels are determined by the application. For example, for displaying images and characters on a personal computer, monitor, or television, quadrangular pixels with a side of 300 μm or less are usually used, and in the case of a large display such as a display panel, pixels with a side on the order of mm should be used. become. In the case of monochrome display, pixels of the same color may be arranged, but in the case of color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type. Then, as the driving method of this matrix, either a line sequential driving method or an active matrix may be used. The line sequential drive has the advantage that the structure is simpler, but when considering the operating characteristics, the active matrix may be superior, so it is necessary to use it properly depending on the application.

In the segment method (type), a pattern is formed so as to display predetermined information, and a predetermined area is made to emit light. For example, time and temperature displays on digital clocks and thermometers, operating status displays of audio equipment and electromagnetic cookers, and panel displays of automobiles can be mentioned.

Examples of the lighting device include a lighting device such as an indoor lighting device, a backlight of a liquid crystal display device, and the like (for example, JP-A-2003-257621, JP-A-2003-277741, JP-A-2004-119211). Etc.). The backlight is mainly used for the purpose of improving the visibility of a display device that does not emit light by itself, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display board, a sign, and the like. In particular, as a backlight for a liquid crystal display device, especially for a personal computer for which thinning is an issue, considering that it is difficult to thin the backlight because the conventional method consists of a fluorescent lamp and a light guide plate, the present embodiment The backlight using the light emitting element according to the above is characterized by being thin and lightweight.

3-2. Other Organic Devices The polycyclic aromatic compounds according to the present invention can be used for producing organic field effect transistors, organic thin film solar cells, and the like, in addition to the above-mentioned organic electroluminescent devices.

The organic field effect transistor is a transistor that controls a current by an electric field generated by a voltage input, and is provided with 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 the flow of electrons (or holes) flowing between the source electrode and the drain electrode can be arbitrarily blocked to control the current. The field effect transistor is easier to miniaturize than a simple transistor (bipolar transistor), and is often used as an element constituting an integrated circuit or the like.

The structure of the organic field effect transistor is usually provided with a source electrode and a drain electrode in contact with the organic semiconductor active layer formed by using the polycyclic aromatic compound according to the present invention, and further in contact with the organic semiconductor active layer. It suffices if the gate electrode is provided so as to sandwich the insulating layer (dielectric layer). Examples of the element structure include the following structures.
(1) Substrate / Gate electrode / Insulator layer / Source electrode / Drain electrode / Organic semiconductor active layer (2) Substrate / Gate electrode / Insulator layer / Organic semiconductor active layer / Source electrode / Drain electrode (3) Substrate / Organic Semiconductor active layer / source electrode / drain electrode / insulator layer / gate electrode (4) Substrate / source electrode / drain electrode / organic semiconductor active layer / insulator layer / gate electrode The organic electric field effect transistor configured in this way is It can be applied as a pixel-driven switching element of an active matrix-driven liquid crystal display or an organic electroluminescence display.

The organic thin-film solar cell has a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are laminated on a transparent substrate such as glass. The photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side. The polycyclic aromatic compound according to the present invention can be used as a material for a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, and an electron transport layer, depending on its physical properties. The polycyclic aromatic compound according to the present invention can function as a hole transport material or an electron transport material in an organic thin film solar cell. In addition to the above, the organic thin-film solar cell may appropriately include a hole block layer, an electron block layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like. For the organic thin-film solar cell, known materials used for the organic thin-film solar cell can be appropriately selected and used in combination.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

<Example of compound synthesis>
First, an example of synthesizing the compound of the present invention will be described below.

Synthesis example (1): Synthesis of compound (1-1627)

The structure of 3-bromo-2,4-di (3-chlorophenoxy) pyridine was confirmed by NMR measurement.
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 6.43 (d, J = 5.2 Hz, 1H), 7.04 (dd, J = 2.3, 8.0 Hz, 1H), 7.10 (Dd, J = 2.3,8.3Hz, 1H), 7.16 (t, J = 1.7Hz, 1H), 7.20-7.29 (m, 3H), 7.35 (t, J = 8.0Hz, 1H), 7.38 (t, 8.0Hz, 1H), 7.92 (d, 5.7Hz, 1H)
¹³ C-NMR (126 MHz, CDCl ₃ ): δ = 97.7 (1C), 108.2 (1C), 118.6 (1C), 119.7 (1C), 120.9 (1C), 122. 0 (1C), 125.3 (1C), 125.9 (1C), 130.2 (1C), 131.0 (1C), 134.8 (1C), 135.5 (1C), 146.4 (1C), 154.2 (1C), 154.8 (1C), 161.4 (1C), 163.2 (1C).

Under a nitrogen atmosphere, a flask containing 3-bromo-2,4-di (3-chlorophenoxy) pyridine (3.29 mg, 8.0 mmol) and mesitylene (40 ml) was cooled to −30 ° C. and n-butyl. Lithium (5.61 ml, 1.57 M, 8.8 mmol) was added dropwise over 10 minutes and stirred at −30 ° C. for 30 minutes. Boron tribromide (817 μl, 8.8 mmol) was added dropwise at −30 ° C., the reaction solution was heated to room temperature, and then stirred for 2 hours. Then, the low boiling component in the reaction solution was distilled off under reduced pressure. After adding 2,6-di-tert-butylpyridine (970 μl, 4.4 mmol) at room temperature, the temperature was raised to 170 ° C. and the mixture was stirred for 6 hours. After allowing the reaction solution to cool to room temperature, it was poured into a saturated aqueous sodium hydrogen carbonate solution, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the obtained solid was washed with acetonitrile and then with methanol to 3,11-dichloro-5,9-dioxa-6-aza-13b-boranaft [3, Compound (1-1627), which is 2,1-de] anthracene, was obtained as a white solid (515 mg, yield 19%).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (500 MHz, DMSO-d6): δ = 7.00 (d, J = 5.7 Hz, 1H), 7.25 (dd, J = 2.3, 8.0 Hz, 1H), 7. 27 (dd, J = 2.3, 8.0Hz, 1H), 7.31 (d, J = 2.3Hz, 1H), 7.32 (d, J = 2.3Hz, 1H), 8.09 (D, J = 8.0, 1H), 8.12 (d, J = 8.0, 1H), 8.17 (d, J = 5.7, 1H).
¹³ C-NMR (126MHz, DMSO-d6): δ = 107.3 (1C), 117.0 (1C), 117.1 (1C), 123.3 (1C), 123.7 (1C), 132 .6 (1C), 132.7 (1C), 134.4 (1C), 134.7 (1C), 148.1 (1C), 157.7 (1C), 158.6 (1C), 163. 7 (1C), 164.2 (1C), The NMR signal of carbon to the boron was not obserbd ..
¹¹ B-NMR (160 MHz, DMSO-d6): δ = -5.6.

Synthesis example (2): Synthesis of compound (1-1618)

Compound (1-1627) (102 mg, 0.30 mmol), carbazole (110 mg, 0.66 mmol), bis (di-tert-butyl (3-methylbut-2-ene-1-yl) phosphine) dichloro under a nitrogen atmosphere. A flask containing palladium (II) (10.9 mg, 0.018 mmol), sodium-tert-butoxide (63.4 mg, 0.66 mmol), and mesitylene (1.5 ml) was heated to 140 ° C. and stirred for 6 hours. did. After allowing the reaction solution to cool to room temperature, it was poured into water and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was washed with acetonitrile by heating and then purified with a silica gel short pass column (eluent: dichloromethane / ethyl acetate = 1/1 (volume ratio)). Further, by heating and washing with ethyl acetate and dichloroethane, 3,11-di (9H-carbazo-9-yl) -5,9-dioxa-6-aza-13b-boranaft [3,2,1] -De] Anthracene compound (1-1618) was obtained as a yellow solid (94.8 mg, 53% yield).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 7.31 (d, J = 5.7 Hz, 1H), 7.37 (dt, J = 3.4, 7.5 Hz, 4H), 7.47 -7.52 (m, 4H), 7.70 (t, J = 8.6Hz, 4H), 7.80 (dt, J = 2.3, 8.0Hz, 2H), 7.94 (d, J = 2.3Hz, 1H), 8.04 (d, J = 2.3Hz, 1H), 8.20 (dd, J = 3.4,7.5Hz, 4H), 8.76 (d, J) = 5.7Hz, 1H), 8.96 (d, J = 8.0Hz, 1H), 8.98 (d, J = 8.0Hz, 1H).

Synthesis example (3): Synthesis of compound (1-1605)

Compound (1-1627) (67.9 mg, 0.20 mmol), 3-biphenylboronic acid (95.1 mg, 0.48 mmol), bis (di-tert-butyl (4-dimethylaminophenyl) phosphine) under a nitrogen atmosphere. ) Dichloropalladium (II) ((AMPhos) ₂ PdCl ₂ ) (8.5 mg, 0.012 mmol), tripotassium phosphate (204 mg, 0.96 mmol), and 1,4-dioxane (2.0 ml). The flask was stirred under heating under reflux for 4 hours. After cooling the reaction solution to room temperature, it was poured into water and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified on a silica gel short pass column (eluent: dichloromethane / ethyl acetate = 1/1 (volume ratio)). Furthermore, by heating and washing with acetonitrile, 3,11-di ([1,1'-biphenyl] -3-yl) -5,9-dioxa-6-aza-13b-boranaft [3,2,1- de] Compound (1-1605) which is anthracene was obtained as a white solid (91.7 mg, yield 80%).

The structure of the compound obtained by NMR measurement was confirmed.
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 7.25 (d, J = 5.7 Hz, 1H), 7.39-7.44 (m, 2H), 7.51 (t, J = 8) .2Hz, 4H), 7.62 (t, 7.5Hz, 2H), 7.67-7.72 (m, 6H), 7.76 (d, 7.5Hz, 2H), 7.80 (dt) , 1.7, 8.0Hz, 2H), 7.93 (d, J = 1.7Hz, 1H), 7.99 (d, J = 1.7Hz, 2H), 8.02 (d, 1. 7Hz, 1H), 8.71 (d, J = 5.7Hz, 1H), 8.80 (d, J = 8.0Hz, 1H), 8.82 (d, J = 8.0Hz, 1H).

Synthesis example (4): Synthesis of compound (1-1603)

Compound (1-1627) (67.9 mg, 0.20 mmol), 2-biphenylboronic acid (95.2 mg, 0.48 mmol), (AMPhos) ₂ PdCl ₂ (8.7 mg, 0.012 mmol) under a nitrogen atmosphere. , Tripotassium Phosphate (203 mg, 0.96 mmol), and 1,4-dioxane (2.0 ml) are stirred under heating reflux for 4 hours. After cooling the reaction solution to room temperature, it is poured into water and the aqueous layer is extracted with dichloromethane. The obtained organic layer is washed with saturated brine and dried over anhydrous magnesium sulfate. This solution is concentrated under reduced pressure, and the residue is purified by a silica gel short pass column (eluent: dichloromethane / ethyl acetate = 1/1 (volume ratio)). Further, by heating and washing with acetonitrile, 3,11-di ([1,1'-biphenyl] -2-yl) -5,9-dioxa-6-aza-13b-boranaft [3,2,1- de] The compound (1-1603) which is anthracene is obtained as a white solid.

Synthesis Example (5): Synthesis Example of Compound (1-382) Compound (1-382) was used in the same manner as in Synthesis Example 1 except that the n-butyllithium hexane solution was changed to a t-butyllithium hexane solution. ).

By appropriately changing the compound of the raw material, the other compound of the present invention can be synthesized by a method according to the above-mentioned synthesis example.

<Effectiveness and oxidative stability of the compound as a dopant>
The structure of the light emitting material with TADF activity was designed using the DFT calculation. After structural optimization of the ground state was performed using the PBE0 / 6-31G (d) method, the vertical excitation energy from the ground state was calculated using the Time-dependent DFT method. All calculations were performed using the quantum chemistry calculation program Firefly (A.A. Granovsky, Firefly version 8).

When used as a blue fluorescent dopant and TADF dopant emission wavelength and Delta] E _ST is important. Further, it is known that deterioration of an organic EL device is one of the causes of oxygen mixed in the device, and that an oxidation reaction by oxygen is more likely to occur in a compound having a higher HOMO. Therefore, the value of HOMO can be used as a reference for evaluating the oxidative stability of a compound. First, these characteristics were calculated using a compound containing no pyridine nitrogen as a comparative compound as shown in the structural formula below.

In the above comparison compound, emission wavelength = 382nm, ΔE _ST = 0.537, the calculation result of HOMO = -4.985eV was obtained. Therefore, in the calculation examples of compounds obtained by introducing a pyridine nitrogen, than the comparative compound, was evaluated as the emission wavelength is effective as a fluorescent dopant if shorter wavelength, effective as TADF dopant smaller the Delta] E _ST It was evaluated that there was, and that the lower the HOMO, the better the oxidative stability.

The following compounds were evaluated as the compounds of the present invention into which pyridine nitrogen was introduced.
The above compounds (1-401-ph), compounds (1-441-ph), compounds (1-481-ph), compounds (1-521-ph), compounds (1-561-ph) and compounds (1- 601-ph) are compound (1-401), compound (1-441), compound (1-481), compound (1-521), compound (1-561) and compound (1-601), respectively. ) Is a compound in which> N-R (R = pyridyl group or pyrimidyl group) is replaced with> N-R (R = phenyl group). It has been confirmed that the difference between this phenyl group and the pyridyl group or pyrimidyl group does not affect the calculation result.

<Calculation Example 1-1>
In compound (1-1), emission wavelength = 332 nm, estimated to ΔE _ST = 0.565eV, which is expected to be effective as a fluorescent dopant. The HOMO was -5.804 eV, which was expected to be excellent in oxidative stability.

<Calculation Example 1-2>
In compound (1-401-ph), emission wavelength = 400 nm, estimated to ΔE _ST = 0.513eV, was expected to be effective as TADF dopant. The HOMO was -5.287 eV, which was expected to be excellent in oxidative stability.

<Calculation Example 1-3>
In compound (1-441-ph), emission wavelength = 363 nm, estimated to ΔE _ST = 0.514eV, which is expected to be effective as a fluorescent dopant and TADF dopant. The HOMO was −5.540 eV, and it was expected that the oxidative stability was excellent.

<Calculation Example 1-4>
In compound (1-481-ph), emission wavelength = 380 nm, estimated to ΔE _ST = 0.49eV, which is expected to be effective as a fluorescent dopant and TADF dopant. The HOMO was -5.851 eV, which was expected to be excellent in oxidative stability.

<Calculation Example 1-5>
In compound (1-521-ph), emission wavelength = 313 nm, estimated to ΔE _ST = 0.625eV, which is expected to be effective as a fluorescent dopant. The HOMO was -6.465 eV, which was expected to be excellent in oxidative stability.

<Calculation Example 1-6>
In compound (1-561-ph), emission wavelength = 337 nm, estimated to ΔE _ST = 0.589eV, which is expected to be effective as a fluorescent dopant. The HOMO was -6.180 eV, which was expected to be excellent in oxidative stability.

<Calculation Example 1-7>
In compound (1-601-ph), emission wavelength = 325 nm, estimated to ΔE _ST = 0.474eV, which is expected to be effective as a fluorescent dopant and TADF dopant. The HOMO was -6.827 eV, which was expected to be excellent in oxidative stability.

The polycyclic aromatic compound of the present invention having pyridine nitrogen, which is an electron-attracting element in the molecule, has a low HOMO level and is more stable to oxygen, and thus is prepared using the compound. The organic EL element has a longer life.

<Example of NEET film evaluation>
The NEET membranes of some compounds were evaluated. Compound (1-382) is promising as a TADF dopant because it has a smaller ΔE (ST) than compound (ref_BN2). Compound (1-1627) and compound (1-1618) have higher Ip, Ea, S1 and T1 than compound (ref_BO2), and are therefore promising as hole blocking materials (hole blocking materials) and electron transporting materials. Is.

<Prediction of physical property values of compounds by DFT calculation>
The physical property values of the compounds of the present application were predicted using the DFT calculation. After structural optimization of the ground state using B3LYP / 6-31G (d), the vertical excitation energy from the ground state was calculated using the Time-dependent DFT method. All calculations were performed using the quantum chemistry calculation program Gaussian 09 (JM Frisch, et al., Revision C.01.).

Comparing compound (calc_ref) with compound (1-1601) and compound (1-841), compound (1-1601) and compound (1-841) have higher S1, higher T1, deep HOMO, and deep LUMO. Therefore, the compound of the present invention is promising as a hole blocking material (hole blocking material) and an electron transporting material. Further, since the compound (1-841) has a smaller ΔE (ST) than the compound (calc_ref), it is also promising as a blue TADF assist dopant.

<Evaluation of coating type organic EL element>
Next, an organic EL device obtained by coating and forming an organic layer will be described.

<Polymer host compound: Synthesis of SPH-101>
SPH-101 was synthesized according to the method described in International Publication No. 2015/008851. A copolymer in which M2 or M3 is bonded is obtained next to M1, and it is estimated from the charging ratio that each unit has a 50:26:24 (molar ratio).

<Polymer hole transport compound: Synthesis of XLP-101>
XLP-101 was synthesized according to the method described in JP-A-2018-61028. A copolymer in which M5 or M6 is bonded is obtained next to M4, and it is estimated from the charging ratio that each unit is 40:10:50 (molar ratio).

<Examples 2-1 to 2-8>
A coating solution of the material forming each layer is prepared to prepare a coating type organic EL device.

<Manufacturing of Organic EL Element of Examples 2-1 to 2-3>
Table 3 shows the material composition of each layer in the organic EL device.

The structure of "ET1" in Table 3 is shown below.

<Preparation of composition (1) for forming a light emitting layer>
The composition for forming a light emitting layer (1) is prepared by stirring the following components until a uniform solution is obtained. By spin-coating the prepared composition for forming a light emitting layer on a glass substrate and heating and drying it under reduced pressure, a coating film having no film defects and excellent smoothness can be obtained.
Compound (A) 0.04% by weight
SPH-101 1.96% by weight
Xylene 69.00% by weight
Decalin 29.00% by weight

The compound (A) is a polycyclic aromatic compound represented by the general formula (1), a multimer thereof, the polycyclic aromatic compound or a multimer thereof, and a monomer (that is, the monomer has a reactive substituent). A polymer compound polymerized as (having), a crosslinked polymer obtained by further cross-linking the polymer compound, a pendant type polymer compound in which the monomer is substituted with a main chain type polymer, or the pendant type polymer. It is a pendant type polymer crosslinked product in which a compound is further crosslinked. A polymer compound or a pendant type polymer compound for obtaining a polymer crosslinked body or a pendant type polymer crosslinked body has a crosslinkable substituent.

<PEDOT: PSS solution>
A commercially available PEDOT: PSS solution (Clevios (TM) P VP AI4083, PEDOT: PSS aqueous dispersion, manufactured by Heraeus Holdings) is used.

<Preparation of OTPD solution>
OTPD (LT-N159, manufactured by Luminescence Technology Corp) and IK-2 (photocationic polymerization initiator, manufactured by San Apro) were dissolved in toluene, and the OTPD concentration was 0.7% by weight and the IK-2 concentration was 0.007% by weight. OTPD solution is prepared.

<Preparation of XLP-101 solution>
XLP-101 is dissolved in xylene at a concentration of 0.6% by weight to prepare a 0.7% by weight XLP-101 solution.

<Preparation of PCz solution>
PCz (polyvinylcarbazole) is dissolved in dichlorobenzene to prepare a 0.7 wt% PCz solution.

<Example 2-1>
A PEDOT: PSS film having a film thickness of 40 nm is formed by spin-coating a PEDOT: PSS solution on a glass substrate on which ITO is deposited to a thickness of 150 nm and firing it on a hot plate at 200 ° C. for 1 hour. (Hole injection layer). Next, the OTPD solution was spin-coated, dried on a hot plate at 80 ° C. for 10 minutes, exposed to an exposure intensity of 100 mJ / cm ² with an exposure machine, and baked on a hot plate at 100 ° C. for 1 hour. An OTPD film having a film thickness of 30 nm, which is insoluble in, is formed (hole transport layer). Next, the composition for forming a light emitting layer (1) is spin-coated and fired on a hot plate at 120 ° C. for 1 hour to form a light emitting layer having a film thickness of 20 nm.

The produced multilayer film was fixed to a substrate holder of a commercially available thin-film deposition equipment (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing ET1, a molybdenum vapor deposition boat containing LiF, and tungsten containing aluminum. Install a vapor deposition boat. After depressurizing the vacuum chamber to 5 × 10 ^-4 Pa, ET1 is heated and vapor-deposited to a film thickness of 30 nm to form an electron transport layer. The vapor deposition rate when forming the electron transport layer is 1 nm / sec. Then, LiF is heated and vapor-deposited at a vapor deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm. Next, aluminum is heated and vapor-deposited to a film thickness of 100 nm to form a cathode. In this way, an organic EL element is obtained.

<Example 2-2>
An organic EL device is obtained in the same manner as in Example 2-1. The hole transport layer is formed by spin-coating an XLP-101 solution and firing it on a hot plate at 200 ° C. for 1 hour to form a film having a film thickness of 30 nm.

<Example 2-3>
An organic EL device is obtained in the same manner as in Example 2-1. The hole transport layer is formed by spin-coating a PCz solution and firing it on a hot plate at 120 ° C. for 1 hour to form a film having a film thickness of 30 nm.

<Manufacturing of Organic EL Devices of Examples 2-4 to 2-6>
Table 4 shows the material composition of each layer in the organic EL device.

<Preparation of compositions (2) to (4) for forming a light emitting layer>
The composition for forming a light emitting layer (2) is prepared by stirring the following components until a uniform solution is obtained.
Compound (A) 0.02% by weight
mCBP 1.98% by weight
Toluene 98.00% by weight

The composition for forming a light emitting layer (3) is prepared by stirring the following components until a uniform solution is obtained.
Compound (A) 0.02% by weight
SPH-101 1.98% by weight
Xylene 98.00% by weight

The composition for forming a light emitting layer (4) is prepared by stirring the following components until a uniform solution is obtained.
Compound (A) 0.02% by weight
DOBNA 1.98% by weight
Toluene 98.00% by weight

In Table 4, "mCBP" is 3,3'-bis (N-carbazolyl) -1,1'-biphenyl and "DOBNA" is 3,11-di-o-tolyl-5,9-dioxa-. It is 13b-boranaft [3,2,1-de] anthracene and "TSPO1" is a diphenyl [4- (triphenylsilyl) phenyl] phosphine oxide. The chemical structure is shown below.

<Example 2-4>
An ND-3202 (manufactured by Nissan Chemical Industries, Ltd.) solution is spin-coated on a glass substrate on which ITO is formed to a thickness of 45 nm, and then heated at 50 ° C. for 3 minutes in an air atmosphere, and further at 230 ° C., 15 By heating for a minute, an ND-3202 film having a film thickness of 50 nm is formed (hole injection layer). Next, the XLP-101 solution is spin-coated and heated on a hot plate at 200 ° C. for 30 minutes in a nitrogen gas atmosphere to form an XLP-101 film having a film thickness of 20 nm (hole transport layer). Next, the light emitting layer forming composition (2) is spin coated and heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere to form a 20 nm light emitting layer.

The produced multilayer film was fixed to a substrate holder of a commercially available thin-film deposition equipment (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing TSPO1, a molybdenum vapor deposition boat containing LiF, and tungsten containing aluminum. Install a vapor deposition boat. After depressurizing the vacuum chamber to 5 × 10 ^-4 Pa, TSPO1 is heated and vapor-deposited to a film thickness of 30 nm to form an electron transport layer. The vapor deposition rate when forming the electron transport layer is 1 nm / sec. Then, LiF is heated and vapor-deposited at a vapor deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm. Next, aluminum is heated and vapor-deposited to a film thickness of 100 nm to form a cathode. In this way, an organic EL element is obtained.

<Examples 2-5 and 2-6>
Using the light emitting layer forming composition (3) or (4), an organic EL device is obtained in the same manner as in Example 2-4.

<Manufacturing of Organic EL Devices of Examples 2-7 to 2-9>
Table 5 shows the material composition of each layer in the organic EL device.

<Preparation of compositions (5) to (7) for forming a light emitting layer>
The composition for forming a light emitting layer (5) is prepared by stirring the following components until a uniform solution is obtained.
Compound (A) 0.02% by weight
2PXZ-TAZ 0.18% by weight
mCBP 1.80% by weight
Toluene 98.00% by weight

The composition for forming a light emitting layer (6) is prepared by stirring the following components until a uniform solution is obtained.
Compound (A) 0.02% by weight
2PXZ-TAZ 0.18% by weight
SPH-101 1.80% by weight
Xylene 98.00% by weight

The composition for forming a light emitting layer (7) is prepared by stirring the following components until a uniform solution is obtained.
Compound (A) 0.02% by weight
2PXZ-TAZ 0.18% by weight
DOBNA 1.80% by weight
Toluene 98.00% by weight

In Table 5, "2PXZ-TAZ" is 10,10'-((4-phenyl-4H-1,2,4-triazole-3,5-diyl) bis (4,1-phenyl)) bis ( 10H-phenoxazine). The chemical structure is shown below.

<Example 2-7>
An ND-3202 (manufactured by Nissan Chemical Industries, Ltd.) solution is spin-coated on a glass substrate on which ITO is formed to a thickness of 45 nm, and then heated at 50 ° C. for 3 minutes in an air atmosphere, and further at 230 ° C., 15 By heating for a minute, an ND-3202 film having a film thickness of 50 nm is formed (hole injection layer). Next, the XLP-101 solution is spin-coated and heated on a hot plate at 200 ° C. for 30 minutes in a nitrogen gas atmosphere to form an XLP-101 film having a film thickness of 20 nm (hole transport layer). Next, the light emitting layer forming composition (5) is spin-coated and heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere to form a 20 nm light emitting layer.

The produced multilayer film was fixed to a substrate holder of a commercially available thin-film deposition equipment (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing TSPO1, a molybdenum vapor deposition boat containing LiF, and tungsten containing aluminum. Install a vapor deposition boat. After depressurizing the vacuum chamber to 5 × 10 ^-4 Pa, TSPO1 is heated and vapor-deposited to a film thickness of 30 nm to form an electron transport layer. The vapor deposition rate when forming the electron transport layer is 1 nm / sec. Then, LiF is heated to deposit at a vapor deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm. Next, aluminum is heated and vapor-deposited to a film thickness of 100 nm to form a cathode. In this way, an organic EL element is obtained.

<Examples 2-8 and 2-9>
Using the light emitting layer forming composition (6) or (7), an organic EL device is obtained in the same manner as in Example 2-7.

In the present invention, by providing a novel polycyclic aromatic compound, the choice of materials for organic EL devices can be increased. Further, by using a novel polycyclic aromatic compound as a material for an organic electroluminescent device, it is possible to provide an excellent organic EL device, a display device provided with the same, a lighting device provided with the same, and the like.

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 (27)

A multimer of a polycyclic aromatic compound represented by the following general formula (1) or a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1).
In the above formula (1),
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are single-bonded). (Or may be attached via a linking group), alkyl, cycloalkyl, alkoxy or aryloxy, at least one hydrogen in which is further substituted with aryl, heteroaryl, alkyl or cycloalkyl. Well,
X ¹ and X ² are independently>N-R,>O,> C (-R) ₂ ,> S or> Se, and both X ¹ and X ² are> C (-R) _2. Never become
The Rs in> N-R and> C (-R) ₂ are independent of hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, and diarylboryl (two aryls are simple). It may be attached via a bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy, in which at least one hydrogen is further substituted with aryl, heteroaryl, alkyl or cycloalkyl. The R of> N-R and> C (-R) ₂ may be independently bonded to at least one ring of the a ring, b ring and c ring by a linking group or a single bond, respectively. Often,
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ are independently = C (-R)-or = N-, and at least one is = N-.
R in = C (-R)-is independent of hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls have a single bond or a linking group). (May be bonded via), alkyl, cycloalkyl, alkoxy or aryloxy, wherein at least one hydrogen in these may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl.
Adjacent groups of R ¹ , R ² , R ³ , R ⁴ and R ⁵ , and = C (-R)-R as Y ^{1 to} Y ⁶ are bonded to each other to form a ring, b. An aryl ring or a heteroaryl ring may be formed together with at least one ring of the ring and the c ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, aryl hetero. Arylamino, diallylboryl (two aryls may be attached via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy may be substituted, in which at least one hydrogen is. , And may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, and
At least one hydrogen in the compound and structure represented by the general formula (1) may be substituted with cyano, halogen or deuterium. In the above formula (1),
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen, aryl with 6 to 30 carbon atoms, heteroaryl with 2 to 30 carbon atoms, and diarylamino (however, each aryl has 6 carbon atoms). ~ 12 aryl), diarylboryl (where aryl is an aryl having 6-12 carbon atoms, and the two aryls may be bonded via a single bond or a linking group), an alkyl having 1 to 12 carbon atoms, It is a cycloalkyl having 3 to 16 carbon atoms, an alkoxy having 1 to 12 carbon atoms or an aryloxy having 6 to 30 carbon atoms, and at least one hydrogen in these is an aryl having 6 to 30 carbon atoms and 2 to 2 carbon atoms. It may be substituted with 30 heteroaryls, alkyls with 1-12 carbon atoms or cycloalkyls with 3-16 carbon atoms.
X ¹ and X ² are independently>N-R,>O,> C (-R) ₂ ,> S or> Se, and both X ¹ and X ² are> C (-R) _2. Never become
The R in> N-R and> C (-R) ₂ are independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, and diarylamino (however, each aryl has carbon number of carbon). 6-12 aryls), diarylboryls (where aryls are 6-12 carbon atoms, and the two aryls may be attached via a single bond or a linking group), alkyls with 1-12 carbon atoms. , Cycloalkyl with 3 to 16 carbon atoms, alkoxy with 1 to 12 carbon atoms or aryloxy with 6 to 30 carbon atoms, in which at least one hydrogen is an aryl with 6 to 30 carbon atoms, 2 carbon atoms. It may be substituted with ~ 30 heteroaryl, an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 16 carbon atoms, and the above-mentioned> N-R and> C (-R) ₂ R are independent of each other. Then, it may be bonded to at least one of the a ring, the b ring and the c ring by −O−, −S−, −C (−R) _2- or a single bond, and the −C (−C (−C). R) _2- R is hydrogen, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms.
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ are independently = C (-R)-or = N-, and at least one is = N-.
The Rs in = C (-R)-are independent of hydrogen, aryls having 6 to 30 carbon atoms, heteroaryls having 2 to 30 carbon atoms, and diarylaminos (however, each aryl has 6 to 12 carbon atoms). ), Diarylboryl (where aryl is an aryl having 6 to 12 carbon atoms, and the two aryls may be bonded via a single bond or a linking group), an alkyl having 1 to 12 carbon atoms, and 3 to 12 carbon atoms. 16 cycloalkyls, alkoxys with 1-12 carbon atoms or aryloxys with 6-30 carbon atoms, at least one of which is an aryl with 6-30 carbon atoms and a heteroaryl with 2-30 carbon atoms. , May be substituted with alkyls having 1-12 carbon atoms or cycloalkyls having 3-16 carbon atoms.
Adjacent groups of R ¹ , R ² , R ³ , R ⁴ and R ⁵ , and = C (-R)-R as Y ^{1 to} Y ⁶ are bonded to each other to form a ring, b. An aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms may be formed together with at least one ring of the ring and the c ring, and at least one hydrogen in the formed ring has 6 carbon atoms. ~ 30 aryls, 2-30 carbon heteroaryls, diarylaminos (where each aryl is 6-12 carbons), diarylboryl (where aryls are 6-12 carbons, and the two aryls are (May be bonded via a single bond or a linking group), alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, alkoxy having 1 to 12 carbon atoms, or aryloxy having 6 to 30 carbon atoms. At least one hydrogen in these may be substituted further, an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms or an alkyl having 1 to 12 carbon atoms or a cycloalkyl having 3 to 16 carbon atoms. May be replaced with, and
At least one hydrogen in the compound and structure represented by the general formula (1) may be substituted with cyano, halogen or deuterium.
The polycyclic aromatic compound according to claim 1 or a multimer thereof. The polycyclic aromatic compound or a multimer thereof according to claim 1 or 2, wherein X ¹ and X ² are independently> N-R or> O, respectively. X ¹ and X ² are independently> N-R or> O, respectively.
Y ^{2, Y} 3, ^{Y 4} and ^{Y 5} are each independently, = C (-R) - and is, ^{Y 1} and ^{Y 6} are each independently, = C (-R) - or = N -And at least one = N-,
The polycyclic aromatic compound according to any one of claims 1 to 3 or a multimer thereof. The polycyclic aromatic compound or a multimer thereof according to any one of claims 1 to 4, which comprises a partial structure represented by any of the following formulas.
The polycyclic aromatic compound according to claim 1 or a multimer thereof, which is represented by any of the following formulas.
A reactive compound in which a polycyclic aromatic compound according to any one of claims 1 to 6 or a multimer thereof is substituted with a reactive substituent. A polymer compound obtained by polymerizing the reactive compound according to claim 7 as a monomer, or a polymer crosslinked product obtained by further cross-linking the polymer compound. A pendant type polymer compound in which a main chain type polymer is substituted with the reactive compound according to claim 7, or a pendant type polymer crosslinked product in which the pendant type polymer compound is further crosslinked. A material for an organic device containing the polycyclic aromatic compound according to any one of claims 1 to 6 or a multimer thereof. A material for an organic device containing the reactive compound according to claim 7. A material for an organic device containing the polymer compound or polymer crosslinked body according to claim 8. A material for an organic device containing the pendant type polymer compound or the pendant type polymer crosslinked body according to claim 9. The material for an organic device according to any one of claims 10 to 13, wherein the material for an organic device is a material for an organic electroluminescent device, a material for an organic field effect transistor, or a material for an organic thin film solar cell. The material for an organic device according to claim 14, wherein the material for the organic electroluminescent element is a material for a light emitting layer. An ink composition containing the polycyclic aromatic compound according to any one of claims 1 to 6 or a multimer thereof, and an organic solvent. An ink composition containing the reactive compound according to claim 7 and an organic solvent. An ink composition containing a main chain polymer, the reactive compound according to claim 7, and an organic solvent. An ink composition containing the polymer compound or the crosslinked polymer according to claim 8 and an organic solvent. An ink composition containing the pendant-type polymer compound or the pendant-type polymer crosslinked product according to claim 9 and an organic solvent. A polycyclic aromatic compound according to any one of claims 1 to 6, or a polymer thereof, a reactive compound according to claim 7, which is arranged between a pair of electrodes composed of an anode and a cathode and the pair of electrodes. An organic electroluminescent element having an organic layer containing the polymer compound or polymer crosslinked body according to claim 8 or the pendant type polymer compound or pendant type polymer crosslinked body according to claim 9. The organic electroluminescent device according to claim 21, wherein the organic layer is a light emitting layer. The light emitting layer is further represented by a compound represented by the following general formula (H1), a compound represented by the following general formula (H2), a compound represented by the following general formula (H3), and a compound represented by the following general formula (H4). 22. The organic electroluminescent element according to claim 22, which comprises a compound containing the above-mentioned structure, a compound represented by the following general formula (H5), and at least one selected from the group consisting of TADF materials.
In the general formula (H1), ^{L 1} is a heteroarylene arylene or C2-30 6 to 30 carbon atoms,
In the above general formula (H2), L ² and L ³ are independently aryls having 6 to 30 carbon atoms or heteroaryls having 2 to 30 carbon atoms.
In the above general formula (H3), MU is a divalent group independently represented by removing any two hydrogen atoms from the aromatic compound, and EC is each independently an arbitrary hydrogen from the aromatic compound. It is a monovalent group represented excluding atoms, with two hydrogens in the MU replaced by EC or MU, where k is an integer of 2-50000.
In the general formula (H4), G is independently = C (−H) − or = N−, and H in the above = C (−H) − is a substituent or another formula (H4). It may be replaced by the structure represented
In the above general formula (H5),
R ^{1 to} R ¹¹ are independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, aryl heteroarylamino, alkyl or cycloalkyl, wherein at least one hydrogen in these is an additional aryl, It may be substituted with heteroaryl, diarylamino, alkyl or cycloalkyl,
Adjacent groups of R ^{1 to} R ¹¹ may be bonded to 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 is It may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl, in which at least one hydrogen is further aryl, heteroaryl, diarylamino, alkyl or cycloalkyl. May be replaced with, and
At least one hydrogen in the compound or structure represented by each of the above formulas may be substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, cyano, halogen or deuterium. It has at least one of an electron transporting layer and an electron injecting layer arranged between the cathode and the light emitting layer, and at least one of the electron transporting layer and the electron injecting layer is a borane derivative, a pyridine derivative, or a fluorantene derivative. , BO-based derivative, anthracene derivative, benzofluorene derivative, phosphine oxide derivative, pyrimidine derivative, carbazole derivative, triazine derivative, benzoimidazole derivative, phenanthroline derivative and quinolinol-based metal complex. The organic electric field light emitting element according to claim 22 or 23. At least one of the electron transport layer and the electron injection layer further comprises an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, and an alkaline earth metal. Contains at least one selected from the group consisting of halides, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals. Item 24. The organic electric field light emitting element. At least one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer is a polymer compound obtained by polymerizing a low molecular compound capable of forming each layer as a monomer, or a polymer compound. , A polymer crosslinked product obtained by further cross-linking the polymer compound, or a pendant type polymer compound obtained by reacting a low molecular weight compound capable of forming each layer with a main chain type polymer, or the pendant type polymer compound. The organic electroluminescent element according to any one of claims 21 to 25, which comprises a pendant type polymer crosslinked body further crosslinked. A display device or a lighting device including the organic electroluminescent element according to any one of claims 21 to 26.