JP6738063B2 - Cycloalkyl-substituted polycyclic aromatic compound - Google Patents

Description

The present invention relates to a cycloalkyl-substituted polycyclic aromatic compound, an organic electroluminescent element, an organic field effect transistor and an organic thin film solar cell using the same, and a display device and a lighting device. In the present specification, the “organic electroluminescent device” may be referred to as “organic EL device” or simply “device”.

Conventionally, a display device using an electroluminescent element has been researched variously because it can be reduced in power consumption and thinned, and an organic electroluminescent element made of an organic material can be easily reduced in weight and size. Therefore, it has been actively studied. In particular, the development of organic materials that have emission characteristics such as blue, which is one of the three primary colors of light, and the development of organic materials that have charge transporting ability (possibly becoming a semiconductor or superconductor) such as holes and electrons. Development has been actively researched so far, regardless of whether it is a high molecular compound or a low molecular compound.

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

As a material for the light emitting layer, for example, a benzofluorene compound has been developed (International Publication No. 2004/061047). As a hole transport material, for example, a triphenylamine compound has been developed (Japanese Patent Laid-Open No. 2001-172232). As an electron transport material, for example, anthracene compounds 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 refers to N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine (TPD) which has already been put into practical use, It is a material characterized in that its planarity is improved by connecting aromatic rings constituting triphenylamine. In this document, for example, the charge-transporting 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. If they are different, the electronic state of the whole compound is different, and therefore the properties obtained from materials other than the NO-linked compound have not yet been known. Other examples of such compounds can be found (WO 2011/107186). For example, a compound having a conjugated structure with high triplet exciton energy (T1) can emit phosphorescence with a shorter wavelength, and thus is useful as a material for a blue light-emitting layer. Further, as an electron transporting material or a hole transporting material sandwiching the light emitting layer, a compound having a novel conjugated structure having a large T1 is required.

The host material of the organic EL device 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 a large HOMO-LUMO gap (bandgap Eg in a thin film) required for a host material is secured by connecting a large number of relatively conjugated aromatic rings. In addition, the host material of the organic EL element using a phosphorescent material or a heat activated delayed fluorescent material, high triplet excitation energy (E _T) is also required, the donor or acceptor properties of the aromatic ring and substituents in the molecule It is possible to improve the triplet excitation energy (E _T ) by connecting SO to localize SOMO1 and SOMO2 in the triplet excited state (T1) and reduce the exchange interaction between both orbitals. Becomes However, the small conjugated aromatic ring does not have sufficient redox stability, and an element using a molecule that connects existing aromatic rings as a host material does not have a long lifetime. 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 as a host material.

International Publication No. 2004/061047 JP 2001-172232 JP 2005-170911 A 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 elements, but in order to increase the choices of materials for organic EL elements, it is desired to develop materials composed of compounds different from conventional ones. There is. In particular, the organic EL characteristics obtained from materials other than the NO-linked compounds reported in Patent Documents 1 to 4 and the manufacturing method thereof are not yet known.

In addition, Patent Document 6 reports a polycyclic aromatic compound containing boron and an organic EL device using the same. However, in order to further improve device characteristics, light emission efficiency and device life can be improved. There is a need for layer materials, especially dopant materials.

The present inventors have conducted extensive studies to solve the above problems, and as a result, a layer containing a cycloalkyl group-introduced polycyclic aromatic compound is arranged between a pair of electrodes to form an organic EL device, for example. The inventors have found that an excellent organic EL device can be obtained, and have completed the present invention. That is, the present invention provides an organic compound such as a cycloalkyl-substituted polycyclic aromatic compound or a polymer thereof as described below, and an organic EL device material or the like containing the cycloalkyl-substituted polycyclic aromatic compound or a polymer as described below. Provide materials for devices.

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

Item 1.
A polycyclic aromatic compound represented by the following general formula (1) or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1).
(In the above formula (1),
A ring, B ring and C ring are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted,
Y ¹ is B, P, P═O, P═S, Al, Ga, As, Si—R or Ge—R, wherein R of Si—R and Ge—R is aryl or alkyl,
X ¹ and X ² are each independently >O, >N—R, >C(—R) ₂ , >S or >Se, and R in >N—R may be substituted. Aryl, optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted cycloalkyl, wherein R in >C(—R) ₂ is hydrogen, optionally substituted aryl Or alkyl, and R of >N—R and/or R of >C(—R) ₂ is bonded to the A ring, B ring and/or C ring by a linking group or a single bond. Well,
At least one hydrogen in the compound or structure represented by formula (1) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound or structure represented by formula (1) is substituted with cycloalkyl. )

Item 2.
Ring A, Ring B and Ring C are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or Unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (two aryls are bonded via a single bond or a linking group )), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy, and these rings are composed of Y ¹ , X ¹ and X ^2. Having a 5-membered ring or a 6-membered ring sharing a bond with the condensed two-ring structure in the center of the above formula,
Y ¹ is B, P, P═O, P═S, Al, Ga, As, Si—R or Ge—R, wherein R of Si—R and Ge—R is aryl or alkyl,
X ¹ and X ² are each independently >O, >N—R, >C(—R) ₂ , >S or >Se, wherein R in >N—R is substituted with alkyl. Optionally aryl, heteroaryl optionally substituted with alkyl, alkyl or cycloalkyl, wherein R in >C(—R) ₂ is hydrogen, aryl optionally substituted with alkyl, or alkyl; , R of >N-R and/or R of >C(-R) ₂ is -O-, -S-, -C(-R) ₂ -or a single bond to form A ring, B ring and/or Alternatively, it may be bonded to a C ring, and R of the above-C(—R) ₂ — is hydrogen or alkyl,
At least one hydrogen in the compound or structure represented by formula (1) may be substituted with deuterium, cyano or halogen,
In the case of a multimer, it is a dimer or trimer having 2 or 3 structures represented by the general formula (1), and
At least one hydrogen in the compound or structure of formula (1) is substituted with cycloalkyl,
Item 1. A polycyclic aromatic compound or a multimer thereof according to Item 1.

Item 3.
Item 6. The polycyclic aromatic compound according to item 1, represented by the following general formula (2).
(In the above formula (2),
R ^{1 to} R ¹¹ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are bonded via a single bond or a linking group. ), alkyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl or alkyl, and when adjacent groups of R ^{1 to} R ¹¹ are adjacent to each other. They may combine with each other to form an aryl ring or a heteroaryl ring together with a ring, b ring or c ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, aryl. Heteroarylamino, diarylboryl (two aryls may be bonded via a single bond or a linking group), alkyl, alkoxy or aryloxy may be substituted, and at least one hydrogen in these is aryl, Optionally substituted with heteroaryl or alkyl,
Y ¹ is B, P, P=O, P=S, Al, Ga, As, Si-R or Ge-R, and R of Si-R and Ge-R is an aryl having 6 to 12 carbon atoms. Or alkyl having 1 to 6 carbon atoms,
X ¹ and X ² are each independently >O, >N—R, >C(—R) ₂ , >S or >Se, and R in >N—R has 6 to 12 carbon atoms. Aryl, heteroaryl having 2 to 15 carbons, alkyl having 1 to 6 carbons or cycloalkyl having 3 to 14 carbons, wherein R of >C(-R) ₂ is hydrogen and aryl having 6 to 12 carbons. Alternatively, it is alkyl having 1 to 6 carbon atoms, and R in the above >N—R and/or R in the above >C(—R) ₂ is —O—, —S—, —C(—R) ₂ —. Alternatively, it may be bonded to the a ring, b ring and/or c ring by a single bond, and R of the above-C(-R) _2- is alkyl having 1 to 6 carbon atoms,
At least one hydrogen in the compound represented by formula (2) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl. )

Item 4.
R ^{1 to} R ¹¹ are each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (provided that aryl is aryl having 6 to 12 carbon atoms), diarylboryl (provided that Aryl is aryl having 6 to 12 carbons, two aryls may be bonded via a single bond or a linking group) or alkyl having 1 to 24 carbons, and R ^{1 to} R ¹¹ Adjacent groups among them 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 a ring, b ring or c ring, and in the formed ring At least one hydrogen may be substituted with aryl having 6 to 10 carbons or alkyl having 1 to 12 carbons,
Y ¹ is B, P, P═O, P═S or Si—R, and R of the Si—R is aryl having 6 to 10 carbons or alkyl having 1 to 4 carbons,
X ¹ and X ² are each independently >O, >N—R, >C(—R) ₂ or >S, wherein R in >N—R is aryl having 6 to 10 carbon atoms or carbon. C1 to C4 alkyl or C5 to C10 cycloalkyl, wherein R of >C(-R) ₂ is hydrogen, C6 to C10 aryl or C1 to C4 alkyl,
At least one hydrogen in the compound represented by formula (2) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl,
Item 6. A polycyclic aromatic compound according to item 3.

Item 5.
R ^{1 to} R ¹¹ are each independently hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 20 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms) or 1 to carbon atoms. 12 alkyls,
Y ¹ is B, P, P=O or P=S,
X ¹ and X ² are each independently >O, >N—R or >C(—R) ₂ and R in >N—R is aryl having 6 to 10 carbons, or 1 to 1 carbons. 4 alkyl or cycloalkyl having 5 to 10 carbons, wherein R of >C(-R) ₂ is hydrogen, aryl having 6 to 10 carbons or alkyl having 1 to 4 carbons, and
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl,
Item 6. A polycyclic aromatic compound according to item 3.

Item 6.
R ^{1 to} R ¹¹ are each independently hydrogen, aryl having 6 to 16 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms) or alkyl having 1 to 12 carbon atoms,
Y ¹ is B,
X ¹ and X ² are both >N—R, or X ¹ is >N—R and X ² is >O, and R in >N—R is an aryl having 6 to 10 carbon atoms. Is alkyl having 1 to 4 carbons or cycloalkyl having 5 to 10 carbons, and
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl,
Item 6. A polycyclic aromatic compound according to item 3.

Item 7.
Item 7. The polycyclic aromatic group according to any one of items 1 to 6, which is substituted with a cycloalkyl-substituted diarylamino group, a cycloalkyl-substituted carbazolyl group, or a cycloalkyl-substituted benzocarbazolyl group. A compound or multimer thereof.

Item 8.
Item 7. The polycyclic aromatic compound according to any one of Items 3 to 6, wherein R ² is a cycloalkyl-substituted diarylamino group or a cycloalkyl-substituted carbazolyl group.

Item 9.
Item 9. The polycyclic aromatic compound according to any one of Items 1 to 8, wherein the cycloalkyl is a cycloalkyl having 3 to 20 carbon atoms.

Item 10.
Item 10. The polycyclic aromatic compound or a multimer thereof according to any one of Items 1 to 9, wherein the halogen is fluorine.

Item 11.
Item 6. The polycyclic aromatic compound according to item 1, which is represented by any one of the following structural formulas.
(In the above structural formulas, "Me" represents a methyl group, and "tBu" represents a t-butyl group.)

Item 12.
Item 12. A reactive compound in which the polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 11 is substituted with a reactive substituent.

Item 13.
A polymer compound obtained by polymerizing the reactive compound according to item 12 as a monomer, or a polymer cross-linked product obtained by further crosslinking the polymer compound.

Item 14.
A pendant polymer compound obtained by substituting the reactive compound according to item 12 for a main chain polymer, or a pendant polymer crosslinked product obtained by further crosslinking the pendant polymer compound.

Item 15.
Item 11. An organic device material containing the polycyclic aromatic compound or the multimer thereof according to any one of Items 1 to 11.

Item 16.
Item 12. An organic device material containing the reactive compound according to item 12.

Item 17.
Item 13. An organic device material containing the polymer compound or polymer cross-linked product according to item 13.

Item 18.
Item 15. An organic device material containing the pendant polymer compound or the pendant polymer crosslinked product according to item 14.

Item 19.
Item 19. The organic device material according to any one of Items 15 to 18, wherein the organic device material is an organic electroluminescent element material, an organic field effect transistor material, or an organic thin film solar cell material.

Item 20.
Item 20. The organic device material according to Item 19, wherein the organic electroluminescent element material is a light emitting layer material.

Item 21.
Item 12. An ink composition containing the polycyclic aromatic compound or the multimer thereof according to any one of Items 1 to 11, and an organic solvent.

Item 22.
Item 12. An ink composition comprising the reactive compound according to item 12, and an organic solvent.

Item 23.
An ink composition comprising a main chain polymer, the reactive compound according to item 12, and an organic solvent.

Item 24.
Item 15. An ink composition comprising the polymer compound or polymer cross-linked product according to item 13 and an organic solvent.

Item 25.
Item 15. An ink composition comprising the pendant polymer compound or the pendant polymer crosslinked product according to Item 14, and an organic solvent.

Item 26.
A pair of electrodes composed of an anode and a cathode, and a polycyclic aromatic compound or a multimer thereof arranged in any one of the items 1 to 11, which is disposed between the pair of electrodes, the reactive compound in the item 12, An organic electroluminescence device, comprising: the polymer compound or the polymer crosslinked product according to item 14; or the organic layer containing the pendant polymer compound or the pendant polymer crosslinked product according to item 14.

Item 27.
A pair of electrodes composed of an anode and a cathode, and a polycyclic aromatic compound or a multimer thereof arranged in any one of the items 1 to 11, which is disposed between the pair of electrodes, the reactive compound in the item 12, An organic electroluminescent device comprising: the polymer compound or the crosslinked polymer according to item 14 or a light emitting layer containing the pendant polymer compound or the crosslinked polymer according to item 14.

Item 28.
The light emitting layer includes a host and the polycyclic aromatic compound as a dopant, a multimer thereof, a reactive compound, a polymer compound, a polymer crosslinked product, a pendant polymer compound or a pendant polymer crosslinked product. Item 27. The organic electroluminescent element according to Item 27.

Item 29.
Item 29. The organic electroluminescent device according to item 28, wherein the host is an anthracene compound, a fluorene compound, or a dibenzochrysene compound.

Item 30.
It has an electron transport layer and/or an electron injection layer disposed between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, a fluoranthene derivative, or BO. Item 26, containing at least one selected from the group consisting of system derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol-based metal complexes. 29. The organic electroluminescent element as described in any of 29 to 29.

Item 31.
The electron-transporting layer and/or the electron-injecting layer may further include 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. Item 30 containing at least one selected from the group consisting of a halide, an oxide of a rare earth metal, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal and an organic complex of a rare earth metal. The organic electroluminescent device as described in 1.

Item 32.
At least one layer 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 crosslinked polymer obtained by further crosslinking the polymer compound, or a pendant polymer compound obtained by reacting a low molecular compound capable of forming each layer with a main chain polymer, or the pendant polymer compound. Item 32. The organic electroluminescence device according to any one of Items 26 to 31, further comprising a crosslinked pendant polymer crosslinked product.

Item 33.
Item 34. A display device or a lighting device including the organic electroluminescent element according to any one of items 26 to 32.

According to a preferred embodiment of the present invention, a novel cycloalkyl-substituted polycyclic aromatic compound that can be used as a material for an organic device such as a material for an organic EL device can be provided. By using an aromatic compound, an excellent organic device such as an organic EL element can be provided.

Specifically, the present inventors have found that a polycyclic aromatic compound (basic skeleton portion) in which an aromatic ring is linked with a hetero element such as boron, phosphorus, oxygen, nitrogen, or sulfur has a large HOMO-LUMO gap (in a thin film). It was found to have a band gap Eg) and a high triplet excitation energy (E _T ). This is because the 6-membered ring containing a hetero element has low aromaticity, so that the reduction of the HOMO-LUMO gap due to the expansion of the conjugated system is suppressed, and the triplet excited state (T1 It is considered that this is caused by the localization of SOMO1 and SOMO2 in (1). Further, in the polycyclic aromatic compound (basic skeleton portion) containing a hetero element according to the present invention, the exchange interaction between both orbitals becomes small due to the localization of SOMO1 and SOMO2 in the triplet excited state (T1). Therefore, the energy difference between the triplet excited state (T1) and the singlet excited state (S1) is small, and the thermally activated delayed fluorescence is exhibited, which is also useful as a fluorescent material for an organic EL element. Further, the material having high triplet excitation energy (E _T), is also useful as an electron transport layer and a hole transport layer of an organic EL element utilizing a phosphorescent organic EL device and heat activated delayed fluorescence. Furthermore, in these polycyclic aromatic compounds (basic skeletons), the introduction of substituents allows the HOMO and LUMO energies to move arbitrarily, so the ionization potential and electron affinity are optimized according to the surrounding materials. It is possible.

In addition to such characteristics of the basic skeleton, the compound of the present invention can be expected to have a lowered melting point or sublimation temperature by introducing a cycloalkyl group. This means that in sublimation refining, which is almost indispensable as a method of refining materials for organic devices such as organic EL elements requiring high purity, refining of materials can be avoided because refining can be performed at a relatively low temperature. Means This is also the same for the vacuum vapor deposition process, which is a powerful means for producing an organic device such as an organic EL element. Since the process can be performed at a relatively low temperature, thermal decomposition of the material can be avoided, As a result, high performance organic devices can be obtained. In addition, since many of the multimers of the polycyclic aromatic compound have a high sublimation temperature due to their high molecular weight and flatness, the reduction of the sublimation temperature by introducing a cycloalkyl group is more effective. .. Further, since the introduction of the cycloalkyl group improves the solubility in an organic solvent, it can be applied to the production of an element using a coating process. However, the present invention is not particularly limited to these principles.

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

1. Cycloalkyl-substituted polycyclic aromatic compounds and multimers thereof The present invention relates to polycyclic aromatic compounds represented by the following general formula (1) or polycyclic aromatic compounds represented by the following general formula (1). It is a multimer of a ring aromatic compound, preferably a polycyclic aromatic compound represented by the following general formula (2) or a polycyclic aromatic compound having a plurality of structures represented by the following general formula (2). It is a multimer and at least one hydrogen in these compounds or structures is substituted with cycloalkyl.

Ring A, ring B and ring C in formula (1) are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted with a substituent. This substituent is a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted diarylamino, a substituted or unsubstituted diheteroarylamino, a substituted or unsubstituted arylheteroarylamino (aryl and An amino group having a heteroaryl), a substituted or unsubstituted diarylboryl (two aryls may be bonded via a single bond or a linking group), a substituted or unsubstituted alkyl, a substituted or unsubstituted alkoxy or Substituted or unsubstituted aryloxy is preferred. When these groups have a substituent, examples of the substituent include aryl, heteroaryl and alkyl. The aryl ring or heteroaryl ring may have a 5-membered ring or a 6-membered ring sharing a bond with the central fused bicyclic structure of the general formula (1) composed of Y ¹ , X ¹ and X ^2. preferable.

Here, the “fused bicyclic structure” means a structure in which two saturated hydrocarbon rings containing Y ¹ , X ¹ and X ² shown in the center of the general formula (1) are condensed. .. Further, the “6-membered ring sharing a bond with the condensed 2-ring structure” means, for example, a ring (benzene ring (6-membered ring)) condensed to the condensed 2-ring structure as shown in the general formula (2). means. Further, "the aryl ring or heteroaryl ring (which is the A ring) has this 6-membered ring" means that the A ring is formed only by this 6-membered ring, or the 6-membered ring is included. This means that the 6-membered ring is further condensed with another ring to form the A ring. In other words, the “aryl ring or heteroaryl ring having a 6-membered ring (which is the A ring)” as used herein means that a 6-membered ring forming all or a part of the A ring is fused to the fused bicyclic structure. It means doing. The same description applies to the "B ring (b ring)", the "C ring (c ring)", and the "5-membered ring".

The ring A (or B ring, C ring) in the general formula (1) is the ring a and its substituents R ^{1 to} R ³ (or the ring b and its substituents R ^{4 to} R ⁷ , c in the general formula (2). Corresponds to the ring and its substituents R ^{8 to} R ¹¹ ). That is, the general formula (2) corresponds to a structure in which “A to C ring having a 6-membered ring” is selected as the A to C ring of the general formula (1). In that sense, each ring of the general formula (2) is represented by small letters a to c.

In the general formula (2), adjacent groups among the substituents R ^{1 to} R ^{11 on} the a ring, b ring and c ring are bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring. At least one hydrogen in the formed ring, which may be formed, is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are bonded via a single bond or a linking group). Optionally bonded), substituted with alkyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl or alkyl. Therefore, the polycyclic aromatic compound represented by the general formula (2) has the following formulas (2-1) and (2-2) depending on the mutual bonding form of the substituents on the a ring, the b ring and the c ring. As shown in, the ring structure constituting the compound changes. The A′ ring, B′ ring and C′ ring in each formula correspond to the A ring, B ring and C ring in formula (1), respectively.

The A′ ring, the B′ ring and the C′ ring in the formula (2-1) and the formula (2-2) are adjacent to each other in the substituents R ^{1 to} R ¹¹ when explained in the general formula (2). Represents an aryl ring or a heteroaryl ring formed together with ring a, ring b and ring c respectively (a condensed ring formed by condensing another ring structure on ring a, ring b or ring c) It can be said that). Although not shown in the formula, there are some compounds in which all of ring a, ring b and ring c are changed to ring A′, ring B′ and ring C′. Further, as can be seen from the above formulas (2-1) and (2-2), for example, R ⁸ of the b ring and R ^{7 of} the c ring, R ¹¹ of the b ring and R ^{1 of} the a ring, and R ^{1 of} the c ring are used. R ⁴ and R ^{3 of the} a ring do not correspond to “adjacent groups”, and they do not bond. That is, the "adjacent group" means groups adjacent to each other on the same ring.

The compound represented by the above formula (2-1) or formula (2-2) is, for example, a benzene ring, an indole ring, a pyrrole ring, or a benzofuran ring with respect to a benzene ring which is a ring (or b ring or c ring). Or a compound having an A′ ring (or a B′ ring or a C′ ring) formed by condensing a benzothiophene ring, and a condensed ring A′ (or a condensed ring B′ or a condensed ring C′) formed by the formation. ) Is a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring, respectively.

Y ¹ in the general formula (1) is B, P, P═O, P═S, Al, Ga, As, Si—R or Ge—R, and R in the above Si—R and Ge—R is aryl. Or alkyl. In the case of P=O, P=S, Si-R or Ge-R, the atom bonded to the A ring, B ring or C ring is P, Si or Ge. Y ¹ is preferably B, P, P=O, P=S or Si-R, and B is particularly preferable. This explanation is the same for Y ¹ in the general formula (2).

X ¹ and X ² in the general formula (1) are each independently >O, >N—R, >C(—R) ₂ , >S or >Se, and R in >N—R is Optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted cycloalkyl, wherein R in >C(—R) ₂ is hydrogen or substituted Which is optionally substituted aryl or alkyl, R in the >N—R and/or R in the >C(—R) ₂ is bonded to the B ring and/or the C ring by a linking group or a single bond. Alternatively, the linking group is preferably -O-, -S- or -C(-R) _2- . In addition, R of said "-C(-R) _2- " is hydrogen or alkyl. This explanation is the same for X ¹ and X ² in the general formula (2).

Here, in the general formula (1), “>R of R and/or R of >C(—R) ₂ is bonded to the A ring, B ring and/or C ring by a linking group or a single bond. the provisions of the by that "is, in general formula (2)"> N-R R and / or the> C _{(-R) 2} of R is -O -, - S -, - C (-R) 2 -Or is bonded to the ring a, ring b and/or ring c by a single bond".

This definition can be represented by a compound represented by the following formula (2-3-1) having a ring structure in which X ¹ and X ² are incorporated in the condensed ring B′ and the condensed ring C′. That is, for example, a B′ ring (or a ring formed by condensing another ring by incorporating X ¹ (or X ² ) into a benzene ring which is the b ring (or c ring) in the general formula (2) (or It is a compound having a C′ ring). The formed condensed ring B′ (or condensed ring C′) is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.

Further, the above definition is a compound represented by the following formula (2-3-2) or formula (2-3-3) having a ring structure in which X ¹ and/or X ² is incorporated in the condensed ring A′. But it can be expressed. That is, for example, a compound having an A′ ring formed by condensing another ring by incorporating X ¹ (and/or X ² ) into the benzene ring which is the a ring in the general formula (2). .. The formed condensed ring A′ thus formed is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.

Examples of the “aryl ring” which is the A ring, B ring and C ring of the general formula (1) include an aryl ring having 6 to 30 carbon atoms, preferably an aryl ring having 6 to 16 carbon atoms, and more preferably an aryl ring having 6 to 16 carbon atoms. An aryl ring having 6 to 12 is more preferable, and an aryl ring having 6 to 10 carbon atoms is particularly preferable. The "aryl ring" is defined as "aryl ring formed by combining adjacent groups of R ^{1 to} R ¹¹ together with a ring, b ring or c ring" defined by the general formula (2). In addition, since ring a (or ring b or ring c) is already composed of a benzene ring having 6 carbon atoms, the total number of carbon atoms in the condensed ring obtained by condensing a 5-membered ring with this is 9 is the lower limit carbon number. Becomes a number.

Specific examples of the “aryl ring” include a benzene ring which is a monocyclic system, a biphenyl ring which is a bicyclic system, a naphthalene ring which is a condensed bicyclic system, and a terphenyl ring (m-terphenyl, o which is a tricyclic system). -Terphenyl, p-terphenyl), a fused tricyclic ring system such as an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, a condensed tetracyclic triphenylene ring, a pyrene ring, a naphthacene ring, and a fused pentacyclic ring system. Examples thereof include a perylene ring and a pentacene ring.

Examples of the “heteroaryl ring” which is the A ring, B ring and C ring of the general formula (1) include a heteroaryl ring having 2 to 30 carbon atoms, and preferably a heteroaryl ring having 2 to 25 carbon atoms. , A heteroaryl ring having 2 to 20 carbon atoms is more preferable, a heteroaryl ring having 2 to 15 carbon atoms is further preferable, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferable. The "heteroaryl ring" includes, for example, a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms. In addition, this "heteroaryl ring" is defined as "heteroaryl formed by bonding adjacent groups of R ^{1 to} R ¹¹ together with a ring, b ring or c ring" defined by the general formula (2). Ring, and since the a ring (or b ring, c ring) is already composed of a benzene ring having 6 carbon atoms, the total number of carbon atoms of the condensed ring in which a 5-membered ring is condensed is 6 is the lower limit. It becomes the carbon number of.

Specific examples of the “heteroaryl ring” include, for example, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, Pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring , Cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxathiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, indolizine ring, furan ring, Examples thereof include a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a furazan ring, an oxadiazole ring and a thianthrene ring.

At least one hydrogen in the above “aryl ring” or “heteroaryl ring” is the first substituent, which is a substituted or unsubstituted “aryl”, a substituted or unsubstituted “heteroaryl”, a substituted or unsubstituted “Diarylamino”, substituted or unsubstituted “diheteroarylamino”, substituted or unsubstituted “arylheteroarylamino”, substituted or unsubstituted “diarylboryl (two aryls are bonded via a single bond or a linking group Optionally substituted)", substituted or unsubstituted "alkyl", substituted or unsubstituted "alkoxy", or substituted or unsubstituted "aryloxy", but the first As a substituent of "aryl" or "heteroaryl", "diarylamino" aryl, "diheteroarylamino" heteroaryl, "arylheteroarylamino" aryl and heteroaryl, "diarylboryl" aryl, Examples of the aryl of "aryloxy" include the monovalent group of "aryl ring" or "heteroaryl ring" described above.

The "alkyl" as the first substituent may be linear or branched, and examples thereof include linear alkyl having 1 to 24 carbons and branched alkyl having 3 to 24 carbons. Alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons) is preferable, alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons) is more preferable, alkyl having 1 to 6 carbons. (C3-C6 branched-chain alkyl) is more preferable, and C1-C4 alkyl (C3-C4 branched-chain alkyl) is particularly preferable.

Specific alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methyl. Pentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, 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.

The "alkoxy" as the first substituent includes, for example, straight-chain C1-24 or branched-chain C3-24 alkoxy. C1-C18 alkoxy (C3-C18 branched chain alkoxy) is preferable, C1-C12 alkoxy (C3-C12 branched chain alkoxy) is more preferable, and C1-C6. Is more preferable (C3-6 branched-chain alkoxy), and C1-C4 alkoxy (C3-4 branched-chain alkoxy) is particularly preferable.

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

Further, as the “aryl” in the “diarylboryl” of the first substituent, the above description of aryl can be cited. In addition, the two aryls may be bonded via a single bond or a linking group (for example, >C(-R) ₂ , >O, >S or >NR). Here, R in >C(-R) ₂ and >N-R is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy (the above, the first substituent), and the first The substituent may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl (above, the second substituent), and specific examples of these groups include the above-mentioned aryl and hetero as the first substituent. Reference may be made to aryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy.

The first substituent is a substituted or unsubstituted “aryl”, a substituted or unsubstituted “heteroaryl”, a substituted or unsubstituted “diarylamino”, a substituted or unsubstituted “diheteroarylamino”, a substituted Or an unsubstituted “arylheteroarylamino”, a substituted or unsubstituted “diarylboryl (two aryls may be bonded via a single bond or a linking group)”, a substituted or unsubstituted “alkyl”, Substituted or unsubstituted "alkoxy" or substituted or unsubstituted "aryloxy" means that at least one hydrogen in them is substituted with a second substituent, as described as substituted or unsubstituted. Good. Examples of the second substituent include aryl, heteroaryl and alkyl, and specific examples thereof include the monovalent group of the above-mentioned “aryl ring” or “heteroaryl ring” and the first substituent. Reference may be made to the description of "alkyl" as a group. Further, in the aryl or heteroaryl as the second substituent, at least one hydrogen in the aryl or heteroaryl is substituted with aryl such as phenyl (specific examples are the above groups) or alkyl such as methyl (specific examples are the above groups). Such a structure is also included in aryl or heteroaryl as the second substituent. As an example thereof, when the second substituent is a carbazolyl group, a carbazolyl group in which at least one hydrogen at the 9-position is substituted with an aryl such as phenyl or an alkyl such as methyl is also a hetero substituent as the second substituent. Included in aryl.

Aryl, heteroaryl, diarylamino aryl, diheteroarylamino heteroaryl, arylheteroarylamino aryl and heteroaryl, diarylboryl aryl, or aryloxy aryl in R ^{1 to} R ¹¹ of the general formula (2). Examples of the monovalent group include the "aryl ring" or "heteroaryl ring" described in the general formula (1). Moreover, as the alkyl or alkoxy in R ^{1 to} R ^11, the description of “alkyl” or “alkoxy” as the first substituent in the description of the general formula (1) can be referred to. Further, the same applies to aryl, heteroaryl or alkyl as a substituent for these groups. In addition, when adjacent groups of R ^{1 to} R ¹¹ are bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, a heteroaryl which is a substituent to these rings. , Diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be linked via a single bond or a linking group), alkyl, alkoxy or aryloxy, and further substituents The same applies to certain aryl, heteroaryl or alkyl.

Specifically, the emission wavelength can be adjusted by the steric hindrance property, electron donating property, and electron withdrawing property of the structure of the first substituent, and a group represented by the following structural formula is preferable, and more preferably , Methyl, t-butyl, phenyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, di-p-. Trilylamino, bis(p-(t-butyl)phenyl)amino, carbazolyl, 3,6-dimethylcarbazolyl, 3,6-di-t-butylcarbazolyl and phenoxy, and more preferably methyl, t. -Butyl, phenyl, o-tolyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis(p-(t-butyl)phenyl)amino, carbazolyl, 3,6 -Dimethylcarbazolyl and 3,6-di-t-butylcarbazolyl. From the viewpoint of ease of synthesis, it is preferable that the steric hindrance is large for selective synthesis, and specifically, t-butyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5 -Xylyl, 2,6-xylyl, 2,4,6-mesityl, di-p-tolylamino, bis(p-(t-butyl)phenyl)amino, 3,6-dimethylcarbazolyl and 3,6-di- -T-Butylcarbazolyl is preferred.

In the following structural formula, "Me" represents methyl and "tBu" represents t-butyl.

R in Si—R and Ge—R in Y ¹ of the general formula (1) is aryl or alkyl, and the aryl or alkyl includes the groups described above. Particularly, aryl having 6 to 10 carbon atoms (eg phenyl, naphthyl etc.) and alkyl having 1 to 4 carbon atoms (eg methyl, ethyl etc.) are preferable. This explanation is the same for Y ¹ in the general formula (2).

R of >N—R in X ¹ and X ² of the general formula (1) is aryl, heteroaryl, alkyl or cycloalkyl which may be substituted with the above-mentioned second substituent, and the aryl or heteroaryl. , At least one hydrogen in alkyl or cycloalkyl may be substituted, for example by alkyl. Examples of the aryl, heteroaryl and alkyl include the groups described above. Further, as the cycloalkyl, the following description can be cited. In particular, aryl having 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.), heteroaryl having 2 to 15 carbon atoms (eg, carbazolyl, etc.), and alkyl having 1 to 4 carbon atoms (eg, methyl, ethyl, etc.) are preferable. This explanation is the same for X ¹ and X ² in the general formula (2).

Is> C (-R) ₂ of R in X ¹ and X ² in the general formula (1), hydrogen, optionally substituted with a second substituent described above is also aryl or alkyl, at least one of aryl Hydrogen may be substituted, for example with alkyl. Examples of the aryl or alkyl include the groups described above. Particularly, aryl having 6 to 10 carbon atoms (eg phenyl, naphthyl etc.) and alkyl having 1 to 4 carbon atoms (eg methyl, ethyl etc.) are preferable. This explanation is the same for X ¹ and X ² in the general formula (2).

R of "-C(-R) _2- " which is the linking group in the general formula (1) is hydrogen or alkyl, and the alkyl includes the groups described above. Particularly, alkyl having 1 to 4 carbon atoms (eg, methyl, ethyl, etc.) is preferable. This explanation is the same for "-C(-R) _2- " which is the linking group in the general formula (2).

Further, the present invention provides a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (1), preferably a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (2). It is a multimer of compounds. The multimer is preferably a 2-6mer, more preferably a 2-3mer, and particularly preferably a dimer. The multimer may be in a form having a plurality of the unit structures in one compound, and for example, the unit structure may be a single bond, an alkylene group having 1 to 3 carbon atoms, a phenylene group, a linking group such as a naphthylene group. In addition to the form in which a plurality of unit structures are combined, any ring (A ring, B ring or C ring, a ring, b ring or c ring) included in the unit structure is bonded so as to be shared by a plurality of unit structures. Or may be a form in which any ring (A ring, B ring or C ring, a ring, b ring or c ring) contained in the above unit structure is bonded so as to be condensed with each other. Good.

Examples of such multimers include the following formula (2-4), formula (2-4-1), formula (2-4-2), formula (2-5-1) to formula (2-5). -4) or a multimeric compound represented by the formula (2-6). The multimeric compound represented by the following formula (2-4) is represented by a plurality of general formulas (2) so as to share the benzene ring which is the a ring, if explained in the general formula (2). It is a multimeric compound having a unit structure in one compound. In addition, the multimeric compound represented by the following formula (2-4-1) has two general formulas (2) by sharing the benzene ring which is the a ring, as described in the general formula (2). It is a multimeric compound having a unit structure represented by: Further, the multimeric compound represented by the following formula (2-4-2) has three general formulas (2) so as to share the benzene ring which is the a ring, if explained in the general formula (2). It is a multimeric compound having a unit structure represented by: In addition, the multimeric compound represented by the following formulas (2-5-1) to (2-5-4) is a benzene ring which is a b ring (or a c ring), as described in the general formula (2). Is a multimeric compound having a plurality of unit structures represented by the general formula (2) in one compound. In addition, the multimeric compound represented by the following formula (2-6) is, for example, a benzene ring which is a b ring (or a ring, c ring) of a certain unit structure and a certain unit, if explained in the general formula (2). It is a multimeric compound having a plurality of unit structures represented by the general formula (2) in one compound so as to be condensed with a benzene ring which is the b ring (or a ring or c ring) of the structure.

The multimeric compound is a multimeric compound represented by the formula (2-4), the formula (2-4-1) or the formula (2-4-2) and the formula (2-5-1) to the formula (2-5-2). -5-4) or a multimeric form represented by the formula (2-6) in combination with each other, and the formula (2-5-1) to the formula (2-5-). 4) may be a combination of a multimerized form represented by the formula (2-6) and a multimerized form represented by the formula (2-6), and may be represented by the formula (2-4) or the formula (2). -4-1) or the multimerized form represented by the formula (2-4-2) and the multimerized form represented by any of the formulas (2-5-1) to (2-5-4). It may be a multimer in which the multimeric form represented by the formula (2-6) is combined.

Further, all or part of the hydrogen in the chemical structures of the polycyclic aromatic compound represented by the general formula (1) or (2) and the polymer thereof may be deuterium, cyano or halogen. For example, in the formula (1), ring A, ring B, ring C (wherein ring A to C is an aryl ring or heteroaryl ring), a substituent to ring A to C, Y ¹ is Si—R or Ge—R. Hydrogen in R (=alkyl, aryl) when X ¹ and X ² is >N—R or >C(—R) ₂ is deuterium or cyano. Or, it may be substituted with halogen, and among them, an embodiment in which all or part of hydrogen atoms in aryl or heteroaryl is substituted with deuterium, cyano or halogen is mentioned. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine.

Further, the polycyclic aromatic compound and its multimer according to the present invention can be used as a material for an organic device. Examples of the organic device include an organic electroluminescent element, an organic field effect transistor, an organic thin film solar cell, and the like. In particular, in an organic electroluminescent device, as a dopant material of the light emitting layer, a compound in which Y ¹ is B, X ¹ and X ² are >N—R, Y ¹ is B, X ¹ is >O, X ² is>. A compound which is NR, and a compound in which Y ¹ is B, X ¹ and X ² are >O are preferable, and Y ¹ is B, X ¹ is >O and X ² is >N- as a host material of the light emitting layer. A compound which is R, a compound wherein Y ¹ is B, and X ¹ and X ² are >O are preferable, and a compound in which Y ¹ is B, X ¹ and X ² are >O, and Y ¹ is P as an electron transport material. Compounds in which ═O, X ¹ and X ² are >O are preferably used.

Further, at least one hydrogen in the chemical structures of the polycyclic aromatic compound represented by the general formula (1) or (2) and its multimer is cycloalkyl-substituted, and all hydrogen or a part of hydrogen is It may be a cycloalkyl group.

As another form of cycloalkyl substitution, a polycyclic aromatic compound represented by the general formula (1) or (2) and a multimer thereof are, for example, a cycloalkyl-substituted diarylamino group or a cycloalkyl-substituted Examples include those substituted with a carbazolyl group or a cycloalkyl-substituted benzocarbazolyl group. Examples of the "diarylamino group" include the groups described as the above "first substituent". Examples of the substitution form of cycloalkyl to the diarylamino group, carbazolyl group and benzocarbazolyl group include an example in which part or all of the hydrogens of the aryl ring or benzene ring in these groups are substituted with cycloalkyl.

Further, as a more specific example, R ² in the polycyclic aromatic compound represented by the general formula (2) and its multimer is a cycloalkyl-substituted diarylamino group or a cycloalkyl-substituted carbazolyl group. An example is given.

An example of this is a polycyclic aromatic compound represented by the following general formula (2-A), or a multimer of polycyclic aromatic compounds having a plurality of structures represented by the following general formula (2-A). .. Cy is a cycloalkyl group, and n is independently an integer of 1 to 5 (preferably 1), and the definition of each symbol in the structural formula is the same as the definition of each symbol in the general formula (2).

Further, specific examples of the cycloalkyl-substituted polycyclic aromatic compound of the present invention and its multimer include at least one hydrogen atom in one or more aromatic rings in the compound, which is one or more. The compound substituted by the cycloalkyl group is mentioned, for example, the compound substituted by 1-2 cycloalkyl groups is mentioned.

Specifically, compounds represented by the following formulas (1-1-Cy) to (1-4401-Cy) can be mentioned. N in the following formula is independently 0 to 2 (however, not all n are 0), preferably 1. In the structural formulas below, "Cy" represents a cycloalkyl group, "OPh" represents a phenoxy group, and "Me" represents a methyl group.

As cycloalkyl, cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, Examples thereof include cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, cycloalkyl having 5 carbon atoms, and the like.

Specific examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (especially methyl)-substituted products thereof 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 can be mentioned.

More specific examples of the cycloalkyl-substituted polycyclic aromatic compound of the present invention include compounds represented by the following structural formulas. In the structural formulas below, “D” represents deuterium, “Me” represents a methyl group, “tBu” represents a t-butyl group, and “Ph” represents a phenyl group.

The polycyclic aromatic compound represented by the general formula (1) and the multimer thereof according to the present invention are polymer compounds obtained by polymerizing a reactive compound in which a reactive substituent is substituted as a monomer. The monomer for obtaining a molecular compound has a polymerizable substituent), or a polymer crosslinked product obtained by further crosslinking the polymer compound (the polymer compound for obtaining the polymer crosslinked product is a crosslinkable substituent). Or a pendant polymer compound obtained by reacting a main chain polymer with the reactive compound (the reactive compound for obtaining the pendant polymer compound has a reactive substituent), Alternatively, as a pendant polymer cross-linked product obtained by further cross-linking the pendant polymer compound (the pendant polymer compound for obtaining the pendant polymer cross-linking product has a cross-linkable substituent), the organic device is also used. It can be used as a material, for example, a material for an organic electroluminescence device, a material for an organic field effect transistor or a material for an organic thin film solar cell.

Examples of the reactive substituent (including the polymerizable substituent, the crosslinkable substituent, and the reactive substituent for obtaining the pendant type polymer, hereinafter also simply referred to as “reactive substituent”) A substituent capable of polymerizing the above polycyclic aromatic compound or a multimer thereof, a substituent capable of further crosslinking the polymer compound thus obtained, and a substituent capable of pendant reaction with the main chain polymer The substituent 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 a bonding position.

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

Details of the use of such a polymer compound, a polymer crosslinked body, a pendant polymer compound and a pendant polymer crosslinked body (hereinafter, also simply referred to as “polymer compound and polymer crosslinked body”) will be described later.

2. Method for producing cycloalkyl-substituted polycyclic aromatic compound and multimer thereof The polycyclic aromatic compound represented by the general formula (1) or (2) and its multimer are basically prepared by a ring) and the B ring (b ring) and the C ring (c ring) are bonded with a bonding group (a group containing X ¹ and X ² ) to produce an intermediate (first reaction), and thereafter, The final product can be produced by linking A ring (a ring), B ring (b ring) and C ring (c ring) with a bonding group (group containing Y ¹ ) (second reaction). In the first reaction, for example, a general reaction such as a nucleophilic substitution reaction and an Ullmann reaction can be used in the case of an etherification reaction, and a general reaction such as a Buchwald-Hartwig reaction can be used in the case of an amination reaction. In the second reaction, a tandem hetero Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, the same applies below) can be used. Further, at any of these reaction steps, by using a cycloalkyl-substituted starting material or by adding a step of introducing a cycloalkyl group, a compound of the present invention in which a desired position is cycloalkyl-substituted is obtained. It can be manufactured.

The second reaction is a reaction for introducing Y ¹ which bonds the A ring (a ring), the B ring (b ring) and the C ring (c ring), as shown in the following schemes (1) and (2). As an example, the case where Y ¹ is a boron atom and X ¹ and X ² are oxygen atoms is shown below. First, the hydrogen atom between X ¹ and X ² is orthometallated with n-butyllithium, sec-butyllithium, t-butyllithium, or the like. Then, after adding boron trichloride, boron tribromide or the like to carry out a lithium-boron metal exchange, and then adding a Bronsted base such as N,N-diisopropylethylamine to cause a tandem Bora Friedel-Crafts reaction, You can get things. In the second reaction, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction. In addition, in the following schemes (1) and (2), and further in the subsequent schemes (3) to (28), the definitions of the symbols in the respective structural formulas are the same as the above-mentioned definitions.

The above schemes (1) and (2) mainly show the method for producing the polycyclic aromatic compound represented by the general formulas (1) and (2). It can be produced by using an intermediate having an A ring (a ring), a B ring (b ring) and a C ring (c ring). Details will be described in the following schemes (3) to (5). In this case, the target product can be obtained by doubling the amount of the reagent such as butyllithium used to triple the amount.

In the above scheme, lithium was introduced at a desired position by orthometalation, but a bromine atom or the like was introduced at a position where lithium was desired to be introduced as shown in the following schemes (6) and (7), and halogen-metal exchange was also performed. Lithium can be introduced at a desired position.

In addition, regarding the method for producing a multimer described in scheme (3), a halogen such as a bromine atom or a chlorine atom is introduced at a position where lithium is to be introduced as in the above schemes (6) and (7), and a halogen-metal Lithium can also be introduced into a desired position by exchange (the following schemes (8), (9) and (10)).

According to this method, the desired product can be synthesized even in the case where orthometalation cannot be performed due to the influence of the substituent, which is useful.

By appropriately selecting the above-mentioned synthesis method and appropriately selecting the starting materials to be used, cycloalkyl substitution is carried out at a desired position, a substituent is present at a desired position, and Y ¹ is a boron atom, X ¹ and X ² are A polycyclic aromatic compound which is an oxygen atom and a multimer thereof can be synthesized.

Next, as an example, the case where Y ¹ is a boron atom and X ¹ and X ² are nitrogen atoms is shown in the following schemes (11) and (12). Similarly to the case where X ¹ and X ² are oxygen atoms, first, the hydrogen atom between X ¹ and X ² is orthometallated with n-butyllithium or the like. Then, after adding boron tribromide or the like to perform lithium-boron metal exchange and then adding a Bronsted base such as N,N-diisopropylethylamine, a tandem-Bora-Friedel-Crafts reaction is performed to obtain the desired product. You can Here, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction. Further, at any of these reaction steps, by using a cycloalkyl-substituted starting material or by adding a step of introducing a cycloalkyl group, a compound of the present invention in which a desired position is cycloalkyl-substituted is obtained. It can be manufactured.

Further, regarding a multimer in which Y ¹ is a boron atom and X ¹ and X ² are nitrogen atoms, halogens such as a bromine atom and a chlorine atom are introduced at a position where lithium is to be introduced as in the above schemes (6) and (7). And lithium can be introduced into a desired position by halogen-metal exchange (the following schemes (13), (14) and (15)).

Next, as an example, the case where Y ¹ is a phosphorus sulfide, phosphorus oxide or phosphorus atom and X ¹ and X ² are oxygen atoms is shown in the following schemes (16) to (19). As before, first, the hydrogen atom between X ¹ and X ² is orthometallated with n-butyllithium or the like. Then, phosphorus trichloride and sulfur are added in this order, and finally a Lewis acid such as aluminum trichloride and a Bronsted base such as N,N-diisopropylethylamine are added to cause a tandem phospha Friedel-Crafts reaction, and Y ¹ is phosphorus. A compound that is a sulfide can be obtained. The obtained Rinsurufido compound Y ¹ is able to obtain the compound is a phosphorus oxide by treatment with at m- chloroperbenzoic acid (m-CPBA), Y ¹ by treatment with triethyl phosphine phosphorus It is possible to obtain compounds which are atoms. Further, at any of these reaction steps, by using a cycloalkyl-substituted starting material or by adding a step of introducing a cycloalkyl group, a compound of the present invention in which a desired position is cycloalkyl-substituted is obtained. It can be manufactured.

Further, regarding a multimer when Y ¹ is a phosphorus sulfide and X ¹ and X ² are oxygen atoms, a halogen such as a bromine atom or a chlorine atom is introduced at the position where lithium is to be introduced as in the above schemes (6) and (7). And lithium can be introduced into a desired position by halogen-metal exchange (the following schemes (20), (21) and (22)). Further, a multimer produced in the case where Y ¹ is a phosphorus sulfide and X ¹ and X ² are oxygen atoms can be prepared as described in schemes (18) and (19) above using m-chloroperbenzoic acid ( A compound in which Y ¹ is a phosphorus oxide can be obtained by treating with m-CPBA), and a compound in which Y ¹ is a phosphorus atom can be obtained by treating with triethylphosphine.

Here, an example in which Y ¹ is B, P, P=O or P=S and X ¹ and X ² are O or NR is described, but by appropriately changing the raw material, Y ¹ is A compound which is Al, Ga, As, Si-R or Ge-R, or in which X ¹ and X ² are S can also be synthesized.

Specific examples of the solvent used in the above reaction are t-butylbenzene and xylene.

Further, in the general formula (2), adjacent groups among the substituents R ^{1 to} R ¹¹ of the a ring, b ring and c ring are bonded to each other to form an aryl ring or heteroaryl together with the a ring, b ring or c ring. It may form a ring, and at least one hydrogen in the formed ring may be substituted with aryl or heteroaryl. Therefore, the polycyclic aromatic compound represented by the general formula (2) may be represented by the formula (2- As shown in 1) and the formula (2-2), the ring structure constituting the compound changes. These compounds can be synthesized by applying the synthetic methods shown in the above schemes (1) to (19) to the intermediates shown in the following schemes (23) and (24). Further, at any of these reaction steps, by using a cycloalkyl-substituted raw material or by adding a step of introducing a cycloalkyl group, a compound of the present invention in which a desired position is cycloalkyl-substituted is obtained. It can be manufactured.

The A′ ring, the B′ ring and the C′ ring in the above formulas (2-1) and (2-2) are bonded to adjacent groups of the substituents R ^{1 to} R ¹¹ to form a, respectively. An aryl ring or heteroaryl ring formed together with the ring, b ring and c ring is shown (also referred to as a condensed ring formed by condensing another ring structure on the a ring, b ring or c ring). Although not shown in the formula, there are some compounds in which all of ring a, ring b and ring c are changed to ring A′, ring B′ and ring C′.

In addition, in the general formula (2), “R of >N—R and/or R of the above >C(—R) ₂ is —O—, —S—, —C(—R) ₂ — or a single bond. “A ring, b ring, and/or c ring is bound” means that X ¹ or X ² is a condensed ring B′ represented by the formula (2-3-1) of the following scheme (25). And a compound having a ring structure incorporated into the condensed ring C′, or X ¹ and X ² represented by the formula (2-3-2) or the formula (2-3-3) incorporated into the condensed ring A′. It can be represented by a compound having a closed ring structure. These compounds can be synthesized by applying the synthetic method shown in the above schemes (1) to (19) to the intermediate shown in the following scheme (25). Further, at any of these reaction steps, by using a cycloalkyl-substituted starting material or by adding a step of introducing a cycloalkyl group, a compound of the present invention in which a desired position is cycloalkyl-substituted is obtained. It can be manufactured.

In addition, in the synthetic methods of the above schemes (1) to (17) and (20) to (25), before adding boron trichloride, boron tribromide or the like, a hydrogen atom between X ¹ and X ² (or An example of tandem hetero Friedel-Crafts reaction by orthometallizing (halogen atom) with butyllithium was shown, but boron trichloride and tribromide were obtained without orthometallation using butyllithium. The reaction can be advanced by adding boron or the like.

When Y ¹ is phosphorus, as shown in the following schemes (26) and (27), the hydrogen atom between X ¹ and X ² (O in the following formula) is n-butyllithium, sec- Tandem phospha Friedel Crafts is formed by orthometallation with butyllithium or t-butyllithium, then bisdiethylaminochlorophosphine is added, lithium-phosphorus metal exchange is performed, and then a Lewis acid such as aluminum trichloride is added. The reaction product can be obtained by the reaction. This reaction method is also described in WO 2010/104047 (for example, page 27). Further, at any of these reaction steps, by using a cycloalkyl-substituted starting material or by adding a step of introducing a cycloalkyl group, a compound of the present invention in which a desired position is cycloalkyl-substituted is obtained. It can be manufactured.

In addition, also in the above schemes (26) and (27), a multimeric compound is synthesized by using an orthometallating reagent such as butyllithium in a molar amount of 2 times or 3 times the molar amount of the intermediate 1. can do. In addition, a halogen such as a bromine atom or a chlorine atom is previously introduced into a position where a metal such as lithium is desired to be introduced, and the metal can be introduced into a desired position by performing halogen-metal exchange.

In addition, for the polycyclic aromatic compound represented by the general formula (2-A), a cycloalkyl-substituted intermediate is synthesized and cyclized as shown in the following scheme (28) to obtain a desired compound. A polycyclic aromatic compound whose position is substituted with a cycloalkyl group can be synthesized. In the scheme (28), X represents halogen or hydrogen, and the definitions of other symbols are the same as the definitions of the symbols in the general formula (2).

The intermediate before cyclization in scheme (28) can also be synthesized by the method shown in scheme (1) or 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 such as a nucleophilic substitution reaction and an Ullmann reaction. In these reactions, a commercially available product may be used as the raw material to be the cycloalkyl-substituted precursor.

The compound of general formula (2-A) having a cycloalkyl-substituted diphenylamino group can also be synthesized, for example, by the following method. That is, after introducing a cycloalkyl-substituted diphenylamino group by an amination reaction such as a Buchwald-Hartwig reaction between a cycloalkyl-substituted bromobenzene and a trihalogenated aniline, X ¹ and X ² are NR In an amination reaction such as Buchwald-Hartwig reaction, when X ¹ and X ² are O, they are derivatized to an intermediate (M-3) by etherification with phenol, and then, for example, butyl. Tandem Bora Friedel by reacting a metallizing reagent such as lithium to transmetallate, reacting with a boron halide such as boron tribromide, and then reacting with a Bronsted base such as diethylisopropylamine. The compound of general formula (2-A) can be synthesized by the Krafts reaction. These reactions can be applied to other cycloalkyl-substituted compounds.

The orthometalation reagents used in the above schemes (1) to (28) include alkyllithium such as methyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium, lithium diisopropylamide, lithium tetramethyl. Organic alkali compounds such as piperidide, lithium hexamethyldisilazide, potassium hexamethyldisilazide and the like can be mentioned.

As the metal exchange reagent metal -Y ¹ used in the above Scheme (1) to (28), a three-fluoride ^{Y 1,} trichloride of ^{Y 1,} tribromide of ^{Y 1,} triiodide of ^{Y 1} halides of ^{Y 1} such as halide, CIPN _{(NEt 2)} 2 amination halide ^{Y 1,} such as, alkoxides of ^{Y 1,} an aryloxy compound of ^{Y 1} are mentioned.

The Bronsted bases used in the above schemes (1) to (28) include N,N-diisopropylethylamine, triethylamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6. - pentamethylpiperidine, N, N-dimethylaniline, N, N-dimethyl toluidine, 2,6-lutidine, sodium tetraphenylborate, potassium tetraphenyl borate, triphenyl borane, tetraphenyl _silane, Ar 4 BNA, Ar ₄ BK, Ar ₃ B, Ar ₄ Si (Ar is aryl such as phenyl) and the like.

Examples of the Lewis acid used in the above schemes (1) to (28) include AlCl ₃ , AlBr ₃ , AlF ₃ , BF ₃ .OEt ₂ , BCl ₃ , BBr ₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , InBr ₃ , and InBr ₃ . _{In (OTf) 3, SnCl 4} , SnBr 4, AgOTf, ScCl 3, Sc (OTf) 3, ZnCl 2, ZnBr 2, Zn (OTf) 2, MgCl 2, MgBr 2, Mg (OTf) 2, LiOTf, NaOTf , KOTf, Me ₃ SiOTf, Cu(OTf) ₂ , CuCl ₂ , YCl ₃ , Y(OTf) ₃ , TiCl ₄ , TiBr ₄ , ZrCl ₄ , ZrBr ₄ , FeCl ₃ , FeBr ₃ , CoCl ₃ , CoBr ₃ and CoBr. Can be mentioned.

In the above schemes (1) to (28), a Bronsted base or a Lewis acid may be used to promote the tandem hetero Friedel-Crafts reaction. However, the three fluoride Y ^1, trichloride of Y ^1, tribromide of Y ^1, in the case of using a halide of Y ¹ such as triiodide of Y ^1, with the progress of electrophilic aromatic substitution Since hydrogen, hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, and other acids are produced, it is effective to use a Bronsted base that captures the acid. On the other hand, amination halides Y ^1, in the case of using alkoxides of Y ^1, with the progress of the aromatic electrophilic substitution reaction, an amine, for the alcohol to produce, often use Bronsted base Although it is not necessary, the use of a Lewis acid that promotes the elimination is effective because the elimination ability of amino groups and alkoxy groups is low.

Further, the polycyclic aromatic compound and multimers thereof of the present invention also include compounds in which at least a part of hydrogen atoms are substituted with deuterium or cyano, and compounds in which halogen such as fluorine or chlorine is substituted. However, such a compound or the like can be synthesized in the same manner as above by using a raw material in which a desired position is deuterated, cyanated, fluorinated or chlorinated.

3. Organic Device The cycloalkyl-substituted polycyclic aromatic compound according to the present invention can be used as a material for an organic device. Examples of the organic device include an organic electroluminescent element, an organic field effect transistor, an organic thin film solar cell, and the like.

3-1. Organic Electroluminescent Device Hereinafter, the organic EL device according to this embodiment will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an organic EL element according to this embodiment.

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

In the organic EL element 100, the manufacturing order is reversed, and 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 107. On the electron-transporting layer 106, the light-emitting layer 105 on the electron-transporting layer 106, the hole-transporting layer 104 on the light-emitting layer 105, and the hole-transporting layer 104. The hole injection layer 103 provided in the hole injection layer 103 and the anode 102 provided on the hole injection layer 103 may be provided.

Not all of the above layers are necessary, but the minimum constitutional unit is constituted by 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 layer are provided. The layer 107 is an optional layer. Each of the above layers may be composed of a single layer or plural layers.

In addition to the above-mentioned "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode" configuration mode, the layer configuration of the organic EL device includes " "Substrate/Anode/Hole transport layer/Light emitting layer/Electron transport layer/Electron injection layer/Cathode", "Substrate/Anode/Hole injection layer/Light emitting layer/Electron transport layer/Electron injection layer/Cathode", "Substrate/ Anode/hole injection layer/hole transport layer/light emitting layer/electron injection layer/cathode”, “substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode”, “substrate/ "Anode/light emitting layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole transport layer/light emitting layer/electron injection layer/cathode", "substrate/anode/hole transport layer/light emitting layer/electron" "Transport layer/cathode", "substrate/anode/hole injection layer/light emitting layer/electron injection layer/cathode", "substrate/anode/hole injection layer/light emitting layer/electron transport layer/cathode", "substrate/anode" The constitutional modes of "/light emitting layer/electron transport layer/cathode" and "substrate/anode/light emitting layer/electron injection layer/cathode" may be used.

<Substrate in organic electroluminescent device>
The substrate 101 is a support for the organic EL 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 according to 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, glass plates and plates made of transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable. As the glass substrate, soda lime glass, non-alkali glass, or the like is used, and since the thickness is sufficient as long as the mechanical strength is maintained, it may be 0.2 mm or more, for example. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. Regarding the material of the glass, non-alkali glass is preferable because it is preferable that the amount of ions eluted from the glass is small, but soda lime glass coated 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 improve 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 surface, and a plate, film or sheet made of a synthetic resin having particularly low gas barrier property is used as the substrate 101. When used, it is preferable to provide a gas barrier film.

<Anode in organic electroluminescent device>
The anode 102 plays a role of injecting holes into the light emitting layer 105. When the hole injection layer 103 and/or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 via these. ..

Examples of the material forming the anode 102 include inorganic compounds and organic compounds. 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 oxide). (IZO)), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass and the like. Examples of the organic compound include polythiophenes such as poly(3-methylthiophene), 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 EL element.

The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but is preferably low resistance 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 low resistance products with /□. 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 electroluminescence device>
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 through the hole injection layer 103 to the light emitting layer 105. The hole injecting layer 103 and the hole transporting layer 104 are respectively formed by laminating and mixing one or more kinds of hole injecting/transporting materials, or formed by a mixture of the hole injecting/transporting material and a polymer binder. To be done. Further, an inorganic salt such as iron (III) chloride may be added to the hole injecting/transporting material to form the layer.

As a hole injecting/transporting substance, it is necessary to efficiently inject/transport holes from the positive electrode between the electrodes to which an electric field is applied. The hole injection efficiency is high, and the injected holes are efficiently transported. It is desirable to do. Therefore, it is preferable that the ionization potential is small, the hole mobility is large, the stability is excellent, and the impurities serving as traps are less likely to be generated during manufacturing and use.

The material for forming the hole injection layer 103 and the hole transport layer 104 is a compound that is conventionally used as a hole charge transport material in photoconductive materials, a p-type semiconductor, and a hole injection layer of an organic EL device. Any compound can be selected and used from the known compounds used for the hole transport layer. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), bis(N-arylcarbazole), biscarbazole derivatives such as bis(N-alkylcarbazole), triarylamine derivatives (aromatic tertiary Polymers having amino as the main chain or side chain, 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) Amino) triphenylamine derivatives such as triphenylamine, starburst amine derivatives, etc., stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives. , Quinoxaline derivatives (eg, 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilane, etc. In the polymer system, a polycarbonate having a side chain of the above monomer, a styrene derivative, polyvinylcarbazole, polysilane, or the like is preferable, but a thin film necessary for manufacturing a light emitting element is formed and holes can be injected from an anode, Further, it is not particularly limited as long as it is a compound capable of transporting holes.

It is also known that the conductivity of an organic semiconductor is strongly affected by its doping. Such an organic semiconductor matrix material 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 literature “M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(22), 3202-3204 (1998)” and the literature “J. Blochwitz, M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(6), 729-731 (1998)). These generate so-called holes by an electron transfer process in an electron donating base material (hole transport material). Depending on the number and mobility of holes, the conductivity of the base material changes considerably. Known matrix materials having hole-transporting properties are, for example, benzidine derivatives (TPD, etc.) or starburst amine derivatives (TDATA, etc.), or specific metal phthalocyanines (especially zinc phthalocyanine (ZnPc), etc.). JP 2005-167175).

The material for hole injection layer and the material for hole transport layer described above are a polymer compound obtained by polymerizing a reactive compound having a reactive substituent substituted therein as a monomer, or a polymer cross-linked product thereof, or A pendant polymer compound obtained by reacting the main chain polymer with the reactive compound or a pendant polymer cross-linked product thereof can also be used as the material for the hole layer. As the reactive substituent in this case, the description on the polycyclic aromatic compound represented by the formula (1) can be cited.
Details of applications of such polymer compounds and polymer cross-linked products will be described later.

<Light-emitting layer in organic electroluminescent device>
The light emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between the electrodes to which an electric field is applied. As a material for forming the light emitting layer 105, any compound (light emitting compound) that is excited by recombination of holes and electrons to emit light can be used, and a stable thin film shape can be formed, and a solid state can be formed. It is preferable that the compound has a strong emission (fluorescence) efficiency. In the present invention, a host material and, for example, a polycyclic aromatic compound represented by the above general formula (1) as a dopant material 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, each of which is formed of a light emitting layer material (host material, dopant material). Each of the host material and the dopant material may be one kind or a combination of a plurality of kinds. The dopant material may be contained in the entire host material, partially contained, or either. The doping method may be a co-evaporation method with a host material, but it may be mixed with the host material in advance and then evaporated at the same time.

The amount of the host material used varies depending on the type of the host material, and may be determined according to the characteristics of the host material. The amount of the host material used is preferably 50 to 99.999% by weight, more preferably 80 to 99.95% by weight, and further preferably 90 to 99.9% by weight, based on the total weight of the light emitting layer material. Is.

The amount of the dopant material used depends 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, further preferably 0.1 to 10% by weight, based on the entire light emitting layer material. is there. The above range is preferable, for example, in that the concentration quenching phenomenon can be prevented.

As the host material, a condensed ring derivative such as anthracene, pyrene, dibenzochrysene or fluorene, which has been known as a light emitter, a bisstyryl derivative such as a bisstyrylanthracene derivative or a distyrylbenzene derivative, a tetraphenylbutadiene derivative, a cyclopentadiene derivative, etc. And so on. In particular, anthracene compounds, fluorene compounds or dibenzochrysene compounds are preferable.

<Anthracene compound>
The anthracene-based compound as the host is, for example, a compound represented by the following general formula (3).

In formula (3),
X and Ar ⁴ are each independently hydrogen, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted diarylamino, optionally substituted diheteroarylamino, Optionally substituted arylheteroarylamino, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted Aryloxy, optionally substituted arylthio or optionally substituted silyl, wherein all X and Ar ⁴ are not hydrogen at the same time,
At least one hydrogen in the compound represented by formula (3) may be substituted with halogen, cyano, deuterium or optionally substituted heteroaryl.

Further, a multimer (preferably a dimer) may be formed with the structure represented by the formula (3) as a unit structure. In this case, for example, a form in which the unit structures represented by the formula (3) are bonded to each other via X, and as the X, a single bond, arylene (phenylene, biphenylene, naphthylene, etc.) and heteroarylene (pyridine ring, Groups having a divalent bond value such as a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring and a phenyl-substituted carbazole ring).

The details of the above aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio or silyl will be described in the section of the preferred embodiments below. Further, examples of the substituent to these include aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio or silyl. Details will also be described in the section of preferable embodiments below.

Preferred embodiments of the anthracene compound will be described below. The definitions of the symbols in the following structure are the same as the above definitions.

In the general formula (3), X is independently a group represented by the formula (3-X1), the formula (3-X2) or the formula (3-X3), and the formula (3-X1) and the formula (3-X1) The group represented by (3-X2) or formula (3-X3) is bonded to the anthracene ring of formula (3) at *. Preferably, two X's are not a group represented by the formula (3-X3) at the same time. More preferably, two X's do not simultaneously form a group represented by formula (3-X2).

Further, a multimer (preferably a dimer) may be formed with the structure represented by the formula (3) as a unit structure. In this case, for example, a form in which the unit structures represented by the formula (3) are bonded to each other via X, and as the X, a single bond, arylene (phenylene, biphenylene, naphthylene, etc.) and heteroarylene (pyridine ring, Groups having a divalent bond value such as a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring and a phenyl-substituted carbazole ring).

The naphthylene moiety in formula (3-X1) and formula (3-X2) may be condensed with one benzene ring. The structure condensed in this way is as follows.

Ar ¹ and Ar ² are each independently hydrogen, phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or the above formula (A). A group represented (including a carbazolyl group, a benzocarbazolyl group, and a phenyl-substituted carbazolyl group). In addition, when Ar ¹ or Ar ² is a group represented by the formula (A), the group represented by the formula (A) is represented by * in the formula (3-X1) or the formula (3-X2). Combines with naphthalene ring.

Ar ³ is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (carbazolyl group, benzocarbyl group. Azolyl group and phenyl-substituted carbazolyl group are also included). When Ar ³ is a group represented by formula (A), the group represented by formula (A) is bonded to a single bond represented by a straight line in formula (3-X3) in *. .. That is, the anthracene ring of formula (3) and the group of formula (A) are directly bonded.

Further, Ar ³ may have a substituent, and at least one hydrogen in Ar ³ is further alkyl having 1 to 4 carbons, cycloalkyl having 5 to 10 carbons, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl. , Fluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (including a carbazolyl group and a phenyl-substituted carbazolyl group). Incidentally, when the substituent group of the Ar ³ is a group represented by the formula (A), a group represented by the formula (A) binds to Ar ³ in the formula (3-X3) in the *.

Ar ^{4 s} are each independently substituted with hydrogen, phenyl, biphenylyl, terphenylyl, naphthyl, or alkyl having 1 to 4 carbons (methyl, ethyl, t-butyl, etc.) and/or cycloalkyl having 5 to 10 carbons. This is Cyril.

Examples of the alkyl having 1 to 4 carbon atoms which substitutes for silyl include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, cyclobutyl, etc., and three hydrogens in silyl are each independently , Substituted with these alkyls.

Specific examples of "silyl substituted with alkyl having 1 to 4 carbon atoms" include trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, trisec-butylsilyl, tri-t-butylsilyl, ethyl. Dimethylsilyl, propyldimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyl Diethylsilyl, t-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropylsilyl, methyldii-propylsilyl, ethyldii-propylsilyl, Examples include butyldi i-propylsilyl, sec-butyldi i-propylsilyl, t-butyldi i-propylsilyl and the like.

Cycloalkyl having 5 to 10 carbon atoms which is substituted with silyl includes cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornenyl, 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, decahydronaphthalenyl, decahydro Azulenyl and the like, and three hydrogens in silyl are each independently substituted with these cycloalkyls.

Specific examples of "silyl substituted with cycloalkyl having 5 to 10 carbon atoms" include tricyclopentylsilyl, tricyclohexylsilyl and the like.

Examples of the substituted silyl include dialkylcycloalkylsilyl substituted with two alkyls and one cycloalkyl and alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyls. Substituted alkyl and cycloalkyl Specific examples of the above include the groups described above.

Further, hydrogen in the chemical structure of the anthracene compound represented by the general formula (3) may be substituted with the group represented by the above formula (A). When the group represented by the formula (A) is substituted, the group represented by the formula (A) substitutes at least one hydrogen in the compound represented by the formula (3) in *.

The group represented by the formula (A) is one of the substituents that the anthracene compound represented by the formula (3) may have.

In the formula (A), Y is —O—, —S— or >N—R ²⁹ , and R ^{21 to} R ²⁸ are each independently hydrogen, optionally substituted alkyl, or optionally substituted. Good cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio, trialkylsilyl, Tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, optionally substituted amino, halogen, hydroxy or cyano, wherein adjacent groups of R ^{21 to} R ²⁸ are bonded to each other to form a hydrocarbon ring. , An aryl ring or a heteroaryl ring may be formed, and R ²⁹ is hydrogen or an optionally substituted aryl.

The “alkyl” of the “optionally substituted alkyl” for R ^{21 to} R ²⁸ may be linear or branched, and is, for example, a linear alkyl having 1 to 24 carbons or a linear alkyl having 3 to 24 carbons. Branched chain alkyl is mentioned. Alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons) is preferable, alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons) is more preferable, alkyl having 1 to 6 carbons. (C3-C6 branched-chain alkyl) is more preferable, and C1-C4 alkyl (C3-C4 branched-chain alkyl) is particularly preferable.

Specific "alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -Propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, Examples thereof include n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicosyl.

The "cycloalkyl" of "optionally substituted cycloalkyl" for R ^{21 to} R ²⁸ is cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms. , Cycloalkyl having 3 to 14 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, cycloalkyl having 5 carbon atoms, and the like.

Specific examples of “cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (especially methyl)-substituted products thereof 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 can be mentioned.

Examples of the “aryl” of the “optionally substituted aryl” in R ^{21 to} R ²⁸ include aryl having 6 to 30 carbon atoms, aryl having 6 to 16 carbon atoms is preferable, and aryl having 6 to 12 carbon atoms is preferable. Is more preferable, and an aryl having 6 to 10 carbon atoms is particularly preferable.

Specific examples of "aryl" include phenyl which is a monocyclic system, biphenylyl which is a bicyclic system, naphthyl which is a condensed bicyclic system, and terphenylyl which is a tricyclic system (m-terphenylyl, o-terphenylyl, p-terphenylyl). , Fused tricyclic acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, fused tetracyclic triphenylenyl, pyrenyl, naphthacenyl, fused pentacyclic perylenyl, pentacenyl and the like.

Examples of the "heteroaryl" of "optionally substituted heteroaryl" for R ^{21 to} R ²⁸ include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and Heteroaryl having 2 to 20 carbon atoms is more preferable, heteroaryl having 2 to 15 carbon atoms is further preferable, and heteroaryl having 2 to 10 carbon atoms is particularly preferable. The heteroaryl includes, for example, a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring-constituting atom.

Specific examples of “heteroaryl” include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-. Indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathinyl, phenoxazinyl, phenothiazinyl, phenothiazinyl. Examples thereof include phenazinyl, indoridinyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzo[b]thienyl, dibenzothienyl, flazanyl, oxadiazolyl, thianthrenyl, naphthobenzofuranyl and naphthobenzothienyl.

Examples of the "alkoxy" of "optionally substituted alkoxy" in R ^{21 to} R ²⁸ include straight-chain C1-24 or branched-chain C3-24 alkoxy. C1-C18 alkoxy (C3-C18 branched chain alkoxy) is preferable, C1-C12 alkoxy (C3-C12 branched chain alkoxy) is more preferable, and C1-C6. Is more preferable (C3-6 branched-chain alkoxy), and C1-C4 alkoxy (C3-4 branched-chain alkoxy) is particularly preferable.

Specific "alkoxy" includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.

The "aryloxy" of "optionally substituted aryloxy" in R ^{21 to} R ²⁸ is a group in which hydrogen of an -OH group is substituted with aryl, and the aryl is the same as in R ^{21 to} R ²⁸ described above. The groups described as "aryl" can be cited.

The "arylthio" of the "optionally substituted arylthio" in R ^{21 to} R ²⁸ is a group in which hydrogen of the -SH group is substituted with aryl, and the aryl is the "aryl in R ^{21 to} R ²⁸ described above. The groups described as "can be cited.

Examples of the “trialkylsilyl” in R ^{21 to} R ²⁸ include a group in which three hydrogens in a silyl group are independently substituted with alkyl, and this alkyl is the same as the “alkyl” in R ^{21 to} R ²⁸ described above. The groups mentioned can be quoted. Preferable alkyl for substitution is alkyl having 1 to 4 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl and cyclobutyl.

Specific examples of “trialkylsilyl” include trimethylsilyl, triethylsilyl, tripropylsilyl, tri i-propylsilyl, tributylsilyl, trisec-butylsilyl, trit-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i-propyl. Dimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, t-butyldiethylsilyl, methyl Dipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropylsilyl, methyldi i-propylsilyl, ethyldi i-propylsilyl, butyldi i-propylsilyl, sec-butyldi i -Propylsilyl, t-butyldi i-propylsilyl and the like can be mentioned.

Examples of the "tricycloalkylsilyl" in R ^{21 to} R ²⁸ include a group in which three hydrogens in the silyl group are independently substituted with cycloalkyl, and the cycloalkyl is the above-mentioned "tricycloalkylsilyl" in R ^{21 to} R ²⁸ . The groups described as "cycloalkyl" can be cited. Preferred cycloalkyl to be substituted is cycloalkyl having 5 to 10 carbon atoms, specifically, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, 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, Examples include decahydronaphthalenyl and decahydroazulenyl.

Specific examples of “tricycloalkylsilyl” include tricyclopentylsilyl, tricyclohexylsilyl and the like.

Specific examples of the dialkylcycloalkylsilyl substituted with two alkyls and one cycloalkyl and the alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyl are selected from the above specific alkyls and cycloalkyls. An example is silyl in which the above group is substituted.

The “substituted amino” of “optionally substituted amino” in R ^{21 to} R ²⁸ includes, for example, an amino group in which two hydrogen atoms are substituted with aryl or heteroaryl. Amino in which two hydrogens are replaced by aryl is diaryl-substituted amino, amino in which two hydrogens are replaced by heteroaryl is diheteroaryl-substituted amino, and amino in which two hydrogens are replaced by aryl and heteroaryl Is an arylheteroaryl-substituted amino. As the aryl or heteroaryl, the groups described as "aryl" or "heteroaryl" in R ^{21 to} R ²⁸ described above can be cited.

Specific examples of "substituted amino" include diphenylamino, dinaphthylamino, phenylnaphthylamino, dipyridylamino, phenylpyridylamino, naphthylpyridylamino and the like.

Examples of the “halogen” for R ^{21 to} R ²⁸ include fluorine, chlorine, bromine and iodine.

Some of the groups described as R ^{21 to} R ²⁸ may be substituted as described above, and the substituent in this case includes alkyl, cycloalkyl, aryl or heteroaryl. As the alkyl, cycloalkyl, aryl or heteroaryl, the groups described as "alkyl", "cycloalkyl", "aryl" or "heteroaryl" in R ^{21 to} R ²⁸ described above can be referred to.

R ²⁹ in the "> N-R ^29" as Y is hydrogen or aryl which may be substituted, be cited a group described as the "aryl" in R ²¹ to R ²⁸ described above as the aryl As the substituent, the groups described as the substituents for R ^{21 to} R ²⁸ can be cited.

Adjacent groups of R ^{21 to} R ²⁸ may be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring. The case where no ring is formed is a group represented by the following formula (A-1), and the case where a ring is formed is, for example, a group represented by the following formula (A-2) to formula (A-14). To be Note that at least one hydrogen in the group represented by any of the formulas (A-1) to (A-14) is alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl, It may be substituted with tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, diaryl substituted amino, diheteroaryl substituted amino, arylheteroaryl substituted amino, halogen, hydroxy or cyano.

Examples of the ring formed by bonding adjacent groups to each other include a hydrocarbon ring such as a cyclohexane ring, and examples of the aryl ring and the heteroaryl ring include “aryl” and “heteroaryl” in R ^{21 to} R ²⁸ described above. And the ring structure described above in ".". These rings are formed so as to be condensed with one or two benzene rings in the above formula (A-1).

Examples of the group represented by the formula (A) include groups represented by any of the above formulas (A-1) to (A-14), and the above formulas (A-1) to (A). -5) and groups represented by any of the formulas (A-12) to (A-14) are preferable, and groups represented by any of the above formulas (A-1) to (A-4). Is more preferable, a group represented by any of the above formula (A-1), formula (A-3) and formula (A-4) is further preferable, and a group represented by the above formula (A-1) is Particularly preferred.

The group represented by the formula (A) includes a naphthalene ring in the formula (3-X1) or the formula (3-X2), a single bond in the formula (3-X3), and a formula in * in the formula (A). As described above, it is bonded to Ar ³ in (3-X3) and is replaced with at least one hydrogen in the compound represented by Formula (3). Alternatively, a form in which the naphthalene ring in formula (3-X2), the single bond in formula (3-X3) and/or Ar ^{3 in} formula (3-X3) are bonded is preferable.

In the structure of the group represented by the formula (A), a naphthalene ring in the formula (3-X1) or the formula (3-X2), a single bond in the formula (3-X3), a formula (3-X3). ), a position at which Ar ³ is bonded, and a position in the structure of the group represented by formula (A) to be replaced with at least one hydrogen in the compound represented by formula (3) are represented by formula (A). May be at any position in the structure of, for example, one of the two benzene rings in the structure of formula (A), or an adjacent group of R ^{21 to} R ^{28 in} the structure of formula (A). It may be bonded to any ring formed by being bonded to each other or at any position in R ²⁹ in “>N—R ²⁹ ”as Y in the structure of formula (A).

Examples of the group represented by the formula (A) include the following groups. Y and * in the formula have the same definitions as above.

Further, hydrogen in the chemical structure of the anthracene compound represented by the general formula (3) may be wholly or partially deuterium.

Specific examples of the anthracene-based compound include compounds represented by the following formulas (3-1) to (3-72). In the structural formulas below, “Me” represents a methyl group, “D” represents deuterium, and “tBu” represents a t-butyl group.

The anthracene compound represented by the formula (3) is a compound having a reactive group at a desired position of the anthracene skeleton and a compound having a reactive group in a partial structure such as X, Ar ⁴ and the structure of the formula (A). Can be produced by applying Suzuki coupling, Negishi coupling, and other known coupling reactions using as a starting material. Examples of the reactive group of these reactive compounds include halogen and boronic acid. As a specific production method, for example, the synthesis method in paragraphs [0089] to [0175] of WO 2014/141725 can be referred to.

<Fluorene compound>
The compound represented by the general formula (4) basically functions as a host.

In the above formula (4),
R ¹ to R ¹⁰ are each independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the fluorene skeleton in the above formula (4) through a linking group), diarylamino, dihetero. Arylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl,
Further, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ or R ⁹ and R ¹⁰ are independently bonded. To form a condensed ring or a spiro ring, and at least one hydrogen in the formed ring is aryl or heteroaryl (the heteroaryl may be bonded to the formed ring via a linking group). ), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, wherein at least one hydrogen is aryl, heteroaryl, alkyl or cycloalkyl. May be replaced with, and
At least one hydrogen in the compound represented by formula (4) may be substituted with halogen, cyano or deuterium.

For the details of each group in the definition of the above formula (4), the description on the polycyclic aromatic compound of the above formula (1) can be cited.

Examples of the alkenyl in R ¹ to R ¹⁰ include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and having 2 to 6 carbon atoms. Alkenyl is more preferable, and alkenyl having 2 to 4 carbon atoms is particularly preferable. Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, It is 3-hexenyl, 4-hexenyl, or 5-hexenyl.

In addition, as a specific example of the heteroaryl, any one of compounds represented by the following formula (4-Ar1), formula (4-Ar2), formula (4-Ar3), formula (4-Ar4) or formula (4-Ar5) is used. Monovalent groups represented by removing one hydrogen atom are also included.
In formula (4-Ar1) to formula (4-Ar5), Y ¹ is each independently O, S or N—R, R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen,
At least one hydrogen in the structures of the above formulas (4-Ar1) to (4-Ar5) may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl or butyl.

These heteroaryls may be bonded to the fluorene skeleton in the above formula (4) via a linking group. That is, not only may the fluorene skeleton in formula (4) and the heteroaryl be directly bonded, but they may be bonded to each other via a linking group. As the linking group, phenylene, biphenylene, naphthylene, anthracenylene, methylene, _{ethylene, -OCH 2 CH 2 -, -} CH 2 CH 2 O-, _or, -OCH 2 _CH 2 O- and the like.

In addition, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ^7, or R ⁷ and R ⁸ in the formula (4) are independently bonded to each other. And R ⁹ and R ¹⁰ may combine to form a spiro ring. The condensed ring formed by R ¹ to R ⁸ is a ring condensed with the benzene ring in formula (4), and is an aliphatic ring or an aromatic ring. An aromatic ring is preferred, and examples of the structure including the benzene ring in the formula (4) include a naphthalene ring and a phenanthrene ring. The spiro ring formed by R ⁹ and R ¹⁰ is a ring that spiro-bonds to the 5-membered ring in formula (4), and is an aliphatic ring or an aromatic ring. An aromatic ring is preferable, and a fluorene ring and the like can be mentioned.

The compound represented by the general formula (4) is preferably a compound represented by the following formula (4-1), formula (4-2) or formula (4-3). ), a compound in which a benzene ring formed by combining R ¹ and R ² is condensed, a compound in which a benzene ring formed by combining R ³ and R ⁴ in the general formula (4) is condensed, ) Is a compound in which none of R ¹ to R ⁸ is bound.

The definitions of R ¹ to R ¹⁰ in formula (4-1), formula (4-2) and formula (4-3) are the same as the corresponding R ¹ to R ¹⁰ in formula (4), and formula (4- The definitions of R ¹¹ to R ¹⁴ in 1) and formula (4-2) are also the same as R ¹ to R ¹⁰ in formula (4).

The compound represented by the general formula (4) is more preferably a compound represented by the following formula (4-1A), formula (4-2A) or formula (4-3A). -1), formula (4-1) or formula (4-3) is a compound in which R ⁹ and R ¹⁰ are bonded to each other to form a spiro-fluorene ring.

R ² to R ⁷ in formula (4-1A), formula (4-2A) and formula (4-3A) are defined in formula (4-1), formula (4-2) and formula (4-3). corresponding the same from ^{R 2} and ^{R 7, R} in the formula also defined formula (4-1) of the ^{R 14} from ^{R 11} in (4-1A) and (4-2A) and (4-2) ¹¹ To R ¹⁴ are the same.

Further, hydrogen in the compound represented by the formula (4) may be wholly or partially substituted with halogen, cyano or deuterium.

<Dibenzochrysene-based compound>
The dibenzochrysene compound as the host is, for example, a compound represented by the following general formula (5).

In the above formula (5),
R ¹ to R ¹⁶ are each independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the dibenzochrysene skeleton in the above formula (5) via a linking group), diarylamino, diaryl Heteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl,
In addition, adjacent groups of R ¹ to R ¹⁶ may be bonded to each other to form a condensed ring, and at least one hydrogen in the formed ring is aryl or heteroaryl (the heteroaryl is linked via a linking group). May be bonded to the formed ring), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, at least One hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, and
At least one hydrogen in the compound represented by formula (5) may be substituted with halogen, cyano or deuterium.

For the details of each group in the definition of the above formula (5), the description on the polycyclic aromatic compound of the above formula (1) can be cited.

Examples of the alkenyl in the definition of the above formula (5) include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and 2 to carbon atoms. Alkenyl having 6 carbon atoms is more preferable, and alkenyl having 2 to 4 carbon atoms is particularly preferable. Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, It is 3-hexenyl, 4-hexenyl, or 5-hexenyl.

In addition, as a specific example of the heteroaryl, any one of the compounds of the following formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) is used. Monovalent groups represented by removing one hydrogen atom are also included.
In formula (5-Ar1) to formula (5-Ar5), Y ¹ is each independently O, S or N—R, R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen,
At least one hydrogen in the structures of the above formulas (5-Ar1) to (5-Ar5) may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl or butyl.

These heteroaryls may be bonded to the dibenzochrysene skeleton in the above formula (5) via a linking group. That is, not only may the dibenzochrysene skeleton in the formula (5) and the above heteroaryl be directly bonded, but they may be bonded via a linking group between them. As the linking group, phenylene, biphenylene, naphthylene, anthracenylene, methylene, _{ethylene, -OCH 2 CH 2 -, -} CH 2 CH 2 O-, _or, -OCH 2 _CH 2 O- and the like.

In the compound represented by the general formula (5), R ¹ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹² , R ¹³ and R ¹⁶ are preferably hydrogen. In this case, R ² , R ³ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ in the formula (5) are each independently hydrogen, phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl. A monovalent group having a structure of the formula (5-Ar1), the formula (5-Ar2), the formula (5-Ar3), the formula (5-Ar4) or the formula (5-Ar5). valent group, phenylene, biphenylene, naphthylene, anthracenylene, methylene, _{ethylene, -OCH 2 CH 2 -, -} CH 2 CH 2 O-, _or via a -OCH 2 _CH 2 O-, the formula (5) (Which may be bonded to the dibenzochrysene skeleton in the above), methyl, ethyl, propyl, or butyl is preferable.

The compound represented by formula (5) is more preferably R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹² , R ¹³ , R ¹⁵ and R. ¹⁶ is hydrogen. In this case, at least one (preferably one or two, more preferably one) of R ³ , R ⁶ , R ¹¹ and R ¹⁴ in formula (5) is a single bond, phenylene, biphenylene, naphthylene, anthracenylene, methylene, _{ethylene, -OCH 2 CH 2 -, -} CH 2 CH 2 O-, _or, -OCH 2 _CH 2 O- was over, the formula (5-Ar @ 1), the formula (5-Ar2), wherein A monovalent group having the structure of (5-Ar3), formula (5-Ar4) or formula (5-Ar5),
Other than at least one (that is, other than the position where the monovalent group having the above structure is substituted) is hydrogen, phenyl, biphenylyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl, and at least one of these Hydrogen may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl.

Further, R ² , R ³ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ in the formula (5) are represented by the formula (5-Ar1) to the formula (5-Ar5). When a monovalent group having a structure is selected, at least one hydrogen in the structure may be bonded to any ^one of R ¹ to R ^{16 in} the formula (5) to form a single bond. ..

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

<Example of polymer host material>

In formula (SPH-1),
MU is each independently a divalent aromatic compound, EC is each independently a monovalent aromatic compound, two hydrogen atoms in MU are replaced with EC or MU, and k is an integer of 2 to 50,000. is there.

More specifically,
MU's are each independently arylene, heteroarylene, diarylenearylamino, diarylenearylboryl, oxaborin-diyl, azaborin-diyl,
EC is 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 to 50,000, more preferably 100 to 50,000.

At least one hydrogen in MU and EC in formula (SPH-1) may be substituted with alkyl having 1 to 24 carbons, cycloalkyl having 3 to 24 carbons, halogen or deuterium, and further Any —CH ₂ — in alkyl may be substituted with —O— or —Si(CH ₃ ) ₂ —, and —CH ₂ — directly linked to EC in formula (SPH-1) in the above alkyl. arbitrary -CH 2 except _- may be substituted arylene of 6 to 24 carbon atoms, arbitrary hydrogen in the alkyl may be substituted by fluorine.

Examples of 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, a MU binds to another MU or EC at *.

Further, examples of EC include a monovalent group represented by any of the following structures. In these, EC binds to MU at *.

From the viewpoint of solubility and coating film-forming property, the compound represented by the formula (SPH-1) has 10 to 100% of the total number (k) of MUs in the molecule have an alkyl group having 1 to 24 carbon atoms. More preferably, 30 to 100% of the total number (k) of MUs in the molecule has an alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms), and the total number of MU groups in the molecule ( It is further preferred that 50 to 100% of MUs of k) have alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). 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 (k) of MUs in the molecule have an alkyl group having 7 to 24 carbon atoms, and the total number (k) of MUs in the molecule (k). It is more preferable that 30 to 100% of MUs of () have alkyl having 7 to 24 carbon atoms (branched alkyl having 7 to 24 carbon atoms).

Details of applications of such polymer compounds and polymer cross-linked products will be described later.

<Electron 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 electrons injected from the cathode 108 or electrons injected from the cathode 108 via the electron injection layer 107 to the light emitting layer 105. The electron-transporting layer 106 and the electron-injecting layer 107 are each formed by laminating and mixing one or more electron-transporting/injecting materials, or a mixture of the electron-transporting/injecting material and the polymer binder.

The electron injecting/transporting layer is a layer in charge of injecting electrons from the cathode and further transporting the electrons, and has high electron injecting efficiency, and it is desirable to efficiently inject the injected electrons. For that purpose, it is preferable that the substance has a high electron affinity, a high electron mobility, an excellent stability, and an impurity that becomes a trap is less likely to be generated during production and use. However, when considering the transport balance of holes and electrons, the electron transporting ability is not so high when the role mainly capable of efficiently blocking the holes from the anode from flowing to the cathode side without recombining. Even if it is not high, it has the same effect of improving the luminous efficiency as a material having a high electron transporting ability. Therefore, the electron injecting/transporting layer in the present embodiment may include a function of a layer capable of efficiently blocking the movement of holes.

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

The material used for the electron transport layer or the electron injection layer, a compound consisting of an aromatic ring or a heteroaromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus, It is preferable to contain at least one selected from a pyrrole derivative, a condensed ring derivative thereof, and a metal complex having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4′-bis(diphenylethenyl)biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives , Quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives and indole derivatives. Examples of the metal complex having electron-accepting nitrogen include a hydroxyazole complex such as a hydroxyphenyloxazole complex, an azomethine complex, a tropolone metal complex, a flavonol metal complex, and a benzoquinoline metal complex. These materials may be used alone or may be used as a mixture 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, oxadiazoles. 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.), thiadiazole derivative, oxine derivative metal complex, quinolinol metal complex, quinoxaline derivative, quinoxaline derivative polymer, benzazole compound, gallium complex, pyrazole derivative, perfluorinated phenylene derivative, triazine derivative, pyrazine derivative, benzoquinoline Derivatives (2,2'-bis(benzo[h]quinolin-2-yl)-9,9'-spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris(N-phenylbenzimidazole- 2-yl)benzene etc.), benzoxazole derivative, benzothiazole derivative, quinoline derivative, oligopyridine derivative such as terpyridine, bipyridine derivative, terpyridine derivative (1,3-bis(4′-(2,2′:6′2 "-Terpyridinyl))benzene etc.), naphthyridine derivatives (bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide etc.), aldazine derivatives, carbazole derivatives, indole derivatives, phosphorus oxide derivatives , And bisstyryl derivatives.

Further, a metal complex having an electron-accepting nitrogen can be used, and examples thereof include a hydroxyazole complex such as a quinolinol-based metal complex and a hydroxyphenyloxazole complex, an azomethine complex, a tropolone metal complex, a flavonol metal complex, and a benzoquinoline metal complex. can give.

The above-mentioned materials may be used alone, but may be used as a mixture with different materials.

Among the above materials, borane derivative, pyridine derivative, fluoranthene derivative, BO-based derivative, anthracene derivative, benzofluorene derivative, phosphine oxide derivative, pyrimidine derivative, carbazole derivative, triazine derivative, benzimidazole derivative, phenanthroline derivative, and quinolinol-based metal Complexes 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 represent hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, or optionally substituted nitrogen. It is at least one of a heterocycle or cyano, and R ^{13 to} R ¹⁶ are each independently alkyl which may be substituted, cycloalkyl which may be substituted, or aryl which may be substituted. X is an optionally substituted arylene, Y is an optionally substituted aryl having 16 or less carbon atoms, a substituted boryl, or an optionally substituted carbazolyl, and n is an integer of 0-3 each independently. Further, examples of the substituent in the case of “optionally 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 each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, or optionally substituted nitrogen. It is at least one of a containing heterocycle or cyano, and R ^{13 to} R ¹⁶ are each independently alkyl which may be substituted, cycloalkyl which may be substituted, or aryl which may be substituted. And R ²¹ and R ²² are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. At least one, X ¹ is an optionally substituted arylene having 20 or less carbon atoms, n is each independently an integer of 0 to 3, and m is independently 0 to 4 Is an integer. Further, examples of the substituent in the case of “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, cycloalkyl and the like.
In formula (ETM-1-2), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, or optionally substituted nitrogen. It is at least one of a containing heterocycle or cyano, and R ^{13 to} R ¹⁶ are each independently alkyl which may be substituted, cycloalkyl which may be substituted, or aryl which may be substituted. And X ¹ is an optionally substituted arylene having 20 or less carbon atoms, and n is each independently an integer of 0 to 3. Further, examples of the substituent in the case of “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, cycloalkyl and the like.

Specific examples of X ¹ include a divalent group represented by any of the following formulas (X-1) to (X-9).
(In each formula, R ^a is each independently an alkyl group, a cycloalkyl group or an optionally substituted phenyl group.)

Specific examples of the borane derivative include the following compounds.

This borane derivative can be produced 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 formula (ETM-2-1), R ^{11 to} R ¹⁸ each independently represent hydrogen, alkyl (preferably alkyl having 1 to 24 carbons), cycloalkyl (preferably cyclo having 3 to 12 carbons). Alkyl) or aryl (preferably aryl having 6 to 30 carbon atoms).

In the above formula (ETM-2-2), R ¹¹ and R ¹² are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbons), cycloalkyl (preferably cyclo having 3 to 12 carbons). Alkyl) or aryl (preferably aryl having 6 to 30 carbon atoms), and R ¹¹ and R ¹² may be bonded to each other 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 each independently an alkyl or carbon atom having 1 to 4 carbon atoms. It may be substituted with cycloalkyl of the number 5 to 10. Further, the pyridine-based substituent may be bonded to φ, an anthracene ring or a fluorene ring in each formula via a phenylene group or a naphthylene group.

The pyridine-based substituent is one of the above formulas (Py-1) to (Py-15), and among these, one of the following formulas (Py-21) to (Py-44). It is preferable.

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

The “alkyl” for R ^{11 to} R ¹⁸ may be linear or branched, and examples thereof include linear alkyl having 1 to 24 carbons and branched alkyl having 3 to 24 carbons. Preferred “alkyl” is alkyl having 1 to 18 carbons (branched chain alkyl having 3 to 18 carbons). More preferable "alkyl" is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More desirable "alkyl" is alkyl having 1 to 6 carbons (branched chain alkyl having 3 to 6 carbons). Particularly preferred “alkyl” is alkyl having 1 to 4 carbons (branched chain alkyl having 3 to 4 carbons).

Specific "alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -Propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, Examples thereof include n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicosyl.

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

Examples of the “cycloalkyl” for R ^{11 to} R ¹⁸ include cycloalkyl having 3 to 12 carbon atoms. Preferred "cycloalkyl" is cycloalkyl having 3 to 10 carbon atoms. More preferable "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. More desirable "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms.
Specific "cycloalkyl" includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.

As the "aryl" for R ^{11 to} R ¹⁸ , preferred aryl is aryl having 6 to 30 carbon atoms, more preferred aryl is aryl having 6 to 18 carbon atoms, and further preferred is aryl having 6 to 14 carbon atoms. And particularly preferably aryl having 6 to 12 carbon atoms.

Specific examples of “aryl having 6 to 30 carbon atoms” include phenyl which is monocyclic aryl, (1-,2-)naphthyl which is condensed bicyclic aryl, and acenaphthylene-( which is condensed tricyclic aryl). 1-,3-,4-,5-)yl, fluoren-(1-,2-,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-,2 -,3-,4-,9-)phenanthryl, fused tetracyclic aryl triphenylene-(1-,2-)yl, pyrene-(1-,2-,4-)yl, naphthacene-(1- ,2-,5-)yl, fused pentacyclic aryls such as perylene-(1-,2-,3-)yl, and pentacene-(1-,2-,5-,6-)yl. ..

Preferred “aryl having 6 to 30 carbon atoms” include phenyl, naphthyl, phenanthryl, chrysenyl or triphenylenyl, etc., more preferably phenyl, 1-naphthyl, 2-naphthyl or phenanthryl, particularly preferably phenyl, 1 -Naphthyl or 2-naphthyl may be mentioned.

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

Specific examples of this pyridine derivative include the following compounds.

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

<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 heteroaryl. Here, examples of the substituent when it is substituted include aryl, heteroaryl, alkyl, and cycloalkyl.

Specific examples of the fluoranthene derivative include the following compounds.

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

R ^{1 to} R ¹¹ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, 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, arylheteroarylamino, 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 replaced with halogen or deuterium.

For the description of the substituents and the form of ring formation in the formula (ETM-4), the description of the polycyclic aromatic compound represented by the general formula (1) can be cited.

Specific examples of the BO derivative include the following compounds.

This BO derivative can be produced by using known raw materials and known synthesis methods.

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

Ar is each independently divalent benzene or naphthalene, and R ^{1 to} R ⁴ are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons or carbon. 6-20 aryl.

Ars can be independently selected from divalent benzene or naphthalene, and the two Ars may be different or the same, but are the same from the viewpoint of ease of synthesis of the anthracene derivative. Is preferred. Ar is bonded to pyridine to form a “site consisting of Ar and pyridine”, and this site is an anthracene group represented by any of the following formulas (Py-1) to (Py-12). Are bound to.

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). More preferred are groups represented by The two “moieties consisting of Ar and pyridine” that bind to anthracene may have the same or different structures, but preferably have 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 two “sites composed of Ar and pyridine” have the same or different structures.

The alkyl having 1 to 6 carbon atoms in R ^{1 to} R ⁴ may be linear or branched. 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 alkyl having 1 to 4 carbons (branched chain alkyl having 3 to 4 carbons). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl and the like can be mentioned, and methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl is preferable. , Methyl, ethyl, or t-butyl are more preferred.

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

The aryl having 6 to 20 carbon atoms in R ^{1 to} R ⁴ is preferably an aryl having 6 to 16 carbon atoms, more preferably an aryl having 6 to 12 carbon atoms, and particularly preferably an aryl having 6 to 10 carbon atoms.

Specific examples of the "aryl having 6 to 20 carbon atoms" include monocyclic aryl such as phenyl, (o-, m-, p-)tolyl, (2,3-, 2,4-, 2,5-). , 2,6-,3,4-,3,5-)xylyl, mesityl (2,4,6-trimethylphenyl), (o-,m-,p-)cumenyl, bicyclic aryl (2 -,3-,4-)biphenylyl, condensed bicyclic aryl (1-,2-)naphthyl, tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4 '-Yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -Yl, m-terphenyl-3-yl, m-terphenyl-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-,3-,4-,9-)phenanthryl, fused tetracyclic aryl triphenylene-(1-,2-)yl, pyrene-(1-,2-,4-)yl, tetracene-(1 Examples include -,2-,5-)yl and fused pentacyclic aryl such as perylene-(1-,2-,3-)yl.

Preferred "aryl having 6 to 20 carbon atoms" is 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, most preferably phenyl.

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

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

Ar ^{2 s} are each independently aryl having 6 to 20 carbon atoms, and the same description as the “aryl having 6 to 20 carbon atoms” in the above formula (ETM-5-1) can be cited. 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, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl and the like.

R ^{1 to} R ⁴ are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons or aryl having 6 to 20 carbons, and are each represented by the above formula (ETM-5-1). The description in can be cited.

Specific examples of these anthracene derivatives include the following compounds.

These anthracene derivatives can be produced by 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's are each independently an aryl having 6 to 20 carbons, and the same explanation as the “aryl having 6 to 20 carbons” in the above formula (ETM-5-1) can be cited. 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, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl and the like.

Ar ^{2 s} are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbons), cycloalkyl (preferably cycloalkyl having 3 to 12 carbons) or aryl (preferably aryl having 6 to 30 carbons). ), and two Ar ^{2 s} may combine to form a ring.

The “alkyl” in Ar ² may be linear or branched, and examples thereof include linear alkyl having 1 to 24 carbons and branched alkyl having 3 to 24 carbons. Preferred “alkyl” is alkyl having 1 to 18 carbons (branched chain alkyl having 3 to 18 carbons). More preferable "alkyl" is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More desirable "alkyl" is alkyl having 1 to 6 carbons (branched chain alkyl having 3 to 6 carbons). Particularly preferred “alkyl” is alkyl having 1 to 4 carbons (branched chain alkyl having 3 to 4 carbons). Specific "alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like can be mentioned.

Examples of “cycloalkyl” in Ar ² include cycloalkyl having 3 to 12 carbon atoms. Preferred "cycloalkyl" is cycloalkyl having 3 to 10 carbon atoms. More preferable "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. More desirable "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms. Specific "cycloalkyl" includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl and the like.

"Aryl" in Ar ^2, preferred aryl is aryl of 6 to 30 carbon atoms, and more preferred aryl is aryl of 6 to 18 carbon atoms, more preferably an aryl of 6 to 14 carbon atoms, in particular Preferred is aryl having 6 to 12 carbon atoms.

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

Two Ar ^2's may combine to form a ring, and as a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene or indene is spiro-bonded to the 5-membered ring of the fluorene skeleton. May be.

Specific examples of the benzofluorene derivative include the following compounds.

This benzofluorene derivative can be produced by using known raw materials and known synthesis methods.

<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 WO 2013/079217.
R ⁵ is substituted or unsubstituted alkyl having 1 to 20 carbons, cycloalkyl having 3 to 16 carbons, aryl having 6 to 20 carbons or heteroaryl having 5 to 20 carbons,
R ⁶ is CN, substituted or unsubstituted alkyl having 1 to 20 carbons, cycloalkyl having 3 to 16 carbons, heteroalkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, and having 5 to 5 carbons. 20 heteroaryl, alkoxy having 1 to 20 carbons or aryloxy having 6 to 20 carbons,
R ⁷ and R ⁸ are each independently a substituted or unsubstituted aryl having 6 to 20 carbons or heteroaryl having 5 to 20 carbons,
R ⁹ is oxygen or sulfur,
j is 0 or 1, k is 0 or 1, r is an integer of 0 to 4, and q is an integer of 1 to 3.
Here, examples of the substituent when it is substituted include aryl, heteroaryl, alkyl, and cycloalkyl.

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 each is hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a cycloalkylthio group, an aryl ether group. , Aryl thioether group, aryl group, heterocyclic group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, amino group, nitro group, silyl group, and among condensed rings formed with adjacent substituents Chosen from.

Ar ¹ may be the same or different and is an arylene group or a heteroarylene group. Ar ² may be the same or different and is an aryl group or a 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 of 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.

Of these substituents, the alkyl group represents 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 in the case of being 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 carbon number of the alkyl group is not particularly limited, but is usually in the range of 1 to 20 from the viewpoint of easy availability and cost.

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

The aralkyl group refers to, for example, an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group and a phenylethyl group, and the aliphatic hydrocarbon and the aromatic hydrocarbon are both unsubstituted and substituted. It doesn't matter. The carbon number of the aliphatic portion is not particularly limited, but is usually in the range of 1-20.

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

The cycloalkenyl group means, for example, an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group and a cyclohexene group, which may be unsubstituted or substituted. I don't care.

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

Further, the alkoxy group refers to, 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. Although the carbon number of the alkoxy group is not particularly limited, it is usually in the range of 1 to 20.

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

Further, the cycloalkylthio group is a group in which an oxygen atom of an ether bond of a cycloalkoxy group is substituted with a sulfur atom.

In addition, the aryl ether group refers to, 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 carbon number of the aryl ether group is not particularly limited, but is usually in the range of 6-40.

The aryl thioether group is a group in which an oxygen atom of an ether bond of the aryl ether group is substituted with a sulfur atom.

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

The heterocyclic group means, for example, a furanyl group, a thiophenyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, a carbazolyl group, or another cyclic structure group having an atom other than carbon, which is unsubstituted or substituted. I don't care. The carbon number of the heterocyclic group is not particularly limited, but is usually in the range of 2 to 30.

Halogen means fluorine, chlorine, bromine, and iodine.

The aldehyde group, carbonyl group, and amino group can also include groups substituted with an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocycle, or the like.

Further, the aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, and heterocycle may be unsubstituted or substituted.

The silyl group refers to, for example, 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 silicon number is usually 1 to 6.

The condensed ring formed between adjacent substituents includes, 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 , Ar ¹ and It is a conjugated or non-conjugated condensed ring formed between Ar ^{2 and the} like. Here, when n is 1, two R ^{1 s} may form a conjugated or non-conjugated condensed ring. These condensed rings may contain a nitrogen atom, an oxygen atom, or a sulfur atom in the ring structure, or may be condensed with another ring.

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

This phosphine oxide derivative can be produced by using known raw materials and known synthesis methods.

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

Ar is each independently an optionally substituted aryl or an optionally substituted heteroaryl. 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 aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferably, it is aryl having 6 to 12 carbon atoms.

Specific examples of “aryl” include phenyl which is a monocyclic aryl, (2-,3-,4-)biphenylyl which is a bicyclic aryl, and (1-,2-)naphthyl which is a condensed bicyclic aryl. , Tricyclic aryl terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-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) , A fused tricyclic aryl, acenaphthylene-(1-,3-,4-,5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenalene-(1 -,2-)yl, (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), fused tetracyclic aryl triphenylene-(1-,2 -)Yl, pyrene-(1-,2-,4-)yl, naphthacene-(1-,2-,5-)yl, fused pentacyclic aryl perylene-(1-,2-,3-). )Yl, pentacene-(1-,2-,5-,6-)yl and the like.

Examples of the "heteroaryl" of "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. The heteroaryl includes, for example, a heterocycle having 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring-constituting atom.

Specific heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, flazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl. , Pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathinyl, thianthrenyl, indoridinyl and the like.

The aryl and heteroaryl may be substituted, and each may be substituted with, for example, the aryl or heteroaryl.

Specific examples of the pyrimidine derivative include the following compounds.

This pyrimidine derivative can be produced using a known starting material and a known synthesis 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 them are bound by a single bond or the like. Details are described in U.S. Publication No. 2014/0197386.

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

Examples of the “aryl” of the “optionally substituted aryl” include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferably, it is aryl having 6 to 12 carbon atoms.

Specific examples of “aryl” include phenyl which is a monocyclic aryl, (2-,3-,4-)biphenylyl which is a bicyclic aryl, and (1-,2-)naphthyl which is a condensed bicyclic aryl. , Tricyclic aryl terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-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) , A fused tricyclic aryl, acenaphthylene-(1-,3-,4-,5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenalene-(1 -,2-)yl, (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), fused tetracyclic aryl triphenylene-(1-,2 -)Yl, pyrene-(1-,2-,4-)yl, naphthacene-(1-,2-,5-)yl, fused pentacyclic aryl perylene-(1-,2-,3-). )Yl, pentacene-(1-,2-,5-,6-)yl and the like.

Examples of the "heteroaryl" of "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. The heteroaryl includes, for example, a heterocycle having 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring-constituting atom.

Specific heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, flazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl. , Pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathinyl, thianthrenyl, indoridinyl and the like.

The aryl and heteroaryl may be substituted, and each may be substituted with, for example, the aryl or heteroaryl.

The carbazole derivative may be a multimer in which a plurality of compounds represented by the formula (ETM-9) are bound by a single bond or the like. In this case, other than a 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 the carbazole derivative include the following compounds.

This carbazole derivative can be produced using a known raw material and a known synthesis 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). The details are described in US Publication No. 2011/0156013.

Ar is each independently an optionally substituted aryl or an optionally substituted heteroaryl. n is an integer of 1 to 3, preferably 2 or 3.

Examples of the “aryl” of the “optionally substituted aryl” include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferably, it is aryl having 6 to 12 carbon atoms.

Specific examples of “aryl” include phenyl which is a monocyclic aryl, (2-,3-,4-)biphenylyl which is a bicyclic aryl, and (1-,2-)naphthyl which is a condensed bicyclic aryl. , Tricyclic aryl terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-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) , A fused tricyclic aryl, acenaphthylene-(1-,3-,4-,5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenalene-(1 -,2-)yl, (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), fused tetracyclic aryl triphenylene-(1-,2 -)Yl, pyrene-(1-,2-,4-)yl, naphthacene-(1-,2-,5-)yl, fused pentacyclic aryl perylene-(1-,2-,3-). )Yl, pentacene-(1-,2-,5-,6-)yl and the like.

Examples of the "heteroaryl" of "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. The heteroaryl includes, for example, a heterocycle having 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring-constituting atom.

Specific heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, flazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl. , Pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathinyl, thianthrenyl, indoridinyl and the like.

The aryl and heteroaryl may be substituted, and each may be substituted with, for example, the aryl or heteroaryl.

Specific examples of the triazine derivative include the following compounds.

This triazine derivative can be produced by using known raw materials and known synthesis methods.

<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, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. The “benzimidazole-based substituent” means that 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 replaced with deuterium.

R ¹¹ in the benzimidazole group is hydrogen, alkyl having 1 to 24 carbons, cycloalkyl having 3 to 12 carbons or aryl having 6 to 30 carbons, and has the formula (ETM-2-1) and formula (ETM-2-1). The description of R ¹¹ in ETM-2-2) can be cited.

Further, φ is preferably an anthracene ring or a fluorene ring, and the structure in this case can be referred to the description in the above formula (ETM-2-1) or formula (ETM-2-2). For R ^{11 to} R ¹⁸ in the formula, the description in the 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 bonded to each other, but when these are replaced with benzimidazole-based substituents, May be replaced with a benzimidazole substituent (ie, n=2), or any one of the pyridine substituents may be replaced with a benzimidazole substituent and the other pyridine substituent may be replaced with R ¹¹ ~R ¹⁸ may be substituted (ie n=1). Furthermore, 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 the benzimidazole derivative include, for example, 1-phenyl-2-(4-(10-phenylanthracen-9-yl)phenyl)-1H-benzo[d]imidazole and 2-(4-(10-( Naphthalen-2-yl)anthracen-9-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 2-(3-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl) -1-Phenyl-1H-benzo[d]imidazole, 5-(10-(naphthalen-2-yl)anthracen-9-yl)-1,2-diphenyl-1H-benzo[d]imidazole, 1-(4 -(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 2-(4-(9,10-di(naphthalen-2-yl)) Anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 1-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-2- Phenyl-1H-benzo[d]imidazole, 5-(9,10-di(naphthalen-2-yl)anthracen-2-yl)-1,2-diphenyl-1H-benzo[d]imidazole and the like can be mentioned.

This benzimidazole derivative can be produced by using known raw materials and known synthesis methods.

<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 WO 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 in} each formula are independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbons), cycloalkyl (preferably cycloalkyl having 3 to 12 carbons) or aryl (preferably carbon). The aryl of the number 6 to 30). Further, in the above formula (ETM-12-1), any 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 replaced 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, in addition to the above-mentioned examples, φ may be, for example, the following structural formula. In addition, R in the following structural formulas are each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl.

Specific examples of the phenanthroline derivative include, for example, 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and 9,10-di(1,10- Phenanthroline-2-yl)anthracene, 2,6-di(1,10-phenanthroline-5-yl)pyridine, 1,3,5-tri(1,10-phenanthroline-5-yl)benzene, 9,9′ -Difluoro-bi(1,10-phenanthroline-5-yl), bathocuproine, 1,3-bis(2-phenyl-1,10-phenanthroline-9-yl)benzene, compounds represented by the following structural formula, etc. can give.

This phenanthroline derivative can be produced by using known raw materials and known synthesis methods.

<Quinolinol-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 each independently hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy or aryl, M is Li, Al, Ga, Be or Zn, n is an integer of 1 to 3.

Specific examples of the quinolinol-based metal complex include 8-quinolinol lithium, tris(8-quinolinolato)aluminum, tris(4-methyl-8-quinolinolato)aluminum, tris(5-methyl-8-quinolinolato)aluminum, tris(3). ,4-Dimethyl-8-quinolinolato)aluminum, tris(4,5-dimethyl-8-quinolinolato)aluminum, tris(4,6-dimethyl-8-quinolinolato)aluminum, bis(2-methyl-8-quinolinolato)( (Phenolato)aluminum, bis(2-methyl-8-quinolinolato)(2-methylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(3-methylphenolato)aluminum, bis(2-methyl-8-) Quinolinoleate)(4-methylphenolate)aluminum, bis(2-methyl-8-quinolinolato)(2-phenylphenolate)aluminum, bis(2-methyl-8-quinolinolato)(3-phenylphenolate)aluminum, bis (2-Methyl-8-quinolinolato)(4-phenylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2,3-dimethylphenolato)aluminum, bis(2-methyl-8-quinolinolato)( 2,6-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-quinolinolato)(2,4,5,6-tetramethylphenolate)aluminum, bis(2-methyl-8-quinolinolato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinolato)(2 -Naphtholate) aluminum, bis(2,4-dimethyl-8-quinolinolato)(2-phenylphenolato) aluminum, bis(2,4-dimethyl-8-quinolinolato) )(3-Phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolato)(4-phenylphenolato)aluminum, bis(2,4-dimethyl-8-quinolinolato)(3,5-dimethylphenolo) Aluminum), bis(2,4-dimethyl-8-quinolinolate)(3,5-di-t-butylphenolate)aluminum, bis(2-methyl-8-quinolinolato)aluminum-μ-oxo-bis(2 -Methyl-8-quinolinolato) aluminum, bis(2,4-dimethyl-8-quinolinolato)aluminum-μ-oxo-bis(2,4-dimethyl-8-quinolinolato)aluminum, bis(2-methyl-4-ethyl) -8-Quinolinolato)aluminum-μ-oxo-bis(2-methyl-4-ethyl-8-quinolinolato)aluminum, bis(2-methyl-4-methoxy-8-quinolinolato)aluminum-μ-oxo-bis(2 -Methyl-4-methoxy-8-quinolinolato)aluminum, bis(2-methyl-5-cyano-8-quinolinolato)aluminum-μ-oxo-bis(2-methyl-5-cyano-8-quinolinolato)aluminum, bis (2-Methyl-5-trifluoromethyl-8-quinolinolato)aluminum-μ-oxo-bis(2-methyl-5-trifluoromethyl-8-quinolinolato)aluminum, bis(10-hydroxybenzo[h]quinoline) Beryllium is an example.

This quinolinol-based metal complex can be produced by using known raw materials and known synthesis methods.

<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 in 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 "Thiazol-based substituent" and "benzothiazole-based substituent" are the "pyridine-based substituents" in the formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2). The pyridyl group in the "substituent" is a substituent in which the following thiazole group or benzothiazole group is replaced, and at least one hydrogen in the thiazole derivative and the benzothiazole derivative may be replaced with deuterium.

Further, φ is preferably an anthracene ring or a fluorene ring, and the structure in this case can be referred to the description in the above formula (ETM-2-1) or formula (ETM-2-2). For R ^{11 to} R ¹⁸ in the formula, the description in the formula (ETM-2-1) or the formula (ETM-2-2) can be cited. Further, in the formula (ETM-2-1) or the formula (ETM-2-2), two pyridine-based substituents are bonded to each other. However, these are substituted with a thiazole-based substituent (or a benzothiazole-based substituent). Group), both pyridine-based substituents may be replaced with thiazole-based substituents (or benzothiazole-based substituents) (that is, n=2), and any one pyridine-based substituent is replaced with a thiazole-based substituent. A group (or a benzothiazole type substituent) may be substituted and the other pyridine type substituent may be substituted with R ^{11 to} R ¹⁸ (that is, n=1). Furthermore, 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 include a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As the reducing substance, various substances can be 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, and alkali metal. 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 (same as 2.28 eV), Rb (same as 2.16 eV), Cs (same as 1.95 eV), and Ca (same as 2.95 eV). 9eV), Sr (2.0 to 2.5eV in the same), Ba (2.52eV in the same), and the like, and alkaline earth metals such as Ba (2.52eV in the same), and a substance having a work function of 2.9eV or less is particularly preferable. Among these, more preferable reducing substances are K, Rb or Cs alkali metals, more preferable are Rb or Cs, and most preferable are 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, it is possible to improve the emission brightness and extend the life of the organic EL device. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of two or more kinds of these 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 addition to the material forming the electron transport layer or the electron injection layer can improve the emission brightness and extend the life of the organic EL device.

The electron injecting layer material and the electron transport layer material described above are polymer compounds obtained by polymerizing a reactive compound in which a reactive substituent is substituted as a monomer, or a polymer cross-linked product thereof, or A pendant polymer compound obtained by reacting a chain polymer with the above reactive compound, or a pendant polymer cross-linked product thereof can also be used as a material for an electronic layer. As the reactive substituent in this case, the description on the polycyclic aromatic compound represented by the formula (1) can be cited.
Details of applications of such polymer compounds and polymer cross-linked products will be described later.

<Cathode in organic electroluminescent device>
The cathode 108 plays a role of injecting electrons into the light emitting layer 105 via the electron injection layer 107 and the electron transport layer 106.

The material 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 the same material as the material 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 alloys thereof (magnesium-silver alloy, magnesium). -Indium alloy, aluminum-lithium alloy such as lithium fluoride/aluminum) and the like are preferable. In order to improve the electron injection efficiency and improve the device characteristics, lithium, sodium, potassium, cesium, calcium, magnesium or an alloy containing these low work function metals is effective. However, these low work function metals are generally often unstable in the atmosphere. In order to improve this point, for example, a method is known in which an organic layer is doped with a small amount of lithium, cesium or magnesium and an electrode having high stability is used. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide and cesium oxide can also be used. However, it is not limited to these.

Further, for protecting electrodes, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic substances such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride. As a preferable example, it is preferable to stack a hydrocarbon-based polymer compound. The method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam evaporation, sputtering, ion plating and coating.

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

<Method for manufacturing organic electroluminescent device>
Each layer that constitutes the organic EL element is a thin film formed by a method such as a vapor deposition method, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method, casting method, or coating method. It can be formed by The film thickness of each layer thus formed is not particularly limited and can be appropriately set depending on the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can be usually measured by a crystal oscillation type film thickness measuring device or the like. When a thin film is formed using the vapor deposition method, the vapor deposition conditions vary 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 a boat heating temperature of +50 to +400° C., a vacuum degree of 10 ⁻⁶ to 10 ⁻³ Pa, a vapor deposition rate of 0.01 to 50 nm/sec, a substrate temperature of −150 to +300° C., and a film thickness of 2 nm to 5 μm. It is preferable to set it appropriately within the range.

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

Next, as an example of a method for producing an organic EL element, an organic EL element composed of anode/hole injection layer/hole transport layer/light emitting layer composed of host material and dopant material/electron transport layer/electron injection layer/cathode The manufacturing method of is explained.

<Vapor deposition method>
After forming a thin film of an anode material on a suitable substrate by a vapor deposition method or the like to form an anode, a thin film of a hole injection layer and a hole transport layer is formed on this anode. A host material and a dopant material are co-deposited on this to form a thin film as a light emitting layer, an electron transport layer and an electron injection layer are formed on this light emitting layer, and a thin film made of a substance for the cathode is deposited by a vapor deposition method or the like. The target organic EL element is obtained by forming it and using it as a cathode. In the production of the above-mentioned organic EL element, the production order may be reversed, and 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 may be produced in this order. Is.

<Wet film forming method>
The wet film formation method is carried out by preparing a low molecular weight compound capable of forming each organic layer of an organic EL element as a liquid composition for forming an organic layer and using the composition. If there is no suitable organic solvent that dissolves this low molecular weight compound, it will be added together with other monomers or main chain type polymers having a solubility function as a reactive compound obtained by substituting the low molecular weight compound with a reactive substituent. You may prepare the composition for organic layer formation from the polymerized compound etc.

In the wet film forming method, generally, a coating film is formed by going through a coating step of coating a composition for forming an organic layer on a substrate and a drying step of removing a solvent from the coated composition for forming an organic layer. When the polymer compound has a crosslinkable substituent (this is also referred to as a crosslinkable polymer compound), the polymer is further crosslinked by this drying step to form a polymer crosslinked body. Depending on the coating process, the spin coater method is the spin coat method, the slit coater method is the slit coat method, the plate method is gravure, offset, reverse offset, flexographic printing method, and the ink jet printer method is the ink jet method. The method of spraying in a mist 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 multiple times using different methods and conditions. Also, different methods may be used in combination, such as firing under reduced pressure.

The wet film formation method is a film formation method using a solution, and examples thereof include some printing methods (inkjet method), spin coating method or casting method, coating method, and the like. Unlike the vacuum deposition method, the wet deposition method does not require the use of an expensive vacuum deposition apparatus and can form a film under atmospheric pressure. In addition, the wet film-forming method enables a large area and continuous production, which leads to a reduction in manufacturing cost.

On the other hand, when compared with the vacuum vapor deposition method, it may be difficult to stack the wet film formation method. When forming a laminated film using a wet film formation method, it is necessary to prevent the lower layer from being dissolved by the composition of the upper layer, and the composition of which solubility is controlled, the lower layer of cross-linking and the orthogonal solvent (orthogonal solvent) are dissolved. No solvent) is 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, generally, a method is adopted in which only some layers are formed by a wet film forming method, and the remaining layers are formed by a vacuum evaporation method.

For example, a procedure for partially applying the wet film forming method to produce an organic EL element will be described below.
(Procedure 1) Film formation by vacuum evaporation method of anode (Procedure 2) Film formation by wet film formation method of composition for forming hole injection layer containing hole injection layer material (Step 3) Material for hole transport layer Of a composition for forming a hole transport layer containing a film by a wet film formation method (procedure 4) Film 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) Film formation by vacuum evaporation method (procedure 6) Film formation of electron injection layer by vacuum evaporation method (procedure 7) Film formation by cathode vacuum evaporation method (anode/hole injection layer/hole transport) An organic EL device including a layer/a light emitting layer composed of a host material and a dopant material/an electron transport layer/an electron injection layer/a cathode is obtained.
Of course, there is a means for preventing the dissolution of the lower light emitting layer, or by using a means for forming a film from the cathode side in the reverse of the above procedure, a layer formation including a material for an electron transport layer or a material for an electron injection layer is formed. Can be formed into a film by a wet film forming method.

<Other film forming methods>
A laser heating drawing method (LITI) can be used for forming a film of the composition for forming an organic layer. LITI is a method in which a compound attached to a base material is heated and vaporized with a laser, and a composition for forming an organic layer can be used as a material applied to the base material.

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

A photolithography technique can be used for forming the bank. As a bank material that can be used in photolithography, a positive resist material and a negative resist material can be used. Further, a patternable printing method such as an ink jet method, gravure offset printing, reverse offset printing, screen printing or the like can be used. In that case, a permanent resist material can also be used.

Materials used for the bank include polysaccharides and their derivatives, homopolymers and copolymers of hydroxyl-containing ethylenic monomers, biopolymer compounds, polyacryloyl compounds, polyesters, polystyrenes, polyimides, polyamideimides, polyetherimides. , Polysulfide, polysulfone, polyphenylene, polyphenyl ether, polyurethane, epoxy (meth)acrylate, melamine (meth)acrylate, polyolefin, cyclic polyolefin, acrylonitrile-butadiene-styrene copolymer (ABS), silicone resin, polyvinyl chloride, chlorine Fluorinated polymers such as fluorinated polyethylene, chlorinated polypropylene, polyacetate, polynorbornene, synthetic rubber, polyfluorovinylidene, polytetrafluoroethylene, polyhexafluoropropylene, fluoroolefin-hydrocarbon olefin copolymers, and fluorocarbon polymers. However, it is not limited thereto.

<Organic layer forming composition used in wet film forming method>
The composition for forming an organic layer is obtained by dissolving a low molecular compound capable of forming each organic layer of an organic EL element or a high molecular compound obtained by polymerizing the low molecular compound in an organic solvent. For example, the composition for forming a light emitting layer comprises a polycyclic aromatic compound (or a polymer compound thereof) which is at least one dopant material as a first component, at least one 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 imparts a smooth and uniform surface shape due to the controlled evaporation rate of the third component itself during coating.

<Organic solvent>
The composition for forming an organic layer contains at least one organic solvent. By controlling the evaporation rate of the organic solvent during 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, during film formation using the inkjet method, the meniscus stability in the pinhole of the inkjet head can be controlled, and the ejection property can be controlled/improved. In addition, by controlling the drying rate of the film and the orientation of the derivative molecules, the electrical characteristics, the light emission characteristics, the efficiency, and the life of the organic EL device having an organic layer obtained from the composition for forming an organic layer are improved. You can

(1) Physical Properties of Organic Solvent The boiling point of at least one organic solvent is 130°C to 300°C, preferably 140°C to 270°C, more preferably 150°C to 250°C. When the boiling point is higher than 130° C., it is preferable from the viewpoint of ink jet dischargeability. 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. It is more preferable that the organic solvent contains two or more kinds of organic solvents from the viewpoints of good ink jetting property, film forming property, smoothness and low residual solvent. On the other hand, in some cases, in consideration of transportability and the like, the composition may be in a solid state by removing the solvent from the composition for forming an organic layer.

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

The difference in solubility (S _GS -S _PS ) is preferably 1% or more, more preferably 3% or more, and further preferably 5% or more. The difference in boiling point (BP _PS -BP _GS ) is preferably 10°C or higher, more preferably 30°C or higher, and further preferably 50°C or higher.

After forming the film, the organic solvent is removed from the coating film by a drying process such as vacuum, reduced pressure and heating. When the heating is performed, it is preferable to perform the heating at a glass transition temperature (Tg) of at least one solute of +30° C. or lower from the viewpoint of improving coating film-forming property. From the viewpoint of reducing the residual solvent, it is preferable to heat at least one glass transition point (Tg) of the solute at −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, and 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 alkylbenzene solvents, phenyl ether solvents, alkyl ether solvents, cyclic ketone solvents, aliphatic ketone solvents, monocyclic solvents. Examples thereof include ketone solvents, solvents having a diester skeleton and fluorine-containing solvents, and specific examples include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, and hexan-2-ol. Heptane-2-ol, octane-2-ol, decane-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. Anisole, anisole, 2,3-dimethylpyrazine, bromobenzene, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethylanisole, mesitylene, 1,2,4-trimethylbenzene, t-butylbenzene, 2-methyl Anisole, phenetole, benzodioxole, 4-methylanisole, s-butylbenzene, 3-methylanisole, 4-fluoro-3-methyl Anisole, cymene, 1,2,3-trimethylbenzene, 1,2-dichlorobenzene, 2-fluorobenzonitrile, 4-fluoroveratrol, 2,6-dimethylanisole, n-butylbenzene, 3-fluorobenzonitrile, Decalin (decahydronaphthalene), neopentylbenzene, 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3,5-dimethylanisole, diphenyl ether, 1-fluoro-3,5-dimethoxybenzene, benzoic acid Methyl, isopentylbenzene, 3,4-dimethylanisole, o-tolunitrile, 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'-bitryl, 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 benzyl butyl ether, benzyl pentyl ether, benzyl hexyl ether, benzyl heptyl ether, benzyl octyl ether and the like, but are not limited thereto. Further, the solvents may be used alone or may be mixed.

<Arbitrary ingredients>
The composition for forming an organic layer may contain optional components as long as the properties thereof are not impaired. Examples of the optional component include a binder and a surfactant.

(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 bonds the obtained film to the substrate. Further, it plays a role of 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, 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) resins, phenolic resins, epoxy resins, melamine resins, urea resins, alkyd resins, polyurethanes, 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 plural kinds.

(2) Surfactant The organic layer-forming composition contains, for example, a surfactant for controlling the uniformity of the film surface of the organic layer-forming composition, the solvophilicity of the film surface, and the liquid repellency. Good. Surfactants are classified into ionic and nonionic based on the structure of the hydrophilic group, and further classified into alkyl-based, silicon-based and fluorine-based based on the structure of the hydrophobic group. The molecular structure 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 a side chain or branching. In addition, the composition is classified into a single system and a mixed system in which two or more kinds of surfactants and a base material are mixed. 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.), Disperbyk 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181, Disper. Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, manufactured by Big Chemie Japan KK), KP-341, KP-358, KP-368, KF-96-50CS, KF. -50-100CS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Futgent 222F, Futgent 251, FTX-218 ( Trade name, Neos Co., Ltd., EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (trade name, manufactured by Mitsubishi Materials Corporation), MegaFac F- 470, MegaFac F-471, MegaFac F-475, MegaFac R-08, MegaFac F-477, MegaFac F-479, MegaFac F-553, MegaFac F-554 (trade name, DIC (stock )), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether) ), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amino sulfonate, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene Stearate, polyoxyethylene lauryl amine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, Polyoxyethylene sorbitan oleate, Polio Mention may be made of xoxyethylene naphthyl ether, alkylbenzene sulfonates and alkyldiphenyl ether disulfonates.

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

<Composition and Physical Properties of Organic Layer-Forming Composition>
The content of each component in the composition for forming an organic layer is obtained from the good solubility of each component in the composition for forming an organic layer, storage stability and film formability, and the composition for forming an organic layer. Good film quality of the coating film, good dischargeability when using an inkjet method, good electrical characteristics, light emission characteristics, efficiency, and lifetime of an 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, and the second component is for forming a light emitting layer, based on the total weight of the composition for forming a light emitting layer. 0.0999 wt% to 8.0 wt% with respect to the total weight of the composition, and 90.0 wt% to 99.9 wt% of the third component with respect to the total weight of the composition for forming a light emitting layer. preferable.

More preferably, the first component is 0.005 wt% to 1.0 wt% with respect to the total weight of the composition for forming a light emitting layer, and the second component is relative to the total weight of the composition for forming a light emitting layer. 0.095 wt% to 4.0 wt%, and the third component is 95.0 wt% to 99.9 wt% with respect to the total weight of the composition for forming a light emitting layer. More preferably, the first component is 0.05 wt% to 0.5 wt% with respect to the total weight of the composition for forming a light emitting layer, and the second component is relative to the total weight of the composition for forming a light emitting layer. 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 stirring, mixing, heating, cooling, dissolution, dispersion and the like of the above-mentioned components by a known method. After the preparation, filtration, degassing (also referred to as degassing), ion exchange treatment, inert gas replacement/encapsulation treatment, etc. may be appropriately selected and performed.

As for the viscosity of the composition for forming an organic layer, the higher the viscosity, the better the film-forming property and the better the ejection property when the inkjet method is used. On the other hand, a lower viscosity makes it easier 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 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 defect-free coating film can be obtained. On the other hand, the higher the value, the better the inkjet ejection property. From this, the viscosity of the composition for forming an organic layer preferably has a surface tension at 25° C. of 20 to 40 mN/m, and more preferably 20 to 30 mN/m. In the present invention, the surface tension is a value measured by the hanging drop method.

<Crosslinkable Polymer Compound: Compound Represented by General Formula (XLP-1)>
Next, the 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 definitions as MU, EC and k in the above formula (SPH-1), provided 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 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 a bonding position.

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

Examples of the divalent aromatic compound having a crosslinkable substituent include compounds having the following partial structure.

<Method for producing 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 (SPH-1) 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, for example, dimethoxyethane, 2-(2-methoxyethoxy)ethane, 2-(2 -Ethoxyethoxy)ethane and the like.

Further, 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 formula (SPH-1) and the compound of (XLP-1) are produced, they may be produced in one step or may be produced in multiple steps. Further, it may be carried out by a batch polymerization method in which all the raw materials are put in a reaction vessel and then the reaction is started, or by a dropping polymerization method in which the raw materials are dropped and added to the reaction vessel, and the product is used for the reaction progress. It may be carried out by a precipitation polymerization method in which precipitation is accompanied, and these can be synthesized in an appropriate combination. For example, when the compound represented by the formula (SPH-1) is synthesized in one step, the reaction product is obtained in a state where the monomer unit (MU) and the end cap unit (EC) are added to the reaction product. .. Moreover, when synthesizing the compound represented by the general formula (SPH-1) in multiple steps, the monomer unit (MU) is polymerized to a desired molecular weight, and then the end cap unit (EC) is added to react the compound. Get things. A polymer having a concentration gradient with respect to the structure of the monomer unit can be produced by adding different types of monomer units (MU) in multiple stages and performing the reaction. In addition, after the precursor polymer is prepared, the target polymer can be obtained by the subsequent reaction.

Further, the primary structure of the polymer can be controlled by selecting the polymerizable group of the monomer unit (MU). For example, as shown in Synthesis Schemes 1 to 3, 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 can be synthesized. And can be used in appropriate combination depending on the intended 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 2010-189630 A, International Publication No. 2012/086671, International Publication No. 2013/191088, International Publication No. 2002/045184, International Publication No. 2011/049241. No., International Publication No. 2013/146806, International Publication No. 2005/049546, International Publication No. 2015/145871, JP 2010-215886, JP 2008-106241 JP, JP 2010-215886 JP, International It can be synthesized according to the method described in Publication 2016/031639, JP 2011-174062 Publication, International Publication 2016/031639, International Publication 2016/031639, International Publication 2002/045184. ..

Further, for specific polymer synthesis procedure, JP 2012-036388 JP, WO 2015/008851, JP 2012-36381 JP, JP 2012-144722 JP, WO 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 methods described in Publication No. 2016/125560, International Publication No. 2015/145871, International Publication No. 2011/049241, and Japanese Patent Laid-Open No. 2012-144722.

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

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 electroluminescence (EL) display (for example, JP-A-10-335066 and JP-A-2003-321546). Japanese Patent Laid-Open No. 2004-281086). Further, examples of the display system of the display include a matrix and/or segment system. The matrix display and the segment display may coexist in the same panel.

In the matrix, pixels for display are two-dimensionally arranged in a lattice or mosaic, and a set of pixels displays a character or an image. The shape and size of the pixel are determined by the application. For example, a square pixel with a side of 300 μm or less is usually used for displaying images and characters on a personal computer, a monitor, or a television, and in the case of a large display such as a display panel, a pixel with a side of mm is 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. The driving method of this matrix may be either a line-sequential driving method or an active matrix. The line-sequential driving has an advantage that the structure is simple, but in consideration of the operation characteristics, the active matrix may be superior, and thus it is necessary to use the active matrix depending on the application.

In the segment system (type), a pattern is formed so as to display predetermined information, and a predetermined area is made to emit light. Examples thereof include time and temperature display on digital clocks and thermometers, operation status display of audio equipment and electromagnetic cookers, and automobile panel display.

Examples of the illuminating device include an illuminating device such as indoor lighting and a backlight of a liquid crystal display device (for example, JP 2003-257621 A, JP 2003-277741 A, JP 2004-119211 A). Etc.). The backlight is mainly used for 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, in particular, a personal computer for which thinning is an issue, considering that it is difficult to reduce the thickness because the conventional method is composed of a fluorescent lamp and a light guide plate, 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 compound according to the present invention can be used for producing an organic field effect transistor, an organic thin film solar cell, or the like, in addition to the organic electroluminescent element described above.

An organic field effect transistor is a transistor that controls a current by an electric field generated by voltage input, and has a gate electrode in addition to a source electrode and a drain electrode. An electric field is generated when a voltage is applied to the gate electrode, and the current can be controlled by arbitrarily stopping the flow of electrons (or holes) flowing between the source electrode and the drain electrode. A 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 generally such that a source electrode and a drain electrode are provided in contact with an organic semiconductor active layer formed by using the polycyclic aromatic compound according to the present invention, and further contact with the organic semiconductor active layer. The gate electrode may be provided with the insulating layer (dielectric layer) sandwiched therebetween. 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 field effect transistor configured in this way is It can be applied as a pixel drive switching element of an active matrix drive type 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 described in more detail with reference to Examples, but the present invention is not limited thereto. First, a synthesis example of a polycyclic aromatic compound will be described below.

Synthesis Example (1): Synthesis of Compound (1-25)

Under a nitrogen atmosphere, 4-(1-adamantyl)aniline (15.0 g) was dissolved in acetonitrile (300 ml), bromine (21.1 g) was added dropwise under ice cooling, and the mixture was stirred for 0.5 hr. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then toluene was further added, and the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified by a silica gel short column (eluent: toluene) and then washed with heptane to obtain an intermediate (IA) (21.0 g).

Under a nitrogen atmosphere, the intermediate (IA) (21.0 g) was dissolved in acetonitrile (200 ml), and t-butyl nitrite (8.4 g) dissolved in acetonitrile (50 ml) at 60° C. was dissolved therein. The mixture was added dropwise and stirred at the same temperature for 30 minutes. After the reaction, diluted hydrochloric acid and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified by a silica gel short column (eluent: toluene/heptane=1/3 (volume ratio)) to obtain an intermediate (IB) (16.0 g).

Under a nitrogen atmosphere, intermediate (IB) (12.0 g), N-(3-tertbutylphenyl)-3,5-ditertbutylaniline (21.0 g), and dichlorobis[(di-t as a palladium catalyst. -Butyl(4-dimethylaminophenyl)phosphino)palladium (Pd-132, 0.21 g), sodium-t-butoxide (NaOtBu, 7.1 g) and xylene (120 ml) were placed in a flask and 1.5 at 100°C. Heated for hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified by a silica gel short column (eluent: toluene/heptane=2/8 (volume ratio)) to obtain an intermediate (IC) (26.0 g).

A flask containing intermediate (IC) (24.0 g) and tert-butylbenzene (120 ml) was charged with 1.56 M tert-butyllithium in pentane (33.5 ml) at 0° C. under a nitrogen atmosphere. Was added. After the dropping was completed, the temperature was raised to 60° C. and the mixture was stirred for 1 hour, and then components having a lower boiling point than tert-butylbenzene were distilled off under reduced pressure. The mixture was cooled to -50°C, boron tribromide (13.1 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hr. Then, the mixture was cooled to 0° C. again, N,N-diisopropylethylamine (6.8 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then heated to 100° C. and stirred with heating for 1 hour. The reaction solution was cooled to room temperature, and an aqueous solution of sodium acetate cooled in an ice bath and then ethyl acetate were added to separate the layers. After concentrating the organic layer, it was purified with a silica gel short column (eluent: toluene/heptane=2/8 (volume ratio)). The obtained crude product was dissolved in toluene and reprecipitated with methanol to obtain compound (1-25) (6.0 g).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ=1.21 (s, 18H), 1.36 (s, 36H), 1.48-1.66 (m, 12H), 1.89 (s, 3H). , 6.18 (s, 2H), 6.78 (s, 2H), 7.22 (d, 4H), 7.25-7.28 (m, 2H), 7.59 (t, 2H), 8.86 (d, 2H).

Synthesis example (2): Synthesis of compound (1-16)

Under a nitrogen atmosphere, intermediate (IB) (10.0 g), N-(4-tert-butylphenyl)-4-tert-butylaniline (14.0 g), Pd-132 (0.18 g) as a palladium catalyst, Sodium-t-butoxide (NaOtBu, 5.9 g) and xylene (80 ml) were placed in a flask and heated at 100° C. for 1.5 hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. The crude product was purified by a silica gel short column (eluent: toluene) to obtain an intermediate (ID) (13.1 g).

A flask containing intermediate (ID) (13.0 g) and tert-butylbenzene (100 ml) was charged with 1.56 M tert-butyllithium in pentane (18.3 ml) at 0° C. under a nitrogen atmosphere. Was added. After the dropping was completed, the temperature was raised to 70° C. and the mixture was stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. The mixture was cooled to -50°C, boron tribromide (7.0 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hr. Then, the mixture was cooled to 0° C. again, N,N-diisopropylethylamine (3.6 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then heated to 80° C. and stirred with heating for 1 hour. The reaction solution was cooled to room temperature, and an aqueous solution of sodium acetate cooled in an ice bath and then ethyl acetate were added to separate the layers. The organic layer was concentrated, a small amount of ethyl acetate was added to dissolve the organic layer under heating, heptane was added, and the mixture was cooled. Then, the precipitated crystals were separated by filtration, and the crystals were washed with cooled heptane. The crystal was purified by a silica gel short column (eluent: toluene). Heptane was added to the obtained crude product, and the mixture was heated with stirring and cooled, and the obtained crystals were separated by filtration. Then, the compound (1-16) was obtained by dissolving in toluene and concentrating, repeating the process of adding heptane and precipitating a crystal|crystallization and filtering (5.3g).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ=1.46 (s, 18H), 1.47 (s, 18H), 1.51-1.54 (m, 9H), 1.62-1.65( m, 3H), 1.87-1.89 (m, 3H), 6.05 (s, 2H), 6.79 (d, 2H), 7.30 (d, 4H), 7.50 (dd , 2H), 7.69 (d, 4H), 8.98 (d, 2H).

Synthesis Example (3): Synthesis of Compound (1-321)

Under a nitrogen atmosphere, the intermediate (IE) (40.0 g) was dissolved in chloroform (100 ml), iron (powder) (0.53 g) was added thereto, and bromine (45 g) was added dropwise at room temperature. The mixture was stirred at the same temperature for 4 hours. After adding water, sodium carbonate was gradually added until effervescence was settled, and then sodium bisulfite was added in an appropriate amount. After washing the organic layer with water, the organic layer was concentrated to obtain a crude product. The crude product was purified by silica gel short column (eluent: heptane), and then the organic layer was concentrated to obtain a crude product. Heptane was added to the crude product, and the mixture was cooled and then filtered to obtain an intermediate (IF) (44.0 g).

Under a nitrogen atmosphere, intermediate (IG) (10.0 g), intermediate (IF) (11.8 g), Pd-132 (0.26 g) as a palladium catalyst, sodium-t-butoxide (NaOtBu, 5.3 g) and xylene (70 ml) were placed in a flask and heated at 100° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Then, heptane was added to the crude product obtained by concentrating the organic layer and the mixture was cooled, and then the obtained crystal was filtered. The crude product was purified by a silica gel short column (eluent: toluene/heptane=1/1 (volume ratio)), and the organic layer was concentrated, and heptane was added to the crude product, which was obtained after cooling. The crystal|crystallization was filtered and the intermediate body (IH) was obtained (10.0g).

Under a nitrogen atmosphere, intermediate (I-H) (10.0 g), N-(4-tert-butylphenyl)-4-tert-butylaniline (12.8 g), bis(dibenzylideneacetone)palladium (0)(Pd). (Dba) ₂ , 0.24 g), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (SPhos), sodium-t-butoxide (NaOtBu, 5.0 g). And xylene (80 ml) was placed in a flask and heated at 100° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Heptane was added to the crude product obtained by concentrating the organic layer, the mixture was cooled, and the crystals obtained were filtered. The crude product was purified by a silica gel short column (eluent: toluene), the organic layer was concentrated, heptane was added to the crude product obtained, and after cooling, the resulting crystals were filtered to obtain an intermediate (I- I) was obtained (10.2 g).

A flask containing intermediate (II) (10.0 g) and tert-butylbenzene (70 ml) was charged with 1.56 M tert-butyllithium in pentane (13.5 ml) at 0° C. under a nitrogen atmosphere. Was added. After the dropping was completed, the temperature was raised to 70° C. and the mixture was stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. The mixture was cooled to -50°C, boron tribromide (5.2 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hr. Then, the mixture was cooled to 0° C. again, N,N-diisopropylethylamine (2.7 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then heated to 80° C. and stirred with heating for 1 hour. The reaction solution was cooled to room temperature, an aqueous solution of sodium acetate cooled in an ice bath was added, and then ethyl acetate was added and the mixture was stirred for 1 hour. The deposited yellow precipitate was filtered, and the filtered product was washed with methanol, distilled water, and methanol in this order. did. The yellow precipitate was washed twice with hot heptane and then further purified by a silica gel short column (eluent: toluene/heptane=3/7 (volume ratio)). Then, the compound (1-321) was obtained by repeating the process of melt|dissolving in toluene and concentrating, adding heptane, and filtering after precipitating a crystal|crystallization (5.5g).

¹ H-NMR (CDCl ₃ ): δ=1.33 (s, 18H), 1.46 (s, 18H), 1.72-1.80 (m, 6H), 1.84-1.85 ( m, 6H), 2.07-2.09 (m, 3H), 5.69 (s, 2H), 6.67 (d, 2H), 6.86-6.92 (m, 5H), 7 .03-7.07 (m, 4H), 7.14 (dt, 4H), 7.43-7.46 (m, 6H), 8.94 (d, 2H).

Synthesis example (4): Synthesis of compound (1-328)

Under a nitrogen atmosphere, 4-(1-adamantyl)aniline (25.0 g), intermediate (IF) (32.0 g), Pd-132 (0.78 g) as a palladium catalyst, sodium-t-butoxide (NaOtBu). , 15.9 g) and xylene (100 ml) were placed in a flask and heated at 130° C. for 2 hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Then, methanol was added to the crude product obtained by concentrating the organic layer and the mixture was cooled, and then the obtained crystal was filtered. The crude product was purified by a silica gel short column (eluent: toluene), the organic layer was concentrated, heptane was added to the crude product obtained, the mixture was cooled, and the obtained crystals were filtered to obtain an intermediate (I -J) was obtained (41.0 g).

Under a nitrogen atmosphere, intermediate (IJ) (7.6 g), intermediate (IK) (8.0 g), Pd-132 (0.12 g) as a palladium catalyst, sodium-t-butoxide (NaOtBu, 2.5 g) and xylene (40 ml) were placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Heptane was added to the crude product obtained by concentrating the organic layer, the mixture was cooled, and the crystals obtained were filtered. The crystals were purified by a silica gel short column (eluent: toluene), and the crude product obtained by concentrating the organic layer was added with heptane and cooled, and the obtained crystals were filtered to obtain an intermediate (IL). ) Was obtained (13.6 g).

A flask containing intermediate (IL) (13.5 g) and tert-butylbenzene (100 ml) was charged with 1.56 M tert-butyllithium in pentane (18.9 ml) at 0° C. under a nitrogen atmosphere. Was added. After the dropping was completed, the temperature was raised to 70° C. and the mixture was stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. The mixture was cooled to -50°C, boron tribromide (7.2 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hr. Then, the mixture was cooled to 0° C. again, N,N-diisopropylethylamine (3.7 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then heated to 90° C. and stirred with heating for 1 hour. The reaction solution was cooled to room temperature, and an aqueous solution of sodium acetate cooled in an ice bath was added, and then ethyl acetate was added and the mixture was stirred for 1 hour, and heptane was further added, and then the precipitated yellow precipitate was filtered, and the filtered product was methanol, distilled water. And washed with methanol in that order. The yellow precipitate was washed with hot toluene and then further purified with a silica gel short column (eluent: toluene). Then, the compound (1-328) was obtained by dissolving in toluene and concentrating, repeating the process of adding heptane and precipitating a crystal|crystallization and filtering (5.7g).

¹ H-NMR (CDCl ₃ ): δ=1.47 (s, 9H), 1.48 (s, 9H), 1.78-1.87 (m, 12H), 2.07-2.09( m, 12H), 2.14-2.18 (m, 6H), 2.17 (s, 3H), 5.95 (d, 1H), 6.68 (d, 2H), 7.27 (t. , 2H), 7.28 (d, 2H), 7.45 (dd, 1H), 7.49 (dd, 1H), 7.64 (dd, 2H), 7.67 (dd, 2H), 8 .98 (d, 1H), 9.01 (d, 1H).

Synthesis example (5): Synthesis of compound (1-327)

Under a nitrogen atmosphere, intermediate (IJ) (5.9 g), intermediate (IM) (6.0 g), Pd-132 (0.10 g) as a palladium catalyst, sodium-t-butoxide (NaOtBu, 1.9 g) and xylene (30 ml) were placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Heptane was added to the crude product obtained by concentrating the organic layer, the mixture was cooled, and the crystals obtained were filtered. The crystals were purified by a silica gel short column (eluent: toluene), and the crude product obtained by concentrating the eluent was added heptane and cooled, and the obtained crystals were filtered to obtain an intermediate (IN). ) Was obtained (7.0 g).

A flask containing intermediate (IM) (7.0 g) and tert-butylbenzene (60 ml) was charged with 1.56 M tert-butyllithium in pentane (11.1 ml) at 0° C. under a nitrogen atmosphere. Was added. After the dropping was completed, the temperature was raised to 70° C. and the mixture was stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. The mixture was cooled to -50°C, boron tribromide (4.2 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hr. Then, the mixture was cooled to 0° C. again, N,N-diisopropylethylamine (2.2 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then heated to 80° C. and stirred with heating for 1 hour. The reaction solution was cooled to room temperature, and an aqueous solution of sodium acetate cooled in an ice bath was added, and then ethyl acetate was added and the mixture was stirred for 1 hour, and heptane was further added, and then the precipitated yellow precipitate was filtered. And washed with methanol in that order. Further purification was performed using a silica gel short column (eluent: toluene). Then, the compound (1-327) was obtained by repeating the process of melt|dissolving in toluene and concentrating, adding heptane, and filtering after precipitating a crystal|crystallization (3.0-g).

¹ H-NMR (CDCl ₃ ): δ=1.45 (s, 9H), 1.49 (s, 9H), 1.79-1.86 (m, 12H), 2.05-2.10( m, 12H), 2.15-2.17 (m, 6H), 6.11 (d, 1H), 6.13 (d, 1H), 6.74 (d, 2H), 7.24 (t. , 2H), 7.28 (d, 2H), 7.30 (d, 2H), 7.47 (dd, 1H), 7.52 (dd, 1H), 7.64 (dd, 2H), 7 .67 (dd, 2H), 9.00 (d, 1H), 9.02 (d, 1H).

Synthesis example (6): Synthesis of compound (1-332)

Under a nitrogen atmosphere, intermediate (I-J) (6.6 g), intermediate (I-O) (5.0 g), Pd-132 (0.11 g) as a palladium catalyst, sodium-t-butoxide (NaOtBu, 2.2 g) and xylene (35 ml) were placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Ethyl acetate was added to the crude product obtained by concentrating the organic layer and the mixture was cooled, and the crystals obtained were filtered. The crystals were purified by a silica gel short column (eluent: toluene), and the crude product obtained by concentrating the eluent was added heptane and cooled, and the obtained crystals were filtered to obtain an intermediate (IP). ) Was obtained (9.6 g).

A flask containing intermediate (IP) (9.5 g) and tert-butylbenzene (100 ml) was charged with 1.56 M tert-butyllithium in pentane (18.9 ml) at 0° C. under a nitrogen atmosphere. Was added. After the dropping was completed, the temperature was raised to 70° C. and the mixture was stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. The mixture was cooled to -50°C, boron tribromide (7.2 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hr. Then, the mixture was cooled to 0° C. again, N,N-diisopropylethylamine (3.7 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then heated to 80° C. and stirred with heating for 1 hour. The reaction solution was cooled to room temperature, an aqueous solution of sodium acetate cooled in an ice bath and then ethyl acetate were added, and the mixture was stirred for 1 hour, then, the organic layer was separated. After the organic solvent was distilled off, the residue was purified with a silica gel short column (eluent: toluene/heptane=2/8 (volume ratio)). Then, the compound (1-332) was obtained by repeating the process of melt|dissolving in toluene and concentrating, adding heptane, and filtering after depositing a crystal|crystallization (3.8g).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ=1.81-1.87 (m, 12H), 2.05-2.07 (m, 12H), 2.16-2.17 (m, 6H), 6.09 (d, 1H), 6.16 (d, 1H), 6.75 (dd, 2H), 7.23-7.31 (m, 6H), 7.39 (d, 2H), 7 .43 (dt, 1H), 7.50 (dd, 1H), 7.59 (dt, 1H), 7.65 (dd, 2H), 7.69 (t, 2H), 8.88 (d, 1H), 8.93 (d, 1H).

Synthesis example (7): Synthesis of compound (1-334)

Under a nitrogen atmosphere, 4-(1-adamantyl)aniline (12.7 g), 3,5-di-t-butylbromobenzene (15.0 g), Pd-132 (0.39 g) as a palladium catalyst, and sodium-t. -Butoxide (NaOtBu, 8.0 g) and xylene (100 ml) were placed in a flask and heated at 130°C for 2 hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, Solmix (A-11) was added to the crude product obtained by concentrating the organic layer and the mixture was cooled, and the obtained crystal was filtered. The crude product was purified by a silica gel short column (eluent: toluene), the organic layer was concentrated, heptane was added to the crude product obtained, the mixture was cooled, and the obtained crystals were filtered to obtain an intermediate (I -Q) was obtained (16.0 g).

Under a nitrogen atmosphere, intermediate (I-Q) (8.0 g), intermediate (I-K) (8.9 g), Pd-132 (0.14 g) as a palladium catalyst, sodium-t-butoxide (NaOtBu, 2.8 g) and xylene (40 ml) were placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and toluene were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Heptane was added to the crude product obtained by concentrating the organic layer, the mixture was cooled, and the crystals obtained were filtered. The crystals were purified by a silica gel short column (eluent: toluene), and the crude product obtained by concentrating the organic layer was added heptane and cooled, and the obtained crystals were filtered to obtain an intermediate (IR). Was obtained (13.0 g).

A flask containing intermediate (I-R) (13.0 g) and tert-butylbenzene (100 ml) was charged with 1.56 M tert-butyllithium in pentane (20.9 ml) at 0° C. under a nitrogen atmosphere. Was added. After the dropping was completed, the temperature was raised to 70° C. and the mixture was stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. The mixture was cooled to -50°C, boron tribromide (7.9 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hr. Then, the mixture was cooled to 0° C. again, N,N-diisopropylethylamine (4.1 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then heated to 90° C. and stirred with heating for 1 hour. The reaction solution was cooled to room temperature, an aqueous solution of sodium acetate cooled in an ice bath and then ethyl acetate were added, the mixture was stirred for 1 hour, and then the organic layer was separated by liquid separation. After the organic solvent was distilled off, the residue was purified with a silica gel short column (eluent: toluene). Then, the compound (1-334) was obtained by dissolving in toluene and concentrating, repeating the process of adding ethyl acetate and depositing a crystal|crystallization and filtering.

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ=1.37 (s, 18H), 1.47 (s, 9H), 1.49 (s, 9H), 1.79-1.85 (m, 6H). , 2.10-2.11 (m, 6H), 2.15-2.16 (m, 6H), 5.96 (s, 1H), 5.97 (s, 1H), 6.68 (d , 1H), 6.70 (d, 1H), 7.20 (d, 2H), 7.26-7.28 (m, 2H), 7.47 (dd, 1H), 7.50 (dd, 2H), 7.60 (t, 2H), 7.67 (tt, 2H), 9.00 (d, 1H), 9.01 (d, 1H).

Synthesis Example (8): Synthesis of Compound (1-339)

Under a nitrogen atmosphere, 2,3-dichloroaniline (10.0 g), 4-cyclohexyl bromobenzene (36.9 g), Pd-132 (0.44 g) as a palladium catalyst, sodium-t-butoxide (NaOtBu, 14.8 g). ) And xylene (120 ml) were placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. The crude product obtained by concentrating the organic layer was purified by a silica gel short column (eluent: toluene/heptane = 2/8 (volume ratio)), and the eluent was concentrated to obtain a crude product. The mixture (A-11) was added and cooled, and the obtained crystals were filtered to obtain an intermediate (IS) (25.5 g).

Under a nitrogen atmosphere, N-(4-tert-butylphenyl)-4-tert-butylaniline (4.5 g), intermediate (IS) (36.9 g), Pd-132 (0.11 g) as a palladium catalyst, Sodium-t-butoxide (NaOtBu, 2.3 g) and xylene (35 ml) were placed in a flask and heated at 120° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. The crude product obtained by concentrating the organic layer was purified by a silica gel short column (eluent: toluene), and the crude product obtained by concentrating the eluent was added heptane and cooled to obtain crystals. The intermediate body (IT) was obtained by filtering (10.5g).

A flask containing intermediate (IT) (10.5 g) and tert-butylbenzene (100 ml) was charged with 1.56 M tert-butyllithium in pentane (19.1 ml) at 0° C. under a nitrogen atmosphere. Was added. After the dropping was completed, the temperature was raised to 70° C. and the mixture was stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. The mixture was cooled to -50°C, boron tribromide (7.2 g) was added, the temperature was raised to room temperature, and the mixture was stirred for 0.5 hr. Then, the mixture was cooled to 0° C. again, N,N-diisopropylethylamine (3.7 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, then heated to 80° C. and stirred with heating for 1 hour. The reaction solution was cooled to room temperature, an aqueous solution of sodium acetate cooled in an ice bath and then ethyl acetate were added, the mixture was stirred for 1 hour, heptane was added, and the deposited yellow precipitate was filtered. The obtained precipitate was purified by a silica gel short column (eluent: toluene). Then, the compound (1-339) was obtained by dissolving in toluene and concentrating, repeating the process of adding ethyl acetate and further adding heptane and precipitating and crystallizing, and filtering (5.3-g).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ=1.25-1.64 (m, 28H), 1.79-1.81 (m, 2H), 1.89-1.93 (m, 4H), 2.03-2.07 (m, 4H), 2.61-2.70 (m, 2H), 6.12 (t, 2H), 6.71 (d, 1H), 6.74 (d, 1H), 7.22-7.30 (m, 6H), 7.48-7.53 (m, 3H), 7.67 (d, 2H), 8.83 (d, 1H), 8.99. (D, 1H).

The other polycyclic aromatic compound of the present invention can be synthesized by a method according to the above-described synthesis example by appropriately changing the raw material compound.

Next, in order to explain the present invention in more detail, examples of organic EL devices using the compound of the present invention will be shown, but the present invention is not limited thereto.

<Evaluation of vapor deposition type organic EL device>
The organic EL devices according to Example 1, Examples 2 to 3 and Examples 4 to 28 were produced, and the voltage (V), the emission wavelength (nm), and the external quantum efficiency (%), which are characteristics when emitting light at 1000 cd/m ^2. ) Was measured, and then the time for maintaining 90% or more of the initial brightness when driven at constant current at a current density of 10 mA/cm ² was measured.

The quantum efficiency of a light emitting device includes an internal quantum efficiency and an external quantum efficiency. The internal quantum efficiency is such that the external energy injected as an electron (or a hole) into the light emitting layer of the light emitting device is purely converted into a photon. It shows the percentage. On the other hand, the external quantum efficiency is calculated based on the amount of the photons emitted to the outside of the light emitting element, and some of the photons generated in the light emitting layer continue to be absorbed or reflected inside the light emitting element. For example, the external quantum efficiency is lower than the internal quantum efficiency because it is not emitted to the outside of the light emitting device.

The method of measuring the external quantum efficiency is as follows. A voltage/current generator R6144 manufactured by Advantest was used to apply a voltage at which the brightness of the device was 1000 cd/m ² to cause the device to emit light. Spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface using a spectral radiance meter SR-3AR manufactured by TOPCON. Assuming that the light emitting surface is a perfect diffusion surface, the value of the measured spectral radiance of each wavelength component divided by the wavelength energy and multiplied by π is the number of photons at each wavelength. Next, the number of photons in all observed wavelength regions was integrated to obtain the total number of photons emitted from the device. The external quantum efficiency is the number obtained by dividing the applied current value by the elementary charge and the number of carriers injected into the device, and the number of all photons emitted from the device divided by the number of carriers injected into the device.

<Example 1>
The material constitution of each layer and the EL characteristic data in the organic EL device according to Example 1 are shown in Tables 1A and 1B below.

In Table 1A, "HI" is ^N 4, N ^{4 '-} diphenyl ^-N 4, N ^4' - bis (9-phenyl -9H- carbazol-3-yl) - [1,1'-biphenyl] -4, 4'-diamine, "HAT-CN" is 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile, and "HT-1" is N-([1,1'-biphenyl. ]-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine [1,1′-biphenyl]-4 -Amine, "HT-2" is N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1"-terphenyl] -4-amine, "BH-1" is 2-(10-phenylanthracen-9-yl)naphtho[2,3-b]benzofuran, and "ET-1" is 4,6,8,10. -Tetraphenyl[1,4]benzoxaborinino[2,3,4-kl]phenoxaborinine, wherein "ET-2" is 3,3'-((2-phenylanthracene-9,10-diyl ) Bis(4,1-phenylene))bis(4-methylpyridine). The chemical structure is shown below together with "Liq".

A 26 mm×28 mm×0.7 mm glass substrate (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO formed to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (Showa Vacuum Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, BH-1, compound (1-25), ET. A molybdenum vapor deposition boat containing -1 and ET-2, and an aluminum nitride vapor deposition boat containing Liq, LiF, and aluminum were attached.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was decompressed to 5×10 ⁻⁴ Pa, first, HI was heated to vapor-deposit to have a film thickness of 40 nm, and then HAT-CN was heated to vapor-deposit to have a film thickness of 5 nm. Next, HT-1 is heated and vapor-deposited so as to have a film thickness of 45 nm, and then HT-2 is heated and vapor-deposited so as to have a film thickness of 10 nm to form a hole layer composed of four layers. did. Next, BH-1 and the compound (1-25) were simultaneously heated and vapor-deposited so as to have a film thickness of 25 nm to form a light emitting layer. The vapor deposition rate was adjusted so that the weight ratio of BH-1 and compound (1-25) was about 98:2. Further, ET-1 is heated and vapor-deposited so as to have a film thickness of 5 nm, then ET-2 and Liq are simultaneously heated and vapor-deposited so as to have a film thickness of 25 nm to form an electronic layer composed of two layers. Formed. The vapor deposition rate was adjusted so that the weight ratio of ET-2 and Liq was about 50:50. The vapor deposition rate of each layer was 0.01 to 1 nm/sec. Then, LiF is heated to vapor-deposit at a vapor deposition rate of 0.01 to 0.1 nm/sec so as to have a film thickness of 1 nm, and then aluminum is heated to vapor-deposit to have a film thickness of 100 nm to form a cathode. Then, an organic EL device was obtained.

A DC voltage was applied with the ITO electrode as the anode and the LiF/aluminum electrode as the cathode, and the characteristics at 1000 cd/m ² light emission were measured. As a result, blue light emission with a wavelength of 458 nm was obtained, the driving voltage was 3.68 V, and the external quantum efficiency was external. Was 7.96%. In addition, the time for holding 90% or more of the initial brightness was 329 hours.

<Examples 2 and 3>
The material configurations of the respective layers and the EL characteristic data in the organic EL devices according to Examples 2 and 3 are shown in Tables 2A and 2B below.

<Example 2>
A 26 mm×28 mm×0.7 mm glass substrate (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO formed to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (Showa Vacuum Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, BH-1, compound (1-16), ET. A molybdenum vapor deposition boat containing -1 and ET-2, and an aluminum nitride vapor deposition boat containing Liq, LiF, and aluminum were attached.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was decompressed to 5×10 ⁻⁴ Pa, first, HI was heated to vapor-deposit to have a film thickness of 40 nm, and then HAT-CN was heated to vapor-deposit to have a film thickness of 5 nm. Next, HT-1 is heated and vapor-deposited so as to have a film thickness of 45 nm, and then HT-2 is heated and vapor-deposited so as to have a film thickness of 10 nm to form a hole layer composed of four layers. did. Next, BH-1 and the compound (1-16) were simultaneously heated and vapor-deposited so as to have a film thickness of 25 nm to form a light emitting layer. The vapor deposition rate was adjusted so that the weight ratio of BH-1 to compound (1-16) was about 98:2. Further, ET-1 is heated and vapor-deposited so as to have a film thickness of 5 nm, then ET-2 and Liq are simultaneously heated and vapor-deposited so as to have a film thickness of 25 nm to form an electronic layer composed of two layers. Formed. The vapor deposition rate was adjusted so that the weight ratio of ET-2 and Liq was about 50:50. The vapor deposition rate of each layer was 0.01 to 1 nm/sec. Then, LiF is heated to vapor-deposit at a vapor deposition rate of 0.01 to 0.1 nm/sec so as to have a film thickness of 1 nm, and then aluminum is heated to vapor-deposit to have a film thickness of 100 nm to form a cathode. Then, an organic EL device was obtained.

A DC voltage was applied with the ITO electrode as the anode and the LiF/aluminum electrode as the cathode, and the characteristics at 1000 cd/m ² light emission were measured. As a result, blue light emission with a wavelength of 464 nm was obtained, the drive voltage was 3.49 V, and the external quantum efficiency was external. Was 8.57%. In addition, the time for holding 90% or more of the initial brightness was 111 hours.

<Example 3>
An organic EL device was produced by the method according to Example 2 (Table 2A), and EL characteristics were measured (Table 2B).

<Examples 4 to 28>
Table 3A and Table 3B below show the material constitution of each layer and the EL characteristic data in the organic EL devices according to Examples 4 to 28.

<Example 4>
A 26 mm×28 mm×0.7 mm glass substrate (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO formed to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (Showa Vacuum Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, BH-1, compound (1-16), ET. A molybdenum vapor deposition boat containing -1 and ET-2, and an aluminum nitride vapor deposition boat containing Liq, LiF, and aluminum were attached.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was decompressed to 5×10 ⁻⁴ Pa, first, HI was heated to vapor-deposit to have a film thickness of 40 nm, and then HAT-CN was heated to vapor-deposit to have a film thickness of 5 nm. Next, HT-1 is heated and vapor-deposited so as to have a film thickness of 45 nm, and then HT-2 is heated and vapor-deposited so as to have a film thickness of 10 nm to form a hole layer composed of four layers. did. Next, BH-1 and the compound (1-16) were simultaneously heated and vapor-deposited so as to have a film thickness of 25 nm to form a light emitting layer. The vapor deposition rate was adjusted so that the weight ratio of BH-1 to compound (1-16) was about 98:2. Further, ET-1 is heated and vapor-deposited so as to have a film thickness of 5 nm, then ET-2 and Liq are simultaneously heated and vapor-deposited so as to have a film thickness of 25 nm to form an electronic layer composed of two layers. Formed. The vapor deposition rate was adjusted so that the weight ratio of ET-2 and Liq was about 50:50. The vapor deposition rate of each layer was 0.01 to 1 nm/sec. Then, LiF is heated to vapor-deposit at a vapor deposition rate of 0.01 to 0.1 nm/sec so as to have a film thickness of 1 nm, and then aluminum is heated to vapor-deposit to have a film thickness of 100 nm to form a cathode. Then, an organic EL device was obtained.

A DC voltage was applied with the ITO electrode as the anode and the LiF/aluminum electrode as the cathode, and the characteristics at 1000 cd/m ² light emission were measured. As a result, blue light emission with a wavelength of 464 nm was obtained, the drive voltage was 3.49 V, and the external quantum efficiency was external. Was 8.57%. In addition, the time for holding 90% or more of the initial brightness was 111 hours.

<Examples 5 to 28>
An organic EL device was produced by the method according to Example 4 (Table 3A) and EL characteristics were measured (Table 3B).

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

<Synthesis of high molecular host compound: SPH-101>
SPH-101 was synthesized according to the method described in WO 2015/008851. A copolymer having M2 or M3 bonded is obtained next to M1, and it is estimated from the charging ratio that each unit is 50:26:24 (molar ratio).

<Synthesis of High Molecular Hole Transport Compound: XLP-101>
XLP-101 was synthesized according to the method described in JP-A-2018-61028. A copolymer having M2 or M3 bonded is obtained next to M7, and it is estimated from the charging ratio that each unit is 40:10:50 (molar ratio).

<Examples 29 to 37>
A coating solution of a material forming each layer is prepared to prepare a coating type organic EL device.

<Production of Organic EL Devices of Examples 29 to 31>
Table 4 shows the material constitution of each layer in the organic EL element.

The structure of "ET1" in Table 4 is shown below.

<Preparation of composition (1) for forming light emitting layer>
A composition (1) for forming a light emitting layer 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 under reduced pressure, a coating film having no film defect and excellent in 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 polymer thereof, a monomer of the polycyclic aromatic compound or a polymer thereof (that is, the monomer has a reactive substituent). And a polymer cross-linked product obtained by further cross-linking the polymer compound. The polymer compound for obtaining the polymer crosslinked product has a crosslinkable substituent.

<PEDOT:PSS solution>
A commercially available PEDOT:PSS solution (Clevios(TM) P VP AI4083, an aqueous dispersion of PEDOT:PSS, 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 Co., Ltd.) were dissolved in toluene to give an OTPD concentration of 0.7% by weight and an IK-2 concentration of 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 29>
A PEDOT:PSS solution was spin-coated on a glass substrate on which ITO was deposited to a thickness of 150 nm, and baked on a hot plate at 200° C. for 1 hour to form a PEDOT:PSS film with a thickness of 40 nm. (Hole injection layer). Then, 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 to obtain a solution. An OTPD film having a film thickness of 30 nm which is insoluble in is formed (hole transport layer). Then, the composition (1) for forming a light emitting layer is spin-coated and baked on a hot plate at 120° C. for 1 hour to form a light emitting layer having a film thickness of 20 nm.

The prepared multilayer film was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing ET1, a molybdenum vapor deposition boat containing LiF, and a tungsten vapor containing aluminum. Attach the evaporation 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 that the film thickness becomes 1 nm. Next, aluminum is heated and vapor-deposited to have a film thickness of 100 nm to form a cathode. In this way, an organic EL device is obtained.

<Example 30>
An organic EL device is obtained in the same manner as in Example 29. Note that the hole-transporting layer is formed by spin-coating a solution of XLP-101 and baking it on a hot plate at 200° C. for 1 hour to form a film having a thickness of 30 nm.

<Example 31>
An organic EL device is obtained in the same manner as in Example 29. The hole-transporting layer is formed by spin-coating a PCz solution and baking it on a hot plate at 120° C. for 1 hour to form a film having a thickness of 30 nm.

<Production of Organic EL Devices of Examples 32 to 34>
Table 5 shows the material constitution of each layer in the organic EL device.

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

A light emitting layer forming composition (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

A light emitting layer forming composition (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 5, "DOBNA" is 3,11-di-o-tolyl-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene. The chemical structure is shown below.

<Example 32>
After spin coating a solution of ND-3202 (manufactured by Nissan Chemical Industries, Ltd.) on a glass substrate on which ITO was deposited to a thickness of 45 nm, it was 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 thickness of 50 nm is formed (hole injection layer). Then, an XLP-101 solution is spin-coated and heated at 200° C. for 30 minutes on a hot plate in a nitrogen gas atmosphere to form an XLP-101 film having a thickness of 20 nm (hole transport layer). Then, the composition for forming a light emitting layer (2) is spin-coated and heated at 130° C. for 10 minutes in a nitrogen gas atmosphere to form a light emitting layer having a thickness of 20 nm.

The prepared multilayer film was fixed to a substrate holder of a commercially available vapor deposition apparatus (Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing TSPO1, a molybdenum vapor deposition boat containing LiF, and a tungsten vapor containing aluminum. Attach the evaporation 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 that the film thickness becomes 1 nm. Next, aluminum is heated and vapor-deposited to have a film thickness of 100 nm to form a cathode. In this way, an organic EL device is obtained.

<Examples 33 and 34>
Using the composition (3) or (4) for forming a light emitting layer, an organic EL device is obtained in the same manner as in Example 32.

<Production of Examples 35 to 37 organic EL device>
Table 6 shows the material constitution of each layer in the organic EL element.

<Preparation of Compositions (5) to (7) for Forming Light Emitting Layer>
A composition for forming a light emitting layer 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

A composition for forming a light emitting layer 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

A composition for forming a light emitting layer 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 6, “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 35>
After spin coating a solution of ND-3202 (manufactured by Nissan Chemical Industries, Ltd.) on a glass substrate on which ITO was deposited to a thickness of 45 nm, it was 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 thickness of 50 nm is formed (hole injection layer). Then, an XLP-101 solution is spin-coated and heated at 200° C. for 30 minutes on a hot plate in a nitrogen gas atmosphere to form an XLP-101 film having a thickness of 20 nm (hole transport layer). Then, the composition (5) for forming a light emitting layer is spin-coated and heated at 130° C. for 10 minutes in a nitrogen gas atmosphere to form a light emitting layer having a thickness of 20 nm.

The prepared multilayer film was fixed to a substrate holder of a commercially available vapor deposition apparatus (Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing TSPO1, a molybdenum vapor deposition boat containing LiF, and a tungsten vapor containing aluminum. Attach the evaporation 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 that the film thickness becomes 1 nm. Next, aluminum is heated and vapor-deposited to have a film thickness of 100 nm to form a cathode. In this way, an organic EL device is obtained.

<Examples 36 and 37>
Using the composition (6) or (7) for forming a light emitting layer, an organic EL device is obtained in the same manner as in Example 35.

In the present invention, by providing a novel cycloalkyl-substituted polycyclic aromatic compound, it is possible to increase the choice of materials for organic devices such as materials for organic EL devices. In addition, by using a novel cycloalkyl-substituted polycyclic aromatic compound as a material for an organic EL device, for example, an organic EL device having excellent luminous efficiency and device life, a display device including the same, and a lighting device including the same, etc. Can be provided.

100 Organic Electroluminescent Element 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 (21)

A polycyclic aromatic compound represented by the following general formula (1).
(In the above formula (1),
Ring A, Ring B and Ring C are each independently an aryl ring , and at least one hydrogen in these rings may be substituted with aryl, diarylamino, alkyl, alkoxy or aryloxy. At least one hydrogen in may be substituted with aryl or alkyl ,
Y ¹ is B ,
X ¹ and X ² are each independently >NR , wherein R in >NR is aryl, alkyl or cycloalkyl , and at least one hydrogen in these is substituted with alkyl. Well,
At least one hydrogen in the compound represented by formula (1) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound represented by formula (1) is substituted with cycloalkyl. ) A polycyclic aromatic compound represented by the following general formula (2).
(In the above formula (2),
R ^{1 to} R ¹¹ are each independently hydrogen, aryl, diarylamino, alkyl, alkoxy or aryloxy , in which at least one hydrogen may be substituted with aryl or alkyl ; Adjacent groups of ^{1 to} R ¹¹ may be bonded to each other to form an aryl ring together with a ring, b ring or c ring, and at least one hydrogen in the formed ring is aryl, diarylamino, Optionally substituted with alkyl, alkoxy or aryloxy , in which at least one hydrogen is optionally substituted with aryl or alkyl ,
Y ¹ is B ,
X ¹ and X ² are each independently >NR , and R in >NR is an aryl having 6 to 12 carbons, an alkyl having 1 to 6 carbons, or an alkyl having 3 to 14 carbons. Cycloalkyl ,
At least one hydrogen in the compound represented by formula (2) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl. ) R ^{1 to} R ¹¹ are each independently hydrogen, aryl having 6 to 30 carbon atoms, diarylamino (where aryl is aryl having 6 to 12 carbon atoms) or alkyl having 1 to 24 carbon atoms , and R 1 Adjacent groups of ^{1 to} R ¹¹ may be bonded to each other to form an aryl ring having 9 to 16 carbon atoms with a ring, b ring or c ring, and at least one hydrogen in the formed ring is It may be substituted with aryl having 6 to 10 carbons or alkyl having 1 to 12 carbons,
Y ¹ is B ,
X ¹ and X ² are each independently >NR , and R in >NR is an aryl having 6 to 10 carbons, an alkyl having 1 to 4 carbons, or an alkyl having 5 to 10 carbons. Cycloalkyl,
At least one hydrogen in the compound represented by formula (2) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl,
The polycyclic aromatic compound according to claim 2. R ^{1 to} R ¹¹ are each independently hydrogen, aryl having 6 to 16 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms) or alkyl having 1 to 12 carbon atoms ,
Y ¹ is B ,
X ¹ and X ² are each independently >NR , and R in >NR is an aryl having 6 to 10 carbons, an alkyl having 1 to 4 carbons, or an alkyl having 5 to 10 carbons. Cycloalkyl, and
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl,
The polycyclic aromatic compound according to claim 2. R ^{1 to} R ¹¹ are each independently hydrogen, aryl having 6 to 16 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms) or alkyl having 1 to 12 carbon atoms,
Y ¹ is B,
X ¹ and X ² are each independently >NR , and R in >NR is an aryl having 6 to 10 carbons, an alkyl having 1 to 4 carbons, or an alkyl having 5 to 10 carbons. Cycloalkyl, and
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl,
The polycyclic aromatic compound according to claim 2. The polycyclic aromatic compound according to any one of claims 1 to 5, which is substituted with a cycloaryl- substituted diarylamino group . The polycyclic aromatic compound according to claim ² , wherein R ² is a cycloaryl-substituted diarylamino group . The polycyclic aromatic compound according to claim 1, wherein the cycloalkyl is a cycloalkyl having 3 to 20 carbon atoms. The polycyclic aromatic compound according to claim 1, wherein the halogen is fluorine. The polycyclic aromatic compound according to claim 1, which is represented by any one of the following structural formulas.
(In the above structural formulas, "Me" represents a methyl group, and "tBu" represents a t-butyl group.) The material for organic devices containing the polycyclic aromatic compound in any one of Claims 1-10. The organic device material according to claim 11 , wherein the organic device material is an organic electroluminescent element material, an organic field effect transistor material, or an organic thin film solar cell material. The material for an organic device according to claim 12 , wherein the material for an organic electroluminescent element is a material for a light emitting layer. An ink composition comprising the polycyclic aromatic compound according to claim 1, and an organic solvent. An organic electroluminescent device comprising a pair of electrodes composed of an anode and a cathode, and an organic layer which is disposed between the pair of electrodes and which contains the polycyclic aromatic compound according to claim 1 . The organic electroluminescent device according to claim 15 , wherein the organic layer is a light emitting layer. The organic electroluminescent device according to claim 16 , wherein the light emitting layer contains a host and the polycyclic aromatic compound as a dopant. The organic electroluminescent device according to claim 17 , wherein the host is an anthracene compound, a fluorene compound, or a dibenzochrysene compound. It has an electron transport layer and/or an electron injection layer disposed between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, a fluoranthene derivative, or BO. system derivative, anthracene derivative, containing benzo fluorene derivative, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, at least one member selected from the group consisting of phenanthroline derivatives and quinolinol-based metal complexes, claim The organic electroluminescent element as described in any one of 15 to 18 . The electron-transporting layer and/or the electron-injecting layer may further include 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. Claims containing 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. 19. The organic electroluminescent device according to item 19 . A display device or a lighting device comprising the organic electroluminescent element according to claim 15 .