WO2019198699A1

WO2019198699A1 - Cycloalkyl-substituted polycyclic aromatic compound

Info

Publication number: WO2019198699A1
Application number: PCT/JP2019/015410
Authority: WO
Inventors: 琢次畠山; 一志枝連; 笹田　康幸; 詠希町田
Original assignee: 学校法人関西学院; Jnc株式会社
Priority date: 2018-04-12
Filing date: 2019-04-09
Publication date: 2019-10-17
Also published as: KR20240113603A; TW201945374A

Abstract

The present invention can increase the number of choices of materials for organic devices such as materials for organic EL elements, by introducing a cycloalkyl group into a novel polycyclic aromatic compound which comprises a plurality of aromatic rings connected by, for example, a boron atom and an oxygen atom. The novel cycloalkyl-substituted polycyclic aromatic compound can be used as a material for organic EL elements to provide, for example, an organic EL element excellent in terms of luminescent efficiency and element life.

Description

Cycloalkyl-substituted polycyclic aromatic compounds

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, a display device and a lighting device. In the present specification, “organic electroluminescent device” may be referred to as “organic EL device” or simply “device”.

2. Description of the Related Art Conventionally, display devices using light emitting elements that emit electroluminescence have been studied variously because they can be reduced in power and thinned. Further, organic electroluminescent elements made of organic materials can be easily reduced in weight and size. Therefore, it has been actively studied. In particular, the development of organic materials with emission characteristics such as blue, which is one of the three primary colors of light, and the organic materials with charge transporting ability (possibility of becoming semiconductors and superconductors) such as holes and electrons. Development has been actively researched regardless of whether it is a high molecular compound or a low molecular compound.

The organic EL element has a structure composed of a pair of electrodes composed of an anode and a cathode, and one layer or a plurality of layers including an organic compound disposed between the pair of electrodes. Examples of the layer containing an organic compound include a light-emitting layer and a charge transport / injection layer that transports or injects charges such as holes and electrons. 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). Further, 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, an anthracene compound has been developed (Japanese Patent Laid-Open No. 2005-170911).

In recent years, a material obtained by improving a triphenylamine derivative as a material used for an organic EL device or an organic thin film solar cell has been reported (International Publication No. 2012/118164). This material is based on 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 enhanced by linking aromatic rings constituting triphenylamine. In this document, for example, the charge transport property of a NO-linked compound (Compound 1 on page 63) is evaluated, but a method for producing a material other than the NO-linked compound is not described, and the element to be linked is not described. Since the electronic state of the entire compound is different if it is different, the characteristics obtained from materials other than NO-linked compounds are not yet known. Other examples of such compounds can be found (WO 2011/107186). For example, a compound having a conjugated structure with a large triplet exciton energy (T1) can emit phosphorescence having a shorter wavelength, and thus is useful as a blue light-emitting layer material. In addition, a compound having a novel conjugated structure having a large T1 is also required as an electron transport material or a hole transport material sandwiching the light emitting layer.

The host material of the organic EL element is generally a molecule in which a plurality of existing aromatic rings such as benzene and carbazole are connected by a single bond, phosphorus atom or silicon atom. This is because a large HOMO-LUMO gap (band gap Eg in a thin film) required for the host material is secured by connecting a large number of relatively conjugated aromatic rings. Furthermore, a host material of an organic EL device using a phosphorescent material or a thermally activated delayed fluorescent material also requires high triplet excitation energy (E _T ), but the molecule has a donor or acceptor aromatic ring or substituent. Can be combined to localize SOMO1 and SOMO2 in the triplet excited state (T1) and reduce the exchange interaction between the two orbitals, thereby improving the triplet excitation energy (E _T ). It becomes. However, a small conjugated aromatic ring does not have sufficient redox stability, and a device using a molecule formed by connecting existing aromatic rings as a host material does not have a sufficient lifetime. On the other hand, polycyclic aromatic compounds having an extended π-conjugated system generally have excellent redox stability, but have a low HOMO-LUMO gap (band gap Eg in a thin film) and triplet excitation energy (E _T ). It has been considered unsuitable for host materials.

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

As described above, various materials have been developed as materials for use in organic EL elements, but in order to increase the choice of materials for organic EL elements, development of materials made of compounds different from conventional ones is desired. Yes. In particular, the organic EL characteristics obtained from materials other than the NO-linked compounds reported in Patent Documents 1 to 4 and the production method thereof are not yet known.

Further, in Patent Document 6, a polycyclic aromatic compound containing boron and an organic EL device using the same are reported. However, in order to further improve device characteristics, light emission that can improve luminous efficiency and device lifetime. There is a need for layer materials, particularly dopant materials.

As a result of intensive studies to solve the above problems, the present inventors have arranged a layer containing a polycyclic aromatic compound into which a cycloalkyl group has been introduced between a pair of electrodes, for example, to constitute an organic EL device. The present inventors have found that an excellent organic EL device can be obtained and completed the present invention. That is, the present invention relates to organic materials such as the following cycloalkyl-substituted polycyclic aromatic compounds or multimers thereof, and organic EL device materials containing the following cycloalkyl-substituted polycyclic aromatic compounds or multimers thereof. Providing device materials.

In this specification, the chemical structure or substituent may be represented by the number of carbons. However, the number of carbons in the case where a substituent is substituted on the chemical structure or the substituent is further substituted on the chemical group is the chemical structure. And the number of carbon atoms of each substituent, and does not mean the total number of carbon atoms of the chemical structure and the substituent, or the total number of carbon atoms of the substituent and the substituent. For example, “substituent B of carbon number Y substituted by substituent A of carbon number X” means that “substituent B of carbon number Y” is substituted for “substituent B of carbon number Y”. The carbon number Y is not the total carbon number of the substituent A and the substituent B. Further, for example, “substituent B having carbon number Y substituted with substituent A” means that “substituent A having no carbon number” is substituted for “substituent B having carbon number Y”. 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 polycyclic aromatic compounds 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 in the 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 An aryl, an optionally substituted heteroaryl, an optionally substituted alkyl or an optionally substituted cycloalkyl, wherein R of> C (—R) ₂ is hydrogen, an optionally substituted aryl Or 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.
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 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 bonded via a single bond or a linking group) Optionally substituted), 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 A 5- or 6-membered ring sharing a bond with the fused bicyclic 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 in the 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 R may be aryl, alkyl optionally substituted with heteroaryl, alkyl or cycloalkyl, and R in> C (—R) ₂ is hydrogen, aryl or alkyl optionally substituted with alkyl, and R of> N—R and / or R of> C (—R) ₂ may be —O—, —S—, —C (—R) ₂ — or a single bond to form A ring, B ring and / or Or it may be bonded to the C ring, R in the —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 represented by formula (1) is substituted with cycloalkyl,
Item 9. The polycyclic aromatic compound or a multimer thereof according to Item 1.

Item 3.
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 (the two aryls are bonded via a single bond or a linking group). And at least one hydrogen in these may be substituted with aryl, heteroaryl or alkyl, and adjacent groups of R ¹ to R ¹¹ may be It may be bonded 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 May be bonded via a single bond or a linking group), substituted with alkyl, alkoxy or aryloxy, wherein at least one hydrogen is substituted with aryl, heteroaryl or alkyl You can,
Y ¹ is B, P, P═O, P═S, Al, Ga, As, Si—R or Ge—R, where R in Si—R and Ge—R is 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, aryl having 6 to 12 carbons Or R of> N—R and / or R of> 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 in the —C (—R) ₂ — is alkyl having 1 to 6 carbon atoms,
At least one hydrogen in the compound of formula (2) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound represented by the 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 (wherein aryl is aryl having 6 to 12 carbon atoms), diarylboryl (provided that Aryl is aryl having 6 to 12 carbons, and 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 may be bonded 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. At least one hydrogen may be substituted with aryl having 6 to 10 carbon atoms or alkyl having 1 to 12 carbon atoms;
Y ¹ is B, P, P═O, P═S or Si—R, and R in the Si—R is aryl having 6 to 10 carbon atoms or alkyl having 1 to 4 carbon atoms,
X ¹ and X ² are each independently>O,>N—R,> C (—R) ₂ or> S, where R in> N—R is aryl having 6 to 10 carbon atoms, carbon An alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, wherein R of> C (—R) ₂ is hydrogen, aryl having 6 to 10 carbon atoms or alkyl having 1 to 4 carbon atoms;
At least one hydrogen in the compound of 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. The 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 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 , wherein R in> N—R is aryl having 6 to 10 carbons, 1 to C 4 alkyl or cycloalkyl having 5 to 10 carbon atoms, wherein R of> C (—R) ₂ is hydrogen, aryl having 6 to 10 carbon atoms or alkyl having 1 to 4 carbon atoms, and
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl;
Item 4. The 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, where R in> N—R is aryl having 6 to 10 carbon atoms , An alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, and
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl;
Item 4. The 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. 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 the multimer thereof according to any one of Items 1 to 9, wherein the halogen is fluorine.

Item 11.
Item 9. The polycyclic aromatic compound according to Item 1, represented by any of the following structural formulas.

(In the above structural formulas, “Me” represents a methyl group, and “tBu” represents a t-butyl group.)

Item 12.
12. A reactive compound, wherein 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.
Item 13. A polymer compound obtained by polymerizing the reactive compound described in Item 12 as a monomer, or a polymer crosslinked product obtained by further crosslinking the polymer compound.

Item 14.
Item 13. A pendant polymer compound obtained by substituting the reactive compound described in Item 12 for a main chain polymer, or a pendant polymer crosslinked product obtained by further crosslinking the pendant polymer compound.

Item 15.
Item 12. 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 13. An organic device material comprising the reactive compound according to Item 12.

Item 17.
Item 14. An organic device material comprising the polymer compound or polymer crosslinked 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 comprising the polycyclic aromatic compound or the multimer thereof according to any one of Items 1 to 11 and an organic solvent.

Item 22.
Item 13. An ink composition comprising the reactive compound according to Item 12 and an organic solvent.

Item 23.
An ink composition comprising a main chain type polymer, the reactive compound described in Item 12, and an organic solvent.

Item 24.
Item 14. An ink composition comprising the polymer compound or polymer crosslinked 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.
Item 11. A pair of electrodes composed of an anode and a cathode, a polycyclic aromatic compound according to any one of Items 1 to 11 or a multimer thereof disposed between the pair of electrodes, a reactive compound according to Item 12, an item 13 Or an organic layer containing the pendant-type polymer compound or pendant-type polymer cross-linked product according to Item 14.

Item 27.
Item 11. A pair of electrodes composed of an anode and a cathode, a polycyclic aromatic compound according to any one of Items 1 to 11 or a multimer thereof disposed between the pair of electrodes, a reactive compound according to Item 12, an item 13 An organic electroluminescent device comprising the polymer compound or crosslinked polymer described in 1) or the light-emitting layer containing the pendant polymer compound or pendant crosslinked polymer described in 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 body, a pendant polymer compound, or a pendant polymer crosslinked body. Item 27. The organic electroluminescent device according to Item 27.

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

Item 30.
An electron transport layer and / or an electron injection layer disposed between the cathode and the light emitting layer, wherein at least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, a fluoranthene derivative, BO Item 26 containing at least one selected from the group consisting of a series derivative, anthracene derivative, benzofluorene derivative, phosphine oxide derivative, pyrimidine derivative, carbazole derivative, triazine derivative, benzimidazole derivative, phenanthroline derivative, and quinolinol metal complex 30. The organic electroluminescence device as described in any one of .about.29.

Item 31.
The electron transport layer and / or the electron injection layer further includes an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or an alkaline earth metal. Item 30 contains at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes. The organic electroluminescent element of description.

Item 32.
A polymer compound in which at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer is polymerized using a low molecular compound capable of forming each layer as a monomer, or A polymer crosslinked product 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 electroluminescent device according to any one of Items 26 to 31, further comprising a crosslinked pendant polymer crosslinked body.

Item 33.
Item 33. A display device or illumination device comprising 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 element can be provided. An organic device such as an excellent organic EL element can be provided by using an aromatic compound.

Specifically, the present inventors have found that a polycyclic aromatic compound (basic skeleton portion) in which aromatic rings are connected with heteroelements such as boron, phosphorus, oxygen, nitrogen, and sulfur has a large HOMO-LUMO gap (in a thin film). It has been found that it has a band gap Eg) and a high triplet excitation energy (E _T ). This is because a 6-membered ring containing a hetero element has low aromaticity, so that the reduction of the HOMO-LUMO gap accompanying expansion of the conjugated system is suppressed, and the triplet excited state (T1) is caused by electronic perturbation of the hetero element. ) SOMO1 and SOMO2 are considered to be localized. In addition, the polycyclic aromatic compound (basic skeleton portion) containing a hetero element according to the present invention has less exchange interaction between both orbitals due to localization of SOMO1 and SOMO2 in the triplet excited state (T1). Therefore, since the energy difference between the triplet excited state (T1) and the singlet excited state (S1) is small and shows thermally activated delayed fluorescence, it is also useful as a fluorescent material for organic EL elements. A material having a high triplet excitation energy (E _T ) is also useful as an electron transport layer or a hole transport layer of a phosphorescent organic EL device or an organic EL device using thermally activated delayed fluorescence. Furthermore, since these polycyclic aromatic compounds (basic skeleton parts) can move the energy of HOMO and LUMO arbitrarily by introducing substituents, the ionization potential and electron affinity are optimized according to the surrounding materials. It is possible.

In addition to the characteristics of the basic skeleton part, the compound of the present invention can be expected to lower the melting point and sublimation temperature by introducing a cycloalkyl group. This means that sublimation purification, which is almost indispensable as a purification method for materials for organic devices such as organic EL elements that require high purity, can be purified at a relatively low temperature, so that thermal decomposition of the material can be avoided. Means. This also applies to the vacuum deposition process, which is a powerful means for producing organic devices such as organic EL elements, and since the process can be carried out at a relatively low temperature, thermal decomposition of the material can be avoided, As a result, a high performance organic device can be obtained. In addition, multimers of polycyclic aromatic compounds have many compounds with high sublimation temperature due to high molecular weight and high flatness, and therefore, the reduction of sublimation temperature by introducing a cycloalkyl group becomes more effective. . In addition, since the solubility in an organic solvent is improved by introducing a cycloalkyl group, it can also be applied to device fabrication 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 provides a polycyclic aromatic compound represented by the following general formula (1) or a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1). A polymer of cyclic aromatic compounds, 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) Multimers, wherein at least one hydrogen in these compounds or structures is substituted with cycloalkyl.

The A ring, B ring and C ring in the general 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 substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino (with aryl Amino groups having heteroaryl), substituted or unsubstituted diarylboryl (two aryls may be linked via a single bond or linking group), substituted or unsubstituted alkyl, 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 or 6-membered ring sharing a bond with the central condensed bicyclic structure composed of Y ¹ , X ¹ and X ^2. preferable.

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

A ring (or B ring, C ring) in general formula (1) is the ring a and its substituents R ¹ to R ³ (or b ring and its substituents R ⁴ to R ⁷ , c) in general formula (2). Corresponding 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 rings having a 6-membered ring” are selected as the A to C rings of the general formula (1). In that sense, each ring of the general formula (2) is represented by lower case letters a to c.

In the general formula (2), adjacent groups of 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 a heteroaryl ring together with the a ring, b ring, or c ring. And at least one hydrogen in the ring formed is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are connected via a single bond or a linking group). Optionally substituted), optionally substituted with alkyl, alkoxy or aryloxy, wherein 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 in the a-ring, b-ring and c-ring. As shown, the ring structure constituting the compound changes. A ′ ring, B ′ ring and C ′ ring in each formula correspond to A ring, B ring and C ring in general formula (1), respectively.

In the formula (2-1) and the formula (2-2), the A ′ ring, the B ′ ring and the C ′ ring are adjacent to the substituents R ¹ to R ^{11 in} the general formula (2). The aryl ring or heteroaryl ring formed together with the a ring, b ring and c ring, respectively (the condensed ring formed by condensing another ring structure to the a ring, b ring or c ring) It can also be said). Although not shown in the formula, there are compounds in which all of the a-ring, b-ring and c-ring are changed to A′-ring, B′-ring and C′-ring. As can be seen from the above formulas (2-1) and (2-2), for example, b-ring R ⁸ and c-ring R ⁷ , b-ring R ¹¹ and a-ring R ¹ , c-ring R ¹ R ⁴ and R ^{3 in the} a ring do not correspond to “adjacent groups” and they are not bonded. That is, “adjacent group” means an adjacent group 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, 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 B ′ ring or C ′ ring) formed by condensation of a benzothiophene ring, and a formed condensed ring A ′ (or condensed ring B ′ or condensed ring C ′) Are respectively a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring.

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 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 particularly preferably B. 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 An optionally substituted aryl, an optionally substituted heteroaryl, an optionally substituted alkyl or an optionally substituted cycloalkyl, wherein R in> C (—R) ₂ is hydrogen, substituted Aryl or alkyl which may be substituted, and R of> N—R and / or R of> C (—R) ₂ are bonded to the B ring and / or C ring by a linking group or a single bond. The linking group is preferably —O—, —S— or —C (—R) ₂ —. R in the “—C (—R) ₂ —” is hydrogen or alkyl. This description is the same for X ¹ and X ² in the general formula (2).

In the general formula (1), “> N—R and / or> C (—R) ₂ R are bonded to the A ring, B ring and / or C ring by a linking group or a single bond. “In general formula (2), R in> N—R and / or R in> C (—R) ₂ is —O—, —S—, —C (—R) _2. It corresponds to the definition of “bonded to the a ring, b ring and / or c ring by a single bond”.

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

In addition, the above definition is a compound having a ring structure in which X ¹ and / or X ² is incorporated into the condensed ring A ′, which is represented by the following formula (2-3-2) or formula (2-3-3) But it can be expressed. That is, for example, a compound having an A ′ ring formed by condensing another ring so as to incorporate 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 ′ is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.

Examples of the “aryl ring” that is A ring, B ring and C ring in the general formula (1) include aryl rings having 6 to 30 carbon atoms, preferably aryl rings having 6 to 16 carbon atoms, An aryl ring having 6 to 12 carbon atoms is more preferable, and an aryl ring having 6 to 10 carbon atoms is particularly preferable. The “aryl ring” is defined as “an aryl ring formed by bonding adjacent groups of R ¹ to R ¹¹ together with a ring, b ring or c ring” defined in the general formula (2). In addition, since the a ring (or the b ring or the 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 a carbon having a lower limit. Number.

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

Examples of the “heteroaryl ring” that is A ring, B ring and C ring in the general formula (1) include heteroaryl rings having 2 to 30 carbon atoms, preferably heteroaryl rings 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 more preferable, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferable. Examples of the “heteroaryl ring” include a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom. The “heteroaryl ring” is a heteroaryl formed together with a ring, b ring or c ring by bonding adjacent groups of “R ¹ to R ¹¹ ” defined in the general formula (2). In addition, 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 lower limit. The number of carbons.

Specific examples of the “heteroaryl ring” include pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, 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, Ndorijin ring, a furan ring, benzofuran ring, isobenzofuran ring, a dibenzofuran ring, a thiophene ring, benzothiophene ring, dibenzothiophene ring, furazan ring, an oxadiazole ring, and thianthrene ring.

At least one hydrogen in the above “aryl ring” or “heteroaryl ring” is the first substituent, which 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 connected via a single bond or a linking group) Optionally substituted) ”, substituted or unsubstituted“ alkyl ”, substituted or unsubstituted“ alkoxy ”, or substituted or unsubstituted“ aryloxy ”. As the substituents of `` aryl '', `` heteroaryl '', `` diarylamino '' aryl, `` diheteroarylamino '' Roaryl, aryl and heteroaryl of “arylheteroarylamino”, aryl of “diarylboryl”, and aryl of “aryloxy” include the monovalent groups of the above-mentioned “aryl ring” or “heteroaryl ring” .

The “alkyl” as the first substituent may be either linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms and branched alkyl having 3 to 24 carbon atoms. 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, and alkyl having 1 to 6 carbons. (Branched alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms) is particularly preferable.

Specific examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, and 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-hepta Sill, n- octadecyl, such as n- eicosyl, and the like.

The “alkoxy” as the first substituent includes, for example, straight-chain alkoxy having 1 to 24 carbon atoms or branched alkoxy having 3 to 24 carbon atoms. C1-C18 alkoxy (C3-C18 branched alkoxy) is preferred, C1-C12 alkoxy (C3-C12 branched alkoxy) is more preferred, and C1-C6 Of alkoxy (C3-C6 branched chain alkoxy) is more preferable, and C1-C4 alkoxy (C3-C4 branched chain alkoxy) is particularly preferable.

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

As the “aryl” in the “diarylboryl” of the first substituent, the above-mentioned explanation of aryl can be cited. The two aryls may be bonded via a single bond or a linking group (eg,> C (—R) ₂ ,>O,> S or> N—R). Here, R in> C (—R) ₂ and> N—R is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy (hereinafter, the first substituent), and the first The substituent may be further substituted with aryl, heteroaryl, alkyl or cycloalkyl (hereinafter, the second substituent). Specific examples of these groups include aryl, hetero as the first substituent described above. References can be made to aryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy.

The first substituent, 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 may be bonded via a single bond or a linking group)”, substituted or unsubstituted “alkyl”, Substituted or unsubstituted “alkoxy” or substituted or unsubstituted “aryloxy” has at least one hydrogen substituted with a second substituent as described as substituted or unsubstituted. Also 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. In addition, in aryl or heteroaryl as the second substituent, at least one hydrogen in them is substituted with aryl such as phenyl (specific examples are the groups described above) or alkyl such as methyl (specific examples are the groups described above). These structures are also included in the aryl or heteroaryl as the second substituent. For example, 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 used 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 general formula (2) The monovalent group of “aryl ring” or “heteroaryl ring” described in the general formula (1). 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) described above can be referred. Further, aryl, heteroaryl or alkyl as a substituent for these groups is the same. In addition, when adjacent groups of R ¹ to R ¹¹ are bonded to form an aryl ring or a heteroaryl ring together with a ring, b ring or c ring, heteroaryl which is a substituent for these rings , Diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be linked via a single bond or linking group), alkyl, alkoxy or aryloxy, and further substituents The same applies to certain aryls, heteroaryls or alkyls.

Specifically, the emission wavelength can be adjusted by the steric hindrance, electron donating property, and electron withdrawing property of the structure of the first substituent, preferably a group represented by the following structural formula, 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- Tolylamino, bis (p- (t-butyl) phenyl) amino, carbazolyl, 3,6-dimethylcarbazolyl, 3,6-di-t-butylcarbazolyl and phenoxy, 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, carba Lil, a 3,6-dimethyl-carbazolyl and 3,6-di -t- butyl-carbazolyl. From the viewpoint of ease of synthesis, a larger steric hindrance is preferable for selective synthesis. 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 examples of the aryl and alkyl include the groups described above. In particular, aryl having 6 to 10 carbon atoms (for example, phenyl and naphthyl) and alkyl having 1 to 4 carbon atoms (for example, methyl and ethyl) are preferable. This explanation is the same for Y ¹ in the general formula (2).

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

R in “—C (—R) ₂ —” as the linking group in the general formula (1) is hydrogen or alkyl, and examples of the alkyl include the groups described above. In particular, alkyl having 1 to 4 carbon atoms (eg, methyl, ethyl, etc.) is preferable. This explanation is the same for “—C (—R) ₂ —” which is a linking group in the general formula (2).

The present invention also provides a multimer of polycyclic aromatic compounds having a plurality of unit structures represented by the general formula (1), preferably a polycyclic aromatic having a plurality of unit structures represented by the general formula (2). A multimer of compounds. The multimer is preferably a dimer to hexamer, more preferably a dimer to trimer, and particularly preferably a dimer. The multimer may be in a form having a plurality of the above unit structures in one compound. For example, the unit structure is a single bond, a linking group such as an alkylene group having 1 to 3 carbon atoms, a phenylene group, or a naphthylene group. In addition to a plurality of bonded structures, 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 In addition, any ring (A ring, B ring or C ring, a ring, b ring or c ring) included in the unit structure may be combined to be condensed. 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 formula (2-6). The multimeric compound represented by the following formula (2-4) can be represented by a plurality of general formulas (2) so as to share a benzene ring which is a ring, as explained by 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) can be expressed by two general formulas (2) such that a benzene ring which is a ring is shared, as explained by the general formula (2). A multimeric compound having a unit structure represented by the formula: Further, the multimeric compound represented by the following formula (2-4-2) can be described by the general formula (2), so that the benzene ring which is the a ring is shared, so that the three general formulas (2) A multimeric compound having a unit structure represented by the formula: In addition, the multimeric compound represented by the following formulas (2-5-1) to (2-5-4) can be represented by the general formula (2) as a benzene ring which is a b ring (or a c ring). Is a multimeric compound having a plurality of unit structures represented by the general formula (2) in one compound. Further, the multimeric compound represented by the following formula (2-6) can be represented by the general formula (2), for example, a benzene ring which is a b ring (or a ring or c ring) having a certain unit structure and a certain unit. It is a multimeric compound having a plurality of unit structures represented by the general formula (2) in one compound by condensing with a benzene ring which is a b ring (or a ring or c ring) of the structure.

The multimeric compound includes a multimerized form represented by formula (2-4), formula (2-4-1) or formula (2-4-2), and formulas (2-5-1) to (2) -5-4) or a multimer in combination with a multimerized form represented by formula (2-6) may be used, and may be represented by formula (2-5-1) to formula (2-5) 4) may be a multimer in which the multimerized form represented by any one of 4) and the multimerized form represented by formula (2-6) are combined. Formula (2-4) and formula (2) -4-1) or the multimerized form represented by formula (2-4-2) and the multimerized form represented by any of formulas (2-5-1) to (2-5-4) A multimer combined with the multimerized form represented by the formula (2-6) may be used.

In addition, all or part of the polycyclic aromatic compounds represented by the general formula (1) or (2) and the chemical structures of the multimers thereof may be deuterium, cyano, or halogen. For example, in the formula (1), A ring, B ring, C ring (A to C rings are aryl rings or heteroaryl rings), a substituent to the A to C rings, Y ¹ is Si—R or Ge—R And R (= alkyl, aryl) when X ¹ and X ² are> N—R or> C (—R) ₂ is deuterium, cyano Alternatively, halogen may be substituted, and among these, an embodiment in which all or part of hydrogen in aryl or heteroaryl is substituted with deuterium, cyano or halogen can be mentioned. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine.

Moreover, the polycyclic aromatic compound and its multimer according to the present invention can be used as a material for organic devices. As an organic device, an organic electroluminescent element, an organic field effect transistor, an organic thin film solar cell, etc. are mention | raise | lifted, for example. In particular, in an organic electroluminescent device, as a dopant material for 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, and X ² is> A compound in which N—R 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 the host material of the light-emitting layer. compound is R, ^{Y 1} is B, ^{X 1} and ^{X 2>} O compounds wherein preferably, as an electron transport material, compound ^{Y 1} is B, ^{X 1} and ^{X 2} is> O, ^{Y 1} is P Compounds in which ═O, X ¹ and X ² are> O are preferably used.

In addition, at least one hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (1) or (2) and the multimer thereof is cycloalkyl-substituted, and all or some of the hydrogen is substituted. It may be a cycloalkyl group.

As other forms of cycloalkyl substitution, polycyclic aromatic compounds represented by the general formula (1) or (2) and multimers thereof, for example, cycloalkyl-substituted diarylamino groups, cycloalkyl-substituted Examples are substituted with a carbazolyl group or a cycloalkyl-substituted benzocarbazolyl group. Examples of the “diarylamino group” include the groups described above as the “first substituent”. Examples of the substituted form of cycloalkyl to the diarylamino group, carbazolyl group, and benzocarbazolyl group include examples in which a part or all of the hydrogen of the aryl ring or benzene ring in these groups is substituted with cycloalkyl.

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 each 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).

In addition, specific examples of the cycloalkyl-substituted polycyclic aromatic compound and multimers thereof according to the present invention include one or more hydrogen atoms in one or more aromatic rings in the compound. Examples include compounds substituted with a cycloalkyl group, and examples include compounds substituted with 1 to 2 cycloalkyl groups.

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

Examples of cycloalkyl include 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, and cycloalkyl having 5 carbon atoms.

Specific examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (particularly methyl) substituents having 1 to 4 carbon atoms, norbornenyl, 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, decahydroazurenyl and the like.

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 a polymer compound obtained by polymerizing a reactive compound having a reactive substituent substituted thereon as a monomer (this polymer 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 crosslinking substituent) Or a pendant polymer compound obtained by reacting a main chain polymer and the reactive compound (the reactive compound for obtaining the pendant polymer compound has a reactive substituent), Alternatively, a pendant polymer crosslinked product obtained by further crosslinking the pendant polymer compound (the pendant polymer compound for obtaining this pendant polymer crosslinked product is a crosslinkable compound). Even the having) substituent, an organic device material, for example, can be used a material for an organic electroluminescence device, an organic field effect transistor materials or organic thin film solar cell material.

As the above-mentioned reactive substituent (including the polymerizable substituent, the crosslinkable substituent, and the reactive substituent for obtaining a pendant polymer, hereinafter, also simply referred to as “reactive substituent”) A substituent capable of increasing the molecular weight of the 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 a main chain polymer Although it will not specifically limit if it is group, the substituent of the following structures is preferable. * In each structural formula indicates a bonding position.

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

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

2. Process for Producing Cycloalkyl-Substituted Polycyclic Aromatic Compounds and Multimers thereof The polycyclic aromatic compounds represented by the general formulas (1) and (2) and the multimers thereof are basically first of the A ring ( An intermediate is produced by bonding a ring) to B ring (b ring) and C ring (c ring) with a linking group (a group containing X ¹ and X ² ) (first reaction). A final product can be produced by bonding A ring (a ring), B ring (b ring) and C ring (c ring) with a linking group (a 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 for an etherification reaction, and a general reaction such as a Buchwald-Hartwig reaction can be used for an amination reaction. In the second reaction, a tandem hetero Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, the same applies hereinafter) can be used. Further, by using a cycloalkyl-substituted raw material somewhere in these reaction steps, or by adding a step of introducing a cycloalkyl group, the compound of the present invention in which the desired position is cycloalkyl-substituted can be obtained. Can be manufactured.

As shown in the following schemes (1) and (2), the second reaction is a reaction for introducing Y ¹ that connects the A ring (a ring), the B ring (b ring), and the C ring (c ring). 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, a hydrogen atom and n- butyllithium between ^{X 1} and ^{X 2,} ortho-metalated with sec- butyllithium or t- butyl lithium, and the like. Next, boron trichloride, boron tribromide, etc. are added, and after lithium-boron metal exchange, Bronsted base such as N, N-diisopropylethylamine is added to cause 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 the following schemes (1) and (2), the definitions of symbols in the structural formulas in the subsequent schemes (3) to (28) are the same as those described above.

In addition, although the said scheme (1) and (2) mainly show the manufacturing method of the polycyclic aromatic compound represented by General formula (1) or (2), about the multimer, about several It can manufacture by using the intermediate body which has A ring (a ring), B ring (b ring), and 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 setting the amount of the reagent such as butyl lithium to be doubled or tripled.

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

Also, in 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). Lithium can be introduced into a desired position also by exchange (the following schemes (8), (9) and (10)).

This method is useful because the target product can be synthesized even in the case where ortho-metalation is not possible due to the influence of substituents.

By appropriately selecting the synthesis method described above and appropriately selecting the raw materials to be used, the desired position is substituted with cycloalkyl, the substituent is present at the desired position, Y ¹ is a boron atom, and X ¹ and X ² are A polycyclic aromatic compound that 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). As in the case where X ¹ and X ² are oxygen atoms, the hydrogen atom between X ¹ and X ² is first ortho-metalated with n-butyllithium or the like. Next, boron tribromide and the like are added, and after lithium-boron metal exchange, Brensted base such as N, N-diisopropylethylamine is added to cause tandem Bora Friedel-Crafts reaction to obtain the target product. Can do. Here, a Lewis acid such as aluminum trichloride may be added to promote the reaction. Further, by using a cycloalkyl-substituted raw material somewhere in these reaction steps, or by adding a step of introducing a cycloalkyl group, the compound of the present invention in which the desired position is cycloalkyl-substituted can be obtained. Can be manufactured.

As for the multimer in the case where Y ¹ is a boron atom and X ¹ and X ² are nitrogen 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 the desired position also by halogen-metal exchange (Schemes (13), (14) and (15) below).

Next, as an example, the following schemes (16) to (19) show cases where Y ¹ is a phosphorus sulfide, phosphorus oxide or phosphorus atom, and X ¹ and X ² are oxygen atoms. As before, first ortho-metalated with n- butyl lithium, etc. a hydrogen atom between X ¹ and X ^2. Then, phosphorus trichloride were added in the order of sulfur, finally by adding three Lewis acid such as aluminum chloride and N, Bronsted base such as N- diisopropylethylamine, tandem phosphorylase Fafu Riedel is Crafts reaction, Y ¹ is phosphorus Compounds that are sulfides can be obtained. Further, by treating the obtained phosphide compound with m-chloroperbenzoic acid (m-CPBA), a compound in which Y ¹ is phosphorus oxide can be obtained, and by treating with triethylphosphine, Y ¹ becomes phosphorus Compounds that are atoms can be obtained. Further, by using a cycloalkyl-substituted raw material somewhere in these reaction steps, or by adding a step of introducing a cycloalkyl group, the compound of the present invention in which the desired position is cycloalkyl-substituted can be obtained. Can be manufactured.

In addition, with respect to multimers in which 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 located 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 also by halogen-metal exchange (the following schemes (20), (21) and (22)). Further, the thus-produced multimer in which Y ¹ is a phosphorous sulfide and X ¹ and X ² are oxygen atoms is also represented by m-chloroperbenzoic acid (in the above schemes (18) and (19)). A compound in which Y ¹ is a phosphorus oxide can be obtained by treatment with m-CPBA), and a compound in which Y ¹ is a phosphorus atom can be obtained by treatment 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. However, by appropriately changing the raw materials, Y ¹ is A compound in which Al, Ga, As, Si—R or Ge—R, or X ¹ and X ² are S can also be synthesized.

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

In the general formula (2), adjacent groups of 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. A ring may be formed, 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) has the formula (2-) in the following schemes (23) and (24) depending on the mutual bonding form of the substituents in the a-ring, b-ring and c-ring. As shown in 1) and formula (2-2), the ring structure constituting the compound changes. These compounds can be synthesized by applying the synthesis methods shown in the above schemes (1) to (19) to the intermediates shown in the following schemes (23) and (24). Further, by using a cycloalkyl-substituted raw material somewhere in these reaction steps, or by adding a step of introducing a cycloalkyl group, the compound of the present invention in which the desired position is cycloalkyl-substituted can be obtained. Can be manufactured.

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

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

Further, in the synthesis 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 a tandem hetero Friedel-Crafts reaction by orthometalation of a halogen atom) with butyllithium or the like was shown. However, boron trichloride or tribromide can be used without orthometalation with butyllithium or the like. The reaction can also be advanced by adding boron or the like.

When Y ¹ is phosphorus-based, as shown in the following schemes (26) and (27), the hydrogen atom between X ¹ and X ² (O in the following formula) is replaced with n-butyllithium, sec- Orthometalation with butyllithium or t-butyllithium, etc., followed by addition of bisdiethylaminochlorophosphine, metal exchange of lithium-phosphorus, and addition of Lewis acid such as aluminum trichloride The target product can be obtained by reaction. This reaction method is also described in International Publication No. 2010/104047 (for example, page 27). Further, by using a cycloalkyl-substituted raw material somewhere in these reaction steps, or by adding a step of introducing a cycloalkyl group, the compound of the present invention in which the desired position is cycloalkyl-substituted can be obtained. Can be manufactured.

In the above schemes (26) and (27), a multimeric compound is synthesized by using an orthometalation reagent such as butyl lithium in a molar amount twice or three times that of the intermediate 1. can do. Further, by introducing a halogen such as a bromine atom or a chlorine atom in advance at a position where a metal such as lithium is to be introduced, and replacing the halogen-metal, the metal can be introduced at a desired position.

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

The intermediate before cyclization in Scheme (28) can also be synthesized by the method shown in Scheme (1) and the like. That is, an intermediate having a desired substituent can be synthesized by appropriately combining Buchwald-Hartwig reaction, Suzuki coupling reaction, or etherification reaction such as nucleophilic substitution reaction or Ullmann reaction. In these reactions, a commercially available product can be used as a raw material to be a cycloalkyl-substituted precursor.

The compound of the 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 amination reaction such as Buchwald-Hartwig reaction between cycloalkyl-substituted bromobenzene and trihalogenated aniline, X ¹ and X ² are N—R In an amination reaction such as the Buchwald-Hartwig reaction, when X ¹ and X ² are O, they are induced to an intermediate (M-3) by etherification with phenol, and then, for example, butyl Tandem Bora Friedel by transmetallation with a metalation reagent such as lithium, followed by a boron halide such as boron tribromide, followed by a Bronsted base such as diethylisopropylamine A compound of general formula (2-A) is synthesized by a Crafts reaction. Door can be. These reactions can also be applied to other cycloalkyl-substituted compounds.

The orthometalation reagents used in the above schemes (1) to (28) include alkyllithiums such as methyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium, lithium diisopropylamide, and lithium tetramethyl. Examples include organic alkali compounds such as piperidide, lithium hexamethyldisilazide, and potassium hexamethyldisilazide.

The metal exchange reagent for metal-Y ¹ used in the above schemes (1) to (28) includes Y ¹ trifluoride, Y ¹ trichloride, Y ¹ tribromide, Y ¹ triiodide. 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 base used in the above schemes (1) to (28) includes N, N-diisopropylethylamine, triethylamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6. -Pentamethylpiperidine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2,6-lutidine, sodium tetraphenylborate, potassium tetraphenylborate, triphenylborane, tetraphenylsilane, Ar ₄ BNa, Ar ₄ BK, Ar ₃ B, Ar ₄ Si (where Ar is an aryl such as phenyl) and the like.

As the Lewis acid used in the above schemes (1) to (28), AlCl ₃ , AlBr ₃ , AlF ₃ , BF ₃ .OEt ₂ , BCl ₃ , BBr ₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , 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, NaT , 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, etc. Can be mentioned.

In the above schemes (1) to (28), a Bronsted base or a Lewis acid may be used to promote the tandem heterofriedel crafts reaction. However, when Y ¹ halides such as Y ¹ trifluoride, Y ¹ trichloride, Y ¹ tribromide, Y ¹ triiodide are used, the aromatic electrophilic substitution reaction proceeds. Since an acid such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide is generated, 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 of the amino group or alkoxy group is effective because of its low ability to remove an amino group or an alkoxy group.

The polycyclic aromatic compounds and multimers thereof of the present invention also include compounds in which at least some of the hydrogen atoms are substituted with deuterium or cyano, or compounds with halogen such as fluorine or chlorine. However, such a compound can be synthesized in the same manner as described 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. As an organic device, an organic electroluminescent element, an organic field effect transistor, an organic thin film solar cell, etc. are mention | raise | lifted, for example.

3-1. Organic electroluminescent element Below, the organic EL element which concerns on this embodiment is demonstrated in detail based on drawing. FIG. 1 is a schematic cross-sectional view showing an organic EL element according to this embodiment.

<Structure of organic electroluminescence device>
An organic EL element 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. The hole transport layer 104 provided, the light emitting layer 105 provided on the hole transport layer 104, the electron transport layer 106 provided on the light emitting layer 105, and the electron transport layer 106 are provided. The electron injection layer 107 and the cathode 108 provided on the electron injection layer 107 are provided.

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

Not all of the above layers are necessary, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection. The layer 107 is an arbitrarily provided layer. Moreover, each said layer may consist of a single layer, respectively, and may consist of multiple layers.

As an aspect of the layer constituting the organic EL element, in addition to the above-described configuration aspect of “substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode”, “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 / emission layer / electron injection layer / cathode", "substrate / anode / hole injection layer / emission layer / electron transport" / Cathode "," substrate / anode / light emitting layer / electron transporting layer / cathode "may be configured aspect of the" substrate / anode / light emitting layer / electron injection layer / cathode ".

<Substrate in organic electroluminescence device>
The substrate 101 is a support for the organic EL element 100, and quartz, glass, metal, plastic, or the like is usually used. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape according to the purpose. 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 transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable. In the case of a glass substrate, soda lime glass, non-alkali glass, or the like is used, and the thickness only needs to be sufficient to maintain the mechanical strength. The upper limit value of the thickness is, for example, 2 mm or less, preferably 1 mm or less. The glass material is preferably alkali-free glass because it is better to have less ions eluted from the glass. However, soda lime glass with a barrier coat such as SiO ₂ is also commercially available, so it can be used. it can. Further, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one surface in order to improve the gas barrier property, and a synthetic resin plate, film or sheet having a low gas barrier property is used as the substrate 101. When used, it is preferable to provide a gas barrier film.

<Anode in organic electroluminescence device>
The anode 102 serves to inject holes into the light emitting layer 105. When the hole injection layer 103 and / or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. .

Examples of the material for forming the anode 102 include inorganic compounds and organic compounds. Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide) Products (IZO), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, and the like. Examples of the organic compound include polythiophene such as poly (3-methylthiophene), conductive polymer such as polypyrrole and polyaniline, and the like. In addition, it can select suitably from the substances used as an anode of an 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 300Ω / □ or less functions as an element electrode, but at present, since it is possible to supply a substrate of about 10Ω / □, for example, 100 to 5Ω / □, preferably 50 to 5Ω. It is particularly desirable to use a low resistance product of / □. The thickness of ITO can be arbitrarily selected according to the resistance value, but is usually used in a 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 serves to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 via the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are each formed by laminating and mixing one kind or two or more kinds of hole injection / transport materials or a mixture of the hole injection / transport material and the polymer binder. Is done. In addition, an inorganic salt such as iron (III) chloride may be added to the hole injection / transport material to form a layer.

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

As a material for forming the hole injection layer 103 and the hole transport layer 104, a compound conventionally used as a charge transport material for holes in a photoconductive material, a p-type semiconductor, and a hole injection layer of an organic EL element are used. And any compound can be selected and used from known compounds used in the hole transport layer. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (aromatic tertiary class). Polymer having amino as 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 , 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 ( Triphenylamine derivatives such as 3-methylphenyl (phenyl) amino) triphenylamine, starburstamine 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-2,3,6,7,1 , 11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonates, styrene derivatives, polyvinylcarbazole, polysilanes, etc. having the aforementioned monomers in the side chain are preferred, but light emitting devices There is no particular limitation as long as it is a compound that can form a thin film necessary for the fabrication, inject holes from the anode, and further transport holes.

It is also known that the conductivity of organic semiconductors is strongly influenced by the 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 of electron donor materials. (For example, the document “M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 (1998)”) and the document “J. Blochwitz, M 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 varies considerably. Known matrix substances having hole transporting properties include, for example, benzidine derivatives (TPD and the like), starburst amine derivatives (TDATA and the like), and specific metal phthalocyanines (particularly zinc phthalocyanine (ZnPc) and the like) ( JP-A-2005-167175).

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

<Light emitting layer in organic electroluminescent element>
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 electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state It is preferable that the compound exhibits a strong light emission (fluorescence) efficiency. In the present invention, a host material and, for example, a polycyclic aromatic compound represented by the general formula (1) as a dopant material can be used as the material for the light emitting layer.

The light emitting layer may be either a single layer or a plurality of layers, each 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 plurality of combinations. The dopant material may be included in the host material as a whole, or may be included partially. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited.

∙ The amount of host material used depends on the type of host material and can be determined according to the characteristics of the host material. The standard of the amount of the host material used is preferably 50 to 99.999% by weight of the entire light emitting layer material, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight. It is.

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

Host materials include fused ring derivatives such as anthracene, pyrene, dibenzochrysene or fluorene that have been known as light emitters, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, and cyclopentadiene derivatives. Etc. In particular, an anthracene compound, a fluorene compound, or a dibenzochrysene compound is preferable.

<Anthracene compounds>
An anthracene compound as a 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, Arylheteroarylamino which may be substituted, alkyl which may be substituted, cycloalkyl which may be substituted, alkenyl which may be substituted, alkoxy which may be substituted, which may be substituted Aryloxy, optionally substituted arylthio or optionally substituted silyl, and all X and Ar ⁴ are not simultaneously hydrogen;
At least one hydrogen in the compound represented by the formula (3) may be substituted with halogen, cyano, deuterium or an 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. Examples of X include a single bond, arylene (such as phenylene, biphenylene, and naphthylene), and heteroarylene (a pyridine ring, A group having a divalent valence such as a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring and a phenyl-substituted carbazole ring).

Details of the aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio or silyl will be described in the following preferred embodiments. 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 preferred embodiments below.

The preferable aspect of the said anthracene type compound is demonstrated below. The definition of the code | symbol in the following structure is the same as the definition mentioned above.

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

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

Ar ¹ and Ar ² are each independently hydrogen, phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrycenyl, triphenylenyl, pyrenylyl, or the above formula (A) Represented groups (including carbazolyl, benzocarbazolyl and phenyl-substituted carbazolyl groups). In the case where Ar ¹ or Ar ² is a group represented by the formula (A), the group represented by the formula (A) is the same as that in the formula (3-X1) or (3-X2) Bonds with the 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) A zolyl group and a phenyl-substituted carbazolyl group). In addition, when Ar ³ is a group represented by the formula (A), the group represented by the formula (A) is bonded to a single bond represented by a straight line in the formula (3-X3) at *. . That is, the anthracene ring of formula (3) and the group represented by formula (A) are directly bonded.

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, chrycenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (including a carbazolyl group and a phenyl-substituted carbazolyl group). Note that when the substituent that Ar ³ has is a group represented by the formula (A), the group represented by the formula (A) is bonded to Ar ³ in the formula (3-X3) at *.

Ar ⁴ is each independently substituted with hydrogen, phenyl, biphenylyl, terphenylyl, naphthyl, or alkyl having 1 to 4 carbon atoms (methyl, ethyl, t-butyl, etc.) and / or cycloalkyl having 5 to 10 carbon atoms. Has been silyl.

Examples of the alkyl having 1 to 4 carbon atoms to be substituted with silyl include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, cyclobutyl and the like. Are substituted with these alkyls.

Specific examples of “silyl substituted with alkyl having 1 to 4 carbon atoms” include trimethylsilyl, triethylsilyl, tripropylsilyl, trii-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-pro Rushiriru, ethyldi i- propyl silyl, butyl di i- propyl silyl, sec- butyl di i- propyl silyl, such as t- butyl di i- propyl silyl, and the like.

Cycloalkyl having 5 to 10 carbon atoms to be substituted with silyl is 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 the three hydrogens in silyl are each independently substituted with these cycloalkyls.

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

Substituted silyls include dialkylcycloalkylsilyl substituted with two alkyls and one cycloalkyl, and alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyls. Substituted alkyls and cycloalkyls Specific examples of these 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 a group represented by the above formula (A). When substituted with a group represented by formula (A), the group represented by formula (A) substitutes at least one hydrogen in the compound represented by formula (3) at *.

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 above 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, and adjacent groups of R ²¹ to R ²⁸ are bonded to each other to form a hydrocarbon ring. , may form an aryl or heteroaryl ring, R ²⁹ may be hydrogen or substituted A reel.

The “alkyl” of “optionally substituted alkyl” in R ²¹ to R ²⁸ may be either linear or branched, for example, linear alkyl having 1 to 24 carbon atoms or having 3 to 24 carbon atoms. A branched alkyl. 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, and alkyl having 1 to 6 carbons. (Branched alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms) is particularly preferable.

Specific examples of “alkyl” include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -Propylpentyl, 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-he Tadeshiru, n- octadecyl, such as n- eicosyl, and the like.

“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, or 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) substituents thereof having 1 to 4 carbon atoms, norbornenyl, 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, decahydroazurenyl and the like.

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

Specific “aryl” includes monocyclic phenyl, bicyclic biphenylyl, fused bicyclic naphthyl, tricyclic terphenylyl (m-terphenylyl, o-terphenylyl, p-terphenylyl) And condensed tricyclic systems such as acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, condensed tetracyclic systems such as triphenylenyl, pyrenyl, naphthacenyl, and condensed pentacyclic systems such as perylenyl and pentacenyl.

Examples of the “heteroaryl” in the “optionally substituted heteroaryl” in R ²¹ to R ²⁸ include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, A heteroaryl having 2 to 20 carbon atoms is more preferred, a heteroaryl having 2 to 15 carbon atoms is more preferred, and a heteroaryl having 2 to 10 carbon atoms is particularly preferred. Examples of the heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

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, phenoxazinyl, phenoxazinyl, phenoxazinyl, Phenazinyl, indolizinyl, furyl, benzofuranyl, isobenzo Ranil, dibenzofuranyl, thienyl, benzo [b] thienyl, dibenzothienyl, furazanyl, oxadiazolyl, thianthrenyl, naphthaldehyde benzofuranyl, such as naphthaldehyde benzothienyl and the like.

Examples of “alkoxy” of “optionally substituted alkoxy” in R ²¹ to R ²⁸ include straight-chain alkoxy having 1 to 24 carbon atoms or branched alkoxy having 3 to 24 carbon atoms. C1-C18 alkoxy (C3-C18 branched alkoxy) is preferred, C1-C12 alkoxy (C3-C12 branched alkoxy) is more preferred, and C1-C6 Of alkoxy (C3-C6 branched chain alkoxy) is more preferable, and C1-C4 alkoxy (C3-C4 branched chain alkoxy) is particularly preferable.

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

“Aryloxy” of “optionally substituted aryloxy” in R ²¹ to R ²⁸ is a group in which hydrogen of —OH group is substituted with aryl, and this aryl is the above-mentioned R ²¹ to R ²⁸ . Reference may be made to groups described as “aryl”.

The “arylthio” of the “optionally substituted arylthio” in R ²¹ to R ²⁸ is a group in which the hydrogen of the —SH group is substituted with aryl, and this aryl is the “aryl” in R ²¹ to R ²⁸ described above. Can be cited.

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

Specific examples of “trialkylsilyl” include trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, trisec-butylsilyl, tri-t-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, methyldii-propylsilyl, ethyldiip Pirushiriru, butyl di i- propyl silyl, sec- butyl di i- propyl silyl, such as t- butyl di i- propyl silyl, and the like.

The "tricycloalkyl silyl" in R ^{21 ~} R ^28, have been substituted with a cycloalkyl mentioned three hydrogen in the silyl group is independently, in R ^{21 ~} R ²⁸ The cycloalkyl mentioned above " Reference may be made to the groups described as “cycloalkyl”. Preferred cycloalkyl for substitution 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, Decahydronaphthalenyl, decahydroazulenyl and the like can be mentioned.

Specific “tricycloalkylsilyl” includes tricyclopentylsilyl, tricyclohexylsilyl and the like.

Specific examples of dialkylcycloalkylsilyl substituted with two alkyls and one cycloalkyl and alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyls are selected from the specific alkyls and cycloalkyls described above And silyl substituted with the above group.

Examples of the “substituted amino” of the “optionally substituted amino” in R ²¹ to R ²⁸ include an amino group in which two hydrogens are substituted with aryl or heteroaryl. An amino in which two hydrogens are substituted with aryl is a diaryl-substituted amino, an amino in which two hydrogens are substituted with a heteroaryl is a diheteroaryl-substituted amino, and an amino in which two hydrogens are substituted with aryl and heteroaryl Is an arylheteroaryl-substituted amino. As the aryl and heteroaryl, the groups described as “aryl” and “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 “halogen” in R ²¹ to R ²⁸ include fluorine, chlorine, bromine and iodine.

Of the groups described as R ²¹ to R ²⁸ , some may be substituted as described above, and examples of the substituent in this case include alkyl, cycloalkyl, aryl, and heteroaryl. This alkyl, cycloalkyl, aryl or heteroaryl can refer to the groups described as “alkyl”, “cycloalkyl”, “aryl” or “heteroaryl” in R ²¹ to R ²⁸ described above.

R ²⁹ in the "> N-R ^29" as Y is hydrogen or aryl which may be substituted, it is cited a group described as the "aryl" in R ^{21 ~} R ²⁸ described above as the aryl Further, 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 includes, for example, groups represented by the following formulas (A-2) to (A-14): It is done. Note that at least one hydrogen in the group represented by any of 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 cyclohexane ring as long as it is a hydrocarbon ring, and examples of the aryl ring and heteroaryl ring include “aryl” and “heteroaryl” in R ²¹ to R ²⁸ described above. And the ring is 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 a group represented by any of formulas (A-12) to (A-14) are preferred, and a group represented by any of the above formulas (A-1) to (A-4) Is more preferable, a group represented by any one of the above formulas (A-1), (A-3) and (A-4) is more preferable, and a group represented by the above formula (A-1) is more preferable. Particularly preferred.

The group represented by the formula (A) is represented by * in 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 As described above, it binds to Ar ³ in (3-X3) and substitutes at least one hydrogen in the compound represented by formula (3). Among these bonding forms, formula (3-X1) Alternatively, a form in which the naphthalene ring in the formula (3-X2), the single bond in the formula (3-X3) and / or Ar ³ in the formula (3-X3) is 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 In the structure of the group represented by the formula (A), the position at which Ar ³ is bonded to at least one hydrogen in the compound represented by the formula (3) is Any one of the two benzene rings in the structure of the formula (A) or an adjacent group among R ²¹ to R ^{28 in} the structure of the formula (A) Any ring formed by bonding to each other, or any position in R ²⁹ in “> NR ²⁹ ” as Y in the structure of formula (A) can be bonded.

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

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

Specific examples of the anthracene 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) includes 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 the structure of X, Ar ⁴ and the formula (A) Can be produced by applying Suzuki coupling, Negishi coupling, and other known coupling reactions. 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 International Publication No. 2014/141725 can be referred to.

<Fluorene compounds>
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) via a linking group), diarylamino, dihetero Arylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, wherein at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl;
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 bonded independently. May 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 through a linking group). ), Diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, wherein at least one hydrogen is aryl, heteroaryl, alkyl or cycloalkyl And may be substituted with
At least one hydrogen in the compound represented by the formula (4) may be substituted with halogen, cyano or deuterium.

The details of each group in the definition of the above formula (4) can be referred to the description of the polycyclic aromatic compound of the formula (1) described above.

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 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, 3-hexenyl, 4-hexenyl, or 5-hexenyl.

As specific examples of heteroaryl, any one of the compounds of the following formula (4-Ar1), formula (4-Ar2), formula (4-Ar3), formula (4-Ar4) or formula (4-Ar5) may be used. Also included are monovalent groups represented by removing one hydrogen atom.

In formulas (4-Ar1) to (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 the fluorene skeleton in the formula (4) and the heteroaryl are directly bonded but also a bond between them may be bonded. Examples of this linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, —OCH ₂ CH ₂ —, —CH ₂ CH ₂ O—, or —OCH ₂ CH ₂ O—.

In the formula (4), 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 are bonded independently. R ⁹ and R ¹⁰ may be combined to form a spiro ring. The condensed ring formed by R ¹ to R ⁸ is a ring condensed with the benzene ring in the 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 formula (4) include a naphthalene ring and a phenanthrene ring. The spiro ring formed by R ⁹ and R ¹⁰ is a ring that is spiro-bonded to the 5-membered ring in formula (4), and is an aliphatic ring or an aromatic ring. Preferred is an aromatic ring, such as a fluorene ring.

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). ) In which R ¹ and R ² are combined to form a condensed benzene ring, in general formula (4), a compound in which R ³ and R ⁴ are combined to form a condensed benzene ring, general formula (4 ) In which none of R ¹ to R ⁸ is bonded.

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). The definitions of R ¹¹ to R ¹⁴ in 1) and formula (4-2) are 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), a compound having a spiro-fluorene ring formed by combining R ⁹ and R ¹⁰ in formula (4-1) or formula (4-3).

The definitions of 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 from is the same as ^{R 14.}

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

<Dibenzochrysene compounds>
The dibenzochrysene-type compound as a host is a compound represented, for example by 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;
Further, adjacent groups of R ¹ to R ¹⁶ may be bonded to form a condensed ring, and at least one hydrogen in the formed ring is aryl or heteroaryl (the heteroaryl is connected via a linking group). Which may be bonded to the ring formed), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, at least of which One hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, and
At least one hydrogen in the compound represented by the formula (5) may be substituted with halogen, cyano or deuterium.

The details of each group in the definition of the above formula (5) can be referred to the description of the polycyclic aromatic compound of the formula (1) described above.

Examples of 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 2 carbon atoms. More preferred is alkenyl having 6 carbon atoms, and particularly preferred is alkenyl having 2 to 4 carbon atoms. 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, 3-hexenyl, 4-hexenyl, or 5-hexenyl.

As specific examples of 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) may be used. Also included are monovalent groups represented by removing one hydrogen atom.

In formulas (5-Ar1) to (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 the dibenzochrysene skeleton in the formula (5) and the heteroaryl are directly bonded, but may be bonded via a linking group between them. Examples of this linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, —OCH ₂ CH ₂ —, —CH ₂ CH ₂ O—, or —OCH ₂ CH ₂ O—.

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 formula (5) are each independently hydrogen, phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl. A monovalent group having the structure of the above formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) (1 having the structure) The valent group is represented by the above formula (5) via phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, —OCH ₂ CH ₂ —, —CH ₂ CH ₂ O—, or —OCH ₂ CH ₂ O—. And may be bonded to the dibenzochrysene skeleton), methyl, ethyl, propyl, or butyl.

The compound represented by the general 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, Via the anthracenylene, methylene, ethylene, —OCH ₂ CH ₂ —, —CH ₂ CH ₂ O—, or —OCH ₂ CH ₂ O—, the above formula (5-Ar1), formula (5-Ar2), formula A monovalent group having a structure of (5-Ar3), formula (5-Ar4) or formula (5-Ar5);
Other than the at least one (that is, other than the position where the monovalent group having the 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 above formulas (5-Ar1) to (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} formula (5) to form a single bond. .

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

In the formula (SPH-1),
MU is each independently a divalent aromatic compound, EC is each independently a monovalent aromatic compound, two hydrogens in MU are replaced with EC or MU, and k is an integer of 2 to 50000 is there.

More specifically,
MUs are each independently arylene, heteroarylene, diarylene arylamino, diarylene arylboryl, oxaborin-diyl, azaborin-diyl,
Each 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 an integer of 100 to 50,000.

At least one hydrogen in MU and EC in the formula (SPH-1) may be substituted with alkyl having 1 to 24 carbons, cycloalkyl having 3 to 24 carbons, halogen or deuterium, and Any —CH ₂ — in the alkyl may be substituted with —O— or —Si (CH ₃ ) ₂ —, and —CH ₂ — directly connected to EC in the formula (SPH-1) in the alkyl Any —CH ₂ — except for may be substituted with arylene having 6 to 24 carbon atoms, and any hydrogen in the alkyl may be substituted with 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, the MU binds to other MUs or ECs in *.

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

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

Details of the use of such a polymer compound and polymer crosslinked product will be described later.

<Electron injection layer and electron transport layer in organic electroluminescence 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 through the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport / injection materials or a mixture of the electron transport / injection material and the polymer binder.

The electron injection / transport layer is a layer that is responsible for injecting electrons from the cathode and further transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. For this purpose, it is preferable to use a substance that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate trapping impurities during production and use. However, considering the transport balance between holes and electrons, if the role of effectively preventing the holes from the anode from flowing to the cathode side without recombination is mainly played, the electron transport capability is much higher. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material having a high electron transport capability. Therefore, the electron injection / transport layer in this embodiment may include a function of a layer that can efficiently block 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 transport compound in a photoconductive material, used for an electron injection layer and an electron transport layer of an organic EL element It can be used by arbitrarily selecting from known compounds.

As a material used for the electron transport layer or the electron injection layer, a compound composed 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 pyrrole derivatives, condensed ring derivatives thereof, and metal complexes 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 metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials can be used alone or in combination 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 derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated compounds Nylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis (benzo [h] quinolin-2-yl) -9,9'-spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzo Imidazole derivatives (such as tris (N-phenylbenzimidazol-2-yl) benzene), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis (4 ′-(2,2 ′: 6′2 ″ -terpyridinyl)) benzene), naphthyridine derivatives (bis (1-naphthyl) -4- (1,8-naphthyridin-2-yl) phenylphosphine oxide), aldazine Derivative, carbazole derivative, in Lumpur derivatives, phosphorus oxide derivatives, such as bis-styryl derivatives.

In addition, metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. can give.

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

Among the materials described above, borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol metals 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 are each independently hydrogen, alkyl, cycloalkyl, aryl that may be substituted, silyl that is substituted, or nitrogen that may be substituted It is at least one of a heterocycle or cyano, and R ¹³ to R ¹⁶ are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl. And 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 each independently an integer of 0 to 3. In addition, examples of the substituent in the case of “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, and cycloalkyl.

Among the compounds represented by the general formula (ETM-1), compounds represented by the following general formula (ETM-1-1) and compounds represented by the following general formula (ETM-1-2) are preferable.

In the formula (ETM-1-1), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which is substituted, nitrogen which may be substituted -Containing heterocycle, or at least one of cyano, and R ¹³ to R ¹⁶ each independently represents an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl. 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 a and, X ¹ is substituted carbon atoms and optionally more than 20 arylene, n are each independently an integer of 0 to 3 And, m is an integer of 0 to 4 independently. In addition, examples of the substituent in the case of “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, and cycloalkyl.

In the formula (ETM-1-2), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which is substituted, nitrogen which may be substituted -Containing heterocycle, or at least one of cyano, and R ¹³ to R ¹⁶ each independently represents an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl. X ¹ is an optionally substituted arylene having 20 or less carbon atoms, and n is each independently an integer of 0 to 3. In addition, examples of the substituent in the case of “optionally substituted” or “substituted” include aryl, heteroaryl, alkyl, and cycloalkyl.

Specific examples of X ¹ include divalent groups represented by any of the following formulas (X-1) to (X-9).

(In each formula, each R ^a is independently an alkyl group, a cycloalkyl group, or an optionally substituted phenyl group.)

Specific examples of this 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 above formula (ETM-2-1), R ¹¹ to R ¹⁸ are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbons), cycloalkyl (preferably cyclohexane 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 carbon atoms), cycloalkyl (preferably cyclohexane having 3 to 12 carbon atoms). Alkyl) or aryl (preferably aryl having 6 to 30 carbon atoms), and R ¹¹ and R ¹² may be bonded to form a ring.

In each formula, the “pyridine substituent” is any of the following formulas (Py-1) to (Py-15), and each pyridine substituent is independently an alkyl or carbon having 1 to 4 carbon atoms. It may be substituted with cycloalkyl of several 5-10. Further, the pyridine-based substituent may be bonded to φ, anthracene ring or fluorene ring in each formula through a phenylene group or a naphthylene group.

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

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

“Alkyl” in R ¹¹ to R ¹⁸ may be either linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms and branched alkyl having 3 to 24 carbon atoms. Preferred “alkyl” is alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms). More preferable “alkyl” is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More preferable “alkyl” is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred “alkyl” is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).

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

Examples of “cycloalkyl” in R ¹¹ to R ¹⁸ include cycloalkyl having 3 to 12 carbon atoms. Preferred “cycloalkyl” is cycloalkyl having 3 to 10 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 8 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 6 carbon atoms.
Specific examples of “cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.

As the “aryl” in 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 still more preferred is aryl having 6 to 14 carbon atoms. And particularly preferred is aryl having 6 to 12 carbon atoms.

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

Preferable “aryl having 6 to 30 carbon atoms” includes phenyl, naphthyl, phenanthryl, chrycenyl, triphenylenyl and the like, more preferably phenyl, 1-naphthyl, 2-naphthyl and phenanthryl, particularly preferably phenyl, 1 -Naphthyl or 2-naphthyl.

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

Specific examples of the pyridine derivative include the following compounds.

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

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

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

Specific examples of the fluoranthene derivative include the following compounds.

<BO derivatives>
The BO derivative is, for example, a polycyclic aromatic compound represented by the following formula (ETM-4) or a multimer of polycyclic aromatic compounds 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, in which at least one hydrogen May be substituted with aryl, heteroaryl, alkyl or cycloalkyl.

Further, adjacent groups of R ¹ to R ¹¹ may be bonded 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, wherein at least one hydrogen is aryl, heteroaryl, alkyl or It may be substituted with cycloalkyl.

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

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

Specific examples of this BO derivative include the following compounds.

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

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

Ar is 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 number 6 to 20 aryls.

Ar can be independently selected as appropriate from divalent benzene or naphthalene, and the two Ar may be different or the same, but the same from the viewpoint of the ease of synthesis of the anthracene derivative. It is preferable that Ar is bonded to pyridine to form a “part consisting of Ar and pyridine”. This part is an anthracene as a group represented by any of the following formulas (Py-1) to (Py-12), for example. Is bound to.

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

The alkyl having 1 to 6 carbon atoms in R ¹ to R ⁴ may be linear or branched. That is, it is a linear alkyl having 1 to 6 carbon atoms or a branched alkyl having 3 to 6 carbon atoms. More preferred is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, Examples include 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc., preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. More preferred are methyl, ethyl, or t-butyl.

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, and dimethylcyclohexyl.

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 “aryl having 6 to 20 carbon atoms” include monocyclic aryl 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, (1-, 2-) naphthyl which is a condensed bicyclic aryl, terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4) which is a tricyclic aryl '-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-terphe Lu-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl ), Condensed tricyclic aryl, anthracene- (1-, 2-, 9-) yl, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, and triphenylene- (4), a condensed tetracyclic aryl. 1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, tetracene- (1-, 2-, 5-) yl, perylene- (1-, 2) which is a fused pentacyclic aryl -, 3-) Ill and the like.

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 preferred is phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, and most preferred is 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 is independently an aryl having 6 to 20 carbon atoms, and the same description as “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 preferred, aryl having 6 to 12 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred. 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 the above formula (ETM-5-1) The explanation in can be cited.

Specific examples of these anthracene derivatives include the following compounds.

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

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

Ar ¹ is independently an aryl having 6 to 20 carbon atoms, and the same description as “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 preferred, aryl having 6 to 12 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl and the like.

Ar ² is independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably aryl having 6 to 30 carbon atoms). And two Ar ² may be bonded to form a ring.

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

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 preferred “cycloalkyl” is cycloalkyl having 3 to 8 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 6 carbon atoms. Specific examples of “cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.

As “aryl” in Ar ² , preferred aryl is aryl having 6 to 30 carbon atoms, more preferred aryl is aryl having 6 to 18 carbon atoms, still more preferred is aryl having 6 to 14 carbon atoms, 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 may be bonded to form a ring. 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 using a known raw material and a known synthesis method.

<Phosphine oxide derivative>
The phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1). Details are also described in International Publication No. 2013/079217.

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 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or 5 to 5 carbon atoms. 20 heteroaryl, alkoxy having 1 to 20 carbons or aryloxy having 6 to 20 carbons;
R ⁷ and R ⁸ are each independently substituted or unsubstituted aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms;
R ⁹ is oxygen or sulfur;
j is 0 or 1, k is 0 or 1, r is an integer of 0 to 4, and q is an integer of 1 to 3.
Here, examples of the substituent when 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 are hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, alkylthio group, cycloalkylthio group, aryl ether group , Arylthioether group, aryl group, heterocyclic group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, amino group, nitro group, silyl group, and a condensed ring formed between 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. When n is 0, there is no unsaturated structure, and when n is 3, R ¹ does not exist.

Of these substituents, the alkyl group represents, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or 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 common to the following description. The number of carbon atoms of the alkyl group is not particularly limited, but is usually in the range of 1 to 20 from the viewpoint of availability and cost.

Further, the cycloalkyl group represents 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 moiety is not particularly limited, but is usually in the range of 3-20.

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

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

The cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexene group, which may be unsubstituted or substituted. It doesn't matter.

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

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

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.

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

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

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

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

Halogen means fluorine, chlorine, bromine and iodine.

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

In addition, the aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, and heterocyclic ring 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 3-20. The number of silicon is usually 1-6.

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 A conjugated or non-conjugated fused ring formed between Ar ^{2 and the} like. Here, when n is 1, it may be formed conjugated or non-conjugated fused ring with two of R ¹ each other. These condensed rings may contain a nitrogen, oxygen, or sulfur atom in the ring structure, or may be further condensed with another ring.

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

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

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

Ar is 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 “aryl” in “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 preferred is aryl having 6 to 12 carbon atoms.

Specific examples of “aryl” include monocyclic aryl phenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, condensed bicyclic aryl (1-, 2-) naphthyl. Terphenylyl which is a tricyclic aryl (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) Asena, which is a fused tricyclic aryl Tylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1 -, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl which is a tetracyclic aryl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl) -3-yl, 5′-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensed tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1- , 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, condensed pentacyclic aryl perylene- (1-, 2-, 3-) yl, pentacene- (1-, 2-, 5-, 6-) yl and the like.

Examples of the “heteroaryl” in the “optionally substituted heteroaryl” include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferred, heteroaryl having 2 to 15 carbons is more preferred, and heteroaryl having 2 to 10 carbons is particularly preferred. Examples of the heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring constituent atoms.

Specific heteroaryl includes, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl , Pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, Enajiniru, phenoxathiinyl, thianthrenyl, etc. indolizinyl the like.

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

Specific examples of this pyrimidine derivative include the following compounds.

This pyrimidine derivative can be produced using a known raw 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 such carbazole derivatives are bonded by a single bond or the like. Details are described in US 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.

The carbazole derivative may be a multimer in which a plurality of compounds represented by the above formula (ETM-9) are bonded by a single bond or the like. In this case, in addition to 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 used.

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), and preferably a compound represented by the following formula (ETM-10-1). 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.

Specific examples of the triazine derivative include the following compounds.

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

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

φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4 The “benzimidazole substituent” means that the pyridyl group in the “pyridine substituent” in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) is benzo It is a substituent substituted with an imidazole group, and at least one hydrogen in the benzimidazole derivative may be substituted with deuterium.

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

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), In the formula, R ¹¹ to R ¹⁸ can be referred to the description of the above formula (ETM-2-1) or formula (ETM-2-2). Further, in the above formula (ETM-2-1) or formula (ETM-2-2), it is explained in a form in which two pyridine-based substituents are bonded. However, when these are replaced with benzimidazole-based substituents, May be replaced with a benzimidazole substituent (ie, n = 2), or any one pyridine substituent may be replaced with a benzimidazole substituent and the other pyridine substituent may be replaced with R ^11. May be replaced by ~ R ¹⁸ (ie n = 1). Further, for example, at least one of R ¹¹ to R ¹⁸ in the above formula (ETM-2-1) may be replaced with a benzimidazole substituent, and the “pyridine substituent” may be replaced with R ¹¹ to R ¹⁸ .

Specific examples of this benzimidazole derivative include, for example, 1-phenyl-2- (4- (10-phenylanthracen-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- ( Naphthalen-2-yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (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) anthracene-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] and imidazole.

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

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

R ¹¹ to R ^{18 in} each formula are independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably carbon (Aryl of formula 6 to 30). 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 ~ ^{R 18,} cycloalkyl and aryl may be cited to the description of ^R 11 ^{~ R 18} in the formula (ETM-2). In addition to the above example, φ includes the following structural formula, for example. In the following structural formulas, each R is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl.

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

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

<Quinolinol metal complex>
The quinolinol-based metal complex is, for example, a compound represented by the following general formula (ETM-13).

Wherein 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 quinolinol metal complexes 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) ( Phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolato) aluminum, bis (2-methyl-8- Quinolinolato) (4- Tylphenolate) 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-dimethyl) Phenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2 -Methyl-8-quinolinolate) (3,5-di-t- Tylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (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-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenyl) Phenolate) aluminum, bis (2,4-dimethyl-8-quinolinola) G) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethyl) Phenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (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-) -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 and the like.

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

<Thiazole derivatives and benzothiazole derivatives>
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 The “thiazole-based substituent” and “benzothiazole-based substituent” are “pyridine-based” in the above 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 substituted, and at least one hydrogen in the thiazole derivative and the benzothiazole derivative may be substituted with deuterium.

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), In the formula, R ¹¹ to R ¹⁸ can be referred to the description of the above formula (ETM-2-1) or formula (ETM-2-2). Further, in the above formula (ETM-2-1) or formula (ETM-2-2), it is described in the form of two pyridine-based substituents bonded to each other, but these are represented by thiazole-based substituents (or benzothiazole-based substituents). Group), both pyridine-based substituents may be replaced with thiazole-based substituents (or benzothiazole-based substituents) (ie, n = 2), and any one pyridine-based substituent may be replaced with thiazole-based substituents. A group (or a benzothiazole substituent) may be substituted, and the other pyridine substituent may be substituted with R ¹¹ to R ¹⁸ (ie, n = 1). Further, for example, at least one of R ¹¹ to R ¹⁸ in the above formula (ETM-2-1) is replaced with a thiazole substituent (or benzothiazole substituent) to replace the “pyridine substituent” with R ¹¹ to R ^18. May be replaced.

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

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

Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2. 9eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and alkaline earth metals such as those having a work function of 2.9 eV or less are particularly preferable. Among these, a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of two or more alkali metals is also preferable. Particularly, a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by adding to the material for forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended.

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

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

The material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as the material for forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or alloys thereof (magnesium-silver alloy, magnesium -Indium alloys, aluminum-lithium alloys such as lithium fluoride / aluminum, etc.) are preferred. Lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective for increasing the electron injection efficiency and improving device characteristics. However, these low work function metals are often 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 a highly stable electrode 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.

Furthermore, for electrode protection, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride Lamination of hydrocarbon polymer compounds and the like is a preferred example. 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 materials used for the hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can form each layer alone, but as a polymer binder, polyvinyl chloride, polycarbonate, Polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin It can also be used by dispersing it in solvent-soluble resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, etc. is there.

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

When a DC voltage is applied to the organic EL device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. When a voltage of about 2 to 40 V is applied, a transparent or translucent electrode is applied. Luminescence 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 alternating current waveform to be applied may be arbitrary.

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

<Vapor deposition method>
A thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-evaporated to form a thin film to form a light emitting layer. An electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by vapor deposition. By forming it as a cathode, a target organic EL element can be obtained. In the production of the above-mentioned organic EL device, the production order can 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 can be produced in this order. It is.

<Wet deposition method>
The wet film forming method is carried out by preparing a low molecular compound capable of forming each organic layer of an organic EL element as a liquid organic layer forming composition and using it. If there is no suitable organic solvent that dissolves the low molecular weight compound, the reactive compound obtained by substituting a reactive substituent on the low molecular weight compound is highly reactive along with other monomers having a solubility function and main chain type polymers. A composition for forming an organic layer may be prepared from a polymerized polymer compound.

In the wet film forming method, generally, a coating film is formed by performing a coating process for coating the substrate with the organic layer forming composition and a drying process for removing the solvent from the coated organic layer forming composition. When the polymer compound has a crosslinkable substituent (also referred to as a crosslinkable polymer compound), the polymer is further crosslinked by this drying step to form a polymer crosslinked product. 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 the 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 form is called a spray method. Examples of the drying process include air drying, heating, and drying under reduced pressure. The drying step may be performed only once, or may be performed a plurality of times using different methods and conditions. Further, for example, different methods may be used together, such as firing under reduced pressure.

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

On the other hand, when compared with the vacuum deposition method, the wet film formation method may be difficult to stack. When making a laminated film using the wet film formation method, it is necessary to prevent dissolution of the lower layer by the upper layer composition. The composition with controlled solubility, the lower layer cross-linking and the orthogonal solvent (Orthogonalentsolvent, which dissolves each other) Not a solvent). However, even if these techniques are used, it may be difficult to use a wet film formation method for coating all films.

Therefore, generally, a method is employed in which only a few layers are formed using a wet film forming method, and the rest are formed using a vacuum vapor deposition method.

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

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

<Arbitrary process>
Appropriate treatment steps, washing steps, and drying steps may be appropriately added 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 an appropriate solvent, and heat treatment. Furthermore, a series of steps for producing a bank is also included.

Photolithography technology can be used for the production of the bank. As a bank material that can be used for photolithography, a positive resist material and a negative resist material can be used. In addition, a patternable printing method such as an inkjet method, gravure offset printing, reverse offset printing, or screen printing can also be used. In this case, a permanent resist material can be used.

Materials used for the bank include polysaccharides and derivatives thereof, 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 Polyethylene, chlorinated polypropylene, polyacetate, polynorbornene, synthetic rubber, polyfluorovinylidene, polytetrafluoroethylene, polyhexa Le Oro propylene fluoride such as polymers, fluoroolefin - hydrocarbonoxy olefin copolymer, but fluorocarbon polymers include, but are not limited to.

<Composition for forming organic layer used in wet film formation method>
The composition for forming an organic layer is obtained by dissolving, in an organic solvent, 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. For example, the composition for forming a light emitting layer includes a polycyclic aromatic compound (or a polymer compound thereof) that 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. A 1st component functions as a dopant component of the light emitting layer obtained from this composition, and a 2nd component functions as a host component of a light emitting layer. The third component functions as a solvent that dissolves the first component and the second component in the composition, and gives a smooth and uniform surface shape at the time of application due to the controlled evaporation rate of the third component itself.

<Organic solvent>
The composition for forming an organic layer contains at least one organic solvent. By controlling the evaporation rate of the organic solvent at the time of film formation, the film formability, the presence or absence of defects in the coating film, the surface roughness, and the smoothness can be controlled and improved. Further, during film formation using the ink jet method, the meniscus stability at the pinhole of the ink jet head can be controlled, and the discharge performance can be controlled and improved. In addition, by controlling the drying speed of the film and the orientation of the derivative molecules, the electrical characteristics, light emitting characteristics, efficiency, and lifetime of the organic EL device having an organic layer obtained from the organic layer forming composition are improved. Can do.

(1) Physical properties of organic solvent The boiling point of at least one organic solvent is 130 ° C to 300 ° C, more preferably 140 ° C to 270 ° C, and further preferably 150 ° C to 250 ° C. When the boiling point is higher than 130 ° C., it is preferable from the viewpoint of ink jetting properties. Moreover, when a boiling point is lower than 300 degreeC, it is preferable from a viewpoint of the defect of a coating film, surface roughness, a residual solvent, and smoothness. The organic solvent is more preferably composed of two or more organic solvents from the viewpoints of good ink jet discharge properties, film formability, smoothness and low residual solvent. On the other hand, depending on the case, the composition may be a solid state by removing the solvent from the organic layer forming composition in consideration of transportability and the like.

Furthermore, the organic solvent contains a good solvent (GS) and a poor solvent (PS) for at least one kind of 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). A low configuration is particularly preferred.
By adding a poor solvent having a high boiling point, a good solvent having a low boiling point is volatilized first at the time of film formation, and the concentration of inclusions in the composition and the concentration of the poor solvent are increased, thereby promptly forming a film. Thereby, a coating film with few defects, a small surface roughness, and high smoothness is obtained.

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

The organic solvent is removed from the coating film by a drying process such as vacuum, reduced pressure or heating after the film formation. When heating, from the viewpoint of improving the coating film formability, it is preferable to carry out at least one glass transition temperature (Tg) of the solute + 30 ° C. or less. 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. Moreover, drying may be performed a plurality of times at different temperatures, or a plurality of drying methods may be used in combination.

(2) Specific examples of organic solvents Examples of organic solvents used in the organic layer forming composition include alkylbenzene solvents, phenyl ether solvents, alkyl ether solvents, cyclic ketone solvents, aliphatic ketone solvents, and monocyclic solvents. Examples include ketone solvents, solvents having a diester skeleton, and fluorine-containing solvents. Specific examples include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexane-2-ol, Heptan-2-ol, octan-2-ol, decan-2-ol, dodecan-2-ol, cyclohexanol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, terpineol (mixture), ethylene glycol Monomethyl ester Teracetate, 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 buty 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-chlorobenzo Fluoride, cumene, toluene, 2-chloro-6-fluorotoluene, 2-fluoroanisole, anisole, 2,3-dimethylpyrazine, bromobenzene, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethylanisole, Mesitylene, 1,2,4-trimethylbenzene, t-butylbenzene, 2-methylanisole, phenetole, benzodioxole, 4-methylanisole, s-butylbenzene, 3-methylanisole, 4-fluoro-3-methylanis Sole, 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-me Lunaphthalene, butyl benzoate, 2-methylbiphenyl, 3-phenoxytoluene, 2,2′-vitryl, dodecylbenzene, dipentylbenzene, tetramethylbenzene, trimethoxybenzene, trimethoxytoluene, 2,3-dihydrobenzofuran, 1 -Methyl-4- (propoxymethyl) benzene, 1-methyl-4- (butyloxymethyl) benzene, 1-methyl-4- (pentyloxymethyl) benzene, 1-methyl-4- (hexyloxymethyl) benzene, Examples include, but are not limited to, 1-methyl-4- (heptyloxymethyl) benzenebenzyl butyl ether, benzyl pentyl ether, benzyl hexyl ether, benzyl heptyl ether, benzyl octyl ether, and the like. Moreover, a solvent may be used alone or may be mixed.

<Optional component>
The composition for forming an organic layer may contain an optional component as long as its properties are not impaired. Examples of optional components 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. In addition, it plays a role of dissolving, dispersing and binding other components in the organic layer forming composition.

Examples of the binder used in the organic layer forming composition 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) resin, phenol resin, epoxy resin, melamine resin, urea resin, alkyd resin, polyurethane, and copolymer of the above resin and polymer, Re not limited to.

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 composition for forming an organic layer contains, for example, a surfactant for controlling film surface uniformity, lyophilicity and liquid repellency of the composition for forming an organic layer. Also good. Surfactants are classified into ionic and nonionic based on the structure of the hydrophilic group, and further classified into alkyl, silicon, and fluorine based on the structure of the hydrophobic group. Further, 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 and a branch. Moreover, it classify | categorizes into the mixed system which mixed the single system and 2 or more types of surfactant and the base material from a composition. As the surfactant that can be used in the composition for forming an organic layer, all kinds of surfactants can be used.

As the surfactant, for example, Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, polyflow no. 95 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181 and Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, manufactured by Big Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF -50-100CS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Footent 222F, Footage 251, FTX-218 (trade name, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (trade name, Mitsubishi Materials Corp.) ), Megafuck F-470, Megafuck F-471, Megafuck F-475, Megafuck R-08, Megafuck F-477, Megafuck F-479, Megafuck F-553, Megafuck F-554 (Trade name, manufactured by DIC Corporation), fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (F Oroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene Oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, poly Oxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene Mention may be made of nonnaphthyl ethers, alkylbenzene sulfonates and alkyl diphenyl ether disulfonates.

Further, 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, storage stability and film formability of each component in the composition for forming an organic layer, and the composition for forming an organic layer. Good film quality of the coating film, good dischargeability when using the ink jet method, and good electrical characteristics, light emission characteristics, efficiency, and lifetime of the organic EL device having an organic layer produced using the composition It is decided in consideration of the viewpoint. 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 with respect to the total weight of the composition for forming a light emitting layer, and the second component is for forming a light emitting layer. 0.0999 wt% to 8.0 wt% based on the total weight of the composition, and the third component is 90.0 wt% to 99.9 wt% based on the total weight of the composition for forming the 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 light emitting layer forming composition, and the second component is with respect to the total weight of the light emitting layer forming composition, 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 light emitting layer forming composition. More preferably, the first component is 0.05% by weight to 0.5% by weight relative to the total weight of the light emitting layer forming composition, and the second component is based on the total weight of the light emitting layer forming composition. The amount of the third component is 97.0% by weight to 99.7% by weight with respect to 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 and stirring the above-described components by a known method such as stirring, mixing, heating, cooling, dissolution, and dispersion. Further, after preparation, filtration, degassing (also referred to as degas), ion exchange treatment, inert gas replacement / encapsulation treatment, and the like may be selected as appropriate.

As the viscosity of the composition for forming an organic layer, the higher the viscosity, the better the film formability and the better the discharge property when using the ink jet method. On the other hand, it is easier to make a thin film with a low viscosity. From this, the viscosity of the composition for forming an organic layer is preferably 0.3 to 3 mPa · s, more preferably 1 to 3 mPa · s at 25 ° C. 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 organic layer forming composition, the better the film formability and the coating film without defects. On the other hand, higher ink jetting properties can be obtained. Accordingly, the viscosity of the composition for forming an organic layer is preferably 20 to 40 mN / m, more preferably 20 to 30 mN / m, at a surface tension at 25 ° C. In the present invention, the surface tension is a value measured using the hanging drop method.

<Crosslinkable polymer compound: compound represented by general formula (XLP-1)>
Next, the case where the above-described 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 the 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). Preferably, 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, and more preferably 1 to 20% by weight.

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

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 production method of the polymer compound and the crosslinkable polymer compound will be described using the compound represented by the 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.

Also, the reaction may be performed in a two-phase system. When reacting in a two-phase system, a phase transfer catalyst such as a quaternary ammonium salt may be added as 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 through multiple steps. Moreover, it may be carried out by a batch polymerization method in which the reaction is started after all the raw materials are put in the reaction vessel, or may be carried out by a dropping polymerization method in which the raw material is dropped into the reaction vessel and the product is used for the progress of the reaction. It may be carried out by a precipitation polymerization method in which precipitation is accompanied, and they can be synthesized by appropriately combining them. For example, when the compound represented by the formula (SPH-1) is synthesized in one step, the target product is obtained by carrying out the reaction with the monomer unit (MU) and the end cap unit (EC) added to the reaction vessel. . In addition, when the compound represented by the general formula (SPH-1) is synthesized in multiple stages, the monomer unit (MU) is polymerized to the target molecular weight, and then the end cap unit (EC) is added and reacted. Get things. If the reaction is carried out by adding different types of monomer units (MU) in multiple stages, a polymer having a concentration gradient with respect to the structure of the monomer units can be produced. Moreover, after preparing a precursor polymer, a target polymer can be obtained by a post reaction.

Also, if the polymerizable group of the monomer unit (MU) is selected, the primary structure of the polymer can be controlled. For example, as shown in Synthesis Schemes 1 to 3, it is possible to synthesize polymers with random primary structures (Synthesis Scheme 1), regular primary structures (Synthesis Schemes 2 and 3), etc. And can be used in appropriate combination depending on the object. Furthermore, if a monomer unit having three or more polymerizable groups is used, a hyperbranched polymer or a dendrimer can be synthesized.

Examples of monomer units 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, Japanese Unexamined Patent Publication No. 2010-215886, Japanese Unexamined Patent Publication No. 2008-106241, Japanese Unexamined Patent Publication No. 2010-215886, International Publication No. It can be synthesized according to the methods described in Published 2016/031639, JP 2011-174062, Published 2016/031639, Published 2016/031639, Published 2002/045184 .

For specific polymer synthesis procedures, JP 2012-036388 A, International Publication No. 2015/008851, JP 2012-36381 A, JP 2012-144722 A, International Publication No. 2015/194448. , International Publication No. 2013/146806, International Publication No. 2015/145871, International Publication No. 2016/031639, International Publication No. 2016/125560, International Publication No. 2016/031639, International Publication No. 2016/031639, International Publication No. The compound 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 Unexamined Patent Publication No. 2012-144722.

<Application examples of organic electroluminescent devices>
The present invention can also be applied to a display device including an organic EL element or a lighting device including an organic EL element.
The display device or lighting device including the organic EL element can be manufactured by a known method such as connecting the organic EL element according to the present embodiment and a known driving device, such as DC driving, pulse driving, or AC driving. It can drive using a well-known drive method suitably.

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). Gazette, JP-A-2004-281086, etc.). Examples of the display method of the display include a matrix and / or segment method. Note that the matrix display and the segment display may coexist in the same panel.

In the matrix, pixels for display are two-dimensionally arranged such as a grid or mosaic, and characters and images are displayed with a set of pixels. 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, monitor, TV, and a pixel with a side of mm order for a large display such as a display panel. become. In monochrome display, pixels of the same color may be arranged. However, in 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 matrix driving method may be either a line sequential driving method or an active matrix. The line-sequential driving has an advantage that the structure is simple. However, the active matrix may be superior in consideration of the operation characteristics, so that it is necessary to properly use it depending on the application.

In the segment method (type), a pattern is formed so as to display predetermined information, and a predetermined region is caused to emit light. For example, the time and temperature display in a digital clock or a thermometer, the operation state display of an audio device or an electromagnetic cooker, the panel display of an automobile, and the like can be mentioned.

Examples of the illuminating device include an illuminating device such as indoor lighting, a backlight of a liquid crystal display device, and the like (for example, JP 2003-257621 A, JP 2003-277741 A, JP 2004-119211 A). Etc.) The backlight is used mainly for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, a sign, and the like. In particular, as a backlight for a liquid crystal display device, especially a personal computer application where thinning is an issue, considering that it is difficult to thin the conventional method because it is made of a fluorescent lamp or a light guide plate, this embodiment The backlight using the light emitting element according to the present invention is 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 or an organic thin film solar cell in addition to the above-described organic electroluminescent element.

An organic field effect transistor is a transistor that controls current by an electric field generated by voltage input, and includes a gate electrode in addition to a source electrode and a drain electrode. When a voltage is applied to the gate electrode, an electric field is generated, and the current can be controlled by arbitrarily blocking the flow of electrons (or holes) flowing between the source electrode and the drain electrode. Field effect transistors are easier to miniaturize than simple transistors (bipolar transistors), and are often used as elements constituting integrated circuits and the like.

The structure of the organic field effect transistor is usually provided with a source electrode and a drain electrode in contact with the organic semiconductor active layer formed using the polycyclic aromatic compound according to the present invention, and further in contact with the organic semiconductor active layer. The gate electrode may be provided with the insulating layer (dielectric layer) interposed 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 It can be applied as a pixel driving switching element for an active matrix driving type liquid crystal display or an organic electroluminescence display.

Organic thin-film solar cells have 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 more specifically with reference to examples, but the present invention is not limited to these examples. First, the synthesis example of a polycyclic aromatic compound is demonstrated 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 thereto under ice cooling, and the mixture was stirred for 0.5 hours. 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. Thereafter, the organic layer was concentrated to obtain a crude product. The crude product was purified with a silica gel short column (eluent: toluene) and then washed with heptane to obtain intermediate (IA) (21.0 g).

Under a nitrogen atmosphere, 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 solution was added dropwise and stirred at the same temperature for 30 minutes. After the reaction, dilute hydrochloric acid and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the organic layer was concentrated to obtain a crude product. The crude product was purified with a silica gel short column (eluent: toluene / heptane = 1/3 (volume ratio)) to obtain intermediate (IB) (16.0 g).

Under a nitrogen atmosphere, intermediate (IB) (12.0 g), N- (3-tertbutylphenyl) -3,5-ditertbutylaniline (21.0 g), dichlorobis [(di-t -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. Thereafter, 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 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 completion of the dropwise addition, the mixture was heated to 60 ° C. and stirred for 1 hour, and then components having a lower boiling point than tert-butylbenzene were distilled off under reduced pressure. After cooling to −50 ° C., boron tribromide (13.1 g) was added, and the mixture was warmed to room temperature and stirred for 0.5 hour. Thereafter, the mixture was cooled again to 0 ° C., N, N-diisopropylethylamine (6.8 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, and then heated to 100 ° C. and heated and stirred for 1 hour. The reaction solution was cooled to room temperature, and an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added to separate the layers. The organic layer was concentrated and then 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 compound obtained by NMR measurement was confirmed.
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-tertbutylphenyl) -4-tertbutylaniline (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 the 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. Thereafter, the organic layer was concentrated to obtain a crude product. The crude product was purified with a silica gel short column (eluent: toluene) to obtain Intermediate (ID) (13.1 g).

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

The structure of the compound obtained by NMR measurement was confirmed.
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, 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. Stir for 4 hours at the same temperature. After adding water, sodium carbonate was gradually added until foaming subsided, and then an appropriate amount of sodium bisulfite was added. After the organic layer was washed with water, the organic layer was concentrated to obtain a crude product. The crude product was purified with a 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 after cooling, intermediate (IF) was obtained (44.0 g).

In 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, the crystal | crystallization obtained after adding heptane to the crude product obtained by concentrating an organic layer and cooling was filtered. The crude product was purified with a silica gel short column (eluent: toluene / heptane = 1/1 (volume ratio)), and obtained by cooling the crude product obtained by concentrating the organic layer by adding heptane. The crystals were filtered to obtain intermediate (IH) (10.0 g).

Under a nitrogen atmosphere, intermediate (IH) (10.0 g), N- (4-tertbutylphenyl) -4-tertbutylaniline (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) 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. Crystals obtained after adding heptane to the crude product obtained by concentrating the organic layer and cooling were filtered. The crude product was purified with a silica gel short column (eluent: toluene) and the crude product obtained by concentrating the organic layer was cooled by adding heptane to the intermediate product (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 completion of the dropping, the temperature was raised to 70 ° C. and stirred for 1 hour, and then components having a lower boiling point than tert-butylbenzene were distilled off under reduced pressure. After cooling to −50 ° C., boron tribromide (5.2 g) was added, and the mixture was warmed to room temperature and stirred for 0.5 hour. Thereafter, the mixture was cooled again to 0 ° C., N, N-diisopropylethylamine (2.7 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, and then heated to 80 ° C. and heated and stirred for 1 hour. The reaction solution was cooled to room temperature, an aqueous sodium acetate solution cooled in an ice bath, and then ethyl acetate was added. After stirring for 1 hour, the precipitated yellow precipitate was filtered, and the filtrate was washed with methanol, distilled water, and methanol in this order. did. The yellow precipitate was washed twice with hot heptane and further purified with a silica gel short column (eluent: toluene / heptane = 3/7 (volume ratio)). Then, it was dissolved in toluene and concentrated, and the step of filtering after adding heptane to precipitate crystals was repeated to obtain compound (1-321) (5.5 g).

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. Thereafter, methanol was added to the crude product obtained by concentrating the organic layer and cooled, and then the resulting crystals were filtered. The crude product was purified with a silica gel short column (eluent: toluene), the crude product obtained by concentrating the organic layer was added with heptane and cooled, and the resulting 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. Crystals obtained after adding heptane to the crude product obtained by concentrating the organic layer and cooling were filtered. The crystals were purified with a silica gel short column (eluent: toluene) and the crude product obtained by concentrating the organic layer was cooled by adding heptane to the intermediate product (IL). ) Was obtained (13.6 g).

To a flask containing intermediate (IL) (13.5 g) and tert-butylbenzene (100 ml) was added 1.56 M tert-butyllithium pentane solution (18.9 ml) at 0 ° C. under a nitrogen atmosphere. Was added. After completion of the dropping, the temperature was raised to 70 ° C. and stirred for 1 hour, and then components having a lower boiling point than tert-butylbenzene were distilled off under reduced pressure. After cooling to −50 ° C., boron tribromide (7.2 g) was added, and the mixture was warmed to room temperature and stirred for 0.5 hour. Thereafter, the mixture was cooled again to 0 ° C., N, N-diisopropylethylamine (3.7 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, and then heated to 90 ° C. and heated and stirred for 1 hour. The reaction solution was cooled to room temperature, an aqueous sodium acetate solution cooled in an ice bath, then ethyl acetate was added, and the mixture was stirred for 1 hour. After further adding heptane, the precipitated yellow precipitate was filtered, and the filtrate was methanol, distilled water. Then, it was washed with methanol in this order. The yellow precipitate was washed with hot toluene and 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 crystals, followed by filtration, to obtain (5.7 g).

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. Crystals obtained after adding heptane to the crude product obtained by concentrating the organic layer and cooling were filtered. The crystals were purified with a silica gel short column (eluent: toluene), and the eluent was concentrated. The crude product obtained by adding heptane to the crude product was cooled, and the resulting 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 completion of the dropping, the temperature was raised to 70 ° C. and stirred for 1 hour, and then components having a lower boiling point than tert-butylbenzene were distilled off under reduced pressure. After cooling to −50 ° C., boron tribromide (4.2 g) was added, and the mixture was warmed to room temperature and stirred for 0.5 hour. Thereafter, the mixture was cooled again to 0 ° C., N, N-diisopropylethylamine (2.2 g) was added, and the mixture was stirred at room temperature until the exotherm subsided. Then, the temperature was raised to 80 ° C. and heated and stirred for 1 hour. The reaction solution was cooled to room temperature, an aqueous sodium acetate solution cooled in an ice bath, then ethyl acetate was added, and the mixture was stirred for 1 hour. After further addition of heptane, the precipitated yellow precipitate was filtered, and the filtrate was methanol, distilled water. Then, it was washed with methanol in this order. Further purification was performed with a silica gel short column (eluent: toluene). Then, the compound (1-327) was obtained (3.0 g) by repeating the process of dissolving in toluene and concentrating, adding heptane and precipitating crystals and then filtering.

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 (IJ) (6.6 g), intermediate (IO) (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. Crystals obtained after adding ethyl acetate to the crude product obtained by concentrating the organic layer and cooling were filtered. The crystals were purified with a silica gel short column (eluent: toluene), and the eluent was concentrated. After adding heptane to the crude product obtained and cooling, the resulting crystals were filtered to obtain an intermediate (IP). ) Was obtained (9.6 g).

To a flask containing intermediate (IP) (9.5 g) and tert-butylbenzene (100 ml) was added 1.56 M tert-butyllithium pentane solution (18.9 ml) at 0 ° C. under a nitrogen atmosphere. Was added. After completion of the dropping, the temperature was raised to 70 ° C. and stirred for 1 hour, and then components having a lower boiling point than tert-butylbenzene were distilled off under reduced pressure. After cooling to −50 ° C., boron tribromide (7.2 g) was added, and the mixture was warmed to room temperature and stirred for 0.5 hour. Thereafter, the mixture was again cooled to 0 ° C., N, N-diisopropylethylamine (3.7 g) was added, and the mixture was stirred at room temperature until the exotherm subsided. Then, the temperature was raised to 80 ° C. and heated and stirred for 1 hour. The reaction solution was cooled to room temperature, an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added and stirred for 1 hour, and then the organic layer was separated. After distilling off the organic solvent, the residue was purified with a silica gel short column (eluent: toluene / heptane = 2/8 (volume ratio)). Thereafter, the mixture was dissolved in toluene and concentrated, and the step of filtering after adding heptane to precipitate crystals was repeated to obtain Compound (1-332) (3.8 g).

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 1.81-1.87 (m, 12H), 2.05 to 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, 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 crystals obtained after cooling were filtered. The crude product was purified with a silica gel short column (eluent: toluene), the crude product obtained by concentrating the organic layer was added with heptane and cooled, and the resulting crystals were filtered to obtain an intermediate (I -Q) was obtained (16.0 g).

Under a nitrogen atmosphere, intermediate (IQ) (8.0 g), intermediate (IK) (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. Crystals obtained after adding heptane to the crude product obtained by concentrating the organic layer and cooling were filtered. The crystals were purified with a silica gel short column (eluent: toluene) and the crude product obtained by concentrating the organic layer was cooled by adding heptane to the intermediate (IR). ) Was obtained (13.0 g).

A flask containing intermediate (IR) (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 completion of the dropping, the temperature was raised to 70 ° C. and stirred for 1 hour, and then components having a lower boiling point than tert-butylbenzene were distilled off under reduced pressure. After cooling to −50 ° C., boron tribromide (7.9 g) was added, and the mixture was warmed to room temperature and stirred for 0.5 hour. Thereafter, the mixture was cooled again to 0 ° C., N, N-diisopropylethylamine (4.1 g) was added, and the mixture was stirred at room temperature until the exotherm subsided, and then heated to 90 ° C. and heated and stirred for 1 hour. The reaction solution was cooled to room temperature, an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added and stirred for 1 hour, and then the organic layer was separated by liquid separation. After distilling off the organic solvent, purification was performed with a silica gel short column (eluent: toluene). Then, the compound (1-334) was obtained by dissolving in toluene and concentrating, repeating the step of filtering after adding ethyl acetate to precipitate crystals (7.2 g).

The structure of the compound obtained by NMR measurement was confirmed.
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 with a silica gel short column (eluent: toluene / heptane = 2/8 (volume ratio)), and the eluent was concentrated to obtain a crude product. The intermediate (IS) was obtained by filtering the crystals obtained after adding the mix (A-11) and cooling (25.5 g).

Under a nitrogen atmosphere, N- (4-tertbutylphenyl) -4-tertbutylaniline (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 with a silica gel short column (eluent: toluene), and heptane was added to the crude product obtained by concentrating the eluent to cool the resulting crystals. The intermediate (IT) was obtained by filtration (10.5 g).

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 completion of the dropping, the temperature was raised to 70 ° C. and stirred for 1 hour, and then components having a lower boiling point than tert-butylbenzene were distilled off under reduced pressure. After cooling to −50 ° C., boron tribromide (7.2 g) was added, and the mixture was warmed to room temperature and stirred for 0.5 hour. Thereafter, the mixture was again cooled to 0 ° C., N, N-diisopropylethylamine (3.7 g) was added, and the mixture was stirred at room temperature until the exotherm subsided. Then, the temperature was raised to 80 ° C. and heated and stirred for 1 hour. The reaction mixture was cooled to room temperature, an aqueous sodium acetate solution cooled in an ice bath and then ethyl acetate were added, and the mixture was stirred for 1 hour. Heptane was added, and the precipitated yellow precipitate was filtered. The resulting precipitate was purified with a silica gel short column (eluent: toluene). Thereafter, the mixture was dissolved in toluene and concentrated, and the step of filtering after adding ethyl acetate and further adding heptane to precipitate crystals was repeated to obtain compound (1-339) (5.3 g).

The structure of the compound obtained by NMR measurement was confirmed.
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).

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

Next, in order to describe the present invention in more detail, examples of the organic EL device 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 element>
The organic EL elements according to Example 1, Examples 2 to 3, and Examples 4 to 28 were manufactured, and the voltage (V), emission wavelength (nm), and external quantum efficiency (%), which are characteristics at 1000 cd / m ² emission. ) Was measured, and the time for maintaining a luminance of 90% or more of the initial luminance when driven at a constant current 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 that the external energy injected as electrons (or holes) into the light emitting layer of the light emitting device is converted into pure photons. The ratio is shown. On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light emitting device, and some of the photons generated in the light emitting layer continue to be absorbed or reflected inside the light emitting device. In other words, the external quantum efficiency is lower than the internal quantum efficiency because it is not emitted to the outside of the light emitting element.

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

<Example 1>
Table 1A and Table 1B below show the material configuration of each layer and the EL characteristic data in the organic EL element according to Example 1.

In Table 1A, “HI” refers to 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-hexaazatriphenylenehexacarbonitrile, 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 An amine, “HT-2” being N, N-bis (4- (dibenzo [b, d] furan-4-yl) phenyl)-[1,1 ′: 4 ′, 1 ″ -terphenyl] -4-amine, “BH-1” is 2- (10-phenylanthracene-9- Yl) naphtho [2,3-b] benzofuran, “ET-1” is 4,6,8,10-tetraphenyl [1,4] benzoxabolinino [2,3,4-kl] phenoxaboli “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 glass substrate (manufactured by Opto Science Co., Ltd.) of 26 mm × 28 mm × 0.7 mm obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, BH-1, compound (1-25), ET A molybdenum evaporation boat containing -1 and ET-2, and an aluminum nitride evaporation boat containing Liq, LiF and aluminum, respectively, were mounted.

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

When a direct current voltage was applied using an ITO electrode as an anode and a LiF / aluminum electrode as a cathode, and the characteristics at 1000 cd / m ² emission were measured, blue emission with a wavelength of 458 nm was obtained, the driving voltage was 3.68 V, and the external quantum efficiency Was 7.96%. The time for maintaining the luminance of 90% or more of the initial luminance was 329 hours.

<Examples 2 and 3>
Table 2A and Table 2B below show the material configuration of each layer and the EL characteristic data in the organic EL elements according to Examples 2 and 3.

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

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

When a direct current voltage was applied using an ITO electrode as an anode and a LiF / aluminum electrode as a cathode, the characteristics at 1000 cd / m ² light emission were measured. Was 8.57%. Further, the time for maintaining the luminance of 90% or more of the initial luminance was 111 hours.

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

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

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

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

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

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

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

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

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

The structure of “ET1” in Table 4 is shown below.

<Preparation of light emitting layer forming composition (1)>
A light emitting layer forming composition (1) is prepared by stirring the following components until a uniform solution is obtained. The prepared light emitting layer forming composition is spin-coated on a glass substrate and dried by heating under reduced pressure, whereby a coating film free from film defects and excellent in smoothness can be obtained.
Compound (A) 0.04% by weight
SPH-101 1.96 wt%
Xylene 69.00 wt%
Decalin 29.00 wt%

The compound (A) is a polycyclic aromatic compound represented by the general formula (1), a multimer thereof, the polycyclic aromatic compound or the multimer as a monomer (that is, the monomer has a reactive substituent). ), Or a crosslinked polymer obtained by further crosslinking the polymer compound. The polymer compound for obtaining a crosslinked polymer has a crosslinkable substituent.

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

<Preparation of OTPD solution>
OTPD (LT-N159, manufactured by Luminescence Technology Corp) and IK-2 (photo cation polymerization initiator, manufactured by San Apro) were dissolved in toluene to give an OTPD concentration of 0.7% by weight and an IK-2 concentration of 0.007% by weight. Prepare a solution of OTPD.

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

The produced multilayer film is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing ET1, a molybdenum vapor deposition boat containing LiF, and tungsten containing aluminum. A vapor deposition boat is installed. After depressurizing the vacuum chamber to 5 × 10 ⁻⁴ Pa, ET1 is heated and evaporated to a film thickness of 30 nm to form an electron transport layer. The deposition rate for forming the electron transport layer is 1 nm / second. Thereafter, LiF is heated and deposited at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, aluminum is heated and evaporated to a thickness of 100 nm to form a cathode. In this way, an organic EL element 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 spin-coated with an XLP-101 solution and baked on a hot plate at 200 ° C. for 1 hour to form a film with a thickness of 30 nm.

<Example 31>
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 PCz solution and baking on a hot plate at 120 ° C. for 1 hour to form a film with a thickness of 30 nm.

<Preparation of organic EL elements of Examples 32-34>
Table 5 shows the material structure of each layer in the organic EL element.

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

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

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

In Table 5, “DOBNA” is 3,11-di-o-tolyl-5,9-dioxa-13b-boranaft [3,2,1-de] anthracene. The chemical structure is shown below.

<Example 32>
An ND-3202 (Nissan Chemical Industries) solution was spin-coated on a glass substrate on which ITO was deposited to a thickness of 45 nm, and then heated at 50 ° C. for 3 minutes in an air atmosphere, and further 230 ° C., 15 By heating for 50 minutes, an ND-3202 film having a thickness of 50 nm is formed (hole injection layer). Next, an XLP-101 solution is spin-coated and heated on a hot plate at 200 ° C. for 30 minutes in a nitrogen gas atmosphere to form an XLP-101 film having a thickness of 20 nm (hole transport layer). Next, the light emitting layer forming composition (2) is spin-coated, and heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere to form a 20 nm light emitting layer.

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

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

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

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

The composition for light emitting layer formation is prepared by stirring the following component until it becomes a uniform solution.
Compound (A) 0.02% by weight
2PXZ-TAZ 0.18 wt%
SPH-101 1.80 wt%
Xylene 98.00 wt%

The composition for light emitting layer formation is prepared by stirring the following component until it becomes a uniform solution.
Compound (A) 0.02% by weight
2PXZ-TAZ 0.18 wt%
DOBNA 1.80 wt%
Toluene 98.00 wt%

In Table 6, “2PXZ-TAZ” means 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>
An ND-3202 (Nissan Chemical Industries) solution was spin-coated on a glass substrate on which ITO was deposited to a thickness of 45 nm, and then heated at 50 ° C. for 3 minutes in an air atmosphere, and further 230 ° C., 15 By heating for 50 minutes, an ND-3202 film having a thickness of 50 nm is formed (hole injection layer). Next, an XLP-101 solution is spin-coated and heated on a hot plate at 200 ° C. for 30 minutes in a nitrogen gas atmosphere to form an XLP-101 film having a thickness of 20 nm (hole transport layer). Next, the light emitting layer forming composition (5) is spin-coated, and heated at 130 ° C. for 10 minutes in a nitrogen gas atmosphere to form a 20 nm light emitting layer.

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

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

DESCRIPTION OF SYMBOLS 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

A polycyclic aromatic compound represented by the following general formula (1) or a multimer of polycyclic aromatic compounds 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 in the 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 An aryl, an optionally substituted heteroaryl, an optionally substituted alkyl or an optionally substituted cycloalkyl, wherein R of> C (—R) 2 is hydrogen, an optionally substituted aryl Or 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. )
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 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 bonded via a single bond or a linking group) Optionally substituted), 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 A 5- or 6-membered ring sharing a bond with the fused bicyclic 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 in the 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 R may be aryl, alkyl optionally substituted with heteroaryl, alkyl or cycloalkyl, and R in> C (—R) 2 is hydrogen, aryl or alkyl optionally substituted with alkyl, and R of> N—R and / or R of> C (—R) 2 may be —O—, —S—, —C (—R) 2 — or a single bond to form A ring, B ring and / or Or it may be bonded to the C ring, R in the —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 represented by formula (1) is substituted with cycloalkyl,
The polycyclic aromatic compound or multimer thereof according to claim 1.
The polycyclic aromatic compound represented by the following general formula (2) according to claim 1.

(In the above formula (2),
R 1 to R 11 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryls are bonded via a single bond or a linking group). And at least one hydrogen in these may be substituted with aryl, heteroaryl or alkyl, and adjacent groups of R 1 to R 11 may be It may be bonded 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 May be bonded via a single bond or a linking group), substituted with alkyl, alkoxy or aryloxy, wherein at least one hydrogen is substituted with aryl, heteroaryl or alkyl You can,
Y 1 is B, P, P═O, P═S, Al, Ga, As, Si—R or Ge—R, where R in Si—R and Ge—R is 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, aryl having 6 to 12 carbons Or R of> N—R and / or R of> 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 in the —C (—R) 2 — is alkyl having 1 to 6 carbon atoms,
At least one hydrogen in the compound of formula (2) may be substituted with deuterium, cyano or halogen, and
At least one hydrogen in the compound represented by the formula (2) is substituted with cycloalkyl. )
R 1 to R 11 are each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diarylboryl (provided that Aryl is aryl having 6 to 12 carbons, and 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 may be bonded 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. At least one hydrogen may be substituted with aryl having 6 to 10 carbon atoms or alkyl having 1 to 12 carbon atoms;
Y 1 is B, P, P═O, P═S or Si—R, and R in the Si—R is aryl having 6 to 10 carbon atoms or alkyl having 1 to 4 carbon atoms,
X 1 and X 2 are each independently>O,>N—R,> C (—R) 2 or> S, where R in> N—R is aryl having 6 to 10 carbon atoms, carbon An alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, wherein R of> C (—R) 2 is hydrogen, aryl having 6 to 10 carbon atoms or alkyl having 1 to 4 carbon atoms;
At least one hydrogen in the compound of 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 3.
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 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 , wherein R in> N—R is aryl having 6 to 10 carbons, 1 to C 4 alkyl or cycloalkyl having 5 to 10 carbon atoms, wherein R of> C (—R) 2 is hydrogen, aryl having 6 to 10 carbon atoms or alkyl having 1 to 4 carbon atoms, and
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl;
The polycyclic aromatic compound according to claim 3.
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, where R in> N—R is aryl having 6 to 10 carbon atoms , An alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, and
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl;
The polycyclic aromatic compound according to claim 3.
The polycyclic aromatic group according to any one of claims 1 to 6, which is substituted with a cycloalkyl-substituted diarylamino group, a cycloalkyl-substituted carbazolyl group or a cycloalkyl-substituted benzocarbazolyl group. Group compounds or multimers thereof.
7. The polycyclic aromatic compound according to claim 3, wherein R 2 is a cycloalkyl substituted diarylamino group or a cycloalkyl substituted carbazolyl group.
The polycyclic aromatic compound according to any one of claims 1 to 8, wherein the cycloalkyl is a cycloalkyl having 3 to 20 carbon atoms.
The polycyclic aromatic compound or multimer thereof according to any one of claims 1 to 9, wherein the halogen is fluorine.
The polycyclic aromatic compound according to claim 1 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.)
A reactive compound obtained by substituting a reactive substituent on the polycyclic aromatic compound or multimer thereof according to any one of claims 1 to 11.
A polymer compound obtained by polymerizing the reactive compound according to claim 12 as a monomer, or a polymer crosslinked product obtained by further crosslinking the polymer compound.
A pendant polymer compound obtained by substituting the reactive compound according to claim 12 to a main chain polymer, or a pendant polymer crosslinked material obtained by further crosslinking the pendant polymer compound.
An organic device material comprising the polycyclic aromatic compound according to any one of claims 1 to 11 or a multimer thereof.
An organic device material containing the reactive compound according to claim 12.
An organic device material containing the polymer compound or polymer crosslinked product according to claim 13.
An organic device material containing the pendant polymer compound or the pendant polymer crosslinked product according to claim 14.
The organic device material according to any one of claims 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.
The organic device material according to claim 19, wherein the organic electroluminescent element material is a light emitting layer material.
An ink composition comprising the polycyclic aromatic compound or multimer thereof according to any one of claims 1 to 11 and an organic solvent.
An ink composition comprising the reactive compound according to claim 12 and an organic solvent.
An ink composition comprising a main chain polymer, the reactive compound according to claim 12, and an organic solvent.
An ink composition comprising the polymer compound or crosslinked polymer according to claim 13 and an organic solvent.
An ink composition comprising the pendant polymer compound or pendant polymer cross-linked product according to claim 14 and an organic solvent.
A pair of electrodes consisting of an anode and a cathode, a polycyclic aromatic compound or a multimer thereof according to any one of claims 1 to 11 disposed between the pair of electrodes, a reactive compound according to claim 12, An organic electroluminescent device comprising the polymer compound or crosslinked polymer according to claim 13, or the organic layer containing the pendant polymer compound or pendant crosslinked polymer according to claim 14.
A pair of electrodes consisting of an anode and a cathode, a polycyclic aromatic compound or a multimer thereof according to any one of claims 1 to 11 disposed between the pair of electrodes, a reactive compound according to claim 12, An organic electroluminescent device comprising the polymer compound or crosslinked polymer according to claim 13, or a light-emitting layer containing the pendant polymer compound or pendant crosslinked polymer according to claim 14.
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 body, a pendant polymer compound, or a pendant polymer crosslinked body. The organic electroluminescent element according to claim 27.
The organic electroluminescence device according to claim 28, wherein the host is an anthracene compound, a fluorene compound, or a dibenzochrysene compound.
An electron transport layer and / or an electron injection layer disposed between the cathode and the light emitting layer, wherein at least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, a fluoranthene derivative, BO And at least one selected from the group consisting of a series derivative, anthracene derivative, benzofluorene derivative, phosphine oxide derivative, pyrimidine derivative, carbazole derivative, triazine derivative, benzimidazole derivative, phenanthroline derivative, and quinolinol metal complex. 26. The organic electroluminescence device according to any one of 26 to 29.
The electron transport layer and / or the electron injection layer further includes an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or an alkaline earth metal. The material contains at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes. 30. The organic electroluminescent device according to 30.
A polymer compound in which at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer is polymerized using a low molecular compound capable of forming each layer as a monomer, or A polymer crosslinked product 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. The organic electroluminescence device according to any one of claims 26 to 31, further comprising a crosslinked pendant polymer crosslinked body.
A display device or illumination device comprising the organic electroluminescent element according to any one of claims 26 to 32.