KR20200143438A - Cycloalkyl-substituted polycyclic aromatic compounds - Google Patents

Abstract

By introducing a cycloalkyl group into a novel polycyclic aromatic compound in which a plurality of aromatic rings are connected with a boron atom and an oxygen atom, etc., it is possible to increase the selection of materials for organic devices such as materials for organic EL devices, and By using a cycloalkyl-substituted polycyclic aromatic compound as a material for an organic EL device, for example, an organic EL device excellent in luminous efficiency and device life can be provided.

Description

Cycloalkyl-substituted polycyclic aromatic compounds

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

BACKGROUND ART Conventionally, a display device using an electroluminescent light emitting device can be reduced in power or thinner, and thus various studies have been conducted, and an organic light emitting device made of an organic material has been actively studied because it is easy to reduce weight or increase in size. In particular, for the development of organic materials having luminescence properties such as blue, which is one of the three primary colors of light, and development of organic materials having the ability to transport holes and electrons (possibly becoming a semiconductor or superconductor), polymers Regardless of compounds and low molecular weight compounds, research has been actively conducted so far.

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

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

In addition, in recent years, as a material for use in organic EL devices or organic thin-film solar cells, a material obtained by improving a triphenylamine derivative has also been reported (International Publication No. 2012/118164). This material refers to N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), which is already in practical use, and It is a material characterized in that the planarity is improved by connecting aromatic rings constituting phenylamine. In this document, for example, the charge transport characteristics of the NO-linked compound (compound 1 on page 63) are evaluated, but the method for producing materials other than the NO-linked compound is not described, and the elements to be linked If is different, since the electronic state of the whole compound is different, the properties obtained from materials other than the NO-linked compound are not yet known. Examples of such compounds are also found (International Publication No. 2011/107186). For example, a compound having a conjugated structure having a large triplet exciton energy (T1) can emit phosphorescence of a shorter wavelength, and is thus advantageous as a material for a blue light emitting layer. Further, a compound having a novel conjugated structure having a large T1 is also required as an electron transport material or a hole transport material that sandwiches the light emitting layer.

The host material of the organic EL device is generally a molecule in which a plurality of existing aromatic rings such as benzene or carbazole are connected by a single bond or a phosphorus atom or a silicon atom. This is because a large HOMO-LUMO gap (band gap Eg in a thin film) required for a host material is secured by connecting a large number of aromatic rings having a relatively small conjugation system. In addition, a host material of an organic EL device using a phosphorescent material or a thermally active delayed fluorescent material requires a high triplet excitation energy (E _T ), but by connecting a donor or acceptor aromatic ring or substituent to the molecule, By localizing SOMO1 and SOMO2 in the triplet excited state (T1) to reduce the exchange interaction between both orbits, it becomes possible to improve the triplet excitation energy (E _T ). However, an aromatic ring having a small conjugated system does not have sufficient redox stability, and a device using a molecule connecting an existing aromatic ring as a host material does not have a sufficient lifespan. 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 a triplet excitation energy (E _T ), so that the host material It has been considered inappropriate.

International Publication No. 2004/061047 Japanese Unexamined Patent Publication No. 2001-172232 Japanese Laid-Open Patent 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 devices, but in order to increase the selection of materials for organic EL devices, development of materials made of compounds different from those of the prior art is desired. In particular, the organic EL properties obtained from materials other than the NO-linked compound reported in Patent Documents 1 to 4 and a method for producing the same are not yet known.

In addition, in Patent Document 6, a polycyclic aromatic compound containing boron and an organic EL device using the same are reported, but in order to further improve device characteristics, a material for a light-emitting layer capable of improving luminous efficiency and device life, especially a dopant material Is required.

The present inventors, as a result of careful examination in order to solve the above problems, by disposing a layer containing a polycyclic aromatic compound into which a cycloalkyl group is introduced between a pair of electrodes, for example, constituting an organic EL device, It discovered that an excellent organic EL device could be obtained, and the present invention was completed. That is, the present invention provides materials for organic devices, such as a material for organic EL devices containing the following cycloalkyl-substituted polycyclic aromatic compounds or their multimers, and the following cycloalkyl-substituted polycyclic aromatic compounds or their multimers. .

In the present specification, although the chemical structure or substituent is sometimes expressed by carbon number, the number of carbon atoms in the case where a substituent is substituted in the chemical structure or a substituent is further substituted on the substituent is determined by the number of carbon atoms of each chemical structure or substituent. It means, and does not mean the total carbon number of a chemical structure and a substituent, or the total carbon number of a substituent and a substituent. For example, ``substituent B of carbon number Y substituted with substituent A of carbon number X'' means that ``substituent A of carbon number X'' is substituted for ``substituent group B of carbon number Y'', and carbon number Y is substituent A and substituent It is not the number of carbon atoms in the sum of B. In addition, for example, ``the substituent B of the carbon number Y substituted with the substituent A'' means that the ``substituent A (without limitation on the number of carbons) is substituted for the ``substituent B of the carbon number Y'', and the carbon number Y represents the substituent A and It is not the total number of carbon atoms of the substituent B.

Clause 1.

A polycyclic aromatic compound represented by the following general formula (1), or a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1).

(In the above formula (1),

Ring A, Ring B, and Ring C are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted,

Y ¹ is B, P, P=O, P=S, Al, Ga, As, Si-R or Ge-R, and R of Si-R and Ge-R is aryl or alkyl,

X ¹ and X ² are each independently >O, >NR, >C(-R) ₂ , >S or >Se, and R of >NR is an optionally substituted aryl or optionally substituted heteroaryl , Optionally substituted alkyl or optionally substituted cycloalkyl, wherein R of >C(-R) ₂ is hydrogen, optionally substituted aryl or alkyl, and R of >NR and/or said >C( R of -R) ₂ may be bonded to the A ring, B ring and/or C ring by a linking group or a single bond,

At least one hydrogen in the compound or structure represented by formula (1) may be substituted with deuterium, cyano, or halogen, and,

At least one hydrogen in the compound or structure represented by formula (1) is substituted with cycloalkyl.)

Item 2.

Ring A, Ring B, and Ring C are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted Diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (two aryls may be bonded through a single bond or a linking group), substituted Or it may be substituted with unsubstituted alkyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted aryloxy, and these rings are bonded to the condensed bicyclic structure in the center of the above formula consisting of Y ¹ , X ¹ and X ² Has a 5- or 6-membered ring that shares

Y ¹ is B, P, P=O, P=S, Al, Ga, As, Si-R or Ge-R, and R of Si-R and Ge-R is aryl or alkyl,

X ¹ and X ² are each independently >O, >NR, >C(-R) ₂ , >S or >Se, and R of >NR is substituted with aryl or alkyl which may be substituted with alkyl May be heteroaryl, alkyl, or cycloalkyl, wherein R of >C(-R) ₂ is aryl or alkyl which may be substituted with hydrogen or alkyl, and R of >NR and/or the >C(-R) ) R ₂ is -O-, -S-, -C (-R) 2 - or by a single bond and may be bonded ring and the a ring, B ring and / or C, the -C (-R) ₂ R of-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 two or three structures represented by 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 according to item 1 or a multimer thereof.

Clause 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, diaryl boryl (two aryls may be bonded through a single bond or a linking group. ), alkyl, alkoxy or aryloxy, and at least one hydrogen in them may be substituted with aryl, heteroaryl or alkyl, and adjacent groups of R ¹ to R ¹¹ are bonded to each other to form a ring, b ring, or An aryl ring or heteroaryl ring may be formed together with the c ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls May be bonded through a single bond or a linking group), alkyl, alkoxy, or aryloxy may be substituted, and at least one hydrogen in these may be substituted with aryl, heteroaryl or alkyl,

Y ¹ is B, P, P=O, P=S, Al, Ga, As, Si-R or Ge-R, wherein R of Si-R and Ge-R is an aryl or carbon number of 6 to 12 carbon atoms It is 1-6 alkyl,

X ¹ and X ² are each independently >O, >NR, >C(-R) ₂ , >S or >Se, wherein R of >NR is an aryl having 6 to 12 carbon atoms, and having 2 to 15 carbon atoms. Heteroaryl, alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, and R of >C(-R) ₂ is hydrogen, aryl having 6 to 12 carbon atoms or alkyl having 1 to 6 carbon atoms, and the> R of NR and/or R of >C(-R) ₂ is -O-, -S-, -C(-R) ₂ -or bonded to the a ring, b ring and/or c ring by a single bond R of -C(-R) ₂ -is an alkyl having 1 to 6 carbon atoms,

At least one hydrogen in the compound represented by formula (2) may be substituted with deuterium, cyano, or halogen, and,

At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl.)

Item 4.

R ¹ to R ¹¹ are each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (however, aryl is an aryl having 6 to 12 carbon atoms), diaryl boryl (however, aryl is Aryl having 6 to 12 carbon atoms, two aryl may be bonded through a single bond or a linking group) or alkyl having 1 to 24 carbon atoms, and adjacent groups among R ¹ to R ¹¹ are bonded to each other to form a ring a or a ring b Or, together with the c ring, an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms may be formed, and at least one hydrogen in the formed ring is substituted with an aryl having 6 to 10 carbon atoms or an alkyl having 1 to 12 carbon atoms. May be

Y ¹ is B, P, P=O, P=S or Si-R, and R of Si-R is a C6-C10 aryl or C1-C4 alkyl,

X ¹ and X ² are each independently >O, >NR, >C(-R) ₂ or >S, and R in >NR is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or 5 to 10 cycloalkyl, wherein R of >C(-R) ₂ is hydrogen, C 6 to C 10 aryl or C 1 to C 4 alkyl,

At least one hydrogen in the compound represented by formula (2) may be substituted with deuterium, cyano, or halogen, and,

At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl,

The polycyclic aromatic compound according to item 3.

Item 5.

R ¹ to R ¹¹ are each independently hydrogen, a C 6 to C 16 aryl, a C 2 to C 20 heteroaryl, a diarylamino (however, aryl is a C 6 to C 10 aryl) or a C 1 to C 12 alkyl, ,

Y ¹ is B, P, P=O or P=S,

X ¹ and X ² are each independently >O, >NR, or >C(-R) ₂ , and R of >NR is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or 5 to 10 carbon atoms 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 item 3.

Clause 6.

R ¹ to R ¹¹ are each independently hydrogen, aryl having 6 to 16 carbon atoms, diarylamino (however, 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 >NR, or, X ¹ is >NR and X ² is >O, and R of >NR is an aryl having 6 to 10 carbon atoms, an alkyl having 1 to 4 carbon atoms, or 5 to 10 carbon atoms Is a cycloalkyl of, and,

At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl,

The polycyclic aromatic compound according to item 3.

Item 7.

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

Item 8.

R ² is a polycyclic aromatic compound according to any one of items 3 to 6, which is a diarylamino group substituted with a cycloalkyl or a carbazolyl group substituted with a cycloalkyl.

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.

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

Clause 11.

The polycyclic aromatic compound according to item 1 represented by any one of the following structural formulas.

("Me" in each of the above structural formulas represents a methyl group, and "tBu" represents a tert-butyl group.)

Item 12.

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

Item 13.

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

Item 14.

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

Item 15.

A material for an organic device containing the polycyclic aromatic compound according to any one of items 1 to 11 or a multimer thereof.

Clause 16.

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

Clause 17.

A material for an organic device containing the polymer compound or polymer crosslinked product according to item 13.

Clause 18.

A material for organic devices containing the pendant polymer compound or pendant polymer crosslinked product according to item 14.

Clause 19.

The material for an organic device according to any one of items 15 to 18, wherein the material for organic devices is a material for an organic light emitting device, a material for an organic field effect transistor, or a material for an organic thin film solar cell.

Item 20.

The material for an organic device according to item 19, wherein the material for an organic electroluminescent device is a material for a light emitting layer.

Clause 21.

An ink composition comprising the polycyclic aromatic compound according to any one of items 1 to 11 or a multimer thereof, and an organic solvent.

Clause 22.

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

Clause 23.

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

Clause 24.

An ink composition comprising the polymer compound or polymer crosslinked product according to item 13 and an organic solvent.

Item 25.

An ink composition comprising the pendant polymer compound or crosslinked pendant polymer according to item 14 and an organic solvent.

Clause 26.

A pair of electrodes consisting of an anode and a cathode, and a polycyclic aromatic compound according to any one of items 1 to 11 or a multimer thereof, a reactive compound according to item 12, and a polymer according to item 13 disposed between the pair of electrodes and An organic electroluminescent device having a compound or a polymer crosslinked product, or an organic layer containing the pendant polymeric compound or pendant polymer crosslinked product according to item 14.

Clause 27.

A pair of electrodes consisting of an anode and a cathode, and a polycyclic aromatic compound according to any one of items 1 to 11 or a multimer thereof, a reactive compound according to item 12, and a polymer according to item 13 disposed between the pair of electrodes and An organic electroluminescent device having a light emitting layer containing the compound or polymer crosslinked product, or the pendant polymeric compound or pendant polymer crosslinked product according to item 14.

Clause 28.

The organic electroluminescent device according to item 27, wherein the light-emitting layer includes a host and the polycyclic aromatic compound as a dopant, its multimer, a reactive compound, a polymer compound, a polymer crosslinker, a pendant polymer compound, or a pendant polymer crosslinker. .

Clause 29.

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

Item 30.

Having an electron transport layer and/or an electron injection layer disposed between the cathode and the light emitting layer, at least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, a fluoranthene derivative, a BO-based derivative, an anthracene derivative , Benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol-based metal complexes containing at least one selected from the group consisting of The organic electroluminescent device according to any one of items 26 to 29.

Clause 31.

The electron transport layer and/or the electron injection layer is an alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal oxide, The organic electroluminescent device according to item 30, further comprising at least one selected from the group consisting of a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal.

Clause 32.

At least one of the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer is a polymer compound obtained by polymerizing a low-molecular compound capable of forming each layer as a monomer, or further crosslinking the polymer compound. Items 26 to 26, including a polymer crosslinked product, a pendant polymer compound obtained by reacting a low molecular compound capable of forming each layer with a main chain polymer, or a pendant polymer crosslinked product obtained by crosslinking the pendant polymer compound further. The organic electroluminescent device according to any one of 31.

Clause 33.

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

According to a preferred aspect of the present invention, it is possible to provide a novel cycloalkyl-substituted polycyclic aromatic compound that can be used as a material for organic devices, such as, for example, an organic EL device material, and the cycloalkyl-substituted polycyclic aromatic compound is By using it, an excellent organic device such as an organic EL element can be provided.

Specifically, the inventors of the present invention have a polycyclic aromatic compound (basic skeleton moiety) in which an aromatic ring is connected with a hetero element such as boron, phosphorus, oxygen, nitrogen, sulfur, etc., has a large HOMO-LUMO gap (band gap Eg in a thin film) And have a high triplet excitation energy (E _T ). This means that since the 6-membered ring containing the hetero element has low aromaticity, the reduction of the HOMO-LUMO gap due to the expansion of the conjugated system is suppressed, and the triplet excited state due to the electronic perturbation of the hetero element ( It is believed that the localization of SOMO1 and SOMO2 in T1) is the cause. In addition, in the polycyclic aromatic compound (basic skeleton moiety) containing the hetero element according to the present invention, the exchange interaction between both orbitals becomes small due to the localization of SOMO1 and SOMO2 in the triplet excited state (T1). Since the energy difference between the singlet excited state (T1) and the singlet excited state (S1) is small and exhibits thermally active delayed fluorescence, it is also useful as a fluorescent material for an organic EL device. Further, a material having a high triplet excitation energy (E _T ) is useful also as an electron transport layer or a hole transport layer of a phosphorescent organic EL device or an organic EL device using thermally active delayed fluorescence. In addition, since this polycyclic aromatic compound (basic skeleton moiety) can arbitrarily move the energy of HOMO and LUMO by introducing a substituent, the ionization potential and electron affinity can be optimized according to the surrounding materials.

In addition to the characteristics of the basic skeleton moiety, the compound of the present invention can expect a lowering of the melting point and sublimation temperature by introducing a cycloalkyl group. This means that in sublimation purification, which is almost indispensable as a material purification method for organic devices such as organic EL devices, which requires high purity, since the purification can be performed at a relatively low temperature, thermal decomposition of the material and the like are avoided. In addition, this also applies to the vacuum evaporation process, which is a powerful means for manufacturing organic devices such as organic EL devices, and since the process can be performed at a relatively low temperature, thermal decomposition of the material can be avoided, and as a result, high-performance organic Materials for devices can be obtained. In addition, since there are many compounds with high sublimation temperature due to the high molecular weight or high planarity of the polycyclic aromatic compound, the reduction of the sublimation temperature by introducing a cycloalkyl group is more effective. In addition, since the solubility in an organic solvent is improved by introduction of a cycloalkyl group, it can be applied to device fabrication using a coating process. However, the present invention is not particularly limited to these principles.

1 is a schematic cross-sectional view showing an organic EL device according to the present embodiment.

1. Cycloalkyl-substituted polycyclic aromatic compounds and multimers thereof

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

Ring A, ring B, and ring C 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 (aryl and Amino group having heteroaryl), substituted or unsubstituted diarylboryl (two aryls may be bonded through a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy or substituted or unsubstituted Aryloxy of is preferred. Examples of the substituent when these groups have a substituent include aryl, heteroaryl or alkyl. In addition, it is preferable that the aryl ring or heteroaryl ring has a 5-membered ring or a 6-membered ring that shares a bond with the central condensed bicyclic structure of General Formula (1) consisting of Y ¹ , X ¹ and X ² .

Here, the "condensed bicyclic structure" means a structure in which two saturated hydrocarbon rings including Y ¹ , X ¹ and X ² shown in the center of the general formula (1) are condensed. In addition, "a 6-membered ring which shares a condensed bicyclic structure and a bond" means, for example, a ring condensed with the condensed bicyclic structure (benzene ring (6-membered ring)) as represented by the general formula (2). it means. In addition, "(ring A) an aryl ring or heteroaryl ring having this 6-membered ring" means that ring A is formed only with this 6-membered ring, or another ring or the like is condensed to this 6-membered ring including this 6-membered ring It means that a ring is formed. In other words, "the aryl ring or heteroaryl ring (which is a ring A) having a 6-membered ring" here means that the 6-membered ring constituting all or part of the A ring is condensed into the condensed bicyclic structure. The same description applies to "B ring (b ring)", "C ring (c ring)", and "5-membered ring".

The A ring (or B ring, C ring) in the general formula (1) is a ring a and its substituents R ¹ to R ³ (or ring b and its substituents R ⁴ to R ⁷ , c ring and its It corresponds to substituents R ⁸ to R ¹¹ ). That is, the general formula (2) corresponds to the structure in which "the A to C ring having a six-membered ring" is 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 lowercase letters a to c.

In the general formula (2), adjacent groups among the substituents R ¹ to R ¹¹ of the a ring, b ring and c ring may be bonded to each other to form an aryl ring or heteroaryl ring together with the a ring, b ring or c ring, At least one hydrogen in the ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be bonded through a single bond or a linking group), alkyl, alkoxy Alternatively, they may be substituted with aryloxy, and at least one hydrogen in these may be substituted with aryl, heteroaryl or alkyl. Therefore, the polycyclic aromatic compound represented by the general formula (2) is represented by the following formulas (2-1) and (2-2) by the mutual bonding form of the substituents in the a ring, b ring and c ring. As described above, the ring structure constituting the compound is changed. The A'ring, B'ring, and C'ring in each formula correspond to the A ring, B ring, and C ring respectively in General formula (1).

The A'ring, B'ring, and C'ring in the above formulas (2-1) and (2-2) are, when explained by general formula (2), adjacent groups of substituents R ¹ to R ¹¹ are bonded to each other, Represents an aryl ring or heteroaryl ring formed together with ring a, ring b, and ring c, respectively (it may also be referred to as a condensed ring formed by condensation of another ring structure with ring a, b or c). And, although not shown in the formula, there are also compounds in which all of the a ring, b ring, and c ring are changed to the A'ring, B'ring, and C'ring. In addition, as can be seen from the formulas (2-1) and (2-2), for example, R ⁸ of ring b and R ^{7 of} ring c, R ¹¹ of ring b and R ¹ of ring a, R of ring c R ³ etc. of the ⁴ and a ring do not correspond to "adjacent groups", and they do not combine. That is, "adjacent group" means a group adjacent on the same ring.

The compound represented by the above formula (2-1) or formula (2-2) is, for example, a benzene ring, an indole ring, a pyrrole ring, or a benzofuran with respect to a benzene ring which is a ring (or b ring or c ring). A compound having an A'ring (or a B'ring or a C'ring) formed by condensation of a ring or a benzothiophene ring, and the formed condensed ring A'(or a condensed ring B'or a condensed ring C') is each naphthalene Ring, carbazole ring, indole ring, dibenzofuran ring or dibenzothiophene ring.

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

X ¹ and X ² in the general formula (1) are each independently >O, >NR, >C(-R) ₂ , >S or >Se, and R of >NR is an optionally substituted aryl , Optionally substituted heteroaryl, optionally substituted alkyl, or optionally substituted cycloalkyl, wherein R of >C(-R) ₂ is hydrogen, optionally substituted aryl or alkyl, and R of >NR and / Or R of >C(-R) ₂ may be bonded to the B ring and/or C ring by a linking group or a single bond, and as a linking group, -O-, -S- or -C(-R) ₂ -Is preferred. In addition, R of "-C(-R) ₂ -" is hydrogen or alkyl. This explanation is also the same for X ¹ and X ² in General Formula (2).

Here, in the general formula (1), "R of >NR and/or R of >C(-R) ₂ is bonded to the ring A, ring B and/or ring C by a linking group or a single bond." In general formula (2), ``R of >NR and/or R of >C(-R) ₂ is -O-, -S-, -C(-R) ₂ -or by a single bond. It corresponds to the rule of "bonded with ring a, ring b and/or ring c".

This regulation can be expressed by a compound having a ring structure in which X ¹ or X ² is accepted in the condensed ring B'and the condensed ring C', represented by the following formula (2-3-1). That is, for example, the B'ring (or C'ring formed by condensation of other rings by accepting X ¹ (or X ² ) with respect to the benzene ring that is the b ring (or c ring) in the general formula (2)) ). 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 regulation is also a compound having a ring structure in which X ¹ and/or X ² is accepted in the condensed ring A′, represented by the following formula (2-3-2) or formula (2-3-3). I can express it. That is, for example, it is a compound having an A'ring formed by condensing other rings to accept X ¹ (and/or X ² ) with respect to 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.

As the "aryl ring" which is the A ring, the B ring and the C ring of the general formula (1), for example, there is an aryl ring having 6 to 30 carbon atoms, an aryl ring having 6 to 16 carbon atoms is preferable, and an aryl ring having 6 to 12 carbon atoms is More preferably, an aryl ring having 6 to 10 carbon atoms is particularly preferable. In addition, this "aryl ring" corresponds to "an aryl ring formed together with a ring a, a ring b, or a ring c by bonding adjacent groups among R ¹ to R ¹¹ in general formula (2)", and Since (or ring b, ring c) is already composed of a benzene ring having 6 carbon atoms, the total number of carbon atoms of the condensed ring condensed with the 5-membered ring is 9 as the lower limit.

Specific examples of the "aryl ring" include a monocyclic benzene ring, a bicyclic biphenyl ring, a condensed bicyclic naphthalene ring, a tricyclic terphenyl ring (m-terphenyl, o-terphenyl, p-terphenyl), and condensation. Examples include a tricyclic phosphorus, an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, a condensed tetracyclic triphenylene ring, a pyrene ring, a naphthacene ring, and a condensed pentacyclic perylene ring, a pentacene ring, and the like.

As the "heteroaryl ring" which is the A ring, the B ring, and the C ring of the general formula (1), for example, there is a C2-C30 heteroaryl ring, a C2-C25 heteroaryl ring is preferable, and a C2-C20 A heteroaryl ring of is more preferable, a C2-C15 heteroaryl ring is still more preferable, and a C2-C10 heteroaryl ring is particularly preferable. In addition, examples of the "heteroaryl ring" include, for example, a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom. In addition, this "heteroaryl ring" corresponds to "a heteroaryl ring formed with a ring a, a ring b, or a ring c by bonding adjacent groups among R ¹ to R ¹¹ in general formula (2)", and Since the a ring (or b ring, c ring) is already composed of a benzene ring having 6 carbon atoms, the total number of carbon atoms of the condensed ring condensed with the 5-membered ring is 6 carbon atoms at the lower limit.

As a specific "heteroaryl ring", for example, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, Pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring , Isoquinoline ring, cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxatiin ring, phenoxazine ring, pheno Thiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazane ring, oxadiazole ring, tian Trenfan and others.

At least one hydrogen in the "aryl ring" or "heteroaryl ring" is a first substituent, a substituted or unsubstituted "aryl", a substituted or unsubstituted "heteroaryl", a substituted or unsubstituted "dia Rylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "diarylboryl (two aryls are bonded through a single bond or a linking group, May be)", substituted or unsubstituted "alkyl", substituted or unsubstituted "alkoxy", or substituted or unsubstituted "aryloxy", but may be substituted with "aryl" or "hetero" as the first substituent. Aryl", aryl of "diarylamino", heteroaryl of "diheteroarylamino", aryl and heteroaryl of "arylheteroarylamino", aryl of "diarylboryl", and aryl of "aryloxy" are described above. A monovalent group of one "aryl ring" or "heteroaryl ring" is exemplified.

Moreover, as "alkyl" as a 1st substituent, either linear or branched chain may be sufficient, and for example, C1-C24 linear-chain alkyl or C3-C24 branched-chain alkyl is mentioned. Alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms) is preferred, alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms) is more preferred, and alkyl having 1 to 6 carbon atoms (3 carbon atoms Branched chain alkyl of -6) is more preferable, and alkyl having 1 to 4 carbon atoms (branched-chain alkyl having 3 to 4 carbon atoms) is particularly preferable.

Specific examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1- Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n -Dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, and the like are exemplified.

Moreover, as "alkoxy" as a 1st substituent, a C1-C24 linear or C3-C24 branched alkoxy is mentioned, for example. C1-C18 alkoxy (C3-C18 branched chain alkoxy) is preferred, C1-C12 alkoxy (C3-C12 branched chain alkoxy) is more preferred, and C1-C6 alkoxy ( Branched chain alkoxy having 3 to 6 carbon atoms) is more preferable, and alkoxy having 1 to 4 carbon atoms (branched alkoxy having 3 to 4 carbon atoms) is particularly preferable.

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

In addition, as the "aryl" in the "diaryl boryl" of the first substituent, the description of aryl described above can be cited. In addition, these two aryls may be bonded through a single bond or a linking group (eg >C(-R) ₂ , >O, >S, or >NR). Here, R of >C(-R) ₂ and >NR is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy (above, the first substituent), and the first substituent is also aryl , Heteroaryl, alkyl or cycloalkyl (above, the second substituent) may be substituted, and specific examples of these groups include aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryl as the first substituent described above. You can cite Oxy's explanation.

The first substituent, a substituted or unsubstituted "aryl", a substituted or unsubstituted "heteroaryl", a substituted or unsubstituted "diarylamino", a substituted or unsubstituted "diheteroarylamino", a substituted or unsubstituted Substituted “arylheteroarylamino”, substituted or unsubstituted “diarylboryl (two aryls may be bonded through a single bond or a linking group)”, substituted or unsubstituted “alkyl”, substituted or unsubstituted "Alkoxy" or substituted or unsubstituted "aryloxy" may be substituted with at least one hydrogen in these with a second substituent, as described as substituted or unsubstituted. Examples of the second substituent include aryl, heteroaryl, or alkyl, and specific examples thereof are the monovalent group of the aforementioned "aryl ring" or "heteroaryl ring", and "alkyl" as the first substituent. You can refer to the description of. In addition, in the aryl or heteroaryl as the second substituent, at least one hydrogen in these is a structural diagram in which at least one hydrogen is substituted with an aryl such as phenyl (a specific example is a group described above) or an alkyl such as methyl (a specific example is a group described above). It is contained in aryl or heteroaryl as the second substituent. As an example, when the second substituent is a carbazolyl group, a carbazolyl group in which at least one hydrogen at the 9th position is substituted with an aryl such as phenyl or an alkyl such as methyl is included in the heteroaryl as the second substituent. .

Aryl in R ¹ ~R ¹¹ of Formula (2), a heteroaryl group, a diaryl amino aryl, di-heteroaryl-amino of the heteroaryl, aryl-amino-heteroaryl group of the aryl and heteroaryl, diaryl boryl aryl, or Examples of the aryl of aryloxy include a monovalent group of the "aryl ring" or "heteroaryl ring" described in the general formula (1). In addition, as the alkyl or alkoxy for R ¹ to R ¹¹ , the description of "alkyl" or "alkoxy" as the first substituent in the description of the aforementioned general formula (1) can be referred to. In addition, aryl, heteroaryl or alkyl as a substituent for these groups is also the same. In addition, when adjacent groups of R ¹ to R ¹¹ are bonded to each other to form an aryl ring or heteroaryl ring together with a ring, b ring, or c ring, heteroaryl, diarylamino, dihetero, which are substituents to these rings. The same applies to arylamino, arylheteroarylamino, diarylboryl (two aryls may be bonded through a single bond or a linking group), alkyl, alkoxy or aryloxy, and another substituent aryl, heteroaryl or alkyl. .

Specifically, the luminous wavelength can be adjusted by the steric hindrance of the structure of the first substituent, electron donating property and electron withdrawing property, preferably a group represented by the following structural formula, more preferably methyl, tert-butyl , Phenyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, di-p-tolyl Amino, bis(p-(tert-butyl)phenyl)amino, carbazolyl, 3,6-dimethylcarbazolyl, 3,6-di-tert-butylcarbazolyl and phenoxy, more preferably, Methyl, tert-butyl, phenyl, o-tolyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis(p-(tert-butyl)phenyl) Amino, carbazolyl, 3,6-dimethylcarbazolyl and 3,6-di-tert-butylcarbazolyl. From the viewpoint of ease of synthesis, those having a large steric hindrance are preferable for selective synthesis, and specifically, tert-butyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5-xylyl, 2 ,6-xylyl, 2,4,6-mesityl, di-p-tolylamino, bis(p-(tert-butyl)phenyl)amino, 3,6-dimethylcarbazolyl and 3,6-di- Tert-butylcarbazolyl is preferred.

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

R of Si-R and Ge-R in Y ¹ in the general formula (1) is aryl or alkyl, but examples of the aryl or alkyl include the groups described above. In particular, aryl having 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.) and alkyl having 1 to 4 carbon atoms (eg, methyl, ethyl, etc.) are preferable. This explanation is also the same for Y ¹ in General Formula (2).

R of >NR in X ¹ and X ² in the general formula (1) is an aryl, heteroaryl, alkyl or cycloalkyl which may be substituted with the second substituent described above, and in the aryl, heteroaryl, alkyl or cycloalkyl At least one hydrogen of may be substituted with, for example, alkyl. Examples of such aryl, heteroaryl and alkyl include the groups described above. In addition, description mentioned later can be cited as cycloalkyl. In particular, C6-C10 aryl (e.g., phenyl, naphthyl, etc.), C2-C15 heteroaryl (e.g., carbazolyl, etc.), C1-C4 alkyl (e.g., methyl, Ethyl, etc.) are preferred. This explanation is also the same for X ¹ and X ² in General Formula (2).

An aryl or alkyl which is represented by the general formula ⁽¹⁾ X 1 and X ² in> R a C (-R) ₂ is optionally substituted with hydrogen, the aforementioned second substituent, at least one hydrogen on the aryl, For example, it may be substituted with alkyl. Examples of such aryl and alkyl include the groups described above. In particular, aryl having 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.) and alkyl having 1 to 4 carbon atoms (eg, methyl, ethyl, etc.) are preferable. This explanation is also the same for X ¹ and X ² in General Formula (2).

R of "-C(-R) ₂ -" which is a linking group in the general formula (1) is hydrogen or alkyl, but examples of the alkyl include the groups described above. In particular, alkyl having 1 to 4 carbon atoms (for example, methyl, ethyl, etc.) is preferable. This explanation is also the same in "-C(-R) ₂ -" which is a linking group in General Formula (2).

In addition, the present invention is a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (1), preferably, a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (2). . The multimer is preferably a dimer to a hexamer, more preferably a dimer to a trimer, and particularly preferably a dimer. The multimer may be a form having a plurality of the unit structures in one compound, for example, a form in which the unit structure is multiple bonded with a linking group such as a single bond, an alkylene group having 1 to 3 carbon atoms, a phenylene group, or a naphthylene group. In addition, arbitrary rings (A ring, B ring, or C ring, a ring, b ring, or c ring) included in the unit structure may be combined to share a plurality of unit structures, and the unit structure Arbitrary rings (A ring, B ring, or C ring, a ring, b ring, or c ring) contained in may be condensed and bonded to each other.

As such a multimer, for example, the following formula (2-4), formula (2-4-1), formula (2-4-2), formula (2-5-1) to formula (2-5) There is a multimeric compound represented by -4) or formula (2-6). The multimeric compound represented by the following formula (2-4), when explained by the general formula (2), makes the a ring, the benzene ring, share, so that the unit structures represented by the plurality of general formulas (2) are incorporated in one compound. Branches are multimeric compounds. In addition, the multimer compound represented by the following formula (2-4-1), when explained by the general formula (2), makes the a ring, the benzene ring, share, and the unit structure represented by the two general formulas (2) is It is a multimeric compound having in one compound In addition, the multimer compound represented by the following formula (2-4-2), when explained by the general formula (2), makes the a ring, the benzene ring, share, and the unit structure represented by the three general formulas (2) is It is a multimeric compound having in one compound In addition, the multimeric compound represented by the following formula (2-5-1) to formula (2-5-4) is explained by the general formula (2) so that the benzene ring which is the b ring (or c ring) is shared. Thus, it is a multimer compound having a unit structure represented by a plurality of general formulas (2) in one compound. In addition, the multimer compound represented by the following formula (2-6) is described by the general formula (2), for example, a benzene ring which is a b ring (or a ring, c ring) of a certain unit structure and a certain unit structure. It is a multimer compound having a unit structure represented by a plurality of general formulas (2) in one compound by condensing the benzene ring as the b ring (or a ring, c ring).

The multimeric compound is a multimerization form represented by formula (2-4), formula (2-4-1) or formula (2-4-2), and formulas (2-5-1) to (2- Any one of 5-4) or a multimer in which a multimerization form represented by formula (2-6) is combined may be used, and by any one of formulas (2-5-1) to (2-5-4) A multimer in which the multimerization form expressed and the multimerization form expressed by Equation (2-6) may be combined, and Equation (2-4), Equation (2-4-1), or Equation (2-4-2) A combination of the multimerization form represented by ), the multimerization form represented by any one of formulas (2-5-1) to (2-5-4) and the multimerization form represented by formula (2-6) It may be a multimer.

In addition, all or part of hydrogen in the chemical structure of the polycyclic aromatic compound represented by General Formula (1) or General Formula (2) and its multimer may be deuterium, cyano, or halogen. For example, in formula (1), A ring, B ring, C ring (rings A to C are aryl rings or heteroaryl rings), substituents to rings A to C, and Y ¹ is Si-R or Ge-R When R (=alkyl, aryl, and X ¹ and X ² are >NR or >C(-R) ₂ When hydrogen in R (=alkyl, aryl) is substituted with deuterium, cyano or halogen, However, among these, there is an embodiment in which all or part of hydrogen in aryl or heteroaryl is substituted with deuterium, cyano, or halogen. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. , More preferably fluorine or chlorine.

Further, the polycyclic aromatic compound and its multimer according to the present invention can be used as a material for an organic device. Examples of the organic device include an organic light emitting device, an organic field effect transistor, or an organic thin film solar cell. In particular, in an organic electroluminescent device, as a dopant material of a light emitting layer, a compound in which Y ¹ is B, X ¹ and X ² are >NR, a compound in which Y ¹ is B, X ¹ is >O, and X ² is >NR, A compound in which Y ¹ is B, X ¹ and X ² are >O, and as the host material of the light emitting layer, a compound in which Y ¹ is B, X ¹ is >O, and X ² is >NR, and Y ¹ is B, X ^A compound in which ¹ and X ² are >O is preferred, and as the electron transport material, a compound in which Y ¹ is B, X ¹ and X ² is >O, Y ¹ is P=O, and X ¹ and X ² are >O Compounds 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 its multimer is cycloalkyl substituted, and all hydrogens or some hydrogens may be cycloalkyl groups.

As another form of cycloalkyl substitution, a polycyclic aromatic compound represented by general formula (1) or (2) and its multimers are, for example, a cycloalkyl substituted diarylamino group, a cycloalkyl substituted carbazolyl group. Or an example substituted with a cycloalkyl substituted benzocarbazolyl group is mentioned. As for the "diarylamino group", the group described in the above "first substituent" can be exemplified. Examples of the substitution form of cycloalkyl with a diarylamino group, a carbazolyl group and a benzocarbazolyl group include examples in which some or all hydrogens of the aryl ring or benzene ring in these groups are substituted with cycloalkyl.

Further, as a more specific example, examples in which 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.

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

Further, specific examples of the cycloalkyl-substituted polycyclic aromatic compound and its multimer of the present invention include compounds in which at least one hydrogen in one or more aromatic rings among the compounds is substituted with one or more cycloalkyl groups. And, for example, there are compounds substituted with 1 to 2 cycloalkyl groups.

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

As cycloalkyl, a C3-C24 cycloalkyl, a C3-C20 cycloalkyl, a C3-C16 cycloalkyl, a C3-C14 cycloalkyl, a C5-C10 cycloalkyl, a C5-C8 cyclo Alkyl, a C5-C6 cycloalkyl, a C5 cycloalkyl, etc. are mentioned.

As cycloalkyl, specifically, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (especially methyl) substituents of 1 to 4 carbon atoms, norbor Neyl, bicyclo[1.0.1]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[ 2.1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl, and the like are exemplified.

As a more specific example of the cycloalkyl-substituted polycyclic aromatic compound of the present invention, a compound represented by the following structural formula may be mentioned. In the following structural formula, "D" represents deuterium, "Me" represents a methyl group, "tBu" represents a tert-butyl group, and "Ph" represents a phenyl group.

The polycyclic aromatic compound represented by the general formula (1) and its multimer according to the present invention are polymerized by using a reactive compound substituted with a reactive substituent thereon as a monomer (the monomer for obtaining this polymer compound is polymerized). Having a sex substituent), or a polymer crosslinked product in which the polymer compound is further crosslinked (the polymer compound for obtaining this polymer crosslinked product has a crosslinkable substituent), or a pendant type in which the main chain polymer and the reactive compound are reacted A polymer compound (the reactive compound for obtaining this pendant polymer compound has a reactive substituent) or a pendant polymer crosslinked product obtained by further crosslinking the pendant polymer compound (the pendant polymer for obtaining this pendant polymer crosslinker) Even if the compound has a crosslinkable substituent), it can be used for a material for organic devices, such as a material for an organic electroluminescent device, a material for an organic field effect transistor, or a material for an organic thin film solar cell.

As the above-described reactive substituent (including the polymerizable substituent, the crosslinkable substituent, and a reactive substituent for obtaining a pendant polymer, hereinafter also referred to only as a ``reactive substituent''), the polycyclic aromatic compound or a multimer thereof A substituent capable of molecular weight, a substituent capable of further crosslinking the polymer compound thus obtained, and a substituent capable of pendant reaction to the main chain polymer are not particularly limited, but a substituent having the following structure is preferable. * In each structural formula represents a bonding position.

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

Details of the use of such a polymer compound, a polymer crosslinked product, a pendant polymeric compound, and a pendant polymeric crosslinked product (hereinafter, also referred to only as "polymer compound and polymeric crosslinked product") will be described later.

2. Cycloalkyl-substituted polycyclic aromatic compound and method for producing a multimer thereof

Polycyclic aromatic compounds represented by general formula (1) or general formula (2) and their multimers are basically, first, ring A (ring a), ring B (ring b), and ring C (ring C) as a bonding group. (A group containing X ¹ or X ² ) to prepare an intermediate (first reaction), and then, ring A (ring a), ring B (ring b), and ring C (ring C) are combined with a linking group ( A final product can be prepared by bonding with a group containing Y ¹ ) (second reaction). In the first reaction, for example, if it is an etherification reaction, a general reaction such as a nucleophilic substitution reaction or a Ulman reaction can be used, and if it is an amination reaction, a general reaction such as a Buchwald-Hartwig reaction is used. I can. In addition, in the second reaction, a tandem hetero Plidelkraft reaction (continuous aromatic electrophilic substitution reaction, the same hereinafter) can be used. In addition, somewhere in this reaction step, a cycloalkyl-substituted raw material is used or a step of introducing a cycloalkyl group is added, whereby a cycloalkyl-substituted compound of the present invention can be produced.

The second reaction is a reaction of introducing Y ¹ that combines the A ring (a ring), B ring (b ring) and C ring (c ring) as shown in the following schemes (1) and (2). , As an example, the case where Y ¹ is a boron atom and X ¹ and X ² are oxygen atoms is shown below. First, a hydrogen atom between X ¹ and X ² is orthometalized with n-butyllithium, sec-butyllithium or tert-butyllithium. Next, boron trichloride, boron tribromide, or the like is added to perform metal exchange of lithium-boron, and then a Bronsted base such as N,N-diisopropylethylamine is added to perform a tandem Bora Friedel Kraft reaction, Objects can be obtained. In the second reaction, in order to accelerate the reaction, a Lewis acid such as aluminum trichloride may be added. In addition, in the following schemes (1) and (2), and in subsequent schemes (3) to (28), the definitions of symbols in each structural formula are the same as those described above.

In addition, the above schemes (1) and (2) mainly represent a method for producing a polycyclic aromatic compound represented by general formula (1) or general formula (2), but for its multimer, a plurality of A rings ( It can be produced by using an intermediate having ring a), ring B (ring b), and ring C (ring c). In detail, it demonstrates in the following scheme (3)-scheme (5). In this case, a target product can be obtained by making the amount of a reagent such as butyllithium to be used twice or three times.

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

In addition, with respect to the method for producing a multimer described in scheme (3), 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 scheme (6) and (7), Lithium can also be introduced into a desired position by metal exchange (Scheme (8), Scheme (9) and Scheme (10) below).

According to this method, even in a case in which orthometalization cannot be performed due to the influence of a substituent, a target object can be synthesized and is useful.

By appropriately selecting the above-described synthesis method and appropriately selecting the raw materials to be used, a desired position is fluorinated and a polycyclic aromatic compound in which Y ¹ is a boron atom, X ¹ and X ² are oxygen atoms, and Its multimers 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). Similar to the case where X ¹ and X ² are oxygen atoms, first, a hydrogen atom between X ¹ and X ² is orthometalized with n-butyllithium or the like. Next, boron tribromide or the like is added to perform a metal exchange of lithium-boron, and then a Bronsted base such as N,N-diisopropylethylamine is added to perform a tandem Bora Friedel kraft reaction to obtain the target product. have. Here, in order to accelerate the reaction, a Lewis acid such as aluminum trichloride may be added. In addition, somewhere in this reaction step, a cycloalkyl-substituted raw material is used or a step of introducing a cycloalkyl group is added, whereby a cycloalkyl-substituted compound of the present invention can be produced.

In addition, for a multimer in the case where Y ¹ is a boron atom and X ¹ and X ² are nitrogen atoms, as in the scheme (6) and (7), a bromine atom or a chlorine atom is used at the position where lithium is to be introduced. Halogen can be introduced and lithium can be introduced at a desired position by halogen-metal exchange (the following scheme (13), scheme (14), and scheme (15)).

Next, as an example, the case where Y ¹ is an insulfide, phosphorus oxide, or phosphorus atom, and X ¹ and X ² are oxygen atoms is shown in the following schemes (16) to (19). As so far, first, a hydrogen atom between X ¹ and X ² is orthometalized with n-butyllithium or the like. Next, phosphorus trichloride and sulfur are added in this order, and finally, a Lewis acid such as aluminum trichloride and a Bronsted base such as N,N-diisopropylethylamine are added to react with tandemphosphafridelkraft. And Y ¹ is an insulfide compound can be obtained. Further, by treating the obtained insulfide compound with m-chloroperbenzoic acid (m-CPBA), a compound in which Y ¹ is phosphorus oxide can be obtained, and by treatment with triethylphosphine, a compound in which Y ¹ is a phosphorus atom can be obtained. In addition, somewhere in this reaction step, a cycloalkyl-substituted raw material is used or a step of introducing a cycloalkyl group is added, whereby a cycloalkyl-substituted compound of the present invention can be produced.

In addition, for a multimer in the case where Y ¹ is an insulfide and X ¹ and X ² are oxygen atoms, as in the scheme (6) and (7), a bromine atom or a chlorine atom is used at the position where lithium is to be introduced. Halogen can be introduced, and lithium can also be introduced at a desired position by halogen-metal exchange (the following scheme (20), scheme (21), and scheme (22)). In addition, the multimer in the case where Y ^{1 thus formed} is an insulfide, and X ¹ and X ² are oxygen atoms is also used as m-chloroperbenzoic acid (m-CPBA) in the same manner as in the above scheme (18) and (19). By treatment, a compound in which Y ¹ is a phosphorus oxide can be obtained, and by treatment with triethylphosphine, a compound in which Y ¹ is a phosphorus atom can be obtained.

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

Specific examples of the solvent used in the above reaction are tert-butylbenzene, xylene, and the like.

Further, in the general formula (2), adjacent groups among the substituents R ¹ to R ¹¹ of ring a, ring b and ring c may be bonded to each other to form an aryl ring or heteroaryl ring together with ring a, ring b, or ring c. , 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) is represented by the formula (2-1) of the following schemes (23) and (24) according to the mutual bonding form of the substituents in the a ring, b ring and c ring. ) And formula (2-2), the ring structure constituting the compound is changed. These compounds can be synthesized by applying the synthesis methods shown in Schemes (1) to (19) to intermediates shown in Schemes (23) and (24) below. In addition, somewhere in this reaction step, a cycloalkyl-substituted raw material is used or a step of introducing a cycloalkyl group is added, whereby a cycloalkyl-substituted compound of the present invention can be produced.

The A'ring, B'ring, and C'ring in the above formulas (2-1) and (2-2) are bonded to adjacent groups among substituents R ¹ to R ¹¹ , respectively, and each of the a ring, b ring and c ring and It represents an aryl ring or heteroaryl ring formed together (it may also be referred to as a condensed ring formed by condensation of another ring structure with a ring a, a ring b, or a ring c). And, although not shown in the formula, there are also compounds in which all of the a ring, b ring and c ring are changed into A'ring, B'ring, and C'ring.

In addition, in the general formula (2), "R of >NR and/or R of >C(-R) ₂ are -O-, -S-, -C(-R) ₂ -or by a single bond. The regulation of "bonded with ring a, ring b, and/or ring c" is represented by formula (2-3-1) of the following scheme (25), wherein X ¹ or X ² is a condensed ring B'and a condensed ring C A compound having a ring structure accepted by', or a compound having a ring structure in which X ¹ or X ² is accepted by condensed ring A'represented by formula (2-3-2) or formula (2-3-3) It can be expressed as These compounds can be synthesized by applying the synthesis method shown in the above schemes (1) to (19) to the intermediates shown in the following scheme (25). In addition, somewhere in this reaction step, a cycloalkyl-substituted raw material is used or a step of introducing a cycloalkyl group is added, whereby a cycloalkyl-substituted compound of the present invention can be produced.

In addition, in the synthesis method of the above schemes (1) to (17) and schemes (20) to (25), before adding boron trichloride or boron tribromide, the hydrogen atom between X ¹ and X ² (or halogen Atom) was orthometalized with butyllithium or the like to give an example in which a tandem hetero Plidelkraft reaction was carried out, but the reaction was not carried out by addition of boron trichloride or boron tribromide without performing orthometalization using butyllithium or the like. You can also proceed.

In addition, when Y ¹ is phosphorus, as shown in the following scheme (26) or scheme (27), the hydrogen atom between X ¹ and X ² (O in the following formula) is represented by n-butyllithium and sec-butyllithium. Or orthometallization with tert-butyllithium or the like, followed by addition of bisdiethylaminochlorophosphine to perform metal exchange of lithium-phosphorus, followed by addition of a Lewis acid such as aluminum trichloride to react with tandem phosphafridelkraft Let it be, and the target object can be obtained. This reaction method is also described in International Publication No. 2010/104047 (eg, page 27). In addition, somewhere in this reaction step, a cycloalkyl-substituted raw material is used or a step of introducing a cycloalkyl group is added, whereby a cycloalkyl-substituted compound of the present invention can be produced.

Also in the above schemes 26 and 27, a multimer compound can be synthesized by using an orthometallization reagent such as butyllithium in a molar amount of 2 or 3 times the molar amount of Intermediate 1. Further, a halogen such as a bromine atom or a chlorine atom is introduced in advance at a position where a metal such as lithium is to be introduced, and the metal can be introduced at a desired position by halogen-metal exchange.

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 polycyclic aromatic compound in which the desired position is substituted with a cycloalkyl group. Can be synthesized. In the scheme (28), X represents halogen or hydrogen, and the definition of other signs is the same as that of the signs in General Formula (2).

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

The compound of the general formula (2-A) having a cycloalkyl-substituted diphenylamino group can also be synthesized by, for example, the following method. In other words, after introducing a cycloalkyl-substituted diphenylamino group by an amination reaction such as Buchwald-Hartwig reaction between cycloalkyl-substituted bromobenzene and trihalogenated aniline, when X ¹ and X ² are NR, Buchwald-Hartwig reaction In the amination reaction as described above, when X ¹ and X ² are O, it is induced to the intermediate (M-3) by etherification with phenol, and then, a metallization reagent such as butyllithium is applied. After transmetallization by reaction, a boron halide such as boron tribromide is reacted, and then a Bronsted base such as diethylisopropylamine is reacted by a tandem Bora Friedel Kraft reaction, the general formula (2-A) A compound of can be synthesized. This reaction can also be applied to other cycloalkyl-substituted compounds.

In addition, as the orthometallization reagent used in the above schemes (1) to (28), alkyl lithium such as methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium diisopropylamide, lithium Organic alkali compounds, such as tetramethylpiperidide, lithium hexamethyldisiladide, and potassium hexamethyldisiladide, are mentioned.

Also, the schemes (1) to the scheme as metal-metal exchange of the reagent used in the -Y ¹ 28, 3 fluoride, chloride, 3, 3-bromide, iodide 3 of Y ¹ Y ¹ of the Y ¹ Y ¹ of and the like of Y ¹ of halide, CIPN (NEt _{2) 2,} etc., such as the amination halides, aryloxy product of the alkoxide, Y ¹ Y ¹ of the Y ¹ as an example.

In addition, as a Bronsted base used in the above schemes (1) to (28), 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 (and Ar is an aryl such as phenyl), and the like.

As Lewis acids 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, NaOTf , KOTf, Me ₃ SiOTf, Cu(OTf) ₂ , CuCl ₂ , YCl ₃ , Y(OTf) ₃ , TiCl ₄ , TiBr ₄ , ZrCl ₄ , ZrBr ₄ , FeCl ₃ , FeBr ₃ , CoCl ₃ , CoBr ₃ etc. For example.

In the above schemes (1) to (28), a Bronsted base or Lewis acid may be used in order to promote the tandem hetero Plidelkraft reaction. However, when using the three-fluoride, halide of Y ^1, such as 3-chloride, 3-bromide, 3-iodide of Y ¹ of the Y ¹ of the Y ¹ of Y ¹ includes, along with the progress of the aromatic electrophilic substitution reaction, fluoride Since acids such as hydrogen, hydrogen chloride, hydrogen bromide, and hydrogen iodide are produced, the use of a Bronsted base to capture the acid is effective. On the other hand, in the case of using an alkoxy hwamulreul of aminated halide, Y ¹ of the Y ¹ is, with the progress of the aromatic electrophilic substitution reaction, an amine, since the alcohol is produced, it does not have to use a lot of cases, the Bronsted base, an amino group Since the ability of the alkoxy group to desorb is low, the use of Lewis acid to accelerate the desorption is effective.

In addition, the polycyclic aromatic compound or its multimer of the present invention includes compounds in which at least some of the hydrogen atoms are substituted with deuterium or cyano, or compounds in which halogens such as fluorine or chlorine are substituted, but such a compound is at a desired position. By using a deuterated, cyanoated, fluorinated or chlorinated raw material, it can be synthesized in the same manner as described above.

3. Organic device

The cycloalkyl-substituted polycyclic aromatic compound according to the present invention can be used as a material for organic devices. Examples of the organic device include an organic light emitting device, an organic field effect transistor, or an organic thin film solar cell.

3-1. Organic light emitting device

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

<Structure of organic light emitting device>

The organic EL device 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole injection layer 103. ), the hole transport layer 104 installed on the hole transport layer 104, the light emitting layer 105 provided on the hole transport layer 104, the electron transport layer 106 installed on the light emitting layer 105, and the electron injection layer 107 provided on the electron transport layer 106 , Has a cathode 108 installed on the electron injection layer 107.

In addition, the organic EL element 100 reverses the order of fabrication, for example, the substrate 101, the cathode 108 provided on the substrate 101, and the electron injection layer 107 provided on the cathode 108. ), the electron transport layer 106 provided on the electron injection layer 107, the light-emitting layer 105 provided on the electron transport layer 106, the hole transport layer 104 provided on the light-emitting layer 105, and the hole transport layer 104 A configuration including the provided hole injection layer 103 and the anode 102 provided on the hole injection layer 103 may be employed.

It is not necessary to have all of the above layers, and the minimum structural unit is composed of an anode 102, a light emitting layer 105, and a cathode 108, and a hole injection layer 103, a hole transport layer 104, and an electron transport layer (106), the electron injection layer 107 is a layer provided arbitrarily. In addition, each of the layers described above may be formed of a single layer, or may be formed of a plurality of layers.

As an aspect of the layer constituting the organic EL device, in addition to the configuration aspect of the aforementioned ``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/Emitting layer/Electron transport layer/Anode'', ``Substrate/Anode/Emitting layer/Electron transport layer/Electron injection layer/Anode'', ``Substrate/Anode/Hole transport layer/Emitting layer/ Electron injection layer/cathode", ``substrate/anode/hole transport layer/light-emitting layer/electron transport layer/cathode'', ``substrate/anode/hole injection layer/light-emitting layer/electron injection layer/cathode'', ``substrate/anode/hole injection layer/ The configuration of a light emitting layer/electron transport layer/cathode", "substrate/anode/light emitting layer/electron transport layer/cathode", and "substrate/anode/light emitting layer/electron injection layer/cathode" may be used.

<Substrate in an organic light emitting device>

The substrate 101 is a support for the organic EL element 100, and usually quartz, glass, metal, plastic, or the like is used. The substrate 101 is formed in a plate shape, a film shape, or a sheet shape depending on the purpose, and, for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Among them, a glass plate and a board made of a synthetic resin transparent to polyester, polymethacrylate, polycarbonate, polysulfone, and the like are preferable. In the case of a glass substrate, soda-lime glass, alkali-free glass, or the like is used, and the thickness may be a sufficient thickness to maintain mechanical strength, for example, 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, and preferably 1 mm or less. As for the material of the glass, since it is preferable that there are few eluted ions from the glass, alkali-free glass is preferable. However, since soda-lime glass subjected to a barrier coating such as SiO _{2 is} also commercially available, it can be used. Further, on the substrate 101, in order to increase the gas barrier property, a gas barrier film such as a dense silicon oxide film may be formed on at least one surface. In particular, a board, film, or sheet made of a synthetic resin having low gas barrier property is used as the substrate 101. In the case of using as ), it is preferable to form a gas barrier film.

<Anode in organic light emitting device>

The anode 102 serves to inject holes into the light emitting layer 105. In addition, when the hole injection layer 103 and/or the hole transport layer 104 is provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these.

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 (IZO)) Etc.), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass or Nesa glass. Examples of the organic compound include polythiophene such as poly(3-methylthiophene), and conductive polymers such as polypyrrole and polyaniline. In addition, it can be appropriately selected and used from materials used as anodes of organic EL devices.

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

<Hole injection layer, hole transport layer in organic light emitting device>

The hole injection layer 103 serves to efficiently inject 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 the holes injected from the anode 102 or the holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are, respectively, one or two or more of a hole injection/transport material are laminated or mixed, or a mixture of a hole injection/transport material and a polymer binder Is formed by Further, an inorganic salt such as iron (III) chloride may be added to the hole injection/transport material to form a layer.

As a hole injection/transport material, it is necessary to efficiently inject and transport holes from the anode between electrodes to which an electric field is applied, and it is preferable to have high hole injection efficiency and to efficiently transport the injected holes. For this, it is preferable that the ionization potential is small, the hole mobility is large, furthermore, the stability is excellent, and the impurities used as traps are not easily generated during manufacture 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, a hole injection layer and a hole of an organic EL device Arbitrary compounds can be selected and used from known compounds used in the transport layer. Specific examples of these include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole), triarylamine Derivatives (polymers having aromatic tertiary amino in the main chain or side chain, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N'-diphenyl-N,N'-di(3 -Methylphenyl)-4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, N,N'-diphenyl-N ,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine, N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl 1,1'-diamine, N ^4, N ^{4 '-} diphenyl -N ^4, N ^4' - bis (9-phenyl -9H- carbazole-3-yl) [1,1'-biphenyl] ^{4,4'-diamine, N 4, N 4, N} 4 ', N 4' - tetrahydro [1,1'-biphenyl] -4-yl) - [1,1'-biphenyl] -4, Triphenylamine derivatives such as 4'-diamine, 4,4',4''-tris(3-methylphenyl(phenyl)amino)triphenylamine, starburstamine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free , Copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (e.g., 1,4,5,8,9,12-hexaazatri Phenylene-2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, and polysilanes. In the polymer system, polycarbonate, styrene derivatives, polyvinylcarbazole, and polysilane having the above monomers in the side chain are preferable, but a thin film required for manufacturing a light emitting device can be formed and holes can be injected from the anode. It does not specifically limit as long as it is a transportable compound.

It is also known that the conductivity of an organic semiconductor is strongly influenced by its doping. Such an organic semiconductor matrix material is composed of a compound having good electron-providing properties or a compound having good electron-accepting properties. For the doping of electron-providing materials, strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are used. It is known (e.g., M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(22), 3202-3204 (1998)” and J. Blochwitz , M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(6), 729-731(1998)). They generate so-called holes by an electron transfer process in an electron-providing base material (hole transport material). Depending on the number and mobility of the holes, the conductivity of the base material varies considerably. As a matrix material having hole transport properties, for example, a benzidine derivative (TPD, etc.) or a stavastamine derivative (TDATA, etc.), or a specific metal phthalocyanine (in particular, zinc phthalocyanine (ZnPc), etc.) is known (Japanese Patent Laid-Open Patent). 2005-167175 publication).

The above-described material for a hole injection layer and a material for a hole transport layer are a polymer compound obtained by polymerizing a reactive compound substituted with a reactive substituent as a monomer, or a cross-linked polymer thereof, or a main chain polymer and the reactive compound. Even if it is a pendant polymer compound or a pendant polymer crosslinked product, it can be used for a material for a hole layer. As the reactive substituent in this case, the description of the polycyclic aromatic compound represented by formula (1) can be cited.

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

<Emitting layer in organic light emitting device>

The light-emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound (luminescent compound) that is excited by recombination of holes and electrons to emit light, and a stable thin film shape can be formed, and at the same time, strong light emission (fluorescence) efficiency in a solid state It is preferably a compound shown. In the present invention, as the material for the light emitting layer, a host material and, for example, a polycyclic aromatic compound represented by the general formula (1) as a dopant material can be used.

The light-emitting layer may be a single layer, may consist of a plurality of layers, or may be any, and each is formed of a material for light-emitting layers (host material, dopant material). The host material and the dopant material may each be one type, a combination of a plurality, or any one. The dopant material may be included in the entire host material, partially included, or any of the dopant materials may be used. As the doping method, it can be formed by a co-deposition method with a host material, but it may be simultaneously evaporated after mixing with the host material in advance.

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

The amount of dopant material used varies depending on the type of dopant material, and may be determined according to the characteristics of the dopant material. The basis of the amount of the dopant material used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and still more preferably 0.1 to 10% by weight of the total light emitting layer material. If it is the above-described range, it is preferable, for example, from the viewpoint of preventing concentration quenching.

As host materials, condensed cyclic derivatives such as anthracene, pyrene, dibenzochrysene or fluorene, which have been known as light emitters, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, cyclo Pentadiene derivatives and the like are exemplified. In particular, an anthracene-based compound, a fluorene-based compound or a dibenzochrysene-based compound is preferable.

<Anthracene compound>

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

In equation (3),

X and Ar ⁴ are each independently hydrogen, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted diarylamino, optionally substituted diheteroarylamino, optionally substituted arylheteroarylamino , May be substituted alkyl, may be substituted cycloalkyl, may be substituted alkenyl, may be substituted alkoxy, may be substituted aryloxy, may be substituted arylthio or may be substituted silyl, all X And Ar ⁴ do not simultaneously become hydrogen, and at least one hydrogen in the compound represented by formula (3) may be substituted with halogen, cyano, deuterium or optionally substituted heteroaryl.

Further, a multimer (preferably a dimer) may be formed by using the structure represented by formula (3) as a unit structure. In this case, for example, a form in which unit structures represented by formula (3) are bonded through X can be exemplified, and as this X, a single bond, arylene (phenylene, biphenylene, naphthylene, etc.) And heteroarylene (a group having a divalent bonding value such as a pyridine ring, 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 column of the following preferred embodiments. . In addition, examples of the substituents thereto include aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio or silyl, and the like. And the details of these are also described in the column of the following preferred embodiments.

Preferred embodiments of the anthracene compound will be described below. The definition of the sign in the following structure is the same as the definition described above.

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

Further, a multimer (preferably a dimer) may be formed by using the structure represented by the formula (3) as a unit structure. In this case, for example, a form in which unit structures represented by formula (3) are bonded through X can be exemplified, and as this X, a single bond, arylene (phenylene, biphenylene, naphthylene, etc.) And heteroarylene (a group in which a pyridine ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring, and a phenyl substituted carbazole ring has a divalent bonding value), and the like.

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

Ar ¹ and Ar ² are each independently hydrogen, phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrene Nilyl or a group represented by the formula (A) (including a carbazolyl group, a benzocarbazolyl group, and a phenyl substituted carbazolyl group). And when Ar ¹ or Ar ² is a group represented by the formula (A), the group represented by the formula (A) bonds to the naphthalene ring in the formula (3-X1) or (3-X2) in *.

Ar ³ is phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or the formula (A) It is a group represented by (including a carbazolyl group, a benzocarbazolyl group, and a phenyl substituted carbazolyl group). And when Ar ³ is a group represented by formula (A), the group represented by formula (A) bonds with a single bond represented by a straight line in formula (3-X3) in *. That is, the anthracene ring of formula (3) and the group represented by formula (A) are directly bonded.

In addition, Ar ³ may have a substituent, and at least one hydrogen in Ar ³ is also alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, phenyl, biphenylyl, terphenylyl, naphthyl, phenane. It may be substituted with tril, fluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (including a carbazolyl group and a phenyl substituted carbazolyl group). And, when the substituent which Ar ³ has is a group represented by formula (A), the group represented by formula (A) bonds with Ar ³ in formula (3-X3) in *.

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

Examples of the alkyl substituted with silyl having 1 to 4 carbon atoms include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, tert-butyl, and cyclobutyl, and the three hydrogens in silyl are each Independently, these alkyls are substituted.

Specific examples of "silyl substituted with alkyl having 1 to 4 carbon atoms" include trimethylsilyl, triethylsilyl, tripropylsilyl, trii-propylsilyl, tributylsilyl, trisec-butylsilyl, tritert-butylsilyl, ethyl Dimethylsilyl, propyldimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, tert-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl , sec-butyldiethylsilyl, tert-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, tert-butyldipropylsilyl, methyldii-propylsilyl , Ethyldii-propylsilyl, butyldii-propylsilyl, sec-butyldii-propylsilyl, tert-butyldii-propylsilyl, and the like are exemplified.

Cycloalkyl having 5 to 10 carbon atoms 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, deca Hydroazulenyl and the like are exemplified, 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 dialkylcycloalkylsilyls substituted by two alkyls and 1 cycloalkyl, and alkyldicycloalkylsilyls substituted by 1 alkyl and 2 cycloalkyls. As a specific example, the group mentioned above is mentioned.

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 formula (A). When substituted with a group represented by formula (A), the group represented by formula (A) is substituted with at least one hydrogen in the compound represented by formula (3) in *.

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

In the formula (A), Y is -O-, -S-, or >NR ²⁹ , and R ²¹ to R ²⁸ are each independently hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted Aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, May be substituted amino, halogen, hydroxy or cyano, adjacent groups among R ²¹ to R ²⁸ may be bonded to each other to form a hydrocarbon ring, aryl ring or heteroaryl ring, and R ²⁹ is hydrogen or substituted It is aryl that may be present.

As the "alkyl" of the "optionally substituted alkyl" in R ²¹ to R ²⁸ , either straight chain or branched chain may be used, for example, straight chain alkyl having 1 to 24 carbon atoms or branched chain alkyl having 3 to 24 carbon atoms. There is this. Alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms) is preferred, alkyl having 1 to 12 carbon atoms (branched chain alkyl having 3 to 12 carbon atoms) is more preferred, and alkyl having 1 to 6 carbon atoms (3 carbon atoms Branched chain alkyl of -6) is more preferable, and alkyl having 1 to 4 carbon atoms (branched-chain alkyl having 3 to 4 carbon atoms) is particularly preferable.

Specific examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethyl Hexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl , n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, etc. have.

Examples of the "cycloalkyl" of the "optionally substituted cycloalkyl" in R ²¹ to R ²⁸ include cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, and 3 to 14 carbon atoms. Cycloalkyl of, C5-10 cycloalkyl, C5-C8 cycloalkyl, C5-C6 cycloalkyl, C5 cycloalkyl, etc. are mentioned.

Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (especially 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, decahydroazulenyl, and the like are exemplified.

As the "aryl" of the "optionally substituted aryl" in R ²¹ to R ²⁸ , for example, there is an aryl having 6 to 30 carbon atoms, aryl having 6 to 16 carbon atoms is preferable, and an aryl having 6 to 12 carbon atoms is It is more preferable, and C6-C10 aryl is especially preferable.

Specific examples of "aryl" include monocyclic phenyl, bicyclic biphenylyl, condensed bicyclic naphthyl, tricyclic terphenylyl (m-terphenylyl, o-terphenylyl, p-terphenylyl), Examples include condensed tricyclic, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, condensed tetracyclic triphenylenyl, pyrenyl, naphthacenyl, and condensed pentacyclic perylenyl, pentacenyl, etc. have.

Examples of the "heteroaryl" of the "optionally substituted heteroaryl" for R ²¹ to R ²⁸ include, for example, heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and A 20 heteroaryl is more preferable, a C2-C15 heteroaryl is still more preferable, and a C2-C10 heteroaryl is especially preferable. Further, examples of the heteroaryl include, for example, heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom.

As a specific "heteroaryl", for example, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxathiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyri Dill, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, Isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxatinyl, phenoxazinyl, phenothiazinyl, Phenazinyl, indolizinyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzo[b]thienyl, dibenzothienyl, furazanyl, thianthrenyl, naphthobenzofuran Ranil and naphthobenzothienyl.

As the "alkoxy" of the "optionally substituted alkoxy" in R ²¹ to R ²⁸ , for example, there is a C1-C24 linear or C3-C24 branched alkoxy. C1-C18 alkoxy (C3-C18 branched chain alkoxy) is preferable, C1-C12 alkoxy (C3-C12 branched chain alkoxy) is preferable, and C1-C6 alkoxy (carbon number 3-6 branched chain alkoxy) is more preferable, and C1-C4 alkoxy (C3-C4 branched alkoxy) is especially preferable.

Specific examples of "alkoxy" include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, etc. Can be lifted.

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

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

R ²¹ ~R Examples of "trialkylsilyl" at ^28, and three of the hydrogen in the silyl group include groups each independently substituted by alkyl, for example, the alkyl is the above-mentioned R ²¹ ~R "alkyl" in the ²⁸ The group described as can be cited. Preferred alkyl for substitution is alkyl having 1 to 4 carbon atoms, and specifically, methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, tert-butyl, cyclobutyl, and the like are exemplified.

Specific examples of "trialkylsilyl" include trimethylsilyl, triethylsilyl, tripropylsilyl, trii-propylsilyl, tributylsilyl, trisec-butylsilyl, tritert-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i -Propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, tert-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, tert-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, tert-butyldipropylsilyl, methyldii-propylsilyl, ethyldii-propylsilyl, Butyldii-propylsilyl, sec-butyldii-propylsilyl, tert-butyldii-propylsilyl, and the like are exemplified.

Examples of the "tricycloalkylsilyl" in R ²¹ to R ²⁸ include a group in which three hydrogens in the silyl group are each independently substituted with cycloalkyl, and this cycloalkyl is represented by the aforementioned R ²¹ to R ²⁸ The groups described as "cycloalkyl" can be cited. Preferred cycloalkyl to be substituted is a cycloalkyl having 5 to 10 carbon atoms, and 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, decahydronaphthal Renyl, decahydroazulenyl, and the like are exemplified.

As a specific "tricycloalkylsilyl", tricyclopentylsilyl, tricyclohexylsilyl, etc. are mentioned.

As a specific example of the dialkylcycloalkylsilyl substituted by 2 alkyl and 1 cycloalkyl, and the alkyldicycloalkylsilyl substituted by 1 alkyl and 2 cycloalkyl, a group selected from the specific alkyl and cycloalkyl described above is substituted. One can be lifted.

As the "substituted amino" of "amino which may be substituted" in R ²¹ to R ²⁸ , for example, there is an amino group in which two hydrogens are substituted with aryl or heteroaryl. Amino in which two hydrogens are substituted with aryl is diaryl-substituted amino, amino in which two hydrogens are substituted with heteroaryl is diheteroaryl-substituted amino, and amino in which two hydrogens are substituted with aryl and heteroaryl is arylheteroaryl Is substituted amino. As the aryl or heteroaryl, the groups described above for "aryl" or "heteroaryl" in R ²¹ to R ²⁸ can be cited.

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

Examples of the "halogen" of R ²¹ to R ²⁸ airs include fluorine, chlorine, bromine and iodine.

Some of the groups described as R ²¹ to R ²⁸ may be substituted as described above, and examples of the substituent in this case include alkyl, cycloalkyl, aryl or heteroaryl. As the alkyl, cycloalkyl, aryl or heteroaryl, the groups described as "alkyl", "cycloalkyl", "aryl" or "heteroaryl" for R ²¹ to R ²⁸ can be cited.

R ²⁹ in ">NR ²⁹ " as Y is hydrogen or aryl which may be substituted, and as this aryl, the groups described as "aryl" in R ²¹ to R ²⁸ can be cited, and as the substituent, R ²¹ The groups described as the substituent for -R ²⁸ can be cited.

Adjacent groups among R ²¹ to R ²⁸ may be bonded to each other to form a hydrocarbon ring, an aryl ring, or a heteroaryl ring. When a ring is not formed, it is a group represented by the following formula (A-1), and when a ring is formed, for example, there are groups represented by the following formulas (A-2) to (A-14). . And, at least one hydrogen in the group represented by any one 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.

As a ring formed by bonding of adjacent groups to each other, if it is a hydrocarbon ring, there is, for example, a cyclohexane ring, and as an aryl ring or heteroaryl ring, the above-described R ²¹ to R ²⁸ aryl or as described in ``heteroaryl'' There is a ring structure, and these rings are formed so as to condense with one or two benzene rings in the above formula (A-1).

As a group represented by formula (A), for example, there is a group represented by any one of formulas (A-1) to (A-14), and formulas (A-1) to (A-5) And a group represented by any one of formulas (A-12) to (A-14), more preferably a group represented by any one of formulas (A-1) to (A-4), and the formula ( The group represented by any one of A-1), formula (A-3) and formula (A-4) is more preferred, and the group represented by the above formula (A-1) is particularly preferred.

The group represented by formula (A) is a naphthalene ring in formula (3-X1) or formula (3-X2) in * in formula (A), a single bond in formula (3-X3), and formula (3-X3 ) Is bonded to Ar ³ , and substituted with at least one hydrogen in the compound represented by formula (3) is as described above, but among these bond forms, formula (3-X1) or formula (3-X2) The naphthalene ring in, a single bond in formula (3-X3), and/or a form bonded with Ar ³ in formula (3-X3) are preferable.

In addition, in the structure of the group represented by formula (A), the naphthalene ring in formula (3-X1) or formula (3-X2), single bond in formula (3-X3), and Ar ³ in formula (3-X3) In the structure of the group represented by formula (A), the position at which at least one hydrogen is substituted in the compound represented by formula (3) is any position in the structure of formula (A). It may be, for example, any one of two benzene rings in the structure of formula (A), any one ring formed by bonding of adjacent groups among R ²¹ to R ²⁸ in the structure of formula (A), or formula It can bond at any one of R ²⁹ in "> NR ²⁹ " as Y in the structure of (A).

As a group represented by formula (A), there are the following groups, for example. Y and * in the formula are the same definitions as above.

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

As a specific example of an anthracene-based compound, there is a compound represented by any one of the following formulas (3-1) to (3-72). In the following structural formula, "Me" represents a methyl group, "D" represents deuterium, and "tBu" represents a tert-butyl group.

The anthracene-based compound represented by formula (3) is a compound having a reactive group at a desired position of the anthracene skeleton, and a compound having a reactive group in a partial structure such as the structure of X, Ar ⁴ and formula (A) as starting materials, It can be manufactured by applying Suzuki coupling, Negishi coupling, and other known coupling reactions. As a reactive group of this reactive compound, halogen, boronic acid, etc. are mentioned. As a specific manufacturing method, the synthesis method in paragraphs [0089] to [0175] of International Publication No. 2014/141725 may be referred to, for example.

<Fluorene compound>

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

In the above formula (4),

R ¹ to R ¹⁰ are each independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the fluorene skeleton of formula (4) through a linking group), diarylamino, diheteroarylamino , Arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl,

In addition, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ or R ⁹ and R ¹⁰ are each independently bonded and condensed Ring or spiro ring may be formed, and at least one hydrogen in the formed ring is aryl, heteroaryl (the heteroaryl may be bonded to the formed ring through a linking group), diarylamino, diheteroarylamino, aryl Heteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy may be substituted, and at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, and,

At least one hydrogen in the compound represented by formula (4) may be substituted with halogen, cyano, or deuterium.

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

Examples of the alkenyl in R ¹ to R ¹⁰ include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and 2 Alkenyl of -6 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-phen Tenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl.

And, as a specific example of heteroaryl, any 1 from the compound of the following formula (4-Ar1), formula (4-Ar2), formula (4-Ar3), formula (4-Ar4) or formula (4-Ar5) And a monovalent group represented by removing two hydrogen atoms.

In formulas (4-Ar1) to (4-Ar5), Y ¹ is each independently O, S or NR, R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen,

At least one hydrogen in the structures of formulas (4-Ar1) to (4-Ar5) is substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl. It may be.

These heteroaryl may be bonded to the fluorene skeleton in the formula (4) through a linking group. That is, not only the fluorene skeleton in formula (4) and the heteroaryl are directly bonded, but may be bonded through a linking group therebetween. 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-. I can.

In addition, in 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 each independently bonded to each other to form a condensed ring And R ⁹ and R ¹⁰ may be bonded to each other to form a spiro ring. The condensed ring formed by R ¹ to R ⁸ is a ring condensed with the benzene ring in formula (4), and is an aliphatic ring or an aromatic ring. It is preferably an aromatic ring, and examples of the structure including a benzene ring in formula (4) include a naphthalene ring, a phenanthrene ring, and the like. The spiro ring formed by R ⁹ and R ¹⁰ is a ring spiro bonded to the 5-membered ring in formula (4), and is an aliphatic ring or an aromatic ring. Preferably, it is an aromatic ring, and a fluorene ring etc. are mentioned.

The compound represented by the general formula (4) is preferably a compound represented by the following formula (4-1), formula (4-2), or formula (4-3), respectively, in the general formula (4) A compound in which a benzene ring formed by bonding of R ¹ and R ² is condensed, a compound in which a benzene ring formed by bonding of R ³ and R ⁴ in the general formula (4) is condensed, and in the general formula (4) R ¹ to R ⁸ It is a compound in which all of are not bound.

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

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

The definitions of R ² to R ⁷ in formulas (4-1A), (4-2A) and (4-3A) are formulas (4-1), (4-2) and (4-3) It is the same as the corresponding R ² to R ^{7 in,} and the definitions of R ¹¹ to R ¹⁴ in formulas (4-1A) and (4-2A) are also in formulas (4-1) and (4-2) It is the same as R ¹¹ to R ¹⁴ of.

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

<Dibenzochrysene compound>

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

In the above formula (5),

R ¹ to R ¹⁶ are each independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the dibenzochrysene skeleton in the formula (5) through a linking group), diarylamino, dihetero Arylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl,

In addition, adjacent groups of R ¹ to R ¹⁶ may be bonded to each other to form a condensed ring, and at least one hydrogen in the formed ring may be 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 may be substituted, and at least one hydrogen in these may be aryl, heteroaryl, alkyl or cyclo May be substituted with alkyl, and,

At least one hydrogen in the compound represented by formula (5) may be substituted with halogen, cyano, or deuterium.

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

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

And, as a specific example of heteroaryl, any 1 from the compound of the following formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) The monovalent groups that are represented by the removal of two hydrogen atoms are mentioned.

In formulas (5-Ar1) to (5-Ar5), Y ¹ is each independently O, S or NR, R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen,

At least one hydrogen in the structures of formulas (5-Ar1) to (5-Ar5) is substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl. It may be.

These heteroaryl may be bonded to the dibenzochrysene skeleton in the formula (5) through a linking group. That is, not only the dibenzochrysene skeleton in formula (5) and the heteroaryl are directly bonded, but may be bonded through a linking group therebetween. 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-. I can.

As for the compound represented by 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, anthra Senyl, phenanthrenyl, a monovalent group having a structure of the formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) (above A monovalent group having a structure is phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH ₂ CH ₂ -, -CH ₂ CH ₂ O-, or -OCH ₂ CH ₂ O- It is preferable that it is methyl, ethyl, propyl, or butyl, which may be bonded to the dibenzochrysene skeleton in the above formula (5).

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 of R ³ , R ⁶ , R ¹¹ and R ¹⁴ in formula (5) (preferably 1 or 2, more preferably 1) is a single bond, phenylene, or ratio Through phenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH ₂ CH ₂ -, -CH ₂ CH ₂ O-, or, -OCH ₂ CH ₂ O-, the above formula (5-Ar1), formula It is a monovalent group having a structure of (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5),

Other than the at least one (i.e., other than the position where the monovalent group having the above structure is substituted) is hydrogen, phenyl, biphenylyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl, at least in these One hydrogen may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl.

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

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

<Example of polymer host material>

In formula (SPH-1),

MU is each independently a divalent aromatic compound, EC is each independently a monovalent aromatic compound, two hydrogens in MU are substituted with EC or MU, and k is an integer of 2 to 500,000.

More specifically,

MU is, each independently, arylene, heteroarylene, diaylene arylamino, diaylene aryl boryl, oxaborin-diyl, azaborin-diyl,

EC is each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, or aryloxy,

At least one hydrogen in MU and EC may also be substituted with aryl, heteroaryl, diarylamino, alkyl and cycloalkyl,

k is an integer of 2 to 500,000.

It is preferable that k is an integer of 20-500,000, and it is more preferable that it is an integer of 100-500,000.

At least one hydrogen in MU and EC in formula (SPH-1) may be substituted with alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, halogen or deuterium, and optionally- CH ₂ - is -O- or -Si (CH _{3) 2} - may be substituted with, -CH ₂ that is directly connected to the EC in the formula (SPH-1) in the alkyl-random except for the -CH ₂ - May be substituted with an arylene having 6 to 24 carbon atoms, and any hydrogen in the alkyl may be substituted with fluorine.

As MU, for example, there is a divalent group represented by excluding any two hydrogen atoms from any of the following compounds.

More specifically, a divalent group represented by any one of the following structures is exemplified. In these, the MU binds to another MU or EC in *.

In addition, as EC, for example, there is a monovalent group represented by any of the following structures. In these, EC binds to MU in *.

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

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

<Electron injection layer and electron transport layer in organic light emitting devices>

The electron injection layer 107 serves to efficiently inject electrons moving from the cathode 108 into the light emitting layer 105 or into the electron transport layer 106. The electron transport layer 106 serves to efficiently transport 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 formed by laminating and mixing one or two or more electron transport/injection materials, or a mixture of an electron transport/injection material and a polymeric binder, respectively.

The electron injection/transport layer is a layer in which electrons are injected from the cathode and is responsible for transporting electrons, and it is preferable to have high electron injection efficiency and to efficiently transport the injected electrons. For this purpose, it is preferable that the material has high electron affinity, high electron mobility, excellent stability, and does not readily generate trapping impurities during manufacture and use. However, in the case of considering the transport balance of holes and electrons, in the case where it mainly plays a role of efficiently preventing holes from flowing to the cathode side without recombining, it improves luminous efficiency even if the electron transport ability is not so high. The effect is equivalent to a material having a high electron transport capacity. Therefore, the electron injection/transport layer in the present embodiment may also contain a function of a layer capable of effectively preventing the movement of holes.

As a material (electron transport material) 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, an electron injection layer and an electron transport layer of an organic EL device. It can be arbitrarily selected and used from known compounds used.

As the material used for the electron transport layer or the electron injection layer, a compound consisting of an aromatic ring or a heteroaromatic ring consisting of at least one atom selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus, a pyrrole derivative and a condensed ring derivative thereof, and It is preferable to contain at least one type selected from metal complexes having electron accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives typified by 4,4'-bis(diphenylethenyl)biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives , Quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, indole derivatives, and the like. 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 may be used alone, but may be used by mixing with different materials.

In addition, as specific examples of other electron transfer compounds, pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone Derivatives, perylene derivatives, oxadiazole derivatives (1,3-bis[(4-tert-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 auxin derivatives, quinolinol-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazoles Compound, gallium complex, pyrazole derivative, perfluorinated phenylene derivative, triazine derivative, pyrazine derivative, benzoquinoline derivative (2,2'-bis(benzo[h]quinolin-2-yl)-9,9' -Spirobifluorene), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris(N-phenylbenzimidazol-2-yl)benzene, etc.), 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, etc.), naphthyridine derivatives (Bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide, etc.), aldazine derivatives, carbazole derivatives, indole derivatives, phosphor oxide derivatives, bisstyryl derivatives, etc. Can be mentioned.

In addition, metal complexes having electron-accepting nitrogen may be used, for example, hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes And benzoquinoline metal complexes.

The above-described materials may be used alone, but may be used by mixing with different materials.

Among the aforementioned materials, 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-based metal complexes are preferred.

<borane derivative>

The borane derivative is, for example, a compound represented by the following general formula (ETM-1), and is specifically disclosed in Japanese Laid-Open Patent No. 2007-27587.

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

Among the compounds represented by the general formula (ETM-1), a compound represented by the following general formula (ETM-1-1) or a compound represented by the following general formula (ETM-1-2) is preferred.

In formula (ETM-1-1), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyanide. At least one of the furnaces, and R ¹³ to R ¹⁶ are each independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, and R ²¹ and R ²² are each independently hydrogen , Alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or at least one of cyano, X ¹ is an optionally substituted arylene having 20 or less carbon atoms and n are each independently an integer of 0 to 3, and m is each independently an integer of 0 to 4. In addition, examples of the substituent in the case of "which may be substituted" or "is substituted" include aryl, heteroaryl, alkyl, or cycloalkyl.

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

As a specific example of X ¹ , a divalent group represented by any one of the following formulas (X-1) to (X-9) can be mentioned.

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

As a specific example of this borane derivative, there exist the following compounds, for example.

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), and preferably a compound represented by a formula (ETM-2-1) or a 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 It is an integer.

In the above formula (ETM-2-1), R ¹¹ to R ¹⁸ are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably, cycloalkyl having 3 to 12 carbon atoms) 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, cycloalkyl 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 one of the following formulas (Py-1) to (Py-15), and the pyridine substituents are each independently alkyl having 1 to 4 carbon atoms or 5 to 10 carbon atoms. It may be substituted with cycloalkyl. Further, the pyridine-based substituent may be bonded to φ in each formula, an anthracene ring, or a fluorene ring through a phenylene group or a naphthylene group.

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

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

As the "alkyl" for R ¹¹ to R ¹⁸ , either linear or branched chain may be used, for example, linear alkyl having 1 to 24 carbon atoms or branched chain 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 C1-C12 alkyl (C3-C12 branched chain alkyl). A more preferable "alkyl" is alkyl having 1 to 6 carbon atoms (branched chain alkyl having 3 to 6 carbon atoms). Particularly preferred "alkyl" is alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms).

Specific examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethyl Hexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl , n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, etc. have.

As the C1-C4 alkyl substituted with the pyridine-based substituent, the description of the above alkyl can be cited.

As the "cycloalkyl" for R ¹¹ to R ¹⁸ , there is, for example, a cycloalkyl having 3 to 12 carbon atoms. A preferable "cycloalkyl" is a C3-C10 cycloalkyl. A more preferable "cycloalkyl" is a C3-C8 cycloalkyl. A more preferable "cycloalkyl" is a C3-C6 cycloalkyl. Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl or dimethylcyclohexyl.

As the "aryl" in R ¹¹ to R ¹⁸ , preferred aryl is a C 6 to C 30 aryl, more preferred aryl is a C 6 to C 18 aryl, more preferably C 6 to C 14 aryl, particularly preferably Is aryl having 6 to 12 carbon atoms.

Specific examples of "aryl having 6 to 30 carbon atoms" include monocyclic aryl phenyl, condensed bicyclic aryl (1-, 2-)naphthyl, fused tricyclic aryl, acenaphthylene-(1-, 3-, 4 -, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenalene-(1-, 2-)yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, 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 are exemplified.

Preferred "aryl having 6 to 30 carbon atoms" includes phenyl, naphthyl, phenanthryl, chrysenyl, triphenylenyl, and the like, more preferably phenyl, 1-naphthyl, 2-naphthyl or phenanthryl. For example, phenyl, 1-naphthyl, or 2-naphthyl is particularly preferred.

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

As a specific example of this pyridine derivative, there are the following compounds, for example.

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 specifically disclosed in International Publication No. 2010/134352.

In the formula (ETM-3), X ^{12 to} X ²¹ are hydrogen, halogen, straight chain, branched or cyclic alkyl, straight chain, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. Represents. Here, examples of the substituent in the case of being substituted include aryl, heteroaryl, alkyl or cycloalkyl.

Specific examples of this fluoranthene derivative include, for example, the following compounds.

<BO-based derivative>

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

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

In addition, adjacent groups of R ¹ to R ^{11 may be} bonded to each other to form an aryl ring or heteroaryl ring together with a ring, b ring, or c ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, dia. It may be substituted with rylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl. .

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

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

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

This BO-based 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 a divalent benzene or naphthalene, and R ¹ to R ⁴ are each independently hydrogen, an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 20 carbon atoms.

Ar may each independently be appropriately selected from divalent benzene or naphthalene, and the two Ar may be different or the same, but the same is preferable from the viewpoint of the ease of synthesis of an anthracene derivative. Ar is bonded to pyridine to form a "site consisting of Ar and pyridine", and this site is, for example, an anthracene as a group represented by any one of the following formulas (Py-1) to (Py-12) Is bound to.

Among these groups, a group represented by any one of the formulas (Py-1) to (Py-9) is preferred, and a group represented by any of the formulas (Py-1) to (Py-6) is more preferred. . Two "sites consisting of Ar and pyridine" bonded to anthracene may have the same or different structures, but are preferably the same structure from the viewpoint of ease of synthesis of an anthracene derivative. However, from the viewpoint of device characteristics, the structures of the two "sites consisting of Ar and pyridine" may be the same or different.

Regarding the alkyl having 1 to 6 carbon atoms in R ¹ to R ⁴ , either linear or branched chain may be used. That is, straight-chain alkyl having 1 to 6 carbon atoms or branched-chain alkyl having 3 to 6 carbon atoms. More preferably, it is C1-C4 alkyl (C3-C4 branched chain alkyl). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methyl Pentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, or 2-ethylbutyl, etc. may be exemplified, and methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl , Or tert-butyl is preferred, and methyl, ethyl, or tert-butyl is more preferred.

Specific examples of the cycloalkyl having 3 to 6 carbon atoms in R ¹ to R ⁴ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl or dimethylcyclohexyl. Can be lifted.

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

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, condensed bicyclic aryl (1-, 2-)naphthyl, tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl , m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl- 2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), 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, condensed tetracyclic aryl triphenylene-(1-, 2-)yl, pyrene-(1-, 2-, 4-)yl, tetracene (1- , 2-, 5-)yl, and condensed pentacyclic aryl perylene-(1-, 2-, 3-)yl, and the like.

Preferred "C6-C20 aryl" is phenyl, biphenylyl, terphenylyl, or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2-naphthyl or m-terphenyl -5'-yl, more preferably phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, most preferably phenyl.

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

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

Each of Ar ² is independently an aryl having 6 to 20 carbon atoms, and the same explanation as for "aryl having 6 to 20 carbon atoms" in the formula (ETM-5-1) can be cited. C6-C16 aryl is preferable, C6-C12 aryl is more preferable, and C6-C10 aryl is especially preferable. As specific examples, phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetrasenyl, perylenyl, and the like. I can.

R ¹ to R ⁴ are each independently hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 20 carbon atoms, and the description in the above formula (ETM-5-1) is cited. can do.

Specific examples of these anthracene derivatives include, for example, the following compounds.

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

<Benzofluorene derivative>

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

Each of Ar ¹ is independently an aryl having 6 to 20 carbon atoms, and the same explanation as for "aryl having 6 to 20 carbon atoms" in the above formula (ETM-5-1) can be cited. C6-C16 aryl is preferable, C6-C12 aryl is more preferable, and C6-C10 aryl is especially preferable. As specific examples, phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetrasenyl, perylenyl, and the like. I can.

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

As the "alkyl" in Ar ² , either linear or branched chain may be used, for example, straight chain alkyl having 1 to 24 carbon atoms or branched chain 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 C1-C12 alkyl (C3-C12 branched chain alkyl). A more preferable "alkyl" is alkyl having 1 to 6 carbon atoms (branched chain alkyl having 3 to 6 carbon atoms). Particularly preferred "alkyl" is alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms). Specific examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, and the like are exemplified.

As the "cycloalkyl" in Ar ² , there is a cycloalkyl having 3 to 12 carbon atoms, for example. Preferred "cycloalkyl" is a C3-C10 cycloalkyl. A more preferable "cycloalkyl" is a C3-C8 cycloalkyl. A more preferable "cycloalkyl" is a C3-C6 cycloalkyl. Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl or dimethylcyclohexyl.

As the "aryl" in Ar ² , a preferable aryl is a C6-C30 aryl, a more preferable aryl is a C6-C18 aryl, more preferably a C6-C14 aryl, and particularly preferably a C6 aryl. It is -12 aryl.

Specific examples of "aryl having 6 to 30 carbon atoms" include phenyl, naphthyl, acenaphthyrenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, naphthacenyl, perylenyl, pentacenyl, and the like. Can be lifted.

Two Ar ² may be bonded to form a ring, and as a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, indene, and the like are spiro bonded to the 5-membered ring of the fluorene skeleton. You may have it.

As a specific example of this benzofluorene derivative, there are the following compounds, for example.

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 disclosed in International Publication No. 2013/079217.

R ⁵ is a substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, aryl having 6 to 20 carbon atoms, or heteroaryl having 5 to 20 carbon atoms,

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, heteroaryl having 5 to 20 carbon atoms, It is a C1-C20 alkoxy or C6-C20 aryloxy,

R ⁷ and R ⁸ are each independently a 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 in the case of being substituted include aryl, heteroaryl, alkyl or 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 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.

Ar ¹ may be the same or different, an arylene group or a heteroarylene group, and Ar ² may be the same or different, and there 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 between adjacent substituents. n is an integer from 0 to 3, and when n is 0, there is no unsaturated structure part, and when n is 3, R ¹ does not exist.

Among 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. There is no restriction|limiting in particular as a substituent in the case of being substituted, For example, there exist an alkyl group, an aryl group heterocyclic group, etc., and this point is also common in the following description. In addition, the number of carbon atoms in the alkyl group is not particularly limited, but it is usually in the range of 1 to 20 in consideration of availability and cost.

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

In addition, the aralkyl group represents an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group, and both aliphatic hydrocarbons and aromatic hydrocarbons may be unsubstituted or substituted. The number of carbon atoms in the aliphatic moiety is not particularly limited, but is usually in the range of 1 to 20.

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

In addition, the cycloalkenyl group represents an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, and a cyclohexene group, which may be unsubstituted or substituted.

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

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

Further, the alkylthio group is a group in which the oxygen atom of the ether bond of the alkoxy group is substituted with a sulfur atom.

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

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

Further, the arylthioether 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, and a pyrenyl group. The aryl group may be unsubstituted or substituted. The number of carbon atoms in the aryl group is not particularly limited, but is usually in the range of 6 to 40.

In addition, the heterocyclic group represents a cyclic structural group having an atom other than carbon such as a furanyl group, a thiophenyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group, which may be unsubstituted or substituted. It may be. The number of carbon atoms in the heterocyclic group is not particularly limited, but is usually in the range of 2 to 30.

Halogen represents fluorine, chlorine, bromine and iodine.

The aldehyde group, carbonyl group, and amino group may contain groups substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocycles, and the like.

Further, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocycles may be unsubstituted or substituted.

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

Condensed rings formed between adjacent substituents are, for example, Ar ¹ and R ² , Ar ¹ and R ³ , Ar ² and R ² , Ar ² and R ³ , R ² and R ³ , Ar ¹ and Ar ² It is a conjugated or non-conjugated condensed ring formed between, etc. Here, when n is 1, two R ^1s may form a conjugated or non-conjugated condensed ring. These condensed rings may contain nitrogen, oxygen, and sulfur atoms in the intra-ring structure, or may be further condensed with other rings.

As a specific example of this phosphine oxide derivative, there exist the following compounds, for example.

This phosphine oxide derivative can be prepared 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 disclosed in International Publication No. 2011/021689.

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

As the "aryl" of the "optionally substituted aryl", for example, there is an aryl having 6 to 30 carbon atoms, preferably an aryl having 6 to 24 carbon atoms, more preferably an aryl having 6 to 20 carbon atoms, even more preferably 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, and tricyclic aryl inter Phenylyl (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), condensed tricyclic aryl phosphorus , Acenaphthylene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenalene-(1-, 2- )Yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl, quarterphenylyl (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, etc. are mentioned.

As the "heteroaryl" of the "optionally substituted heteroaryl", for example, there is a heteroaryl having 2 to 30 carbon atoms, a heteroaryl having 2 to 25 carbon atoms is preferable, and a heteroaryl having 2 to 20 carbon atoms is more preferable. And, C2-C15 heteroaryl is more preferable, and C2-C10 heteroaryl is especially preferable. Further, examples of the heteroaryl include, for example, heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom.

As a specific heteroaryl, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxathiazolyl, 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, pteri Denyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxatiinyl, thianthrenyl, indolizinyl, and the like.

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

As a specific example of this pyrimidine derivative, there are the following compounds, for example.

This pyrimidine derivative can be prepared using a known raw material and a known synthesis method.

<Carbazole derivatives>

The carbazole derivative is, for example, a compound represented by the following formula (ETM-9), or a multimer in which a plurality of it is bonded by a single bond or the like. Details are set forth in US Publication No. 2014/0197386.

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

As the "aryl" of the "optionally substituted aryl", for example, there is an aryl having 6 to 30 carbon atoms, preferably an aryl having 6 to 24 carbon atoms, more preferably an aryl having 6 to 20 carbon atoms, even more preferably 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, and tricyclic aryl inter Phenylyl (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), condensed tricyclic aryl phosphorus , Acenaphthylene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenalene-(1-, 2- )Yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl, quarterphenylyl (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, etc. are mentioned.

As the "heteroaryl" of "the heteroaryl which may be substituted," for example, there is a heteroaryl having 2 to 30 carbon atoms, a heteroaryl having 2 to 25 carbon atoms is preferable, and a heteroaryl having 2 to 20 carbon atoms is more preferable. And, C2-C15 heteroaryl is more preferable, and C2-C10 heteroaryl is especially preferable. Further, examples of the heteroaryl include, for example, heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom.

As a specific heteroaryl, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxathiazolyl, furazanyl, thiadiazolyl, Triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triaziniru, benzofuranyl, isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-inda Zolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cynnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, p Teridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxatinyl, thianthrenyl, indozinyl, and the like.

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

The carbazole derivative may be a multimer in which a plurality of compounds represented by the formula (ETM-9) are bonded by a single bond or the like. In this case, in addition to a single bond, it may be bonded in an aryl ring (preferably a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring, or triphenylene ring). .

Specific examples of this carbazole derivative include, for example, 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 aryl which may be substituted, or heteroaryl which may be substituted. n is an integer of 1 to 3, preferably 2 or 3.

As the "aryl" of the "optionally substituted aryl", for example, there is an aryl having 6 to 30 carbon atoms, preferably an aryl having 6 to 24 carbon atoms, more preferably an aryl having 6 to 20 carbon atoms, even more preferably 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, and tricyclic aryl inter Phenylyl (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), condensed tricyclic aryl phosphorus , Acenaphthylene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenalene-(1-, 2- )Yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl, quarterphenylyl (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, etc. are mentioned.

As the "heteroaryl" of "the heteroaryl which may be substituted," for example, there is a heteroaryl having 2 to 30 carbon atoms, a heteroaryl having 2 to 25 carbon atoms is preferable, and a heteroaryl having 2 to 20 carbon atoms is more preferable. And, C2-C15 heteroaryl is more preferable, and C2-C10 heteroaryl is especially preferable. Further, examples of the heteroaryl include, for example, heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom.

As a specific heteroaryl, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxathiazolyl, furazanyl, thiadiazolyl, Triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triaziniru, benzofuranyl, isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-inda Zolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cynnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, p Teridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxatinyl, thianthrenyl, indozinyl, and the like.

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

Specific examples of this triazine derivative include, for example, the following compounds.

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

<Benzimidazole derivatives>

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 1 to 4 It is an integer, and the "benzimidazole-based substituent" is the pyridyl group in the "pyridine-based substituent" in the above formulas (ETM-2), (ETM-2-1) and formula (ETM-2-2). It is a substituent substituted with an imidazole group, and one or more hydrogens 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, wherein the formula (ETM-2-1) and formula (ETM The description of R ¹¹ in -2-2) can be cited.

φ is also preferably an anthracene ring or a fluorene ring, and the structure in this case can refer to the description in the above formula (ETM-2-1) or (ETM-2-2), and R in each formula ¹¹ to R ¹⁸ can refer to the description in the above formula (ETM-2-1) or (ETM-2-2). In addition, in the above formula (ETM-2-1) or (ETM-2-2), two pyridine-based substituents are combined, but when replacing them with a benzimidazole-based substituent, both pyridine-based substituents May be substituted with a benzimidazole-based substituent (that is, n=2), one pyridine-based substituent may be substituted with a benzimidazole-based substituent, and the other pyridine-based substituent may be substituted with R ¹¹ to R ¹⁸ (i.e. n=1). Further, for example, at least one of R ¹¹ to R ¹⁸ in the above formula (ETM-2-1) may be substituted with a benzimidazole-based substituent, and ``pyridine-based substituent” may be substituted with R ¹¹ to R ¹⁸ .

As a specific example of this benzimidazole derivative, for example 1-phenyl-2-(4-(10-phenylanthracene-9-yl)phenyl)-1H-benzo[d]imidazole, 2-(4-(10 -(Naphthalen-2-yl)anthracene-9-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 2-(3-(10-(naphthalen-2-yl)anthracene-9-yl) )Phenyl)-1-phenyl-1H-benzo[d]imidazole, 5-(10-(naphthalen-2-yl)anthracene-9-yl)-1,2-diphenyl-1H-benzo[d]im Dazole, 1-(4-(10-(naphthalen-2-yl)anthracene-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]imidazole and the like.

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 (ETM-12-1). Details are described in International Publication No. 2006/021982.

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

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

One or more hydrogens in each phenanthroline derivative may be substituted with deuterium.

R ¹¹ as alkyl, cycloalkyl and aryl in ~R ^18, it is possible to cite the description of the formula the R ¹¹ ~R ¹⁸ in (ETM-2). In addition, in addition to the above example, φ has, for example, the following structural formula. In addition, R in the following structural formula is each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, or terphenylyl.

As a specific example of this phenanthroline derivative, for example, 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9, 10-di(1,10-phenanthrolin-2-yl)anthracene, 2,6-di(1,10-phenanthroline-5-yl)pyridine, 1,3,5-tri(1,10- Phenanthroline-5-yl)benzene, 9,9'-difluoro-bis(1,10-phenanthroline-5-yl), vasocuproin or 1,3-bis(2-phenyl-1) ,10-phenanthroline-9-yl)benzene or a compound represented by the following structural formula.

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

<Quinolinol-based metal complex>

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

In the formula, R ¹ to R ⁶ are each independently hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy or aryl, and M is Li, Al, Ga, Be or Zn, n is an integer of 1 to 3.

Specific examples of the quinolinol-based metal complex include 8-quinolinol lithium, tris(8-quinolinolate) aluminum, tris(4-methyl-8-quinolinolate) aluminum, and tris(5-methyl-8-) Quinolinolate) aluminum, tris (3,4-dimethyl-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, tris (4,6-dimethyl-8 -Quinolinoleate) aluminum, bis(2-methyl-8-quinolinolate)(phenolate)aluminum, bis(2-methyl-8-quinolinolate)(2-methylphenolate)aluminum, bis (2-methyl-8-quinolinolate) (3-methylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (4-methylphenolate) aluminum, bis (2-methyl-8 -Quinolinolate)(2-phenylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(3-phenylphenolate)aluminum, bis(2-methyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,6 -Dimethylphenolate) aluminum, bis(2-methyl-8-quinolinolate)(3,4-dimethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(3,5-dimethyl Phenolate) aluminum, bis(2-methyl-8-quinolinolate)(3,5-di-tert-butylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(2,6 -Diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2 ,4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,4,5,6-tetramethylphenolate) aluminum, bis (2-methyl-8-quinoli) Nolate) (1-naphtholate) aluminum, bis (2-methyl-8-quinolinolate) (2-naphtholate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (2- Phenylphenolate) aluminum, bis(2,4-dimethyl-8-quinolinolate)(3-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolate)(4-phenylphenol Rate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-dimethylphenole Yt) aluminum, bis(2,4-dimethyl-8-quinolinolate)(3,5-di-tert-butylphenolate)aluminum, bis(2-methyl-8-quinolinolate)aluminum-μ -Oxo-bis(2-methyl-8-quinolinolate) aluminum, bis(2,4-dimethyl-8-quinolinolate) aluminum-μ-oxo-bis(2,4-dimethyl-8-qui Nolinoleate) aluminum, bis(2-methyl-4-ethyl-8-quinolinolate)aluminum-μ-oxo-bis(2-methyl-4-ethyl-8-quinolinolate)aluminum, bis( 2-Methyl-4-methoxy-8-quinolinolate)aluminum-μ-oxo-bis(2-methyl-4-methoxy-8-quinolinolate)aluminum, bis(2-methyl-5- Cyano-8-quinolinolate) aluminum-μ-oxo-bis(2-methyl-5-cyano-8-quinolinolate) aluminum, bis(2-methyl-5-trifluoromethyl-8 -Quinolinolate)aluminum-μ-oxo-bis(2-methyl-5-trifluoromethyl-8-quinolinolate)aluminum, bis(10-hydroxybenzo[h]quinoline)beryllium, etc. I can.

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 It is an integer of 4, and "thiazole-type substituent" or "benzothiazole-type substituent" is "pyridine in formula (ETM-2), formula (ETM-2-1), and formula (ETM-2-2) The pyridyl group in the "system substituent" is a substituent substituted with the following thiazole group or benzothiazole group, and at least one hydrogen in the thiazole derivative and benzothiazole derivative may be substituted with deuterium.

φ is also preferably an anthracene ring or a fluorene ring, and the structure in this case can refer to the description in the above formula (ETM-2-1) or (ETM-2-2), and R in each formula ¹¹ to R ¹⁸ can refer to the description in the above formula (ETM-2-1) or (ETM-2-2). In addition, in the above formula (ETM-2-1) or (ETM-2-2), two pyridine-based substituents are combined, but when these are substituted with thiazole-based substituents (or benzothiazole-based substituents), Both pyridine-based substituents may be substituted with thiazole-based substituents (or benzothiazole-based substituents) (that is, n=2), and either pyridine-based substituents may be substituted with thiazole-based substituents (or benzothiazole-based substituents) and the other You may substitute a pyridine-based substituent with R ¹¹ to R ¹⁸ (that is, n=1). In addition, for example, one or more of R ¹¹ to R ¹⁸ in the above formula (ETM-2-1) is substituted with a thiazole-based substituent (or benzothiazole-based substituent), and “pyridine-based substituent” is replaced with R ¹¹ to R ^You may substitute ¹⁸ .

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

The electron transport layer or electron injection layer may further contain a material capable of reducing the material for forming the electron transport layer or the electron injection layer. If the reducing material has a certain reducibility, various materials are used. For example, alkali metal, alkaline earth metal, rare earth metal, oxide of alkali metal, halide of alkali metal, oxide of alkaline earth metal, alkali At least one selected from the group consisting of halides of earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals can be preferably used. .

Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (work function 2.28 eV), Rb (work function 2.16 eV) or Cs (work function 1.95 eV), or Ca (work function 2.9 eV), Alkaline earth metals such as Sr (work function 2.0 to 2.5 eV) or Ba (work function 2.52 eV) are exemplified, and a material having a work function of 2.9 eV or less is particularly preferable. Among these, a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and the most preferable one is Cs. These alkali metals have particularly high reducing ability, and by adding a relatively small amount to a material forming the electron transport layer or the electron injection layer, the luminance of light emission in the organic EL device and the lifespan thereof can be increased. In addition, as a reducing material having a work function of 2.9 eV or less, a combination of two or more alkali metals is also preferred, and in particular, a combination including Cs, for example, Cs and Na, Cs and K, Cs and Rb, or Cs and A combination of Na and K is preferred. By including Cs, the reducing ability can be exhibited efficiently, and by addition to a material forming the electron transport layer or the electron injection layer, the luminance of light emission in the organic EL device and the lifespan thereof can be increased.

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

<Cathode in organic light emitting device>

The cathode 108 serves to inject 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 is a material capable of efficiently injecting 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 alloy, aluminum-lithium alloy such as lithium fluoride/aluminum, etc.) and the like are preferred. In order to increase the electron injection efficiency and improve device characteristics, lithium, sodium, potassium, cesium, calcium, magnesium, or an alloy containing these low work function metals is effective. However, these low work function metals are generally unstable in the atmosphere in many cases. In order to improve this point, for example, a method of using an electrode having high stability by doping an organic layer with a trace amount of lithium, cesium or magnesium is known. 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.

In addition, for electrode protection, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic substances such as silica, titania, and silicon nitride, polyvinyl alcohol, vinyl chloride, Lamination of a hydrocarbon-based polymer compound or the like is exemplified as a preferred example. The manufacturing method of these electrodes is not particularly limited as long as it can conduct such as resistance heating, electron beam evaporation, sputtering, ion plating and coating.

<Binder that can be used in each layer>

Materials used for the above hole injection layer, hole transport layer, light emitting layer, electron transport layer, and electron injection layer can form each layer independently, but as a polymer binder, polyvinyl chloride, polycarbonate, polystyrene, poly(N-vinylcar) Bazol), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS Also used by dispersing in solvent-soluble resins such as resins and polyurethane resins, curable resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins and silicone resins. It is possible.

<Method of manufacturing organic light emitting device>

For each layer constituting the organic EL device, the material constituting each layer is deposited by a vapor deposition method, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method, casting method, coating method, etc. It can be formed by forming a thin film by a method. 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. In the case of forming a thin film using a vapor deposition method, the vapor deposition conditions differ depending on the kind of material, the target crystal structure and association structure of the film, and the like. In general, deposition conditions, a boat heating temperature is + 400 + 50~ ℃, the degree of vacuum 10 ^-6 ~10 ^{- 3} Pa, the deposition rate 0.01~50 nm / second, substrate temperature -150~ + 300 ℃, the film thickness in the range of 2nm~5㎛ It is desirable to set it appropriately.

In the case of applying a DC voltage to the organic EL device thus obtained, the positive electrode may be applied as a polarity of + and the negative electrode may be applied as a polarity of -. When a voltage of about 2 to 40 V is applied, the transparent or semi-transparent electrode side (positive or negative electrode , And both) can be observed. Further, this organic EL element emits light even when a pulse current or an alternating current is applied. In addition, the waveform of the alternating current to be applied may be arbitrary.

Next, as an example of a method of manufacturing an organic EL device, a method of fabricating an organic EL device comprising an anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode made of a host material and a dopant material will be described. do.

<Deposition method>

On a suitable substrate, a thin film of an anode material is formed by a vapor deposition method or the like to prepare an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. On this, a host material and a dopant material are co-deposited and a thin film is formed to form a light emitting layer, and an electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a material for a cathode is formed as a cathode by evaporation or the like. An EL element is obtained. Further, in the fabrication of the organic EL device described above, the fabrication order may be reversed, and thus a cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer, and an anode may be produced in this order.

<Wet Formation Method>

The wet film formation method is carried out by preparing a low-molecular compound capable of forming each organic layer of an organic EL element as a composition for forming a liquid organic layer, and using this. In the absence of an appropriate organic solvent for dissolving the low molecular weight compound, a composition for forming an organic layer is prepared from a polymer compound polymerized with another monomer or main chain polymer having a solubility function as a reactive compound in which a reactive substituent is substituted for the low molecular compound You can prepare.

In the wet film forming method, generally, a coating film is formed by going through a coating step of applying a composition for forming an organic layer to a substrate and a drying step of removing a solvent from the applied composition for forming an organic layer. When the polymer compound has a crosslinkable substituent (this is also referred to as a crosslinkable polymer compound), it is further crosslinked by this drying step to form a crosslinked polymer. Depending on the difference in the application process, the spin coater is used as the spin coating method, the slit coater is used as the slit coating method, and the plate is used as gravure, offset, reverse offset, flexo printing, and inkjet printers. The method of use is called the inkjet method, and the method of spraying in the form of mist is called the spray method. The drying process includes methods such as air drying, heating, and vacuum drying. The drying process may be performed only once, or may be performed multiple times using other methods or conditions. Further, for example, other methods may be used in combination, 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, a cast method, a coating method, or the like. Unlike the vacuum evaporation method, the wet film forming method does not require the use of an expensive vacuum vapor deposition apparatus, and the film can be formed under atmospheric pressure. In addition, the wet film forming method enables a large area and continuous production, leading to a reduction in manufacturing cost.

On the other hand, in the case of comparison with the vacuum evaporation method, lamination may be difficult in the wet film forming method. When manufacturing a laminated film using the wet film forming method, it is necessary to prevent the dissolution of the lower layer by the composition of the upper layer, and the composition with controlled solubility, the crosslinking and orthogonal solvent of the lower layer (orthogonal solvent, solvent that does not dissolve each other), etc. This is spoken. However, even when such a technique is used, it may be difficult to use a wet film forming method for coating all films.

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

For example, the procedure of manufacturing an organic EL element by applying a part of a wet film forming method is shown below.

(Procedure 1) Film formation by vacuum evaporation on the anode

(Procedure 2) Film formation of a composition for forming a hole injection layer including a material for a hole injection layer by a wet film forming method

(Procedure 3) Formation of a composition for forming a hole transport layer including a material for a hole transport layer by a wet film forming method

(Procedure 4) Formation of a composition for forming a light emitting layer containing a host material and a dopant material by a wet film forming method

(Procedure 5) Formation of electron transport layer by vacuum evaporation method

(Procedure 6) Formation of electron injection layer by vacuum evaporation method

(Procedure 7) Film formation by vacuum evaporation on the cathode

By passing through this procedure, an organic EL device comprising an anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode composed of a host material and a dopant material is obtained.

Of course, by using a means for preventing dissolution of the light emitting layer in the lower layer, or by using a means for forming a film from the cathode side contrary to the above procedure, prepared as a composition for forming a layer comprising a material for an electron transport layer or a material for an electron injection layer, These can be formed into a film by a wet film forming method.

<Other tabernacle methods>

For forming a film of the composition for forming an organic layer, a laser heating drawing method (LITI) can be used. LITI is a method in which a compound attached to a substrate is deposited by heating with a laser, and a composition for forming an organic layer can be used for a material applied to the substrate.

<random process>

Before and after each step of film formation, an appropriate treatment step, washing step, and drying step may be appropriately put. Examples of the treatment process include exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, cleaning treatment using an appropriate solvent, and heat treatment. In addition, a series of processes for producing a bank are also exemplified.

Photolithography techniques can be used to fabricate the bank. As a bank material that can use photolithography, a positive resist material and a negative resist material can be used. In addition, patternable printing methods such as inkjet method, gravure offset printing, reverse offset printing, and screen printing can also be used. In that case, a permanent resist material can also be used.

Materials used in the bank include polysaccharides and derivatives thereof, homopolymers and copolymers of ethylenic monomers having hydroxyl, biopolymer compounds, polyacryloyl compounds, polyesters, polystyrenes, polyimides, polyamideimides, and polyethers. Mid, polysulfide, polysulfone, polyphenylene, polyphenyl ether, polyurethane, epoxy (meth) acrylate, melamine (meth) acrylate, polyolefin, cyclic polyolefin, acrylonitrile-butadiene-styrene copolymer (ABS ), silicone resin, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyacetate, polynorbornene, synthetic rubber, polyfluorovinylidene, polytetrafluoroethylene, fluorinated polymer such as polyhexafluoropropylene, fluorine Although a copolymer of olefin-hydrocarbon olefin and a fluorocarbon polymer can be exemplified, it is not limited thereto.

<Composition for organic layer formation used in wet film formation>

The composition for forming an organic layer is obtained by dissolving a low-molecular compound capable of forming each organic layer of an organic EL device or a high-molecular compound obtained by polymerizing the low-molecular compound in an organic solvent. For example, the composition for forming a light emitting layer may include 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 at least one as a third component. Contains species of organic solvent. The first component functions as a dopant component of the light emitting layer obtained from the composition, and the second component functions as a host component of the light emitting layer. The third component functions as a solvent that dissolves the first component and the second component in the composition, and when applied, gives a smooth and uniform surface shape by the controlled evaporation rate of the third component itself.

<Organic solvent>

The composition for forming an organic layer contains at least one organic solvent. By controlling the evaporation rate of the organic solvent at the time of film formation, it is possible to control and improve film formation properties, the presence or absence of defects in the coating film, surface roughness, and smoothness. In addition, at the time of film formation using the ink jet method, the meniscus stability in the pinhole of the ink jet head can be controlled, and ejection properties can be controlled and improved. In addition, by controlling the drying rate of the film and the orientation of the derivative molecules, it is possible to improve the electrical properties, luminescence properties, efficiency, and lifetime of an organic EL device having an organic layer obtained from the organic layer-forming composition.

(1) Physical properties of organic solvent

The boiling point of the at least one organic solvent is 130°C to 300°C, more preferably 140°C to 270°C, and even more preferably 150°C to 250°C. When the boiling point is higher than 130°C, it is preferable from the viewpoint of ink jet ejection properties. Further, when the boiling point is lower than 300° C., it is preferable from the viewpoint of defects of the coating film, surface roughness, residual solvent and smoothness. The organic solvent is more preferably composed of two or more organic solvents from the viewpoints of excellent ink jet ejection properties, film-forming properties, smoothness and low residual solvent. On the other hand, in some cases, a composition obtained in a solid state by removing the solvent from the composition for forming an organic layer may be employed in consideration of transportability and the like.

In addition, the organic solvent contains a good solvent (GS) and a sub-solvent (PS) for at least one of the solutes, and the boiling point (BPGS) of the good solvent (GS) is lower than the boiling point (BPPS) of the sub-solvent (PS). , The configuration is particularly preferred. By adding a high-boiling sub-solvent, the low-boiling good solvent first volatilizes during film formation, and the concentration of the contained substances and the sub-solvent in the composition increase, thereby promoting rapid film formation. Thereby, a coating film with few defects, small surface roughness and high smoothness can be obtained.

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

After film formation, the organic solvent is removed from the coating film by a drying process such as vacuum, reduced pressure, or heating. In the case of heating, it is preferable to carry out at least one of the solutes at a glass transition temperature (Tg) of +30°C or less from the viewpoint of improving the coating film-forming properties. In addition, 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, since the film becomes thin, the organic solvent is sufficiently removed. Further, 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 solvent

Organic solvents used in the composition for forming an organic layer include alkylbenzene solvents, phenyl ether solvents, alkyl ether solvents, cyclic ketone solvents, aliphatic ketone solvents, monocyclic ketone solvents, diester skeleton solvents, and fluorine. Containing solvents, etc. can be mentioned, as specific examples, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexan-2-ol, heptane- 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 ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, di Propylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl Ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, p-xylene, m-xylene, o-xylene, 2,6- Lutidine, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 2-chlorobenzo trifluoride, cumene, toluene, 2-chloro-6-fluoro toluene, 2-fluoroanisole, no Sol, 2,3-dimethylpyrazine, bromobenzene, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethylanisole, mesitylene, 1,2,4-trimethylbenzene, tert- Butylbenzene, 2-methylanisole, phenethyl, benzodioxole, 4-methylanisole, sec-butylbenzene, 3-methylanisole, 4-fluoro-3-methylanisole, cymene, 1,2, 3-trimethylbenzene, 1,2-dichlorobenzene, 2-fluorobenzonitrile, 4-fluoroveratrol, 2,6-dimethylanisole, n-butylbenzene, 3-fluorobenzonitrile, decalin (decahydro Naphthalene), neopentylbenzene, 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3,5-dimethylanisole, diphenyl ether, 1-fluoro-3,5-dimethoxybenzene, methyl benzoate, isopentylbenzene, 3,4-dimethylanisole , o-tolunitrile, n-amylbenzene, veratrol, 1,2,3,4-tetrahydronaphthalene, ethyl benzoate, n-hexylbenzene, propyl benzoate, cyclohexylbenzene, 1-methylnaphthalene, butyl benzoate, 2-methylbiphenyl, 3-phenoxytoluene, 2,2'-bitolyl, 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, 1-methyl-4- (heptyloxymethyl) benzene, benzyl butyl ether, benzyl pentyl ether, benzyl hexyl ether, benzyl heptyl ether, benzyl octyl ether, and the like, but are not limited thereto. In addition, the solvent may be used singly or may be mixed.

<optional ingredient>

The composition for forming an organic layer may contain an optional component as long as the properties are not impaired. As an optional component, a binder, a surfactant, etc. are mentioned.

(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 serves to dissolve, disperse, and bind other components in the composition for forming an organic layer.

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

The binder used in the composition for forming an organic layer may be used alone or in combination of a plurality of types.

(2) surfactant

The composition for forming an organic layer may contain, for example, a surfactant for controlling the film surface uniformity of the composition for forming an organic layer, the hydrophilicity of the film surface, and liquid repellency. Surfactants are classified into ionic and nonionic depending on the structure of the hydrophilic group, and are classified into alkyl, silicone, and fluorine based on the structure of the hydrophobic group. Further, according to the structure of the molecule, they are classified into monomolecular systems having a simple structure with a relatively small molecular weight, and polymer systems having a large molecular weight and side chains or branches. In addition, it is classified into a single system, a mixed system in which two or more types of surfactants and a base material are mixed by composition. As the surfactant that can be used in the composition for forming an organic layer, all kinds of surfactants can be used.

As a surfactant, for example, Polyflow No.45, Polyflow KL-245, Polyflow No.75, Polyflow No.90, Polyflow No.95 (trade name, Kyoeisha Chemical) Industrial Co., Ltd.), Disperbyk 161, Disperbyk 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181, Disperbake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (brand name, manufactured by Big Chem 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, Suflon KH-40 (trade name, manufactured by Semichemical Co., Ltd.), Ptta FTERGENT 222F, Ptagent 251, FTX-218 (brand name, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (brand name, Mitsubishi Material Co., Ltd.), Megapack F-470, Megapack F-471, Megapack F-475, Megapack R-08, Megapack F-477, Megapack F-479, Megapack F-553, Megapack F-554 (trade name, manufactured by DIC Corporation), fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoro Roalkyl sulfonate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylenenonylphenyl ether, polyoxyethyleneoctylphenylether, polyoxyethylenealkyl Ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid Ester, polyoxy Ethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitanoleate, polyoxyethylene naphthyl ether, alkylbenzenesulfonate and alkyldiphenylether disulfonate have.

In addition, surfactants may be used alone or in combination of two or more.

<Composition and properties of the composition for forming an organic layer>

The content of each component in the composition for forming an organic layer is the good solubility, storage stability, and film-forming properties of each component in the composition for forming an organic layer, and the quality of the coating film obtained from the composition for forming an organic layer, and the inkjet method. The case of using is determined in consideration of the viewpoints of good discharge properties, good electrical characteristics, luminous characteristics, efficiency, and lifespan of an organic EL device having an organic layer prepared using the composition. For example, in the case of the composition for forming a light-emitting layer, the first component is 0.0001% to 2.0% by weight, based on the total weight of the composition for forming the light-emitting layer, and the second component is 0.0999% by weight, based on the total weight of the composition for forming the light-emitting layer. % To 8.0% by weight, and the third component is preferably 90.0% by weight to 99.9% by weight based on the total weight of the composition for forming a light emitting layer.

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

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

As the viscosity of the composition for forming an organic layer, a composition having a high viscosity provides good film-forming properties and good ejection properties when an inkjet method is used. On the other hand, those with low viscosity are easy to make thin films. In view of these points, the viscosity of the composition for forming an organic layer is preferably 0.3 to 3 mPa·s, and more preferably 1 to 3 mPa·s at 25°C. In the present invention, the viscosity is a value measured using a conical flat plate rotational viscometer (cone plate type).

As the surface tension of the composition for forming an organic layer, a low one provides good film-forming properties and a coating film without defects. On the other hand, a high one can obtain good inkjet ejection properties. In view of this, the surface tension of the organic layer-forming composition is preferably 20 to 40 mN/m, and more preferably 20 to 30 mN/m at 25°C. In the present invention, the surface tension is a value measured by using the hyeonjeok method (懸滴法).

<Crosslinkable polymer compound: compound represented by general formula (XLP-1)>

Next, a 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 are the same definitions as MU, EC and k in the above formula (SPH-1), except 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, more preferably 1 to 20% by weight.

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

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

As a divalent aromatic compound having a crosslinkable substituent, there is a compound having the following partial structure, for example. * In the following structural formula represents a bonding position.

<Method for producing a polymer compound and a crosslinkable polymer compound>

With respect to the method for producing the polymer compound and the crosslinkable polymer compound, a compound represented by the above formula (SPH-1) and a compound represented by the formula (XLP-1) will be described 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.

In addition, the reaction may be performed in a two-phase system. In the case of reacting in a two-phase system, if necessary, a phase transfer catalyst such as a quaternary ammonium salt may be added.

When preparing the compound of formula (SPH-1) and the compound of (XLP-1), it may be prepared in one step or may be prepared through multiple steps. Further, it may be carried out by a batch polymerization method in which the reaction is initiated after putting all of the raw materials in the reaction vessel, or by dropping polymerization method in which the raw materials are added dropwise to the reaction vessel, and the product precipitates as the reaction proceeds. It may be carried out by a polymerization method, or these can be appropriately combined and synthesized. For example, in the case of synthesizing a compound represented by the formula (SPH-1) in one step, a target product is obtained by reacting while adding a monomer unit (MU) and an end cap unit (EC) to a reaction vessel. In addition, in the case of synthesizing the compound represented by the formula (SPH-1) in multiple steps, the monomer unit (MU) is polymerized to a desired molecular weight, and then an end cap unit (EC) is added to react to obtain a target product. If the reaction is carried out by adding different types of monomer units (MU) in multiple steps, a polymer having a concentration gradient with respect to the structure of the monomer unit can be produced. Further, after preparing the precursor polymer, a target polymer can be obtained by reaction later.

In addition, 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, polymers having a random primary structure (synthetic scheme 1), polymers having a regular primary structure (synthetic schemes 2 and 3), etc. It is possible, and can be used in appropriate combinations depending on the object. In addition, if a monomer unit having three or more polymerizable groups is used, a hyperbranched polymer or a dendrimer can be synthesized.

As a monomer unit that can be used in the present invention, Japanese Patent Publication No. 2010-189630, International Publication No. 2012/086671, International Publication No. 2013/191088, International Publication No. 2002/045184, International Publication No. 2011/049241 , International Publication No. 2013/146806, International Publication No. 2005/049546, International Publication No. 2015/145871, Japanese Patent Publication No. 2010-215886, Japanese Patent Publication No. 2008-106241, Japanese Patent Publication No. 2010 -215886, International Publication No. 2016/031639, Japanese Patent Publication No. 2011-174062, International Publication No. 2016/031639, International Publication No. 2016/031639, International Publication No. 2002/045184 It can be synthesized accordingly.

In addition, for specific polymer synthesis procedures, Japanese Unexamined Patent Publication No. 2012-036388, International Publication No. 2015/008851, Japanese Unexamined Patent Publication No. 2012-36381, Japanese Unexamined Patent Publication No. 2012-144722, and 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. 2016/125560, International Publication No. 2015/145871, International Publication No. 2011/049241, and Japanese Patent Publication No. 2012-144722 can be synthesized according to the method described.

<Application examples of organic light emitting devices>

Further, the present invention can 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 provided with 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, and known such as direct current drive, pulse drive, and AC drive. It can be driven by appropriately using the driving method of

Examples of display devices include panel displays such as color flat panel displays, and flexible displays such as flexible color organic electroluminescence (EL) displays (e.g., Japanese Laid-Open Patent Publication No. Hei 10-335066, Japanese Laid-Open Patent Publication No. 2003-321546, Japanese Laid-Open Patent No. 2004-281086, etc.). In addition, as a display method of the display, there are, for example, a matrix and/or segment method. In addition, the matrix display and the segment display may coexist in the same panel.

In the matrix, pixels for display are arranged two-dimensionally, such as a grid or a mosaic, and characters or images are displayed as a set of pixels. The shape or size of the pixel is determined according to the application. For example, in the display of images and characters on computers, monitors, and televisions, a square pixel having a side of 300 mu m or less is usually used, and in the case of a large display such as a display panel, a pixel of the order of mm is used. In the case of black-and-white display, pixels of the same color may be arranged, but in the case of color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type. As a driving method of this matrix, either a line sequential driving method or an active matrix may be used. The linear sequential driving has the advantage of having a simple structure, but when the operation characteristics are considered, the active matrix may be superior, and it is necessary to use this as well according to the application.

In the segment method (type), a pattern is formed to display predetermined information, and a predetermined area is illuminated. For example, there are display of time and temperature on a digital clock or thermometer, display of operating states of audio equipment and electronic cookers, and panel display of automobiles.

Examples of lighting devices include lighting devices such as indoor lighting and backlights for liquid crystal display devices (for example, Japanese Unexamined Patent Publication No. 2003-257621, Japanese Unexamined Patent Publication No. 2003-277741, Japanese Unexamined Publication See Patent No. 2004-119211, etc.). The backlight is mainly used 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, and a sign. Particularly, as a backlight for a liquid crystal display device, especially for a computer whose thickness reduction is a problem, considering that the conventional method is made of a fluorescent lamp or a light guide plate, it is difficult to reduce the thickness, the backlight using the light emitting element according to the present embodiment is thin. It features light weight.

3-2. Other organic devices

The polycyclic aromatic compound according to the present invention can be used in fabrication of an organic field effect transistor or an organic thin film solar cell, in addition to the above-described organic electroluminescent device.

The organic field effect transistor is a transistor that controls current by an electric field generated by a 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 is controlled by arbitrarily blocking the flow of electrons (or holes) flowing between the source electrode and the drain electrode. Field-effect transistors are easy to downsize compared to 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, in general, the source electrode and the drain electrode are formed in contact with the organic semiconductor active layer formed using the polycyclic aromatic compound according to the present invention, and the insulating layer (dielectric layer) in contact with the organic semiconductor active layer is sandwiched. Thus, it is sufficient that the gate electrode is provided. As the device structure, there are, for example, the following structures.

(1) Substrate/gate electrode/insulator layer/source electrode/drain electrode/organic semiconductor active layer

(2) Substrate/gate electrode/insulator layer/organic semiconductor active layer/source electrode/drain electrode

(3) Substrate/organic semiconductor active layer/source electrode/drain electrode/insulator layer/gate electrode

(4) Substrate/source electrode/drain electrode/organic semiconductor active layer/insulator layer/gate electrode

The organic field effect transistor configured as described above can be applied as a liquid crystal monitor of an active matrix driving method, a pixel driving switching element of an organic light emitting element display, or the like.

An organic thin film solar cell has a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are stacked 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 suitably include a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, and a smoothing layer. In the organic thin-film solar cell, known materials used for the organic thin-film solar cell can be appropriately selected and used in combination.

[Example]

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited thereto. First, a synthesis example of a polycyclic aromatic compound will be described below.

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

In a nitrogen atmosphere, 4-(1-adamantyl)aniline (15.0 g) was dissolved in acetonitrile (300 ml), and bromine (21.1 g) was added dropwise thereto under ice cooling, followed by stirring for 0.5 hours. After the reaction, water and ethyl acetate were added to the reaction solution, followed by stirring, toluene was further added, and the organic layer was separated and washed with water. After that, 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 an intermediate (I-A) (21.0 g).

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

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

To a flask containing the intermediate (I-C) (24.0 g) and tert-butylbenzene (120 ml), a pentane solution (33.5 ml) of 1.56 M tert-butyllithium was added at 0° C. under a nitrogen atmosphere. After completion of the dropwise addition, the temperature was raised to 60°C and stirred for 1 hour, and then a component having a boiling point lower than that of tert-butylbenzene was distilled off under reduced pressure. It cooled to -50 degreeC, boron tribromide (13.1 g) was added, the temperature was raised to room temperature, and it stirred for 0.5 hours. Then, it cooled to 0 degreeC again, N,N-diisopropylethylamine (6.8g) was added, and after stirring at room temperature until heat generation cooled, it heated up to 100 degreeC, 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 to perform liquid separation. The organic layer was concentrated and then purified by a silica gel short column (eluent: toluene/heptane = 2/8 (volume ratio)). The obtained crude product was dissolved in toluene and re-precipitated with methanol to obtain compound (1-25) (6.0 g).

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

¹ H-NMR (CDCl ₃ ): δ=1.21 (s, 18H), 1.36 (s, 36H), 1.48-1.66 (m, 12H), 1.89 (s, 3H), 6.18 (s, 2H), 6.78 ( s, 2H), 7.22 (d, 4H), 7.25-7.28 (m, 2H), 7.59 (t, 2H), 8.86 (d, 2H).

Synthesis Example (2): Synthesis of Compound (1-16)

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

To a flask containing the intermediate (I-D) (13.0 g) and tert-butylbenzene (100 ml), a 1.56 M pentane solution (18.3 ml) of tert-butyllithium was added at 0° C. under a nitrogen atmosphere. After completion of the dropwise addition, the temperature was raised to 70°C and stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. It cooled to -50 degreeC, boron tribromide (7.0 g) was added, it heated up to room temperature, and it stirred for 0.5 hours. Then, it cooled to 0 degreeC again, N,N-diisopropylethylamine (3.6g) was added, and after stirring at room temperature until heat generation cooled, it heated up to 80 degreeC, 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 to perform liquid separation. After concentrating the organic layer, a small amount of ethyl acetate was added for dissolution by heating, heptane was added, and after cooling, the precipitated crystal was filtered, and the crystal was washed with cooled heptane. The crystal was purified with a silica gel short column (eluent: toluene). Heptane was added to the obtained crude product, heated and stirred, and then cooled, and the obtained crystals were filtered. Then, it dissolved in toluene, concentrated, and after adding heptane to precipitate crystals, the step of filtering was repeated to obtain compound (1-16) (5.3 g).

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

¹ H-NMR (CDCl ₃ ): δ=1.46 (s, 18H), 1.47 (s, 18H), 1.51-1.54 (m, 9H), 1.62-1.65 (m, 3H), 1.87-1.89 (m, 3H) ), 6.05 (s, 2H), 6.79 (d, 2H), 7.30 (d, 4H), 7.50 (dd, 2H), 7.69 (d, 4H), 8.98 (d, 2H).

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

Under a nitrogen atmosphere, 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, followed by stirring at the same temperature for 4 hours. did. After adding water, sodium carbonate was gradually added until the foaming subsided, and then, sodium hydrogen sulfite was added in an appropriate amount. After washing the organic layer with water, the organic layer was concentrated to obtain a crude product. The crude product was purified with a silica gel short column (eluent: heptane), and the organic layer was concentrated to obtain a crude product. Heptane was added to the crude product, cooled, and filtered to obtain an intermediate (I-F) (44.0 g).

Under nitrogen atmosphere, intermediate (IG) (10.0g), intermediate (IF) (11.8g), Pd-132 (0.26g) as palladium catalyst, sodium-tert-butoxide (NaOtBu, 5.3g) and xylene (70ml) Was put into a flask and heated at 100°C for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution, followed by stirring, and the organic layer was separated and washed with water. Thereafter, heptane was added to the crude product obtained by concentrating the organic layer, followed by cooling, and the obtained crystals were filtered. The crude product was purified with a silica gel short column (eluent: toluene/heptane = 1/1 (volume ratio)), heptane was added to the crude product obtained by concentrating the organic layer, and the resulting crystal was filtered to obtain an intermediate (IH). (10.0 g).

Under nitrogen atmosphere, intermediate (IH) (10.0g), N-(4-tertbutylphenyl)-4-tertbutylaniline (12.8g), bis(dibenzylideneacetone) palladium(0)(Pd(dba) ₂ , 0.24g), dicyclohexyl (2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine (SPhos), sodium-tert-butoxide (NaOtBu, 5.0g) And xylene (80 ml) were put in a flask, and heated at 100°C for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution, followed by stirring, and the organic layer was separated and washed with water. Heptane was added to the crude product obtained by concentrating the organic layer, and after cooling, the obtained crystals were filtered. The crude product was purified with a silica gel short column (eluent: toluene), heptane was added to the crude product obtained by concentrating the organic layer, cooled, and the obtained crystal was filtered to obtain an intermediate (II) (10.2 g).

To a flask containing the intermediate (I-I) (10.0 g) and tert-butylbenzene (70 ml), a 1.56 M pentane solution (13.5 ml) of tert-butyllithium was added at 0°C under a nitrogen atmosphere. After completion of the dropwise addition, the temperature was raised to 70°C and stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. It cooled to -50 degreeC, boron tribromide (5.2 g) was added, and it heated up to room temperature and stirred for 0.5 hours. Then, it cooled to 0 degreeC again, N,N-diisopropylethylamine (2.7g) was added, and after stirring at room temperature until heat generation cooled, it heated up to 80 degreeC, 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, followed by stirring for 1 hour, and the precipitated yellow precipitate was filtered, and the filtrate was washed with methanol, distilled water, and methanol in that order. The yellow precipitate was washed twice with hot heptane, and then further purified with a silica gel short column (eluent: toluene/heptane = 3/7 (volume ratio)). Then, it dissolved in toluene, concentrated, and after adding heptane to precipitate crystals, the step of filtration 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 nitrogen atmosphere, 4-(1-adamantyl)aniline (25.0 g), intermediate (IF) (32.0 g), Pd-132 (0.78 g) as a palladium catalyst, sodium-tert-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, followed by stirring, and the organic layer was separated and washed with water. Thereafter, methanol was added to the crude product obtained by concentrating the organic layer, followed by cooling, and the obtained crystals were filtered. The crude product was purified with a silica gel short column (eluent: toluene), heptane was added to the crude product obtained by concentrating the organic layer, and the resulting crystal was filtered to obtain an intermediate (I-J) (41.0 g).

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

To a flask containing the intermediate (I-L) (13.5 g) and tert-butylbenzene (100 ml), a pentane solution (18.9 ml) of 1.56 M tert-butyllithium was added at 0° C. under a nitrogen atmosphere. After completion of the dropwise addition, the temperature was raised to 70°C and stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. It cooled to -50 degreeC, boron tribromide (7.2g) was added, it heated up to room temperature, and it stirred for 0.5 hours. Then, it cooled to 0 degreeC again, N,N-diisopropylethylamine (3.7 g) was added, and after stirring at room temperature until heat generation cooled, it heated up to 90 degreeC, 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 and stirred for 1 hour, and then heptane was added and the precipitated yellow precipitate was filtered, and the filtrate was methanol, distilled water, and methanol in that order. Washed with. The yellow precipitate was washed with hot toluene, and then further purified with a silica gel short column (eluent: toluene). Then, it dissolved in toluene, concentrated, and after adding heptane to precipitate crystals, the step of filtration was repeated to obtain compound (1-328) (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 nitrogen atmosphere, intermediate (IJ) (5.9 g), intermediate (IM) (6.0 g), Pd-132 (0.10 g) as a palladium catalyst, sodium-tert-butoxide (NaOtBu, 1.9 g) and xylene (30 ml) Was put into a flask and heated at 120°C for 1 hour. After the reaction, water and toluene were added to the reaction solution, followed by stirring, and the organic layer was separated and washed with water. Heptane was added to the crude product obtained by concentrating the organic layer, and after cooling, the obtained crystals were filtered. The crystal was purified with a silica gel short column (eluent: toluene), heptane was added to the crude product obtained by concentrating the eluent, and the resulting crystal was filtered to obtain an intermediate (I-N) (7.0 g).

To a flask containing the intermediate (I-M) (7.0 g) and tert-butylbenzene (60 ml), a 1.56 M pentane solution (11.1 ml) of tert-butyllithium was added at 0°C under a nitrogen atmosphere. After completion of the dropwise addition, the temperature was raised to 70°C and stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. It cooled to -50 degreeC, boron tribromide (4.2 g) was added, the temperature was raised to room temperature, and it stirred for 0.5 hours. Then, it cooled to 0 degreeC again, N,N-diisopropylethylamine (2.2g) was added, and after stirring at room temperature until heat generation cooled, it heated up to 80 degreeC, 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 and stirred for 1 hour, and then after heptane was added, the precipitated yellow precipitate was filtered, and the filtrate was methanol, distilled water, and methanol in that order. Washed with. Further purification was performed with a silica gel short column (eluent: toluene). Then, it dissolved in toluene, concentrated, and after the crystals were precipitated by adding heptane, the step of filtering was repeated to obtain compound (1-327) (3.0 g).

¹ H-NMR (CDCl ₃ ): δ=1.45 (s, 9H), 1.49 (s, 9H), 1.79-1.86 (m, 12H), 2.05-2.10 (m, 12H), 2.15-2.17 (m, 6H) ), 6.11 (d, 1H), 6.13 (d, 1H), 6.74 (d, 2H), 7.24 (t, 2H), 7.28 (d, 2H), 7.30 (d, 2H), 7.47 (dd, 1H) , 7.52 (dd, 1H), 7.64 (dd, 2H), 7.67 (dd, 2H), 9.00 (d, 1H), 9.02 (d, 1H).

Synthesis Example (6): Synthesis of Compound (1-332)

Under nitrogen atmosphere, intermediate (IJ) (6.6 g), intermediate (IO) (5.0 g), Pd-132 (0.11 g) as a palladium catalyst, sodium-tert-butoxide (NaOtBu, 2.2 g) and xylene (35 ml) Was put into a flask and heated at 120°C for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution, followed by stirring, and the organic layer was separated and washed with water. Ethyl acetate was added to the crude product obtained by concentrating the organic layer, and after cooling, the obtained crystals were filtered. The crystal was purified by a silica gel short column (eluent: toluene), heptane was added to the crude product obtained by concentrating the eluent, and the resulting crystal was filtered to obtain an intermediate (I-P) (9.6 g).

To a flask containing the intermediate (I-P) (9.5 g) and tert-butylbenzene (100 ml), a pentane solution (18.9 ml) of 1.56 M tert-butyllithium was added at 0° C. under a nitrogen atmosphere. After completion of the dropwise addition, the temperature was raised to 70°C and stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. It cooled to -50 degreeC, boron tribromide (7.2g) was added, it heated up to room temperature, and it stirred for 0.5 hours. Then, it cooled to 0 degreeC again, N,N-diisopropylethylamine (3.7 g) was added, and after stirring at room temperature until heat generation cooled, it heated up to 80 degreeC, 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, followed by ethyl acetate, and stirred for 1 hour, and then the organic layer was separated. After the organic solvent was removed in midstream, it was purified by silica gel short column (eluent: toluene/heptane = 2/8 (volume ratio)). Then, it dissolved in toluene, concentrated, and after adding heptane to precipitate crystals, the step of filtration was repeated to obtain compound (1-332) (3.8 g).

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

¹ H-NMR (CDCl ₃ ): δ=1.81-1.87 (m, 12H), 2.05-2.07 (m, 12H), 2.16-2.17 (m, 6H), 6.09 (d, 1H), 6.16 (d, 1H) ), 6.75 (dd, 2H), 7.23-7.31 (m, 6H), 7.39 (d, 2H), 7.43 (dt, 1H), 7.50 (dd, 1H), 7.59 (dt, 1H), 7.65 (dd, 2H), 7.69 (t, 2H), 8.88 (d, 1H), 8.93 (d, 1H).

Synthesis Example (7): Synthesis of Compound (1-334)

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

Under nitrogen atmosphere, intermediate (IQ) (8.0 g), intermediate (IK) (8.9 g), Pd-132 (0.14 g) as a palladium catalyst, sodium-tert-butoxide (NaOtBu, 2.8 g) and xylene (40 ml) Was put into a flask and heated at 120°C for 1 hour. After the reaction, water and toluene were added to the reaction solution, followed by stirring, and the organic layer was separated and washed with water. Heptane was added to the crude product obtained by concentrating the organic layer, and after cooling, the obtained crystals were filtered. The crystal was purified with a silica gel short column (eluent: toluene), heptane was added to the crude product obtained by concentrating the organic layer, and the resulting crystal was filtered to obtain an intermediate (I-R) (13.0 g).

To a flask containing the intermediate (I-R) (13.0 g) and tert-butylbenzene (100 ml), a pentane solution (20.9 ml) of 1.56 M tert-butyllithium was added at 0° C. under a nitrogen atmosphere. After completion of the dropwise addition, the temperature was raised to 70°C and stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. It cooled to -50 degreeC, boron tribromide (7.9 g) was added, the temperature was raised to room temperature, and it stirred for 0.5 hours. Then, it cooled again to 0 degreeC, N,N-diisopropylethylamine (4.1 g) was added, and after stirring at room temperature until heat generation cooled, it heated up to 90 degreeC, and heated and stirred for 1 hour. The reaction solution was cooled to room temperature, an aqueous sodium acetate solution cooled with an ice bath, followed by ethyl acetate, and stirred for 1 hour, and the organic layer was separated by liquid separation. After the organic solvent was removed in midstream, it was purified with a silica gel short column (eluent: toluene). Then, it dissolved in toluene, concentrated, and the step of filtration after adding ethyl acetate to precipitate crystals was repeated to obtain compound (1-334) (7.2 g).

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

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

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

Under nitrogen atmosphere, 2,3-dichloroaniline (10.0g), 4-cyclohexylbromobenzene (36.9g), Pd-132 (0.44g) as a palladium catalyst, sodium-tert-butoxide (NaOtBu, 14.8g) And xylene (120 ml) were put into a flask, and heated at 120° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution, followed by stirring, and 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 a sol mix (A-11) was added to the crude product obtained by concentrating the eluent, followed by cooling. The crystal was filtered to obtain an intermediate (IS) (25.5 g).

Under nitrogen atmosphere, N-(4-tertbutylphenyl)-4-tertbutylaniline (4.5g), intermediate (IS) (36.9g), Pd-132 (0.11g) as a palladium catalyst, sodium-tert-butoxide (NaOtBu, 2.3 g) and xylene (35 ml) were put into a flask and heated at 120° C. for 1 hour. After the reaction, water and ethyl acetate were added to the reaction solution, followed by stirring, and 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 was added to the crude product obtained by concentrating the eluent, and the resulting crystal was filtered to obtain an intermediate (I-T) (10.5 g).

To a flask containing the intermediate (I-T) (10.5 g) and tert-butylbenzene (100 ml), a pentane solution (19.1 ml) of 1.56 M tert-butyllithium was added at 0° C. under a nitrogen atmosphere. After completion of the dropwise addition, the temperature was raised to 70°C and stirred for 1 hour, and then a component having a lower boiling point than tert-butylbenzene was distilled off under reduced pressure. It cooled to -50 degreeC, boron tribromide (7.2 g) was added, and it heated up to room temperature, and stirred for 0.5 hours. Then, it cooled to 0 degreeC again, N,N-diisopropylethylamine (3.7 g) was added, and after stirring at room temperature until heat generation cooled, it heated up to 80 degreeC, and heated and stirred for 1 hour. The reaction solution was cooled to room temperature, an aqueous sodium acetate solution cooled with an ice bath, and then ethyl acetate was added, followed by stirring for 1 hour, then heptane was added, and the precipitated yellow precipitate was filtered. The obtained precipitate was purified by silica gel short column (eluent: toluene). Thereafter, it was dissolved in toluene, concentrated, ethyl acetate was added, heptane was added to precipitate crystals, and then the step of filtration was repeated to obtain compound (1-339) (5.3 g).

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

¹ H-NMR (CDCl ₃ ): δ=1.25-1.64 (m, 28H), 1.79-1.81 (m, 2H), 1.89-1.93 (m, 4H), 2.03-2.07 (m, 4H), 2.61-2.70 (m, 2H), 6.12(t, 2H), 6.71(d, 1H), 6.74(d, 1H), 7.22-7.30(m, 6H), 7.48-7.53(m, 3H), 7.67(d, 2H) ), 8.83 (d, 1H), 8.99 (d, 1H).

By appropriately changing the compound of the raw material, another polycyclic aromatic compound of the present invention can be synthesized by a method similar to the synthesis example described above.

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

<Evaluation of deposition type organic EL device>

An organic EL device according to Example 1, Examples 2 to 3, and Examples 4 to 28 was fabricated, and the voltage (V), emission wavelength (nm), and external quantum efficiency (%), which are characteristics at 1000 cd/m ² light emission. Was measured, and then, the time to maintain the luminance of 90% or more of the initial luminance when driven at a constant current at a current density of 10 mA/cm ² was measured.

The quantum efficiency of the light emitting device includes internal quantum efficiency and external quantum efficiency, but the internal quantum efficiency represents a ratio at which external energy injected as electrons (or holes) into the light emitting layer of the light emitting device is purely converted into photons. On the other hand, the external quantum efficiency is calculated based on the amount of this photon emitted to the outside of the light emitting element, and a part of the photon generated in the light emitting layer is absorbed or continuously reflected inside the light emitting element. Since it is not emitted, the external quantum efficiency becomes lower than the internal quantum efficiency.

The method of measuring the external quantum efficiency is as follows. Using the voltage/current generator R6144 manufactured by Advanteist, the device was emitted by applying a voltage such that the luminance of the device was 1000 cd/m ² . Using a spectroradiometer SR-3AR manufactured by TOPCON, the spectral radiance of the visible light region was measured from the direction perpendicular to the light-emitting surface. Assuming that the light emitting surface is a fully diffused surface, the value of the measured spectral radiance of each wavelength component divided by the wavelength energy and multiplied by π is the number of photons at each wavelength. Next, the number of photons was accumulated over the entire observed wavelength range to obtain the total number of photons emitted from the device. External quantum efficiency is obtained by dividing the applied current value by the small charge as the number of carriers injected into the device, and dividing the total number of photons emitted from the device by the number of carriers injected into the device.

<Example 1>

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

[Table 1A]

[Table 1B]

In Table 1A, and "HI" is N ^4, N ^{4 '-} diphenyl -N ^4, N ^4' - bis (9-phenyl -9H- carbazole-3-yl) [1,1'-biphenyl ]-4,4'-diamine, "HAT-CN" is 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile, "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, "HT-2" is N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1"-terphenyl]-4-amine And "BH-1" is 2-(10-phenylanthracene-9-yl)naphtho[2,3-b]benzofuran, and "ET-1" is 4,6,8,10-tetraphenyl[ 1,4]benzoxabolinino[2,3,4-kl]phenoxabolinine, and "ET-2" is 3,3'-((2-phenylanthracene-9,10-diyl)bis(4 ,1-phenylene))bis(4-methylpyridine) The chemical structure is shown below together with "Liq".

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

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

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

<Examples 2 and 3>

The material constitution of each layer and EL characteristic data in the organic EL devices according to Examples 2 and 3 are shown in Tables 2A and 2B below.

[Table 2A]

[Table 2B]

<Example 2>

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

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

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

<Example 3>

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

<Examples 4 to 28>

The material configuration and EL characteristic data of each layer in the organic EL device according to Examples 4 to 28 are shown in Tables 3A and 3B below.

[Table 3A]

[Table 3B]

<Example 4>

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

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

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

<Examples 5 to 28>

An organic EL device was manufactured by the method according to Example 4 (Table 3A), and EL characteristics were measured (Table 3B).

<Evaluation of coated organic EL device>

Next, an organic EL device obtained by coating and forming an organic layer will be described.

<Polymer host compound: Synthesis of SPH-101>

SPH-101 was synthesized according to the method described in International Publication No. 2015/008851. Next to M1, a copolymer in which M2 or M3 is bonded is obtained, and each unit is estimated to be 50:26:24 (molar ratio) from the input ratio.

<Polymer hole transport compound: Synthesis of XLP-101>

XLP-101 was synthesized according to the method described in Japanese Patent Application Laid-Open No. 2018-61028. Next to M7, a copolymer in which M2 or M3 is bonded is obtained, and each unit is estimated to be 40:10:50 (molar ratio) from the input ratio.

<Examples 29-37>

A coating-type organic EL device is prepared by preparing a coating solution for the material forming each layer.

<Production of organic EL devices of Examples 29 to 31>

Table 4 shows the material configuration of each layer in the organic EL device.

[Table 4]

In Table 4, the structure of "ET1" is shown below.

<Preparation of the light-emitting layer-forming composition (1)>

The composition for forming a light emitting layer (1) is prepared by stirring the following components until a uniform solution is obtained. The prepared composition for forming a light-emitting layer is spin-coated on a glass substrate and then dried by heating under reduced pressure to obtain a coating film having no film defects and excellent smoothness.

Compound (A) 0.04% by weight

SPH-101 1.96% by weight

xylene 69.00% by weight

Decalin 29.00% by weight

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

<PEDOT:PSS solution>

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

<Preparation of OTPD solution>

OTPD (LT-N159, manufactured by Luminescence Technology Corp) and IK-2 (optical cation (cation) polymerization initiator, manufactured by San Apro) were dissolved in toluene, and the OTPD concentration was 0.7% by weight and the IK-2 concentration was 0.007% by weight. Prepare the OTPD solution.

<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% by weight PCz solution.

<Example AB1>

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

The produced multilayer film is fixed to the substrate holder of a commercially available evaporation apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum evaporation boat containing ET1, a molybdenum evaporation boat containing LiF, and a tungsten evaporation boat containing aluminum. Mount the boat. After reducing the pressure in the vacuum bath to 5 × 10 ^-4 Pa, ET1 is heated to evaporate to a thickness of 30 nm to form an electron transport layer. The deposition rate at the time of forming the electron transport layer is 1 nm/sec. Thereafter, LiF is heated to evaporate at a deposition rate of 0.01 to 0.1 nm/sec so that the film thickness becomes 1 nm. Next, aluminum is heated and deposited to a film thickness of 100 nm to form a cathode. In this way, an organic EL device is obtained.

<Example 30>

An organic EL device was obtained in the same manner as in Example 29. Then, the hole transport layer is spin-coated with the XLP-101 solution and fired on a hot plate at 200° C. for 1 hour to form a film having a thickness of 30 nm.

<Example 31>

An organic EL device was obtained in the same manner as in Example 29. Then, the hole transport layer is spin-coated with a PCz solution and fired on a hot plate at 120° C. for 1 hour to form a film having a thickness of 30 nm.

<Production of organic EL devices of Examples 32 to 34>

Table 5 shows the material configuration of each layer in the organic EL device.

[Table 5]

<Preparation of composition for light emitting layer formation (2) to (4)>

The composition for forming a light-emitting layer (2) is prepared by stirring the following components until a uniform solution is obtained.

Compound (A) 0.02% by weight

mCBP 1.98% by weight

toluene 98.00% by weight

The composition for light-emitting layer formation (3) is prepared by stirring the following components until a uniform solution is obtained.

Compound (A) 0.02% by weight

SPH-101 1.98% by weight

xylene 98.00% by weight

The composition for light-emitting layer formation (4) is prepared by stirring the following components until a uniform solution is obtained.

Compound (A) 0.02% by weight

DOBNA 1.98% by weight

toluene 98.00% by weight

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

<Example 32>

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

The produced multilayer film is fixed to the substrate holder of a commercially available evaporation apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum evaporation boat containing TSPO1, a molybdenum evaporation boat containing LiF, and a tungsten evaporation boat containing aluminum. Mount the boat. After reducing the pressure in the vacuum bath to 5 × 10 ^-4 Pa, TSPO1 is heated to evaporate to a thickness of 30 nm to form an electron transport layer. When forming the electron transport layer, the deposition rate is 1 nm/sec. Thereafter, LiF is heated to evaporate at a deposition rate of 0.01 to 0.1 nm/sec so that the film thickness becomes 1 nm. Next, aluminum is heated and deposited to a film thickness of 100 nm to form a cathode. In this way, an organic EL device is obtained.

<Examples 33 and 34>

An organic EL device was obtained in the same manner as in Example 32 using the light emitting layer-forming composition (3) or (4).

<Production of organic EL devices of Examples 35 to 37>

Table 6 shows the material configuration of each layer in the organic EL device.

[Table 6]

<Preparation of composition for light emitting layer formation (5) to (7)>

The composition for forming a light-emitting layer is prepared by stirring the following components until a uniform solution is obtained.

Compound (A) 0.02% by weight

2PXZ-TAZ 0.18% by weight

mCBP 1.80% by weight

toluene 98.00% by weight

The composition for forming a light-emitting layer is prepared by stirring the following components until a uniform solution is obtained.

Compound (A) 0.02% by weight

2PXZ-TAZ 0.18% by weight

SPH-101 1.80% by weight

xylene 98.00% by weight

The composition for forming a light-emitting layer is prepared by stirring the following components until a uniform solution is obtained.

Compound (A) 0.02% by weight

2PXZ-TAZ 0.18% by weight

DOBNA 1.80% by weight

toluene 98.00% by weight

In Table 6, "2PXZ-TAZ" is 10,10'-((4-phenyl-4H-1,2,4-triazole-3,5-diyl))bis(4,1-phenyl))bis (10H-phenoxazine). The chemical structure is shown below.

<Example 35>

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

The produced multilayer film is fixed to the substrate holder of a commercially available evaporation apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum evaporation boat containing TSPO1, a molybdenum evaporation boat containing LiF, and a tungsten evaporation boat containing aluminum. Mount the boat. After reducing the pressure in the vacuum bath to 5 × 10 ^-4 Pa, TSPO1 is heated to evaporate to a thickness of 30 nm to form an electron transport layer. When forming the electron transport layer, the deposition rate is 1 nm/sec. Thereafter, LiF is heated to evaporate at a deposition rate of 0.01 to 0.1 nm/sec so that the film thickness becomes 1 nm. Next, aluminum is heated and deposited to a film thickness of 100 nm to form a cathode. In this way, an organic EL device is obtained.

<Examples 36 and 37>

An organic EL device was obtained in the same manner as in Example 35 using the light-emitting layer-forming composition (6) or (7).

[Industrial availability]

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

100: organic electroluminescent device
101: substrate
102: anode
103: hole injection layer
104: hole transport layer
105: light emitting layer
106: electron transport layer
107: electron injection layer
108: cathode

Claims (33)

A polycyclic aromatic compound represented by the following general formula (1), or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1):

(In the above formula (1),
Ring A, ring B, and ring C are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted,
Y ¹ is B, P, P=O, P=S, Al, Ga, As, Si-R or Ge-R, and R of Si-R and Ge-R is aryl or alkyl,
X ¹ and X ² are each independently >O, >NR, >C(-R) ₂ , >S or >Se, and R of >NR is optionally substituted aryl, optionally substituted heteroaryl, substituted Alkyl which may be substituted or cycloalkyl which may be substituted, R of >C(-R) ₂ is hydrogen, aryl which may be substituted or alkyl, and R of >NR and >C(-R) ₂ At least one of R of may be bonded to at least one of the A ring, B ring and C ring by a linking group or a single bond,
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). The method of claim 1,
Ring A, Ring B, and Ring C are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted dia Rylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (two aryls may be bonded through a single bond or a linking group), substituted or It may be substituted with unsubstituted alkyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted aryloxy, and these rings are condensed bicyclic structures in the center of the above formula (1) consisting of Y ¹ , X ¹ and X ² Has a 5- or 6-membered ring that shares a bond with,
Y ¹ is B, P, P=O, P=S, Al, Ga, As, Si-R or Ge-R, and R of Si-R and Ge-R is aryl or alkyl,
X ¹ and X ² are each independently >O, >NR, >C(-R) ₂ , >S or >Se, and R of >NR may be substituted with aryl or alkyl which may be substituted with alkyl. Is heteroaryl, alkyl or cycloalkyl, wherein R of >C(-R) ₂ is aryl or alkyl optionally substituted with hydrogen or alkyl, and R of >NR and of >C(-R) ₂ At least one of R may be bonded to at least one of ring A, ring B, and ring C by a single bond -O-, -S-, -C(-R) _2- ) ₂ -of R 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 two or three structures represented by general formula (1), and,
At least one hydrogen in the compound or structure represented by formula (1) is substituted with cycloalkyl,
Polycyclic aromatic compounds or multimers thereof. The method of claim 1,
Polycyclic aromatic compound represented by the following general formula (2):

(In the above formula (2),
R ¹ to R ¹¹ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be bonded through a single bond or a linking group) , Alkyl, alkoxy or aryloxy, and at least one hydrogen in these may be substituted with aryl, heteroaryl or alkyl, and adjacent groups of R ¹ to R ¹¹ are bonded to each other to form a ring, b ring, or c An aryl ring or heteroaryl ring may be formed together with the ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, and diarylboryl (two aryls are May be bonded through a single bond or a linking group), alkyl, alkoxy, or aryloxy may be substituted, and at least one hydrogen in these may be substituted with aryl, heteroaryl or alkyl,
Y ¹ is B, P, P=O, P=S, Al, Ga, As, Si-R or Ge-R, wherein R of Si-R and Ge-R is an aryl or carbon number of 6 to 12 carbon atoms It is 1-6 alkyl,
X ¹ and X ² are each independently >O, >NR, >C(-R) ₂ , >S or >Se, and R of >NR is a C6-C12 aryl, a C2-C15 heteroaryl , C1-C6 alkyl or C3-C14 cycloalkyl, wherein R of >C(-R) ₂ is hydrogen, C6-C12 aryl or C1-C6 alkyl, and >NR R and at least one of R of >C(-R) ₂ is -O-, -S-, -C(-R) ₂ -or at least one of the a ring, b ring and c ring by a single bond May be bonded, and R of -C(-R) ₂ -is alkyl having 1 to 6 carbon atoms,
At least one hydrogen in the compound represented by formula (2) may be substituted with deuterium, cyano, or halogen, and,
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl). The method of claim 3,
R ¹ to R ¹¹ are each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (however, aryl is an aryl having 6 to 12 carbon atoms), diaryl boryl (however, aryl is a carbon number 6 to 12 aryl, two aryl may be bonded through a single bond or a linking group) or alkyl having 1 to 24 carbon atoms, and adjacent groups of R ¹ to R ¹¹ are bonded to each other to form a ring, b ring, or With the c ring, an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms may be formed, and at least one hydrogen in the formed ring is substituted with an aryl having 6 to 10 carbon atoms or an alkyl having 1 to 12 carbon atoms May be,
Y ¹ is B, P, P=O, P=S or Si-R, and R of Si-R is a C6-C10 aryl or C1-C4 alkyl,
X ¹ and X ² are each independently >O, >NR, >C(-R) ₂ or >S, and R of >NR is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or 5 to carbon atoms 10 cycloalkyl, 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 represented by formula (2) may be substituted with deuterium, cyano, or halogen, and,
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl, a polycyclic aromatic compound. The method of claim 3,
R ¹ to R ¹¹ are each independently hydrogen, a C 6 to C 16 aryl, a C 2 to C 20 heteroaryl, a diarylamino (however, aryl is a C 6 to C 10 aryl) or a C 1 to C 12 alkyl,
Y ¹ is B, P, P=O or P=S,
X ¹ and X ² are each independently >O, >NR, or >C(-R) ₂ , and R of >NR is a C6-C10 aryl, a C1-C4 alkyl, or a C5-C10 cyclo Alkyl, and 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, a polycyclic aromatic compound. The method of claim 3,
R ¹ to R ¹¹ are each independently hydrogen, aryl having 6 to 16 carbon atoms, diarylamino (however, aryl is an 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 >NR, or, X ¹ is >NR and X ² is >O, and R of >NR is an aryl having 6 to 10 carbon atoms, an alkyl having 1 to 4 carbon atoms, or 5 to 10 carbon atoms Is a cycloalkyl of, and,
At least one hydrogen in the compound represented by formula (2) is substituted with cycloalkyl, a polycyclic aromatic compound. The method according to any one of claims 1 to 6,
A polycyclic aromatic compound or a multimer thereof substituted with a diarylamino group substituted with a cycloalkyl, a carbazolyl group substituted with a cycloalkyl, or a benzocarbazolyl group substituted with a cycloalkyl. The method according to any one of claims 3 to 6,
R ² is a diarylamino group substituted with a cycloalkyl or a carbazolyl group substituted with a cycloalkyl, a polycyclic aromatic compound. The method according to any one of claims 1 to 8,
The cycloalkyl is a C3-C20 cycloalkyl, a polycyclic aromatic compound. The method according to any one of claims 1 to 9,
The halogen is fluorine, a polycyclic aromatic compound or a multimer thereof. The method of claim 1,
Polycyclic aromatic compound represented by any one of the following structural formulas:

("Me" in each of the above structural formulas represents a methyl group, and "tBu" represents a tert-butyl group). A reactive compound in which a reactive substituent is substituted with the polycyclic aromatic compound according to any one of claims 1 to 11 or a multimer thereof. A polymer compound obtained by polymerizing the reactive compound according to claim 12 as a monomer, or a crosslinked polymer obtained by crosslinking the polymer compound further. A pendant polymer compound obtained by substituting the reactive compound according to claim 12 for a main chain polymer, or a pendant polymer crosslinked product obtained by further crosslinking the pendant polymer compound. A material for organic devices containing the polycyclic aromatic compound according to any one of claims 1 to 11 or a multimer thereof. A material for organic devices containing the reactive compound according to claim 12. A material for organic devices containing the polymer compound or polymer crosslinked product according to claim 13. An organic device material containing the pendant polymer compound or crosslinked pendant polymer according to claim 14. The method according to any one of claims 15 to 18,
The material for organic devices, wherein the material for organic devices is a material for an organic electroluminescent device, a material for an organic field effect transistor, or a material for an organic thin film solar cell. The method of claim 19,
The material for an organic device, wherein the material for an organic electroluminescent device is a material for a light emitting layer. An ink composition comprising the polycyclic aromatic compound according to any one of claims 1 to 11 or a multimer thereof, 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 polymer crosslinked product according to claim 13 and an organic solvent. An ink composition comprising the pendant polymer compound or crosslinked pendant polymer according to claim 14 and an organic solvent. A pair of electrodes consisting of an anode and a cathode, and disposed between the pair of electrodes, the polycyclic aromatic compound according to any one of claims 1 to 11 or a multimer thereof, the reactive compound according to claim 12, An organic electroluminescent device having an organic layer containing the polymer compound or crosslinked polymer according to claim 13, or the pendant polymer compound or crosslinked pendant polymer according to claim 14. A pair of electrodes consisting of an anode and a cathode, and disposed between the pair of electrodes, the polycyclic aromatic compound according to any one of claims 1 to 11 or a multimer thereof, the reactive compound according to claim 12, An organic electroluminescent device having a light emitting layer containing the polymer compound or crosslinked polymer according to claim 13, or the pendant polymer compound or crosslinked pendant polymer according to claim 14. The method of claim 27,
The organic electroluminescent device, wherein the light-emitting layer comprises a host and the polycyclic aromatic compound as a dopant, a multimer thereof, a reactive compound, a polymer compound, a polymer crosslinked product, a pendant polymer compound, or a pendant polymer crosslinked product. The method of claim 28,
The organic electroluminescent device, wherein the host is an anthracene compound, a fluorene compound, or a dibenzochrysene compound. The method according to any one of claims 26 to 29,
Having an electron transport layer and/or an electron injection layer disposed between the cathode and the light emitting layer, at least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, a fluoranthene derivative, a BO-based derivative, an anthracene derivative , Benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol-based metal complexes containing at least one selected from the group consisting of , Organic electroluminescent device. The method of claim 30,
The electron transport layer and/or the electron injection layer is an alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal oxide, An organic electroluminescent device further comprising at least one selected from the group consisting of a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. The method according to any one of claims 26 to 31,
At least one of the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer and the electron injection layer is a polymer compound obtained by polymerizing a low molecular compound capable of forming each layer as a monomer, or a polymer compound obtained by crosslinking the polymer compound. Organic electroluminescence comprising a polymer crosslinked product, a pendant polymer compound obtained by reacting a low molecular compound capable of forming each layer with a main chain polymer, or a pendant polymer crosslinked product obtained by crosslinking the pendant polymer compound device. A display device or a lighting device comprising the organic electroluminescent device according to any one of claims 26 to 32.

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