KR20190090333A - Organic electroluminescent element - Google Patents

Abstract

상기 식(2) 중, 피렌 부분의 적어도 1개의 수소는, 탄소수 6∼10의 아릴 등으로 치환되어 있어도 되고, Ar은 탄소수 14∼40의 아릴 또는 탄소수 12∼40의 헤테로아릴이며, 이들은 탄소수 6∼10의 아릴 등으로 치환되어 있어도 되고, s 및 p는 각각 독립적으로 1 또는 2의 정수이며, s 및 p는 동시에 2가 되지는 않으며, 식(2)으로 표시되는 화합물에서의 적어도 1개의 수소는, 각각 독립적으로, 할로겐, 시아노 또는 중수소로 치환되어 있어도 된다.An object of the present invention is to provide an organic EL device exhibiting excellent luminous efficiency and good balance. According to the present invention, a polycyclic aromatic compound having a pyrene-based compound represented by the following formula (2) as a host material and a plurality of aromatic rings linked with a boron atom and a nitrogen atom or an oxygen atom is used as a dopant ) Material for a light emitting layer is used to manufacture an organic EL device, for example, an organic EL device having excellent light emitting efficiency.

Ar represents an aryl group having from 14 to 40 carbon atoms or a heteroaryl group having from 12 to 40 carbon atoms, which may have a carbon number of 6 And s and p are each independently an integer of 1 or 2, s and p are not simultaneously divalent, and at least one hydrogen in the compound represented by the formula (2) May be independently substituted with halogen, cyano or deuterium.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic electroluminescent device,

The present invention relates to an organic electroluminescent device having a luminescent layer containing a polycyclic aromatic compound as a dopant material and a specific pyrene compound as a host material, and a display device and a lighting device using the organic electroluminescent device.

Conventionally, a display device using electroluminescent light emitting elements has been studied in various ways because of being capable of power saving and thinning, and an organic electroluminescent element (hereinafter referred to as an organic EL element) made of an organic material is lightweight and easy to enlarge Has been studied actively. In particular, the development of an organic material having light emission characteristics such as blue, which is one of the three primary colors of light, and a combination of a plurality of materials exhibiting optimal light emission characteristics have been actively studied regardless of a polymer compound or a low molecular compound.

The organic EL element has a structure comprising a pair of electrodes composed of an anode and a cathode, and a layer or a plurality of layers arranged between the pair of electrodes and containing an organic compound. The layer containing an organic compound includes a light-emitting layer, a charge transporting / injecting 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, benzofluorene-based compounds and the like have been developed (WO 2004/061047). As the hole transporting material, for example, triphenylamine-based compounds and the like have been developed (JP-A-2001-172232). As an electron transporting material, for example, an anthracene-based compound has been developed (JP-A-2005-170911).

Recently, compounds having boron or the like as a central atom and condensing a plurality of aromatic rings have also been reported (International Publication No. 2015/102118). In this document, a compound condensed with a plurality of aromatic rings is selected as a dopant material of the light emitting layer, and an organic EL element (hereinafter, referred to as " organic EL element " Evaluation has been carried out. However, the combinations other than the above are not specifically verified. Further, since the luminescent characteristics are different when the combination constituting the light emitting layer is different, the characteristics obtained from other combinations are not yet known.

International Publication No. 2004/061047 Japanese Patent Application Laid-Open No. 2001-172232 Japanese Patent Application Laid-Open No. 2005-170911 International Publication No. 2015/102118

As described above, various materials used as organic EL devices have been developed. However, in order to further improve the luminescent characteristics or to increase the choice of materials for the light-emitting layer, development of a material combination different from the conventional one is desired. In particular, the organic EL characteristics (specifically, the optimum luminescence characteristics) obtained from a specific combination of the host and the dopant reported in the examples of Patent Document 4 are not known.

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive investigations to solve the above-mentioned problems. As a result of intensive studies, the present inventors have found that a pair of aromatic rings containing a boron atom and a nitrogen atom or a polycyclic aromatic compound, It has been found that an excellent organic EL element can be obtained by arranging the organic EL element between the electrodes, and the present invention has been accomplished.

According to a preferred embodiment of the present invention, it is possible to provide a compound represented by the formula (2) in which the compound represented by the formula (1) and the compound represented by the formula Thereby producing an organic EL device excellent in at least one of chromaticity, driving voltage and quantum efficiency.

Section 1.

An organic electroluminescent device comprising a pair of electrodes made of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes,

Wherein the light emitting layer comprises at least one of a compound represented by the following general formula (1) and a multimer having a plurality of structures represented by the following general formula (1), at least one of the pyrene compounds represented by the following general formula (2) Organic electroluminescent device.

In the above formula (1)

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

X ¹ and X ² are each independently> O or> NR, and R in the> NR is optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted cycloalkyl, The R of> NR may be bonded to the A ring, B ring and / or C ring by a linking group or a single bond,

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

In the above formula (2)

the s pyrene portions and the p Ar portions join at any one of the positions of the pyrene portion * and the Ar portion,

At least one hydrogen of the pyrene moiety is independently selected from the group consisting of aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, , Alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, and at least one hydrogen in these groups is independently selected from the group consisting of aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or aryloxy having 6 to 30 carbon atoms,

Ar is independently an aryl having from 14 to 40 carbon atoms or a heteroaryl having from 12 to 40 carbon atoms, and at least one hydrogen in these is independently selected from the group consisting of aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms , Alkyl of 1 to 30 carbon atoms, cycloalkyl of 3 to 24 carbon atoms, alkenyl of 2 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, or aryloxy of 6 to 30 carbon atoms,

s and p are each independently an integer of 1 or 2, s and p are not simultaneously divalent, and when s is 2, the two pyrene moieties may be structurally identical or different, including substituents, , when p is 2, the two Ar moieties may be structurally identical or different, including substituents,

The at least one hydrogen in the compound represented by the formula (2) may be independently substituted with halogen, cyano or deuterium.

Section 2.

The organic electroluminescent device according to item 1, wherein each of Ar 1 s is independently a group represented by the following formula (Ar-1) or (Ar-2)

In the above formulas,

Z is > CR ₂ , > NR, > O or > S,

And R < ₂ > in CR < ₂ > each independently represent an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, an aryl having 6 to 12 carbon atoms, or a heteroaryl having 2 to 12 carbon atoms, At least one hydrogen may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, R may be bonded to each other to form a ring,

> NR in NR is alkyl of 1 to 4 carbon atoms, cycloalkyl of 5 to 10 carbon atoms, aryl of 6 to 12 carbon atoms, or heteroaryl of 2 to 12 carbon atoms, and at least one hydrogen in the aryl and heteroaryl is An alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms,

R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ each independently represent hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, Alkoxy having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, at least one of which may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms , Adjacent groups of R ¹ to R ⁸ or adjacent groups of R ¹⁰ to R ¹⁹ may be bonded to each other to form a condensed ring, and the formed rings may each independently be an aryl group having 6 to 10 carbon atoms, Cycloalkyl having 3 to 24 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, or aryloxy having 6 to 30 carbon atoms may be substituted with a heteroaryl group having 1 to 11 carbon atoms, Is at least one hydrogen of 1 to 6 carbon atoms or an alkyl of 3 to 14 carbon atoms Optionally substituted by a cycloalkyl, and, and,

At least one hydrogen in the group represented by the formula (Ar-1) or (Ar-2) may be independently substituted with halogen, cyano or deuterium,

In the formula (2), the pyrene moiety is bonded at any position among the groups represented by the formula (Ar-1) or (Ar-2).

Section 3.

The organic electroluminescent device according to item 1 or 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (1 ').

(In the above formula (1 '),

R ¹ to R ¹¹ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, wherein at least one hydrogen May be independently substituted with aryl, heteroaryl, alkyl or cycloalkyl, and adjacent groups of R ¹ to R ¹¹ may be bonded to form a ring, b or c ring to form an aryl or heteroaryl ring And at least one hydrogen in the ring formed is independently selected from the group consisting of aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy substitution And at least one hydrogen in these may be independently substituted with aryl, heteroaryl, alkyl or cycloalkyl,

X ¹ and X ² are each independently> O or> NR, and> R in the above NR is an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms Alkyl, and at least one hydrogen in the aryl or heteroaryl may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and R of> NR is -O-, -S- , -C (-R) ₂ - or a single bond, and R in the -C (-R) ₂ - may be an alkyl having 1 to 6 carbon atoms or a carbon Cycloalkyl of 3 to 14 carbon atoms,

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

Section 4.

Wherein Ar is independently any one of the following formulas (Ar-1-1) to (Ar-1-12) and (Ar-2-1) to (Ar-2-4) The organic electroluminescent device according to any one of items 1 to 3, which is represented by one.

In the above formulas,

Z is > CR ₂ , > NR, > O or > S,

> R in CR ₂ is independently an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, or an aryl having 6 to 12 carbon atoms, R may be bonded to each other to form a ring,

> R in N-R is alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, or aryl having 6 to 12 carbon atoms,

At least one hydrogen in the groups represented by the above formulas is independently selected from the group consisting of aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms or cycloalkyl having 3 to 24 carbon atoms And,

At least one hydrogen in the groups represented by the above-mentioned formulas may be independently substituted with halogen, cyano or deuterium,

In the formula (2), the pyrene moiety is represented by any one of the formulas (Ar-1-1) to (Ar-1-12) and (Ar-2-1) to (Ar-2-4) Lt; RTI ID = 0.0 > position. ≪ / RTI >

Item 5.

The organic electroluminescent device according to any one of items 1 to 4, wherein the pyrene compound represented by the general formula (2) is a compound represented by any one of the following structural formulas.

Section 6.

Wherein at least one of the electron transport layer and the electron injection layer has a structure selected from the group consisting of a borane derivative, a pyridine derivative, a fluoranthene derivative, a BO-based derivative, an anthracene derivative At least one selected from the group consisting of a benzotriazole derivative, a benzofluorene derivative, a phosphine oxide derivative, a pyrimidine derivative, a carbazole derivative, a triazine derivative, a benzimidazole derivative, a phenanthroline derivative, To < RTI ID = 0.0 > 1, < / RTI >

Item 7.

Wherein the electron-transporting layer and / or the electron-injecting layer is made of a material selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metal oxides, alkaline earth metal halides, The organic electroluminescent device according to item 6, 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.

Section 8.

A display device comprising the organic electroluminescent device described in any one of items 1 to 7.

Section 9.

A lighting device comprising the organic electroluminescent device according to any one of items 1 to 7.

Item 10.

A pyrene-based compound represented by the following general formula (2).

Wherein,

the s pyrene portions and the p Ar portions join at any one of the positions of the pyrene portion * and the Ar portion,

At least one hydrogen in the pyrene moiety is independently selected from the group consisting of aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, , Alkoxy having 1 to 30 carbon atoms or aryloxy having 1 to 30 carbon atoms, and at least one hydrogen in these may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms,

Ar is a group represented by the following formula (Ar-1) or (Ar-3)

In the above formulas,

Z is > CR ₂ ,

And R < ₂ > in CR < ₂ > each independently represent an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, an aryl having 6 to 12 carbon atoms, or a heteroaryl having 2 to 12 carbon atoms, At least one hydrogen may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, R may be bonded to each other to form a ring,

R ¹ to R ⁸ and R ²⁰ to R ³⁵ each independently represent hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, Alkoxy having 1 to 30 carbon atoms, aryloxy having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, or aryloxy having 1 to 30 carbon atoms, wherein at least one hydrogen may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms , Adjacent groups of R ¹ to R ^{8 may} combine with each other to form a condensed ring, adjacent groups of R ²⁰ to R ³⁵ may be bonded to each other to form a condensed ring, and the formed rings may each independently have a carbon number Aryl having 6 to 10 carbons, heteroaryl having 2 to 11 carbons, alkyl having 1 to 30 carbons, cycloalkyl having 3 to 24 carbons, alkenyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons or aryl having 1 to 30 carbons Oxy, and at least one hydrogen in these may be substituted with carbon An alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms,

s and p are each independently an integer of 1 or 2, s and p are not simultaneously divalent, and when s is 2, the two pyrene moieties may be structurally identical or different, including substituents, , when p is 2, two Ar moieties may be structurally identical or different, including substituents,

The at least one hydrogen in the compound represented by the formula (2) may be independently substituted with halogen, cyano or deuterium.

Section 11.

The pyrene-based compound according to item 10, represented by any one of the following structural formulas.

According to a preferred embodiment of the present invention, a polycyclic aromatic compound represented by the formula (1) and a pyrene-based compound represented by the formula (2) in which an optimum light emission property is obtained in combination with the polycyclic aromatic compound can be provided, It is possible to provide an organic EL device which exhibits excellent luminous efficiency and excellent balance performance by producing an organic EL device by using a material for a light emitting diode.

Further, by introducing a cycloalkyl group into the compound of the above general formula (1) and a multimer thereof, a lowering of the melting point or sublimation temperature can be expected. This means that pyrolysis of the material can be avoided because it can be purified at relatively low temperatures in sublimation tablets, which are indispensable as a method for purifying organic device materials such as organic EL devices requiring high purity. This also applies to a vacuum deposition process, which is a powerful means for manufacturing an organic device such as an organic EL device. Since the process can be performed at a relatively low temperature, thermal decomposition of the material can be avoided, Can be obtained for an organic device. Further, since the multimer has a high sublimation temperature due to high molecular weight and high planarity, the lowering of the sublimation temperature by introducing the cycloalkyl group is more effective. Further, since the solubility in an organic solvent is improved by the introduction of a cycloalkyl group, it can be applied to production of a device using a coating process. In addition, concentration quenching can be suppressed by introducing a substituent having a large size such as cycloalkyl. However, the present invention is not particularly limited to these principles.

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

[Mode for Carrying Out the Invention]

1. An organic electroluminescent device

The present invention is an organic electroluminescent device comprising a pair of electrodes composed of a positive electrode and a negative electrode and a light emitting layer disposed between the pair of electrodes, wherein the light emitting layer comprises a polycyclic aromatic compound represented by the following general formula (1) Is an organic electroluminescent device comprising at least one of a multimer having a structure represented by the following general formula (1) and at least one of pyrene-based compounds represented by the following general formula (2).

The definitions of the symbols in the expressions (1) and (2) are the same as those described above. In the following expressions, the definitions of the signs are the same as those in the expressions same.

2. Polycyclic aromatic compounds and their multimers

The polycyclic aromatic compound and its multimer used in the present invention are compounds represented by the following general formula (1) or multimers thereof having a plurality of structures represented by the following general formula (1) A compound represented by the formula (1 '), or a multimer having a plurality of structures represented by the following formula (1'). These compounds basically function as dopants.

The A ring, the B ring, and the C ring in the general formula (1) are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted with a substituent. The substituent is selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino Substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy is preferable. As the substituent in the case where these groups have a substituent, aryl, heteroaryl, alkyl or cycloalkyl may be exemplified. The aryl or heteroaryl ring preferably has a 5-membered ring or a 6-membered ring sharing a bond with the central condensed bicyclic structure of the general formula (1) composed of the central element B (boron), X ¹ and X ² Do.

Here, the "condensed bicyclic structure" means a structure in which two saturated hydrocarbon rings including the central element B (boron), X ¹ and X ² shown in the center of the general formula (1) are condensed . The "6-membered ring sharing a bond with the condensed bicyclic structure" means a 6-membered ring having a ring (benzene ring (6-membered ring)) condensed to the condensed bicyclic structure, as shown by the above general formula (1 ' . The phrase " (A ring) A ring or heteroaryl ring having these six-membered rings " means that an A ring is formed only by the six-membered ring, or another ring or the like is condensed to the six- Which means that a ring is formed. In other words, the term "(A-ring) aryl ring or heteroaryl ring having 6-membered ring" means that the 6-membered rings constituting all or part of the A ring are condensed to the condensed bicyclic structure. The same explanation applies to "B ring (ring b)", "C ring (c ring)" and "5 ring".

The A ring (or the B ring and the C ring) in the general formula (1) is a ring formed by substituting the a ring in the general formula (1 ') and the substituent R ¹ to R ³ (or the b ring and its substituent groups R ⁸ to R ¹¹ , Its substituent R ⁴ to R ⁷ ). That is, the general formula (1 ') corresponds to a structure in which "A to C rings having 6-membered rings" are selected as the A to C rings of the general formula (1). In this sense, each ring of formula (1 ') is denoted by lowercase letters a to c.

In the general formula (1 '), the adjacent groups among the substituents R ¹ to R ¹¹ of the a, b, and c rings may be bonded to form an aryl or heteroaryl ring together with the a, b, or c ring, At least one hydrogen in the ring formed may be optionally substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, wherein at least one hydrogen May be substituted with aryl, heteroaryl, alkyl or cycloalkyl. Therefore, the polycyclic aromatic compound represented by the general formula (1 ') is a compound represented by the following formulas (1'-1) and (1'-2) by the mutual bonding form of the substituent in the a, , The ring structure constituting the compound is changed. The A 'ring, the B' ring and the C 'ring in the respective formulas correspond to the A ring, the B ring and the C ring in the general formula (1), respectively.

Is described by the formula (1'-1) and (1'-2) of the A 'ring, B' and ring C 'ring, the general formula (1'), the groups neighboring with each other of the substituents R ¹ ~R ¹¹ (Which may be referred to as a condensed ring in which other ring structures are condensed in an a ring, a b ring or a c ring), which is bonded together with an a ring, a b ring and a c ring. In addition, although not shown in the formulas, there are compounds in which a, b, and c rings are all changed to A 'ring, B' ring, and C 'ring. As can be seen from the formulas (1'-1) and (1'-2), for example, R ⁸ of b ring and R ⁷ of c ring, R ¹¹ of b ring and R ¹ and c of a ring R ⁴ in the ring and R ^{3 in the} a ring do not correspond to "adjacent groups" and do not bond to each other. That is, " adjacent groups " means adjacent groups on the same ring (upper).

The compound represented by the formula (1'-1) or the formula (1'-2) can be produced, for example, by reacting a benzene ring, which is a ring (or b ring or c ring), with a benzene ring, (Or a condensed ring B 'or a condensed ring C') formed by condensing a benzofuran ring or a benzothiophene ring and having an A 'ring (or a B' ring or a C 'ring) Are each a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophen ring.

X ¹ and X ² in the general formula (1) are each independently> O or> NR, and> NR in the above NR is optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkyl or And R may be bonded to the B ring and / or the C ring by a linking group or a single bond, and the linking group may be -O-, -S-, or -C (-R) ₂ - is preferred. And R in the above-mentioned "-C (-R) ₂ -" is hydrogen, alkyl or cycloalkyl. This explanation is also the same in X ¹ and X ² in the general formula (1 ').

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

This specification can be expressed as a compound represented by the following formula (1'-3-1), wherein X ¹ or X ² has a ring structure taken in the condensed ring B 'and condensed ring C'. That is, for example, a B 'ring (or a C' ring) in which another ring is condensed to receive X ¹ (or X ² ) with respect to the benzene ring as the b ring (or c ring) in the general formula (1 ' ). The condensed ring B '(or condensed ring C') formed and formed is, for example, a phenoxazine ring, a phenothiazine ring, or an acridine ring.

The above-mentioned definition is also applicable to a compound represented by the following formula (1'-3-2) or (1'-3-3) wherein X ¹ and / or X ² has a cyclic structure taken in the condensed ring A ' Can also be expressed. That is, for example, a compound having an A 'ring in which other rings are condensed to form X ¹ (and / or X ² ) to the benzene ring as the a ring in the general formula (1'). The condensed ring A 'thus formed is, for example, a phenoxazine ring, a phenothiazine ring, or an acridine ring.

Examples of the "aryl ring" as the A ring, the B ring and the C ring in the general formula (1) include an aryl ring having 6 to 30 carbon atoms, preferably an aryl ring having 6 to 16 carbon atoms, And more preferably an aryl ring having 6 to 10 carbon atoms. This "aryl ring" corresponds to "an aryl ring formed by bonding adjacent groups of R ¹ to R ¹¹ to form a ring, b ring or c ring" defined in the general formula (1 '), 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 a 5-membered ring is 9 here.

Specific examples of the "aryl ring" include benzene rings, bicyclic biphenyl rings, condensed bicyclic naphthalene rings, tricyclic ring terphenyl rings (m-terphenyl, o-terphenyl, p-terphenyl) A triene ring, an acenaphthylene ring, a fluorene ring, a phenylene ring, a phenanthrene ring, a condensed ring system triphenylene ring, a pyrene ring, a naphthacene ring, a condensed ring system perylene ring, a pentacene ring and the like.

Examples of the "heteroaryl ring" as the A ring, the B ring and the C ring in the general formula (1) include a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms, More preferably a heteroaryl ring having 2 to 15 carbon atoms, and particularly preferably a heteroaryl ring having 2 to 10 carbon atoms. The "heteroaryl ring" includes, for example, a heterocyclic ring containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring-constituting atom. This "heteroaryl ring" corresponds to the "heteroaryl ring formed by bonding adjacent groups of R ¹ to R ¹¹ together with a ring, b ring or c ring" defined in the general formula (1 '), Since the a-rings (or b-rings, c-rings) are already composed of benzene rings having 6 carbon atoms, the total number of carbon atoms in the condensed rings condensed with the 5-member rings is 6 here.

Specific examples of the "heteroaryl ring" include pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, A benzimidazole ring, a benzimidazole ring, a benzimidazole ring, a benzimidazole ring, a benzimidazole ring, a benzimidazole ring, a benzimidazole ring, a benzimidazole ring, a pyrimidine ring, a pyrimidine ring, , Isoquinoline ring, cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxathine ring, Benzofuran ring, dibenzofuran ring, thiophen ring, benzothiophen ring, dibenzothiophen ring, furan ring, thianthrene ring, and the like are exemplified as the furan ring, furan ring, indolizin ring, furan ring, benzofuran ring, .

The at least one hydrogen in the above "aryl ring" or "heteroaryl ring" may be substituted or unsubstituted "aryl" which is the first substituent, substituted or unsubstituted "heteroaryl", substituted or unsubstituted " Substituted or unsubstituted arylamino, substituted or unsubstituted arylamino, substituted or unsubstituted heteroarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, Aryloxy "as the first substituent," aryl "or" heteroaryl "as the first substituent, aryl of" diarylamino "," diheteroarylamino " Aryl and heteroaryl of " arylheteroarylamino ", and the aryl of " aryloxy " includes the monovalent group of the above-mentioned "aryl ring" or "heteroaryl ring".

The "alkyl" as the first substituent may be either straight chain or branched chain, and examples thereof include straight chain alkyl of 1 to 24 carbon atoms or branched chain alkyl of 3 to 24 carbon atoms. (Branched alkyl having 3 to 12 carbon atoms) is more preferable, and alkyl having 1 to 6 carbon atoms (having 3 to 18 carbon atoms) is preferable More preferably branched alkyl of 1 to 6 carbon atoms, and particularly preferably alkyl of 1 to 4 carbon atoms (branched alkyl of 3 to 4 carbon atoms).

Specific examples of the alkyl include alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n- pentyl, isopentyl, neopentyl, Methylbutyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, N-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, N-hexadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, and the like.

Examples of the "cycloalkyl" as the first substituent include a cycloalkyl group having 3 to 24 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms , Cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, cycloalkyl having 5 carbon atoms, and the like.

Specific examples of the cycloalkyl include cyclopropyl, methylcyclopropyl, cyclobutyl, methylcyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, methylcycloheptyl, cyclooctyl, methylcyclooctyl, Bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [ Cyclohexyl [2.2.1] octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.

The "alkoxy" as the first substituent includes, for example, straight chain or branched alkoxy of 1 to 24 carbon atoms and branched chain of 3 to 24 carbon atoms. More preferably an alkoxy of 1 to 18 carbon atoms (branched chain alkoxy of 3 to 18 carbon atoms), more preferably an alkoxy of 1 to 12 carbon atoms (branched chain alkoxy of 3 to 12 carbon atoms) Branched alkoxy having 3 to 6 carbon atoms) is more preferable, and alkoxy having 1 to 4 carbon atoms (alkoxy having 3 to 4 carbon atoms) is particularly preferable.

Specific alkoxy is exemplified by methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like have.

Substituted or unsubstituted heteroaryl, substituted or unsubstituted " diarylamino ", substituted or unsubstituted " diheteroarylamino ", substituted or unsubstituted " The substituted or unsubstituted alkyloxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted aryloxy may be substituted or unsubstituted, At least one hydrogen in these may be substituted with a second substituent, as described in the case of substitution or non-substitution. Examples of the second substituent include aryl, heteroaryl, alkyl or cycloalkyl, and specific examples thereof include a monovalent group of the above-mentioned "aryl ring" or "heteroaryl ring" The terms " alkyl " or " cycloalkyl " In the aryl or heteroaryl as the second substituent, it is preferable that at least one of the hydrogen atoms in these is substituted with an aryl such as phenyl (a specific example is the above-mentioned group) or an alkyl such as methyl (specific examples are the above groups) or cyclohexyl Is included in aryl or heteroaryl as the second substituent of the airway substituted with a cycloalkyl (specific examples are the groups described above). As an example thereof, when the second substituent is a carbazolyl group, at least one hydrogen at the 9-position is substituted with aryl such as phenyl, alkyl such as methyl, or cycloalkyl such as cyclohexyl, And is included in the heteroaryl as a substituent.

Examples of aryl, heteroaryl, aryl of diarylamino, heteroaryl of diheteroarylamino, aryl and heteroaryl of arylheteroarylamino, or aryl of aryloxy in R ¹ to R ¹¹ in general formula (1 ' Include a monovalent group of the "aryl ring" or the "heteroaryl ring" described in the general formula (1). As the alkyl, cycloalkyl or alkoxy in R ¹ to R ¹¹ , the description of "alkyl", "cycloalkyl" or "alkoxy" as the first substituent in the description of the aforementioned general formula (1) have. The same applies also to aryl, heteroaryl, alkyl or cycloalkyl as a substituent to these groups. In the case where adjacent groups of R ¹ to R ¹¹ are bonded to form an aryl group or a heteroaryl group together with an a, b, or c ring, heteroaryl, diarylamino, dihetero The same applies to arylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and also the substituent aryl, heteroaryl, alkyl or cycloalkyl.

R in > NR in X ¹ and X ² of the general formula (1) is aryl, heteroaryl, alkyl or cycloalkyl which may be substituted with the above-mentioned second substituent, and aryl, heteroaryl, alkyl or cycloalkyl At least one hydrogen may be substituted with, for example, alkyl or cycloalkyl. Examples of the aryl, heteroaryl, alkyl or cycloalkyl include the groups described above. (For example, phenyl, naphthyl, etc.), heteroaryl (for example, carbazolyl etc.) having 2 to 15 carbon atoms, alkyl having 1 to 4 carbon atoms (for example, methyl, Ethyl and the like), and cycloalkyl having 3 to 16 carbon atoms (for example, bicyclooctyl and adamantyl). This explanation is also the same in X ¹ and X ² in the general formula (1 ').

R in the "-C (-R) ₂ -" as a linking group in the general formula (1) is hydrogen, alkyl or cycloalkyl, and examples of the alkyl or cycloalkyl include the groups described above. Particularly preferably an alkyl having 1 to 4 carbon atoms (e.g., methyl, ethyl, etc.). This explanation is also the same in the linking group "-C (-R) ₂ -" in the general formula (1 ').

The present invention also relates to a process for producing a polycarbonate resin composition comprising a polycondensation product of a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (1), preferably a polycondensation product of a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (1 ' to be. The oligomer is preferably a dimer to a hexamer, more preferably a dimer to a trimer, and particularly preferably a dimer. The multimer may be any one having a plurality of the above-described unit structures in one compound. For example, the unit structure may have a form in which the unit structure is bonded to a linking group such as a single bond, an alkylene group having 1 to 3 carbon atoms, a phenylene group or a naphthylene group (A ring, B ring or C ring, a ring, b ring or c ring) contained in the unit structure may be shared by a plurality of unit structures and may be combined. In addition, (A ring, B ring or C ring, a ring, b ring or c ring) included in the ring may be bonded to each other to be condensed.

Examples of such a multimer include the following formulas (1'-4), (1'-4-1), (1'-4-2) (1'-5-4) or a multimer compound represented by the formula (1'-6). The multimer compound represented by the following formula (1 '- 4) is a compound represented by the general formula (1') in which a benzene ring as an a ring is shared and a unit structure represented by a plurality of general formula Lt; / RTI > is a multimeric compound. The multimer compound represented by the following formula (1'-4-1) is a compound represented by the general formula (1 ') in which the benzene ring as the a ring is shared, Is a polymer compound having a unit structure in one compound. The multimer compound represented by the following formula (1'-4-2) is a compound represented by the following general formula (1 ') in which the benzene ring as the a ring is shared, Is a polymer compound having a unit structure in one compound. The multimer compound represented by the following formulas (1'-5-1) to (1'-5-4) has a benzene ring represented by the formula (1 ' To share a unit structure represented by a plurality of general formula (1 ') in one compound. The multimer compound represented by the following formula (1'-6) can be exemplified by a compound represented by the general formula (1 '), for example, a benzene ring of a b- Is a multimer compound having a unit structure represented by a plurality of general formulas (1 ') in one compound such that a benzene ring as a b ring (or a ring or c ring) of the unit structure is condensed.

The multimer compound is a compound represented by the formula (1'-4), the formula (1'-4-1) or the formula (1'-4-2) (1'-5-1) to (1'-5) may be used in combination with any one of the formula (1'-5-4) (1'-4) and (4'-4), and a large amount of cherries in combination with the mass-increasing form represented by the formula (1'-6) (1'-5-1) to (1'-5-4) and the massing form expressed by the formula (1'-4-2) -6) may also be used.

The hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (1) or the general formula (1 ') and its multimer may be substituted with halogen, cyano or deuterium in whole or in part. For example, in the formula (1), A ring, B ring, C ring (A to C ring is an aryl ring or heteroaryl ring), a substituent in the A to C ring, and X ¹ and X ² are> NR Hydrogen in R (= aryl, heteroaryl, alkyl, cycloalkyl) may be substituted with halogen, cyano or deuterium, but all or some of the hydrogen in the aryl or heteroaryl may be substituted with halogen, cyano or Examples of which are deuterium substituted with deuterium. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine.

Specific examples of the polycyclic aromatic compound of the present invention include compounds represented by the following structural formulas. "Me" in the following structural formula represents a methyl group, "tBu" represents a tert-butyl group, "iPr" represents an isopropyl group, "Ph" represents a phenyl group, and "D" represents deuterium.

3. Polycyclic aromatic compound represented by the formula (1) and a method for producing the multimer thereof

The polycyclic aromatic compounds represented by the general formula (1) or general formula (1 ') and their multimers can be produced according to the methods described in many publicly known documents including International Publication No. 2015/102118. For reference, a specific production method of the polycyclic aromatic compound is described in Synthesis Examples to be described later.

Basically, an intermediate is first prepared by coupling an A ring (a ring), a B ring (b ring) and a C ring (c ring) with a bonding group (a group including X ¹ or X ² ) , Then the end product can be prepared by coupling the A ring (a ring), the B ring (b ring) and the C ring (c ring) with a bonding group (group containing the central element B (boron) 2 reaction). In the first reaction, for example, in the case of an etherification reaction, a general reaction such as a nucleophilic substitution reaction and a Wollmann reaction can be used. In the case of an amination reaction, a reaction such as a Buchwald-Hartwig reaction General reactions can be used. Further, in the second reaction, a Tandem Hetero-Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, the same applies hereinafter) can be used. It is also possible to produce halogenated, cyanated or deuterated compounds at desired positions by using halogenated, cyanated or deuterated raw materials, or by adding halogenating, cyanating or deuterated processes somewhere in this reaction step .

The second reaction is carried out in the same manner as in Scheme 1 or Scheme 2 except that the central element B which bonds the A ring (a ring), B ring (b ring) and C ring (c ring) Boron) is introduced. For example, the case where X ¹ and X ² are> 0 is shown below. First, a hydrogen atom between X ¹ and X ² is Ortho metalized 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 the mixture to obtain Tandem Bora -Friedel-Crafts) to give the desired product. In the second reaction, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction. The definitions of the symbols in the structural formulas in the following schemes (1) and (2) are the same as those described above.

The schemes (1) and (2) mainly show a process for producing a polycyclic aromatic compound represented by the general formula (1) or the general formula (1 '), (a ring), B ring (b ring) and C ring (c ring). This will be described in detail in the following schemes (3) to (5). In this case, the target product can be obtained by adjusting the amount of the reagent such as butyllithium to be used in two times and three times.

Also in the case where X ¹ and X ² are> NR or either one is> NR, an amine compound is used as an intermediate.

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

Examples of the orthomethalization reagent include alkyl lithiums such as methyllithium, n-butyllithium, sec-butyllithium and tert-butyllithium, lithium diisopropylamide, lithium tetramethylpipereryem, lithium hexamethyldisilazide, Potassium hexamethyldisilazide, and other organic alkaline compounds.

Examples of the Bronsted base include N, N-diisopropylethylamine, triethylamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine Ar ₄ BNa, Ar ₄ BK, Ar ₄ BK, Ar ₄ BK, Ar ₄ BK, Ar ₄ BK, Ar ₄ BK, Ar ₄ BK, Ar ₃ B, Ar ₄ Si (and Ar is aryl such as phenyl), and the like.

Examples of the Lewis acid include 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, Me3SiOTf, Cu (OTf) 2, For example, CuCl ₂ , YCl ₃ , Y (OTf) ₃ , TiCl ₄ , TiBr ₄ , ZrCl ₄ , ZrBr ₄ , FeCl ₃ , FeBr ₃ , CoCl ₃ and CoBr ₃ .

4. Pyrene compound represented by the general formula (2)

The pyrene-based compound represented by the general formula (2) basically functions as a host.

In the above formula (2)

the s pyrene portions and the p Ar portions join at any one of the positions of the pyrene portion * and the Ar portion,

At least one hydrogen of the pyrene moiety is independently selected from the group consisting of aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, , Alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, and at least one hydrogen in these groups is independently selected from the group consisting of aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or aryloxy having 6 to 30 carbon atoms,

Ar is independently an aryl having from 14 to 40 carbon atoms or a heteroaryl having from 12 to 40 carbon atoms, and at least one hydrogen in these is independently selected from the group consisting of aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms , Alkyl of 1 to 30 carbon atoms, cycloalkyl of 3 to 24 carbon atoms, alkenyl of 2 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, or aryloxy of 6 to 30 carbon atoms,

s and p are each independently an integer of 1 or 2, s and p are not simultaneously divalent, and when s is 2, the two pyrene moieties may be structurally identical or different, including substituents, , when p is 2, the two Ar moieties may be structurally identical or different, including substituents,

The at least one hydrogen in the compound represented by the formula (2) may be independently substituted with halogen, cyano or deuterium.

Ar is an aryl group having from 14 to 40 carbon atoms or a heteroaryl group having from 12 to 40 carbon atoms, and various substituents can be bonded to the aryl group. Specific examples of Ar include a group represented by the following formula (Ar-1) And a group to be displayed. R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ are substituents.

Examples of the groups represented by the formula (Ar-2) in which adjacent R ¹⁸ and R ¹⁹ are bonded to each other to form a condensed ring include the groups represented by the following formula (Ar-3). R ²⁰ to R ³⁵ are substituents.

More specific examples of the group represented by formula (Ar-1) or (Ar-2) include groups represented by any one of the following general formulas. Among them, a compound represented by the formula (Ar-1-1), a formula (Ar-1-2), a formula (Ar-1-3), a formula (Ar- (Ar-2-4) is preferable, and the group represented by the formula (Ar-1-2), the formula (Ar-1-3), the formula (Ar- Is more preferable. In the following structural formulas, substituents are not specified, but at least one hydrogen in each structure may be substituted. The group represented by the following formula (Ar-2-4) corresponds to the group represented by the formula (Ar-3).

Aryl having from 14 to 40 carbon atoms or heteroaryl having from 12 to 40 carbon atoms as Ar, a first substituent group (an aryl group having from 6 to 10 carbon atoms, a heteroaryl group having from 2 to 11 carbon atoms, an alkyl group having from 1 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms) and a second substituent (the number of carbon atoms is 6 Aryl having 2 to 11 carbons, heteroaryl having 2 to 11 carbons, alkyl having 1 to 30 carbons, cycloalkyl having 3 to 24 carbons, alkenyl having 2 to 30 carbons, alkoxy having 1 to 30 carbons or aryloxy having 6 to 30 carbons , preferably having a carbon number of 6 to 10 aryl), and substituent group (formula (Ar-1) of R ¹ ~R ^8, formula (Ar-2) of R ¹⁰ ~R ^19, formula (Ar-3) to Ar Aryl groups having 6 to 10 carbon atoms, heteroaryl groups having 2 to 11 carbon atoms, and aryl groups having 1 to 20 carbon atoms, which are substituents not shown in R ²⁰ to R ³⁵ and in the formulas (Ar-1-1) to (Ar- 30, alkyl Cycloalkyl having 3 to 24 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, preferably alkyl having 1 to 30 carbon atoms) will be summarized below .

The aryl group having 14 to 40 carbon atoms or the heteroaryl group having 12 to 40 carbon atoms as Ar is preferably an aryl group having 14 to 35 carbon atoms or a heteroaryl group having 12 to 35 carbon atoms and more preferably an aryl group having 14 to 30 carbon atoms, More preferably an aryl having from 14 to 25 carbon atoms or a heteroaryl having from 12 to 25 carbon atoms, particularly preferably an aryl having from 14 to 20 carbon atoms or a heteroaryl having from 12 to 20 carbon atoms, Is aryl having from 14 to 18 carbon atoms or heteroaryl having from 12 to 18 carbon atoms.

Specific examples of aryl include monocyclic phenyl, bicyclic biphenyl, condensed bicyclic naphthyl, tricyclic ring terphenyl (m-terphenyl, o-terphenyl, p-terphenyl), condensation 3 Anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, condensed ring systems such as triphenylenyl, naphthacenyl, condensed ring systems such as perylenyl and pentacenyl, and the like.

Specific examples of heteroaryl include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazoyl, tetrazolyl, pyrazolyl, pyridyl, Pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, Thienyl, quinoxalinyl, phthalazinyl, naphthyridinyl, furinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiinyl, phenoxazinyl, phenothiazinyl, phenazinyl , Indolizinyl, pryl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzo [b] thienyl, dibenzothienyl, furazanyl, oxadiazolyl, thianthrenyl, naphtho Benzofuranyl, and naphthobenzothienyl, and the like.

Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl or naphthyl, the heteroaryl group having 2 to 11 carbon atoms, the aryl group having 2 to 12 carbon atoms, As specific examples, mention may be made from among the above-mentioned heteroaryl groups.

The aryloxy having 6 to 30 carbon atoms is a group in which hydrogen of the hydroxyl group is substituted with aryl having 6 to 30 carbon atoms, and the aryl is preferably aryl having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms More preferably an aryl group having 6 to 15 carbon atoms, particularly preferably an aryl group having 6 to 10 carbon atoms, and specific examples of the aryl group include the aryl groups described above.

The alkyl having 1 to 30 carbon atoms may be either straight chain or branched chain. For example, straight chain alkyl having 1 to 24 carbon atoms or branched alkyl having 3 to 24 carbon atoms is preferable, and alkyl having 1 to 18 carbon atoms More preferably a branched alkyl having 3 to 12 carbon atoms), still more preferably a C1 - C6 alkyl (branched alkyl having 3 to 6 carbon atoms) And particularly preferably methyl, ethyl, isopropyl or tert-butyl, and more preferably methyl or tert-butyl (especially methyl or ethyl) Is most preferable.

Specific examples of the alkyl include alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n- pentyl, isopentyl, neopentyl, Methylbutyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, N-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, N-hexadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicosyl, and the like.

The cycloalkyl having 3 to 24 carbon atoms is, for example, a cycloalkyl having 3 to 20 carbon atoms, a cycloalkyl having 3 to 16 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, a cycloalkyl having 5 to 10 carbon atoms, Cycloalkyl, cycloalkyl having 5 to 6 carbon atoms, cycloalkyl having 5 carbon atoms, and the like.

Specific examples of the cycloalkyl include cycloalkyl such as cyclopropyl, methylcyclopropyl, cyclobutyl, methylcyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, methylcycloheptyl, cyclooctyl, methylcyclooctyl, Bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [ Cyclohexyl [2.2.1] octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.

The alkenyl having 2 to 30 carbon atoms is, for example, preferably an alkenyl having 2 to 20 carbon atoms, more preferably an alkenyl having 2 to 10 carbon atoms, still more preferably an alkenyl having 2 to 6 carbon atoms , And particularly preferably an alkenyl having 2 to 4 carbon atoms.

Specific examples of alkenyl include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Decenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl and 5-hexenyl.

The alkoxy having 1 to 30 carbon atoms is preferably, for example, alkoxy having 1 to 24 carbon atoms (branched chain alkoxy having 3 to 24 carbon atoms), more preferably alkoxy having 1 to 18 carbon atoms Branched chain alkoxy having 1 to 12 carbon atoms), more preferably alkoxy having 1 to 12 carbon atoms (branched chain alkoxy having 3 to 12 carbon atoms), particularly preferably alkoxy having 1 to 6 carbon atoms (alkoxy having 3 to 6 carbon atoms ), And most preferably an alkoxy of 1 to 4 carbon atoms (alkoxy of branched chain having 3 to 4 carbon atoms).

Specific alkoxy is exemplified by methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy and octyloxy have.

In the formulas (Ar-1) and (Ar-2), adjacent groups of R ¹ to R ⁸ and adjacent groups of R ¹⁰ to R ¹⁹ may be bonded to each other to form a condensed ring. The adjacent groups are combinations other than R ⁴ and R ⁵ , R ¹³ and R ¹⁴ , for example, R ¹ and R ² . (Ar-1-2) to (Ar-1-12) or the above formulas (Ar-2-2) to (Ar-2-4) (Ar-1-1) and (Ar-2-1) do not include a condensed ring. Examples of the condensed ring formed include a benzene ring, a naphthalene ring , A phenanthrene ring, a thiophene ring, a pyrrole ring, or a furan ring, and preferably a benzene ring, a naphthalene ring or a phenanthrene ring, which is an aryl ring, and more preferably a benzene ring.

The condensed rings formed by bonding adjacent groups to each other are preferably selected from the group consisting of aryl of 6 to 10 carbon atoms, heteroaryl of 2 to 11 carbon atoms, alkyl of 1 to 30 carbon atoms, cycloalkyl of 3 to 24 carbon atoms, alkenyl of 2 to 30 carbon atoms, Or an aryloxy group having 6 to 30 carbon atoms, and further, they may be substituted with an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms, Can be quoted.

Also, Z is,> CR _2,> NR,> is O or> S, Of these, preferably> is CR ₂ or> O, and more preferably> is CR _2,> R (the number of carbon atoms of from CR ₂ Alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, alkyl having 1 to 4 carbon atoms, aryl having 6 to 12 carbon atoms which may be substituted with cycloalkyl having 5 to 10 carbon atoms, A heteroaryl having 2 to 12 carbon atoms which may be substituted with 5 to 10 cycloalkyl), and R in NR> (alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, For example, aryl having 6 to 12 carbon atoms which may be substituted with 5 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or heteroaryl having 2 to 12 carbon atoms which may be substituted with cycloalkyl having 5 to 10 carbon atoms) Details of these groups refer to the description of alkyl, cycloalkyl, aryl and heteroaryl described above Can.

As for Z> CR ₂ , the R may be bonded to each other to form a ring, and in this case, a spiro structure is formed.

(2) means that s pyrene moieties and p Ar moieties are bonded at the position (position 1 and / or position 2) of the pyrene moiety, and s and p each independently represent 1 Or an integer of 2, and s and p are not simultaneously divalent. In the case of s = 1 and p = 1 or s = 2 and p = 1, the first and second positions of the pyrene portion can be represented by * in two places, but s = 1, In the case of p = 2, it is indicated by six * that two Ar portions can be bonded to six positions of the pyrene portion, respectively. When s is 2, the two pyrene moieties may be structurally identical or different, including substituents, and when p is 2, the two Ar moieties may be structurally identical, including substituents, have. That is, the pyrene moiety may have various substituent groups bonded to the pyrene structure as described above, and when the substituent moiety is bonded, the pyrenylene moiety is also included including a bonded substituent group. Similarly, the Ar moiety constitutes an Ar moiety including a bonded substituent. When a pyrene compound represented by the formula (2) contains a plurality of pyrene moieties or Ar moieties, pyrene moieties containing substituents and Ar moieties containing substituents may be structurally identical or different, The same is preferable.

Regarding the combination of the pyrene moiety and the Ar moiety, in the pyrene moiety, Ar is bonded at the position of * (position 1 and / or position 2). Alternatively, the pyrene moiety is bonded at any position in the Ar moiety do. For example, in formula (Ar-1) or formula (Ar-2) which is an example of Ar, a pyrene moiety may be bonded at any position of R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ , When they are bonded to each other to form a condensed ring, they may be bonded to the condensed ring. When a substituent such as aryl is selected as R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ in any position of the aryl in the case where a substituent such as aryl is selected and R of> CR ₂ and> NR as Z, Or may be bonded at any one position in the aryl of the < RTI ID = 0.0 > Among these bonding positions, one of the positions of R ¹ to R ⁸ or R ¹⁰ to R ^{19 in} the formula (Ar-1) or (Ar-2) is preferably one position. This explanation is also applicable to the lower expressions of the formulas (Ar-1) and (Ar-2).

The hydrogen in the pyrene-based compound represented by the formula (2) may be completely or partially substituted by halogen, cyano or deuterium. For example, in the formula (2), hydrogen in the pyrene moiety or the Ar moiety may be substituted with halogen, cyano or deuterium. The halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.

Specific examples of the pyrene-based compound of the present invention include compounds represented by the following structural formulas. "Me" in the following structural formula represents a methyl group, "Et" represents an ethyl group, "tBu" represents a tert-butyl group, "iPr" represents an isopropyl group, and "D" represents deuterium.

Of the above compounds, the compounds represented by formulas (2-1), (2-2) to (2-20), (2-41) to (2-43) (2-174), (2-174), (2-175) to (2-215), (2-351) to (2-354) 356), Expression (2-357), Expression (2-358), Expression (2-359), Expressions (2-360) to Expression (2-430), Expression (2-1001) ) To formula (2-1012), formula (2-1080), and formula (2-1081) to formula (2-1091).

(2-1), (2-174), (2-350), (2-356), (2-359), (2-1001) , And (2-1080) are more preferable.

5. Production method of pyrene-based compound represented by formula (2)

The pyrene compound represented by the formula (2) has a structure in which various substituents are bonded to the skeleton of the pyrene skeleton or the compound represented by Ar, and can be produced by a known method. An intermediate is produced by a commonly used halogenation reaction, a boron oxidation reaction or a boronic acid esterification reaction, and a Suzuki coupling reaction or other metalization reaction is carried out using the intermediate prepared, and a cross- Ring reaction (Negishi coupling reaction, Kumada-Tamao coupling reaction, Kosugi-Miita-Stille coupling reaction, etc.) , A pyrene-based compound represented by the formula (2) can be suitably produced. Further, an intermediate having a substituent such as an alkoxy group such as a methoxy group can be prepared, followed by a de-methylation reaction using a pyridine hydrochloride or the like to obtain an -OH form, and then a sulfonic acid ester such as an anhydrous trifluoromethanesulfonic acid And a cross coupling reaction such as a Suzuki coupling reaction is carried out to obtain a pyrene-based compound represented by the formula (2). In addition, commercially available materials such as halogens, boronic acids, boronic acid esters or sulfonic acid ester-containing intermediates may be used. For reference, a specific production method of the pyrene-based compound is described in the synthesis examples to be described later.

6. Organic electroluminescent device

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

≪ Structure of Organic Electroluminescent Device >

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 A light emitting layer 105 provided on the hole transporting layer 104; an electron transporting layer 106 provided on the light emitting layer 105; and an electron injection layer 103 provided on the electron transporting layer 106. [ A layer 107, and a cathode 108 provided on the electron injection layer 107. [

The organic EL element 100 has a substrate 101 and a cathode 108 provided on the substrate 101 and an electron injecting layer (not shown) provided on the cathode 108, for example, An electron transport layer 106 provided on the electron injection layer 107, a light emission layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light emission layer 105, A hole injection layer 103 provided on the hole injection layer 104 and an anode 102 provided on the hole injection layer 103 may be used.

It is not necessary that all of the layers described above are present and that the minimum constitutional unit is constituted of the anode 102, the light emitting layer 105 and the cathode 108 and the hole injecting layer 103, the hole transporting layer 104, the electron transporting layer 106) and the electron injection layer 107 are arbitrarily installed layers. Each of the layers described above may be a single layer or a plurality of layers.

Examples of the layer constituting the organic EL element include a substrate, an anode, a hole transporting layer, and a light emitting layer in addition to the above-described constitution of the above-described "substrate / anode / hole injecting layer / hole transporting layer / light emitting layer / electron transporting layer / electron injecting layer / Electron transport layer / electron injection layer / cathode "," substrate / anode / hole injection layer / hole transport layer / light emission layer / electron injection layer / cathode " Cathode / anode / hole transport layer / hole transport layer / light emitting layer / electron transport layer / cathode "," substrate / anode / light emitting layer / electron transport layer / electron injection layer / cathode " Cathode / anode / hole transport layer / cathode "," substrate / anode / hole injection layer / light emitting layer / electron injection layer / cathode "," substrate / anode / hole injection layer / cathode " Emitting layer / electron transporting layer / cathode "," substrate / anode / light emitting layer / cathode " Here is a configuration aspect of injecting layer / cathode ".

≪ Substrate in Organic Electroluminescent Device >

The substrate 101 is a support for the organic EL element 100, and typically quartz, glass, metal, plastic, or the like is used. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape, depending on the purpose. 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 plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable. If the glass substrate is made of soda lime glass, alkali-free glass or the like is used, the thickness may be sufficient to maintain the mechanical strength. For example, it may be 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. With regard to the material of the glass, since it is preferable that the elution ions from the glass be small, it is preferable that the glass is an alkali-free glass, but a soda lime glass having a barrier coating such as SiO ₂ is also commercially available and can be used . A gas barrier film such as a dense silicon oxide film may be formed on at least one surface of the substrate 101 in order to improve the gas barrier property. In particular, a plate, film, or sheet made of synthetic resin having low gas barrier property may be formed on the substrate 101 ), It is preferable to form a gas barrier film.

≪ Positive electrode in organic electroluminescent device >

The anode 102 serves to inject holes into the light emitting layer 105. When the hole injecting layer 103 and / or the hole transporting layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through the hole injecting layer 103 and / or the hole transporting layer 104.

As a material for forming the anode 102, an inorganic compound and an organic compound are exemplified. Examples of the inorganic compound include metals (aluminum, gold, silver, nickel, palladium, chromium and the like), metal oxides (oxides of indium, oxides of tin, indium-tin oxide (ITO) Etc.), metal halides (such as copper iodide), copper sulfide, carbon black, and ITO glass and nese glass. Examples of the organic compound include conductive (conductive) polymers such as polythiophene such as poly (3-methylthiophene), polypyrrole, and polyaniline. In addition, it can be appropriately selected from the materials used as the anode of the organic EL device.

The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but it is preferable that the resistance is low in view of the power consumption of the light emitting element. For example, an ITO substrate of 300 OMEGA / & squ & or less functions as an element electrode. However, since it is possible to supply a substrate of about 10 OMEGA / & squ & It is particularly preferable to use a resistor product. Thickness of ITO can be arbitrarily selected in accordance with the resistance value, but it is often used in a range of usually 50 to 300 nm.

≪ Hole injection layer and hole transport layer in organic electroluminescent device >

The hole injection layer 103 serves to efficiently inject holes that migrate from the anode 102 into the light emitting layer 105 or into the hole transport layer 104. The hole transport layer 104 efficiently transports 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 efficiently. The hole injecting layer 103 and the hole transporting layer 104 may be formed by laminating or mixing one or more kinds of hole injecting and transporting materials or by mixing a mixture of a hole injecting and transporting material and a polymer binder . Further, an inorganic salt such as iron (III) chloride may be added to the hole injecting and transporting material to form a layer.

As the hole injecting and transporting material, it is necessary to efficiently inject and transport holes from the anode between the electrodes to which an electric field is applied, and it is preferable that the hole injecting efficiency is high and the injected holes are efficiently transported. For this purpose, it is preferable that the material has a small ionization potential, a high hole mobility, an excellent stability, and an impurity which is a trap, which is not easily generated during production and use.

As a material for forming the hole injection layer 103 and the hole transporting layer 104, a compound which is conventionally used as a charge transporting material for a hole, a p-type semiconductor, a hole injection Layer and the hole transporting layer, any of the known compounds may be selected and used. Specific examples thereof include biscarbazole derivatives such as carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole and the like), bis (N-arylcarbazole) and bis (N-alkylcarbazole), trilaurylamine derivatives (Polymer having aromatic tertiary amino group in the main chain or side chain), 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N'- , N'-di (3-methylphenyl) -4,4'-diaminophenyl, N, N'-diphenyl-N, N'-dinaphthyl- -Diphenyl-N'-di (3-methylphenyl) -4,4'-diphenyl-1,1'-diamine, N, N'-dinaphthyl- 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'- Triphenylamine derivatives such as phenyl] -4,4'-diamine, 4,4 ', 4 "-tris (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives and the like) , Pyrazoline derivatives, hydrazine compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (for example, 1,4,5,8,9 , 12-hexaazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, etc.), a phosgenating compound such as a phthalin derivative, and polysilane. In the polymer system, Polycarbonate, styrene derivatives, polyvinylcarbazole and polysilane are preferable, but the compound is not particularly limited as long as it can form a thin film necessary for manufacturing a light emitting device, inject holes from the anode, and transport holes Do not.

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 a good electron acceptor or a compound having a good electron accepting property. For doping the electron donor, a strong electron acceptor such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) 73 (22), 3202-3204 (1998), and J. Blochwitz, J. < RTI ID = 0.0 > , M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998)]. These produce so-called holes by the electron transfer process in the electron donor type base material (hole transport material). Due to the number of holes and the degree of mobility, the conductivity of the base material varies greatly. As the matrix material having the hole transporting property, for example, a benzidine derivative (TPD), a starburst amine derivative (TDATA or the like) or a specific metal phthalocyanine (particularly zinc phthalocyanine (ZnPc) or the like) 2005-167175).

≪ Light Emitting Layer in Organic Electroluminescent Device >

The light emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. As a material for forming the light emitting layer 105, a compound (luminescent compound) that excites by the recombination of holes and electrons to emit light can be used to form a stable thin film shape, and a strong luminescence (fluorescence) efficiency Or a compound represented by the formula In the present invention, as the material for the light-emitting layer, for example, a pyrene-based compound represented by the general formula (2) as a host material and a polycyclic aromatic compound represented by the general formula (1) And a multimer thereof can be used.

The light emitting layer may be a single layer or a plurality of layers or may be formed of a light emitting layer material (host material, dopant material). Each of the host material and the dopant material may be either one or a combination of two or more. The dopant material may be included in the whole host material, or may be partially included. As a doping method, it is possible to form it by a co-deposition method with a host material, but it may be vapor-deposited after mixing with a host material in advance.

The amount of the host material to be used differs depending on the type of the host material and may be determined according to the characteristics of the host material. The amount of the host material to be used 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 based on the total weight of the light emitting layer material.

The amount of the dopant material to be used differs depending on the kind of the dopant material and may be determined in accordance with the characteristics of the dopant material. The amount of the dopant to be used is preferably from 0.001 to 50% by weight, more preferably from 0.05 to 20% by weight, and still more preferably from 0.1 to 10% by weight, based on the entire material of the light emitting layer. Within the above-mentioned range, for example, concentration density extinction phenomenon can be prevented.

Examples of the host material that can be used in combination with the pyrene-based compound represented by the formula (2) include condensed ring derivatives such as anthracene, which have been known as phosphors, bisstyryl derivatives such as bisstyryl anthracene derivatives and distyrylbenzene derivatives, Phenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, benzofluorene derivatives, and the like.

The polycyclic aromatic compound represented by the formula (1) and its multimers can be used in combination. The dopant material is not particularly limited and a known compound can be used and can be selected from various materials according to a desired luminescent color . Specific examples thereof include condensed ring derivatives such as phenanthrene, anthracene, tetracene, pentacene, perylene, rubrene and chrysene, benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, A thiazole derivative, a thiazole derivative, a thiazole derivative, a thiazole derivative, a thiazole derivative, a thiazole derivative, a pyrazoline derivative, a stilbene derivative, a thiophene derivative, a tetraphenylbutadiene derivative, a cyclopentadiene derivative , Bisstyryl derivatives such as bisstyryl anthracene derivatives and distyryl benzene derivatives (Japanese Unexamined Patent Publication No. 1-245087), bisstyryl arylene derivatives (Japanese Unexamined Patent Application Publication No. 2-247278), diazinedazine (2-methylphenyl) isobenzofuran, di (2-trifluoromethylphenyl) isobenzofurane, di (2-methylphenyl) isobenzofurane, di Isobenzofuran derivatives such as isobenzofuran derivatives such as nisobenzofuran, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7- Benzimidazolylcoumarin derivatives, and 3-benzoxazolylcoumarin derivatives; dicyanomethylenepyran derivatives; dicyanomethylenethiopyran derivatives; polymethine derivatives; A cyanine derivative, an oxobenzanthracene derivative, a xanthene derivative, a rhodamine derivative, a fluororesin derivative, a pyrylium derivative, a carbostyryl derivative, an acridine derivative, an oxazine derivative, a phenylene oxide derivative, a quinacridone derivative, Pyrrolopyrrole derivatives, pyruropyridine derivatives, pyromethene derivatives, pyrrolone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, What it includes anthrone derivatives, phenazine derivatives, acridine derivatives, money, to aza flavin derivatives, fluorene derivatives, and benzo fluorene derivative.

≪ Electron injection layer and electron transport layer in organic electroluminescent device >

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 transporting layer 106. The electron transporting layer 106 efficiently transports electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 into the light emitting layer 105. The electron transporting layer 106 and the electron injecting layer 107 are each formed by laminating or mixing one or more kinds of electron transporting / injecting materials or by a mixture of an electron transporting / injecting material and a polymer binder.

The electron injection / transport layer is a layer which is responsible for injecting electrons from the cathode and transporting electrons, and it is preferable that the electron injection efficiency is high and the injected electrons are efficiently transported. For this purpose, it is preferable that the electron affinity is large, the electron mobility is large, the stability is excellent, and the impurities which become trap are not easily generated at the time of production and use. However, in consideration of the transport balance of holes and electrons, in the case of mainly performing the function of effectively preventing the holes from the anode from flowing to the cathode side without recombining, it is necessary to improve the luminous efficiency even when the electron- The effect is equivalent to that of materials with high electron transport capability. Therefore, the electron injecting and transporting layer in the present embodiment may also include the function of a layer capable of effectively blocking the movement of holes.

Examples of the material (electron transporting material) for forming the electron transporting layer 106 or the electron injecting layer 107 include a compound conventionally used as an electron transporting compound in the photoconductive material, an electron injecting layer and an electron transporting layer of the organic EL device Any of the known compounds which are used can be selected and used.

Examples of the material used for the electron transporting layer or the electron injecting layer include compounds containing an aromatic ring or a heteroaromatic ring composed of at least one atom selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus, pyrrole derivatives and condensed ring derivatives thereof, And a metal complex having an electron-accepting nitrogen. Specific examples thereof include condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4'-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives , Quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives and indole derivatives. Examples of the metal complex having electron-accepting nitrogen include a hydroxyazole complex such as a hydroxyphenyloxazole complex, an azomethine complex, a tropolone metal complex, a flavonol metal complex, and a benzoquinoline metal complex . These materials may be used alone or in combination with different materials.

Specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, (4-tert-butylphenyl) 1,3,4-oxadiazolyl] phenylene), thiophene derivatives, triazole derivatives (N- Naphthyl-2,5-diphenyl-1,3,4-triazole, etc.), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, (Benzo [h] quinolin-2-yl) -9,9 ', 6'-benzopyranone derivatives, - spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives Benzophenone derivatives, tris (N-phenylbenzimidazol-2-yl) benzene), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, -Bis (4 '- (2,2': 6'2 "-terpyridinyl)) benzene), a naphthyridine derivative (bis (1-naphthyl) -4- (1,8- Phenylphosphine oxide, etc.), aldazine derivatives, carbazole derivatives, indole derivatives, phosphorus oxide derivatives, and bisstyryl derivatives.

Further, a metal complex having electron-accepting nitrogen may be used. For example, a metal complex such as a quinolinol-based metal complex or a hydroxyphenyloxazole complex, such as a hydroxyazole complex, an azomethine complex, a tropolone metal complex, And benzoquinoline metal complexes.

The above-described materials may be used alone, or they may be mixed with different materials.

Among the above-mentioned materials, preferred are borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, Phenanthroline derivatives, and quinolinol-based metal complexes are preferable.

<Borane derivative>

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

In the formula (ETM-1), R ¹¹ and R ¹² each independently represent a hydrogen, an alkyl, a cycloalkyl, an optionally substituted aryl, a substituted silyl, a heterocyclic compound having a nitrogen atom which may be substituted, Or cyano, and R ¹³ to R ¹⁶ each independently represent optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl, X is optionally substituted arylene, Y is optionally substituted aryl having up to 16 carbon atoms, substituted boryl, or optionally substituted carbazolyl, and n is each independently an integer of 0 to 3. Examples of the substituent in the case of "optionally substituted" or "substituted" include aryl, heteroaryl, alkyl or cycloalkyl, and the like.

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

In the formula (ETM-1-1), R ¹¹ and R ¹² each independently represent a hydrogen, an alkyl, a cycloalkyl, an optionally substituted aryl, a substituted silyl, a heterocyclic compound having a nitrogen atom which may be substituted , Or cyano; R ¹³ to R ¹⁶ each independently represent optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl; R ²¹ and R ²² are each, independently of one another, A substituted or unsubstituted heterocyclic compound having a nitrogen atom which may be substituted, or cyano, and X ¹ is at least one selected from the group consisting of substituted or unsubstituted Arylene, n is independently an integer of 0 to 3, and m is independently an integer of 0 to 4. Examples of the substituent in the case of "optionally substituted" or "substituted" include aryl, heteroaryl, alkyl or cycloalkyl, and the like.

In the formula (ETM-1-2), R ¹¹ and R ¹² are each independently a hydrogen, an alkyl, a cycloalkyl, an optionally substituted aryl, a substituted silyl, a heterocyclic compound having a nitrogen atom which may be substituted , Or cyano, and R ¹³ to R ¹⁶ each independently represent optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, and X ¹ is optionally substituted C 20 And n is an integer of 0 to 3 independently of each other. Examples of the substituent in the case of "optionally substituted" or "substituted" include aryl, heteroaryl, alkyl or cycloalkyl, and the like.

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

(In the formulas, R &lt; ^a &gt; each independently represents an alkyl group, a cycloalkyl group, or an optionally substituted phenyl group.)

Concrete examples of the borane derivative include, for example, the following compounds.

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

<Pyridine Derivatives>

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

φ is, n-valent, and aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, a benzo fluorene ring, a penal renhwan, phenanthrene renhwan or triphenyl renhwan), n is from 1 to 4 It is an integer.

In the formula (ETM-2-1), R ¹¹ to R ¹⁸ each independently represent 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 formula (ETM-2-2), R ¹¹ and R ¹² each independently represent hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms, cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms Or aryl (preferably having 6 to 30 carbon atoms), and R &lt; ¹¹ &gt; and R &lt; ¹² &gt; may combine to form a ring.

In the formulas, &quot; pyridine-based substituent &quot; is any one of the following formulas (Py-1) to (Py-15), the pyridine substituents are each independently an alkyl having 1 to 4 carbon atoms, And may be substituted with cycloalkyl. Further, pyridine-based substituent may be bonded to φ, anthracene ring or a fluorene ring via a group of the formula each naphthylene group or phenylene group.

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

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

As the &quot; alkyl &quot; in R ¹¹ to R ¹⁸ , a straight chain or branched chain may be used, and for example, there may be a straight chain alkyl group having 1 to 24 carbon atoms or a branched chain alkyl group having 3 to 24 carbon atoms. Preferable &quot; alkyl &quot; is alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms). More preferable &quot; alkyl &quot; is alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms). More preferred &quot; alkyl &quot; is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferable &quot; alkyl &quot; is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).

Specific examples of the "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n-pentyl, isopentyl, neopentyl, Methylbutyl, 2-ethylbutyl, 1-methylhexyl, n-octyl, Hexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, , n-decyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, have.

As the alkyl having 1 to 4 carbon atoms to be substituted with a pyridine substituent, the description of the alkyl may be cited.

The "cycloalkyl" for R ¹¹ to R ¹⁸ includes, for example, cycloalkyl having 3 to 12 carbon atoms. Preferable "cycloalkyl" is cycloalkyl having 3 to 10 carbon atoms. More preferred &quot; cycloalkyl &quot; is cycloalkyl having 3 to 8 carbon atoms. More preferable &quot; cycloalkyl &quot; is cycloalkyl having 3 to 6 carbon atoms.

Specific examples of the "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.

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

As the "aryl" for R ¹¹ to R ¹⁸ , preferable aryl is aryl having 6 to 30 carbon atoms, more preferably aryl is aryl having 6 to 18 carbon atoms, more preferably aryl having 6 to 14 carbon atoms, particularly preferably Is aryl having from 6 to 12 carbon atoms.

Specific examples of the "aryl having 6 to 30 carbon atoms" include acenaphthylene- (1-, 3-, 4-naphthyl) which is a monocyclic aryl, phenyl, a condensed bicyclic aryl, (1-, 2-, 3-, 4-, 6- or 7-membered heteroaryl) (1-, 2-, 4-) yl, naphthacene- (1-, 2- or 3-furanyl) (1-, 2-, 5- or 6-yl), which is a condensed pentacyclic aryl, and the like.

Preferable &quot; aryl having 6 to 30 carbon atoms &quot; is exemplified by phenyl, naphthyl, phenanthryl, chrysenyl or triphenylenyl, more preferably phenyl, 1-naphthyl, 2-naphthyl or phenanthryl And particularly preferably phenyl, 1-naphthyl or 2-naphthyl are exemplified.

R ¹¹ and R ¹² in the formula (ETM-2-2) may combine to form a ring. As a result, the 5-membered ring of the fluorene skeleton may be substituted with at least one member selected from the group consisting of cyclobutane, cyclopentane, cyclopentene, cyclopentadiene , Cyclohexane, fluorene, indene, or the like may be spiro-bonded.

Specific examples of the pyridine derivative include the following compounds.

These pyridine derivatives can be prepared by using known methods and known synthesis methods.

<Fluoranthene derivatives>

The fluoranthene derivative is, for example, a compound represented by the following general formula (ETM-3), and is disclosed in detail in International Publication WO 2010/134352.

In the formula (ETM-3), X ^{12 to} X ²¹ are independently selected from the group consisting of hydrogen, halogen, straight chain, branched or cyclic alkyl, straight chain, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl . Examples of the substituent when it is substituted include aryl, heteroaryl, alkyl or cycloalkyl, and the like.

Specific examples of the fluoranthene derivative include the following compounds.

&Lt; BO derivative >

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

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

The adjacent groups of R ¹ to R ^{11 may be} bonded to form an aryl or heteroaryl ring together with the a, b, or c ring, and at least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, Cycloalkyl, alkoxy or aryloxy, and at least one of the hydrogen atoms may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, .

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

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

As specific examples of this BO-based derivative, there are, for example, the following compounds.

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

<Anthracene derivatives>

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

Ar is independently a divalent benzene or naphthalene, and 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.

Ar may be independently selected from divalent benzene or naphthalene, and two Ar may be the same or different, but the same is preferable from the viewpoint of ease of synthesis of the anthracene derivative. Ar is bonded to pyridine to form a &quot; Ar and pyridine moiety &quot;, and this moiety is a moiety represented by any one of the following formulas (Py-1) to (Py-12) Lt; / RTI &gt;

Among these groups, a group represented by any one of the above formulas (Py-1) to (Py-9) is preferable, and a group represented by any one of the formulas (Py-1) to . The two "Ar and pyridine bonding sites" bonded to the anthracene may have the same or different structures, but from the viewpoint of easiness of synthesis of the anthracene derivative, the same structure is preferable. However, from the viewpoint of device characteristics, the two "Ar and pyridine sites" may be the same or different.

The alkyl having 1 to 6 carbon atoms for R ¹ to R ⁴ may be either straight chain or branched chain. That is, straight chain alkyl of 1 to 6 carbon atoms or branched alkyl of 3 to 6 carbon atoms. More preferably, it is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n- pentyl, Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, isobutyl, sec-butyl, Or tert-butyl is preferable, and methyl, ethyl, or tert-butyl is more preferable.

Specific examples of the cycloalkyl having 3 to 6 carbon atoms for R ¹ to R ⁴ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl or dimethylcyclohexyl, For example.

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

Specific examples of the "aryl having 6 to 20 carbon atoms" include phenyl, (o-, m-, p-) tolyl, (2-, 3-, (2-, 3-, 4- or 6-membered heterocyclic group), which is a heterocyclic aryl group, , 4-biphenylyl, condensed bicyclic aryl (1-, 2-) naphthyl, tricyclic aryl interferyl (m-terphenyl-2'- , m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl- (1-, 2-, 9-), acenaphthylene- (1-, 2- or 7- membered heteroaryl) which is a condensed tricyclic aryl, (1-, 2-, 3-, 4-, 5-, 5- or 6-membered heterocyclic ring) (1-, 2-, 4-) yl, tetracene (1-, 2- or 4-), which is a condensed tetracyclic ring, , 2-, 5-), and perylene- (1-, 2-, 3-) yl, which is a condensed pentacyclic aryl.

Preferable &quot; aryl of 6 to 20 carbon atoms &quot; is phenyl, biphenyl, terphenyl or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2- Yl, more preferably phenyl, biphenyl, 1-naphthyl or 2-naphthyl, and most preferably phenyl.

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

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

Ar ² is, independently of each other, an aryl having 6 to 20 carbon atoms, and the same explanation as the "aryl of 6 to 20 carbon atoms" in the formula (ETM-5-1) can be cited. Aryl having 6 to 16 carbon atoms is preferable, aryl having 6 to 12 carbon atoms is more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable. Specific examples include phenyl, biphenylyl, naphthyl, terphenyl, anthracenyl, acenaphthyrenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl and the like. .

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 formula (ETM-5-1) can do.

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

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

<Benzofluorene derivative>

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

Ar ¹ is, independently of each other, an aryl having 6 to 20 carbon atoms, and the same explanation as the "aryl of 6 to 20 carbon atoms" in the formula (ETM-5-1) can be cited. Aryl having 6 to 16 carbon atoms is preferable, aryl having 6 to 12 carbon atoms is more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable. Specific examples include phenyl, biphenylyl, naphthyl, terphenyl, anthracenyl, acenaphthyrenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl and the like. .

Ar ² are, each independently, hydrogen, alkyl (preferably alkyl of 1 to 24 carbon atoms), cycloalkyl (preferably a cycloalkyl having a carbon number of 3 to 12) or an aryl group (preferably an aryl group having a carbon number of 6 to 30) And two Ar &lt; ² &gt; may combine to form a ring.

As &quot; alkyl &quot; in Ar ² , a straight chain or branched chain may be used, and for example, straight chain alkyl of 1 to 24 carbon atoms or branched chain alkyl of 3 to 24 carbon atoms. Preferable &quot; alkyl &quot; is alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms). More preferable &quot; alkyl &quot; is alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms). More preferred &quot; alkyl &quot; is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferable &quot; alkyl &quot; is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms). Specific examples of the "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n-pentyl, isopentyl, neopentyl, Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl and 1-methylhexyl.

As &quot; cycloalkyl &quot; in Ar ² , for example, there is cycloalkyl having 3 to 12 carbon atoms. Preferable &quot; cycloalkyl &quot; is cycloalkyl having 3 to 10 carbon atoms. More preferable &quot; cycloalkyl &quot; is cycloalkyl having 3 to 8 carbon atoms. More preferred &quot; cycloalkyl &quot; is cycloalkyl having 3 to 6 carbon atoms. Specific examples of the "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.

As &quot; aryl &quot; in Ar ² , preferred aryl is aryl having 6 to 30 carbon atoms, more preferred aryl is aryl having 6 to 18 carbon atoms, more preferably aryl having 6 to 14 carbon atoms, Lt; / RTI &gt;

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

The two Ar ² may be combined to form a ring. As a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene or indene are spiro-bonded to the five-membered ring of the fluorene skeleton .

Specific examples of the benzofluorene derivatives include the following compounds.

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

&Lt; Phosphine oxide derivative >

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

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

R ⁶ represents CN, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, heteroaryl having 5 to 20 carbon atoms, An alkoxy of 1 to 20 carbon atoms, or aryloxy of 6 to 20 carbon atoms,

R ⁷ and R ^{8 are} each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 carbon atoms,

R &lt; ⁹ &gt; 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.

Examples of the substituent when it is substituted include aryl, heteroaryl, alkyl or cycloalkyl, and the like.

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

R ¹ to R ³ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a cycloalkylthio group, An aryl group, a heterocyclic group, a halogen, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an amino group, a nitro group, a silyl group, and a fused ring formed between adjacent substituents.

Ar ¹ may be the same or different and is an allylene group or a heteroalylene group. Ar ² may be the same or different and is an aryl group or a heteroaryl group. Provided that at least one of Ar ¹ and Ar ² has a substituent or forms a condensed ring with the adjacent substituent. n is an integer of 0 to 3, and when n is 0, the unsaturated structural moiety does not exist, and when n is 3, R ¹ does not exist.

Of these substituents, the alkyl group represents, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, which may be unsubstituted or substituted. The substituent when it is substituted is not particularly limited and includes, for example, an alkyl group, an aryl group, and a heterocyclic group, and this point is also common in the following description. The number of carbon atoms of the alkyl group is not particularly limited, but is usually in the range of 1 to 20 in consideration of the availability and cost.

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

The aralkyl group represents an aromatic hydrocarbon group, for example, through an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group. The aliphatic hydrocarbon and the aromatic hydrocarbon may be both unsubstituted or substituted. The number of carbon atoms in the aliphatic portion is not particularly limited, but usually ranges from 1 to 20.

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

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

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

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

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.

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.

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 substituted or unsubstituted. The number of carbon atoms of the aryl ether group is not particularly limited, but is usually in the range of 6 to 40.

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

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

The heterocyclic group 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 or a carbazolyl group, which may be unsubstituted or substituted . The number of carbon atoms of 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, the carbonyl group, and the amino group may be substituted with an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic ring, or the like.

Aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocyclic rings may be unsubstituted or substituted.

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

The condensed rings formed between adjacent substituents include, 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 And the like. Here, when n is 1, two R ¹ 's may be condensed rings of conjugated or non-conjugated rings. These condensed rings may contain nitrogen, oxygen, or sulfur atoms in the ring structure, and may also be condensed with other rings.

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

The phosphine oxide derivative can be produced by using known raw materials and a known synthesis method.

<Pyrimidine derivatives>

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

Ar is, independently of each other, optionally substituted aryl or optionally substituted heteroaryl. n is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 2 or 3.

The "aryl" of "optionally substituted aryl" includes, for example, aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, Is aryl having from 6 to 12 carbon atoms.

Specific examples of &quot; aryl &quot; include phenyl which is monocyclic aryl, (2-, 3-, 4-) biphenylyl which is bicyclic aryl, (1-, 2-) naphthyl which is condensed bicyclic aryl, M-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'- Yl, o-terphenyl-2-yl, o-terphenyl-2-yl, P-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic aryl , Acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m, naphthyl) (1, 2-yl), pyrene- ((2-methylphenyl) (1-, 2-, 3-) yl, naphthacene- (1-, 2-, 5-) 1-, 2-, 5-, 6-yl, and the like.

The "heteroaryl" of "heteroaryl which may be substituted" includes, for example, heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, more preferably heteroaryl having 2 to 20 carbon atoms More preferably a heteroaryl having 2 to 15 carbon atoms, and particularly preferably a heteroaryl having 2 to 10 carbon atoms. The heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring-constituting atom.

Specific examples of heteroaryl include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, Triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, , Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, Decyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolizinyl, and the like.

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

Specific examples of the pyrimidine derivative include the following compounds.

These pyrimidine derivatives can be prepared by using known methods and well-known synthetic methods.

<Carbazole derivatives>

The carbazole derivative is, for example, a compound represented by the following formula (ETM-9), or a multimer having plural bonds bonded thereto by a single bond or the like. The details are described in U.S. Publication No. 2014/0197386.

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

The "aryl" of "optionally substituted aryl" includes, for example, aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, Is aryl having from 6 to 12 carbon atoms.

Specific examples of &quot; aryl &quot; include phenyl which is monocyclic aryl, (2-, 3-, 4-) biphenylyl which is bicyclic aryl, (1-, 2-) naphthyl which is condensed bicyclic aryl, M-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'- Yl, o-terphenyl-2-yl, o-terphenyl-2-yl, P-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic aryl , Acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m, naphthyl) (1, &lt; / RTI &gt; 2-yl), pyrene- ( (1-, 2-, 3-) yl, naphthacene- (1-, 2-, 5-) 1-, 2-, 5-, 6-yl, and the like.

The "heteroaryl" of "heteroaryl which may be substituted" includes, for example, heteroaryl having 2 to 30 carbon atoms, heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms are more preferable More preferably a heteroaryl having 2 to 15 carbon atoms, and particularly preferably a heteroaryl having 2 to 10 carbon atoms. The heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring-constituting atom.

Specific heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl , Thiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, Benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, furylinyl, Tetradinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolizinyl, and the like.

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

The carbazole derivative may be a compound in which a compound represented by the formula (ETM-9) is bonded in a single bond or the like in plural. In this case, in addition to the single bond, they may be bonded with an aryl ring (preferably a polyvalent benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a benzofluorene ring, a phenylene ring, a phenanthrene ring or a triphenylene ring) .

Specific examples of the carbazole derivative include the following compounds.

The carbazole derivative can be produced by using a known synthesis method and a known raw material.

<Triazine Derivative>

The triazine derivative is, for example, a compound represented by the following formula (ETM-10), preferably a compound represented by the following formula (ETM-10-1). The details are described in U.S. Publication No. 2011/0156013.

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

The "aryl" of "optionally substituted aryl" includes, for example, aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, Is aryl having from 6 to 12 carbon atoms.

Specific examples of &quot; aryl &quot; include phenyl which is monocyclic aryl, (2-, 3-, 4-) biphenylyl which is bicyclic aryl, (1-, 2-) naphthyl which is condensed bicyclic aryl, M-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'- Yl, o-terphenyl-2-yl, o-terphenyl-2-yl, P-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic aryl , Acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m, naphthyl) (1, 2-yl), pyrene- ((2-methylphenyl) (1-, 2-, 3-) yl, naphthacene- (1-, 2-, 5-) 1-, 2-, 5-, 6-yl, and the like.

The "heteroaryl" of "heteroaryl which may be substituted" includes, for example, heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, more preferably heteroaryl having 2 to 20 carbon atoms More preferably a heteroaryl having 2 to 15 carbon atoms, and particularly preferably a heteroaryl having 2 to 10 carbon atoms. The heteroaryl includes, for example, a heterocyclic ring containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring-constituting atom.

Specific examples of heteroaryl include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furanzanyl, thiadiazolyl, Triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, , Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, Decyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolizinyl, and the like.

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

Specific examples of the triazine derivative include the following compounds.

The triazine derivative can be produced by using known raw materials and a known synthesis method.

&Lt; Benzimidazole derivative >

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

φ is, n-valent, and aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, a benzo fluorene ring, a penal renhwan, phenanthrene renhwan or triphenyl renhwan), n is from 1 to 4 And the "benzimidazole-based substituent" is an integer in which the pyridyl group in the "pyridine group substituent" in the formula (ETM-2), the formula (ETM-2-1) and the formula (ETM- And at least one hydrogen in the benzimidazole derivative may be substituted with deuterium.

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

φ is also an anthracene ring or a fluorene Whanin preferably, the structure in this case may be cited for explanation in the formula (ETM-2-1) or a group represented by the formula (ETM-2-2), R in each formula ¹¹ ~R ¹⁸ can be cited for explanation in the formula (ETM-2-1) or a group represented by the formula (ETM-2-2). In the formula (ETM-2-1) or the formula (ETM-2-2), two pyridine-based substituents are described as being bonded. When these substituents are substituted with benzimidazole-based substituents, both pyridine- (That is, n = 2), one of the pyridine substituents may be substituted with a benzimidazole substituent, and the other substituent may be substituted with R ¹¹ to R ¹⁸ n = 1). For example, at least one of R ¹¹ to R ¹⁸ in the formula (ETM-2-1) may be substituted with a benzimidazole-based substituent and the "pyridine-based substituent" may be substituted with R ¹¹ to R ¹⁸ .

Specific examples of the benzimidazole derivative include 1-phenyl-2- (4- (10-phenylanthracene-9-yl) phenyl) -1H- benzo [d] imidazole, 2- Yl) phenyl] -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (naphthalen- Benzo [d] imidazole, 5- (10- (naphthalen-2-yl) anthracene-9-yl) -1,2-diphenyl- Benzo [d] imidazole, 2- (4- (9,10-di (tert-butoxycarbonyl) (Naphthalen-2-yl) anthracene-2-yl) phenyl) -1-phenyl-1H- benzo [d] imidazole, 1- (4- (9,10- Yl) -1,2-diphenyl-lH-benzo [d] imidazole, 5- (9,10- Benzo [d] imidazole, and the like.

These benzimidazole derivatives can be prepared by using known raw materials and known synthesis methods.

&Lt; Phenanthroline derivatives >

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

φ is, n-valent, and aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, a benzo fluorene ring, a penal renhwan, phenanthrene renhwan or triphenyl renhwan), n is from 1 to 4 It is an integer.

R ¹¹ to R ¹⁸ in each formula are each independently selected from the group consisting of hydrogen, alkyl (preferably having 1 to 24 carbon atoms), cycloalkyl (preferably having 3 to 12 carbon atoms) Aryl of 6 to 30). In the formula (ETM-12-1), any one of R ¹¹ to R ¹⁸ is bonded to an aryl ring ?.

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

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

Specific examples of the phenanthroline derivative include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, (1,10-phenanthroline-5-yl) pyridine, 1,3,5-tri (1,10- 5-yl) benzene, 9,9'-difluoro-bis (1,10-phenanthroline-5-yl) 9-yl) benzene, a compound represented by the following structural formula, and the like.

These phenanthroline derivatives can be prepared by using known methods and well-known synthetic methods.

<Quinolinol-based metal complexes>

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

Wherein, R ¹ ~R ⁶ are, each independently, a hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, an alkoxy, or aryl, M is Li, Al, Ga, Be, or Zn, n is an integer of 1 to 3;

Specific examples of the quinolinol-based metal complexes include 8-quinolinolithium, tris (8-quinolinolato) aluminum, tris (4-methyl-8- quinolinolato) aluminum, tris (5-methyl- Quinolinolato) aluminum, tris (3,4-dimethyl-8-quinolinolato) aluminum, tris (4,5- -Quinolinolate) aluminum, bis (2-methyl-8-quinolinolate) (phenolate) aluminum, bis (2- (2-methyl-8-quinolinolate) (3-methylphenolate) aluminum, bis (2-methyl- (2-methyl-8-quinolinolate) aluminum, bis (2-methyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinol (2-methyl-8-quinolinolate) aluminum (2,2-dimethylphenolate) aluminum, bis (2-methyl- (3,5-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-methyl-8-quinolinolate) Aluminum, bis (2-methyl-8-quinolinolate) (2,6-diphenylphenolate) aluminum, bis (2- Aluminum (2,4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) Aluminum, bis (2-methyl-8-quinolinolate) (1-naphtholate) aluminum, bis (2-naphtholate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2,4- (3,5-dimethylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-di- (2-methyl-8-quinolinolate) aluminum-mu- (2-methyl-8-quinolinolate) (2-methyl-4-ethyl-8-quinolinolate) aluminum-mu-oxo-bis (2-methyl- -Ethyl-8-quinolinolate) aluminum, bis (2-methyl-4-methoxy-8-quinolinolate) aluminum- Aluminum, bis (2-methyl-5-cyano-8-quinolinolate) aluminum-mu-oxo-(2-methyl-5-trifluoromethyl-8-quinolinolate) aluminum,? - oxo-bis 10-hydroxybenzo [h] quinoline) beryllium and the like.

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

&Lt; 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 of the equations is, n-valent aryl ring is a (preferably n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, a benzo fluorene ring, a penal renhwan, phenanthrene renhwan or triphenyl renhwan), n is 1 , "Thiazole-based substituent" or "benzothiazole-based substituent" is an integer of 1 to 4 in the formula (ETM-2) System substituent "is a substituent substituted by a thiazole group or a benzothiazole group, and at least one hydrogen in the thiazole derivative or the benzothiazole derivative may be substituted with deuterium.

φ is also an anthracene ring or a fluorene Whanin preferably, the structure in this case may be cited for explanation in the formula (ETM-2-1) or a group represented by the formula (ETM-2-2), R in each formula ¹¹ ~R ¹⁸ can be cited for explanation in the formula (ETM-2-1) or a group represented by the formula (ETM-2-2). In the formula (ETM-2-1) or the formula (ETM-2-2), two pyridine-based substituents are described as being bonded. When these substituents are substituted with a thiazole-based substituent (or a benzothiazole substituent) Both pyridine substituents may be substituted with a thiazole substituent (or a benzothiazole substituent) (that is, n = 2), one of the pyridine substituents may be substituted with a thiazole substituent (or a benzothiazole substituent) The pyridine substituent may be substituted by R ¹¹ to R ¹⁸ (that is, n = 1). Also, for example, the formula ^{(ETM-2-1) R 11 ~R} 18 thiazole substituent one or more of (or benzo thiazole substituent) R and the substituted "pyridine-based substituent" in ~R ¹¹ in ¹⁸ .

These thiazole derivatives or benzothiazole derivatives can be prepared by using well-known synthesis methods and known raw materials.

The electron transporting layer or the electron injecting layer may further include a material capable of reducing the material forming the electron transporting layer or the electron injecting layer. The reducing material is a material having a certain reducing property, and various materials are used. For example, an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, At least one selected from the group consisting of a halide of a rare earth metal, an oxide of a rare earth metal, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal and an organic complex of a rare earth metal can be preferably used.

Preferred examples of the reducing material include alkaline 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) An alkaline earth metal such as Sr (work function 2.0 to 2.5 eV) or Ba (work function 2.52 eV), and a material having a work function of 2.9 eV or less is particularly preferable. Among them, the more preferable reducing material is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have a high reducing ability, and by the addition of a relatively small amount to a material for forming the electron transporting layer or the electron injecting layer, the luminescence brightness and the longevity of the organic EL element are improved. A combination of two or more kinds of alkali metals is also preferable as a reducing material having a work function of 2.9 eV or less. In particular, a combination including Cs, for example, Cs and Na, Cs and K, Cs and Rb, The combination of Na and K is preferred. By including Cs, the reducing ability can be efficiently exerted, and the addition of the material to the electron transporting layer or the material forming the electron injecting layer improves the luminescence brightness and the longevity of the organic EL device.

&Lt; Negative electrode in organic electroluminescent 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 electrons can be efficiently injected 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 -Indium alloy, an aluminum-lithium alloy such as lithium fluoride / aluminum) and the like are preferable. In order to increase the electron injection efficiency and improve the device characteristics, alloys comprising lithium, sodium, potassium, cesium, calcium, magnesium or their low work function metals are effective. However, these low work function metals are generally unstable in the atmosphere. In order to solve this problem, for example, a method is known in which an organic layer is doped with a small amount of lithium, cesium or magnesium to use an electrode having high stability. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide and cesium oxide may also be used. However, the present invention is not limited to these.

In order to protect the electrodes, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium or alloys using these metals and inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, A hydrocarbon-based polymer compound or the like may be laminated as a preferable example. The production method of these electrodes is not particularly limited as long as it is able to conduct such as resistance heating, electron beam beam deposition, sputtering, ion plating and coating.

&Lt; Binder agent which can be used in each layer >

The above materials used for the hole injection layer, the hole transporting layer, the light emitting layer, the electron transporting layer, and the electron injecting layer can form each layer alone. However, as the polymer binder, polyvinyl chloride, polycarbonate, polystyrene, poly Polyvinyl pyrrolidone, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethylcellulose, vinyl acetate resin, ABS resin, A resin soluble in a solvent such as a resin or a polyurethane resin or a curable resin such as a phenol resin, a xylene resin, a petroleum resin, a urea resin, a melamine resin, an unsaturated polyester resin, an alkyd resin, an epoxy resin, It is possible.

&Lt; Method for producing organic electroluminescent device &

Each layer constituting the organic EL element can be formed by a method such as a vapor deposition method, a resistance heating deposition method, an electron beam deposition method, a sputtering method, a molecular lamination method, a printing method, a spin coating method, a casting method, To form a thin film. The film thickness of each layer thus formed is not particularly limited and may be appropriately set in accordance with the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can be generally measured by a crystal oscillation type film thickness measuring apparatus or the like. In the case of thinning using a vapor deposition method, the deposition conditions depend on the type of material, crystal (crystal) structure and assembly structure to be the target of the film, and the like. The deposition conditions are generally in the range of boat heating temperature + 50 to + 400 占 폚, vacuum degree ^10-6 to ^10-3 Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature -150 to + 300 占 폚, It is desirable to set it appropriately.

Next, a description will be given of a method for producing an organic EL device comprising an anode / a hole injecting layer / a hole transporting layer / a light emitting layer / an electron transporting layer / an electron injecting layer / a cathode made of a host material and a dopant as an example of a method of manufacturing an organic EL device do. A thin film of a cathode material is formed on a suitable substrate by a vapor deposition method or the like to produce a cathode, and a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-deposited to form a thin film to form a light emitting layer, an electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a material for a negative electrode is formed by evaporation or the like, The desired organic EL device can be obtained. In the fabrication of the above-described organic EL device, the cathode, the electron injecting layer, the electron transporting layer, the light emitting layer, the hole transporting layer, the hole injecting layer, and the anode may be fabricated in this order.

When a direct current voltage is applied to the thus obtained organic EL device, the positive electrode may be applied as the positive polarity and the negative polarity may be applied as the negative polarity. If a voltage of approximately 2 to 40 V is applied, the transparent or semi- , And both) can be observed. Further, this organic EL element emits light even when a pulse current or an alternating current is applied. The waveform of the applied alternating current can be arbitrarily set.

&Lt; Example of application of organic electroluminescent device &

The present invention can also be applied to a display device having an organic EL device or a lighting device having an organic EL device.

The display device or the illumination device provided with the organic EL device can be manufactured by a known method such as connecting the organic EL device according to the present embodiment and a known drive device and can be manufactured by a known method such as direct current drive, It is possible to drive by using the driving method of FIG.

As the display device, there are, for example, a panel display such as a color flat panel display and a flexible display such as a flexible color organic electroluminescence (EL) display (for example, Japanese Laid-Open Patent Publication No. 10-335066, 2003-321546, Japanese Patent Application Laid-Open No. 2004-281086, etc.). The display method of the display includes, for example, a matrix and / or a segment method. The matrix display and the segment display may coexist in the same panel.

In the matrix, pixels for display are arranged two-dimensionally such as a lattice type or a mosaic type, and a character or an image is displayed as a set of pixels. The shape and size of the pixel are determined depending on the application. For example, in the case of a large-sized display such as a display panel, a square pixel of 300 mu m or less is usually used for image and character display of a PC, a monitor, and a television, do. In the case of monochrome display, it is preferable to arrange pixels of the same color, but in the case of color display, red, green and blue pixels are arranged and displayed. In this case, there are typically a delta type and a stripe type. The driving method of the matrix may be either a line sequential driving method or an active matrix. The line-sequential drive has a simple structure. However, when the operating characteristics are taken into account, the active matrix may be advantageous.

In the segment method (type), a pattern is formed so as to display predetermined information, and the determined area is caused to emit light. For example, there are a time and temperature display in a digital clock or a thermometer, an operation status display of an audio device or an electromagnetic cooker, and a panel display of an automobile.

Examples of the illumination device include an illumination device such as an indoor illumination, a backlight of a liquid crystal display device, and the like (see, for example, JP-A-2003-257621, JP-A-2003-277741, Patent Document No. 2004-119211, etc.). The backlight is used mainly for the purpose of improving the visibility of a display device which does not emit light, and is used for a liquid crystal display device, a watch, an audio device, an automobile panel, a display panel, and a marking. Particularly, as a backlight of a liquid crystal display device, particularly a PC for which thinning is a problem, since the conventional system is a fluorescent lamp or a light guide plate (light guide plate), considering that it is difficult to reduce the thickness, The backlight is characterized by being thin and lightweight.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. First, synthesis examples of a polycyclic aromatic compound and a pyrene-based compound will be described below.

Synthesis Example (1): Synthesis of Compound (1-290)

Under a nitrogen atmosphere, the flask containing methyl 4-methoxysalicylate (50.0 g) and pyridine (dehydrated) (350 ml) was cooled in an ice bath. Next, trifluoromethanesulfonic anhydride (154.9 g) was added dropwise to this solution. After completion of the dropwise addition, the ice bath was removed, stirred at room temperature for 2 hours, and water was added to stop the reaction. The organic layer was separated by adding toluene and then purified by silica gel short pass column (eluent: toluene) to obtain methyl 4-methoxy-2 - (((trifluoromethyl) sulfonyl) oxy) benzoate (86.0 g ).

(25.4 g) was added to a solution of methyl 4-methoxy-2 - (((trifluoromethyl) sulfonyl) oxybenzoate (23.0 g) 3 potassium (31.1g), toluene (184ml), ethanol (27.6ml), and to the suspension a solution of water _{(27.6ml), Pd (PPh 3} ) was added to ₄ (2.5g), reflux (還流) was stirred for 3 hours at a temperature did. The reaction solution was cooled to room temperature, water and toluene were added to separate the organic layer, and the solvent of the organic layer was distilled off under reduced pressure. The resulting solid was purified by silica gel column (eluent: heptane / toluene mixed solvent) to obtain methyl 4 '- (diphenylamino) -5-methoxy- [1,1'-biphenyl] -2-carboxylate (29.7 g). At this time, with reference to the method described in "Organic Chemistry Experiment Guide (1) -Material Handling Method and Separation and Refinement Method" published by Kagaku Dojin Publishing Co., Ltd., page 94, the proportion of toluene in the eluent was gradually increased to elute ).

(111.4 ml) solution of methyl 4 '- (diphenylamino) -5-methoxy- [1,1'-biphenyl] -2-carboxylate (11.4 g) in a nitrogen atmosphere was cooled Methylmagnesium bromide THF solution (1.0 M, 295 ml) was added dropwise to the solution. After completion of dropwise addition, the water bath was removed, and the mixture was heated to reflux temperature and stirred for 4 hours. Thereafter, the reaction mixture was cooled in an ice bath, and an aqueous ammonia solution was added to stop the reaction. Ethyl acetate was added to separate the organic layer, and the solvent was distilled off under reduced pressure. The resulting solid was purified by silica gel column (eluant: toluene) to give 2- (4'- (diphenylamino) -5-methoxy- [1,1'- biphenyl] -2-yl) propan- (8.3 g).

(27.0 g) and TAYCACURE-15 (13.5 g) were added to a solution of 2- (4'- (diphenylamino) -5-methoxy- [ g) and toluene (162 ml) were stirred at a reflux temperature for 2 hours. The reaction solution was cooled to room temperature and TAYCACURE-15 was removed by passing through a silica gel short pass column (eluent: toluene), and then the solvent was distilled off under reduced pressure to obtain 6-methoxy-9,9'-dimethyl- N-diphenyl-9H-fluorene-2-amine (25.8 g).

(25.0 g), pyridine hydrochloride (36.9 g), and N-methyl-2-pyrrolidinecarboxylate were added to a solution of 6-methoxy-9,9'- (NMP) (22.5 ml) was stirred at reflux temperature for 6 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added, and the organic layer was separated. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column (eluant: toluene) to obtain 7- (diphenylamino) -9,9'-dimethyl-9H-fluoren-3-ol (22.0 g).

Under nitrogen atmosphere, 14.1 g of 7- (diphenylamino) -9,9'-dimethyl-9H-fluoren-3-ol, 3.6 g of 2-bromo-1,3-difluorobenzene, A flask containing potassium carbonate (12.9 g) and NMP (30 ml) was heated and stirred at reflux temperature for 5 hours. After the reaction was stopped, the reaction solution was cooled to room temperature, and water was added to precipitate the precipitate, which was collected by suction filtration. The obtained precipitate was washed with water and then with methanol and then purified by silica gel column (eluent: heptane / toluene mixed solvent) to obtain 6,6 '- ((2-bromo-1,3-phenylene) )) Bis (9,9-dimethyl-N, N-diphenyl-9H-fluoren-2-amine) (12.6 g). At this time, the proportion of toluene in the eluent was gradually increased to elute the target product.

(9,9-dimethyl-N, N-diphenyl-9H-fluorene-2- (4-methoxyphenyl) Amine) (11.0 g) and xylene (60.5 ml) was cooled to -40 ° C, and 2.6 M n-butyllithium hexane solution (5.1 ml) was added dropwise. After completion of dropwise addition, the mixture was stirred at this temperature for 0.5 hours, then heated to 60 ° C and stirred for 3 hours. Thereafter, the reaction solution was reduced in pressure and the low boiling point component was distilled off, and then cooled to -40 DEG C and boron tribromide (4.3 g) was added. After the mixture was heated to room temperature and stirred for 0.5 hour, the mixture was cooled to 0 deg. C, and N-ethyl-N-isopropylpropane-2-amine (3.8 g) was added and the mixture was heated and stirred at 125 DEG C for 8 hours. The reaction solution was cooled to room temperature, and an aqueous solution of sodium acetate was added to stop the reaction. Toluene was added to separate the organic layer. The organic layer was purified with a silica gel short pass column, followed by silica gel column (eluent: heptane / toluene = 4 (volume ratio)) and an activated carbon column (eluent: toluene) to obtain 1.290 g of a compound (1-290).

The structure of the compound (1-290) obtained by NMR measurement was confirmed.

^{1 H-NMR (400MHz, CDCl} 3): δ = 8.64 (s, 2H), 7.75 (m, 3H), 7.69 (d, 2H), 7.30 (t, 8H), 7.25 (s, 2H), 7.20 ( m, 10H), 7.08 (m, 6H), 1.58 (s, 12H).

Synthesis Example (2): Synthesis of Compound (1-139)

Compound (1-139) was synthesized using the same method as the above-mentioned synthesis example.

The structure of the compound (1-139) obtained by NMR measurement was confirmed.

^{1 H-NMR (500MHz, CDCl} 3): δ = 1.47 (s, 36H), 2.17 (s, 3H), 5.97 (s, 2H), 6.68 (d, 2H), 7.28 (d, 4H), 7.49 ( dd, 2H), 7.67 (d, 4H), 8.97 (d, 2H).

Synthesis Example (3): Synthesis of compound (1-151)

Compound (1-151) was synthesized using the same method as in the above-mentioned synthesis example.

The structure of the compound (1-151) obtained by NMR measurement was confirmed.

^{1 H-NMR (500MHz, CDCl} 3): δ = 1.46 (s, 18H), 1.47 (s, 18H), 6.14 (d, 2H), 6.75 (d, 2H), 7.24 (t, 1H), 7.29 ( d, 4H), 7.52 (dd, 2H), 7.67 (d, 4H), 8.99 (d, 2H).

Synthesis Example (4): Synthesis of Compound (2-1) "11,11-diphenyl-6- (pyrene-1-yl) -11H-benzo [a]

(9.5 g), bis (pinacolato) diboron (12.2 g), potassium acetate (11.8 g) and (1,1'-dicyclohexylcarbodiimide) as a palladium catalyst were added to a flask under a nitrogen atmosphere. Palladium (II) dichloride · dichloromethane complex (0.98 g) and cyclopentyl methyl ether (CPME, 143 mL) were placed in a flask, and the mixture was stirred at a reflux temperature for 4 hours under a nitrogen atmosphere . The reaction solution was cooled to room temperature, water was added, and further ethyl acetate was added to separate the solution. The organic layer was separated, dried and concentrated, and purified with an activated carbon short pass column (eluant: toluene) to obtain Intermediate A (11.3 g).

Tetrakis (triphenylphosphine) palladium (1.4 g) and toluene (85 mL) as a palladium catalyst were added to a solution of the intermediate A (11.3 g), methyl 2-bromobenzoate (8.6 g), potassium phosphate , Ethanol (17 mL) and water (9 mL) were placed in a flask, and the mixture was stirred under a nitrogen atmosphere at a reflux temperature for 7 hours. The reaction solution was cooled to room temperature, water was added, and toluene was added thereto to effect liquid separation. The organic layer was separated, dried and concentrated. The crude product was purified by silica gel column (eluant: toluene) to obtain intermediate B (9.1 g).

A 1 M aqueous solution of phenylmagnesium bromide / THF (94 mL) was added dropwise to the flask under nitrogen atmosphere, and the mixture was stirred at room temperature for 3 hours. Stir at a time reflux temperature. After cooling, a saturated aqueous solution of ammonium chloride was added to quench the reaction, and ethyl acetate was added to extract the solvent. The organic layer was separated, dried and concentrated, and the crude product was purified by silica gel column (eluant: toluene) to obtain Intermediate C (12.3 g).

Under a nitrogen atmosphere, a flask was charged with Intermediate C (12.3 g) and acetic acid (117 mL) into a flask, and 1 drop of concentrated sulfuric acid was added thereto, followed by stirring at 90 캜 for 3 hours under a nitrogen atmosphere. After cooling, water was added, the precipitate was filtered, and the precipitate was washed with water and dried to obtain Intermediate D (10.6 g).

(10.6 g), pyridine hydrochloride (15.4 g) and N-methylpyrrolidone (NMP, 10 mL) were placed in a flask, and the mixture was stirred at 185 캜 for 4 hours under a nitrogen atmosphere. After cooling, water was added, the precipitate was filtered, and the precipitate was washed with water and dried to obtain Intermediate E (10.1 g).

Intermediate E (10 g) and pyridine (100 mL) were placed in a flask under a nitrogen atmosphere, cooled in an ice bath, and then trifluoromethanesulfonic anhydride (18.3 g) was added dropwise under a nitrogen atmosphere. After stirring for 3 hours as it was, water was added to stop the reaction. The precipitate was filtered and purified by silica gel short pass column (eluant: toluene) to obtain Intermediate F (13.4 g).

(2.1 g), potassium phosphate (2.5 g), tetrakis (triphenylphosphine) palladium (0.2 g) as a palladium catalyst, 1,2,4- Trimethylbenzene (24 mL), tert-butyl alcohol (3 mL) and water (1.5 mL) were placed in a flask, and the mixture was stirred at a reflux temperature for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and toluene was added thereto to effect liquid separation. The organic layer was separated, dried and concentrated. The crude product was purified by silica gel column (eluant: toluene / heptane = 3/1 (volume ratio)) and then purified by sublimation to obtain 1.2 g of compound (2-1) .

The structure of the compound (2-1) obtained by NMR measurement was confirmed.

_{^{1 H-NMR (CDCl 3)}} : 6.0 (d, 1H), 6.6 (dt, 1H), 7.0 (dt, 1H), 7.2~7.5 (m, 13H), 7.9~8.0 (m, 5H), 8.0 ( t, 1 H), 8.2-8.3 (m, 5 H), 8.4 (d, 1 H).

Synthesis Example (5): Synthesis of Compound (2-46) Synthesis of "6- (6- (naphthalen-2-yl) pyrene-1-yl) -11,11-diphenyl-11H-benzo [a] fluorene"

(2.7 g), 2-naphthylboronic acid (1.7 g), potassium carbonate (2.7 g) and tetrakis (triphenylphosphine) palladium (0.3 g, ), Toluene (35 mL), and water (9 mL) were placed in a flask, and the mixture was stirred under a nitrogen atmosphere at a reflux temperature for 3 hours. The reaction solution was cooled to room temperature, water was added, and toluene was added thereto to effect liquid separation. The organic layer was separated, dried and concentrated. The crude product was purified by silica gel column (eluant: toluene / heptane = 6/1 (volume ratio)) to obtain Intermediate G (2.1 g).

(7 g), bis (pinacolato) diboron (4.1 g), potassium acetate (4.0 g) and palladium catalyst (1,1'-bis (diphenylphosphino) ferrocene) palladium II) A dichloride · dichloromethane complex (0.3 g) and cyclopentyl methyl ether (CPME, 67 mL) were placed in a flask, and the mixture was stirred at a reflux temperature for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and ethyl acetate was added thereto to effect liquid separation. The organic layer was separated, dried and concentrated, and purified with an activated carbon short pass column (eluant: toluene) to obtain Intermediate H (4.6 g).

(0.9 g), potassium phosphate (0.9 g), tetrakis (triphenylphosphine) palladium (0.1 g) as a palladium catalyst, 1,2,4-trimethylbenzene (12 mL), tert-butyl alcohol (2 mL) and water (1 mL) were placed in a flask, and the mixture was stirred under a nitrogen atmosphere at a reflux temperature for 14 hours. The reaction solution was cooled to room temperature, water was added, and toluene was added to perform liquid fraction extraction. The organic layer was separated, dried and concentrated. The crude product was purified by silica gel column (eluant: toluene / heptane = 1/3 (volume ratio)) and then purified by sublimation to obtain compound (2-46) .

The structure of the compound (2-46) obtained by NMR measurement was confirmed.

_{^{1 H-NMR (CDCl 3)}} : 6.0 (d, 1H), 6.6 (dt, 1H), 7.0 (dt, 1H), 7.2~7.6 (m, 15H), 7.8~8.2 (m, 14H), 8.2~ 8.3 (m, 2H).

Synthesis Example (6): Synthesis of Compound (2-1001) "3,9-di (pyrene-1-yl) spiro [benzo [a] fluorene-11,9'-

Under a nitrogen atmosphere, a flask containing pyrene-1-boronic acid (5 g), ethylene glycol (3.8 g) and toluene (30 mL) was stirred at reflux temperature for 3 hours. After the reaction, the mixture was cooled, water was added and stirred, and the organic layer was separated, and the organic layer was concentrated under reduced pressure to obtain a crude product. After passing the crude through a silica gel short pass column (eluent: toluene), the eluent was concentrated to obtain 2- (pyrene-1-yl) -1,3,2-dioxaborolane (4.2 g).

(3.8 g), 2- (pyrene-1-yl) -1,3,2-dioxaborolane (3.3 g) synthesized by the method described in JP-A-2009-184993, Palladium (II) (19 mg), potassium carbonate (3.2 g), and tetrabutylammonium bromide (2 g) as a palladium catalyst, TBAB, 0.6 g), cyclopentyl methyl ether (CPME, 20 mL) and water (2 mL) were placed in a flask, and the mixture was heated and stirred at reflux temperature for 9 hours. After the reaction, the reaction mixture was cooled, water was added to the reaction mixture, and the mixture was stirred. Then, the precipitate was filtered. The precipitate was dried and then dissolved by heating in chlorobenzene, followed by filtration with a silica gel short pass column (eluant: toluene) and concentration of the eluate. The resulting solid was filtered, dried and purified to obtain the compound (2-1001) (2.2 g).

The structure of the compound (2-1001) obtained by NMR measurement was confirmed.

_{^{1 H-NMR (CDCl 3)}} : 6.9~7.0 (m, 4H), 7.2 (t, 2H), 7.4 (dd, 1H), 7.4 (dt, 2H), 7.7 (dd, 1H), 7.8~7.9 ( m, 2H), 7.9-8.1 (m, 9H), 8.1-8.2 (m, 13H).

Synthesis Example (7): Compound (2-350) Synthesis of "2- (pyrene-1-yl) triphenylene"

Under a nitrogen atmosphere, 4,4,5,5-tetramethyl-2- (triphenylene-2-yl) -1,3,2-dioxaborolane (3.0 g), 1-bromoprene Palladium (II) (25 mg), potassium carbonate (2.2 g), and bromine (2 g) as a palladium catalyst, Tetrabutylammonium (TBAB, 0.8 g), cyclopentyl methyl ether (CPME, 20 mL) and water (2 mL) were placed in a flask, and the mixture was heated and stirred at a reflux temperature for 2 hours. After the reaction, the reaction mixture was cooled, water was added to the reaction mixture, and the mixture was stirred. Then, the precipitate was filtered. The precipitate was dried and then dissolved by heating in chlorobenzene, followed by filtration with a silica gel short pass column (eluant: toluene) and concentration of the eluate. The resulting solid was filtered, dried and purified to obtain a compound (2-350) 3.3 g).

The structure of the compound (2-350) obtained by NMR measurement was confirmed.

_{^{1 H-NMR (CDCl 3)}} : 7.6~7.7 (m, 4H), 7.9 (dd, 1H), 8.0 (m, 2H), 8.1~8.2 (m, 4H), 8.2 (m, 1H), 8.3 ( m, 2H), 8.7-8.8 (m, 4H), 8.8 (d, 1H), 8.9 (d, 1H).

Synthesis Example (8): Compound (2-1080) "3,9-Bis (7- (tert-butyl) Synthesis of

Intermediate J (1.7 g), 2-bromo-7- (tert-butyl) pyrene (2 g) synthesized by the method described in International Publication No. 2015/141608 and chlorophenyl allyl , Potassium carbonate (1.6 g), tetrabutylammonium bromide (TBAB, 0.3 g), cyclopentyl (2-methylphenyl) imidazol-2-ylidene] palladium Methyl ether (CPME, 20 mL) and water (2 mL) were placed in a flask, and the mixture was heated and stirred at reflux temperature for 4 hours. After the reaction, the reaction mixture was cooled, water was added to the reaction mixture, and the mixture was stirred. Then, the precipitate was filtered. The precipitate was dried and then dissolved in chlorobenzene, followed by filtration with a silica gel short pass column (eluant: toluene) and concentration of the eluate. The resulting solid was filtered, dried, and then purified by sublimation to obtain a compound (2-1080) (1.6 g).

The structure of the compound (2-1080) obtained by NMR measurement was confirmed.

_{^{1 H-NMR (CDCl 3)}} : 1.6 (s, 9H), 1.6 (s, 9H), 6.9 (d, 2H), 6.9 (d, 1H), 7.1 (dt, 2H), 7.2 (d, 1H) , 7.5 (dt, 2H), 7.6 (dd, IH), 7.9 (dd, IH), 8.0-8.2 (m, 19H), 8.3 (s, 3H).

Synthesis Example (9): Synthesis of Compound (2-174) "2- (Pyran-1-yl) naphtho [2,3- b] benzofuran"

To a solution of 1-pyrenoboronic acid (1.0 g) and 2-bromobenzo [b] naphtho [2,3-d] furan synthesized by the method described in International Publication No. 2014/141725 ), Tetrakis (triphenylphosphine) palladium (0.09 g), potassium phosphate (1.7 g), xylene (15 mL), tert-butyl alcohol (5 mL) and water (3 mL) as a palladium catalyst were charged in a flask, At room temperature for 2 hours. After the reaction, the reaction mixture was cooled, water and ethyl acetate were added to the reaction mixture, and the mixture was stirred. The precipitate was filtered and washed with water and methanol. The precipitate was dried and then dissolved by heating in chlorobenzene, followed by filtration with a silica gel short pass column (eluent: toluene), and the eluate was concentrated. The obtained solid was further purified by chlorobenzene / re-precipitation. The obtained solid was dried and then purified by sublimation to obtain the compound (2-174) (1.0 g).

The structure of the compound (2-174) obtained by NMR measurement was confirmed.

¹ H-NMR (CDCl ₃ ): 7.5 (m, 1H), 7.5-7.6 (m, 1H), 7.7-7.8 (m, 2H), 8.0-8.3 (m, 13H), 8.5 (s, 1H).

Synthesis Example (10): Synthesis of Compound (2-356) "2- (Pyrene-1-yl) dibenzo [g, p]

3-bromodibenzo [g, p] chrysene (14 g) and tetrahydrofuran (THF, 200 mL) synthesized by the method described in JP-A No. 2011-006397 were placed in a flask, The mixture was cooled to -78 ° C in a dry ice-acetone bath, and 1.6M n-butyllithium / hexane solution (28 mL) was added dropwise. After stirring at the same temperature for 0.5 hours, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (12.8 g) was added. After stirring at the same temperature for 3 hours, the temperature was raised and diluted hydrochloric acid was added to stop the reaction. After toluene was added and extracted, the organic layer was concentrated, and the obtained crude product was purified by silica gel column (eluent: toluene / heptane = 7/3 (volume ratio)) to obtain Intermediate K (11.5 g).

(1.0 g), 1-bromopyrrene (0.59 g), bis (di-tert-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (16 mg) and potassium phosphate 0.9 g), xylene (10 mL), tert-butyl alcohol (3 mL) and water (2 mL) were placed in a flask and stirred at reflux temperature for 2 hours. After the reaction, the reaction solution was cooled, water and ethyl acetate were added, and the mixture was stirred, and then the deposited precipitate was filtered. The obtained crude product was purified by a silica gel short pass column (eluant: toluene), followed by reprecipitation with toluene / heptane. The obtained solid was dried and then purified by sublimation to obtain the compound (2-356) (0.7 g).

The structure of the compound (2-356) obtained by NMR measurement was confirmed.

¹ H-NMR (CDCl ₃ ): 7.7 (m, 6H), 7.9 (dd, 1H) 8.0-8.1 (m, 2H), 8.1-8.3 (m, 5H), 8.3 (M, 1H), 8.7 (d, 1H), 9.0 (d, 1H).

Synthesis Example (11): Synthesis of Compound (2-359) Synthesis of 1,6-bis (naphtho [2,3-b] benzofuran-2-yl) -3a ¹ , 5a ¹ -dihydropyrene

B] naphtho [2,3-d] furan (10.8 g) synthesized by the method described in International Publication No. 2014/141725 and tetrahydrofuran (THF, 200 mL) Was placed in a flask and cooled to -78 캜 in a dry ice-acetone bath. 1.6M of n-butyllithium / heptane solution (25 mL) was added dropwise thereto. After stirring at the same temperature for 1 hour, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10 g) was added. After stirring at the same temperature for 2 hours, the temperature was raised and diluted hydrochloric acid was added to stop the reaction. After toluene was added and extracted, the organic layer was concentrated, and the obtained crude product was purified by silica gel column (eluent: toluene / heptane = 7/3 (volume ratio)) to obtain Intermediate L (9.2 g).

(1.0 g), Intermediate L (2.0 g), bis (di-tert-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (20 mg) as a palladium catalyst, Potassium phosphate (2.4 g), xylene (15 mL), tert-butyl alcohol (3 mL) and water (2 mL) were placed in a flask and stirred at reflux temperature for 2 hours. After the reaction, the reaction solution was cooled, water and ethyl acetate were added and stirred, and the precipitated precipitate was filtered. The obtained crude product was purified by a silica gel short pass column (eluant: toluene), washed with hot chlorobenzene, and purified. The obtained solid was dried and then purified by sublimation to obtain a compound (2-359) (1.6 g).

The compound (2-359) obtained by LC-MS measurement was confirmed.

MS (ACPI) m / z = 635 (M + H) &lt;

Other compounds used in the present invention can be synthesized by the method according to the above-mentioned synthesis example by suitably changing the compound of the starting material.

Hereinafter, to describe the present invention in more detail, examples of the organic EL device using the compound of the present invention are shown, but the present invention is not limited thereto.

The organic EL devices according to Examples 1 to 12 and Comparative Example 1 were fabricated and the voltage (V), the emission wavelength (nm) and the external quantum efficiency (%), which are characteristics at the time of light emission of 1000 cd / m ² , were measured.

The quantum efficiency of the light emitting device has an internal quantum efficiency and an external quantum efficiency, but the internal quantum efficiency indicates a ratio at which external energy injected as electrons (or holes) into the light emitting layer of the light emitting device is converted purely into photons. On the other hand, the external quantum efficiency is calculated based on the amount of the 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, , The external quantum efficiency is lower than the internal quantum efficiency.

The method of measuring the external quantum efficiency is as follows. Using a voltage / current generator R6144 manufactured by Advan Test Co., a voltage of 1000 cd / m ² was applied to the device to emit light. The spectral radiance of the visible light region was measured from the vertical direction with respect to the light-emitting surface using the spectro radiance luminance meter SR-3AR manufactured by TOPCON. Assuming that the light emitting surface is a complete diffusing surface, the value obtained by dividing the value of the spectral radiance of each wavelength component measured by the wavelength energy and multiplying by π is the photon number at each wavelength. Next, the photon number was integrated in the entire observed wavelength region to obtain the total photon number emitted from the device. The numerical value obtained by dividing the applied current value by the absolute value is taken as the carrier number injected into the device and the numerical value obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency.

The material composition of each layer in the organic EL device according to Examples 1 to 12 and Comparative Example 1 and the EL characteristic data are shown in Table 1 below.

[Table 1]

In Table 1, &quot; HI &quot; represents N ⁴ , N ^{4 '} -diphenyl-N ⁴ , N ^{4 '} -bis (9-phenyl-9H-carbazol- HAT-CN "is 1,4,5,8,9,12-hexaazatriphenylene hexacharonitrile," HT-1 "is N - ([1, Phenyl] -9H-fluoren-2-amine [1, 1'-biphenyl] (Dibenzo [b, d] furan-4-yl) phenyl) - [1, 1 ': 4 (1, 1'-biphenyl) -2-yl) -N- (9,9-dimethyl-9H- 2-yl) -9,9'-spiro [fluorene] -4-amine and ET-1 is 4,6,8,10-tetraphenyl [1,4] benzoxalbolinino (2-phenylanthracene-9,10-diyl) bis (4,1-phenylene)) bis ( 9-dimethyl-9H-fluoren-2-yl) -3,6-dimethyl-9H-carbaldehyde ET-4 "refers to 4- (3- (4- (10-phenylanthracen-9-yl) Talren-1-yl) phenyl) pyridine, and, in Comparative Example 9 Compound A is - ([1,2'- binaphthalene] is 7-yl) -10-phenylanthracene. Together with &quot; Liq &quot;

&Lt; Example 1 >

&Lt; Device in which the host is the compound (2-1) and the dopant is the compound (1-139)

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Optoscience Co., Ltd.), in which ITO formed to a thickness of 180 nm by polishing was sputtered to 150 nm, was used as a transparent support substrate. This transparent support substrate was fixed to a substrate holder of a commercially available evaporation apparatus (manufactured by Showa Vacuum), and HI, HAT-CN, HT-1, HT-2, 1), compound (1-139), molybdenum boats with ET-1 and ET-2 respectively, and aluminum nitride boats with Liq, magnesium and silver respectively.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was reduced to 5 x 10 &lt; ^-4 &gt; Pa. First, HI was heated to deposit a film having a thickness of 40 nm. Next, HAT-CN was heated to deposit a film with a thickness of 5 nm. Was heated to a thickness of 15 nm. Next, HT-2 was heated to a thickness of 10 nm to form a hole injection / transport layer having four layers. Next, the compound (2-1) and the compound (1-139) were simultaneously heated and vapor-deposited to a film thickness of 25 nm to form a light emitting layer. The deposition rate was controlled so that the weight ratio of the compound (2-1) to the compound (1-139) was about 98 to 2. Next, ET-1 was heated and vapor-deposited to a film thickness of 5 nm to form an electron transport layer 1. Next, ET-2 and Liq were simultaneously heated and evaporated to a film thickness of 25 nm to form an electron transport layer 2. The deposition rate was adjusted so that the weight ratio of ET-2 and Liq was about 50 to 50. The deposition rate of each layer was 0.01 to 1 nm / sec. Thereafter, Liq was heated to a thickness of 1 nm to deposit at a deposition rate of 0.01 to 0.1 nm / sec. Then, magnesium and silver were simultaneously heated to deposit a film having a thickness of 100 nm to form a cathode, thereby obtaining an organic EL device . At this time, the deposition rate was adjusted between 0.1 nm and 10 nm / sec so that the atomic ratio between magnesium and silver was 10: 1.

A DC voltage was applied to the ITO electrode as a positive electrode and a magnesium / silver electrode as a negative electrode, and the characteristics at the time of light emission of 1000 cd / m ² were measured to obtain a blue cold light having a wavelength of 462 nm. The driving voltage was 4.1 V and the external quantum efficiency was 6.7%.

&Lt; Examples 2 to 12 and Comparative Example 1 &

The material described in Table 1 was selected as the material of each layer, and an organic EL device was obtained by the method according to Example 1. In Example 11, ET-1 and LIq were co-deposited to a thickness of 30 nm to form a single electron transport layer. The organic EL characteristics were also evaluated in the same manner as in Example 1 (Table 1). Then, blue luminescence was obtained in all devices.

As described above, a part of the compound according to the present invention was evaluated as a material for a light-emitting layer of an organic EL device and showed the usefulness thereof. However, other compounds that did not undergo evaluation had the same basic skeleton, And can be understood to be a material for a light-emitting layer which is equally excellent to those skilled in the art.

According to a preferred embodiment of the present invention, a polycyclic aromatic compound represented by the formula (1) and a pyrene-based compound represented by the formula (2) in which an optimum luminescent property can be obtained in combination with the polycyclic aromatic compound can be provided, By producing the organic EL device using the material for the light emitting layer, it is possible to provide an organic EL device exhibiting excellent luminous efficiency and excellent balance.

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 (11)

An organic electroluminescent device comprising a pair of electrodes made of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes,
Wherein the light emitting layer comprises at least one of a compound represented by the following general formula (1) and a multimer having a plurality of structures represented by the following general formula (1), at least one of the pyrene compounds represented by the following general formula (2) Organic electroluminescent device comprising:

In the above general formula (1)
The A ring, the B ring, and the C ring are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted,
X ¹ and X ² are each independently> O or> NR, and R in the> NR is optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted cycloalkyl, The R of> NR 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 the general formula (1) may be independently substituted with halogen, cyano or deuterium,
In the above general formula (2)
the s pyrene portions and the p Ar portions join at any one of the positions of the pyrene portion * and the Ar portion,
At least one hydrogen of the pyrene moiety is independently selected from the group consisting of aryl of 6 to 10 carbon atoms, heteroaryl of 2 to 11 carbon atoms, alkyl of 1 to 30 carbon atoms, cycloalkyl of 3 to 24 carbon atoms, alkenyl of 2 to 30 carbon atoms, Alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, and at least one hydrogen in these groups is independently selected from the group consisting of aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms,
Ar is independently an aryl having from 14 to 40 carbon atoms or a heteroaryl having from 12 to 40 carbon atoms, and at least one hydrogen in these is independently selected from the group consisting of aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, A cycloalkyl of 3 to 24 carbon atoms, an alkenyl of 2 to 30 carbon atoms, an alkoxy of 1 to 30 carbon atoms, or aryloxy of 6 to 30 carbon atoms,
s and p are each independently an integer of 1 or 2, s and p are not simultaneously divalent, and when s is 2, the two pyrene moieties may be structurally identical or different, including substituents, , when p is 2, the two Ar moieties may be structurally identical or different, including substituents,
At least one hydrogen in the compound represented by the general formula (2) may be independently substituted with halogen, cyano or deuterium. The method according to claim 1,
Wherein Ar is independently a group represented by the following formula (Ar-1) or (Ar-2)

In the above formulas,
Z is> CR _2,> NR, is> O or> S,
And R &lt; ₂ > in CR &lt; ₂ &gt; each independently represent an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, an aryl having 6 to 12 carbon atoms, or a heteroaryl having 2 to 12 carbon atoms, One hydrogen may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and R may be bonded to each other to form a ring,
> NR in NR is alkyl of 1 to 4 carbon atoms, cycloalkyl of 5 to 10 carbon atoms, aryl of 6 to 12 carbon atoms, or heteroaryl of 2 to 12 carbon atoms, and at least one hydrogen in the aryl and heteroaryl is An alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms,
R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ each independently represent hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, An alkoxy having 1 to 30 carbon atoms, or an aryloxy having 6 to 30 carbon atoms, at least one of which may be substituted with an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms, Adjacent groups of R ¹ to R ⁸ or adjacent groups of R ¹⁰ to R ¹⁹ may be bonded to each other to form a condensed ring, and the formed rings may each independently be an aryl group having 6 to 10 carbon atoms, Heteroaryl, alkyl of 1 to 30 carbon atoms, cycloalkyl of 3 to 24 carbon atoms, alkenyl of 2 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, or aryloxy of 6 to 30 carbon atoms, One hydrogen is an alkyl having 1 to 6 carbon atoms or an alkyl having 3 to 14 carbon atoms And may be substituted with cycloalkyl,
At least one hydrogen in the group represented by the formula (Ar-1) or (Ar-2) may be independently substituted with halogen, cyano or deuterium,
In the general formula (2), the pyrene moiety is bonded at any position of the group represented by the formula (Ar-1) or (Ar-2). 3. The method according to claim 1 or 2,
Wherein the compound represented by the general formula (1) is a compound represented by the following general formula (1 '):

(In the above general formula (1 '),
R ¹ to R ¹¹ are each independently selected from the group consisting of hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, Each of adjacent groups of R ¹ to R ¹¹ may be bonded to form an aryl or heteroaryl ring together with an a, b, or c ring to form an aryl or heteroaryl ring, And at least one hydrogen in the ring formed may each independently be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, At least one hydrogen in these groups may be independently substituted with aryl, heteroaryl, alkyl or cycloalkyl,
X ¹ and X ² are each independently> O or> NR, and> R in the above NR is an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 14 carbon atoms Alkyl, and at least one hydrogen in the aryl or heteroaryl may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and R of> NR is -O-, -S- , -C (-R) ₂ - or a single bond, and R in the -C (-R) ₂ - may be an alkyl having 1 to 6 carbon atoms or a carbon Cycloalkyl of 3 to 14 carbon atoms,
At least one hydrogen in the compound represented by the general formula (1 ') may be independently substituted with halogen, cyano or deuterium. 4. The method according to any one of claims 1 to 3,
Ar is independently selected from any one of the following formulas (Ar-1-1) to (Ar-1-12) and (Ar-2-1) to (Ar- 2-4) Organic electroluminescent device:

In the above formulas,
Z is> CR _2,> NR, is> O or> S,
> R in CR ₂ is an aryl of 6 to 12 carbon atoms, cycloalkyl or alkyl having 1 to 6 carbon atoms of 3-14, each independently, R is bonded to each other and may form a ring,
> R in NR is alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms or aryl having 6 to 12 carbon atoms,
At least one hydrogen in the group represented by each formula is independently selected from the group consisting of aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, or cycloalkyl having 3 to 24 carbon atoms And,
At least one hydrogen in the groups represented by the above-mentioned formulas may be independently substituted with halogen, cyano or deuterium,
In the general formula (2), the pyrene moiety is a group represented by the general formula (Ar-1-1) to the general formula (Ar-1-12) ). &Lt; / RTI &gt; 5. The method according to any one of claims 1 to 4,
Wherein the pyrene compound represented by the general formula (2) is a compound represented by any one of the following structural formulas:

. 6. The method according to any one of claims 1 to 5,
Wherein at least one of the electron transport layer and the electron injection layer has a structure selected from the group consisting of a borane derivative, a pyridine derivative, a fluoranthene derivative, a BO-based derivative, an anthracene derivative At least one compound selected from the group consisting of a benzotriazole derivative, a benzofluorene derivative, a phosphine oxide derivative, a pyrimidine derivative, a carbazole derivative, a triazine derivative, a benzimidazole derivative, a phenanthroline derivative and a quinolinol- , An organic electroluminescent element. The method according to claim 6,
Wherein the electron-transporting layer and / or the electron-injecting layer is made of a material selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metal oxides, alkaline earth metal halides, An organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. The organic electroluminescent device according to claim 1, wherein the organic electroluminescent device further comprises at least one selected from the group consisting of a rare earth metal halide, an alkali metal organic complex, A display device comprising the organic electroluminescent device according to any one of claims 1 to 7. An illumination device comprising the organic electroluminescent device according to any one of claims 1 to 7. A pyrene-based compound represented by the following general formula (2):

In the above general formula (2)
the s pyrene portions and the p Ar portions join at any one of the positions of the pyrene portion * and the Ar portion,
At least one hydrogen of the pyrene moiety is independently selected from the group consisting of aryl of 6 to 10 carbon atoms, heteroaryl of 2 to 11 carbon atoms, alkyl of 1 to 30 carbon atoms, cycloalkyl of 3 to 24 carbon atoms, alkenyl of 1 to 30 carbon atoms, An alkoxy of 1 to 30 carbon atoms, or aryloxy of 1 to 30 carbon atoms, and at least one hydrogen in these may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms,
Ar is a group represented by the following formula (Ar-1) or (Ar-3)

In the above formulas,
Z is > CR ₂ ,
And R &lt; ₂ &gt; in CR &lt; ₂ &gt; each independently represent an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, an aryl having 6 to 12 carbon atoms, or a heteroaryl having 2 to 12 carbon atoms, One hydrogen may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and R may be bonded to each other to form a ring,
R ¹ to R ⁸ and R ²⁰ to R ³⁵ each independently represent hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, Alkoxy having 1 to 30 carbon atoms, aryloxy having 1 to 30 carbon atoms, aryloxy having 1 to 30 carbon atoms, or aryloxy having 1 to 30 carbon atoms, wherein at least one hydrogen may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, Adjacent groups of R ¹ to R ^{8 may} be bonded to each other to form a condensed ring and adjacent groups of R ²⁰ to R ³⁵ may be bonded to each other to form a condensed ring, Aryl having 1 to 10 carbons, heteroaryl having 2 to 11 carbons, alkyl having 1 to 30 carbons, cycloalkyl having 3 to 24 carbons, alkenyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons or aryloxy having 1 to 30 carbons And at least one hydrogen in these may be substituted with a carbon It can be optionally substituted with alkyl or cycloalkyl of 3-14 carbon atoms of 1 to 6, and,
s and p are each independently an integer of 1 or 2, s and p are not simultaneously divalent, and when s is 2, the two pyrene moieties may be structurally identical or different, including substituents, , when p is 2, two Ar moieties may be structurally identical or different, including substituents,
At least one hydrogen in the compound represented by the general formula (2) may be independently substituted with halogen, cyano or deuterium. 11. The method of claim 10,
A pyrene-based compound represented by any one of the following structural formulas:

.

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