KR20230041616A - Polycyclic aromatic compounds, organic electroluminescent element, display device and lighting apparatus - Google Patents

Abstract

The present invention is provide a novel polycyclic aromatic compound and an organic electroluminescent element, a display device, and a lighting apparatus using the same. By manufacturing an organic electroluminescent element using the novel polycyclic aromatic compound as an electron transport material, for example, the organic electroluminescent element is excellent in driving voltage, luminous efficiency, and device life, and particularly in luminous efficiency and device life.

Description

Polycyclic aromatic compounds, organic electroluminescent devices, display devices and lighting devices

The present invention relates to a polycyclic aromatic compound, an organic electroluminescent element using the same, an organic field effect transistor, an organic thin film solar cell, and an organic device such as a wavelength conversion filter, and a display device and a lighting device. In addition, in this specification, "organic electroluminescence element" may be expressed as "organic EL element" or simply "element".

Conventionally, display devices using electroluminescent light-emitting elements have been frequently researched because power reduction and thinning are possible, and organic electroluminescent elements made of organic materials have been actively studied because they are easy to reduce in weight and increase in size. In particular, for the development of organic materials having light-emitting properties such as blue, which is one of the three primary colors of light, and the development of organic materials having charge transport capabilities (possibly becoming semiconductors or superconductors) such as holes and electrons, polymer compounds , regardless of low molecular weight compounds, have been actively studied so far.

An organic EL element has a structure consisting of a pair of electrodes composed of an anode and a cathode, and one layer or a plurality of layers disposed between the pair of electrodes and containing an organic compound. Layers containing organic compounds include a light emitting layer and a charge transport/injection layer that transports or injects charges such as holes and electrons. Various organic materials suitable for these layers have been developed.

For example, as a material used for an organic EL device or an organic thin-film solar cell, a material obtained by improving a triphenylamine derivative has also been reported (International Publication No. 2012/118164). This material refers to N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), which is already in practical use, It is a material characterized by improving its planarity while arranging nitrogen at the center of the ring structure by linking aromatic rings constituting phenylamine with each other. In this document, for example, the charge transport properties of NO-linked compounds (Compound 1 on page 63) are evaluated, but no method for producing materials other than NO-linked compounds is described. Furthermore, if the elements to be linked are different, Since the electronic state of the entire compound is different, properties obtained with materials other than NO-linked compounds have not been known.

Under such circumstances, recently, a compound in which a plurality of aromatic rings are condensed with boron or the like as a central atom has also been reported (International Publication No. 2015/102118). In this document, evaluation of an organic EL device using a compound obtained by condensing a plurality of aromatic rings as a material for a charge transport layer such as an electron as well as a material for a light emitting layer is performed. In addition, an example in which such a compound is further multiplied (International Publication No. 2018/212169) or an example in which a conjugated system is expanded by a linking group in a molecule has been reported (Korean Patent Publication No. 10-2020-0121228, International Publication No. 2020/217229).

International Publication No. 2012/118164 International Publication No. 2015/102118 International Publication No. 2018/212169 Korean Patent Publication No. 10-2020-0121228 International Publication No. 2020/217229

As reported in Patent Literatures 1 to 5, various materials have been developed as materials used for organic EL devices, but in order to increase the choice of materials for organic EL devices, development of materials composed of compounds different from those of the prior art is expected. there is. In particular, it is useful to search for organic EL properties obtained with materials other than NO-linked compounds in which nitrogen is arranged at the center of the ring structure and a method for producing the same.

Further, in Patent Documents 2 to 5, boron-containing polycyclic aromatic compounds and organic EL devices using the same are reported, but a large number of compounds are disclosed in those documents. It is beneficial to search for a material for a charge transport layer, particularly a material for an electron transport layer or a material for an electron injection layer, which can improve organic EL characteristics such as lifetime.

In addition, as a method of forming an organic layer constituting an organic EL element, a wet film forming method is currently used in addition to the vacuum deposition method. , it is also beneficial to search for such an ink material.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that, for example, an organic EL element is constituted by disposing a layer containing a polycyclic aromatic compound having a novel structure between a pair of electrodes, thereby providing an excellent organic EL element. was obtained, and the present invention was completed. That is, the present invention provides materials for organic devices, such as materials for organic EL devices, containing the following polycyclic aromatic compounds and furthermore, the following polycyclic aromatic compounds.

In addition, in the present specification, chemical structures and substituents are sometimes expressed as carbon atoms. In the case where a substituent is substituted in a chemical structure or a substituent is further substituted in a substituent, the number of carbon atoms in the chemical structure or substituent means the number of carbon atoms in each of the substituents. , It does not mean the total number of carbon atoms of the chemical structure and substituents, or the total number of carbon atoms of substituents and substituents. For example, "substituent B of carbon number Y substituted with substituent A of carbon number X" means that "substituent A of carbon number X" is substituted for "substituent B of carbon number Y", and carbon number Y is substituent A and substituent It is not the carbon number of the sum of B. Further, for example, "substituent B of carbon number Y substituted with substituent A" means that "substituent A (with no carbon number limitation)" is substituted for "substituent B of carbon number Y", and carbon number Y is substituent A and It is not the carbon number of the sum of the substituents B.

Section 1.

A polycyclic aromatic compound represented by the following general formula (1).

In the above formula (1),

R ¹ to R ¹¹ are each independently hydrogen, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl , trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkyldicycloalkylsilyl, the two aryls of the diarylamino may be bonded through a linking group, and the two heteroaryls of the diheteroarylamino Aryl may be bonded through a linking group, the aryl and heteroaryl of the arylheteroarylamino may be bonded through a linking group, and the two aryls of the diarylboryl may be bonded through a linking group,

Adjacent groups among R ¹ to R ¹¹ are bonded together to form a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbocyclic ring together with at least one of ring a, ring b, and ring c. A basol ring may be formed, and at least one hydrogen in the formed ring is each independently diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, It may be substituted with alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkyldicycloalkylsilyl, and the two aryls of the diarylamino form a linking group may be bonded through, the two heteroaryls of the diheteroarylamino may be bonded through a linking group, the aryl and heteroaryl of the arylheteroarylamino may be bonded through a linking group, and two of the diarylboryls The dog aryl may be bonded through a linking group,

However, at least one group represented by the general formula (G) is bonded to the "a ring" or "the ring formed with the a ring", and the "b ring" or "the ring formed with the b ring" is represented by the general formula (G) At least one of the groups represented is bonded, and at least one group represented by the general formula (G) is bonded to "c ring" or "ring formed with c ring", and these groups represented by formula (G) may be the same or different, respectively. become,

In the above formula (G),

Cy ¹ and Cy ² are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted. and at least one hydrogen in these rings is each independently diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio , triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, or cyano may be substituted, and the two aryls of the diarylamino may be bonded through a linking group. , The two heteroaryls of the diheteroarylamino may be bonded through a linking group, the aryl and heteroaryl of the arylheteroarylamino may be bonded through a linking group, and the two aryls of the diarylboryl are a linking group may be bonded through, and * is a bond position to a ring, b ring, c ring, and a ring formed together with those rings, and,

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

clause 2.

In the above formula (1),

R ¹ to ^{R 11} are each independently hydrogen, diarylamino (provided that aryl is an aryl having 6 to 12 carbon atoms), diheteroarylamino (provided that heteroaryl is a heteroaryl having 2 to 15 carbon atoms), and arylheteroarylamino. (provided that aryl is aryl having 6 to 12 carbon atoms, heteroaryl is heteroaryl having 2 to 15 carbon atoms), diarylboryl (but aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, and carbon atoms 3 to 24 Cycloalkyl, alkenyl of 1 to 24 carbon atoms, alkoxy of 1 to 24 carbon atoms, aryloxy of 6 to 30 carbon atoms, arylthio of 6 to 30 carbon atoms, triarylsilyl (where aryl is aryl of 6 to 12 carbon atoms), tri Alkylsilyl (provided that alkyl is C1-C12 alkyl), tricycloalkylsilyl (provided that cycloalkyl is C3-C12 cycloalkyl), dialkylcycloalkylsilyl (provided that alkyl is C1-C12 alkyl, cycloalkyl is cycloalkyl having 3 to 12 carbon atoms), or alkyldicycloalkylsilyl (provided that alkyl is alkyl having 1 to 12 carbon atoms and cycloalkyl is cycloalkyl having 3 to 12 carbon atoms), and two aryls of the diarylamino are a linking group may be bonded through, the two heteroaryls of the diheteroarylamino may be bonded through a linking group, the aryl and heteroaryl of the arylheteroarylamino may be bonded through a linking group, and of the diarylboryl The two aryls may be bonded through a linking group, and the linking group is a single bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ -, -CH=CH-, -CR= CR-, -C≡C-, -N(-R)-, -O-, -S-, -C(-R) ₂ -, -Si(-R) ₂ -, or -Se-; are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, and at least one hydrogen in R may be substituted with alkyl or cycloalkyl,

Adjacent groups among R ¹ to R ¹¹ are bonded together to form a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbocyclic ring together with at least one of ring a, ring b, and ring c. A basol ring may be formed, and at least one hydrogen in the formed ring is each independently diarylamino (provided that aryl has 6 to 12 carbon atoms), diheteroarylamino (provided that heteroaryl has 2 carbon atoms) to 15 heteroaryl), arylheteroarylamino (provided that aryl is an aryl having 6 to 12 carbon atoms, and heteroaryl is a heteroaryl having 2 to 15 carbon atoms), diarylboryl (provided that aryl is an aryl having 6 to 12 carbon atoms), carbon atoms Alkyl of 1 to 24 carbon atoms, cycloalkyl of 3 to 24 carbon atoms, alkenyl of 1 to 24 carbon atoms, alkoxy of 1 to 24 carbon atoms, aryloxy of 6 to 30 carbon atoms, arylthio of 6 to 30 carbon atoms, triarylsilyl (provided that Aryl is aryl having 6 to 12 carbon atoms), trialkylsilyl (provided that alkyl is alkyl having 1 to 12 carbon atoms), tricycloalkylsilyl (provided that cycloalkyl is cycloalkyl having 3 to 12 carbon atoms), dialkylcycloalkylsilyl (provided that Alkyl is alkyl having 1 to 12 carbon atoms, cycloalkyl is cycloalkyl having 3 to 12 carbon atoms), or alkyldicycloalkylsilyl (however, alkyl is alkyl having 1 to 12 carbon atoms, and cycloalkyl is cycloalkyl having 3 to 12 carbon atoms). may be substituted, the two aryls of the diarylamino may be bonded through a linking group, the two heteroaryls of the diheteroarylamino may be bonded through a linking group, and the aryl and heteroaryl of the arylheteroarylamino Aryl may be bonded through a linking group, and the two aryls of the diarylboryl may be bonded through a linking group, and the linking group is a single bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ -, -CH=CH-, -CR=CR-, -C≡C-, -N(-R)-, -O-, -S-, -C(-R) ₂ -, - Si(-R) ₂ -, or -Se-, R is independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, and at least one hydrogen in R Is may be substituted with alkyl or cycloalkyl,

However, at least one group represented by the general formula (G) is bonded to the "a ring" or "the ring formed with the a ring", and the "b ring" or "the ring formed with the b ring" is represented by the general formula (G) At least one of the groups represented is bonded, and at least one group represented by the general formula (G) is bonded to "c ring" or "ring formed with c ring", and these groups represented by formula (G) may be the same or different, respectively. become,

In the above formula (G),

Cy ¹ and Cy ² are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted. And, at least one hydrogen in these rings is each independently diarylamino (provided that aryl is an aryl having 6 to 12 carbon atoms), diheteroarylamino (provided that heteroaryl is a heteroaryl having 2 to 15 carbon atoms), Arylheteroarylamino (where aryl is aryl having 6 to 12 carbon atoms, heteroaryl is heteroaryl having 2 to 15 carbon atoms), diarylboryl (where aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, carbon atoms Cycloalkyl of 3 to 24 carbon atoms, alkenyl of 1 to 24 carbon atoms, alkoxy of 1 to 24 carbon atoms, aryloxy of 6 to 30 carbon atoms, arylthio of 6 to 30 carbon atoms, triarylsilyl (provided that aryl has 6 to 12 carbon atoms aryl), trialkylsilyl (provided that alkyl has 1 to 12 carbon atoms), tricycloalkylsilyl (provided that cycloalkyl is cycloalkyl having 3 to 12 carbon atoms), dialkylcycloalkylsilyl (provided that alkyl has 1 to 12 carbon atoms) may be substituted with alkyl, cycloalkyl is cycloalkyl of 3 to 12 carbon atoms), alkyldicycloalkylsilyl (provided that alkyl is alkyl of 1 to 12 carbon atoms and cycloalkyl is cycloalkyl of 3 to 12 carbon atoms), or cyano; The two aryls of the diarylamino may be bonded through a linking group, the two heteroaryls of the diheteroarylamino may be bonded through a linking group, and the aryl and heteroaryl of the arylheteroarylamino are bonded through a linking group The two aryls of the diarylboryl may be bonded through a linking group, and the linking group is a single bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ - , -CH=CH-, -CR=CR-, -C≡C-, -N(-R)-, -O-, -S-, -C(-R) ₂ -, -Si(-R) ₂ -, or -Se-, R is independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, and at least one hydrogen in R is alkyl or It may be substituted with cycloalkyl, and * is a bonding position to a ring, b ring, c ring, and a ring formed together with those rings, and

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

The polycyclic aromatic compound according to claim 1.

clause 3.

In the above formula (1),

R ¹ to R ¹¹ are each independently hydrogen, diarylamino (provided that aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, alkoxy having 1 to 24 carbon atoms, Aryloxy of 6 to 30 carbon atoms or arylthio of 6 to 30 carbon atoms, and the two aryls of the diarylamino may be bonded through a linking group, and the linking group is a single bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ -, -CH=CH-, -CR=CR-, -C≡C-, -N(-R)-, -O-, -S-, -C (-R) ₂ -, -Si(-R) ₂ -, or -Se-, and R is, each independently, hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, corresponding At least one hydrogen in R may be substituted with alkyl or cycloalkyl,

Adjacent groups among R ¹ to R ¹¹ are bonded together to form a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbocyclic ring together with at least one of ring a, ring b, and ring c. A basol ring may be formed, and at least one hydrogen in the formed ring is each independently diarylamino (provided that aryl is an aryl having 6 to 12 carbon atoms), an alkyl having 1 to 24 carbon atoms, and an alkyl having 3 to 24 carbon atoms. may be substituted with cycloalkyl, alkoxy having 1 to 24 carbon atoms, aryloxy having 6 to 30 carbon atoms, or arylthio having 6 to 30 carbon atoms, and the two aryls of the diarylamino may be bonded through a linking group, The linking group is a single bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ -, -CH=CH-, -CR=CR-, -C≡C-, -N( -R)-, -O-, -S-, -C(-R) ₂ -, -Si(-R) ₂ -, or -Se-, wherein R is, each independently, hydrogen, aryl, heteroaryl , Alkyl, alkenyl, alkynyl, or cycloalkyl, and at least one hydrogen in R may be substituted with alkyl or cycloalkyl,

However, at least one group represented by the general formula (G) is bonded to the "a ring" or "the ring formed with the a ring", and the "b ring" or "the ring formed with the b ring" is represented by the general formula (G) At least one of the groups represented is bonded, and at least one group represented by the general formula (G) is bonded to "c ring" or "ring formed with c ring", and these groups represented by formula (G) may be the same or different, respectively. become,

In the above formula (G),

Cy ¹ and Cy ² are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted. , and at least one hydrogen in these rings is each independently diarylamino (provided that aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, and 1 to 24 carbon atoms. Alkoxy of 24, aryloxy of 6 to 30 carbon atoms, arylthio of 6 to 30 carbon atoms, or cyano may be substituted, and the two aryls of the diarylamino may be bonded through a linking group, and the linking group is bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ -, -CH=CH-, -CR=CR-, -C≡C-, -N(-R)-, -O-, -S-, -C(-R) ₂ -, -Si(-R) ₂ -, or -Se-, wherein R is, each independently, hydrogen, aryl, heteroaryl, alkyl, alkenyl , Alkynyl, or cycloalkyl, and at least one hydrogen in R may be substituted with alkyl or cycloalkyl, and * is a bond position to a ring, b ring, c ring, and the rings formed together with those rings is, and

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

The polycyclic aromatic compound according to claim 1.

clause 4.

In the above formula (1),

R ¹ to ^{R 11} are each independently hydrogen, diarylamino (provided that aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, or cycloalkyl having 3 to 24 carbon atoms;

Adjacent groups among R ¹ to R ¹¹ are bonded together to form a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbocyclic ring together with at least one of ring a, ring b, and ring c. A basol ring may be formed, and at least one hydrogen in the formed ring is each independently diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, or carbon atoms 3 to 12 may be substituted with cycloalkyl of 24;

However, at least one group represented by the general formula (G) is bonded to the "a ring" or "the ring formed with the a ring", and the "b ring" or "the ring formed with the b ring" is represented by the general formula (G) At least one of the groups represented is bonded, and at least one group represented by the general formula (G) is bonded to "c ring" or "ring formed with c ring", and these groups represented by formula (G) may be the same or different, respectively. become,

In the above formula (G),

Cy ¹ and Cy ² are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted. , and at least one hydrogen in these rings is each independently diarylamino (provided that aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, or cyano. may be substituted, and * is a bonding position with a ring, b ring, c ring, and a ring formed together with those rings, and

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

The polycyclic aromatic compound according to claim 1.

Section 5.

In the above formula (1),

R ¹ to ^{R 11} are each independently hydrogen or alkyl having 1 to 24 carbon atoms;

However, at least one of R ¹ to R ³ in the a ring, at least one of R ⁴ to ^{R 7} in the b ring, and at least one of R ⁸ to R ¹¹ in the c ring are represented by the general formula ( It is a group represented by G), and these groups represented by formula (G) may be the same or different, respectively,

In the above formula (G),

Cy ¹ and Cy ² are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted. And, at least one hydrogen in these rings may be each independently substituted with an alkyl having 1 to 24 carbon atoms or cyano, and * is a bonding position to the a ring, b ring, and c ring, and

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

The polycyclic aromatic compound according to claim 1.

clause 6.

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

clause 7.

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

Section 8.

A pair of electrodes comprising an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and a polycyclic aromatic compound according to any one of items 1 to 7 disposed between the cathode and the light emitting layer. An organic electroluminescent device having at least one layer of an electron transporting layer and an electron injection layer.

clause 9.

A display device comprising the organic electroluminescent element according to claim 8.

Section 10.

A lighting device comprising the organic electroluminescent element according to claim 8.

According to a preferred aspect of the present invention, it is possible to provide a polycyclic aromatic compound having a novel structure that can be used as, for example, a material for organic devices such as a material for organic EL devices. By using this polycyclic aromatic compound, driving It is possible to provide an organic device such as an organic EL element excellent in voltage, luminous efficiency, and element life, particularly excellent in luminous efficiency and element life.

1 is a schematic cross-sectional view showing an organic EL element according to this embodiment.

One. dahwan aromatic compounds

<Description of the overall structure of the compound>

The present invention is a polycyclic aromatic compound represented by the following general formula (1), characterized by having a group represented by the following general formula (G). On the other hand, the definitions of the symbols in the following structural formulas are the same as the above-mentioned definitions, and furthermore, the definitions of the symbols in all the structural formulas shown in this paragraph and later are also the same as the above-mentioned definitions.

The compound of formula (1) has a structure in which ring a, ring b, and ring c are condensed in a condensed bicyclic structure. The condensed bicyclic structure refers to a structure in which two 6-membered saturated hydrocarbon rings are condensed, and in the above structural formula, it refers to a decahydronaphthalene type structure composed of B (boron) and two O (oxygen).

The group represented by formula (G) is a group in which Cy ¹ and Cy ² having a specific ring structure are bonded, and Cy ¹ and Cy ² are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, and a quinoline ring. , a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted. The group represented by formula (G) is bonded to the structure of formula (1) in *. The bond form of the group represented by formula (G) will be described in detail later.

< a ring , b ring , and of c ring substituent R ^One ~R ¹¹ description>

Ring a, ring b, and ring c in formula (1) each have R ¹ to R ³ , R ⁴ to ^{R 7} , and R ⁸ to R ¹¹ , and these R ¹ to R ¹¹ are each independently Hydrogen, diarylamino (two aryls may be bonded through a linking group), diheteroarylamino (two heteroaryls may be bonded through a linking group), arylheteroarylamino (aryl and heteroaryl may be bonded through a linking group) may be bonded through), diarylboryl (two aryls may be bonded through a linking group), alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricyclo alkylsilyl, dialkylcycloalkylsilyl, or alkyldicycloalkylsilyl. On the other hand, the details of the substituents enumerated here will be summarized and described later.

<Description of changes in ring structure due to bonding between substituents>

Adjacent groups among R ¹ to ^{R 3} on ring a are bonded to each other together with ring a, a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbazole ring (where the N position is substituted with a phenyl group). carbazole rings are also included) may be formed (these rings are referred to as “rings formed together with a-rings”).

Adjacent groups among R ⁴ to ^{R 7} on the b ring are bonded together with the b ring to a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbazole ring (where the N position is substituted with a phenyl group). carbazole rings are also included) may be formed (these rings are referred to as “rings formed with ring b”).

Adjacent groups among R ⁸ to ^{R 11} on ring c are bonded together with ring c, a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbazole ring (where the N position is substituted with a phenyl group). carbazole rings are also included) may be formed (these rings are referred to as “rings formed with c-rings”).

A benzene ring, a naphthalene ring, a benzothiophene ring, a benzofuran ring, or an indole ring formed by bonding adjacent groups among R ¹ to R ³ (or R ⁴ to ^{R 7} or R ⁸ to ^{R 11} ), or ring a (or b ring or c ring) by condensation with respect to the benzene ring, respectively, a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbazole ring is formed.

Specific examples in which the ring structure has changed are shown below. R ¹ to R ¹¹ for unchanged rings are omitted.

In formula (1-fr1-ex), two adjacent R ¹ and R ² in ring a in formula (1) combine to form a benzene ring, and this benzene ring together with the benzene ring of ring a is a' It is an example in which the naphthalene ring represented by is formed. Arbitrary substituents on the naphthalene ring a' are represented by n pieces of R other than R ³ , and the upper limit of n is the maximum number of substituents.

In formula (1-fr2-ex), two adjacent R ⁵ and R ⁶ in ring b in formula (1) combine to form an indole ring, and this indole ring, together with the benzene ring of ring b, is b' It is an example in which the carbazole ring represented by is formed. Arbitrary substituents on the carbazole ring b' are represented by n pieces of R other than R ⁴ and R ⁷ , and the upper limit of n is the maximum number of substituents. On the other hand, the carbazole ring in which the N position is substituted with a phenyl group is also included in this carbazole ring.

In formula (1-fr3-ex), two adjacent R ⁴ and R ⁵ in ring b in formula (1) combine to form a benzene ring, and this benzene ring, together with the benzene ring of ring b, is b' A naphthalene ring represented by is formed, two adjacent R ¹⁰ and R ¹¹ in the c ring are bonded to form a benzofuran ring, and this benzofuran ring, together with the benzene ring of the c ring, dibenzo represented by c' This is an example of the formation of a furan ring. Arbitrary substituents on the naphthalene ring b' and the dibenzofuran ring c' are each represented by n pieces of R other than R ⁶ to R ⁹ , and the upper limit of n is the maximum number of substituents.

The above description can similarly be applied to any form other than the specific example mentioned above.

<Description of Substituents to Changed Ring Structure>

At least one hydrogen in the ring formed together with ring a, ring b, or ring c (a' ring, b' ring, and c' ring described above) is each independently diarylamino (two aryls are a linking group may be bonded through), diheteroarylamino (two heteroaryls may be bonded through a linking group), arylheteroarylamino (aryl and heteroaryl may be bonded through a linking group), diarylboryl ( two aryls may be bonded through a linking group), alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkyl It may be substituted with dicycloalkylsilyl. On the other hand, the details of the substituents enumerated here will be summarized and described later.

<Description of Group Represented by Formula (G)>

The group represented by formula (G) is a group in which Cy ¹ and Cy ² having a specific ring structure are bonded, and Cy ¹ and Cy ² are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, and a quinoline ring. , a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted.

In order of Cy ¹ and Cy ² ,

A group bonded to a benzene ring by a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted;

A group bonded to a naphthalene ring by a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted;

A group bonded to a phenanthrene ring by a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted;

A group bonded to a pyridine ring by a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted;

A group bonded to a quinoline ring by a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted;

A group bonded to a dibenzofuran ring by a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted;

A group bonded to a dibenzothiophene ring by a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted;

A benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a phenyl ring in the N position may be phenyl substituted with respect to the carbazole ring in which the N position may be phenyl substituted. The group to which the carbazole ring couple|bonded is mentioned.

Preferably, in the order of Cy ¹ and Cy ² , a group in which two benzene rings are bonded, a group in which a benzene ring and a naphthalene ring are bonded, a group in which a pyridine ring and a benzene ring are bonded, a group in which two pyridine rings are bonded, a group in which a benzene ring and a pyridine ring are bonded, a benzene ring and A group in which a carbazole ring may be substituted with a phenyl group at position N, a group in which a benzene ring and a dibenzofuran ring are bonded, a group in which a dibenzofuran ring and a benzene ring are bonded, a group in which a benzene ring and a quinoline ring are bonded, a group in which a benzene ring and a dibenzothiophene ring are bonded, A group in which a benzene ring and a phenanthrene ring are bonded, and a group in which two carbazole rings may be substituted at the N position by a phenyl group are bonded.

<Explanation of the substituent to the group represented by formula (G)>

At least one hydrogen in Cy ¹ and Cy ² is each independently diarylamino (two aryls may be bonded through a linking group), diheteroarylamino (two heteroaryls are bonded through a linking group, may be present), arylheteroarylamino (aryl and heteroaryl may be bonded through a linking group), diarylboryl (two aryls may be bonded through a linking group), alkyl (preferably having 1 to 4 carbon atoms) alkyl, more preferably methyl), cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, or cyano It may be substituted with a furnace. A preferable substituent is C1-C4 alkyl (more preferably methyl) or cyano. On the other hand, the details of the substituents enumerated here will be summarized and described later.

<Description of bonding of group of formula (G) to structure of formula (1)>

The group represented by formula (G) is bonded to the structure of formula (1) in *.

Specifically, in formula (1),

a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbane ring formed together with ring a by bonding with each other among adjacent groups among R ¹ to ^{R 3} on ring a as described above; When at least one group of formula (G) is bonded to the sol ring (ie "ring formed with ring a"), and the groups represented by formula (G) are plural, they may be the same or different, respectively;

b ring, or a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbane ring formed together with the b ring by bonding adjacent groups among R ⁴ to ^{R 7} on the b ring as described above. When at least one group of formula (G) is bonded to the sol ring (ie, "ring formed with ring b"), and the groups represented by formula (G) are plural, they may be the same or different, respectively.

c ring, or a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbane ring formed together with the c ring by bonding adjacent groups among R ⁸ to R ¹¹ on the c ring as described above. When at least one group of formula (G) is bonded to the sol ring (ie, "ring formed with ring c"), and the groups represented by formula (G) are plural, they may be the same or different.

Therefore, the compound of formula (1) is characterized by having at least three groups of formula (G). The groups represented by a plurality of formulas (G) may be the same or different, and preferably have the same structure.

The group represented by formula (G) bonded to ring a, bonded to ring b, or bonded to ring c means that at least one of R ¹ to ^{R 3} of ring a is respectively R ⁴ to ^{R 7} of ring b At least one of or at least one of R ⁸ to R ¹¹ in the c ring is a group represented by formula (G).

The number of bonds of the group represented by formula (G) to each ring is 1 to 4, preferably 1 to 3, more preferably 1 to 2, even more preferably 1.

<Specific description of the substituent>

Next, the details of the substituents enumerated in the above description will be summarized and described.

"Diarylamino" is an amino group substituted by two aryls, and the two aryls may be bonded via a linking group.

"Diheteroarylamino" is an amino group substituted by two heteroaryls, and the two heteroaryls may be bonded via a linking group.

"Arylheteroarylamino" is an amino group substituted by aryl and heteroaryl, and aryl and heteroaryl may be bonded via a linking group.

"Diaryl boryl" is a boryl group substituted by two aryls, and the two aryls may be bonded via a linking group.

Details of these aryls, heteroaryls, and linking groups are as follows.

"Aryl" is, for example, an aryl having 6 to 30 carbon atoms, preferably an aryl having 6 to 20 carbon atoms, an aryl having 6 to 16 carbon atoms, an aryl having 6 to 12 carbon atoms, or an aryl having 6 to 10 carbon atoms. .

Specific "aryl" includes, for example, monocyclic phenyl, condensed bicyclic naphthyl (1-naphthyl or 2-naphthyl), condensed tricyclic acenaphthylene-(1-, 3-, 4- , or 5-)yl, fluorene-(1-, 2-, 3-, 4-, or 9-)yl, phenalen-(1- or 2-)yl, or phenanthrene-(1-, 2 -, 3-, 4-, or 9-)yl, fused tetracyclic, triphenylene-(1- or 2-)yl, pyrene-(1-, 2-, or 4-)yl, or naphthacene -(1-, 2-, or 5-)yl, or perylene-(1-, 2-, or 3-)yl, or pentacene-(1-, 2-, 5-, which is a condensed pentacyclic ring system) , or 6-) days, etc.

"Arylene (ring)" is, for example, arylene having 6 to 30 carbon atoms, preferably arylene having 6 to 20 carbon atoms, arylene having 6 to 16 carbon atoms, arylene having 6 to 12 carbon atoms, or and arylene having 6 to 10 carbon atoms.

Examples of specific "arylene" include a structure made into a divalent group by removing one hydrogen from the aforementioned "aryl" (monovalent group).

"Heteroaryl" is, for example, a heteroaryl having 2 to 30 carbon atoms, preferably a heteroaryl having 2 to 25 carbon atoms, a heteroaryl having 2 to 20 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or a heteroaryl having 2 to 15 carbon atoms. heteroaryl of 10; and the like. Further, "heteroaryl" is a monovalent group such as a heterocyclic ring containing, for example, 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as ring-constituting atoms.

Specific examples of "heteroaryl" include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyrid denyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzooxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl , isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phenanthrolinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathinyl, Phenoxazinil, phenothiazinil, phenazinyl, phenazacillinyl, indolizinil, furanil, benzofuranil, isobenzofuranil, dibenzofuranil, naphthobenzofuranil, thiophenyl, benzothiophenyl, Isobenzothiophenyl, dibenzothiophenyl, naphthobenzothiophenyl, benzophosphoryl, dibenzophosphoryl, monovalent group of benzophosphole oxide ring, monovalent group of dibenzophosphole oxide ring, furazanyl, thianthrenyl , indolocarbazolyl, benzoindolocarbazolyl, benzobenzoindolocarbazolyl, imidazolinyl, oxazolinyl, or dibenzosilacyclopentadienyl.

"Heteroarylene (ring)" is, for example, a heteroarylene having 2 to 30 carbon atoms, preferably a heteroarylene having 2 to 25 carbon atoms, a heteroarylene having 2 to 20 carbon atoms, or a heteroarylene having 2 to 15 carbon atoms. heteroarylene or heteroarylene having 2 to 10 carbon atoms. In addition, "heteroarylene" is a divalent group such as a heterocycle containing, for example, 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as ring-constituting atoms.

Specific examples of the "heteroarylene" include a structure obtained by removing one hydrogen from the above-described "heteroaryl" (monovalent group) to form a divalent group.

A "linking group" is, for example, a single bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ -, -CH=CH-, -CR=CR-, -C≡C -, -N(-R)-, -O-, -S-, -C(-R) ₂ -, -Si(-R) ₂ -, or -Se-, for example: structure can be found. On the other hand, R in “-CHR-CHR-”, R in “-CR ₂ -CR ₂ -”, R in “-CR=CR-”, R in “-N(-R)-”, R in “-C R in (-R) ₂ -” and R in “-Si(-R) ₂ -” are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, and At least one hydrogen in R may be substituted with alkyl or cycloalkyl. Further, “-CHR-CHR-”, “-CR ₂ -CR ₂ -”, “-CR=CR-”, “-C(-R) ₂ -”, and “-Si(-R) ₂ -” Two adjacent Rs in may be bonded to form a cycloalkylene ring, an arylene ring, and a heteroarylene ring (refer to the rightmost structural formula in the following structural formulas). On the other hand, the details of the substituents enumerated here will be collectively described above or later.

As the linking group, a single bond, -CR=CR-, -N(-R)-, -O-, -S-, -C(-R) ₂ -, -Si(-R) ₂ -, and -Se- is preferable, and single bonds, -CR=CR-, -N(-R)-, -O-, -S-, and -C(-R) ₂ - are more preferable, and single bonds, -CR=CR -, -N(-R)-, -O-, and -S- are more preferred, and a single bond and -CR=CR- are most preferred.

The position at which two R are bonded by a linking group is not particularly limited as long as it can be bonded, but it is preferable to bond at the most adjacent position, for example, when the two R's are a phenyl group, "C" in the phenyl group It is preferable to bond to each other at positions ortho (2nd position) based on the bonding position (1st position) of "Si" (refer to the above structural formula).

"Alkyl" may be either straight chain or branched chain, and is, for example, straight chain alkyl having 1 to 24 carbon atoms or branched chain alkyl having 3 to 24 carbon atoms, preferably, alkyl having 1 to 18 carbon atoms (C 3 to 24 carbon atoms). branched chain alkyl of 18), alkyl of 1 to 12 carbon atoms (branched chain alkyl of 3 to 12 carbon atoms), alkyl of 1 to 6 carbon atoms (branched chain alkyl of 3 to 6 carbon atoms), alkyl of 1 to 5 carbon atoms (3 carbon atoms) to 5 branched chain alkyl), C1-4 alkyl (C3-4 branched chain alkyl), and the like.

Specific "alkyl" includes, for example, methyl, ethyl, n-propyl, isopropyl, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1,2-trimethylpropyl, 1,1 ,2,2-tetramethylpropyl, 1-ethyl-1,2,2-trimethylpropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-ethylbutyl, 1,1-dimethylbutyl, 3 ,3-dimethylbutyl, 1,1-diethylbutyl, 1-ethyl-1-methylbutyl, 1-propyl-1-methylbutyl, 1,1,3-trimethylbutyl, 1-ethyl-1,3-dimethyl Butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl), 1-methylpentyl, 2-propylpentyl, 1,1-dimethylpentyl, 1-ethyl-1-methylpentyl, 1-propyl -1-methylpentyl, 1-butyl-1-methylpentyl, 1,1,4-trimethylpentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 1,1-dimethylhexyl, 1-ethyl-1 -Methylhexyl, 1,1,5-trimethylhexyl, 3,5,5-trimethylhexyl, n-heptyl, 1-methylheptyl, 1-hexylheptyl, 1,1-dimethylheptyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, n-octyl, t-octyl (1,1,3,3-tetramethylbutyl), 1,1-dimethyloctyl, n-nonyl, n-decyl, 1-methyldecyl , n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, or n-eicosyl.

Regarding "alkenyl", the description of "alkyl" described above can be referred to, and it is a group in which the C-C single bond in the structure of "alkyl" is substituted with a C=C double bond, and not only one but two or more groups Also included are groups in which a bond is replaced by a double bond (also called alkadien-yl or alkathien-yl).

Regarding "alkynyl", the description of "alkyl" described above can be referred to, and it is a group in which the C-C single bond in the structure of "alkyl" is substituted with a C≡C triple bond, and not only one but two or more bonds are substituted. Groups in which a single bond is replaced by a triple bond (also called alkadiyn-yl or alkathrin-yl) are also included.

"Cycloalkyl" is, for example, a cycloalkyl of 3 to 24 carbon atoms, preferably a cycloalkyl of 3 to 20 carbon atoms, a cycloalkyl of 3 to 16 carbon atoms, a cycloalkyl of 3 to 14 carbon atoms, or a cycloalkyl of 3 to 12 carbon atoms. cycloalkyl, cycloalkyl of 5 to 10 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, or cycloalkyl of 5 carbon atoms.

Specific "cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, or alkyls having 1 to 5 carbon atoms or 1 to 4 carbon atoms (especially methyl) substituent, norbornenyl, bicyclo[1.1.0]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.1.0]pentyl, bicyclo[2.1.1]hexyl, bicyclo[3.1.0 ]hexyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, adamantyl, diamantyl, decahydronaphthalenyl, or decahydroazulenyl, and the like.

"Cycloalkylene (ring)" is, for example, a cycloalkylene having 3 to 24 carbon atoms, preferably a cycloalkylene having 3 to 20 carbon atoms, a cycloalkylene having 3 to 16 carbon atoms, or a cycloalkylene having 3 to 14 carbon atoms. Cycloalkylene, C3-C12 cycloalkylene, C5-C10 cycloalkylene, C5-8 cycloalkylene, C5-C6 cycloalkylene, or C5 cycloalkylene.

Specific examples of "cycloalkylene" include a structure made into a divalent group by removing one hydrogen from the aforementioned "cycloalkyl" (monovalent group).

Regarding "cycloalkenyl", the description of "cycloalkyl" described above can be referred to, and it is a group in which the C-C single bond in the structure of "cycloalkyl" is substituted with a C=C double bond, and not only one but two Also included are groups in which two or more single bonds are replaced with double bonds (also called cycloalkadien-yl or cycloalkatrien-yl).

"Alkoxy" may be either straight-chain or branched, and is, for example, straight-chain alkoxy having 1 to 24 carbon atoms or branched-chain alkoxy having 3 to 24 carbon atoms, and preferably alkoxy having 1 to 18 carbon atoms (carbon atoms 3 to 24). 18 branched alkoxy), C1-12 alkoxy (C3-12 branched alkoxy), C1-6 alkoxy (C3-6 branched alkoxy), C1-5 alkoxy (C3 -5 branched alkoxy), C1-C4 alkoxy (C3-C4 branched alkoxy), and the like.

Specific "alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, 1-ethyl-1-methylpropoxy, 1,1-diethylpropoxy, 1,1,2- Trimethylpropoxy, 1,1,2,2-tetramethylpropoxy, 1-ethyl-1,2,2-trimethylpropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, 2 -Ethylbutoxy, 1,1-dimethylbutoxy, 3,3-dimethylbutoxy, 1,1-diethylbutoxy, 1-ethyl-1-methylbutoxy, 1-propyl-1-methylbutoxy, 1,1,3-trimethylbutoxy, 1-ethyl-1,3-dimethylbutoxy, n-pentyloxy, isopentyloxy, neopentyloxy, t-pentyloxy (t-amyloxy), 1-methylpentyl Oxy, 2-propylpentyloxy, 1,1-dimethylpentyloxy, 1-ethyl-1-methylpentyloxy, 1-propyl-1-methylpentyloxy, 1-butyl-1-methylpentyloxy, 1,1, 4-trimethylpentyloxy, n-hexyloxy, 1-methylhexyloxy, 2-ethylhexyloxy, 1,1-dimethylhexyloxy, 1-ethyl-1-methylhexyloxy, 1,1, 5-trimethylhexyloxy, 3,5,5-trimethylhexyloxy, n-heptyloxy, 1-methylheptyloxy, 1-hexylheptyloxy, 1,1-dimethylheptyloxy, 2,2-dimethylheptyloxy , 2,6-dimethyl-4-heptyloxy, n-octyloxy, t-octyloxy (1,1,3,3-tetramethylbutyloxy), 1,1-dimethyloctyloxy, n-nonyloxy, n -decyloxy, 1-methyldecyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy cy, n-heptadecyloxy, n-octadecyloxy, or n-eicosyloxy, and the like.

"Aryloxy" is a group represented by "Ar-O- (Ar is an aryl group)", and the description of "aryl" described above can be cited for details of this aryl.

"Arylthio" is a group represented by "Ar-S- (Ar is an aryl group)", and the description of "aryl" described above can be cited for details of this aryl.

"Triarylsilyl" is a silyl group substituted with three aryls, and the description of "aryl" described above can be cited for details of this aryl.

Specific examples of "triarylsilyl" include triphenylsilyl, diphenylmononaphthylsilyl, monophenyldinaphthylsilyl, and trinaphthylsilyl.

"Trialkylsilyl" is a silyl group substituted with three alkyls, and the description of "alkyl" described above can be cited for details of this alkyl.

Specific "trialkylsilyl" includes, for example, trimethylsilyl, triethylsilyl, trin-propylsilyl, triisopropylsilyl, trin-butylsilyl, triisobutylsilyl, tris-butylsilyl, trit- Butylsilyl, ethyldimethylsilyl, n-propyldimethylsilyl, isopropyldimethylsilyl, n-butyldimethylsilyl, isobutyldimethylsilyl, s-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, n-propyldi Ethylsilyl, isopropyldiethylsilyl, n-butyldiethylsilyl, s-butyldiethylsilyl, t-butyldiethylsilyl, methyldi-n-propylsilyl, ethyldi-n-propylsilyl, n-butyldin- propylsilyl, s-butyldin-propylsilyl, t-butyldin-propylsilyl, methyldiisopropylsilyl, ethyldiisopropylsilyl, n-butyldiisopropylsilyl, s-butyldiisopropylsilyl, or t-butyldiisopropylsilyl and the like.

"Tricycloalkylsilyl" is a silyl group substituted with three cycloalkyls, and the description of "cycloalkyl" described above can be cited for details of this cycloalkyl.

Specific "tricycloalkylsilyl" is, for example, tricyclopentylsilyl or tricyclohexylsilyl.

"Dialkylcycloalkylsilyl" is a silyl group substituted with two alkyls and one cycloalkyl, and the descriptions of "alkyl" and "cycloalkyl" described above can be cited for details of these alkyls and cycloalkyls. .

"Alkyldicycloalkylsilyl" is a silyl group substituted with one alkyl and two cycloalkyls, and for details of these alkyls and cycloalkyls, the descriptions of "alkyl" and "cycloalkyl" described above can be cited. .

A substituent affects the emission wavelength of a polycyclic aromatic compound by virtue of the steric hindrance, electron donating, and electron withdrawing properties of its structure, and therefore, the emission wavelength can be adjusted by selecting the substituent. It is preferably a group represented by the following structural formula, more preferably methyl, t-butyl, bicyclooctyl, cyclohexyl, adamantyl, phenyl, o-tolyl, p-tolyl, 2,4-xylyl , 2,5-xylyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis(p-(t-butyl)phenyl)amino, diphenyl boryl, dimethylboryl, dibenzooxaboryl, phenyldibenzodivorinyl, carbazolyl, 3,6-dimethylcarbazolyl, 3,6-di-t-butylcarbazolyl and phenoxy; Even more preferably, methyl, t-butyl, phenyl, o-tolyl, 2,6-xylyl, 2,4,6-mesityl, diphenylamino, di-p-tolylamino, bis(p-( t-butyl)phenyl)amino, carbazolyl, 3,6-dimethylcarbazolyl, 3,6-di-t-butylcarbazolyl, and tribenzoazepinyl. From the viewpoint of the ease of synthesis, a larger steric hindrance is preferred for selective synthesis, specifically, t-butyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 2,4,6-mesityl, di-p-tolylamino, bis(p-(t-butyl)phenyl)amino, 3,6-dimethylcarbazolyl and 3,6-di -t-butylcarbazolyl is preferred.

In the structural formulas below, "Me" represents methyl, "tBu" represents t-butyl, "tAm" represents t-amyl, "tOct" represents t-octyl, and * represents a bonding position.

<Deuterium, Cyano , or description of substitution by halogen>

At least one hydrogen (hydrogen in the group represented by formula (G) and hydrogen in a part other than the group represented by formula (G)) in the polycyclic aromatic compound of the present invention is deuterium, cyano or halogen may be substituted. In addition, at least one hydrogen in a moiety other than the group represented by formula (G) in the polycyclic aromatic compound of the present invention may be substituted with heavy hydrogen, cyano or halogen. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine.

<of the present invention dahwan Description of Specific Examples of Aromatic Compounds>

Specific examples of polycyclic aromatic compounds include compounds represented by the following structural formulas. On the other hand, "Me" in the following structural formula represents a methyl group, "CN" represents a cyano group, and "D" represents a deuterium.

< dahwan Application of Aromatic Compounds to Polymers>

The polycyclic aromatic compound according to the present invention is a polymer compound obtained by polymerizing a reactive compound in which a reactive substituent is substituted thereto as a monomer (the monomer for obtaining the polymer compound has a polymerizable substituent), or the polymer compound is further A crosslinked polymer compound (the polymer compound for obtaining the crosslink polymer has a crosslinkable substituent), or a pendant polymer compound obtained by reacting a main chain polymer and the reactive compound (to obtain the pendant polymer compound) The reactive compound has a reactive substituent), or as a pendant polymer crosslinked product obtained by further crosslinking the pendant polymer compound (the pendant polymer compound for obtaining the pendant polymer crosslinked product has a crosslinkable substituent), organic It can be used for a material for a device, for example, a material for an organic electroluminescent device, a material for an organic field effect transistor, or a material for an organic thin film solar cell.

As the above-mentioned reactive substituent (including the polymerizable substituent, the crosslinkable substituent, and a reactive substituent for obtaining a pendant-type polymer, hereinafter also simply referred to as a "reactive substituent"), the polycyclic aromatic compound can be made high in molecular weight. It is not particularly limited as long as it is a substituent that is present, a substituent capable of further crosslinking the polymer compound thus obtained, and a substituent capable of pendant reaction with the main chain polymer, but the following structural substituents are preferable. * in each structural formula represents a bonding position.

L is each independently a single bond, -O-, -S-, >C=O, -O-C(=O)-, C1-C12 alkylene, C1-C12 oxyalkylene, and C1 -12 polyoxyalkylene. Among the above substituents, a group represented by formula (XLS-1), formula (XLS-2), formula (XLS-3), formula (XLS-9), formula (XLS-10) or formula (XLS-17) is preferable. and a group represented by formula (XLS-1), formula (XLS-3) or formula (XLS-17) is more preferable.

Such high molecular compounds, crosslinked polymers, pendant type polymer compounds, and crosslinked pendant type polymers, in addition to the repeating units of the polycyclic aromatic compound according to the present invention, may contain substituted or unsubstituted triarylamines and substituted or unsubstituted fluorenes. , substituted or unsubstituted anthracene, substituted or unsubstituted tetracene, substituted or unsubstituted triazine, substituted or unsubstituted carbazole, substituted or unsubstituted tetraphenylsilane, substituted or unsubstituted spirofluorene, At least one selected from the group consisting of substituted or unsubstituted triphenylphosphine, substituted or unsubstituted dibenzothiophene, and substituted or unsubstituted dibenzofuran may be included as a repeating unit.

As a substituent in these repeating units, for example, aryl, heteroaryl, diarylamino (two aryls may be bonded via a linking group), diheteroarylamino (two heteroaryls are bonded via a linking group, may be), arylheteroarylamino (aryl and heteroaryl may be bonded through a linking group), diarylboryl (two aryls may be bonded through a linking group), alkyl, cycloalkyl, alkoxy, aryloxy, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkyldicycloalkylsilyl; and the like. The "aryl" of triarylamine and the details of these substituents can be cited from the description of the polycyclic aromatic compound according to the present invention.

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

2. Represented by formula (1) dahwan Method for producing aromatic compounds

The polycyclic aromatic compound represented by the general formula (1) can be produced according to methods described in many known documents including International Publication No. 2015/102118.

Basically, an intermediate is prepared by first bonding ring a, ring b, and ring c with an ether group (first reaction), and then ring a, ring b, and ring c are converted into groups containing central element B (boron). By combining, the final product can be prepared (second reaction). In the first reaction, a general etherification reaction such as a nucleophilic substitution reaction or a Ullman reaction can be used. In addition, in the second reaction, a tandem hetero Friedel Crafts reaction (continuous aromatic electron transfer reaction, hereinafter the same) can be used.

In addition, by using a raw material having a group represented by formula (G) somewhere in these reaction steps or by adding a step of introducing a group represented by formula (G), the group represented by formula (G) is added to a desired position. Combined compounds can be prepared. In addition, by using a deuterated, cyanated, or halogenated raw material somewhere in this reaction step, or by adding a deuterated, cyanated, or halogenated step, the desired position is deuterated, cyanated, or halogenated. compounds can be prepared.

As shown in the following scheme (1), the second reaction is a reaction for introducing central element B (boron) that binds ring a, ring b, and ring c. First, a hydrogen atom between two ether bonds is ortho-metalized with n-butyllithium, sec-butyllithium, t-butyllithium or the like. Then, boron trichloride, boron tribromide, etc. are added to perform metal exchange of lithium-boron, and then a Bronsted base such as N,N-diisopropylethylamine is added to cause a tandem Bora Friedel Crafts reaction , the target can be obtained. In the second reaction, a Lewis acid such as aluminum trichloride may be added to promote the reaction.

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

Further, as the ortho-metalation reagent, alkyllithium such as methyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, lithium diisopropylamide, lithium tetramethylpiperidide, lithium hexamethyldisilazide, Organic alkali compounds, such as potassium hexamethyl disilazide, are mentioned.

Further, as the metal-B (boron) metal exchange reagent, boron halides such as boron trifluoride, boron trichloride, boron tribromide, and boron triiodide, CIPN(NEt ₂ ) ₂ , etc. An aminated halide of boron, an alkoxide of boron, an aryloxide of boron, and the like are exemplified.

In addition, as Bronsted base, N,N-diisopropylethylamine, triethylamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine Dean, N,N-dimethylaniline, N,N-dimethyltoluidine, 2,6-lutidine, sodium tetraphenylborate, potassium tetraphenylborate, triphenylborane, tetraphenylsilane, Ar ₄ BNa, Ar ₄ BK, Ar ₃ B, Ar ₄ Si (where Ar is aryl such as phenyl), and the like.

Further, as Lewis acids, AlCl ₃ , AlBr ₃ , AlF ₃ , BF ₃ OEt ₂ , BCl ₃ , BBr ₃ , GaCl 3 , GaBr ₃ , InCl _{3 ,} InBr ₃ , In(OTf) ₃ , SnCl ₄ , SnBr ₄ , AgOTf, ScCl ₃ , Sc(OTf) ₃ , ZnCl ₂ , ZnBr ₂ , Zn(OTf) ₂ , MgCl ₂ , MgBr ₂ , Mg(OTf) ₂ , LiOTf, NaOTf, KOTf, Me ₃ SiOTf, Cu(OTf) ₂ , CuCl ₂ , YCl ₃ , Y(OTf) ₃ , TiCl ₄ , TiBr ₄ , ZrCl ₄ , ZrBr ₄ , FeCl ₃ , FeBr ₃ , CoCl ₃ , CoBr ₃ and the like.

In each of the above schemes, a Bronsted base or a Lewis acid may be used to promote the tandem hetero Friedel Crafts reaction. However, when boron halides such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide, etc. are used, along with the progress of the aromatic electron substitution reaction, hydrogen fluoride, hydrogen chloride, and bromination Since acids such as hydrogen and hydrogen iodide are produced, the use of a Bronsted base to capture the acid is effective. On the other hand, when an aminated halide of boron or an alkoxide of boron is used, amines and alcohols are formed as the aromatic electron transfer reaction proceeds, so in many cases it is not necessary to use a Bronsted base, but amino groups Since the elimination ability of the alkoxy group is low, the use of a Lewis acid that promotes the elimination is effective.

3. organic device

In the chemical structural formulas illustrated below, "Me" represents a methyl group, and "tBu" represents a t-butyl group.

The polycyclic aromatic compound according to the present invention can be used as a material for organic devices. As an organic device, an organic electroluminescent element, an organic field effect transistor, an organic thin-film solar cell, or a wavelength conversion filter etc. are mentioned, for example.

3-1. abandonment electric field light emitting element

The polycyclic aromatic compound according to the present invention can be used, for example, as a material for an organic electroluminescent device. Hereinafter, the organic EL element according to the present embodiment will be described in detail based on the drawings. 1 is a schematic cross-sectional view showing an organic EL element according to the present embodiment.

<Structure of organic electroluminescent device>

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

In addition, the organic EL element 100 is manufactured by reversing the manufacturing order, for example, the substrate 101, the cathode 108 provided on the substrate 101, and the electron injection layer provided on the cathode 108 ( 107), an electron transport layer 106 provided on the electron injection layer 107, a light emitting layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light emitting layer 105, and a hole transport layer It is good also as a structure which has the hole injection layer 103 provided on 104, and the anode 102 provided on the hole injection layer 103.

All of the above layers are not indispensable, and the minimum structural unit is composed of an anode 102, a light emitting layer 105, and a cathode 108, and a hole injection layer 103, a hole transport layer 104, and an electron transport layer. (106), the electron injection layer 107 is an arbitrarily provided layer. In addition, each said layer may consist of a single layer, respectively, and may consist of multiple layers.

As an aspect of the layer constituting the organic EL element, in addition to the constitutional aspect of the above-described "substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole transport layer/ Emitting layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole injection layer/emission layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole injection layer/hole transport layer/emission layer/electron injection layer" / cathode", "substrate/anode/hole injection layer/hole transport layer/emission layer/electron transport layer/cathode", "substrate/anode/emission layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole transport layer/emission layer" /electron injection layer/cathode", "substrate/anode/hole transport layer/light emitting layer/electron transport layer/cathode", "substrate/anode/hole injection layer/light emitting layer/electron injection layer/cathode", "substrate/anode/hole injection layer" /Light emitting layer/electron transport layer/cathode”, “substrate/anode/light emitting layer/electron transport layer/cathode”, or “substrate/anode/light emitting layer/electron injection layer/cathode” may be used.

<Substrate in organic electroluminescence device>

The substrate 101 is a support for the organic EL element 100, and usually quartz, glass, metal, plastic or the like is used. The substrate 101 is formed in the shape of a plate, film, or sheet depending on the purpose, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Especially, a glass plate and a board made of transparent synthetic resin, such as polyester, polymethacrylate, polycarbonate, and polysulfone, are preferable. In the case of a glass substrate, soda-lime glass, non-alkali glass, etc. are used, and thickness should just be sufficient thickness to maintain mechanical strength, so what is necessary is just 0.2 mm or more, for example. As an upper limit of thickness, it is 2 mm or less, for example, Preferably it is 1 mm or less. Regarding the material of the glass, an alkali-free glass is preferable since it is preferable to have fewer ions eluted from the glass, but soda lime glass coated with a barrier coat of SiO ₂ or the like is also commercially available and can be used. In addition, a gas barrier film such as a dense silicon oxide film may be formed on at least one side of the substrate 101 to improve gas barrier properties, and in particular, a plate, film or sheet made of synthetic resin having low gas barrier properties is used as the substrate. When using in (101), it is preferable to form a gas barrier film.

<Anode in Organic Electroluminescence Device>

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

Materials forming the anode 102 include inorganic compounds and organic compounds. Examples of the inorganic compound include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide (IZO)) etc.), metal halides (such as copper iodide), copper sulfide, carbon black, ITO glass and Nessa glass. As an organic compound, conductive polymers, such as polythiophene, such as poly(3-methylthiophene), polypyrrole, and polyaniline, etc. are mentioned, for example. In addition, it can be used suitably selected from materials used as anodes of organic EL elements.

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 preferably low resistance from the viewpoint of power consumption of the light emitting element. For example, an ITO substrate of 300 Ω/□ or less functions as an element electrode, but currently it is possible to supply a substrate of about 10 Ω/□, so for example, 100 to 5 Ω/□, preferably 50 to 5 Ω/□. It is particularly preferable to use a low-resistance product of The thickness of ITO can be arbitrarily selected according to the resistance value, but it is usually used between 50 and 300 nm in many cases.

<Hole Injection Layer, Hole Transport Layer in Organic Electroluminescent Device>

The hole injection layer 103 serves to efficiently inject holes moving from the anode 102 into the light emitting layer 105 or into the hole transport layer 104 . The hole transport layer 104 serves to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105 . The hole injection layer 103 and the hole transport layer 104 are formed by laminating or mixing one or more hole injection/transport materials, or a mixture of a hole injection/transport material and a polymeric binder, respectively. Alternatively, a layer may be formed by adding an inorganic salt such as iron (III) chloride to the hole injection/transport material.

As the hole injection/transport material, it is necessary to efficiently inject/transport holes from the positive electrode between the electrodes to which an electric field is applied, and it is preferable to have high hole injection efficiency and efficiently transport the injected holes. For this purpose, it is preferable that the material has a small ionization potential, a high hole mobility, and excellent stability, and is difficult to generate trap impurities during production and use.

As the material (hole transport material) forming the hole injection layer 103 and the hole transport layer 104, a compound conventionally used as a charge transport material for holes in a photoconductive material, a p-type semiconductor, or an organic EL device Any compound may be selected and used from known compounds used in the hole injection layer and the hole transport layer. In the present invention, a polycyclic aromatic compound represented by the above general formula (1) can be used as the hole transport material.

Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole), triarylamine Derivatives (polymer having aromatic tertiary amino in main chain or side chain, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N'-diphenyl-N,N'-di(3 -Methylphenyl) -4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, N,N'-diphenyl-N ,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine, N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl -1,1'-diamine, N ⁴ ,N ^{4 '} -diphenyl-N ⁴ ,N ^{4 '} -bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl] -4,4'-diamine, N ⁴ ,N ⁴ ,N ^{4 '} ,N ^4' -tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4 Triphenylamine derivatives such as ,4'-diamine, 4,4',4"-tris(3-methylphenyl(phenyl)amino)triphenylamine, starburstamine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free , copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone-based compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (e.g., 1,4,5,8,9,12-hexaazatri phenylene-2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, and polysilanes. Although vinylcarbazole and polysilane are preferred, any compound capable of forming a thin film necessary for manufacturing a light emitting device, injecting holes from an anode, and transporting holes is not particularly limited.

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

The material for the hole injection layer and the material for the hole transport layer described above are a polymer compound obtained by polymerizing a reactive compound having a reactive substituent substituted thereto as a monomer, or a crosslinked polymer thereof, or a main chain polymer and the reactive compound reacted A pendant-type polymer compound or a pendant-type polymer crosslinked product thereof can also be used for the hole layer material. As the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the above general formula (1) can be cited.

The details of the use of such a high molecular compound and high molecular crosslinked product will be described later.

<Light-emitting layer in organic electroluminescent device>

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

The light emitting layer may be a single layer or may consist of a plurality of layers, and is formed of materials for the light emitting layer (host material, dopant material), respectively. The host material and the dopant material may be of one type, a combination of a plurality of materials, or any of them. In addition, the material for the hole transport layer or the material for the electron transport layer may be mixed with the host material, or a combination thereof may be used. The dopant material may be included in the entire host material, or partially included, or any of them may be used. As the doping method, it can be formed by co-evaporation with the host material, but it may be deposited simultaneously after mixing with the host material in advance, or formed into a film by wet film forming after mixing with the host material in advance with an organic solvent.

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

The usage amount of the dopant material varies depending on the type of the dopant material, and may be determined according to the characteristics of the dopant material. The amount of the dopant used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, still more preferably 0.1 to 10% by weight of the total light emitting layer material. The above range is preferable in that, for example, the concentration quenching phenomenon can be prevented. From the standpoint of durability, it is also preferable that part or all of the hydrogen atoms of the dopant material are deuterated.

On the other hand, in an organic EL device using a thermally activated delayed fluorescent dopant material, a low concentration of the dopant material is preferable in that concentration quenching can be prevented, but a high concentration of the dopant material is used in a thermally activated delayed fluorescent device. is preferable from the efficiency point of view. Further, in an organic EL device using a heat-activated delayed fluorescence assist dopant material, from the viewpoint of the efficiency of the heat-activated delayed fluorescence device of the assist dopant material, the amount of dopant material used is preferably lower than that of the assist dopant material.

In the case where the assist dopant material is used, the host material, the assist dopant material, and the amount of the dopant material used are 40 to 99.999% by weight, 59 to 1% by weight, and 20 to 0.001% by weight of the total light emitting layer material, respectively. is preferably 60 to 99.99% by weight, 39 to 5% by weight and 10 to 0.01% by weight, more preferably 70 to 99.95% by weight, 29 to 10% by weight and 5 to 0.05% by weight, respectively. .

As the host material, condensed ring derivatives such as anthracene, pyrene, dibenzochrysene or fluorene, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, cyclo A pentadiene derivative etc. are mentioned. In particular, an anthracene-based compound, a fluorene-based compound, or a dibenzochrysene-based compound is preferred. Moreover, it is also preferable that some or all of the hydrogen atoms of the host material are deuterated from the viewpoint of durability. It is also preferable to configure the light emitting layer by combining a host compound in which some or all of the hydrogen atoms are deuterated and a dopant compound in which some or all of the hydrogen atoms are deuterated.

The triplet energy of the host material is preferably higher than the triplet energy of the dopant or assist dopant having the highest triplet energy in the light emitting layer, from the viewpoint of promoting the generation of TADF in the light emitting layer without hindering it. In this case, the triplet energy of the host material is preferably 0.01 eV or more, more preferably 0.03 eV or more, and still more preferably 0.1 eV or more. Further, a compound having TADF activity may be used for the host material.

As a host material, for example, a compound represented by the following general formula (H1), a compound represented by the following general formula (H2), a compound represented by the following general formula (H3), a compound represented by the following general formula (H4) A compound containing a structure, a compound represented by the following general formula (H5), a compound represented by the following general formula (H6), and a TADF material. Preferably it is a compound represented by general formula (H1).

<Compound represented by general formula (H1)>

In the formula (H1), L ¹ represents arylene having 6 to 30 carbon atoms or heteroarylene having 2 to 30 carbon atoms, preferably arylene having 6 to 24 carbon atoms, and more preferably arylene having 6 to 16 carbon atoms, , arylene having 6 to 12 carbon atoms is more preferred, arylene having 6 to 10 carbon atoms is particularly preferred, heteroarylene having 2 to 25 carbon atoms is more preferred, and heteroarylene having 2 to 20 carbon atoms is more preferred. Preferably, heteroarylene having 2 to 15 carbon atoms is more preferable, and heteroarylene having 2 to 10 carbon atoms is particularly preferable. Specific examples of the arylene include a benzene ring, a biphenyl ring, a naphthalene ring, a terphenyl ring, an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a naphthacene ring, a perylene ring, and Divalent groups, such as a pentacene ring, are mentioned. In addition, as heteroarylene, specifically, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, and a pyridine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzoimidazole ring, benzooxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, iso Quinoline ring, cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxathiine ring, phenoxazine ring, phenothiazine ring , phenazine ring, phenazacillin ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazan ring, tiant and divalent groups such as a rene ring, an indolocarbazole ring, a benzoindolocarbazole ring, a benzobenzoindolocarbazole ring, and a naphthobenzofuran ring.

At least one hydrogen in the compound represented by formula (H1) may be substituted with C1-C6 alkyl, C3-C14 cycloalkyl, cyano, halogen, or deuterium.

<Compound represented by general formula (H2)>

In the formula (H2), L ² and L ³ each independently represent an aryl having 6 to 30 carbon atoms or a heteroaryl having 2 to 30 carbon atoms. The aryl is preferably an aryl having 6 to 24 carbon atoms, more preferably an aryl having 6 to 16 carbon atoms, even more preferably an aryl having 6 to 12 carbon atoms, and particularly preferably an aryl having 6 to 10 carbon atoms. , benzene ring, biphenyl ring, naphthalene ring, terphenyl ring, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, triphenylene ring, pyrene ring, naphthacene ring, perylene ring and pentacene ring, etc. monovalent can lift As the heteroaryl, a heteroaryl having 2 to 25 carbon atoms is preferable, a heteroaryl having 2 to 20 carbon atoms is more preferable, a heteroaryl having 2 to 15 carbon atoms is still more preferable, and a heteroaryl having 2 to 10 carbon atoms is particularly preferable. And, specifically, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring. , pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzoimidazole ring, benzooxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, new Nolin ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxathiine ring, phenoxazine ring, phenothiazine ring, phenazine ring, phenazacillin ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazan ring, thianthrene ring, indolo Monovalent groups, such as a carbazole ring, a benzoindolocarbazole ring, a benzobenzoindolocarbazole ring, and a naphthobenzofuran ring, are mentioned.

At least one hydrogen in the compound represented by formula (H2) may be substituted with C1-C6 alkyl, C3-C14 cycloalkyl, cyano, halogen, or deuterium.

<Compound represented by general formula (H3) (an example of polymer host material)>

In formula (H3),

MU is a divalent group each independently represented by removing any two hydrogen atoms from an aromatic compound, EC is a monovalent group each independently represented by removing any one hydrogen atom from an aromatic compound, and 2 of MU A number of hydrogens are substituted with EC or MU, and k is an integer from 2 to 50000.

More specifically,

MU is each independently arylene, heteroarylene, diarylene arylamino, diarylene arylboryl, oxaborine-diyl, azaborin-diyl,

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

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

k is an integer from 2 to 50000;

It is preferable that k is an integer of 20-50000, and it is more preferable that it is an integer of 100-50000.

At least one hydrogen in MU and EC in the formula (H3) may be substituted with an alkyl having 1 to 24 carbon atoms, a cycloalkyl having 3 to 24 carbon atoms, a halogen or a deuterium, and any -CH in the alkyl _2- may be further substituted with -O- or -Si(CH ₃ ) ₂ -, and any -CH 2 - except for -CH ₂ - directly connected to EC in formula (H3) in the above alkyl _is It may be substituted with arylene having 6 to 24 carbon atoms, and any hydrogen in the alkyl may be substituted with fluorine.

Examples of MU include divalent groups represented by removing two arbitrary hydrogen atoms from any one of the compounds below.

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

Moreover, as EC, the monovalent group represented by the structure of any one of the following is mentioned, for example. In these, EC binds to MU in *.

The compound represented by formula (H3) preferably has 10 to 100% of MU of the total number of MUs (k) in the molecule having alkyl having 1 to 24 carbon atoms, from the viewpoint of solubility and coating film forming property, and the total number of MUs in the molecule ( It is more preferable that 30 to 100% of MU of k) has an alkyl having 1 to 18 carbon atoms (branched chain alkyl having 3 to 18 carbon atoms), and 50 to 100% of MU of the total number of MUs in the molecule (k) has 1 carbon atom. It is even more preferable to have ~12 alkyl (branched chain alkyl having 3 to 12 carbon atoms). On the other hand, from the viewpoint of in-plane orientation and charge transport, it is preferable that 10 to 100% of the MUs of the total number of MUs (k) in the molecule have alkyls having 7 to 24 carbon atoms, and 30 to 100% of the total number of MUs (k) in the molecule It is more preferable that MU of has C7-C24 alkyl (C7-C24 branched chain alkyl).

<Compound containing structure represented by general formula (H4)>

The compound is a compound containing a structure represented by the following formula (H4), and includes a plurality of structures, preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2. , Most preferably, one is included, and when a plurality is included, the structures are directly bonded to each other by a single bond or bonded to a specific linking group.

In the above general formula (H4), G is each independently "=C(-H)-" or "=N-", and H in "=C(-H)-" is a substituent or another formula (H4) may be substituted with the structure represented by

As the compound containing the structure represented by the general formula (H4), for example, compounds described in International Publication No. 2012/153780 and International Publication No. 2013/038650 can be used, and are prepared according to the method described in the above literature. can do.

Examples of substituents in the case where H in "=C(-H)-" which is G is substituted are as follows, but are not limited thereto.

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

Specific examples of the "heteroaryl group" as a substituent include pyrrolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridyl, triazinyl, indolyl, isoindolyl, imidazolyl, benzimidazolyl, Indazolyl, imidazo[1,2-a]pyridinyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, azadibenzofuranyl, thiophenyl, benzothienyl, dibenzothienyl, aza Dibenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, naphthyridinyl, carbazolyl, azacarbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothia Zinyl, phenoxazinyl, oxazolyl, oxadiazolyl, furazanil, benzoxazolyl, thiazolyl, thiadiazolyl, benzthiazolyl, triazolyl, tetrazolyl and the like, preferably dibenzofuranyl , dibenzothienyl, carbazolyl, pyridyl, pyrimidinyl, triazinyl, azadibenzofuranyl and azadibenzothienyl. Even more preferred are dibenzofuranyl, dibenzothienyl, azadibenzofuranyl or azadibenzothienyl.

The "substituted silyl group" as a substituent is also preferably a group selected from the group consisting of a substituted or unsubstituted trialkylsilyl group, a substituted or unsubstituted arylalkylsilyl group, and a substituted or unsubstituted triarylsilyl group.

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

It is also preferable that the "substituted phosphine oxide group" which is a substituent is a substituted or unsubstituted diarylphosphine oxide group. Specific examples of the substituted or unsubstituted diarylphosphine oxide group include diphenylphosphine oxide and ditolylphosphine oxide.

As a "substituted carboxyl group" which is a substituent, benzoyloxy etc. are mentioned, for example.

Examples of the linking group for bonding a plurality of structures represented by formula (H4) include divalent to tetravalent, divalent to trivalent, or divalent derivatives of the above-mentioned aryl and heteroaryl.

The specific example of the compound containing the structure represented by general formula (H4) is shown below.

<Compound represented by general formula (H5)>

In the formula (H5),

R ¹ to ^{R 11} are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, or cycloalkyl (above, first substituent), and corresponding R ¹ to R At least one hydrogen in ¹¹ may be further substituted with aryl, heteroaryl, diarylamino, alkyl or cycloalkyl (above, second substituent);

Adjacent groups among R ¹ to R ¹¹ may be bonded together to form an aryl ring or heteroaryl ring together with ring a, b or c, and at least one hydrogen in the formed ring is aryl, heteroaryl, It may be substituted with diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl (above, first substituent), and at least one hydrogen in these substituents is aryl, heteroaryl, diarylamino, may be further substituted with alkyl or cycloalkyl (above, second substituent);

Arbitrary “-C(-R)=” (where R is R ¹ to R ¹¹ ) in ring a, ring b, and ring c may be substituted with “-N=”;

At least one hydrogen in the compound represented by formula (H5) may each independently be substituted with a halogen or deuterium.

Arbitrary “-C(-R)=” (where R is R ¹ to R ¹¹ ) in ring a, ring b, and c in formula (H5) is substituted with “-N=”, and pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, and other nitrogen-containing heteroaryl rings.

Preferably, in the formula (H5),

R ¹ to R ¹¹ are each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 12 carbon atoms, or Cycloalkyl having 3 to 16 carbon atoms, and at least one hydrogen in R ¹ to R ¹¹ is aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, or diarylamino (wherein aryl is 6 to 12 carbon atoms) aryl), may be further substituted with C1-C12 alkyl or C3-C16 cycloalkyl,

Adjacent groups of R ¹ to R ¹¹ may be bonded together to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a ring, b ring or c ring, and at least One hydrogen is aryl of 6 to 30 carbon atoms, heteroaryl of 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl of 6 to 12 carbon atoms), alkyl of 1 to 12 carbon atoms, or cycloalkyl of 3 to 16 carbon atoms. It may be substituted, and at least one hydrogen in these substituents is aryl of 6 to 30 carbon atoms, heteroaryl of 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl of 6 to 12 carbon atoms), carbon atoms of 1 to 12 It may be further substituted with alkyl or C3-C16 cycloalkyl.

Even more preferably, in the formula (H5),

R ¹ to ^{R 11} are each independently hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms), alkyl having 1 to 6 carbon atoms, or Cycloalkyl having 3 to 14 carbon atoms, and at least one hydrogen in R ¹ to R ¹¹ is aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, or diarylamino (wherein aryl is 6 to 10 carbon atoms) aryl), may be further substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms,

Adjacent groups of R ¹ to R ¹¹ may be bonded together to form an aryl ring having 9 to 12 carbon atoms or a heteroaryl ring having 6 to 12 carbon atoms together with the a ring, b ring, or c ring, and at least One hydrogen is aryl of 6 to 16 carbon atoms, heteroaryl of 2 to 15 carbon atoms, diarylamino (wherein aryl is aryl of 6 to 10 carbon atoms), alkyl of 1 to 6 carbon atoms, or cycloalkyl of 3 to 14 carbon atoms. It may be substituted, and at least one hydrogen in these substituents is aryl of 6 to 16 carbon atoms, heteroaryl of 2 to 15 carbon atoms, diarylamino (wherein aryl is aryl of 6 to 10 carbon atoms), carbon atoms of 1 to 6 It may be further substituted with alkyl or C3-C14 cycloalkyl.

In the first substituent and the second substituent, examples of "aryl" and "heteroaryl" in aryl, heteroaryl, diarylamino, diheteroarylamino, and arylheteroarylamino include the following examples.

Specific examples of "aryl" include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, more preferably aryls having 6 to 20 carbon atoms, and more preferably aryl having 6 to 16 carbon atoms. More preferably, an aryl having 6 to 12 carbon atoms is particularly preferable, and an aryl having 6 to 10 carbon atoms is most preferable. For example, phenyl which is a monocyclic aryl, (2-, 3-, 4-)biphenylyl which is a bicyclic aryl, (1-, 2-) naphthyl which is a condensed bicyclic aryl, and terphenylyl which is a tricyclic aryl. (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl , p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-ter phenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic aryl, acene Naphthylene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenalen-(1-, 2-)yl , (1-, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-ter Phenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensed tetracyclic aryl triphenylene-(1-, 2-)yl, pyrene-(1- , 2-, 4-) day, naphthacene- (1-, 2-, 5-) day, condensed pentacyclic aryl perylene- (1-, 2-, 3-) day, pentacene- (1- , 2-, 5-, 6-) days and the like.

Specific examples of the "heteroaryl" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, more preferably heteroaryl having 2 to 20 carbon atoms, and having 2 to 15 carbon atoms. The heteroaryl of is more preferred, and the heteroaryl having 2 to 10 carbon atoms is particularly preferred. For example, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyridine Dazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzooxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cin Nolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathynyl, phenoxazinyl, phenothiazinyl, phenazinyl, Fenazasilinil, Indolizinil, Furanil, Benzofuranil, Isobenzofuranil, Dibenzofuranil, Naphthobenzofuranil, Thiophenyl, Benzothiophenyl, Isobenzothiophenyl, Dibenzothiophenyl, Naf Tobenzothiophenyl, benzophosphoryl, dibenzophosphoryl, monovalent group of benzophosphole oxide ring, monovalent group of dibenzophosphole oxide ring, furazanyl, thianthrenyl, indolocarbazolyl, benzoindolocar bazolyl and benzobenzoindolocarbazolyl; and the like.

In the first substituent and the second substituent, "alkyl" may be either straight chain or branched chain, and examples thereof include straight chain alkyl having 1 to 24 carbon atoms or branched chain alkyl having 3 to 24 carbon atoms. , C1-C18 alkyl (C3-C18 branched chain alkyl) is preferable, C1-C12 alkyl (C3-C12 branched chain alkyl) is more preferable, C1-C6 alkyl (C1-C6 alkyl) Branched chain alkyl of 3 to 6 carbon atoms) is more preferred, and alkyl of 1 to 5 carbon atoms (branched chain alkyl of 3 to 5 carbon atoms) and alkyl of 1 to 4 carbon atoms (branched chain alkyl of 3 to 4 carbon atoms) is particularly preferred. and methyl is most preferred. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl), n -Hexyl, 1-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl (1,1,3,3-tetramethylbutyl), 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n -Undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n -Ecosil etc. can be mentioned. Also, for example, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1,1,4-trimethylpentyl, 1, 1,2-trimethylpropyl, 1,1-dimethyloctyl, 1,1-dimethylpentyl, 1,1-dimethylheptyl, 1,1,5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl- 1,3-dimethylbutyl, 1,1,2,2-tetramethylpropyl, 1-butyl-1-methylpentyl, 1,1-diethylbutyl, 1-ethyl-1-methylpentyl, 1,1,3 -Trimethylbutyl, 1-propyl-1-methylpentyl, 1,1,2-trimethylpropyl, 1-ethyl-1,2,2-trimethylpropyl, 1-propyl-1-methylbutyl, 1,1-dimethylhexyl etc. can also be mentioned.

In the first substituent and the second substituent, "cycloalkyl" includes cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, and cycloalkyl having 3 to 14 carbon atoms. Cycloalkyl of 5 to 10 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, cycloalkyl of 5 carbon atoms, and the like. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (particularly methyl) substituents having 1 to 4 carbon atoms or bicyclo[1.1.0] Butyl, bicyclo[1.1.1]pentyl, bicyclo[2.1.0]pentyl, bicyclo[2.1.1]hexyl, bicyclo[3.1.0]hexyl, bicyclo[2.2.1]heptyl, bicyclo[ 2.2.2] octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.

When the first substituent is aryl, the substitution position is preferably R ¹ , R ³ , R ⁴ , R ⁵ , R ¹⁰ and R ¹¹ , for example, substitution with R ¹ and R ³ , R ⁵ and R ¹⁰ Substitution with R ⁴ and R ¹¹ is more preferable, and aryl is preferably a phenyl group.

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

As a specific example of the compound represented by formula (H5), the compound represented by the following structural formula is mentioned, for example. In addition, "Me" in formula is a methyl group.

The compound represented by formula (H5) is prepared by first preparing an intermediate by bonding rings a to c with a bonding group (-O-) (first reaction), and then bonding rings a to c with B (boron). The final product can be prepared (second reaction). In the first reaction, for example, a general etherification reaction such as a nucleophilic substitution reaction or a Ullman reaction can be used. In addition, in the second reaction, a tandem hetero Friedel Crafts reaction (continuous aromatic electron transfer reaction) can be used. For details of the first and second reactions, the description described in International Publication No. 2015/102118 can be referred to.

<Compound represented by general formula (H6)>

In the formula (H6),

R ¹ to R ¹⁶ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, or cycloalkyl (above, first substituent), and corresponding R ¹ to R At least one hydrogen in ¹⁶ may be further substituted with aryl, heteroaryl, diarylamino, alkyl or cycloalkyl (above, second substituent);

Adjacent groups among R ¹ to ^{R 16} may be bonded together to form an aryl ring or heteroaryl ring together with the a ring, b ring, c ring, or d ring, and at least one hydrogen in the formed ring is aryl , heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl or cycloalkyl (above, first substituent) may be substituted, and at least one hydrogen in these substituents is aryl, heteroaryl, may be further substituted with diarylamino, alkyl or cycloalkyl (above, second substituent);

At least one hydrogen in the compound represented by formula (H6) may each independently be substituted with a halogen or heavy hydrogen.

Preferably, in the formula (H6),

R ¹ to R ¹⁶ are each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 12 carbon atoms, or Cycloalkyl having 3 to 16 carbon atoms, and at least one hydrogen in R ¹ to ^{R 16} is aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, or diarylamino (wherein aryl is 6 to 12 carbon atoms) aryl), may be further substituted with C1-C12 alkyl or C3-C16 cycloalkyl,

Adjacent groups among R ¹ to ^{R 16} may be bonded together to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a ring, b ring, c ring, or d ring, and the formed ring At least one hydrogen in is aryl of 6 to 30 carbon atoms, heteroaryl of 2 to 30 carbon atoms, diarylamino (provided that aryl is aryl of 6 to 12 carbon atoms), alkyl of 1 to 12 carbon atoms or 3 to 16 carbon atoms may be substituted with cycloalkyl, and at least one hydrogen in these substituents is aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), carbon atoms It may be further substituted with an alkyl of 1 to 12 or a cycloalkyl of 3 to 16 carbon atoms.

Even more preferably, in the formula (H6),

R ¹ to R ¹⁶ are each independently hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms), alkyl having 1 to 6 carbon atoms, or Cycloalkyl having 3 to 14 carbon atoms, and at least one hydrogen in R ¹ to R ¹⁶ is aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, or diarylamino (provided that aryl has 6 to 10 carbon atoms). aryl), may be further substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms,

Adjacent groups among R ¹ to ^{R 16} may be bonded together to form an aryl ring having 9 to 12 carbon atoms or a heteroaryl ring having 6 to 12 carbon atoms together with the a ring, b ring, c ring, or d ring, and the formed ring At least one hydrogen in is aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms), alkyl having 1 to 6 carbon atoms, or carbon atoms 3 to 14 may be substituted with cycloalkyl, and at least one hydrogen in these substituents is aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms), carbon atoms It may be further substituted with an alkyl of 1 to 6 or a cycloalkyl of 3 to 14 carbon atoms.

In the first substituent and the second substituent, examples of "aryl" and "heteroaryl" in aryl, heteroaryl, diarylamino, diheteroarylamino, and arylheteroarylamino include the following examples.

Specific examples of "aryl" include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, more preferably aryls having 6 to 20 carbon atoms, and more preferably aryl having 6 to 16 carbon atoms. More preferably, an aryl having 6 to 12 carbon atoms is particularly preferable, and an aryl having 6 to 10 carbon atoms is most preferable. For example, phenyl which is a monocyclic aryl, (2-, 3-, 4-)biphenylyl which is a bicyclic aryl, (1-, 2-) naphthyl which is a condensed bicyclic aryl, and terphenylyl which is a tricyclic aryl. (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl , p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-ter phenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic aryl, acene Naphthylene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenalen-(1-, 2-)yl , (1-, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-ter Phenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensed tetracyclic aryl triphenylene-(1-, 2-)yl, pyrene-(1- , 2-, 4-) day, naphthacene- (1-, 2-, 5-) day, condensed pentacyclic aryl perylene- (1-, 2-, 3-) day, pentacene- (1- , 2-, 5-, 6-) days and the like.

Specific examples of the "heteroaryl" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, more preferably heteroaryl having 2 to 20 carbon atoms, and having 2 to 15 carbon atoms. The heteroaryl of is more preferred, and the heteroaryl having 2 to 10 carbon atoms is particularly preferred. For example, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyridine Dazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzooxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cin Nolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathynyl, phenoxazinyl, phenothiazinyl, phenazinyl, Fenazasilinil, Indolizinil, Furanil, Benzofuranil, Isobenzofuranil, Dibenzofuranil, Naphthobenzofuranil, Thiophenyl, Benzothiophenyl, Isobenzothiophenyl, Dibenzothiophenyl, Naf Tobenzothiophenyl, benzophosphoryl, dibenzophosphoryl, monovalent group of benzophosphole oxide ring, monovalent group of dibenzophosphole oxide ring, furazanyl, thianthrenyl, indolocarbazolyl, benzoindolocar bazolyl and benzobenzoindolocarbazolyl; and the like.

In the first substituent and the second substituent, "alkyl" may be either straight chain or branched chain, and examples thereof include straight chain alkyl having 1 to 24 carbon atoms or branched chain alkyl having 3 to 24 carbon atoms. , C1-C18 alkyl (C3-C18 branched chain alkyl) is preferable, C1-C12 alkyl (C3-C12 branched chain alkyl) is more preferable, C1-C6 alkyl (C1-C6 alkyl) Branched chain alkyl of 3 to 6 carbon atoms) is more preferred, and alkyl of 1 to 5 carbon atoms (branched chain alkyl of 3 to 5 carbon atoms) and alkyl of 1 to 4 carbon atoms (branched chain alkyl of 3 to 4 carbon atoms) is particularly preferred. and methyl is most preferred. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl), n -Hexyl, 1-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl (1,1,3,3-tetramethylbutyl), 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n -Undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n -Ecosil etc. can be mentioned. Also, for example, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1,1,4-trimethylpentyl, 1, 1,2-trimethylpropyl, 1,1-dimethyloctyl, 1,1-dimethylpentyl, 1,1-dimethylheptyl, 1,1,5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl- 1,3-dimethylbutyl, 1,1,2,2-tetramethylpropyl, 1-butyl-1-methylpentyl, 1,1-diethylbutyl, 1-ethyl-1-methylpentyl, 1,1,3 -Trimethylbutyl, 1-propyl-1-methylpentyl, 1,1,2-trimethylpropyl, 1-ethyl-1,2,2-trimethylpropyl, 1-propyl-1-methylbutyl, 1,1-dimethylhexyl etc. can also be mentioned.

In the first substituent and the second substituent, "cycloalkyl" includes cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, cycloalkyl having 3 to 14 carbon atoms, and cycloalkyl having 3 to 14 carbon atoms. Cycloalkyl of 5 to 10 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, cycloalkyl of 5 carbon atoms, and the like. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (particularly methyl) substituents having 1 to 4 carbon atoms or bicyclo[1.1.0] Butyl, bicyclo[1.1.1]pentyl, bicyclo[2.1.0]pentyl, bicyclo[2.1.1]hexyl, bicyclo[3.1.0]hexyl, bicyclo[2.2.1]heptyl, bicyclo[ 2.2.2] octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.

The compound represented by formula (H6) can be manufactured with reference to the description described in International Publication No. 2014/042197.

<TADF material>

By reducing the energy difference between the singlet excited state and the triplet excited state, the opposite energy transfer from the triplet excited state, which usually has a low transition probability, to the excited singlet state is produced with high efficiency, thereby emitting light from the singlet (thermal activation). delayed fluorescence, TADF) is expressed. In normal fluorescence emission, since 75% of triplet excitons generated by current excitation pass through the thermal deactivation pathway, they cannot be extracted as fluorescence. On the other hand, in TADF, all excitons can be used for fluorescence, and a highly efficient organic EL device is realized.

Examples of TADF materials that can be used for such a purpose include compounds represented by the following general formula (H7) or compounds having the following general formula (H7) as a partial structure.

In Formula (H7), ED is an electron-donating group, Ln is a bonding group, EA is an electron-accepting group, and the singlet energy (S ¹ ) and triplet energy (T ¹ ) of the compound represented by Formula (H7) The energy difference (ΔS ¹ T ¹ ) is 0.2 eV or less (Hiroki Uoyama, Kenichi Goushi, Katsuyuki Shizu, Hiroko Nomura, Chihaya Adachi, Nature, 492,234-238 (2012)). The energy difference (ΔS ¹ T ¹ ) is preferably 0.15 eV or less, more preferably 0.10 eV or less, still more preferably 0.08 eV or less.

TADF materials are designed to localize HOMO and LUMO in a molecule using an electron-donating substituent called a donor and an electron-accepting substituent called an acceptor, so that efficient reverse intersystem crossing occurs. - It is preferable that it is an acceptor type TADF compound (D-A type TADF compound).

Here, in the present specification, "electron-donating substituent" (donor) means a substituent and partial structure in which the LUMO orbital is localized in a TADF compound molecule, and "electron-accepting substituent" (acceptor) means a TADF compound molecule Among them, substituents and partial structures in which the HOMO orbital is localized are meant.

In general, a TADF compound using a donor or acceptor has a large spin-orbit coupling (SOC) due to its structure, and also has a small exchange interaction between HOMO and LUMO and a small ΔE(ST), so it is very Fast inverse interterm crossing velocities are obtained. On the other hand, a TADF compound using a donor or acceptor exhibits greater structural relaxation in the excited state (in some molecules, since the stable structures are different between the ground state and the excited state, conversion from the ground state to the excited state by external stimuli) If this occurs, the structure is then changed to a stable structure in an excited state), giving a wide luminescence spectrum, so when used as a luminescent material, color purity may be reduced.

When the color purity is lowered by the TADF material, a fluorescent compound may be added to the light emitting layer or a layer adjacent to the light emitting layer as another component. The TADF material functions as an assisting dopant and the other components as an emitter dopant. As the other component, any compound whose absorption spectrum of the compound overlaps at least a part of the emission peak of the assisting dopant is sufficient.

As a structure of donor property and acceptor property used for TADF material, the structure described in Chemistry of Materials, 2017, 29, 1946-1963 can be used, for example. Examples of ED include functional groups containing sp ³ nitrogen, and more specifically, carbazole, dimethylcarbazole, di-t-butylcarbazole, dimethoxycarbazole, tetramethylcarbazole, and benzo. Fluorocarbazole, benzothienocarbazole, phenyldihydroindolocarbazole, phenylbicarbazole, bicarbazole, tercarbazole, diphenylcarbazolylamine, tetraphenylcarbazolyldiamine, phenoxazine, di Hydrophenazine, phenothiazine, dimethyldihydroacridine, diphenylamine, bis(t-butylphenyl)amine, N ¹ -(4-(diphenylamino)phenyl)-N ⁴ ,N ⁴ -diphenylbenzene groups derived from -1,4-diamine, dimethyltetraphenyldihydroacridinediamine, tetramethyl-dihydro-indenoacridine, and diphenyl-dihydrodibenzoazacillin; and the like. Examples of EA include sp ² nitrogen-containing aromatic rings, CN-substituted aromatic rings, ketone-containing rings and cyano groups, more specifically, sulfonyldibenzene, benzophenone, phenylenebis(phenylmethanone), Benzonitrile, isonicotinonitrile, phthalonitrile, isophthalonitrile, paraphthalonitrile, triazole, oxazole, thiadiazole, benzothiazole, benzobis(thiazole), benzooxazole, benzobis(oxa sol), quinoline, benzoimidazole, dibenzoquinoxaline, heptaazaphenalene, thioxanthone dioxide, dimethylanthracenone, anthracenedione, pyridine, 5H-cyclopenta[1,2-b:5,4-b' ]Dipyridine, benzenetricarbonitrile, fluorenedicarbonitrile, pyrazinedicarbonitrile, pyridinedicarbonitrile, dibenzoquinoxalinedicarbonitrile, pyrimidine, phenylpyrimidine, methylpyrimidine, triazine, triphenyltrile and groups derived from azine, bis(phenylsulfonyl)benzene, dimethylthioxanthene dioxide, thianthrene tetraoxide and tris(dimethylphenyl)borane. Examples of Ln include single bonds and arylene, and more specifically, phenylene, biphenylene, naphthylene and the like. In any structure, hydrogen may be substituted with alkyl, cycloalkyl or aryl. Particularly, as partial structures, carbazole, phenoxazine, acridine, triazine, pyrimidine, pyrazine, thioxanthene, benzonitrile, phthalonitrile, isophthalonitrile, diphenylsulfone, triazole, oxadiazole, thia It is preferably a compound having at least one selected from diazole and benzophenone.

The compound represented by the general formula (H7) is, more specifically, a compound represented by any one of the following general formulas (H7-1), (H7-2) and (H7-3).

Among the formulas (H7-1), (H7-2) and (H7-3),

M is, each independently, a single bond, -O-, >N-Ar, or >C(-Ar) ₂ , and is the depth of the HOMO and the height of the excitation singlet energy level and the excitation triplet energy level of the partial structure to be formed. From the point of view, it is preferably a single bond, -O- or >N-Ar,

J is a spacer structure that divides the donor substructure and the acceptor substructure, and each independently is an arylene having 6 to 18 carbon atoms, from the viewpoint of the size of the conjugate exuded from the donor substructure and the acceptor substructure, Arylene having 6 to 12 carbon atoms is preferable, and more specifically, phenylene, methylphenylene and dimethylphenylene are exemplified,

Q is each independently =C(-H)- or =N-, and from the viewpoint of the shallowness of the LUMO of the substructure to be formed and the height of the excitation singlet energy level and the excitation triplet energy level, preferably = is N-,

Ar is each independently hydrogen, aryl having 6 to 24 carbon atoms, heteroaryl having 2 to 24 carbon atoms, alkyl having 1 to 12 carbon atoms, or cycloalkyl having 3 to 18 carbon atoms, and the depth and excitation of the HOMO of the partial structure to be formed From the viewpoint of the height of the singlet energy level and the triplet excitation energy level, preferably hydrogen, aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 14 carbon atoms, alkyl having 1 to 4 carbon atoms or cycloalkyl having 6 to 10 carbon atoms. and, more preferably, hydrogen, phenyl, tolyl, xylyl, mesityl, biphenyl, pyridyl, bipyridyl, triazinyl, carbazolyl, dimethylcarbazolyl, di-t-butylcarbazolyl, benzoimidazole or phenylbenzoimidazole, even more preferably hydrogen, phenyl or carbazolyl;

m is 1 or 2;

n is an integer of 2 to (6-m), and is preferably an integer of 4 to (6-m) from the viewpoint of steric hindrance.

In addition, at least one hydrogen in the compounds represented by the above formulas may be substituted with halogen or heavy hydrogen.

As a compound represented by formula (H7), the compound represented by the following structure is mentioned, for example. In the structural formula, * indicates a bonding position, "Me" indicates a methyl group, and "tBu" indicates a t-butyl group.

As the compound represented by the general formula (H7), among the above specific compounds, particularly 4CzBN, 4CzBN-Ph, 5CzBN, 3Cz2DPhCzBN, 4CzIPN, 2PXZ-TAZ, Cz-TRZ3, BDPCC-TPTA, MA-TA, PA-TA, FA- TA, PXZ-TRZ, DMAC-TRZ, BCzT, DCzTrz, DDCzTrz, spiroAC-TRZ, Ac-HPM, Ac-PPM, Ac-MPM, TCzTrz, TmCzTrz and DCzmCzTrz are preferred.

In addition, as a dopant material, a known compound can be used, and it can select from various materials according to the desired emission color. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene and chrysene, benzoxazole derivatives, and benzothiazole derivatives, benzoimidazole derivatives, benzotriazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, Tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives (Japanese Patent Laid-Open No. 1-245087), bisstyrylarylene derivatives (Japanese Patent Laid-Open No. 2 -247278), diazaindacene derivatives, furan derivatives, benzofuran derivatives, phenyl isobenzofuran, dimethyl isobenzofuran, di(2-methylphenyl)isobenzofuran, di(2-trifluoromethylphenyl)iso Isobenzofuran derivatives such as benzofuran and phenylisobenzofuran, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7 -Coumarin derivatives such as acetoxycoumarin derivatives, 3-benzothiazolylcoumarin derivatives, 3-benzoimidazolylcoumarin derivatives, and 3-benzooxazolylcoumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives, oxobenzoanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyril derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, Quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2,5-thiadiazolopyrene derivatives, pyrimethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, bioranthrone derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives and benzofluorene derivatives, and the like.

When exemplified by color emission, examples of blue to blue-green dopant materials include aromatic hydrocarbon compounds such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, and chrysene, derivatives thereof, furan, pyrrole, and thi Ophene, silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyl Aromatic heterocyclic compounds such as ridine, quinoxaline, pyrrolopyridine, and thioxanthen or their derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazoles, thiazoles, thiadia azole derivatives such as sol, carbazole, oxazole, oxadiazole, and triazole, metal complexes thereof, and N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl Aromatic amine derivatives typified by -1,1'-diamine; and the like.

Further, as the green to yellow dopant material, coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, rubrene, etc. naphthacene derivatives of , and compounds exemplified as the blue to blue-green dopant material are introduced with substituents such as aryls, heteroaryls, arylvinyls, aminos, and cyanos that enable long wavelengths. can be heard as

Further, examples of the orange to red dopant material include naphthalimide derivatives such as bis(diisopropylphenyl)perylenetetracarboxylic acid imide, perinone derivatives, and Eu using acetylacetone, benzoylacetone, phenanthroline, and the like as ligands. Rare earth complexes such as complexes, 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran and analogs thereof, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhoda Mineral compounds, deazaflavin derivatives, coumarin derivatives, quinacridone derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrrolopyridine derivatives, squarylium derivatives, bioanthrone derivatives, phenazine derivatives, fenoxa Zoned derivatives and thiadiazolopyrene derivatives, etc., and substituents that enable long wavelengths such as aryl, heteroaryl, arylvinyl, amino, cyano, etc. in the compounds exemplified as the blue to cyan and green to yellow dopant materials Compounds introduced with are also cited as preferable examples.

In addition, as a dopant, it can be used suitably selected from the compound etc. which are described in the chemical industry, June 2004 issue, page 13, and the reference literature published therein.

Among the above-described dopant materials, amines having a stilbene structure, perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives, or pyrene derivatives are particularly preferred.

An amine having a stilbene structure is represented by the following formula, for example.

In the formula, Ar ¹ is an m-valent group derived from an aryl having 6 to 30 carbon atoms, Ar ² and Ar ³ are each independently an aryl having 6 to 30 carbon atoms, and at least one of Ar ¹ to ^{Ar 3} is stilbene has a structure, Ar ¹ to ^{Ar 3} may be substituted with aryl, heteroaryl, alkyl, cycloalkyl, tri-substituted silyl (silyl tri-substituted with at least one of aryl, alkyl and cycloalkyl) or cyano, and m is an integer from 1 to 4.

As for the amine having a stilbene structure, diaminostilbene represented by the following formula is more preferable.

In the formula, Ar ² and Ar ³ are each independently an aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ are aryl, heteroaryl, alkyl, cycloalkyl, trisubstituted silyl (among aryl, alkyl and cycloalkyl). at least one tri-substituted silyl) or cyano may be substituted.

Specific examples of aryl having 6 to 30 carbon atoms include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, and naphtha. Cenyl, perylenyl, stilbenyl, distyrylphenyl, distyrylbiphenyl, distyrylfluorenyl, etc. are mentioned.

Specific examples of amines having a stilbene structure are N,N,N',N'-tetra(4-biphenylyl)-4,4'-diaminostilbene, N,N,N',N'- Tetra(1-naphthyl)-4,4'-diaminostilbene, N,N,N',N'-tetra(2-naphthyl)-4,4'-diaminostilbene, N,N' -di(2-naphthyl)-N,N'-diphenyl-4,4'-diaminostilbene, N,N'-di(9-phenanthryl)-N,N'-diphenyl-4, 4'-diaminostilbene, 4,4'-bis[4"-bis(diphenylamino)styryl]-biphenyl, 1,4-bis[4'-bis(diphenylamino)styryl]- Benzene, 2,7-bis [4'-bis (diphenylamino) styryl] -9,9-dimethylfluorene, 4,4'-bis (9-ethyl-3-carbazovinylene) -biphenyl , 4,4'-bis(9-phenyl-3-carbazobinylene)-biphenyl, and the like.

Moreover, you may use the amine which has a stilbene structure described in Unexamined-Japanese-Patent No. 2003-347056, Unexamined-Japanese-Patent No. 2001-307884, etc.

Examples of the perylene derivative include 3,10-bis(2,6-dimethylphenyl)perylene, 3,10-bis(2,4,6-trimethylphenyl)perylene, and 3,10-diphenylphenyl. Rylene, 3,4-diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3-(1'-pyrenyl)- 8,11-di (t-butyl) perylene, 3- (9'-anthryl) -8,11-di (t-butyl) perylene, 3,3'-bis (8,11-di (t -butyl) perylenyl) and the like.

Further, Japanese Unexamined Patent Publication No. 11-97178, Japanese Unexamined Patent Publication No. 2000-133457, Japanese Unexamined Patent Publication No. 2000-26324, Japanese Unexamined Patent Publication No. 2001-267079, Japanese Unexamined Patent Publication No. 2001-267078, Japanese Patent You may use the perylene derivative described in Unexamined-Japanese-Patent No. 2001-267076, Unexamined-Japanese-Patent No. 2000-34234, Unexamined-Japanese-Patent No. 2001-267075, Unexamined-Japanese-Patent No. 2001-217077, etc.

Examples of the borane derivative include 1,8-diphenyl-10-(dimethyl boryl) anthracene, 9-phenyl-10-(dimethyl boryl) anthracene, and 4-(9'-anthryl) dimes. Tylborylnaphthalene, 4- (10'-phenyl-9'-antryl) dimesitylborylnaphthalene, 9- (dimethylboryl) anthracene, 9- (4'-biphenylyl) -10- (dimesy Tylboryl) anthracene, 9-(4'-(N-carbazolyl)phenyl)-10-(dimethyl boryl) anthracene, etc. are mentioned.

In addition, you may use the borane derivative described in the pamphlet of International Publication No. 2000/40586, etc.

An aromatic amine derivative is represented by the following formula, for example.

In the formula, Ar ⁴ is an n-valent group derived from an aryl having 6 to 30 carbon atoms, Ar ⁵ and Ar ⁶ are each independently an aryl having 6 to 30 carbon atoms, and Ar ⁴ to ^{Ar 6} are aryl, heteroaryl, It may be substituted with alkyl, cycloalkyl, tri-substituted silyl (silyl tri-substituted with at least one of aryl, alkyl and cycloalkyl), or cyano, and n is an integer of 1 to 4.

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

Specific examples of aryl having 6 to 30 carbon atoms include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, and naphtha. Cenyl, perylenyl, pentacenyl, etc. are mentioned.

Examples of the aromatic amine derivative include N,N,N',N'-tetraphenylchrysene-6,12-diamine, N,N,N',N'-tetra(p-tolyl) as the chrysene type. Chrysene-6,12-diamine, N,N,N',N'-tetra(m-tolyl)chrysene-6,12-diamine, N,N,N',N'-tetrakis(4-iso Propylphenyl) chrysene-6,12-diamine, N,N,N',N'-tetra(naphthalen-2-yl)chrysene-6,12-diamine, N,N'-diphenyl-N,N '-di(p-tolyl)chrysene-6,12-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl)chrysene-6,12-diamine, N,N' -Diphenyl-N,N'-bis(4-isopropylphenyl)chrysene-6,12-diamine, N,N'-diphenyl-N,N'-bis(4-t-butylphenyl)chrysene -6,12-diamine, N,N'-bis(4-isopropylphenyl)-N,N'-di(p-tolyl)chrysene-6,12-diamine, etc. are mentioned.

Examples of the pyrene type include N,N,N',N'-tetraphenylpyrene-1,6-diamine, N,N,N',N'-tetra(p-tolyl)pyrene-1, 6-diamine, N,N,N',N'-tetra(m-tolyl)pyrene-1,6-diamine, N,N,N',N'-tetrakis(4-isopropylphenyl)pyrene-1 ,6-diamine, N,N,N',N'-tetrakis(3,4-dimethylphenyl)pyrene-1,6-diamine, N,N'-diphenyl-N,N'-di(p- Tolyl) pyrene-1,6-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl)pyrene-1,6-diamine, N,N'-diphenyl-N,N' -bis(4-isopropylphenyl)pyrene-1,6-diamine, N,N'-diphenyl-N,N'-bis(4-t-butylphenyl)pyrene-1,6-diamine, N,N '-bis(4-isopropylphenyl)-N,N'-di(p-tolyl)pyrene-1,6-diamine, N,N,N',N'-tetrakis(3,4-dimethylphenyl) -3,8-diphenylpyrene-1,6-diamine, N,N,N,N-tetraphenylpyrene-1,8-diamine, N,N'-bis(biphenyl-4-yl)-N, N'-diphenylpyrene-1,8-diamine, N ¹ , N ⁶ -diphenyl-N ¹ ,N ⁶ -bis-(4-trimethylsilanyl-phenyl)-1H,8H-pyrene-1,6- Diamine etc. are mentioned.

Examples of the anthracene type include N,N,N,N-tetraphenylanthracene-9,10-diamine, N,N,N',N'-tetra(p-tolyl)anthracene-9,10- Diamine, N,N,N',N'-tetra(m-tolyl)anthracene-9,10-diamine, N,N,N',N'-tetrakis(4-isopropylphenyl)anthracene-9,10 -diamine, N,N'-diphenyl-N,N'-di(p-tolyl)anthracene-9,10-diamine, N,N'-diphenyl-N,N'-di(m-tolyl)anthracene -9,10-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl)anthracene-9,10-diamine, N,N'-diphenyl-N,N'-bis( 4-isopropylphenyl)anthracene-9,10-diamine, N,N'-diphenyl-N,N'-bis(4-t-butylphenyl)anthracene-9,10-diamine, N,N'-bis (4-isopropylphenyl)-N,N'-di(p-tolyl)anthracene-9,10-diamine, 2,6-di-t-butyl-N,N,N',N'-tetra (p -Tolyl)anthracene-9,10-diamine, 2,6-di-t-butyl-N,N'-diphenyl-N,N'-bis(4-isopropylphenyl)anthracene-9,10-diamine, 2,6-di-t-butyl-N,N'-bis(4-isopropylphenyl)-N,N'-di(p-tolyl)anthracene-9,10-diamine, 2,6-dicyclohexyl -N,N'-bis(4-isopropylphenyl)-N,N'-di(p-tolyl)anthracene-9,10-diamine, 2,6-dicyclohexyl-N,N'-bis(4 -Isopropylphenyl)-N,N'-bis(4-t-butylphenyl)anthracene-9,10-diamine, 9,10-bis(4-diphenylamino-phenyl)anthracene, 9,10-bis( 4-di(1-naphthylamino)phenyl)anthracene, 9,10-bis(4-di(2-naphthylamino)phenyl)anthracene, 10-di-p-tolylamino-9-(4-di- p-Tolylamino-1-naphthyl)anthracene, 10-diphenylamino-9-(4-diphenylamino-1-naphthyl)anthracene, 10-diphenylamino-9-(6-diphenylamino-2 -naphthyl) anthracene; and the like.

In addition, [4-(4-diphenylamino-phenyl)naphthalen-1-yl]-diphenylamine, [6-(4-diphenylamino-phenyl)naphthalen-2-yl]-diphenylamine , 4,4'-bis[4-diphenylaminonaphthalen-1-yl]biphenyl, 4,4'-bis[6-diphenylaminonaphthalen-2-yl]biphenyl, 4,4"-bis[ 4-diphenylaminonaphthalen-1-yl]-p-terphenyl, 4,4"-bis[6-diphenylaminonaphthalen-2-yl]-p-terphenyl, and the like.

Moreover, you may use the aromatic amine derivative described in Unexamined-Japanese-Patent No. 2006-156888 etc.

Examples of coumarin derivatives include coumarin-6 and coumarin-334.

In addition, you may use the coumarin derivative described in Unexamined-Japanese-Patent No. 2004-43646, Unexamined-Japanese-Patent No. 2001-76876, Unexamined-Japanese-Patent No. 6-298758, etc.

As a pyran derivative, the following DCM, DCJTB, etc. are mentioned.

Further, Japanese Unexamined Patent Publication No. 2005-126399, Japanese Unexamined Patent Publication No. 2005-097283, Japanese Unexamined Patent Publication No. 2002-234892, Japanese Unexamined Patent Publication No. 2001-220577, Japanese Unexamined Patent Publication No. 2001-081090, and Japanese Patent You may use the pyran derivative described in Unexamined-Japanese-Patent No. 2001-052869 etc.

The above-mentioned materials for the light emitting layer (host material and dopant material) are polymer compounds obtained by polymerizing a reactive compound having a reactive substituent substituted thereto as a monomer, or a cross-linked polymer thereof, or a main chain polymer and the reactive compound. The reacted pendant type polymer compound or its pendant type polymer crosslinked product can also be used for the material for the light emitting layer. As the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the above general formula (1) can be cited.

The details of the use of such a high molecular compound and high molecular crosslinked product will be described later.

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

The electron injection/transport layer is a layer responsible for injecting electrons into the cathode and transporting the electrons, and preferably has high electron injection efficiency and efficiently transports the injected electrons. For this purpose, it is preferable to use a material that has high electron affinity, high electron mobility, excellent stability, and is difficult to generate trap impurities during production and use. However, in the case of considering the transport balance of holes and electrons, in the case where the role of efficiently preventing the flow of holes to the anode without recombination to the cathode side is mainly performed, even if the electron transport capacity is not so high, the luminous efficiency is improved. The effect is equivalent to that of a material having a high electron transport ability. Therefore, the electron injection/transport layer in the present embodiment may also include a function of a layer capable of effectively blocking the movement of holes.

As the material (electron transport material) forming the electron transport layer 106 or the electron injection layer 107, a compound conventionally used as an electron transport compound in photoconductive materials, an electron injection layer and an electron transport layer of an organic EL device. It can be used by selecting it arbitrarily from known compounds in use. In the present invention, a polycyclic aromatic compound represented by the above general formula (1) can be used as the electron transport material.

As the material used for the electron transport layer or the electron injection layer, compounds comprising an aromatic ring or heteroaromatic ring composed of at least one atom selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, pyrrole derivatives, and condensates thereof It is preferable to contain at least one selected from ring derivatives and metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4'-bis(diphenylethenyl)biphenyl, perinone derivatives, coumarin derivatives, and 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 hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. Although these materials are used alone, you may mix and use them with other materials.

In addition, as specific examples of other electron transfer compounds, pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone Derivatives, perylene derivatives, oxadiazole derivatives (1,3-bis[(4-t-butylphenyl)1,3,4-oxadiazolyl]phenylene, etc.), thiophene derivatives, triazole derivatives (N- naphthyl-2,5-diphenyl-1,3,4-triazole, etc.), thiadiazole derivatives, metal complexes of auxin derivatives, quinolinol-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazoles compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis(benzo[h]quinolin-2-yl)-9,9' -spirofluorene, etc.), imidazopyridine derivatives, borane derivatives, benzoimidazole derivatives (tris(N-phenylbenzoimidazol-2-yl)benzene, etc.), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, Oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis(4'-(2,2':6'2"-terpyridinyl))benzene, etc.), naphthyridine derivatives (bis (1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide, etc.), aldazine derivatives, carbazole derivatives, indole derivatives, inoxide derivatives, bisstyryl derivatives, etc. can

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

The above materials are used alone, but may be used in combination with other materials.

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

<Boranic derivative>

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

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

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

In formula (ETM-1-1), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyanocyclic group. at least one of N, R ¹³ to ^{R 16} are each independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, and R ²¹ and R ²² are each independently hydrogen; At least one of alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, X ¹ is optionally substituted arylene having 20 or less carbon atoms, and n are each independently an integer of 0 to 3, and m is each independently an integer of 0 to 4. Moreover, as a substituent in the case of "may be substituted" or "is substituted", aryl, heteroaryl, alkyl, or cycloalkyl etc. are mentioned.

In formula (ETM-1-2), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyanocyclic group. at least one of N, R ¹³ to ^{R 16} are each independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, and X ¹ is optionally substituted aryl having 20 or less carbon atoms; Ren, and n is an integer of 0 to 3 each independently. Moreover, as a substituent in the case of "may be substituted" or "is substituted", aryl, heteroaryl, alkyl, or cycloalkyl etc. are mentioned.

Specific examples of X ¹ include divalent groups represented by any of the following formulas (X-1) to (X-9). * in each structural formula represents a bonding position.

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

As a specific example of this borane derivative, the following compounds are mentioned, for example.

This borane derivative can be produced using known raw materials and known synthetic methods.

<Pyridine derivative>

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

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

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

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

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

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

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

"Alkyl" in R ¹¹ to ^{R 18} may be straight-chain or branched, and examples thereof include straight-chain alkyl having 1 to 24 carbon atoms or branched-chain alkyl having 3 to 24 carbon atoms. Preferable "alkyl" is C1-C18 alkyl (C3-C18 branched chain alkyl). More preferable "alkyl" is C1-C12 alkyl (C3-C12 branched chain alkyl). More preferable "alkyl" is C1-C6 alkyl (C3-C6 branched chain alkyl). Especially preferable "alkyl" is C1-C4 alkyl (C3-C4 branched chain alkyl).

Specific examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl) , n-hexyl, 1-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl (1,1,3,3-tetramethylbutyl ), 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl , n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl , n-eicosyl, and the like.

Also, for example, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1,1,4-trimethylpentyl, 1, 1,2-trimethylpropyl, 1,1-dimethyloctyl, 1,1-dimethylpentyl, 1,1-dimethylheptyl, 1,1,5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl- 1,3-dimethylbutyl, 1,1,2,2-tetramethylpropyl, 1-butyl-1-methylpentyl, 1,1-diethylbutyl, 1-ethyl-1-methylpentyl, 1,1,3 -Trimethylbutyl, 1-propyl-1-methylpentyl, 1,1,2-trimethylpropyl, 1-ethyl-1,2,2-trimethylpropyl, 1-propyl-1-methylbutyl, 1,1-dimethylhexyl etc. can also be mentioned.

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

As "cycloalkyl" in ^R11 - ^R18 , C3-C12 cycloalkyl is mentioned, for example. Preferable "cycloalkyl" is a C3-C10 cycloalkyl. More preferable "cycloalkyl" is a C3-C8 cycloalkyl. Even more preferable "cycloalkyl" is a cycloalkyl having 3 to 6 carbon atoms.

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

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

As the "aryl" for R ¹¹ to ^{R 18} , an aryl having 6 to 30 carbon atoms is preferable, an aryl having 6 to 18 carbon atoms is more preferable, and an aryl having 6 to 14 carbon atoms is even more preferable. Preferably, it is an aryl of 6 to 12 carbon atoms.

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

Preferable examples of "aryl having 6 to 30 carbon atoms" include phenyl, naphthyl, phenanthryl, chrysenyl, or triphenylenyl, and more preferably phenyl, 1-naphthyl, 2-naphthyl, or phenanthryl. , and particularly preferably phenyl, 1-naphthyl or 2-naphthyl.

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

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

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

<Fluoranthene derivatives>

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

In the formula (ETM-3), X ¹² to X ²¹ are hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. indicates Here, as a substituent in the case of being substituted, an aryl, heteroaryl, alkyl, or cycloalkyl etc. are mentioned.

As a specific example of this fluoranthene derivative, the following compounds are mentioned, for example.

<BO derivative>

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

R ¹ to ^{R 11} are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be bonded via a single bond or a linking group) ), alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in R ¹ to R ¹¹ may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.

In addition, adjacent groups among R ¹ to R ¹¹ may be bonded together to form an aryl ring or heteroaryl ring together with ring a, b or c, and at least one hydrogen in the formed ring is aryl or heteroaryl. May be substituted with diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be bonded through a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy, At least one hydrogen in these substituents may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.

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

For the description of the substituent and ring formation in formula (ETM-4) and the multimer formed by combining a plurality of structures of formula (ETM-4), the description described in International Publication No. 2015/102118 can be cited. can

As a specific example of this BO type derivative, the following compounds are mentioned, for example.

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

<Anthracene derivatives>

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

Ar is each independently divalent benzene or naphthalene, and R ¹ to R ⁴ are each independently hydrogen, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, or aryl of 6 to 20 carbon atoms.

Ar can each independently be appropriately selected from divalent benzene or naphthalene, and the two Ars may be different or the same, but from the viewpoint of the ease of synthesis of the anthracene derivative, they are preferably the same. Ar is bonded to pyridine to form "a moiety composed of Ar and pyridine", and this moiety is, for example, a group represented by any of the following formulas (Py-1) to (Py-12), and is bonded to anthracene are doing * in each structural formula represents a bonding position.

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

Alkyl having 1 to 6 carbon atoms in R ¹ to ^{R 4} may be either straight-chain or branched-chain. That is, it is C1-C6 straight-chain alkyl or C3-C6 branched chain alkyl. More preferably, it is C1-C4 alkyl (C3-C4 branched chain alkyl). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl), n- hexyl, 1-methylpentyl, 3,3-dimethylbutyl, or 2-ethylbutyl; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t- Butyl is preferred, and methyl, ethyl, or t-butyl is more preferred.

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

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

Specific examples of "aryl having 6 to 20 carbon atoms" include phenyl which is a monocyclic aryl, (o-, m-, p-) tolyl, (2,3-, 2,4-, 2,5-, 2,6- , 3,4-, 3,5-) xylyl, mesityl (2,4,6-trimethylphenyl), (o-, m-, p-) cumenyl, bicyclic aryl (2-, 3- , 4-) biphenylyl, condensed bicyclic aryl (1-, 2-) naphthyl, tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl , m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl- 2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic aryl, anthracene-(1-, 2-, 9-)yl, acenaphthylene-(1- , 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenalene-(1-, 2-)yl, (1-, 2 -, 3-, 4-, 9-) phenanthryl, condensed tetracyclic aryl triphenylene-(1-, 2-)yl, pyrene-(1-, 2-, 4-)yl, tetracene-( 1-, 2-, 5-)yl, perylene-(1-,2-,3-)yl which is a condensed pentacyclic aryl, etc. are mentioned.

Preferred "aryl having 6 to 20 carbon atoms" is phenyl, biphenylyl, terphenylyl or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2-naphthyl or m-terphenyl. -5'-yl, more preferably phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, most preferably phenyl.

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

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

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

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

Specific examples of these anthracene derivatives include the following compounds.

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

<Benzofluorene derivative>

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

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

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

As "alkyl" for Ar ² , either straight-chain or branched chain may be used, and examples thereof include straight-chain alkyl having 1 to 24 carbon atoms or branched-chain alkyl having 3 to 24 carbon atoms. Preferable "alkyl" is C1-C18 alkyl (C3-C18 branched chain alkyl). More preferable "alkyl" is C1-C12 alkyl (C3-C12 branched chain alkyl). More preferable "alkyl" is C1-C6 alkyl (C3-C6 branched chain alkyl). Especially preferable "alkyl" is C1-C4 alkyl (C3-C4 branched chain alkyl). Specific examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl) , n-hexyl, 1-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like.

As "cycloalkyl" in ^Ar2 , C3-C12 cycloalkyl is mentioned, for example. Preferable "cycloalkyl" is a C3-C10 cycloalkyl. More preferable "cycloalkyl" is a C3-C8 cycloalkyl. Even more preferable "cycloalkyl" is a C3-C6 cycloalkyl. Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, or dimethylcyclohexyl.

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

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

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

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

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

<Phosphine oxide derivative>

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

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

R ⁷ and R ⁸ are each independently a substituted or unsubstituted aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms;

R ⁹ is oxygen or sulfur;

j is 0 or 1, k is 0 or 1, r is an integer of 0 to 4, and q is an integer of 1 to 3.

Here, as a substituent in the case of being substituted, an aryl, heteroaryl, alkyl, or cycloalkyl etc. are mentioned.

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

R ¹ to ^{R 3} , which may be the same or different, are hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a cycloalkylthio group, an arylether group, and an arylthio group. It is selected from an ether 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 condensed ring formed between adjacent substituents.

Ar ¹ may be the same or different, and is an arylene group or a heteroarylene group. Ar ² may be the same or different, and is an aryl group or a heteroaryl group. However, at least one of Ar ¹ and Ar ² has a substituent or forms a condensed ring between adjacent substituents. n is an integer of 0 to 3, and when n is 0, no unsaturated structure moiety exists, and when n is 3, R ¹ does not exist.

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

In addition, a cycloalkyl group represents a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, and adamantyl, for example, and 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.

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

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

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

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

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

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

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

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

In addition, an arylthio ether group is a group in which the oxygen atom of the ether bond of an aryl ether group is substituted with a sulfur atom.

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

In addition, the heterocyclic group represents, for example, a cyclic structural group having atoms other than carbon such as a furanyl group, a thiophenyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group, which is unsubstituted or substituted. It doesn't matter if there is Although the number of carbon atoms in the heterocyclic group is not particularly limited, it 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 include a group substituted with an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, or a heterocyclic ring.

In addition, an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a heterocyclic ring may be unsubstituted or substituted.

A silyl group represents a silicon compound group, such as a trimethylsilyl group, for example, and this may be unsubstituted or substituted. Although the number of carbon atoms in the silyl group is not particularly limited, it is usually in the range of 3 to 20. Moreover, the number of silicon is 1-6 normally.

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

As a specific example of this phosphine oxide derivative, the following compounds are mentioned, for example.

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

<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). Details are also described in International Publication No. 2011/021689.

Ar is each independently an 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.

Examples of the “aryl” of the “aryls which may be substituted” include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, more preferably aryls having 6 to 20 carbon atoms, and more More preferably, it is an aryl of 6 to 12 carbon atoms.

Specific examples of "aryl" include phenyl which is a monocyclic aryl, (2-, 3-, 4-)biphenylyl which is a bicyclic aryl, (1-, 2-) naphthyl which is a fused bicyclic aryl, and tertiary aryl which is a tricyclic aryl. Phenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4' -yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o -terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic aryl , acenaphthylene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenalene-(1-, 2- ) day, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m -terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensed tetracyclic aryl triphenylene-(1-, 2-)yl, pyrene-( 1-, 2-, 4-)yl, naphthacen-(1-,2-,5-)yl, condensed pentacyclic aryl perylene-(1-,2-,3-)yl, pentacene-( 1-, 2-, 5-, 6-) days, etc. are mentioned.

Examples of the "heteroaryl" of the "heteroaryl which may be substituted" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. More preferably, a heteroaryl having 2 to 15 carbon atoms is still more preferable, and a heteroaryl having 2 to 10 carbon atoms is particularly preferable. Moreover, as a heteroaryl, the heterocyclic etc. which contain 1-5 hetero atoms selected from oxygen, sulfur, and nitrogen other than carbon as a ring constituting atom are mentioned, for example.

Specific examples of heteroaryl include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, Pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzooxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, iso Quinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathinyl, phenoxazinyl, phenothia Zinyl, phenazinyl, phenazacillinyl, indolizinyl, furanil, benzofuranil, isobenzofuranil, dibenzofuranil, naphthobenzofuranil, thiophenyl, benzothiophenyl, dibenzothiophenyl, naph Tobenzothiophenyl, benzophosphoryl, dibenzophosphoryl, monovalent group of benzophosphole oxide ring, monovalent group of dibenzophosphole oxide ring, furazanyl, thianthrenyl, indolocarbazolyl, benzoindolocar bazolyl and benzobenzoindolocarbazolyl; and the like.

In addition, at least one hydrogen in the said aryl and heteroaryl may be substituted, and may be substituted with the said aryl or heteroaryl, respectively, for example.

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

This pyrimidine derivative can be produced using known raw materials and known synthetic methods.

<Carbazole derivatives>

A carbazole derivative is, for example, a compound represented by the following formula (ETM-9) or a multimer in which a plurality of them are bonded with a single bond or the like. Details are described in the specification of US Patent Application Publication No. 2014/0197386.

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

Examples of the “aryl” of the “aryls which may be substituted” include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, more preferably aryls having 6 to 20 carbon atoms, and more More preferably, it is an aryl of 6 to 12 carbon atoms.

Specific examples of "aryl" include phenyl which is a monocyclic aryl, (2-, 3-, 4-)biphenylyl which is a bicyclic aryl, (1-, 2-) naphthyl which is a fused bicyclic aryl, and tertiary aryl which is a tricyclic aryl. Phenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4' -yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o -terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic aryl , acenaphthylene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenalene-(1-, 2- ) day, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m -terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensed tetracyclic aryl triphenylene-(1-, 2-)yl, pyrene-( 1-, 2-, 4-)yl, naphthacen-(1-,2-,5-)yl, condensed pentacyclic aryl perylene-(1-,2-,3-)yl, pentacene-( 1-, 2-, 5-, 6-) days, etc. are mentioned.

Examples of the "heteroaryl" of the "heteroaryl which may be substituted" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. More preferably, a heteroaryl having 2 to 15 carbon atoms is still more preferable, and a heteroaryl having 2 to 10 carbon atoms is particularly preferable. Moreover, as a heteroaryl, the heterocyclic etc. which contain 1-5 hetero atoms selected from oxygen, sulfur, and nitrogen other than carbon as a ring constituting atom are mentioned, for example.

Specific examples of heteroaryl include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, Pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzooxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, iso Quinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathinyl, phenoxazinyl, phenothia Zinyl, phenazinyl, phenazacillinyl, indolizinil, furanil, benzofuranil, isobenzofuranil, dibenzofuranil, naphthobenzofuranil, thiophenyl, benzothiophenyl, dibenzothiophenyl, naph Tobenzothiophenyl, benzophosphoryl, dibenzophosphoryl, monovalent group of benzophosphole oxide ring, monovalent group of dibenzophosphole oxide ring, furazanyl, thianthrenyl, indolocarbazolyl, benzoindolocar bazolyl and benzobenzoindolocarbazolyl; and the like.

In addition, at least one hydrogen in the said aryl and heteroaryl may be substituted, and may be substituted with the said aryl or heteroaryl, respectively, for example.

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

As a specific example of this carbazole derivative, the following compounds are mentioned, for example.

This carbazole derivative can be produced using known raw materials and known synthetic methods.

<Triazine derivatives>

The triazine derivative is, for example, a compound represented by the following formula (ETM-10), preferably a compound represented by the following formula (ETM-10-1). Details are described in the specification of US Patent Application Publication No. 2011/0156013.

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

Examples of the “aryl” of the “aryls which may be substituted” include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, more preferably aryls having 6 to 20 carbon atoms, and more More preferably, it is an aryl of 6 to 12 carbon atoms.

Specific examples of "aryl" include phenyl which is a monocyclic aryl, (2-, 3-, 4-)biphenylyl which is a bicyclic aryl, (1-, 2-) naphthyl which is a fused bicyclic aryl, and tertiary aryl which is a tricyclic aryl. Phenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4' -yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o -terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic aryl , acenaphthylene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenalene-(1-, 2- ) day, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m -terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensed tetracyclic aryl triphenylene-(1-, 2-)yl, pyrene-( 1-, 2-, 4-)yl, naphthacen-(1-,2-,5-)yl, condensed pentacyclic aryl perylene-(1-,2-,3-)yl, pentacene-( 1-, 2-, 5-, 6-) days, etc. are mentioned.

Examples of the "heteroaryl" of the "heteroaryl which may be substituted" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. More preferably, a heteroaryl having 2 to 15 carbon atoms is still more preferable, and a heteroaryl having 2 to 10 carbon atoms is particularly preferable. Moreover, as a heteroaryl, the heterocyclic etc. which contain 1-5 hetero atoms selected from oxygen, sulfur, and nitrogen other than carbon as a ring constituting atom are mentioned, for example.

Specific examples of heteroaryl include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, Pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzooxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, iso Quinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathinyl, phenoxazinyl, phenothia Zinyl, phenazinyl, phenazacillinyl, indolizinil, furanil, benzofuranil, isobenzofuranil, dibenzofuranil, naphthobenzofuranil, thiophenyl, benzothiophenyl, dibenzothiophenyl, naph Tobenzothiophenyl, benzophosphoryl, dibenzophosphoryl, monovalent group of benzophosphole oxide ring, monovalent group of dibenzophosphole oxide ring, furazanyl, thianthrenyl, indolocarbazolyl, benzoindolocar bazolyl and benzobenzoindolocarbazolyl; and the like.

In addition, at least one hydrogen in the said aryl and heteroaryl may be substituted, and may be substituted with the said aryl or heteroaryl, respectively, for example.

As a specific example of this triazine derivative, the following compounds are mentioned, for example.

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

<Benzimidazole derivatives>

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

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

R ¹¹ in the benzoimidazole 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 is represented by the formulas (ETM-2-1) and (ETM The description of R ¹¹ in -2-2) can be cited.

φ is also preferably an anthracene ring or a fluorene ring, and the structure in this case can refer to the explanation in the above formula (ETM-2-1) or formula (ETM-2-2), and in each formula For R ¹¹ to ^{R 18} , the description in the above formula (ETM-2-1) or formula (ETM-2-2) can be cited. In addition, in the above formula (ETM-2-1) or formula (ETM-2-2), two pyridine-based substituents are described in a bonded form. When these are substituted with benzoimidazole-based substituents, both pyridine-based substituents may be substituted with a benzoimidazole-based substituent (ie n = 2), or one pyridine-based substituent may be substituted with a benzoimidazole-based substituent and the other pyridine-based substituent may be substituted with R ¹¹ to R ¹⁸ (ie n =1). Further, for example, at least one of R ¹¹ to ^{R 18} in the formula (ETM-2-1) may be substituted with a benzoimidazole substituent, and the “pyridine substituent” may be substituted with R ¹¹ to ^{R 18} .

Specific examples of this benzoimidazole derivative include, for example, 1-phenyl-2-(4-(10-phenylanthracen-9-yl)phenyl)-1H-benzo[d]imidazole, 2-(4-(10) -(naphthalen-2-yl)anthracen-9-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 2-(3-(10-(naphthalen-2-yl)anthracen-9-yl )phenyl)-1-phenyl-1H-benzo[d]imidazole, 5-(10-(naphthalen-2-yl)anthracen-9-yl)-1,2-diphenyl-1H-benzo[d]imidazole Dazole, 1-(4-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 2-(4-(9,10-di (naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 1-(4-(9,10-di(naphthalen-2-yl)anthracen-2 -yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 5-(9,10-di(naphthalen-2-yl)anthracen-2-yl)-1,2-diphenyl-1H- Benzo[d]imidazole etc. are mentioned.

This benzoimidazole derivative can be produced using known raw materials and known synthetic methods.

<Phenanthroline derivatives>

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

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

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

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

As the alkyl, cycloalkyl and aryl in R ¹¹ to ^{R 18} , the descriptions of R ¹¹ to ^{R 18} in the formula (ETM-2) can be cited. In addition, phi includes the following structural formulas, for example, in addition to the above examples. On the other hand, R in the following structural formula is each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl. In addition, * in each structural formula represents a bonding position.

Specific examples of the phenanthroline derivative include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9, 10-di (1,10-phenanthrolin-2-yl) anthracene, 2,6-di (1,10-phenanthrolin-5-yl) pyridine, 1,3,5-tri (1,10- Phenanthrolin-5-yl) benzene, 9,9'-difluoro-bi(1,10-phenanthrolin-5-yl), bassocuproin, 1,3-bis(2-phenyl-1 , 10-phenanthrolin-9-yl) benzene, compounds represented by the following structural formula, and the like.

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

<Quinolinol-based metal complexes>

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

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

Specific examples of the quinolinol-based metal complex include 8-quinolinollithium, tris(8-quinolinolato) aluminum, tris(4-methyl-8-quinolinolato) aluminum, tris(5-methyl-8- Quinolinolato) Aluminum, Tris(3,4-dimethyl-8-quinolinolato) Aluminum, Tris(4,5-dimethyl-8-quinolinolato) Aluminum, Tris(4,6-dimethyl-8 -Quinolinolato)aluminum, bis(2-methyl-8-quinolinolato)(phenolato)aluminum, bis(2-methyl-8-quinolinolato)(2-methylphenolato)aluminum, bis (2-methyl-8-quinolinolato)(3-methylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(4-methylphenolato)aluminum, bis(2-methyl-8 -Quinolinolato)(2-phenylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(3-phenylphenolato)aluminum, bis(2-methyl-8-quinolinolato) (4-phenylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2,3-dimethylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2,6 -Dimethylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(3,4-dimethylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(3,5-dimethyl phenolato)aluminum, bis(2-methyl-8-quinolinolato)(3,5-di-t-butylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2,6 -Diphenylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2,4,6-triphenylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2 ,4,6-trimethylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2,4,5,6-tetramethylphenolato)aluminum, bis(2-methyl-8-quinolinato) Norato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) ( 2-phenylphenolato)aluminum, bis(2,4-dimethyl-8-quinolinolato)(3-phenylphenolato)aluminum, bis(2,4-dimethyl-8-quinolinolato)(4- Phenylphenolato)aluminum, bis(2,4-dimethyl-8-quinolinolato)(3,5-dimethylphenolato)aluminum, bis(2,4-dimethyl-8-quinolinolato)(3, 5-di-t-butylphenolato)aluminum, bis (2-methyl-8-quinolinolato)aluminum-μ-oxo-bis(2-methyl-8-quinolinolato)aluminum, bis(2,4-dimethyl-8-quinolinolato)aluminum- μ-Oxo-bis(2,4-dimethyl-8-quinolinolato)aluminum, bis(2-methyl-4-ethyl-8-quinolinolato)aluminum-μ-oxo-bis(2-methyl- 4-ethyl-8-quinolinolato)aluminum, bis(2-methyl-4-methoxy-8-quinolinolato)aluminum-μ-oxo-bis(2-methyl-4-methoxy-8- Quinolinolato)aluminum, bis(2-methyl-5-cyano-8-quinolinolato)aluminum-μ-oxo-bis(2-methyl-5-cyano-8-quinolinolato)aluminum , bis(2-methyl-5-trifluoromethyl-8-quinolinolato)aluminum-μ-oxo-bis(2-methyl-5-trifluoromethyl-8-quinolinolato)aluminum, bis (10-hydroxybenzo [h] quinoline) beryllium; and the like.

This quinolinol-type metal complex can be produced using known raw materials and known synthetic methods.

<Thiazole derivatives and benzothiazole derivatives>

A thiazole derivative is a compound represented by the following formula (ETM-14-1), for example.

A benzothiazole derivative is a compound represented by the following formula (ETM-14-2), for example.

φ in each formula is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is 1 It is an integer of to 4, and "thiazole-based substituent" or "benzothiazole-based substituent" is "pyridine The pyridyl group in "substituent group" is a substituent substituted with the following thiazole group or benzothiazole group, and at least one hydrogen in the thiazole derivative and benzothiazole derivative may be substituted with a deuterium. * in the following structural formula represents a bonding position.

φ is also preferably an anthracene ring or a fluorene ring, and the structure in this case can refer to the explanation in the above formula (ETM-2-1) or formula (ETM-2-2), and in each formula For R ¹¹ to ^{R 18} , the description in the above formula (ETM-2-1) or formula (ETM-2-2) can be cited. In addition, in the above formula (ETM-2-1) or formula (ETM-2-2), two pyridine-based substituents are described in a bonded form, and when they are substituted with a thiazole-based substituent (or benzothiazole-based substituent), Both pyridine-based substituents may be substituted with thiazole-based substituents (or benzothiazole-based substituents) (that is, n = 2), and either pyridine-based substituent is substituted with a thiazole-based substituent (or benzothiazole-based substituent) and the other pyridine The system substituent may be substituted with R ¹¹ to R ¹⁸ (ie, n = 1). Further, for example, at least one of R ¹¹ to R ¹⁸ in the formula (ETM-2-1) is substituted with a thiazole-based substituent (or benzothiazole-based substituent), and “pyridine-based substituent” is replaced with R ¹¹ to R ¹⁸ may be replaced with

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

<Silole derivatives>

A silole derivative is a compound represented by the following formula (ETM-15), for example. Details are described in Japanese Unexamined Patent Publication No. 9-194487.

X and Y are each independently alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, aryl, or heteroaryl, and these may be substituted. For details of these groups, the description in the above general formula (1) and further the description in the above formula (ETM-7-2) can be cited. In addition, alkenyloxy and alkynyloxy are groups in which the alkyl moiety in alkoxy is substituted with alkenyl or alkynyl, respectively, and the details of these alkenyl and alkynyl are in the above formula (ETM-7-2) explanations can be cited.

Further, X and Y may be bonded to form a cycloalkyl ring (and a ring in which a part thereof is unsaturated), and the details of this cycloalkyl ring can be referred to the description of cycloalkyl in the above general formula (1) there is.

R ¹ to ^{R 4} are each independently hydrogen, halogen, alkyl, cycloalkyl, alkoxy, aryloxy, amino, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, azo group, alkylcarbonyloxy , arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, sulfinyl, sulfonyl, sulfanyl, silyl, carbamoyl, aryl, heteroaryl, alkenyl, alkynyl, nitro, formyl, nitroso , formyloxy, isocyano, cyanate group, isocyanate group, thiocyanate group, isothiocyanate group, or cyano group, which may be substituted with alkyl, cycloalkyl, aryl or halogen, adjacent substituents A condensed ring may be formed between and.

For details of halogen, alkyl, cycloalkyl, alkoxy, aryloxy, amino, aryl, heteroaryl, alkenyl and alkynyl in R ¹ to ^{R 4} , the description in the above general formula (1) is cited. can do.

Alkyl among alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy and aryloxycarbonyloxy in R ¹ to R ⁴ ; The description in the said general formula (1) can be cited also about the details of an aryl and an alkoxy.

Examples of the silyl include a silyl group and a group in which at least one of the three hydrogens of the silyl group is independently substituted with aryl, alkyl or cycloalkyl, preferably trisubstituted silyl, triarylsilyl, trialkyl silyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, and alkyldicycloalkylsilyl; and the like. For the details of aryl, alkyl and cycloalkyl in these, the description in the above general formula (1) can be cited.

The condensed ring formed between adjacent substituents is, for example, a conjugated or non-conjugated condensed ring formed between R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , and the like. These condensed rings may contain nitrogen, oxygen, or sulfur atoms in the intra-ring structure, or may further condense with other rings.

However, preferably, when R ¹ and R ⁴ are phenyl groups, X and Y are not alkyl or phenyl. Also, preferably, when R ¹ and R ⁴ are thienyl groups, X and Y are alkyl, R ² and R ³ are alkyl, aryl, alkenyl, or R ² and R ³ are bonded to form a ring. It is a structure that does not simultaneously satisfy cycloalkyl. Also preferably, when R ¹ and R ⁴ are silyl groups, R ² , R ³ , X and Y are each independently not hydrogen or alkyl having 1 to 6 carbon atoms. Further, preferably, in the case of a structure in which benzene rings are condensed in R ¹ and R ² , X and Y are not alkyl and phenyl.

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

<Azoline derivatives>

An azoline derivative is a compound represented by the following formula (ETM-16), for example. Details are described in International Publication No. 2017/014226.

In formula (ETM-16),

φ is an m-valent group derived from an aromatic hydrocarbon having 6 to 40 carbon atoms or an m-valent group derived from an aromatic heterocyclic ring having 2 to 40 carbon atoms, and at least one hydrogen in φ is an alkyl having 1 to 6 carbon atoms, or an alkyl having 3 to 14 carbon atoms. may be substituted with cycloalkyl, aryl of 6 to 18 carbon atoms or heteroaryl of 2 to 18 carbon atoms,

Y is each independently -O-, -S- or >N-Ar, Ar is aryl having 6 to 12 carbon atoms or heteroaryl having 2 to 12 carbon atoms, and at least one hydrogen of Ar is 1 to 4 carbon atoms may be substituted with alkyl, cycloalkyl of 5 to 10 carbon atoms, aryl of 6 to 12 carbon atoms or heteroaryl of 2 to 12 carbon atoms, R ¹ to ^{R 5} are each independently hydrogen, alkyl of 1 to 4 carbon atoms or carbon atoms Cycloalkyl of 5 to 10, provided that Ar in the above >N-Ar and any one of R ¹ to R ⁵ is a site bonded to L;

L is each independently selected from the group consisting of a divalent group represented by the following formula (L-1) and a divalent group represented by the following formula (L-2),

In formula (L-1), X ¹ to X ⁶ are each independently =CR ⁶ - or =N-, at least two of X ¹ to X ⁶ are =CR ⁶ -, and 2 of X ¹ to ^{X 6} R ⁶ in =CR ⁶ - of dog is a site that binds to φ or an azoline ring, and R ⁶ in =CR ⁶ - other than that is hydrogen;

In formula (L-2), X ⁷ to X ¹⁴ are each independently =CR ⁶ - or =N-, at least two of X ⁷ to X ¹⁴ are =CR ⁶ -, and 2 of X ⁷ to X ¹⁴ R ⁶ in =CR ⁶ - of dog is a site that binds to φ or an azoline ring, and R ⁶ in =CR ⁶ - other than that is hydrogen;

At least one hydrogen of L may be substituted with C1-C4 alkyl, C5-C10 cycloalkyl, C6-C10 aryl or C2-C10 heteroaryl,

m is an integer of 1 to 4, and when m is 2 to 4, the group formed by the azoline ring and L may be the same or different, and

At least one hydrogen in the compound represented by formula (ETM-16) may be substituted with heavy hydrogen.

A specific azoline derivative is a compound represented by the following general formula (ETM-16-1) or general formula (ETM-16-2).

Among formulas (ETM-16-1) and formulas (ETM-16-2),

φ is an m-valent group derived from an aromatic hydrocarbon having 6 to 40 carbon atoms or an m-valent group derived from an aromatic heterocyclic ring having 2 to 40 carbon atoms, and at least one hydrogen in φ is an alkyl having 1 to 6 carbon atoms, or an alkyl having 3 to 14 carbon atoms. may be substituted with cycloalkyl, aryl of 6 to 18 carbon atoms or heteroaryl of 2 to 18 carbon atoms,

In formula (ETM-16-1), Y is each independently -O-, -S- or >N-Ar, Ar is an aryl having 6 to 12 carbon atoms or a heteroaryl having 2 to 12 carbon atoms, and Ar At least one hydrogen may be substituted with an alkyl having 1 to 4 carbon atoms, a cycloalkyl having 5 to 10 carbon atoms, an aryl having 6 to 12 carbon atoms, or a heteroaryl having 2 to 12 carbon atoms,

In formula (ETM-16-1), R ¹ to ^{R 4} are each independently hydrogen, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, provided that R ¹ and R ² are the same, and R ³ and R ⁴ are the same;

In formula (ETM-16-2), R ¹ to R ⁵ are each independently hydrogen, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, provided that R ¹ and R ² are the same, and R ³ and R ⁴ are the same,

Among formulas (ETM-16-1) and formulas (ETM-16-2),

L is each independently selected from the group consisting of a divalent group represented by the following formula (L-1) and a divalent group represented by the following formula (L-2),

In formula (L-1), X ¹ to X ⁶ are each independently =CR ⁶ - or =N-, at least two of X ¹ to X ⁶ are =CR ⁶ -, and 2 of X ¹ to ^{X 6} R ⁶ in =CR ⁶ - of dog is a site that binds to φ or an azoline ring, and R ⁶ in =CR ⁶ - other than that is hydrogen;

In formula (L-2), X ⁷ to X ¹⁴ are each independently =CR ⁶ - or =N-, at least two of X ⁷ to X ¹⁴ are =CR ⁶ -, and 2 of X ⁷ to X ¹⁴ R ⁶ in =CR ⁶ - of dog is a site that binds to φ or an azoline ring, and R ⁶ in =CR ⁶ - other than that is hydrogen;

At least one hydrogen of L may be substituted with C1-C4 alkyl, C5-C10 cycloalkyl, C6-C10 aryl or C2-C10 heteroaryl,

m is an integer of 1 to 4, and when m is 2 to 4, the group formed by the azoline ring and L may be the same or different, and

At least one hydrogen in the compound represented by formula (ETM-16-1) or formula (ETM-16-2) may be substituted with heavy hydrogen.

Preferably, φ is a monovalent group represented by the following formulas (φ1-1) to (φ1-18), a divalent group represented by the following formulas (φ2-1) to (φ2-34), and the following It is selected from the group consisting of trivalent groups represented by formulas (φ3-1) to (φ3-3) and tetravalent groups represented by the following formulas (φ4-1) to (φ4-2), wherein at least One hydrogen may be substituted by C1-C6 alkyl, C3-C14 cycloalkyl, C6-C18 aryl, or C2-C18 heteroaryl. * in the following structural formula represents a bonding position.

Z in the above formula is >CR ₂ , >N-Ar, >NL, -O-, or -S-, and R in >CR ₂ is each independently an alkyl having 1 to 4 carbon atoms or an alkyl having 5 to 5 carbon atoms. Cycloalkyl of 10, aryl of 6 to 12 carbon atoms or heteroaryl of 2 to 12 carbon atoms, R may be bonded to each other to form a ring, > Ar in N-Ar is aryl of 6 to 12 carbon atoms or carbon atoms It is a heteroaryl of 2 to 12, and L in >NL is L in the formula (ETM-16), formula (ETM-16-1) or formula (ETM-16-2).

Preferably, L is benzene, naphthalene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, and pteridine. It is a divalent group of rings selected from the group consisting of, at least one hydrogen of L is substituted with C1-C4 alkyl, C5-C10 cycloalkyl, C6-C10 aryl or C2-C10 heteroaryl, There may be.

Preferably, Ar in >N-Ar as Y or Z is phenyl, naphthyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, naphthyl It is selected from the group consisting of ridinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl, and pteridinyl, and at least one of Ar in >N-Ar as Y has 1 to 4 carbon atoms may be substituted with an alkyl of , a cycloalkyl of 5 to 10 carbon atoms, or an aryl of 6 to 10 carbon atoms.

Preferably, R ¹ to ^{R 4} are each independently hydrogen, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, provided that R ¹ and R ² are the same, and R ³ and R ⁴ are the same; Also, when all of R ¹ to R ⁴ do not become hydrogen at the same time, m is 1 or 2, and m is 2, the group formed from the azoline ring and L is the same.

Specific examples of the azoline derivative include the following compounds. In addition, "Me" in structural formula represents a methyl group.

More preferably, φ consists of a divalent group represented by the following formulas (φ2-1), formula (φ2-31), formula (φ2-32), formula (φ2-33) and formula (φ2-34) It is selected from the group, and at least one hydrogen of φ may be substituted with an aryl having 6 to 18 carbon atoms, * in each structural formula represents a bonding position,

L is a ring divalent group selected from the group consisting of benzene, pyridine, pyrazine, pyrimidine, pyridazine, and triazine, and at least one hydrogen in L is an alkyl having 1 to 4 carbon atoms or a cyclo having 5 to 10 carbon atoms may be substituted with alkyl, aryl of 6 to 10 carbon atoms or heteroaryl of 2 to 14 carbon atoms;

Ar in >N-Ar as Y is selected from the group consisting of phenyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl, and at least one hydrogen of the Ar has 1 to 4 carbon atoms may be substituted with an alkyl, a cycloalkyl of 5 to 10 carbon atoms or an aryl of 6 to 10 carbon atoms,

R ¹ to ^{R 4} are each independently hydrogen, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, provided that R ¹ and R ² are the same, R ³ and R ⁴ are the same, and R ¹ -R ⁴ do not all become hydrogen at the same time, and

m is 2, and the group formed from the azoline ring and L is the same.

Other specific examples of the azoline derivative include, for example, the following compounds. In addition, "Me" in structural formula represents a methyl group.

For details of alkyl, cycloalkyl, aryl or heteroaryl in each of the above formulas defining this azoline derivative, the description in the above general formula (1) can be cited.

This azoline derivative can be produced using known raw materials and known synthetic methods.

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

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

The material for the electron injection layer and the material for the electron transport layer described above are a polymer compound obtained by polymerizing a reactive compound having a reactive substituent substituted thereon as a monomer, or a polymer crosslinked product thereof, or a main chain polymer and the reactive compound reacted A pendant-type polymer compound or a pendant-type polymer crosslinked product thereof can also be used for the electronic layer material. As the reactive substituent in this case, the description of the polycyclic aromatic compound represented by the above general formula (1) can be cited.

The details of the use of such a high molecular compound and high molecular crosslinked product will be described later.

<Cathode in organic electroluminescence 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 forming the cathode 108 is not particularly limited as long as it is a material capable of efficiently injecting electrons into the organic layer, but the same material as the material forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or alloys thereof (magnesium-silver alloy, magnesium -Indium alloy, aluminum-lithium alloy such as lithium fluoride/aluminum, etc.), etc. are preferable. In order to improve device characteristics by increasing electron injection efficiency, lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective. However, these low work function metals are generally unstable in air in many cases. In order to improve this point, a method is known in which, for example, 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 can also be used. However, it is not limited to these.

In addition, metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, or alloys using these metals, and inorganic substances such as silica, titania, and silicon nitride, polyvinyl alcohol, vinyl chloride, and hydrocarbons for electrode protection Preferred examples include laminating a polymeric compound or the like. Methods for producing these electrodes are not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam evaporation, sputtering, ion plating and coating.

<Binder that can be used in each layer>

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

<Method of manufacturing organic electroluminescence device>

For each layer constituting the organic EL device, the material constituting each layer is formed into a thin film by a method such as evaporation, resistance heating evaporation, electron beam evaporation, sputtering, molecular lamination method, printing method, spin coating method, casting method, or coating method. By doing so, it can be formed. The film thickness of each layer formed in this way is not particularly limited and can be appropriately set depending on the nature of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like. In the case of thinning using the vapor deposition method, the deposition conditions differ depending on the type of material, the target crystal structure and association structure of the film, and the like. Deposition conditions are generally boat heating temperature +50 to +400 ° C, vacuum degree 10 ^-6 to ^{10 -3} Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature -150 to +300 ° C, film thickness 2 nm to 5 μm. It is desirable to set appropriately within the range.

In the case of applying a direct current voltage to the organic EL element obtained in this way, the anode may be applied with + and the cathode as the polarity, and when a voltage of about 2 to 40 V is applied, the transparent or translucent electrode side (anode or cathode) , and both) can observe luminescence. In addition, this organic EL element emits light even when a pulse current or an alternating current is applied. In addition, the waveform of the alternating current to apply may be arbitrary.

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

<Deposition method>

After fabricating an anode by forming a thin film of anode material on a suitable substrate by vapor deposition or the like, thin films of a hole injection layer and a hole transport layer are formed on the anode. A host material and a dopant material are co-evaporated thereon to form a thin film to form a light emitting layer, an electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by a vapor deposition method or the like to form a cathode. An organic EL element is obtained. In addition, in fabricating the organic EL device described above, it is also possible to reverse the fabrication order and fabricate the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer and anode in this order.

<Wet film forming method>

The wet film forming method is performed by preparing a low-molecular compound capable of forming each organic layer of an organic EL element as a liquid composition for forming an organic layer, and using the same. When there is no suitable organic solvent that dissolves the low molecular weight compound, a composition for forming an organic layer is made of a reactive compound obtained by substituting a reactive substituent in the low molecular weight compound and polymerized together with other monomers or main chain polymers having a soluble function. you can prepare

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

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

On the other hand, when compared with the vacuum deposition method, the wet film formation method sometimes makes lamination difficult. When a multilayer film is produced using a wet film forming method, it is necessary to prevent dissolution of the lower layer by the composition of the upper layer, so a composition with controlled solubility, cross-linking of the lower layer and orthogonal solvent (solvent that does not dissolve in each other), etc. this is spoken However, even if these techniques are used, there are cases where it is difficult to use the wet film formation method for coating all films.

Therefore, generally, a method of fabricating an organic EL device by using a wet film forming method for only a few layers and vacuum evaporation is employed for the rest.

For example, a procedure for fabricating an organic EL device by partially applying a wet film forming method is shown below.

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

(Procedure 2) Formation of a composition for forming a hole injection layer containing a material for a hole injection layer by a wet film forming method

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

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

(Procedure 5) Film formation of the electron transport layer by vacuum evaporation

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

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

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

Of course, there is a means for preventing the dissolution of the lower light emitting layer, or a means for forming a film from the cathode side contrary to the above procedure is used to prepare a composition for forming a layer containing a material for an electron transport layer or a material for an electron injection layer, , these can be formed into a film by a wet film forming method.

<Other Tabernacling Methods>

A laser heating drawing method (LITI) can be used for film formation of the composition for forming an organic layer. LITI is a method of heating and depositing a compound attached to a substrate with a laser, and a composition for forming an organic layer can be used for a material applied to the substrate.

<Random process>

Appropriate treatment steps, washing steps, and drying steps may be suitably incorporated before and after each step of film formation. Examples of the treatment step include exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, washing treatment using an appropriate solvent, heat treatment, and the like. In addition, a series of steps for producing a bank are also mentioned.

A photolithography technique can be used for fabrication of the bank. As a usable bank material for photolithography, a positive resist material and a negative resist material can be used. In addition, patternable printing methods such as inkjet printing, gravure offset printing, reverse offset printing, and screen printing can also be used. In this case, a permanent resist material may be used.

Materials used for the bank include polysaccharides and their derivatives, homopolymers and copolymers of hydroxyl-containing ethylenic monomers, biomolecular compounds, polyacryloyl compounds, polyesters, polystyrenes, polyimides, polyamideimides, and polyethers. Mead, polysulfide, polysulfone, polyphenylene, polyphenylether, polyurethane, epoxy (meth)acrylate, melamine (meth)acrylate, polyolefin, cyclic polyolefin, acrylonitrile-butadiene-styrene copolymer (ABS ), silicone resin, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyacetate, polynorbornene, synthetic rubber, fluorinated polymers such as polyfluorovinylidene, polytetrafluoroethylene, polyhexafluoropropylene, fluoropolymers Copolymers of olefin-hydrocarbon olefins and fluorocarbon polymers are exemplified, but are not limited thereto.

<Composition for Forming Organic Layer Used in Wet Film Formation>

A composition for forming an organic layer is obtained by dissolving a low-molecular compound capable of forming each organic layer of an organic EL device or a high-molecular compound obtained by polymerizing the low-molecular compound in an organic solvent. For example, a composition for forming a light emitting layer includes at least one polycyclic aromatic compound (or a polymer compound thereof) as a dopant material as a first component, at least one host material as a second component, and at least one as a third component. Contains a species of organic solvent. The first component functions as a dopant component of the light emitting layer obtained from the composition, and the second component functions as a host component of the light emitting layer. The third component functions as a solvent that dissolves the first and second components in the composition, and upon application, imparts a smooth and uniform surface shape by the controlled evaporation rate of the third component itself.

<Organic Solvent>

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

(1) physical properties of organic solvents

The boiling point of the at least one organic solvent is 130°C to 300°C, more preferably 140°C to 270°C, still more preferably 150°C to 250°C. When the boiling point is higher than 130°C, it is preferable from the viewpoint of inkjet ejection properties. In addition, when the boiling point is lower than 300°C, it is preferable from the viewpoint of defects, surface roughness, residual solvent and smoothness of the coating film. The organic solvent is more preferably composed of two or more organic solvents from the viewpoints of good inkjet ejection properties, film formability, smoothness, and low residual solvent. On the other hand, depending on the case, a composition made into a solid state by removing the solvent from the composition for forming an organic layer may be used in consideration of transportability and the like.

Furthermore, the organic solvent includes a good solvent (GS) and a poor solvent (PS) for at least one of the solutes, and the boiling point of the good solvent (GS) (BP _GS ) is the boiling point of the poor solvent (PS) (BP _PS ) A configuration lower than that is particularly preferred.

By adding a poor solvent with a high boiling point, the good solvent with a low boiling point volatilizes first at the time of film formation, and the concentration of the content and the concentration of the poor solvent in the composition increase, thereby promoting rapid film formation. Thereby, a coating film with few defects, small surface roughness, and high smoothness is obtained.

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

After film formation, the organic solvent is removed from the coating film by a drying process such as vacuum, reduced pressure, or heating. When heating is performed, it is preferable to perform heating at a glass transition temperature (Tg) of at least one of the solutes +30°C or less from the viewpoint of improving coating film formability. Further, from the viewpoint of reducing the residual solvent, it is preferable to heat the glass transition point (Tg) of at least one of the solutes to -30°C or higher. Since the film is thin even when the heating temperature is lower than the boiling point of the organic solvent, the organic solvent is sufficiently removed. Moreover, drying may be performed a plurality of times at different temperatures, or a plurality of drying methods may be used in combination.

(2) Specific examples of organic solvents

Examples of organic solvents used in the composition for forming an organic layer include alkylbenzene solvents, phenyl ether solvents, alkyl ether solvents, cyclic ketone solvents, aliphatic ketone solvents, monocyclic ketone solvents, solvents having a diester skeleton, and fluorine-based solvents and the like, and specific examples include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexan-2-ol, heptan-2- Ol, octan-2-ol, decan-2-ol, dodecan-2-ol, cyclohexanol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, ter Pineol (mixture), ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, Triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, p-xylene, m-xylene, o-xylene, 2,6-lutidine , 2-fluoro-m-xylene, 3-fluoro-o-xylene, 2-chlorobenzotrifluoride, cumene, toluene, 2-chloro-6-fluorotoluene, 2-fluoroanisole, anisole, 2,3-dimethylpyrazine, bromobenzene, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethylanisole, mesitylene, 1,2,4-trimethylbenzene, t-butylbenzene , 2-methylanisole, phenetole, benzodioxole, 4-methylanisole, s-butylbenzene, 3-methylanisole, 4-fluoro-3-methylanisole, cymene, 1,2,3- Trimethylbenzene, 1,2-dichlorobenzene, 2-fluorobenzonitrile, 4-fluoroveratrol, 2,6-dimethylanisole, n-butylbenzene, 3-fluorobenzonitrile, decalin (decahydronaphthalene) , neopentylbenzene, 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile , 3,5-dimethylanisole, diphenyl ether, 1-fluoro-3,5-dimethoxybenzene, methyl benzoate, isopentylbenzene, 3,4-dimethylanisole, o-tolunitrile, n-amyl Benzene, veratrol, 1,2,3,4-tetrahydronaphthalene, ethyl benzoate, n-hexylbenzene, propyl benzoate, cyclohexylbenzene, 1-methylnaphthalene, butyl benzoate, 2-methylbiphenyl, 3-phenoxy Toluene, 2,2'-bitril, dodecylbenzene, dipentylbenzene, tetramethylbenzene, trimethoxybenzene, trimethoxytoluene, 2,3-dihydrobenzofuran, 1-methyl-4-(propoxy Methyl)benzene, 1-methyl-4-(butyloxymethyl)benzene, 1-methyl-4-(pentyloxymethyl)benzene, 1-methyl-4-(hexyloxymethyl)benzene, 1-methyl-4-( Heptyloxymethyl) benzene benzyl butyl ether, benzyl pentyl ether, benzyl hexyl ether, benzyl heptyl ether, benzyl octyl ether and the like, but are not limited thereto. In addition, a solvent may be used singly or may be mixed.

<Optional ingredients>

The composition for forming an organic layer may contain arbitrary components within a range that does not impair its properties. As an arbitrary component, a binder, surfactant, etc. are mentioned.

(1) Binder

The composition for forming an organic layer may contain a binder. The binder forms a film during film formation and bonds the obtained film to the substrate. In addition, it serves to dissolve, disperse, and bind other components in the composition for forming the organic layer.

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

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

(2) Surfactant

The composition for forming an organic layer may contain, for example, a surfactant for controlling the uniformity of the film surface and the solvent affinity and liquid repellency of the film surface of the composition for forming an organic layer. Surfactants are classified into ionic and nonionic according to the structure of the hydrophilic group, and also classified into alkyl, silicon, and fluorine based according to the structure of the hydrophobic group. In addition, according to the structure of the molecule, it is classified into a monomolecular system having a relatively small molecular weight and a simple structure, and a macromolecular system having a large molecular weight and side chains or branches. In addition, according to the composition, it is classified into a single system and a mixed system in which two or more types of surfactants and a substrate are mixed. As the surfactant that can be used in the organic layer-forming composition, all kinds of surfactants can be used.

As surfactant, for example, Polyflow No.45, Polyflow KL-245, Polyflow No.75, Polyflow No.90, Polyflow No.95 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.) , Disperbyk 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181, Disperbake 182, BYK300 , BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, manufactured by Big Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (brand name, manufactured by Shin-Etsu Chemical Co., Ltd.), Suplon SC-101, Suplon KH-40 (brand name, manufactured by Seimi Chemical Co., Ltd.), Phtagent 222F, Phtagent 251, FTX-218 (brand name, ( Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (trade name, manufactured by Mitsubishi Materials Co., Ltd.), Megapack F-470, Megapack F -471, Megapack F-475, Megapack R-08, Megapack F-477, Megapack F-479, Megapack F-553, Megapack F-554 (trade name, manufactured by DIC Co., Ltd.), Fluoro Alkylbenzenesulfonate, fluoroalkylcarbonate, fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylsulfonate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether ), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonic acid salt, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene Stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate , polyoxyethylene sorbitanste Arate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyl diphenyl ether disulfonate.

In addition, surfactant may be used by 1 type, and may use 2 or more types together.

<Composition and physical properties of composition for forming organic layer>

The content of each component in the composition for forming an organic layer depends on the good solubility, storage stability and film formability of each component in the composition for forming an organic layer, the quality of a coating film obtained from the composition for forming an organic layer, and the inkjet method. It is determined in consideration of the good ejection properties in the case of use, and the good electrical characteristics, light emitting characteristics, efficiency, and lifetime of an organic EL device having an organic layer produced using the composition. For example, in the case of the composition for forming a light emitting layer, the first component is 0.0001% to 2.0% by weight based on the total weight of the composition for forming a light emitting layer, and the second component is 0.0999% by weight based on the total weight of the composition for forming a light emitting layer. % to 8.0% by weight, and the third component is preferably 90.0% to 99.9% by weight with respect to the total weight of the composition for forming a light emitting layer.

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

The composition for forming an organic layer can be prepared by appropriately selecting and performing stirring, mixing, heating, cooling, dissolution, dispersion, etc. of the above-mentioned components by a known method. After preparation, filtration, degassing (also referred to as degassing), ion exchange treatment, and inert gas replacement/encapsulation treatment may be appropriately selected and performed.

As for the viscosity of the composition for forming an organic layer, those with high viscosity give good film formability and good ejection properties in the case of using the inkjet method. On the other hand, it is easy to make a thin film of low viscosity. From these points, it is preferable that the viscosity in 25 degreeC is 0.3-3 mPa*s, and, as for the viscosity of the said composition for organic layer formation, it is more preferable that it is 1-3 mPa*s. In the present invention, the viscosity is a value measured using a cone-plate rotational viscometer (conical plate type).

As for the surface tension of the composition for forming an organic layer, the lower the surface tension, the better film formability and defect-free coating can be obtained. On the other hand, the higher the better, the better inkjet ejection properties are obtained. From these points, it is preferable that the surface tension in 25 degreeC is 20-40 mN/m, and, as for the surface tension of the said composition for organic layer formation, it is more preferable that it is 20-30 mN/m. In the present invention, the surface tension is a value measured using the hanging drop method.

<Crosslinkable High Polymer Compound: Compound Represented by Formula (XLP-1)>

Next, the case where the above-mentioned high molecular compound has a crosslinkable substituent is demonstrated. Such a crosslinkable high molecular compound is, for example, a compound represented by the following general formula (XLP-1).

In formula (XLP-1),

MUx, ECx, and k are the same definitions as MU, EC, and k in the formula (H3), provided that the compound represented by the formula (XLP-1) has at least one crosslinkable substituent (XLS), and preferably Preferably, the content of the monovalent or divalent aromatic compound having a crosslinkable substituent is 0.1 to 80% by weight in the molecule.

0.5 to 50 weight% is preferable, and, as for content of the monovalent or divalent aromatic compound which has a crosslinkable substituent, 1 to 20 weight% is more preferable.

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

L is each independently a single bond, -O-, -S-, >C=O, -O-C(=O)-, C1-C12 alkylene, C1-C12 oxyalkylene, and C1 -12 polyoxyalkylene. Among the above substituents, a group represented by formula (XLS-1), formula (XLS-2), formula (XLS-3), formula (XLS-9), formula (XLS-10) or formula (XLS-17) is preferable. and a group represented by formula (XLS-1), formula (XLS-3) or formula (XLS-17) is more preferred.

As a divalent aromatic compound which has a crosslinkable substituent, the compound which has the following partial structure is mentioned, for example. * in the following structural formula represents a bonding position.

<Method for producing high molecular compound and crosslinkable high molecular compound>

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

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

Also, the reaction may be performed in a two-phase system. When making it react in a two-phase system, you may add a phase transfer catalyst, such as a quaternary ammonium salt, as needed.

When the compound of formula (H3) and the compound of formula (XLP-1) are produced, they may be produced in one step or may be produced through multiple steps. Alternatively, it may be carried out by a batch polymerization method in which the reaction is started after all the raw materials are put into a reaction vessel, or may be carried out by a dropping polymerization method in which the raw materials are added dropwise into a reaction vessel, or the product precipitates as the reaction proceeds. Precipitation polymerization may be carried out, and these can be synthesized by appropriately combining them. For example, when synthesizing the compound represented by formula (H3) in one step, the target product is obtained by reacting with the monomer unit (MU) and the end cap unit (EC) added to the reaction vessel. Further, when synthesizing the compound represented by the general formula (H3) in multiple stages, the monomer unit (MU) is polymerized to a desired molecular weight, and then the end cap unit (EC) is added and reacted to obtain the desired product. When the reaction is performed by adding different types of monomer units (MU) in multiple steps, a polymer having a concentration gradient with respect to the structure of the monomer units can be produced. In addition, after preparing the precursor polymer, the target polymer can be obtained by post-reaction.

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

As the monomer unit usable in the present invention, Japanese Patent Application Laid-Open No. 2010-189630, International Publication No. 2012/086671, International Publication No. 2013/191088, International Publication No. 2002/045184, International Publication No. 2011/049241 . , It is compoundable according to the method described in Unexamined-Japanese-Patent No. 2011-174062.

In addition, regarding the specific polymer synthesis procedure, Japanese Patent Laid-Open No. 2012-036388, International Publication No. 2015/008851, Japanese Patent Laid-Open No. 2012-36381, Japanese Patent Laid-Open No. 2012-144722, International Publication No. 2015/194448 International Publication No. 2013/146806, International Publication No. 2015/145871, International Publication No. 2016/031639, International Publication No. 2016/125560, and International Publication No. 2011/049241. .

<Application example of organic electroluminescence device>

Further, the present invention can also be applied to a display device including an organic EL element or a lighting device including an organic EL element.

A display device or lighting device including an organic EL element can be manufactured by a known method such as connecting the organic EL element according to the present embodiment to a known drive device, and known DC drive, pulse drive, AC drive, etc. It can be driven by appropriately using the driving method of .

Examples of the display device include a panel display such as a color flat panel display, a flexible display such as a flexible color organic electroluminescent (EL) display, and the like (eg, Japanese Patent Laid-Open No. 10-335066, Japanese Unexamined Patent Publication No. 2003-321546, Japanese Unexamined Patent Publication No. 2004-281086, etc.). In addition, as a display method of a display, a matrix method, a segment method, etc. are mentioned, for example. Also, the matrix display and the segment display may coexist in the same panel.

In the matrix, pixels for display are two-dimensionally arranged in a lattice or mosaic form, and characters or images are displayed by a set of pixels. The shape or size of the pixel is determined according to the purpose. For example, for displaying images and characters on computers, monitors, and televisions, square pixels with sides of 300 μm or less are usually used, and in the case of large displays such as display panels, pixels on the order of mm are used. will do In the case of monochrome display, pixels of the same color may be arranged, but in the case of color display, pixels of red, green, and blue are arranged and displayed. In this case, there are typically a delta type and a stripe type. Incidentally, as a driving method for this matrix, either a line-sequential driving method or an active matrix may be used. Line-sequential driving has the advantage of having a simple structure, but when operating characteristics are taken into account, the active matrix may be superior, so it is necessary to use this also according to the purpose.

In the segment method (type), a pattern is formed to display predetermined information, and a predetermined area is illuminated. For example, time or temperature display in a digital watch or thermometer, operation status display of an audio device or electric cooker, and panel display of an automobile may be cited.

Examples of the lighting device include lighting devices such as indoor lighting, backlights of liquid crystal display devices, and the like (for example, Japanese Patent Laid-Open No. 2003-257621, Japanese Patent Laid-Open No. 2003-277741, Japanese Patent). Publication No. 2004-119211, etc.). Backlights are mainly used for the purpose of improving the visibility of display devices that do not emit light themselves, and are used for liquid crystal display devices, clocks, audio devices, automobile panels, display panels, and signs. In particular, considering that it is difficult to reduce the thickness of a liquid crystal display device, especially a backlight for a computer where thinning is a problem, because the conventional method consists of a fluorescent lamp or a light guide plate, the backlight using the light emitting element according to the present embodiment is thin. and is characterized by being lightweight.

3-2. other organic device

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

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

The structure of the organic field effect transistor is usually provided with a source electrode and a drain electrode in contact with the organic semiconductor active layer formed using the polycyclic aromatic compound according to the present invention, and furthermore, an insulating layer (dielectric layer) in contact with the organic semiconductor active layer is interposed therebetween. and the gate electrode is installed. As the element structure, the following structures are mentioned, for example.

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

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

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

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

The organic field effect transistor configured in this way can be applied as a pixel drive switching element of an active matrix drive type liquid crystal display or an organic light emitting device display.

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

For the purpose of wide color gamut of displays, quantum dots having a narrow emission half-width are used as phosphors of wavelength conversion filters. On the other hand, there are problems such as instability to oxidation, high aggregation due to being nano-sized fine particles, and metals used being regulated as contaminants. The polycyclic aromatic compound according to the present invention can be used as a phosphor of a wavelength conversion filter. As the matrix for dispersing the polycyclic aromatic compound, a polymer material having high transparency, low water vapor permeability, low oxygen permeability, and high thermal stability is preferable, and examples thereof include (meth)acrylic acid such as polymethyl (meth)acrylate. Cycloolefin polymers, such as a polymer and Zeonex, etc. are mentioned.

[Example]

Hereinafter, the present invention will be described more specifically by means of examples, but the present invention is not limited thereto. First, synthesis examples of polycyclic aromatic compounds are described below.

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

Under a nitrogen atmosphere, intermediate (X-1) (75.0 g), intermediate (X-2) (178.7 g), cesium carbonate (429.8 g), and N-methyl-2-pyrrolidone (NMP, 750 ml) were added to the flask. and heated at 110°C for 8 hours. After completion of the reaction, water and toluene were added to the reaction mixture and stirred, and then the organic layer was separated and washed with water. Thereafter, the crude product obtained by concentrating the organic layer was purified with a silica gel short column (eluent: toluene/heptane = 1/4 (volume ratio)) to obtain an intermediate (X-3) (201.6 g).

Intermediate (X-3) (190.6 g) and xylene (2 L) were placed in a flask under a nitrogen atmosphere, and after cooling to -5°C, n-butyllithium hexane solution (197.6 ml) was added dropwise. After stirring for 30 minutes, the mixture was cooled again to -57°C, boron tribromide (84.3 g) was added, the temperature was raised to 0°C, and the mixture was stirred for 0.5 hour. Thereafter, N,N-diisopropylethylamine (DIEPA, 72.4 g) was added, and after stirring at room temperature until heat generation subsided, the temperature was raised to 120°C and the mixture was heated and stirred for 5 hours. The reaction solution was cooled to room temperature, potassium acetate aqueous solution and heptane were added, and the precipitated crude product was purified with a silica gel short column (eluent: toluene) and washed with heptane to obtain an intermediate (X-4) (59 g).

Under nitrogen atmosphere, intermediate (X-4) (15.0 g), intermediate (X-5) (6.6 g), potassium phosphate (10.5 g), palladium acetate (0.28 g), 2-dicyclohexylphosphino-2' , 6'-dimethoxybiphenyl (SPhos, 1.0 g), toluene (200 ml), cyclopentyl methyl ether (CPME, 200 ml), ethanol (30 ml), and water (30 ml) were added, and the mixture was stirred under heating and reflux for 1 hour. . After completion of the reaction, water and toluene were added to the reaction mixture and stirred, and then the organic layer was separated and washed with water. Thereafter, the crude product obtained by concentrating the organic layer was purified by a silica gel short column (eluent: toluene/ethyl acetate = 1/1 (volume ratio)). The obtained crude product was recrystallized from toluene to obtain compound (1-16) (12.7 g).

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=751.

Synthesis Example (2): Synthesis of Compound (1-17)

Compounds (1-17) were synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=751.

Synthesis Example (3): Synthesis of Compound (1-40)

Compound (1-40) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=751.

Synthesis Example (4): Synthesis of Compound (1-3)

Compound (1-3) was synthesized in the same manner as in Synthesis Example (1) described above.

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

¹ H-NMR (CDCl ₃ ): δ = 8.29 (d, 2H), 7.51-7.45 (m, 12H), 7.37 (d, 2H), 7.22-7.17 (m, 15H), 6.95 (s, 2H), 6.94 (dd, 2H).

Synthesis Example (5): Synthesis of Compound (1-2)

Compound (1-2) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=726.

Synthesis Example (6): Synthesis of Compound (1-7)

Compounds (1-7) were synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=726.

Synthesis Example (7): Synthesis of Compound (1-6)

Compounds (1-6) were synthesized in the same manner as in Synthesis Example (1) described above.

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

¹ H-NMR (CDCl ₃ ): δ = 8.76 (d, 2H), 7.99-7.97 (m, 3H), 7.84 (d, 2H), 7.75-7.65 (m, 14H), 7.60-7.57 (m, 3H) ), 7.54(s, 2H), 7.51-7.47 (m, 6H), 7.41-7.38 (m, 3H).

Synthesis Example (8): Synthesis of Compound (1-80)

Compound (1-80) was synthesized in the same manner as in Synthesis Example (1) described above.

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

¹ H-NMR (CDCl ₃ ): δ = 8.62 (d, 2H), 8.29 (d, 2H), 7.94 (s, 1H), 7.80-7.79 (m, 1H), 7.60-7.38 (m, 16H), 7.25-7.14 (m, 10H), 7.00 (d, 2H).

Synthesis Example (9): Synthesis of compound (1-77)

Compound (1-77) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=727.

Synthesis Example (10): Synthesis of Compound (1-53)

Compound (1-53) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=728.

Synthesis Example (11): Synthesis of Compound (1-88)

Compound (1-88) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=778.

Synthesis Example (12): Synthesis of Compound (1-95)

Compound (1-95) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=815.

Synthesis Example (13): Synthesis of Compound (1-96)

Compound (1-96) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=816.

Synthesis Example (14): Synthesis of Compound (1-98)

Compound (1-98) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=777.

Synthesis Example (15): Synthesis of Compound (1-110)

Compound (1-110) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=826.

Synthesis Example (16): Synthesis of Compound (1-121)

Compound (1-121) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=761.

Synthesis Example (17): Synthesis of Compound (1-123)

Compound (1-123) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=1056.

Synthesis Example (18): Synthesis of Compound (1-125)

Compound (1-125) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=726.

Synthesis Example (19): Synthesis of Compound (1-132)

Compound (1-132) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=751.

Synthesis Example (20): Synthesis of Compound (1-135)

Compound (1-135) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=726.

Synthesis Example (21): Synthesis of Compound (1-154)

Compound (1-154) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=728.

Synthesis Example (22): Synthesis of Compound (1-178)

Compound (1-178) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=727.

Synthesis Example (23): Synthesis of Compound (1-184)

Compound (1-184) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=727.

Synthesis Example (24): Synthesis of Compound (1-204)

Compound (1-204) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=728.

Synthesis Example (25): Synthesis of Compound (1-224)

Compound (1-224) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=728.

Synthesis Example (26): Synthesis of Compound (1-233)

Compound (1-233) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=729.

Synthesis Example (27): Synthesis of Compound (1-271)

Compound (1-271) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=729.

Synthesis Example (28): Synthesis of Compound (1-276)

Compound (1-276) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=729.

Synthesis Example (29): Synthesis of compound (1-287)

Compound (1-287) was synthesized in the same manner as in Synthesis Example (1) described above.

The structure of the obtained compound was confirmed by mass spectrometry.

EI-MS, M/Z=730.

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

Next, fabrication and evaluation of an organic EL device using the compound of the present invention will be described. However, the application of the compound of the present invention is not limited to the examples shown below, and the film thickness and constituent materials of each layer can be appropriately changed depending on the basic physical properties of the compound of the present invention.

<Evaluation of vapor deposition type organic EL device>

Organic EL devices according to Example 1-1 to Example 1-17 and Comparative Example 1-1 to Comparative Example 1-7 were fabricated, and drive voltage (V) and external quantum efficiency as characteristics at 1000 cd/m ² emission (%) was measured, and then the time to retain the luminance of 90% or more of the initial luminance when driven with a constant current at a current density of 10 mA/cm ² was measured.

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

The external quantum efficiency is measured as follows. Using a voltage/current generator R6144 manufactured by Advantist, a voltage at which the luminance of the element reaches 1000 cd/m ² was applied to light the element. Spectroradiance in the visible region was measured from a direction perpendicular to the light emitting surface using a spectroradiometer SR-3AR manufactured by TOPCON. Assuming that the light emitting surface is a completely diffusing surface, the measured spectral radiance value of each wavelength component divided by the wavelength energy and multiplied by π is the number of photons at each wavelength. Next, the number of photons was accumulated in the observed full-wave field region, and the total number of photons emitted from the device was determined. The value obtained by dividing the applied current value by the basic charge is the number of carriers injected into the device, and the 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.

Materials of each layer in the organic EL devices produced in Examples 1-1 to 1-17, 1-18 to 1-29, and Comparative Examples 1-1 to 1-7 The composition and EL characteristic data are shown in the table below. On the other hand, the electron transport layer 2 is formed by co-evaporation so that the weight ratio of the compounds listed in the table and Liq is 1/1.

[Table 1A]

[Table 1B]

[Table 1C]

[Table 1D]

[Table 2A]

[Table 2B]

In the above tables, "HI", "IL", "HT-1", "HT-2", "BH-1", "BD-1", "ET-1", "Liq", comparative compounds ( The chemical structures of 1), Comparative Compound (2), Comparative Compound (3), Comparative Compound (4), Comparative Compound (5), Comparative Compound (6), and Comparative Compound (7) are shown below.

<Example 1-1>

A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Opto Science Co., Ltd.) obtained by polishing ITO film formed to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate was fixed to a substrate holder of a commercially available evaporation apparatus (manufactured by Choshu Sangyo Co., Ltd.), and HI, IL, HT-1, HT-2, BH-1, BD-1, ET-1, and An evaporation boat made of tantalum containing compound (1-2) and an evaporation boat made of aluminum nitride containing Liq, Mg, and Ag, respectively, were installed.

Each of the following layers was sequentially formed on the ITO film of the transparent support substrate. Depressurize the vacuum chamber to 5×10 ^-4 Pa, first heat HI to deposit a film thickness of 40 nm, then heat IL to deposit a film thickness of 5 nm, and then heat HT-1 and deposited to a film thickness of 15 nm, and then, HT-2 was heated and deposited to a film thickness of 10 nm to form a four-layered hole layer. Next, BH-1 and BD-1 were simultaneously heated and deposited to have a film thickness of 25 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH-1 to BD-1 was about 98:2. Then, ET-1 was heated and deposited to a film thickness of 5 nm to form an electron transport layer 1. Furthermore, compound (1-2) and Liq were simultaneously heated and deposited 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 compound (1-2) and Liq was about 50:50. The deposition rate of each layer was 0.01 to 1 nm/sec. After that, Liq was heated and deposited at a deposition rate of 0.01 to 0.1 nm/sec to a film thickness of 1 nm, and then magnesium and silver were simultaneously heated and deposited to a film thickness of 100 nm to form a cathode to obtain an organic EL device. . At this time, the deposition rate was adjusted between 0.1 nm and 10 nm/sec so that the atomic number ratio of magnesium and silver was 10:1.

Each EL characteristic was measured by applying a DC voltage using the ITO electrode as an anode and the magnesium/silver electrode as a cathode.

<Example 1-2 to Example 1-17, Example 1-18 to Example 1-29, Comparative Example 1-1 to Comparative Example 1-7>

Example 1-2 to Example 1-17, Example 1-18 to Example 1-29, and Organic EL devices of Comparative Example 1-1 to Comparative Example 1-7 were obtained. In addition, each EL characteristic was measured by applying a DC voltage using the ITO electrode as an anode and the magnesium/silver electrode as a cathode.

<Evaluation of coating type organic EL device>

Next, an organic EL element obtained by application and formation of an organic layer will be described.

<Synthesis of polymer host compound: SPH-101>

According to the method described in International Publication No. 2015/008851, SPH-101 was synthesized. A copolymer in which M2 or M3 is bonded next to M1 is obtained, and from the input ratio, it is estimated that each unit is 50:26:24 (molar ratio). In the structural formula below, Me is a methyl group, Bpin is a pinacolatboryl group, and * is a linking position of each unit.

<Polymer Hole Transport Compound: Synthesis of XLP-101>

According to the method described in Japanese Unexamined Patent Publication No. 2018-61028, XLP-101 was synthesized. A copolymer in which M5 or M6 is bonded next to M4 is obtained, and from the input ratio, it is estimated that each unit is 40:10:50 (molar ratio). In the structural formula below, Me is a methyl group, Bpin is a pinacolatboryl group, and * is a linking position of each unit.

<Example 2-1 to Example 2-9>

A coating solution for the material forming each layer is prepared to fabricate a coating type organic EL device.

<Production of Organic EL Devices of Examples 2-1 to 2-3>

Table 3 shows the material configuration of each layer in the organic EL device.

[Table 3]

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

<Preparation of Composition for Forming Light-Emitting Layer (1)>

The composition for forming a light emitting layer (1) is prepared by stirring the following components until they become a uniform solution. The prepared composition for forming a light-emitting layer is spin-coated on a glass substrate and heat-dried under reduced pressure to obtain a coated film free from film defects and excellent in smoothness.

Compound (A) 0.04% by weight

SPH-101 1.96% by weight

Xylene 69.00% by weight

Decalin 29.00% by weight

On the other hand, compound (A) is a polycyclic aromatic compound represented by general formula (1) (for example, compound (1-2)), the polycyclic aromatic compound as a monomer (ie, the monomer has a reactive substituent) It is a polymerized polymer compound or a polymer crosslinked product obtained by further crosslinking the polymer compound. A polymer compound for obtaining a polymer crosslinked product has a crosslinkable substituent.

<PEDOT:PSS solution>

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

<Preparation of OTPD solution>

OTPD (LT-N159, manufactured by Luminescence Technology Corp.) and IK-2 (photocationic polymerization initiator, manufactured by San-Apro) were dissolved in toluene to prepare an OTPD solution having an OTPD concentration of 0.7% by weight and an IK-2 concentration of 0.007% by weight. .

<Preparation of XLP-101 solution>

A 0.6 wt% XLP-101 solution was prepared by dissolving XLP-101 in xylene at a concentration of 0.6 wt%.

<Preparation of PCz solution>

PCz (polyvinylcarbazole) is dissolved in dichlorobenzene to prepare a 0.7% by weight PCz solution.

<Example 2-1>

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

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

<Example 2-2>

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

<Example 2-3>

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

<Evaluation of organic EL devices of Examples 2-1 to 2-3>

It can be expected that the coating type organic EL device obtained as described above will also have excellent drive voltage and external quantum efficiency similarly to the vapor deposition type organic EL device.

<Production of Organic EL Devices of Examples 2-4 to 2-6>

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

[Table 4]

<Preparation of Compositions (2) to (4) for Forming Light-Emitting Layer>

A composition for forming a light emitting layer (2) is prepared by stirring the following components until they become a uniform solution.

Compound (A) 0.02% by weight

mCBP 1.98% by weight

Toluene 98.00% by weight

The composition for forming a light emitting layer (3) is prepared by stirring the following components until they become a uniform solution.

Compound (A) 0.02% by weight

SPH-101 1.98wt%

Xylene 98.00% by weight

The composition for forming a light emitting layer (4) is prepared by stirring the following components until they become a uniform solution.

Compound (A) 0.02% by weight

DOBNA 1.98% by weight

Toluene 98.00% by weight

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

<Example 2-4>

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

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

<Example 2-5 and Example 2-6>

An organic EL element was obtained in the same manner as in Example 2-4 using the composition (3) or (4) for forming a light emitting layer.

<Evaluation of organic EL devices of Examples 2-4 to 2-6>

It can be expected that the coating type organic EL device obtained as described above will also have excellent drive voltage and external quantum efficiency similarly to the vapor deposition type organic EL device.

<Production of Organic EL Devices of Examples 2-7 to 2-9>

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

[Table 5]

<Preparation of Compositions (5) to (7) for Forming Light-Emitting Layer>

A composition for forming a light emitting layer (5) is prepared by stirring the following components until they become a uniform solution.

Compound (A) 0.02% by weight

2PXZ-TAZ 0.18% by weight

mCBP 1.80% by weight

Toluene 98.00% by weight

A composition for forming a light emitting layer (6) is prepared by stirring the following components until they become a uniform solution.

Compound (A) 0.02% by weight

2PXZ-TAZ 0.18% by weight

SPH-101 1.80% by weight

Xylene 98.00% by weight

A composition for forming a light emitting layer (7) is prepared by stirring the following components until they become a uniform solution.

Compound (A) 0.02% by weight

2PXZ-TAZ 0.18% by weight

DOBNA 1.80% by weight

Toluene 98.00% by weight

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

<Example 2-7>

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

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

<Example 2-8 and Example 2-9>

An organic EL element was obtained in the same manner as in Example 2-7 using the composition for forming a light emitting layer (6) or (7).

<Evaluation of organic EL devices of Examples 2-7 to 2-9>

It can be expected that the coating type organic EL device obtained as described above will also have excellent drive voltage and external quantum efficiency similarly to the vapor deposition type organic EL device.

As described above, some of the compounds according to the present invention were evaluated as materials for organic EL devices, showing that they were excellent materials, but other compounds not evaluated also had the same basic skeleton and had a similar structure as a whole. Since it is a compound having, it can be understood by those skilled in the art that it is similarly an excellent material for organic EL devices.

According to a preferred aspect of the present invention, by producing an organic EL device using an electron transport material containing a polycyclic aromatic compound represented by Formula (1), excellent driving voltage, luminous efficiency, and device lifetime, particularly luminous efficiency and an organic EL device having excellent device lifetime.

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 (10)

polycyclic aromatic compounds represented by the following general formula (1);

In the above formula (1),
R ¹ to R ¹¹ are each independently hydrogen, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl , trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkyldicycloalkylsilyl, the two aryls of the diarylamino may be bonded through a linking group, and the two heteroaryls of the diheteroarylamino Aryl may be bonded through a linking group, the aryl and heteroaryl of the arylheteroarylamino may be bonded through a linking group, and the two aryls of the diarylboryl may be bonded through a linking group,
Adjacent groups among R ¹ to ^{R 11} are bonded together to form a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbocyclic ring together with at least one of ring a, ring b, and ring c. A basol ring may be formed, and at least one hydrogen in the formed ring is each independently diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, It may be substituted with alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkyldicycloalkylsilyl, and the two aryls of the diarylamino form a linking group may be bonded through, the two heteroaryls of the diheteroarylamino may be bonded through a linking group, the aryl and heteroaryl of the arylheteroarylamino may be bonded through a linking group, and two of the diarylboryls The dog aryl may be bonded through a linking group,
However, at least one group represented by the general formula (G) is bonded to the "a ring" or "the ring formed with the a ring", and the "b ring" or "the ring formed with the b ring" is represented by the general formula (G) At least one of the groups represented is bonded, and at least one group represented by the general formula (G) is bonded to "c ring" or "ring formed with c ring", and these groups represented by formula (G) may be the same or different, respectively. become,
In the above formula (G),
Cy ¹ and Cy ² are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted. and at least one hydrogen in these rings is each independently diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio , triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, or cyano may be substituted, and the two aryls of the diarylamino may be bonded through a linking group. , The two heteroaryls of the diheteroarylamino may be bonded through a linking group, the aryl and heteroaryl of the arylheteroarylamino may be bonded through a linking group, and the two aryls of the diarylboryl are a linking group may be bonded through, and * is a bond position to a ring, b ring, c ring, and a ring formed together with those rings, and,
At least one hydrogen in the compound represented by the formula (1) may be substituted with heavy hydrogen, cyano or halogen. According to claim 1,
In the above formula (1),
R ¹ to ^{R 11} are each independently hydrogen, diarylamino (provided that aryl is an aryl having 6 to 12 carbon atoms), diheteroarylamino (provided that heteroaryl is a heteroaryl having 2 to 15 carbon atoms), and arylheteroarylamino. (provided that aryl is aryl having 6 to 12 carbon atoms, heteroaryl is heteroaryl having 2 to 15 carbon atoms), diarylboryl (but aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, and carbon atoms 3 to 24 Cycloalkyl, alkenyl of 1 to 24 carbon atoms, alkoxy of 1 to 24 carbon atoms, aryloxy of 6 to 30 carbon atoms, arylthio of 6 to 30 carbon atoms, triarylsilyl (where aryl is aryl of 6 to 12 carbon atoms), tri Alkylsilyl (provided that alkyl is C1-C12 alkyl), tricycloalkylsilyl (provided that cycloalkyl is C3-C12 cycloalkyl), dialkylcycloalkylsilyl (provided that alkyl is C1-C12 alkyl, cycloalkyl is cycloalkyl having 3 to 12 carbon atoms), or alkyldicycloalkylsilyl (provided that alkyl is alkyl having 1 to 12 carbon atoms and cycloalkyl is cycloalkyl having 3 to 12 carbon atoms), and two aryls of the diarylamino are a linking group may be bonded through, the two heteroaryls of the diheteroarylamino may be bonded through a linking group, the aryl and heteroaryl of the arylheteroarylamino may be bonded through a linking group, and of the diarylboryl The two aryls may be bonded through a linking group, and the linking group is a single bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ -, -CH=CH-, -CR= CR-, -C≡C-, -N(-R)-, -O-, -S-, -C(-R) ₂ -, -Si(-R) ₂ -, or -Se-; are each independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, and at least one hydrogen in R may be substituted with alkyl or cycloalkyl,
Adjacent groups among R ¹ to ^{R 11} are bonded together to form a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbocyclic ring together with at least one of ring a, ring b, and ring c. A basol ring may be formed, and at least one hydrogen in the formed ring is each independently diarylamino (provided that aryl has 6 to 12 carbon atoms), diheteroarylamino (provided that heteroaryl has 2 carbon atoms) to 15 heteroaryl), arylheteroarylamino (provided that aryl is an aryl having 6 to 12 carbon atoms, and heteroaryl is a heteroaryl having 2 to 15 carbon atoms), diarylboryl (provided that aryl is an aryl having 6 to 12 carbon atoms), carbon atoms Alkyl of 1 to 24 carbon atoms, cycloalkyl of 3 to 24 carbon atoms, alkenyl of 1 to 24 carbon atoms, alkoxy of 1 to 24 carbon atoms, aryloxy of 6 to 30 carbon atoms, arylthio of 6 to 30 carbon atoms, triarylsilyl (provided that Aryl is aryl having 6 to 12 carbon atoms), trialkylsilyl (provided that alkyl is alkyl having 1 to 12 carbon atoms), tricycloalkylsilyl (provided that cycloalkyl is cycloalkyl having 3 to 12 carbon atoms), dialkylcycloalkylsilyl (provided that Alkyl is alkyl having 1 to 12 carbon atoms, cycloalkyl is cycloalkyl having 3 to 12 carbon atoms), or alkyldicycloalkylsilyl (however, alkyl is alkyl having 1 to 12 carbon atoms, and cycloalkyl is cycloalkyl having 3 to 12 carbon atoms). may be substituted, the two aryls of the diarylamino may be bonded through a linking group, the two heteroaryls of the diheteroarylamino may be bonded through a linking group, and the aryl and heteroaryl of the arylheteroarylamino Aryl may be bonded through a linking group, and the two aryls of the diarylboryl may be bonded through a linking group, and the linking group is a single bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ -, -CH=CH-, -CR=CR-, -C≡C-, -N(-R)-, -O-, -S-, -C(-R) ₂ -, - Si(-R) ₂ -, or -Se-, R is independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, and at least one hydrogen in R Is may be substituted with alkyl or cycloalkyl,
However, at least one group represented by the general formula (G) is bonded to the "a ring" or "the ring formed with the a ring", and the "b ring" or "the ring formed with the b ring" is represented by the general formula (G) At least one of the groups represented is bonded, and at least one group represented by the general formula (G) is bonded to "c ring" or "ring formed with c ring", and these groups represented by formula (G) may be the same or different, respectively. become,
In the above formula (G),
Cy ¹ and Cy ² are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted. And, at least one hydrogen in these rings is each independently diarylamino (provided that aryl is an aryl having 6 to 12 carbon atoms), diheteroarylamino (provided that heteroaryl is a heteroaryl having 2 to 15 carbon atoms), Arylheteroarylamino (where aryl is aryl having 6 to 12 carbon atoms, heteroaryl is heteroaryl having 2 to 15 carbon atoms), diarylboryl (where aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, carbon atoms Cycloalkyl of 3 to 24 carbon atoms, alkenyl of 1 to 24 carbon atoms, alkoxy of 1 to 24 carbon atoms, aryloxy of 6 to 30 carbon atoms, arylthio of 6 to 30 carbon atoms, triarylsilyl (provided that aryl has 6 to 12 carbon atoms aryl), trialkylsilyl (provided that alkyl has 1 to 12 carbon atoms), tricycloalkylsilyl (provided that cycloalkyl is cycloalkyl having 3 to 12 carbon atoms), dialkylcycloalkylsilyl (provided that alkyl has 1 to 12 carbon atoms) may be substituted with alkyl, cycloalkyl is cycloalkyl of 3 to 12 carbon atoms), alkyldicycloalkylsilyl (provided that alkyl is alkyl of 1 to 12 carbon atoms and cycloalkyl is cycloalkyl of 3 to 12 carbon atoms), or cyano; The two aryls of the diarylamino may be bonded through a linking group, the two heteroaryls of the diheteroarylamino may be bonded through a linking group, and the aryl and heteroaryl of the arylheteroarylamino are bonded through a linking group The two aryls of the diarylboryl may be bonded through a linking group, and the linking group is a single bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ - , -CH=CH-, -CR=CR-, -C≡C-, -N(-R)-, -O-, -S-, -C(-R) ₂ -, -Si(-R) ₂ -, or -Se-, R is independently hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, and at least one hydrogen in R is alkyl or It may be substituted with cycloalkyl, and * is a bonding position to a ring, b ring, c ring, and a ring formed together with those rings, and
At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium, cyano or halogen,
polycyclic aromatic compounds. According to claim 1,
In the above formula (1),
R ¹ to R ¹¹ are each independently hydrogen, diarylamino (provided that aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, alkoxy having 1 to 24 carbon atoms, Aryloxy of 6 to 30 carbon atoms or arylthio of 6 to 30 carbon atoms, and the two aryls of the diarylamino may be bonded through a linking group, and the linking group is a single bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ -, -CH=CH-, -CR=CR-, -C≡C-, -N(-R)-, -O-, -S-, -C (-R) ₂ -, -Si(-R) ₂ -, or -Se-, and R is, each independently, hydrogen, aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl, corresponding At least one hydrogen in R may be substituted with alkyl or cycloalkyl,
Adjacent groups among R ¹ to ^{R 11} are bonded together to form a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbocyclic ring together with at least one of ring a, ring b, and ring c. A basol ring may be formed, and at least one hydrogen in the formed ring is each independently diarylamino (provided that aryl is an aryl having 6 to 12 carbon atoms), an alkyl having 1 to 24 carbon atoms, and an alkyl having 3 to 24 carbon atoms. may be substituted with cycloalkyl, alkoxy having 1 to 24 carbon atoms, aryloxy having 6 to 30 carbon atoms, or arylthio having 6 to 30 carbon atoms, and the two aryls of the diarylamino may be bonded through a linking group, The linking group is a single bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ -, -CH=CH-, -CR=CR-, -C≡C-, -N( -R)-, -O-, -S-, -C(-R) ₂ -, -Si(-R) ₂ -, or -Se-, wherein R is, each independently, hydrogen, aryl, heteroaryl , Alkyl, alkenyl, alkynyl, or cycloalkyl, and at least one hydrogen in R may be substituted with alkyl or cycloalkyl,
However, at least one group represented by the general formula (G) is bonded to the "a ring" or "the ring formed with the a ring", and the "b ring" or "the ring formed with the b ring" is represented by the general formula (G) At least one of the groups represented is bonded, and at least one group represented by the general formula (G) is bonded to "c ring" or "ring formed with c ring", and these groups represented by formula (G) may be the same or different, respectively. become,
In the above formula (G),
Cy ¹ and Cy ² are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted. , and at least one hydrogen in this ring is each independently diarylamino (provided that aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, and 1 to 24 carbon atoms. Alkoxy of 24, aryloxy of 6 to 30 carbon atoms, arylthio of 6 to 30 carbon atoms, or cyano may be substituted, and the two aryls of the diarylamino may be bonded through a linking group, and the linking group is bond, -CH ₂ -CH ₂ -, -CHR-CHR-, -CR ₂ -CR ₂ -, -CH=CH-, -CR=CR-, -C≡C-, -N(-R)-, -O-, -S-, -C(-R) ₂ -, -Si(-R) ₂ -, or -Se-, wherein R is, each independently, hydrogen, aryl, heteroaryl, alkyl, alkenyl , Alkynyl, or cycloalkyl, and at least one hydrogen in R may be substituted with alkyl or cycloalkyl, and * is a bond position to a ring, b ring, c ring, and the rings formed together with those rings is, and
At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium, cyano or halogen,
polycyclic aromatic compounds. According to claim 1,
In the above formula (1),
R ¹ to ^{R 11} are each independently hydrogen, diarylamino (provided that aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, or cycloalkyl having 3 to 24 carbon atoms;
Adjacent groups among R ¹ to R ¹¹ are bonded together to form a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbocyclic ring together with at least one of ring a, ring b, and ring c. A basol ring may be formed, and at least one hydrogen in the formed ring is each independently diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, or carbon atoms 3 to 12 may be substituted with cycloalkyl of 24;
However, at least one group represented by the general formula (G) is bonded to the "a ring" or "the ring formed with the a ring", and the "b ring" or "the ring formed with the b ring" is represented by the general formula (G) At least one of the groups represented is bonded, and at least one group represented by the general formula (G) is bonded to "c ring" or "ring formed with c ring", and these groups represented by formula (G) may be the same or different, respectively. become,
In the above formula (G),
Cy ¹ and Cy ² are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted. , and at least one hydrogen in these rings is each independently diarylamino (provided that aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, or cyano. may be substituted, and * is a bonding position with a ring, b ring, c ring, and a ring formed together with those rings, and
At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium, cyano or halogen,
polycyclic aromatic compounds. According to claim 1,
In the above formula (1),
R ¹ to ^{R 11} are each independently hydrogen or alkyl having 1 to 24 carbon atoms;
However, at least one of R ¹ to ^{R 3} in the a ring, at least one of R ⁴ to ^{R 7} in the b ring, and at least one of R ⁸ to R ¹¹ in the c ring are represented by the general formula ( It is a group represented by G), and these groups represented by formula (G) may be the same or different, respectively,
In the above formula (G),
Cy ¹ and Cy ² are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring in which the N position may be phenyl substituted. And, at least one hydrogen in these rings may be each independently substituted with an alkyl having 1 to 24 carbon atoms or cyano, and * is a bonding position to the a ring, b ring, and c ring, and
At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium, cyano or halogen,
polycyclic aromatic compounds. According to claim 1,
A polycyclic aromatic compound represented by any one of the following structural formulas.

According to claim 1,
A polycyclic aromatic compound represented by any one of the following structural formulas.

A pair of electrodes comprising an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and a polycyclic aromatic compound according to any one of claims 1 to 7 disposed between the cathode and the light emitting layer. An organic electroluminescent device having at least one layer of an electron transport layer and an electron injection layer containing a compound. A display device comprising the organic electroluminescent element according to claim 8. A lighting device comprising the organic electroluminescent element according to claim 8.

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