Polycyclic aromatic compound, organic electroluminescent element, and display device or illumination device

Abstract

The present application relates to a polycyclic aromatic compound represented by formula (1) or a multimer of a polycyclic aromatic compound having a plurality of structures represented by formula (1) below, a compound, a crosslinked body, a material, and a device containing the same. The compound or the multimer of the present application is effective as a material for organic devices such as an organic EL element.

Description

Technical Field

[0001] This invention relates to a polycyclic aromatic compound, organic electroluminescent elements using the same, organic field-effective transistors and organic thin-film solar cells, as well as display devices and lighting devices. Furthermore, in this specification, "organic electroluminescent element" is sometimes referred to as "organic EL (Electroluminescence) element" or simply as "element," and particularly relates to a polycyclic aromatic compound or a polymer of a polycyclic aromatic compound, compounds containing the same, crosslinks, materials, and devices. Background Technology

[0002] Previously, display devices using electroluminescent elements were extensively researched due to their ability to achieve low power consumption or thinness. Furthermore, organic electroluminescent elements incorporating organic materials have been actively studied because they are easily lightweight and large-scale. In particular, the development of organic materials with luminescent properties such as blue (one of the three primary colors of light), and the development of organic materials with charge transport capabilities including holes and electrons (possibly having the potential to become semiconductors or superconductors), have been actively researched to date, involving both high-molecular-weight and low-molecular-weight compounds.

[0003] Organic EL devices have a structure comprising: a pair of electrodes including an anode and a cathode, and one or more layers disposed between the pair of electrodes and containing an organic compound. Among the layers containing the organic compound are light-emitting layers, or charge transport / injection layers for transporting or injecting charges such as holes and electrons, and various organic materials suitable for these layers have been developed.

[0004] In recent years, a boron-containing polycyclic aromatic compound has been developed as a material for the light-emitting layer, and an organic EL element using the aforementioned polycyclic aromatic compound has been reported (Patent Document 1). Furthermore, a polycyclic aromatic compound formed by introducing cycloalkyl groups into the aromatic ring of the compound has been developed, and an organic EL element using the aforementioned polycyclic aromatic compound has been reported (Patent Documents 2 and 3).

[0005] [Existing Technical Documents]

[0006] [Patent Literature]

[0007] [Patent Document 1] International Publication No. 2015 / 102118

[0008] [Patent Document 2] International Publication No. 2018 / 216990

[0009] [Patent Document 3] International Publication No. 2019 / 198699 Summary of the Invention

[0010] [The problem the invention aims to solve]

[0011] As mentioned above, various materials have been developed for use in organic EL devices, but in order to increase the selection of materials for organic EL devices, it is desirable to develop a material containing compounds that are different from those used before.

[0012] The problem of the present invention is to provide a novel compound that can be effectively used as a material for organic devices such as organic EL elements.

[0013] [Technical means to solve the problem]

[0014] The inventors conducted diligent research to solve the aforementioned problems and discovered that, for example, an organic EL element can be constructed by configuring a layer of a polycyclic aromatic compound containing a linker group introduced between an aromatic ring and a cycloalkyl group of a compound described in Patent Document 2 or Patent Document 3 between a pair of electrodes, thereby obtaining an excellent organic EL element, and thus completing the present invention. Specifically, the present invention provides a polycyclic aromatic compound or polymer thereof having a structure in which a cycloalkyl group is bonded to an aromatic ring via a linker group, and materials for organic devices, such as materials for organic EL elements containing such polycyclic aromatic compounds or polymers thereof.

[0015] <1> A polycyclic aromatic compound or a polymer of a polycyclic aromatic compound, the polycyclic aromatic compound being represented by the following formula (1), and the polymer of the polycyclic aromatic compound having a plurality of structures represented by the following formula (1).

[0016]

[0017] (In formula (1),)

[0018] Rings A, B, and C are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen atom in these rings may be substituted. Rings B and C may be linked by single bonds or linker bonds.

[0019] Y 1 The components are B, P, P=O, P=S, Al, Ga, As, Si-R, or Ge-R, wherein the R in Si-R and Ge-R is aryl or alkyl.

[0020] X 1 and X 2Each of the following can be independently represented as >O, >NR, >C(-R)2, >S, or >Se, wherein the R in >NR is a substituted aryl, substituted heteroaryl, substituted alkyl, or substituted cycloalkyl, and the R in >C(-R)2 is hydrogen, a substituted aryl, a substituted heteroaryl, a substituted alkyl, or a substituted cycloalkyl. Furthermore, the R in >NR and / or the R in >C(-R)2 can be bonded to the A, B, and / or C rings via a linking group or a single bond.

[0021] At least one of the aryl or heteroaryl rings in the compound represented by formula (1) or its polymer may be condensed from at least one cycloalkane, wherein at least one hydrogen atom in the cycloalkane may be substituted, and at least one -CH2- atom in the cycloalkane may be substituted with -O-.

[0022] In the compound represented by formula (1) or its polymer, at least one of the aryl ring or heteroaryl ring is substituted by at least one L-Cy, where L is a linear alkylene group having 1 to 6 carbons or a branched alkylene group having 2 to 6 carbons, at least one of the linear alkylene groups having 1 to 6 carbons or a branched alkylene group having 2 to 6 carbons having at least one -CH2- group substituted by -O-, -S-, -CO-, -COO-, -OCO- or -OCOO-, or at least one of the linear alkylene groups having 2 to 6 carbons having at least one -(CH2)2- group substituted by -CH=CH- or -C≡C-, and Cy is a cycloalkyl group.

[0023] (At least one hydrogen atom in the compound or polymer represented by formula (1) may be substituted by deuterium, cyano or halogen.)

[0024] <2> The polycyclic aromatic compound or polymer of the polycyclic aromatic compound described in <1>, wherein Cy is a cycloalkyl group having 3 to 20 carbon atoms.

[0025] <3> The polycyclic aromatic compound or polymer of the polycyclic aromatic compound according to <1> or <2>, wherein L is -CH2-, -CH2CH2-, -CH2CH2CH2-, -C(CH3)2-, -C(CH3)2CH2- or -C(CH3)2CH2CH2-.

[0026] <4> The polycyclic aromatic compound or polymer of a polycyclic aromatic compound according to any one of <1> to <3>, which is a polycyclic aromatic compound represented by formula (1-a), (1-b), (1-c), (1-d), (1-e) or (1-f) below, or a polymer of a polycyclic aromatic compound having a plurality of structures represented by formula (1-a), (1-b), (1-c), (1-d), (1-e) or (1-f) below.

[0027]

[0028] (In equations (1-a), (1-b), (1-c), (1-d), (1-e), and (1-f),

[0029] R 1 ~R 11 Each of the following is independently hydrogen, aryl, heteroaryl, diarylamino, diheterarylamino, arylheterarylamino, diarylboryl (the two aryl groups may be linked by a single bond or a linker group), alkyl, cycloalkyl, alkoxy, aryloxy, or substituted silyl, wherein at least one hydrogen atom may be substituted by an aryl, heteroaryl, alkyl, cycloalkyl, or substituted silyl group, R 1 ~R 11 The adjacent groups in the ring can be bonded to each other and together with ring a, ring b, or ring c to form an aryl ring or a heteroaryl ring. At least one hydrogen in the formed ring can be substituted by an aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryl groups can be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, aryloxy, or substituted silyl group. At least one hydrogen in these groups can be substituted by an aryl, heteroaryl, alkyl, cycloalkyl, or substituted silyl group. In formula (1-a), R 7 and R 8 They can bond with each other to form single bonds or linker groups.

[0030] X X Each of the following can be independently >O, >S, >NR, or >C(-R)2, wherein the R in >NR is a substituted aryl, a substituted heteroaryl, a substituted alkyl, or a substituted cycloalkyl, and the R in >C(-R)2 can be independently hydrogen, an aryl group substituted by an alkyl or cycloalkyl group, a heteroaryl group substituted by an alkyl or cycloalkyl group, an alkyl, or a cycloalkyl.

[0031] Y 1 The components are B, P, P=O, P=S, Al, Ga, As, Si-R, or Ge-R, wherein the R in Si-R and Ge-R is aryl or alkyl.

[0032] X 1 and X 2 Each can be independently represented as >O, >C(-R)2, or >NR, wherein the R in >NR is an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 15 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 14 carbon atoms. The aryl group having 6 to 12 carbon atoms and the heteroaryl group having 2 to 15 carbon atoms in the R of >NR can be substituted by an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, or a substituted silyl group. The R of >NR can be bonded to at least one of the a, b, and c rings via -O-, -S-, -C(-R)2-, or a single bond.

[0033] The R in the >C(-R)2 group is independently hydrogen, an aryl group with 6 to 12 carbon atoms, a heteroaryl group with 2 to 15 carbon atoms, an alkyl group with 1 to 6 carbon atoms, or a cycloalkyl group with 3 to 14 carbon atoms. The aryl group with 6 to 12 carbon atoms and the heteroaryl group with 2 to 15 carbon atoms in the R of the >C(-R)2 group can be substituted by an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 3 to 14 carbon atoms, or a substituted silyl group. The two R groups in the >C(-R)2 group can be bonded together to form a ring.

[0034] At least one of the aryl or heteroaryl rings in the compounds or polymers represented by formulas (1-a), (1-b), (1-c), (1-d), (1-e), and (1-f) may be condensed from at least one cycloalkane having 3 to 24 carbon atoms, wherein at least one hydrogen atom in the cycloalkane may be substituted by an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkyl group having 1 to 24 carbon atoms, or a cycloalkyl group having 3 to 24 carbon atoms, and at least one -CH2- atom in the cycloalkane may be substituted by -O- atom.

[0035] In each of the compounds or polymers represented by formulas (1-a), (1-b), (1-c), (1-d), (1-e), and (1-f), at least one of the aryl or heteroaryl rings is substituted by at least one L-Cy, where L is a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 2 to 6 carbon atoms, at least one of the linear alkylene groups having 1 to 6 carbon atoms or a branched alkylene group having 2 to 6 carbon atoms having at least one -CH2- group substituted by -O-, -S-, -CO-, -COO-, -OCO-, or -OCOO-, or at least one of the linear alkylene groups having 2 to 6 carbon atoms having at least one -(CH2)2- group substituted by -CH=CH- or -C≡C-, and Cy is a cycloalkyl group.

[0036] In each of the compounds or polymers represented by formulas (1-a), (1-b), (1-c), (1-d), (1-e), and (1-f), at least one hydrogen atom may be substituted by a cyano group, a halogen, or a deuterium group, and,

[0037] In the case of polymers, they are dimers or trimers having two or three structures represented by formula (1-a), (1-b), (1-c), (1-d), (1-e), or (1-f).

[0038] <5> The polycyclic aromatic compound or polymer of the polycyclic aromatic compound described in <4> is a polycyclic aromatic compound represented by formula (1-a) or a polymer of polycyclic aromatic compounds having a plurality of structures represented by formula (1-a).

[0039] <6> The polycyclic aromatic compound or polymer of the polycyclic aromatic compound described in <5> is represented by any of the following structural formulas.

[0040]

[0041]

[0042] (In the above structural formulas, "Me" represents methyl and "tBu" represents tert-butyl.)

[0043] <7> The polycyclic aromatic compound or polymer of the polycyclic aromatic compound described in <4> is a polycyclic aromatic compound represented by formula (1-b) or a polymer of a plurality of polycyclic aromatic compounds having the structure represented by formula (1-b).

[0044] <8> The polycyclic aromatic compound or polymer of the polycyclic aromatic compound described in <7> is represented by the following structural formula.

[0045]

[0046] (In the structural formula, "Me" represents methyl)

[0047] <9> A reactive compound formed by substituting a reactive substituent into a polycyclic aromatic compound or a polymer of a polycyclic aromatic compound according to any one of <1> to <8>.

[0048] <10> A polymeric compound or a polymeric crosslinker, wherein the polymeric compound is obtained by polymerizing the reactive compound according to <9> as a monomer, and the polymeric crosslinker is obtained by further crosslinking the polymeric compound.

[0049] <11> A suspended polymer compound or a suspended polymer crosslinker, wherein the suspended polymer compound is formed by substituting a reactive compound according to <9> into a main-chain polymer, and the suspended polymer crosslinker is formed by further crosslinking the suspended polymer compound.

[0050] <12> A material for an organic device, comprising a polycyclic aromatic compound or a polymer of a polycyclic aromatic compound according to any one of <1> to <8>, a reactive compound according to <9>, a polymeric compound or a polymeric crosslinker according to <10>, or a suspended polymeric compound or a suspended polymeric crosslinker according to <11>.

[0051] <13> The organic device material according to <12>, wherein the organic device material is an organic electroluminescent element material, an organic field-effective transistor material, or an organic thin-film solar cell material.

[0052] <14> The organic device material according to <13>, wherein the organic electroluminescent element material is a light-emitting layer material.

[0053] <15> A composition comprising a polycyclic aromatic compound or a polymer thereof according to any one of <1> to <8>, a reactive compound according to <9>, a polymeric compound or a polymeric crosslinker according to <10>, or a suspended polymeric compound or a suspended polymeric crosslinker according to <11>, and an organic solvent.

[0054] <16> An organic electroluminescent element comprising: a pair of electrodes, including an anode and a cathode; and an organic layer disposed between the pair of electrodes, and containing a polycyclic aromatic compound or a polymer of a polycyclic aromatic compound according to any one of <1> to <8>, a reactive compound according to <9>, a polymeric compound or a polymeric crosslinker according to <10>, or a suspended polymeric compound or a suspended polymeric crosslinker according to <11>.

[0055] <17> An organic electroluminescent element comprising: a pair of electrodes, including an anode and a cathode; and a light-emitting layer disposed between the pair of electrodes, and containing a polycyclic aromatic compound or a polymer of a polycyclic aromatic compound according to any one of <1> to <8>, a reactive compound according to <9>, a polymeric compound or a polymeric crosslinker according to <10>, or a suspended polymeric compound or a suspended polymeric crosslinker according to <11>.

[0056] <18> The organic electroluminescent element according to <17>, wherein the light-emitting layer comprises a host, and the polycyclic aromatic compound or polymer of the polycyclic aromatic compound as a dopant, the reactive compound, the polymer compound or polymer crosslinker, or the suspended polymer compound or suspended polymer crosslinker.

[0057] <19> The organic electroluminescent element according to <18>, wherein the main body is anthracene compound, fluorene compound, or dibenzo[a]benzene compound. System of compounds.

[0058] <20> An organic electroluminescent element according to any one of <16> to <19>, having an electron transport layer and / or an electron injection layer disposed between the cathode and the light-emitting layer, wherein at least one of the electron transport layer and the electron injection layer contains at least one selected from the group consisting of borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzo[a]fluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, aryl nitrile derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, hydroxyquinoline metal complexes, thiazole derivatives, benzo[a]thiazole derivatives, thiophene derivatives, and azoline derivatives.

[0059] <21> The organic electroluminescent element according to <20>, wherein the electron transport layer and / or electron injection layer further comprises at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals.

[0060] <22> An organic electroluminescent element according to any one of <16> to <21>, wherein at least one layer of the organic layer disposed between the pair of electrodes comprises a polymeric compound formed by polymerizing a low-molecular-weight compound capable of forming each layer as a monomer, or a polymeric cross-linked compound formed by further cross-linking the polymeric compound, or a suspended polymeric compound formed by reacting a low-molecular-weight compound capable of forming each layer with a main-chain polymer, or a suspended polymeric cross-linked compound formed by further cross-linking the suspended polymeric compound.

[0061] <23> A display device or lighting device comprising an organic electroluminescent element according to any one of <16> to <22>.

[0062] [The effects of the invention]

[0063] This invention provides a novel polycyclic aromatic compound. The polycyclic aromatic compound of this invention can be used as a material for organic devices, such as materials for organic EL elements. Attached Figure Description

[0064] Figure 1 This is a schematic cross-sectional view showing the organic EL element of this embodiment.

[0065] Explanation of symbols

[0066] 100: Organic electroluminescent element

[0067] 101: Substrate

[0068] 102: Anode

[0069] 103: Hole Injection Layer

[0070] 104: Hole Transport Layer

[0071] 105: Emissive layer

[0072] 106: Electron Transport Layer

[0073] 107: Electron Injection Layer

[0074] 108: Cathode Detailed Implementation

[0075] The present invention will now be described in detail. The descriptions of the constituent elements described below are sometimes based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. Furthermore, in this specification, the numerical range indicated by “~” refers to the range including the values ​​described before and after “~” as both the lower and upper limits. Additionally, in this specification, “hydrogen” in the description of the structural formula refers to “hydrogen atom (H)”.

[0076] Furthermore, in this specification, the number of carbon atoms is sometimes used to represent chemical structures or substituents. However, when a substituent is substituted in a chemical structure, or when a substituent is further substituted on a substituent, the number of carbon atoms refers to the individual carbon atom of the chemical structure or substituent, and not the total number of carbon atoms of the chemical structure and the substituent, or the total number of carbon atoms of the substituents. For example, the phrase "substituent B with carbon atom number X replaced by substituent A with carbon atom number X" means that "substituent A with carbon atom number X" is substituted on "substituent B with carbon atom number Y," and the number of carbon atoms Y is not the total number of carbon atoms of substituent A and substituent B. Similarly, the phrase "substituent B with carbon atom number Y replaced by substituent A" means that "substituent A (without a specific number of carbon atoms) is substituted on "substituent B with carbon atom number Y," and the number of carbon atoms Y is not the total number of carbon atoms of substituent A and substituent B.

[0077] 1. Polycyclic aromatic compounds and their polymers

[0078] The present invention relates to a polycyclic aromatic compound represented by the following formula (1) or a polymer of a plurality of polycyclic aromatic compounds having the structure represented by the following formula (1).

[0079] The polycyclic aromatic compounds represented by formula (1) are polycyclic aromatic compounds with a basic skeleton formed by linking aromatic rings using heterogeneous elements such as boron, phosphorus, oxygen, nitrogen, and sulfur. Compounds with this basic skeleton have a large highest occupied molecular orbital (HOMO) - lowest unoccupied molecular orbital (LUMO) gap (band gap Eg of the thin film) and a high triplet excitation energy (Eg). T The reason is believed to be that the 6-membered ring containing the heteroelement has low aromaticity, thus suppressing the reduction of the HOMO-LUMO gap associated with the expansion of the conjugation system. Furthermore, the electronic perturbation of the heteroelement leads to the localization of the single-occupied molecular orbitals (SOMO1) and SOMO2 in the triplet excited state (T1). Additionally, in polycyclic aromatic compounds with the aforementioned basic skeleton, the localization of SOMO1 and SOMO2 in the triplet excited state (T1) reduces the exchange interaction between the two orbitals, thus decreasing the energy difference (ΔE) between the triplet excited state (T1) and the singlet excited state (S1). S1T1 It has a small fluorescence density and exhibits thermally active delayed fluorescence, making it effective as a fluorescent material for organic EL devices. Furthermore, it possesses a high triplet excitation energy (Et). T These materials are also effectively used as electron transport layers or hole transport layers in phosphorescent organic EL elements or organic EL elements utilizing thermally active delayed fluorescence. Furthermore, the energies of HOMO and LUMO can be arbitrarily varied by introducing substituents into these polycyclic aromatic compounds (the basic skeleton), thus optimizing the ionization potential or electron affinity according to the surrounding materials.

[0080] In addition to the characteristics of this basic framework, the compounds of the present invention, by introducing cycloalkyl groups, can be expected to have a lower melting point or sublimation temperature. This means that in sublimation purification, which is almost indispensable in the purification methods for organic devices such as organic EL elements requiring high purity, purification can be carried out at a relatively low temperature, thus avoiding thermal decomposition of the material. Furthermore, this also applies to vacuum evaporation processes, which are powerful means of manufacturing organic devices such as organic EL elements; the process can be carried out at a relatively low temperature, thus avoiding thermal decomposition of the material, resulting in high-performance materials for organic devices. Moreover, polymers of polycyclic aromatic compounds are often compounds with high sublimation temperatures due to their high molecular weight or high planarity; therefore, the reduction in sublimation temperature caused by introducing cycloalkyl groups becomes more effective. In addition, the increased solubility in organic solvents due to the introduction of cycloalkyl groups also allows for application in the fabrication of elements using coating processes. Furthermore, in the compounds of the present invention, the cycloalkyl group is bonded to the basic skeletal portion of the polycyclic aromatic compound via a linking group, thereby achieving direct bonding of the cycloalkyl group. This results in improved solubility in organic solvents, fewer film defects during coating processes, and the provision of coating films with excellent smoothness. Additionally, by using the compounds of the present invention with this structure in component materials, components with higher efficiency and longer lifespans can be provided.

[0081] The polycyclic aromatic compound represented by formula (1) or a polymer of a plurality of polycyclic aromatic compounds having the structure represented by formula (1) below is preferably a polycyclic aromatic compound or a polymer thereof represented by formula (1-a), formula (1-b), formula (1-c), formula (1-d), formula (1-e) or formula (1-f) below.

[0082]

[0083] In addition, in each structural formula, “A” to “C” and “a” to “c” are symbols representing ring structures represented by a ring, a benzene ring or a 5-membered ring, respectively, and the other symbols are the same as those defined above.

[0084] The polycyclic aromatic compound represented by formula (1) or a polymer of a polycyclic aromatic compound having a structure represented by multiple formulas (1), or at least one of the aryl rings or heteroaryl rings in the structure is bonded to a cycloalkyl group via a linking group. Specifically, at least one of the aryl rings or heteroaryl rings is substituted with at least one L-Cy. Here, L is a linking group and Cy is a cycloalkyl group.

[0085] The linker L is a straight-chain alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 2 to 6 carbon atoms; at least one of the straight-chain alkylene groups having 1 to 6 carbon atoms or a branched alkylene group having 2 to 6 carbon atoms is a linker group in which -CH2- is substituted by -O-, -S-, -CO-, -COO-, -OCO- or -OCOO-; or at least one of the straight-chain alkylene groups having 2 to 6 carbon atoms is a linker group in which -(CH2)2- is substituted by -CH=CH- or -C≡C-.

[0086] The cycloalkyl group is preferably a cycloalkyl group having 3 to 24 carbon atoms, more preferably a cycloalkyl group having 3 to 20 carbon atoms, and even more preferably a cycloalkyl group having 3 to 16 carbon atoms, particularly preferably a cycloalkyl group having 3 to 14 carbon atoms. The cycloalkyl group may also be a cycloalkyl group having 5 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a cycloalkyl group having 5 carbon atoms, etc. Furthermore, in this specification, "cycloalkyl group" includes not only monocyclic cycloalkyl groups such as cyclohexyl, but also polycyclic cycloalkyl groups such as adamantyl.

[0087] Specific examples of cycloalkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and their alkyl (especially methyl) substituted derivatives having 1 to 5 carbon atoms, or norbornane, bicyclo[1.0.1]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.2.2]octyl, adamantyl, diadamantyl, decahydronaphthalenyl, decahydroazulenyl, etc. Preferably, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and their alkyl (especially methyl) substituted derivatives having 1 to 5 carbon atoms, or norbornene, bicyclo[1.0.1]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.2.2]octyl, adamantyl, and particularly preferably cyclohexyl, norbornene, bicyclo[2.2.2]octyl, adamantyl, and diadamantyl.

[0088] The linker L is a straight-chain alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 2 to 6 carbon atoms. At least one of the following links—a straight-chain alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 2 to 6 carbon atoms—is a linker group in which at least one of the -CH2- groups is substituted with -O-, -S-, -CO-, -COO-, -OCO-, or -OCOO-, or at least one of the straight-chain alkylene groups having 2 to 6 carbon atoms—is a linker group in which at least one of the -(CH2)2- groups is substituted with -CH=CH- or -C≡C-. Preferably, it is a straight-chain alkylene group having 1 to 6 carbon atoms, a branched alkylene group having 3 to 6 carbon atoms, or -O-, and particularly preferably a straight-chain alkylene group having 1 to 3 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms. Specifically, it is preferably -CH2-, -CH2CH2-, -CH2CH2CH2-, -C(CH3)2-, -C(CH3)2CH2-, or -C(CH3)2CH2CH2-. Furthermore, -C(CH3)2CH2- and -C(CH3)2CH2CH2- are preferably bonded to Cy with the right-hand side, i.e., -C(CH3)2CH2-Cy and -C(CH3)2CH2CH2-Cy, respectively, as L-Cy. Additionally, the linker L is more preferably -CH2-, -C(CH3)2-, or -C(CH3)2CH2CH2-. This linker structure further improves solubility in organic solvents, and by using compounds with this structure in component materials, components with higher efficiency and longer lifespans can be provided.

[0089] Furthermore, the preferred linking group is a linear alkyl group bonded to the aromatic ring (aryl ring or heteroaryl ring) in a polymer of a polycyclic aromatic compound represented by formula (1) or a polycyclic aromatic compound having a structure represented by multiple formulas (1), and has at least one substituted hydrogen atom bonded to a carbon atom adjacent to a carbon atom of the aromatic ring; more preferably, it is a linking group substituted with two hydrogen atoms. Examples of such substituents include alkyl groups having 1 to 5 carbon atoms (especially methyl), halogens (especially fluorine), and deuterium.

[0090] In formula (1), rings A, B, and C are each an aryl ring or a heteroaryl ring. At least one hydrogen atom in these rings may be substituted.

[0091] Preferably, at least one of rings A, B, and C is an aryl ring having at least one substituent or a heteroaryl ring having at least one substituent. More preferably, rings A, B, and C are all aryl rings having at least one substituent or heteroaryl rings having at least one substituent. More preferably, rings A, B, and C are aryl rings having one substituent or heteroaryl rings having one substituent, respectively.

[0092] As substituents at this time, L-Cy is preferred, along with substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino (an amino group having both aryl and heteroaryl groups), substituted or unsubstituted diarylboroyl (the two aryl groups may be linked by a single bond or a linker), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, or substituted silyl. Examples of substituents when these groups have substituents include: L-Cy, aryl, heteroaryl, alkyl, cycloalkyl, diarylamino, and substituted silyl.

[0093] As substituents other than L-Cy, substituted or unsubstituted alkyl groups (especially neopentyl) and cycloalkyl groups such as adamantyl are particularly preferred. Additionally, tertiary alkyl groups (tR) are preferred. This is because the large volume of the substituent increases the intermolecular distance, thereby improving the photoluminescence quantum yield (PLQY).

[0094] The tertiary alkyl group is represented by the following formula (tR).

[0095]

[0096] In equation (tR), R a R b and R c Each is an alkyl group having 1 to 24 carbon atoms, wherein any -CH2- in the alkyl group may be substituted with -O-, and the group represented by formula (tR) is substituted at * with at least one hydrogen atom in the compound or structure represented by formula (1).

[0097] R a R b and R c The term "alkyl group having 1 to 24 carbon atoms" can be either straight-chain or branched. Examples include: straight-chain alkyl groups having 1 to 24 carbon atoms or branched alkyl groups having 3 to 24 carbon atoms, alkyl groups having 1 to 18 carbon atoms (branched alkyl groups having 3 to 18 carbon atoms), alkyl groups having 1 to 12 carbon atoms (branched alkyl groups having 3 to 12 carbon atoms), alkyl groups having 1 to 6 carbon atoms (branched alkyl groups having 3 to 6 carbon atoms), and alkyl groups having 1 to 4 carbon atoms (branched alkyl groups having 3 to 4 carbon atoms).

[0098] In equation (1), R in equation (tR) a R b and R c The total number of carbons is preferably 3 to 20, and more preferably 3 to 10.

[0099] As Ra R b and R c Specific alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, etc.

[0100] Examples of groups represented by formula (tR) include: tert-butyl, tert-pentyl, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1,1,3,3-tetramethylbutyl, 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. Among these, tert-butyl and tert-pentyl are preferred.

[0101] Furthermore, substituted or unsubstituted diarylamino groups are preferred as substituents. This is because the large substituent increases the intermolecular distance, thus improving the luminescent quantum yield (PLQY). Examples include R in polycyclic aromatic compounds represented by formula (1-a) and their polymers. 2 It is a compound of substituted or unsubstituted diarylamino group (preferably unsubstituted diarylamino group).

[0102] Other preferred examples of substituents in rings A, B, and C include diarylamino groups substituted with the group of formula (tR), carbazolyl groups substituted with the group of formula (tR), or benzocarbazolyl groups substituted with the group of formula (tR). Regarding "diarylamino group," groups described below as "first substituents" can be listed. Examples of substitution forms for the group of formula (tR) of diarylamino, carbazolyl, and benzocarbazolyl groups, where some or all of the hydrogen atoms in the aryl ring or benzene ring are substituted with the group of formula (tR), can be listed.

[0103] The aryl rings or heteroaryl rings in rings A, B, and C may have the same characteristics as those containing Y. 1 X 1 and X 2 The central condensed two-ring structure of formula (1) has a total of 5-membered or 6-membered rings with bonds.

[0104] Here, the so-called "condensed two-ring structure" refers to the structure shown in the center of equation (1) that contains Y. 1 X 1 and X 2 The structure is formed by the condensation of two saturated hydrocarbon rings. Furthermore, the term "a 6-membered ring sharing bonds with the condensed bicyclic structure" refers to a 6-membered ring (e.g., a benzene ring) condensed within the condensed bicyclic structure. Additionally, the term "(as ring A) aryl ring or heteroaryl ring having the 6-membered ring" means that ring A is formed solely by the 6-membered ring, or that ring A is formed by the condensation of other rings within the 6-membered ring in a manner that includes the 6-membered ring. In other words, the term "(as ring A) aryl ring or heteroaryl ring having a 6-membered ring" as used here refers to the condensation of all or part of the 6-membered ring constituting ring A within the condensed bicyclic structure. The same explanation applies to "ring B," "ring C," and "5-membered ring."

[0105] In formula (1), ring A corresponds to ring a and its substituent R in formulas (1-a), (1-b), (1-c), (1-d), (1-e), and (1-f). 1 ~Substituent R 3 The B ring in equation (1) corresponds to the b ring and its substituent R in equations (1-a), (1-b), and (1-c). 8 ~Substituent R 11 The b ring in formula (1-d) and its substituent R 10 and substituent R 11 and the b ring and its substituent R in formulas (1-e) and (1-f) 8 and substituent R 9 The C ring in equation (1) corresponds to the c ring in equation (1-a) and its substituent R. 4 ~Substituent R 7The c-ring and its substituent R in formulas (1-b), (1-d), and (1-f) 4 and substituent R 5 and the c ring and its substituent R in formulas (1-c) and (1-e) 6 and substituent R 7 That is, equation (1-a) corresponds to selecting a ring with at least a 6-membered ring structure as the structure of rings A to C in equation (1), and equations (1-b), (1-c), (1-d), (1-e), and (1-f) correspond to selecting a ring with at least a 6-membered ring structure and a ring with at least a 5-membered ring structure as the structure of rings A to C in equation (1), respectively. In this sense, each ring in equation (1-a) is represented by lowercase letters a to c.

[0106] X in equations (1-b), (1-c), (1-d), (1-e), and (1-f) X Each of the above can be independently >O, >S, >NR, or >C(-R)2. Here, the R in >NR is a substituted aryl, a substituted heteroaryl, a substituted alkyl, or a substituted cycloalkyl, preferably a substituted aryl, more preferably an unsubstituted aryl. Additionally, the R in >C(-R)2 can be independently hydrogen, an aryl that can be substituted by an alkyl or cycloalkyl, a heteroaryl that can be substituted by an alkyl or cycloalkyl, an alkyl or cycloalkyl, preferably an alkyl, more preferably methyl. The two Rs in >C(-R)2 are preferably the same. Furthermore, the two Rs in >C(-R)2 are also preferably bonded together to form a ring.

[0107] In equations (1-a), (1-b), (1-c), (1-d), (1-e), and (1-f), R 1 ~R 11 Each of these groups can be independently L-Cy, hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboroyl (the two aryl groups may be linked by a single bond or a linker), alkyl, cycloalkyl, alkoxy, aryloxy, or substituted silyl. At least one hydrogen group may be substituted by an aryl, heteroaryl, alkyl, cycloalkyl, or substituted silyl group. The aryl and heteroaryl groups may be substituted by L-Cy.

[0108] R 1 ~R 11 Each of the following is preferably L-Cy, hydrogen, alkyl (especially the tertiary alkyl (tR), neopentyl, etc.), cycloalkyl (e.g., adamantyl alkyl), substituted or unsubstituted diarylamino, or substituted silyl (triphenylsilyl, trimethylsilyl, etc.).

[0109] Preferably, R in formulas (1-a), (1-b), (1-c), (1-d), (1-e), and (1-f) is preferred. 1 ~R 3 In this group, 0 to 1 group are non-hydrogen groups (especially the preferred substituents) and the rest are hydrogen groups, R 4 ~R 7 In this group, 0 to 1 group are non-hydrogen groups (especially the preferred substituents) and the rest are hydrogen groups, R 8 ~R 11 In this group, 0 to 1 group are non-hydrogen groups (especially the preferred substituents), and the others are hydrogen.

[0110] More preferably: R 1 ~R 3 In this group, one is a group other than hydrogen (especially the preferred substituents) and the others are hydrogen, R 4 ~R 7 In this group, one is a group other than hydrogen (especially the preferred substituents) and the others are hydrogen, R 8 ~R 11 In this group, one is a group other than hydrogen (especially the preferred substituents) and the others are hydrogen.

[0111] In formulas (1-a), (1-b), (1-c), (1-d), (1-e), and (1-f), the substituents R of rings a, b, and c are... 1 ~Substituent R 11 The adjacent groups in the ring can be bonded to each other and together with ring a, ring b, or ring c to form an aryl ring or a heteroaryl ring. At least one hydrogen atom in the formed ring can be substituted by L-Cy, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryl groups can be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, aryloxy, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkyldicycloalkylsilyl. Additionally, at least one hydrogen atom in these groups can be substituted by aryl, heteroaryl, alkyl, or cycloalkyl. The aryl and heteroaryl groups in these groups can be substituted by L-Cy.

[0112] Therefore, for the polycyclic aromatic compounds represented by formulas (1-a), (1-b), (1-c), (1-d), (1-e), and (1-f), the ring structure of the compound changes depending on the bonding morphology of the substituents in rings a, b, and c. For example, for the polycyclic aromatic compound represented by formula (1-a), the ring structure of the compound changes as shown in formulas (1-a-1) and (1-a-2) below. In each formula, rings A', B', and C' correspond to rings A, B, and C in formula (1), respectively.

[0113]

[0114] If explained using formula (1-a), then the A' ring, B' ring, and C' ring in formulas (1-a-1) and (1-a-2) represent substituents R. 1 ~Substituent R 11 The adjacent groups in the formula are bonded to each other and together with the a ring, b ring, and c ring to form an aryl ring or heteroaryl ring (also referred to as a fused ring formed by the condensation of other ring structures in the a ring, b ring, or c ring). Furthermore, although not shown in the formula, there are compounds in which the a ring, b ring, and c ring are all transformed into the A' ring, B' ring, and C' ring, respectively. Additionally, as can be seen from formulas (1-a-1) and (1-a-2), for example, the R of the b ring in formula (1-a)... 8 R with c ring 7 R of ring b 11 R with ring a 1 R of c ring 4 R with ring a 3 Examples of such bases do not meet the requirement of "adjacent bases to each other," and unless otherwise specified, they will not form bonds. That is, "adjacent bases" refers to bases that are adjacent to each other on the same ring.

[0115] The compound represented by formula (1-a-1) or formula (1-a-2) is, for example, a compound having a benzene ring, indole ring, pyrrole ring, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, cyclopentadiene ring, or indene ring formed by condensation of a benzene ring (or b ring or c ring) as ring a in formula (1-a) to form a ring A' (or b ring or c ring), wherein the formed fused ring A' (or b ring or c ring) is a naphthylene ring, carbazole ring, indole ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, indene ring, or fluorene ring.

[0116] Furthermore, in formulas (1-b), (1-c), (1-d), (1-e), and (1-f), fused rings formed by the condensation of other ring structures in ring a, ring b, or ring c can also be formed in the same way. For example, the benzene ring, which is ring a or ring b, can be condensed with other ring structures in the same way as the benzene ring in formula (1-a) to form a fused ring.

[0117] In equations (1-b), (1-c), (1-d), (1-e), and (1-f), it is particularly preferred that R is in a 5-membered ring that is either a b-ring or a c-ring. 4 ~R 11 Adjacent bases in the rings bond together to form rings, thus forming fused rings. For example, in the c-ring of equations (1-b) and (1-c), and the b-ring and c-ring of equations (1-d), (1-e), and (1-f), R 3 ~R 11The adjacent groups in the ring bond together to form a ring, thereby forming a B' ring or C' ring as a fused ring. Examples of fused rings where the formed ring is a benzene ring include: indole ring, benzofuran ring, and benzothiophene ring.

[0118] For example, in equations (1-b), (1-c), (1-d), (1-e), and (1-f), for example, when X X When the value is >0, ring b or ring c becomes a furan ring, but the ring corresponding to ring B' or ring C' of formula (1-a-1) formed by the condensation of the benzene ring with respect to the furan ring is a benzofuran ring.

[0119] Additionally, for example, in equations (1-b), (1-c), (1-d), (1-e), and (1-f), for instance, when X X When the value is greater than S, the b ring or c ring becomes a thiophene ring, but the ring corresponding to the B' ring or C' ring of formula (1-a-1) formed by the condensation of the benzene ring with respect to the thiophene ring is a benzothiophene ring.

[0120] As an example, the following shows R in a 5-membered ring that is a c-ring in equation (1-b). 4 and R 5 Examples of fused rings formed by bonding together to form benzene rings.

[0121]

[0122] In equation (1-b-1), R 1 R 2 R 3 R 8 R 9 R 10 R 11 X X Y 1 X 1 and X 2 The meanings of R are the same as those in equation (1-b), and the preferred ranges are also the same. 4b R 5b R 6b R 7b The substituent is L-Cy, hydrogen, or a substituent selected from the group consisting of aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboroyl (the two aryl groups may be linked by a single bond or a linker), alkyl, cycloalkyl, alkoxy, aryloxy, and substituted silyl, wherein at least one hydrogen atom in these substituents may be substituted by an aryl, heteroaryl, alkyl, cycloalkyl, or substituted silyl. Additionally, the aryl and heteroaryl groups in these groups may be substituted by L-Cy. 4b R 5b R 6b R7b Preferably, 0 to 2 of the substituents are other than hydrogen and the rest are hydrogen; more preferably, 1 of the substituents is other than hydrogen and the rest are hydrogen. Regarding substituents other than hydrogen, a preferred range can be found in the description of substituents described below as first substituents (which may have second substituents). As substituents other than hydrogen, alkyl groups (especially the aforementioned tertiary alkyl (tR), neopentyl, etc.), cycloalkyl groups (e.g., adamantyl, etc.), or substituted or unsubstituted diarylamino groups are particularly preferred.

[0123] Y in equation (1) 1 For B, P, P=O, P=S, Al, Ga, As, Si-R, or Ge-R. Y 1 In Si-R and Ge-R, the R is independently aryl or alkyl, respectively. In Y... 1 In the cases of P=O, P=S, Si-R, or Ge-R, the atoms bonded to ring A, ring B, or ring C are P, Si, or Ge. 1 Preferably, it is B, P, P=O, P=S, or Si-R, more preferably B, P, or P=O, and particularly preferably B. The description also applies to Y in formulas (1-a), (1-b), (1-c), (1-d), (1-e), (1-f), (1-a-3-1) to (1-a-3-3), (1-a-7-1), (1-a-7-2), (1-a-4), (1-a-4-1), (1-a-4-2), (1-a-5-1), (1-a-5-2), (1-a-5-3), (1-a-5-4), and (1-a-6). 1 .

[0124] X in equation (1) 1 and X 2 Each of these can be independently defined as >O, >NR, >C(-R)2, >S, or >Se, preferably >O, >C(-R)2, or >NR. X in equation (1) 1 and X 2 Preferably, at least one of them is >NR, more preferably both are >NR or X. 1 and X 2 If one of them is >NR and the other is >C(-R)2, the optimal choice is that both are >NR.

[0125] X 1 and X 2In the >C(-R)2, each R is independently hydrogen, a substituted aryl group, a substituted heteroaryl group, a substituted alkyl group, or a substituted cycloalkyl group, preferably an aryl group substituted by L-Cy, an alkyl group, or a cycloalkyl group; a heteroaryl group, an alkyl group, or a cycloalkyl group substituted by L-Cy, an alkyl group, or a cycloalkyl group. Here, as an aryl group, aryl groups with 6 to 10 carbon atoms (e.g., phenyl, naphthyl, etc.) are particularly preferred; as a heteroaryl group, heteroaryl groups with 2 to 15 carbon atoms (e.g., carbazolyl, etc.) are particularly preferred; as an alkyl group, alkyl groups with 1 to 5 carbon atoms (e.g., methyl, ethyl, etc.) are particularly preferred; as a cycloalkyl group, cycloalkyl groups with 5 to 10 carbon atoms (preferably cyclohexyl or adamantyl). The two Rs in >C(-R)2 are preferably the same, and the two Rs can be bonded to form a ring. The two Rs in >C(-R)2 are particularly preferably both methyl groups. Compounds that form a ring by two R bonds can be listed as compounds such as the following compounds (1-303).

[0126]

[0127] X 1 and X 2 In the case of >NR, R can be a substituted aryl group (of which, as a substituent, amino is preferred), a substituted heteroaryl group, a substituted alkyl group, or a substituted cycloalkyl group. Examples of aryl, heteroaryl, alkyl, or cycloalkyl groups described later can be listed. In particular, as an aryl group, aryl groups with 6 to 10 carbon atoms (e.g., phenyl, naphthyl, etc.) are preferred; as a heteroaryl group, heteroaryl groups with 2 to 15 carbon atoms (e.g., carbazolyl, etc.) are preferred; as an alkyl group, alkyl groups with 1 to 5 carbon atoms (e.g., methyl, ethyl, etc.) are preferred; and as a cycloalkyl group, cycloalkyl groups with 5 to 10 carbon atoms (preferably cyclohexyl or adamantyl). Furthermore, as a second substituent, alkyl groups such as L-Cy, methyl, tert-butyl, and pentyl, substituted silanes such as p-tert-butylphenyl and trimethylsilyl are preferred. The substitution position of the alkyl group is preferably para-position relative to the substitution position of N.

[0128] Specifically, X 1 and X 2 In the case of >NR, R is preferably an aryl group of 6-12 carbons or an alkyl group of 1-6 carbons that can be substituted by L-Cy, an alkyl group of 1-5 carbons, or a cycloalkyl group of 5-10 carbons. More preferably, it is a phenyl group that can be substituted by L-Cy or an alkyl group of 1-5 carbons. Even more preferably, it is an o-biphenyl group (a phenyl group with a phenyl group at the ortho position relative to N, or a 2-biphenyl group) that can be substituted by L-Cy or an alkyl group of 1-5 carbons. X is particularly preferred. 1 and X 2In the formula, >NR is either o-biphenyl. As an example, compounds represented by the following formula (1-221) can be listed.

[0129]

[0130] X 1 and X 2 The R in >NR can be bonded to at least one of the A, B, and C rings via a linker group or a single bond. Preferably, the linker group is -O-, -S-, or -C(-R)2-. Furthermore, the R in "-C(-R)2-" is hydrogen, alkyl, or cycloalkyl. This specification can be represented, for example, by a compound represented by the following formula (1-a-3-1) and having X. 1 or X 2 The ring structure introduced into fused rings B' and C'. That is, for example, a ring structure with other rings to introduce X. 1 (or X) 2 Compounds that form a B' ring (or C' ring) by condensation of a benzene ring, which is the b ring (or c ring) in formula (1-a). The resulting fused ring B' (or fused ring C') is, for example, a carbazole ring, a phenoxazine ring, a phenothiazine ring, or an acridine ring.

[0131] Alternatively, the specification can also be represented by a compound, which is represented by formula (1-a-3-2) or formula (1-a-3-3) and has X. 1 and / or X 2 The ring structure introduced into the fused ring A'. That is, for example, a ring structure with other rings to introduce X. 1 (and / or X) 2 Compounds that form an A' ring by condensation of the benzene ring, which is the a ring in formula (1-a), in a manner that allows for the formation of a fused ring A'. The resulting fused ring A' can be, for example, a carbazole ring, a phenoxazine ring, a phenothiazine ring, or an acridine ring.

[0132]

[0133] X in equations (1-a), (1-b), (1-c), (1-d), (1-e), and (1-f) 1 and X 2 Each can be independently >O, >C(-R)2, or >NR, with respect to the preferred range or specific examples of R, and X in equation (1). 1 and X 2 same.

[0134] The B and C rings of formula (1) or the b and c rings of formula (1-a) can be bonded using single bonds or linking groups. This configuration is represented by formula (1-a-7-1) or formula (1-a-7-2). In formulas (1-a-7-1) and (1-a-7-2), Xz represents a single bond or a linking group. Preferably, the linking group is -O-, -S-, or -C(-R)2-. Furthermore, the R in "-C(-R)2-" is hydrogen, alkyl, or cycloalkyl, and the two Rs can form a ring.

[0135]

[0136] The "aryl ring" of rings A, B and C in formula (1) can be aryl rings with 6 to 30 carbons, preferably aryl rings with 6 to 16 carbons, more preferably aryl rings with 6 to 12 carbons, and particularly preferably aryl rings with 6 to 10 carbons.

[0137] Specific examples of "aryl rings" include: benzene rings as monocyclic systems, biphenyl rings as bicyclic systems, naphthalene rings and indene rings as condensed bicyclic systems, terphenyl rings (m-terphenyl, o-terphenyl, p-terphenyl) as tricyclic systems, acenaphthene rings, fluorene rings, phenaene rings and phenanthrene rings as condensed tricyclic systems, triphenylene rings, pyrene rings and tetraphenylene rings as condensed tetracyclic systems, and perylene rings and pentaphenyl rings as condensed pentacyclic systems.

[0138] The "heteroaryl ring" of rings A, B, and C in formula (1) can be exemplified by heteroaryl rings having 2 to 30 carbon atoms, preferably heteroaryl rings having 2 to 25 carbon atoms, more preferably heteroaryl rings having 2 to 20 carbon atoms, and even more preferably heteroaryl rings having 2 to 15 carbon atoms, particularly preferably heteroaryl rings having 2 to 10 carbon atoms. Furthermore, the "heteroaryl ring" can be exemplified by heterocycles containing one to five heteroatoms selected from oxygen, sulfur, and nitrogen as ring-forming atoms, excluding carbon atoms. Moreover, the "heteroaryl ring" corresponds to the inclusion of X in formulas (1-b), (1-c), (1-d), (1-e), and (1-f). X The 5-membered ring or the "R" specified in equations (1-a), (1-b), (1-c), (1-d), (1-e), and (1-f) 1 ~R 11 "The adjacent groups in the ring are bonded to each other and together with the a ring, b ring or c ring to form a heteroaryl ring."

[0139] Specific examples of "heteroaryl rings" include: pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, oxadiazole ring, thiadiazole ring, triazole ring, tetraazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnamon ring, quinazoline ring, quinoxaline ring. Phthalorazine ring, naphthidine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxthia ring, phenoxazine ring, phenthiazine ring, phenazine ring, phenazasiline ring, indazine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazine ring, thiathracene ring, indole-carbazole ring, benzoindole-carbazole ring, benzobenzoindole-carbazole ring, naphthobenzofuran ring, etc.

[0140] At least one hydrogen atom in the "aryl ring" or "heteroaryl ring" may be a first substituent of a substituted or unsubstituted "aryl", a substituted or unsubstituted "heteroaryl", a substituted or unsubstituted "diarylamino", a substituted or unsubstituted "diheteroarylamino", a substituted or unsubstituted "arylheteroarylamino", a substituted or unsubstituted "diarylboroyl" (the two aryl groups may be linked by a single bond or a linker group), or a substituted or unsubstituted "alkyl". The substitution may be a substituted or unsubstituted "cycloalkyl", a substituted or unsubstituted "alkoxy", a substituted or unsubstituted "aryloxy", or a substituted "silyl", but the "aryl" or "heteroaryl", "aryl of "diarylamino", "heteroaryl of "diheteroarylamino", "aryl and heteroaryl of "arylheteroarylamino", "aryl of "diarylboryl" and "aryloxy" may be a monovalent group of the "aryl ring" or "heteroaryl ring".

[0141] Furthermore, the "alkyl" as the first substituent can be either straight-chain or branched, for example, straight-chain alkyl with 1 to 24 carbon atoms or branched alkyl with 3 to 24 carbon atoms. Preferably, it is an alkyl with 1 to 18 carbon atoms (branched alkyl with 3 to 18 carbon atoms), more preferably an alkyl with 1 to 12 carbon atoms (branched alkyl with 3 to 12 carbon atoms), further preferably an alkyl with 1 to 8 carbon atoms (branched alkyl with 3 to 8 carbon atoms), particularly preferably an alkyl with 1 to 6 carbon atoms (branched alkyl with 3 to 6 carbon atoms), and most preferably an alkyl with 1 to 5 carbon atoms (branched alkyl with 3 to 5 carbon atoms).

[0142] Specific alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl (t-pentyl)(t-amyl), n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-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-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, etc.

[0143] In addition, examples include: 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.

[0144] In addition, examples of "cycloalkyl" as the first substituent include cycloalkyl with 3 to 24 carbons, cycloalkyl with 3 to 20 carbons, cycloalkyl with 3 to 16 carbons, cycloalkyl with 3 to 14 carbons, cycloalkyl with 5 to 10 carbons, cycloalkyl with 5 to 8 carbons, cycloalkyl with 5 to 6 carbons, and cycloalkyl with 5 carbons.

[0145] Specific examples of cycloalkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and their alkyl (especially methyl) substituted derivatives having 1 to 5 carbon atoms, or norbornene, bicyclo[1.0.1]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.2.2]octyl, adamantyl, diadamantyl, decahydronaphthyl, decahydroazyl, etc.

[0146] Furthermore, examples of "alkoxy groups" as the first substituent include straight-chain alkoxy groups having 1 to 24 carbon atoms or branched-chain alkoxy groups having 3 to 24 carbon atoms. Preferably, it is an alkoxy group having 1 to 18 carbon atoms (branched-chain alkoxy groups having 3 to 18 carbon atoms), more preferably an alkoxy group having 1 to 12 carbon atoms (branched-chain alkoxy groups having 3 to 12 carbon atoms), and even more preferably an alkoxy group having 1 to 6 carbon atoms (branched-chain alkoxy groups having 3 to 6 carbon atoms), and particularly preferably an alkoxy group having 1 to 5 carbon atoms (branched-chain alkoxy groups having 3 to 5 carbon atoms).

[0147] Specific alkoxy groups include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, tert-pentoxy, pentoxy, hexoxy, heptoxy, octoxy, etc.

[0148] Furthermore, "substituted silyl" as the first substituent can be exemplified by silyl groups substituted with three substituents selected from the group consisting of alkyl, cycloalkyl, and aryl groups. Examples include: trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, triarylsilyl, dialkylarylsilyl, and alkyldiarylsilyl.

[0149] As "trialkylsilyl", a group in which each of the three hydrogens in a silyl group is independently replaced by an alkyl group can be listed, and the alkyl group can be referred to as "alkyl" in the first substituent. For substitution, the preferred alkyl group is an alkyl group having 1 to 5 carbon atoms, and specifically, examples include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, tert-amyl, etc.

[0150] Specific examples of trialkylsilyl groups include: trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, trisec-butylsilyl, tritert-butylsilyl, tritert-pentylsilyl, ethyl dimethylsilyl, propyl dimethylsilyl, isopropyl dimethylsilyl, butyl dimethylsilyl, sec-butyl dimethylsilyl, tert-butyl dimethylsilyl, tert-pentyl dimethylsilyl, methyl diethylsilyl, propyl diethylsilyl, isopropyl dimethylsilyl, methyl diethylsilyl, propyl diethyl ... Ethyl silane, butyl diethyl silane, sec-butyl diethyl silane, tert-butyl diethyl silane, tert-pentyl diethyl silane, methyl dipropyl silane, ethyl dipropyl silane, butyl dipropyl silane, sec-butyl dipropyl silane, tert-butyl dipropyl silane, tert-pentyl dipropyl silane, methyl diisopropyl silane, ethyl diisopropyl silane, butyl diisopropyl silane, sec-butyl diisopropyl silane, tert-butyl diisopropyl silane, tert-pentyl diisopropyl silane, etc.

[0151] As "tricycloalkylsilyl", a group in which the three hydrogens of the silyl group are each independently replaced by a cycloalkyl group can be listed, and the cycloalkyl group can be referred to as "cycloalkyl" in the first substituent. Preferred cycloalkyl groups for substitution are cycloalkyl groups with 5 to 10 carbon atoms, specifically including: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, decahydronaphthyl, decahydroazyl, etc.

[0152] Specific examples of tricycloalkylsilyl groups include tricyclopentylsilyl and tricyclohexylsilyl.

[0153] As specific examples of substituted dialkylcycloalkylsilyl groups with two alkyl groups and one cycloalkyl group, and substituted alkyldicycloalkylsilyl groups with one alkyl group and two cycloalkyl groups, examples include silyl groups substituted with groups selected from the specific alkyl and cycloalkyl groups.

[0154] Specific examples of dialkylarylsilyl substituted with two alkyl groups and one aryl group, alkyldiarylsilyl substituted with one alkyl group and two aryl groups, and triarylsilyl substituted with three aryl groups include silyl substituted with groups selected from the specific alkyl and aryl groups. Specifically, triphenylsilyl substituted is a specific example of a triarylsilyl substituted alkyl group.

[0155] Additionally, the "aryl" in "diarylboryl" of the first substituent can be referenced from the description of the aryl group. Furthermore, the two aryl groups can be linked via a single bond or a linking group (e.g., >C(-R)2, >O, >S, or >NR). Here, R in >C(-R)2 and >NR is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy (the above are the first substituents), which may be further substituted with aryl, heteroaryl, alkyl, or cycloalkyl (the above are the second substituents). Specific examples of these groups can be referenced from the description of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy as the first substituent.

[0156] As a first substituent, substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "diarylboroyl (the two aryl groups may be linked by a single bond or a linker group)", substituted or unsubstituted "alkyl", substituted or unsubstituted "cycloalkyl", substituted or unsubstituted "alkoxy", substituted or unsubstituted "aryloxy", or substituted "silyl" as described above, at least one hydrogen atom of which may be substituted by a second substituent. Examples of the second substituent include, for example, aryl, heteroaryl, alkyl, cycloalkyl, or substituted silyl, with specific examples referring to the description of the monovalent group of the "aryl ring" or "heteroaryl ring" and the "alkyl" or "cycloalkyl" as the first substituent. Furthermore, in the aryl or heteroaryl groups that are the second substituents, structures in which at least one hydrogen atom is replaced by an aryl group such as phenyl (specifically, the groups described above), an alkyl group such as methyl, tert-butyl (specifically, the groups described above), or a cycloalkyl group such as cyclohexyl (specifically, the groups described above) are also included in the aryl or heteroaryl groups that are the second substituents. As an example, when the second substituent is a carbazolyl group, a carbazolyl group in which at least one hydrogen atom at the 9-position is replaced by an aryl group such as phenyl, an alkyl group such as methyl, or a cycloalkyl group such as cyclohexyl is also included in the heteroaryl group that is the second substituent.

[0157] The emission wavelength can be adjusted by the steric hindrance, electron-donating, and electron-withdrawing properties of the first substituent. Preferably, the radicals are those represented by the following structural formulas, more preferably methyl, tert-butyl, tert-pentyl, tert-octyl, neopentyl, cyclohexyl, adamantyl, phenyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 2,4,6-trimethylyl, diphenylamino, di-p-tolylamino, bis(p-(tert-butyl)phenyl)amino, carbazole, 3,6-dimethylcarbazole, 3,6-di-tert-butylcarbazole, and phenoxy, and even more preferably methyl, tert-butyl, tert-pentyl, tert-octyl, neopentyl, adamantyl, phenyl, o-tolyl, 2,6-xylyl, 2,4,6-trimethylylyl, diphenylamino, di-p-tolylamino, bis(p-(tert-butyl)phenyl)amino, carbazole, 3,6-dimethylcarbazole, and 3,6-di-tert-butylcarbazole. From the viewpoint of ease of synthesis, sterically hindered groups are preferred for selective synthesis. Specifically, tert-butyl, tert-pentyl, tert-octyl, adamantyl, o-tolyl, p-tolyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 2,4,6-trimethylyl, di-p-tolylamino, bis(p-(tert-butyl)phenyl)amino, 3,6-dimethylcarbazole, and 3,6-di-tert-butylcarbazole are preferred.

[0158] In the following structural formula, "Me" represents methyl, "tBu" represents tert-butyl, "tAm" represents tert-pentyl, "tOct" represents tert-octyl, and * represents the bond position.

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169] Furthermore, the present invention relates to a polymer of a polycyclic aromatic compound having a unit structure represented by a plurality of formulas (1), preferably a polymer of a polycyclic aromatic compound having a unit structure represented by a plurality of formulas (1-a), (1-b), (1-c), (1-d), (1-e), or (1-f). The polymer is preferably a dimer to a hexamer, more preferably a dimer to a trimer, and particularly preferably a dimer. Polymers can be any form in which multiple said unit structures are present in a compound. For example, in addition to the form in which multiple said unit structures are bonded by single bonds or linkage groups such as alkylene, phenylene, and naphthylene with 1 to 3 carbon atoms (linked polymers), they can also be formed by sharing any ring (A ring, B ring, or C ring, or a ring, b ring, or c ring, etc.) contained in the unit structure (ring-shared polymers). In addition, they can also be formed by the condensation of any ring (A ring, B ring, or C ring, or a ring, b ring, or c ring) contained in the unit structure (ring-condensed polymers). Ring-shared polymers and ring-condensed polymers are preferred, and ring-shared polymers are more preferred.

[0170] Regarding such polymers, for example, polymers of polycyclic aromatic compounds having multiple unit structures represented by formula (1-a) can be listed as polymers represented by the following formulas (1-a-4), (1-a-4-1), (1-a-4-2), (1-a-5-1) to (1-a-5-4), or (1-a-6). The meanings of the symbols in these formulas are the same as those in formula (1-a), and the preferred ranges are also the same. The polymer compound represented by formula (1-a-4) is a polymer compound having multiple unit structures represented by formula (1-a) in one compound in a manner that shares a benzene ring as the a ring in formula (1-a). The polymer compound represented by formula (1-a-4-1) is a polymer compound having two unit structures represented by formula (1-a) in one compound in a manner that shares a benzene ring as the a ring in formula (1-a). The polymeric compound represented by formula (1-a-4-2) below is a polymeric compound having three unit structures represented by formula (1-a) in one compound, in which a benzene ring, which is the a ring in formula (1-a), is shared. The polymeric compounds represented by formulas (1-a-5-1) to (1-a-5-4) below are polymeric compounds having multiple unit structures represented by formula (1-a) in one compound, in which a benzene ring, which is the b ring (or c ring) in formula (1-a), is shared. If we describe it using formula (1-a), then the polymeric compound represented by formula (1-a-6) below is a polymeric compound having multiple unit structures represented by formula (1-a) in one compound, in which a benzene ring, for example, a b ring (or a ring, c ring) as a unit structure is condensed with a benzene ring, which is the b ring (or a ring, c ring) as a unit structure. Furthermore, if explained using formula (1-a), the polymeric compound represented by the following formula (1-a-7) is a polymeric compound having multiple unit structures represented by formula (1-a) in one compound by condensing a benzene ring b, which is a unit structure, and a benzene ring c, which is a unit structure, with a benzene ring c (or b), which is a unit structure, respectively.

[0171]

[0172]

[0173] The polymeric compound can be a polymer formed by combining the polymerized form represented by formula (1-a-4), formula (1-a-4-1), or formula (1-a-4-2) with any of formulas (1-a-5-1) to (1-a-5-4) or the polymerized form represented by formula (1-a-6). It can also be a polymer formed by combining the polymerized form represented by any of formulas (1-a-5-1) to (1-a-5-4) with the polymerized form represented by formula (1-a-6). It can also be a polymer formed by combining the polymerized form represented by formula (1-a-4), formula (1-a-4-1), or formula (1-a-4-2) with the polymerized forms represented by any of formulas (1-a-5-1) to (1-a-5-4) and the polymerized form represented by formula (1-a-6).

[0174] Furthermore, all or part of the hydrogen in the chemical structure of the polycyclic aromatic compounds and their polymers represented by formula (1) may be deuterium, cyano, or halogen. For example, in formula (1), ring A, ring B, ring C (rings A to C are aryl or heteroaryl rings), substituents for rings A to C, and X 1 and X 2 When the hydrogen atom is >NR or >C(-R)2, the hydrogen atom in R (=alkyl, cycloalkyl, aryl) can be substituted with deuterium, cyano, or halogen. Examples of aryl or heteroaryl groups in which all or part of the hydrogen atom is substituted with deuterium, cyano, or halogen are listed. The halogen is fluorine, chlorine, bromine, or iodine, preferably fluorine, chlorine, or bromine, more preferably fluorine or chlorine, and most preferably fluorine.

[0175] For example, as described above, preferably at least one (preferably all) of the hydrogen on the L of L-Cy is replaced by a halogen (preferably fluorine).

[0176] Furthermore, in the chemical structures of polycyclic aromatic compounds and their polymers represented by formula (1) or formulas (1-a), (1-b), (1-c), (1-d), (1-e), or (1-f), at least one of the aryl ring or heteroaryl ring may be condensed from at least one cycloalkane. Additionally, in this specification, when an L-Cy is bonded to any carbon on either the aryl ring condensed from a cycloalkane or the heteroaryl ring condensed from a cycloalkane, it is also assumed that the L-Cy is bonded to the aryl ring or the heteroaryl ring.

[0177] For example, aryl rings and heteroaryl rings in aryl rings and heteroaryl rings of rings A, B, C, a, b, and c; aryl (aryl moiety of aryl, diarylamino, arylheteroarylamino, diarylboryl, or aryloxy) and heteroaryl (heteroaryl, diarylamino, or heteroarylamino) moiety of the first and second substituents in rings A to C; aryl (same as above) and heteroaryl (same as above) as the first and second substituents for rings a, b, and c; and as (as X) 1 X 2 At least one of the aryl (same as above) and heteroaryl (same as above) of R in C(-R)2 can be condensed from at least one cycloalkane.

[0178] Preferably, the following are preferred: aryl rings and heteroaryl rings as rings A, B, C, a, b, and c; aryl (aryl moiety of aryl, diarylamino, diarylboryl, or aryloxy) and heteroaryl (heteroaryl or heteroaryl moiety of diheteroarylamino) as the first substituents of rings A to C; aryl (same as above) and heteroaryl (same as above) as the first substituents for rings a to c; and as (as X) 1 X 2 At least one of the aryl (same as above) and heteroaryl (same as above) of R in C(-R)2 can be condensed from at least one cycloalkane.

[0179] More preferably: an aryl ring as ring A, ring B, ring C, ring a, ring b, and ring c; an aryl group (aryl moiety of aryl or diarylamino) and a heteroaryl group (heteroaryl moiety of heteroaryl) as the first substituent in rings A to C; an aryl group (same as above) and a heteroaryl group (same as above) as the first substituent for rings a, b, and c; and as (as X) 1 X 2 At least one of the aryl groups of R in C(-R)2 > NR and > C(-R)2 (as described above) can be condensed by at least one cycloalkane.

[0180] Furthermore, the preferred options are: an aryl ring as ring A, ring B, ring C, ring a, ring b, and ring c; an aryl group (aryl moiety of aryl or diarylamino) as the first substituent in rings A through C; an aryl group as the first substituent for rings a, b, and c (same as above); and an aryl group as (as X) 1 X 2 At least one of the aryl groups of R in C(-R)2 > NR and > C(-R)2 (as described above) can be condensed by at least one cycloalkane.

[0181] Examples of "cycloalkanes" include: cycloalkanes with 3 to 24 carbon atoms, cycloalkanes with 3 to 20 carbon atoms, cycloalkanes with 3 to 16 carbon atoms, cycloalkanes with 3 to 14 carbon atoms, cycloalkanes with 5 to 10 carbon atoms, cycloalkanes with 5 to 8 carbon atoms, cycloalkanes with 5 to 6 carbon atoms, and cycloalkanes with 5 carbon atoms.

[0182] Specific examples of cycloalkanes include: cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, norbornene, bicyclo[1.0.1]butane, bicyclo[1.1.1]pentane, bicyclo[2.0.1]pentane, bicyclo[1.2.1]hexane, bicyclo[3.0.1]hexane, bicyclo[2.1.2]heptane, bicyclo[2.2.2]octane, adamantane, diadamantane, decahydronaphthalene and decahydroazine, as well as their alkyl (especially methyl) substituted derivatives, halogen (especially fluorine) substituted derivatives, and deuterium substituted derivatives, etc., having carbon numbers from 1 to 5.

[0183] Among these, a structure in which at least one hydrogen atom is substituted on the α-carbon of the cycloalkane (in a cycloalkane condensed in an aryl ring or heteroaryl ring, the carbon atom adjacent to the carbon at the condensation site) is preferred; a structure in which two hydrogen atoms on the α-carbon are substituted is more preferred; and a structure in which a total of four hydrogen atoms on the two α-carbons are substituted is even more preferred. Examples of substituents include alkyl (especially methyl) derivatives having 1 to 5 carbon atoms, halogen (especially fluorine) derivatives, and deuterium derivatives.

[0184] A particularly preferred structure is one in which a partial structure represented by formula (B10) or formula (B11) is bonded to an adjacent carbon atom in an aryl ring or heteroaryl ring.

[0185]

[0186] In formulas (B10) and (B11), Me represents a methyl group. * indicates the bonding position, where the group represented by formula (B10) or (B11) is bonded to two adjacent elements on the aryl or heteroaryl ring to which it is bonded.

[0187] Examples of compounds with this structure include the following compounds.

[0188]

[0189] The number of cycloalkanes condensed in an aryl ring or heteroaryl ring is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. For example, examples are shown below of one or more cycloalkanes condensed in a benzene ring (phenyl). Cycloalkanes condensed as in formulas (Cy-1-4) and (Cy-2-4) can also condense with each other. This is the same whether the condensed ring (group) is an aryl ring or heteroaryl ring other than a benzene ring (phenyl), or whether the condensed cycloalkanes are cycloalkanes other than cyclopentane or cyclohexane.

[0190]

[0191] At least one -CH2- in a cycloalkane may be substituted with -O-. For example, the following shows examples of one or more -CH2- in a cycloalkane condensed on a benzene ring (phenyl) being substituted with -O-. This is the same whether the condensed ring (group) is an aryl ring or heteroaryl ring other than a benzene ring (phenyl), or whether the cycloalkane undergoing condensation is a cycloalkane other than cyclopentane or cyclohexane.

[0192]

[0193] At least one hydrogen atom in the cycloalkane may be substituted as a substituent, such as L-Cy, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (the two aryl groups may be linked by a single bond or a linker), alkyl, cycloalkyl, alkoxy, aryloxy, substituted silyl, deuterium, cyano, or halogen, details of which can be found in the description of the first substituent. Among these substituents, alkyl (e.g., alkyl with 1 to 6 carbon atoms), cycloalkyl (e.g., cycloalkyl with 3 to 14 carbon atoms), halogen (e.g., fluorine), and deuterium are preferred. Furthermore, when cycloalkyl is substituted, it may be in a spirocyclic form, as illustrated in the examples below.

[0194]

[0195] Other forms of cycloalkane condensation include: polycyclic aromatic compounds and their polymers represented by formula (1) or formulas (1-a), (1-b), (1-c), (1-d), (1-e), or (1-f) having, for example, R being >NR, a diarylamino group condensed from a cycloalkane (condensed to its aryl moiety), a carbazolyl group condensed from a cycloalkane (condensed to its benzene ring moiety), or a benzo[a]carbazolyl group condensed from a cycloalkane (condensed to its benzene ring moiety). Regarding "diarylamino," groups described as the "first substituent" can be cited.

[0196] Furthermore, as more specific examples, one can list the R in polycyclic aromatic compounds and their polymers represented by formula (1) or formula (1-a), formula (1-b), formula (1-c), formula (1-d), formula (1-e) or formula (1-f). 2 Examples include diarylamino groups condensed from cycloalkanes (condensed to their aryl moiety) or carbazole groups condensed from cycloalkanes (condensed to their benzene ring moiety).

[0197] When polycyclic aromatic compounds and their polymers represented by formula (1) or formulas (1-a), (1-b), (1-c), (1-d), (1-e), or (1-f) are used as dopant materials for the light-emitting layer of organic electroluminescent elements, Y is preferred. 1 For B and X 1 and X 2 Compounds with a NR greater than 1; Y 1 For B and X 1 For >O, X 2 Compounds with a NR greater than 1; Y 1 For B and X 1 and X 2 When a compound with a value greater than 0 is used as the host material of the light-emitting layer, Y is preferred. 1 For B and X 1 For >O, X 2 Compounds with a NR greater than 1; Y 1 For B and X 1 and X 2 For compounds with >0, Y can be preferably used as an electron transport material. 1 For B and X 1 and X 2 Compounds with >O; Y 1 For P=O, X 1 and X 2 Compounds with a value greater than O.

[0198] As described above, in the chemical structures of polycyclic aromatic compounds and their polymers represented by formulas (1), (1-a), (1-b), (1-c), (1-d), (1-e), or (1-f), at least one of the aryl rings or heteroaryl rings is substituted with at least one L-Cy. This substitution can be made by substituting at least one L-Cy for all aryl rings and heteroaryl rings, or by substituting at least one L-Cy for a portion of the aryl rings and heteroaryl rings, or by substituting at least one L-Cy for one of multiple aryl rings or heteroaryl rings.

[0199] Examples of aryl or heteroaryl rings substituted with L-Cy include rings A, B, or C in formula (1), and X. 1 and X2 The preferred example is the aryl ring or heteroaryl ring contained in R when the NR is greater than NR. For example, it is preferred that R is selected from formulas (1-a) and (1-b). 2 and R 9 At least one of the groups is L-Cy, chosen from X. 1 and X 2 At least one of the groups is >NR where R is a phenyl group substituted with L-Cy; or selected from R. 2 and R 9 At least one of the groups formed is L-Cy, and the choice is X. 1 and X 2 At least one of the groups is >NR where R is a phenyl group substituted with L-Cy.

[0200] Other examples of L-Cy-substituted forms include polycyclic aromatic compounds and their polymers represented by formulas (1), (1-a), (1-b), (1-c), (1-d), (1-e), or (1-f), for example, those substituted by at least one L-Cy-substituted diarylamino group, at least one L-Cy-substituted carbazole group, or at least one L-Cy-substituted benzocarbazole group. Regarding "diarylamino group," the group described as the "first substituent" can be listed. As for the substituted forms of cycloalkyl groups of diarylamino, carbazole, and benzocarbazole groups, examples can be listed where some or all of the hydrogen atoms in the aryl ring or benzene ring of these groups are substituted by L-Cy.

[0201] Furthermore, as a more concrete example, R in polycyclic aromatic compounds and their polymers represented by formula (1-a) can be listed. 2 Examples include a diarylamino group substituted with at least one L-Cy or a carbazole group substituted with at least one L-Cy.

[0202] As an example, examples include polycyclic aromatic compounds represented by formula (2-A) below, or polymers of polycyclic aromatic compounds having multiple structures represented by formula (2-A) below. n is an integer from 1 to 5 (preferably 1) independently, and the definitions of each symbol in the structural formula are the same as those in formula (1-a).

[0203]

[0204] In addition, as specific examples of the polycyclic aromatic compounds and polymers thereof of the present invention, compounds in which one or more aromatic rings are replaced by, for example, one to two L-Cy rings can be listed.

[0205] Specifically, compounds represented by any of the following formulas can be listed. In the following formulas, n is independently 0 to 2 (wherein n will not all be 0), preferably 1. Furthermore, in the following structural formulas, "L" represents a linking group, "Cy" represents a cycloalkyl group, "OPh" represents a phenoxy group, "Me" represents a methyl group, and in "L-Cy", L is set as the bonding position.

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215] As more specific examples of the cycloalkyl-substituted polycyclic aromatic compounds of the present invention, compounds represented by the following structural formulas can be listed. Furthermore, in the following structural formulas, "D" represents deuterium, "Me" represents methyl, "tBu" represents tert-butyl, "Ph" represents phenyl, and "Mes" represents mesitylene.

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240] The polycyclic aromatic compounds and their polymers represented by formula (1) of the present invention can also be used as the following polymers (the monomers used to obtain the polymers have polymerizable substituents) or polymer crosslinkers (the polymers used to obtain the polymer crosslinkers have crosslinking substituents), or the following suspended polymers (the reactive compounds used to obtain the suspended polymers have reactive substituents) or suspended polymer crosslinkers (the suspended polymers used to obtain the suspended polymer crosslinkers have crosslinking substituents) in materials for organic devices, such as materials for organic electroluminescent elements, materials for organic field-effective transistors, or materials for organic thin-film solar cells. The polymer is obtained by polymerizing a reactive compound, which is obtained by substituting reactive substituents in the polycyclic aromatic compounds and their polymers represented by formula (1), as a monomer. The polymer crosslinkers are obtained by further crosslinking the polymers. The suspended polymers are obtained by reacting a main-chain polymer with the reactive compound. The suspended polymer crosslinkers are obtained by further crosslinking the suspended polymers.

[0241] The reactive substituents (including the polymerizable substituents, the crosslinking substituents, and the reactive substituents for obtaining suspended polymers, hereinafter also simply referred to as "reactive substituents") are not particularly limited as long as they are substituents that can increase the molecular weight of the polycyclic aromatic compound or its polymers, substituents that can further crosslink the polymer obtained in this manner, and substituents that can carry out suspension reactions in main-chain polymers. However, substituents with the following structures are preferred. * in each structural formula indicates a bond position.

[0242]

[0243] L X Each of the substituents is independently a single bond, -O-, -S-, >C=O, -OC(=O)-, alkylene group having 1 to 12 carbon atoms, oxoalkylene group having 1 to 12 carbon atoms, or polyoxoalkylene group having 1 to 12 carbon atoms. The substituents are preferably those represented by formulas (XLS-1), (XLS-2), (XLS-3), (XLS-9), (XLS-10), or (XLS-17), and more preferably those represented by formulas (XLS-1), (XLS-3), or (XLS-17).

[0244] Details regarding the uses of such polymers, polymer crosslinkers, suspended polymers and suspended polymer crosslinkers (hereinafter also referred to as "polymers and polymer crosslinkers") will be described later.

[0245] 2. Methods for manufacturing polycyclic aromatic compounds and their polymers

[0246] Regarding the polycyclic aromatic compounds and their polymers represented by formula (1), preferably the polycyclic aromatic compounds and their polymers represented by formulas (1-a), (1-b), (1-c), (1-d), (1-e), and (1-f), basically, the bonding group (containing X) is first utilized. 1 or X 2 The group (containing Y) bonds ring A (a ring) to ring B (b ring) and ring C (c ring), thereby creating an intermediate (first reaction). Then, using the bonding group (containing Y) 1The A ring (a ring), B ring (b ring), and C ring (c ring) are bonded together by the group ( ), thereby producing the final product (second reaction). In the first reaction, for example, if it is an etherification reaction, a conventional reaction such as a nucleophilic substitution reaction or a Ullmann reaction can be used; if it is an amination reaction, a conventional reaction such as a Buchwald-Hartwig reaction can be used. In addition, in the second reaction, a tandem Hetero-Friedel-Crafts reaction (a continuous aromatic electrophilic substitution reaction, the same below) can be used. Furthermore, by using a starting material substituted with L-Cy at some point in these reaction steps, or by adding an additional step of introducing L-Cy, the compounds of the present invention with cycloalkyl substitution at the desired position can be produced.

[0247] As shown in process (1) or process (2) below, the second reaction is to introduce Y-linked rings that bond A (ring a), B (ring b) and C (ring c). 1 The reaction of Y, as an example, is shown below. 1 Boron atoms, X 1 and X 2 In the case of oxygen atoms, firstly, using n-butyllithium, sec-butyllithium, or tert-butyllithium, etc., to target X... 1 With X 2 The hydrogen atoms between them undergo ortho-metallization. Then, boron trichloride or boron tribromide is added for lithium-boron metal exchange, followed by the addition of a Bronsted base such as N,N-diisopropylethylamine, thereby initiating a tandem Bora-Friedel-Crafts reaction to obtain the target compound. In the second reaction, a Lewis acid such as aluminum trichloride may be added to promote the reaction. Furthermore, the definitions of the symbols for each structural formula in processes (1) and (2) below, and in subsequent processes (3) to (28), are the same as those described above.

[0248] Process (1)

[0249]

[0250] Process (2)

[0251]

[0252] Furthermore, process (1) or process (2) mainly illustrates a method for manufacturing polycyclic aromatic compounds represented by formula (1) or formula (1-a), but regarding their polymers, they can be manufactured by using intermediates having multiple A rings (a ring), B rings (b ring), and C rings (c ring). In detail, this will be explained by processes (3) to (5) below. In this case, the target compound can be obtained by setting the amount of reagents such as butyllithium used to 2 or 3 times the normal amount.

[0253] Process (3)

[0254]

[0255] Process (4)

[0256]

[0257] In the process described above, lithium is introduced to the desired position by ortho metallization, but bromine atoms or the like can be introduced to the position where lithium is to be introduced, as shown in processes (6) and (7) below, and lithium can also be introduced to the desired position by halogen-metal exchange.

[0258] Process (6)

[0259]

[0260] Process (7)

[0261]

[0262] In addition, regarding the method for manufacturing polymers described in process (3), halogens such as bromine or chlorine atoms can be introduced at the desired lithium position as shown in processes (6) and (7), and lithium can also be introduced at the desired position through halogen-metal exchange (processes (8), (9) and (10) below).

[0263] Process (8)

[0264]

[0265] Process (9)

[0266]

[0267] Process (10)

[0268]

[0269] According to the method described, the target compound can be synthesized even when ortho-metallization is not possible due to the influence of substituents, which is therefore useful.

[0270] By appropriately selecting the synthetic method and the starting materials used, it is possible to synthesize a product with cycloalkyl substitution at the desired position, a substituent at the desired position, and Y 1 Boron atoms, X 1 and X 2 Polycyclic aromatic compounds and their polymers containing oxygen atoms.

[0271] Then, Y 1 Boron atoms, X 1 and X 2 The case of nitrogen atoms is shown as an example in processes (11) and (12) below. (With X) 1 and X 2 Similarly, in the case of oxygen atoms, firstly, using n-butyllithium, etc., to target X... 1 With X 2 The hydrogen atoms between them undergo ortho-metallization. Subsequently, boron tribromide or similar substances are added for lithium-boron metal exchange, followed by the addition of a Brinzyl base such as N,N-diisopropylethylamine, thereby conducting a tandem borazorid-Krawtz reaction to obtain the target compound. Here, a Lewis acid such as aluminum trichloride may also be added to promote the reaction. Furthermore, by using a starting material substituted with L-Cy at some point in these reaction steps, or by adding an additional step to introduce L-Cy, compounds of the present invention with cycloalkyl substitution at the desired position can be produced.

[0272] Process (11)

[0273]

[0274] Process (12)

[0275]

[0276] In addition, regarding Y 1 Boron atoms, X 1 and X 2 When the polymer is nitrogen atom, halogens such as bromine or chlorine atoms can also be introduced at the desired lithium position as shown in processes (6) and (7), and lithium can also be introduced at the desired position through halogen-metal exchange (processes (13), (14) and (15) below).

[0277] Process (13)

[0278]

[0279] Process (14)

[0280]

[0281] Process (15)

[0282]

[0283] Then, Y 1 It is phosphorus sulfide, phosphorus oxide, or phosphorus atom and X 1 and X 2 The case of oxygen atoms is shown as an example in the following processes (16) to (19). As before, X is first treated with n-butyllithium, etc. 1 With X 2 The hydrogen atoms between them undergo ortho-metallization. Then, phosphorus trichloride and sulfur are added sequentially, followed by Lewis acids such as aluminum trichloride and Brønsted bases such as N,N-diisopropylethylamine, thus initiating a tandem phosphafried-Krawtz reaction to obtain Y. 1 It is a phosphorus sulfide compound. Furthermore, Y can be obtained by treating the obtained phosphorus sulfide compound with m-chloroperbenzoic acid (m-CPBA). 1 Y is a phosphorus-oxidizing compound, which can be obtained by treatment with triethylphosphine. 1 Compounds containing phosphorus atoms. Furthermore, by using a starting material substituted with L-Cy at some point in these reaction steps, or by adding an additional step to introduce L-Cy, compounds of the present invention with desired cycloalkyl substitutions can be produced.

[0284] Process (16)

[0285]

[0286] Process (17)

[0287]

[0288] Process (18)

[0289]

[0290] Process (19)

[0291]

[0292] In addition, regarding Y 1 Phosphorus sulfide, X 1 and X 2 The polymer with oxygen atoms can also introduce halogens such as bromine or chlorine atoms at the desired lithium-ion site, as shown in processes (6) and (7), and introduce lithium at the desired site through halogen-metal exchange (processes (20), (21), and (22) below). Furthermore, regarding the Y formed in the manner described... 1 Phosphorus sulfide, X 1 and X2 The polymer with oxygen atoms, as shown in processes (18) and (19), can be obtained by treatment with m-chloroperbenzoic acid (m-CPBA). 1 Y is a phosphorus-oxidizing compound, which can be obtained by treatment with triethylphosphine. 1 Compounds containing phosphorus atoms.

[0293] Process (20)

[0294]

[0295] Process (21)

[0296]

[0297] Process (22)

[0298]

[0299] Here, Y is recorded. 1 For B, P, P=O or P=S and X 1 and X 2 Examples of O or NR can be used, but Y can also be synthesized by appropriately changing the raw materials. 1 Compounds of Al, Ga, As, Si-R or Ge-R, or X 1 and X 2 Compounds containing S.

[0300] Specific examples of solvents used in the above reactions include tert-butylbenzene or xylene.

[0301] In addition, in formula (1-a), the substituents R of rings a, b, and c are... 1 ~R 11 The adjacent groups in the ring can bond to each other and together with the a, b, or c rings to form an aryl or heteroaryl ring, wherein at least one hydrogen atom in the formed ring can be substituted by an aryl or heteroaryl group. Therefore, the ring structure of the polycyclic aromatic compound represented by formula (1-a) changes depending on the bonding morphology of the substituents in the a, b, and c rings, as shown in formulas (1-a-1) and (1-a-2) of processes (23) and (24) below. These compounds can be synthesized by applying the synthetic methods shown in processes (1) to (19) to the intermediates shown in processes (23) and (24) below. Furthermore, by using a starting material substituted with L-Cy at some point in these reaction steps, or by adding a step to introduce L-Cy, compounds of the present invention with desired cycloalkyl substitution can be produced.

[0302] Process (23)

[0303]

[0304] Process (24)

[0305]

[0306] In formulas (1-a-1) and (1-a-2), rings A', B', and C' represent substituents R. 1 ~Substituent R 11 The adjacent groups in the formula are bonded to each other and together with the a, b, and c rings to form aryl or heteroaryl rings (also known as fused rings formed by the condensation of other ring structures in the a, b, or c rings). Furthermore, although not shown in the formula, there are also compounds in which the a, b, and c rings are all transformed into A', B', and C' rings, respectively.

[0307] Furthermore, the stipulation in formula (1-a) that “R of >NR and / or R of >-C(-R)2- are bonded to the a ring, b ring and / or c ring by -O-, -S-, -C(-R)2- or a single bond” can be represented by a compound that is represented by formula (1-a-3-1) of the following process (25) and has X 1 or X 2 The ring structure introduced into fused ring B' and fused ring C'; or represented by equation (1-a-3-2) or equation (1-a-3-3) and having X 1 or X 2 The ring structure is introduced into the fused ring A'. These compounds can be synthesized by applying the synthetic methods shown in processes (1) to (19) to the intermediates shown in process (25) below. In addition, by using a starting material substituted with L-Cy at some point in these reaction steps, or by adding a step to introduce L-Cy, the compounds of the present invention with cycloalkyl substitution at the desired position can be produced.

[0308] Process (25)

[0309]

[0310] Furthermore, in the synthesis methods described in processes (1) to (17) and processes (20) to (25), it is shown that before adding boron trichloride or boron tribromide, etc., X is treated with butyllithium or the like. 1 With X 2 Examples of tandem heterofried-Krawtz reactions involve the ortho-metallization of hydrogen atoms (or halogen atoms) between hydrogen atoms, but the reaction can also proceed without the ortho-metallization using butyllithium or the like, by adding boron trichloride or boron tribromide.

[0311] Additionally, in Y 1In the case of a phosphorus-based system, as shown in process (26) or process (27) below, n-butyllithium, sec-butyllithium, or tert-butyllithium, etc., are used to treat X. 1 With X 2 The hydrogen atoms between (where O is in the following formula) are ortho-metallized, followed by the addition of bis(diethylamino)chlorophosphine for lithium-phosphine metal exchange, and then the addition of Lewis acids such as aluminum trichloride to carry out a tandem phosphafried-Krawtz reaction, thereby obtaining the target compound. This reaction method is also described in International Publication No. 2010 / 104047 (e.g., page 27). Furthermore, by using a starting material substituted with L-Cy at some point in these reaction steps, or by adding an additional step of introducing L-Cy, compounds of the present invention with cycloalkyl substitution at the desired position can be produced.

[0312] Process (26)

[0313]

[0314] Process (27)

[0315]

[0316] Furthermore, in process (26) or process (27), a 2- or 3-times molar amount of a butyllithium or other ortho-metallizing agent relative to the molar amount of intermediate 1 can be used to synthesize a polymer compound. Alternatively, a halogen such as a bromine or chlorine atom can be introduced beforehand at the position where a metal such as lithium is to be introduced, and a halogen-metal exchange can be performed, thereby introducing the metal to the desired position.

[0317] Furthermore, regarding the polycyclic aromatic compound represented by formula (2-A), as shown in the following procedure (28), the desired L-Cy-substituted polycyclic aromatic compound can be synthesized by synthesizing an L-Cy-substituted intermediate and then cyclizing it. In procedure (28), Hal... 1 Hal 2 Hal 3 and Hal 4 All of these represent halogens, X represents halogen or hydrogen, and the definitions of other symbols are the same as those in equation (1-a).

[0318] The method for introducing L-Cy is described below. An example is a compound where the linker L is an alkylene group.

[0319] First, a compound having A, B, or C rings is reacted with a chloride of a carboxylic acid having the corresponding cycloalkyl group, for example, in the presence of a Lewis acid, using a Friedel-Crafts reaction to derivatize it into a ketone (first reaction). Then, if the carbonyl group is reduced by reduction, a cycloalkyl group having an alkylene group as a linking group can be introduced. If more than two equal amounts of magnesium methyl halide or lithium methyl are acted on the carbonyl group, a linking group having a dimethylmethylene group can be formed. If a fluorinating agent such as dimethylamino sulfur fluoride (DAST) is acted on the carbonyl group, a fluorinated alkylene group can be set as a linking group (second reaction). Alternatively, by reacting a compound having A, B, or C rings with an alkyl halide having the corresponding cycloalkyl group and performing a Friedel-Crafts reaction in the presence of a Lewis acid, a compound having an alkylene group as a linking group can be directly synthesized.

[0320] Next, we will take compounds with the linker group L as an ether group as an example for explanation.

[0321] First, phenolic compounds having A, B, and C rings are reacted with alkyl halides having corresponding cycloalkyl groups in the presence of a base such as potassium carbonate or sodium hydride, thereby deriving compounds having ether bonds on the linking group.

[0322] Next, we will take compounds with the linker group L as an ester group as an example for explanation.

[0323] First, phenolic compounds or carboxylic acids with A, B, and C rings and carboxylic acids or alcohols with corresponding cycloalkyl groups can be derived into compounds with ester bonds on the linking group in the presence of catalysts such as dimethylaminopyridine (DMAP) and using dehydrating agents such as N,N-dicyclohexylcarbodiimide (DCC).

[0324] Process (28)

[0325]

[0326] The intermediate before cyclization in process (28) can also be synthesized using the methods shown in process (1), etc. That is, intermediates with desired substituents can be synthesized by appropriately combining Buchwald-Hartwig reactions or Suzuki coupling reactions, or etherification reactions using nucleophilic substitution reactions or Ullmann reactions, etc. In these reactions, commercially available starting materials that serve as precursors for cycloalkyl substitution can also be used.

[0327] Compounds of formula (2-A) having a diphenylamino group substituted with L-Cy can also be synthesized, for example, by the following method: L-Cy-substituted diphenylamino group is introduced into a trihalomethane with an L-Cy-substituted bromobenzene via an amination reaction such as the Buchwald-Hartwig reaction, and then... 1 X 2 In the case of NR, it is derived into an intermediate (M-3) by an amination reaction such as the Buchwald-Hartwig reaction, in X 1 X 2 In the case of O, the intermediate (M-3) is derived by etherification using phenol, and then, through a tandem borosifried-Krawtz reaction involving trans-metallation with a metallizing agent such as butyllithium, followed by the action of a boron halide such as boron tribromide, and then the action of a Brinzyl base such as diethylisopropylamine, the compound of formula (2-A) can be synthesized. These reactions can also be applied to other compounds substituted with L-Cy.

[0328] In addition, examples of ortho-metallizing reagents used in processes (1) to (28) include alkyl lithiums such as methyl lithium, n-butyl lithium, sec-butyl lithium, and tert-butyl lithium, and organic basic compounds such as lithium diisopropylamide, lithium tetramethylpiperidide, lithium hexamethyldisilamide, and potassium hexamethyldisilamide.

[0329] Furthermore, the metal Y used in processes (1) to (28) is... 1 Metal exchange reagents, such as Y, can be listed as follows: 1 trifluoride, Y 1 trichloride, Y 1 tribromide, Y 1 Triiodide, etc. 1 Halides, such as CIPN(NEt2)2, etc. 1 The amino-halides, Y 1 alkoxylates, Y 1 Aryloxy compounds, etc.

[0330] Furthermore, examples of Brønsted bases used in processes (1) to (28) include: N,N-diisopropylethylamine, triethylamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2,6-dimethylpyridine, sodium tetraphenylborate, potassium tetraphenylborate, triphenylborane, tetraphenylsilane, Ar4BNa, Ar4BK, Ar3B, Ar4Si (where Ar is phenyl or other aryl groups), etc.

[0331] Lewis acids used in processes (1) to (28) can be listed as follows: AlCl3, AlBr3, AlF3, BF3·OEt2, BCl3, BBr3, GaCl3, GaBr3, InCl3, InBr3, In(OTf)3, SnCl4, SnBr4, AgOTf, ScCl3, Sc(OTf)3, ZnCl2, ZnBr2, Zn(OTf)2, MgCl2, MgBr2, Mg(OTf)2, LiOTf, NaOTf, KOTf, Me3SiOTf, Cu(OTf)2, CuCl2, YCl3, Y(OTf)3, TiCl4, TiBr4, ZrCl4, ZrBr4, FeCl3, FeBr3, CoCl3, CoBr3, etc.

[0332] In processes (1) to (28), Brønsted bases or Lewis acids may be used to promote the tandem heterofried-Krawtz reaction. Specifically, when using Y... 1 trifluoride, Y 1 trichloride, Y 1 tribromide, Y 1 Triiodide, etc. 1 In the case of halides, acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide are generated as aromatic electrophilic substitution reactions proceed. Therefore, it is effective to use Brenstein bases that capture acids. On the other hand, when using Y... 1 Aminated halides, Y 1 In the case of alkoxylates, amines and alcohols are generated as aromatic electrophilic substitution reactions proceed. Therefore, in most cases, it is not necessary to use a Brentstein base. However, due to the low desorption capacity of amino or alkoxy groups, it is effective to use Lewis acids that promote their desorption.

[0333] In addition, the polycyclic aromatic compounds or polymers thereof of the present invention also contain compounds in which at least some hydrogen atoms are replaced by deuterium or cyano groups or by halogens such as fluorine or chlorine. Such compounds can be synthesized in the same manner as described above using raw materials that have been deuterated, cyanated, fluorinated or chlorinated at the desired positions.

[0334] 3. Organic devices

[0335] The compounds of the present invention (polycyclic aromatic compounds and their polymers represented by formula (1), reactive compounds formed by substituting reactive substituents in any of the above, polymeric compounds formed by polymerizing any of the above, polymeric crosslinkers, suspended polymeric compounds, or suspended polymeric crosslinkers) can be used as materials for organic devices. Examples of organic devices include organic electroluminescent elements, organic field-effective transistors, or organic thin-film solar cells.

[0336] 3-1. Organic electroluminescent element

[0337] The compounds of the present invention can be used, for example, as materials for organic electroluminescent elements. Hereinafter, the organic EL element of this embodiment will be described in detail based on the accompanying drawings. Figure 1 This is a schematic cross-sectional view showing the organic EL element of this embodiment.

[0338] 3-1-1. Structure of Organic Electroluminescent Element

[0339] Figure 1 The organic EL element 100 shown includes: a substrate 101, an anode 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode 102, a hole transport layer 104 disposed on the hole injection layer 103, a light-emitting layer 105 disposed on the hole transport layer 104, an electron transport layer 106 disposed on the light-emitting layer 105, an electron injection layer 107 disposed on the electron transport layer 106, and a cathode 108 disposed on the electron injection layer 107.

[0340] Furthermore, the organic EL element 100 can also be fabricated in reverse order to form a structure such as the following, which includes: a substrate 101, a cathode 108 disposed on the substrate 101, an electron injection layer 107 disposed on the cathode 108, an electron transport layer 106 disposed on the electron injection layer 107, a light-emitting layer 105 disposed on the electron transport layer 106, a hole transport layer 104 disposed on the light-emitting layer 105, a hole injection layer 103 disposed on the hole transport layer 104, and an anode 102 disposed on the hole injection layer 103.

[0341] Not all of the layers are indispensable. The smallest structural unit is set to include an anode 102, a light-emitting layer 105, and a cathode 108. The hole injection layer 103, hole transport layer 104, electron transport layer 106, and electron injection layer 107 are arbitrarily arranged layers. In addition, each layer may consist of a single layer or multiple layers.

[0342] Furthermore, in this specification, the layers containing organic compounds, such as the light-emitting layer, hole injection layer, hole transport layer, electron transport layer, and electron injection layer in an organic EL element, are sometimes collectively referred to as organic layers.

[0343] In addition to the aforementioned structure of "substrate / anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode", the morphology of the layers constituting an organic EL device can also be "substrate / anode / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole injection layer / light-emitting layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole injection layer / hole transport layer / light-emitting ...". The structural forms are: “substrate / anode / electron transport layer / electron injection layer / cathode”, “substrate / anode / hole transport layer / electron injection layer / cathode”, “substrate / anode / hole transport layer / electron transport layer / electron injection layer / cathode”, “substrate / anode / hole transport layer / electron transport layer / cathode”, “substrate / anode / hole injection layer / electron injection layer / cathode”, “substrate / anode / hole injection layer / electron transport layer / cathode”, “substrate / anode / electron transport layer / cathode”, “substrate / anode / electron transport layer / cathode”.

[0344] 3-1-2. Substrate in organic electroluminescent devices

[0345] The substrate 101 is the support for the organic EL element 100, and can typically be made of quartz, glass, metal, plastic, etc. The substrate 101 is formed into a plate, film, or sheet shape depending on the purpose, and can be made of glass plates, metal plates, metal foils, plastic films, plastic sheets, etc. Preferably, it is made of glass plates or plates made of transparent synthetic resins such as polyester, polymethyl methacrylate, polycarbonate, or polysulfone. If it is a glass substrate, soda-lime glass or alkali-free glass can be used. Furthermore, the thickness only needs to be sufficient to maintain mechanical strength; for example, 0.2 mm or more is sufficient. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. Regarding the glass material, since the amount of dissolved ions from the glass should be minimal, alkali-free glass is preferred. Since soda-lime glass with a barrier coating such as SiO2 is also commercially available, soda-lime glass can be used. In addition, to improve gas barrier properties, a fine gas barrier film such as a silicon oxide film may be provided on at least one side of the substrate 101. When a plate, film or sheet made of synthetic resin with low gas barrier properties is used as the substrate 101, it is particularly preferable to provide a gas barrier film.

[0346] 3-1-3. Anode in organic electroluminescent devices

[0347] The anode 102 functions to inject holes into the light-emitting layer 105. Furthermore, when a hole injection layer 103 and / or a hole transport layer 104 are provided between the anode 102 and the light-emitting layer 105, holes are injected into the light-emitting layer 105 via these layers.

[0348] Materials forming the anode 102 can include both inorganic and organic compounds. Examples of inorganic compounds include: metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (oxides of indium, oxides of tin, indium tin oxide (ITO), indium zinc oxide (IZO), etc.), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, or NESA glass. Examples of organic compounds include: conductive polymers such as poly(3-methylthiophene), polypyrrole, and polyaniline. Furthermore, appropriate materials can be selected from those used as anodes in organic EL elements.

[0349] The resistance of the transparent electrode is not limited as long as it can supply sufficient current for the light-emitting element to emit light, but from the viewpoint of power consumption of the light-emitting element, low resistance is ideal. For example, if it is an ITO substrate with a resistance of 300Ω / □ or less, it functions as an electrode of the element, but nowadays substrates with a resistance of around 10Ω / □ are also available. Therefore, it is particularly ideal to use a low-resistance product, such as 100Ω / □ to 5Ω / □, preferably 50Ω / □ to 5Ω / □. The thickness of the ITO can be arbitrarily selected according to the resistance value, but it is usually used in the range of 50nm to 300nm.

[0350] 3-1-4. Hole injection layer and hole transport layer in organic electroluminescent devices

[0351] Hole injection layer 103 efficiently injects holes migrating from anode 102 into light-emitting layer 105 or hole transport layer 104. Hole transport layer 104 efficiently transports holes injected from anode 102, or holes injected from anode 102 via hole injection layer 103, to light-emitting layer 105. Hole injection layer 103 and hole transport layer 104 are formed by layering or mixing one or more hole injection / transport materials, or by a mixture of hole injection / transport materials and polymer binders. Alternatively, inorganic salts such as ferric chloride (III) can be added to the hole injection / transport materials to form the layers.

[0352] As a hole injection / transport material, it is necessary to efficiently inject / transport holes from the positive electrode between electrodes to which an electric field is applied. Ideally, it should have high hole injection efficiency and efficient transport of the injected holes. Therefore, a material with a low ionization potential, high hole mobility, and thus excellent stability, and which is less likely to generate impurities that could become traps during manufacturing and use, is preferred.

[0353] As the material for forming the hole injection layer 103 and the hole transport layer 104, any compound can be selected from those compounds commonly used as hole charge transport materials in photoconductive materials, p-type semiconductors, and known compounds used in hole injection layers and hole transport layers of organic EL devices. Specific examples of these compounds include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), bis(N-arylcarbazole) or bis(N-alkylcarbazole) and other biscarbazole derivatives, triarylamine derivatives (polymers with aromatic tertiary amino groups on the main chain or side chain), 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine, N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl-1,1'-diamine, N 4 N 4' -diphenyl-N 4 N 4' -Bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4,4'-diamine, N 4 N 4 N 4' N 4' -Tetra[1,1'-biphenyl]-4-yl-[1,1'-biphenyl]-4,4'-diamine, 4,4',4”-tris(3-methylphenyl(phenyl)amino)triphenylamine and other triphenylamine derivatives, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (e.g., 1,4,5,8,9,12-hexaazatriphenyl-2,3,6,7,10,11-hexacarbononitrile, etc.), porphyrin derivatives and other heterocyclic compounds, polysilanes, etc. In polymer systems, polycarbonate or styrene derivatives, polyvinylcarbazole and polysilanes having the aforementioned monomers on the side chains are preferred, but there is no particular limitation as long as it is a compound that forms a thin film required for the fabrication of a light-emitting element and can inject holes from the anode and then transport holes.

[0354] Furthermore, it is known that the conductivity of organic semiconductors is strongly affected by their doping. The matrix material of such organic semiconductors contains compounds with good electron-donating or electron-accepting properties. For doping with electron-donating materials, strong electron acceptors such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluorotetetracyano-1,4-benzoquinone dimethylethane (F4TCNQ) are known (see, for example, the literature "M. Pfeiffer, A. Bayer, T. Fritz, K. Leo"). Beyer, T. Fritz, K. Leo, Appl. Phys. Letters, 73(22), 3202-3204 (1998) and the literature J. Blochwitz, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Letters, 73(6), 729-731 (1998)). They generate so-called holes through electron migration processes in electron-donating basic matter (hole-transporting matter). The conductivity of the basic matter varies considerably depending on the number and mobility of holes. As matrix materials with hole transport properties, known examples include benzidine derivatives (N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)benzidine (TPD), etc.) or starburst amine derivatives (4,4',4”-tris(N,N-diphenylamino)triphenylamine (TDATA), etc.), or specific metal phthalocyanines (especially zinc phthalocyanine (ZnPc), etc.) (Japanese Patent Application Publication No. 2005-167175).

[0355] The hole injection layer material and the hole transport layer material may also be used in the hole layer material as the following polymeric compounds or their polymeric crosslinks, or as the following suspended polymeric compounds or their suspended polymeric crosslinks. The polymeric compound is obtained by polymerizing a reactive compound, which is a monomer obtained by replacing reactive substituents in the hole injection layer material and the hole transport layer material. The suspended polymeric compound is obtained by reacting a main-chain polymer with the reactive compound. As for the reactive substituents in the above cases, the description of the polycyclic aromatic compounds represented by formula (1) can be referenced.

[0356] Details regarding the applications of this polymer compound and its crosslinked polymers will be described later.

[0357] 3-1-5. The light-emitting layer in organic electroluminescent devices

[0358] The light-emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 with electrons injected from the cathode 108 between electrodes to which an electric field is applied. As the material for forming the light-emitting layer 105, any compound that emits light upon excitation by the recombination of holes and electrons (a luminescent compound) is acceptable, and preferably a compound that can form a stable thin film shape and exhibits strong luminescence (fluorescence) efficiency in the solid state.

[0359] The light-emitting layer can be a single layer or multiple layers, either of which is acceptable, and each layer is formed from a light-emitting layer material (a host material and a dopant material). The host material and the dopant material can each be one type or a combination of multiple types, either of which is acceptable. The dopant material can be contained entirely within the host material or partially within the host material, either of which is acceptable. As for the doping method, it can be formed by co-evaporation with the host material, or it can be mixed with the host material beforehand and then evaporated simultaneously.

[0360] The compounds of the present invention are preferably used as materials for light-emitting layers, and particularly preferably as dopant materials.

[0361] The amount of main material used varies depending on the type of main material, and can be determined by considering the characteristics of the main material. The preferred basis for the amount of main material used is 50% to 99.999% of the total mass of the material used in the light-emitting layer, more preferably 80% to 99.95% of the total mass, and even more preferably 90% to 99.9% of the total mass.

[0362] The amount of dopant material used varies depending on the type of dopant material, and can be determined in accordance with the characteristics of the dopant material. The preferred amount of dopant is 0.001% to 50% of the total mass of the material used in the luminescent layer, more preferably 0.05% to 20% by mass, and even more preferably 0.1% to 10% by mass. If it falls within this range, it is preferred, for example, in terms of preventing concentration quenching.

[0363] As the main materials, anthracene, pyrene, and dibenzoxane can be listed as previously known luminescent materials. Fluorene or other fused-ring derivatives, bis(styrene) anthracene derivatives or styrene benzene derivatives, bis(styrene) derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, etc. Particularly preferred are anthracene compounds, fluorene compounds or dibenzo[a]benzene compounds. System of compounds.

[0364] <Anthracene compounds>

[0365] The anthracene compounds that form the main body are, for example, compounds represented by the following formula (3).

[0366]

[0367] In equation (3),

[0368] X and Ar 4 Each of the following is independently hydrogen, a substituted aryl group, a substituted heteroaryl group, a substituted diarylamino group, a substituted diheteroarylamino group, a substituted arylheteroarylamino group, a substituted alkyl group, a substituted cycloalkyl group, a substituted alkenyl group, a substituted alkoxy group, a substituted aryloxy group, a substituted arylthio group, or a substituted silyl group, X and Ar 4 Not all of them will become hydrogen at the same time.

[0369] At least one hydrogen atom in the compound represented by formula (3) may be substituted by a halogen, cyano, deuterium or a substituted heteroaryl group.

[0370] Alternatively, the structure represented by formula (3) can be used as a unit structure to form a polymer (preferably a dimer). In this case, for example, the forms in which the unit structures represented by formula (3) are linked to each other via X bonds can be listed. As X, examples include: single bonds, arylene groups (phenylene, biphenylene, and naphthylene, etc.) and heteroarylene groups (pyridine ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, benzocarbazole ring, and phenyl-substituted carbazole ring, etc., which have divalent bonding valences).

[0371] Details of the aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, or silyl groups will be described in the preferred forms section below. Furthermore, as substituents for these groups, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, or silyl groups can be listed, and details of these will also be described in the preferred forms section below.

[0372] The preferred forms of the anthracene compounds are described below. The definitions of the symbols in the following structures are the same as those described above.

[0373]

[0374] In equation (3), X is independently the base represented by equation (3-X1), equation (3-X2), or equation (3-X3), and the base represented by equation (3-X1), equation (3-X2), or equation (3-X3) is bonded to the anthracene ring of equation (3) at the * position. Preferably, the two X's will not simultaneously be the base represented by equation (3-X3). More preferably, the two X's will not simultaneously be the base represented by equation (3-X2).

[0375] Alternatively, the structure represented by formula (3) can be used as a unit structure to form a polymer (preferably a dimer). In this case, for example, the forms in which the unit structures represented by formula (3) are linked to each other via X bonds can be listed. As X, examples include: single bonds, arylene groups (phenylene, biphenylene, and naphthylene, etc.) and heteroarylene groups (pyridine ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, benzocarbazole ring, and phenyl-substituted carbazole ring, etc., which have divalent bonding valences).

[0376] The naphthyl group in formulas (3-X1) and (3-X2) can be formed by the condensation of a benzene ring. The structure formed by the condensation in this manner is shown below.

[0377]

[0378] Ar 1 and Ar 2 Each of the following is independently hydrogen, phenyl, biphenyl, terphenyl, tetraphenyl, naphthyl, phenanthrene, fluorene, benzo[2]fluorene, The group consisting of hydroxyl, triphenylene, pyrene, or any group represented by formula (A) (including carbazole, benzocarbazole, and phenyl-substituted carbazole). Furthermore, in Ar... 1 Or Ar 2 In the case of the base represented by formula (A), the base represented by formula (A) is bonded at its * position to the naphthalene ring in formula (3-X1) or formula (3-X2).

[0379] Ar 3 It is phenyl, biphenyl, terphenyl, tetraphenyl, naphthyl, phenanthryl, fluorenyl, benzo[a]fluorenyl, The group consisting of hydroxyl, triphenylene, pyrene, or any group represented by formula (A) (including carbazole, benzocarbazole, and phenyl-substituted carbazole). Furthermore, in Ar... 3 In the case of the base represented by equation (A), the base represented by equation (A) is bonded at its * position to the single bond represented by the straight line in equation (3-X3). That is, the anthracene ring in equation (3) is directly bonded to the base represented by equation (A).

[0380] Additionally, Ar 3 It can also have substituents, Ar 3At least one hydrogen atom may be derived from an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a fluorene group, or a phenyl group. Substitution with alkyl, triphenylene, pyrene, or any group represented by formula (A) (including carbazole and phenyl-substituted carbazole groups). Furthermore, in Ar... 3 In the case where the substituent is the base represented by formula (A), the base represented by formula (A) is analogous to Ar in formula (3-X3) at its * position. 3 Bond.

[0381] Ar 4 Each is independently hydrogen, phenyl, biphenyl, terphenyl, naphthyl, or a silyl group substituted with an alkyl group having 1 to 4 carbon atoms (methyl, ethyl, tert-butyl, etc.) and / or a cycloalkyl group having 5 to 10 carbon atoms.

[0382] Examples of alkyl groups with 1 to 4 carbon atoms that can be substituted in silanes include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, and cyclobutyl, etc., in which the three hydrogens in the silane are independently substituted by these alkyl groups.

[0383] Specific examples of "silyl groups substituted with alkyl groups having 1 to 4 carbon atoms" include: trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, trisec-butylsilyl, tritert-butylsilyl, ethyl dimethylsilyl, propyl dimethylsilyl, isopropyl dimethylsilyl, butyl dimethylsilyl, sec-butyl dimethylsilyl, tert-butyl dimethylsilyl, methyl diethylsilyl, propyl diethylsilyl, isopropyl diethylsilyl, butyl diethylsilyl, sec-butyl diethylsilyl, tert-butyl diethylsilyl, methyl dipropylsilyl, ethyl dipropylsilyl, butyl dipropylsilyl, sec-butyl dipropylsilyl, tert-butyl diisopropylsilyl, methyl diisopropylsilyl, ethyl diisopropylsilyl, butyl diisopropylsilyl, sec-butyl diisopropylsilyl, tert-butyl diisopropylsilyl, etc.

[0384] Examples of cycloalkyl groups with 5 to 10 carbon atoms that can be substituted in silanes include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornane, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.2.2]octyl, adamantyl, decahydronaphthyl, decahydroazyl, etc., in which the three hydrogens in the silane are independently substituted by these cycloalkyl groups.

[0385] Specific examples of "silyl groups substituted by cycloalkyl groups having 5 to 10 carbon atoms" include tricyclopentylsilane and tricyclohexylsilane.

[0386] As substituted silyl groups, there are also dialkylcycloalkylsilyl groups substituted with two alkyl groups and one cycloalkyl group, and alkyldicycloalkylsilyl groups substituted with one alkyl group and two cycloalkyl groups. As specific examples of substituted alkyl and cycloalkyl groups, the groups described above can be listed.

[0387] Furthermore, the hydrogen in the chemical structure of the anthracene compound represented by formula (3) may also be substituted by the group represented by formula (A). In the case of substitution by the group represented by formula (A), the group represented by formula (A) is substituted at its * position with at least one hydrogen in the compound represented by formula (3).

[0388] The group represented by formula (A) is one of the substituents that the anthracene compounds represented by formula (3) may have.

[0389]

[0390] In equation (A), Y is -O-, -S-, or >NR. 29 R 21 ~R 28 Each of the following is independently hydrogen, a substituted alkyl group, a substituted cycloalkyl group, a substituted aryl group, a substituted heteroaryl group, a substituted alkoxy group, a substituted aryloxy group, a substituted arylthio group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, an alkyldicycloalkylsilyl group, a substituted amino group, a halogen, a hydroxyl group, or a cyano group, R. 21 ~R 28 The adjacent groups in R can bond with each other to form hydrocarbon rings, aryl rings, or heteroaryl rings. 29 It is hydrogen or a substituted aryl group.

[0391] As R 21 ~R 28 The "alkyl" in "substitutable alkyl" can be either straight-chain or branched, for example, straight-chain alkyl with 1 to 24 carbon atoms or branched alkyl with 3 to 24 carbon atoms. Preferably, it is an alkyl with 1 to 18 carbon atoms (branched alkyl with 3 to 18 carbon atoms), more preferably an alkyl with 1 to 12 carbon atoms (branched alkyl with 3 to 12 carbon atoms), even more preferably an alkyl with 1 to 6 carbon atoms (branched alkyl with 3 to 6 carbon atoms), and particularly preferably an alkyl with 1 to 4 carbon atoms (branched alkyl with 3 to 4 carbon atoms).

[0392] Specific examples of "alkyl groups" include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, etc.

[0393] As R 21 ~R 28 The "cycloalkyl" in "substitutable cycloalkyl" can be exemplified by: cycloalkyl with 3 to 24 carbon atoms, cycloalkyl with 3 to 20 carbon atoms, cycloalkyl with 3 to 16 carbon atoms, cycloalkyl with 3 to 14 carbon atoms, cycloalkyl with 5 to 10 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, cycloalkyl with 5 carbon atoms, etc.

[0394] Specific examples of "cycloalkyl" include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and their alkyl (especially methyl) substituted derivatives having 1 to 4 carbon atoms, or norbornene, bicyclo[1.0.1]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.2.2]octyl, adamantyl, diadamantyl, decahydronaphthyl, decahydroazyl, etc.

[0395] As R 21 ~R 28 The "aryl" in "substitutable aryl" can be exemplified by aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 16 carbon atoms, more preferably aryl groups having 6 to 12 carbon atoms, and particularly preferably aryl groups having 6 to 10 carbon atoms.

[0396] Specific examples of "aryl" groups include: phenyl as a monocyclic compound, biphenyl as a bicyclic compound, naphthyl as a condensed bicyclic compound, terphenyl as a tricyclic compound (m-terphenyl, o-terphenyl, p-terphenyl), acenaphthene, fluorenyl, phenatenyl, and phenanthrene as condensed tricyclic compounds, triphenylene, pyrene, and tetraphenyl as condensed tetracyclic compounds, and perylene and pentaphenyl as condensed pentacyclic compounds.

[0397] As R 21 ~R 28The term "heteroaryl" in "substitutable heteroaryl" can include, for example, heteroaryl groups with 2 to 30 carbon atoms, preferably heteroaryl groups with 2 to 25 carbon atoms, more preferably heteroaryl groups with 2 to 20 carbon atoms, and even more preferably heteroaryl groups with 2 to 15 carbon atoms, particularly preferably heteroaryl groups with 2 to 10 carbon atoms. Furthermore, examples of heteroaryl groups include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen as ring-forming atoms, in addition to carbon atoms.

[0398] Specific examples of "heteroaryl" groups include: pyrrole, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazole, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, triazinyl, indole, isoindole, 1H-indazole, benzimidazole, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, and isoquinolinyl. , ...

[0399] As R 21 ~R 28 The "alkoxy group" in "substitutable alkoxy group" can include, for example, straight-chain alkoxy groups with 1 to 24 carbon atoms or branched-chain alkoxy groups with 3 to 24 carbon atoms. Preferably, it is an alkoxy group with 1 to 18 carbon atoms (branched-chain alkoxy groups with 3 to 18 carbon atoms), more preferably an alkoxy group with 1 to 12 carbon atoms (branched-chain alkoxy groups with 3 to 12 carbon atoms), and even more preferably an alkoxy group with 1 to 6 carbon atoms (branched-chain alkoxy groups with 3 to 6 carbon atoms), and particularly preferably an alkoxy group with 1 to 4 carbon atoms (branched-chain alkoxy groups with 3 to 4 carbon atoms).

[0400] Specific examples of "alkoxy groups" include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy, heptoxy, octoxy, etc.

[0401] R 21 ~R 28 In the phrase "substitutable aryloxy group", the "aryloxy group" is a group in which the hydrogen of the -OH group is replaced by an aryl group, and the aryl group can be referenced as the R group. 21 ~R 28 The "aryl" in the text refers to the base.

[0402] R 21 ~R 28 The "arylthio" in "substitutable arylthio" refers to a group in which the hydrogen of the -SH group is replaced by an aryl group, and the aryl group can be referenced as the R.21 ~R 28 The "aryl" in the text refers to the base.

[0403] As R 21 ~R 28 The term "trialkylsilyl" can be an example of a silyl group in which each of the three hydrogens is independently replaced by an alkyl group, and the alkyl group can be referenced as R. 21 ~R 28 The "alkyl" in the text refers to the group. For substitution, the preferred alkyl group is an alkyl group having 1 to 4 carbon atoms, specifically including: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclobutyl, etc.

[0404] Specific examples of "trialkylsilyl" include: trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, trisec-butylsilyl, tritert-butylsilyl, ethyl dimethylsilyl, propyl dimethylsilyl, isopropyl dimethylsilyl, butyl dimethylsilyl, sec-butyl dimethylsilyl, tert-butyl dimethylsilyl, methyl diethylsilyl, propyl diethylsilyl, isopropyl diethylsilyl, butyl diethylsilyl, sec-butyl diethylsilyl, tert-butyl diethylsilyl, methyl dipropylsilyl, ethyl dipropylsilyl, butyl dipropylsilyl, sec-butyl dipropylsilyl, tert-butyl diisopropylsilyl, methyl diisopropylsilyl, ethyl diisopropylsilyl, butyl diisopropylsilyl, sec-butyl diisopropylsilyl, tert-butyl diisopropylsilyl, etc.

[0405] As R 21 ~R 28 The term "tricycloalkylsilyl" can be an example of a silyl group in which each of the three hydrogens is independently replaced by a cycloalkyl group, and the cycloalkyl group can be referenced as R. 21 ~R 28 The term "cycloalkyl" refers to the group used for substitution. Preferred cycloalkyl groups for substitution are those with 5 to 10 carbon atoms, specifically including: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, decahydronaphthyl, decahydroazyl, etc.

[0406] Specific examples of "tricycloalkylsilyl" include tricyclopentylsilyl and tricyclohexylsilyl.

[0407] As specific examples of substituted dialkylcycloalkylsilyl groups with two alkyl groups and one cycloalkyl group, and substituted alkyldicycloalkylsilyl groups with one alkyl group and two cycloalkyl groups, examples include silyl groups substituted with groups selected from the specific alkyl and cycloalkyl groups.

[0408] As R 21 ~R 28 The term "substituted amino group" in the phrase "substituteable amino group" can include, for example, amino groups in which two hydrogen atoms are substituted by an aryl or heteroaryl group. An amino group in which two hydrogen atoms are substituted by an aryl group is a diaryl-substituted amino group, an amino group in which two hydrogen atoms are substituted by a heteroaryl group is a dihexanel-substituted amino group, and an amino group in which both hydrogen atoms are substituted by an aryl and a heteroaryl group is an arylhexanel-substituted amino group. The aryl or heteroaryl group can be referenced as R. 21 ~R 28 The group is described by the "aryl" or "heteroaryl" in the text.

[0409] Specific examples of "substituted amino groups" include: diphenylamino, dinaphthylamino, phenylnaphthylamino, dipyridylamino, phenylpyridylamino, naphthylpyridylamino, etc.

[0410] As R 21 ~R 28 The "halogens" mentioned include: fluorine, chlorine, bromine, and iodine.

[0411] As R 21 ~R 28 Among the groups described, several groups can also be substituted in the manner described above. Examples of substituents in this case include alkyl, cycloalkyl, aryl, or heteroaryl groups. The alkyl, cycloalkyl, aryl, or heteroaryl groups can be referenced as R. 21 ~R 28 The group is indicated by "alkyl", "cycloalkyl", "aryl" or "heteroaryl".

[0412] As Y > NR 29 R in " 29 The aryl group is hydrogen or a substituted aryl group, which can be referenced as R. 21 ~R 28 The "aryl" in the text refers to the group, and furthermore, as the substituent, it can be cited as a group targeting R. 21 ~R 28 The base is explained by the substituent.

[0413] R 21 ~R 28The adjacent groups in the formula can bond with each other to form a hydrocarbon ring, aryl ring, or heteroaryl ring. The group that does not form a ring is represented by the group in formula (A-1) below; for example, the groups represented by formulas (A-2) to (A-14) below can be listed as ring-forming groups. Furthermore, at least one hydrogen atom in any of the groups represented by formulas (A-1) to (A-14) can be substituted by an alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, diaryl-substituted amino, diheteroaryl-substituted amino, arylheteroaryl-substituted amino, halogen, hydroxyl, or cyano group.

[0414]

[0415] A ring formed by the mutual bonding of adjacent groups, if it is a hydrocarbon ring, for example, the cyclohexane ring; if it is an aryl ring or a heteroaryl ring, the R group can be listed as an example. 21 ~R 28 The ring structures described in “aryl” or “heteroaryl” are formed by condensation with one or both benzene rings of formula (A-1).

[0416] As a basis represented by formula (A), for example, any of the formulas (A-1) to (A-14) can be listed as a basis, preferably any of the formulas (A-1) to (A-5) and (A-12) to (A-14) as a basis, more preferably any of the formulas (A-1) to (A-4) as a basis, and even more preferably any of the formulas (A-1), (A-3) and (A-4) as a basis, and particularly preferably the basis represented by formula (A-1).

[0417] As described above, the base represented by formula (A) at the * position in formula (A) is related to the naphthalene ring in formula (3-X1) or formula (3-X2), the single bond in formula (3-X3), or the Ar in formula (3-X3). 3 In addition, the bonds are substituted with at least one hydrogen atom in the compound represented by formula (3), but in these bond forms, the preferred substitutions are with the naphthalene ring in formula (3-X1) or formula (3-X2), the single bond in formula (3-X3), and / or the Ar atom in formula (3-X3). 3 The shape of the bond.

[0418] Additionally, regarding the naphthalene ring in formula (3-X1) or formula (3-X2), the single bond in formula (3-X3), and the Ar in formula (3-X3)... 3The positions where the bonding occurs in the structure of the base represented by formula (A) and the positions where at least one hydrogen atom in the compound represented by formula (3) is substituted in the structure of the base represented by formula (A) can be any positions in the structure of formula (A), for example, on either of the two benzene rings in the structure of formula (A), or on R in the structure of formula (A). 21 ~R 28 On any ring formed by the mutual bonding of adjacent bases in the equation (A), or as Y in the structure of equation (A), ">NR 29 "R" 29 Bonding can be performed at any position within the structure.

[0419] As a basis represented by equation (A), the following bases can be listed for example. The definitions of Y and * in the equation are the same as those above.

[0420]

[0421] In addition, all or part of the hydrogen in the chemical structure of the anthracene compounds represented by formula (3) can be deuterium.

[0422] Specific examples of anthracene compounds include those represented by formulas (3-1) to (3-72) below. Furthermore, in the following structural formulas, "Me" represents methyl, "D" represents deuterium, and "tBu" represents tert-butyl.

[0423]

[0424]

[0425]

[0426]

[0427] The anthracene compounds represented by formula (3) can be compounds with reactive groups at desired positions on the anthracene skeleton, as well as compounds with reactive groups at X, Ar, and other positions. 4 Compounds with reactive groups in the structure of formula (A) or other parts thereof are used as starting materials and manufactured by applying Suzuki coupling, Negishi coupling, or other known coupling reactions. Examples of reactive groups in these reactive compounds include halogens or boric acids. For specific manufacturing methods, for example, refer to the synthesis methods described in paragraphs

[0089] to

[0175] of International Publication No. 2014 / 141725.

[0428] <Fluorene compounds>

[0429] The compound represented by equation (4) essentially functions as the main component.

[0430]

[0431] In the above formula (4),

[0432] R 1 To R 10 Each of the following groups is independently hydrogen, aryl, heteroaryl (the heteroaryl group may be bonded to the fluorene skeleton in formula (4) via a linker), diarylamino, diheterarylamino, arylheterarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, or aryloxy, wherein at least one hydrogen atom may be substituted by aryl, heteroaryl, alkyl, or cycloalkyl.

[0433] Additionally, R 1 With R 2 R 2 With R 3 R 3 With R 4 R 5 With R 6 R 6 With R 7 R 7 With R 8 Or R 9 With R 10 They can be independently bonded to form fused rings or spiro rings, and at least one hydrogen in the formed ring can be replaced by an aryl, heteroaryl (the heteroaryl can be bonded to the formed ring via a linker), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, or aryloxy group, and at least one hydrogen in these groups can be replaced by an aryl, heteroaryl, alkyl, or cycloalkyl group, and moreover,

[0434] At least one hydrogen atom in the compound represented by formula (4) may be substituted by halogen, cyano or deuterium.

[0435] For details of each group in the definition of formula (4), please refer to the description of polycyclic aromatic compounds in formula (1) above.

[0436] As R 1 To R 10 The alkenyl group in the text can be, for example, an alkenyl group with 2 to 30 carbon atoms, preferably an alkenyl group with 2 to 20 carbon atoms, more preferably an alkenyl group with 2 to 10 carbon atoms, and even more preferably an alkenyl group with 2 to 6 carbon atoms, particularly preferably an alkenyl group with 2 to 4 carbon atoms. Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl.

[0437] Furthermore, as specific examples of heteroaryl groups, monovalent groups can also be represented by removing any one hydrogen atom from compounds of the following formulas (4-Ar1), (4-Ar2), (4-Ar3), (4-Ar4), or (4-Ar5).

[0438]

[0439] In equations (4-Ar1) to (4-Ar5), Y 1 Each can be independently O, S, or NR, where R is phenyl, biphenyl, naphthyl, anthracene, or hydrogen.

[0440] At least one hydrogen atom in the structures of formulas (4-Ar1) to (4-Ar5) may be substituted by phenyl, biphenyl, naphthyl, anthraceneyl, phenanthryl, methyl, ethyl, propyl or butyl.

[0441] These heteroaryl groups can be bonded to the fluorene skeleton in formula (4) via a linker group. That is, the fluorene skeleton in formula (4) can be directly bonded to the heteroaryl group, or they can be bonded to each other via a linker group. Examples of such linker groups include: phenylene, biphenylene, naphthylene, anthraceneylene, methylene, ethylene, -OCH2CH2-, -CH2CH2O-, or -OCH2CH2O-.

[0442] In addition, R in equation (4) 1 With R 2 R 2 With R 3 R 3 With R 4 R 5 With R 6 R 6 With R 7 Or R 7 With R 8 They can be bonded independently to form fused rings, R 9 With R 10 They can be bonded to form a helical ring. (From R) 1 To R 8 The formed fused ring is a ring condensed with the benzene ring in formula (4) and is either an aliphatic ring or an aromatic ring. An aromatic ring is preferred; examples of structures containing the benzene ring in formula (4) include naphthalene rings or phenanthrene rings. From R... 9 With R 10 The formed spiral ring is a ring that is helically bonded to the 5-membered ring in formula (4) and is either an aliphatic ring or an aromatic ring. An aromatic ring is preferred, such as a fluorene ring.

[0443] The compound represented by formula (4) is preferably a compound represented by formula (4-1), formula (4-2) or formula (4-3) below, and R in formula (4) is respectively a compound represented by R. 1With R 2 Compounds formed by the condensation of benzene rings through bonding, in formula (4) R 3 With R 4 Compounds formed by the condensation of benzene rings through bonding, in formula (4) R 1 To R 8 A compound in which neither of the elements is bonded.

[0444]

[0445] R in equations (4-1), (4-2) and (4-3) 1 To R 10 The definition of R corresponding to equation (4) 1 To R 10 The same, and R in equations (4-1) and (4-2) 11 To R 14 The definition is also the same as R in equation (4). 1 To R 10 same.

[0446] The compound represented by formula (4) is preferably a compound represented by formula (4-1A), formula (4-2A) or formula (4-3A), wherein R is in formula (4-1), formula (4-2) or formula (4-3), respectively. 9 With R 10 Compounds that form spirofluorene rings through bonding.

[0447]

[0448] R in equations (4-1A), (4-2A) and (4-3A) 2 To R 7 The definition of R corresponding to equations (4-1), (4-2), and (4-3) 2 To R 7 The same, and R in equations (4-1A) and (4-2A) 11 To R 14 The definition is also the same as R in equations (4-1) and (4-2). 11 To R 14 same.

[0449] In addition, all or part of the hydrogen in the compound represented by formula (4) may be replaced by halogen, cyano or deuterium.

[0450] <Dibenzo-p-ethyl System compounds >

[0451] dibenzo[a] as the main component The compounds are, for example, those represented by the following formula (5).

[0452]

[0453] In the above formula (5),

[0454] R 1 To R 16 Each of the following is independently hydrogen, aryl, or heteroaryl (the heteroaryl group can be linked to the dibenzo[a] in formula (5) via a linker). (Skeleton bond), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, or aryloxy, wherein at least one hydrogen atom may be substituted by an aryl, heteroaryl, alkyl, or cycloalkyl group.

[0455] Additionally, R 1 To R 16 The adjacent groups in the ring can bond to each other to form a fused ring, and at least one hydrogen in the formed ring can be replaced by an aryl, heteroaryl (the heteroaryl can be bonded to the formed ring via a linker), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, or aryloxy group, and at least one hydrogen in these groups can be replaced by an aryl, heteroaryl, alkyl, or cycloalkyl group, and moreover,

[0456] At least one hydrogen atom in the compound represented by formula (5) may be substituted by halogen, cyano or deuterium.

[0457] For details of each group in the definition of formula (5), please refer to the description of polycyclic aromatic compounds in formula (1) above.

[0458] As an alkenyl group defined in formula (5), examples include alkenyl groups with 2 to 30 carbon atoms, preferably alkenyl groups with 2 to 20 carbon atoms, more preferably alkenyl groups with 2 to 10 carbon atoms, and even more preferably alkenyl groups with 2 to 6 carbon atoms, particularly preferably alkenyl groups with 2 to 4 carbon atoms. Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl.

[0459] Furthermore, as specific examples of heteroaryl groups, monovalent groups can also be represented by removing any one hydrogen atom from compounds of the following formulas (5-Ar1), (5-Ar2), (5-Ar3), (5-Ar4), or (5-Ar5).

[0460]

[0461] In equations (5-Ar1) to (5-Ar5), Y 1 Each can be independently O, S, or NR, where R is phenyl, biphenyl, naphthyl, anthracene, or hydrogen.

[0462] At least one hydrogen atom in the structures of formulas (5-Ar1) to (5-Ar5) may be substituted by phenyl, biphenyl, naphthyl, anthraceneyl, phenanthryl, methyl, ethyl, propyl or butyl.

[0463] These heteroaryl groups can bind to the dibenzo[a] in formula (5) via a linker group. Skeletal bonding. That is, the dibenzo[a] in formula (5) The skeleton and the heteroaryl group can be directly bonded, or they can be bonded together via a linker group. Examples of such linker groups include: phenylene, biphenylene, naphthylene, anthraceneylene, methylene, ethylene, -OCH2CH2-, -CH2CH2O-, or -OCH2CH2O-.

[0464] The compound represented by formula (5) is preferably R. 1 R 4 R 5 R 8 R 9 R 12 R 13 and R 16 It is hydrogen. In this case, R in equation (5) 2 R 3 R 6 R 7 R 10 R 11 R 14 and R 15 Preferably, the monovalent group is independently hydrogen, phenyl, biphenyl, naphthyl, anthracene, phenanthrene, or has the structure of formula (5-Ar1), (5-Ar2), (5-Ar3), (5-Ar4), or (5-Ar5). (The monovalent group having the structure can be associated with the diphenyl group in formula (5) via phenylene, biphenylene, naphthylene, anthracene, methylene, ethylene, -OCH2CH2-, -CH2CH2O-, or -OCH2CH2O-.) (Skeleton bonds), methyl, ethyl, propyl or butyl.

[0465] The compound represented by formula (5) is more preferably R. 1 R 2 R 4 R 5 R 7 R 8 R 9 R 10 R 12 R 13 R 15 and R 16It is hydrogen. In this case, R in equation (5) 3 R 6 R 11 and R 14 At least one (preferably one or two, more preferably one) is a monovalent group having a structure of formula (5-Ar1), (5-Ar2), (5-Ar3), (5-Ar4), or (5-Ar5) separated by a single bond, phenylene, biphenylene, naphthylene, anthraceneylene, methylene, ethylene, -OCH2CH2-, -CH2CH2O-, or -OCH2CH2O-.

[0466] The least one other (i.e., the position other than that replaced by the monovalent group having the structure) is hydrogen, phenyl, biphenyl, naphthyl, anthracene, methyl, ethyl, propyl or butyl, wherein at least one hydrogen may be substituted by phenyl, biphenyl, naphthyl, anthracene, methyl, ethyl, propyl or butyl.

[0467] Furthermore, when selecting a monovalent base having the structure represented by equations (5-Ar1) to (5-Ar5) as R in equation (5) 2 R 3 R 6 R 7 R 10 R 11 R 14 and R 15 In the case that at least one hydrogen in the structure can react with R in formula (5) 1 To R 16 A single bond is formed by bonding any one of the bonds.

[0468] The light-emitting layer material (both the host material and the dopant material) may also be used in the light-emitting layer material as a polymeric compound or a polymeric crosslink thereof, or as a suspended polymeric compound or a suspended polymeric crosslink thereof. The polymeric compound is obtained by polymerizing a reactive compound, which is a monomer formed by replacing reactive substituents in the light-emitting layer material (both the host material and the dopant material). The suspended polymeric compound is obtained by reacting a main-chain polymer with the reactive compound. The description of the reactive substituent in the above cases can be found in the polycyclic aromatic compounds represented by formula (1).

[0469] Details regarding the applications of this polymer compound and its crosslinked polymers will be described later.

[0470] <An Example of a Polymer Host Material>

[0471]

[0472] In formula (SPH-1),

[0473] MU is a divalent aromatic compound, EC is a monovalent aromatic compound, the two hydrogens in MU are substituted with EC or MU, and k is an integer from 2 to 50000.

[0474] More specifically,

[0475] MU can be independently arylene, heteroarylene, diarylenearylamino, diarylenearylboryl, oxaborane-diyl, or azaborane-diyl.

[0476] EC can be independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, or aryloxy, respectively.

[0477] At least one hydrogen in MU and EC may be further substituted with aryl, heteroaryl, diarylamino, alkyl and cycloalkyl, where k is an integer from 2 to 50,000.

[0478] k is preferably an integer from 20 to 50,000, and more preferably an integer from 100 to 50,000.

[0479] At least one hydrogen in MU and EC in formula (SPH-1) may be substituted by an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, a halogen, or deuterium. Furthermore, any -CH2- in the alkyl group may be substituted by -O- or -Si(CH3)2-. Any -CH2- in the alkyl group other than the -CH2- that is directly bonded to EC in formula (SPH-1) may be substituted by an aryl group having 6 to 24 carbon atoms. Any hydrogen in the alkyl group may be substituted by fluorine.

[0480] As a MU, for example, a divalent group can be represented by removing any two hydrogen atoms from any of the following compounds.

[0481]

[0482] More specifically, examples of divalent bases represented by any of the following structures can be listed. In these, MU is bonded to other MU or EC at the * position.

[0483]

[0484]

[0485]

[0486]

[0487] Furthermore, as an EC, one can exemplify any of the following structures representing a monovalent base. In these, the EC is bonded to MU at *.

[0488]

[0489]

[0490] From the viewpoint of solubility and coating film-forming properties, the compound represented by formula (SPH-1) preferably has 10% to 100% of the total number of MUs (k) in the molecule having alkyl groups with 1 to 24 carbons, more preferably 30% to 100% of the total number of MUs (k) in the molecule having alkyl groups with 1 to 18 carbons (branched alkyl groups with 3 to 18 carbons), and even more preferably 50% to 100% of the total number of MUs (k) in the molecule having alkyl groups with 1 to 12 carbons (branched alkyl groups with 3 to 12 carbons). On the other hand, from the viewpoint of in-plane orientation and charge transport, it is preferable that 10% to 100% of the total number of MUs (k) in the molecule has alkyl groups with 7 to 24 carbons, more preferably 30% to 100% of the total number of MUs (k) in the molecule having alkyl groups with 7 to 24 carbons (branched alkyl groups with 7 to 24 carbons).

[0491] Details regarding the applications of this polymer compound and its crosslinked polymers will be described later.

[0492] 3-1-6. Electron injection layer and electron transport layer in organic electroluminescent devices

[0493] The electron injection layer 107 efficiently injects electrons migrating from the cathode 108 into the light-emitting layer 105 or the electron transport layer 106. The electron transport layer 106 efficiently transports electrons injected from the cathode 108, or electrons injected from the cathode 108 via the electron injection layer 107, to the light-emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are formed by laminating or mixing one or more electron transport / injection materials, or by forming a mixture of electron transport / injection materials and a polymer binder.

[0494] The electron injection / transport layer is a layer responsible for injecting electrons from the cathode and then transporting them. Ideally, it should have high electron injection efficiency and efficient electron transport. Therefore, materials with high electron affinity and high electron mobility, resulting in excellent stability and minimizing the formation of impurities that could become traps during manufacturing and use, are preferred. However, considering the balance between hole and electron transport, when the primary function is to efficiently prevent unrecombined holes from the anode from flowing to the cathode, even materials with lower electron transport capabilities can achieve the same effect of improving luminous efficiency as materials with high electron transport capabilities. Therefore, the electron injection / transport layer in this embodiment may also include the function of a layer that efficiently prevents hole migration.

[0495] The material (electron transport material) used to form the electron transport layer 106 or the electron injection layer 107 can be arbitrarily selected from compounds commonly used as electron transport compounds in photoconductive materials, and compounds known to be used in electron injection layers and electron transport layers of organic EL elements.

[0496] The materials used in the electron transport layer or electron injection layer are preferably compounds containing at least one of the following: compounds containing an aromatic ring or heteroaromatic ring comprising one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus; pyrrole derivatives and their fused-ring derivatives; and metal complexes with electron-accepting nitrogen. Specifically, examples include: fused-ring aromatic ring derivatives such as naphthalene and anthracene; styryl aromatic ring derivatives represented by 4,4'-bis(diphenylvinyl)biphenyl; violet ketone derivatives; coumarin derivatives; naphthalenedicarboximide derivatives; quinone derivatives such as anthraquinone or biphenylquinone; phosphorus oxide derivatives; aryl nitrile derivatives; and indole derivatives. Examples of metal complexes with electron-accepting nitrogen include: hydroxyazole complexes such as hydroxyphenyloxazole complexes; methylimine complexes; cycloheptatrienolone metal complexes; flavonol metal complexes; and benzoquinoline metal complexes. These materials can be used alone or in combination with different materials.

[0497] In addition, specific examples of other electron-transfer compounds include: pyridine derivatives, naphthalene derivatives, anthracene derivatives, benzo[a]fluorene derivatives, phenanthroline derivatives, violet ketone derivatives, coumarin derivatives, naphthalenedicarboximide derivatives, anthraquinone derivatives, biphenylquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives (such as 1,3-bis[(4-tert-butylphenyl)1,3,4-oxadiazolyl]benzene), thiophene derivatives, triazole derivatives (such as N-naphthyl-2,5-diphenyl-1,3,4-triazole), thiadiazole derivatives, metal complexes of 8-hydroxyquinoline derivatives, hydroxyquinoline-based metal complexes, quinoxoline derivatives, polymers of quinoxoline derivatives, indole (benzazole) compounds, gallium complexes, and pyrazoles. Derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis(benzo[h]quinoline-2-yl)-9,9'-spirodifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris(N-phenylbenzimidazole-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”-terpyridyl))benzene, naphthidine derivatives (bis(1-naphthyl)-4-(1,8-naphthidyl-2-yl)phenylphosphine oxide, etc.), aldehyde azo derivatives, aryl nitrile derivatives, indole derivatives, phosphine oxide derivatives, bisstyrene derivatives, etc.

[0498] Alternatively, metal complexes with electron-accepting nitrogen can be used, such as hydroxyquinoline metal complexes or hydroxyphenyloxazole complexes, methylimine complexes, cycloheptatrienolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes.

[0499] The material can be used alone or in combination with different materials.

[0500] The preferred materials are borane derivatives, pyridine derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzo[a]fluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, aryl nitrile derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and hydroxyquinoline-based metal complexes.

[0501] <Boronane Derivatives>

[0502] Borane derivatives, for example, are compounds represented by the following formula (ETM-1), which are disclosed in detail in Japanese Patent Application Publication No. 2007-27587.

[0503]

[0504] In formula (ETM-1), R 11 and R 12 R is independently one of hydrogen, alkyl, cycloalkyl, substituted aryl, substituted silyl, substituted nitrogen-containing heterocycle or cyano. 13 ~R 16 Each of the following groups can be independently substituted: alkyl, cycloalkyl, or aryl; X can be substituted: arylene; Y can be substituted: aryl with 16 or fewer carbon atoms, substituted: boronyl, or substituted: carbazoyl; and n can be independently an integer from 0 to 3. Examples of substituents for "substitutable" or "substituted" include: aryl, heteroaryl, alkyl, or cycloalkyl.

[0505] The compounds represented by formula (ETM-1) are preferably those represented by formula (ETM-1-1) or those represented by formula (ETM-1-2).

[0506]

[0507] In formula (ETM-1-1), R 11 and R 12 R is independently one of hydrogen, alkyl, cycloalkyl, substituted aryl, substituted silyl, substituted nitrogen-containing heterocycle or cyano. 13 ~R 16 R is independently a substituted alkyl, a substituted cycloalkyl, or a substituted aryl group. 21 and R 22 Each of the following is independently one of hydrogen, alkyl, cycloalkyl, substituted aryl, substituted silyl, substituted nitrogen-containing heterocycle, or cyano, X 1 The substituent is an arylene group with 20 or fewer carbon atoms that can be substituted, where n is an integer from 0 to 3, and m is an integer from 0 to 4. Examples of substituents for "substitutable" or "substituted" include aryl, heteroaryl, alkyl, or cycloalkyl groups.

[0508]

[0509] In formula (ETM-1-2), R 11 and R 12 R is independently one of hydrogen, alkyl, cycloalkyl, substituted aryl, substituted silyl, substituted nitrogen-containing heterocycle or cyano. 13 ~R 16 Each of the following is independently a substituted alkyl, a substituted cycloalkyl, or a substituted aryl group, X 1It is a substitutable aryl group with 20 or fewer carbon atoms, and n is an integer from 0 to 3. In addition, examples of substituents as "substitutable" or "substituted" include aryl, heteroaryl, alkyl or cycloalkyl, etc.

[0510] As X 1 Specific examples can be listed as the divalent base represented by any of the following equations (X-1) to (X-9).

[0511]

[0512] (In each formula, R) a Each is independently an alkyl, cycloalkyl, or substituted phenyl group (* indicates the bond position).

[0513] Specific examples of the borane derivatives include the following compounds.

[0514]

[0515] The borane derivatives can be manufactured using known raw materials and known synthetic methods.

[0516] <Pyridine Derivatives>

[0517] The pyridine derivative is, for example, a compound represented by the following formula (ETM-2), preferably a compound represented by formula (ETM-2-1) or formula (ETM-2-2).

[0518] φ—(pyridine substituent)n (ETM-2)

[0519]

[0520] φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzo[a]fluorene ring, finadene ring, phenanthrene ring, or triphenylene ring), and n is an integer from 1 to 4.

[0521] In equation (ETM-2-1), R 11 ~R 18 Each of the following can be independently hydrogen, alkyl (preferably alkyl with 1 to 24 carbons), cycloalkyl (preferably cycloalkyl with 3 to 12 carbons) or aryl (preferably aryl with 6 to 30 carbons).

[0522] In equation (ETM-2-2), R 11 and R 12 Each of the following is independently hydrogen, alkyl (preferably alkyl with 1 to 24 carbons), cycloalkyl (preferably cycloalkyl with 3 to 12 carbons), or aryl (preferably aryl with 6 to 30 carbons), R 11 and R 12 They can bond together to form a ring.

[0523] In each formula, the "pyridine substituent" is any one of the following formulas (Py-1) to (Py-15) (where * indicates the bonding position), and the pyridine substituent may be independently substituted by an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, with methyl being preferred. Furthermore, the pyridine substituent may be bonded to the φ, anthracene ring, or fluorene ring in each formula via a phenylene or naphthylene group.

[0524]

[0525] The pyridine substituents are any of formulas (Py-1) to (Py-15) (where * indicates the bonding position), and among these, any of formulas (Py-21) to (Py-44) are preferred.

[0526]

[0527] At least one hydrogen atom in each pyridine derivative may be substituted with deuterium. In addition, one of the two “pyridine substituents” in formula (ETM-2-1) and formula (ETM-2-2) may be substituted with aryl.

[0528] R 11 ~R 18 The term "alkyl" can be either straight-chain or branched, for example, straight-chain alkyl with 1 to 24 carbon atoms or branched alkyl with 3 to 24 carbon atoms. Preferred "alkyl" is an alkyl with 1 to 18 carbon atoms (branched alkyl with 3 to 18 carbon atoms). More preferably, an alkyl with 1 to 12 carbon atoms (branched alkyl with 3 to 12 carbon atoms). Even more preferably, an alkyl with 1 to 6 carbon atoms (branched alkyl with 3 to 6 carbon atoms). Particularly preferred "alkyl" is an alkyl with 1 to 4 carbon atoms (branched alkyl with 3 to 4 carbon atoms).

[0529] Specific examples of "alkyl groups" include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, etc.

[0530] The description of the alkyl group can be cited as an example of an alkyl group having 1 to 4 carbon atoms that is substituted in a pyridine substituent.

[0531] As R 11 ~R 18 The term "cycloalkyl" can be exemplified by cycloalkyl groups having 3 to 12 carbon atoms. Preferably, the "cycloalkyl" is a cycloalkyl group having 3 to 10 carbon atoms. More preferably, the "cycloalkyl" is a cycloalkyl group having 3 to 8 carbon atoms. Even more preferably, the "cycloalkyl" is a cycloalkyl group having 3 to 6 carbon atoms.

[0532] Specific examples of "cycloalkyl groups" include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, or dimethylcyclohexyl, etc.

[0533] As R 11 ~R 18 The "aryl" in the text is preferably an aryl group with 6 to 30 carbon atoms, more preferably an aryl group with 6 to 18 carbon atoms, and even more preferably an aryl group with 6 to 14 carbon atoms, and particularly preferably an aryl group with 6 to 12 carbon atoms.

[0534] Specific examples of "aryl groups with 6 to 30 carbon atoms" include: phenyl as a monocyclic aryl group; (1-, 2-)naphthyl as a condensed bicyclic aryl group; acenaphthene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenaten-(1-, 2-)yl, and (1-, 2-, 3-, 4-, 9-)phenanthyl as condensed tricyclic aryl groups; triphenylene-(1-, 2-)yl, pyrene-(1-, 2-, 4-)yl, and tetraphenyl-(1-, 2-, 5-)yl as condensed tetracyclic aryl groups; and perylene-(1-, 2-, 3-)yl and pentaphenyl-(1-, 2-, 5-, 6-)yl as condensed pentacyclic aryl groups.

[0535] Preferred aryl groups with 6 to 30 carbon atoms include phenyl, naphthyl, phenanthrene, etc. The compounds may be phenyl, 1-naphthyl, 2-naphthyl or phenanthrene, and are particularly preferably phenyl, 1-naphthyl or 2-naphthyl.

[0536] R in equation (ETM-2-2) 11 and R 12 It can bond to form rings, resulting in the formation of cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, or indene, etc., on the 5-membered ring of the fluorene skeleton.

[0537] Specific examples of the pyridine derivatives include the following compounds.

[0538]

[0539] The pyridine derivative can be manufactured using known raw materials and known synthetic methods.

[0540] <Fluoranthracene derivatives>

[0541] Fluoranthracene derivatives are, for example, compounds represented by the following formula (ETM-3), which are disclosed in detail in International Publication No. 2010 / 134352.

[0542]

[0543] In formula (ETM-3), X 12 ~X 21 This refers to hydrogen, halogen, straight-chain, branched, or cyclic alkyl, straight-chain, branched, or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. Examples of substituents when substituted include aryl, heteroaryl, alkyl, or cycloalkyl.

[0544] Specific examples of the fluoranthene derivatives include the following compounds.

[0545]

[0546] <BO-series derivatives>

[0547] BO derivatives are, for example, polycyclic aromatic compounds represented by the following formula (ETM-4), or polymers of polycyclic aromatic compounds having a plurality of structures represented by the following formula (ETM-4).

[0548]

[0549] R 1 ~R 11 Each of the following is independently hydrogen, aryl, heteroaryl, diarylamino, diherylamino, arylherylamino, alkyl, cycloalkyl, alkoxy, or aryloxy, wherein at least one hydrogen atom may be substituted by aryl, heteroaryl, alkyl, or cycloalkyl.

[0550] Additionally, R 1 ~R 11 The adjacent groups in the ring can be bonded to each other and together with the a ring, b ring or c ring to form an aryl ring or a heteroaryl ring. At least one hydrogen in the formed ring can be replaced by an aryl, heteroaryl, diarylamino, diarylamino, arylhexylamino, alkyl, cycloalkyl, alkoxy or aryloxy group. At least one hydrogen in the ring can be replaced by an aryl, heteroaryl, alkyl or cycloalkyl group.

[0551] In addition, at least one hydrogen atom in the compound or structure represented by formula (ETM-4) may be substituted with halogen or deuterium.

[0552] For an explanation of the morphology of the substituents or rings in formula (ETM-4), please refer to the description of polycyclic aromatic compounds represented by formula (1) or formula (1-a).

[0553] Specific examples of the BO-based derivatives include the following compounds.

[0554]

[0555] The BO-based derivatives can be manufactured using known raw materials and known synthetic methods.

[0556] <Anthracene derivatives>

[0557] One example of anthracene derivatives is a compound represented by the following formula (ETM-5).

[0558]

[0559] Ar 1 Each of these can be independently a single bond, a divalent benzene, naphthalene, anthracene, fluorene, or finasteride.

[0560] Ar 2Each aryl group is independently composed of 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, more preferably 6 to 12 carbon atoms, and particularly preferably 6 to 10 carbon atoms. Specific examples of "aryl groups with 6 to 20 carbon atoms" include: phenyl, (o-, m-, p-)tolyl, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-)xylyl, mesityleneyl (2,4,6-trimethylphenyl), (o-, m-, p-)cumenel as monocyclic aryl groups; (2-, 3-, 4-)biphenyl as bicyclic aryl groups; (1-, 2-)naphthyl as condensed bicyclic aryl groups; and terphenyl as tricyclic aryl groups (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-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), anthracene-(1-, 2-, 9-)yl, acenaphthene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenaten-(1-, 2-)yl, (1-, 2-, 3-, 4-, 9-)phenanthrene-, triphenylene-(1-, 2-)yl, pyrene-(1-, 2-, 4-)yl, benzotetraphenyl-(1-, 2-, 5-)yl, perylene-(1-, 2-, 3-)yl, etc., which are condensed tricyclic aryl groups. Specific examples of "aryl groups with 6 to 10 carbon atoms" include: phenyl, biphenyl, naphthyl, terphenyl, anthracene, acenaphthene, fluorenyl, phenatenyl, phenylene, pyrene, tetraphenyl, perylene, etc.

[0561] R 1 ~R 4 Each of the following can be independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0562] R 1 ~R 4 The alkyl group having 1 to 6 carbon atoms can be either straight-chain or branched. That is, it can be a straight-chain alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms. More preferably, it can be an alkyl group having 1 to 4 carbon atoms (or a branched alkyl group having 3 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, or 2-ethylbutyl, etc., preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, more preferably methyl, ethyl, or tert-butyl.

[0563] As R1 ~R 4 Specific examples of cycloalkyl groups having 3 to 6 carbon atoms include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, or dimethylcyclohexyl, etc.

[0564] Regarding R 1 ~R 4 The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms. As a specific example of "aryl group having 6 to 20 carbon atoms", Ar... 2 Specific examples of "aryl group having 6 to 20 carbon atoms". Preferred "aryl group having 6 to 20 carbon atoms" is phenyl, biphenyl, terphenyl or naphthyl, more preferably phenyl, biphenyl, 1-naphthyl, 2-naphthyl or meta-terphenyl-5'-yl, further preferably phenyl, biphenyl, 1-naphthyl or 2-naphthyl, and most preferably phenyl.

[0565] Specific examples of these anthracene derivatives include the following compounds.

[0566]

[0567] These anthracene derivatives can be manufactured using known raw materials and known synthetic methods.

[0568] <Benzofluorene derivatives>

[0569] Benzo[a]fluorene derivatives are, for example, compounds represented by the following formula (ETM-6).

[0570]

[0571] Ar 1 Each is an aryl group, independently having 6 to 20 carbon atoms, and can be referenced in Ar of formula (ETM-5). 2 The same description applies to "aryl group with 6 to 20 carbon atoms". Preferably, it is an aryl group with 6 to 16 carbon atoms, more preferably an aryl group with 6 to 12 carbon atoms, and particularly preferably an aryl group with 6 to 10 carbon atoms. Specific examples include: phenyl, biphenyl, naphthyl, terphenyl, anthracene, acenaphthene, fluorenyl, phenatenyl, phenylene, pyrene, tetraphenyl, perylene, etc.

[0572] Ar 2 Each of the two Ar groups is independently hydrogen, alkyl (preferably alkyl with 1 to 24 carbons), cycloalkyl (preferably cycloalkyl with 3 to 12 carbons), or aryl (preferably aryl with 6 to 30 carbons). 2 They can bond together to form a ring.

[0573] Ar 2The term "alkyl" can be either straight-chain or branched, for example, straight-chain alkyl with 1 to 24 carbon atoms or branched alkyl with 3 to 24 carbon atoms. Preferred "alkyl" is an alkyl with 1 to 18 carbon atoms (branched alkyl with 3 to 18 carbon atoms). More preferably, an alkyl with 1 to 12 carbon atoms (branched alkyl with 3 to 12 carbon atoms). Further preferred "alkyl" is an alkyl with 1 to 6 carbon atoms (branched alkyl with 3 to 6 carbon atoms). Particularly preferred "alkyl" is an alkyl with 1 to 4 carbon atoms (branched alkyl with 3 to 4 carbon atoms). Specific examples of "alkyl" include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, etc.

[0574] As Ar 2 The term "cycloalkyl" can be exemplified by cycloalkyl groups having 3 to 12 carbon atoms. Preferably, the "cycloalkyl" is a cycloalkyl group having 3 to 10 carbon atoms. More preferably, the "cycloalkyl" is a cycloalkyl group having 3 to 8 carbon atoms. Even more preferably, the "cycloalkyl" is a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, or dimethylcyclohexyl.

[0575] As Ar 2 The "aryl" in the text is preferably an aryl group with 6 to 30 carbon atoms, more preferably an aryl group with 6 to 18 carbon atoms, and even more preferably an aryl group with 6 to 14 carbon atoms, and particularly preferably an aryl group with 6 to 12 carbon atoms.

[0576] Specific examples of "aryl groups with 6 to 30 carbon atoms" include: phenyl, naphthyl, acenaphthel, fluorenyl, phenatenyl, phenylene, pyrene, tetraphenyl, peryl, pentaphenyl, etc.

[0577] Two Ar 2 It can bond to form rings, resulting in the formation of cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, or indene, etc., on the 5-membered ring of the fluorene skeleton.

[0578] Specific examples of the benzo[a]fluorene derivatives include the following compounds.

[0579]

[0580] The benzo[a]fluorene derivative can be manufactured using known raw materials and known synthetic methods.

[0581] <phosphine oxide derivatives>

[0582] Phosphine oxide derivatives are, for example, compounds represented by the following formula (ETM-7-1). Details are also described in International Publication Nos. 2013 / 079217 and 2013 / 079678.

[0583]

[0584] R 5 It can be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 5 to 20 carbon atoms.

[0585] R 6 CN, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 16 carbon atoms, heteroalkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, heteroaryl groups having 5 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, or aryloxy groups having 6 to 20 carbon atoms.

[0586] R 7 and R 8 They are independently substituted or unsubstituted aryl groups with 6 to 20 carbon atoms or heteroaryl groups with 5 to 20 carbon atoms.

[0587] R 9 It is oxygen or sulfur.

[0588] j is 0 or 1, k is 0 or 1, r is an integer from 0 to 4, and q is an integer from 1 to 3.

[0589] Here, examples of substituents that are substituted include: aryl, heteroaryl, alkyl, or cycloalkyl.

[0590] Phosphine oxide derivatives may be, for example, compounds represented by the following formula (ETM-7-2).

[0591]

[0592] R 1 ~R 3 They may be the same or different, and are selected from hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, alkylthio, cycloalkylthio, aryl ether (aryl ether group), aryl thioether (aryl thioether group), aryl, heterocyclic group, halogen, cyano, formyl, carbonyl, carboxyl, amino, nitro, silyl, and fused rings formed between them and adjacent substituents.

[0593] Ar 1 They can be the same or different, and are either aryl or heteroaryl. Ar 2 They can be the same or different, and can be aryl or heteroaryl. Among them, Ar 1 and Ar 2At least one of them has a substituent, or forms a fused ring with an adjacent substituent. n is an integer from 0 to 3. When n is 0, there is no unsaturated structural part; when n is 3, there is no R. 1 .

[0594] Among these substituents, the term alkyl refers to, for example, saturated aliphatic hydrocarbon groups such as methyl, ethyl, propyl, and butyl. The alkyl group may be unsubstituted or substituted. There are no particular limitations on the substituents used when substituted; examples include alkyl, aryl, and heterocyclic groups, and this will be consistent throughout the following description. Furthermore, there is no particular limitation on the number of carbon atoms in the alkyl group; it is generally in the range of 1 to 20, considering ease of acquisition and cost.

[0595] Furthermore, the term "cycloalkyl" refers to, for example, saturated alicyclic hydrocarbon groups such as cyclopropyl, cyclohexyl, norbornyl, and adamantyl, which may be unsubstituted or substituted. The number of carbon atoms in the alkyl moiety is not particularly limited, typically ranging from 3 to 20.

[0596] Furthermore, the term "aralkyl" refers to aromatic hydrocarbon groups such as benzyl and phenylethyl, which are separated by an aliphatic hydrocarbon. Both aliphatic and aromatic hydrocarbons can be unsubstituted or substituted. The number of carbon atoms in the aliphatic moiety is not particularly limited, and is usually in the range of 1 to 20.

[0597] Furthermore, the term "alkenyl" refers to, for example, unsaturated aliphatic hydrocarbon groups containing double bonds such as vinyl, allyl, and butadienyl. The alkenyl group may be unsubstituted or substituted. The number of carbon atoms in the alkenyl group is not particularly limited, but is typically in the range of 2 to 20.

[0598] In addition, the term "cycloalkenyl" refers to, for example, unsaturated alicyclic hydrocarbon groups containing double bonds such as cyclopentenyl, cyclopentadienyl, and cyclohexenyl, and the cycloalkenyl group may be unsubstituted or substituted.

[0599] Furthermore, the term "alkynyl" refers to, for example, an acetylenic group or other unsaturated aliphatic hydrocarbon group containing a triple bond, which may be unsubstituted or substituted. The number of carbon atoms in the alkynyl group is not particularly limited, but is typically in the range of 2 to 20.

[0600] In addition, the term alkoxy refers to an aliphatic hydrocarbon group, such as a methoxy group, separated by an ether bond. The aliphatic hydrocarbon group may be unsubstituted or substituted. The number of carbon atoms in an alkoxy group is not particularly limited, but is typically in the range of 1 to 20.

[0601] In addition, the oxygen atom in the ether bond of the so-called alkoxy group is replaced by a sulfur atom.

[0602] In addition, the so-called cycloalkanethio group is a group in which the oxygen atom of the ether bond of the cycloalkoxy group is replaced by a sulfur atom.

[0603] In addition, the term aryl ether refers to an aromatic hydrocarbon group, such as phenoxy, separated by an ether bond. The aromatic hydrocarbon group may be unsubstituted or substituted. There is no particular limitation on the number of carbon atoms in aryl ethers, which is usually in the range of 6 to 40.

[0604] In addition, so-called aryl thioethers are aryl ethers in which the oxygen atom of the ether bond is replaced by a sulfur atom.

[0605] In addition, the term "aryl" can refer to aromatic hydrocarbon groups such as phenyl, naphthyl, biphenyl, phenanthryl, terphenyl, and pyrene. Aryl groups can be unsubstituted or substituted. The number of carbon atoms in an aryl group is not particularly limited, typically ranging from 6 to 40.

[0606] Furthermore, the term "heterocyclic group" refers to cyclic groups with atoms other than carbon, such as furanyl, thiophene, oxazolyl, pyridinyl, quinolinyl, and carbazoleyl. These heterocyclic groups may be unsubstituted or substituted. The number of carbon atoms in the heterocyclic group is not particularly limited, but is typically in the range of 2 to 30.

[0607] The term halogen refers to fluorine, chlorine, bromine, and iodine.

[0608] The formyl, carbonyl, and amino groups may also contain groups substituted by aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocycles, etc.

[0609] In addition, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocyclic hydrocarbons can be unsubstituted or substituted.

[0610] The term silyl group refers to silicon compounds such as trimethylsilyl, which may be unsubstituted or substituted. The number of carbon atoms in the silyl group is not particularly limited, typically ranging from 3 to 20. Additionally, the number of silicon atoms is typically from 1 to 6.

[0611] The so-called fused ring formed between the substituent and the adjacent substituent is, for example, in Ar 1 With R 2 Ar 1 With R 3 Ar 2 With R 2 Ar 2 With R 3 R 2 With R 3 Ar 1 with Ar 2 Conjugate or non-conjugate condensed rings formed between them. Here, when n is 1, the two R... 1 They can form conjugated or non-conjugated fused rings. These fused rings can contain nitrogen, oxygen, and sulfur atoms in their internal structure, and can further condense with other rings.

[0612] Specific examples of the phosphine oxide derivatives include the following compounds.

[0613]

[0614] The phosphine oxide derivative can be manufactured using known raw materials and known synthetic methods.

[0615] <Pyrimidine Derivatives>

[0616] 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). Further details are described in International Publication No. 2011 / 021689.

[0617]

[0618] Ar is independently a substituted aryl group or a substituted heteroaryl group. n is an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 2 or 3.

[0619] The "aryl" as "substitutable aryl" can be exemplified by aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, and even more preferably aryl groups having 6 to 12 carbon atoms.

[0620] Specific examples of "aryl" groups include: phenyl as a monocyclic aryl group; (2-, 3-, 4-)biphenyl as a dicyclic aryl group; (1-, 2-)naphthyl as a condensed dicyclic aryl group; terphenyl as a tricyclic aryl group (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); and condensed tricyclic aryl groups. Acenatho-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenaten-(1-, 2-)yl, (1-, 2-, 3-, 4-, 9-)phenanthyl, tetraphenyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-tetraphenyl) as tetracyclic aryl, triphenyl-(1-, 2-)yl, pyrene-(1-, 2-, 4-)yl, and tetraphenyl-(1-, 2-, 5-)yl as condensed tetracyclic aryl, and perylene-(1-, 2-, 3-)yl and pentaphenyl-(1-, 2-, 5-, 6-)yl as condensed pentacyclic aryl, etc.

[0621] The term "heteroaryl" as "substitutable heteroaryl" can include, for example, heteroaryl groups with 2 to 30 carbon atoms, preferably heteroaryl groups with 2 to 25 carbon atoms, more preferably heteroaryl groups with 2 to 20 carbon atoms, and even more preferably heteroaryl groups with 2 to 15 carbon atoms, and particularly preferably heteroaryl groups with 2 to 10 carbon atoms. Furthermore, heterocycles containing one to five heteroatoms selected from oxygen, sulfur, and nitrogen as ring-forming atoms, in addition to carbon, can be cited as examples.

[0622] Specific heteroaryl groups include, for example: furanyl, thiopheneyl, pyrroleyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazoleyl, pyrazolyl, oxadiazolyl, furazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo[b]thiopheneyl, indolyl, isoindolyl, 1H-indolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinolinyl, quinazolinyl, quinoxolinyl, phthalazinyl, naphridinyl, purineyl, pteridinyl, carbazolyl, acridineyl, phenoxazinyl, phenthiazolyl, phenoxazinyl, thiazolyl, thiazolyl, inazinyl, etc.

[0623] In addition, the aryl and heteroaryl groups can be substituted, for example, by the aryl or heteroaryl groups respectively.

[0624] Specific examples of the pyrimidine derivatives include the following compounds.

[0625]

[0626] The pyrimidine derivatives can be manufactured using known raw materials and known synthetic methods.

[0627] <Aryl nitrile derivatives>

[0628] Aryl nitrile derivatives are, for example, compounds represented by the following formula (ETM-9), or polymers thereof formed by bonding by single bonds, etc. Details are described in U.S. Patent Application Publication No. 2014 / 0197386.

[0629]

[0630] From the perspective of rapid electron transport, Ar ni Preferably, Ar has a higher carbon number, which is desirable from the perspective of high T1. ni Preferably, it has a low carbon number. Specifically, when used as a layer adjacent to the light-emitting layer, it is preferable to have a high T1, thereby increasing the Ar... niThe aryl group has 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Regarding the number of nitrile group substitutions n, from the viewpoint of high T1, a higher number is preferable, and from the viewpoint of high S1, a lower number is preferable. Specifically, the number of nitrile group substitutions n is an integer from 1 to 4, preferably an integer from 1 to 3, more preferably an integer from 1 to 2, and even more preferably 1.

[0631] Ar is independently a substituted aryl or a substituted heteroaryl. From the viewpoint of high S1 and high T1, a donor heteroaryl is preferred, and since it serves as an electron transport layer, a small number of donor heteroaryl groups is preferable. From the viewpoint of charge transport, an aryl or heteroaryl group with a large number of carbon atoms is preferred, and a large number of substituents is also preferred. Specifically, the number of substitutions m of Ar is an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 1 to 2.

[0632] The "aryl" as "substitutable aryl" can be exemplified by aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, and even more preferably aryl groups having 6 to 12 carbon atoms.

[0633] Specific examples of "aryl" groups include: phenyl as a monocyclic aryl group; (2-, 3-, 4-)biphenyl as a dicyclic aryl group; (1-, 2-)naphthyl as a condensed dicyclic aryl group; terphenyl as a tricyclic aryl group (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); and condensed tricyclic aryl groups. Acenatho-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenaten-(1-, 2-)yl, (1-, 2-, 3-, 4-, 9-)phenanthyl, tetraphenyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-tetraphenyl) as tetracyclic aryl, triphenyl-(1-, 2-)yl, pyrene-(1-, 2-, 4-)yl, and tetraphenyl-(1-, 2-, 5-)yl as condensed tetracyclic aryl, and perylene-(1-, 2-, 3-)yl and pentaphenyl-(1-, 2-, 5-, 6-)yl as condensed pentacyclic aryl, etc.

[0634] The term "heteroaryl" as "substitutable heteroaryl" can include, for example, heteroaryl groups with 2 to 30 carbon atoms, preferably heteroaryl groups with 2 to 25 carbon atoms, more preferably heteroaryl groups with 2 to 20 carbon atoms, and even more preferably heteroaryl groups with 2 to 15 carbon atoms, and particularly preferably heteroaryl groups with 2 to 10 carbon atoms. Furthermore, heterocycles containing one to five heteroatoms selected from oxygen, sulfur, and nitrogen as ring-forming atoms, in addition to carbon, can be cited as examples.

[0635] Specific heteroaryl groups include, for example: furanyl, thiopheneyl, pyrroleyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazoleyl, pyrazolyl, oxadiazolyl, furazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo[b]thiopheneyl, indolyl, isoindolyl, 1H-indolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinolinyl, quinazolinyl, quinoxolinyl, phthalazinyl, naphridinyl, purineyl, pteridinyl, carbazolyl, acridineyl, phenoxazinyl, phenthiazolyl, phenoxazinyl, thiazolyl, thiazolyl, inazinyl, etc.

[0636] In addition, the aryl and heteroaryl groups can be substituted, for example, by the aryl or heteroaryl groups respectively.

[0637] Aryl nitrile derivatives can be polymers obtained by bonding compounds represented by multiple formulas (ETM-9) using single bonds or the like. In this case, in addition to single bonds, aryl rings (preferably polyvalent benzene rings, naphthyl rings, anthracene rings, fluorene rings, benzo[a]fluorene rings, phenanthracene rings, or triphenylene rings) can also be used for bonding.

[0638] Specific examples of the aryl nitrile derivatives include the following compounds.

[0639]

[0640] The aryl nitrile derivatives can be manufactured using known raw materials and known synthetic methods.

[0641] <Triazine Derivatives>

[0642] Triazine derivatives are, for example, compounds represented by the following formula (ETM-10), preferably compounds represented by the following formula (ETM-10-1). Details are described in U.S. Patent Application Publication No. 2011 / 0156013.

[0643]

[0644] Ar can be independently a substituted aryl group or a substituted heteroaryl group. n is an integer from 1 to 3, preferably 2 or 3.

[0645] The "aryl" as "substitutable aryl" can be exemplified by aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, and even more preferably aryl groups having 6 to 12 carbon atoms.

[0646] Specific examples of "aryl" groups include: phenyl as a monocyclic aryl group; (2-, 3-, 4-)biphenyl as a dicyclic aryl group; (1-, 2-)naphthyl as a condensed dicyclic aryl group; terphenyl as a tricyclic aryl group (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); and condensed tricyclic aryl groups. Acenatho-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenaten-(1-, 2-)yl, (1-, 2-, 3-, 4-, 9-)phenanthyl, tetraphenyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-tetraphenyl) as tetracyclic aryl, triphenyl-(1-, 2-)yl, pyrene-(1-, 2-, 4-)yl, and tetraphenyl-(1-, 2-, 5-)yl as condensed tetracyclic aryl, and perylene-(1-, 2-, 3-)yl and pentaphenyl-(1-, 2-, 5-, 6-)yl as condensed pentacyclic aryl, etc.

[0647] The term "heteroaryl" as "substitutable heteroaryl" can include, for example, heteroaryl groups with 2 to 30 carbon atoms, preferably heteroaryl groups with 2 to 25 carbon atoms, more preferably heteroaryl groups with 2 to 20 carbon atoms, and even more preferably heteroaryl groups with 2 to 15 carbon atoms, and particularly preferably heteroaryl groups with 2 to 10 carbon atoms. Furthermore, heterocycles containing one to five heteroatoms selected from oxygen, sulfur, and nitrogen as ring-forming atoms, in addition to carbon, can be cited as examples.

[0648] Specific heteroaryl groups include, for example: furanyl, thiopheneyl, pyrroleyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazoleyl, pyrazolyl, oxadiazolyl, furazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo[b]thiopheneyl, indolyl, isoindolyl, 1H-indolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinolinyl, quinazolinyl, quinoxolinyl, phthalazinyl, naphridinyl, purineyl, pteridinyl, carbazolyl, acridineyl, phenoxazinyl, phenthiazolyl, phenoxazinyl, thiazolyl, thiazolyl, inazinyl, etc.

[0649] In addition, the aryl and heteroaryl groups can be substituted, for example, by the aryl or heteroaryl groups respectively.

[0650] Specific examples of the triazine derivatives include the following compounds.

[0651]

[0652] The triazine derivative can be manufactured using known raw materials and known synthetic methods.

[0653] <Benzimazole derivatives>

[0654] Benzimidazole derivatives are, for example, compounds represented by the following formula (ETM-11).

[0655] φ-(benzimidazole substituent)n (ETM-11)

[0656] φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthyl ring, anthracene ring, fluorene ring, benzo[a]fluorene ring, finadene ring, phenanthrene ring, or triphenylene ring), n is an integer from 1 to 4, "benzimidazole substituent" is a substituent formed by replacing the pyridyl group with a benzimidazole group in the "pyridine substituent" of formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2), and at least one hydrogen in the benzimidazole derivative may be replaced by deuterium.

[0657] * indicates the location of the bond.

[0658] The R in the benzimidazole group 11 It is hydrogen, an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and R in formulas (ETM-2-1) and (ETM-2-2) can be referenced. 11 Explanation.

[0659] φ is preferably an anthracene ring or a fluorene ring, the structure of which can be described by referring to the description in formula (ETM-2-1) or formula (ETM-2-2), where R in each formula11 ~R 18 The description in ETM-2-1 or ETM-2-2 can be referenced. Furthermore, ETM-2-1 or ETM-2-2 is described in the form of two pyridine substituents, but when they are replaced with benzimidazole substituents, both pyridine substituents can be replaced by a benzimidazole substituent (i.e., n=2), or any one pyridine substituent can be replaced by a benzimidazole substituent and then R... 11 ~R 18 The other pyridine substituent (i.e., n=1) can be replaced. Furthermore, for example, R in formula (ETM-2-1) can be replaced by a benzimidazole substituent. 11 ~R 18 At least one of and by R 11 ~R 18 Replace "pyridine substituents".

[0660] Specific examples of the benzimidazole derivatives include: 1-phenyl-2-(4-(10-phenylanthracene-9-yl)phenyl)-1H-benzimidazole, 2-(4-(10-(naphthyl-2-yl)anthracene-9-yl)phenyl)-1-phenyl-1H-benzimidazole, 2-(3-(10-(naphthyl-2-yl)anthracene-9-yl)phenyl)-1-phenyl-1H-benzimidazole, 5-(10-(naphthyl-2-yl)anthracene-9-yl)-1,2-diphenyl-1H-benzimidazole Imidazole, 1-(4-(10-(naphth-2-yl)anthracene-9-yl)phenyl)-2-phenyl-1H-benzo[d]imidazol, 2-(4-(9,10-bis(naphth-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazol, 1-(4-(9,10-bis(naphth-2-yl)anthracene-2-yl)phenyl)-2-phenyl-1H-benzo[d]imidazol, 5-(9,10-bis(naphth-2-yl)anthracene-2-yl)-1,2-diphenyl-1H-benzo[d]imidazol, etc.

[0661]

[0662] The benzimidazole derivative can be manufactured using known raw materials and known synthetic methods.

[0663] <Phenanthroline derivatives>

[0664] Phenanthroline derivatives are, for example, compounds represented by the following formula (ETM-12) or formula (ETM-12-1). Details are described in International Publication No. 2006 / 021982.

[0665]

[0666] φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzo[a]fluorene ring, finadene ring, phenanthrene ring, or triphenylene ring), and n is an integer from 1 to 4.

[0667] Various R 11 ~R 18 Each of these components is independently hydrogen, alkyl (preferably an alkyl group having 1 to 24 carbon atoms), cycloalkyl (preferably a cycloalkyl group having 3 to 12 carbon atoms), or aryl (preferably an aryl group having 6 to 30 carbon atoms). Furthermore, in formula (ETM-12-1), R... 11 ~R 18 Either of them becomes a bond with φ, which is an aryl ring.

[0668] At least one hydrogen atom in each phenanthrene derivative may be substituted with deuterium.

[0669] As R 11 ~R 18 The alkyl, cycloalkyl, and aryl groups in the formula (ETM-2) can be referenced from R. 11 ~R 18 The explanation is as follows. In addition to the examples described above, other structural formulas for φ may also be listed below. Furthermore, in the following structural formulas, R is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenyl, or terphenyl, and * indicates the bond position.

[0670]

[0671] Specific examples of the phenanthroline derivatives include: 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-bis(1,10-phenanthroline-2-yl)anthracene, 2,6-bis(1,10-phenanthroline-5-yl)pyridine, 1,3,5-tris(1,10-phenanthroline-5-yl)benzene, 9,9'-difluoro-bis(1,10-phenanthroline-5-yl), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline (bathocuproine), 1,3-bis(2-phenyl-1,10-phenanthroline-9-yl)benzene, or compounds represented by the following structural formulas.

[0672]

[0673] The phenanthroline derivative can be manufactured using known raw materials and known synthetic methods.

[0674] <Hydroxyquinoline metal complexes>

[0675] Hydroxyquinoline metal complexes are, for example, compounds represented by the following formula (ETM-13).

[0676]

[0677] In the formula, R 1 ~R 6 Each of the following can be independently hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy, or aryl, where M is Li, Al, Ga, Be, or Zn, and n is an integer from 1 to 3.

[0678] Specific examples of hydroxyquinoline-based metal complexes include: lithium 8-hydroxyquinoline, tris(8-hydroxyquinoline)aluminum, tris(4-methyl-8-hydroxyquinoline)aluminum, tris(5-methyl-8-hydroxyquinoline)aluminum, tris(3,4-dimethyl-8-hydroxyquinoline)aluminum, tris(4,5-dimethyl-8-hydroxyquinoline)aluminum, tris(4,6-dimethyl-8-hydroxyquinoline)aluminum, bis(2-methyl-8-hydroxyquinoline)(phenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2-methylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(3-methylphenol)aluminum, bis( 2-Methyl-8-hydroxyquinoline)(4-methylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2-phenylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(3-phenylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(4-phenylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2,3-dimethylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2,6-dimethylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(3,4-dimethylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(3,5-dimethylphenol)aluminum Aluminum, bis(2-methyl-8-hydroxyquinoline)(3,5-di-tert-butylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2,6-diphenylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2,4,6-triphenylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2,4,6-trimethylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2,4,5,6-tetramethylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(1-naphthol)aluminum, bis(2-methyl-8-hydroxyquinoline)(2-naphthol)aluminum, bis(2,4-dimethyl... bis(2,4-dimethyl-8-hydroxyquinoline)(2-phenylphenol)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(3-phenylphenol)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(4-phenylphenol)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(3,5-dimethylphenol)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(3,5-di-tert-butylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)aluminum-μ-oxo-bis(2,4-di ...4-Dimethyl-8-hydroxyquinoline)aluminum, bis(2-methyl-4-ethyl-8-hydroxyquinoline)aluminum-μ-oxo-bis(2-methyl-4-ethyl-8-hydroxyquinoline)aluminum, bis(2-methyl-4-methoxy-8-hydroxyquinoline)aluminum-μ-oxo-bis(2-methyl-4-methoxy-8-hydroxyquinoline)aluminum, bis(2-methyl-5-cyano-8-hydroxyquinoline)aluminum-μ-oxo-bis(2-methyl-5-cyano-8-hydroxyquinoline)aluminum, bis(2-methyl-5-trifluoromethyl-8-hydroxyquinoline)aluminum-μ-oxo-bis(2-methyl-5-trifluoromethyl-8-hydroxyquinoline)aluminum, bis(10-hydroxybenzo[h]quinoline)beryllium, etc.

[0679] The hydroxyquinoline-based metal complexes can be manufactured using known raw materials and known synthetic methods.

[0680] <Thiazole derivatives and benzothiazole derivatives>

[0681] Thiazole derivatives are, for example, compounds represented by the following formula (ETM-14-1).

[0682] φ—(thiazole substituent)n (ETM-14-1)

[0683] Benzothiazole derivatives are, for example, compounds represented by the following formula (ETM-14-2).

[0684] φ-(benzothiazole substituent)n (ETM-14-2)

[0685] In each formula, φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthyl ring, anthracene ring, fluorene ring, benzo[a]fluorene ring, finadene ring, phenanthrene ring, or triphenylene ring), where n is an integer from 1 to 4. The "thiazolium substituent" or "benzo[a]thiazolium substituent" is a substituent formed by replacing the pyridyl group in the "pyridine substituent" of formula (ETM-2), formula (ETM-2-1), and formula (ETM-2-2) with the following thiazolium group or benzo[a]thiazolium group. At least one hydrogen in the thiazolium derivative and the benzo[a]thiazolium derivative may be substituted with deuterium.

[0686] * indicates the location of the bond.

[0687] φ is preferably an anthracene ring or a fluorene ring, the structure of which can be described by referring to the description in formula (ETM-2-1) or formula (ETM-2-2), where R in each formula 11 ~R 18The description in formula (ETM-2-1) or formula (ETM-2-2) can be referenced. Furthermore, formula (ETM-2-1) or formula (ETM-2-2) is described in the form of two pyridine substituents, but when they are replaced with thiazole substituents (or benzothiazole substituents), both pyridine substituents (i.e., n=2) can be replaced by a thiazole substituent (or a benzothiazole substituent), or any one pyridine substituent can be replaced by a thiazole substituent (or a benzothiazole substituent) and R... 11 ~R 18 The other pyridine substituent can be replaced (i.e., n = 1). Furthermore, for example, R in formula (ETM-2-1) can be replaced by a thiazole substituent (or a benzothiazole substituent). 11 ~R 18 At least one of and by R 11 ~R 18 Replace "pyridine substituents".

[0688] These thiazole derivatives or benzothiazole derivatives can be manufactured using known raw materials and known synthetic methods.

[0689] <Thiophene derivatives>

[0690] Thiol derivatives are, for example, compounds represented by the following formula (ETM-15). Details are described in Japanese Patent Application Publication No. 9-194487.

[0691]

[0692] X and Y are independently alkyl, cycloalkyl, alkenyl, alkoxy, alkenyloxy, alkynyl, aryl, and heteroaryl groups, which may be substituted. For details regarding these groups, please refer to the descriptions in formulas (1) and (1-a), as well as in formula (ETM-7-2). Furthermore, alkenyloxy and alkynyloxy groups are formed by substituting the alkyl portion of an alkoxy group with an alkenyl or alkynyl group, respectively. For details regarding these alkenyl and alkynyl groups, please refer to the descriptions in formula (ETM-7-2).

[0693] In addition, X and Y can bond together to form a cycloalkyl ring (and a portion of which becomes unsaturated), and details of the cycloalkyl ring can be found in the description of cycloalkyl in formulas (1) and (1-a).

[0694] R 1 ~R 4They are, independently, hydrogen, halogen, alkyl, cycloalkyl, alkoxy, aryloxy, amino, alkyl carbonyl, aryl carbonyl, alkoxy carbonyl, aryloxy carbonyl, azo, alkyl carbonyloxy, aryl carbonyloxy, alkoxy carbonyloxy, aryloxy carbonyloxy, sulfinyl, sulfonyl, sulfanyl, silyl, carbamoyl, aryl, heteroaryl, alkenyl, alkynyl, nitro, formyl, nitroso, formyloxy, isocyano, cyanate, isocyanate, thiocyanate, isothiocyanate, or cyano, and may be substituted by alkyl, cycloalkyl, aryl, or halogen, or may form a fused ring with adjacent substituents.

[0695] Regarding R 1 ~R 4 For details on the halogens, alkyl groups, cycloalkyl groups, alkoxy groups, aryloxy groups, amino groups, aryl groups, heteroaryl groups, alkenyl groups, and alkynyl groups, please refer to the descriptions in formulas (1) and (1-a).

[0696] Regarding R 1 ~R 4 For details on the alkyl, aryl, and alkoxy groups in alkyl carbonyl, aryl carbonyl, alkoxy carbonyl, aryl carbonyl, alkoxy carbonyl, and aryl carbonyl, please refer to the descriptions in formulas (1) and (1-a).

[0697] As silyl groups, examples include silyl groups and groups in which at least one of the three hydrogens of a silyl group is independently substituted by an aryl, alkyl, or cycloalkyl group, preferably trisubstituted silyl groups, such as triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, and alkyldicycloalkylsilyl, etc. For details regarding the aryl, alkyl, and cycloalkyl groups among them, please refer to the descriptions in formulas (1) and (1-a), etc.

[0698] The so-called fused ring formed between the adjacent substituent is, for example, in R 1 With R 2 R 2 With R 3 R 3 With R 4 Fused rings, whether conjugated or non-conjugated, can be formed between rings. These fused rings may contain nitrogen, oxygen, and sulfur atoms within their internal structure, and may further condense with other rings.

[0699] Among them, the preferred one is when R 1 and R 4 When R is phenyl, X and Y are not alkyl or phenyl. Furthermore, it is preferable that they do not simultaneously satisfy the condition when R... 1 and R 4 When X is thiophene, X and Y are alkyl groups and R is... 2and R 3 It is alkyl, aryl, alkenyl or R 2 With R 3 A cycloalkyl structure formed by bonding. Additionally, it is preferable when R... 1 and R 4 When it is silane, R 2 R 3 X and Y are each independently not hydrogen or an alkyl group having 1 to 6 carbon atoms. Furthermore, it is preferable that R is... 1 and R 2 When a structure containing a benzene ring is condensed, X and Y are not alkyl and phenyl groups, respectively.

[0700] These thiophene derivatives can be manufactured using known raw materials and known synthetic methods.

[0701] <Azoline derivatives>

[0702] Azoline derivatives are, for example, compounds represented by the following formula (ETM-16). Details are described in International Publication No. 2017 / 014226.

[0703]

[0704] In formula (ETM-16),

[0705] 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 heterocycle having 2 to 40 carbon atoms. At least one hydrogen atom of φ may be substituted by an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heteroaryl group having 2 to 18 carbon atoms.

[0706] Y is independently -O-, -S-, or >N-Ar, where Ar is an aryl group with 6 to 12 carbon atoms or a heteroaryl group with 2 to 12 carbon atoms, and at least one hydrogen atom of Ar can be substituted by an alkyl group with 1 to 4 carbon atoms, a cycloalkyl group with 5 to 10 carbon atoms, an aryl group with 6 to 12 carbon atoms, or a heteroaryl group with 2 to 12 carbon atoms. R 1 ~R 5 Each is independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms, wherein the Ar in the >N-Ar and the R are... 1 ~R 5 Any one of them is a site that forms an L-bond.

[0707] L is independently selected from the groups consisting of the divalent bases represented by equation (L-1) and the divalent bases represented by equation (L-2), respectively.

[0708]

[0709] In equation (L-1), X 1 ~X 6Each independently = CR 6 -or = N-, X 1 ~X 6 At least two of them are =CR 6 -, X 1 ~X 6 The two in =CR 6 -in R 6 For sites that are bonded to φ or the zoline ring, the remainder is equal to CR. 6 -in R 6 It is hydrogen.

[0710] In equation (L-2), X 7 ~X 14 Each independently = CR 6 -or = N-, X 7 ~X 14 At least two of them are =CR 6 -, X 7 ~X 14 The two in =CR 6 -in R 6 For sites that are bonded to φ or the zoline ring, the remainder is equal to CR. 6 -in R 6 It is hydrogen.

[0711] At least one hydrogen atom of L may be substituted by an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heteroaryl group having 2 to 10 carbon atoms.

[0712] m is an integer from 1 to 4. When m is 2 to 4, the groups formed by the zoline ring and L can be the same or different, and...

[0713] At least one hydrogen atom in the compound represented by formula (ETM-16) may be substituted with deuterium.

[0714] The specific azoline derivatives are compounds represented by the following formula (ETM-16-1) or formula (ETM-16-2).

[0715]

[0716] In equations (ETM-16-1) and (ETM-16-2),

[0717] 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 heterocycle having 2 to 40 carbon atoms. At least one hydrogen atom of φ may be substituted by an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heteroaryl group having 2 to 18 carbon atoms.

[0718] In formula (ETM-16-1), Y is independently -O-, -S-, or >N-Ar, Ar is an aryl group with 6 to 12 carbon atoms or a heteroaryl group with 2 to 12 carbon atoms, and at least one hydrogen atom of Ar can be substituted by an alkyl group with 1 to 4 carbon atoms, a cycloalkyl group with 5 to 10 carbon atoms, an aryl group with 6 to 12 carbon atoms, or a heteroaryl group with 2 to 12 carbon atoms.

[0719] In formula (ETM-16-1), R 1 ~R 4 Each is independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms, wherein R 1 With R 2 Same, and R 3 With R 4 same,

[0720] In formula (ETM-16-2), R 1 ~R 5 Each is independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms, wherein R 1 With R 2 Same, and R 3 With R 4 same,

[0721] In equations (ETM-16-1) and (ETM-16-2),

[0722] L is independently selected from the groups consisting of the divalent bases represented by equation (L-1) and the divalent bases represented by equation (L-2), respectively.

[0723]

[0724] In equation (L-1), X 1 ~X 6 Each independently = CR 6 -or = N-, X 1 ~X 6 At least two of them are =CR 6 -, X 1 ~X 6 The two in =CR 6 -in R 6 For sites that are bonded to φ or the zoline ring, the remainder is equal to CR. 6 -in R 6 It is hydrogen.

[0725] In equation (L-2), X 7 ~X 14 Each independently = CR 6 -or = N-, X 7 ~X 14 At least two of them are =CR6 -, X 7 ~X 14 The two in =CR 6 -in R 6 For sites that are bonded to φ or the zoline ring, the remainder is equal to CR. 6 -in R 6 It is hydrogen.

[0726] At least one hydrogen atom of L may be substituted by an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heteroaryl group having 2 to 10 carbon atoms.

[0727] m is an integer from 1 to 4. When m is 2 to 4, the groups formed by the zoline ring and L can be the same or different, and...

[0728] At least one hydrogen atom in the compound represented by formula (ETM-16-1) or formula (ETM-16-2) may be substituted with deuterium.

[0729] Preferably, φ is selected from the group consisting of a monovalent group represented by formula (φ1-1) to (φ1-18), a divalent group represented by formula (φ2-1) to (φ2-34), a trivalent group represented by formula (φ3-1) to (φ3-3) and a tetravalent group represented by formula (φ4-1) to (φ4-2), wherein at least one hydrogen of φ may be substituted by an alkyl group having 1 to 6 carbons, a cycloalkyl group having 3 to 14 carbons, an aryl group having 6 to 18 carbons, or a heteroaryl group having 2 to 18 carbons.

[0730]

[0731]

[0732] In the formula, Z represents >CR2, >N-Ar, >NL, -O-, or -S-. In >CR2, R is independently an alkyl group with 1-4 carbon atoms, a cycloalkyl group with 5-10 carbon atoms, an aryl group with 6-12 carbon atoms, or a heteroaryl group with 2-12 carbon atoms. R can bond with each other to form a ring. In >N-Ar, Ar is an aryl group with 6-12 carbon atoms or a heteroaryl group with 2-12 carbon atoms. In >NL, L is L in formula (ETM-16), formula (ETM-16-1), or formula (ETM-16-2). * indicates the bonding position.

[0733] Preferably, L is a divalent group of a ring selected from the group consisting of benzene, naphthalene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, naphthidine, phthalazine, quinoxaline, quinazoline, cyclophosphine, cyclophosphine, and pteridine, and at least one hydrogen of L may be substituted by an alkyl group having 1 to 4 carbons, a cycloalkyl group having 5 to 10 carbons, an aryl group having 6 to 10 carbons, or a heteroaryl group having 2 to 10 carbons.

[0734] Preferably, the Ar in the >N-Ar of Y or Z is selected from the group consisting of phenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, naphthidyl, phthalazinyl, quinoxolinyl, quinazolinyl, cycloazolinyl, cycloazolinyl, and pteridinyl, and at least one hydrogen atom in the >N-Ar of Y may be substituted by an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0735] Preferred option: R 1 ~R 4 Each is independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms, wherein R 1 With R 2 Same, R 3 With R 4 Same, and R 1 ~R 4 Not all of them will become hydrogen at the same time, and m is 1 or 2. When m is 2, the group formed by the azoline ring and L is the same.

[0736] Specific examples of azoline derivatives include the following compounds. Furthermore, "Me" in the structural formula represents a methyl group.

[0737]

[0738] More preferably, φ is selected from the group consisting of divalent groups represented by the following formulas (φ2-1), (φ2-31), (φ2-32), (φ2-33), and (φ2-34), wherein at least one hydrogen atom of φ may be substituted by an aryl group having 6 to 18 carbon atoms.

[0739]

[0740] (* indicates the location of the bond)

[0741] L is a divalent group of a ring selected from the group consisting of benzene, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. At least one hydrogen atom of L may be substituted by an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heteroaryl group having 2 to 14 carbon atoms.

[0742] The Ar in the >N-Ar of Y is selected from the group consisting of phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl, and at least one hydrogen atom of Ar may be substituted by an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0743] R 1 ~R 4 Each is independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms, wherein R 1 With R2 Same, R 3 With R 4 Same, and R 1 ~R 4 Not all of them will become hydrogen at the same time, and,

[0744] m is 2, and the group formed by the zoline ring and L is the same.

[0745] Other specific examples of azoline derivatives include the following compounds. Furthermore, "Me" in the structural formula represents a methyl group.

[0746]

[0747] For details regarding the alkyl, cycloalkyl, aryl, or heteroaryl groups in the various formulas specifying the zoline derivatives, refer to the descriptions in formulas (1) and (1-a), etc.

[0748] The azoline derivative can be manufactured using known raw materials and known synthetic methods.

[0749] <Reducing substances>

[0750] The electron transport layer or electron injection layer may also contain a substance capable of reducing the material forming the electron transport layer or electron injection layer. The reducing substance can be any substance possessing a certain reducing property, and for example, preferably at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals.

[0751] Preferred reducing agents include alkali metals such as Na (work function 2.36 eV), K (work function 2.28 eV), Rb (work function 2.16 eV), or Cs (work function 1.95 eV), or alkaline earth metals such as Ca (work function 2.9 eV), Sr (work function 2.0 eV–2.5 eV), or Ba (work function 2.52 eV), with substances having a work function of 2.9 eV or less being particularly preferred. Among these, K, Rb, or Cs are more preferred as alkali metals, Rb or Cs are more preferred, and Cs is most preferred. These alkali metals have particularly high reducing power, and by adding a relatively small amount of these alkali metals to the material forming the electron transport layer or electron injection layer, the luminous brightness or lifetime of organic EL devices can be improved. Furthermore, combinations of two or more of these alkali metals are preferred as reducing agents with a work function of 2.9 eV or less, and combinations containing Cs are particularly preferred, such as Cs with Na, Cs with K, Cs with Rb, or Cs with Na and K. By including Cs, the reducing ability can be effectively utilized, and by adding it to the material forming the electron transport layer or electron injection layer, the luminous brightness or lifetime of organic EL devices can be improved.

[0752] <Other>

[0753] The electron injection layer material and the electron transport layer material may also be used in the electron layer material as the following polymeric compounds or their polymeric crosslinks, or as the following suspended polymeric compounds or their suspended polymeric crosslinks. The polymeric compounds are obtained by polymerizing a reactive compound, in which reactive substituents are substituted in the electron injection layer material and the electron transport layer material, as a monomer. The suspended polymeric compounds are obtained by reacting a main-chain polymer with the reactive compound. The description of the reactive substituents in the above cases can be found in the polycyclic aromatic compounds represented by formula (1).

[0754] Details regarding the applications of this polymer compound and its crosslinked polymers will be described later.

[0755] 3-1-7. Cathode in Organic Light-Emitting Devices

[0756] The cathode 108 functions to inject electrons into the light-emitting layer 105 via the electron injection layer 107 and the electron transport layer 106.

[0757] The material forming the cathode 108 is not particularly limited if it is a substance capable of efficiently injecting electrons into the organic layer, and the same material as the material forming the anode 102 can be used. Preferred materials include 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 alloys, magnesium-indium alloys, lithium fluoride / aluminum and other aluminum-lithium alloys, etc.). To improve electron injection efficiency and thus enhance device characteristics, 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 the atmosphere. To improve this, methods such as doping the organic layer with trace amounts of lithium, cesium, or magnesium and using a highly stable electrode are known. Inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used as other dopants. However, these are not the only options.

[0758] Furthermore, the following are preferred examples: To protect the electrodes, metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, or alloys of these metals, as well as inorganic materials such as silicon dioxide, titanium dioxide, and silicon nitride, polyvinyl alcohol, vinyl chloride, and hydrocarbon polymers are layered. There are no particular restrictions on the methods used to fabricate these electrodes, as long as they are methods that achieve conductivity, such as resistance heating, electron beam evaporation, sputtering, ion plating, and coating.

[0759] 3-1-8. Adhesives that can be used in each layer

[0760] The materials used in the hole injection layer, hole transport layer, light emission layer, electron transport layer, and electron injection layer can be formed individually or dispersed in solvent-soluble resins such as polyvinyl chloride, polycarbonate, polystyrene, poly(N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene ether, polybutadiene, hydrocarbon resins, ketone resins, phenoxy resins, polyamides, ethyl cellulose, vinyl acetate resins, acrylonitrile butadiene styrene (ABS) resins, and polyurethane resins, or curable resins such as phenolic resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, and silicone resins.

[0761] 3-1-9. Fabrication method of organic electroluminescent elements

[0762] The layers constituting an organic electroluminescent (EL) element can be formed by depositing thin films of the materials to be constituting each layer using methods such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination, printing, spin coating, casting, and coating. The film thickness of each layer formed in these methods is not particularly limited and can be appropriately set according to the properties of the material, but is typically in the range of 2 nm to 5000 nm. The film thickness can usually be measured using a crystal oscillating film thickness measuring device. When using vapor deposition for thin film formation, the vapor deposition conditions vary depending on the type of material, the target crystalline structure of the film, and the associative structure. The preferred vapor deposition conditions are typically a boat heating temperature of +50°C to +400°C and a vacuum degree of 10... -6 Pa~10 -3 The Pa, evaporation rate (0.01 nm / sec to 50 nm / sec), substrate temperature (-150℃ to +300℃), and film thickness (2 nm to 5 μm) are appropriately set within the range.

[0763] When a DC voltage is applied to the organic EL element obtained in the manner described above, it is sufficient to apply the voltage with the anode as the positive polarity and the cathode as the negative polarity. If a voltage of approximately 2V to 40V is applied, light emission can be observed from the transparent or semi-transparent electrode side (anode or cathode, or both). Furthermore, the organic EL element also emits light when a pulsed current or alternating current is applied. Moreover, the waveform of the applied alternating current can be arbitrary.

[0764] Subsequently, as an example of a method for fabricating an organic EL device, a method for fabricating an organic EL device comprising an anode / hole injection layer / hole transport layer / light-emitting layer containing a host material and a dopant material / electron transport layer / electron injection layer / cathode will be described.

[0765] <Evaporation Method>

[0766] An anode is fabricated on a suitable substrate by forming a thin film of anode material using a vapor deposition method. Then, a hole injection layer and a hole transport layer are formed on the anode. A light-emitting layer is formed by co-depositing a host material and a dopant material on the light-emitting layer. An electron transport layer and an electron injection layer are formed on the light-emitting layer. Finally, a thin film containing a cathode material is formed using a vapor deposition method to serve as the cathode, thereby obtaining the target organic EL device. Alternatively, the fabrication order of the organic EL device can be reversed, with the order being cathode, electron injection layer, electron transport layer, light-emitting layer, hole transport layer, hole injection layer, and anode.

[0767] <Wet film formation method>

[0768] A liquid organic layer-forming composition is prepared by using low-molecular-weight compounds capable of forming organic layers of an organic EL element, and then wet film formation is performed using this composition. In the absence of a suitable organic solvent for dissolving the low-molecular-weight compounds, an organic layer-forming composition can also be prepared from polymeric compounds that are polymerized together with other monomers or main-chain polymers that are reactive compounds formed by substituting reactive substituents into the low-molecular-weight compounds and thus possess solubility.

[0769] Wet film-forming methods typically form a coating film through a coating process involving applying an organic layer-forming composition onto a substrate and a drying process involving removing the solvent from the coated organic layer-forming composition. In cases where the polymer compound has crosslinking substituents (also referred to as a crosslinked polymer compound), the drying process further crosslinks the polymer to form a crosslinked polymer. Depending on the coating process, methods using a spin coater are called spin coating, methods using a slot coater are called slot coating, methods using a printing plate are called gravure, offset, reverse offset, or flexographic printing, methods using an inkjet printer are called inkjet printing, and methods using a mist are called spraying. Drying processes include air drying, heating, and vacuum drying. The drying process can be performed only once or multiple times using different methods or conditions. Furthermore, different methods can be used, for example, such as calcination under reduced pressure.

[0770] Wet film deposition is a film-forming method that uses a solution, such as partial printing (inkjet printing), spin coating, casting, or plating. Unlike vacuum evaporation, wet film deposition does not require expensive vacuum evaporation equipment and can be performed under atmospheric pressure. Furthermore, wet film deposition allows for large-area or continuous production, resulting in lower manufacturing costs.

[0771] On the other hand, compared with vacuum evaporation, wet film deposition methods are difficult to laminate. When using wet film deposition methods to fabricate laminated films, it is necessary to prevent the dissolution of the lower layer caused by the composition of the upper layer, and to use compositions with controlled solubility, crosslinking of the lower layer, and orthogonal solvents (mutually insoluble solvents). However, even with these techniques, it is difficult to apply wet film deposition methods to the coating of all types of films.

[0772] Therefore, the following method can usually be used: use wet film deposition to form only a few layers, and use vacuum evaporation to form the remaining layers, thereby fabricating organic EL devices.

[0773] For example, the following shows a part of the procedure for fabricating organic EL elements using a wet film deposition method.

[0774] (Program 1) Film formation of the anode using vacuum evaporation method

[0775] (Program 2) Film formation using a wet film formation method for a composition containing a material for a hole injection layer.

[0776] (Procedure 3) Film formation of a hole transport layer composition containing a hole transport layer material using a wet film formation method.

[0777] (Procedure 4) Film formation using a wet film formation method for a composition comprising a host material and a dopant material for forming a light-emitting layer.

[0778] (Procedure 5) Electron transport layer film formation using vacuum evaporation method

[0779] (Procedure 6) Electron injection layer film formation using vacuum evaporation method

[0780] (Program 7) Film formation of the cathode using vacuum evaporation method

[0781] An organic EL device comprising an anode / hole injection layer / hole transport layer / light emission layer containing host material and dopant material / electron transport layer / electron injection layer / cathode can be obtained through the aforementioned process.

[0782] Of course, for the electron transport layer and the electron injection layer, a layer-forming composition containing materials for the electron transport layer and the electron injection layer can be used respectively, and the film can be formed by a wet film-forming method. In this case, it is preferable to use a means to prevent the dissolution of the underlying light-emitting layer, or to form the film from the cathode side in the opposite manner to the above procedure.

[0783] <Other film-forming methods>

[0784] Laser-induced thermal imaging (LITI) can be used in the film formation of compositions for forming organic layers. LITI is a method that uses a laser to heat and vaporize a compound attached to a substrate, and the composition for forming organic layers can be used in materials coated on a substrate.

[0785] <Any process>

[0786] Appropriate treatment, cleaning, and drying processes can be added before and after each step of the film formation process. Examples of treatment processes include: exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, cleaning treatment using appropriate solvents, and heat treatment. Furthermore, a series of processes for creating the bank can also be listed.

[0787] Photolithography can be used in the fabrication of the embankment. Positive and negative resist materials can be used as embankment materials suitable for photolithography. Alternatively, printing methods that can create patterns, such as inkjet printing, gravure printing, reverse lithography, and screen printing, can also be used. In these cases, permanent resist materials can also be used.

[0788] Materials used for embankments include, but are not limited to, polysaccharides and their derivatives, homopolymers and copolymers of hydroxyl-containing vinyl monomers, biopolymers, polyacrylamide compounds, polyesters, polystyrene, polyimide, polyamide-imide, polyether-imide, polysulfone, polyphenylene, polyphenylene ether, polyurethane, epoxy methacrylate, melamine methacrylate, polyolefins, cyclic polyolefins, acrylonitrile-butadiene-styrene copolymers (ABS), silicone resins, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyacetate, polynorbornene, synthetic rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene and other fluorinated polymers, fluoroolefin-hydrocarbon olefin copolymers, and fluorocarbon polymers.

[0789] <Organic layer-forming compositions used in wet film-forming methods>

[0790] The composition for forming an organic layer is obtained by dissolving a low-molecular-weight compound capable of forming organic EL elements, or a high-molecular-weight compound obtained by polymerizing the low-molecular-weight compound, in an organic solvent. For example, the composition for forming a light-emitting layer contains at least one dopant material, namely a polycyclic aromatic compound (or its polymeric compound), as a first component, at least one host material as a second component, and at least one organic solvent as a third component. The first component functions as a dopant component of the light-emitting layer obtained from the composition, and the second component functions as a host component of the light-emitting layer. The third component functions as a solvent for dissolving the first and second components in the composition, and a smooth and uniform surface shape is obtained during coating by the controlled evaporation rate of the third component itself.

[0791] <Organic solvent>

[0792] The composition for forming an organic layer contains at least one organic solvent. By controlling the evaporation rate of the organic solvent during film formation, film-forming properties, the presence or absence of coating defects, surface roughness, and smoothness can be controlled and improved. Furthermore, when using inkjet printing for film formation, the meniscus stability at the inkjet head's pinhole can be controlled, and ejection properties can be controlled / improved. In addition, by controlling the film drying rate and the orientation of derivative molecules, the electrical properties, luminescent properties, efficiency, and lifetime of organic EL devices having an organic layer obtained from the aforementioned composition for forming an organic layer can be improved.

[0793] (1) Properties of organic solvents

[0794] The boiling point of at least one organic solvent is 130°C to 300°C, more preferably 140°C to 270°C, and even more preferably 150°C to 250°C. From the viewpoint of inkjet ejection performance, a boiling point higher than 130°C is preferred. Furthermore, from the viewpoint of coating defects, surface roughness, residual solvent, and smoothness, a boiling point lower than 300°C is preferred. From the viewpoint of good inkjet ejection performance, film formation, smoothness, and low residual solvent, the organic solvent is more preferably composed of two or more organic solvents. On the other hand, depending on the circumstances, considering factors such as transportability, a composition prepared into a solid state by removing the solvent from the organic layer forming composition may also be used.

[0795] 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 (BP) of the good solvent (GS) is particularly preferred. GS ) lower than the boiling point (BP) of the unsuitable solvent (PS) PS The composition of ).

[0796] By adding a high-boiling-point undesirable solvent, while the low-boiling-point good solvent evaporates first during film formation, the concentration of the contents and the concentration of the undesirable solvent in the composition increase, promoting rapid film formation. This results in a coating film with fewer defects, lower surface roughness, and higher smoothness.

[0797] Difference in solubility (S) GS -S PS The content of boiling point difference (BP) is preferably 1% or more, more preferably 3% or more, and even more preferably 5% or more. PS -BP GS Preferably, the temperature is 10°C or higher, more preferably 30°C or higher, and even more preferably 50°C or higher.

[0798] After film formation, the organic solvent is removed from the coating film through drying processes such as vacuum, reduced pressure, and heating. When heating is performed, from the viewpoint of improving film formation properties, it is preferable to heat at a temperature below 30°C above the glass transition temperature (Tg) of at least one solute. Furthermore, from the viewpoint of reducing residual solvent, it is preferable to heat at a temperature above 30°C below the glass transition temperature (Tg) of at least one solute. Even if the heating temperature is below the boiling point of the organic solvent, the organic solvent is sufficiently removed due to the thin film. Additionally, multiple drying processes can be performed at different temperatures, and various drying methods can be used in combination.

[0799] (2) Specific examples of organic solvents

[0800] Organic solvents used in compositions for forming organic layers include alkylbenzene solvents, phenyl ether solvents, alkyl ether solvents, cyclic ketone solvents, aliphatic ketone solvents, monocyclic ketone solvents, solvents with a diester skeleton, and fluorine-containing solvents. Specific examples include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecylol, dodecanol, tetradecylol, hexane-2-ol, heptane-2-ol, octane-2-ol, decane-2-ol, dodecane-2-ol, cyclohexanol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, terpineol (mixtures), ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and 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-dimethylpyridine, 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, Trimethylbenzene, 1,2,4-Trimethylbenzene, Tert-Butylbenzene, 2-Methylanisole, Phenethyl ether, Benzodioxole, 4-Methylanisole, Sec-Butylbenzene, 3-Methylanisole, 4-Fluoro-3-Methylanisole, Cymene, 1,2,3-Trimethylbenzene, 1,2-Dichlorobenzene, 2-Fluorobenzonitrile, 4-Fluoro-dimethoxybenzene, 2,6-Dimethylanisole, n-Butylbenzene, 3-Fluorobenzonitrile, Decalin (Decahydronaphthalene), Neopentylbenzene 2,5-Dimethyl anisole, 2,4-Dimethyl anisole, benzonitrile, 3,5-Dimethyl anisole, diphenyl ether, 1-fluoro-3,5-dimethoxybenzene, methyl benzoate, isopentylbenzene, 3,4-dimethyl anisole, o-toluenenitrile, n-pentylbenzene, o-dimethoxybenzene, 1,2,3,4-tetrahydronaphthalene, ethyl benzoate, n-hexylbenzene, propyl benzoate, cyclohexylbenzene, 1-methylnaphthalene, butyl benzoate, 2-methylbiphenyl, 3-phenoxytoluene, 2,2'-dimethylbiphenyl, dodecylbenzene, dipentylbenzene, tetramethylbenzene, trimethoxybenzene, trimethoxytoluene, 2,3-Dihydrobenzofuran, 1-Methyl-4-(propoxymethyl)benzene, 1-Methyl-4-(butoxymethyl)benzene, 1-Methyl-4-(pentoxymethyl)benzene, 1-Methyl-4-(hexyloxymethyl)benzene, 1-Methyl-4-(heptoxymethyl)benzene, benzylbutyl ether, benzylpentyl ether, benzylhexyl ether, benzylheptyl ether, benzyloctyl ether, etc., but not limited to these. Furthermore, the solvent can be used alone or in mixtures.

[0801] <Any ingredient>

[0802] The composition for forming organic layers may contain any components without impairing its properties. Examples of such components include adhesives and surfactants.

[0803] (1) Adhesive

[0804] The composition for forming an organic layer may also contain an adhesive. The adhesive bonds the resulting film to the substrate during film formation. Additionally, it plays a role in dissolving, dispersing, and binding other components in the organic layer-forming composition.

[0805] Examples of adhesives used in compositions for forming organic layers include, but are not limited to, acrylic resins, polyethylene terephthalate, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, acrylonitrile-ethylene-styrene (AES) copolymers, ionomers, chlorinated polyethers, diallyl phthalate resins, unsaturated polyester resins, 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 said resins and polymers.

[0806] The adhesive used in the composition for forming organic layers may be a single type or a mixture of multiple types.

[0807] (2) Surfactants

[0808] For example, to control the film surface uniformity, solvent affinity, and liquid repellency of the organic layer forming composition, the organic layer forming composition may also contain a surfactant. Surfactants are classified as ionic or nonionic based on the structure of their hydrophilic groups, and further classified as alkyl, silicon, and fluorinated based on the structure of their hydrophobic groups. Additionally, they are classified according to molecular structure as monomolecular systems with simple structures and polymeric systems with large molecular weights and side chains or branches. Furthermore, they are classified according to composition as single-component systems and mixed systems containing two or more surfactants and a substrate. All types of surfactants can be used as surfactants in the organic layer forming composition.

[0809] Examples of surfactants include: Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 (trade name, manufactured by Kyoei Chemical Industry Co., Ltd.); Disperbyk 161, Disperbyk 162, Disperbyk 163, and Disperbyk 16... 4. Disperbyk 166, Disperbyk 170, Disperbyk 180, Disperbyk 181, Disperbyk 182, BYK 300, BYK 306, BYK 310, BYK 320, BYK 330, BYK 342, BYK 344, BYK 346 (trade name, BYK-Chemie Japan) (manufactured by Japan) (stock); KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.); Ftergent 222F, Ftergent 251, FTX-218 (trade name, manufactured by NEOS Co., Ltd.); EFTOP EF-351, EFTOP EF-352, EFTOP (E FTOP EF-601, EFTOP EF-801, EFTOP EF-802 (trade name, manufactured by Mitsubishi Material (stock)); Megafac F-470, Megafac F-471, Megafac F-475, Megafac R-08, Megafac F-477, Megafac F-479, Megafac F-553, Megafac F-554 (trade name, manufactured by DIC (stock));Fluoroalkylbenzene sulfonates, fluoroalkyl carboxylates, fluoroalkyl polyoxyethylene ethers, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonates, diglycerol tetra(fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethylammonium salt, fluoroalkyl aminosulfonates, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, dehydrated sorbitol laurate, dehydrated sorbitol palmitate, dehydrated sorbitol stearate, dehydrated sorbitol oleate, dehydrated sorbitol fatty acid ester, polyoxyethylene dehydrated sorbitol laurate, polyoxyethylene dehydrated sorbitol palmitate, polyoxyethylene dehydrated sorbitol stearate, polyoxyethylene dehydrated sorbitol oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonates, and alkyl diphenyl ether disulfonates.

[0810] In addition, one surfactant may be used, or two or more surfactants may be used in combination.

[0811] <Composition and Properties of the Composition for Organic Layer Formation>

[0812] The content of each component in the organic layer-forming composition is determined from the perspectives of good solubility, storage stability, and film-forming properties of each component, high-quality film quality of the coating obtained from the organic layer-forming composition, good ejectibility when using inkjet printing, and good electrical properties, luminescence properties, efficiency, and lifetime of the organic EL element with the organic layer formed using the composition. For example, in the case of a light-emitting layer-forming composition, it is preferable that: the first component is 0.0001% to 2.0% by mass relative to the total mass of the light-emitting layer-forming composition, the second component is 0.0999% to 8.0% by mass relative to the total mass of the light-emitting layer-forming composition, and the third component is 90.0% to 99.9% by mass relative to the total mass of the light-emitting layer-forming composition.

[0813] More preferably, the first component is 0.005% to 1.0% by mass relative to the total mass of the composition for forming the light-emitting layer, the second component is 0.095% to 4.0% by mass relative to the total mass of the composition for forming the light-emitting layer, and the third component is 95.0% to 99.9% by mass relative to the total mass of the composition for forming the light-emitting layer. Even more preferably, the first component is 0.05% to 0.5% by mass relative to the total mass of the composition for forming the light-emitting layer, the second component is 0.25% to 2.5% by mass relative to the total mass of the composition for forming the light-emitting layer, and the third component is 97.0% to 99.7% by mass relative to the total mass of the composition for forming the light-emitting layer.

[0814] The composition for forming an organic layer can be manufactured by appropriately selecting the components through stirring, mixing, heating, cooling, dissolving, dispersing, etc., using known methods. Alternatively, after preparation, it can be appropriately subjected to filtration, degassing (also known as degassing), ion exchange treatment, and inert gas replacement / sealing treatment, etc.

[0815] Regarding the viscosity of the composition for forming the organic layer, high viscosity provides good film-forming properties and good ejection properties when using inkjet printing. On the other hand, low viscosity facilitates the fabrication of thin films. Therefore, the viscosity of the composition for forming the organic layer is preferably 0.3 mPa·s to 3 mPa·s at 25°C, more preferably 1 mPa·s to 3 mPa·s. In this invention, the viscosity is a value measured using a cone-plate type rotational viscometer.

[0816] Regarding the surface tension of the composition for forming the organic layer, a low surface tension results in good film-forming properties and a defect-free coating. Conversely, a high surface tension results in good inkjet ejection properties. Therefore, the surface tension of the composition for forming the organic layer is preferably 20 mN / m to 40 mN / m at 25°C, more preferably 20 mN / m to 30 mN / m. In this invention, the surface tension is a value measured using the pendant drop method.

[0817] <Cross-linked polymers: compounds represented by formula (XLP-1)>

[0818] Next, the case where the polymer compound has cross-linking substituents will be described. Such cross-linking polymer compounds are, for example, compounds represented by the following formula (XLP-1).

[0819]

[0820] In equation (XLP-1),

[0821] The definitions of MUx, ECx, and k are the same as those of MU, EC, and k in formula (SPH-1), wherein the compound represented by formula (XLP-1) has at least one crosslinking substituent (XLS), preferably a monovalent or divalent aromatic compound having a crosslinking substituent, and the content of the compound in the molecule is 0.1% to 80% by mass.

[0822] The content of the monovalent or divalent aromatic compound having crosslinking substituents is preferably 0.5% to 50% by mass, more preferably 1% to 20% by mass.

[0823] As a crosslinking substituent (XLS), there are no particular limitations if it is a group that can further crosslink the polymer compound, but substituents with the following structures are preferred. * in each structural formula indicates a bond position.

[0824]

[0825] L Y Each of the substituents is independently a single bond, -O-, -S-, >C=O, -OC(=O)-, alkylene group having 1 to 12 carbon atoms, oxoalkylene group having 1 to 12 carbon atoms, or polyoxoalkylene group having 1 to 12 carbon atoms. The substituents are preferably those represented by formulas (XLS-1), (XLS-2), (XLS-3), (XLS-9), (XLS-10), or (XLS-17), and more preferably those represented by formulas (XLS-1), (XLS-3), or (XLS-17).

[0826] Examples of divalent aromatic compounds having crosslinking substituents include compounds having the following partial structures.

[0827]

[0828]

[0829] <Methods for manufacturing polymers and cross-linked polymers>

[0830] The methods for manufacturing polymeric compounds and cross-linked polymeric compounds will be described using compounds represented by formula (SPH-1) and formula (XLP-1) as examples. These compounds can be synthesized by appropriately combining known manufacturing methods.

[0831] Examples of solvents used in reactions include aromatic solvents, saturated / unsaturated hydrocarbon solvents, alcohol solvents, and ether solvents. Examples of such solvents include dimethoxyethane, 2-(2-methoxyethoxy)ethane, and 2-(2-ethoxyethoxy)ethane.

[0832] Alternatively, the reaction can also be carried out in a two-phase system. In the case of a two-phase system reaction, a phase transfer catalyst such as a quaternary ammonium salt can be added as needed.

[0833] When manufacturing compounds of formula (SPH-1) and formula (XLP-1), they can be produced in a single stage or in multiple stages. Alternatively, they can be synthesized via a general polymerization method where all starting materials are placed in the reaction vessel, a dropwise polymerization method where starting materials are added dropwise to the reaction vessel, or a precipitation polymerization method where the product precipitates as the reaction proceeds. These methods can be appropriately combined. For example, when synthesizing a compound of formula (SPH-1) in a single stage, the target compound is obtained by reacting a monomer with a polymerizable group bonded in the monomer unit (MU) and a monomer with a polymerizable group bonded in the end-capping unit (EC) in a reaction vessel. Conversely, when synthesizing a compound of formula (SPH-1) in multiple stages, the target compound is obtained by polymerizing a monomer with a polymerizable group bonded in the monomer unit (MU) to the target molecular weight, then adding a monomer with a polymerizable group bonded in the end-capping unit (EC) and reacting it. By introducing monomers with polymerizable groups bonded to different types of monomer units (MUs) in multiple stages of the reaction, polymers with concentration gradients relative to the structure of the monomer units can be produced. Furthermore, after preparing the precursor polymer, the target polymer can be obtained through subsequent reactions.

[0834] Furthermore, by selecting the polymerizable groups of the monomers, the primary structure of the polymer can be controlled. For example, as shown in synthesis procedures 1-3, polymers with random primary structures (synthesis procedure 1) and polymers with regular primary structures (synthesis procedures 2 and 3) can be synthesized, and appropriate combinations can be used depending on the target material. Moreover, if monomers with three or more polymerizable groups are used, hyperbranched polymers or dendritic polymers can be synthesized. r ).

[0835] a, b = MU or MUx

[0836] Polymerization group = x, y (x and y bonds respectively)

[0837] 1) Polymers synthesized using two monomers (xay) and one monomer (xby)

[0838]

[0839] 2) Polymers synthesized using two monomers (xax) and monomer (yby)

[0840]

[0841] 3) Polymers synthesized using two monomers (xay) and monomer (yby)

[0842]

[0843] As monomers that can be used in this invention, they can be based on Japanese Patent Application Publication No. 2010-189630, International Publication No. 2012 / 086671, International Publication No. 2013 / 191088, International Publication No. 2002 / 045184, International Publication No. 2011 / 049241, International Publication No. 2013 / 146806, International Publication No. 2005 / 049546, and International Publication No. 2015 / 145871. The method described in Japanese Patent Application Publication No. 2010-215886, Japanese Patent Application Publication No. 2008-106241, Japanese Patent Application Publication No. 2010-215886, International Publication No. 2016 / 031639, Japanese Patent Application Publication No. 2011-174062, International Publication No. 2016 / 031639, International Publication No. 2016 / 031639, and International Publication No. 2002 / 045184 is used to synthesize the material.

[0844] Furthermore, regarding the specific polymer synthesis procedure, please refer to Japanese Patent Application Publication No. 2012-036388, International Publication No. 2015 / 008851, Japanese Patent Application Publication No. 2012-36381, Japanese Patent Application Publication No. 2012-144722, International Publication No. 2015 / 194448, International Publication No. 2013 / 146806, International Publication No. 2015 / 145871, and other relevant publications. The method described in International Publication No. 2016 / 031639, International Publication No. 2016 / 125560, International Publication No. 2016 / 031639, International Publication No. 2016 / 125560, International Publication No. 2015 / 145871, International Publication No. 2011 / 049241, and Japanese Patent Application Publication No. 2012-144722 is used to synthesize the material.

[0845] 3-1-10. Examples of applications of organic electroluminescent elements

[0846] Organic EL elements can also be used in display devices that include organic EL elements or lighting devices that include organic EL elements.

[0847] Display devices or lighting devices including organic EL elements can be manufactured by known methods such as connecting the organic EL element of this embodiment to a known driving device, and can be driven by known driving methods such as DC driving, pulse driving, and AC driving.

[0848] Examples of display devices include: panel displays such as color flat panel displays, flexible displays such as flexible color organic electroluminescent (EL) displays (see, for example, Japanese Patent Application Publication No. 10-335066, Japanese Patent Application Publication No. 2003-321546, and Japanese Patent Application Publication No. 2004-281086). Furthermore, examples of display methods include matrix and / or segmented display methods. Moreover, matrix display and segmented display can coexist on the same panel.

[0849] In a matrix, pixels for display are arranged two-dimensionally in a grid or mosaic pattern, so that text or images are displayed by the collection of pixels. The shape or size of the pixels is determined by the application. For example, in the image and text display of personal computers, monitors, and televisions, quadrilateral pixels with one side less than 300μm are usually used. In the case of large displays such as display panels, pixels with one side in the millimeter range are used. In the case of monochrome display, pixels of the same color are simply arranged. In the case of color display, red, green, and blue pixels are displayed side by side. Typical patterns in these cases are triangular and striped. Moreover, the driving method of the matrix can be either a line-sequential driving method or an active matrix. Line-sequential driving has the advantage of simple structure, but when considering operating characteristics, sometimes an active matrix is ​​superior. Therefore, the driving method also needs to be selected according to the application.

[0850] In the segmented method (type), a pattern is formed to display pre-determined information, and the determined area is illuminated. Examples include: time or temperature displays in digital clocks or thermometers, operating status displays in audio equipment or induction cookers, and panel displays in automobiles.

[0851] Examples of lighting devices include indoor lighting and backlights for liquid crystal displays (see, for example, Japanese Patent Application Publication Nos. 2003-257621, 2003-277741, and 2004-119211). Backlights are primarily used to improve the visibility of display devices that do not emit light themselves, and are used in liquid crystal displays, clocks, audio devices, automotive panels, display boards, and signs. In particular, for backlights used in personal computers where thinness is a problem in liquid crystal displays, the backlight using the light-emitting element of this embodiment is thin and lightweight, considering that existing methods are difficult to make thin due to the inclusion of fluorescent lamps or light guide plates.

[0852] 3-2. Other organic devices

[0853] In addition to being used in the organic electroluminescent elements, the compounds of the present invention can also be used in the fabrication of organic electro-effective transistors or organic thin-film solar cells.

[0854] An organic field-effect transistor (FET) is a transistor that controls current by using an electric field generated by a voltage input. In addition to source and drain electrodes, it also has a gate electrode. An organic field-effect transistor works as follows: when a voltage is applied to the gate electrode, an electric field is generated, which can arbitrarily block the flow of electrons (or holes) between the source and drain electrodes to control the current. Compared to a single transistor (bipolar transistor), FETs are easier to miniaturize and are commonly used as components in integrated circuits.

[0855] Regarding the structure of an organic field-effective transistor, generally, the source electrode and drain electrode are simply provided in contact with the organic semiconductor active layer formed using the polycyclic aromatic compound of the present invention, and the gate electrode is provided in contact with an insulating layer (dielectric layer) in contact with the organic semiconductor active layer. Examples of such device structures include the following.

[0856] (1) Substrate / Gate electrode / Insulator layer / Source electrode and drain electrode / Organic semiconductor active layer

[0857] (2) Substrate / Gate electrode / Insulator layer / Organic semiconductor active layer / Source electrode and drain electrode

[0858] (3) Substrate / Organic semiconductor active layer / Source electrode and drain electrode / Insulator layer / Gate electrode

[0859] (4) Substrate / Source and Drain Electrodes / Organic Semiconductor Active Layer / Insulator Layer / Gate Electrode

[0860] The organic field-active transistor constructed in the manner described above can be used as a pixel driving switching element in an active matrix driven liquid crystal display or an organic electroluminescent display.

[0861] Organic thin-film solar cells have a structure in which an anode, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode, such as ITO, are stacked on a transparent substrate such as glass. The photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side. The polycyclic aromatic compounds of the present invention, depending on their physical properties, can be used as materials for the hole transport layer, p-type semiconductor layer, n-type semiconductor layer, and electron transport layer. In organic thin-film solar cells, the polycyclic aromatic compounds of the present invention can function as hole transport materials or electron transport materials. In addition to the aforementioned layers, organic thin-film solar cells may also appropriately include hole blocking layers, electron blocking layers, electron injection layers, hole injection layers, smoothing layers, etc. In organic thin-film solar cells, known materials used in organic thin-film solar cells can be appropriately selected and combined.

[0862] [Example]

[0863] The present invention will be described in more detail below through examples, but the present invention is not limited to these examples. First, examples of the synthesis of polycyclic aromatic compounds will be described below.

[0864] Synthetic Example (1): Synthesis of Compounds (1-25)

[0865]

[0866] Compound (IA) was dissolved in acetonitrile (300 ml) under nitrogen atmosphere. Bromine was added dropwise while the mixture was cooled in an ice bath and stirred. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. Toluene was then added, the organic layer was separated, and washed with water. The organic layer was then concentrated to obtain the crude product. The crude product was purified using a short silica gel column to obtain compound (IB).

[0867]

[0868] Under nitrogen atmosphere, tert-butyl nitrite and copper(II) chloride were suspended in acetonitrile. An intermediate (IB) dissolved in acetonitrile was added dropwise at 60°C, and the mixture was stirred at this temperature. After the reaction, dilute hydrochloric acid and ethyl acetate were added to the reaction solution and stirred. The organic layer was then separated and washed with water. The organic layer was then concentrated to obtain the crude product. The crude product was purified using a short silica gel column to obtain compound (IC).

[0869]

[0870] Under nitrogen atmosphere, intermediate (IC), N-(3-tert-butylphenyl)-3,5-di-tert-butylaniline, dichlorobis(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium (Pd-132) as a palladium catalyst, sodium tert-butoxide (NaOtBu), and xylene were placed in a flask and heated with stirring at 100°C. After the reaction, water and ethyl acetate were added to the reaction solution and stirred. The organic layer was then separated and washed with water. The organic layer was then concentrated to obtain the crude product. The crude product was purified using a short silica gel column to obtain compound (ID) (26.0 g).

[0871]

[0872] Under nitrogen atmosphere and at 0°C, a 1.56 M solution of tert-butyllithium in pentane was added to a flask containing compound (ID) and tert-butylbenzene. After the addition was complete, the temperature was raised to 60°C and stirred for 1 hour. Then, the component with a boiling point lower than tert-butylbenzene was removed by vacuum distillation. The mixture was cooled to -50°C and boron tribromide was added. The temperature was raised to room temperature and stirred for 0.5 hours. Then, the mixture was cooled again to 0°C and N,N-diisopropylethylamine was added. The mixture was stirred at room temperature until heating ceased, then the temperature was raised to 100°C and stirred for 1 hour. The reaction mixture was cooled to room temperature, and sodium acetate aqueous solution cooled in an ice bath and ethyl acetate were added sequentially for separation. The organic layer was concentrated and purified using a short silica gel column. The crude product was dissolved in toluene and reprecipitated with methanol to obtain compound (1-25).

[0873] The obtained compound was identified as compound (1-25) by mass spectrometry analysis.

[0874] Electron ionization mass spectrometry (EI-MS): m / z = 933.

[0875]

[0876] Synthesis Example (2): Synthesis of Compound (1-327)

[0877]

[0878] The compound represented by formula (1-327) was synthesized using the same method as in the synthetic example (1).

[0879]

[0880] The structure of the obtained compound was confirmed by nuclear magnetic resonance (NMR) measurements.

[0881] 1H-NMR (CDCl3): σ=1.46(s,9H),1.47(s,9H),1.59~1.76(m,24H),2.00(br ,3H),2.01(br,3H),2.52(s,2H),2.53(s,2H),6.12(d,1H),6.13(d,1H), 6.67(d,1H),6.73(d,1H),7.18(dd,1H),7.25(t,1H),7.26(d,2H),7.29( d,2H),7.37(d,2H),7.51(dd,1H),7.67(d,2H),8.64(d,1H),8.95(d,1H).

[0882] Synthesis Example (3): Synthesis of Compound (1-416)

[0883]

[0884] The compound represented by formula (1-416) was synthesized using the same method as in the synthetic example (1).

[0885]

[0886] The structure of the obtained compound was confirmed by NMR determination.

[0887] 1 H-NMR (CDCl3): σ=1.60~1.76(m,24H),1.97(br,3H),2.02(br,3H),2.54(s,2H),2.58(s,2H),6.06(d,1H),6.16(d,1H),6.33(d,1H),6.57( d,1H),6.95(t,1H),7.17(dd,1H),7.25~7.30(m,3H),7.32(t,1H),7.39(d,2H),7.53(dd,2H),7.69~7.76(m,3H),8.00(d,1H),8.50(d,1H).

[0888] Synthesis Example (4): Synthesis of Compound (1-417)

[0889]

[0890] The compound represented by formula (1-417) was synthesized using the same method as in synthetic example (1).

[0891]

[0892] The structure of the obtained compound was confirmed by NMR determination.

[0893] 1 H-NMR (CDCl3): σ=1.15(s,9H),1.31(s,9H),1.35(s,9H),1.44(s,9H),1.53~1.67(m,12H),1.92(br,3H),2.48(m,2H),5. 50(s,1H),5.65(s,1H),6.73(d,2H),6.87~6.92(m,6H),6.99~7.15(m,12H),7.38~7.47(m,5H),8.55(d,1H),8.89(d,1H).

[0894] Synthesis Example (5): Synthesis of Compound (1-418)

[0895]

[0896] The compound represented by formula (1-418) was synthesized using the same method as in the synthetic example (1).

[0897]

[0898] The structure of the obtained compound was confirmed by NMR determination.

[0899] 1 H-NMR (CDCl3): σ=1.10(s,9H),1.45(s,18H),1.47(s,9H),1.54~1.69(m,12H),1.93(br,3H),2.49(m,2H),6.08(d,1H),6.25(d,1H),6.72(d ,2H),6.97(d,2H),7.05(d,2H),7.13(dd,1H),7.23~7.30(m,4H),7.49(dd,1H),7.60(dd,1H),7.65~7.68(m,3H),8.56(d,1H),8.91(d,1H).

[0900] Synthesis Example (6): Synthesis of Compound (1-419)

[0901]

[0902] The compound represented by formula (1-419) was synthesized using the same method as in the synthetic example (1).

[0903]

[0904] The structure of the obtained compound was confirmed by NMR determination.

[0905] 1H-NMR (CDCl3): σ=0.73~0.92(m,4H),1.00~1.27(m,12H),1.41(s,6H),1.44 (s,6H),1.46(s,9H),1.48(s,9H),1.56~1.74(m,14H),6.12(d,1H),6.13(d, 1H),6.73(d,1H),6.75(d,1H),7.24(t,1H),7.29(d,2H),7.30(d,2H),7.43 (dd,1H),7.52(dd,1H),7.61(d,2H),7.67(d,2H),8.90(d,1H),8.97(d,1H).

[0906] Synthesis Example (7): Synthesis of Compound (1-420)

[0907]

[0908] The compound represented by formula (1-420) was synthesized using the same method as in synthetic example (1).

[0909]

[0910] The structure of the obtained compound was confirmed by NMR determination.

[0911] 1 H-NMR (CDCl3): σ=0.78~0.92(m,4H),1.06~1.26(m,12H),1.41(s,6H),1.48(s,6 H),1.57~1.74(m,12H),1.76~1.80(m,2H),6.06(d,1H),6.17(d,1H),6.33(d,1H ),6.63(d,1H),6.96(t,1H),7.27(t,1H),7.29(d,2H),7.33(t,1H),7.41(dd,1H ),7.53~7.55(m,2H),7.62(d,2H),7.69~7.75(m,3H),7.99(d,1H),8.74(d,1H).

[0912] Synthesis Example (8): Synthesis of Compound (1-423)

[0913]

[0914] The compound represented by formula (1-423) was synthesized using the same method as in the synthetic example (1).

[0915]

[0916] The structure of the obtained compound was confirmed by NMR determination.

[0917] 1 H-NMR (CDCl3): σ=0.74~0.90(m,8H),1.00~1.26(m,24H),1.42(s,12H),1.44(s,12H),1.56~1.74(m ,28H),2.14(s,3H),5.91(s,2H),6.70(dd,2H),7.29(d,4H),7.41(d,2H),7.61(d,4H),8.88(d,2H).

[0918] Synthesis Example (9): Synthesis of Compound (1-424)

[0919]

[0920] The compound represented by formula (1-424) was synthesized using the same method as in the synthetic example (1).

[0921]

[0922] The structure of the obtained compound was confirmed by NMR determination.

[0923] 1 H-NMR (CDCl3): σ=0.73~0.91(m,4H),0.98~1.24(m,12H),1.27(s,6H),1.33(s,9H) ,1.43(s,6H),1.47(s,9H),1.56~1.73(m,14H),5.55(s,1H),5.63(s,3H),6.70(d, 1H),6.76(d,1H),6.88(t,2H),6.94(d,4H),7.06(t,4H),7.13(d,2H),7.14(d,2H) ,7.37(dd,1H),7.39(d,2H),7.44(d,2H),7.45(dd,1H),8.87(d,1H),8.94(d,1H).

[0924] Comparative Synthesis Example (1): Synthesis of Compound (BD-1)

[0925]

[0926] Compound (BD-1) was synthesized according to the method of preparation of compound (1-25) as described in International Publication No. 2019 / 198699.

[0927] Comparative Synthesis Example (2): Synthesis of Compound (BD-2)

[0928]

[0929] Compound (BD-2) was synthesized according to the method of preparation of compound (1-327) as described in International Publication No. 2019 / 198699.

[0930] Comparative Synthesis Example (3): Synthesis of Compound (BD-3)

[0931]

[0932] Compound (BD-3) was synthesized according to the method of preparation of compound (1-334) disclosed in International Publication No. 2019 / 198699.

[0933] Comparative Synthesis Example (4): Synthesis of Compound (BD-4)

[0934]

[0935] Compound (BD-4) was synthesized according to the method of preparation of compound (1-321) as described in International Publication No. 2019 / 198699.

[0936] Comparative Synthesis Example (5): Synthesis of Compound (BD-5)

[0937]

[0938] Compound (BD-5) was synthesized according to the method of preparation of compound (1-401) disclosed in International Publication No. 2015 / 102118.

[0939] Comparative Synthesis Example (6): Synthesis of Compound (BD-6)

[0940]

[0941] Compound (BD-6) was synthesized according to the method of preparation of compound (1-339) as described in International Publication No. 2019 / 198699.

[0942] Comparative Synthesis Example (7): Synthesis of Compound (BD-7)

[0943]

[0944] Compound (BD-7) was synthesized according to the method of preparation of compound (2-1A-18) as described in International Publication No. 2020 / 054676.

[0945] Subsequently, examples of organic EL elements using the compounds of the present invention are shown to illustrate the invention in more detail, but the invention is not limited to these examples.

[0946] <Evaluation of Vapor Deposited Organic EL Devices>

[0947] Organic EL elements of Examples 1 to 13 and Comparative Examples 1 to 8 were prepared and measured to be 1000 cd / m 2 The characteristics of emission during emission, including voltage (V), emission wavelength (nm), and external quantum efficiency (%), were determined, followed by the following time intervals: at 10 mA / cm². 2 The time during which the brightness remains above 90% of the initial brightness when driven by a constant current density.

[0948] The quantum efficiency of a light-emitting element (LED) has internal and external quantum efficiencies. Internal quantum efficiency represents the proportion of external energy injected as electrons (or holes) into the LED's emitting layer that is purely converted into photons. On the other hand, external quantum efficiency is calculated based on the amount of photons released to the outside of the LED. Since some photons generated in the emitting layer are continuously absorbed or reflected inside the LED and not released to the outside, external quantum efficiency is lower than internal quantum efficiency.

[0949] The method for measuring external quantum efficiency is as follows. Using an Advantest voltage / current generator R6144, the applied element's brightness was set to 1000 cd / m². 2 The element emits light due to the voltage applied. Using a Topcon SR-3AR spectroradiometer, the spectroradiance in the visible light region was measured from a direction perpendicular to the emitting surface. Assuming the emitting surface is a perfectly diffused surface, the number of photons at each wavelength was obtained by dividing the measured spectroradiance value of each wavelength component by the wavelength energy and multiplying by π. The number of photons was then accumulated over the observed entire wavelength region and set as the total number of photons emitted from the element. The number of carriers injected into the element was determined by dividing the applied current value by the elementary charge, and the external quantum efficiency was obtained by dividing the total number of photons emitted from the element by the number of carriers injected into the element.

[0950] <Examples 1 to 13 and Comparative Examples 1 to 8>

[0951] The material composition and EL characteristics of each layer in the organic EL elements of Examples 1 to 13 and Comparative Examples 1 to 8 are shown in Tables 1A and 1B below.

[0952] [Table 1A]

[0953]

[0954] [Table 1B]

[0955]

[0956] In Table 1A, “HI” represents N. 4 N 4' -diphenyl-N 4 N 4' -bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4,4'-diamine, "HAT-CN" is 1,4,5,8,9,12-hexaazatriphenylhexacarbononitrile, "HT-1" is N-([1,1'-biphenyl]-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluorene-2-amine, "HT-2" is N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1”-triphenyl]-4-amine, "HT-3" is N-([1,1'-biphenyl]-2-yl)-N-(9,9-dimethyl-9H-fluorene) -2-yl)-9,9'-spirobis[fluorene]-4-amine, "BH-1" is 2-(10-phenylanthracene-9-yl)naphtho[2,3-b]benzofuran, "BH-2" is 2-(10-phenylanthracene-9-yl)dibenzo[b,d]furan, "BH-3" is 9-phenyl-10-(4-phenylnaphtho-1-yl)anthracene, "ET-1" is 4,6,8,10-tetraphenyl[1,4]benzoxoborhexacyclohexene[2,3,4-k1]phenoxyborocyclohexene, and "ET-2" is 3,3'-((2-phenylanthracene-9,10-diyl)bis(4,1-phenylene))bis(4-methylpyridine). The chemical structures are shown below together with "Liq".

[0957]

[0958] <Example 1>

[0959] A 26mm × 28mm × 0.7mm glass substrate (manufactured by Opto Science, Inc.) with an ITO film thickness of 180nm ground to 150nm was used as a transparent support substrate. The transparent support substrate was fixed on the substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum, Inc.), and a molybdenum vapor deposition boat containing HI, HAT-CN, HT-1, HT-2, BH-1, compound (1-25), ET-1, and ET-2, and an aluminum nitride vapor deposition boat containing Liq, LiF, and aluminum, respectively, were installed.

[0960] The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10⁻⁶. -4 First, HI is heated and vapor-deposited to a thickness of 40 nm. Then, HAT-CN is heated and vapor-deposited to a thickness of 5 nm. Next, HT-1 is heated and vapor-deposited to a thickness of 45 nm. Then, HT-2 is heated and vapor-deposited to a thickness of 10 nm to form a hole layer comprising four layers. Next, BH-1 and compound (1-25) are simultaneously heated and vapor-deposited to a thickness of 25 nm to form a light-emitting layer. The vapor deposition rate is adjusted to maintain a mass ratio of approximately 98:2 for BH-1 to compound (1-25). Then, ET-1 is heated and vapor-deposited to a thickness of 5 nm. Next, ET-2 and Liq are simultaneously heated and vapor-deposited to a thickness of 25 nm to form an electron layer comprising two layers. The vapor deposition rate is adjusted to maintain a mass ratio of approximately 50:50 for ET-2 to Liq. The evaporation rate of each layer is 0.01 nm / sec to 1 nm / sec. Then, LiF is heated and evaporation is performed at a rate of 0.01 nm / sec to 0.1 nm / sec to achieve a film thickness of 1 nm. Subsequently, aluminum is heated and evaporation is performed to achieve a film thickness of 100 nm to form a cathode, thereby obtaining an organic EL device.

[0961] A DC voltage was applied using an ITO electrode as the anode and a LiF / aluminum electrode as the cathode, and the voltage was measured at 1000 cd / m². 2 The emission characteristics were studied, resulting in blue emission at a wavelength of 458 nm, a driving voltage of 3.68 V, and an external quantum efficiency of 8.35%. Furthermore, the brightness was maintained at over 90% of its initial value for 365 hours.

[0962] <Examples 2 to Examples 13>

[0963] Each organic EL element was manufactured according to Example 1 and the layer structure described in Table 1A, and EL characteristic data were measured (Table 1B).

[0964] <Comparative Examples 1 to 8>

[0965] Each organic EL element was manufactured according to Example 1 and the layer structure described in Table 1A, and EL characteristic data were measured (Table 1B).

[0966] For example, it is known that compound (1-327) has the same structure as compound (BD-2) except for the presence or absence of a linker group with a cycloalkyl group. However, when comparing Example 2 and Comparative Example 3, which use them respectively, Example 2 provides higher external quantum efficiency and longer brightness retention time compared to Comparative Example 3.

[0967] <Example 14 and Comparative Examples 9-10>

[0968] To evaluate the solubility of the compounds of the present invention in organic solvents, a dissolution test was performed. 1.0 g of the test compound was placed in 30 mL of toluene and stirred at 100°C. The dissolution of the test compound was then verified. Examples where the compound completely dissolved in toluene to obtain a homogeneous solution were defined as "dissolved," while examples where unwanted residues remained were defined as "poorly soluble." The results are shown in Table 2A.

[0969] [Table 2A]

[0970]

[0971] <Examples 15 to 17 and Comparative Examples 11 to 12>

[0972] Perform a solubility test on the compound. Place 0.5 g of the test compound into 30 mL of toluene, stir at 100 °C, and then verify whether the test compound dissolves. The results are shown in Table 2B.

[0973] [Table 2B]

[0974]

[0975] <Examples 18 to 21 and Comparative Examples 13 to 17>

[0976] Perform a solubility test on the compound. Place 0.5 g of the test compound into 30 mL of toluene, stir at 60 °C, and then verify whether the test compound dissolves. The results are shown in Table 2C.

[0977] [Table 2C]

[0978]

[0979] <Example 22 and Comparative Example 18>

[0980] Perform a solubility test on the compound. Place 0.3 g of the test compound into 30 mL of toluene, stir at 80 °C, and then verify whether the test compound dissolves. The results are shown in Table 2D.

[0981] [Table 2D]

[0982]

[0983] Based on the dissolution tests of the compounds shown in Tables 2A to 2D, it can be seen that the compounds of the present invention having a linking group with a cycloalkyl group have high solubility in organic solvents.

[0984] [Industry availability]

[0985] In this invention, by providing novel polycyclic aromatic compounds, the options for materials used in organic devices, such as materials for organic EL elements, are increased. Furthermore, by using novel cycloalkyl-substituted polycyclic aromatic compounds as materials for organic EL elements, it is possible to provide, for example, organic EL elements with excellent luminous efficiency or element lifespan, display devices including said organic EL elements, and lighting devices including said organic EL elements.

Claims

1. A polycyclic aromatic compound, said polycyclic aromatic compound being represented by the following formula (1); In equation (1), Rings A, B, and C are each independently an aryl ring having 6 to 16 carbon atoms or a heteroaryl ring having 2 to 15 carbon atoms. At least one hydrogen atom in these rings may be substituted with L-Cy, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted arylheteroarylamino group, an alkyl group, a cycloalkyl group, or a substituted silyl group. The substituted or unsubstituted substituent is L-Cy, an aryl group, a heteroaryl group, an alkyl group, a cycloalkyl group, a diarylamino group, or a substituted silyl group. The substituted silyl group is a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, an alkyldicycloalkylsilyl group, a triarylsilyl group, a dialkylarylsilyl group, or an alkyldiarylsilyl group. Y 1 For B, X 1 and X 2 Each is independently designated as >NR; the R in >NR is an aryl group having 6 to 12 carbon atoms, wherein the aryl group having 6 to 12 carbon atoms may be substituted by L-Cy, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms. In the compound represented by formula (1), at least one of the aryl ring or heteroaryl ring may be bonded with a partial structure represented by formula (B10) or formula (B11). In formulas (B10) and (B11), Me represents methyl. The group indicated by formula (B10) or (B11) is bonded to two adjacent carbon atoms on the aryl or heteroaryl ring to which it is bonded. In the compound represented by formula (1), at least one of the aryl ring or heteroaryl ring is substituted by at least one L-Cy, where L is a straight-chain alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 2 to 6 carbon atoms, and at least one of the straight-chain alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 2 to 6 carbon atoms is a linker group in which -CH2- is substituted by -O- or -S-, and Cy is a cycloalkyl group. At least one hydrogen atom in the compound represented by formula (1) may be substituted by deuterium, cyano, or halogen. In the compounds represented by formula (1), the alkyl, cycloalkyl, aryl, and heteroaryl groups without a specified number of carbons are straight-chain alkyl groups with 1 to 24 carbons or branched alkyl groups with 3 to 24 carbons, cycloalkyl groups with 3 to 24 carbons, aryl groups with 6 to 10 carbons, and heteroaryl groups with 2 to 10 carbons, respectively.

2. The polycyclic aromatic compound according to claim 1, wherein, Cy is a cycloalkyl group with 3 to 20 carbon atoms.

3. The polycyclic aromatic compound according to claim 1 or 2, wherein, L can be -CH2-, -CH2CH2-, -CH2CH2CH2-, -C(CH3)2-, -C(CH3)2CH2-, or -C(CH3)2CH2CH2-.

4. The polycyclic aromatic compound according to claim 1 or 2, wherein it is a polycyclic aromatic compound represented by formula (1-a), formula (1-b) or formula (1-d); In equations (1-a), (1-b), and (1-d), R 1 ~R 11 Each of the following is independently hydrogen, L-Cy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, alkyl, cycloalkyl, or substituted silyl, wherein the arylheteroarylamino is an amino group having aryl and heteroaryl groups, and the substituent when substituted or unsubstituted is L-Cy, aryl, heteroaryl, alkyl, cycloalkyl, diarylamino, or substituted silyl, R 1 ~R 11 The adjacent groups in the formula (1-b) can bond to each other and together with the a, b, or c rings, which are benzene rings, to form a naphthol ring, carbazole ring, indole ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, indene ring, or fluorene ring. In formulas (1-b) and (1-d), R 4 and R 5 They can bond to each other and together with the c ring to form an indole ring, a benzofuran ring, or a benzothiophene ring, in formula (1-d), R 10 and R 11 They can bond together with each other and form an indole ring, benzofuran ring, or benzothiophene ring together with ring b. At least one hydrogen in the formed ring can be substituted by L-Cy, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted diheteroarylamino group, a substituted or unsubstituted arylheteroarylamino group, an alkyl group, a cycloalkyl group, or a substituted silyl group, wherein the arylheteroarylamino group is an amino group having an aryl group and a heteroaryl group. The substituted or unsubstituted substituent is L-Cy, an aryl group, a heteroaryl group, an alkyl group, a cycloalkyl group, a diarylamino group, or a substituted silyl group. The substituted silyl group is a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, an alkyldicycloalkylsilyl group, a triarylsilyl group, a dialkylarylsilyl group, or an alkyldiarylsilyl group. X X Each can be independently >O, >S, >NR, or >C(-R)2, where R in >NR is aryl, and R in >C(-R)2 is methyl. Y 1 For B, X 1 and X 2 Each is independently designated as >NR, where R in >NR is an aryl group having 6 to 12 carbon atoms, and the aryl group having 6 to 12 carbon atoms may be substituted by L-Cy, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms. In the compounds represented by formulas (1-a), (1-b), and (1-d), at least one of the aryl ring or heteroaryl ring may be bonded with a partial structure represented by formula (B10) or (B11). In the compounds represented by formulas (1-a), (1-b), and (1-d), at least one of the aryl ring or heteroaryl ring is substituted by at least one L-Cy, where L is a straight-chain alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 2 to 6 carbon atoms, and at least one of the straight-chain alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 2 to 6 carbon atoms is a linker group in which -CH2- is substituted by -O- or -S-, and Cy is a cycloalkyl group. In the compounds represented by formulas (1-a), (1-b), and (1-d), at least one hydrogen atom may be substituted by a cyano group, a halogen, or a deuterium group, and, In the compounds represented by formulas (1-a), (1-b), and (1-d), the alkyl, cycloalkyl, aryl, and heteroaryl groups without a specified number of carbons are straight-chain alkyl groups with 1 to 24 carbons or branched-chain alkyl groups with 3 to 24 carbons, cycloalkyl groups with 3 to 24 carbons, aryl groups with 6 to 10 carbons, and heteroaryl groups with 2 to 10 carbons, respectively.

5. The polycyclic aromatic compound according to claim 4, wherein it is a polycyclic aromatic compound represented by formula (1-a).

6. The polycyclic aromatic compound according to claim 5, wherein it is represented by any of the following structural formulas; In each of the structural formulas, "Me" represents methyl and "tBu" represents tert-butyl.

7. The polycyclic aromatic compound according to claim 4, wherein it is a polycyclic aromatic compound represented by formula (1-b).

8. The polycyclic aromatic compound according to claim 7, wherein it is represented by the following structural formula; In the structural formula, "Me" represents methyl.

9. An organic electroluminescent element comprising: a pair of electrodes, including an anode and a cathode; and an organic layer disposed between the pair of electrodes, and containing a polycyclic aromatic compound as claimed in any one of claims 1 to 8.

10. An organic electroluminescent element comprising: a pair of electrodes, including an anode and a cathode; and a light-emitting layer disposed between the pair of electrodes, and containing a polycyclic aromatic compound as claimed in any one of claims 1 to 8.

11. The organic electroluminescent element according to claim 10, wherein, The light-emitting layer comprises a host and the polycyclic aromatic compound as a dopant.

12. The organic electroluminescent element according to claim 11, wherein, The main component is anthracene compounds, fluorene compounds, or dibenzo[a]benzene compounds.

13. A display device or lighting device comprising an organic electroluminescent element as claimed in any one of claims 9 to 12.

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